\?

NEW SYSTEM
OF

CHEMICAL PHILOSOPHY.

PART

I.

BY

JOHN DALTON.

-MMNii9l!li(MMf**i

iWancijegter

Printed by S. Russell, is5t Oeanigate,

FOR
R.

BICKERSTAFF, STRAND, LONDON.

1808.

Reproduced

in Facsimile

BY

William Dawson
102

WiGMORE

& Sons Ltd.

Street,

London, W.l
AND Printed by

Henderson

& Spalding

Sylvan Grove, Old Kent Road,

London, S.E.I 5

V. 1

This Edition

is

limited to

i^

27

T 5 1

1,000

copies

TO THE

PROFESSORS OF THE UNIVERSITIES,

AND OTHER

RESIDENTS,

OF

EDINBURGH AND GLASGOW,

who

gave

THEIR ATTENTION AND ENCOURAGEMENT

TO THS

Lectures on

Heat and Chemieal Elements,

Delivered in those Cities in 1807

AXD

TO THE MEMBERS OF THE

LITERARY AND PHILOSOPHICAL SOCIETY

OF MANCHESTER,
wbo

have

VNIFORMLY PROMOTED

THIS

HIS RESEARCHES;

WORK IS RESPECTFULLY INSCRIBED,

BY THS

JUTHOR.

PREFACE.
I T was the author's
to press to publish

now

it

intention
entire

induced to publish

it

when

work was put

this

one volume

in

two

in

but he

is

for reasons

parts,

it
may be proper to announce.
Various essays of his were read before the Literary
and Philosophical Society of Manchester, chiefly on

which

heat and elastic fluids, and

Volume of
which

their

these

Memoirs,

several

The

Philosophical

tianslated into

French

in the 5tb

The new view*

1802,

essays developed,

curious and important.

in

were published
in

were considered both

essays

were republished

Journals,

soon

and

after

and circulated

and German,

abroad through the medium of the foreign Journals.

The author was not remiss in prosecuting his researches,
in

which he was considerably

assisted

the applica-

by

tion of principles derived from the above essays.

In

1803, he was gradually led to those primary Law,

which seem to obtain in regard to heat^ and to chemical combinations, and which it is the object of the
present

work

to exhibit

and elucidate.

brief outline

publicly given the ensuing winter in

a course of Lectures on Natural Philosophy, at the

of them was

Royal

first

Institution in

London, and was

left for
;

informed whether that was done.

The

ever since been occasionally urged by

publica-

but he

tion in the Journals of the Institution

is

not

author has

several

of his

philosophical friends to lose no time in communicating

the results of his enquiries to the public, alledging, that

the interests of science, and his

own

reputation,

might

PREFACE.

VI,

suffer

by

delay.

In the spring of

807, he was induced

to offer the exposition of the principles herein contained

in a course of Lectures,

which were twice read

in

On these occasiot^
Edinburgh, and once in Glasgow.
he was honoured with the attention of gentlemen,
universally acknowledged to be of the first respectability
for their scientific attainments:

most of

whom

were

pleased to express their desire to see the publication of

the doctrine in the present form, as soon as convenient.

the author's return to Manchester he began to

Upon

prepare for the press. Several experiments required to be

repeated ; other new ones were to be made ; almost
the whole system both in matter and manner was to be
new, and consequently required more time for the

composition and arrangement. These considerations^

together with the daily avocations of profession, have
delayed the
past,

it

pleted.

work

nearly a year

and, judging from the

it can be comrequire another year before

In the mean time, as the doctrine of heat, and

may

the general principles of Chemical Synthesis, are in a

of the future details, there
degree independent

good
can no great detriment

arise to the author,

venience to his readers, in submitting what

to the inspection of the public.
prepared,

MAY, 1808.

or inconis

already

CONTENTS OF PART

FIRST.

-----

Chap. i. On Heat or Caloric

Section l On Temperature and
.

ments/or measuring

5.

6.

On

On

&(c.

the

8.

On

9.

On

arising

On the
Section 1. On

from
-

in-

133

Constitution of Bodies

141

the constitution of pure elastic

2.

On

3.

On the

the

constitution

elastic fluids

------

constitution of liquids,

mechanical

145

of mixed

relations

150

and
beJ

94

On the constitution of solids

On Chemical Synthesis - - -

208

211

JExplanaiion of the Plates -

217

4.
III.

99

the Con-

twixt liquids atid elastic fluids

Ch.4P.

82

the

'

75

-------123

Phenomena of

the

fiuids

Temperature of the atmo-

the

gelation of water
ii.

motion and communica-

equality of temperature

sphere

Chap.

or absolute privation of

tion of heat,

es

--------

heat
7.

-----

the natural Zero of tempera-

ture,

the Quantity of heat evolved by

combustion,

On

of elastic fluids
..

it

4.

3.

the instru-

23
On Expansion hy heat - - 47
On the specific heat of bodies On the Theory of the specific heat

2.

FACt

NEW SYSTEM
OF

CHEMICAL PHILOSOPHY.

W0IW

CHAP.

I.

ON HEAT OR CALORIC.
HE most probable
nature of caloric,
tic

fluid

of

is,

great

opinion concerning the

its being an elas-

that of

the

subtilty,

which repel one another, but

all

particles of

are attracted

by

other bodies.

surrounding bodies are of one

the heat attached to them
then
temperature,
is in a quiescent state ; the absolute quantities

When

all

of heat in any two bodies in this case are not

we take the bodies of ec-ual
equal, whether

Each kind of
weights or of equal bulks.
matter has its peculiar aflBnity for heat, by
a certain portion of the fluid,
which it
requires

in order to
at

be

in equilibrium

a certain temperature.

with other bodies

Were

the whole

ON HEAT OR CALORIC.

gjiantities of heat in bodies of equal

weight or

bulk,

or even the relative quantitieSy

rately

ascertained, for

any temperature,

numbers expressing those

constitute a table

accu-

quantities

the

would

of specific heats, analogous

to a table of specific gravities,

and would be

an important acquisition to science. Attempts

of this kind have been made with very considerable success.

Whether

the specific heats, could they be

thus obtained for one temperature,

would ex-

press the relation at evefy other temperature,

whilst the bodies retained their form, is an

enquiry of some moment.

From

the experi-

ments hitherto made there seems little doubt of

being nearly so ; but it is perhaps more correct to deduce the specific heat of bodies from
It is
very
equal bfdks than from equal iveights.
its

two methods will not give prebecause the expansions

same
the
results,
cisely
of different bodies by equal increments of

certain that the

same.
But before
temperature are not the
we should
be
well
can
considered,
subject
settle

what

is

temperature.

this
first

intended to be meant by the word

ON TEMPERATURE.

SECTION

1.

ON TEMPERATURE,
And
The

the Instruments for measuring

it.

notion of the specific heat of bodies

and of temperature, may be well conceived

from a system of cylindrical vessels of different
diameters connected with each other by pipes
at the bottom, and a small cylindrical tube
attached to the system, all capable of holding
water or any other liquid, and placed perhorizon. (See Plate
pendicular to the

The

cylinders are

specific

to

heats of bodies

1.
Fig. 1.)
the different

represent
and the small tube,
;
to

represent
being divided into equal parts,
the thermometer or measure of temperature.
If water be poured into one vessel it rises to
is

the same level in

in,

them

all,

and

in the

thermo-

equal portions be successively poured

there will be equal rises in the vessels and

meter

if

the water is obviously intended

heat
or caloric.
to represent
According to this
that
evident
it
is
notion, then,
equal incre-

in the tube

ments of heat

in any body correspond to equal

increments of temperature.
This view of the subject necessarily requires,

that if

two bodies be taken of any one tempe-

ON TEMPERATURE.

and then be

rature,

perature,

any other tem-

raised to

additional

the

quantities

of heat

received by each will be exactly proportioned

to the

whole quantities of that fluid previously

This conclusion, though

contained in them.
it

may be

ral,

is

nearly consistent with facts in gene-

not

certainly

elastic fluids,

it

is

strictly

true.

known, an

well

hulk occasions an increase

of

For,

in

increase of

specific

heat,

and temperature continue

probable then that solids and

though the weight

the same.

It

is

bulk by heat,

liquids too, as they increase in

increase in their capacity or capability of re-

ceiving

vided

all

This circumstance, however,

more.

conclusion above, probodies increased in one and the same

might not

affect the

proportion by heat ; but as this is not the case,

the objection to the conclusion appears of validity.
Suppose it were allowed that a ther-

mometer ought

to

indicate the accession of

equal increments of
caloric, to the

the

fluid

body of which

it

denominated

was

to

shew

the temperature ;
suppose too that a measure
of air or elastic fluid was to be the bodyj query,

"whether ought the air to be suflTered to expand

by the temperature, or to be confined to the same

space of one measure

most

likely in theory to

appears to me the
procure a standard

It

capacity for heat by subjecting a body to heat.

ON TEMPERATURE.
whilst Us bulk

is

kept constanthj the same. Let

z= the quantity of heat necessary to raise the

elastic fluid 10* in

then

771 -f- rf

==

the same 10,

temperature in this case

the quantity necessary to raise

when

suffered to

expand,

fi

being

the difference of the absolute quantities of heat

contained by the body in the two cases. Now,

tV m

the quantity of heat necessary to raise

the

temperature 1 in the first case ; but

T-V [m-i-d) can not be the quantity necessary in
the second case ; it will be a less quantity in
the lower degrees, and a greater in the higher.
If these principles be admitted, they may be
applied to liquids and solids ; a liquid, as wa-

cannot be raised in temperature equally by

equal increments of heat, unless it is confined
within the same space by an extraordinary and
ter,

perhaps incalculable force ; if we suffer it to

take its ordinary course of expansion, then,
not equal, but increasing increments of heat
will raise

its

temperature uniformly.

If

suffi-

were applied to condense a liquid

there can be no doubt but heat would

cient force

or solid,

be given
It

out, as with elastic fluids.

may perhaps be urged by some

difference of heat in
air,

that the

condensed and rarefied

and by analogy probably in the supposed

and solids, is too small to have

cases of liquids

sensible influence

on the capacities or

affinities

ON TEMPERATURE.

f bodies for heat

as only to raise

few degrees
of heat

that the effects are such,

;
or depress the temperature a

when perhaps

equivalent to

is

such degrees

two

the

whole mass

or three thousand

and that a volume of

air sup-

posed to contain 2005 of temperature being

rarefied

till it

become

2000, or lost 5 of tem-

be considered as having its

perature, may
invariable.
This may be granted if
capacity
still

the data are admissible

the true changes

; but
of temperature consequent to the condensation
and rarefaction of air have never been deter-

mined.
Vol.
ting

5, Pt.
air

have shewn, (Manchester

2.) that in

into

condensed

air,

a vacuum,
the

affected as if in a

lower temperature

Mem.

the process of admit-

and of liberating

inclosed thermometer

is

medium

of 50 higher or
but the effects of instan-

taneously doubling the density of air, or rebe derived

plenishing a vacuum, cannot easily

from those or any other facts I am acquainted

with ; they may perhaps raise the temperature
one hundred degrees or more. The great heat
is a
proof of a
air.
inclosed
in
the
of
capacity
great change
it
be
then
whole
the
concluded,
may
Upon

produced

in

charging an air-gun

same body by
change of temperature, is productive of considerable effect on its capacity for heat, but

that the change of bulk in the

ON TEMPERATURE.

we

that

are not yet in possession of data to

determine

effect

its

on liquids and

Jess

on

elastic fluids,

solids..

and

M. De Luc

still

found,

mixing equal weights of water at the

freezing and boiling temperatures, 32 and 212",
that in

the mixture indicated nearly 119" of Fahrenheit's mercurial thermometer; but the numerical

mean
water

is

122

at 32

mean of

he had mixed equal bulks of

Now

115.

experiment
too high

if

and 2 12, he would have found a

in both

for,

the means determined

by

these

ways are probably

water of these two temperatures

being mixed, loses about l-90th of its bulk ;

this condensation of volume (whether
arising

from an increased

affinity of aggregation, or
the effect of external mechanical compression,
is all one) must expel a quantity of heat, and

the temperature above the true mean.

not improbable that the true mean temperature between 32 and 212 may be as low

raise
It is

as

10 of Fahrenheit.

been generally admitted

It has

that if

two

portions of any liquid, of equal weight but

of different temperatures, be mixed
together,
the mixture must indicate the true

perature

and

ponds with
perature.

be correct,

it

that
is

But
it

mean tem-

instrument which corres-

an accurate measure of temif

the preceding observations

may be

questioned whether any

ON TEMPERATURE.

two

liquids will agree in giving the

same mean

temperature upon being mixed as above.

In the present imperfect mode of estimating
the equable expansion of mercury is adopted as a scale for its measure.
This cannot be correct for two reasons; 1st.

temperature,

the mixture of water of different temperatures

is
always below the mean by the mercurial

thermometer

for instance,

water of 32 and

212 being mixed, gives 119" by the thermometer ; whereas it appears from the preceding
remarks, that the temperature of such mixture

be found above the mean 122; 2d.

mercury appears by the most recent experiments to expand by the same law as water j

ought

to

as the square of the temperature from

The apparently
the point of greatest density.
equal expansion of mercury arises from our

namely,

taking a small portion of the scale of expanand that at some distance from the free-

sion,

zing point of the liquid.

From what has been remarked
that

we have

not yet any

cable for ascertaining

mode

what

is

it

appears

easily practi-

the true

mean

between any two temperatures, as those of

freezing and boiling water ; nor any thermometer which can be considered as approximating nearly to accuracy.

Heat

is

a very important agent in nature

it

ON TEMPERATURE.

cannot be doubted that so active a principle

must be subject

nomena

do not take a

If the phe*

to general laws.

indicate otherwise,
sufficiently

it

is

because

we

comprehensive view

of them.

Philosophers have sought, but in

vain, for a body that should expand uniformly,
or in arithmetical progression, by equal incre-

ments of heat;

liquids

have been

found to expand unequally,

panding more

tried,

and

of them ex-

all

in the higher temperatures than

no two exactly alike. Mercury has appeared to have the least variation*
or approach nearest to uniform expansion, and
in the lower, but

on

that

and other accounts has been generally

preferred in the construction of thermometers.

Water has been

most unequally

rejected, as the

expanding liquid yet

known. Since

the publi-

cation of
elastic

my experiments on the expansion of

fluids by heat, and those of
Gay Lussac,
both demon-

immediately succeeding them,

strating the perfect sameness in all
elastic fluids in this respect

it

permanently

has been ima-

gined by some that gases expand equally ; but

is not corroborated
by experience from

this

other sources.

Some time ago

that water

it

occurred to

me

as probable,

and mercury, notwithstanding

apparent diversity,

actually

expand by

their

the

same law, and that the

quantity of expansion

ON TEMPERATURE.

lO
is

as the square of the temperature from their

Water very nearly

accords with this law according to the present
scale of temperature, and the little deviation
respective freezing points.

observable

exactly of the sort that ought

known error of the equal

is

to exist, from the

division of the mercurial scale.

By

prosecut-

enquiry I found that the mercurial

and water scales divided according to the prin-^

ing

this

ciple just mentioned, would perfectly accord,

as far as they were comparable ; and that the

law

will probably extend to all

other pure

liquids j but not to heterogeneous

as liquid solutions of salts.

compounds,

If the law of the expansion of liquids be such

as just mentioned,

other

phenomena

of the same law.

it

is

natural to expect that

of heat will be characteristic

It

may be

seen in

my

Essay

on the Force of Steam (Man. Mem. Vol.

Part

2.)

5,

that the elastic force or tension of

steam in contact with water, .increases nearly

in a geometrical progression to equal increments of temperature, as measured by the coni'

mon mercurial
prising to

me

scale

at

it

was not a

little

sur-

the time to find such an ap-

proach to a regular progression, and I was then

inclined to

think, that

the

want of

perfect

coincidence was owing to inaccuracy in the

division of the received thermometer j but

ON TEMPERATURE.

overawed by the authority of Crawford, who

seemed to have proved past doubt that the error
of the thermometer no where amounted to

mare than one or two degrees, I durst not

venture to throw out more than a suspicion at
the conclusion of the essay, on the expansion
of elastic fluids by heat, that the error was
determined ;
probably 3 or 4**, as De Luc had
the
in
of
an
error
to admit
supposed mean,

amounting to 12% seemed unwarrantable.

How-

ever it now appears that the force of steam in

contact with water, increases accurately in
to equal increments of
geometrical progression
those increments are
temperature, provided
a thermometer of water or mer,
measured

by

cury, the scales of

which

are divided accord-

ing to the above-mentioned law.

The Force
vary by

of Steam having been found to

it was natural to ex-

the above law,

pect that of air to do the same

for,

elastic fluid)

air

and

(meaning any permanently

steam are essentially the same, differing only
in certain

modifications.

found upon

trial

that air

Accordingly it wz%
expands in geometri-

cal progression to equal increments of

rature,

measured as above.

from water, by which

it is

tempeSteam detachel

rendered incapable

of increase or diminution in quantity,

by Gay

Lussac, to

was found

have the same quantity ot

ON TEMPERATURE,

12

expansion as the permanently elastic fluids.

I had formerly conjectured that air expands
as the cube of the temperature from absolute

privation, as hinted in the essay

tioned;

am now

but I

above-men-

obliged to abandon

that conjecture.

The union

of so

many

analogies in favour

the preceding hypothesis

of

almost sufficient to establish

it;

temperature is
but one remark-

able trait of temperature derived from experiments on the heating and cooling of bodies,
which does not accord with the received scale,

and which,
sideration,

nevertheless, claims
is,

special con-

that a body in cooling loses heat

in pi^oportion to its excess

that of the cooling

of temperature above
the tem; or that

medium

perature descends in geometrical progression

Thus if a body
in equal moments of time.

were 1000" above

the

medium

the times in cool-

ing from 1000 to 100, from 100 to 10,and from

10 to r, ought all to be the same. This,
not accurately true, if we
>
adopt the common scale, as is well known
of
the times in the lower intervals
temperature

though nearly,

is

are found longer than in the upper ; but the new

scale
shortening the lower de-

proposed, by

grees,

and lengthening the higher,

perfectly according
heat.

to

this

is

found

remarkable law of

ON TEMPERATURE.

13

Temperature then will be found to have four

most remarkable analogies to support it.
All pure homogenous liquids, as water
1st.
and mercury, expand from the point of their
a quantity
congelation, or greatest density,
always as the square of the temperature from
that point.
2.

The

force of steam from pure liquids,

as water, ether, &c. constitutes a geometrical

progression to increments of temperature in

arithmetical progression.
The expansion of permanent elastic
3.
is in
geometrical progression to equal
increments of temperature.
The refrigeration of bodies is in geo4.

fluids

metrical

progression

in

equal increments of

time.

A mercurial thermometer graduated according to this principle will differ from the ordinary one with equidifferential scale, by having
its

lower degrees smaller and the upper ones

the mean between

and
;
freezing
boiling water, or 122 on the new scale, will
be found about 1 10 on the old one. The
larger

following Table exhibits the numerical calculations illustrative of the principles inculcated

above.

ON TEMPERATURE.

14

NEW TABLE OF TEMPERATURE.

True

Roots,

equal

or intet-

inter-

vals of

Mercury.
Same as
preceding

vals of tempe-

column,
40

tempe-

rature,

or Faren

Titure.

com.dif

heit's

=.4103

scale.

'75
-

68

-5^
-48

-38
-

18
8
s

13

43803
4 7908
5.2013
5.6118
6.0223
6.4328

68433
7.a338

76643
8.0748

84853
63
7*
82
9^
10a
112
112
J3
143

8.8958
9 3063
9.7108
10.1373

105378
10.9483
11.3588

n. 769^3
12.1798
la

5903

13 0008

34"3
162
172
182

13.8218
i4.233
14.6428

jgz

5433

202
312

i5-463

312

'9-9793
24 0843
28.1893
3a 2943

41a
512
I2
71"

15*743

336.399

ON TEMPERATURE*

15

Explanation of the Table.

The

column contains the degrees of

temperature, of which there are supposed to
first

be 180 between freezing and boiling water,

according to Fahrenheit. The concurrence
of so many analogies as have been mentioned,
as well as experience, indicate that those de-

grees are produced by e<|ual increments of

the matter of heat, or caloric ; but then it

should be understood they are to be applied

to a body of uniform bulk and capacity, such
as

air

confined within a

water, fof instance, in

its

If

given space.

be raised successively through equal

temperature, as measured by this

to

is

ordinary state,

intervals
scale,

of

thea

unequal increments of heat will be requisite,

by reason of its increased capacity. The first

number

in the

point

ed

40.

column,

which mercury

at

10 from

The

68

175", denotes the

freezes, hitherto

calculations are
to

made

212"; above the

ber, for every 100.

mark-

for every

num-

last

this

column

By comparing
with the 5th, the correspondences of the
scale and the common one are perceived
greatest

difference

observable at
agrees with

new
:

the

between S2 and 212

122 of the

new

110' of the old,

scale,

the

is

which

diflference

ON TEMPERATURE.

16

but below 32 and above 212%

become more remarkable.
The 2d and 3d columns are two series,

being 12

the

differences

one of

They

and the other of

roots,

are obtained thus

in the

opposite 32,

the

their squares.

placed in the 3d, 72, being

the number of degrees or equal parts in Fahren-

first

column,

heit's

water

is

scale from freezing

;

252 in

mercury

and opposite 2 1 2
the 3d, being 212

in the

to freezing

first is

40, the

placed

number

equal parts) between

and boiling water.
The
square roots of these two numbers, 72" and
252, are found and placed opposite to them
of degrees

(or rather

mercury

freezing

second column.

in the

represents the

The number 8.4853

relative quantity

of real tem-

perature between freezing mercury and free-

zing water; and the number 15.8743 represents the

between freezing mercury and

like

water

boiling

consequently the

difference

7.3890 represents the relative quantity between

freezing water and boiling water, and 7.3890
-^ 18

=.4 105

ponding

to

represents the quantity corres-

each interval of

10.

By adding

.4105 successively to 8.4853, or subtracting it

from it, the rest of the numbers in the column
are obtained,
tical

which are of course

progression.

column

The numbers

arc all obtained

in arithme-

in

the

3d

by squaring those of

ON TEMPERATURE.

The unequal

to them.

2d opposite

the

1*7

dif-

column mark the expansions

of mercury due to equal increments of temThe inconvenient
perature, by the theory.
ferences in the 3d

its being carried

length of the table prevents
to
the point of freedown by ifitervals of 10"
is found to be
however
zing mercury, which

at

175.

The

4th column

is

the

the difference of 40, to

common method

the

same

as the 5d,

make

it

with

conform

to

of numbering on Fahren-

heit's scale.

The

5th

column

is

the

4th corrected, on

account of the unequal expansion of Glass

The apparent expansion

is

of mercury in glass

than the real, by the expansion of the

itself; this, however, would not disturb the

less

glass

law of expansion of the liquid, both apparent

and real being subject to the same, provided
the glass expands equally ; this will be shewn
But

hereafter.

that

Luc,

it

glass

has been shewn by De

less in the lower

expands

the higher ; this must

occasion the mercury apparently to expand
more in the lower half than what is dictated

half of the scale than

law

of expansion.
By calculating
Luc's data, I find, that the mercury
in the middle of the scale, or 122, ought to be

by

the

from

De

found nearly

higher than would be, were

it

ON TEMPERATURE.

13

not for

this increase.

Not however

the effect, I have taken

the

number

in the 5th, and the rest of the

rected

to over-rate

only at r.7, making

108% 3 in the 4th column, 110
it

accordingly.

column cannot well

column

is

cor-

The numbers in this

be extended much beyond

the interval from freezing to boiling water, for

want of experiments on

By viewing

this

the expansion of glass.

column along with the

1st,

the

quantity of the supposed error in the common

scale may be perceived ; and any observations

on the old thermometer may be reduced

the new.

The

6th

column contains

natural series

1,

2, 3,

to

the squares of the

&c. representing the

expansion of water by equal intervals of temThus, if a portion of water at

perature.
42" expands a quantity represented by 289, at
the boiling temperature, then at 52 it will be
found to have expanded I, at 62, 4 parts, &c.

&c.
tion

Water expands by cold or the abstracof heat in the same way below the point

of greatest density, as will be illustrated when

to consider the absolute expansion of

we come

The apparent greatest density too

does not happen at 39,3 old scale ; but about
42 ; and the greatest real density is at or near
bodies.

36 of the same.

The

7th column contains a series of

num-

ON tEMPERATURE.

19

bers in Geometrical Progression, denoting the

expansion of air, or elastic fluids. The volume

is taken 1000, and at 212% 1376 accord-

at 32'

Gay

Lussac's and

for the

at

ing to

As

expansion

my own

experiments.

intermediate degrees.

General Roi makes the temperature at midway of total expansion, 1 I6i old scale from
;

the results of ray former experiments, (Manch.

Mem. Vol. 5, Part 2, page 599) the tem-

perature may be estimated at 1 194 ; but I had

not then an opportunity of having air at 32%
By more recent experiments T am convinced
that dry air of 32' will
tity

from that

as from the

expand the same

to 117 or 118

last

qiian-

of common scale,

term to 212.

According to

the theory in the above Table it appears, that

air of 117 will be 1188, or have
acquired one

Now

half its total expansion.

if the
theory accord so well with experiment in the middle of

we cannot expect
wise in the intermediate points.

the interval,

it

to

do other-

The 8th column contains the force of aqueous vapours in contact with water
expressed
in inches of mercury, at the
respective temIt constitutes a
geometrical prothe
numbers opposite 32 and 212,
gression;
namely, .200 and 30.0 are derived from ex-

peratures.

periments, (ibid, page 559)

determined from theory.

It

and the
is

rest are

remarkable that

ON TEMPERATURE.

20

numbers do not

those

just referred to,

from the table

differ

which was the

tual experience, so

much

result

as 2 in

of ac-

any part; a

might even exist between two

thermometers of the same kind.

difference that

The

9th column exhibits the force of the

of

vapour

liquid ether

sulphuric

which

contact with

ether in

a geometrical progression, having a less ratio than that of water.

Since writing my former Essay on the Force

of Steam,

am

is

enabled to correct one of the

conclusions therein contained

committed by trusting

common

the error

was

to the

accuracy of the
mercurial thermometer.
Experience

me that the force of vapour from

water of nearly 2 2% varied from a change of
temperature as much as vapour from ether of
confirmed

Hence I deduced this general

" that the variation of the force
Jaw, namely,
of vapour from all liquids is the same for the
nearly

same

100.

variation of temperature, reckoning from

vapour of any given force."

But

now

find

that 30 of temperature in the lower part of

the common scale is much more than 30 in

the higher: and therefore the vapours of ether

are not subject to the same change

and water

of force by equal increments of temperature.

truth is, vapour from water, ether and

The

other liquids, increases in force in geometri-

ON TEMPERATURE.
cal progression to
ratio

is

temperature; but the

Ether as

the

different in different fluids.

manufactured

the large

in

a very homogeneous liquid.

it

in

2l

way, appears to be
I have purchased

London, Edinburgh, Glasgow and Man-

chester, at very different times, of precisely the

same quality
such as

in respect to its

when thrown up

vapour

into a

;
namely,
barometer

would depress the mercury 15 inches

at the

temperature of 68. Nor does it lose any of

its effect by time ; I have now a barometer

with a few drops of ether on the mercury, that

has continued with invaried efBcacy for eight

The numbers

or nine years.

in

the results

of

repeated

above ether barometer

above and beloW

80,

many

are

on the

observations

for

are

column

the

between the temperatures of 20 and

years

those

obtained from direct

to 212 ; the low

experiment as far as from
found
were
ones
by subjecting the vacuum of
the barometer to an artificial cold mixture ;

and the higher ones were found

related in
force has

my

been

in the

manner

only the highest

considerably increased from

former Essays

formerly had it, in consequence of

supplying the manometer with more ether i

what

it

having been found to leave little or no liquid

at the temperature of 212 ; and in order

when

to obtain the

maximum

effect

it

is

indispen-

ON EXPANSION.

22
sible

have a portion of liquid remaining

to

in contact with the vapour.

The

10th column shews the force of va-

pour from alcohol, or rather common spirit of

wine, determined by experiment in the same
way as the vapour of water. This is not a
geometrical progression, probably because the
I susliquid is not pure and homogeneous.

pect the elastic fluid in this case

of aqueous and alcoholic vapour*

is

a mixture

SECTION 2.

EXPANSION BY HEAT.
One

important effect of heat

sion of bodies of every kind.

is

the expan-

Solids are least

expanded ; liquids more ; and elastic fluids

The quantities of increase in
most of all.
bulk have in many instances been determined;
but partly through the want of a proper ther-

mometer,

little

general information has been

The
experiments.
force necessary to counteract the expansion
derived

from

particular

has not been ascertained, except in the case

of elastic fluids s but there is no doubt it is
very great.

The

quantity and law of expan-

sion of all pernianeBt elastic fluids have alreadjr

23

ON EXPANSION.
bcen'given

and

remains then to advert to liquid

it

solid bodies.

In order
it

liquids,

understand the expansion of

to

expedient to

is

propositions

premise

certain

Suppose a thermometrical vessel of glass,

filled with any liquid up to

1st.

metal, &c., were

certain

known

mark

in the stem

and that

it

was

the vessel and the liquid had precisely

the same expansion, bulk for bulk, with the

same change of temperature ; then it must be

evident

upon

little

consideration, that what-

ever change of temperature took place, the

liquid must remain at the same mark.
2.

as

Suppose

before,

except

that

both

bodies expand uniformly with the temperature, but the liquid at a greater rate than the
vessel

then

it

is

evident by an increase of

temperature, the liquid w^ould appear to ascend

uniformly a quantity equal to the difference

of the absolute expansion of the two bodies.

3. Suppose as in the last case, but that Ihe li-

quid expands
liquid

at a less rate

than the vessel ; the

would then descend, and

that uniformly

by an

increase of temperature, a quantity equal

to the difference of the absolute expansions.

Suppose as before, only the vessel now

expands uniformly, and the liquid with a ve4.

locity uniformly accelerated,

commencing from

ON EXPANSION'.

24
rest

in

this case

if

temperature be added

uniformly, the liquid will appear to descend

with a velocity uniformly retarded to a certain

point, there to be stationary, and afterwards to
ascend with an uniformly accelerated velocity,
of the same

sort

the velocity with

as

the

former.

For,

as

which the

liquid expands is
must
successively pass
unifornrly accelerative,
to any assigned
through all degrees from
it

quantity,

and must therefore

ment be

the

same

therefore, for that

in

some moand

as that of the vessel,

moment, the

liquid must ap-

previously to that time the

pear stationary
liquid must have descended by the third proposition, and must afterwards ascend, by the
:

Let the absolute

uniformly.
the
liquid at the moment
space expanded by
of equal velocities be denoted by 1, then that
2d.

but

not

of the vessel in the same time must be 2

cause

the velocity acquired

accelerating force,

is

be-

by an uniformly

such as to

move

body

through twice the space in the same time. It

follows then that the liquid must have sunk
1,

being the excess of the expansion of the

above that of the liquid. Again, let

vessel

another portion of temperature equal to the

former be added, then the absolute expansion
of the liquid will be 4, reckoned from the com-

mencement J and

the expansion of the vessel

ON EXPANSION.
the place of the liquid will be the

also 4

as at

first,

ascend
tion

23

and therefore

it

by the 2d portion.

same

must apDarently
Let a third por-

of heat equal to one of the former be

added, and it will make the total expansion

of the liquid 9, or give 5 additional expansion, from which deducting 2, that of the
remains 3 for the apparent expansion by the 3d portion ; in like manner 5
will be due for the 4th, and 7 for the 5th, &c.,

vessel, there

odd numbers.

series of

being the

But the

aggregate of these forms a series of squares,

as

is

well

Hence

known.

sion will proceed by the

the apparent expan-

same law

as the real,

If
only starting from a higher temperature.
the law of expansion of the liquid be such
that either the addition or abstraction of tem-

perature, that

is,

alike,

expansion

greatest density
will

still

real.

either heat or cold produces

reckoned from the point of

then the apparent expansion

be guided by the same law as the

For^

if

when

point of the scale,

heat, it ascends to 1

the liquid

is

at the

lowest

we withdraw
;

or

is

a portion of
in the circumstance

of greatest density, and no expansion as at

the commencement; if then we withdraw

another portion, it will expand 1 by hypothesis, but the vessel will contract 2, which must

make

the apparent expansion o the liquid 3

ON EXPANSION.

26

by another portion

will

it

be

5,

by another

7,

&c., as before.

The

truth of the above proposition

otherwise shewn thus

Let

1,

4, 9,

16, 25, &c., represent the ab-

of the liquid, and /), 2 p,

those of the vessel by

solute expansions

3 p, 4

/?,

/;,

may be

&c.,

/?,
equal increments of temperature, then 1
2p, 93/7, 164/7, 25 5 p, &c., will

represent the

apparent expansion of the

li-

quid the differences of these last quantities,

namely 3 /;, 5 p, 7 p^ 9 p, &c., form
;

series in arithmetical progression, the

mon

difference of

which

is

But

2.

it

comde-

is

monstrated by algebraists, that the differences

of a series of square numbers, whose roots are

an arithme-

in arithmetical .progression, form

tical progression,

and

ence of the terms of

that

the

common

this progression

differ-

is

equal
square of the difference of the
twice the square of 1,
Hence, as 2

to twice the
roots.

we

have the above arithmetical

series 3

p,

5/), &c., equal to the differences of a series

cf squares, the common difference of the roots

of which

Now

is

1.

to apply these
principles

solid bodies

are

generally allowed to expand uniformly

within the common range of temperature at
all events the
quantity is so small compared
:

ON EXPANSION.

27

with the expansion of liquids, such as water,that

the deviation from uniformity cannot require
notice in

Water being supposed

cases.

many

to the square of the

to

expand according
perature from that of greatest

density,

tem-

we may

derive the following conclusions.

The laws of uniformly acceleCor.
1.

motion, are the same as those of the

rated

expansion of water, whether absolute or appaone denoting the temperature

rent, the time in

in the other,

and the space denoting the ex-

that

is, if ^
pansion
V
velocity, and s
:

=
=

time or temperature,
space or expansion

then,
/% or tvj or v^ are as

i tV:^
V

IS

j-

Cor.

from

as

is

as 2

^ ^

is

as

2.

s.

tf

The

maximum

being supposed constant, &c.

real

expansion

density for

grees of temperature,

is

of

water

any number of de-

the same as the ap-

parent expansion from apparent greatest denvessel for the same number of
sity in any

For instance, if water in a glass

appears to be of greatest density, or
descends lowest at 42 of common scale, and apdegrees.
vessel

pears to

expand iV of its

first

volume from thenct

ON EXPANSION.

28
to 212

then

may be

it

inferred that the real

water from greatest density by

expansion of
volume ; so that the absolute
i^s
o^
is
170
Vt

water is determinable this way,

expansion of
without knowing either at what temperature
its

is

density

greatest,

vessel containing

or the expansion of the

it.

If the expansion of any vessel

3.
Cor.
can be obtained; then may the temperature
at which water is of greatest density be ob-

tained

and

vice

versa.

This furnishes us

with an excellent method of ascertaining both

the

and absolute expansion

relative

solid bodies that can be formed

of

all

into vessels

water.
Cc.pable of holding
If the apparent expansion of water
Cor. 4.

from

maximum

density for

180

were

to

be

equalled by a body expanding uniformly, its

velocity must be equal to that of water at 90%
or mid-way.

And

to have the

if
any solid body be found
same expansion as water at 10*

from max. density; then its expansion for 180*

must be ^ of that of water, &;c. Because in
water v

By

vessels,

them

is

as

t^

&c.

graduating
filling

several

them

with

glass

thermometer

water,

to different temperatures,

exposing
and comparing

I have found the

apparent expansion
of water in glass for every 10 of the common

results,

ON EXPANSION.
or old scale (as

I shall henceforward call

and the new one,

as under.

EXPANSION OF WATER.
LD SCALE.

29
it)

ON EXPANSION.

80
1804, Dr.

for

Hope

has given a paper on

tlie

contraction of water by heat in low temperatures.

(See also Nicholson's Journal, Vol. 12.)

Jn

paper we find an excellent history of

and opinions relative to this remarkable

this

facts

question in physics, with original experiments.

two opinions respecting the temperature at which water obtains

Tliere appear to have been

maximum

its

density

the one stating it to

the other at
;

be at the freezing point, or 32

Previously to the publication of the above

essay, I had embraced the opinion that the
40.

point was S2, chiefly from some experiments

about to be related. Dr. Hope argued from
his

own

experiments in favour of the other

IMy attention was again turned

opinion.
the subject,

and

to

of

facts, I

found them

upon

re-examination

concur

to

in giving
the point of greatest density at the temperature
56", or mid-way between the points formerly

supposed.

In

two

all

letters

son's Journal, Vol. 13

ed

to

shew

supported

that Dr.

this

inserted

and

Hope's

experiments

conclusion and no

now shew

in Nichol-

endeavour-

14, I

other.

my own

experiments on
the apparent expansion of water in different
vessels, coincide with them in establishing the
shall

that

same conclusion.

The

results

of

my

experiments,

without

ON EXPANSION.

SI

those deductions, were published in Nichol-

Since then some small

son's Journal, Vol. 10.

additions

and corrections have been made.

that small vessels, capable

ounces of water, were
one
or
two
of holding
different
the
of
made
materials, and such as

It

may be observed

that glass tubes could be cemented into them

when full of water, so as to resemble and act

as a

common

follow

The

observations

ittionary.

Con eeponding points

thermometer.

Water

of expansion.
1

Brown earthen ware

Common

white ware, and 7

32

&

44

^,^

^^

&

48 -f

32

8c

521

& 53
& 59
& 60
& 60f
& 64+
& 67

38

at

stone ware,

Flint glass

42

Iron

42-1-

32

Copper

45-|-

32

Brass

4-5|

02

Pewter

4-6

32

Zinc

48

32

Lead

49

32

ware by heat
been
ascertained, we cannot
has never before
and
second experiments
first
the
make use of

As

the expansion of earthen

to find the temperature of greatest density

that

we can

learn from

must be below

According

them

is,

it

all

38.

to

Smeaton, glass expands

in length for 180 of temperature

ly

that the point

expands -^^

in bulk.

ttW

consequent-

But water expands

ON EXPANSION.

32
*T,
^,7-

more than

or rather

theretore the

mean

8 times as

much

velocity of the expansion

that at 90% or half way) is

of water (which is
18 times more than that of

glass,

which

is

equal to the expansion of water at 42 ; this

last must therefore be -^-^ of the former ; consequently water of 42 has passed through
tV of the temperature to the mean, or -t^ of

90

of new scale

5,

the temperature
greatest

= 4 of old scale, above

which

at

it

is

absolutely of

This conclusion however

density.

cannot be accurate

for,

it

appears from the

the temperature
preceding paragraph
must be below 38. The inaccuracy arises, I
have no doubt, from the expansion of glass
that

having been under-rated by Smeaton ; not from

any mistake of his, but from the peculiar

Rods and tubes of glass are

nature of glass.
if ever properly annealed ; hence
they

seldom
are

in

a state of violent

energy, and

often

break spontaneously or with a slight scratch

of a file tubes have been found to expand
:

more than

rods,

and

thin bulbs should

might be expected that

expand more still, because
it

they do not require annealing hence too the

great strength of thin glass, its being less brit;

tle,

and more susceptible of sudden transitions

From the above experiments

of temperature.
it

seems that the expansion due

to

glass,

such

ON EXPANSION.

S3

as the bulbs of ordinary thermometers,

little less

is

very

than that of iron.

Iron expands nearly

^4t5-

length by 18Cr

in

is
;
nearly ^V of
-r- 12 = 7'
90
hence
of
the expansion
water;
of true mean temperature = 6" of common

of heat, or TFT in bulk

common
water

taken from 42+, leaves 36 of

this

scale;

is

this

which

scale for the temperature at

of greatest density.

Copper

is

to

iron

as

2 in expansion;

therefore if 6 be the allowance for iron, that

for

copper must be

hence 45~

36,

for the temperature as before.

Brass expands about ,V more than copper j

9l = 36, for the
we shall have 4-5l

hence

temperature as above.
Fine pewter is to iron as

according to Smeaton

sion,

11=

1 1

from
temperature
but this being a mixed
not so much to be relied upon.

35^ for the

it is

as derived

the vessel of pewter

metal,

6 in expanhence 46
:

Zinc expands TIT in bulk for 180, if we

may credit Smeaton hence water expands 5^
17 of
times as much as zinc ; and 90 -^ 5i:

new

scale

13-|

zinc.

13^ of old scale

whence 48

case the expansion of the vessel

it

341 for the temperature derived from

It seems highly probable that in ibis

was found

to

be

less

is

over-rated

than that of lead,

S4

ON EXPANSION.

whereas Smeaton makes it more. The vessel

was made of the patent malleable zinc of Hodson and Sylvester.

Perhaps

which

tion of tin,

contains a por-

it

will account for the devia-

tion.

Lead expands ^^-^ of its bulk for 180;

water therefore expands about 5$ times as

much

this gives

90

13 of old scale

-^ 51

16! of new scale

whence 49*

13

36%

as before.

From

these experiments

seems demon-

it

the greatest density of water is

at or near the 36 of the old scale, and 37 or

strated, that

new

38 of the

scale

and

further, that the

expansion of thin glass is nearly the same as

that of iron, whilst that of stone ware is y,

and brown earthen ware ^ of the same.

The apparent expansion of mercury in a

thermometrical glass for 180* I find to be .0163
from
.0037

1.

That of thin

= ir^,

which

glass

is

may be

stated at

rather less than iron,

Consequently the real expansion of merfrom

32 to 212 is equal to the sum of
cury

^<.^.

these

= .02 or -^.

DeLuc makes

and most other authors make

they have
glass.

0163

all

under-rated

Hence we
:

180

::

.0037

derive
:

it

the

it,

less

.01836,

because

expansion of

this

proportion,
ex-

41 nearly, which

presses the effect of the expansion of glass

on

ON EXPANSION.
the mercurial thermometer

cury would

rise

41

that

is,

higher on

the mer-

the

temperature of boiling water,

at the

had no expansion.

glass

35

De Luc

scale
if

the

makes the

expansion of a glass tube from 32 to 212

.00083 in length, and from 32=" to 122 only

This inequality arises in part at least,

apprehend, from the want of equilibrium in

.00035.
I

the original fixation of glass tubes, the outside

being hard when the inside is soft.

Liquids

may be denominated pure when

are not

they

decomposed by heat and

Solutions of salts in water cannot be

such

because their constitution

is

cold.

deemed

affected

by

Thus, if a solution of sulphate

temperature.
of soda in water be cooled, a portion of the

and leaves the remaining liquid

than before; whereas water and
the
when
congealed, leave

salt crystallizes,

less

saline

partially
of the same quality as before.
liquid
remaining
Most acid liquids are similar to saline solutions
Alcohol as we commonly
in this respect.

mercury,

in a
pure alcohol
and
water
of
less portion
probably
greater or
would be affected by congelation like other
Ether is one of the purest liquids,
solutions.

have

it,

is

a solution of

except water and mercury.

and

Oils, both fixed

for the most part

volatile, are probably
in the sense we use it. Notwithstand-

impure,

36

EXPANSION.

O-N

ing these observations,

remarkable

is

it

how

nearly those liquids approximate to the law of

expansion observed in water and mercury.

Few authors have made experiments on these
subjects; and their results in several instances
are incorrect.

My

own

investigations have

chiefly directed to water and mercury ;

but it may be proper to give the results of my

been

enquiries on the other liquids as far as they

have been prosecuted.

Alcohol expands about ^ of its bulk for
The relative expan8 to 172.
180**, from

sions of this liquid are given by De Luc

from 32" to 212; but the results of my experiments do not seem to accord with his. Ac-

cording to him alcohol expands 35 parts for

the first 90, and 45 parts for the second 90".

The

strength of his alcohol

gun-powder

but

this

From my experiments
been very weak.
of .817

was such

as to

an indefinite

fire

test.

judge it must have

1000 parts of alcohol

I find

temperature 50 betemperature 170 of the

sp. gravity at the

came 1079

common
is at

is

at the

mercurial scale

110 the alcohol

at

below the

1039, or balf a division

mean. AVhen the

sp. gravity

is

.86, 1 find

true

1000

become 1072 at 170 ; at 110' the

1035 +, whence the disproportion of

parts at 50

bulk
the

is

two

parts of the scale

is

not

so

much

OK EXPANSION.
in

as

case

this

When

35 to 37.

the

sp.

1000 parts become

and 10291 at llO^j hence the

,937, I find

is

gravity

37

1062

at

ratio

of the expansion becomes 291 to 321.

When

170",

the sp. gravity

is

per cent, water, I find

come 1040

,967, answering to 75
1000 parts at 50* be-

170% and 10171 at 110, giving

which is the same as De;
;
alcohol.
It is true he takes an

at

a ratio of 35 to 45

Luc

gives for

interval of temperature =x
for 120* only

but

concile our results.

hol from
jectural,

still

As

180% and

take one

impossible to rethe expansion of alcoit

is

172' to 212 must have been con-

perhaps be

has over-rated

it.

In

I have not taken into

reporting these results
account the expansion of the glass vessel, a

thermometrical bulb, containing about

grains of water, and having a tube pro-

large

750

portionally

wide

consequently the real ex-

pansions must be considered as more rather

than less than above stated. The graduation
of the vessel having been repeatedly examined,
and being the same that was used in deter-

mining the expansion of water, I can place

confidence in the

results.

Particular care

was

taken in these experiments to have the bulb

and stem both immersed in water of the pro-

posed temperature.
As alcohol of .817

at
sp. gravity contains

ON EXPANSION.

38

per cent, water, it is fair to infer from

the above that a thermometer of pure alcohol

least 8

would in no apparent degree differ from one

of mercury in the interval of temperature from
But when we consider that the
SO** to 170*.
relative expansions of glass,

hol for this interval, are as

mercury and alco1,52 and 22 re-

it must be obvious that the

inequathe
of
expansion of glass in the higher
lity
and lower parts of the scale, which tends to

spectively,

equalise the apparent expansion of mercury,

little influence on alcohol, by reason of its

has

comparative insignificance. Hence it may be

presumed that a spirit thermometer would be

more equable
rial

This

it

in

its

divisions than a

mercu-

a vessel of uniform expansion.

ought to be by theory, because the

one,

in

point of greatest density or congelation of

alcohol is below that of mercury.
Water being densest at 36, and alcohol at

a very remote temperature below,

it

was

to

be expected that mixtures of these would be

densest at intermediate temperatures, and those
higher as the water prevailed j thus we find the
disproportion, so observable in the expansion
of water, growing greater and greater in the

mixtures as they approach to pure water.

Water saturated with common salt expands
as follows

1000 parts at 32 become 1050

ON EXPANSION.
at

212*;

122

at

it

is

39

which

nearly 1023,

gives the ratio of 23 to 27 for the correspondThis is

ing equal intervals of mercury.

nearly the same as De Luc's ratio of 36. S to

This solution is said to congeal at
43.7.
7,

and probably expands nearly

as the square of

temperature from that point. It differs

from most other saline solutions in regard to

the

its

expansion by temperature.
Olive and linseed oils expand about 8 per
cent, by 180 of temperature ; De Luc finds
the expansion of olive oil nearly correspond
to

mercury

with

me

ate, nearly agreeing

it is

more disproportion-

with water saturated with

salt.

Oil of turpentine expands about 7 per cent,

j it expands much more in the higher

for 180

than in the lower part of the scale, as

it

ought to

do, the freezing point being stated at

16.

The

ratio

is

somewhere about

Several authors have

boils at 560

it

I do not

14 or

3 to

5.

that oil of turpentine

know how

the mis-

take originated; but it boils below 212, like

the rest of the essential oils.
Sulphuric acid, sp. gravity K85 expands
about 6 per cent, from 32 to 212. It accords
with mercury as nearly as possible in every
Dr. Thomson says the
part of the scale.
freezing point of acid of this strength

is

at

ON EXPANSION.

40

36

below

or

same law

as

whence

it

accords with the

water and mercury.

I find that

even the glacial sulphuric acid, or that of

1.78 sp. gravity, which remains congealed at
45,

or nearly like the

continues liquid.

expands uniformly,

other, whilst

it

Nitric acid, sp. gravity 1.40, expands about

11 per cent, from 32 to 212; the expansion

is nearly of the same rate as that of
mercury,

the disproportion not being more than 27 to

28 or thereabouts. The freezing point of acid

of this strength

is

mercury.
Muriatic acid,

near the freezing point of

sp. gravity

about 6 per cent,

from

more disproportionate

1.137, expands

32 to 212;

than

nitric

it

acid,

is

as

might be expected, being so largely diluted

with water. The ratio is nearly 6 to 7.
Sulphuric ether expands after the rate of
I have
7 per cent, for 180 of temperature.
of
this liquid
the
expansion
compared
only

with

that

of mercury from 60 to 90^

In
it accords so
nearly with mercury

this interval

that I could perceive

their rates.

From what
seen that water
liquids

yet

no sensible difference

It is said to freeze at

it

has been observed

less

it

may be

than most other

expands
ought to be considered

ing in reality the

greatest

in

46.

rate

as hav-

of expansion.

ON EXPANSION.
Alcohol and

pand

which appear

to ex-

much, do not excel, or even equal

so

water,

nitric acid,

41

we

if

estimate their

expansion from,

the temperature of greatest density, and

com-

pare them with water in like circumstances.

It is because we begin with them at 100 or 200*
above the point of greatest density, and observe their expansion

for

180 further, that

Water, if it
they appear to expand so largely.
continued liquid, would expand three times
as

much

in

does in the

the second interval of

first,

reckoning from

180" as

it

36,

EXPANSION OF SOLIDS.
No general law has hitherto been discovered
respecting the expansion of solid bodies ; but
as elastic fluids and liquids appear to be subject to their respective laws in this paxticular,
we may confidently expect that solids will be

As it may be presumed tnat

no
change of form, by the abundergo
straction of heat, it is probable that whatever

found so

too.

olids

the law

may be, it will respect the point at

wiiich temperature commences, or what may
be called, absolute cold. It is not our prlent business to enquire how low this point is
',

but

it

may be

observed that every phenomenoB

ON EXPANSION.

42
indicates

than

may

it

to

be very low, or much lower

commonly apprehended.

is

hereafter be demonstrated

Perhaps

it

that the inter-

val of temperature from 32 to 212* of Fahrenheit, constitutes the 10th, 1 5th, or 20th interval from absolute cold.

we may
is

Judging from analogy,

conjecture that the expansion of solids

progressively increasing with the tempera-

; but whether it is a geometrical progression as elastic fluids, or one increasing as the

ture

square of the temperature, like liquids, or as

the 3d or any power of the temperature, still
if

it

be estimated from absolute cold, it must

to be nearly uniform, or in arithmetical

appear

progression to the temperature, for so small

interval of temperature as

and remote an

that between freezing and boiling water. The

truth of this observation will appear from the

following calculation

let

us suppose the interthen the real

;

val in question to be the 15th

temperature of freezing water will be 2520

mid-way to boiling 2610% and boiling

water 2700% reckoned from absolute cold.
the

Dif.

= 196
T4j^* = 210f

TO*

14|.
3

rip
14-'^

17^*

225

14^'

l7l

Dif.

2744

= 3048|
=

304^
326J

3375

ON EXPANSION.

Now

43

the differences above represent the

ratios of expansion for 90 of temperature ;

they are in the former case as 57 to 59, and in

the latter as 14 to iS nearly.

perature being supposed

the

new

scale, the

mean

to
is

Bat the tem-

be measured by
about 110 of the

;
expansion of solids
should be as 57 or 14 from 32 to 1 10, and as

old scale

therefore the

59 or 15 from 110 to 212 of the old

scale.

If these conjectures be right, the expansion of

solids ought to be something greater in the lower part of the old scale, and something less in

the higher part.

Experience at present does
not enable us to decide the question. For all
practical purposes

we may

adopt the notion of

the equable expansion of solids.

Only

glass

has been found to expand increasingly with the

from its
temperature, and this arises probably
obbeen
has
as
constitution,
already
peculiar
served.

Various pyrometers, or instruments for meahave been insuring the expansion of solids,
vented,

of which

accounts

may be

books of natural philosophy.

to

seen

ascertain the expansion in length of

proposed subject.

The

Thus,

if

will

is

any

longitudinal expansion

found, that of the bulk

being
from it, and

in

Their object

may be

derived

be three times as much.

a bar of 1000 expand to 1001 by a

ON EXPANSION.

44

certain temperature

1000 cubic inches

then

of the same will become 1003 by the same

temperature.

The following Table exhibits the expansion

of the principal subjects hitherto determined,
for 180 of temperature; that is, from 32 to
The bulk and

212 of Fahrenheit.

the articles at 32 are denoted by

length of

1.

EXPANSION.
lu bulk.

SOLIDS.
Stooft

Glass

ware

In length,

.0012:

Brown earthen ware......

,0023

rod J and tubps

= Z^3

TTSTJ

.0025=,^^
.co;i7 = j|^

bulbs (thin)

7T7>

Platinum ..............

.002;;=:^

Steel

.oo.u=^^

TjTT
T5T t

.00:38=^^3.

Iron

Gold
Bismuth

.0042=^^
...

.oo-i-2=.yy^

0051

........

Cnppi-r
Brass

Silvrr

-..--....,

Fine Pewter
Tin
Lead
Zinc

= ,^^

. .

TTT
tils

t
t

Sulphuric acid

Muriatic Acid
Oil of turpentine..

Ether
Fixed oils
Alrohnl

I
1-

TTT
I

.0086=_J.
0093 =,i^

7JT
1

0200 =^y
.04-66

sat. wiili salt

=-jV..Y

.0500 =J^
.0600 =.rV
.0600 =/,.

0700=.j'^
,0700=^j
.0800=^1.,

.0110= ^

Nitric acid .......

0110= J

ELASTIC FLUIDS.
Cases of all kinds..

.376

Smcaton,

t
t
t

.0000=^^,^
TJ7
.007

rh

.005o=-f^
.00u8

LIQUIDS.

Mercury

Water
Water

* "Ellicott.

% Borda.

OK EXPANSION.

45

Wedgwood's Thermometer.

The

spirit

thermometer serves

measure

to

the greatest degrees of cold we are acquainted

with, and the mercurial thermometer measures

400 above boiling water, by the old scale, or

about 250 by the new one, at which temperaThis is short of red
ture the mercury boils.
heat,

and very

An

high temperatures

is

the

Wedgwood's

is

there

great

is

still

of the highest attaininstrument to measure

far short

able temperature.

very desirable
best

room

for

and Mr.

we have

yet

but

improvement.

Small cylindrical pieces of clay, composed in

manner of earthen ware, and slightly

the

baked, are the thermometrical pieces. When

used, one of them is exposed in a crucible to
the heat proposed to be measured, and after
it is

cooling,

portion

found to be contracted,

to the

in

heat previously sustained

pro;

the

indiquantity of contraction being measured,

The whole range of
cates the temperature.
this

thermometer

degrees,

is

divided into 240 equal

each of which

is

equal to 130 of Fahrenheit.

calculated to be

The

lowest, or 0,

isfoundabout 1077of Fahrenheit (supposing the

common
cury,)

scale continued

and

above boiling mer-

the highest 32277.

According to

the nevv views of temperature in the preceding

45

out

EX FANS 10 V.

is reason to think these numbers

pages, there
too
are much
large.

The

following Table exhibits some of the

more remarkable temperatures in the whole

range, according to the present state of our
knowledge.
Wedg.
Extremity of Wedgwood*s thermometer....,
Pig iron, cobalt and nickel, melt from 130'

2i0*
to......

Furnaces

for glass

150
125

Greatest beat of a Smith's forge

and earthen ware, from 40

124

to

Gold melts

32

Settling heat of flint glass

29

Silver melts

28

Copper melts .^

27

Brass melts

21

Diamond burns

14

Red

heat risible in day-light

Fahrenheit*
old scale.

Hydrogen and

charcoal burn 800 to

1000

Antimony melts

809

Zinc

700
612
600

Lead

Mercury
Linseed

boils

600

oil boils

Sulphuric acid boils

590

Bismuth...

476

Tin

442

Sulphur burns slowly

30^

Nitric acid boils

240

Water and

essential oils boil

^ismutk 5

parts, tia 3

213
210

and lead

2,

melt

....#,.

ON

SPECIFIC HEAT.

47
Fahrenheit.

Alcohol boils

174

Beeswax

142

melts

Ether boils.

98

Blood heat 96 to

98

Summer heat

75" to..............

80

when congealed, begins to melt

45

in this climate

Sulphuric acid

(1 .78)

Mixtureof

and water

Milk

ice

freezes

Vinegar freezes

50

28

Strong wines freeze about....

Snow

32

..............

3 parts, salt2.......

.........

................ 7

Cold observed on the snow at Kendal, 179 1......

Pitto at Glasgow, 1780

Mercury

freezes

Createst

artificial

..

20

................

tO
23
39
90

cold observed

SECTION

3.

ON THS

HEAT OF

SPECIFIC

BODIES.

If the whole quantity of heat in a mcasate

of water of a certain temperature be denoted
by 1, that in the same measure of mercury will

be denoted by

.5

nearly

hence the

specific

heats of water and mercury, of equal bulks,

may be

signified

by

and

.5 respectively.

If the specific heats be taken from equal

heights of the two liquids ; then they will be

ON SPECIFIC HEAT.

48
denoted by

have

and .04 nearly

to divide .5

because

we

by 13.6, the specific gravity

of mercury.

That bodies
heats,
1.

differ

much

in

their specific

manifest from the following facts.

If a measure of
mercury of 212*
is

mixed with a measure of water of

mixture will be

far below the

be

32", tbo

mean tempera-

ture.
2.
If a measure of mercury of 32 be mixed with a measure of water of 212% the

mixture will be
3.

If

far

above the mean.

two equal and

like vessels

be

filled,

the one with hot water, the other with hot

mercury

the latter will cool in about half

the time of the former.

4.

If a measure of sulphuric acid be

mixed

with a measure of water of the same temperature, the mixture will assume a temperature
about 240 higher.

These

facts

clearly

shew

that bodies

have

various affinities for heat, and that those bodies

which have the

strongest attraction or affinity

for heat, possess the

stances

in other

most of

it

in like

circum-

words, they are said to have

the greatest capacity for heat, or the greatest

It is found too that the same
specihc heat.
body changes its capacity for heat, or apparently assumes a

new

affinity,

with a change of

ON SPECIFIC HEAT.
This no doubt

form.

from

arises

arrangement or disposition of

49

new

ultimate particles, by which their atmospheres of heat are

Thus a solid body, as ice, on beinfluenced
its

coming

liquid, acquires

heat, even

its

though

a larger capacity for

bulk

is

diminished

and

a liquid, as water, acquires a larger capacity

for heat on being converted into an elastic
fluid

this last increase is

conceive,

occasioned,

we may

being increased in

its

by

solely

bulk, in consequence of which every atom of

liquid possesses a larger sphere than before.
very important enquiry is, whether the

same state undergoes any

change of capacity by change of temperature.

same body

in

the

Does water, for

same capacity for
all

instance, at
heat, as at

the intermediate degrees

and most writers

32 possess the

212% and through

?

Dr. Crawford,

him, contend, that the

after

are
capacities of bodies in such circumstances
doctrine
of
outline
As
an
nearly permanent.
this

may be

admitted

possible, to ascertain,

but

it

is

requisite,

if

whether the small change

of capacity induced by temperature, is such as

to increase the capacity, or to diminish it ; and
also,

whether the increase or diminution

uniform or otherwise. Till

it is

of

little

use to

this point

mix water of

is

is

settled,

32 and 212>

ON SPECIFIC HEAT.

50

with a view to obtain the true mean temperature.

That water increases

in

its

capacity for heat

with the increase of temperature, I consider

demonstrable from the following arguments :
1st.

measure of water of any one temperamixed with a measure at any other

ture being

temperature, the mixture is less than two

measures.
Now a condensation of volume
is

a certain mark of diminution of capacity

and increase of temperature, whether the condensation be the effect of chemical

agency, as
in the mixture of sulphuric acid and water,
or the effect of mechanical pressure, as with
elastic

fluids.

2.

When

the

same body sud-

denly changes
capacity by a change of form,
a less to a greater^ as the
it is
from
always
its

temperature ascends ; for instance, ice, water

and vapour.
3. Dr. Crawford
acknowledges

from
acid,

his

own

experience, that dilute sulphuric

and most other

found to increase

liquids he tried,

in their capacity for heat

wer
with

the increase of temperature.

Admitting the force of these arguments, it

when water of 52' and 212" are

follows that

mixed, and give a temperature denoted by

119" of the common thermometer, we must
conclude that the true mean temperature is
I have already
that degree.

somewhere below

ON

SPECIFIC HEAT.

assigned the reasons

why

51

mean

I place the

at

110.

With

water
respect to the question whether

varies uniformly or otherwise in

I

am

its

capacity,

inclined to think the increase, in this re-

to the
spect, will be found nearly proportional
increase in bulk, and consequently will be four

times as

much

at

212" as at the mean.

haps the expressions for the bulk

for the capacity

if so,

Per-

may

serve

the ratios of the capa-

32% 122* and 212* of the new scale,

may be denoted by 22, 22| and 23. I should
cities at

rather expect, however, that the ratios are

much nearer equality, and that 200, 201 and

204, would be nearer the truth.*

* In the Lectures
in the spring

gow

the capacity of water at

nearly.

The

Edinburgh and Glasgave it as my opinion that

32 was to that at 2I2>, as 5 to 6,

I delivered in

of 1807,

opinion was founded on the fact

had just

before observed, that a small mercurial thermometer at the

rose to

31!''
being plunged into boilifjg water,
15"; but the same at 212 being plunged into

temperature

202O

in

jce-cold water,

was

8" in descending to 42

estimating

the capacities to be reciprocally as the times of cooling, it

I
gave the ratio of 5 to 6. On more mature consideration

am

persuaded this difference

is

occasioned, not so

the difference of capacities, as

fluidity.

and

Water of 212

is

by
more

much by

the different degrees of

fluid

distributes the temperature with

than water of 32,

greater facility.

a subsequent experiment too, I find, that

mercury

By

cools a

ON SPECIFIC HEAT.

52

when investigating the accommon thermometer, was aware,

Dr. Crawford,
curacy ot the
that

if

equal

portions

of water of different

temperatures were mixed together, and the

thermometer always indicated the mean, this

was not an

He

proof of its accuracy.

water have an increasing

infallible

allows that

if

and the mercury expand increasingly

with the temperature, an equation may be
formed so as to deceive us. This is in fact
capacity,

the case in some degree ; and he appears to

have been deceived by it. Yet the increased
capacity of water,

is

by no means

sufficient to

balance the increased expansion of the mercury, as appears from the following experiments.
I took a vessel of tinned iron, the capacity

of which was found to be

equal to 2 oz. of

were put 58 ourjces of water,

water;
= 60 ounces of water. The
the
sum
making
whole was raised to any proposed temperainto this

ture,

and then two ounces of

in and melted; the temperature

served, as follows

thermometer twice

ice

were put

was then ob-

as fast as water,

though

it

has but half

the times in which a thermometer

its

capacity for heat

in

cooling in fluids, are not, therefore, tests of their specific

heals.

is

ON

53

SPECIFIC HEAT.

60 oz.water of 212 + 2 oz.ice of 32% gave 200"f

60 oz.water of 1 30+ 2 oz.ice of 32, gave 1 22*'
60 oz.water of 50+ 2

of these, 30 parts of water

1^ each, or 345% and 1 part water of

From
lost

oz.ice of 32", gave 43".3

the

first

168i
32 gained 168l; the difference 345
of
the
number
degrees of
176|, expresses

as are found between 200

temperature (such
old
the
of
212
and
scale) entering into ice of

32 to convert
calculations

we

into

These

nearly as 5, 6

much

water of 32.

being made

find in the second,

128.

as

it

heat

three

and
is

7.

Similar

for the other

150% and
resulting

Hence

two,

in the third,

numbers are

it

follows that

necessary to raise water 5 in

the lower part of the old scale, as is required

to raise it 7 in the higher, and 6 in the mid
die.*

Methods of finding

the Specific

Heats of

Bodies.

The most obvious method of ascertaining

the

of bodies that have no chemical

specific heats
*

Perhaps the above results

may

account for the diver-

authors respecting the quantity of latent heat

sity in

(im-

Respecting the doctrine of

properly so called) in water.
Black on Latent Heat, see an excellent note of Leslie.
(Inquiry, page 529.)

ON SPECIFIC HEAT.

54
affinity for

water,

mix equal weights of

to

is

water, and any proposed body of two known

temperatures, and to mark, the temperature of
the mixture.

Thus,

pound of water of

if

32% and a pound of mercury of 212% be

mixed, and brought to a common temperature, the water will be raised vi degrees, and
the

degrees; and their

?i

mercury depressed

capacities or specific heats will be inversely

as those

water

Way

numbers ;

or,

specific heat

'-

Black,

Irvine,

of

'.

'.

specific heat

mercury.

In

of

this

Crawford and Wilcke,

approximated to the capacities of various bodies. Such bodies as have an affinity for water,

may be

confined in a vessel of

and plunged into water so as

or cooled, as in the former case.
city,

The

known
to

capa-

be heated

obtained by this method

1st. the authors
objections

results already

are liable to

two

presume the capacities of bodies while they

retain their form are permanent j that is, the
heat increases exactly in proportion to
specific
the temperature; and 2d, that the common mercurial thermometer is a true test of temperature.

But

it

has been

positions

The

is

shewn

that

neither of these

warrantable.

calorimeter of Lavoisier and Laplace

for the purpose of

was an ingenious contrivance

investigating specific heat

it

was calculated

to

ON

gPECIFiC HEAT.

shew the quantity of

ice

5$

which any body heatIt was

to a given temperature could melt.

ed

therefore not liable to the

Unfortunately

this

2d objection above.

instrument does not seem to

have answered well

Meyer attempted

in practice.
to

find the capacities of

dried woods, by observing the times in which

given equal volumes of them were in cooling.

These times he considered

to the

as

proportionate

capacities bulk for bulk

and when

the times were divided by the specific gravities,

the quotient represented the capacities of equal

weights. (Annal. de ChemieTom. 30). Leslie

has since
liquids,

on

am

5 of

recommended a

and given us the

them.

similar

mode

for

results of his trials

From my own experience I

method

inclined to adopt this

tible of great precision.

The

as suscep-

times in

which

bodies cool in like circumstances appear to

be ascertainable this way with uncommon
exactness,

and as they are mostly very

diiferent,

consequence. The
results too I find to agree with those by mixture ; and they have the advantage of not

a very small error

is

of

little

being affected by any error in the thermometric scale.

The formulae for exhibiting the phenomena

of the specific heats of bodies are best conceived from the contemplation of cylindrical

ON SPECIFIC HEAT.

56

I.
Fig. l).
unequal bases. (See plate
a quantity
to
be
heat
by
represented
Supposing

vessels of

of liquid in each vessel, and temperature by

the height of the liquid in the vessel, the
base denoting the zero or total privation of
heat ; then the specific heats of bodies at any
temperature, Xy will be denoted by
multipling the area of the several bases by

given

Those

x.

the height or temperature,

specific

as
directly as the bases, or

heats too will be

the increments of heat necessary to produce

equal changes of temperature.

W=

the weights of two cold

Let w and
and hot bodies; c and C their capacities
for heat at the same temperature (or the bases

d=

the difference of the

of the cylinders) ;
before mixture,
two
bodies
the
of
temperature

reckoned in degrees
colder body,

warmer

and

?i

w=

the elevation of the

the depression of the

after mixture, (supposing

no chemical

action)

then

we

m+

them

lowing equations.
1.

m=

to

have

obtain the

= d.

WCd

wc+W C

fol-

ON

SPECIFIC HEAT.

4.

l^

C c,

If

JV=

then, 5.

Wy then, 6.

57

WCn
wm

m = _-
tV-T w

C=

""

""

To find the zero, or point of absolute privation of temperature, from observations on

the change of capacity in the same body.
Let c
city,

= the less, and C = the greater capam = the number of degrees of the less

capacity requisite to

produce the change in

equal weights, ft = the number of degrees

of the greater capacity, x =. the whole num-

ber of degrees of temperature

down

to zero

then,

7.

Cx cx = Cn = cm,
_ Cn cm

from mixing two bodies

of the same temperature which act chemically,
and produce a change of temperature. Let
= caw, W, c, C &; X, be as before j \tt
=
the
n
and
degrees of
pacity of the mixture,

To

find the zero

ON SPECIFIC HEAT.

5S

heat or cold produced then the quantity of

in both bodies will he
fc to + C W) x
:

heat

+ W)

(w

9.

It

is

and

to

MX

.r

(w

(w

+ W)

IV)

ji.

Mn

(c w + C W)

c/3

be regretted that so

ment has been made

(IV

little

+ W) M
improve-

for the last fifteen years in

department of science. Some of the earliest

and most incorrect results are still obtruded

this

upon

the notice of students

least reflection

errors

their

though with the

are obvious.

have made great number of experiments with

a view to enlarge, but more especially, to
correct the Tables of Specific Heat.

be proper

For

to

relate

some of

the

It

may

particulars.

used an egg-shaped thin glass

capable of holding eight ounces of

liquids I

vessel,

water; to

this

was adapted a cork, with a

small circular hole, sufficient to admit the stem

of a delicate thermometer tube,

two

small marks with a

and the other

cork

when

file,

which had

the one at

92%

both being above the

the cork was in the neck of
at

82,

the bottle, the bulb of the thermometer

in the centre of the internal capacity.

was

When

an experiment was made the bottle was filled

v/ith the proposed liquid, and heated a little

above 92

suspended in the
and the time accurately

was then

It

69

SPECIFIC HEAT.

ON

middle of a room,

noted when the thermometer was

when

again

was

it

and

same time indicating the temperature

at the

of the air in the room.

glass vessel

was found

The mean
were

at 92,

thermometer

82, another

as follow

The

capacity of the
water.

= f oz. of

of several experiments

results
:

Air

Room

in the

52.
Minutes*

Water

29

cooled from 92'' to 82, in

29

Milk(1.026)

28|

Solution of carbonate of potash (1.30)

ammonia (1.035)

Solution of carbonate of

Ammoniacal

Common

solution

28f
28|

(.948)

27f

vinegar (1.02)

Solution of

common

SoluUon of

soft sugar,

salt,

88

W.

W.

+ 32

S.

(1.197)

-f 4 S. (1.17)

27

26f

Kitric acid (1.20)

26{

NLtrlcacid (1.30)

25$

Nitricacid (1.36)

25

Sulphuric acid (1.844) and water, equal bulks fl. 535)

23|

Muriaticacid (1.153)
Acetic acid (1.056) from Acet. Cop

21

2i

Sulphuric acid (1.844)

19|

Alcohol {.85)

19f

Ditto

(.817)

I7i

Ether sulphuric (.76)

15|

Spermaceti

oil

(.87)

14

These times would express accurately the

specific

heats of the several bodies> bulk for

bulk, provided the heat of the glass vessel did

ON SPECIFIC HEAT.

60

not enter into consideration.

But

as the beat

of that was proved to be equal to i of an

ounce of water, or to -j of an ounce measure
of

oil,

it

is

evident

we must

consider the

heat disengaged in the 1st experiment, as from

8 i ounces of water, and in the last as from

ounce measures of

oil.

On

this

account

the numbers below 29 will require a small

reduction, before they can be allowed to represent the times of cooling of equal bulks of
the different liquids; in the last experiment

the reduction will be one minute, and less in

all the

It

preceding ones.

may be proper

to observe, that the

above

do not depend upon one trial of the

several articles ; most of the experiments were

results

repeated several times, and the times of cooling were found not to differ more than half a

minute

indeed,

in

general,

there

was no

room was,
below 52% the due

sensible differences. If the air in the

in any case, a

little

above or

allowance was made.

I found the specific heat of mercury, by
mixture with water, and by the time of its cooling in a smaller vessel than the above, to be
to that of water of equal bulk, as, .55 to

nearly.

I found the specific heats of the metals

other solids after the

and

manner of Wiicke and

ON SPECIFIC KEAT.

having procured a goblet, of very

I found its
capacity

Crawford

thin glass

and small stem,

then put water into

for heat;

61

it,

such that

the water, together with the value of the glass

in water, might be equal to the weight of

The

the solid.

was

solid

and

raised to 212,

and the spesuddenly plunged

cific heats of equal weights of the solid and
the water, were inferred to be inversely as
into the water,

the changes of temperature which they expeSome

rienced, according to the 6th formula.

regard was paid to the correction, on account

of the error of the common thermometer,

which was used on the occasion.

I

were

tried

iron,

nickel,

antimony,

results differed little

Crawford

their

lead,

copper,

glass, pitcoal,

The

solids

tin,

zinc,

The

&c.

from those of Wilcke and

numbers may,

therefore,

be

adopted without any material error, till greater

In the following
precision can be attained.

Table

have not carried the decimals bevond

two

places ; because present experience will

not warrant further extension
the first place
of decimals may, I believe, be relied upon as
:

accurate, and the second

a few instances

wrong

it

except from

specific heats of the

which

generally so, but in

may, perhaps, be

I shall further

this

gases

observation,

or 2

the

by Crawford, on

remark.

CN SPECIFIC HEAT

62

TABLE OF SPECIFIC HEATS.

"

ON SPECIFIC HEAT.
Remarks on

The

articles

63

the Table.

marked *

arc from Crawford.

Notwithstanding the ingenuity and address

displayed in his experiments on the capacities
of the elastic

fluids, there is

reason to believe

his results are not very near approximations to

never expect accuracy v^hea

; we can
depends upon the observation of 1 or 2

the truth
it

tenths of a degree of temperature after a tedi-

ous and complicated process.

undoubtedly due

The

difference

to

him

between

Great merit

for the attempt.

arterial

is

and venous

blood, on which he has founded the beautiful

system

and deserves

From

of

animal

heat,

is

remarkable,

further enquiry.

the observed capacities of water, so-

ammonia, and the combustibles, into

which hydrogen enters, together with its small

lution of

specific gravity,

we cannot doubt

but that

this

element possesses a very superior specific heat.

Oxygen, and azote

likewise, undoubtedly stand

high, as water and ammonia indicate ; but the

compound of these two elements denominated
nitric acid, being so low, compared with the
same joined to hydrogen, or water and ammonia, we must conclude that the superiority of

the

two

last articles

gen they contain.

is

chiefly

The

due to the hydro-

elements, charcoal and

ON SPECIFIC HEAT,

6'l

and carry their

character along with them into compounds, as
sulphur, are remarkably low,

oil,

sulphuric acid, &c.

Water appears

to possess the greatest capaof any pure liquid yet known,

be compared with equal bulks or

city for heat

whether
weights

it

indeed

solid

any

it

may be doubted, whether

or liquid whatever

contains more

heat than an equal bulk of water of the same

temperature.
arises

The

great

from the strong

capacity of water

affinity,

which both

elements, hydrogen, and oxygen,

heat.

Hence

it

is

that

have

its

for

solutions of salts in

water, contain generally less heat in a given

volume than pure water: for, salts increase
the

volume of water

as well as the

density,

and having mostly a small capacity for heat,

they enlarge the volume of the water more
than proportional to the heat they contribute.
Pure ammonia seems to possess a high specific
heat, judging from the aqueous solution,

contains only about

which

10 per cent.
If it could
be exhibited pure in a liquid form, it would
probably exceed water in this particular.

The compounds

of hydrogen and carbon,

oil, ether and alcohol,

under the characters of

and the woods, all fall below the two last

mentioned j the reason seems to be, because
charcoal

is

an clement of a low

specific heat.

ON

The
in

65

SPECIFIC HEAT.

acids form an interesting class of bedies

regwd

to their specific heats.

Lavoisier

is

the only one who is nearly correcl in regard to

nitiic acid ; he finds the specific heat of the
acid 1.3 to be .66

this

with sonae other of his

results I find rather too low.

that

the

63 per

water in

imich heat in

loses

it

whence

have,

and

cent,

tiie

It is

remaikable^

acid of

this

strength is

should

have

as the
it

compound

should seiem that

principal part of

with water.

This

nearly

is

as

found to

is

the

acid

heat on cooibining
more observable in

its

still

muriatic acid, which contains 80 per cent, of

water, and its specific heat is only .66 j whence

not only the heat of the acid gas, but part of

that in the water is expelled on the union ; this

accounts for the great heat produced by the

this acid gas with water.

union of

The specific heat of sulphuric acid has been

Gadolin and
well approximated by several.

Leslie
finds

make

it

.43,

it

.34, Lavoisier .33-)-

Crawford

but he must probably have had a

diluted acid.

CoHimon vinegar, being water whh 4 or 5

per cent, of acid, does not differ materially
from water in its specific heat; it has been
stated at .39 and at .10; but such results do
not require animadversion.

The

acetic acid

ON SPECIFIC HEAT.

6B

I used contained

33

this acid therefore, in

expo's

much

pure

acidj

combining with water,

heat.

Quicklime

Crawford

per cent,

is

determined by Lavoisier and

I think they have under;

be .22

to

it
find quicklime to
impart as much
or more heat than carbonate of lime, when
inclosed in a vessel and plunged in water, or

rated

when mixed with

oil.

Hydrat of lime

(that

quicklime 3 parts and water 1 part, or dry

slaked lime) is fixed at .28 bv Gadolin
it
is,

was

.25

find

by my first experiments ; but I since

have underrated it. The subject will be

adverted to in a future section.

SECTION

4.

THEORY OF THE SPECIFIC HEAT OF

ELASTIC FLUIDS.
Since the preceding section was
printed off,
some time in
considering the
constitution of elastic fluids with
regard to
I have spent

heat.

The

relied

upon

results

already obtained cannot be

difficult to conceive and

execute experiments less
exceptionable than
those of Crawford.
It is
extremely important.
;

yet

it is

THEORY OF SPECIFIC HEAT.

67

to

obtain the exact specific heat of

elastic fluids,

because the phenomena of com-

however,

bustion and of heat

in

and conse-

general,

quently a great part of chemical agency, are

intimately connected therewith.

In speaking of the uncertainty of Crawford's

results
it

on the

specific heat of

must not be understood

are equally implicated.

elastic fluids,

that

The

all

of

them

reiterated ex-

periments on the heat giveti out by the combustion of hydrogen, in which it was found
that 1 1 measures of mixed gases, when fired

by

electricity

2. 4

ble

heated 20.5 measures of water

(page 263) at a medium, were susceptiof very considerable accuracy, and are

therefore entitled to credit.

The comparative

heat of atmospheric air and water, which rested

on the observance of nearrly 4 of a degree of
temperature, is probably not very far from the
truth

but the very small differences in the

heats communicated by equal bulks of oxygen,

hydrogen, carbonic acid, azotic gas and com-

mon

air, together with the great importance

of those differences in the calculation, render

He justly observes^
the
heats
imparted by
suppose
equal bulks of these gases to be equal, it will
not aflfect his doctrine. The tenor of it neces-

the results very uncertain.

that if

sarily led

we

him

to estimate the heat

of oxygen

THEORY OF SPECIFIC HEAT.

68

high, compared with equal weights of carbo*

nic acid and aqueous vapour, and of azotic

was then

gas or phlogisticated

air, as

under the idea of

being an opjxjsite to oxy-

its

gen or dephlogisticated

it

Indeed

air.

called,

his de-

ductions respecting azotic gas, are not consistent with his expcrioients
for he makes no
:

use of experiments 12 and 13, which are the

only direct ones for the purpose, but he infers
the beat of azotic gas from the observed differ-

ence between oxygen and common

result gives
air

any

it

less

whereas from the

3th experiment, scarcely

was perceived between

sensible difference

He

them.
rated

it

has in

all

The
common

air.

than half that of

much

probability

but his errors in

this respect

under-

what-

may be, do not affect his system.

When we consider that all elastic fluids are

ever they

equally expanded by temperature, and that

liquids and solids are not so, it should seem
tha* a general law for the affection of elastic
fluids for heat,

ought to be more

easily deduci-

ble and more simp^le than one for liquids^ or

solids.

There

to elastic fluids
1

the

are three suppositions in

regard

which merit

discussion.

elastic fluids

Equal iveights of
same quantity of heat under
.

stances of temperature

The

and

may have

like circum-

pressure.

truth of this supposition

is

disproTed

THEORY OF

SPECIFIC HEAT.

69

oxygen and hydrogen upon

union give out much heat, though they
form 8team on elastic fluid of the same

by

several facts

their

weight as the elements composing it. Nitrous

gas aiui oxygen unite under similar circumis formed by the unioa
a
of low specific heat^
substance
of charcoal,
with oxygen ; much heat is given out, which

stances.

must be
If

Carbonic acid

principally derived from the

then the charcoal contain

oxygen combining with

carbonic acid must be

little

it

oxygen ;
and the

heat,

be reduced, the
heat to an

far inferior in

equal weight of oxygenous gas.

Equal bulks of elastic fluids may hcpve

sdme quantity of heat with the same prep^
sure and temperature.
2.

the

This appears much more plausible ; the

diminution of volume when a mixture of oxygen and hydrogen is converted into steam, may

be occasioned by a proportionate diminution

of the absolute heat j the same may be said of
a mixture of nitrous gas and oxygen. The
minute differences observed by Crawford, may
have been inaccuracies occasioned by the complexity of

his experiments.

But

there are

other considerations which render this supposition

extremely improbable, if they do not

it.
Carbonic acid contains

altogether disprove
it

own bulk

of oxygen

the heat given outat

THEORY OF SPECIFIC HEAT.

70
its

formation must therefore be exactly equal

whole heat previously contained in the

to the

charcoal on
the

supposition ; but the heat by

of one pound of charcoal

tliis

combustion

seems, at

least,

equal to the heat by the com-

bustion of a quantity of hydrogen sufficient to

produce one pound of water, and this last is

equal to, or more than the heat retained by
the water, because steam is nearly twice the
density of the elastic mixture from which

produced

it

should

therefore

it is

that

follow,

charcoal should be found of the same specific

it is
only about -^ of it*

heat as water, whereas

Were

this supposition true, the specific heats

elastic

fluids

of

of equal weights would be in-

If

that of
steam or aqueous vapour were represented by
1, oxygen would be .64, hydrogen 8.4, azote
But the supposi.72, and carbonic acid ,46.

versely as their specific gravities.

tion
3.

is

untenable.

The quantity of heat belonging

to

the

ultimate particles of all elastic fluids, must be

the same under the same pressure and tem-

perature.
It is evident the

number of ultimate

par-

molecules in a given weight of volume

of one gas is not the same as in another for,

ticles or

equal measures of azotic and oxygenous

gases were mixed, and could be instantly
if

THEORY OF SPECIFIC HEAT.

71

united chemically, they would form nearly two

measures of nitrous gas, having the same
as the

weight

number of

two

original measures

one half of that before the union.

elastic

but the

ultimate particles could at most be

fluids,

therefore,

probably,

No two
have the

same number of

particles, either in the same

volume or the same weight. Suppose, then,
a given volume of any elastic fluid to be con-

stituted of particles,

each surrounded with an

atmosphere of heat repelling each other through

the medium of those atmospheres, and in a
of equilibrium under the pressure of a
constant force, such as the earth's
atmosphere,
state

at the

temperature of the surrounding

suppose further, that by some sudden
change each malecule of air was endued with
a stronger aflinity for heat ;
query the

also

bodies

change

that

would take place

last supposition

be given,

as

it

in

consequence of this
The only answer that can

appears to me,

is

this. The

particles will condense their respective atmos-

pheres of heat, by which their mutual repulsion will be diminished, and the external
pressure will therefore

eflfect a
proportionate condensation in the volume of air
neither an
:

increase nor diminution in the

quantity of heat
around each malecule, or around the whole,
will take
place.

Hence

the truth of the sup^

THEORY OP SPECIFIC HEAT.

72

position, or as
tion,

it

may now be

called, proposi-.

demonstrated.

is

Corol. 1. The specific heats of equal weights

of any two elastic fluids, are inversely as the
weights of their atoms or molecules.
2.

The

specific heats

fluids, are

of equal

6?///r^

of elastic

directly as their specific gravities,

and inversely as the weights of their atoms.

3. Those elastic fluids that have their atoms
the most condensed, have the strongest attracj the greater attraction is spent

tion for heat

accumulating more heat in a given space or

volume, but does not increase the quantity
in

around any single atom;,

4. When two elastic atoms unite by chemical aflinrty to form one elastic atom, one half
of

their heat

unite, then

gaged, &cparticles

disengaged.

When

thirds of their heat

And

in general,

is

when

is

three
disen^

m elastic

by chemical union become n

heat given out

is

is

two

to the heat retained as

the

m n

to n.

One

objection to this proposition

it

may be

said,

an increase

in the specific attraction of each

atom must

proper to obviate

produce the

it

same

will

effect

be

on the system as mi

increase of external 'pressure.

is

known

the absolute heat

Now

this last

of
give out a quantity
therefore the former must

to express or

THEORY OF SPECIFIC HEAT.

do

This conclusion must be admit-

the same.

ted

and

it

73

tends to establish the truth of the

The heat expressed by

of
the
any elastic fluid amounts
doubling
density

preceding proposition.

to about 50, according to

ments J

this

heat

is

not so

my

former experi-

much

as

one hun-

part of the whole, as will be shewn

hereafter, and therefore does not materially

dreth

affect the specific heat

it

seems to be merely

the interstitial heat amongst the small globular

molecules of

and scarcely can be

air,

said to

belong to them, because it is equally found in

a vacuum or space devoid of air, as is proved

by

the increase of temperature

air into

upon admitting

a vacuum.

we can apply this doctrine to find the

of elastic fluids, we must first
heat
specific
ascertain the relative weights of their ultimate
Before

particles.

Assuming

at present

that

proved hereafter,

atom of hydrogen be

1,

if

the

that of

what

will

be

weight of an

oxygen

will

be

7, azote 5, nitrous gas 12, nitrous oxide 17,

carbonic acid 19, ammoniacal gas 6, carbu-

retted

hydrogen

7, olefiant gas

6, nitric acid

19, carbonic oxide 12, sulphuretted

16, muriatic acid 22,

hydrogen

aqueous vapour

8, ethe^

vapour 11, and alcoholic vapour 16; we

shall have the specific heats of the several

real

elastic fluids

as

in

the following

table.

In

THEORY OF SPECIFIC HEAT.

74

order to compare them with that of water,

we shall further assume the specific heat of

water

that of steam as 6

to

to 7, or as

to

1.166.

Table of the

specific heats of elastic fluids.

Ilvdro^cn

9.382

Olefiant gas

Azote

1.866

Nitric acid

Oxvaen

1.333

Carbonic oxide

Atmos.air

1.759

777

Sulph. hydrogen .583

Muriatic acid.. .424

Nitrous gas
Nitrous oxide

1.555

491
.777

549

Aqueous vapour 1 .166

Carbonic acid... .491

Ether, vapour... .848

Animon. gas

Alcohol, vapour .586

1.000
Water

...

1.555

Carb. hydrogen 1.333

Let us

now

how

see

far these

results will

accord with experience. It is remarkable that

the heat of common air comes out nearly the

same

Crawford found

as

also, hydrogen excels

mined

but oxygen

is

all

it

by experiment;

the rest as he deter-

much lower and

azote

The

higher.
principles of Crawford's doctrine
of animal heat and combustion, however, are

not at

all

affected

with the change.

Besides

the reason already assigned for thinking that

azote has been rated too low, we see from the

Table, page 62, that ammonia, a

compound

ON HEAT BY COMBUSTION.

75

of hydrogen and azote, has a higher specific

compound of hydro-

heat than water, a similar

gen and oxygen.

Upon

the whole, there

is

not any established

fact in regard to the specific heats of bodies,

whether

elastic or liquid, that is

the above table as far as I

know

repugnant
;

and

it is

to
to

be hoped, that some principle analogous to

the one here adopted, may soon be extended
to solid

and liquid bodies

in general.

SECTION

5.

ON THE

QUANTITY OF HEAT EVOLVED

BY COMBUSTION.
When

certain bodies unite chemically wuth

oxygen, the process is denominated combustion^

and is generally accompanied with the evolution of heat, in
consequence of the diminished

The fine attempt

of Lavoisier and
Laplace to find the quantities
of heat disengaged
during different species of
capacities of the products.

combustion, has not been followed up with

the attention

ic deserves.
Perhaps this may
have been owing to the
supposed necessity of

ON HEAT BY COMBUSTION.

76

using the calorimeter of the above philosophers,

and to a notion that its results are not always

depended upon. Much important information may, however, be obtained on this

subject by the use of a very simple apparatus,
as will appear from what follows:

to be

took a bladder, the bulk of which,

extended with

air,

was equal

whea

to 3CXX)0 grains

this was filled with any combustible

;
and a pipe and stop-cock adapted to it
a tinned vessel, capable of containing 30000

of water

gas,

grains of water was provided, and its capacity

for heat being found, so much water was put
into

it

as to

make the

vessel

and water together,

30000 grains of water. The gas was

and
the point of the small flame was
lighted,
the
to
concavity of the bottom of the
applied

equal to

till the whole of the

gas was
the increase of the temperature of

tinned vessel,

consumed

the water was then carefully noted; whence the

effect of the combustion of a given volume

of gas, of the

common

pressure and tempera-

ture, in raising the temperature of

volume of water,

was

an equal

ascertained, except a

very small loss of heat by radiation, &c. which

this

method must be

liable to,

and which pro-

bably does not exceed ^ or T^th of the whole.

The mean results of several trials of the
different

gases are stated

below

-,

when

the

ON HEAT BY COMBUSTION.
performed with due

experiments are
there

is

77
care,

any sensible differences in

with the same species of gas. The

scarcely

the results

point of the flame should just touch the bottom

of the vessel.

Hydrogen, combustion of it raises an

equal volume of water
Coal gas, or carburetted hydrogen
defiant gas
Carbonic oxide
Oil, alcohol,

4.5
10,

14.

4.5

and

lamp, &c. and the

ether,
effect

were burned in a

observed as under

Oil, spermaceti, combustion of 10 grs.

raised

30000

grs.

water

of turpentine (much smoke unburnt)

Alcohol (.8)7)

5.

2.9

Ether, sulphuric

3.1

Tallow and wax..

5.2

Phosphor.
Charcoal

Ogrs. heated SOOOOgrs. water 3

Sulphur

Camphor

3.5

Caoutchouc

2.1

The five last articles were placed upon a

convenient stand, and burned under the vessel
of water ; except charcoal, a piece of which

ON HEAT EV COMBUSTION.

78

was

ignited, then

tion

was maintained by a gentle

weighed, and the combusblast from a

blow-pipe, directing the heat as much as posupon the bottom of the vessel ; after the

sible

operation it was again weighed, and the loss

ascertained ; the result never amounted to 2"
for ten grains,

but generally approached

it

nearly.

In order

to exhibit the

comparative effects
be
may
proper to reduce the
clearly,
articles to a common weight, and to place

more

it

along with them the quantity of oxygen known

The quantity of heat
to combine with them.
given out may well be expressed by the num^
ber of pounds of ice which it would melt,

taking

it

for

granted that the quantity neces-

sary to melt ice, is equal to that which would

raise water 1 50 of the new scale.
The re-

may be

sults

lib.

hydrogen takes

seen in the following table.

7lbs.

carbur. hydrogen,

defiant gas,

3.5

carbonic oxide,
oil,

wax and

tal.

.,8

oxygen, prod, 8

melts 320lbs: ke.

water,

&

car. acid

4.5

3.5

1.58 carb. acid

4.5

ether,

posphorus

1.5

charcoal

2.8

sulphur

"

camphor

Ibss

5 wj

w.

& car.

25
ac.

carb. acid

sulph.

w.

&

104

62

2.5 phoi. acid

3,8

85
88

acid

car. ac;

60
40
ao
70

ON HEAT BY COMBUSTION.
Lavoisier has

a similar table derived

left us

from experiments on the calorimeter,

gen, phosphorus, charcoal, oil

Crawford

for

79

hydrogen,

for

hydro-

and wax

charcoal,

and

and

oil

w^ax, derived from their combustion in ano-

By reducing Crawford^s

ther apparatus.
to a

sults

they will both appear as follows

according to
Lavosier.
lib

Hydrogen by combustion melts

295lbs. ice

lOO

Phosphorus

Charcoal
Wax
_ Oil

96-5
133.

148

according to

Crawford.
48olbs, ice.

69

97
89

The near coincidence of I^-

Hydrogen.
vosier's

and mine

result

favour of their accuracy.

is

an argument

Crawford,

method of determining
by

it,

electricity,

in

think,

must have overrated the heat produced

the gases

re-

comparative scale with Lavoisier's,

his

by the explosion of
seems however

sus-

and ought to be repeatceptible of precision,

The truth perhaps lies between the two.
ed.
Phosphorus.

Lavoisier's result,

which

is

I think, be too
greater than mine, must,
66
is as much as can be
I
that
high.
suspect

much

fairly inferred.

Charcoal.

The

those of Crawford

is

inferiority of

my

results to

what might be expected.

ON HEAT BY COMBUSTION.

80

Mine must
other

be

necessarily

But Lavoisier

is

articles,

in

as

this

rather too low.

well as

all

the

excepted, unwarthink Crawford will

hydrogen
I

rantably too high.

be found too high

his

experiments on the heat

produced by the respiration of animals, support this supposition.

Wax

and Oil.

Crawford's

results are

lower than mine, which they ought not to

and
Lavoiare doubtless below the truth.
be,

little

sier's certainly

cannot be supported. This great

philosopher was well aware of

of his
ingly.

the uncertainty

and expresses himself accordseems not to have had an adequate

results,

He

idea of the heat of hydrogen gas, which contributes so much to the quantity given out by
its

; he
compares, and expects to
an equation, between the heat given out

combustion

find

by burning wax, &c. and

the heat given out

by

the combustion of equal weights of hydro-

gen and charcoal in their separate state j but

cannot be expected, as both hydrogen and

this

charcoal in a state of combination must contain

less

heat than

when

separate, agreeably to the

of heat on comgeneral law of the evolution

In fact, both Crawford and Lavoibination.

in some degree, led away by

the notion, that oxygenous gas was the sole
or principal source of the light and heat pro-

sier

have been,

ON HEAT BY COMBUSTION.

81

duced by combustion. This is the more remarkable of the former, after he had proved
that hydrogenous gas, one of the most frequent

and abundant combustibles, possessed nearly

five times as much heat as the same weight of
oxygenous

gas.

Azote, another combustible,

possesses as high and probably higher specific

heat than oxygen. Oil, wax, tallow, alcohol,
&c. would be far from being low in the table

of specific heat, provided a table were formed

comprehending bodies of every class. Charcoal and

Upon

sulphur rank but low in the table.

we cannot adopt the
'^
that inflammable
of Crawford,

the whole then,

language
" bodies contain

"

" bustion
**

little

is

absolute

and

is

the inflammable body."

be

heat,"

produced by comderived from the air, and not from

heat which

that the

This language may

to the ordinary
nearly right as applied

com-

bustion of charcoal and pitcoal ; but cannot

be so when applied universally to combustible
bodies.

After these remarks

it is

almost unnecessary

and probably the light

must be conevolved
combustion,
also,
by
ceived to be derived both from the oxygen
and that each
and the combustible body

to

add that the

heat,

contributes, for aught

we know

to the con-

ON HEAT BY COMBUSTION.

82

heat before

trary, in proportion to its specific

the combustion.

similar

observation

may

be made upon the heat produced by the union

of sulphur with the metals, and every other
chemical union

wc

Before

proper

to

in

is

evolved.

this section

it

add, for the sake of those

more immediately
fuel,

which heat

conclude

that

interested in the

the heat

given out

may be
who are

economy

of

by the com-

bustion of lib. of charcoal, and perhaps also

of pitcoal, is sufficient (if there were no loss)

to raise 45 or 50 lbs. of water from the freezeor it is sufficiing to the boiling temperature
8
lbs.
of
into steam.
water
7
or
convert
to
ent
;

If more than this weight of coal be used, there

a proportionate quantity of heat

ought, if possible, to be avoided.

is

SECTION

lost,

which

6.

ON THE

NATURAL ZERO
Oi' absolute

If

we

of

TEMPERATURE

Privation of Heat.

suppose a body at the ordinary tempe-

rature to contain a given quantity of heat, like

as a vessel contains a given quantity of water,

ON THE ZERO OF TEMPERATURE.

it is

plain that

83

by abstracting successively small

equal portions, the body v/ould finally be exIt is an

hausted of the fluid.
object of priin
the
doctrine
of heat to
mary importance

how many

determine,

scale of temperature

sed before

would

it

absolutely cold.

ing

this

degrees of the ordinary

a body must be depres-

lose all its heat, or

We

direct experiment

by

become

have no means of
;

effect-

but v/e can

acquire data for a calculus, from which the

zero may be approximated with considerable
accuracy.
The data requisite for the calculus are the
exact specific heats of the several bodies ope-

and the quantity of heat evolved,

or absorbed by bodies, in cases of their chemical combinations or otherwise. These data
rated upon,

be acquired without great care

and hence the great

are not to

and circumspection;

of the results hitherto obtained in

diversity

this difficult investigation.

the zero

common

is

According

to

some,

estimated to be 900 below the

;
whilst, according to
8000
below the same.
others,
nearly
These are the extremes ; but various deter-

temperature

it

is

minations of an intermediate nature are to be

found.

The most

simple ca82 in theory

is

that of

84

ON THE ZERO OF TEMPERATURE.

and water

ice

two bodies

these

supposing the capacities of

to be as 9 to 10, at the

temperature of 32,

much

32 requires as

to convert

160,

melt

it

it

is

known

that ice of

heat as would raise water

into water of 32, or to

Consequently, according to the 8th

formula, page 57, water of 32, must contain
it.

10 times

as

much

heat, or

the zero must be placed at

1500.
1

temperature of freezing water.

That

is,

500 below the

Unfortunately,

however, the capacity of ice has not been

determined with sufficient accuracy, partly
because of its being a solid of a bad conbut principally because the

ducting power,

degrees of the common thermometer below

freezing, are very erroneous from the equal
division of the scale.

one already mentioned, the

principal subjects that have been used in this
investigation are, 1st, mixtures of sulphuric
Besides the

acid and

water

water;

2d, mixtures of lime and

3d, mixture or combination of nitric

acid and lime

and 4th, combustion of hydro-

gen, phosphorus and charcoal.

it

will

Upon

these

be necessary to enlarge.

Mixture of Sulphuric Acid and Water.

According to the experiments of Lavoisier

ON THE ZERO OF TEMPERATURE.

85

and Laplace on the calorimeter, a mixture of

sulphuric acid and water in the proportion of
4

to 3 by weight, determines the zero at

7292 below freezing water, reckoning by
Fahrenheit.
But a mixture of 4 acid with 5

water, determines the same at 2630.

Gadolin made several experiments on mixacid and water, the results

tures of sulphuric

of which are as accurate as can be expected

He has not dein a first essay of the kind.

termined the zero from his experiments, but

taking it for granted to be 1400 below the
point on the supposition that the
capacities of ice and water are as 9 to 10, he

freezing

has enquired how far his experiments corroborate the same, by comparing the capacities
of the

mixtures by experiment

with those

calculated from the previous assumption.

His
results are thus curtailed in their utility j but as

he has given us data

sufficient

to calculate the

zero from each experiment, it will be proper

to see how far they accord with Lavoisier's,
or those of others.

Taking the

specific heat of

water at

1,

Ga-

dolin finds, by direct experiment, the specific

heat bf concentrated sulphuric acid to be

.339 (See Crawford on heat, page 465) ; he

then mixes the acid and water in various

86

ON THE ZERO OF TEMPERATURE.

proportions, observes the increase of temperature, and then finds the capacities of the

Whence we have

data to find the

zero by formula 9, page 58.

In giving his

mixtures.

numbers,

have changed

grade, to Fahrenheit's.

Add

his scale, the centi-

ON THE ZEUO OF TEMPERATURE.

Acid

Water

sp. gr.

5.77

4-

(1.78)

160

heat evol.

87

capa. of mix.

zero

.420

6400o

1.6

+1

(1.520)

260

.553

4150

(1.230)

100

.764

6G0Q

I reject

all

mixtures where the heat

is

less

than 100, because the difference between the

observed capacity of the

mean

capacity

with precision.
from Gadolin's.
to

These

results differ materially

I believe they will

be nearer approximations

"When the two

and the

mixture,

too small to be determined

is

liquids are

to

be found

the

mixed

truth.

in

nearly
equal weights, the results give the zero less
remote than otherwise ; this appears to be the
case both with Gadolin
yet been able

and

me

have not

to discover the cause of

haps the capacity of such mixture

it ;

per-

increases

with the temperature more than in the other

cases.

Lime and Wafer.

Quicklime, that
a strong

affinity

is,

for

lime recently burned, has

watery

when mixed

in

due proportion an intense heat is produced ;

the lime falls, or becomes slaked, and then

may be denominated
water
slake

is
it,

hydrat of lime. IF no more

put to quicklime than is sufficient to
or pulverize

it,

three parts of lime,

ON THE ZERO OF TEMPERATURE.

88

by weight, form four

parts

of hydrat, a per-

dry powder, from which the water

cannot be expelled under a red heat. If more
fectly

water

added, the mixture forms mortar, a

is

pasty compound, from which the

excess of

water may be expelled by a boiling heat, and

the hydrat remains a dry powder.
When
hydrat of lime and water are mixed, no heat
is

evolved

hence the two form a mere mix-

The
ture, and not a chemical compound.
heat then which is evolved in slaking lime,
arises from the chemical union of three parts
of lime and one of water, or from the formation of the hydrat,

and any excess of water

diminishes the sensible heat produced. Before

any use can be made of these facts for deter-

mining the

zero,

it

becomes necessary

to de-

termine the specific

heat of dry hydrat of

For this purpose a given weight of

lime.

lime

is

to

be slaked with an excess of water

the excess must then

be expelled by heat till

the hydrat is 4- heavier than the lime.
given
weight of this powder may then be mixed

with the same, or any other weight of water

of another temperature, and its specific heat
determined accordingly. By a variety of experiments made in this way, and with sundry
variations, I find the specific heat of hydrat of

ON THE ZERO OF TEMPERATURE.

89

lime about .40, and not .25 as in the table*

page 62. Lime itself I find to be nearly .30.

Crawford undervalues lime, by mixing cold
lime with hot alcohol

duce a
it

sufficient effect

the lime does not pro-

on the alcohol, because

contains water, which acts

upon the

lime.

I have no doubt a different specific heat would

have been found, if cold alcohol had been

poured on hot lime.

The

heat evolved in the

formation of hydrat of lime may be found as

follows
If 1 oz. of lime be put into 4 oz. of
water, the temperature of the mixture will be
:

raised 100"; in this case l^oz. hydrat

ed,

and the heat evolved

3|- oz.

water 100

times the heat that

therefore the

heat

but

3-^

Whence

hydrat of lime does ;

given out is sufficient to
14-

to raise the

once the hy-

the heat evolved by

3 parts of lime and

form-

it

raise 8 times the hydrat 100", or

drat 800.

is

together with
water contains 7

raises

of water,

new compound

800.

is

mixing

sufficient

Applying

then the tlieorem in page 58, we obtain the

zero
4260 below the common temperature.

Nitric Jcid and Lime.

According to the experiments of Lavoisier

and Laplace, the specific heat of nitric acid,
sp.gr. 1.3, is .661, and that of lime .217, and a

compound

of 9y parts of said acid, and one

90

ON THE ZERO OF TEMPERATURB.

of lime,

is

no change

Bat supposing there was

.619.

of capacity

upon combination,

this

only have the capacity .618 ;

in
mixture produces an inthe
fact,
whereas,

compound should
crease

temperature of about 180, and

ought to be found with a diminished

of

therefore

capacity, or one

below

to be established,

it

.618.

Were

this fact

would exhibit an inex-

plicable phenomenon, unless to those who

adopt the notion oH free caloric and combined
caloric existing in the

more properly, of
retain all
loric

its

same body, or
combined

caloric

characteristic

combined

properties,

so as to lose the

to

speak

so as to

and

car

whole of them.

Oae

error in this statement has already been

pointed out, in regard to the capacity of lime.
If we adopt the specific heat of lime to be
.30,

and apply the theorem for the zero, W

it to be 15770 below the common

shall find

temperature, as deduced from the above date

io corrected.

I took a specimen of nitric aeid of the spe-

gravity 1.2, and found, by repeated trials,

.76 by weight.
Into
specific heat to be
4600 grains of this acid of 35 temperature,

cific
its

657 grains of lime were gradually dropped, and the mixture moderately
agitated ^ in one or two minutes after 3>4>ths of

in a thin flask,

the lime

was in and

dissolved, the thermometer

ON THE ZERO OF TEMPERATURE.

5-056

nearly to 212,

ginning

when

to boil

it

and the

was

rose to

again

the

boiling point;

and

out,

cool 20",

was added, and

grains of insoluble residuum

were taken

was be-

iTiixture

suffered to

the rest oF the lime

91

were

about

left.

it

15

These

their place supplied

by

15 grains of fresh lime, which were dissolved^

and left a clear liquid nearly saturated, of

1.334

The
The

sp. gravity.

found to be

.69.

being called 200, and

being

we

.30,

of this
specific heat

was

increase of temperature
the specific heat of lime

zero to be

find the

1000 be-

low the freezing temperature. The experiment was varied by taking acids of different
strengths,

and various proportions of lime, but

gave the zero more remote than

the results still

either of the previous methods.

reason

may be that lime

is still

Perhaps the

under-rated.

Combustion of Hydrogen.
Lavoisier finds the combustion of lib.

hydrogen
of

to melt 295lbs. of ice.

of

results

320lbs, and Crawford's

my

480.

The

experience givecan
^Till

this

fact

be more accurately

we may

take 400ibs. as approxi-

mating to the truth.

Or, which amounts to

ascertained,

the same thing,

the combustion of Jib. of

hydrogen takes 7lbs. of oxygen, and gives out

heat which would raise 8lbs. of water 7500*

ON THE ZERO OF TEMPERATURE.

92

By adopting Crawford's

capacities of hydro-

gen and oxygen, and applying the theorem,

page 58, we find the zero 1290 from the

common

But If we adopt the

of
the
preceding theory
specific heat of elastic
temperature.

and apply the 4th

fluids,

must conclude that

in the

corol.

page 72,

one half of the whole heat of both

ments

is

given out

we

formation of steam,
it^

ele*

the conversion of 81bs of

steam into water, will give out heat sufficient

to melt 56lbs. of ice; therefore one half of the

whole heat

in

lib.

of hydrogen, and 7lbs. of

which is the same thing,

oxygen
the whole heat in lib. of hydrogen, or Tibs, of
together, or

oxygen

separately,

row

if

288

for the

from 688

will melt 344lbs. of ice

we

lbs.

of

take 400, there remain

ice,

which the heat

8lbs. of water, at the ordinary temperature,

sufficient to melt, or the heat in lib.

in
is

is

capable
of melting 36lbs. of ice hence the zero will
be 5400 below freezing water.
:

Combustion of Phosphorus.

One pound

of phosphorus requires ^Ib. of

The specific
66lbs. of ice.

oxygen, and melts

heat of phosphorus is not known but from

analogy one may suppose it to have as much
heat as oil, wax, tallow, &c. which is nearly
;

half as

much

as water.

From

the last article

ON THE ZERO OF TEMPERATURE.

it

seems, that the whole heat in each

gen

is

lb. of
oxymelt 50lbs. of ice; whence

sufficient to

the whole heat

combustion,

93

in

both

articles,

to

sufficient

is

From which

93lbs. of ice.

previous to

75+18

melt

deducting- 66,

there remains 27 for the pounds of ice,

which

the heat in 2.5lbs. of phosphoric acid

ought to
melt.
This would give the specific heat of
that acid .30, a supposition not at all
improThe result of the combustion of

bable.

phorus seems then

to

phoscorroborate that from

hydrogen.

Combustion of Chaixoal.
Crawford's data are, specific heat of charcoal .26, oxygen 4.749, carbonic acid
1.0454^
and the heat given out by
burning lib. of

charcoal

established

69lbs. ice

beyond doubt,

requires 2.6lbs. of

carbonic acid.

rem, page 58,

10350.

It

is

oxygen

to convert

it

If

into

From

we

these data, by the theodeduce the zero

4400.

But Crawford himself has not noticed

deduction.

now

that lib. of charcoal

this

we

adopt the theory of specific

heat, and the table founded on it, combined
with the supposition of the zero
being 6000

below the common temperature,

v/e shall have from

equation.

(see

pag 74)

the general formula,

thiwS

ON THE ZERO OF TEMPERATURt,

94

(1+
1

.26

X
2.6) X .491
+2.6 x~i.'333~^
//

3.6

">r749i~

^^^''

where h represents the degrees of temperature

which the combustion of Jib. of charcoal

would

raise the

bonic acid.

But

would

heat

this

= 6650

product, or 3.6ibs. of carthis, h is found = 6650'.

From

.491

lib. of water, 11750"

of

raise

or

3.6lbs. of

Or

3265.
it

it

would melt

Lavoisier finds the effect

ice.

and Crawford

finds

it

water

would

raise

78lbs.

961bs.

So that the

69.

supposed distance of the zero is not discountenanced by the combustion of charcoal, as

far as the theory is concerned.
Combustion of

We

Oil,

Wax and

do not know the exact

Talloic.

cotistitution

of

compounds, nor the quantity of oxygen

which they require ; but from the experiments
these

of Lavoisier, as well as from some attempts

of

my own,

am

inclined to think, that they

are formed of about 5 parts of charcoal

and

of hydrogen by weight, and that 6 parts require 21 of oxygen for their combustion, form-

ing 19 parts of carbonic acid and 8 of water.

Let it be supposed that the zero is 6900 be-

low freezing water,

of 32,

is

or that the heat in water

sufficient to

melt 46lbs. of

ice,

then

ON"

THE ZERO OF TEMFER ATURB.

the heat in steam

will

be

sufficient to

9'5

melt

applying Cor. I, at page 72, we

heat in oxygenous gas = 60.5lbs.
find
the
shall

By

SSlfcs.

affidd

in carbonic aoid, 22.3lbs.

The

heat in

lib. of m\y &c. equal to half that oi water

28lbs. which being added to 211.7, the

heat in

3.6lbs, of

oxygen, gives 234.7lbs. of

ice, whidh would be nwhed by all the heat

in lib, of oil and 3.5 of oxygen ; but the products of combustion ate l.Slb. of watser, and

3.2lbs. of carbonic acid, together containing as

mtjch heat as would melt 1 3 1 .2lbs. of ice ; this

being subtracted from 23^4.7, leaves 103.5 for

the ice to be melted by the boat evolved dum
ing the combustioai of lib. of oil, wax or tallow, which agrees with the experiment. The
conclusion then supports the supposition, that
the zero

is

690(y below freezir^ wfiter.

Combustion of EihePy

8Cc.

I have pretty accurately ascertained the products of the combustion of lib. of ether to be
1.75 water, and 2.25 carbonic acid, derived

from

its

union with

Slbs.

of oxygen.

By m-

stituting a calculation similar to the above,

but on the supposition of the zero being 6000'

below freezing water, I find the heat given

out on the combustion of ether, ought to be

= 67lbs. of ice

it

was observed

to

be 62, and

ON THE ZERO OF TEMPERATURE.

95

the difference
loss

may

well be attributed to the

unavoidable in

my method

of observa-

tion.

I might here enquire into the results of the

combustion of the other articles mentioned in

the table, page 78, as

but

they affect the

consider those above

far as

present question
noticed as the most to be depended upon.
From the result of olefiant gas we may learn,
s,

that a combustible

body

in

the gaseous state,

does not give out

much more

in a liquid state

for, oil

tainly

do not

differ

much

and

heat than

when

olefiant gas cer-

in their constitution

one would therefore have expected the same

weight of olefiant gas to have yielded more
heat than

oil,

because of the heat required to

; but it should seem

maintain the elastic state

that the heat requisite to convert a liquid to

an elastic fluid, is but a small portion of the

whole, a conclusion evidently countenanced

by the experiments and observations contained
in the preceding pages.
It

may be proper now

to

draw up

the re-

experience, reported in the present

section, into one point of view.

sults of

my

ON THE ZERO OF TEMPERATURE.

97
Zero below

32
Fahrcnh'it.

From a mixture

of 5.77 sulphuric acid and

water

4130

6000

4^60

lime

7 nitric acid

lime

phosphorus

5400

charcoal

6000

oil,

wax and

tallow

these

all

authorised then,

till

6900
6000

ether

of

11000

5400

the combustion of hydrogen

The mean

6400^

1.6

iTom

is

6150.

something more

We

are

decisive

appear, to consider the natural zero of temperature as being about 6000 below the temperature of freezing water, according to the
divisions of Fahrenheit's scale. The differences

of the above results are not greater than what

may be ascribed to inaccuracies, except the

2d and

5th.

to reconcile
it is

I believe

it

two

to

these

will

be impossible

each other, unless

upon the supposition of a change of capa-

with change of temperature in one or

both of the mixtures. This deserves farther
city

enquiry.

Heat produced

The

by Percussion and Frictio n

heat produced by the percussion and

friction of solid bodies,

arises

from one and

ON THE ZERO OF TEMPERATURE.

ija

the same cause, namely, from a condensation

and consequent diminution of

the
excited body ; exactly in the
of
capacity
same manner as the condensation of air proof

volume,

duces heat.

and other

come

It is

a well

known

metals, by being

hot and condensed in

fact, that iron

hammered, be
volume at the

same time; and if a diminution of capacity

has not been observed it is because it is small,
and has not been investigated with sufficient
That a change of capacity actually

accuracy.

takes place cannot be doubted, when it is

considered, that a piece of iron once hammered
in this

way,

is

unfitted for a repetition of the

heated in a fire and

Count Rumford has furnished us with some important facts on the
has been

effect,

tin

cooled

gradually.

it

He found that
production of heat by friction.
in boring a cannon for 30 minutes, the temperature

was

raised 70

and

that

it

suffered a

837 grains by the dust, and scales torn

which amounted to -^-gr part of the cylin^

loss of
ofT,

der.

On

the supposition that all the heat

was

given out by these scales, he finds they must

have lost 66360 of temperature j when at the
same time he found their specific heat not sensibly diminished.

But

this

incorrect view of the subject

manifestly an
the heat ex.cited

is
:

does not arise from the scales merely, else

how

ON THE MOTION OF HEAT.

99

should hammering make a body red hot withThe fact is, the whole
out any loss of scales ?

mass of metal

is

more or

less

condensed by

and a

the violence used in

rise of
boring,
100
is too small to
of
70
or
protemperature
duce a sensible diminution in its capacity for

heat.
in

this

Does Count Rumiford suppose,

that if

the quantity of metal operated

been lib. and the dust produced

case

upon had
same as above, that the whole quantity of
heat evolved would have been the same ?

the

The phenomena

of heat produced by fricand percussion, however, sufficiently shew

that the zero of temperature cannot be placed

tion

at so small a distance as 1000 or 1500"

the

common

below

temperature, as has been deter-

mined by some philosophers.

SECTION

7.

ON THE

MOTION AND COMMUNICATION

OF HEAT,
Arising from inequaliti) of Temperature.

As from
bodies

is

various sources the temperature of

liable to

perpetual

becomes of importance

to

fluctuation,

I't

determine the nature

ON THE MOTION 07 HEAT.

100

in the same body, and

one
from
body to another, arispassage
its incessant tendency to an equilifrom
ing
brium.

of the motion of heat

in

its

solid bar

exposed

being heated

to the air, the heat

and

in the air,

partly

at

is

one end, and

partly dissipated

conducted along the bar,

exhibiting a gradation of temperature from

This power of
the hot to the cold end.

conducting heat varies greatly, according to

the nature of the subject

in

general, metals,

and those bodies which are good conductors

of electricity, are likewise good conductors of

heat

and

When

vice versa.

a fluid

is

heated at

its

surface, the

heat gradually and slowly descends in the

same manner as along a solid 3 and fluids seem
to have a difference in their conducting

analogous to that of solids. But

heat is applied to the bottom of
containing a fluid, the case
the heated particles of the

is

power

when

the

a vessel,

very different ;
in conse-

fluid,

quence of their diminished specific gravity,

form an ascending current and rise to the sur-

communicating a portion of heat in their

ascent to the contiguous particles, but still
retaining a superiority of temperature ; so that

face,

the increase of temperature in the mass

observed at

the

surface,

and

is

is first

constantly

ON THE MOTION OF HEAT.

greatest there

till

the

lition in liquids, at

ture

is

commencement

101
of ebul-

which period the tempera-

The conducting power

uniform.

fluids then arises from two distinct sources

one

is

of
the

the same as in solids, namely, a gradual

to particle,
progress of the heat from particle
exclusive of any motion of the particles themselves

the other arises from the internal

mo-

tion of the particles of the fluid, by which the

extremes of hot and cold are perpetually

brought into contact, and the heat is thus difThe latter source
fused with great celerity.
is

so

that

much more

sufficient

effectual than the

been

som.e have

to

reason,

led,

former,

though without

doubt the existence of

the former, or that fluids do convey heat in the

same manner

as solids.

Nothing appears, then, but

that the

com-

munication of heat from particle to particle,

performed

in the

the rapidity of

same way

its

is

in fluids as in solids;

diffusion in fluids,

is

to

be

But there
ascribed to an hydrostatical law.
is another method by which heat is propagated
through a vacuum, and through

which demands our particular

elastic

fluids,

notice.

By
we receive the heat of the sun and by
this, when in a room, we receive the heat of

this

an ordinary

fire.

It is called

the radiation of

ON THE MOTION OF HEAT.

102
heat

and the

heat, so propelled,

is

called ra^

diant heat.
Till lately

we have been

used to consider

the light and heat of the sun as the same

thing. But Dr. Herschel has shewn, that there
are rays

which

of light
light

which

heat proceeding from the sun,

the rays

they are subject to reflection, like

to refraction, but in a less degree,

and
is

the cause of their separability from

velocity of radiant heat is not

The

light.

known
same

of

are separable by a prism from

but

as that

to the

it

maybe presumed

of light,

contrary.

An

till

to

be the

something appears

ordinary

fire,

red hot

charcoal, or indeed any heated body, radiates

heat, which is capable of being reflected to a
focus, like the light
it

and heat of the sun

should seem to be not of sufficient

but

energy

to penetrate glass, or other transparent bodies

so as to be refracted to an efficient focus.

Several new and important facts relative to

the radiation of heat, have lately been ascer-

tained by Professor Leslie, and published in

"
Enquiry on Heat." Having invented

his

an ingenious and

delicate air

thermometer,

he was enabled
well adapted
in a great
of
effects
radiation
ma
k
the
to
and
of
cases
circumstances, with more
variety
for the purpose,

precision than

had previously been done. Some

ON THE MOTION OF HEAT.

103

of the principal facts respecting the radlati<$r>

of heat, which have either been discovered or

con6rmed by him,

be proper

will

it

to

mtVr

tion.

given vessel be filled with hot water,

the quantity of heat which radiates from it,
If a

1.

depends

chiefly

upon the nature of the

tenor surface of the vessel.

ter

Thuv

ex-

a canis-

if

of tinned iron be the vessel, then a certain

quantity of heat radiates from

&c,

glass,

it

the said

if

it;

with

black paint, paper,

will then radiate 8 times as much

vessel be covered

heat in like circumstances.

2. If the

ed with
heat

is

bulb of the thermometer be cover-

tinfoil, the

impression of the radiant

only |th of that upon

the glass sur-

face.

3.

metallic

mirror reflects

IG times aj

much

heat from an ordinary fire, or from any

heated body, as a similar glass mirror does.

This

last is

found to

reflect the

heat from

its

anterior surface, and not from the quicksilvered one, which is the most essential in refkcting
solar light

Here then

and heat.

ing difference

between

solar

is

strik-

and culinary

heat.

From

these facts

it

appears,

tliat

mets^

and other bodies which are eminently disposed to rcjiect radiant heat, are not disposed to

ON THE MOTION OF HEAT.

104

any remarkable degree whereas,

black paint, paper, glass, &c. are disposed to
in

absorb

it

absorb

it,

and consequently

to radiate

it

again

in proper circumstances.
4.

Screens of glass, paper,

&c. being

tinfoil,

and the
placed between the radiating body
reflector, were proved to intercept the radiant
heat completely ; but being heated themselves
by the direct radiant heat, in time the ther-

mometer was

by their radiation.
The heat radiating from hot water, does not
then seem capable of being transmitted through
affected

the solar heat.

glass, like
5.

Radiant heat

passage through
radiant

vided

it

flector,
6.

suffers

the

air

no
;

sensible loss in

its

greater or less

body produces the same effect, prosubtends the same angle at the reagreeing with light in this respect.
intensity of reflected heat diminishes

The

inversely as the distance ; whereas, in light,

it is the same at all distances; the focus
of

heat too differs from that of light ; it is nearer

the reflector ; the heating effect diminishes
rapidly in going outwards, but slowly in goThis seems
ing inwards towards the reflector.

to intimate the

want of perfect

elasticity in

radiant heat.

hollow globe of tin, four inches in

diameter, being filled with hot water, cooled
7.

ON THE MOTION OF HEAT.

from 35

to 25 centigrade in

105

156 minutes; the

same painted with lamp-black, cooled from

35 to 25 in 81 minutes.
The air of the room

was

15.

8.

the

When

a heated

body

is

whirled through

the additional cooling effect

air,

is

directly

proportional to the velocity.

9.

In

glass globe

of cooling of a hollowwith hot water, and that of

the rate

air

filled

the same globe covered with

is

tinfoil, is

The

stant at all temperatures.

not con-

disproportion

low temperatures, and less in

Thus, in the present case, Mr. Leslie

greater in

high.

finds the
glass,

variable

and

as

50

ratio

be

to

h for

tin,

as

105

where

sents the elevation of temperature in

-i-

1l

h for

repre-

degrees.

According to this the rate of cooling of a

vitreous and a metallic surface is nearly the

same
as

but
at very high temperatures
105 to 50, when h is very little.
;

is

nearly

No

dif-

ferences are observed in their rates of cooling

in water.

and

10. After a long

investigation,

power of

Mr.

the air

intricate,

Leslie

finds

but ingenious
the cooling

upon a hollow sphere, six

and filled with boiling

inches in diameter,
water,

to

be

as

follows

minute of time the

fluid

namely,

loses

in

each

the following

ON THE MOTION OF HEAT.

106

fractional parts

of

its

excess of temperature,

the three distinct sources of refrigeration in

hy

the air undermentioned

abduction, that

is, the proper conductBy

of
the
524th.
air,
ing power
By recession, that is, the perpendicular cur-

rent of air excited by the heated body, the

21715th.

By

pulsation, or radiation, the

2533d part

from a metahc surface, and eight times as

much, or the 317th part from a surface of

paper j (It should be observed, that Mr. Lescontends that air is instrumental in the ra-

lie

diation of heat,

which

is

contrary to the re-

ceived opinion.)
11
air,

body cools more slowly

than in air of the

common

in

rarefied

density

and

the different species of air have their respective

refrigerating powers.

Common

genous gas exhibit remarkable

air

and hydro-

difJerences.

Ac-

cording to Mr. Leslie, if the cooling power

of common air upon a vitreous surface be de-

noted by unity, that of hydrogenous gas will

be denoted by 2,2857 ; and upon a metallic
surface the ratio
air the loss

diation,

is

.5 to

1.7857.

from a vitreous surface

and

.43

by the other

loss

common

.57

by

ra-

two causes from

a metallic surface, .07 and .43.

nous gas the

In
is

In hydrogefrom a vitreous surface is .57

ON THE MOTION" OF HEAT.

107

by radiation, and 1.71 by the other causes j

He finds
from a metallic surface, .07 and 1 .7 1
the
same
in
be
the
two
to
the radiation
'gases,
.

and
tion

be very little diminished by rarefacbut the effects of the other refrigerating

to
;

powers rapidly diminish with the density.

Those who wish to see the experiments

and reasonings from which these important

conclusions are derived, must have recourse to

Mr.

work

Leslie's

but as some of the facts

and opinions appear from

I

shall

questionable,
what has occurred to
I have no

the

first

my experience to be
now proceed to state
me on these subjects.

reason to withhold

articles

but

my

the last

assent from
3

are not

equally satisfactory.

Before
ments,

it

we
will

enter

upon a

be proper

detail of
experi-

to point out the cor-

respondence of the new thermometric scale

with the old one in the higher parts, it
being
only given briefly in the table, page 14.

ON THE MOTION OF HEAT.

108

Correspondences of the Tkermometric Scales.

old

scale.

109

ON THE MOTION OF HEAT.

successive intervals took place, the times

were

in the higher,
always observed to be rather less
and more in the lower parts of the scale.

From this experiment it appears, that the

thermometer was raised 400 above the temor to 600 of the old scale ;
perature of the air,
it lost 200 of temperature in the first interval
of time, 100' in the second, and 50 in the
This' result goes to establish

third.

ciple

announced

to the

new

at

page

the

prin-

12, that, according

graduation, the temperature descends

in geometrical progression to equal increments

of time.

Experiment

According

to

Mr.

2.

to

peared
anxious to
to the fact.

me

very

satisfy

same law of

Leslie, the

cooling does not take place

as from a vitreous surface ;

from a metallic
this

myself more

AVith this view,

always ap-

and

surprising,

range from

to

of 12

was

particularly as
I

took another

mercurial thermometer, with a bulb of

diameter, and scale

.7

inch

inches, having a

300 old scale, and corres-

ponding new scale attached to it. This was

heated, and the times of cooling through every
10 degrees of the
noticed repeatedly ; the bulb

successive

new

scale v/ere

was then covered

no
with

ON THE MOTION OF
tinfoil,

pasted upon

it,

HIiAT.

and the surface

made as smoolh as well could be the thermometer was then heated, and the times of
;

cooling
peatedly.

were

again

noticed

The mean

column of the

as

betore,

results follow

re-

and a

differences of the logarithms of

the degrees expressing the elevation of temof the surrounding air,

perature above that
The temperature of the
which was 40.

thermometer was raised to 275 per scale ; that

is, 235 above the air, and it is obviously most
convenient to reckon from the temperature of
in which case 19
the air considered as zero
:

represents the difference

235 and 225, &c.

of the logarithms of

ON THE MOTION OF HEAT.

By

inspecting this table,

it

1 1

appears that the

whole time of cooling when the bnlb was

clear was 8 51 seconds, and when covered!
with

tinfoil

was 1206 seconds, which numbers

17 to 24.
But the times in

nearly as

are

cooling from

175 to

conds respectively

from 95

to

155'*

were 17 and 24

and the times

85 were

34

in

se-

cooling

and 48 respec-

which are exactly in the ratio of the

whole times: and by examining any two cor*

tively,

responding times, they will be found to be as

Whence it follows that t!e
17 to 24 nearly.

same law of progressive cooling applfes

metallic as to a vitreous surface,

the

results

of Mr. Leslie's

must not however

ratio for

correct

the

is

contrary to

experience.

It

be understood that

this

two kinds of

however

surfaces is quite
the
bulb of a thercarefully

mometer may be coated with

face

to a

tinfoil,

the sur-

enlarged, which makes

necessarily

it

cool more quickly than if the metallic Surface

were the very same qviantity as the vitreous.

The

differences of the logarithms

happening

accidentally so nearly to coincide in magttrttnde

with the tim of cooling of tht metallic sur-

no reduction, and

face, tlrcy rcqiitre

an opportunity of seeing

how

f^ar

geometrital progression In cooling

by

this

experhncnf

It

is

we have

the

law of

supported
appears that for 5 or 6

ON THE MOTION OF HEAT.

112

of the highest intervals of temperature, the

times of cooling were rather smaller, and for
the

two

last

rather larger than

required by

the law.

Experiment

As Mr.

Leslie

3.

found the times of cooling:

of metallic surfaces considerably enlarged, in

moderate elevations of temperature more especially, I took another

thermometer having

a smaller bulb, and a scale of an inch for 10

degrees, this

was

ment, and the

treated as in the last

experii

results

Thermom. cooled.

were asunder

ON THE MOTION OF HEAT.

this

than in the former experiment

the bulb being smaller,

113
;

because

was more than pro-

it

portionally increased in surface by the tinfoil,

which was pasted on in small slips, and conse-

quently was twofold in many places.

Being from these results pretty well satisfied
that the surfaces of bodies

law of

do not disturb the

though they ma-

their refrigeration,

terially affect the time, yet in

Mr.

the general accuracy of

ments,
his

was desirous

own way, more

consequence of
Leslie's experi-

to ascertain the results in

particularly because for the

reason assigned above, my method did not give

the true rates of cooling of equal surfaces.

Experiment
I took two new
commonly used for

tin

4.

canisters,

such as are

of a cylindrico-conical
shape, and each capable of holding 15 oz. of
water.
The surface of one of them v>/as cotea,

vered with brown paper pasted on it ; instead

of the usual lid, a cork of 1^ inch, diameter

was adapted

to both,

and through a hole

in

the centre of this, the tube of a delicate ther-

mometer was
graduation
canisters

inserted, with a scale of the

affixed

above the cork.

were contrived

small strings

when

filled

new
Both

be suspended by
with water, and lo

to

114

ON THE MOTION OF HEAT.

have the thermometer with

its

bulb

in

their

They were successively filled with

boiling water, and suspended in the middle of
a room of the temperature 40, and the times of
centers.

cooling

through each successive 10 degrees

as below.

were noticed

ON THE MOTION OF HEAT*

115

be unnecessary to insist upon the accuracy of

ft will be understood that the
the above,
range of cooling was from 205 of the new
of the same, the air being 40% or

scale, to 65

25 below the extremity of the range, which

corresponds with 57 of the old scale.
It will be proper now to enquire into thd
cause of the difference in the times of cooling
Mr.
arising from the variation of surface.

shewn

Leslie has

the surface has no influence

the time of cooling

upon
water

it

when immersed

in

should seem then that the difference

of surfaces in the expenditure of heat arises

from their different powers of radiation solely;
indeed Leslie has proved by direct experiments
that the heat radiating from a vitreous or paper surface

is

8 times as great as that from a

metallic surface.

can

Taking

we

this for granted,

of heat dispersed
easily find the portions

radiation,

by
and conducted away by the atmos-

denote the quantity of heat

conducted away by the atmosphere, from a
vitreous or metallic surface in any given small
phere.

For,

let

portion of time, and x the

quantity radiated
same time ; then

in the

from a metallic surface

8j will be the quantity radiated from a vitreous

surface in that time ; and from the result of
the last experiment
1

we

Srs whence 2

shall have,

4-

16jr

3 4-

::

1+x

3j:,

and

ON THE MOTION OF

IK)

x =z

j-^

this gives

,-^3,

HILAT.

whole heat

for the

discharged by metal, and 1 f-^ for that discharged by glass in the same time, where the
unit expresses the part conducted, and the
fraction the part radiated.

That

from a metallic surface 13 parts of

is,

heat are conducted

away by

the air and

1
part
13 parts
are conducted, and 8 parts radiated, in a
given
time.

radiated

The

from

a vitreous

surface

quantity of heat discharged by radiafavourable surface, there-

tion from the most

probably not more than

fore,

is

and

that

than

.6.

.4 of the whole,
conducted away by the air not less
Mr. Leslie however deduces ,57 for

the former, and .43 for the latter

because he

found the disproportion in the times of cooling

of vitreous and metallic surfaces greater than
I find

it

The

in the lov/er part of the scale.

obvious consequences of this doctrine

in a practical sense are,

1.

In every case where heat

be retained

is

required to

as long as possible, the

containing

vessel should

be of metal, with a bright clear

surface.

Whenever heat is required to be given

out by a body with as much
celerity as possible, the containing vessel, if of metal, ought
2.

to

be painted,

covered

with

paper,

char-

ON THE MOTION OF HEAT.

coal, or

some animal or vegetable matter

which case the heat given out

for 2

117

will

be

in

3 parts

from a metallic surface.

Refrigeration of Bodies in 'various Kinds of

Elastic Fluids.

Bodies cool in very different times in some

Mr. Leslie was the first,
of the clastic nuids.
I believe,

who

noticed this fact

and he has

given us the results of his experiments on common air and hydrogenous gas, of the common
density,
I

and

also rarefied in various degrees.

made some experiments with a view

to de-

termine the relative cooling powers of the

of which it may be proper to
gases, the results

My apparatus

give.

was a strong

phial, con-

a pertaining about \o or 20 cubic inches

forated cork containing the stem of a ther;

mometer was adapted to it, so as to be air

two marks were made with a file on

tight

the tube of the thermometer, comprizing an

The
interval of 15 or 20, about blood heat.
filled with any proposed gas, and
had acquired the temperature of the
surrounding air, the stopper was withdrawn,
and the heated thermometer with its cork was

bottle
after

was

it

instantiv

inserted

the

number of seconds

ON THE MOTION OF HEAT.

118

which elapsed whilst the

mercury descended
from the upper to the under mark were then

The surrounding

noted, as under.

air

was of a

constant temperature.

Thermometer immersed

f cooled in

In carbonic acid gas

sulphuretted hydrogen,

trous oxide,

and defiant >

gas
com.

gas

hyd.
hydrogen

air,

azotic

nitrous

carburet,

The

12 seconds.

100

and oxyg. gas 100

90

or coal gas ....

70
40

refrigerating effect of

remarkable;

ni-"\

hydrogen

is

truly

cooled the thermometer

10

times successively in a bottle of hydrogen gas ;

at each experiment the instrument was taken
out, and the stopper put in, till the original
temperature was restored ; by this, a portion
of the hydrogen escaped each time, and an
equal portion of common air was admitted ;

the times of cooling

regularly

increased as

follows; viz. 40, 43,

46, 48, 51,53, 56, 58,

60 and 62 seconds, respectively ; at this time
the mixture was examined, and found half

hydrogen

and

half

common air.
common

measures of hydrogen and

Equal
were

air

ON THE MOTION OF HEAT.

119

then mixed together, and put into the botand the heated thermometer was found

tle,

to cool

from mark to mark, in 62 seconds as

before.

Condensed

air cools

bodies more rapidly

than air of

common

less rapidly,

whatever be the kind.

sults

were

of

my own

as follows

Density o&the

density

rarefied air

The
common

re-

air

Therm, cools

air.

in

85 seconds,

100

116

t
^
T
tV

128

140

16a
170

,\

small receiver of hydrogen gas,

which
40 seconds, when
took 70 seconds to cool

cooled the thermometer

rarefied 7 or 8 times,

the same.

on

and

experience for

this

But the exact

in

effects

of rarefaction

and the other gases were not deter-

mined.

From Mr.

Leslie,

genous gas, there

we

learn that in hydro-

is little

difference

between

the time of cooling of a vitreous and metallic

surface, the former being as 2.28, and the lat-

ON THE MOTION OF HEAT.

120

ter as 1.78,

from which he justly

*'

infers

this

inequality of effect [between atmospheric air

and hydrogenous gas] proves its influence to

be exerted chiefly, if not entirely, in augmenting the abductive portion."
The expenditure of heat by radiation being
the same in hydrogenous gas as in atmospheric
air,

we may

infer

species of gas

the same in every other

it is

and therefore

is
performed independently of the gas, and is carried on the
Indeed Mr. Leslie
same in vacuo as in air.
;

himself admits

the

that

diminution of the

consequent upon rarefaction is extremely

small, which can scarcely be conceived if air
effect

were the medium of

The

radiation.

of radiation being allowed conthat

of
the density of the air may be
stant,
effect

investigated,

and

will

be found,

I believe, to

vary nearly or accurately as the cube root of the

In order to compare this hypothesis
density.
with observation, let 100 = time of cooling in
1
then
;
atmospheric air, the density being
from what has been said above,. 4 will represent

the heat lost by a vitreous surface by radiation,

and .6 that lost by the conducting power of
the medium.

Let

air of the density

t

the heat lost

conducted away

the time of cooling in

then

if

100

by radiation

is,

.4

v.

-.

.004

but the heat

by hypothesis, as the time

ON THE MOTION OF HEAT.

X

by the cube root of the

121

density

.006

W d; whence .004^+ .006 ty/d=

1,

and

1
3

.004

.006v/rf

Calculating from this formula, we shall find

times of cooling in common air of the

the

several densities as under

Denity of the

air.

Times of cooling.

86.5 seconds.

100

114

^
4
-^

143

170

129

157

TT

182

tU

193

_-i_

250

infinity.

This table accords nearly with the preceding

one, the result of actual observation.

In the

same way might the times of cooling of a metallic surface in rarefied air be found, by sub.0093 for .006 in
stituting .0007 for .004, and
the preceding formula.

The

incooling power of hydrogenous gas

dependent of radiation, may be found thus :

ON THE MOTION OF HEAT.

122
if

100"

.4

::

40"

,84

= the

.16

the heat lost

40 seconds

radiation in that gas in

heat conducted

40", or .021 per second

away by

by

whence

the air in

common

but in

air

the loss per second by abduction is only .006 ;

from this it appears that the refrigerating

power of hydrogenous gas

as that of
It

common

is

3t

tiroes as

great

air.

may be asked what

is

the cause

why

dif-

ferent gases have such different cooling effects,

especially on the supposition of each atom of
all

the

species possessing the

different

heat
quantity of

To

this

that the gases differ from each other in

essential points, in

the

same

we may answer

number

two

of atoms in a

given volume, and in the weight or inertia of

their respective atoms. Now both number and

weight tend
that

is,

if

to retard the

two gases

motion of a current

of particles in a given volume,

same number

possess the

it is

evident that

one will disperse heat most quickly which has

its atoms of the least
weight ; and if other

two

gases have particles

of the same weight,

most disperse heat which has the

number in a given volume because the

that one will

least

resistance will be as the

be moved,
gases that

in

like

number of

particles to

circumstances.

Of

the

have nearly the same number of

particles in the

same volume,

are, hydrogen,^

ON THE TEMPERATURE,

123

StC.

carburetted hydrogen, sulphuretted hydrogen,

nitrous oxide, and carbonic acid. These con-

duct heat

the order they are written, hyand the

;

in

drogen best and carbonic acid worst

increase in
weights of their ultimate particles
Of
those that
the same order (see page 73).
same
the
of
atoms
have their
weight and

number

their

in a

given volume difFerenl, are

oxygen and carburetted hydrogen the latter

has the greater cooling power and the fewer
:

a
particles in

given volume.

SECTION

8.

ON THE TEMPERATURE OF THE

ATMOSPHERE.
It

is

lieve,

a remarkable fact, and has never, I be-

been

atmosphere
to decrease

satisfactorily

accounted

in all places

for, that

and seasons

in temperature

in

is

the

found

proportion as

we ascend, and nearly in an arithmetical

Sometimes the fact may have
progression.
been otherwise,

namely,

that

the air

was

colder at the surface of the earth than above,

of a frost, I
particularly at the breaking
observed

it

so

but

have

this is evidently the effect

ON THE TEMPERATURE

124

of great and extraordinary commotion in the

atmosphere, and is at most of a very short

What

duration.

then

is

the occasion of this

diminution of temperature in ascending ? Before this question can be solved, it

may be pro-

per to consider the defects of the common

solution.
Air, it is said, is not heated by the

direct rays of the sun

any

which pass through

it

medium, without producing

as a transparent

calorific effect,

they arrive at the sur-

till

The

face of the earth.

earth being

heated,

communicates a portion to the contiguous

at-

mosphere, whilst the superior strata in pro-

more remote, receive

portion as they are

forming a

less

of temperature,
similar to what takes place
along a bar of iron
when one of its ends is heated.

heat,

The

first

part of the above solution

bably correct

Air,

in regard to heat

charges

it

gradation

it

it

should seem.

Is

is

pro-

singular

neither receives nor dis-

in a radiant state

if so,

the propaga-

tion of heat through air

must be effected by its

the same as in water.

conducting power,

Now we know
surface of a

that heat applied to the under

column of water

upwards with great

celerity,

is
propagated
by the actual

ascent of the heated particles : it is equally

certain too that heated air ascends.
From

these observations

it

should follow that the

OF THE ATMOSPHERE.

125

causes assigned above for the gradual change

of temperature in a perpendicular column of
the atmosphere, would apply directly to a
state of

temperature the very reverse of the

namely, to one in which the higher the
ascent or the more remote from the earth the
fact

higher should be the temperature.

Whether

this reasoning be correct or not, it

think be universally allowed, that the
fact has not hitherto received a
satisfactory

must

I conceive it to be one involving

explanation.
a new principle of heat; by which I mean a
principle that no other phenomenon of nature

presents us with, and

recognized as such.

The

is

not at present

endeavour

in

what

make

out this position.

The natural equiliprinciple Is this
of heat in an atmosphere, is when

follows to

brium

which

I shall

each atom of air in the same perpejidicular

is possessed of the same
quantity of
heat; and consequently, the natural equili-

column

brium of heat

in

an atmosphere

is

ivhen the

tejnperature gradually diminishes in ascending.

That this is a just consequence cannot be

denied,

when we

consider that air increases in

heat by rarefaction
when the
of
heat
is
or
limited, therefore
quantity
given
the temperature must be regulated
the

its

capacity for

by

density.

ON THE TEMPERATURE

126

is an established
principle that any body
the surface of the earth
unequally heated is

It

on

observed constantly to tend towards an

equality
of temperature ; the new principle announced
above, seems to suggest an exception to this
But if it be examined, it can

law.

scarcely

that light.

in

appear

Equality of heat and

of temperature, when applied to the

in the same state, are found so

equality

same body

uniformly to be associated together, that we

scarcely think of making any distinction be-

tween the two expressions.

No

one would

commonly observed law being

When any body is
in the^e terms

object to the

expressed

unequally heated, the equilibrium

be restored

becomes in
heat.

is found to
when each particle of the body
possession of the same quantity of

Now

the

law thus expressed

is

what I

apprehend

to be the true general law,

applies to

the atmosphere as well as to other

bodies.

It

is

which

an equality of heat, and not an

that nature tends to

equality o^ temperature
restore.

The atmosphere indeed

presents a striking
we see in
us in regard to heat
to
peculiarity
a perpendicular column of air, a body without
:

any change of form, slowly

changing

its

capacity

and gradually
from a less

for heat

OF THE ATMOSPHERE.
to a

greater

but

all

127

other bodies retain

uniform capacity throughout their substance.

If it be asked why an equilibrium of heat
should turn upon the equality
daan in temperature

know

but I

rest the

in

quantity rather

answer that

proof of

do not

upon the fact

it

of the inequality of temperature observed in

ascending into the atmosphere.

If the natural

tendency of the atmosphere was to an equality

of temperature, there does not appear to me

any reason
air

the superior regions of the

why

should not be at least as

warm

as

the

inferior.

The arguments
of the

priaciple

already advanced on behalf

we are endeavouring to

establish, are powerfully corroborated

following

facts

By

the

by the

observations

of

Bouguer, Saussure, and Gay Lussac, we find

that the temperature of the air at an elevation

where

its weight is t that at the surface, is

about 50 Fahrenheit less than that at the sur-

face

Mem.

and from

my

experiments

(Manch.

appears that air

2 to 1 produces
rarefied
from
being suddenly
50 of cold.
Whence we may infer, that a
vol. 5.

page 525.)

it

measure of

air at the earth's surface being

taken up to the height above-mentioned, pre-

serving
to

its

original temperature,

and suffered

expand, would become two measures, and be

ON THE TEMPERATURE

128

reduced to the same temperature as the sur-

rounding

air

or viccy versuy

if

two measures

of air at the proposed height were condensed

into

one measure, their temperature would be

50% and they would become the same in

raised

density and temperature, as the like volume of

In like manner

air at the earth's surface.

may

infer, that

if

earth's surface, to

a volume
the

we

of air from the

summit of the atmo-

sphere were condensed and brought inio a

horizontal position on the earth's surface, it

would become of the same density and temperature as the air around it, without receiving
or parting with any heat whatever.

Another important argument

in

favour of

the theory here proposed may be derived from

the contemplation of an atmosphere of vapour.

Suppose the present aerial atmosphere were to

be annihilated, and one of steam or aqueous
vapour were substituted in its place ; and suppose further, that the temperature of

this at-

mosphere at the earth's surface were every

where 212 and its weight equal to 30 inches
of mercury. Now at the elevation of about
6 miles the weight would be 15 inches or
it
would be
-I of that below, at 12 miles,
7.5 inches, or

-^

the temperature
at

of that at the surface, &c. and

would probably diminish 25

each of those

intervals.

It

could not di-

OP THE ATMOSPHERE.

129

minisb more; for we have seen (page 14) that

a diminution of temperature of 25'' reduces
the force of vapour one half; if therefore a
of temperature were to take
greater reduction
of
the incumbent atmosphere
the
weight
place,

would condense

a portion of the vapour into

and the

general equilibrium would

thus be disturbed perpetually from condensawater,

upper regions. But if we suppose

on the other hand, that the diminution of temperature in each of these intervals is less than
tions in the

25% then the upper regions could admit of

more vapour without condensation ; but it must
take place at the surface, because vapour at
212* cannot sustain more than the weight of

30 inches of mercury.
These three supposed cases of an aqueous
vapour atmosphere may be otherwise stated
thus
1.

The

specific gravity of

steam

at the earth's

surface being supposed .6 of atmospheric air,

and the weight of the atmosphere of steam

equal to SO inches of mercury, its temperature
at the

high,

surface

187; at

would be 212;
12 miles,

137; at 24 miles, 112, &c.

In

6 miles

at

162; at

18 miles,

this Case the

but every
where, would be a maximum, or the greatest

density, not only at

the

surface,

possible for the existing temperature

so that

ON THE TEMPERATURE

130

a perfect equilibriam
having once obtained,
there could be neither condensation nor eva^-

For every 400 yards

poration in any region.
of elevation, the thermometer would descend
I

degree.

atmosphere were constituted just

except that the temperature now
diminished more rapidly than at the rate of
2. If the

as above,

then the temperature of the

25 for 6 miles
higher regions not being sufficient to support
the weight, a condensation must take place j
;

the weight would thus be diminished, but as

the temperature at the surface is always sup-

posed to be kept at 212, evaporation must go

on there with the design to keep up the presThus there would be persure at 30 inches.

between the recently raised vapour

the condensed drops of rain
and
ascending,
petual

strife

descending.
position
the preceding one.
3.

fore,

much

less

likely

than

The same things being supposed as bebut now the temperature decreases more

slowly than

at the rate

of 25 for 6 miles

in

this case the density of the steam at the earth's

surface
ture,

would be a maximum

but no where else

for the

temperaof

so that if a quantity

water were taken up to any elevation it would

evaporate but the increased weight of the
-,

atmosphere would produce a condensation of

OP THE ATMOSPHERE*

131

Steam into water on the ground. In this case

then there would not be that equilibrium,
which we see in the 1st case, and which accords so

much more with

the regularity and

laws of
simplicity generally observable in the
nature.*

owe

to

Mr. Ewart the

elastic fluidii,

ing

in the present section

first

hint of the idea respect-

have endeavoured to expand

he suggested to me some time ago,

which

was probable steam of any low temperature, as 32",

of maximum density, contained the same quantity of absolute heat as the like weight of steam of 212* of maximum

that

it

if it could be gradually
without
heat, that is, if the conany
losing
compressed
with it in increase of temperature,
taing vessel kept pace
there would never be any condensation of steam into water,

density; and that consequently

but

it

In

when

would constantly
fact the heat
it

is

retain

(1000<'),

its

elasticity.

given out by steam

merely heat of comthe affinity of the molecules

which

is

condensed into water,

is no change in
pression; there
of water for heat ; the expulsion

is

is

occasioned solely

by

the approximation of the molecules, and would be precisely

the same whether that approximation was occasioned by exif we estimate
ternal compression or internal attraction. Indeed
the mechanical
the temperature thai would be given out by
from a volume of 2048 to that of 1, by
compression of steam
the density, and supposing as above,
successively doubling
it
of
time
each
that at
doubling, 25 were given out,

would be found that 12 successive operations would reduce

be given out.
the volume to J, and that only 300" would

But

it

is

of
not right to conclude, that the same quantity
would be given out at each of the successive

temperature

ON THE TEMPERATURE,

132

&;C.

That an atmosphere of steam does actually

surround the earth, existing independently of
the other atmospheres with which however it
is

necessarily most intimately mixed,

is

I think

capable of dcmonsti*ation. I have endeavoured

to enforce and illustrate it in several Essays in
the

Memoirs of

Manchester Society, and

which I must refer.

the

in Nicholson's Journal, to

Now

an atmosphere of any elastic fluid,

whether of the weight of 30 inches of mercury, or of half an inch, must observe the same
general

laws

but

should seem that an

it

atmosphere of vapour varies

its

temperature

condensations, though it may be nearly so for most of them :

towards the conclusion, the space occupied by the solid

atom or

particle bears a considerable proportion to the

space occupied by

it

and

atmosphere. At the

its

first

whole

com-

pression, the

atmosphere of heat might be said to be reduced into half the space ; but at the last, the reduction

would be much

greater,

and therefore more heat

given out

than determined by theory.

Since writing the above, Mr. Ewart informs
idea respecting steam, which

Mr. Watt*3.

had from him,

In Black's Lectures, Vol.

author, speaking of

1,

heat

is

is

at least as

diminished."

fact should

that the

originally

page 190, the

Mr. Watt's experiments on steam

" we find that the

low temperatures, observes,

of the steam

me
is

It is

much

at

latent heat

increased as the sensible

wonderful that so remarkable a

have been so long known and so

little

noticed.

ON CONGELATION.
less

of
is

rapidly in ascending than the one

we have

Something of an effect similar to what

pointed out in the 2d case above, ought
air.

therefore to

mosphere
in

138

be

observed

in

our mixed

the higher regions, at the

that evaporation

is

same moment

going on below.

This

actually the case almost every day, as

from their
of air

at-

namely, a condensation of vapour

own

observation

frequently

region below

is

exists

all

is

know

a cloudy stratum

above,

whilst

the

comparatively dry.

SECTION

y.

ON THE PHENOMENA OF THE CONGELATION OF WATER.

Several remarkable

phenomena

are attend-

ant upon the congelation of water, and some

of them are so different from what might be

expected from analogy, that I believe no explanation according with the principles of the

mechanical philosophy has been attempted,

such as to account for all the appearances.

This attempt

is

the

object

of

the

present

It will be expedient previously to state

Essay.
the principal facts.

ON CONGELATION.

134
1

The

specific gravity of ice

is

less

than that

of water in the ratio of 92 to 100.

When

2.

pended

water

is

jar to cool

exposed

in

still

in a

air of

large sus-

20

or

30%

it

cooled 2 or 3 below freezing ; but if

any tremulous motion take place, there appear
instantly a multitude of shining hexangular

may be

spicul(Cy floating,

and slowly ascending

in the

water.
It is

3.

observed that the shoots or ramifica-

commencement, and

tions of ice at the

in the

early stage of congelation are always at an

angle of 60 or 120%
4. Heat is given out during congelation, as

much

as

would

150 of the

raise the

new

temperature of water

The same

scale.

quantity

is

again taken in when the ice is melted. This

t^e whole heat which
quantity may be ^V of

water of 32 contains.
5.

Water

is

or 38 of the
ally

densest at 36 of the old scale,

new

from that point

expands by cooling

it

gradu-

or by heating alike,

according to the law so often mentioned, that

of the square of the temperature.

water be exposed to the air, and to

agitation, it cannot be cooled below 32 ; the
6. If

application of cold freezes a part of the water,

and the mixture of

temperature of 32.

ice

and water requires the

ON CONGELATION.
7. If the

not severe,

135

water be kept still, and the cold be

may be cooled in large quantities

it

below, without freezing ; if the water

be confined in the bulb of a thermometer, it is

to 25 or

difficult to freeze it by any cold mixture

above 15 of the old scale; but it is equally
difficult to cool the water much below that

very

temperature without
tained
it

it

as

low

its

as 7 or

freezing.

have ob-

8% and gradually heated

again without any part of it being frozen.

8. In the last case of what may be called

forced cooling, the law of expansion

observed as given above,
9.

When

a bulb,

but
is

it

if it

water

still

cooled to 15 or below in

is

retains the

is

most perfect transparency

freeze, the

congelation
instantaneous, the bulb becoming in a moaccidentally

ment opake and white like snow, and the

water is projected up the stem.
10. When water is cooled below freezing,
and congelation suddenly takes place, the tem32.
perature rises instantly to
these
to
In order
phenomena, let
explain

it

be conceived that the ultimate or smallest elements of water are

of the same size

atoms be

all

let the

in squares,

globular,

and exactly

arrangement of these

as exhibited

in Fig,

1.

each particle touches four others

in the same horizontal plane. Conceive a second
Plate

3. so that

ON CONGELATION.

13(5

Stratum of particles placed

upon these in like
order of squares, but so that each
globule falls
into the concavity of four others on the

first

and consequently rests upon four

elevated 45 above the centres of the

stratum,
points,

globules.

perpendicular section of such

globule resting upon two diagonal globules of

the square is exhibited in Fig. 3.
Conceive

a third stratum placed in like manner upon the

The whole being similar to a
second, &c.
square pile of shot.
is

'The

above constitution

conceived to represent that of water

temperature of greatest density.

To find the number of globules
vessel, the side of

number of
cube

stratum

particles in

then
;

which

7i*

is

the

is

given

one

number

and because a

in a

cubic

= the

let

line or side

in

at the

of the

any horizontal

line joining the centres

two contiguous particles in different strata

makes an angle of 45 with the horizontal
plane, the number of strata in the given
of

height will be n

Whence

the

=
Now let

vessel

is

7i^

instantly

(Fig2.)

-r-

sine of 45 =^ n

number of

-r-

\\/2.

particles in the cubic

f ^2 n^yj 2.
it be
supposed that the square pile
drawn into the shape of a rhombus
-r-

then each horizontal stratum will

consist of the
fore, only

in

same number of

still

particles as be-

a more condensed form, each

ON CONGELATION.
particle

But

being

now

137

with six others.

in contact

to counteract this condensation, the

se-

veral successive strata are

more elevated than

before, so that the pile

increased in height.

then

is

whether

a vessel of
question
given capacity will hold a greater number of
particles in this or the former disposition ? It
arises

must be observed, that

in the

last

case,

particle of a superior stratum rests only

particles of

an inferior one, and

is

each

on two

therefore

elevated by the sine of 60' as represented in

The

Fig. 4.
1

and

^/l>

bases of the

their heights as

two

Vf

capacities are as the products of

height, or as yf\

\'y that

is,

Vt
tlie

are

as

^^^ ^^^

base and

as .707 to .750

Thus

nearly, or as 94 to 100,

piles

it

appears that

arrangement contains more particles

in a given space than the second by 6 per

the

first

cent.

The

or rhomboidal arrangement is supbe that which the particles of water

last

to

posed
assume upon congelation. The specific gravities of ice and water should therefore be as

94 to 100.

But

it

should be remembered

that water usually contains 2 per cent, in bulk

of atmospheric air

upon congelation

and
and

that this air

is

is

liberated

commonly entangled

amongst the ice in such sort as to increase its

bulk without materially increasing its weight ;

ON CONGELATION,

138
this reduces

the specific gravity of ice 2 per

makes

cent, or

it

with observation.

92,

which agrees exactly

Hence

the

1st

fact

is

ex-

plained.

The

angle of a rhombus
120;

plement

if

is

60% and

its

sup-

any particular angles are

manifested in the act of congelation, therefore

we

ought to expect these, agreeable

2d and 3d phenomena.

Whenever any remarkable change

to the

in

the

internal constitution of any

body takes place,

whether by the accession and junction of new
new arrangements of those
particles, or by
already existing in it ; some modification in
the atmospheres of heat must evidently be re-

quired ; though it may be difficult to estimate

the quantity, and sometimes even the kind of
change so produced, as in the present case.

So

far

therefore the theory

with the 4th

proposed agrees

phenomenon.

In order to explain the other phenomena,

will be requisite to consider

the

mode by which

more

it

particularly

bodies are expanded by

the expansion occasioned simply by

the enlargement of the individual atmospheres

heat.

Is

of the component particles ? This is the case

with elastic fluids, and perhaps with solids,

but certainly not with liquids. How is it poswater should be expanded a portion

sible that

ON CONGELATION.

139

represented by l upon the addition of a certain quantity of heat at one temperature, and
by 340 upon the addition of a like quantity at

when both

another temperature,
are remote from

temperatures
absolute zero, the one

the

The
perhaps 6000 and the other 6170 ?
fact cannot be accounted for on any other supposition than that of a change of arrangement
in

the

component

particles

change from the square

rangement

is

in

to the

and a gradual
rhomboidal ar-

probability effected both

all

by the addition and abstraction of heat. It is to

be supposed then that water of the greatest
possible density has

the square form

heat be added
ticles

particles arranged in

its

a given quantity of
or taken from it, the partheir approach to the rhom-

but

if

to,

commence

boidal form, and consequently the whole is

expanded, and that the same by the same
change of temperature, whether above or

below

that point.

away from water of

If heat be taken

38,

the consequence, and a moof

the particles towards the
derate inclination

then expansion

is

but

rhomboidal form;
small

way

the

whilst

this

mass

only extends a
is subject to a

tremulous motion, so as to relieve the obstructions occasioned

of certain

by

affinities,

friction

the

new

by the energy

form

is

completed

ON CONGELATION.

IK)

a portion of ice formed

heat

in

moment, and

is

then given out which retards the subsequent

formation,

This

But

is

if

till

at

last

the whole

is
congealed.
of congelation.
cooled is kept in a

the ordinary process

the

mass of water

state of perfect

tranquillity, the

gradual ap-

proach to the rhomboidal form can be carried

much farther ; the expansion goes on according to the usual manner, and the slight friction
or adhesion of the particles is sufficient to
counteract the balance of energies in favour of
new formation, till some accidental tremor

the

contributes

to

similar operation

adjust
is

the

equilibrium.

performed

when we

A
lay a

table, and hold a magnet

nearer
and
nearer ; the proximity of
gradually
the approach, without contact, is much assisted

piece of iron

on a

by guarding against any tremulous motion of

the table.

Hence

are accounted for.

the rest of the

phenomena

141

CHAP.

It

ON THB

CONSTITUTION OF BODIES.

HERE are

three distinctions in the kindsof

bodies,or three states,which have more especially

claimed the attention of philosophical chemists;

namely, those which are marked by the terms
miliar instance

is

and

solids.
very faexhibited to us in water, of

elastic Jiuids^ liquids^

a body, which, in certain circumstances,

is

capable of assuming all the three states. In

steam we recognise a perfectly elastic fluid,
in water, a perfect liquid, and in ice a com-

These observations have tacitly

plete solid.
led to the conclusion which seems universally
adopted, that

all

bodies of sensible magnitude,

solid, are constituted of a

whether liquid or
vast

number

of extremely

small particles, or

atoms of matter bound together by a force of

attraction, which is more or less powerful
according to circumstances, and which as it
endeavours to prevent their separation,

is

very

ON THE CONSTITUTION OF

142

BODIES.

properly called in that view, atlraction of

; but as it collects them from a dis-

cohesion

persed state (as from steam into water) it is

attraction of aggregation^ or more

called,

simply,

by, they
It is not

Whatever names it may go

signify one and the same power.

affinity.
still

my

design to call in question this con-

but to

which appears completely satisfactory ;

shew that we have hitherto made no

use of

it,

clusion,

neglect,

and that the consequence of the

very obscure view of

has been a

chemical agency, which

is

so in proportion to the

new

to

be thrown upon

daily

growing more

lights

attempted

it.

The opinions I more particularly allude to,

are those of Berthollet on the Laws of chemical

affinity

such as that chemical agency

is

the mass, and that in all cheproportional to

mical unions, there exist insensible gradations
in the proportions of the constituent principles.

The

inconsistence

of

these

opinions,

both

with reason and observation, cannot, I think,

fail to strike every one who takes a proper

view of the phenomena.

Whether

the

ultimate particles of a body,

all alike, that is, of the

such as water, are

same

figure,

weight, &c.

is

From what

some
known, we have

a question of
is

importance.
no reason to apprehend a diversity in these

ON THE CONSTITUTION OF BODIES.

particulars

if it

does exist in water,

143
it

must

equally exist in the elements constituting water,

Now it is
namely, hydrogen and oxygen.
the aggrehow
conceive
scarcely possible to
should be so unigates of dissimilar particles
of
If
the particles of
some
same.
formly the

water were heavier than others,

if

a parcel

of the liquid on any occasion were constituted

it must
principally of these heavier particles,

be supposed

to affect the specific gravity of the

mass, a circumstance not

servations

Therefore
particles

known.

Similar ob^

be made on other substances.

may
we may conclude
of

all

that the ultimate

homogeneous bodies are per-

fectly alike in weight,

fgure, ^c.

In

other

words, every particle of water is like every

other particle of water , every particle of hy-

drogen is like every other particle of hydrogen, &c.

Besides the

force of attraction,

which, in

one character or another, belongs universally to

ponderable bodies, we find another force that
likewise universal, or acts upon all matter
which comes under our cognisance, namely, a
is

force

and

of repulsion.

This

is

now

I think properly, ascribed to the

generally,

agency of
atmosphere of this subtile fluid
constantly surrounds the atoms of all bodies,
and prevents them from being drawn into

heat.

An

ON THE CONSTITUTION OF BODIES.

144

This appears

actual contact.

be

to

satisfac-

torily proved by the observation, that the bulk

of a body may be diminished by abstracting

some of

its

what has been

heat: But from

stated in the last section,

it

should seem that

enlargement and diminution of bulk depend

perhaps more on the arrangement, than on the
size of the

ultimate particles.

Be

this as

it

may, we cannot avoid inferring from the preceding doctrine on heat, and particularly from
the section on the natural zero of temperature,
that solid bodies, such as ice, contain a large
portion, perhaps

same are found

4-

of the

heat

which the

an

elastic state,

to contain in

as steam.

We

now

are

to consider

how

these

two

of attraction and re

great antagonist powers

pulsion are adjusted, so as to allow of the three
different states
solids.

We

Sections

of clastic

namely,

elastic Jluids

pure
of mixed
of

solids.

first,
;

liquids^

and

and

on the constitution of

second, on the constitution

elastic fluids

tion of liquids f

Jiiiids^

divide the subject into four

shall

third,

fourth, on

on the constituthe constitution

Olf

PURE ELASTIC FLUIDS.

SECTION

145

1.

ON THE CONSTITUTION OF PURE

ELASTIC FLUIDS.

pure elastic fluid is one, the constituent

are all alike, or in no way
particles of which
distinguishable.

Steam, or aqueous vapour,

hydrogenous gas, oxygenous gas, azotic gas,*

and several others are of this kind. These
fluids are

of particles possessing
atmospheres of heat, the capacity

constituted

very diffuse

or bulk of the atmosphere being often one or

two thousand times that of the particle in a

Whatever therefore may

liquid or solid form.
be the shape or figure of the solid atom abstractedly,

when surrounded by such an

at-

must be globular but as all the

mosphere
globules in any small given volume are subject
to the same pressure, they must be equal in
it

bulk, and will therefore be arranged in horivolume

zontal strata, like a pile of shot.

* The novice will all along understand that several

chemical subjects are necessariiy introduced before their
can be discussed.
history and character
general

ON PURE ELASTIC FLUIDS.

146

of elastic fluid
is

pressure

found to expand whenever the

off.
This proves that the re-

exceeds the attraction

pulsion

The

is

taken

such case.

in

absolute attraction and repulsion of the

particles of

an

elastic fluid,

we

have no means

of estimating, though we can have little doubt

but that the cotemporary energy of both is great;

but the excess of the repulsive energy above

the attractive can be estimated, and the law of

and diminution be ascertained

increase

Thus

cases.

in

steam,

the

density

in

many
may be

tAt ^^'^^ ^^ water ; consequently

each particle of steam has 12 times the diameter
that one of water has, and must press
upon
taken at

144 particles of a watery surmce; but the

upon each is equivalent to that of a

pressure

column of water of 34

feet

therefore the ex-

cess of the elastic force in a particle of steam

is

equal to the weight of a column of particles of

water, whose height

And

further,

is

34 X 144

this elastic force

= 4896

distance of the panicles increases.

spect to steam and

by
is

efficacious to

move

With

re-

other elastic fluids then,

the force of cohesion

that of repulsion,

feet

decreases as the

is

entirely counteracted

and the only force which

the particles

is

the excess

of the repulsion above the attraction. Thus, if

the attraction be as 10 and the
repulsion as
12, the

effective repulsive

force

is

as 2.

It

ON

ftTRE ELASTIC FLUIDS.

appears then, that an elastic

requiring any force

147

fluid, so far

to separate

its

from
it

particles,

always requires a force to retain them in their

situation, or to prevent their separation.

A vessel

full

of any pure elastic fluid presents

one full ofsmall

to the
imagination a picture like

shot.
The globules are all of the same size j
but the particles of the fluid differ from those
of the shot, in that they are constituted of an

exceedingly small central atom of solid matwhich is surrounded by an atmosphere of

ter,

heat,

of

great

next the atom, but

density

according to some
whereas those of the

rarer

gradually growing
power of the distance

shot are globules, uniformly hard throughout,

and surrounded

w^ith

atmospheres of heat of

no comparative magnitude.
It is known from experience, that the force
of a mass of elastic fluid is directly as the

Whence

density.

is

derived the law already

mentioned, that the repulsive power of each

particle

is

inversely as

its

diameter.

That

is,

the apparent repulsive power, if we may so

speak ; for the real or absolute force of re-

not known, as long as we remain

When we
of
the attractive force.
ignorant
its
of
elastic
fluid,
particles
expand any volume
pulsion

is

are enlarged, without any material

the quantity of their heatj

it

change

in

follows then, that

ON PURE ELASTIC FLUIDS*

148

the density of the atmospheres of heat must

fluctuate with the pressure.
Thus, suppose a
measure of air were expanded into 8 measures ;

because the diameters of the

tlien,

elastic par-

the cube root of the space, the

distances of the particles would be twice as
are as

ticles

great as

and the

before,

would occupy

did before, with

heat

nearly the

whence we
ratio as the

Some elastic

atmospheres
space they

same quantity of

see that these atmospheres

must be diminished

same

elastic

nearly 8 times the

in density in nearly the

mass of elastic

fluid.

hydrogen, oxygen, &c.

any pressure that has yet been applied
to them.
In such then it is evident the refluids, as

resist

pulsive force of heat

the

is

more than a match

for

of the particles, and the external

To what extent this would
pressure united.
continue we cannot say j but from analogy we
affinity

might apprehend that a

still

greater pressure

would succeed

in giving the attractive force

the superiority,

when

become a

the elastic fluid

would

In other

elastic

liquid or solid.

upon the application of comto

a
certain
pression
degree, the elasticity apfluids, as

steam,

parently ceases altogether, and the particles

collect in small drops of
liquid, and fall down.

This phenomenon requires explanation.

From

the very abrupt transition of steam

ON PURE ELASTIC FLUIDS.

from a volume of 1700 to that of

149
1,

without

any material increase of pressure, one would

be inclined to think that the condensation of
it was
owing to the breaking of a spring, rather
than to the curbing of one.
The last however
I believe is the fact. The condensation arises

from the action of

to that of heat, by
ruled, but not

becoming superior
which the latter is over*

affinity

As

weakened.

the approxima-

tion of the particles takes place, their repulsion

increases

but their

from the condensation of the heat,

it should seem^ in a

affinity increases,

greater ratio, till the approximation has attained a certain degree, when an equilibrium
between those two powers takes place, and

still

the liquid, water,

true explanation

been stated

at

is

the result. That this

we may

learn from

is

the

what has

page 131; wherein

it is shewn
by the condensation of
probability no more than would

that the heat given off

steam,

is

be given

in all
off

by any permanently elastic fluid,

be mechanically condensed into the
like volume, and is moreover a small portion
of the whole heat previously in combination.
could

As

it

far then as

the heat

is

concerned

in this

phenomenon, the circumstances would be the

same, whether the approximation of the particles

was the

effect

mechanical force.

of

affinity,

or of external

ON MIXED ELASTIC FLUIDS.

150

The

constitution of a liquid, as water,

must

then be conceived to be that of an aggregate of

particles, exercising in a most powerful manner
the forces
nearly in

of

attraction

and

an equal degree.

repulsion, but

Of

this

more in

the sequel.

SECTION

2.

ON THE CONSTITUTION OF MIXED

ELASTIC FLUIDS.
When two

or

more

elastic

fluids,

whose

do not unite chemically upon mixture,

are brought together, one measure of each,

particles

they occupy the space

of two measures, but

uniformly diffused through each other,

become

and remain

so,

The

gravities.

whatever may be their specific

admits of no doubt j but

fact

explanations have been given in various ways,

and none of them completely satisfactory. As

the subject is one of primary importance in

we
forming a system of chemical principles,
must enter somewhat more fully into the
discussion.

Dr. Priestley was one of the

the fact

it

naturally struck

earliest to notice

him with

surprise.

ON MIXED ELASTIC FLUIDS.

that

two

elastic fluids,

each

151

having apparently no

should not arrange

themselves according to their specific gravities,
as liquids do in like circumstances.
Though
affinity for

he found

other,

was not the case

this

after the elastic

had once been thoroughly mixed, yet he

if two of such
suggests it as probable, that

fluids

could be exposed to each other without

one specifically heavier would
agitation, the

fluids

retain

much

lower situation.

its

as hint at such gases

mixed

state

by

suggestion of

affinity.

He

does not so

being retained in a

With regard

to his

two

gases being carefully exto each other without agitation, I made

posed
a series of experiments expressly to determine

the question, the results of which are given in

the Manch. Memoirs, Vol. 1. new series.

From

these

it

seems to be decided that gases

always intermingle and gradually diffuse themselves amongst each other, if exposed ever so
carefully

but

it

requires a considerable time

produce a complete intermixture, when

This
the surface of communication is small.

to

time

may vary from

a minute, to a day or more,

according to the quantity of the gases

and the

freedom of communication.

When or by whom the notion of mixed

gases

being held together by chemical affinity was

first
propagated, I do not know ; but it seems

ON MIXED ELASTIC FLUIDS.

152

probable that the notion of water being dis'

solved in air, led to that of air being dissolved
in air.

Philosophers

found that water gra-

dually disappeared or evaporated in

air,

and

elasticity; but steam at a low

was
known to be unable to overtemperature
come the resistance of the air, therefore the

increased

its

was necessary to account for

In the permanently elastic fluids
indeed, this agency did not seem to be so much
agency of

affinity

the effect.

wanted, as they are all able to support themselves; but the diffusion through each other
was a circumstance which did not admit of an
In regard to th
easy solution any other way.
solution of water in air, it was natural to suppose, nay, one might almost have been satisfied
without the aid of experiment, that the differ-

ent gases would have had different affinities for

water, and that the quantities of water dis-

solved

in

like

varied according

Saussure

circumstances,
to

would have

the nature of the

difference in this respect in the solvent

of carbonic acid, hydrogen gas, and

air.

It

gas.

found however that there was no

might be expected that

powers

common

at least the

density of the gas would have some influence

upon its solvent powers, that air of half density

would take

half the water, or the quantity of

in some proportion to

water would diminish

ON MIXED ELASTIC FLUIDS.

the

but

density;

disappointed

even here again

153

we

are

whatever be the rarefaction,

if

water be present, the vapour produces the

same elasticity, and the hygrometer finally

mon

extreme moisture, as

at

settles

density in

like

in air of

com-

circumstances.

These

extreme

difficulty

facts are sufficient to create

how

any principle of affinity

or cohesion between air and water can be the
It is truly astonishing that the same
agent.

in the

conception

to one particle
quantity of vapour should cohere
of air in a given space, as to one thousand in

the

ter;

But the wonder does not

same space.

cease here

and

a torricellian vacuum dissolves wa-

in this instance

independently of

makes

it still

in such
tlty

temperatures

more remarkable

vacuum

and

we have vapour existing

air at all

is

precisely the

force as in

is,

what

the vapour

same

in quan-^

the like volume of any

of extreme moisture.
other considerations which ocand
These
to
some
me
to
curred
years ago, were sufficient

kind of

air

make me

altogether

air dissolving water,

abandon the hypothesis of

and to explain the phe-

other way, or to acknowledge

In the autumn of
were
inexplicable.
they
1801, I hit upon an idea which seemed to be

nomena some

the phenomena
exactly calculated to explain
of vapour ; it gave rise to a great variety of

ON MIXED ELASTIC FLUIDS.

154-

experiments upon which a series of essays were

founded, which were read before the Literary

and Philosophical Society of Manchester, and

in

published
1802.

The

the

5th Vol. of their memoirs,

feature

distinguishing

theory was, that

of

parti 'les of

the

new

the

one gas are

not elastic or repulsive in regard to the parof another gas, but only to the particles
of their own kind.
Consequently when a

ticles

vessel contains

a mixture of

two such

elastic

each acts independently upon the vessel,

with its proper elasticity, just as if the other

fluids,

were absent, whilst no mutual action between

the fluids themselves
tion

observed.

is

most effectually provided

This posi-

for the existence

of vapour of any temperature in the atmosphere, because it could have nothing but its

own weight
obvious why
exist in

air

to support

neither

and

more nor

of extreme

it

was perfectly

less

vapour couid

moisture, than in a

vacuum of

the same temperature.

So far then
the great object of the theory was attained.
The law of the condensation of vapour in the

atmosphere by cold, was evidently the same on

this scheme, as that of the condensation of
pure steam, and experience was found
firm the conclusion at

only thing

now wanting

all

to

temperatures.

con-

The

to completely establish

ON MIXED ELASTIC FLUIDS.

155

the independent existence of aqueous vapour

atmosphere, was the conformity of other

in the

liquids

to water, in

and condensation of

regard to the diffusion

This was

their vapour.

found to take place in several liquids, and

particularly in sulphuric ether, one which was

most

shew any anomaly to advantage

on account of the great change of

likely to

if it existed,

expansibility in
peratures.

The

vapour at ordinary tern*

existence of vapour in the

its

atmosphere and its occasional condensatioQ

for ;
thus accounted
but another

were

question

remained,

a surface of water

how

does

subject

it

to

rise

from

the pressure

The consideration of
of the atmosphere ?
made no part of the essays abovementioned,

this

being apprehended, that if the other two

points could be obtained by any theory, this
it

third

too, would, in the sequel,

be accom-

plished.

From

the novelty, both in the theory

and the

experiments, and their importance, provided

they were correct, the essays were soon circulated, both at

home and

abroad.

The new

and experiments were highly valued,

some of the latter were repeated, and found

facts

correct,

and none of the

results, as

far as

know, have been controverted; but the theory

was almost universally misunderstood, and

ON MIXED ELASTIC

156

FLUIfiS.

This must have

consequently reprobated.
have arisen partly at least from my being too
concise,

and not

sufficiently clear

in

its

ex-

position.

Dr.

who
this

Thomson was

the

first,

publicly animadverted

gentleman, so well

System of Chemistry,
edition of that work,

as far as I

upon

known

for his excellent

observed in

the

the theory

that

know,

the theory

first

would

not account for the equal distribution of gases j

but that, granting the supposition of one gas
neither attracting nor repelling another, the two
must still arrange themselves according to their

But the most general objecquite of a different kind ; it was

specific gravity.

tion to

it

was

admitted, that the theory was adapted so as to

obtain the most uniform and permanent diffusion

of gases j but it was urged, that as one gas

was as a vacuum to another, a measure of any
gas being put to a measure of another, the
two measures ought to occupy the space of

one measure only.

the

subject

wrote an

were

Finding that
thus

my

views on

misapprehended, I

illustration of the theory,

which was

published in the 3d Vol. of Nicholson's JourIn that paper I

nal, for November, 1802.

endeavoured to point out the conditions of

mixed gases more

hypothesis

at large,

according to

my

and particularly touched upon the

ON MIXED ELASTIC FLUIDS.

discriminating feature of
ticles

the

of any gas

known

A,

stated

it,

that of

157

two

par-

repelling each other

by

law, whilst one or more

of another gas B, were interposed in

a direct line, without at all affecting the reparticles

of the said two particles of A.

ciprocal action
Or, if any particle of B were casually to come

one of A, and press against it,

did
not preclude the cotemporary
this pressure
all
the
of
action
surrounding particles of
in contact with

upon

the one in contact with B.

In this

spect the mutual action of particles of the

re-

same

gas was represented as resembling magnetic

action, which is not disturbed by the intervention of a

As

body not magnetic.

the subject has since received the ani-

madversions of several authors, which

to notice

expedient

more or

it

is

less, it will

be

proper to point out the order intended to be

First, I shall consider the objections
pursued.
to the

new

theory

with their
then

ceeding

made by the several authors,

views on the subject ; and

what modifications of the

the experience and reflection of suc-

shall

theory,

own
give

have suggested to me. The

BerthoUet, Dr. Thomson, Mr.

time

authors are

Murray, Dr. Henry, and Mr. Gough.

BerthoUet in his Chemical Statics (1804)
has given a chapter on the constitution of the

ON MIXED ELASTIC FLUIDS.

158

atQiosphere, in

which he has entered

into a discussion of the

new

theory.

largely

This cele-

brated chemist, upon comparing the results of

experiments made by

De Luc,

Saussure, Volta,

Lavoisier, Watt, &c. together with

those of

Gay Lussac, and his own, gives his full assent

to the fact, that vapours of every kind increase
the elasticity of each species of gas alike, and
just as much as the force of the said
in vacuo

and not only

vapours
but that the specific
and vapour in vacuo

so,

gravity of vapour in air

in all cases the same (Vol.

is

1.

Con-

Sect. 4.)

sequently he adopts the theorem for finding

the quantity of vapour which a given volume

of air can dissolve, which I have laid

down ;

namely,

where p represents the pressure upon a given

volume

(1)

mercury,

of dry air, expressed in inches of

the force of the vapour in vacuo

/=

at the temperature, in inches of mercury,

5 r= the space

which the mixture of

air

and
and

vapour occupies under the given pressure, />,

So far therefore we perfectly
after saturation.

which
agree but he objects to the theory by
I attempt to explain these phenomena, and
:

substitutes another of his

The

first

own.

objection I shall notice

is

one that

ON MIXED ELASTIC FLUIDS.

clearly

159

shews Berthollet either does not under-

stand, or does not rightly apply the theory he

opposes

" If one
gas occupied the
of another, as though they were

he

interstices

says,

would not be any augmenta-

vacancies, there
tion

when aqueous

of volume

or ethereal va-

pour was combined with the air; nevertheless

there is one proportional to the quantity of
vapour added

humidity should increase the

whereas it renders

specific gravity of the air,

it

spyecifically

noticed by

as

lighter,

Newton."

which has been

has

This

is

been already
the objection

so frequently urged

even been stated by Mr. Gough,

stand him aright, in

if I

under-

almost the same words

(Nicholson's Journal, Vol. 9, page 162)

this

last

has

it

is

yet

skilled in

gentleman
profoundly
the mechanical action of fluids.
Let a

cylindrical glass vessel containing drv air

tall

be

mercury, and a portion of the

air drawn out by a syphon, till an equilibrium
inverted

over

of pressure is established within and without ;

let a small portion of water, ether, &c. be
then thrown up into the vessel

the vapour
;
and occupies the interstices of the air as
a void; but what is the obvious consequence?

riss

the surface of the mercury being

pressed both by the dry air, and by the

Why,

raised

vapour,

is

now
new

more pressed within than

ON MIXED ELASTIC FLUIDS.

160

without, and an enlargement of the volume of

air

is

in

unavoidable,

order to

in the

restore

the

air:

equilibrium.
Again,
open
suppose
there were no aqueous atmosphere around the
earth, only an azotic one = 23 inches of mef".

6 inches.
cury, and an oxygenous one
air being thus perfectly dry,
evaporation

The
would

The vapour
great speed.
formed being constantly urged to ascend
by that below, and as constantly resisted by the

commence with
first

air,

must, in the

first

two atmospheres
adds

two

its

(for,

force to the

gases,

and

instance, dilate the other

the ascending steam

upward

elasticity

of the

in part alleviates their pressure,

the necessary consequence of which is dilataAt last when all the vapour has astion.)
cended, that the temperature will admit of,
the aqueous atmosphere attains an equilibrium j
no longer presses upon the other two, but

it

upon the earth

the others

return

to

their

and pressure throughout. In

this case it is true, there would not be any
augmentation of volume when aqueous vapour

original density

was combined with the

air;

humidity would

increase the weight of the congregated atmo-

spheres,but diminish their specific gravity under

a given pressure. One would have thought that
this solution

of the

phenomenon upon my

hypothesis was too obvious

to escape the notice

ON MIXED ELASTIC FLUIDS.

161

of any one in any degree conversant with

pneumatic chemistry. Berthollet indeed en" Is such a divsion of the same
pressure

quires,

of the atmosphere analogous with any physical

property yet known ? Can it be conceived that

an

substance exists,

elastic

volume

to that of another,

theless

does not act on

which

adds

its

and which never-

it
by its expansive
can not only conceive
it, but bring an instance that must be allowed
Two magnets repel each
to be in point.

force ?" Certainly

other, that

act

is,

we

upon each other with an ex-

pansive force, yet they do not act upon other

bodies in the same way, but merely as inelastic
bodies ; and this no doubt would be the same
if

they were reduced to atoms

of the same kind of air

ticles

each other

elastically,

inelastically,

when

and

So two par-

may

act

upon

and upon other bodies

therefore

not at

all,

unless

in contact.

"

Berthollet observes,

Hydrogen gas and

oxygen gas form water in a given circumstance;

azotic gas, and oxygen gas, can also produce
nitric acid ; but the reciprocal action which
decides the combinations cannot be considered
as a force
at

which

commencing

it is

long before producing

gradually

at the precise

manifested,

till it

its

it

moment

must have existed

effect,

and increases

becomes preponderant."

It is

ON MIXED ELASTIC FLUIDS.

162

no doubt

true that the opposite powers of atand repulsion are frequently, perhaps
but
constantly, energetic at the same instant

traction

the effect produced in those cases arises from

the difference of the two powers.
When the

excess of the repulsive

tractive

in

different

small and insignificant,

racter

power above the

it

at-

is

comparatively
constitutes that cha-

gases

which may be denominated

neutral,

and

supposed to exist in the class of mixed

which
are not observed to manifest any
gases
I would not be unof
chemical
union.
sign

which

derstood to deny an energetic affinity between

oxygen and hydrogen, &c. in a mixed state ;

but that

by

affinity is

more than counterbalanced

the repulsion of the heat, except in cir-

cumstances which

it is

not necessary at present

to consider.

Again,

" Azotic
gas comports

itself

with

changes occasioned by temoxygen

and
precisely like one and
pressure,
perature
Is it necessary to have recourse
the same gas
gas, in the

to a supposition

which obliges us

to

admit so

great a difference of action without an ostenIt is possible this may appear

sible cause ?"

an objection to a person who does not understand the theory, but it never can be any to
one who does. If a mixture of gas, such as
atmospheric

air,

containing azote

pressing

ON MIXED ELASTIC FLUIDS.

163

with a force equal to 24 inches of mercury,

and oxygen with a force equal to 6 inches,

were suddenly condensed into half the com-

would then

pass, the azotic gas

my

hypothesis,

with

press

evidently,

on

48

force

and the oxygen with a force =12

inches, making
together 60 inches, just
And a similar
the same as any simple gas.
inches,

change

in

the elasticity of each

would take

Will the opposite

place by heat and
be
equally free from this
theory of Berthollet
cold.

objection

We

shall presently

examine

if.

derived from the very

considerable time requisite for a body of hy-

Another objection

is

drogen to descend into one of carbonic acid ;

if one gas were as a vacuum for another, why
is

the equilibrium not

This objection
consider

it

is

more

instantly established

certainly plausible

we

shall

at large hereafter.

In speaking of the pressure of the atmosphere retaining water in a liquid state, which I
deny, Berthollet adopts the idea of Lavoisier,
" that without it the moleculae would be infinitely

Hmit

dispersed,

and

that nothing

their separation, unless their

would

own weight

should collect them to form an atmosphere."

This, I

may remark,

is

not the language dic-

on the subject. Suppose our atmosphere were annihilated, and the

tated

by a

correct notion

ON MIXED ELASTIC FLU1D3.

164

waters on the surface of the globe were inexpanded into steam ; surely the action

stantly

of gravity would collect the moleculs into an

atmosphere of similar constitution to the one

we now possess ; but suppose the whole mass
of water evaporated amounted in weight to
30 inches of mercury, how could it support its

own weight
would

common temperature ? It
time be condensed into water

at the

in a short

merely by its weight, leaving a small portion,

such as the temperature could support, amount*
ing perhaps to half an inch of mercury in
weight, as a permanent atmosphere, which

would
from

effectually

rising,

prevent any more vapour

were an increase of

unless there

Does not every one know that

temperature.
water and other liquids can exist in a Torricel-

vacuum

at low temperatures solely by the

What
of
vapour arising from them ?
pressure
need then of the pressure of the atmosphere in

lian

order to prevent an excess of vapourisation?

After having concluded that " without the
pressure of the aerial atmosphere, liquids would
pass to the elastic state," Berthollet proceeds
in the very next paragraph to

shew

that the

quantity of vapour in the atmosphere may in

fact be much more than would exist if the

atmosphere were suppressed, and hence infers,

" that the
variations of the barometer oo

ON MIXED ELASTIC FLUIDS^

163

casioned by those of the humidity of the atmosphere may be much greater than was beI cannot see
lieved by Saussure and Deluc."

how

the author reconciles the opposite con-

clusions.

The experiments
taining

air,

are

of Fontana on the

and ether

lation of water

adduced

distil-

in close vessels con-

to prove, that vapours

do not penetrate air without resistance. This

is true no doubt ; vapour cannot make its way
in such circumstances through a long and
circuitous route without time,
ternal

and

if

the ex-

atmosphere keep the vessel cool, the

vapour may be condensed by its sides, and

fall down in a liquid form as fast as it is generated, without ever penetrating in any sensible quantity to

We

its

come now

remote extremity.
to the consideration of that

theory which Berthollet adopts

in his explanar
tionof the phenomena of gaseous mixtures. According to his theory, there are two degrees of
affinity.

The one

is

strong,

makes

the particles of

bodies approach nearer to each other,and geneheat the effect of this may be calrally expels
:

for instance, when oxygen

gas
put to nitrous gas, the two combine, give
out heat, are condensed in volume, and become

led combinaiio7i

is

possessed of properties

they had previously.

diflerent

The

other

is

from what

weak

it

ON MIXED ELASTIC FLUIDS.

166

does not sensibly condense the volume of any

mixture, nor give out heat, nor change the
the ingredients
properties of
solution or dissolution
,:

be called

when oxygen

effect

its
;

may

for instance,

gas and azotic gas are mixed in

due proportion, they

in which they retain

constitute atmospheric air,

their

distinguishing pro-

perties.
It

is

upon

elastic fluid in

this supposed solution of one

another that I intend to make a

few observations.

That

have not misre-

presented the author's ideas, will,

think, ap-

"

When
pear from the following quotations.
different gases are mixed, whose action is confined to this solution, no change is observed in
the temperature, or in the volume resulting from
the mixture ; hence it may be concluded, that
this

mutual action of two gases does not proit cannot sur-

duce any condensation, and that

mount

the effort of the elasticity, or the af-

of
finity for caloric, so that the properties

each

"
changed ."
Although
both the solution and combination of two
gas are not sensibly

gases are the effect of a chemical action, which

only differs in its intensity, a real diflference
may be established between them, because

a very material difference between the

the combination of two gases always
leads to a condensation of their volume, and
there

is

results

ON MIXED ELASTIC FLUIDS.

new

gives rise to

properties

common

the gases share in

on

167

their solution,

the changes arising

from compression and temperature, and preindividual properties, which are

the ratio of the slight

serve their

only diminished in
action

which holds them united." (Page

"The mutual

198.)

affinity of the gases can, therefore,

produce between

them

an

effect

which

is

greater than their difference of specific gravity,

but which is inferior to the elastic tension

which belongs to each molecule of both, so

volume is not changed by this action ;
the liquids which take the elastic state, comthat the

port themselves

afterwards

like

the

gases."

(Page 218.) "Solution must be distinguished

from combination, not only because in the
first, each of the substances is retained by an
affinity

sions.

so

weak, that

" (Page 219.)

it

preserves
*'

Again,

It

its

dimen-

cannot be

doubted, that the parts of elastic fluids are not

endued with the force of cohesion, as the sub-

them undergo an equal

which could not happen but by

stances dissolved by
distribution,

the means of a reciprocal chemical attraction

that

which

(Researches into the

Eng. Trans, page

has, I

The

constitutes the force of cohesion."

Laws

57.)

of chemical affinity,

Here the

translator

apprehend, mistaken the English idiom.

author means to say, that the parts of

ON MIXED ELASTIC FLUIDS-

168

clastic fluids

are endued

with the force of

but this he applies only to hetero;

He certainly does not
geneous particles.
mean that the particles of homogeneous elastic
cohesion

fluids possess the force of cohesion.

Newton has demonstrated from the phenomena of condensation and rarefaction that
elastic fluids are constituted

of particles, which

repel one another by forces which increase in

proportion as the distance of their centres

diminishes: in other words, the forces are

This deduction

reciprocally as the distances.

will stand as long as the

Laws

continue to be what they are.

of elastic fluids

What

a pity

it

who

attempt to reason, or to theorise

respecting the constitution of elastic fluids,
should not make themselves thoroughly ac-

is

that all

quainted with this immutable Law, and con^

stantly hold it in their view whenever they

When we contemplate
start any new project
a mixture of oxygenous and hydrogenous gas,
v/hatdoes BerthoUet conceive, are the particles
!

that repel each

tonian

Law

other according to the

The mixture must

New-

consist

of

and he ought in the very first instance

to have
informed us what constitutes the

such

unity of a particle

in

his

grants that each particle of

unity, and each

If

he

retains

its

solution.

oxygen

particle of hydrogen does the

ON MIXED ELASTIC FLUIDS.

same, then

we must

two

action of

169

conclude that the mutual

particles of

is

oxygen

as that of a particle of oxygen,

the

same

and one of

hydrogen, namely, a repulsion according to

Law above stated, which effectually de-

the

supposed solution by chemical

if it be
agency.
supposed that each particle of hydrogen attaches itself to a particle of
the

stroys

But

oxygen, and the two particles so united form

one, from which the repulsive energy emanates;

new

then the

elastic

fluid

form to the Newtonian

may

Law

perfectly conin this case

when

true saturation will take place

the

num-

ber of particles of hydrogen and oxygen in a

mixture happen to be equal, or at least in the
ratio of
1

some simple numbers, such

Now

&c.

to 3,

actually take place

is

like

something

when

as

this

to 2,

does

a real combination

formed, as for instance, steam, and nitric

acid

formed of a mixture

of oxygen

Here we have new

nitrous gas.

and

elastic fluids,

the atoms of which repel one another by the

common Law, heat is given out, a great con-

densation of volume ensues, and

fluids

differ

chemical

from

relations.

mine whether,

is,

in

new

It

remains then to deter-

in the instance of solution, all

these effects take place in a

that

the

their constituents in their

so small a

**

slight" degree ;
degree as not to be

ON MIXED ELASTIC FLUIDS.

170

cognisable to any of the senses.

It

requires an extraordinary stretch of

nation to admit the affirmative.

One

great reason

certainly

the.

imagi-

adoption of

for the

this,

or any other theory on the subject, arises fron>

the evaporation of water.
water taken up and retained in the
It cannot be in the state of
atmosphere ?

the

phenomena of

How

is

vapour,
great

is

it

said,

because the pressure

is

too

there must therefore be a true chemical

solution.

But when

face of water

is

we

consider that the sur-

subject to a pressure equal to

30 inches of mercury, and besides this pressure,

is a sensible
affinity between the particles

there

of water themselves

how

does the hisensible

of the atmosphere for water overcome

both these powers ? It is to me quite inexpliaffinity

cable upon this hypothesis, the leading object of

which is to account for this very phenomenon.

Further,

if

a particle of air

has attached a

water to it, what reason can be

particle of
assigned why a superior particle of air should
rob

an inferior

one of

its

property,

when

each particle possesses the same power? If a

portion of common salt be dissolved in water

and a

little

muriatic acid added

is

there any

reason to suppose the additional acid displaces

that already combined with the soda, and that

upon evaporation the

salt

is

not obtained with

ON MIXED ELASTIC
the identical acid

it

171

FLUIDS.

previously had

oxygen gas be confined by water,

Or,

if

there any
reason to suppose that the hydrogen of the
is

water is constantly giving its oxygen to the air

and receiving an equal quantity from the
same ? Perhaps it will be said in the case of
air dissolving water, that

not the affection

it is

of one particle for one, it is that of a mass of

particles for another mass ; it is the united
of

action

the

all

atoms

the

in

atmosphere

upon the water, which raises up a particle.

But as all these energies are reciprocal, the
water must have a like action on the

air,

and

then an atmosphere over water would press

downward by a force greater than its weight,

which

is

contradicted by experience.
measures of hydrogen and one

When two

of oxygen gas are mixed, and fired by the

spark, the whole is converted into

electric

steam, and

if

the

be

pressure

steam becomes water.

It

is

this

great,

most probable

is the same number of

particles
two measures of hydrogen as in one of

then that there

in

oxygen.

Suppose

hydrogen are

then

three

measures

of

mixed with one of oxygen, and

this slight affinity operates as usual

union effected

According

how

is

the

to the principle

of equal division, each atom of oxygen ought

to have one atom and a half of hydrogen at-

ON MIXED ELASTIC FLU1D3.

172

it ; but this is
impossible ; one half
of the atoms of oxygen must then take two of
But
hydrogen, and the other half, one each.

tached to

the former would be specifically lighter than

the latter, and ought to be found at the top of
j
nothing like this is however
observed on any occasion.
Much more might be advanced to shew the

the solution

absurdity of this doctrine of the solution of one

gas in another, and the insufficiency of it to

explain any of the phenomena ; indeed I
should not

have dwelt so long upon

it,

had

I not apprehended that respectable authority

was likely to give it credit, more than any ar-

guments

in

its

behalf derived from physical

principles.

Dr. Thomson,

in

the

3d

Edition of his

System of Chemistry, has entered into a

cussion on the subject of mixed gases

disj

he

seems to comprehend the excellence and defects of my notions on these subjects, with
great acuteness.
Berthollet,

that

He
on

does not conclude with

my

hypothesis,

" there

would not be any augmentation of volume

when aqueous and ethereal vapour was combined with the air," which has been so com-

mon

There is however one

which
this
objection
gentleman urges, that
shews he does not completely understand the
an objection.

ON MIXED ELASTIC FLUIDS.

17 o>

At page 448,
from
the principles of
Vol. 3. he observes that
" each
particle of a fluid sustains
hydrostatics,

mechanism of my hypothesis.

the whole pressure.

reason

why

Nor can

I perceive any
should
not hold,
principle

this

even on the supposition that Dalton's hypothesis is well founded."

Upon this I would

when once an

observe, that

equilibrium

is

established in any mixture of gases, each particle

of gas

particles of

is

its

pressed as

if

by the surrounding

oivn kind only.

It

is

in the re-

nunciation of that hydrostatical principle that

the leading feature of the theory consists.
The

lowest particle of oxygen in the atmosphere

sustains the weight of all the particles of
oxygen above it, and the weight of no other.

maxim with me, that every

of
is
gas
equally pressed in every diparticle
but
the
rection,
pressure arises from the particles
Indeed when a meaof its own kind only.
It

was

sure of

the

therefore a

oxygen

moment

the

is

put to a measure of azote, at

two

surfaces

come

in contact,

the particles of each gas press against those of

the other with their full force; but the two
gases get gradually intermingled, and the force
which each particle has to sustain proportionally
diminishes,

till

at last

it

becomes the same

that of the original

gas dilated to twice

volume.

The

ratio of the forces

is

as the

as
its

cube

ON MIXED LASTIC FLUIDS.

174
of

root
*

V2

1,

mixture

the

as

inversely

spaces

or as 1.26

nearly.

that

is,

a*

In such a

been mentioned, then,

has just

the common hypothesis supposes the pressure

of each particle of gas to be 1.26; whereas
mine supposes it only to be 1 ; but the sum
of the pressure of both gases on the containing
Tessel, or

any other surface,

is

exactly the same

on both hypotheses.
Excepting the above objection, all the rest
which Dr. Thomson has made, are of a nature
not so easily to be obviated ; he takes notice

of the considerable time which elapses before

two gases are completely diffused through each
other, as Berthollet has done,

and conceives

makes against the supposition, that

one gas is as a vacuum to another. He further
this fact,

objects, that if the particles of different gases

are inelastic to each other

oxygen coming

then a particle of

into actual contact with

hydrogen, ought
particle of water

to unite
;

but,

with

it,

one of

and form a

on the other hand, he

properly observes, that the great facility with

which such combinations are effected in such
instances as a mixture of nitrous
gas,

is

an argument

and oxygen

favour of the hypofounds another objection

in

thesis.

Dr. Thomson

upon

the facility of certain combinations,

Qne of the ingredients

is

in

when

a nascent form

ON MIXED ELASTIC FLUIDS,

that

is,

elastic

just

upon

state

175

the point of assuming the

he observes,

this,

*'

seems

in-

compatible with the hypothesis, that gases are

not mutually elastic,"
Upon the whole. Dr.

Thomson

inclines to the opinion of Berthollet,

that gases have the property of dissolving each

other

and admits, " however problematical

view, that the gases not

each
other, but likewise
only mutually repel
I have no doubt if he had
attract,"
mutually
it

may appear

at

first

taken due time to consider

this conclusion,

would, with me, have pronounced

but of this again in the sequel.

With regard

it

to the objection, that

makes a more durable

he

absurd

one gas

resistance to the entrance

it
ought to do on my hyThis occurred to me in a very early

of another, than
pothesis

period of my speculations ; I devised the train

of reasoning which appeared to obviate the
objection ; but it being necessarily of a mathematical nature, I did not wish to obtrude it

upon

the notice of chemical philosophers, but

rather

wait

to

till

was

it

called

for.

The

which any medium makes to the

motion of a body, depends upon the surface of

resistance

that body,
greater,

same.

all

and

is

greater as

the surface

other circumstances

A ball of lead

with a certain resistance

inch in

being the
diameter meets

in falling

through the

ON MIXED ELASTIC FLUIDS.

176

but the same ball, being made into a

thousand smaller ones of
of an inch diair

-1^,5.

ameter, and

with the same velocity,

10 times the resistance it did

meets with

falling

before

because the force of gravity increases

as the cube of the diameter of any particle,

and

the resistance only as the square of the

diameter.

Hence

it

in order to

appears, that

resistance of particles

increase the

moving

in

any medium, it is only necessary to divide

them, and that the resistance will be a maxi-

mum when

the division

is

maximum.

We

have only then to consider particles of lead

falling

through

air

we may have an

their

by

own

gravity,

and

idea of the resistance of one

gas entering another, only the particles of lead

must be conceived to be irifinitely small, if I

may be allowed
shall

Here we

the expression.

and yet no one, I

that the air and the

find great resistance,

should suppose, will say,

lead are mutually elastic.

The

other

I shall

wave

two objections of Dr. Thomson,

the consideration of at present.

Mr. Murray has

lately edited

a system of

which he has given a very clear

the phenomena of the atmoof
description
and
of
other
similar mixtures of elastic
sphere,
chemistry, in

fluids.

He

has

ably

discussed

the

different

theories that have been proposed on the subject.

ON MIXED ELASTIC FLUIDS.

177

and given a perspicuous view of mine, which

he thinks is ingenious, and calculated to explain several of the phenQmei^a well, but upon
the whole, not equally satisfactory with that

which he adopts. He does not object

mechanism of my hypothesis in regard

to the
to the

independent elasticity of the several gases enbut argues that the

tering into any mixture,
do not require so extraordinary a

phenomena

postulatum ; and more particularly disapproves

of the application of my theory to account for
evaporation.

The

principal

feature

in

Mr. Murray's

theory, and which he thinks distinguishes it

from mine, is " that between mixed gases,

which

are capable, under any circumstances

of combining, an attraction must always be
It is unnecessary to recount the
exerted."

arguments on behalf of
it

this

conclusion, because

Mr. Murray an-

will not be controverted.

views of the constitution of the

"
Perhaps that cheatmosphere, as follows
mical attraction which subsists between the

nounces

his

solid bases of these gases, but

which,

when

they

are merely mixed together, cannot, from the distance at which their particles are placed by
the repulsive power of caloric, bring them into

intimate union,

may

still

be so far exerted, as

to prevent their separation

or,

they

may be

ON MIXED ELASTIC FLUIDS.

178

retained in mixture by that force of adhesion,

which, exerted
retains

them

force."

He

at the surfaces of

in

contact

with

many

bodies,

considerable

supports these notions at length

by various observations, and repeats some of

the observations of Berthollet, whose doctrine
on

subject, as has been seen,

this

is

nearly the

same.
Before
it

we animadvert on

mav be convenient

farther,

and

tween the

to

adopt

as a

particles o^

these principles,

extend the

to

maxim,

first

"

little

that be-.

pure gases, which arc

capable under any circumstances of combining,

an attraction must always be exerted." This,

Mr. Murray cannot

certainly object to, in the

case of steam, a pure elastic fluid, the par-

ticles

of which are

stances to combine.

known in
Nor will

certain circumit

be said that

steam and a permanent gris are different ; for

he justly observes, " this disthiction (between
gases
arises

and vapours) is merely relative, and

from the dilTerence of temperature at

which they

are

formed

the state with regard

to each, while they exist in

same."

it, is

precisely the

steam then constituted of particles

in which the attraction is so far exerted as to
Is

prevent their separation? No: they exhibit

no traces of attraction, more than the like

number

of particles of

oxygen do, when

in

ON MIXED ELASTIC FLUIDS.

the

What

form.

gaseous

elusion

It is this

then

is

?iotivithsta?iding

179
the conit

must be

and

allowed, that all hodieSy at all times,

every situation, attract one aiiotlier

yet

in

in cer^

tain circumstances, they are likewise actuated

ky a repulsive power

force

is

then

the

the only efficient motive

diffierence

of

these two

powers.

From

the circumstance of gases

without

mixing

to-

sensible

gether
experiencing any
diminution of volume, the advocates for the

agency of chemical affinity, characterise it as

"
and " a weak reciprocal
a
slight action,"
action :"

So

far

think they are consistent

when we hear

of this affinity being so far

exerted as to prevent the separation of elastic
with what proparticles, I do not conceive

but

priety

can

be called weak.

Suppose

this

in the case of
affinity should be exercised
steam of 212; then tlie attraction becoming

force which any

equal to the repulsion, the

one

particle

would exercise must be equal to

column of water of 4896 feet

the weight of a

(See page 146.)

high.
It

is

somewhat remarkable
to combine

which are known

that those gases

occasionally, as

azote and oxygen, and those which are never

known to combine, as hydrogen and carbonic
acid, should dissolve

one another with equal

ON MIXED ELASTIC FLUIDS.

180
facility

nay, these

last

exercise this solvent

power with more effect than the former ; for,

hydrogen can draw up carbonic acid from the
bottom

to tlie top of

ing the latter

is

any

20 times

notwithstand-

vessel,

the specific gravity of

One would have

thought that a
be expected in
the particles of steam, than in a mixture of
hydrogen and carbonic acid. But it is the
the former.

force of adhesion

was more

business of those

who

mutual solution

of

to

adopt the theory of the

gases

to

explain

these

difficulties.

In a mixture where are 8 particles of oxygen

1 of
hydrogen, it is demonstrable that the

for

central distances of the

are at a

medium

Now

oxygen.
of

particles of

hydrogen

twice as great as those of

supposing the central distance

particles of hydrogen to be

two adjacent

denoted by 12, query, what is supposed to

be the central distance of any one particle of
hydrogen from that one particle, or those
particles of

by

this

well

if

oxygen with which

weak chemical union

those

the doctrine

present

how

enable those

who

it
?

is

connected

would be

It

understand and maintain

of chemical solution would rethey conceive this to be

who are

a clear idea of the system, and those

dissatisfied

with

it,

it

would

desirous to learn, to obtain

to point out

its

who

are

defects with

ON MIXED ELASTIC FLUIDS.

more

and the

who

greatest possible central

8 i in the above instance,

would be
least

might perhaps be

decries the diagram by

voured to
has

The

precision.

distance

not

either

181

illustrate

my

given us

any

1.

Berthollet,

which

I endea-

ideas on this
subject,

precise

information,

verbally or otherwise, relative to the

collocation of the heterogeneous particles, unless

it is

to

be gathered from the consideration

that the affinity

so

is

weak

affinity

power of

do,

weak

that the mixture of

What can this

when opposed by a repulsive
dimensions.

fluids preserves its

infinite superiority

In discussing the doctrines of elastic fluids

mixed with vapour, Mr. Murray seems dis-

posed to question the accuracy of the

the quantity of vapour

is

the

same

in

fact, that

vacuo as

though he has not attempted to ascertain

which case it more abounds. This is cer-

in air,
in

tainly the touchstone of the

mechanical and

had thought that

admitted
the
truth
of the fact, must
whoever
chemical theories

unavoidably

adopt

and

the

mechanical

theory.

Berthollet however, convinced from his

experience, that the fact

was

own

incontrovertible,

attempts to reconcile it, inimical as it is, to

the chemical theory ; with what success it is
to others to judge.
Mr. Murray joins
with Berthollet in condemning as extravagant
left

ON MIXED ELASTIC FLUIDS.

182

the position which I maintain, that

if

the at-

mosphere were annihilated, we should have

little more aqueous vapour than at present
exists in

that

if

Upon which

it.

either of those

I shall

gentlemen

or give a rough estimate

upon

only remark,
will calculate,

their hypothesis,

f the quantity of aqueous vapour that would be

collected around the earth, on the said supposition, I will engage to discuss the subject with

them more
In

at large.

1802,

Dr.

Henry announced ^ very

which was

curious and important discovery,

afterwards published
actions

in the

Philosophical Trans-

namely, that the quantity of any gas

absorbed by water

is

increased in direct pro-

pressure of the gas on the surportion

face of the water. Previously to this, 1 was
engaged in an investigation of the quantity of
to the

carbonic acid in the atmosphere ; it was matme that lime water should so

ter of surprise to

readily manifest the presence of carbonic acid

in the air, whilst pure water by exposure for
any length of time, gave not the least traces
I
of that acid.
thought that length of time

ought

to

compensate

for

weakness of

affinity*

pursuing the subject I found that the

quantity of this acid taken up by water was
In

greater or less in
less

density in the

proportion to

its

greater or

gaseous mixture, incumbent

0N MIXED ELASTIC
Upon the

18S

FLUIDS.

and therefore ceased

surface,

to

water absorbing so insensible a

the
from
I had not howportion
atmosphere.
ever entertained any suspicion that this lawat

surprised

was

the gases

to

generally applicable

Henry's discovery was announced.

ately

upon

it

this,

struck

me

till

Dr.

Immedi-

as essentially ne-

the quantity of any gas

which a given volume of water will absorb,
that we must be careful the gas is
perfectly

cessary in ascertaining

pure or unmixed with any other gas whatever 5

otherwise the maximum effect for any given
be produced. This thought
pressure cannot

was suggested
be correct

in

Dr. Henry, and found to

consequence of which, it be-

to

came expedient

to

repeat
to

the

some of

his

ex-

quantity of gas

periments relating
absorbed under a given pressure. Upon due
consideration of all these phenomena. Dr.

Henry became convinced,

that

there

was no

system of elastic fluids which gave so simple,

easy and intelligible a solution of them, as the

one

I adopt, namely, that each

gas in any
mixture exercises a distinct pressure, which

continues the same

drawn.
nal,

if the other
gases are withIn the 8th Vol. of Nicholson's Jour-

may be

seen

a letter addressed to

which Dr. Henry has

reasons for

giving

my

me,

in

clearly pointed out his

theory a preference.

ON MIXED ELASTIC FLUIDS.

184

In the 9th Vol.

is

a letter from

Mr. Gough,

containing some animadversions, which vvere

followed by an appropriate reply from Dr.

Henry.
In the

8th, 9th,

cholson's Journal,

and 10th Volumes of Niand

in the

first

Manchester Memoirs fnezv

Vol. of the

series)

may be

some animadversions of Mr. Gough, on

of mixed gases, with some of
doctrine
my
his own opinions on the same subject.
Mr.
seen

Gough conceives the atmosphere to be a

chemical compound of gases, vapour, &c. and
he rests his belief chiefly upon the observance
of certain hygrometrical phenomena, such as
that air absorbs moisture from bodies in certain
cases,

and

in others restores

it

to

them, shew-

ing that air has an affinity for water, which may

be overcome by another more powerful one.

This opinion, as Mr. Murray observes, is the

one we have from Dr. Halley it was supported
;

by Le Roy,

Hamilton

might be considered
till

and

Franklin,

and

as the

prevailing opinion,
Saussure, in his celebrated Essays on hy-

grometry, published in

water was

first

changed

1783, suggested that

into vapour,

and was

in

that state dissolved by the air. This

amphibious
theory of Saussure does not seem to have

any converts to

it,

though

instability of the other.

it

gained
pointed out the

Finally,

the theory

ON MIXED ELASTIC FLUIDS.

of the chemical solution of water in
ceived

its

185
air, re-

death blow in 1791, by the publica-

tion of Pictet's Essay

on Fire, and more par-

by De

Luc's paper on evaporation,

ticularly
the
in
Philosophical Transactions
published
These gentlemen demonstrated,
for 1792.
that

the train of hygrometrical

all

phenomena

takes place just as well, indeed rather quicker,

in a vacuum, than in air, provided the same

AH the
quantity of moisture is present.
influence that any kind or density of air has,
is

to retard

comes

the effect

but in the end

it

be-

the same.

The

only objection which

Mr. Gough has

presented that appears to me to raise any difin regard to the propagation of

ficulty, is that

atmosphere consist chiefly of

two distinct
media, it is urged that
be heard double ; that
to
distant sounds ought

sound

If the

elastic

same sound would be heard twice, acone or other of

cording as it was brought by
is,

the

the atmospheres.
if

sound move

second

ought

in

to

namely.

By
at

calculation

find that

the rate of 1000 feet per

an atmosphere of azotic gas,

move

it

in the other gases as follows

ON MIXED ELASTIC FLUIDS

186

reel.

Sound moves

in azotic

gas

oxygen gas
carb. acid

1000 per second.

930
804

aqueous vap. 1175

According to

this

table, if

a strong

and

loud sound were produced 13 miles off, the

first would be a weak impression of it brought
by the atmosphere of aqueous vapour, in 99
seconds

of

the second

would be the strongest

brought by the atmosphere of azotic

in 684- seconds; the third would be

all,

gass,

much

inferior to the

second, brought by the

oxygenous atmosphere, in 74 seconds; the

fourth and last brought by the carbonic acid
atmosphere would be extremely weak, in 85
seconds.

Now

though observation does not

the theory in this reperfectly accord with

it comes as near
it, perhaps, as it does
spect,
to that of the more simple constitution of the

atmosphere

which

Mr.

Gough

maintains.

Derham, who

number of

has perhaps made the greatest

accurate observations on distant

sounds, remarked that the report of a cannon

fired at the distance of 13 miles from him, did

not strike his ear with a single sound, but that

it was
repeated 5 or 6 times close to each other.

" The two

first

cracks were louder than the

ON MIXED ELASTIC FLUIDS.

third

but the

cracks were lounder than

last

any of the rest."

187

Cavallo, in his experimental

philosophy, after quoting the above observa" this

repetition of the sound

tions, proceeds,

probably originated from the reflection of a

single sound, from hills, houses, or other objects,

much

not

distant

from the cannon.

But

it

appears from general observation, and where

no echo can be suspected, that the sound of a
of 10 or 20 miles,

cannon,

at the distance

different

from the sound when near.

latter case, the

Whereas

is

loud and instantaneous,

we

of which

it is

crack

is

In the

cannot appreciate the height.

the former case, viz. at a distance,

in

a grave sound,

which may be compared to

and instead of
;

a determinate musical sound

being instantaneous,
to

its

it

greatest loudness,

begins softly, swells

and then dies away

growling. Nearly the same thing may be

observed with respect to a clap of thunder,
other sounds are likewise altered in quality
the distance."
(Vol. 2. page 331.)

by

I shall now
proceed to give my present
views on the subject of mixed gases, which
are somewhat different from what they were

when

the

theory

quence of the

was announced, in consewhich succeeding

fresh lights

experience has diffused. In prosecuting my

enquiries into the nature of elastic fluids, I

ON MIXED ELASTIC FLUIDS.

188

soon perceived
of the

size or

was

whether

ascertain
ticles

it

different

volume

in

possible, to

if

necessary,

the

atoms or ultimate pargases are of the

same

like circumstances of tem-

By the size or volume

perature and pressure.
I mean in this place,
an
ultimate
of
particle,
the

it

space

elastic fluid

state of a pure
bulk of the parbulk of the supposed im-

occupies in the
in this sense the

ticle signifies the

with that of its

penetrable nucleus, together
surrounding repulsive atmosphere of heat.
the time I formed the theory of

At

gases,

had a confused

idea, as

mixed

many have,

I suppose, at this time, that the particles of

elastic fluids are all of the same size j that a

volume

given
as

just

of

many

of

oxygenous
as

particles

or

if

hydrogenous
data from which
;

no

be solved.
ing,

the

that

different

same

not their particles of the

the
till

size

page 71, I
gases have
:

and that

following may be adopted as a maxim,

some reason appears to the contrary :

namely,

That every
its

question could
of reason-

train

similar to that exhibited at

became convinced

volume

we had

that

not,

But from a

contains

gas

the same

species of

particles globular

pure

and

that no two species agree

all

elastic

fuid has

of a size

but

in the size of their

ON MIXED ELASTIC
particles i the pressure

189

FLtTIDS.

and temperature being

the same.

There was another

I

was dubious
I

repulsion.

effect

to ascribe re-

force

resembling magnetism,
on one kind of matter, and has no
on another. For, if heat were the cause

pulsion

which

was rather inclined

to

which

thing: concerning^

whether heat was the cause of

acts

of repulsion, there seemed no reason why a

should not repel one of
particle of oxygen
as one of its
hydrogen with the same force
were
botli of a
if
own kind, especially
they
size.

Upon more mature

consideration, I sec

common

sufficient reason for discarding the

no

which

ascribes

opinion,
and I think the

may

still

without

phenomena

accounted

be

the

repulsion

mixed

of

gases

for,

by repulsion,

postulatum, that

their particles

are mutually inelastic, and free from

the

preceding
answered.

When we

heat

to

as

objections

have

such of
left

un-

contemplate upon the disposition

of the globular particles in a volume of pure

elastic fluid,

we

perceive

it

must be analogous

to that of a square pile of shot

must be disposed

the particles

into horizontal strata,

four particles forming a square

each

in a superior

stratum, each particle rests upon four particles

below, the points of its contact with all four

ON MIXED ELASTIC FLUIDS.

190

being 45 above the horizontal plane, or that

plane which passes through the centres of
On this account the presthe four particles.
sure

is

when

steady and uniform throughout.

a measure of one

measure of another

in

But

presented to a

gas

is

any

vessel,

we have

then a surface of elastic globular particles of

one size in contact with an equal surface
in
of particles of another
such case the
of
the
of
contact
heterogeneous parpoints
must vary all the way from 40 to
ticles
:

an

90;
this

be

other.

motion

and

inequality,

kind

two

intestine

the

must

from

arise

particles

those

of

one

of

the
propelled amongst
cause which prevented the

The same

elastic surfaces

from maintaining an equinarticles of

librium, will always subsist, the

one kind being from

their size

to the other, so
properly

that

unable to apply

no equilibrium

can ever take place amongst the heterogeneous

The intestine motion must therefore
particles.
continue

till

the particles arrive at the opposite

surface of the vessel against any point of

they can

rest

with

stability,

which

and the equilibrium

is
acquired when each gas is uniIn the
formly diffused through the other.
atmosphere no equilibrium can take place

at length

open

in such case
far as to

till

the particles have ascended so

be restrained by their

own

weight

ON MIXED ELASTIC FLUIDS.

that

till

is,

they constitute

191

a distinct atmo-

sphere.
is
It
remarkable that when two equal
measures of different gases are thus diffused,
and sustain an invaried pressure, as that of the

atmosphere, the pressure upon each particle

This
after the mixture is less than before.
of diffusion
points out the active principle
fluids are always disposed to
of
particles
to that situation

where the pressure

for,

move
least.

is

Thus, in a mixture of equal measures of oxygen

and hydrogen, the common pressure on each
mixture being denoted by 1,
particle before
that after the mixture

of

half

its

V4-=

density,

when
will

the gas

becomes

denoted

be

by

.794.

This view of the constitution of mixed gases

with that which I have given before, in

agrees
the two

following particulars, which

con-

sider as essential to every theory on the subject

to give
1st.

other

it

plausibility.

The
is

diffusion

effected

of

gases

through each

by means of the repulsion

belonging to the homogenous particles

that principle which

is

or to

always energetic to

produce the dilatation of the gas.

2d. When any two or more

mixed gases

elastic energy of
acquire an equilibrium, the
each against the surface of the vessel or of any

ON MIXED ELASTIC FLUIDS.

192

is

liquid,

the

precisely

same

as if

it

were the

only gas present occupyinjj the whole space,

and all the rest were withdrawn.

In other respects

think the

last

view ac-

cords better with the phenomena, and obviates

the objections which Dr. Thomson has brought
against the former; particularly in regard to
the query, why mixed gases that are known on
certain occasions to combine, do

not always
and why any gaseous particle in its
nascent state is more disposed to combination

combine

than

when

it

has already assumed the elastic

also more clearly explain the

of one gas making so powerful and
durable a resistance to the entrance of another.

form.

It v^ill

reason

One

still

difficulty

remains respecting va-

pour, which neither view of the subject

together removes

al-

subsist

though vapour may

atmosphere upon either supposition, as
as the temperature will admit, not being
:

in the
far

subject to any

from

its

moved,

own
yet

it

more pressure than would arise

particles, were the others re-

may be

enquired,

how

does

it

from the surface of water subject to the

pressure of the atmosphere? how does vapour
which ascends with an elastic force of only
rise

of mercury, detach

half an inch

water when

it

itself

from

has the weight of 30 inches of

mercury to oppose

its

ascent

This

difficulty

ON MIXED ELASTIC

193

FLUIDS.

to all theories of the

applys nearly the same
solution of water in air, and it is therefore

of consequence for every one, let him adopt

what opinion he may, to remove it. Chemical
solution but
air

for

ill

vapour

and yet

it is

explains
is

it

for,

the affinity of

always described as weak,

sufficient to

overcome the pressure

of a powerful force equal to the weight of the

I have endeavoured to shew in

atmosphere.
another place (Manch. Memoirs, Vol.
series,

page 284) what

my own

ideas

1.

new

on the

to me, that it is not till

subject are. It appears
the depth of 10 or 12 strata of particles of

each perany liquid, that the pressure upon

column becomes uniform ; and

pendicular

that several of the particles

stratum
pressure.

are

in

reality

in the

subject

uppermost

to but little

I9i

on LIQUIDS.

SECTION

3.

ON THE

CONSTITUTION OF LIQUIDS,
And

the

Mechanical Relations betwixt Liquids

and Elastic Fluids.

liquid or inelastic fluid

may be

defined

be a body, the parts of which yield to a

very small impression, and are easily moved
to

one upon another.

for

the

This definition may suffice

liquids in an hy-

consideration of

drostatical sense, but not in a chemical sense.

speaking, there is no substance inheat be the cause of elasticity, all

Strictly

if

elastic;

bodies containing it must necessarily be elastic:

but we commonly apply the word elastic to

such

only as have the property of conin a

very conspicuous degree.
a liquid or inelastic fluid ; but if it

fluids

densation

Water

is

compressed by a great force, it yields a little,

and again recovers its original bulk when the
is

pressure

is

Mr. Canton

removed.

We

for a set of

experiments by which

are

indebted to

the compressibility of several liquids

monstrated.
Water, he found, lost

is

de-

about

ON LIQUIDS.
^^l-^th part of

its

195

bulk by the pressure of

the atmosphere.
When we consider the origin of water from

steam,

we have no

gree

it

The

to

the

at its

very small de-

if

water had not

force of steam at 212

of the

pressure

what a prodigious

force must

condensed

18

15

wonder

to

that in a

would be wonderful

this quality.

equal

reason

and

compressibility,

or

it

is

atmosphere ;
have when

We

hundred times?

know that the particles of steam, reduced to

the state of water, still retain the greatest part
What a powerful resistance then
a compressing
ought they not to make against
and
force ? The truth is, water,
by analogy,

of their heat.

other liquids, must be considered as bodies,

under the controul of two most powerful and
energetic

agents,

between which

any compressing
indeed, but in

attraction

there

is

force

such a

and

repulsion,
If

an equilibrium.
is

applied,

it

yield?,

manner, as a strong

when wound up almost

When we attempt to
pitch.

spring would yield,

to the highest

from another,
separate one portion of liquid
here the attraction is the
the case is different
:

and that being balanced by

the repulsion of the heat, a moderate force is
But
the separation.
of

antagonist force,

capable

producing

ON LIQUIDS.

196
even here

we

perceive the

attractive force to

of the
prevail, there being a manifest cohesion
particles.

seem

that

Whence does this arise ? It should

when two particles of steam coalesce

to form water, they take

station so as to

their

effect a perfect equilibrium

between the two

opposite powers ; but if any foreign force intervene, so as to separate the two molecules
an evanescent space, the repulsion decreases
faster than the

attraction,

and

consequently

this last acquires a superiority or excess,

which

the foreign force has to overcome.

were not the case, why do they at

If this

upon

first,

or

the formation of water, pass from the

greater to the less distance ?

With regard to the collocation and arrangement of particles in an aggregate of water or

have already observed

(page 139) that this is not, in all probability,
It seems highly
the same as in air.
improbable

any other

liquid,

from the phenomena

of

the

expansion

The law of expansion

liquids by
unaccountable for, if we confine liquids
hear.

one and the same arrangement of

particles

avoid

in all

temperatures
that

of
is

to

their ultimate

for,

were

we cannot

the case,
concluding,
the expansion would go on in a progressive
way with the heat, like as in air y and there
if

MUTUAL ACTION OF

FLUIDS.

197

would be no such thing observed as a point

of temperature at which the expansion was
stationary.

Reciprocal Pressure of Liquids

and Elastic

Fluids.

When

an

elastic fluid

is

confined by a vessel

of certain materials, such as wood, earthenware, &c.

found slowly to communicate

it is

with the external

till

cessively,

place.

to give

air,

a complete

There

is

and receive suc-

intermixture takes

no doubt but

this

is

oc-

casioned by those vessels being porous, so as

to transmit the fluids.
Other vessels, as those
of metal, glass,

&c. confine

air

most com-

These therefore cannot be porous ;

or rather, their pores are too small to admit of

pletely.

the passage of air.

I believe no sort of vessel
has yet been found to transmit one gas and
confine another; such a one is a desideratum
in practical chemistry.

to

be completely porous,

All the gases appear

as

might be expected,

and therefore operate very temporarily

fining each other.

respect

Do they

How

in

con-

are liquids in this

resemble glass, or earthen-

MUTUAL ACTION OF

198

ware, or gases, in regard

confining

or

gases alike,

transmit others

they are

fluids

clastic

FLUIDS.

to their

Do

power of

they treat

all

do they confine some, and

These are important questions:

not to

be answered

a moment.

in

We

must patiently examine the facts.

Before we can proceed, it will be necessary

to lay

down

a rule,

if

possible,

by which to

distinguish the chemical from the mechanical

action of a liquid

upon an

elastic

fluid.

think the following cannot well be objected

to

When an

elastic Jiuid is kept in

contact

a liquidf if any change is perceived, either

in the elasticity or any other property of the
ivith

elastic Jluid, so far the

pronounced chemical

mutual action must be

but if no

change

is

perceived, either in the elasticity or any other

property of the elastic fluid, then the mutual
action of the tzvo must be pronouiKed wholly

MECHANICAL.
If a quantity of lime be kept in water and
agitated,

lime

falls

upon standing a sufficient time, the

down, and leaves the v/ater trans-

but the water takes a small portion of

parent
of the lime which it permanently retains, con:

trary to the

Laws

of specific gravity.

Because that portion of iime

the water.

is

Why }

dissolved by

If a quantity of air be put to water

MUTUAL ACTION
and

upon standing a

agitated,

the air rises

OF FLUIDS.

up

to the surface

199

sufficient time,

of the water and

transparent; but the water permanently

retains a portion of air, contrary to the Laws
leaves

it

Why

of specific gravity.

Because that small

is dissolved by the water.

So
portion of air
far the two explanations are equally satisfactory.
But if we place the two portions of water

under the receiver of an

the incumbent

air

pump, and exhaust

the whole portion of air

air,

absorbed by the water ascends, and is drawn

out of the receiver ; whereas the lime remains
still

be repeated,

water
an

If now the question

the air retained in the

in solution as before.

why
The answer must

elastic

is

force

which holds

it

in.

in the business.

upon

lime? Let the

surfaces

of the

another species
the pressure.

is

The water

appears passive
But, perhaps, the pressure on

the surface of the water

its affinity

be, because there

on the surface of the water

for air,
air

two

may have some

effect

and none on that

be drawn

off

for

from the

portions of water, and

induced without alleviating

The lime water remains un-

changed ; the air escapes from the other much

The question of the
the same as in vacuo.
relation of water to air appears by this fact to

be

still

more

difficult; at

first

the air

seemed

MUTUAL ACTION OF

200
to

FLUIDS.

be retained by the attraction of the water ;

second case, the water seemed indiffer-

in the

ent

in

the air

the third,

appears as

it

yet in all three,

it is

the

has to act on the same water.

if

repulsive to

same

air that

From

these

facts, there seems reason then for maintaining

three opinions on the subject of the muiual

action of air and water

attracts air, that

that water repels

true

but

;
namely, that water
water does not attract it, and

One

air.

we must

not

of these must be

decide hastily.

Dr.

Priestley once imagined^ that the clay of a

"
porous earthen retort, when red hot,
destroys
for a time the aerial form of whatever air is

exposed to the outside of it j which aerial

form it recovers, after it has been transmitted
in

combination from one

another,
retort."

till it

part of the clay to

has reached

the inside

But he soon discarded

of the

so extravagant

an opinion.

From

the recent experiments of Dr.

with those of

my own,

Henry,

there appears reason

to conclude, that a given volume of water

absorbs the following parts of its bulk of the

several gases.

MUTUAL ACTION OF

ulk of gas

FLUIDS.

201

MUTUAL ACTION OF

202

circumstances

have decided

FLUIDS.

the experiments of Dr.

Henry

this point,

by ascertaining, that
condensed or rarefied in

the exterior gas is

any degree, the gas absorbed
if

condensed or

is

same degree j so that the proabsorbed

portions
given above are absolute.
One remarkable fact, which has been hinted
rarefied in the

at

that

is,

another

no one gas

in vv'ater

it

stantly, like as in a

capable of retaining
escapes, not indeed inis

vacuum, but gradually, like

as carbonic acid escapes

into the atmosphere

from the bottom of a cavity communicating
with it.

remains

It

now

to

decide whether the re-

lation

between water and the abovementioned

gases

is

of a chemical or mechanical nature.

From

the facts just stated, it appears evident

that the elasticity of carbonic acid and the

other

two gases of the

first

class

is

not at

all

remains exactly of
the
water is present or
whether
the same energy
All the other properties of those gases
absent.
affected

by the water.

It

continue just the same, as far as I know,

whether they are alone or blended with water;
I conceive, if we abide
by
down, pronounce the mutual
action between these gases and water to be

we

must therefore,

the

Law just

laid

mechanical.

A very curious

and

instructive

phenomenon

MUTUAL ACTION OF

203

FLUIDS.

takes place when a portion of any of the

above three gases is thrown up into an eudiometer tube of -j-V of an inch diameter over

water; the water ascends and absorbs the gas

with considerable speed

common

air

is

and

to the other,
fine film of

the

two

airs

a small portion of

if

suddenly thrown up,

is

water

come

commonly

That

for a time.

into the

it

ascends

separated

above

by a

instant the

situation, the

water suddenly ceases to ascend in the tube,

but the film of water runs up with great speed,
enlarging the space below, and proportionally
diminishing that above,

This seems

to

sieve through

but not

shew

till

it

finally

that the film

is

which those gases can

common

bursts.

a kind of

easily pass,

air.

In the other gases

it is

very remarkable their

density within the water should be such as to

require the distance of the particles to be just

In olefiant
2, 3 or 4 times what it is without.
gas, the distance of ^he particles within

twice

that without, as

density being ^.

distance

is

is

inferred

is

just

from the

In oxygenous gas, &c. the

times as great, and

4 times.

This

in

hydro-

certainly curious,
genous,
and deserves further investigation ; but at present we liave only to decide whether the geSzc.

neral

phenomena denote

is

the relation to be of

chemical or mechanical nature.

In no case

MUTUAL ACTION OF

204-

FLUIDS.

whatever does it appear that the elasticity of

any of these gases is affected if water takes
;

bulk of any gas, the gas so absorbed,

exerts ^V of the elasticity, that the exterior

^j.

of

its

gas does, and of course it escapes from the

water v\hen the pressure is withdrawn from
its

when

surface, or

against which
far as

known

is

a foreign one

the gases continue the same

oxygenous

containing

certain

of

its

done,
It

induced,

thus, if

be

gas

the union of

nitrous gas,

is

not a proper match.

As
all
the
other
too,
properties of

it is

the

water

admitted

to

two gases

is

which the water takes up -j^

bulk of nitrous gas, as it would have
;

after

if

this

circumstance had not occurred.

seems clear then that the relation

is

a media-

nical one.*

* Dr.

Thomson and Mr. Murray have both

written

largely in defence of the notion that all gases are combined

with water, that a real union by means of a chemical
affinity

which water exercises

towards

all

be of the

gases, takes place

a greater or less degree

in

thjs affinity

is

supposed to

which holds

slight kind, or of that kind

all

gases

one amongst another, without any

The oppposite doctrine was fnst stated in a

in a state of solution,
distinction.

paper of mine,

on

the absorption

(Mancli. Memoirs, new

Vol.

of gases

by water.

1.)

Previously to the

publication of that paper, Dr. Henr}',

who was convinced

from

his

own

series,

experience, that

the connection of

gases

with water was of a mechanical nature, wrote two essavs

MUTUAL ACTION OF

205

FLUIDS.

Carbonic acid gas then presses upon water

first instance
with its whole force
in

in the

a short time

and

the water,

parrly enters

it

then the reaction of the part entered, contrl-

the 8th

9th Vol. of Nicholson's Journal, in vvhich the

ariH

arguinenis lor tJnt opinion are clearly,

stat'^d.

ansu\rnl)iy
discission

Thoriijo

If^ading

absorb such

tween the

argument seems
of each

a portion

anJ,

think, un-

to enter largely into a

then

H^:

of carbonic acid

for

that the

Dr.

" water

lo be, that

gn--,

will

repuUion be-

balances the affinity of

pai tides absorbed, just

water for iheai.'^

afTinity

do not intend

the argiin'er.ts these gentlemen adopt.

ot"

t'a

proceeds to infer,

water

that the

such as nearly to

is

balance the elasticity, that the affinity of okfiant gas for

is
equal to half its elasticity, that of oxygen, ^, and

water

of azote I, &c.

Now

if

a particle of water attract one of

carbonic acid by a force analogous to that of repulsion, it

must increase directly as the distance decreases ; if so, two

such particles must be

if

any other

pelling

it

force

is

in

towards the water, the

Thomson's

would lake one of

any distance

and

the particle of gas pro-

to

two

or coiiie into most intimate contact.

froio Dr.

at

equilibrium

applied

particles nnist unite

Hence,

should infer,

principle, that each particle of water

acid,

and

consequently

lib.

of water

wouhl combine with 2|lbs. of carbonic acid nearly. Mr.

Murray mentions a great many circumstances which he
conceives

make

against

the

mec hanical

hypothesis

for

some of the acid and alkaline gases are known to

be absorbed largely by water, and undoubtedly by affinity ;

instance,

therefore the less absorbable gases must be under the

influence, only in an inferior degree, and that "it

same

would

be impossible to point out the line of distinction between

those where the absorption might beconcLired to be purely

MUTUAL ACTION OF

206

FLUIDS.

butes to support the incumbent atmosphere.

Finally, the gas gets
completely diiTused

through the water, so as to be of the same

the gas within the
;

density within ag without

water then presses on the containing vessel

reacts upon the incumbent gas.

only, and

The water

then sustains no

pressure

either

from the gas within or without- In olefiant

gas the surface of the water supports ~l of
the pressure,

oxygenous, &c. j^, and in

in

hydrogenous, &c.

When

any gas

-Ij-.

is

confined in a vessel over

mechanical, and those where the exertion of affinity must

be allowed to operate." I conceive nothing is more easy
than to point out the exact line of distinction : wherever

water
it is

is

is found to

diminish or destroy the elasticity of any gas,

a chemical agent

wherever

a mechanical agent.

it

does neither of these,

Whoever undertakes

it

to maintain

the chemical thtory of the absorption of gases by water,

should in the outset overturn the following argument pre" The
ferred by Dr. Henry :
quantity of every gas,

absorbed by water, follows exactly the ratio of the presand since it is a rule in philosophizing, that effects
;

sure

qf the same kind, though differing in degree, are produced by the same cause, it is perfectly safe to conclude,
that everj', even the minutest portion of any gas, in a
state of absorption

by water,

is

retained entirely by

incum-

Tliere is no occasion, therefore, to call in

bent pressure.
the aid of the law of chemical affinity, when a me-

chanical

law

pearances.''

fully

and

satisfactorily

explains

the

ap-

MUTUAL ACTION
water

in

207

OF FLUIDS.

the pneumatic trough, so as to

com-

through the
medium of water, that gas must constantly
be filtring through the water into the atmo-

municate

with

the atmosphere

sphere, whilst the atmospheric air is filtring

through the water the contrary way, to sup-

place in the vessel

its

ply

as

that

in

due

air in the vessel

in this respect
it

so

becomes atmospheric,
Water
various chemists have experienced.

time the

admits the

is

an earthenware retort

like

to

gases

both ways

go

at the

same time.
It

is

why water

not easy to assign a reason

should be so permeable to carbonic acid, &c.

and not to the other gases; and why there
should be those differences observable in the
others.

The

densities

4->

iV

^"^

-V> ^lave

most evidently a reference to a mechanical

origin, but none whatever to a chemical one.

No
if

mechanical equilibrium could take place

the densities of the gases within

this

law

but

were not
the

why
regulated by
gases
should not all agree in some one of these forms,
I

do not see any reason.

Upon the whole it appears

that water, like

incapable of forming a perfect barrier to any kind of air ; but it differs

earthenware,

is

from earthenware
alike

permeable to

in

one respect

all

the last

is

the gases, but water

is

ON THE CONSTITUTION OF SOLIDS.

208

much more permeable

Other

others.

examined

to

some gases than

to

liquids have not been sufBciently

in this respect.

The iv.utual action of water, and the greater

number ot acid gases and alkaline gas partaking
most evidently of

chemical nature, will

be

best considered under the headsof the respective

acids and alkalis.

SECTION

4.

ON THE

CONSTITUTION OF SOLIDS.

A solid
a

arc in

great
in

made
is

powers,

suc!^.

force.

body
state

in

r.

is

of

one,

tlie

equilibrium

at'.racllon

nianner,

particles of

that

which

betAixt two

and repulsion, but

can be

no change

their distances without considerable

If an

approximation of the particles

attempted by force, then the heat

resists

it

a separation, then the attraction resists it.

The notion of Boscovich of alternating planes
if

of attraction and repulsion seems unnecessary;

except that upon forcibly

breaking the co-

hesion of any body, the newly exposed surface

must receive such a modification in its atmo-

ON THE CONSTITUTION OF
as
sphere of heat,

may

SOLIDS.

209

prevent the future junc-

tion of the parts, without great force.

The

distinction

essential

between

liquids

perhaps consists in this, that heat

the ultithe
figure of arrangement of
changes
mate particles of the former continually and

and

solids,

whilst they retain their liquid form

gradually,

probable, that change

of temperature does no more than change the
size, and not the arrangement of the ultimate

whereas

in the latter,

it is

particles.

NoJtwithstanding the hardness of solid bodies,

or the difficulty of

moving the

amongst another, there

particles

one

are several that admit

of such motion without fracture, by the application of proper force, especially

if assisted
by
and
malleability of the
ductility
It should
metals, need only to be mentioned.

heat.

The

seem the
face,

particles glide

somewhat

the end

along each others sur-

like a piece of polished iron at

of a magnet, without being at all

The absolute
in their cohesion.

weakened

force of cohesion,

of bodies,

which

constitutes the strength

an enquiry of great practical imIt has been found by experiment,

is

portance.
that wires of the several metals beneath, being

each

T-V

of an inch in diameter, were just

broken by the annexed weights.

ON THE CONSTITUTION OF

210

Lead...

Tin

290,

....

49;;.

299i
360 >
370

Copper.
Brass...
Sil>er

Gold

yard

piece of
1

tice

good oak, an inch square and a

bear in the
>ng, will just

But such

a piece of

4-

or

:^

middle 3301bs.

wood should

not in pracof
time, with
any length
of that weight.
Iron is about

be trusted,

above

Pounds.

450
500

I^on

SOLIDS.

for

10 times as strong as oak, of the same

di-

inens ons.

One would
and

hardness

be apt to suppose that strength

ought to be found propor-

tionate to each other

but this

is

not the case.

harder than iron, yet the latter

the stronger of the two.

Glass

is

Crystallization

xhibits

is

much

to us the effects of

arrangement of the ultimate parof various co npound bodies; but we

the natural
ticles

sulhcieiitly acquainted with

chemical synihesis and analysis to understand
the rationale of this process.
The rhomboidal

are sea cely yet

form may

ari^e

from the proper position of

4, 6, 8 or 9 globular particles, the cubic

from 8

form

particles, the triangular form from 3,

211

ON CffEMlCAL SYNTHESIS.

from

6 or 10 particles, the hexahedral prism

7 particles,

&c.

mav be enabled

in

Perhaps,

due time,

we

number

and.

the

to ascertain

order of elementary particles, constituting any

given compound element,

determine the figure which
crystallization,

and

and

vicd versd

from that

will prefer

it

but

it

on

seems

premature to form any theory on this subject,

till we have discovered from other principles
the

number and order

which combine

to

of the primary elements

form some of the compound

elements of most frequent occurrence

method

for

which

we

shall

the

endeavour to point

out in the ensuing chapter.

(iMWSEIEI0MMM

CHAP.

ON CHEMICAL

W HEN

any body

III.

SYNTHESIS.

exists in the elastic state,

ultimate particles are separated from each

other to a much greater distance than in any

its

other state; each particle occupies the centre

of a comparatively large sphere, and supports

ON CHEMICAL SYNTHESIS,

212
its

which by

the rest,

all

dignity by keeping

their gravity, or otherwise are disposed to en-

croach up

we

it,

attempt

at a respectful distance.

When

number of

particles

to conceive the

in an atmosphere,

it is

number of

ing to conceive the

universe

But

if

we

we

somewhat

like attempt-

the

stars in

are confounded with the thought.

limit the subject,

volume of any

gas,

by taking a given

we seem persuaded

that,

be ever so minute, the number

of particles must be finite j just as in a given

let the divisions

space of the universe, the

planets cannot be infinite.

number of

stars

and

Chemical analysis and synthesis go no

far-

ther than to the separation of particles one

from another, and to

No new

their reunion.

creation or destruction of matter

is

within the

We

reach of chemical agency.

might as well
attempt to introduce a new planet into the
solar system, or

hydrogen.

one already in
or destroy a particle of

to annihilate

existence, as to create

All the changes

we

can produce,

consist in separating particles that are in a state

of cohesion or combination, and joining those

that were previously at a distance.

In

all

chemical investigations,

it

been considered an important object

has justly
to ascer-

tain the relative iveights of the simples

which

ON CHEMICAL SYNTHESIS.

213

compound. But unfortunately the

has terminated here ; whereas from

constitute a

enquiry
the relative weights

the mass, the relative

in

weights of the ultimate particles or atoms of

the bodies might have been inferred, from

which
other
assist

their

number and weight

in

various

compounds would appear, in order

and to guide future investigations, and

Now

correct their results.

it

is

to
to

one great

object of this work, to shew the importance

and advantage of ascertaining the relative

weights of the ultimate particles, both of simple

and compound

bodies, the nuiJiber

of simple
elementary particles ivhich constitute one com-

pound particle, and

the

number of less compound

into the
particles ivhich enter

formation of one

more compound particle.

If there are two bodies,

and B, which

are disposed to combine, the following is the

order in which the combinations may take
place,

beginning

with

the

most simple

namely,
1

atom of

atom of

A
A

atom of

-|-

2 atoms of

B
B

=
=

2 atomsof A-}- I atom ofB=^

I atom of A -}- 3 atoms of B
3 atomsof

-f-

=
atom of B =

I
I

atom of C,

binar\%'

atom of D, ttrnaiy.
atom of E, itniaiy.

atom

o\ F,

quateiuaiy.

atom of G,
quaternary.
&c. &c.

ON CHEMICAL SYNTHESIS.

214

The following general rules may be adopted

as guides in all our investigations respecting
chemical synthesis.
1st. When only one combination of two
bodies can be obtained, it must be presumed to

be a binary one,

unless

some cause appear

to

the contrary.
2d.

When two

combinations are observed,

to be a binary and a

they must be presumed

ternary.

3d. When three combinations are obtained,

we may expect one to be a binary^ and the

other two ternary.

4th. When four combinations are observed,

we should

expect one binaryy two ternary ^ and

one quaternary, &c.

5th.

binary

compound should always be

specifically heavier than the

two

mere mixture of its

ingredients.

ternary compound should be specithan the mixture of a binary

heavier
fically
and a simple, which would, if combined,
6th.

constitute

7th.

equally

itj

The

From

above

apply,

and D,

chemical

&c.

rules

when two

and

observations

bodies,

such

as

and E, &c. are combined.

the application
facts

of these rules, to the

already well ascertained,

we

ON CHEMICAL SYNTHESIS.

215

deduce the following conclusions; 1st. That

water is a binary compound of hydrogen and
oxygen, and the relative weights of the two
elementary atoms are as 1 7, i;early ; 2d. That
:

ammonia
and

binary coinpound of hydrogen

azote, and the relative weights of the two
a

is

atoms are

1:5, nearly

as

That nitrous

3d.

gas is a binary compound of azote and oxygen,

the atoms of which weigh 5 and 7 respectively

that

compound

nitric

acid

according as

a binary or ternary

is
it

is

derived, and con-

of one atom of azote and two of oxygen,

together weighing 19; that nitrous oxide is a
sists

compound

similar to

of one atom

weighing 17;

and

consists

and two of azote,

nitrous acid

that

of nitric

compound

nitric acid,

of oxygen

acid

is

a binary

and nitrous gas,

weighing 31

compound
26

4th.

that oxynitric acid is a

;
binary
of nitric acid and oxvgen,

weighing

That carbonic oxide

is

a binary

com-

pound, consisting of one atom of charcoal, and

one of oxygen, together weighing nearly 12;

that carbonic acid

is

a ternary

compound, (but

sometimes binary) consisting of one atom of

charcoal, and two of oxygen, weighing 19;
&c. &c. In all these cases the weights are
expressed in atoms of hydrogen, each of which
is denoted
by unity.

216

ON CHEMICAL SYNTHESIS.

In the sequel, the facfs and experiments

from which these conclusions are derived, will
be detailed as well as a great variety of others
;

from which are inferred the constitution and

weight of the ultimate particles of the princi"

pal acids, the alkalis, the earths, the metals,
the metallic oxides and sulphurets, the long
train

of neutral

chemical

and

salts,

obtained a

tolerably

in

which

compounds

good

short,

all

the

have

hitherto

analysis.

Several

of the conclusions will be supported by original experiments.

From

the novelty as well as

importance of

the ideas suggested in this chapter,

it is

deemed

expedient to give plates, exhibiting the

mode

of combination in some of the more simple

cases.
specimen of these accompanies this

first

part.

The elements

atoms of such

or

bodies as are conceived at present to be simple,

are denoted by a small circle, with some distinctive

mark

and the combinations

consist in

the juxta-position of two or more of these ;

when three or more particles of elastic fluids
are

combined together

in one,

it is

to be sup-

posed that the particles of the same kind repel

e^ch other, and therefore take their stations
accordingly.

END OF PART THE

FIRST.

//,/A

210

2
/

S.jI,-

- "ooo

Vapou r

-'^00

_-(lOO

VV.Urr
i;>o
(I

52
400-

___

Tkio

IflO

--

|()(>

160
-4i)i)(i

o')o

-ir.o

F
Ice

-iln

.'SOtH)

aix)

200-

--

JO

-lUO

'iooo
If)l>"

"

217

EXPLANATION OF THE PLATES.

PLATE L

Fig. 1. is intended to illustrate the auon the subject of the capacities of bodies for
See page 3.
There are three cylindrical vessels
heat.
placed one within another, having no communication but
over their margins ; the innermost is connected with a la
teral and parallel lube graduated, and supposed to represent the degrees of a thermometer, the scale of which comthor's ideas

mences

at absolute cold; if a liquid (supposed to represent

heat) be poured into the tube, it will flow into the inner
vessel, through an aperture at the bottom, and rise to the
same level in the vessel and the tube. Equal increments
of heat in this case are supposed to produce equal incre-

ments of temperature.

When

the temperature has arrived

at a certain point (suppose 6000) the body may be supposed to change its solid form to the liquid, as from ice to
water, in which case its capacity for heat is increased, and

is to be
considerable
represented by the second vessel.
portion of liquid must then be poured into the tube before
any rise will be perceived, because it flows over the margin of the innermost vessel into the lateral cavity of the

second; at length

it

reaches

the level, and then a pro-

portional rise will ensue, till the body becomes converted

into an elastic fluid, when the thermometer again becomes

whilst a great portion of heat

stationary
the body, now assuming a new capacity.

is

entering into

Fig. 2. is a comparative view of the old and new divisions

of the scale of the mercurial thermometer.
See Table,
page 14. The interval from freezing to boiling: water is
180** on both scales, and the extremes are numbered 32*
and 212" respectively. There are no other points of temperature in which the two scales can agree.
Fig. 3. is a view of the divisions of a water thermometer,

conformably to the new scale of the mercurial ; the lowt-st

point is at 4-5 ; the intervals from 45'* upwards, to 55*,
65, 75**, &c. are as the numbers 1, 4, 9, &c.
Also,
SO* and 60"^ coincide, as do 20 and 70<>, &c.

PLATE n. Fig. 1. represents an air thermometer, or

the expansion of air
by heat ; the numbers are Fahrenheit's,
and the intervals are such as represented in the 7th column
of the table, at
page 14.
Fig. 2. is the logarithmic curve, the ordinates of which
are erected at
equal intervals, and diminish progressively

by

the ratio f

The

intervals of the absciss or base of

the

218

EXPLANATION OF THE PLATES.

curve, represent equal intervals of temperature (25 for

steam or aqu ous vapour, and 34" for ethereal vapour)
the ordinales represent inches of mercury, the weight of
which is equal to the force of steam at the t( mperature.
See thf 8ih and 9lh rnlumns of table, at pagf 14. Thus the
force of steam at 212, and of ethereal vapour at llC,
new scale, is equal to 30 inches of mercury ; at 187 the
force of steam is half as much, or 15 inches, and at 76,
that of ethereal vapour is also 15 inches, &c.
Fig. 3. is a device suggested by Mr. Ewart, to illustrate
the idea which I have developed in the section on the temIt is a
cylindrical vessel cloj;e
perature of the atmosphere.
at one end and open at the other, having a moveable piston sliding within it : the vessel is supposed to contain air,
and a weight is connected with the piston as a counterpoise
to it.
There is also a thermometer supposed to pass
through the side of the vessel, and to be cemented into it.
Now if we may suppose the piston to move without
friction, and the vessel to be taken up into the atmosphere,
the piston will gradually ascend, and suffer the air within
to dilate, so as to correspond every where with the exterior
This dilatation tends to diminish the temair in density.
perature of the air within (provided no heat is acquired
from the vessel.) Surh an instrument would shew what
the theory requires namely, that the temperature of the
air within would every where in the same vertical column
the former would not reagree vvith that without, though
ceive or part with any heat absolutely, or in any manner
communicate with the external air.

PLATE III. See page 135. The balls in Fig. 1 and 2

represent particles of water : in the former, the square
form denotes the arrangement in water, the rhomboidal
form in the latter, deiioit-s the arrangement in ice. The
angle is always 60 or 120.
Fig. 3. represent* the perpendicular section of a ball
upon two others, as 4 and 8, Fig. 1.
Fig. 4. represents the perpendicular section of a ball

resting

The perpenresting upon two balls, as 7 and 5, Fig. 2.

diculars of the triangles shew the heights of the strata in
the two arrangements.
Fig. 5 represents one of the small spiculae of ice formed
upon the sudden congelation of water cooled below the

See page 134.

frerziog point.
Fig. 6. represents the shoots or ramihcations of ice at
the com nencemeat of congelation.
The angles are 60

and 120

Fla/c

Eth Vap

EXPLANATION OF THE PLATES.

219

PLATE

IV.
This plate contains the arbitrary marks
or signs chosen to represent the several chemical elements
or ultimate particles.
Fig.

Fig.
1

Hvdrog.

its rel.

2 Azote,

3 Carbone or,charcoal,

4 Oxygen,

5 13 Iron
7 14 Zinc

5 Phosphorus,
6 Sulphur, 7 Magnesia, 8 Lirae,
9 Soda,
10 Potash,

13 16 Lead

20

21.

An

15
17

2324.

25
26.
27.
28.
29.

Copper
Silver

= -----

its relative weight

;
atom of ammonia, composed of 1 of azote and
1
of hydrogen
An atom of nitrous gas, composed of 1 of azote
and 1 of oxygen
An atom of defiant gas, composed of 1 of carbone
and I of hydrogen
An atom of carbonic oxide composed of 1 of carbone and 1 of oxygen
1
An atom of nitrous oxide, 2 azote
oxygen
An atom of nitric acid, 1 azote -f- 2 oxygen - An atom of carbonic acid, 1 carbone -j- 2 oxygen
An atom of carburelted hydrogen, 1 carbone -{- 2

An

38

56
56
95
100
100
140
167

An atom
An atom

]2

17

------------

of oxv nitric acid,

of sulphuric acid,

An

azote

sulphur

-j-

-f-

oxygen
3 oxygen

-----------

36.
37.

An

6
12
6

19
19

7
26
34
ig
16

-31

gas

An atom
An atom

---------------------------------

atom of sulphuretted hydrogen, 1 sulphur -|- 3

hydrogen
33. An atom of alcohol, 3 carbone -f- 1 hydrogen
34. An atom of nitrous acid, 1 nitric acid -f- 1 nitrous
35.

46
68

atom of water or steam, composed of 1 of

oxygen and 1 of hydrogen, retained in physical
contact by a strong affinity, and supposed to
be surrounded by a common atmosphere of

hydrogen
30.
31.
32.

-----

23 18 Plaiina
28 19 Gold
42 20 Mercury

heat

22.

weight 1|11 Strontites

5.12 Barytes -

of acetous acid, 2 carbone -f- 2 water

of nitrate of ammonia, 1 nitric acid -j-

ammonia

atom of sugar,

water
1

26

------.-33

alcohol

-\- 1

carbonic acid

35

220

EXPLANATION OF THE PLATES.

Enough has been given to shew the method ; it will be

to devise characters and combinations of
quite unnecessary
them to exhibit to view in this way all the subjects that
come under investigation ; nor is it necessary to insist upon
the accuracy of all these compounds, both in number and
weight ; the principle will be entered into more particularly
It is not
bereafter, as far as respects the individual results.
to be understood that all those articles

marked

as simple

substances, are necessarily such by the theory ; they are

Soda and Potash, such
only necessarily of such weights.
are found in combination with acids, are 28 and 42
as

they
to Mr. Davy's very
respectively in weight ; hut according
important discoveries, thev are metallic oxides; the former
then must be considered as composed of an atom of metal,
21, and one of oxygen, 7 ; and the latter, of an atom of
Or, soda contains 75
metal, 35, and one of oxygen, 7.
per cent, metal and 25 oxygen ; potash, 83.3 metal and
It is particularly remarkable, that accord16.7 oxygen.
ing to the above-mentioned gentleman's essay on the Decomposition and Composition of the fixed alkalies, in the
Philosophical Transactions (a copy of which essay be has
" the
largest quanjust favoured me with) it appears that
these experiments was, for
tity of oxygen indicated by
the smallest
20
and
in
100,
parts
potash 17, and for soda,
13 and 19/'

DIRECTIONS TO THE BINDER,

Plate

to face

page 217.

to face

page 218.

3 to follow plate 2.

PKINTED BY

S.

to face

page 219.

RUSSELL, MANCHESTER.

NEW SYSTEM
OP

CHEMICAL PHILOSOPHY.

PART

II.

BY

JOHN DALTON.

MoaNVKHKIiSMMM

Printed by Russell

&

Allen, Deansgate,

ton.

K.

BICKERSTAFF, STKAND, LONDON.

1810.

Reprodlced

in

William Dawson
102

Facsimile

& Sons

Ltd.

WiGMORE Street,
London, W.I

AND Printed

Henderson

by

& Spalding

Sylvan Grove. Old Kent Road.

London, S.E.I 5

Thls Edition

is

limited

to

LOOO copies

TO

HUMPHRY DAVY,

Esq. Sec. R.

S.

PROFESSOR OF CHEMISTRY IN THE ROYAL INSTITUTION, ScC. &C-

AND TO

WILLIAM HENRY, M.
VICE PRESIDENT OF THE LITERARY
SOCIETY, MANCHESTER,

D. F. R.

S.

AND PHlLOSOrHICAL
&.C.

&C.

THE SECOND PART

OF

THIS
AS

WORK IS RESPECTFULLY INSCRIBED,

A TESTIMONY TO THEHl DISTINGCISHFD MERIT IN

PROMOTION OF CHEMICAL SCIENCE,

AND
AS

AN ACKNOWLEDGMENT OF

THEIR FRIENDLY COMMUNICATIONS AND ASSISTANCE,

BY THE

AC/THOB.

THE

PREFACE.

w,HEN

the

part of this

first

work was published,

ex-

pected to complete it in little more than a year ; now two

half have elapsed, and it is yet in a state of imyears aiiJ a

The

perfection.

ments which
in

reason of it is, the great range of experihave found necessary to take. Having been

progress so often misled,

my

by taking for granted the

have determined to write as little as
poscan attest by my own experience. On this

results of others,
sible but.

what

account, the following work will

found to contain more

b(^

original facts and experiments, than

any other of its size,

on the elementary principles of chemistry. I do not mean
to say that 1 have coj)ied the minutes olmy note-book iliis
;

would be almost
experience
mistry,
five

that not

as

writing without any

are conversant in
practical che-

who

those

know

is fit

as reprehensible

more than one new experiment

to be reported to the public

upon due rcilection, to be some way or other

and are useful only as they shew the sources of
the means of avoiding

in

the rest are found,

defective,
error,

and

it.

Finding that my design could not be completed, without

a second volume, I was desirous to finish the 5lb
chapter,

which

now
time

two

treats of the

edited
is

compounds of two element?,

but the work

is

enlarged

."^o

in

the part

much, and the

so far advanced, that I have been

obliged to omit

or three important sections,

particularly the metallic

oxides and sulphurets, which

am aware

will

demand no

inconsiderable share of attention.

of,

After these are disposed

the 6th chapter will treat of
compounds of 3 or more

elements;

this

will

comprehend the vegetable and other

acids not yet noticed, the

hydrosulphureis, the neutral salts,

compound combustibles, &c. &c.

Whatever may be the result of
work somewhat
volume,

I feel

enabled thus

like

plan to render the

present satisfaction in having been

devclope that theory of chemical syn-

great

far to

my

complete, by the addition of another

PREFACE.
thesis, \vhich> the

convinced of

any one

its

longer

irulh.

to form a

contemplate, the moie

Enough

judgment of

is

The

it.

tions yet in reserve, are only of the

ready advanced

if

facts

as those al-

the latter are not sufficient to convince,

little avail.

Iti

time, those who, with nje, adopt the system,

have no doubt, find it a very useful guide in the

mean

will, I

of

prosecution

all

chemical investigations.

In the arrangement of the articles treated

deavoured to preserve order

as are simple, according to

next, those bodies that are

but

am

and observa-

same kind

the addition of the former will be but of

the

already done to enable

in this

stances,

it

have not always succeeded.

For,
has not been quite clear what was
;

have enr

knowledge
compounds of two elements

what compound

of,

namely, to take such bodies

our present
and
;

in others, the

some

in

in-

simple, and

compounds of three or more

elements have been so intimately connected with those of

two, that it was found impracticable to give a
satisfactory

without entering more or

description of the former.

account of the

latter,

less into

In regard to nomenclature, I have

generally adopted
;
perhaps, in a few instances,

what was most current

peculiar views
1

may have

have called those

my

me

led

to deviate

salts carbonates,

from

this rule.

which are constituted

of one atom of carbonic acid united to one of base; and the

But some moderns call the neutral salts
like for other salts.
carbonates, and the former subcarbonalcs

whereas,

should

the neutral carbonates of soda and

potash supercarhonatcs, consisting of two atoms of acid and one of base.
I
call

have, however, continued to

that

call

the

common

nitrates

by

name, though most of them must be considered on

my

system as
head, as

svpeniitrates.

it is

evident that

am
if

not very anxious upon this

the system

I
proceed upon bo
adopted, a general reformation of nomenclature will be the

consequence, having a reference to the

n?<wiifr o/'ft/o//(j, as

well as to the kind of elements,

consliluling the difTerent

compound

bodies,

iVor. 18 !0.

CONTENTS OF PART SECOND.

FACE

On Elementary
Section 1. On Oxygen

Ghap.

IV.

..

.
Chap.

v.

Section

On Hydrogen

3.

On Azote

4.

On Carbone

5,

On Sulphur
On Phosphorus

On

7.

the

or Charcoal

231
234

242

Metals

----- 2C9

Oxygen ivitk Hydrogen

Water

Nitrous gas

-.-

270

309

-3l6

-----.- 277
286
------ 297
-

--------332
-

Nitrous oxide

Oxynitric acid

Nitrous acid

-339

---343

Nitric acid

-----.- 364
-------36t>

Sections. Oxygen uith Carbone

368

Carbonic oxide

------- 370

Carbonic acid

-378

-38S

Oxygai with Sulphur

Sulphurous oxide
Sulphurous acid
Sulphuric acid

5.

221

-----

Oxymuriutic acid
Hyperoxymuriatic acid
Section 2. Oxygen zvith Azote

Skction

238

Muriatic acid

4.

----..-- 240

Fluoric acid

Section

22ft

or Nitrogene

Compounds of two Elements

1

--_----- 225
.------.

2.

6.

Principles

------ 388
------- 394

Oxygen with Phosphorus

Phosphorous acid

Phosphoric acid

407

-410

403

CONTENTS.

Section

6.

Hj/drogemtftth Azote

Section

7.

vjilh

Hydrogen

ii-ith

Hydrogen

Sulphur

Sulphuretted hydrogen

----- 444
----- 450

Supersulphurcttcd hydrogen

Section

9.

10.

453

45G

Hydrogen with Phosphorus

-

I'hosphuretted hydrogen

Section

-415

437

Ctirbiirelted Iiydiogen
8.

Carbone

OUftant gas

Section

--------. 415

Ammonia

Curbonc nith Sulphur, with Phosphorus,

and Sulphur with Phosphorus

462

Section 11. Fixed Alkalies

4GS

Potash

Hydrate of potash

Carbonate ofpotash

-475

479

4S4

Potasium or hydrurct of potash

492

Soda

...

Sodium or hydrurct of soda

Hydrate of soda
Carbonate of soda

Section 12. Earths

Lime

----------

Magnesia
Burytcs

Strontites

--

Glucine
Zirconc

505

524

536
-

342

--------- 543
--------- 544

P.xplanation of Plates

/Appendix

504

------ 527

Silex

Yttria

502

-512
-518

Al'Jjnine or argil

495

------ 497

----- 546
5A^

221

NEW SYSTEM
O.I

CHEMICAL PHILOSOPHY.
PART

CHAP.

IL

IV.

ON ELEMENTARY

PRINCIPLES.

XN order to convey
facts

a knowledge of chemical
and experience the more clearly, it has

been generally deemed best

begin with the

description of such principles or bodies as are
the most simple, then to proceed to those that
are

compounded

of

afterwards to those

two simple elements, and

compounded of three or

more simple elements.

in

view

in

to

This plan will be kept

the following

work,

as

far as is

elementary principles, or
such as have not been

convenient.

By

simple bodies,

we mean

decomposed, but are found

bination with other bodies.

to enter into

We

com-

do not know

222

ON ELEMENTARY PRINCIPLES.

that

any one of the bodies denominated

ele-

indecomposable ; but
be
called
simple, till it can be
ought to
is

mentary,
it

analyzed.

absolutely

The

principal

simple bodies are

names oxygen, hydrogen,

distinguished by the

azote or nitrogeny carbone or charcoal, sulphur ^

phosphorus, and the metals. The fixed alkalis

and the earths were

but

undecomposed

lately

has long been suspected that they were

it

compounds

and

Mr. Davy

has

recently

shewn, by means of galvanic agency, that

some of them contain metals, and have all the
characters of metallic oxides

no harm can

conceived, therefore, from placing

the earths in the same class as he metallic
it

arise,
all

is

oxides.

After the elementary or simple bodies, those

compounded of two elements require next to

be considered.

These compounds form a

in which the new-

highly interesting class,

principles adopted are capable of being exhibited,

and

their

rect experiment.

accuracy investigated by diIn ihis class

we

find several

of the m.ost important

agents in chemistry ;
namely, water, the sulphuric, nitric, muriatic,

the

carbonic and phosphoric acids, most of

compound

gases, the alkalis, earths,

and

metallic oxides.

In the
succeeding classes

we

shall find the

ON OXYGEN.

223

more complex compounds to consist of 3, 4,

more elementary principles, particularly the

or

but in these cases, it generally happens

one compound atom unites to one simple
atom, or one compound to another compound,
salts

that

or perhaps to two compound atoms j rather

than 4 or 6 simple elementary atoms uniting
in the same instant.
Thus the law of che-

mical synthesis

is

observed to be simple, and

numbers of the more

always limited to small

simple

principles

forming

the

more

com-

pound.

SECTION

1.

OXYGEN.
The most
be procured,

The

gas

1st.

simple state in which oxygen can

is that of a
gas or elastic fluid.

may be

obtained,

Without the application ofheut.

Put 2

ounces of red lead (minium) into a 5 ounce

gas bottle ; to which put one ounce of the
strongest sulphuric acid ; then instantly shake
it a little to
promote mixture, and apply the

stopper with a bent tube : suddenly a great

heat is generated, white fumes fill the bottle,

and a copious flow of gas ensues, which may

ON OXYGEN.

224
be received

over water, in the usual

in phials

About 30 cubic inches of

way.

gas

may be

expected. This g^s should be exposed to a

mixture of lime and vi^ater, which absorbs

about

4-

of

it

(carbonic acid), and leaves the

rest nearly pure.

With

2.

the

of heat.

application

ounces of manganese (the

into an iron bottle, or

common

Put 2

black oxide)

barrel properly prepared, to which a recurved tube is adapted.

This is then to be put into a fire, and heated

gun

and may
; oxygenous gas will come over,
be received as before ; it usually contains a

red

small portion of carbonic acid, which may be

Three or four pints
extracted by lime water.

of

air

may

3.

Two

thus be obtained.

ounces of manganese may be put

same weight of sulphuric

the
mixture
;
being made into a paste,
of
a
the
heat
candle or lamp, and the
apply

into a phial, with the

acid

gas comes over as before, nearly pure,

over water.
If an

4.

bottle,

ounce of

and exposed

nitre

and

It consists

azote,

mixed

taken

be put into an iron

to a strong

red

large quantity of gas (2 or 3 gallons)

obtained.

if

heat, a

may be

of about 3 parts oxygen

together.

Put 100 grains of the

salt called oxymuriate of potash into a glass or earthenware

5.

225

PROPERTIES OF OXYGEN.

apply the heat of a lamp, &;c. till the

grows nearly red, and a quantity of oxygenous gas will come over with great rapidity.

retorl

retort

About 100 cubic

from

carbonic

inches will be obtained, free

and

acid,

other respects

in

very pure.

to

Various other methods are occasionally used

obtain this gas, but the above are the

principal

and

experience, or

for one who has not had much

who wants only a small quan-

tity of gas nearly pure, the first and second are

the easiest and most economical.

Properties of Oxygen.

To

enumerate

all

the properties of oxygen,

and the combinations

would be
mistry.

It will

which

into

one half of a

to write

be

sufficient,

it

enters,

treatise

on che-

under the present

head, to point out some of

its

more

distin-

guishing features.
1.

It

the specific gravity of

atmospheric air

be denoted by

1,

that of

oxygen

will

be 1.127

according to Davy, but some have found it

One hundred cubic inches of it,
rather less.
temperature 55, and pressure 30 inches
of mercury, weigh nearly 35 grains; the same
quantity of atmospheric air weighs 31.1

at the

grains.

The weight

of an atom of oxygen

is

denoted

PROPERTIES OF OXYGEN.

226
by

an atom of hydrogen being

7, that of

this

inferred from the relative weights of those

is

elements entering into combination to form

water. The diameter of a particle of oxygen,
in

its

elastic state,

as .794 to
2.

is

to that of one of

hydrogen,

*
unites with hydrogen, charcoal,

Oxygen

azote, phosphorus,

and other bodies denomi-

nated combustible, and that in various manners and proportions;

when mixed with

hy-

drogen and some other elastic fluids, it explodes by an electric spark, with noise, and a
violent concussion of the vessel, together with

the extrication of

much

heat.

This

is

called

In other cases, the union of oxygen with bodies is more slow, but accompanied by heat. This is usually called comdetonation.

bustion, as in the

v]flammationy

burning of charcoal

when accompanied with

as in the burning of

union
*

is still

ozY.

In

-f- specific

other cases, the

is

as ^ y' (weight

gravity of the fluid).

Whence,

noting the weight of an atom of hydrogen by

specific gravity

and

more slow, and consequently with

For, the diameter of an elastic particle

of one atom

flame,

of hydrogenous gas also by

1,

de-

and the

the weight

1,

of an atom of oxygen will be 7, and the specific gravity of

oxygenous
or.TQ^ : I

gas,
:

14-;

we have

then ^^/ri

'

diameter of an atom of oxygen

of one of hydrogen.

'*
:

^^ 'v/l

the diameter

PROPERTIES OF OXYGEN.
little

227

increase of temperature, as in the rusting

This is called oxidation.

of metals.

Bodies burn

in the

rounding the earth,

atmosphere, or
in

air sur-

consequence of the

contains, which is found to be rather

oxygen
more than -^th of the whole mass. Hence it is
it

not surprising, that in pure oxygen they burn

with a rapidity and splendor far superior to

what

ordinary combustion. This

the ignited
easily exhibited, by plunging
full
of
a
into
oxygen ; a taper,
large phial
body
is

observed

in

is

small iron wire, charcoal, and above

all phosburns
with
inconceivable
phorus,
brilliancy in
The nature of the new compounds
this gas.

formed, will be best considered after the properties of the other elementary principles have

been enumerated.

That

part of the atmosphere

cessary

to

the support of animal

genous

gas.

3.

which
life,

Hence, an animal can

is

is

ne-

oxy-

subsist

much

longer in a given quantity of pure oxygenous gas, than in the same quantity of common or atmospheric air. In the process of
of oxygenous gas disan
and
equal one of carbonic acid is
appears,
respiration, a portion

produced j a similar change takes place in the

combustion of charcoal ; hence it is inferred,
that respiration is the source of animal heat.

Atmospheric

air

21
inspired, contains about

228

ON HYDROGEN.

per cent, oxygenous gas ; the air expired, usually contains about 17 per cent, oxygen, and 4

But

carbonic acid.

if

full

expiration of air

be made, and the last portion of the expired

air be examined, it will be found to have 8 or
9 per cent, carbonic acid, and to have

same quantity of oxygenous

4.

Oxygenous gas

is

the

lost

gas.

not sensibly affected

by

continually passing electric sparks or shocks

through it ; nor has any other operation been

found to decompose

it.

SECTION

2.

HYDROGEN.
Hydrogenous gas may be procured by taking half an ounce of iron or zinc filings, turnings, or other small pieces of these metals,
putting them into a phial, wirh two or three
ounces of water, to which pour one quarter as

much

sulphuric acid,

will be produced, with

which may

and

an effervescence

abundance of the

be received

usual way.
Some of its distinguishing properties are
It is the lightest gas with which
1.
are acquainted.

Its

gas,

over water in the

specific gravity
.0805, that of atmospheric air being

we

is

nearly

1.

This

229

Properties of hydrogen.

mean

nearly the

is

attained from the resuUs of

different philosophers.

100 cubic inches of

grains at the

may be

It

same

mon
is

air.

-r^th

find, that

gas weigh nearly 24

mean temperature and

stated 10 be tV^^

oxygen, and
the

Whence we

this

pressure.

of the weight of

of azote, and nearly

that

fractional part of the

weight of com-

The weight

denoted by

1,

of an atom of hydrogen
and is taken for a standard of

the other elementary atoms.

comparison
The diameter of an atom of hydrogen, in its
elastic state, is likewise denoted by unity,
for

and considered
for

as a standard of comparison
the diameters of the atoms of other elastic

fluids.

2.

It

fatal to
3.

extinguishes burning bodies,

animals that breathe it.

If a phial

be

filled

with

and

this gas,

is

and a

lighted taper, or red hot iron, be brought to

mouth, the gas will take fire, and burn

The
gradually till the whole is consumed.

its

flame
4.

is

mixed
if

usually reddish, or yellowish white.

oxygen and hydrogen gas are

When

together,

a lighted taper

no change
is

brought

is

perceived

to the

an electric spark passed through

but

mixture, or
it,

a violent

The two gases unite

explosion takes place.
in a proportion constantly the same, and produce steam, which

in

a cold

medium

is

in-

PROPERTIES OF HYDROGEN.

2S0
stantly

condensed into water.

sures of

hydrogen are

When

mixed with

2 mea-

of oxygen,

and exploded over water, the whole gas disappears, and the vessel becomes filled with
water, in consequence of the formation and
subsequent condensation of the steam.
If 2 measures of atmospheric air be

with

made

mixed

of hydrogen, and the electric spark

to pass through the mixture, an explo-

and

sion ensues,

(he residuary gas

is

found

to

be lA measures, consisting of azote and a small

The portion of the mixportion of hydrogen.

which disappears, \^, being divided by

gives 42 nearly, denoting the oxygen in
two measures of atmospheric air, or 21 per
ture
3,

cent.

The instrument for exploding such mixis called V olio's eiidioyneter.

tures in
5.

Another remarkable property of hydrogen

deserves notice, though

but belongs

it

is

not peculiar to

it,

degree to all other gases that

differ maierially from atmospheric air in speif a
cific gravity
cylindrical jar of 2 or more
in

inches in diameter, be

filled

placed upright and uncovered

two,

nearly the

whole

will

with hydrogen,
for a

moment

vanish,

and

or
its

In this
place be supplied by atmospheric air.
case it must evidently leave the vessel in a

body, and the other enter in the same manner.

But if the jar of hydrogen be held with its

231

ON AZOTE OR NITROGENE.

mouth downwards,

It

slowly and gradually

wastes away, an.d atmospheric air enters in the

same manner ; after several minutes there will

be found traces of hydrogen remaining in the

If a tube of 12 inches long and -^ inch

jar.

internal

there

diameter,

is little

down

held up or

be

filled

be

it is

the gas slowly and gradually

and as
departs in each case,
found

with hydrogen,

difference perceived whether

much may be

10 minutes have expired, as would

2 or 3 seconds if the tube were an

after

after

inch or more in diameter.

If a

3 or 4

ounce

with hydrogen, and a cork

adapted, containing a tube of 2 or 3 inches
long and -pV ^"^^"^ internal diameter, it does not
phial be

filled

make any

material difference in the waste of

the gas whether the phial is held up or down ;

ir will be some hours before the hydrogen gets
dispersed.
6.

Hydrogen gas bears

electrification with-

out any change.

SECTION

3.

ON AZOTE OR NITROGENE.
Azotic or nitrogene gas may be procured

from atmospheric

air,

of which

it

constitutes

the greater part, by various processes

1st.

To

232

PROPERTIES OF AZOTE.

100 measures of atmospheric

nitrous gas

be passed
through water ; it will
time,

put 30 of

air

the mixture having stood

must

two
still

or

three

some
times

contain a small

portion of oxygen ; to the residuum put 5 more

measures of nitrous gas, and proceed as before ;

small portions of the residuum must then be

tried separately,
air,

spheric

by nitrous gas and by atmowhether any diminution

to see

whichever produces a diminution

;
mixture, shews that it is wanting,

takes place
after the

and the other redundant

a small
; consequeritly
addition to the stock must be made accord-

By

ingly.

a few

trials

the

due proportion may

be found, and the gas being then well washed,

may be considered as pure azotic. 2. If a
quantity of liquid sulphuret of lime (a yellow
liquid procured by boiling one ounce of a mixture of equal parts sulphur

of water,

2 or 3 times
time,

it

becomes

till it

its

and lime

bulk of atmospheric

will take out all the

the azotic gas pure.

air.

3.

If

in

a quart

be agitated in

a pint)

air for

some

oxygen, and leave

to 100 measures of

42 of hydrogen be put, and

atmospheric
an electric spark passed through the mixture,
an explosion will take place, and there will be
left

80 measures of azotic

gas,

&c.

The properties of this gas are

of azotic
1. The
specific gravity
;

gas at the

PROPERTIES OF AZOTE.

233

temperature of 55 and pressure 30 inches,

.967 according to Davy, that of air being

is

1.

The weight of 100 cubic inches is nearly 30

The weight of an atom of azote is
grains.
denoted by
1

being

5, that

of an

atom of hydrogen
from the com-

this is inferred chiefly

pound denominated ammonia, and from those

of azote and oxygen, as will be seen here-

The

after.
its

diameter of a particle of azote in

is to that of one of
hydrogen,

elastic state,

as .747 to

I.

Like hydrogen, it extinguishes burning

bodies, and is fatal to animals that breathe it.
2.

Azotic gas

3.

less

is

prone to combination

other gases ; it never

combines with any other gas simply of itself;
but if a mixture of it and oxygen has the

than most,

if

not

all,

it for a
long continuance, a slow combustion of the azote takes

electric spark passed through

place,

and

cases azote

nitric acid

is

formed.

be obtained

may

in

In other

combination

with oxygen in various proportions, and the

compounds can be analyzed, but are not so

formed in the synthetic way.

Azotic gas, as has been noticed, constitutes nearly ^-ths of atmospheric air, notwith-

easily
4.

standing
it

in

its

its

being

unmixed

fatal to

state

genous gas, which

is

animals that breathe

the other ith

is
oxymerely mixed with and
;

ON CARBONE OR CHARCOAL.

234

diffused through the former,

and

mixture

this

constitutes the principal part of the atmosphere,

and
life

is

suited, as

we

perceive, both for animal

and combustion.

5.

Azotic gas

is

not affected by repeated

electrification.

SECTION

4.

ON CARBONE OR CHARCOAL.
If a piece of

wood be put

into a crucible,

and covered with sand, and the whole gra-

wood

dually raised to a red heat, the

composed
fluids

are

is

de-

water, an acid, and several elastic

disengaged,

carbonic

particularly

acid, carburetted hydrogen, and carbonic oxide.

a black, brittle, porous

Finally, there remains
the crucible, called charcoal,

substance in

which

incapable of change by heat in close

but
burns in the open air, and is convessels,
verted into an elastic fluid, carbonic acid.
is

Charcoal constitutes from

the weight of the

5 to

20 per cent, of
it
was

wood from which

derived.

Charcoal

insoluble in water

is

taste or smell,

putrefaction
liable to

in

but contributes

it

much

animal substances.

is

without

to correct
It

is

decay than wood by the action of

less

air

ON CARBONE OR CHARCOAL.

When

and water.

new,

it

235

gradually absorbs

moisture from the atmosphere, amounting to

12 or 15 per cent, of its weight. One half of

may be

the moisture

heat of boiling water,

expelled again by the

if
long continued ; the

other requires a higher temperature, and then

1 took
it a
portion of charcoal.

carries with

350 grains of charcoal

that

had been exposed

to the atmosphere for a long time

this

was

subjected to the heat of boiling water for one

hour and a half ; it lost 7 grains in the first
quarter of an hour, 6 in the second, and finally
it

had

lost

25 grains.

Several authors have maintained that charcoal, after

being heated red, has the property

of absorbing most species of elastic fluids, in

such quantities as to exceed its bulk several

times

by which

we

are to understand a che-

mical union of the elastic fluids with the char-

The results of their experiments on this

head, are so vague and contradictory, as to
leave little credit even to the fact of any such
1
made 1500 grains of charcoal
absorption.

coal.

red hot, then

pulverized

bladder

filled

nected

this

it,

and put

it

into

with a stopcock
to this a
with carbonic acid was con-

a Florence fiask

experiment was continued

for

week, and occasionally examined by weighing

the flask and its contents.
At first there ap-

ON CARBONE OR CHARCOAL.

236

peared an increase of weight of 6 or 7 grains,

from the acid mingling with the common air
in the flask, of less specific gravity j but the

succeeding increase was not more than 6

grains, and arose from the moisture which

permeated
continued

the
as

bladder

bladder

the

for

distended as at

first,

and

finally

upon examination was found to contain noYet carbonic acid

thing but atmospheric air.
is

stated to be the most

coal.

One

asserts

that the

absorbable by char-

of the authors above alluded to,

heat of boiling water

is

sufH-

cient to expel the greater part of the gases so

Now

absorbed.

this

is

certainly

not true, as

Allen and Pepys have shewn ; and most practical chemists know that no air is to be obtained

Hence

from moist charcoal below a red heat.

the weight acquired by fresh
is

in all probability

the moisture

sphere

and

which
it

is

to
it

we

charcoal,

be wholly ascribed to
absorbs from the atmo-

to the

water, and the union of

coal, that

made

decomposition of this
elements with char-

its

obtain such an abundance of

ot a red heat.
gases by the application
It

was the prevailing 0()inion some time

was an oxide of diamond^

nrro that charcoal

but Mr. Tennant, and more recently Messrs.

Allen and Pepys, have shewn that the same

is obtained from the
quantity of carbonic acid

ON CARBONE OR CHARCOAL.

237

combustion of the diamond as from that of an

equal weight of charcoal

we must

therefore

conclude, that the diamond and charcoal are

the same element in different states of aggregation.

Berthollet

contends that charcoal contains

hydrogen ; this doctrine is farther countenanced by some experiments of Berthollet jun.

in the Annales de Chimie, Feb, 1807; Mr.
Davy's experience seems also on the same side.
But their observations do not appear to me to
warrant any other conclusion than that

it

is

obtain and operate upon

charcoal entirely free from water.
Hydrogen
appears no more essential to charcoal than air

extremely

is

difficult to

essential to water.

From

the various combinations of charcoal

with other elements hereafter

the weight of
to

be

its

to

be mentioned,

ultimate particle

is

deduced

5, or perhaps 5.4, that of hydrogen being

denoted bv unity.
Charcoal requires a red heat, just visible bj'
day light, to burn it this corresponds to lOOQ"
:

of Fahrenheit nearly.

ON SULPHUR.

238

SECTION

5.

ON SULPHUR.
Sulphur or brimstone is an article well
it is an element
;
pretty generally disbut
is
abundant
in volcanic
most
seminated,

known

countries,

and

part of what

from

Italy

is

and

Sicily

minerals.

in certain

used in

this

great

is

country
imported
the rest is obtained from

the ores of copper, lead, iron, Src.

Sulphur

is

fused by a heat a

of boiling water.

It

is

above that

little

usually run into cylin-

sulphur.

and upon cooling becomes roU

In this case the rolls become highly

electrical

by

drical molds,

brittle,

friction

they

are

frequently falling in pieces

tact of the

warm

hand.

remarkably

by the con-

Its specific gravity is

1.98 or 1.99.

Sulphur

is

sublimed by a heat more than

sufficient to fuse

the

common

it ;

the sublimate constitutes

fioxvers of sulphur.

The

effects

of the different gradations of heat on sulphur

are somewhat remarkable.
It is fused at 226
or 228 oi Fahrenheit, into a thin fluid
gins

to

grow

thick,

darker,

about 350, and continues so

and
till

it

viscid

beat

600 or up-

wards, the fumes becoming gradually more

239

ON SULPHUR.
copious.

This viscid mass,

poured into wa-

if

continues to retain a degree of tenacity

after being cooled
but finally it becomes of a
ter,

hard and smooth texture, much

common

roll

less brittle

than

sulphur.

certainly known yet, sulphur

an
be
elementary substance. It
appears
enters into composition with various bodies ;

For any thing

to

and from a comparison of several compounds, I

deduce the weight of an atom of sulphur to be
nearly 14 times that of hydrogen

it is

possible

may be somewhat more or less, but I think

Mr,
the error of the above cannot exceed 2.
it

Davy seems

to conclude, from galvanic experiments on sulphur, that it contains oxygen j

this may be the case, from the
great weight of

the elementary particles

but

it

should contain

50 per cent, oxygen, or none at all.

Berthollet jun. seems to conclude that
phur contains hydrogen (Annal.
Feb. 1807).

Mr. Davy

{Philos. Transac. 1807).

sul-

de Chimie,

inclines to this

That some

idea

traces of

hydrogen may be discovered in sulphur there

cannot be much doubt. Dr. Thomson has
well observed the difficulty of obtaining sulphur free from sulphuric acid ; but if sulphuric acid be present, water must also be found,

and consequently hydrogen. A strong argument against the existence of hydrogen as an

ON PHOSPHORUS.

240

essential in sulphur,

is

low

derived from the consi-

heat of sulphur.
If this article contained 7 or 8 per cent, of
deration of the

specific

hydrogen, or 50 per cent, of oxygen, or as

much water, it would not have the low specific

heat of .19.

Sulphur burns in the open air at the temperature of 500 ; it unites with oxygen, hydrogen, the

alkalis, earths

and metals, forming a

which

great variety of interesting compounds,

will be considered in their respective places.

SECTION

6.

ON PHOSPHORUS.
Phosphorus is an article having much the
same appearance and consistency as white

wax.

It is

usually prepared from the bones of

animals, which contain one of

its

compounds,

phosphate of lime, by a laborious and complex

The bones are calcined in an open
process.
fire; when reduced to powder, sulphuric acid
diluted with

water

is

added

this

acid takes

part of the lime, and forms an insoluble compound, but detaches superphosphate of lime,

which

is

state.

water.

soluble in

evaporated, and the

The

solid

is

This solution

is

obtained in a glacial
reduced to powder, and

salt

is

ON PHOSPHORUS.
mixed with half
the mixture

and

weight of charcoal

then

put into an earthenware retort,

is

distilled

its

241

when

by a strong red heat,

the

phosphorus comes over, and is received in the

water into which the tube of the retort is
immersed.
is

Phosphorus

so

extremely

inflammable,

required to be preserved in water

It melts about blood heat ; and in close vesthat

sels

it

it

is

can be heated up

and of course
air,

to 550,

when

it

boils,

When

exposed to the
slow
combustion
but if
;
undergoes

it

distils.

100 or upwards, it is inflamed,

burns with rapidity and the emission of great
heat, accompanied with white fumes. It com-

heated to

hydrogen, sulphur and

other combustible bodies, and with several of
bines with oxygen,

the metals.

Phosphorus

when

is

soluble in expressed

alcohol, ether, &c.

oils, in

agitated with

common

gas, appear luminous

of the
it

oil

in

and other

these solutions,
air or

the dark

oxygenous
:

a portion

being rubbed upon ihe hand, makes

appear luminous.

The
nearly

atom

is

appear

gravity of phosphorus is 1.7

the weight of its ultimate particle or
about 9 times that of hydrogen, as will
specific

when

considered.

its

compounds with oxygen

are

OK THE METALS.

242

SECTION

7,

ON THE METALS.
The

metals at present

30

least to

number

in

known, amount

they form a

class

at

of

bodies which are remarkably distinguishable

from others in several particulars, as well as

from each other.

Gravity.

One

perties of metals

The

is

of the most striking protheir great

weight or

specific

them (excluding the

lately discovered metals, potasium and sodium)
weighs at least six times as much as water, and
gravity.

the heaviest of

lightest of

them 23 times

the supposition that

tuted

of solid

all

particles

as

On

much.

aggregates are constior atoms,

each sur-

rounded by an atmosphere of heat, it

rious and important enquiry, whether

is

a cu-

this

su-

perior specific gravity of the metals is occasioned by the greater specific gravity of their

individual solid particles, or from the greater

of them aggregated into a given vo-

number

lume, owing to some peculiar relation they

may have to heat, or their superior attraction
for

each other.

Upon examination

of the facts

exhibited by the metals, in their combinations

GENERAL PROPERTIES OF THE METALS. 243

with oxygen, sulphur, and the acids, it will
appear that the former of these two positions
is

the true one

namely, that the atoms of

metals are heavier, almost in the same ratio as

their specific gravities
will be found

thus an atom of lead

be 11 or 12 times heavier

to

than one of water, and

equally
that in

its

specific gravity is

must however be admitted,

metals and other solid bodies, as well
so.

It

as in gases, their specific

gravities are by

means exactly proportional

their atoms.

to

no

the weights of

further remarkable of the

It is

metals, that notwithstanding the great weight

of their ultimate particles relatively, those particles

possess no

more, but often

]ess,

heat

than particles of hydrogen, oxygen, or water. If

the heat surrounding a particle of water of any

temperature be denoted by 1, that surrounding

a particle of lead will be found only \ as much,

though the atom of lead

is

12 times the weight

apt to con-

One would be

of that of water.

clude from this circumstance, that an atom of

lead has less attractive

atom of water
follow

but

power
this

nay, the reverse

bable of the two

for,

for heat than

an

does not necessarily

is

perhaps more pro-

the absolute quantity

of heat around anv one particle

in a state

of

aggregation, depends greatly upon the force

of affinity, or the attraction of aggregation ;

244

GENERAL PROPERTIES OF THE METALS.

if this

be great, the heat

but if
;

squeezed out

is

partly expressed or
is

it

little,

retained^

though the attraction ot the particles for heat

An atom of water may
remains unaltered.

have the same attraction

lead has

but the latter

for heat that

may have

attraction of aggregation,

one of

a stronger

by which a quantity

expelled, and consequently less heat

retained by any aggregate of the particles.

of heat

is

Opacilij

and Lustre.

Metals are remark-

ably opake, or destitute of that property which

glass and some other bodies possess, of transmitting

When

light.

reduced to leaves as

thin as possible, such as gold and silver leaf,

they continue to obstruct the passage of light.

Though

the metallic atoms, with

their

atmo-

spheres of heat, are ncarlv the same size as the

atoms of water and their atmospheres, yet it

seems highly probable that the metallic atoms

abstracted from their atmospheres, are much
larger than those of water in like circumstances.

The

former,

conceive, are large

particles

with highly condensed atmospheres , the latter, arc small particles with more extensive
atmospheres, because
attraction for heat.

of their

Hence,

it

less

powerful

may be

supposed, the opacity of metals and their lustre

are occasioned.
great quantity of solid
matter and a high condensation of heat, are

GENERAL PROPERTIES OF THE METALS. 245

of light,
likely to obstruct the passage
reflect

and

to

it.

Malleability and Ductility.

Metals are

dis-

which many of
an eminent degree. By means

tinguished for these properties,

them

possess in

of a

hammer, they may be

flattened

and ex-

tended without losing their cohesion, especially

if assisted by heat.
Cylindrical rods of metal

can be drawn through holes of less diameter,

by which they are extended in length ; and
this successively

til!

they form very small wire.

These properties render them highly useful.

Metals become harder and denser by being
hammered.
Tenacity.

Metals exceed most other bodies

in their tenacity or force of

cohesion

however

other in this
they differ materially from each
iron wire of -rVth of an inch in
An
respect.

diameter, will support 5 or 6 hundred pounds.

Lead is only T-'^th part as strong, and not equal
to some sorts of wood.
Fusibility.

Metals are

fusible or capable of

being melted by heat ; but the temperatures

at which they melt are extremely different.

Most

of the medals possess a considerable

of them, as iron,
degree of hardness ; and some
are susceptible of a high degree of elasticity ;
of heat
they are mostly excellent conductors

and of

electricity.

'2'16

GENKRAL i'ROPEITlES OP THE METALS.

Metals combine

with various portions of

oxygen, and form metallic oxides ; they also

combine with sulphur, and form sidphurets ;
some of them with phosphorus, and form p}iosphiirets

with carbone or charcoal, and form

carburets^ &c. which will be treated of in their

respective places.

Metals

one with another, called

The

relative

of the metals

also

form compounds

alloys.

weights of the ultimate particles

may be investigated, as will be

shewn, from the metallic oxides, from the metallic

sulphurets, or
if

indeed,

from the metallic

salts

com-

the proportions of the several

pounds can be accurately ascertained, I have

no doubt they will all agree in assigning the

same

relative

weight

of the same metal.

knowledge,

to the

elementary particle

In the present state of our

the results approximate to each

other remarkably

well, especially

where the

compounds have been examined with

but the procare, and can be depended upon
portions of the elements in some of the metallic
different

oxides, sulphurets, and

salts,

have not yet been

found with any degree of precision.

The number

of metals hitherto discovered

is

30, including the two derived from the fixed

alkalis ; some of these may, perhaps, be improperly
scarce,

denominated

metals,

as

and have not been subjected

they
to so

are

much

GENERAL PROPERTIES OF THE METALS. 247

The

of these

greater part
experience as others.
metals have been discovered within the
century..

Thomson

Dr.

classes;

Malleable metals

1.

easily fusible metals

fusible metals

such as are

3.

2. Brittle

Brittle

and

known

in

and

difficultly

Refractory metals

4.

last

divides the metals into

that

combination,

is,

it
only
to
exbeen
found
not
practicable
yet
having
hibit them in a separate state.
They may be

arranged as follows

Malleable.

1.

1.

Gold.

2.

Platinum.

10.

3.

Silver.

11. Nickel.

9.

Copper.
Iron.

4.

Mercury.

12. Tin.

5.

Palladium.

13.

6.

Rhodium.

14. Zinc.

Lead.

15. Potasium.

7. Iridium.

Sodium.

8.

Osmium.

1.

Bismuth.

3.

Tellurium.

Antimony.

4.

Arsenic.

2.

2.

16.

Brittle

3. Brittle

and

and

easily fusible.

difficultly fused.

i.

Cobalt.

4.

Molybdenum.

2.

Manganese.
Chromium.

5.

Uranium.

6.

Tungsten,

3.

248 GENERAL PROPERTIES OF THE METALS.

4.

Refractory.

1.

Titanium.

3.

Tantalium.

2.

Columbium.

4.

Cerium.

To

which

last

class also

may

the supposed

metals from the earths be referred.

Tiic following Table exhibits the chief properties of the
metals in an absolute as well as comparative point of

view.

249

ON THE METALS.

More particular

This metal has been

Gold.
the

Properties of the Metals,

earliest times,

and

Its scarcity,

known from

and always highly valued.

several of

its

properties, con-

tribute to make it a proper medium of exchange, which is one of its chief uses. Eng-

gold consists of 1 1 parts byof

pure gold, and 1 part of copper (or
weight
This is usually spoken of as
silver) alloyed.

lish

standard

pure gold being 24 carats

use of the copper is to render the

being 22 carats

The

fine.

alloy harder,

fine,

and consequently more durable

than pure gold.

Gold

lustre in all
Its

splendid yellow colour and

states of the atmosphere unchanged.

retains

when pure, and hamor

19.3,
more; but that of the same

specific

mered,

is

its

gravity,

gold, in other circumstances,

The

may be

from 17.1

to 17.9, accordingly as

it is

with copper, copper and silver, or

well as from other circumstances.
all
it

alloyed

silver, as

It excels

other metals in malleability and ductility ;

may be beaten out so thin, that a leaf weigh-

ing
in

19.2.

of standard gold varies

specific gravity

grain, shall cover

which case the

an inch

leaf

in thickness

is

50 or 60 square inches,
only -^-y ^'aoa th part of

but

it is

capable of be-

250

GOLD.

PLATINA.

ing reduced to y\th of that thickness on silver

Gold melts at 32" of AVedgwood's pywire.
rometer ; that is, a red heat, but one greatly

what mav be obtained bv

inferior to

forge

when

weeks without

state for several

terial

There

weight.

may continue

it

fused,

is

a smith's
in

that

losing any

gold combines with oxygen, sulphur,

but those compounds are
;

and

phosphorus

cultly obtained.

the

It

diffi-

combines with most of

and forms

metals,

ma-

reason to believe that

alloys of various de-

scriptions.

The weight

of an atom of gold

is

not easily

ascertained, because of the uncertainty in the

proportions of the elements forming the com-

which

into

pounds

it

enters.

It is

probably

not less than 140, nor more than 200 times the

weight of an atom of hydrogen.

Platina. This metal has not been found

any where but

state,

it

in

South America.

In

its

crude

consists of small flattened grains of a

metallic lustre, and a grey-while colour.

ore

is

found

of which platina

The

This

be an alloy of several metals,

to

is

usually the most abundant.

grains are dissolved in nitro-muriatic acid,

except a black matter which subsides

the

decanted, and a solution of

clear liquor

is

ammoniac

is

dropped into

pitate falls

this

is

it

sal

a yellow preci-

heated to redness, and the

PLATINA.

251

powder is platina nearly pure. To obtain it

more pure, the process must i)e repeated

SI ill

this

upon

When these grains are

a thin plate of platina, heated

platina.
in

wrapped up

and cautiously hammered, they

unite and form a solid mass of malleable metal.
to

redness,

PlaUna thus obtained,

is

what exceeds
it

exceeds

of a white colour,

In hardness

rather inferior to silver.

it

some-

but in specific gravity

;
other bodies hitherto known.

silver

all

Specimens of it, when hammered, have been

found of the specific gravity of 23 or upwards.
It

nearly as ductile

is

and malleable

fuse

it

welds
in

to

when heated

but

in the

same manner

to

whiteness,

as iron.

any degree altered by exposure

No

water.

ordinary

capable of burning

as gold.

most metals

It requires a greater heat than

artificial

or uniting

It is

to
it

not

lo the air or

heat seems

to oxygen.
be
effected
oxidizement, however, may
and
of
means
galvanism
electricity, and by
by
it

it

Its

exposing

it

the heat excited by the

to

com-

bustion of hydrogen and charcoal in oxygenous

Platina has been united to phosphorus,
gas.

but not to hydrogen, carbone, or sulphur. It

unites with most of the metals to form alloys.

The weight

of the ultimate particle of plathe data we

tina cannot be ascertained from

have

at

present

from

its

combination with

252

SILVER.
it

oxygen,

should seem to be about 100

but,

judging from its great specific gravity, one

would be inclined to think it must be more.

Indeed the proportion of oxygen in the oxides

of platina cannot be considered as ascertained.
Platina

poses

in

is

chiefly

used

consequence of

chemical pur-

for
its

infusibility,

and

and
difficulty of oxidizing it, crucibles
other utensils are made of it, in preference to
every other metal. Platina wires are extremely

the

useful

in

electric

and galvanic researches,

for

like reasons.

Silver.
of the

This metal

is

found

in various parts

world, and in various combinations

but the greatest quantity

is

AmeThe
known.

derived from

Its uses are generally

speciHc gravity of melted silver is 10.474 ; after
being hammered, 10.511. English standard

rica.

silver,

10.2.

Pure

silver

-j^^

is

copper, simply fused, is

extremely malleable and

but inferior in these respects to gold.

It is not
a moderately red heat.
at
melts

ductile
It

containing

oxidized by exposure to the air, but is tarnished or loses its lustre, which is occasioned

by the sulphureous vapours

It

floating in the air.

unites with sulphur in a moderate heat

-,

and may be oxidized by means of galvanism

and electricity ; it burns with a green flame.

MERCURY.
Silver
alloys

253

combines with phosphorus, and forms

with most of the metals.

The relative weight of an atom of silver

admits of a pretty accurate approximation,
from the known proportions of certain compounds

into

which

silver enters

namely, the

oxides and sulphuret of silver, and the salts of

all of these nearly concur in detersilver
:

mining the weis:ht

100

an atom of

ot

be

silver to

times that of hydrogen.

Mercury.
known under

This

which

metal,

name

the

been long discovered and in use.

and

more

brilliant, reflecting

surface, perhaps, than

specific gravity

common

It

has

white

is

from

light

its

any other metal.

13.58.

is

also

is

of quicksilvey\

It

is

fluid

Its

at

temperature of the atmosphere

the

but

temperature
congeals when reduced
It contracts suddenly at
39 Fahrenheit.
of
it

to

the

the point of congelation, contrary to

water

exhibited in

cury becomes malleable

solid

state

When

are

heated

not

what

is

when congealed, mer;

but

easily

its

to

qualities in a

be ascertained.

in the operi air to the

tempera-

ture of 660, or thereabouts, according to the

equidifferentia!
tils

rapidly

vapour
ratures.

scale,

like

mercury

boils,

water, however,

it

and

dis-

rises in

degree at all tempePure liquid mercury has no taste nor

in a greater or less

PALLADIUM. RHODIUM.

254
smell

it

may be taken

without

internally,

producing any remarkable effect on the human

It can be united with oxygen, sulphur,
body.

and phosphorus and it forms alloys, or, as

they are more commonly called, qmalgams^
with most of the metals.
;

The weight of an atom of mercury is determinable from its oxides, its sulphuret, and the
various salts which

a comparison of

all

it

forms with acids

which,

it

seems

to

from

be about

From any

167 times the weight of hydrogen.

thing certainly known, the mercurial atom is

heavier than any other ; though there are two

which exceed

or three metals

it

in

specific

gravity.

Palladium.

This metal was discovered a

few years ago in crude platina, by Dr. Wollaston, of which an account may be seen in the
Philos. Transact,

for

1804.

Jt

is

white

metal, resembling platina

appearance, but
is much harder
it is
one
half of the speonly
in

cific

to

gravity of platina.

fuse

it,

and

is

It requires great

difficultly oxidized.

heat

Palla-

dium combines with oxygen and sulphur, and

forms alloys with several of the metals.
But
we have not yet sufficient data to determine
the weight of

its

ultimate particles.

Rhodium. This metal has been discovered

still more
recently than the last in crude pla-

IRIDIUM AND OSMIUM.

tina,

by Dr. Wollaston.

constitutes about

It

^liyth part of crude platiiia.

255

It

possesses nearly
the same colour and specific gravity as palladium, and agrees with it in other paiticulars ;

but in certain respects they appear to possess

essentially distinct properties.-^The weight of
the ultimate particles of this metal cannot yet
be ascertained.

Iridium and Osmium.

These two metals

lately discovered by Mr. Smithscn Tennant to exist in crude platina. When crude

were

there

dissolved

is

platina

remains

in

nitro-muriatic

of

quantity

black

acid,

shining

powder contains two metals,

one of which Mr. Tennant called Iridium^

powder

this,

from the variety of colours which its solutions

the other Osmhmiy from a peculiar

exhibited

smell which accompanies

its

oxides.

Iridium

a white metal, infusible as platina, diflicultly

it seems to combine with
soluble in any acid
is

oxygen, and
metals.

lour

to

form alloys with some of the

Osmium

has a dark grey or blue coiii the

air, it combines

when heated

with oxyg-en, and the oxide

is

volatile, posses-

In a close vessel,
sing the characterrstic smell.
it resists
any heat that has been applied ; it
also resists the action of acids, but unites with

potash.

It

amalgamates with mercury.

The

256

COPPER.

IRON.

welfrhts of the atoms of these

two metals

are

unknown.
Copper.
It is

This metal has been long known.

of a fine red colour

and nauseous.
8.6 to 8.9.

be drawn

its

Its specific
It

taste

is

styptic

gravity varies from

possesses great ductility, can

and is ca-

into wire as fine as hair,

thin leaves.
pable of being beaten into very
It is fused in a temperature higher than silver,

and lower than gold, about 27 of Wedgwood's thermometer.

Copper unites with
and forms
oxygen, sulphur, and phosphorus ;
alloys

v.'ith

several other metals.

The weight of the ultimate particle of copwith considerable preper, may be ascertained
from the proportions in which it is
found combined with oxygen, sulphur, and
cision,

phosphorus ; as well as from its combinations

with the acids. From a comparison of these,
its

weight seems to be nearly 56 times that of

hydrogen.
Iron. This metal, the most useful
with, has been

we

are

long known.

It

acquainted
seerfis to be found almost in every coun'ry,
and in a great variety of combinations. Its
ores require great heat to expel the foreign
matters, and to melt the iron, which is first

obtained in masses or pigs, called cast iron

IRON.
after

which

undergoes a laborious operation,

it

the object of which

and oxygen which

render

may

carbone

yet contain, and to

'Ibis consists
chiefly in

when heated

the i/on

hammering

to expel the

is

it

maHeable.

it

257

almost

to

fusion.

Iron

is

of a high

susceptible

very hard

it

7.6 to 7.8.

j)olish

It is

distinguishable from
in

metals, by possessing,

or loadstone itself

with certain modifications.

malleability as

it

all

is

is

from
other

high degree,

deed almost exclusively) magnetical

The magnet

it

varies in specific gravity

(in-

attraction.

chiefly iron,

Iron increases in

increases in temperature

its

surpassed by few other metals, as

ductility
its wire admits of extension till it becomes as
is

fine as

of

its

human

hair:

its

which

tenacity,

most valuable properties,

is

one

not equalled

is

by any other body we

are acquainted ^with.

Pure malleable

estimated

158 of

iron

Wedgwood

is

to

melt at

whereas cast iron melts

about 130.
Iron

is

distinguished

with oxygen,
phorus

it

carbone,

forms alloys

for its

combinations

and phoswith several of the

sulphur,

much importance.
I'he weight of an atom of iron may be
found from almost any of its numerous com-

metals, but they are not of

binations, either

its

oxides,

its

sulphurets, or

258
any

NICKEL.
of the salts

which

TIN.

forms with acids

it

all

same weight
namely, 50 times the weight of an

these will be found to give the

nearly

atom of hydrogen.
Nickel. The ore from which
obtained,

found

is

in

Germany

this
:

metal

it

contains several other metals, from which

to

difficult

extract

tolerable purity.

be obtained,

the

in a

nickel

Nickel,

when pure

it

state

as

is

of

can

it

of a silver white colour

is

is

usually

its

and when forged

It is malleable, both hot and cold,
p.. 666.
and may be beaten into a leaf of -j.^-^ of an inch

in thickness.

fuse

as

Jt

it.

much

magnet

is

gravity

specific

is

very great heat

attracted by the

as iron,
itself.

8.279,

is

required to

magnet nearly

and may be converted into a

combines with oxygen, sul-

It

phur, and phosphorus

and may be alloyed

with certain other metals.

The weight of its atom can scarcely yet be

determined, for want of a more accurate knowledge of the compounds into which it enters
perhaps it will be found to weigh about 25, or
:

else

double that number, 50.

Tin.
though
tively.

it

This metal has been long known,

is found but in few
places compara-

Cornwall

is

the

only part of Great

Britain where this metal abounds

mines

and

are the most celebrated in Europe.

its

tin

Tin

LEAD.
is

259

a white metal, nearly resembling silver ; its

It is malleable
is about 7.3.

specific gravity

in a high degree
in ductility

and

but inferior to

tenacity.

many metals

It melts at the

low

When

ex-

temperature of 440 Fahrenheit.

posed

to

the air,

comes grey

be melted

its

and

this

loses

it

its

and be-

lustre,

more rapidly the case if it

becomes grey,
Tin combines
to yellow.

is

surface then soon

in time passes

with oxygen, salphur, and phosphorus, and

forms allovs with most of the metals.

The weight

of an atom of tin

may be

de-

rived from the proportion of the elements in

the oxides, the sulphuret or the phosphuret of

tin ; or from the salts of tin.
It is probably

about 50 times heavier than hydrogen.

This metal seems to have
Lead.

known

in early times

colour, bright
loses

its

lustre

when

it

been

of a blueish white

recently melted, but soon

when exposed

scarcely any taste or smell

deadly poison

is

when taken

to the air.

It

has

but operates as a

internally

it

seems

benumb

the vital functions, and to

destroy
the nervous sensibility, inducing a paralysis,

to

and

finally

death.

The

specific

gravity

of

whether hammered or not, is about 11.3

or 11.4 J it is n)alleable, and may be reduced

lead,

to thin plates.
heit.

It

It

melts about 610 of Fahren-

combines with oxygen, sulphur, and

260

POTASIUM.

ZINC,

phosphorus, and forms alloys with most other

melals.

The

ultimate particle of lead, as deduced

from a comparison of its oxides, suiphuret, and

the salts in which it is found, I estimate at 95
times that of hydrogen.

Zinc

The

ores of this metal are not rare

but the metal has not been extracted from them

in a pure state, at least in Britain, much more
than half a century. Zinc is a brilliant white
Its specific

metal, inclining to blue.

is

from 6.9

to 7 2.

as a brittle metal

It
;

was

but

Sylvester, of Sheffield,

till

lately

gravity

considered

Hobson and

Messrs.

have discovered that

between the temperature of 210 and 300,

zinc yields to the hammer, may be laminated,
wire drawn, &c. and that after being thus
wrought, it continues soft and flexible. It
melts about 680, and above that temperature
Zinc soon loses its
evaporates considerably.

and grows grey but in wabecomes black, and hydrogen gas is

Zinc combines with oxygen ; and
emitted.

lustre in the air,

ter

it

either

it

or

its

oxides combine with sulphur

and phosphorus. It fbrms alloys with most of

the metals, some of which are very useful.

The atom of zinc weighs

much as hydrogen.
PoTAsiuM.

We

nearly 56 times as

are principally indebted to

261

POTASIUM.

Mr. Davy

for

our knowledge of

this

metal

its

oxide, potash, or the fixed vegetable alkali,

is universally known j but the decomposition

of the oxide

is

a recent discovery.

To

obtain

the metal, a small piece (30 or 40 grains) of

been exposed
pure caustic potash, which has

few moments, to acquire a slight

sufficient to render it a
of
moisture,
deigree
conductor of galvanism, is to be exposed to
to the air a

the action of a powerful galvanic battery j by

of the potash is exits
operation, the oxygen
and
fluid
metallic
globules of the appelled,
This
obtained.
are
of
mercury,
pearance

metal has also been produced by Messrs.

Gay

Lussac and Thenard, by exposing potash to

some potasium
iron turnings in a white heat
:

was obtained, and an alloy of potasium and

Mr. Davy has made an experiment
iron.
with a similar result and found that a large
at the same time
quantity of hydrogen gas is
;

given out.
ash as a

This fact seems

compound

to point out pot-

of potasium

and not of potasium and oxygen

chemists argue that potasium

hydrogen and potash

is

but, as

and water,
the French

a compound of
Mr. Davy pro-

their argument amounts to this,

perly observes,
is a
that
compound of hydrogen and

potasium

an

unknown

base,

which compound united

oxygen forms potash.

to

This subject must be

262

SODIUM.
to

left

future experience.

temperature of 32,

Potasium,
and

solid

is

the

at

brittle

and

at
fragments exhibit a crystallized texture
is
and
it
soft
malleable
at
it
is
im50,
60",
;

its

at 100%
and small globules unite

perfectly fluid

be

may
ness.

distilled

by

as

a heat

would seem

notion of

its

perfectly fluid,
in

mercury,

ft

to red-

approaching
this
only 6

Its specific gravity

cumstance

is

it

is

to

cir-

countenance the
Potasium

containing hydrogen.

combines with oxygen, sulphur, and phosphorus and it seems to form alloys with many
;

of fhe metals.

The weight
from

its

of an atom of potasium appears

combination with oxygen to be 35

times that of hydrogen.

Mr. Davy obtained

Sodium.
from the

fixed

mineral alkali,

means of galvanism,
sium.
is

Sodium,

the

metal

same way

common

by

as pota-

temperature,

a solid, white melal, having the appearance

of silver

much
Its

it
-,

softer

specific

being 9348.
is

at

in the

this

or soda,

is
exceedingly malleable, and
than other metallic substances.

gravity
It

is

rather less than water,

begins to melt at 120% and

perfectly fluid at

180^.

It

combines with

oxygen, sulphur, and phosphorus

and forms

alloys with the metals.

The weight of an atom of sodium, as de-

ANTIMONY.

BISMUTH.

duced from

263

combination with oxyj^en.

its

is

nearly 21 times ihe weight of hydrogen.

much more than

of a reddish while colour

by exposure
about 9.8 it

to
is

stroke of a

as a
Its

Germany. Bismuth

ores are found chiefly in

is

known

a century.

This has not been

Bismuth.
distinct metal

the air

loses

it

>

its

its

lustre

specific gravity

is

hard, but breaks with a smart

hammer

it

melts about 480.

In

a blue

a strong red heat, bismurh burns

flame, and emits yellow fumes.

w-ith

with oxygen and sulphur, and

with most of the metals.

forms alloys

The weight

It

combines

of an atom of bismuth,

may be

oxides and sulphuret it seems

to be about 68 times the weight of an atom of
derived from

its

hydrogen.

Some

Antimony.
were known

of the ores ot this metal

to the ancients

but the metal

in-

a pure state, has not been known more than

300 years.
Antimony has a greyish white

and considerable

colour,
cific

gravity

is

6.7 or 6.8

brilliancy
;

it

melts about 810" Fahrenheit

is

it

phorus

and

it

its

spe;

it

loses its lustre

time by exposure to the air.

combines with oxygen, sulphur,
in

very brittle

Antimony
and phos-

forms alloys with most of the

other metals.

The weight

of an atom of antimony,

is

2G4

COBALT.

ARSENIC.

determinable from

its

compounds with oxygen

to be 40 times the

and sulphur, and seems

weight of hydrogen.
Arsenic. Certain compounds of Arsenic
It seems to
were known to the ancients.

known

have been

more

a distinct character for

in

than a century.

Arsenic has a blueish

grey colour, and considerable

brilliancy,

which

soon loses by exposure to the air ; its specific

is stated to be 8.5 ; its
fusing point has
not been ascertained, by reason of its great

it

gravity

volatility

has been heated to 350", at which

it

sublimes quickly, and exhibits

it

temperature

a strong smell resembling that of

is

characteristic of

this

metal.

garlic,
It

which

combines

with oxygen, forming one of the most virulent

poisons ; also with hydrogen, sulphur, and

phosphorus

and

it

forms alloys with most of

the metals.

The weight
from

its

of an atom of arsenic, appears

compounds to be 42 times that of

hydrogen.

Cobalt.

The

ore of this metal has been

long used to tinge glass blue but it was not

till the last
century that a peculiar metal was
;

extracted from

it.

inclining to red
specific gravity

is

melts at 180" of

Cobalt
it

is

of a grey colour,

has not

much

about 7.8;

Wedgwood

it

it

is
is

lustre

brittle;

its
it

attracted

2&5

MANGANESE.
by the magnet, and

is itself

made magnetic, according

capable of being
to

Wenzel.

Co-r

combines with oxygen, sulphur, and phosphorus; and it forms alloys with most of the
bait

metals, but they are of

The weight

little

importance.

atom of cobalt cannot be

of an

accurately obtained from the data we have at

present ; it is probably 50 or 60 times that of

hydrogen.

The dark brown mineral

known and used

Manganese.

called manganese, has been

perhaps more than

but the meral which now goes by

in the glass manufactories,

a century

the same name, was not discovered

40

years ago

in

it

fact,

is

till

not

yet

about

much

known, being obtained with difficulty, and by

a great heat. 1 he metal is of a greyish white
its specific
colour, and considerable brilliancy
:

6.85 or 7

gravity

is

160 of

Wedgwood

it

is

posed

it

is

brittle,

when reduced

attracted by the magnet,

to

be owing

and melts

to

the

to

at

powder,

which

is
supof
iron.
presence

oxygen from the air, beand finally black. It is

brown,
coming grey,
with sulphur and
combined
of
being
capable

Manganese

attracts

phosphorus

and

it

forms alloys with some of

much ex-

the metals, but they have not been

amined.

The weight

of an atom of manganese, as

266 CHROMIUM. URANIUM. MOLYBDENUM.

determined from

40 times

oxides, seems to be about

its

that of hydrogen.

Chromium.

This metal, united

so as to constitute an acid,

The pure

lead ore of Siberia.

obtained,

found

is

white inclining

is

to

to

oxygen

in the

Tcd

metal being

yellow

it

is

It
brittle, and requires a great heat to fuse it.
combines with oxygen. The other properties

of this metal are not yet known.

Its atom,
J 2
of hyabout
times
that
perhaps, weighs

drogen.

Uranium.
Klaproth,
onv.

only

It is

in

This metal was discovered by

mineral found in Sax-

in 1789, in a

obtained with some

small quantities

difficulty,

has,

it

and

therefore,

been examined but by few. The colour of

it
has considerable
uranium is iron grey
;

lustre
is

it

yields to the

8.1, according

to

its

Klaproth

Uranium

to Bucholz.

file

probably with sulphur

specific gravity

9.0,

according

unites with oxygen,

:

its

and

alloys have not been

ascertained.

The weight

of an atom of this metal,

is

bably about 60 times that of hydrogen.

^Molybdenum. The ore from which
metal

dcna

is

reduce

obtained

but
it

is

pro-

this

a sulphuret, called molijb-

requires an extraordinary heat to

the metal has not hitherto been

it

obtained, except in small grains.

It

is

of a

TITANIUM.

TUNGSTEN.

yellowish white colour ;

7.4, according to Hielm

its

267

specific gravity is

but 8.6, according

combines with oxygen, suland

phosphorus ; and it forms alloys
phur,
with several of the metals.

to Bucholz.

It

The atom of molybdenum, probably weighs

about 60 times that of hydrogen.
Tungsten. This metal is one of those recently
discovered.

It

is

difficultly

an excessive heat

for

greyish white colour,

liancy

its

its

obtained, requiring
It is of a
fusion.

and considerable

specific gravity

is

17.2 or 17.6

bril;

it

is

very hard, being scarcely impressed with a file.

It combines with oxygen, sulphur, and
phos-

phorus

We

and

forms alloys with other metals.

sufficient data, from which to

it

have not

determine the weight of an atom of tungsten

as far as we can judge from its oxides, its
:

weight must be 55 times that of hydrogen, or

upwards.

Titanium.
covered.
colour

It
it

is

has

This metal has been lately dissaid ro be of a dark

copper

much

brilliancy,

is

brittle,

and

possesses in small scales a considerable

degree

of elasticity.

It

It

is

highly infusible.

nishes on exposure to the air

heat,

and then becomes

is

blueish.

tar-

oxidized by
It

unites

with phosphorus, and has been alloyed with

iron.

It

detonates

when thrown

into red hot

C68 COLUMBIUM.

tANTALlUM. CERIUM.

The atom of titanium probably weighs

nitre.
about 40 or 50 times that of hydrogen.
CoLUiMBiuM. In 1802, Mr. Hatcheft dis-

new

covered a
taining

iron,

succeed

in

metallic acid in an ore con-

from

He

America.

reducing the acid

from the phenomena

room to doubt of

little

to a

not

did

metal

but,

it

exhibited, there

was

its

containing a peculiar

metal, which he called columbium.

Tantalium.

mist.

This metal has

certain minerals,

of

this

been

lately

M.

Ekeberg, a Swedish chewhite powder is extracted from

discovered by

which appears

metal.

When

this

to be an

oxide

white oxide

is

strongly heated along with charcoal, in a crucible, a metallic button is formed, of external
lustre, but

The

black and void of lustre within.

into the state of a white

acids again convert

it

oxide, which does

not alter

its

colour

this

metal

when

heated to redness.

Cerium.

The oxide

of

tained from a Swedish mineral.

No

is

ob-

one has

yet succeeded completely in reducing this ox-

ide

so

even

its

that

the properties of the metal,

existence, are yet

unknown.

and

But the

earth or supposed oxide, is found to have properties similar to those of other oxides. These,

of course, belong to a future article, the metallic oxides.

269

CHAP.

V.

COMPOUNDS OF TWO ELEMENTS.

xN order to understand
be

signified

&c.

tlie

Some

what

is

intended to

by binary and ternary compounds,

is referred to
page 213 and seq.

reader

persons are used to denominate

all

com-

pounds, where only two elements can be

covered,
stance,

binary

compounds

as nitrous

acid, 8ic. in all of

and oxygen.
our views to

But

such,

for

disin-

gas,

nitrous oxide, nitric

which we

find only azote

more

consistent with

it

is

term binary^

restrict the

to signify

two atoms ;
signify three atoms,
be elementary or
atoms
those
whether
&c.
ternary^ to

otherwise

that

is,

whether they are the atoms

of undecompounded bodies, as hydrogen and

as
oxygen, or the atoms of compound bodies,
and
ammonia.
water

In each of the following sections, we shall

consider the compounds of some two of the

elementary or undecompounded bodies ; becomginning each section with the binary

pounds, then proceeding to the ternary com-

OXYGEN WITH HYDROGEN.

270

pounds, or

those

at least to

three atoms, though they

sense

we

complex

use the term

-,

which

may be

and

so

consist

of

biliary in the

on

to the

more

forms.

This chapter will comprehend all the aeriform bodies that have not been considered in
the

last,

several of the acids, the alkalies, the

earths, and the metallic oxides, sulphurets,

carburets, and phosphurets.

In treating of these articles, I intend to

adopt the most common names for them ; but
it

will

be obvious, that

if

the doctrine herein

contained be established, a renovation of the

chemical nomenclature will in some cases be

expedient.

SECTION

1.

OXYGEN WITFI HYDROGEN.

I

Water,

This liquid, the most useful and abundant

is now well known both
by

of any in nature,
analytic

pound

and synthetic methods,

of the

to be a comtwo elements, oxygen and hy-

drogen.

Canton has proved that water

compressible.

The expansive

is

in degree

effect

of heat

WATER.

271

on water has been already pointed out. The

weight of a cubic foot of water is very near
1000 ounces avoirdupoise. This fluid is com-

monly taken

as the standard for

specific gravities of bodies,

its

comparing the
weight being

denoted by unity.
Distilled water
rain

water

is the
purest ; next to that,
then river water ; and, lastly,

spring water.
By purity in this place, is
meant freedom from any foreign body in a

of solution

but in regard to transpa;

agreeable taste, spring water
Pure water has
generally excels the others.
the quality we call soft
spring and other im-

state

rency, and an

>

water has the quality we call hard.

Every one knows the great difference of waters in these respects ; yet it is seldom that the
pure

hardest spring water contains so

part of
tion.

much as T-p-^jTyth

weight of any foreign body

its

The

substances held

in solu-

in solution are usu-

carbonate and sulphate of lime.

Water usually contains about 2 per cent, of

ally

its

bulk of

common

forced into

it

air.

This

air is originally

by the pressure of the atmo-

no other
sphere ; and can be expelled again
'I his
that
pressure.
way than by removing

may be done by an air-pump

or

it

may

in

the water
great part be effected by subjecting
to ebullition, in which case steam takes the

OXYGEN WITH HYDROGEN.

272

place of the incumbent

air,

and

its

orcssure

is

restrain the dilatation

of

the air in the water, which of course makes

its

found inadequate to

But

escape.

it is

difficult to

either of those

by

from

common

all

expel

operations.

spring water, after

the air

Air expelled
losing 5 or 10

percent, of carbonic acid, consists of 38 per

cent, of oxygen and 62 of azote.

Water

is

for

distinguished

into

entering

To some

combination with other bodies.

it

unites in a small definite

proportion, consti-

tuting a solid
its

This

compound.

combination with the fixed

and with a great number of

the case in

is

alkalies, lime,

salts

the

com-

pounds are either dry powders or crystals.

Such compounds have received the name of
But when the water

hydrates.

place, which

is

the

compound
when common
water.

is

in excess,

combination seems to take

different sort of

called solution.
is

liquid

In this case,

and transparent

as

salt or sugar are dissolved in

When

any body is thus dissolved in

water,
may be uniformly diffused through
any larger quantity of that liquid, and seems to
it

continue so, without manifesting any tendency

to subside, as far as

is

known.

In 1781, the composition and decomposition

of water were ascertained ; the former by

Watt and Cavendish, and

the latter

by Lavoi-

WATER.
sier

273

The

and Mcusnier.

first

was made by Monge,

experiment on

on a

of water

the composition

large scale,

he procured
lb. of water, by the combustion of
about
hydrogen gas, and noted the quantities of hyin

1783

-l-

drogen and oxygen gas which had disappeared.

The second experiment was made by Le
Fevre de Gineau,

waUT

in

1788

he obtained about

The third
2^
was made by Fourcroy, Vauquelin, and Seguin, in 1790, in which more than a pound
of

lbs.

in the

same way.

The

of water was obtained.

was, that 85 parts

general result

by weight of oxygen unite

to 15 of hydrogen to form 100 parts of water.

Experiments

to ascertain the proportion of

the elements arising from the

and

decomposition

made by Le Fevre de Gineau

of water, were

Lavoisier,
by transmitting steam
tube
a
red
hot
containing a quantity
through
of soft iron wire ; the oxygen of the water

by

combined with the

was

iron,

collected in gas.

or 85 parts of oxygen and

found as

in the

and the hydrogen

The same
1

5 of

proportion,

hydrogen, were

composition.

The Dutch chemists, Dieman andTroostwyk,

first

succeeded

in

in 1789.
tricity,

readily

water

is

decomposing water by

The

effect

is

elec-

now produced

The composition of
by galvanism.
and
easily
elegantly shewn, by means

OXYGEN WITH HYDROGEN.

274

of Volta's eudiometer,
greatest importance
clastic

It

fluids.

an instrument of the

researches CQncerning
consists of a strong
grain

duated glass tube, into which a wire

is

metically sealed,' or strongly cemented

ther detached

wire

is

-,

her-

ano-

pushed up the tube,

nearly to meet the former, so that an electric

spark or shock can be sent from one wire to

the other through any portion of gas, or mix-

water or mercury.
tube being immersed in a
explosion takes place, no

ture of gases, confined by

The end of the

liquid, when an

communication with the external

so that the change produced

is

air

can arise

capable of being

ascertained.

The component
established,

it

parts of water being clearly

becomes of importance

termine with as

much

the relative weights of the

stituting that

analysis

and

liquid.

synthesis,

to de-

precision as possible,

two elements con-

The mean

results

of

have given 85 parts of

oxygen and 15 of hydrogen, which are geneIn this estimate, I think, the
rally adopted.
There is
quantity of hydrogen is overrated.
an excellent memoir in the 53d vol. of the

Annal. de Chemie, 1805, by Humboltd and

Gay-Lussac, on the proportion of oxygen and

hydrogen
that the

in

water.

quantity

They make

of aqueous

it

appear,

vapour which

WATER.

275

elastic fluids usually contain, will so far influ-

ence the weight of hydrogen gas, as to change

the more accurate result of Fourcroy, &c. of
85.7 oxygen and 14.3 hydrogen, to 87.4 oxygen and 12.6 hydrogen. Their reasoning ap-

me

pears to

perfectly satisfactory.

lation of these

There

nearly.

seems

two numbers
is

The

re-

that of 7 to

is

put this matter beyond doubt.

to

another consideration which

Jn

Volta's eudiometer, Iwo measures of hydrogen

require just one of

Now,

oxygen

to saturate them.

the accurate experiments of Cavendish

and Lavoisier, have shewn that oxygen

is

nearly 14 times the weight of hydrogen ; the

exact coincidence of this with the conclusion

above deduced,

a sufficient confirmation.

however, any one chooses

If,

common
lation of
1

is

this

estimate of 85 to

to

adopt the

15, then the re-

oxygen to hydrogen will be as .^^ to

would require the weight of oxy-

genous gas to be only Uptimes the weight of

hydrogen.

The

absolute weights of oxygen and

hywater being determined, the relative
drogen
weights of their atoms may be investigated.
in

As

only

drogen

is

compound of oxygen and hycertainly known, it is agreeable to

ojie

the 1st rule, page 214, that water should be

concluded a binary compound,

or,

one atom

OXYGEN WITH HYDROGEN.

276

of oxygen unites with one of hydrogen to form

one of water. Hence, the relative weights of
the atoms of

oxygen and hydrogen

The above

conclusion

is

are 7 to 1.

strongly corrobo-

rated by other considerations.

Whatever may

be the proportions in which oxygen and hydrogen are mixed, whether 20 measures of
oxygen to 2 of hydrogen, or 20 of hydrogen
to 2 of oxygen,

still

when an

electric spark is

passed, water is formed by the union of 2 measures of hydrogen with 1 of oxygen, and the
surplus gas

is

unchanged.

Again, when wa-

decomposed by electricity, or by other

agents, no other elements than oxygen and hyter is

drogen are obtained. Besides, all the other

compounds into which those two elements
enter, will in the sequel

be found

to support

the same conclusion.

After

all,

it

must be allowed

to

be

po'ssible

may be a ternary compound. In

if
two atoms of hydrogen unite to
case,

that water
this

one of oxygen, then an atom of oxygen must

weigh 14 times as much as one of hydrogen 3
if two atoms of oxygen unite to one of hydrogen, then an atom of oxygen must weigh
times one of hydrogen.

3|-

FLUORIC ACID,

27?

2. Fluoric Acid.

The

acid obtained from the fluor spar,

abounds

in

is

which

one of those the base

Derbyshire,
of which has not yet been clearly ascertained

partly
it

have ventured to place

compounds of hydrogen with

by experience,
the

among

oxygen, and

to

rank

plicity of constitution

compound

and

but, guided partly by theoretic reasoning,

I

it

next to water
it

is,

sim-

in

as I conceive, a

of two atoms of oxygen with one

of hydrogen.
Scheele and

Priestley

have distinguished

themselves in investigating the properties of

and Dr. Henry and Mr. Davy have
this acid
;

attempted to decompose it. The acid may be

obtained by taking a quantity of pounded fluor
it into a
gas bottle
spar (fluate of lime), putting
of
same
the
about
with
sulphuric acid
weight

undiluted, and then applying a heat, so as to

raise the temperature to about the boiling heat

The acid is produced in the gaseous

be received over mercury but
must
and
form,
if it is intended to condense it in water, then
of water.

the gas, as

it is

generated,

receiver containing

may be

some water

sent into a

at the

bottom

the water will rapidly absorb the gas, and increase in density.

OXYGEN WITH HYDROGEN.

278

Some

of the* properties of this acid are,

the elastic state

it

and of animal

life

has a pungent smell,

and not less suf-

it

somewhat

like muriatic acid,

focating

its

specific gravity has not

have made,

it

in glass vessels

that case a superfluate of silica

dry

flask,

been ac-

but from some experiments

seems to be extremely heavy

curately obtained

when obtained

In

1.

destructive of combustion,

is

in fact,
:

it is

in

Into a clean

I sent a quantity of fluoric acid gas

some time, the mixture of common air

and acid was corked, and the flask weighed
after

it

had acquired 12

The flask was next

how much would be

grains.

inverted in water, to see

absorbed, and that quantity was taken for the

acid gas.
The capacity of the flask was 26

cubic inches, containing originally 8.2 grains

of common air; 12 cubic inches of acid gas

had
flask

entered.

According

had been

filled

have gained 26 grains

inches of the

and

that of

common

its

specific
air.

if

the
it

whole

would

consequently, 26 cubic

acid gas

grains,

to this,

with the gas,

would weigh 34.2

gravity be 4.17 times

This experiment

was

repeated with a proportional result. The flask

became partially lined with a thin, dry film
of fluate of silica during the operation, which

no doubt contributed something to the weight ;

but I am convinced, from other experiments.

FLUORIC ACID.
that this gas,

when

loaden with

vier than most others.

an inch

silica,

is

hea-

tube, four tenths of

diameter, and 10 inches long, being

this acid gas, and inverted for one

in

with

filled

279

retained only -^V^ths of the gas ;

whereas, with carbonic acid gas, it retained

minute,

4^^ths
2.

gas

and with oxymuriatic acid

Water absorbs a very

but the quantity

gas, ^VVths.

large portion of this

like as

is,

in.

other

si-

milar cases, regulated by the temperature and

pressure conjointly : at the common tempe-

and pressure,

rature

have observed 2 grains

of water take up 200 times their bulk of the

gas, and leave little residuum besides common
air.

It

is

seldom obtained

of this strength j
bulk of the gas,

it

dissolving silica (flint)

it

has imbibed

has a sour taste, and

other characters of acids.

when

in large quantities

when water

is

3.

The

all

its

the

property of

peculiar to this acidj

obtained, as usual, in glass vessels,

is

corrodes the glass, and takes up a portion of

silica, which is held in solution in the transit

parent gas

but as soon as this comes in con-

is
deposited in form
of a white crust, namely, fluate of silica, on
the surface of the water.
4. The gas, when

tact with water, the silica

thrown

into

common

(like muriatic acid)

air,

exhibits white fumes

this

is

owing

to

its

com-

bining with the steam or aqueous vapour,

OXYGEN WITH HVDROGEX.

280

which common

air

always contains

in a dif-

'

fused state.

Fluoric acid combines with

5.

and metallic oxides, form-

the alkalies, earths,

ing

salts

denominated JIuates.

The weight of an atom of fluoric acid may

be investigated from the salts into which it
Of these, the
enters as an integral element.
of lime

filiate

most

is

known. Scheele

is

said to

abundant, and best

have found 57 parts of

lime, and 43 of acid and water, in fluate of lime.

Richter finds Qb lime, and 35 acid

These are the only

authorities I

In order to

differ materially.

took 50 grains of

in this salt.

know

satisfy

they

myself, 1

and

finely pulverized spar,

having mixed with

much, or more, strong

the whole was exposed to a
as

it

sulphuric acid,
heat gradually increasing to redness ; the result was, a hard
dry crust of mixed sulphate
and fluate of lime; this was pulverized, then

weighed,
acid,

and again mixed with

and heated

as

before

sulphuric

this process

was

repeated two or three times, or as long as any

increase of weight was found.
At last, a dry
white powder, of 75 grains, was obtained,

which was pure sulphate of lime. This expetwo or three times repeated, gave al-

riment,

ways 75

grains finally.

Hence, 50 grains of

fluate of Jime contain

just as

much

grains of sulphate of lime:

But sulphate of

lime as

75,

FLUORIC ACID.
lime

is

now,

formed of 34 parts acid + 23 parts lime ;

57 23
75 30
the lime in 50

if

of 60 lime
is

fiuate of lime.

which

281

fluate of lime consists

Hence,

40

100 parts

acid, in

mean between

nearly a

forementioned.

if

Again,

60

40

a result

the
:

nearly, for the weight of fluoric acid

two be:

23

which

15
is

found associated with 23 parts of lime ; but 23

will be found in the sequel to represent the
weight of an atom of lime ; therefore, 15 represents the weight of an atom of fluoric acid,
it

being assumed that fluate of lime is constiatom of acid united to one atom

tuted of one

of lime.

we commence

Before

gation of this acid,

its

it

the analytical investi-

will be proper to discuss

steam or aqueous vapour, which

present to be much misunderstood ;

relation to

appears at

the observations equally apply to muriatic acid

gas,

and

to

some

It is

ticed in their places.

that

common

air

which

others,

will

be no-

universally

known,

over water contains a quantity

way or other com-

of steam or vapour, some

bined or mixed with

pair

of

its

it,

which does not im-

transparency, but which gives it -ji^-th

elastic force, at the temperature of 65 ;

its

the vapour too,

force and
perature.

increases

quantity in

same

and diminishes
ratio

in

with the tem-

Clement and Desormes have shewn,

OXYGEN WITH HYDROGEN.

282

that this vapour

mospheric

is

the

same

in

quantity for at-

oxygen, hydrogen, azote, and

and probably for most other

air,

carbonic acid,

This vapour can be abstracted from the

gases by any body possessing an attraction for
water ; such as sulphuric acid, lime, &c. In
gases.

it

short,

can be taken out, as

far as

is

known,

will take

out pure steam.

by any body
Some authors consider the vapour united to
tliat

the air by a slight affinity

others call

My

it

hy-

opinion on

this
grometrical affinity, &c.
has
already been stated, that the steam
subject

mixed with
steam

air diffi^rs in

no respect from pure

and, consequently,

same laws.

subject to

is

There are some

elastic

however, which have so strong an

the

fluids,

affinity for

water, that they will not permit this steam

quietly to associate with
ric,

them

these are fluo-

muriatic, sulphuric, and nitric acids.

No

sooner are these acid gases presented to any

air containing steam, but they seize upon the

steam

the

two

united, are converted into a

fumes appear, which after playa

while, are observed to fall down,
ing about

liquid

visible

or adhere to the sides of the vessel,

till

the gas

no longer finding any steam present, occupies

the volume of the vessel in a transparent state,
from every atom of vapour. These acid
gases cannot exist one moment along with
free

28S

FLUORIC ACID.

they are no longer elastic fluids, but

of liquid float about, and
liquids ; the drops
the
cause
visibility, till, like rain, they sub-

Steam

they are not reabsorbed ; for, if the sura glass vessel is once moistened with
of
face
side

them,

it

remains

so.

Hence,

it

should seem

that these acid gases, so far from obstinately

retaining their vapour, as

is

commonly ima-

gined, they cannot be induced to admit any

vapour at all, in ordinary circumstances. This

being clearly understood,

we can now proceed

to consider the experiments

on the

analysis of

fluoric acid.

In the Philos. Transact,

has given us an interesting

800, Dr. Henry

set of experiments

for

on the decomposition of the muriatic acid by

at the conclusion, he observes on
electricity
:

fluoric

acid

"

When

electrified

alone, in a

"

with wax, it
glass tube, coated internally
" sustained a diminution of
bulk, and there
*'

remained a portion of hydrogenous gas."

admitting the accuracy of the fact, it

seems fair to infer, that hydrogen is a consti-

Now,

tuent principle of fluoric acid ; and not, as he

supposed, derived from the water it contains,

More

Mr. Davy has

recently,

ascertained, (see

Philos. Transact, for 1808) that potasium burns

in fluoric acid,

ash,

and a

and the

little

result

hydrogen gas

is
is

fluate of pot-

liberated.

In

OXVCMN WITH HYDROGEN.

284
particular,

IOt grains of potasium were burned

14 of which

in 19 cubic inches of fluoric acid,

disappeared, fluate of potash was formed, and

2^ cubic inches of hydrogen were evolved.

Here

it

is

evident, that both

oxygen

arid

hy-

drogen were found in the fluoric acid, and

must have made an integral part of that acid,
as no vapour could subsist in it \ whence it
appears, that both oxygen and hydrogen are
essential to fluoric acid.

Moreover,

it is

highly

probable that the pure acid in the 14 inches of

weighed about 6 grains, (common air being 4^) and the oxygen necessary for \0\ potasium, would be 2 grains ; whence the acid
gas,

entering into composition, would be about

twice the weight of the oxygen united to the

potasium.
I shall now relate some of my own experiments on the decomposition of this acid.
1. Fluoric acid
gas may, 1 find, be kept in

glass tubes for several hours or days,

without

any change of bulk ; it continues at the end

absorbable by water as at first. Two sucwere made, by electrifying about
30 water grain measures of the gas. After
two hours electrification, no change of volume

cessive trials

was produced.
which absorbed
this 14

Water was then admitted,

all

but 4 grain measures

to

measures of hydrogen were added, and

FLUORIC ACID.

285

a sufficient quantity of oxygen ; the whole

was then exploded, and a diminution of 23.3

was observed, denoting 15,5 hydrogen. Here

seems, then, to have been a decomposition of
the acid, and a formation of

This was the

1.5

hydrogen.

of the latter experiment,

result

and the former was

same

to the

effect.

Fluoric acid gas, electrified along with

hydrogen, experiences a diminution, but this
2.

is

much greater in the hydrogen than

The result of one of the most

acid.

experiments follows.

in

the

careful

mixture of 20 mea-

3 of hydrogen, was
hours uninterruptedly, by
a dense stream of sparks ; it diminished from

sures of fluoric acid,

and

electrified for three

33 to 19

of the

drogen, and 4

10 was found to be hy-

loss,

acid.

Here the hydrogen must,

probably, have formed water with part of the

oxygen of the acid.
3.

and

Fluoric acid
electrified

was mixed with oxygen,

one hour

was observed, and the

was tarnished.
4.

Fluoric acid gas

riatic acid

gas

a small diminution

surface of the mercury

was mixed with oxymu-

no sensible change was pro-

duced.

Upon the whole, it appears that the weight

of an atom of fluoric acid is about 15 times
that of hydrogen, that

it

contains hydrogen

OXYGEN WITH HYDROGEN.

286

and oxygen, and nothing besides

certainly

known.

Now,

as far as

atom of hydrogen, and two of oxygen,

make

is

weight of one

as the

15 times that of hydrogen, there

Is

just

great

reason to presume that this must be the constitution of that

strongly in

acid.

Besides,

favour of the conclusion

analogy is
an atom
;

of the other elementary principles, azote, car-

bone, sulphur, and phosphorus, joined to two

atoms of oxygen, each forms a peculiar acid,
as will be

shewn

in the

sequel

why,

then,

should not one atom of hydrogen and two of

oxygen, also form an acid ?

3.

To

Muriatic Acid.

obtain muriatic acid in the elastic state,

a portion of common salt, muriate of soda, is

put into a gas bottle, and about an equal

weight of concentrated sulphuric acid

by the

application of a moderate heat to the mixture,

a gas comes over, which may be exhibited over

; it is muriatic acid gas.

mercury

Some
are:
a

1.

of the properties of muriatic acid gas,

It is

an invisible

pungent smell

for the support of

with

common

air,

it

is

elastic fluid,

unfit

combustion
it

having

for respiration, or
;

when mixed

produces a white cloud.

MURIATIC ACID.
which
and

is

owin^to

its

287

combination with steam,

the consequent formation of innumerable

small drops of liquid muriatic acid.

specific gravity appears to

that of

mine

common

Its

from some experiments of

air,

but, according to Brisson,

2.

be about 1.61 times

it is 1

.43

and

according. to Kirwan, 1.93 at the temperature

of 60, and pressure of 30 inches of mercury.
There are two sources of error obvious in de-

termining

its

specific gravity

if

mercury

in the vessel dry, in

common

air

may be mixed

wliich case

In order
I

its

that

which case the

this

(see

common

weight will be too

trials';

and a

little.

fluoric acid

containing 8.2 grains

partially filled

with mu-

(namely i^ths) acquired just 3

like proportion in several other

from which

given above.

flask

when

air,

riatic acid gas,

;

probably

to find the specific gravity of this gas,

page 278).

grains

is

a quantity of
with the acid gas,
is,

adopted the same method as with

of

is,

is

weight is found too great

the other
Kirwan's error

in

the one

apt to insinuate itself,

the utmost attention is not paid to have the

liquid muriatic acid

3.

find the specific gravity

It possesses the characterisic

that of converting
properties of acids ; namely,
of
to
red,
uniting with alvegetable blues
kalies,

&c.

4.

It

is

rapidly and largely ab-

sorbed by water, which takes up between four

283

OXYGF.N

and

WITH HYDROGEN.

hundred times

five

bulk of the gas, at

lis

common

temperature and pressure ; that

This
than an equal weight.
combination of water and muriatic acid gas,

the
is,

rather

less

common

constitutes the

or spirit of salt of

liquid

commerce

muriatic acid,

but

it is

never

of the strength indicated above.

It is usually
of a yellow colour, owing to some atoms of iron

which

it

The

holds

in solution.

constitution of this acid,

that has long

is

a question

engaged the attention of chemists.

Thisacidseemsmoredifficultly decomposed than

most others. Electricity, so powerful an agent

and decomposition of other

in the composition

acids,

seems

to fail in this.

In the Phil. Tr. for

1800, Dr. Henry has given us the results of a

laborious investigation on this subject.
From
these it appears that pure, dry muriatic acid
gas,

is

scarcely affected by electricity.

small diminution in volume, and

some

A very
traces

of hydrogenous gas, were observed, which he

ascribes to the water or steam which the gas
contains.

we have

But

already

remarked,

(page 283) that muriatic acid gas naturally

contains no steam ; or, if it contains any, it

must be much
It

is

less

than other gases contain.

probable, therefore,

was derived from

the acid.

that the

hydrogen

the decomposition of part of

This conclusion

is

strengthened by

289

MURIATIC ACID.

Mr. Davy,

i^e recent experiments of

in

which

the acid has apparently undergone a complete

In his Electrochemical Re-

decomposition.

searches, in the Philos. Transact, for 1808,

observes
*

riatic

'

When

potasium was heated

acid gas, as dry as

by common

violent chemical action

when

tity,
'

it

in

he

mu-

could be obtained

means, there was a

chemical

with ignition

and

the potasium was in sufficient quanthe muriatic acid gas wholly disap-

peared, and from one third to one fourth of

its volume of hydrogene was evolved, and

muriate of potash was formed.'

Here it is
almost certain a portion of the acid was de-

hydrogen, and the

the potasium into
convert
oxygen
the
elements of the
are
ostensible
only
potash,
acid ; hence we must infer, that muriatic acid

composed

the residuary

required to

is

compound of oxygen and hydrogen.

a subsequent paper

in

the

In

same volume, Mr.

that 8 grains of potasium took

cubic inches of acid gas, and gave 8 inches
of hydrogen. This particular experiment must,

Davy informs us,

'22

hpwever, be incorrect

in

some point;

or other-

wise the general observation before made ;

because they are inconsistent with each other.
For, 22 cubic inches of acid gas weigh 1 1
grains, to which adding 8 grains of potasium,
we obtain 19 grains ; but 8 grains of potasium"

OXYGEN WITH HYDROGEN.*

290

form only 14.6 grains of muriate of potash, to

which adding

grain for the 8 cubic inches

.2

of hydrogen, gives 14.8 instead of 19 grains.

I

would

therefore

adopt

which was confirmed by

and is entirely consistent
potasium

the

fact,

general

several experiments,
;

namely, that when

burned in mu-

in sufficient quantity is

riatic acid gaSy

t/te

whole of the gas disap-

pears ^ and from one third to one fourth of its

volume of hydrogen is evolved, and muriate of
potash formed.

This

is

portant facts that has

the

specting

constitution

of muriatic

re-

acid.

the elements of muriate of potash are

Now,

as follow

gen

one of the most im-

been ascertained,

= 42

35 grains of potasium

of potash

riatic

acid

Vroni

this

it

appears, that the oxygen in muis

nearly I of the weight of the

potash

acid.

According
in

+ 7 of oxy+ 22 mu-

and 42 potash

64 grains of muriate of potash.

riate of

burned

to

this,

when potasium

muriatic acid gas, nearly

whole weight

(for the

-'

is

of the

hydrogen weighs

little)

of the potasium, and

goes to the oxidizement
the remaining | unite with the potash formed.
Jlcnce,

when 22

cubic inches, or II grains

of gas disappear, as in the particular experi-

mentioned, 2i grains nearly must

have been oxv2:en derived from the acid, and

ment

lately

^l grains of acid joined

to

the

potash

so

MURIATIC ACID.

291

But 2A grains of oxygen = 8 cubic

inches, would require 16 inches of hydrogen
formed.

to form water

was not

evident, then, that water

it is

the source of the

oxygen

for,

if it

had, there must have been twice the quantity

of hydrogen evolved.
Mr. Davy has ascertained another fact, exactly similar to the general one just stated; namely, that

coal

is

galvanized

when

in muriatic acid

gas,

char-

mu-

and hydrogen,
mercury
of
to
the
volume
of the gas is
4amounting
riate of

is

He

evolved.

infers

formed,

from

this,

that water

is

form oxide enough to saturate the

but, setting aside the inference I have

present to
acid

that no water can be present with

muriatic acid gas, the oxygen required to form
the oxide in this case as well as the former,

drawn,

if

derived from water, would evolve at least

twice as

much hydrogen.

For, the relation of

the oxygen in the oxide to the acid in the

muriate, is proved by the fact, to be the same
in the

two

cases.

Mt. Davy

has, indeed,

viate any objection that

the source of the

endeavoured to ob-

may be made,

as to

in these

experiments ;
oxygen
he has found that nearly the same weight of
muriate of mercury is formed, by precipisolution by a given volume
tating a mercurial
of muriatic acid gas, as by burning potasiuni

OXYGEN WITH HYDROGEN.

292
in the

same quantity of

'

there

The

acid

the

ferring

to

and then

gas,

mercury

he

was no notable difference

trans-

observes,

in the results.'

inference must, I conceive, be erroneous;

100 cubic inches

of muriatic acid gas, united

must give more muriate of potash,

potasium was burned in the same gas

to potash,

than

if

the weights of the materials necessarily require

it ; unless it be found that the two muriates are

not the same

From

all

salt.

the muriates, or

the muriatic acid enters,

shewn when

it

salts,

appears

into

which

(as will

be

these salts are considered) that the

22 times
weight of an atom of muriatic acid is
after this detersoon
Very

that of hydrogen.

mination,

it

occurred to

me

that

probably the base of the acid

of the acid must consist of

and
just

hydrogen was
an atom

if so,

atom of hydrogen

3 atoms of oxygen, as the weights of these

make up 22. In 1807 this idea was an-

nounced, and a suitable figurative representation of the atom was given, in the Chemical
Lectures

at

Edinburgh and Glasgow but this

was hypothetical, till
;

constitution of the acid

these experiments of

Mr. Davy seem

to put

it

The

application of the theory to

on the suppothe experiments is as follows
sition that the specific gravity of muriatic aCid

past doubt.

gas

is

1.G7,

it

will

be found that

12 measures

MURIATIC ACID.

293

11 aieasures of hydrogen,
and about 164 measures of oxythen if ^th of the acid be decomposed,

of the acid contain

if liberated,

gen

nearly 3 measures of hydrogen will be

rated,

and

atoms of

-f-

libe-

measures of oxygen, and the

oxygen will apply, 1 to 1, to the

atoms of potasium, and furnish potash for the
remaining iths of the acid, (because 1 atom of
this

The very same

acid contains 3 of oxygen).
of muto
the
formation
will
apply
explanation
riate of

mercury.

Here

the hydrogen will

rather less than ^th of the

be

volume of the acid

gas ; but if we adopt Kirwan's specific gravity

of muriatic acid, 1.93, then the hydrogen

evolved will be between 4 and ^th of the volume of acid gas.

Hence we conclude

that an

atom of muriatic

atom of hydrogen and 3

acid gas consists of
of oxygen, or 1 atom of water and 2 of oxy1

22. Moreover, the diagen, and its weight

meter of the acid atom will be found (page 226)

or 12 meahydrogen being 1
as 1 1 meaatoms
as
sures of acid contain
many
1.07, that of

sures of hydrogen, or as 5 ^ of oxygen.

My own

acid gas
experiments on muriatic
of
have not been productive
important results.
I sent

1000 small shocks of

30 measures of gas

there

electricity

was

through

a diminution of

OXYGEN WITH HYDROGEN.

294
1

measure, and on letting up water the whole

was absorbed,

except one measure, which

be
I sent 700 shocks
appeared
hydrogen.
a
mixture
of
acid gas and
muriatic
through
there
was
no
A mixture
;
hydrogen
change.
to

of muriatic acid gas and sulphuretted hydrogen

hydrogen was evolved, and

sulphur deposited, but no change of volume.
It was evident the sulphuretted hydrogen only
being

electrified,

was decomposed.
and hydrogen
gas, water

is

is

When

fired

a mixture of oxygen
along with muriatic acid

formed, and

it

instantly absorbs

nearly
weight of acid gas. From these and
such like unsuccessful attempts to decompose
its

the muriatic acid, the importance of Mr. Davy's

experiments is manifest.

The

relation of muriatic acid to water

now be

considered.

It

must

has been stated that

at the common temperature and pressure,

absorbs 400 or more times its bulk of the acid

water

gas

that

is,

rather less than

its

own

weight.

Now, atoms of water weigh 24, and 1 atom of

the acid gas weighs 22 j it seems probable, then,
3

that the strongest liquid acid that can well be

exhibited,

and

is

compound of

atom of acid

about 48 per cent,

seldom sold of more than half this

3 of water, or contains

acid.

It is

strength.

Mr. Kirwan's

table of the strength

MURIATIC ACID.

295

of muriatic acid of different specific gravities is

very nearly correct ; which, with some little
addition

and modification,

Table of the quantity of

is

as follows

real

acid in

100

parts of liquid muriatic acid, at the tempe-

rature 60.
Atoms.

OXYGEN WITH HYDROGEN.

296

contain so

many grains of pure acid ; the third

contains the grains of acid in 100 water grain

measures

this

is

convenient

in

practice to

prevent the trouble of weighing the acid ; the

fourth contains the specific
gravity of the liquid
acid J and the fifth contains the temperature
at

which

This

acids of the various strengths boil.

last

is
entirely new, I apprehend ; it
shews a remarkable gradation of temperature
:

the strong acid boils at a moderate heat ; as

the acid weakens, the boiling temperature
rises till it gets to 232 ; after which it
gra-

When

dually d'-ops again to 212.

below 12 per cent, is boiled,

it

an acid

loses part of

quantity, but the remainder, T find, is concentrated ; on the other hand, an acid stronger

its

than 12 per cent,

is

rendered more dilute by

aopears from a paper of Dr. R.

Percival in the 4th vol. of the Irish Transacboiling.

It

tions, that in the ordinary

process of

manu-

facturing the muriatic acid, the middle pro-

duct

is

usually of the strength

the

maximum

last

products are

temperature

much

which

but the

stronger.

for these facts will probably

The

be found

boils at
first

and

reasons
in

the

gradation of temperature in the above column.

OXYMURIATIC ACID.

3.

The

297

Oxifnmriatic Acid.

highly interesting compound,

now

de-

nominated oxymuriatic acid, was discovered

by Scheele, in 1774. It may be procured by
applying a moderate heat to a mixture of muriatic acid and oxide of manganese or red
lead

a yellowish coloured gas ascends, which

may be received over water ; it

But this gas, which
acid gas.

is
is

oxymuriatic
largely ob-

tained for the purposes of bleaching,

is

usually

got from a mixture of equal weights of common salt (muriate of soda), oxide of manga-

and a dilute sulphuric acid of the strength

1.4; a heat at least equal to that of boiling

nese,

water, seems required for the expulsion of the

whole of the acid gas. Some of its properties
are

pungent and suffocating smell,

most
other gases in these respects,
exceeding
and it is highly deleterious. Its specific graIt has a

1.

vity I find to

ing

1.

mon

be 2.34, that of

common

air be-

Or, 100 cubic inches of it, at compressure and temperature, weigh 72^^

grains.
2.

Oxymuriatic acid gas

is

absorbed by

water, but in a very small degree compared

with muriatic acid gas. I find that at the

OXYGEN WITH HYDROGEN.

298

temperature of 60 and common pressure of

pure gas, water takes up about twice its bulk
of the gas.

much

is

If the gas be diluted

with

air,

absorbed, but the quantity

not proportionate to the abstract pressure of

then

less

is

is the case with those

gases mentioned at page 201.
Thus, if the pressure of
oxymuriatic acid gas be ^th of atmospheric

the gas, as

pressure, water will be found

of

bulk, which

its

tity

it

ought

Hence

it is

to

take up.^ds

is

more than twice the quan-

to take

by the rule of proportion.

evident, that the absorption of this

gas by water, is partly of a mechanical and

partly of a chemical nature.

Water impregnated with

3.

oxymuriatic

liquid

odour

as the gas,

the liquid acid

first

the gas

It

has

is

called

the

same

and an astringent, not

"When exposed

taste.

was

acid.

is

acid,

to the light of the sun,

gradually decomposed, as

observed bv Berthollet, into

its

ele-

ments, muriatic acid and oxygenous gas j the

former remains combined with the water, and
the latter assumes the gaseous form.
light nor heat has been found

to

Neither

decompose the

acid gas
4. This acid, in the gaseous state or combined
with water, has a singular effect on colouring

matter.

Instead of converting vegetable blue

it abstracts colours

into red, as other acids do,

OXYMURIATIC ACID.
in general

colourless.

299

from bodies, leaving them white or

The oxygen combines with the

colouring principle, and the. muriatic acid remaining dissolves the compound. Hence the
use of this acid in bleachinof.
5.

Combustible bodies burn

in

acid gas more quickly than in

and the combustion

is

oxymuriatic

common

air,

attended with several

remarkable phenomena. Some bodies sponAll the metals

taneously take fire in this gas.
are oxidized by this acid, and afterwards dis-

forming salts denominated viiiriates.

combustible gases, mixed in due proportions with this acid gas, are either burned im-

solved,

The

mediately,

as

sulphurous acid,

hydrogen, nitrous gas,

sulphuretted

&c. or the mixture

is

capable of being exploded by an electric spark,

as hydrogen, carburetted hydrogen, &c. These
facts

shew

that

the

oxygen which combines

with muriatic acid to form oxvmuriatic,

ea-

is

to enter into almost

sily abstracted again
any

other combination.
6.

Oxymuriatic acid seems

to

combine

rea-

dily with the fixed alkalis and the earths when

dissolved in water ; but it decomposes ammoIt is

nia.

remarkable, however, that few,

if

any, neutralized dry salts are to be obtained.

When
and

the saturated solutions are evaporated

crystallized,

two

distinct salts

are

chiefly

ox VOExN WITH HYDROGEN.

SOO

the one a simple itiuriate, and the

;
other a hyperoxygenized muriate,- in which an
acid with an enormous quantity of oxygen is

obtained

found, and

hence called hyperoxipmiriatic

is

acid.

One

7.
riatic

very remarkable property of

cour^f- of

experiments upon

had found

that

if

oxymu-

me

acid has recently occurred to

in

Cruickshanks

it.

hydrogen and oxymuriatic

acid gases were mixed together, and kept in a

well stopped bottle for 24 hours, when the

stopper was withdrawn under water, the gases

Bedisappeared, and water took their place.

the
ascertain
time
defidesirous
to
more
ing
nitely, I

made

meter, and

the mixture in a narrow eudio-

left it

to stand over

water

about

in

three quarters of an hour the greater part of

the

mixture had disappeared.

In

next

the

experiment, the gases, after being put together, seemed to have no effect for one or two

when suddenly the mixture began to

diminish with rapidity, like one of common air
and nitrous gas, except that there were no red

minutes,

fumes.

The diminution went

or three

in

two

minutes nearly the whole had

dis-

on,

till

On

appeared.
repeating the experiment a
^e.\v hours afterwards no such diminution was
observed.

upon

recollected that the sun had shone

the instrument in the former one

it

was

OXYMURIATIC ACID.

SOI

again placed in the direct rays of the sun, and

the diminution was rapid as before.
Upon
repeating the experiment with sundry variait was confirmed, that Light is the occa-

tions,

sion of this rapid combustion of hydrogen in

oxymuriatic acid gas

the light, the

the mixture

that the

more powerful

more rapid is the diminution of

and that if the eudiometer be

covered by an opake body, the mixture will

scarcely be affected with any diminution for a
day, and will not completely disappear in two
or three weeks.
Moreover, when the dimi-

nution

is

going on with speed,

is

if

the hand, or

interposed to cut off the solar

any opake body,

light, the diminution

is

suspended.

instantly

These observations equally apply to mixtures

of carbiiretted hydrogen and carbonic oxide
with the acid gas, except that the former deposits

some charcoal.

Carbonic acid, water,

and muriatic acid, are the

were ascertained

in

results.

June 1809.

These

facts

In the ensu-

1 found that upon mixing hydroand

oxymuriatic acid in a strong phial
gen

ing month,

capable

of containing

COO

and exposing the mixture

grains

of water,

to the solar rays,

an

took place with a

explosion almost instantly
loud report, just as if it had received an electric
spark.

cuum

If the

stopper was well closed, a va-

nearly was formed, which was

instantly

OXYGEN WITH HYDROGEN.

302

when

with water

filled

out under water

It

of

remains

now

happened

generally

violence.

to point out the constitution

AH

this acid.

it

was expelled with

that the stopper

was drawn

the stopper

but

experience shews, that

it is

compound of muriatic acid and oxygen ; but

the exact proportion has not hitherto been
a

ascertained.

Berthollet,

who

investigated the

subject by impregnating water with the acid

gas, and then exposing it to the solar rays till
the oxygen

was

liberated, found

in this

way

the quantity of oxygen

rated.

1 1

consist

of oxy-

Whether

gen, by weight.
liberated

to

it

of 89 parts of muriatic acid, and

is

is

all the
oxygen is
more than doubtful ;

much under-

certainly

Chenevix makes 84 muriatic acid and

16 oxygen to constitute

this

acid

he too has

the oxygen too low ; probably because he estimated all the salt formed by this acid to be

simple muriate, or hyperoxymuriate but there

is no doubt that oxymuriate does exist in the
;

mixture, because
bleaching.

Of

it

all

possesses the property of

the authors I have seen,

Cruickshank comes the nearest

he

says, 2

measures of oxymuriatic acid

and

it is

hence he

known
infers,

gas contain

to the truth

measures of hydrogen require 2.3

to saturate

them

of oxygen ;
that 2.3 measures of this acid

that they require

measure of oxygen.

From

this

OXYMURIATIC ACID.
it

may be

inferred, that

303

100 measures of the

acid gas would afford 43.5 measures of oxygenous gas, and a certain unknown measure

of muriatic acid (not 56.5,

as

Thomson

Dr.

has

Chenevix remarks, that Cruickinferred)'.

shank's gas was obtained from hyperoxymuriate
the substance he obof potash, and that
'

tained was, in fact, not oxygenized muriatic

acid gas, but a mixture of that gas with hyperoxygenized muriatic acid.* Dr. Thomson

'

observes, that
*
*

when

acid

oxymuriatic
shank's method,

is

water, impregnated with

Cruickgas, obtained by

mixed with

is

any gas
bodies combine and form a

nia, scarcely
*

know what
had

for

ing to

reasons these

making

my

ammoThe two

liquid

extricated.
salt.'

do not

two authors may have

these remarks

experience, they are

but, accordentirely with-

The

acid gas obtained from

a mixture of sulphuric acid, muriate of soda,
or from muriatic acid and
and

out foundation.

manganese,
of potmanganese, or from hyperoxymuriate
all
are
muriatic
ash and
acid,
precisely the
same, .vhether we consider their action upon
the combustible gases, upon liquid or aeriform
ammonia, or their absorbability by water.
indeed one small difference, but it
of any material efseem
does not
productive
fect ; the gases obtained by the two former

There

is

o04

OXVGEN WITH HYDROGEN.

methods always deposit some brown oxide

manganese when

treated with

of

ammonia, but

that obtained by the last

The
deposits none.
action of muriatic acid on
hyperoxymuriate of

potash,

evidently

consists in

detaching the

superfluous oxygen from the compound, and

not the hypcroxymuriatic acid particle from the
particle of potash.

As the oxymurlatic acid is of great and increasing importance in a theoretical as well as

practical point of view, I have spent much
time in endeavouring to ascertain the proof

portion

succeeded

its

elements,

at least, 1

and have,

am

think,

pretty well satisfied

myself as to its constitution the methods I have

taken are both synthetical and analytical, but I
:

chiefly rely

upon the

latter.

eudiometer with dry mercury,

and sent up 13 water grain measures of muriatic acid gas, to which were added 9 measures
1.

I filled a

of oxygenous gas of 77 per cent,

purity, which
consequently consisted of 7 oxygen and 2 azote.
The instrument had platina wires. About

1300 small

electric

shocks were passed through

a gradual diminution
;

the mixture of gases

ensued

when
The 22

as

the

mercury became

foul, the

same

oxymuriatic acid is in contact with it.

measures were reduced to 4, which

were not diminished by

v^'ashing.

To

these 4

OXtMURIATIC ACID.

305

measures, 20 hydrogen and 20 common air

were added, and the mixture being exploded,

was 15 measures, correspond-

the diminution

ing to 5 oxygen ; but the common air contained only 4 oxygen ; therefore, 1 measure of

oxygen must have been in the residuary gas,

and probably 1 of azote was originally in the

Here

muriatic acid.

then,

it

seems, 12 mea-

sures of muriatic acid united to 6 measures of

form oxymuriatic acid. If we calculate from the specific gravities of the three

oxygen

to

elastic fluids,

will appear that 12 measures

it

of muriatic acid gas,

gas,

ought to

riatic acid

make

II

This

gas.

but the process

+6

is

measures of oxygen

measures of oxymu-

result

is

nearly right

too laborious to be often re-

as the object can be obpeated, especially

tained much more easily and elegantly by the

analytic method.
2.

Oxymuriatic

acid

gas

and hydrogen,

mixed together over water, explode with an

electric spark, much like a mixture of common air and hydrogen. Cruickshank mixed 3
measures of hydrogen with 4 of the acid, and
exploded them over mercury in this case,
He then
there was a residuum of acid gas.
:

mixed 4 measures with

4,

and

after the ex-

of hydrogen.
plosion found a residuum
these experiments, he infers, that 3

From

measures

OXYGEN WITH HYDROGEN.

506

of hydrogen require 3^ of the acid to saturate

them. I have found the results a little different

but the error

is

not much, and

Whether we

might be expected.

what

is

treat

oxymuriatic acid over mercury or water, we are

sure to lose some of it ; and unless the loss can

be estimated and allowed

of light on
to

we are apt to
Before the action

for,

overrate the acid required.

mixture was discovered,

this

mix known quantities of

the

used

two gases

to-

gether, in a graduated eudiometer of Volta,

over water ; and, after letting the mixture

stand a few minutes, in order to c

diffusion, I passed

ticed the

moment

mixture stood

complete

a spark through, but nobefore at what degree the

in this

way, when there

is

an

excess of hydrogen, the results are accurate ;

the total diminution can be found, and the residuary gas can

be analyzed to find the hy-

drogen left, and the

which is extremely apt
or less degree, in

all

common
to

air

be found

in

(if any),
a greater

oxymuriatic acid obtained

frequent careful trials, I found

that a measure of hydrogen required as near

over water.

By

as possible

an equal measure of the acid to

turate

But since the

it.

effect

sa-

of solar light

was discovered, I have operated in a more

simple and elegant manner ; and the results
appear rather more uniform and accurate. I

OXYMURIATIC ACID.

307

take a graduated tube, capable of containing

200 measures of gas. 1 fill this with water,

and
of

transfer into

known

The

purity

is

finger

tube, and

as

to

fill

the

tube nearly.

then applied to the end of the

is

it

to this a quantity of acid

instantly transferred to

The whole

mercury.

posed

added, so

is

gas

100 measures of hydrogen

it

is

ajar of
then taken, and ex-

to the sun, (if not shining

fully, in

too powerwhich case an explosion may be ap-

prehended) or to the strongest light that can

be obtained ; when, after remaining two or
three minutes without exhibiting any change,
the water, and afterwards the mercury, ascend

the tube with increasing and then diminishing

The
velocity, till they nearly reach the top.
residuary gas

may then be examined, and

the

quantity of hydrogen, acid and common air,

The quantity of water in the
ascertained.

tube becomes visible as the mercury ascends,

and is useful to prevent the action of the acid

on

the" mercury.

The water must

tracted from the capacity of the

acid,

the

hydrogen,

there

sub-

tube, to find

the volume of gases employed, from

taking

l>e

which

remains

the

&c.

From

the

as above, I

mean

am

of five experiments executed

induced to conclude, that 100

measures of hydrogen require 94 measures of

OXYGEN WITH HYDROGEN-.

308

oxymuriatic acid gas to convert them into

In every one of the experiments, the
water.
acid

was

less

than the hydrogen.

The above experiments

in a day of clouds

are highly

and gleams

amusing

the presence

of the direct solar light instantly gives the motion of the mercury a stimulus, and it as

The
quickly abates when a cloud incervenes.
surface of the mercury in the tube always
becomes fine sky blue during the process ; and
so does liquid

ammonia

that has

oxymuriatic acid

decompose
what is the reason

been used to

do not

know

in either case.

From the results above, it appears that 100

measures of oxymuriatic acid gas must consist
of 53 measures of oxygen, united to a certain
portion of muriatic acid gas.

Now, ICO cubic

inches of oxymuriatic acid gas weigh 72 or 73

grains,

and 53 inches of oxygen weigh about

18 grains, which is rather less than ^th of the

above. Hence, if the atom of muriatic acid

weigh 22, that of oxymuriatic acid must weigh

29 and thus we obtain the constitution of this
;

last acid.

An

atom of

it

consists of

one of

muriatic acid and one of oxygen.. united ; the

former weighs 22, the latter 7, together mak-

ing 29

or about 76 muriatic acid, and 24

oxygen, per cent. Thus, it appears, that the

former experiments on the specific gravities of

hYperoxymuriatic acid.

309

those fluids, corroborate the recent ones on

If the constitution of

their constitution.

mu-

be rightly determined, then oxymuriatic acid must consist of 1 atom of hy-

riatic acid

drogen and 4 of oxygen. At all events, 1

atom of muriatic acid must combine with 1 of

oxygen

to form

The

of oxymuriatic acid.

atom of

diameter of the elastic

this

gas

is

same
hydrogen, and may therebe
denoted
fore
by 1, but it is rather less and
the number of atoms in a given volume of this

nearly the

as

gas

is

to

the

number

in the

same volume of

It appears,
hydrogen, as 106 to 100 nearly.
then, that the atoms of oxymuriatic acid are
rather more dense than those of muriatic acid,

or than those of hydrogen.

5.

The

Hyperoxymurialic Acid.

existence of a

compound denominated
been clearly shewn

hyperoxymuriatic acid, has

in a state of

combination

but

it

has not, and

perhaps can not, be exhibited in a separate,

elastic, or even liquid form, probably on ac-

count of the great weight and number of

It is

clearly a

its

compound of

elementary parts.
muriatic acid and an enormous quantity of oxyIt is obtained in combination with the
gen.

OXYGEN WITH IIVDROGEN.

310

and

alkalies

earths,

by sending a stream of oxy-

muriatic acid gas into solutions of these elements, or of their carbonates in water. The acid

combines with the

alkali

but in process of

time, as the solution becomes concentrated, a

change takes place

in

the acid

one atom of

oxymuriatic acid seizes upon an atom of oxygen from each of its neighbouring particles,
and reduces them to ordinary muriatic acid ; in
this state

forms with an atom of alkali an

it

hyperoxymuriate, whilst the other atoms of

It seems that the oxymuacid form muriates.
are difficultly attainable

riates

because,

apt to be resolved and

compounded

as

are so

their solutions are concentrated, they

again, as

above.

BerthoHet
of this acid

more

pointed out the peculiarity

first

but

iis

fully discussed

Chenevix

in 1802.

nature and properties were

by Hoyle

in

1797, and by

These authors made

their

principal experiments on hyperoxymuriate of

potash

they nearly agree as to the constitu-

tion of the salt, but differ in

some of

the cir-

cumstances of its production. It yields by heat

about 2 or 3 per cent, of water, about 38 per
cent, of oxygen,

and 59 or

terable

which Chenevix considers

by heat,

(50

of a

salt

unalas

simple muriate j but Hoyle says it exhibits

traces of oxvmuriatic acid bv sulphuric acid.

HYPEROXYMURIATIC ACID.

The

acid in 59 muriate

20 muriatic

is

added

acid

nearly 20.
to

Sll

Hence,

38 oxygen

by

weight, constitute 58 of hyperoxy muriatic acid

35 muor, as Chenevix states it, 65 oxygen
:

riatic acid
I

judge

100 hyperoxymuriatic acid. This

be very nearly true. Now, if 35

to

muriatic acid require 65 oxygen, 22 will take

41 ; but 22 is the weight of an atom of muriis the
weight of 6 atoms
of hyperthe
hence
constitution
;
An
atom of
is determined.
acid
oxymuriatic
it consists of 1 atom of muriatic acid + 6 atoms

atic acid,

and 41 or 42

of bxygen

of oxygen, or of 1 atom of oxymuriatic acid 45 atoms of oxygen ; and its weight is repre-

We

sented by 64.
may now see what takes
of hyperoxymuriates.
the
formation
in
place

One atom

of oxymuriatic acid deprives 5 sur-

rounding atoms, each of an atom of oxygen ;

an atom of hyperoxymuriate thus necessarily
muriate.
Supproduces 5 atoms of simple
their weights may
posing the salts from potash,
of
An
atom
found
thus
be
potash weighs 42,
:

one of hyperoxymuriatic acid weighs 64, to= 106. Five atoms of muriate of potgether
= 426. Now, if
=
ash
320; the sum of both

426

106

100

25 nearly.

Hence,

in the

formation of hyperoxymuriate of potash, if the

whole potash is formed into muriate and hybe 75 of the former
peroxymuriate, there must

OXYGEN WITH HYDROGEN.

312

and 25 of the

latter.

us on this head

former and

6 of the

The

obscurity.

Hojrle does not inform

Chenevix found 84 of the

Here then

latter.

fact,

believe,

is,

some

is

that there

is
always a greater or less portion of real oxymuriate of potash amongst the salts formed, or
in the mass which Chenevix calls the entire

salt.

Oxymuriatic acid precipitates silver from

and as this was the

nitrate as well as muriatic

test,

it

is

evident Chenevix must have con-

founded a quantity of oxymurrate of potash

with the muriate. The quantity may even be
ascertained.

For,

100 of Chenevix's

if

25

75

16

entire salt, there

48.

In

were then

16 by peroxy muriate, 48 muriate, and the rest

or 36 must have been
oxymuriate.

experiments confirm

this

conclusion

observes that the remaining muriate

hyperoxyrauriate was abstracted)

Hoyle's
j

for,

he

(after the

was

consi-

derably oxygenized, since with the addition of

acids

it

became a powerful

table colours.

destroyer of vege-

This could not be the case with

a muriate, nor even a mixture of muriate and

hyperoxymuriate.

Besides,

it

is

well

known

that the oxymuriate of potash (or oxymuriatic

acid absorbed by potash) was largely used for

the purpose of
bleacliing

now

if

the acid had

immediately resolved itself into muriatic

and

HYPEROXYMURIATIC ACID.
it

hyperoxymuriatic,

313

would have been of no

use for that purpose.

Hyperoxmuriatic acid must then be constir

1 atom of muriatic acid and 6 of
oxy-

tuted of

but as the former is probably composed

atom of hydrogen and 3 of oxygen, we
have 1 atom of hydrogen + 9 of oxygen for

gen

of

the constitution of an atom of the

tioned acid

or

it

consists of 1^^

first

men-

hydrogen

It is no
98|- of oxygen per cent, by weight.
wonder, then, if this acid readily part with its

oxygen, and be apt to explode when treated

nor if it refuse to
"with combustible bodies
;

form an

elastic

such unwieldy par-

fluid of

ticles.

Note on Fluoric and Muriatic Acids.

Since the foregoing articles on fluoric and
oflf, I have seen the

muriatic acid were printed

Journal de Physique, for January 1809, in

which is an abstract of an highly interesting

Memoir on

the Fluoric

and Muriatic Acids,

Their obser-

by Gay-Lussac and Thenard.

vations, supported

by

unison with those

facts, are

remarkably in
have suggested
They
acid gas is admitted to

find that

when

any gas,

and produces fumes, the gas

fluoric

is

dimi-

OXYGEN WITH HYDROGEN.

314-

nished, but only a small quantity

when

that

no fumes appear, no diminution takes place j

they hence conclude, that this acid gas is au
excellent test of the presence of hygrometric

water [steam]

in

gases

and observe that

all

contain such, except fluoric, muriatic,

gases

and probably ammoniacal.

Berthollet, jun.
has proved the last mentioned gas to contain
no combined water ; and Gay-Lussac and

Thenard suspect it contains none hygrometrically but some experiments of Dr. Henry convince me that it does ; and I think its not
;

fuming when mixed with common

proof of
is

it.

They

air

is

when water

observe, that

saturated with fluoric acid gas,

it is

limpid,

smoking, and extremely caustic ; that heat

expels about one fifth of the acid, and the re-

mainder becomes

fixt,

resembling concentrated

sulphuric acid, and requiring a high temperait.

They query from this fact,
whether sulphuric and nitric acid are not naturally gasiform, and owe their liquidity to

ture to boil

the water combined with them.

a drop of water to

acid

gas

They exposed

60 cubic inches of

fluoric

the drop, instead of evaporating,

was increased
oric

in volume by the absorption of

and
hence they conclude, that flu;
acid gas is also free from combined water j

the

conclusion

the acid

is

extended

to

ammoniacal

HYPEROXYMURIATIC ACID.
gas, but not

to muriatic acid gas.

315
I

wonder

exception with regard to muriatic

acid, as every one knows it presents the same
phenomena when a drop of water is admitted ;
at

their

that

is,

acid,

is increased
by the condensed
no evaporation. They allude,
the experiments of Henry and

the drop

and

suffers

to

however,

Berthollet, in

found in a

which water was supposed

to

union with

state of intimate

be

this

acid gas; and they mention some of their own,

in which one fourth of the weight of the gas

was found

to

be water.

This conclusion of

muriatic acid gas being the only gas that conwater combined with it, they consider as

tains

striking

and seem inclined

to consider

as a constituent of the acid, but that the

and hydrogen

water

oxygen

are not in the state of water.

Gay-Lussac and Thenard found that

fluoric

acid gas, detached from fluate of lime by boracic acid, does not dissolve silica, on account

of the boracic acid which

it

Another remarkable

was,

fact

holds in solution.
that fluate of

lime, distilled with sulphuric acid in leaden

vessels,

does not give the fluoric acid in an

elastic,

but in a liquid form.

as

Davy had

They observe,

done, that in burning potasium

in siliceous fluoric acid gas,

some hydrogen

is

given out, amounting successively to about

one third of what would be given out by water.

OXYGEN WITH AZOTE.

316

They seem
composed

think

to

acid

the

that

case

in this

but

de-

is

they have not

advanced any opinion, that either

fluoric

or

muriatic acid gas consists entirely of hydrogen

and oxygen.

SECTION

2.

OXYGEN WITH AZOTE.

The compounds
therto

of oxygen with azote, hi;

they may be disfollowing names ; nitrous

discovered, are five

tinguished by the

gas, nitric acid, nitrous oxide,

and oxynitric

nitrous

acid,

In treating of these,

acid.

it

has been usual to begin with that which con-

oxygen, (nitrous oxide) and to

tains the least

take the others

oxygen.

Our

in

order as they contain more

plan requires a different prin-

namely, to begin with

most simple, or which consists

ciple of arrangement

that

which

is

of the smallest

which

is

number of elementary

commonly

particles,

compound, and
ternary and other higher

a binary

then to proceed to the

compounds. According to this

becomes necessary to ascertain,

principle,
if

it

possible,

whether any of the above, and which of them,

is

a binary compound.

As

far as the

specific

OXYGEN WITH AZOTE.

317

gravities of the two simple gases are indicative

of the weights of their atoms, we should conclude that an atom of azote is to one of oxy-

gen

as 6 to

7 nearly

ammonia and water

such a

ratio.

weights of
countenance to

the relative
also give

But the best

from a comparison of the

criterion

is

derived

of

specific gravities

Nitrous gas
gases themselves.
has the least specific gravity of any of them ;
the

compound

this

indicates

it

to

be a

compound ;
much
be ternary com-

binary

nitrous oxide and nitrous acid are both

heavier; this indicates them to

pounds

and the

latter

being heavier than the

is heavier than

former, indicates that oxygen

azote, as
the latter.

already

oxygen is known to abound most in

Let us now see how far the facts

known

v/ill

corroborate

these

ob-

servations.

According

to

Cavendish and Davy, who

we yet have in regard

are the best authorities

to

these

under

compounds, they are constituted

as

OXYGEN WITH AZOrt.

318

Sp. gr. constitution bv \vcight.

iS'itrousgas 1.102 +0.G azote -|- 13.4- oxy.

Ratios.

H-.2

5.5:7

+2.3
Nitr. oxide 1.6 1 i

-I- 3(i..5

02

2AU 29.5
28
2/;.

The above

table

is

:7

2XIJ1:7
2X5.7:7
2X5.4:7
5.8:7X2

.',if)

-j_70.5
-1-70.4

'2[).(i

5.1:7

-f-38

Cil

Nitric acid

6.

+ 55.8
H-57.7

5.9:7

X
2^
:2>
X^

4-72

5.4:7

4- 74.(3

4.7:7X23

/-

principally taken from

Davy's Researches: where two or more results

are given under one article, they are derived

from

different

column

modes of

In the third

analysis.

are given the ratios of the weights of

azote and oxygen

in

each compound, derived

from the preceding column, and reduced to

the determined weight of an atom of oxygen,
This table corroborates the theoretic views

7.

above stated most remarkably. The weight

of an atom of azote appears to be between 5.4

and

6.1

and

it

is

worthy of notice, that the

from the experi-

theory does not differ more

ments than they

differ

from one another

or,

words, the mean weight of an atom

of azote derived from the above experiments
would equally accommodate the theory and

in other

the experiments.
all

The mean

is

5.6y to

which

We

should

the others might be reduced.

then have an atom of nitrous gas to weigh

12.6, consisting of 1 atom of azote and 1 of

OXYGEN WITH AZOTE.

oxygen

3 IP

an atom of niirous oxide to weigh

and

18.2, consisting of 2 atoms of azote

oxvgen

and an atom of nitrous acid

19.6, consisting of

Nor has

oxygen.

for,

weight of an atom of

the

obvious that

10, or

or

3,

is

it

of

weigh
atom of azote and 2 of

oxygen any influence on the theory

compounds
were taken

to

of these

if

oxygen

any other number,

the ratios of azote to oxygen in the compounds would continue the same the only
difference would be, that the weight of an
atom of azote would rise or fall in proportion

still

as that of oxygen.

I have been solicitous to exhibit this view of

the

compounds of azote and oxygen,

rived from

the experience

of others,

as

de-

rather

because, not having had

similar to mine, the authors

than from

my own

any views

at all

could not have favoured them by deducing the

above results, if they had not been contormablc
to actual observation.

come now

make some

to

the results contained

and

to state those of

in

observations on

the preceding tables,

my own, which

have been

obtained with labour and assiduity.

I

true

the

believe

atom of

mean

or 5.2.

above mean weight of an

and that the
is too
large

azote, 5.6,

is

but

little

above 5; perhaps

do not mean by

this

5.1,

observation to

OXYGEN WITH AZOTE.

:>20

insinuate that the

results

the above

in

table

are derived from inaccurate experiments.

the course of

repeat the

found no

my

investigations,

experiments

results to

ot

his

in

those

vances, however, greater precision

from the same

As

facts.

general
of Mr.

As knowledge

Researches.

for

is

to

but have

ovvqi in

to

In

have had

many

which my

approximated so nearly as

Davy

ad-

attainable

Mr. Cavendish's

important experiments, they were intended to

shew what elements constitute nitric acid, rather than

were made

them

and they
;
of
period
pneumatic

the proportion of
at too early a

chemistry to obtain precision.

The first line of the table contains the proportions of azote and oxygen in nitrous gas, as

determined by the combustion of pyrophorus,

Mr. Davy

justly considers this as least entitled

to confidence.

The second and

third

were

obtained from the combustion of charcoal

nitrous gas.

The second

is

the oxygen found in the carbonic acid.

making

in

grounded upon

the calculation of this from

By

more

re-

cently determined proportions of charcoal and

oxygen,
is

Mr. Davy

The

reduce the azote to 5.4.

derived from the azote

finds 15.4

yield 7.4 of azote

left after

third

combustion.

measures of nitrous gas

or 100 measures of nitrous

gas yield 48 measures of azotic gas.

OXYGEN WITH AZOTE.

Dr. Priestley was the

first

to

321
observe that

the electric spark diminishes nitrous gas, and

finally leaves azotic gas ; he states the reduction

be to one fourth of the volume.

,to

have

experiment with all

to
attention
accuracy ; the exact quan^
possible
several times repeated this

tity

of azote in the nitrous gas

was previously

determined by sulphate of iron, and was commonly 2 per cent. the quantity of jO or 100
;

water grain measures of the gas was put into a

narrow eudiometer tube over water, furnished

with platina wires ; the electrification was for

one or two hours, and uninterruptedly continued till no further diminution was observable.

To

the residuary gas a small portion of

mon
In

com-

was added, and no diminution found.

way, from 100 measures of pure nitrous

air

this

gas there are obtained at a mean 24 measures

of azo^c gas ; or, which is the same thing,
102 measures of the 98 per cent, gas leave a
The deviation was
residuum of 26 azote.

never more than

()er

cent, from the

above

from 100 measures of pure nitrous gas

never obtained more than 25 measures of

that

is,

azote, nor less than 23.

that

24 measures may be

I believe,

therefore,

safely relied

upon

as

an accurate approximation.
This experiment, taken in conjunction with
the last mentioned one of Mr. Davy, is of

oxYonv with azote.

3'22

not only shews the con-

It

great importance.

stitution of nitrous gas,

It

also.

appears, that

actly one half of the

and

its

oxygen

electric

and oxygen,
nitrous gas
it is

rated,

gas,

azotic gas

The immediate

shock

nitric acid

by electrification exis

liberated

joins to the ofher half to

acid.

nitric

but that of

to separate the

is

which by
the

moment

form

of the

effect

atoms of azote

their junction

form

the

libe-

oxygen
atom of

seized by another

is

nitrous

and the two united form an atom of

which escapes into the water. In

other words, ICX) measures of nitrous gas connitric acid

tain

48 of azote

by

electrification,

sures of azote are liberated,

measures acquire the oxygen

mer, and become

24 mea-

and the other C4

by the forwhich are ab-

lost

nitric acid,

sorbed by the water.

repetition of Mr. Cavendish's experiments
\\\\\ be found to confirm the above conclusion.

have

in three

or four instances

undertaken

experiments of the same nature, and with like

results ; but as these are of a laborious kind,
it

is

not so convenient to execute them.

One

of these was more particularly an object of attention, and I shall relate

it

in the detail.

quantity of pure oxygenous gas was diluted

common air by degrees till the mixture

contained 29 measures per cent, of azote, that
with

OXYGEN WITH AZOTE.

323

being presumed to be nearly the due proportion

The test was, exploding
to form nitric acid.
it with hydrogen, and taking -^ of the diminution

for

oxygen.

portion of distilled

water was impregnated with

gases,

and put

Into

with platina wires.

the

mixed gases were

cation

commenced

trification,

it

mixture of

all

and the

electrifi-

several hours elec-

after

50 measures of

this,

put,

was reduced

continued there

this

into a eudiomet-jr furnished

to

20 measures

it

night without any change,

operation was resumed next day, and

These
the gas was reduced to 13 measures.

the

to be 34 azote + 9^ oxygen ; or
73 oxygen per cent.
Hence it
was evident, that 29 measures per cent, of

were found
27 azote

azote were too small

above data,

it

by calculation from the

30 measures

will be found that

of azote unite to 70 of oxygen to form nitric

This gives 27 of azote by weight, and
acid.

73 of oxygen
agrees with

in

the

nitric

mean

acid

which nearly

of Cavendish.

From

weight of an atom of azote comes out

By the experiment on nitrous gas, sup-

this, the

5.15.

posing its specific gravity 1.10, and that of

azote .966, the weight of an atom of azote

comes out

With

5.1.

respect to nitrous oxide, I think

Davy's calculations scarcely

do justice to

Mr.
his

OXYGEN WITH AZOTE.

324

The

experiments.

line

first

derived from the combustion

oxide.

nitrous

Mr. Davy

selects

nitrous oxide

of

results

hydrogen

several

one

which 39 measures of

in

experiments,

and 40 of hydrogen were

fired

each

saturate

just to

residuum of 41 azote

other, leaving a

in

From

together, and seemed

this

shews the

but

residuum must have contained a few atoms

of azote originally mixed with the oxide and

may therefore be supposed

the hydrogen, and

to

be overrated.

we

If

contain 40 azote,

it

suppose 39 oxide to
weight of

will reduce the

an atom of azote from

6,1 to 5.6.

In

my own

equal volumes of nitrous oxide

hydrogen, saturate each other, and the

experience,

and

volume of azote
other two,
purities.

left

is

equal to one of the

making the due allowance for imThis would imply that a measure of

measure of oxygen, should,

when combined, constitute a measure of nibut the united weights are about
trous oxide

azote

half a

5 per cent, too

gravity

little,

hend the oxygen

perhaps

according to the specific

of the oxide given above.

to

this

way

appre-

underrated,

owing

the formation of an

quantity of nitric acid.

we

is

unperceived
In the second line,

have the proportions of azote and oxygen

from the combustion

in nitrous oxide, derived

of both phosphuretted hydrogen and charcoal

OXYGEN WITIf AZOTE.

in

the oxide.

By

325

the former, nitrous oxide

gave an equal volume of azote ; by the latter,

21 measures of oxide produced 21.5 measures
of azote, and 11.5 measures of carbonic acid.

Now, if we suppose that a measure of nitrous

oxide contains an equal volume of azotic gas
weighing .966, and the rest of the weight,
.(548 to

azote
ther,

+
it

be oxygen, the proportion will be 60

40 oxygen per cent, by weight. Furis

now known

that

11.5 measures of

carbonic acid contain 11.5 measures of oxygen ; hence 21 measures of nitrous oxide must
contain 11.5 measures of oxygen

say

20 mea-

sures of oxide, because 9,0 being used in

all,

and 9 pure being abstracted from the residuum,

the remainder 21 must have contained the impurities

in all

the 30 measures,

which could

This gives as before,

scarcely be less than 1.
60 azote + 40 oxygen by weight per cent, in
nitrous oxide.

The

third line gives the results

obtained from the combustion of sulphuretted

hydrogen ; here Mr, Davy found 35 measures

of nitrous oxide saturate 20 measures of

sul-

of
phuretted hydrogen, and leave a residuum
seems
to
of
azote
This
measures
again
35^
:

equal in volume to the

oxide, and consequently will give as before,
60 azote
40
by weight ; and the

shew

that the azote

is

oxygen,

OXVCEN WITH AZOTE.

326

weight of ail atom of azote will be accordingly

found
5.25.

It

is'

remarkable, that

the combustion of

in

in nitrous oxide, the

hydrogen
mated by the

below par
in the

loss of

and

hydrogen)

it is

combustion of

has remarked

(as esti-

oxygen
is

usually found

the same with the azote

Mr. Davy

olefiant gas, as

have found

it

with carburetted hydrogen or coal

prehend when azote disappears,

formation of ammonia.

likewise

so

gas.

it is

I ap-

from the

Besides the three compounds of azote and

oxygen already considered, there are at least
two more. One is called Jii I rous 2ic\d ; it is a

compound
other

of nitric acid

I call

and

oxynitric acid

nitrous gas.
it is

The

compound

of nitric acid and oxygen.

Priestley discovered the fact that nitric acid absorbs nitrous
gas very Jargely, and thereby becomes more
volatile.

He

found that 1?0 ounce measures

of nitrous gas over water disappeared in a day

or two, when a phial containing 96 water
grain measures of strong nitric acid was inclosed with the gas.
The colour of the acid
as it absorbs nitrous
gas is gradually changed

from pale yellow

blue green.

to orange, green,

Mr. Davy has used

to find the
quantity

of

nitrou;.

his

gas

and

finally

endeavours

which

nilric

OJfYGEN WITH AZOTE.

acid absorbs

of 1.475

327

he estimates the blue green acid

84.6 nitric acid,

contain
sp. gr. to

7.4 water, and 8 nitrous gas, by weight

he concludes that dihite acids absorb

and

less ni-

gas in proportion than concentrated

This subject shall be presently consi-

trous
acids.

dered.
Priestley discovered that nitrous gas entered
into combination Vvith

oxygen upon the mixIn

ture of the

tv.'o

to saturate

one of the gases with" the other

but

it

gases.

this

unfortunately happens that

distinct

mixture.

By

to

the

above determined,

it is

two

compound

and

to another

the circumstances of the

constitution
it

easy

or three

are usually formed,

compounds

the proportion of one

varies according

way

of nitric acid

follows that 10 measures

of oxygen will require 18 measures of nitrous

But the
into nitric acid.
gas to convert them

mixture

gen

may be

managed

shall take either 13 or

intermediate
to

so

this

number.

as that 10 of

oxy36 measures, or any

As

the facts relating

matter have not been distinctly stated

by any author

have seen,

I shall

subjoin the

mv own experience.
When 2 measures of nitrous

results of

gas arc put

third of
one
a
tube
in
of
to 1 measure
oxygen,
in
inches
and
5
in
inch
an
diameter,
length,
1,

and

as

soon as the diminution

is

apparently

OXYGEN WITH AZOTE.

328
ceased,

which

will

be half a minute, ihe

resi-

duary gas is transferred into another tube, it

will be found that 1 measure of oxygen and 1.8
of nitrous gas have disappeared
is to be made over water.
2.

When

the mixture

4 measures of oxygen are put to

in a tube two tenths of an

1.3 of nitrous s:as

inch in diameter, and 10 inches long, so as to

it will be found that
measure of oxy;
will
combine
with
1.3
of
nitrous
gen
gas, in 4

fill it

or 5 minutes.
3.

When

trous gas are

measure of oxygen and

mixed

thin stratum of air, not

inch in depth (as in a

will

be found

3 to

3^ measures of

that the

and without any

are mixed, then

more than ^th of an

common
oxygen

tumbler)

will take

nitrous gas in a

agitation.
1

5 of ni-

together, so as to form a

it

from

moment,

If equal measures

oxygen takes about 2.2

nitrous.
4.

When

water has been made

to

imbibe a

given portion of oxygenous gas, and is after-^

wards agitated in nitrous gas, the quantity of
nitrous gas absorbed will always be

exhausted water would take,

more than

by a quantity

equal to 3.4 or 3.6 times the bulk of the oxy-

genous gas.

And,

vice versa^

when water

has imbibed a portion of nitrous gas, and is

then agitated with oxygenous gas, the quantity

OXYGEN WITH AZOTE.

329

absorbed wHl be greater than exbausted'water

would take, by z portion which bears

nitrous the ratio of

These

facts are

tained, and

to the

to 3.6.

of a nature easily to be ascer-

have no doubt will be found near

approximations to the truth, by those who may

repeat them. They are curious and singular ;
as we have few other examples where two
gases form a real chemical union in such varied proportions.

precisely as

above

results will not

mixed

If the gases be not

in a]l the

circumstances, the

be the same.

But

variations I have observed, I have

in

the

all

not found

oxygen to be saturated with less than 1.3, nor

with more than 3.6 measures of nitrous gas.
It is obvious that the presence of water, and
the shortness of the column of the mixed gases,

both contribute to
nitrous gas

the great expenditure of

the latter probably from

its

suf-

fering the union to take place instantaneously.

On

the other hand, a narrow tube

makes

the

operation more slow, and removes the point

of union far from the surface of the water ;
these circumstances

seem

to increase the

quan-

of oxygen entering into combination.

What then are we to conceive of this com-

tity

pound of oxygen and

azote, in

which

mea-

oxygen sometimes combines with 1.3

of nitrous gas, and sometimes with 3.6, and

sure of

OXYGEN WITH AZOTE,

330

according to circumstances takes any intcimediate portion ? Are there indefinite gradaI cannot conceive
tions in the compound ?
this

neither do the facts at

all

require

it.

All

the products that need be admitted lo explain

It has been shewn that
the facts are three.
1

rncasure ot

].8 of nitrous

oxygen requires

gas to form nitric acid, according to the results

derived from the electrification of nitrous gas

and the conclusion

It

facts.

and

4,

is

corroborated by other

appears from the above observations.

that oxygen is found sometimes to

combine with

3.6 times

its

bulk of nitrous gas,

but it is just
;

maximum

and that

this

twice

quantity requisite to form nitric

evident, therefore, that a compound

acid
is

the
it is

formed

in

is

the

which there

are twice

as

many

atoms of nitrous gas as are neccssaiy to form

This then may be called vitrnus
nitric acid.
and the elementary atoms consist of 1
of oxygen and 2 of nitrous gas, united by cheacid

mical afnnity.

minimum

If the other extreme, or the

quantity of nitrous gas to which oxy.9, or half what is

gen had united, had been

found

in

shewn

the union of 2

nitric

acid,

then this would

of nitrous gas, and the

called oxi/uifric acid.

not appear that

we

have

atoms of oxygen with

compound might be

Now, though

are able

as

it

does

yet to

form

OXYGEN WITH AZOTE.

this

compound

probable that

331

exclusively,

yet

it

is

highly

and

that

it

is

always

it

exists,

formed along with niiric acid, and perhaps

even with nitrous acid, when the oxygen consumed is more than 1 measure for 1.8 of nitrous
gas.

AVhen

measure of oxygen unites with

of nitrous gas, as mentioned in the first

observation, I conceive it is not purely nitric
acid that is formed, but a mixture of all the
1.8

three acids, in such proportions that the nitrous

and oxynitric balance each other, and in

when combined with water, these

the sequel,

two become, by

their interchange of principles,

nitric acid.

"We

shall

ticularly

now proceed

on the

and oxygen
here in a

different

but

it

table

may

their

to

remark more parof azote

compounds

not be amiss to state

constitution, as far as

appears from the preceding views and observations.

100 parts by 100 parts by

Wl.

off

Atoms

i2.1

17.2

jSitric acid

19.

Oxynitric acid
x^itious acid

2ti.l

2-1-1

=;

1+2

'20.1

J-fl

4-3

we can only

and nut the absoluLe

100 measures.

4-7 3..S

.>0

19.5 -I-S0.5 22.

:j2.7 4-G7.3'3(i

gravitie.> of the ihicc last not

rately determined,

in

=
=

nieas. contain

ox. azote,

31.2 =z 2 4-3

* The
specific

sures,

contain

uxv azote. OX}'?.

42.1 +37^9 48
-f- 30.6
UO.l
3S 3

fliiatoinl azote,

Nitrous gas
Nitrous oxide

ofl u't.

7(^*

77,9
63 8

being accu-

give the latios of the mea-

quatitities of azoLe

and oxygen

OXYGEN WITH AZOTE.

332

Nitrous gas
nitric acid

Gas.

'droits

I.

is

formed by pouring dilute

upon many of the metals

The

be received over water.

best

it

should

mode of

procuring it is to put a few small pieces or

filings of copper into a gas bottlcj and pour

on

nitric acid of the specific gravity 1.2 or 1.3

to

them

the gas

(except so far as
air)

comes over
it is

a state of purity
diluted with atmospheric
in

and without the application of

The

heat.

common

explanation of ihis process is, that a

of
the
nitric acid is decomposed into the
part
elements nitrous gas and oxygen ; its oxy-

gen unites to the metal

which the rest of the acid

more

to

form an oxide,

dissolves.

Upon a

particular examination of the phenomena,

find, that csiimaiiiig the quantity of real

acid by Kirwan's table, ^ part of the acid is
decomposed to furnish oxygen to the metal,

and
tallic

to yield nitrous
gas,

unites to the

oxide, and the remaining

nitrous gas,

and forms nitrous acid

degree of condensation of the acid,

to hold

more than

therefore evolved.

measures of

nitric

-f

or

^ of

it,

seizes

methe

but in the
it is

and the

unable
rest

is

For example, 200 grain

acid of 1.32 strength, di-

luted with 100 water, dissolved

50 grains of

NITROUS GAS.

333

copper, and yielded 44 cubic inches of nitrous

gas =15 grains. Now, 200 measures of the
acid contained 102 grains of real acid

and 50

of copper require 35 of nitric acid, which is

nearly 4- of 102 j every atom of copper takes

two atoms of oxygen to form the oxide, and

oxide takes two atoms of nitric acid to
form the nitrate of copper (as will be shewn in
the sequel) ; whence it appears that whatever
this

quantity of acid

is

employed

to

oxidize the

copper, an equal quantity is required to unite

to the oxide ; the quantity of nitrous
gas given
out should therefore have been 22 grains, but

was only 15 it seems, then, that 7 grains

of nitrous gas combined with the remaining
acid to form" 7iz/ro7/5' acid, part of which was
it

probably volatilized by the heat excited in the

mixture.
Nitrous gas, according to Kirwan, has the
specific

1.102

gravity
this last

to truth, as far as

1.19
is

according

to

Davy

the neaiest approximation

my

Its ul-

experience goes.

timate particle weighs nearly 12.1 of hydrogen ; the diameter of it in an elastic state is
.958, that of hydrogen being 1 ; if a measure
of hydrogen contain 1000 atoms, the same
measure of nitrous gas will contam 1136
atoms.
This gas is highly deleterious when

inspired in a

dilute

state; if pure,

it

is in-

OXYGEN WITH AZOTE.

334

It extinguishes combustion in
but
pyroj^horus spontaneously takes
general ;
fire in it ; and phosphorus and charcoal in an

stantly fatal.

ignited state burn in

position.

it,

Pure water,

absorbs about ^^th of

all air) I find,

of nitrous gas

and produce a decom(that is, water free from

but only -^^th of

pelled again by other gases

it

it

its

bulk

can be ex-

should seem,

of the gas actually

combines with the water, while the greater
part is, like most other gases, mechanically
then, that a small portion

retained by external pressure.

Nitrous gas, as has been observed, is decomposed by electricity one half of the azote is
:

liberated, and the other half unites with the

evolved oxygen, and forms nitric acid. Ac-

cording to Davy's analysis by charcoal, nitrous

gas

is

constituted of 2.2 azote, and 5

by weight

cent, nearly

by

oxygen

or 42 azote, and 58 oxygen per

;

electricity

which

is

the

same

and other means.

as I

obtain

If completely

decomposed, 100 measures tvould be expanded

to lO'kG, of which 48 would be azote, and
56.6 oxygen.

Dr. Henry has recently discovered that

ni-

decomposed by ammoniacal gas i

the two gases are mixed over mercury in.
Volta's eudiometer, and an electric spark is

trous gas

found

is

sufficient to

explode them.

V/hen an

335

NITROUS GAS.
excess of nitrous gas

is

used, the products are,

azotic gas and water with a small portion of

nitric acid

used, then

when an
azotic

are produced.

excess of

ammonia

is

and hydrogen
ammoniacal gas is sent

gas, water,

When

through a tube, containing

manganese red

hot,

Dr. Milner found that nitrous gas was formed.

These facts exhibit remarkable instances of
the decomposition and Composition of nitrous
gas.

The

degree of purity of nitrous gas

and accuratelv

is

easily

bv means of a

ascertained,

strong solution of certain salts of iron, particularly the common sulphate or green cop-

A measure of the

peras.

row

gas

tube, and the end of

solution

as

is

it

put into a nardipped in the

soon as a small poition of the

liquid has entered the tube, a finger is applied

to the end, and the liquid is agitated ; the

tube

is

again immersed

in

the liquid, and the

linger withdrawn, when a portion of the liquid

enters
the process is repeated till no more
:

gas

is

absorbed.

The

What

remains

is

usually

absorption
rapid, and the
in
a
This fact
minute.
operation completed

azotic gas.

was
to

first

know

is

observed by Dr. Priestley.

Wishing
more

the nature of this combination

minutely, I procured a solution of green sulphate, such that 6 grain measures contained

OXYGEN WITH AZOTE.

33(5

grain of the salt

1,081

this

its

specific

gravity

was agitated with iron

was

filings,

to

reduce any of the red sulphate that might be

in the solution, which is known not to absorb

A eudiometer

the gas, into green sulphate.

was

with mercury, except one measure,

which was filled with the liquid solution ; the
filled

tube was then inverted over mercury, and nitrous gas sent

to the solution,

up

afterwards agitated.
that

measure of the

sures of the gas,

which was

was repeatedly found

solution absorbed 6 meaIt

and was then saturated.

Con-

sequently 1500 grain measures of the solution

would have taken 9000 grain measures of the

gas ; but 1500 of the solution contained 250

of salt, of which |th was iron, as is well

known

and 9000 grain measures of the gas

Here, then, 50 grains of

weigh 12 grains

iron united to 12 grains of nitrous gas.

the weight of an atom of iron

and

that of nitrous ?as

is

12.

is

Now,

50 (page 258),

It therefore fol-

lows, that in the combination

of green sulphate of iron with nitrous gas, each atom of

iron unites with an atom of the gas, agreeably
to the general law of chemical union.

Nitrous gas is still used in eudiometry to

determine the quantity of oxygenous gas in
any mixture ; and on account of the ease and

elegance of

its

application,

and the quickness

NITROUS GAS.
with which

be used.

it

337

attaches that gas,

it

will

always

has been found, however, that

It

the simple mixture of the two gases is not

enough to discover the proportion of oxygen,
by reason of the different compounds that are

The

formed.

object

may be

effectually

ob-

tained, by using an excess of nitrous gas of a

known strength, and then abstracting the sur-

Some
plus by means of sulphate of iron.
authors prefer a solution of green sulphate of
iron saturated with nitrous gas
is

the oxygenous

agitated in a portion of the solution,

gas
the residuary gas

is

washed with a

and

solution ot

the sulphate, unimprcgnated with nitrous gas.

But the quantity of oxygen

is

in certain mixtures

ascertained with equal or greater precision,

by

firing

it

with hydrogen in Volta's eudio-l of the

diminution for

meter, and taking

oxygen

or by agitating the gas in a small

portion of sulphuret of lime, which abstracts

the oxygen.

When

nitrous gas

is

mixed with oxymu-

riatic acid gas over water, an instantaneous

I was in
diminution of volume takes place.
this
would
convert
the
nitrous
expectation that

gas into pure nitric acid, and consequently

the quantity of oxygen necessary would be
ascertainable this way ; but the two gaseSj
like

oxygen and

nitrous gas,

combine

in

va-

OXYGEN WITH AZOTE.

3SS

rious proportions, according as

in excess.

Sometimes

one or other

and some-

are saturated with 2 of the acid,

times w'th 4 measures.

of iron

is

saturated

nitrous gas,

is

measures of nitrous

When

with a

green sulphate

known

and the solution

is

portion of
afterwards agi-

tated with oxygen, the absorption

is

somewhat

with sulphuret of lime) and

slow, (like
the quantity taken up is equal in bulk to the
The liquid, from a dark red or
nitrous gas.
that

black,

becomes of a bright yellowish

red, the

oxide of iron being changed from the green to

the red during the process.
It has been made appear, that by electricity
one half of the atoms of nitrous gas are decom-

posed, in order to oxygenize the other half;

in

like

manner,

in

certain

cases, ont^ lialfoi

the atoms of nitrous gas are

azotize the other half.

This

is

decomposed to
shewn by the

much more
The alkaline

experiments of Priestley, but

curately by those of Davy.
phites, muriate of tin,

and dry sulphures, con-

vert nitrous gas into nitrous oxide.

to

acsul-

Davy, 16 cubic inches of

According
were

nitrous gas

converted into 7.8 of nitrous oxide by sulphite

of potash ; that is, 100 measures gave 48.75

he also found, that muriate of tin and dry sulphures changed 100 measures of nitrous gas
These bodies have
into 48 of nitrous oxide.

KITROUS OXIDE.

an

339

and the

moment they
affinity
oxygen ;
take an atom of
oxygen from one of nitrous
gas, the atpm of azote joins to another of nifor

trous gas,

and forms one of nitrous oxide.

this

way, all the azote remains

oxide, and just one half of the

In

in the nitrous

oxygen. By
from the preceding
table, (page 331) and from the known
specific
gravities of these gases, it appears that 100
the calculation

making

measures of nitrous gas should make 48.5 meaand allow 28.3 measures

sures of nitrous oxide,

of oxygen to combine with the bodies introduced.

It is
very remarkable that these numerical relations should have so
long escaped
observation.

Sulphuretted hydrogen and moistened iron

also convert nitrous
gas into nitrous

filings

but some

ammonia is produced at the

expence of the azote, and consequently less
nitrous oxide
Davy finds about 42 or 44
oxide

per cent.

'J.

The

gas

Nih'ous Oxide.

now denominated

was discovered, and

several of

pointed out, by Priestley

^'sticated nitrous gas.

nitrous oxide,
its

he called

The Dutch

properties
it

dcphlo-

chemists

OXYGEN WITH AZOTE.

340

published an essay on the subject in the Journal

de Physique for 1793, in which the consti-

and properties of the gas were more

tution

In 1800, Mr.

fully investigated.

lished his Researches, containing a

Davy pubmuch more

complete and accurate developement of the

nature of this gas, than had previously been
given, as well as of the other compounds of

azote and oxygen, and several other collateral

ones.

may be obtained from a

Kitrous oxide gas

ammonia, being a comacid, ammonia and water.

nitrate of

salt called

pound of nitric

The

salt is

put into a gas bottle, and heat apfirst fuses the salt, about 300"
;

which

plied,

by continuing the heat, the fluid salt boils,

and is decomposed about 400, emitting nitrous
oxide gas and steam, into which the whole of
the

salt is

principally resolved.

The

gas

may

be received either over water or mercury.

The

constitution of the

monia, according
lized,
ter

to

salt,

Davy,

is

nitrate of

when

crystal-

18.4 ammonia, and 81.6 acid and wa-

Now,

if

we

suppose an atom of

ammonia

to be constituted of one of azote, 5.1,

of hydrogen,

and

am-

1,

as

will

and one

be shewn hereafter,

that an atom of the nitrate is composed of

atom of each of the elements, ammonia,
nitric acid and water, (see
plate 4, fig. 36) j
1

NITROUS OXIDE.

we

shall have, 6.1

19.1

341

+8=

33.2 for the

weight of an atom of the salt. This gives

18.4 ammonia, and 81.6 acid and water, exactly agreeing with the experimental results of

The decomposition

Davy.

of an atom of the

be found to give one atom of nitrous

oxide, weighing 17,2, and two atoms of wasalt will

ter,

weighing

the

salt

16.

100 grains of

AV^hence,

should be resolved by heat into 51.8

of
nitrous oxide, and 48.2 grains of
grains
water.
Mr. Davy decomposed 100
of a
parts

dried nitrate, that

cent, of

its

is,

one which had

lost 8

per
water of crystallization, and ob-

tained 54.4 nitrous oxide, 4.3 nitric acid,

41.3 water.

and

Here,
might be expected, the
oxide exceeds, and the water falls

nitrous

as

short of the calculation, but as nearly as possible in the due proportion.

Thus it appears,
that whether we consider the genesis of nitrous oxide from the nitrate

of ammonia, or

from nitrous gas (page 338), still its constitution must be 2 atoms of azote and 1 of
oxygen.

The

specific gravity of this gas

weight of

its

meter

an

in

is 1

atom 17.2 of hydrogen

elastic

state

(to

.614
j

the

the dia-

hydrogen

l)

is

a measure of hydrogen contain 1000

atoms, one of nitrous oxide will contain 1176
,947

if

Most combustible

bodies burn in nitrous oxide

OXYGEN WITH AZOl

3f?

more vigorously than

unfit for respiration,

in

common

may be
that

it

respired for

air

it

is

but does not so immedi-

ately prove fatal as Dr. Priestley

chemists concluded.

E.

and the Dutch

Mr. Davy found that it

two or three minutes ; and

generally produces sensations analogous

of intcji^ication.
It is absorbed by

to those

water

to the

cording

amount of about 80 per

to n)y

cent, ac

Davy makes it
but he was not aware that

recent

ttials.

only 54 per cent.,

the quantity is increased in proportion to the
Dr. Henry finds
purity of the residuary gas.

from 78 to 86 per cent. This gas of course

expels other gases from water, and is itself
driven off unchanged by heat.
It is a retake so
should
that
water
fact,

markable
nearly,

and yet not exactly,

bulk of

its

this

gas.

Nitrous oxide, by long electrification, loses

10 per cent, of its bulk
some nitric

about
acid

is

oxygen

formed, and a mixture of azote and

is

found

in the

residuum

but no

satis-

obtained this way.

factory decomposition
All the combustible gases, mixed with niis

trous oxide, explode by an electric spark.

Nitrous oxide can be

the fixed alkalies

made

to

combine with

but the nature of the com-

pounds has not been much examined.

343

NITRIC ACIU.

3.

Nitric Acid.

Nitric acid, formerly distinguished by the

names of aqua fortis, and spirit of nitre, has
been known for three or four centuries. It is

now

usually procured by distilling a mixture

of nitrate of potash (saltpetre or nitre) and sulphuric acid. Two parts of the salt by weight,

and one of concentrated acid,* are to be

mixed in a glass retort ; heat is applied, the
mixture becomes liquid, and soon exhibits the
appearance of ebullition, when a yellowish
liquid drops from the retort into a
It

ceiver.

active

is

nitric

and corrosive of

thus obtained,

glass re-

one of the most

acid,

When

the acids.

all

usually pure enough for

the purposes of the arts ; but it mostly con-

tains

it

is

both sulphuric and muriatic acid the

is derived from the acid
employed be:

former

ing in part distilled, espeoially if an excess of

it be used and the heat be
great ; the latter is
* Authors
acid

differ greatly as to the

some say

weights; but

3 salt to

of acid

acid to 2 salt

is

proportion of

salt

and

others say nearly equal

that

which

wij]

nearly sa-

turate the base, and must therefore be right, unless an excess of sulphuric acid be expedient to displace the

which does not appear.

iiitrif,

OXYGEN WITH AZOTE.

344-

derived from the nitre, which usually contains

some muriates mixed with it. To obtain the
acid pure, the nitre should be repeatedly dissolved in warm water, and crystallized, taking

out the

first

when

acid,

formed crystals

for use

and the

obtained, should be treated with

precipitate the sulphuric
of silver to precipitate the

nitrate of barytes to

and

acid,

nitrate

muriatic acid.

The

theory of this process is well underof potash is a compound of

nitric acid and potash
sulphuric acid has a

stood

nitrate

-,

stronger affinity

for

potash

therefore displaces the nitric,

than nitric

it

which with the

water of the sulphuric acid and that of the nitre,

is distilled
by the heat, and the compound of
acid and

water constitutes the liquid nitric

Near the end of the process, the

acid above.

heat

is

acid

advanced

is

partly

to 500

and upwards, and the

decomposed

some oxygen

is

given out, and nitrous gas, which combines

with the acid, and forms nitrous acid vapour.

This acid becomes mixed with the

trous

by

it

heat,

and

and

nitric,

more fuming and volatile. The niacid may be driven from the liquid nitric

renders

and then the

last

becomes

less volatile,

colourless like water.

The

nitric acid
specific gravity of the liquid

thus obtained,

is

usually from 1.4 to l.n

Bv

NITRIC ACID.
fusing the nitre previously,

345

and boiling the

sulphuric acid till its temperature was 600, I

obtained a quantity of acid of 1.52.
Byredistilling

with a moderate heat,

it

may be

obtained of 1.55, and even as high as 1.62,

according to Proust (Journal de Physique,

The

1799).

strength of the acid, that

quantity of real acid

is,

the

in a

given weight of the

in
increases
some
liquid,
proportion with the
as will presently
specific gravity,

be shewn.

Some

of the more remarkable properties o

the liquid nitric acid follow
1. It emits white
:

vapour when exposed to the atmosphere, owing to its combination with steam or aqueous
vapour

this

distillation

is

rendered more evident in the

of nitric acid

if

the elastic vapour

escaping from the receiver, it

exhibits a white cloud when breathed upon.

of the acid

2. It

is

water.

is

sour to the taste,

3.

substances,

It

when

diluted with

corrodes animal and vegetable

and

stains

them yellow.

4. It

combines with water, and, when concentrated,

attracts it from the atmosphere j heat is produced, and a small increase of density. With
it
produces, a great degree of cold, and

snow

instant liquefaction.

5.

It

is

said to be de-

composed by the solar light, giving out oxy6. It

gen, and becoming orange coloured.
inflames several combustibles, such as very dry

OXYGEN WITH AZOTE.

S46
charcoal,
tilled

essential

oils,

over sul[)bur,

it

into sulphuric acid.

8.

&c.

7.

When

converts the
It

dis-

sulphur

oxidizes the metals,

has been observed, and gives out nitrous

9. When the vapour of nitric acid is
gas.
as

passed through a red hot earthen tube, the

acid is decomposed into oxygen and azote.

The same decomposition

nitre red hot in

is effected
by heating
an iron or earthenware retort.

and me-

10. It unites to the alkalies, earths,

tallic

oxides,

forming

salts

denominated

ni-

trates.

One

of the most important considerations

is the determination of

relative to nitric acid

the quantity of real acid in a watery solution

of a given specific gravity. This subject has

encased
mists,

the attention of several eminent che-

particularly

Kirwan, Davy, and Ber-

Their results are widely different.

For instance ; in an acid of 1.298 sp. gravity,
thollet.

Kirwan

Davy

says the real acid

says 48,

is

Journal de Physique,

March

experience in regard to this

*

Berthollet,

3(3?

and Berthollet 32 or

per cent.
33.

(See

1807;.*

My

particular has

by mistake, makes Davy represent the

acid iu question to contain 5'V per cent, of acid

but

it

is

the water which he says is 54- per cent, and the acid 4o,
when the sp. gravity is 1.283 ; so that the difTerencr, great
as

it is^

is

not quite so enonnous.

NITRIC ACID.

been considerable, and

347

now

shall

state

it

briefly

Nitric acid has been stated, on the authority

of Bergman, to boil at 248. This is true, if it

relate to acid of the strength 1.42 ; but ta
acids of

no other strength

in

fs

it

fact,

the

highest possible boiling point of the liquid

acid
but if the acid be stronger or weaker,
:

then the farther

is

the

it

deviates from 1.42, the less

temperature

which

at

it

The

boils.

weakest possible acid must evidently

boil at

SIZ''; but the point at which the strongest

acid boils has not been determined ; it will be

found, in

mon

all

little

probability,

above the com-

temperature of the atmosphere

I

of 1.52,

boils

find,

about

an acid

180 or 185^

of 1.G2 would probably boil

about 100% or about the same degree as elher.
The results of my experience will be noted
acid

Proust's

more

particularly in the following table.

sides this variable

there

is

another

which has been hinted

Paris

Memoirs

for

In the
by others
Lassone
and
Cor1781,
at

nette had ascertained that

acid

is

when weak

nitric

boiled or distilled, the weakest portion

but

when

the acid

comes over

first

centrated,

the strongest portion

first:

Be-

temperature of ebullition,
concomitant circumstance,

is

con-

conies over

In the Irish Transactions, vol.

4,

Dr. R.

OXYGilN

348

Percival has noticed

WITH AZOTE.
some

results in the distil-

lation of nitre; 2 lbs. of nitre

trated sulphuric acid

and

of concen-

were mixed and

distilled

the products were received in 3 portions ; the

first was of the strength
1.494; the second,

1.485; the third, 1.442: Proust, in the Journal de Physique, 1799, relates that he obtained

an acid 1.52

this

being again distilled, gave

product 1.51 ; for the second, 1.51,
nearly colourless, which he expected indicated
;

for the first

a superior specific gravity

him more, was to

and 1.47. This
first

portion was

the

find

residue

1.49,

but what surprised

residue colourless,

was

and the

distilled

rest 1.44.

the

In

another instance an acid 1.55 was obtained;

this redistilled gave,

and
facts,

the residue
it

appeared

first

was
to

me

1.G2, the second 1.53,

1.49.

From

all

these

reasonable to conclude

that an acid of some one strength, and only

one, was incapable of any change of strength
by distillation ; or was of such a nature, that

the distilled part and the residue were always

of the same strength and specific gravity.
The
actual strength of this acid

was a

desirable at-

such an acid evidently marks a

nice adjustment of affinities between the acid

tainment

and water
the two.

for

or a kind of mutual saturation of

By repeated experiments

acid to be of the specific gravity

I find this

1.42;

it is

NITRIC ACID.
remarkable also that

34P

this strength

has the boiling temperature a

is

that

which

maximum,

or

of inferior strength, being

distilled, the weakest part comes over first j
1^48.

Any

acid

and, vice versa, with one of superior strength.

For

instances,

by

distilling part of

an acid of

1.30, I found an acid of 1.25 in the receiver

again,

530 measures of

jected to distillation

acid,

were sub-

1.43

173 measures were drawn

over of 1.433, and 354 of 1.427 were

left

in

the retort: again, by boiling an acid of 1.35

for

some time,

it

became

of 1.48 became 1.46

boiling of any acid,

1.39

and another

continued

in short, the

weak

or strong,

makes

it

approach more and more to the density 1.42,

and

to the

With

temperature 248".

respect to the quantity of real acid in

a solution of given speciHc gravity, I find it

thus
Agreeably to the experience of Kirwan,
Richter, Davy, and my own, I conclude that
:

fused nitre

is

constituted nearly of 47.5 pure

and 52.5 potash per cent. Having dissolved 25 parts of this nitre in 100 water, I

acid,

find the specific

gravity, at

60%

1.130,

and

consequently 110.6 measures of the solution.

Any given nitric acid is saturated ivith pure
carbonate of potash, and reduced to the specific
gravity of 1.130; the measure of the solution

is

then found, and hence

we

have data

350

oxviJEN

WITH

Azorii;.

to calculate the real acid in

Now, lOG

grains of 1.51

the said soliitian.

acid

nitric

248

grains of a solution of potash 1.482, with wa-

gave G65 grain measures of solution of

30 sp, gravity, indicating 150 of

ter,

nitre of 1.1

Hence 106 grains of the acid conpure nitre.

tained 71.2, or 67 per cent, which is 1^ per
cent, less than

may
by

Kirwan deduces

it ;

and

this

from the escape of some acid

mixture with water producing heat.

partly arise
its

Again, 133 grains of 1.42 acid were saturated

with potash
they gave 672 measures of 1.13
solution, indicating 152 nitre; hence 133 acid
;

54 per cent, which nearly

contained 72

real, or

agrees with

Kirwan's.

1.35 acid

Again, 205 grains of

were saturated with 290 grains of

1.48 carbonate of potash; this diluted gave

850 measures of 1.13

solution, indicating 1S^2

205 grains acid contained 91

Teal, 44.4 per cent, which also nearly agrees
with Kirwan. Again, 224 grains of 1.315
nitre

that

acid, took

is,

300 grains of 1,458 carbonate of

potash; thrs diluted gave 804 measures of 1.13

solution, indicating 192 nitre; that is, 224
grains of acid contained 86.5 real,
cent.

this

is

38.6 per
near
Kirwan's
esextremely

timate.

Being thus satisfied with the near approximation to truth of Kirwan's table of nitric acid

351

yriTRIC ACID.

was notwithstanding desirous to discover, it

of error which have inpossible, the sources
I

fluenced the the conchjsions of

on

thoilet

this

subject,

whose

Davy and
results

Ber-

are

so

from each other and from those of

different

Kirwan.

That Mr. Davy has overrated

of real acid

from

this

in

the quantity

different solutions

is

manifest

he finds the acid 1.504 to contain

91.5 per cent. ; now, according to this, an

acid of 1.55 would be nearly pure or free from

water

whereas

nitric acid

has been obtained

of the specific gravity 1.62, without there being any reason to suppose it was free from
water.

Mr. Davy's method of combining

the

and oxygen, in order

to form nitric acid pure and free from v^ater in
the first instance, and then combining the acid
elastic fluids nitrous gas

with a given portion of water, was certainly

higlily ingenious, and it seems to have been
but that the results
executed with great care
way cannot be relied on, I am convinced
;

this

my own

from

experience, some account

of

be given. But what appears most surprising and unaccountable in his

results, is, how the combination of 47.3 parts

which

will presently

of his acid with 52.7 parts of potash should

form

nitre.

He

relates

one, 54 grains of 1.301

two experiments in
acid combined with
;

f>

OXYGEN WITH AZOTE.

52

potash, gave

Q)(S

grains of nitre, at

became 60 by

this

fusion

in the

212% and
other, 90

grains of 1.504 acid, saturated with potash,

In all the similar exgave 173 of dry nitre.

have made, I have uniperiments which

three
quarters of the quanformly found only
have been obtained above,
tity of nitre said to
I

from given quantities of the acid. I conclude,

therefore, that Mr. Davy must have committed

some

oversight in these

two experiments, and

from

that the direct formation of nitre

nitric

acid and potash, accords only with Kirwan's

estimate of the strength of nitric acid.
in the Journal de Physique,
informs
us, that he saturated 100
1807,

Berthollet,

March

of potash with nitric acid of 1.2978

strength, and obtained 170 parts of nitre j he
calculates the acid to contain 32.41 percent,
parts

real,

of

it

by which we may infer that 216 grains

were required. Nitre, according to this,

would be 100 potash

+ 41

70

acid per cent.

nitric acid, or

This

59

much more

is

potash
potash than ever before was detected in nitreare we to be satisfied that the potash

How

used contained no water

water,

and

this

If

would disappear

it

contained any

in

the process,

weight be supplied by nitric acid,

which would not be placed to the acid's acits

count.

That

this

was the

real fact I

have no

NITRIC ACID.
doubt

170 parts

S53

nitre are constituted of

about

89 potash, and 81 nitric acid ; the supposed

100 parts of potash were, I conceive, 89 parts
potash and 1 1 water, which of course caused the
acid to be underrated by

we have

this,

only
bonate of potash, such as

89 parts potash

1 1

parts.*

to take a

is

known

for instance,

To

prove

quantity of carto contain

170 parts of the

dry neutralized carbonate, or 200 crystallized,

Berthollet rightly determines to contain

which
89

parts of potash, and to this add 216 parts of

the above nitric acid, and 170 nitre will be

formed.

This will

also establish another fact

worthy of notice ; namely, that the quantities

of nitric and carbonic acid are the same to a
given weight of potash.

now proceed to give the table of the

of
nitric acid.
I have copied Kirwan
strength
for the strength due to each
I shall

specific gravity,

* Since
writing the above, I have been faroured with
the receipt of " Memoires de
Physique et de Chimie de la
Societe d'Arcueil.

Tome

2."

In

this

there

is,

amonsst

other very important and valuable

papers, one on the proBerportion of the elements of some combinations,

by

thollet.

The author

there determines,
page 5i, that potasli

kept for some time in fusion, still retains between 13 and

14 per cent, of water. Hence, he admits the
of
strength

nitric

acid

above given as

his to

be erroneous.

In the

sequel, he concludes that fused nitrate of potash contains

51.4 potash and 48.6

nitric acid.

OXYGEN WITH AZOTE.

354
except ihe

first

table has not,

and second column, which

and the three

last,

where

hi

think

he has overrated the quantity of acid ; indeed,

the lower part of his table is confessedly less
correct.

have already given

considering his table as

to the truth

made more

reasons for

approximating nearest
it
might be

but have no doubt

correct

have, therefore, only

two places of decimals

column of specific gravity. The column

extended the table

in the

my

to

of acid per cent, by measure, will be found

The
convenient for the practical chemist.
first

column shews the number of atoms of

acid and water in combination or collocation

in

each solution, agreeably to the preceding

j
namely, an atom of acid is

determinations

taken as 19.1 by weight, and an atom of water as 8.

The

last

column exhibits the boiling

as found by
points of the several solutions,

experiment.
experiments,

Those who wish to repeat

may be informed that a

these

small

globular glass receiver, of the capacity of 6 or

7 cubic inches was used, 2 or 3 cubic inches

of acid were put in, and then a loose stopper.

It was then suspended over a charcoal fire.

When

signs of ebullition began to appear, the

stopper was withdrawn, and a thermometer,
previously adjusted at the boiling point of water,

was

inserted.

It

may be proper

to

oh-

355

NITRIC ACID.
acids

{;erve, that

which have not previously

been boiled, or which contain nitrous acid,

usually begin to boil below 212 j but the vapour soon escapes, and the temperature advances to a stationary point. Nitric acid varies

by temperature more than

any other, as may be seen, page 44 ; there is,
however, an error of the press in the table
in specific gravity

alluded

to, for

alcohol and nitric

numbers should be
10" counts 6

that
J. 51

is,

if

.11,

upon the

at 60.

the

Every

it

will be
is

uni^

100 parts of

linui(J

as with Kirvvan.

real

nitric acid^ at the

\V.itcr

at 50",

The expansion with me

Table of the ijuantity of

Atomt,

acid

.011.

third place of decimals

an acid be 1.516

iorm, and not variable

AcM.

and not

acid in

temperature

ct

OXYGEN WITH AZOTE.

'J56

Remarks on

the above Table.

It seems not improbable, but that an acid

from water may be obtained, as repre-

free

sented in the

first

That such

line of the table.

an acid would be

but with

in the liquid state,

a strong elastic steam or vapour over

common

at the

it,

most probable ; in
temperature,
this respect it would resemble ether, but perhaps be more volatile. Seventeen per cent, of
is

water would bring it down to acid of the second line, and such as has actually been obtained

This

by Proust,

agree with ether in

would nearly

last

With

volatility.

to the specific gravity of pure

must be

less

than 1.8

nitric

respect
acid,

it

because a measure of

mixed with a measure of wawould make 2 measures of 1 .4, if there

that sp. gravity

ter,

were no increase of density

density

is

* The theorem

where

for specific gravities

specific gravity,

S
s

gravity,

its

its

is

specific gravit)',
specific

mixture or pompound.

1.8

_ 2.8

1.4.

'

1.8

OS

gravity,

Hence

this

apprehend

-^

represents the weight of the

specific

the

and acid of

nearly half water.*

-j

body

=
ot

Jj

if

',

greatest

the body of least

and

in the

that of

case above,

357

NITRIC ACID.
acid of the second line

gentle heat,

were

distilled

when mixed with

by a very

the strongest

sulphuric acid, that probably an acid free from

water would come over ; at least, a concentration

is

cases of

effected

weaker

by such process

The

acids.

other

in

receiver should

be surrounded with a cold mixture.

By

dis-

I
got
tilling an acid 1.31 off sulphuric acid,
an acid 1.43 ^ and an acid of 1.427 treated in

the same manner, gave an acid of 1.5.

2.

The

acid in the second line, consisting

of 2 atoms of acid and

of water, having only

been obtained by one person, and not particularly examined, we know of no peculiar
properties

it

has, besides the

specific

gravity

and boiling temperature but there can be

little doubt that it
possesses other properties
;

which

would

distinguish

it

from

all

other

acids.
3.
1

The

acid in the third line, consisting of

atom of acid and

of water, has not often

been obtained, and is therefore little known j

it seems to be that acid which fused
nitre, and
the strongest possible sulphuric acid (such as
it is to be had
by that mode of concentration,

which

consists

would give by

in boiling
distillation.

case, I suppose,

acid, not

is

from the

common acid)
The water in this

the

derived from the sulphuric

nitre.

It

may, however.

OXYGEN WITH AZOTE.

358

be oblained by repeated distillations of anjr

acid above 1.42

provided there

quantity of thar, and the

What

taken.
this

acid

nay

first

is

products always

the di*itinguishing properties of

be I have not had an oppoitunity

of i^ivestigaling.
4, The acid which consists of
acid and 2 of water,
It is

peculiarities.

is

fact

in

two elements.
in

that

atom of

which

saturation

Evaporation

constitution

its

possessed of striking

tutes a complete reciprocal

change

a sufficient

consti-

of the

produces

it distills

no

as water,

or any other simple liquid docs, without any

It acquires the temperature 248
alteration.

which is greater than nny oiber

of
the two elements acquires.
At
compound
the
is
acid
most
above
this,
any strength
copiat

boiling,

ously elevated by heat

the

water

most

is

at

any

below,
Pure water

stre-ngth

easily raised.

pnre acid perhaps at 30" ; the

union of both produces a heavier atom than

boils at 212

either,

and requires a higher temperature

for

but in proportion as either prin;

than is necessary for satuciple prevails tnore
ration, then the temperature at ebullition is

ebullition

reduced towards that of the pure element itProust has observed that nitric acid of
self.
1 .48,
produces no mo'-e effervescence with tin
than with sand whereas the lower acids act
-,

359

NITRIC ACID.
most

violently, as

well

is

find as Proust states

it.

to think that acid of 1.48

constitution

but

known.

'Hie fact

This would lead one

was

of

some

peculiar

this characteristic

presume

of nitric acid belongs to that of 1.42, rather

not but that the former certainly
than 1.4 8
:

acts on tin
this

when

but the explanation

conceive

the nitric acid in its action

is

on me-

element
disposed to form ammonia, (an
one of
and
atom
of
azote
constituted of one

tals is

acid and \
hydrogen united) 1 atom of nitric
3
the
atoms of
of water are decomposed
and
azote
the
and
the
metal,
oxygen go to
;

an atom of ammohydrogen unite and form

1
atom of acid
were
there
nia ; if, therefore,
to 2 of water, there could be

atom of watev

detached, which would of course join

remaining acid, and dilute it the more
there

then,

were 2 atoms of acid

for

to the
;

but

it

of water,

detaching 3 atoms of oxygen, would

atom of nitrate of ammonia and 1 ot

leave an

water, constituting the salt of that name, and

one surplus atom of water. In this case, the

remaining acid

is

not diluted with water by

the process, lower than

therefore, (which

is

to

about 1.47)

lowest that can operate upon tin

out any effervescence.

2.

Such acid,

is

probably the

this

way

with-

OXYGEN WITH AZOTE.

360
5.

The

acid

composed of

to 3 water, ha's

not any peculiarity yet discovered.

6.

for
all,

The

acid of

to 4 water,

is

remarkable

being that which freezes the most

namely

at

to Cavendish.

easily of

2 of Fahrenheit,

The

according
of the acid is

strength

such, as that 1000 parts dissolve 418 of marble :

Now, 418 of marble contain 228 of lime, and
these require

370 or 380 of

nitric acid,

therefore agrees with the acid of

and with

that only.

Above

which

to 4 water,

that strength, or

below, the acid requires a greater cold to

freeze it.
The inferior acids appear to have

no remarkable

differences, except such as the

but the temperature of freezing
descends to some undetermined point, and then

table shews

ascends again.
7. The notion of those

who

intensity of acid solutions to

consider the

be proportionate

to the quantity per cent, of the acid, or to their

density,

seems incorrect

to determine.

It

is

with

is

true, the acidity or sour-

ness of the solution, the

fervescence

as far as nitric acid

power

carbonates,

to

produce efand perhaps

other properties, increase nearly as the quantity or strength ; but the freezing and boiling
temperatures,

the

action on metals,

as

tin,

&c. have successive waves, and abrupt termi-

36i

KITRIC ACID.
nations,

which indicate something very difwhich varies

ferent from that gradation in action

in the ratio of the quantity.
I

have frequently attempted

nitric

to exhibit the

acid in a pure elastic form, and free

from water, but have uniformly failed. Some

account of the experiments may, notwithstanding, have

its

In order to form the

use.

from nitrous and oxynitric, I

used large receivers and quantities of gas,
amounting to some hundreds of cubic inches,
nitric acid free

and delivered the nitrous gas

and

vice versa, in the

and slowly

still

to the

oxygen,

centre of the receiver,

the ratio of

oxygen

to nitrous

The experiments were

gas was variable.
made over water. Wishing to exclude water
as

much

as possible, I procured

receivers,

inches

containing from

to these stopcocks

15

some globular
to 60 cubic

were adapted, so

them with the air-pump or with

These were first filled with
other receivers.
as to connect

oxygen gas or common

and then

partially

afterwards they were connected

with receivers over water, containing known

exhausted
ft

air,

quantities of nitrous gas,

opened

the

moment

and a communication

after the nitrous gas

had

entered the globe, the cock was turned ; great

eare was taken to dry the globe previously to
the experiment, and to prevent any water en-

OXYGEN WITH AZOTE.

S62

tering with the

gases

(except the steam which

have, the quantity of which is

air,

commonly

any temperature). The

were mixed, the globe
with dense orange coloured gas,

easily ascertained

instant the

was

filled

two

for

f^ascs

which continued without any change

dewy

appearance on the inside of the glass was always perceived, consisting, no doubt, of con-

densed acid and water.

The

of the experiments are below

results

nitrous gas.

oxygen.

1.
2.

measure look
"

percent.

1.8, residuary 13.6

oxyg.

2.11

6.

nitrous

n
.3.

44-

27.

4.
5.
6.
7.

1.83

4.

8.--

The

residuary gas

in water,

oxyg.

2.29

2.5 nitrous

1.61

7.6 oxyg.

1.65

9.3 nitrous

1.8

2.5 oxyg.

was examined

and washing away the

after letting

acid.

From

evident the quantity of nigas combining with a given volume of

oxygen in such circumstances, is extremely
these results,

it

is

trous

variable,

and much

small quantities in

like

what takes place

tubes.

The

in

coloured gas

36S

l^ITRIC ACID.

is

always, I apprehend, either nitrous or oxythe nitric acid vapour is without

;

nitric acid

colour, and condenses along

on the

sides of the vessel

with the steam

but the o;her acids

colour the liquid.

instantly

By

inclosing

manometer, I endeavoured to find the

force, and the specific gravity of the
acids

elastic

aerial

but from the liquid condensation of a

found the specific gravity variable, and

part, I

always too much.

was commonly about

air.
Mr. Davy

It

three times that of atmospheric

measure of oxygen with 2.32 of

gas, leaving an excess of oxygen, and

combined
nitroiis

calculated the specific

product
that this

at 2.1-4
is

but

gravity

of the aerial

more than probable

the reasons just men-

it is

overrated for

Reasoning by analogy, nitric acid

gas should be of the same weight as carbonic
acid gas, as its atom is of the same weight; or
about the same as nitrous oxide and muriatic
tioned.

aci'.l

hence we

may

infer,

till it

can be ascer-

tained experimentally, that the specific gravity

nitric acid, in the clastic state, is beof

pure

Nitrous acid is probably

1.5 and 2.
about 2.5, and oxynitric about 2 or 2.25.
I was in hopes to ascertain the constitution

tween

of nitric ticid, by decompobing nitre by heat,

and finding the ratio of azote to oxygen
but,
as has been observed by others, the air is of
;

OXYGEN WITH AZOTt.

364

different qualities at different periods of the de-

By one experiment, I obtained

composition.
about 30 grains of air from 100 of nitre in an
iron retort

it

was received

in 5 portions: the

contained 70 per cent, of oxygen, agreeing with the constitution of nitrrc acid exhibited in the table, page 331 ; but the sucfirst

ceeding portions gradually fell off, and the

contained only 50 per cent, oxygen.
It

last

may be proper to remark, that the nitric

commerce is sold under the names of

acid of

double and single aqua fortis ; the former is

intended to be twice the strength of the latter;
the absolute strength of double aqua
not,

I believe,

between the

It

specific gravities

4.

The

uniform.

fortis

commonly
k^^

1,3

and

is

runs

1.4.

Oxijnitric Acid.

existence of oxynitric acid

is

inferred

from the combination of oxygen and nitrous

at
gas, in the second experiment, page 328
;

least

an acid product

more oxygen than

yet I

is

is

obtained, containing

found

have not been able

in nitric acid.

to

obtain

this

As
acid

any other way, and therefore have not had an

OXYNITRIC ACID.

365

opportunity of examining its properties, exI

thought that
cept upon a very small scale.
nitric acid from the
common
the
distilling

oxide of manganese might afford an acid more

I obtained a
product
liighly oxydized ; but
of
the
fumes
oxymuriatic acid, owing
yielding

no doubt
nitric

and

left

peared.

to the muriatic acid previously in the

for,

by boiling, these fumes vanished,

nothing but nitric acid, as far as apThe acid obtained from the gases

abovementioned, is only at best one half oxynitric, and the other half nitric, so that it is
still

but a mixture.

of the acid obtamed by

dilute solution

nitrous

mixing
seems to possess
acid solutions.

and oxygen gas

similar

It is

as

above,

properties to nitric

acid to the taste, changes

vegetable blue to red, and neutralizes the

kalies
its

whether

in this last

case

it

al-

parts with

excess of oxygen, I have not determined.

of oxvnitric acid must, it is pre-

The atom

atom of
it consists of 1
sumed, weigh 26.1
The specific gravity
azote and 3 of oxygen.
;

of the acid in an elastic state

about 2 or 2i.

is

probably

OXYOEN WITH AZOTE.

366

5.

Citrous Acid.

The compound denominated

nitrous acid,

obtained by impregnating liquid nitric acid

with nitrous gas.
This acid, however, is

is

never pure

nitrous

nitric

and nitrous

when

the nitrous

is

acid,

but a mixture of

evident by boiling it,

driven off, and the nitric

as

is

Pure nitrous acid seems to

remains behind.

be obtained by impregnating water with oxygenous gas, and then with nitrous gas ; in this

way

nitrous

measure of oxygen takes about

that

is,

atoms of nitrous gas

acid.
is

[^^

of

atom of oxygen takes 2

The weight

to

form

of nitrous

atom

of the

therefore

31.2.

repeated trials I find that 100 measures

of 1.30 specific gravity, agitated
with nitrous gas, takes up about 20 limes its

By

of

nitric acid

bulk of the gas.

If the acid be of twice the
or
of
the strength, it makes little
half
strength,
difference

the quantity of gas

is

nearly as the

real acid, within certain limits of specific gravity.

Very dilute acid (as 1 to 300 water)
seems to have scarcely any power of absorbing

nitrous gas, besides

Hence,

it

what the water

seems that what

we

itself has.

call nitrous acid.

367

KITROUS ACID.
IS

^ih

only about

of

it

real acid

the rest

is

nitric acid.

Mr. Davy concludes,

that the bright yellow

acid of 1.50 specific gravity, contains nearly 3

cent, of nitrous gas ; the dark orange 5|,

per

the blue green 8 ; the two last being of

the strength 1.48 or 1.47.
From the experiments of Priestley, it is evi-

and

dent that the nitrous acid, or as he called

the phlogistic at ed nitrxnis vapour, is much
volatile than nitric acid ; or, to speak

it,

more
more

Hence the
for v\rat-er.
properly, has less affinity
in great part arises.
acids
the
nitrous
of
fuming
This is further corroborated by the ready ebullition of those acids.

The

acid which I ob-

tained above by saturating nitric acid of 1.30

with nitrous gas, was dark orange, and strongly

fuming it boiled at IGO''; whereas the nitric
:

acid of the

owing

same strength boils at 236. It is

same cause that very dilute ni-

to the

trous acid exhibits the characteristic smell of

the acid

but equally dilute nitric acid has no

nitrous acid is diluted so far as

When

smell.

to contain just

its

owr. bulk of nitrous gas,

it

it rethen attracts oxygen, but very slowly

lime
to
of
as
as
much
sulphuret
agitation
quires
;

saturate
It

it.

does not appear that pure nitrous acid

OXYGEN WITH CARBONE.

368

combines with the

alkalies so as to

salts

or nitrites

seem

to lose the nitrous gas,

form dry

the concentrated solutions

and then the

ni-

traies are obtained.

SECTION

3.

OXYGEN WITH CARBONE.

There are two compounds of oxygen and
ttie one
j
goes by
carbonic acid, the other carbonic

carbone, both elastic fluids

the

name of

oxide

and

appears by the most accurate

oxygen in the former is just

it

analyses, that the

double what

it

is

in

the latter for a given

weight of carbone. Hence, we infer that one

is a binary, and the other a ternary compound ;
it
must be enquired which of the two is
the binary, before we can proceed according
The weight of an atom of carbone
to system.

but

or charcoal,

has not yet been investigated.

two compounds, carbonic acid is that

which has been longest known, and the proportion of its elements more generally investi-

Ot

the

gated.

It consists

of nearly 28 parts of char-

coal by weight, united to 72 of oxygen.

Now

OXYGEN WITH CARBONE.

369

atom of oxygen has been

as the weight of an

determined already to be 7 ; we shall have the

2.7, supposing
weight of an atom of carbone

carbonic acid a binary

compound

we suppose

compound.

it

a ternary

Carbonic acid

lowed, that

to
It

be the ternary or more

must, however, be alis

rather an in-

The

dication than a proof of the fact.

ment

of charcoal

atoms of

it

may be

so

light, that

with one of oxygen, may be specithan one with one.

But there

are certain considerations

inferior to

oxygen
wood, &c.

cohol, ether,

which

in

are

little

compounds

lighter than

form of a permanently

would expect of
carbonic acid

is

Though

oxygen.

is

rea-

does not assume the

elastic fluid,

which one

a very light element.

Besides,

the highest degree of oxidation

of which charcoal
;

it

into

water, a com-

charcoal in a state of extreme division

by heat,

not

principally enter;

pound of hydrogen and oxygen.

dily sublimed

us to
is

Oils, al-

weight.

which hydrogen and charcoal

these are a

incline

element of charcoal

believe, that the

know

ele-

two

lighter

fically

much

if

circumstance

this

but 5.4,

of greater specific gravity

and on that account, it

is

than carbonic oxide

may be presumed
complex element.

is

susceptible, as far as

we

happens under two atoms of

Carbonic acid is easily resolved
by

this rarely

OXYGEN WITH CARBONE.

370
electric

shocks

Into

and carbonic

oxygen

but carbonic oxide does not appear to

be resolved in the same mode into charcoal

oxide

and carbonic
from a

which one might expect

Or^e ot the most

acid,

compound.

triple

common ways

of obtaining carbonic oxide,

is

decompose carbonic acid by some substance

now, oxygen
possessing affinity for oxygen
to

be abstracted from a body possessing two

atoms of it more easily than from one posses-

may

sing only one.

On

all

these accounts, there

can scarcely be a doubt that carbonic oxide is

a binary, and carbonic acid a ternary cora^

pound.

1.

Carbonic Oxide.

This gas was discovered by Dr. Priestley

but

its

distinguishing features were

more

fully

pointed out by Mr. Cruickshanks, in an essay

Aibout the
in Nicholson's Journal, 1801.

same time, another essay ot Desormes and

Clement was published in the Annales de
Chemie, on the same

subject.

These essays

are both of great merit, and highly creditable

to their authors.

Before that time, carbonic

oxide had been confounded with the combustible gases

composed of carbone and hydrogen

CARBONIC OXIDE.

371

but Cruickshanks and Desormes distinctly demonstrated, that in the combustion of this gas
nothing but carbonic acid was produced ; and
that the quantity of

oxygen

for its

requisite

combustion, was not more than half of that

afterwards

contained in

the

carbonic acid

they, therefore, rightly concluded that the gas

was a compwDund of carbone and oxygen, since

which

it

has been

known by

the

name

of car-

bonic oxide.

Carbonic oxide may be procured by various

j but it is mostly
acconipanied with

processes

one or more foreign gases, from some of which

it

difficult to

is

when

it

is

be used as give

filings

it

for this

reason,

it

mixed with gas

that can be

The

following process answers

Let equal weights of clean, dry iron

extracted.

well

separate

wanted pure, such methods must

and pulverized dry chalk, be mixed

together, and put into an

retort be heated red,

increased

gas

will

iron retort

let

the

and the heat gradually

come

over copiously,

which may be received over water

this

gas

be found a mixture of perhaps equal parts

of carbonic oxide and carbonic acid j the last
will

.nay be extracted by due agitation in a mixture of lime and water; \yhat remains is
pure

carbonic oxide, except 2 or 3 per cent, of

common air, from the lime water. The theory

OXYGEN WITH CARBONE.

372

of this process is manifest ; chalk consists of

carbonic acid and lime ; the carbonic acid is

disengaged by heat, and

posed

has a strong

affinity for

immediately ex-

is

which

to the red hot iron,

oxygen

that state

in

the carbonic

acid parts with one half of its oxygen to the

iron, and the residue is carbonic oxide ; but
part of the acid escapes along with it undecompounded. With a proper apparatus, the

gas

may be procured by

transmitting carbonic

acid repeatedly over red hot charcoal in an iron

or porcelain tube.

This gas may be obtained, by exposing to a

red heat, a mixture of charcoal with the oxides
of several metals, or with carbonate of lime,

Bat there

&c.

barytes,

is

great danger in this

way of procuring some hydrogen, and carburetted hydrogen, along with carbonic oxide
and

acid.

Indeed,

wood and from

all

gas

moist charcoal,

procured from
is a mixture of

these four, varying in proportion according to

the heat and the continuance of the process.

According

to

Cruickshanks,

gravity of carbonic oxide

to

is

Desormes and Clement,

hending

that they

the

.956

.924.

had both rated

specific

according

Appreit

too low,

I carefully found the specific gravity of a mixture of 6 parts carbonic oxide

air, at

two

trials

in

one

it

and

common

came out

.945,

373

CARIJONIC OXIDE.

and

in

the other .94

conceive, then, that

.94 may be taken as a near approximation to

the truth

it is

just

the

mean

of the

Carbonic oxide

thors above.

is

two au-

fatal to ani-

combustible, and

mals that breathe

it

burns with a

clear, blue flame, without

fine,

any smoke or the

a bell glass

least

it

is

appearance of dew, if
This cir-

held over the flame.

is

amongst others, distinguishes it

all
from
gases containing hydrogen,
clearly
When mixed with
either mixed or combined.

cumstance,

oxygenous gas, or

common

air,

in Volta's eu-

diometer,
explodes with an electric spark,
and is converted into carbonic acid. Ihe cirit

cumstances attending the explosion are somewhat remarkable j unless the carbonic oxide

amount
not

to at least jth of the mixture,

explode

least -T-V^h

and

of the

quently happens,
for

and

the

it

will

oxygen must be

mixture.

Besides,

when common

air

it

is

at

fre-

used

oxygen, that a smart explosion takes place,

yet both carbonic oxide

be found

in the

disappears
pure.

It

residuum.

and oxygen

shall

This circumstance

if the
oxygen be above 30 per cent
should be observed, that whenever

are
proportions near the extremes above noted,
used, the results become ambiguous ; as a partial

combustion sometimes happens.

When

OXYGEN WITH CARBOKE.

374

100 measures of carbonic oxide are mixed

vvitli

250 of common

air,

which case the

(in

whole of the combustible gas should combine

with the whole of the oxygen) a smart explosion ensues by the

.first

spark

but only

-^ds

of

and a corresponding
proportion of oxygen, remain in the residuum.
AVhen plenty of combustible gas and a minithe gas

mum

burnt

is

the rest,

of oxygen are exploded, the whole of

the

oxygen usually disappears.

Carbonic oxide does not explode by elecat
tricity when mixed with oxymuriatic acid,
any instance I have had, unless a small
but the
portion of common air be present
a
diminution
the
to
mixture being exposed
sun,

least in

soon takes phce ; if the light be pov/erful, 5

or 10 minutes are sufficient to convert 100

iOO of
grain measures of the gas along with
I
and
muriatic
acids.
into
carbonic
the acid,

have

n'

been able

to

determine, from the

lateness of the season (October),

whether the

mixture Would explode by the solar light.

Pure carbonic oxide is not at all affected by
1 was present when Dr. Henry
electricity.

conducted an experiment, in which 35 measures of carbonic oxide received 1 100 small

no change of dimensions took place ;

was no carbonic acid formed, nor oxy-

shocks
there

;-

CARBONIC OXIDE.

375

but the residuary gas being

with oxvgen appeared to be pure car-

gen liberated
fired

bonic oxide.

Water absorbs ^Vth of

oxide.

will be seen

It

its

bulk of carbonic

by reference to page

201, also to the Manchester Memoirs,

vol. 1.-

nnc

Series, pages 272 and 436, that this gas

has perplexed me more than any other, at different periods, as to
to

regard

class to

One

absorption.

mv more

in

what

refer

it,

in

reason was-, that

early experiments I used

sometimes

by means of charcoal ;
was doubtless mixed with

to obtain carbonic oxide

which case

in

more

it

or less of hydrogen

another reason was,

that I did not agitate the water long

this

enough

than any

gas requires longer agitation

1 can now
I have met
with.

other

water take up

.V^h of

full

least in that proportion,

its

according

bulk,

make
or

at

to the [)urity

of the incumbent gas.

The

proportion of carbone and oxygen foimd

in carbonic oxide, has

ment

as

under

been found by experi-

measuies.

measures.

measures.

iGOcarb.ox. prod.92carb.ac. take40oxy.

79
Dcsormes&Cltm.lOO
Cruickshanks

'-'>(>

_
My

own

exp.

_
100

83
91-

34
47

OXYGEN WITH CARBONE.

376

Cruickshanks certainly underrates the oxy-

gen

always

find the

oxygen

equal to

fully

half the carbonic acid, whether fired over mer-

Desofmes' experiments were

cury or water.
made over water, and are therefore rather uncertain as to the quantity of acid

Their

evidently used impure gas.

given above
the other

is

the

two

mean

they have

first

result

of nine experiments

are extremes in regard to acid

and oxygen (Annales de Chimic 39 page 38).

is remarkable, that in one of their deduc-

It

tions (page 44),

on which they seem to rely

carbone 44, and the oxy-

most, they find the

gen 56 parts by a previous experiment, they

had found carbonic acid to- consist of 28.1 car:

bone, and 71.9 oxygen (page 4l); that is, of

41- carbone, and 112
oxygen where the oxy:

gen

is

just double of that

in the

carbonic oxide

to a given quantity of carbone.

This most

striking circumstance seems to have wholly

escaped their notice.

The exact composition of
ascertained by exploding

it

this

with

gas

is

easily

common

air

Let 2 parts of the gas be mixed

of air, and fired ; the residuum must

over water.

with 5

be washed

in lime water, and the quantity left

noted
; then apply a small portion
accurately
of nitrous gas to the residuum, sufficient to take

out the
oxygen

hence

we have

data to find

377

CARBONIC OXIDE.
the quantity of the

two gases which have comIn

bined to form carbonic acid.

this

way, 10

measures cf oxide will be found to take from

4.5 to 5 measures of oxygen.

The

conclusion then

that carbonic oxide

is,

combustion, requires just as much oxyas

it
previously has in its constitution, in
gen
order to be converted into carbonic acid. This

in

its

agrees too with the results derived from the

The gas
gas.
considered as lid!/ burned charcoal ;

of the
specific gravity

may be
it

bears

the same relation to carbonic acid as nitrous

An

gas does to nitric acid.

atom of carbonic

oxide consists then of one of carbone or charcoal,

weighing

5.4,

and one of oxygen, weigh-

The diameter
12.4.
ing
of the atom, in an elastic state, is 1 .02, that
of
being unity. Or, 106 measures
making

7, together

hydrogen

of the gas contain as

sures of hydrogen.*

many atoms

as

100 mea-

* It will,
should
perhaps, be expected that some notice
be takefi here of the opinion of Beilhollet, that carbonic
oxide is a compound of carbone, oxygen, and hydrogen,

and
It

therefore,

may

was formerly

be denominated oxy carburet ted hydrogen.

his

opinion

that

certain gases consist of

hydrogen, and hence are called carburettcd

others consist of carbone, oxygen, and hydrogen,

carbone and
hydrogen

and are denominated

the

Memoirs

as

above.

But

in the

d'Arcueil, he contends that

all

2d volume of
the combustible

OXYGEN WITH CARBONE

378

2.

The

Carbonic Acid.

now denominated

gas

carbonic acid,

has been recognised as an elastic fluid distinct

from atmospherical air, for a longer time per-

haps than any other.

may be

It

have

said to

considered as belonging to these two

gases thai have been
and that
;
are in fact

oxycarbmctted hydrogen

species,

these elements are combined in an indefinite variety of pro-

That the combustible gases produced from moist

charcoal and other bodies, contain oxygen, carbone, and

portions.

hydrogen

in various proportions, is a fact of

doubt
perienced person can

shewn

satisfactorily

by mixing

by any one,

certain proportions of

which no exnot yet

been

that they cannot be

made

but

has

it

two or more of the

fol-

namely, cnrburelted hydrogen (of

carbonic
oxide, olcfiant gas, and hydrogen.
water),
stagnant
As for carbonic oxide, whilst it remains an indisputed

lowing

distinct

species,

fact, that in the

combustion of

nothing hut carbonic acid

it

is

in lueight to the carbonic oxide

produced, and that equal

and

the oxygen,

will require

it

convince any one that

or phosphorus

it

unless

contains the same.

very specious reasoning to

contains either hydrogen, sulphur,

it

be

first

proved that carbonic acid

One argument

of Berthollet

is,

how-

more ingenious than any reply to it which has apit is this, a

compound elastic Jluid ought lobe found
peared

ever,

specifically heavier

fiuidi conelitutin^:

true

but

it

it.

than

the

This

is,

lighter

of

as far as

the

two elementary

know, universally

does not follow th^t carbonic oxide should be

specifically heavier than oxygenous gas.

An atom

of char-

CARBONIC ACID.

379

been known, though very imperfectly,

Towards

ancients.

the close of the

to the

cen-

last

tury, almost all the distinguished chemists

had

occasionally turned their attention to this ar-

and

ticle,

properties

It

veloped.

names

became gradually dehas received at times dilTerent

its

namely, cJioak damp,

acid, mephitic, and calcareous

coal,

it

is

appears,

we

convert

it

than an atom of oxygen

it

specific gravity of an

Water

is

re(|uisite to

produce the

Ether

is

We cannot
;

from

or from

elastic state.

yet

lighter than

it is

could

elastic fluid either

certainly heavier than charcoal

a light elastic fluid.

fluid.,

the weight of the article in a solid or liquid form

the degree of heat

aerial

acid.

would make a lighter elastic

into one by a due degree, ol heat.

probable, then,

judge of the

lighter

^fijced a/?',

it

water

produces
;

but

it

produces a heavier elastic fluid, and at a lower temperature.

Carbonic oxide may be lighter than oxygen, for the same
reason that nitrous gas. is lighter than oxvge n

cause oxygen
into

its

composition.

The answers above

in

nameiy, bethat enter

alluded to

deny the

they produce what ihey connitrous oxide, and nitrons gas ; and

generality of the argument

ceive a parallel case

two elemenls

the heavier of the

is

oxygen, the heavier of tlfe two component elebeing abstracted from nitrous gas, leaves nitrous

allege that

ments,

oxide, which
if

is

the doctrine

specifically heavier than nitrous gas.

we have advanced on

this

liave mistaken /w// of the operation for the

conversion alluded

to, not

only the oxygen

an atom of the nitrous gas, but

azote

is

at the

But

head be true, they

whole;
is

in the

taken from

same moment, the

joined to another atom of the nitrous gas to form one

of nitrons oxide.

OXYGE.V WITH CAP.BONE.

380

Carbonic acid gas is formed by burning charbut it is most easily obtained in a

pure

coal

from chalk, or some of the carbonates,

state

by means of

dilute sulphuric or other acid

may be received

in

it

over mercury or

bottles

water, but the latter absorbs a portion.

This

gas extinguishes flame, and

is

tion

nearly 1.57, as ap-

its

specific gravity

is

unfit for respira-

pears from the experience of all who have

tried
100 cubic inches, at the pressure of 30
:

inches of mercury, and temperature of 60%

weigh from 47 to 48 grains. Carbonic acid is
frequently produced in mines,

wells

it is

known

to

of dioak damp, and proves

them

it

is

and

workmen by

also constantly

fatal

found

to

in

deep

the

name

many

in the

of

atmo-

sphere, constiiuting about -r^j^tb part of the

whole ; its presence is easily detected by lime

water, over which

is

it

forms a film iilmost in-

the breathing of animals this

gas
constantly produced ; about 4 per cent, of
iv\

stantly.

the air expired

by man,

is

usually

carbonic

acid, and the atmospbcric air inspired loses the

same quantity of oxygen.

Water absorbs
acid gas

just

its

own

bulk of carbonic

the density of the gas in the

water after agitation, is the same as the density
;

that

is,

of the incumbent gas above, and the elasticity

of the gas in the water is unimpaired. The

581

CARftONiC ACID.

water so impregnated has the taste and other

This gas is the product
properties of an acid.
of fermentation, and gives to fermented liquors
their brisk and sparkling appearance ; but it
soon escapes from liquids,

they are exposed

if

to the air.

Carbonic acid combines with

alkalies, earths

and metallic oxides, and forms with them

salts

Lime

called carbonates.

water, by agitation
with any gas containing carbonic acid, becomes milky, owing to the generation of chalk
or carbonate of lime,

Hence

water.

this

which

water

is

is

insoluble in

an elegant

the presence of carbonic acid.

The constitution of this gas can be

both by synthesis and analysis

veniently by the former.

test

of

shewn

but more con-

The experiments

of

Lavoisier, Crawford, Desormes and Clement,

and more recently those of Allen and Pepys,

on the combustion of charcoal

have

left

no doubt

in

oxygen

gas,

the quantity of the

as to

elements in carbonic acid

28 parts of char-

coal by weight unite to 72 of oxygen, to form

lOO of carbonic
case too,

it is

carbonic acid
entering

shewn

into

acid, very

nearly.

In

this

remarkable that the volume of

is

the same as that of the

its

constitution.

that carbonic acid

oxygen
Tennant has

may be decomposed

by heating phosphorus with carbonate of Wmt,

OXYGEN WITH CARBONE.

382

phosphate of lime and charcoal

were

ob-

tained.

Carbonic acid

is

decomposed by
and oxygen.

electricity

into carbonic oxide

I assisted

Dr. Henry in an experiment by which 52

measures of carbonic acid were made 59 mea*
sures

by 750 shocks

the

after

being

whence

these

gas

washed became 25 measures

had arisen from the decomposition of 18 measures of acid

these 25 measures consisted of
;

16 carbonic oxide and 9 oxygen

for,

a por-

tion being subjected to nitrous gas, manifested

and the rest was
;
4d of its bulk to be

oxygen

by an electric spark, and appeared to be

almost wholly converted into carbonic acid.

fired

Carbonic acid then appears

to be a ternary

compound, consisting of one atom of charcoal

and two of oxygen j and as their relative
weights
have 36

in
:

the

28

compound

atom of charcoal
of carbonic acid

The diameter
elastic state

is

are as

28

72,

we

the weight of an
and the weight of an atom
:

5.4

19.4 times that of hydrogen.

of an atom of the acid in an
is

almost exactly the same as that

of hydrogen, and

is

therefore represented

by

;
consequently a given volume of this gas
contains the same number of atoms as the same

volume of hydrogen.

SULPHUROUS OXIDE,

SECTION

883

4.

OXYGEN WITH SULPHUR.

Two

distinct

compounds of oxygen and sulfor some time

universally re-

phur have been

cognized

but there exists a third, the nature

and properties of which are yet

sure

unknown.

According

in a great

to the

principles of nomenclature, the

first,

mea-

received

denoting

the lowest degree of oxidizement of sulphur,

may be called sulphurous oxide, or the oxide

of sulphur
degree,

the

highest degree

1.

The
bined

denoting a higher

second,

sulphurous acid

and the

known, sulphuric

third

Sulphurous Oxide.

existence of oxide of sulphur in a

state

was

or

acid.

first

com-

observed by Dr. Thomson.

acid in the gaseous

flowers of
a
vessel
containing
through
sulphur, he obtained a red liquid, which he

By sending oxymuriatic

state,

denominated sulpliuretted muriatic acid j but

it would have been
more properly called 7nu-

OXVGEN WITH SULPHUR.

384

riate of sulphur } as
that of muriate

Now,

stances.

its

formation

of iron, &c.
it

in

similar to

is

like

circum'

has been shewn ihat oxy-

muriatic acid

is

one atom

one; hence the atom of oxygen

to

muriatic acid united to oxygen,

oxidizes an atom of sulphur, and the muriatic

acid unites to the oxide, forming muriate of

more strictly muriate of oxide of

This oxide of sulphur. Dr. Thomson

sulpliur, or

sulphur.
finds,

is

not easily obtained separate

the red liquid

is

poured

for

when

into water, the oxide

resolves itself into sulphur

and sulphuric

(Xicholson's Journal, vol. G

acid.

101-.)

When

sulphuretted hydrogen gas and sulacid

gas are mixed over mercury, in
phurous
the proportion of 6 measures of the former to 5
of the latter, both gases lose their elasticity,
and a solid deposit is made on the sides of the
tube.

The common

fact

that the

explanation given of this

hydrogen of the one gas unites
to the oxygen of the other to form water, and
the sulphur of both gases is precipitated. This
is,

explanation is not correct ; water is indeed

formed, as is stated ; but the deposition consists

of a mixture of

two

solid bodies, the

one

they may
sulphur, the other sulphurous oxide
be distinguished by their colour 3 the former is
:

yellow,

the latter bluish

white

and when

th^y are both thrown into water, the former

SULPHUROUS OXIDE.
soon

falls

down, but the

385
remains for a

latter

long time suspended in the water, and gives

it a
milky appearance, which it retains after
It will appear in the sequel, that 5
filtration.
measures of sulphurous acid contain twice as
much oxygen as the hydrogen in 6 measures

of sulphuretted hydrogen require j it follows,

therefore, that one half of the oxygen ought
still

be found

to

in

the

precipitate,

accords with the above observation.

which
Again,

water, impregnated with each of the gases,

be mixed together till a mutual saturation takes
if

place, or till the smell of neither gas

served after agitation, a milky liquid

tained,

which may be kept

for

is

ob-

is

ob-

some weeks

without any sensible change or tendence to

precipitation.

Its taste is bitter

and somewhat

from a mere mixture of

acid, very different

When

sulphur and water.

boiled, sulphur

precipitated, and sulphuric acid

the clear

liquid.

The

is

milkiness

is

found in

of this

li-

quid seems therefore owing to the oxide of

sulphur.
It

may be proper

flowers of sulphur,

to

remark

commonly

that the white

sold

druggists, are not the oxide of sulphur.

by the

They

are obtained by precipitating a solution of sul-

phuret of lime by sulphuric acid. They consist

of 50 per cent, sulphate of lime and 50 of sul-

OXYGEN WITH SULPHUR.

386

phur, in some state of combination with the

for, the two bodies are not separable
sulphate
^

by

lixiviation.

When sulphur in a watch glass is ignited,

then suddenly extinguished, and placed on a
stand over water, and covered with a receiver,
the sulphur sublime? and

On

white fumes.

fills

the receiver with

standing for

some minutes

or an hour,

the sulphur gradually subsides,

and forms a fine yellow film over the surface of
the water.

The

oxygen by

this process.

is

ignited,

mentioned,
emitting

in the receiver

air

loses

no

But when sulphur

placed in the circumstances aboveit burns

with a fine blue flame,

some
at

white fumes, scarcely

combustion con-

bluish
first

as the

perceptible
tinues these fumes increase, and towards the

when

conclusion,

the

oxygen begins

to

be de-

a copious stream, and

the receiver so that the stand is scarcely
they

ficient,
fill

visible.

It

rise

up

in

portion

of the

air

is

passed

In
through water, it still continues white.
the space of an hour the air in the receiver be-

comes

clear

but no traces of sulphur are seen

The whiteness in

on the surface of the water.

this last case

does not, therefore, seem to

arise

sublimed sulphur, but from the oxide of

sulphur, which is formed when there is not
iro.m

oxygen

sufficient to

form sulphurous acid

ths

SULPHUROUS OXIDE.
last is

fluid.

known to

387

be a perfectly transparent elastic

in this case

Whether the sulphurous oxide

absorbed by the water in that state, or is gradually converted into sulphurous or sulphuric
acid, I have not been able yet to determine.
is

When

a solution of sulphuret of lime has

been exposed to the air for a few weeks, till it

becomes colourless, and sulphur is no longer
precipitated, if a little muriatic acid be added

whole becomes milky, and exhales

sulphurous acid ; after some time sulphur is
to

it,

the

deposited, and the sulphurous acid vanishes,

This
leaving muriate of lime in solution.

milkiness must be occasioned

oxide

for,

by sulphurous

sulphite of lime, treated in like

manner, exhibits no such appearance.

As
is

then, as appears, sulphurous oxide

far,

compound

of oxygen;

it

of one atom of sulphur and one

capable of combining with

is

and perhaps other acids

muriatic,

in water,

pended
ance and a

it

gives

it

when

sus-

a miiky appear-

and the mixture being

changed into sulphur and

bitter taste,

heated, the oxide

is

An atom of sulphur being

acid.
estimated, from other considerations hereafter
sulphuric

to

be mentioned,

gen weighing
sulphur

is

oxygen per

7,

to
it

weigh

constituted
cent.

13,

and one of oxy-

will follow that

oxide of

of 65 sulphur and 35

OXYGEN WITH SULPHUR,

588

Sulphurous Acid.

2.

When
in the

sulphur

ooen

is

it

air,

heated to a certain degree

fire and burns with a

takes

blue flame, producing by its combination with

oxygen an elastic fluid of a well known and

highly suffocating odour ; the fluid is called

Large quantities of this acid
sulphurous acid.
are produced by the combustion of sulphur in
close chambers, for the purpose of bleaching

or whitening flannels and other woollen goods.

In this way, however, the acid never constitutes

of

more than 4 or

air,

and

is

5 per cent, of the

therefore

chemical investigations.

much
It

too

volume

dilute for

may be obtained
To two

nearly pure by the following process

parts of mercury by weight put one part of

concentrated sulphuric acid in a retort; apply

the heat of a lamp, and sulphurous acid gas
will be produced, which may be received
The reason of this is, each
over mercury.
atom of mercury receives an atom of oxygen

from one of sulphuric acid, and the remainder

of the sulphuric atom constitutes one of sulphurous acid, as will be evident from what
follows.

Sulphurous acid is unfit for respiration and

combustion its specific gravity, according

for

SULPHUROUS ACID,
to

Bergman and

to

Kirwan, 2.24

is

Lavoisier,
;

389

2.05

by my own

according
it is

trials,

I sent a stream of the gas, after

2.3.

had passed

it

through a cold vessel connected with the retort, into a flask of common air ; this was after-

wards weighed, and the quantity of acid gas

then ascertained by water ; it appeared by two
trials, agreeing with each other, that 12 ounce
measures of the gas weighed 9 grains more

common

than the same quantity of

this last

7 grains nearly.

weighed
20 times

sorbs about

its

bulk of

mean temperature, according

rience

this

to

but some say more, others

air,

Water

and
ab-

gas at a

my

expe-

The

less.

quantity absorbed, no doubt, will be greater

as the temperature

is

Hence,

less.

it

seems

that water has a chemical affinity for the gas

but the whole of

the

air,

long exposed to
except a small portion which is conit

escapes

if

verted into sulphuric acid.

When
acid,

gen

is

is

water, impregnated with sulphurous

exposed to oxygen in a tube, the oxyslowly imbibed, and sulphuric acid

In twelve days, 150 measures of the

acid, absorbed by water, took 35. of oxygen,

formed.

leaving a residuum of oxygen and sulphurous

acid.
When sulphurous acid gas and oxygen
are
mixed and electrified for an hour over
gas

mercury, sulphuric acid

is

formed; but

do

OXYGEN WITH SiaPHUR,

390

not find that the proportion oF the elements of

the acids can in this way be ascertained ; for,
the

mercury becomes -oxidized, and consean union with either of

({uently liable to form

the acids.

made

The two gases

also

combine, when

through a red hot porcelain tube.

Sulphurous acid is said to be decomposed by
to pass

hydrogen and charcoal at a red heat sulphur is

deposited, and water or carbonic acid formed,
;

When a

according as the case requires.

mea-

sure of oxymuriatic acid gas is put to a measure

of sulphurous acid gas, over mercury, the sul-

phurous acid is converted into sulphuric but

no exact result can be obtained, from the rapid
action of the former gas on mercury.
;

Sulphurous acid oxidizes few of the metals ;

but it possesses the common properties of acids,
and unites with the alkalies, earths, and metallic

oxides, forming with

minated
It

them

salts

deno-

sulphites.

remains

now

to

investigate the

number

and weight of the elements in sulphurous acid.

I
have made a great number of experiments
on the combustion of sulphur in atmospheric
air,

in

various

circumstances

but

those

in a
particularly rely upon, were made
it was
receiver containing 400 cubic inches

more

open

at top,

whicl) an

and had a brass cap, by means of

empty bladder could be attached

to

SULPHUROUS ACID.
the receiver,
air

in

order to receive the expanding

a small stand

was provided, and

was placed on

glass

391

it,

filled

watch

with a

known

weight of the flowers of sulphur ; the whole

was placed on the shelfof a pneumatic trough,

and

as soon as the sulphur

was

lighted by on

ignited body, the receiver was placed over it,

with its margin in the water ; the combustion

was then continued till the blue 6ame expired ;

near the conclusion, white fumes arise copiously,

and

was then
fully

fill

filled

the receiver.

small

phial

with water, inverted, and care-

pushed up into the receiver

to

withdraw

a portion of air for examination ; the receiver

was then removed, and the loss of sulphur

The residuary gas in the phial

with hydrogen in Volta's eudiometer.
of sulphur at a medium was 7 grain?,

ascertained.

was

fired

The

loss

and the oxygen

medium 16

in the

per cent,

residuary gas
or

rather

was

more

at a

the

weight of oxygen, therefore, which had disHence it

appeared, was from 5 to 6 grains.

may be

7 grains of sulphur comof oxygen ; but as the white

fumes are oxidized inferior to sulphurous acid,
said, that

bined with

5-|

it is most
probable that sulphur requires its
ovvn weight of oxygen nearly to form sulphurous acid. In confirmation of this, it is

observable, that no material change of bulk

is

392

the gas by the combustion

effected in
this

WITH SULPHUR.

OXYGL^il

remarked

also

is

bustion of cliarcoal.
gravity of suiphuroMs

in

the analogous

and

com-

Thus, then, the specific

acid should exhibit a

near approximation to twice that of oxygen,

as it is found to do above.
Now, as it would

be contrary

to

all

to suppose sul-

analogy,

phurous acid to consist of

atom of sulphur

of oxygen, we must presume upon its

being of sulphur and 2 of oxygen ; and hence

and

the weight of an atom of salphur will be 14

times that of hydrogen.

Another and more

rigid proof of the consti-

we obtam from

tution of sulphurous acid,

combustion of sulphuretted hydrogen

This compound, it
eudiometer.

shewn, contains exactly

drogen

the rest

is

weights, as appears

must be

to

its

sulphur

the

in Volta's

will

be

own

bulk of hyTheir relative

from the specific gravity,

14 nearly; novv^

when

sulphu-

exploded with plenty of

hydrogen
over
mercury, the whole of the last
oxygen
retted

mentioned gas
sulphurous acid

is

is

converted into
it is

the combustible gas

water and

found that 2 measures of

combine

vvith 3

measures

but 2 measures of hydrogen take

;
measure of oxygen ; therefore, the sulphur

of oxygen
1

takes the other 2 measures

that

is,

the

atom

of sulphur requires 2 atoms of oxygen for

its

SULPHUROUS ACID.

393

combustion, and that of hydrogen

atom of

which gives the same constitution

oxygen
as that deduced above for sulphurous acid.
;

The

proportions of sulphur and oxygen in

this acid,

have been variously stated, mostly

truth.
We have one account that

wide of the

gives 85 sulphur and 15 oxygen. Dr.

in Nicholson's Journal, vol. 6,

Thomson,

page 97, gives

68 sulphur and 32 oxygen ; but in his Appendix to the Sd edition of his Chemistry, he
corrects the numbers to 53 sulphur and 47

oxygen. Desormes and Clement say 59 sulphur and 41 oxygen (ibid. vol. 17 page 42).

to the

preceding conclusions,

According
atom of sulphur be

if

the

then the pro;

to
will
be 60 sulof
oxygen
sulphur
portion
50
or
to
phur
oxygen,
equal weights ; but if
stated at 14

sulphur be denoted by 13, then sulphurous

acid will consist of 48 sulphur and 52 oxygen
per cent., which numbers I consider as the
nearest approximation
elastic

the

diameter of the

atom of sulphurous acid

is

rather less

than that of hydrogen, as appears from the

circumstance that 5 measures of the gas saturate 6

which

measures ot sulphuretted hydrogen,

contain as many atoms as the like

last

measures of hydrogen. On this account, the

diameter of an atom of sulphurous acid may

OXYGEN WITH SULPHUR.

394

be denoted by
in a

and the number of atoms

.95,

given volume, to that of

same volume,

be

will

3.

as

hydrogen in the
120 to 100.

to 5, or

(5

Sulphuric Acid.

The sulphuric acid of commerce, commonly

known in this country by the name of oil of
is

vitriol,
feel, of

a transparent liquid of an unctuous

the specific gravity

corrosive

and very

1.84,

animal and

acts powerfully on

it

vegetable substances, destroying their texture,

and mostly turning them black. This acid

was

formerly obtained from green vitriol (sulphate of iron) by distillation ; hence the name
It

vitriolic acid.

now commonly

is

by burning sulphur, mixed with

obtained

portion of

weight) in leaden
formed and drops
;
into water, which covers the floor of

nitre, (from

-ith

to -jVth of

its

chambers

sulpliuric acid

is

down

the chambers
ficiently

this

with acid,

to evaporation

till

water,
is

the acid

higher degree when

;

and placed
the acid

is

in a

it is

sand bath

distilled

when charged

drawn
is

off,

suf-

and subjected

concenirated in a

put into glass retorts,

the weaker part of

into

receivers,

others concentrated nearly as

much

and the

as

is

pos-

SaLPHURIC ACID.

395

The acid in the

down and treated as

the circumstances.

sible in

receivers

is

again boiled

before.

Some

authors have affected to consider the

theory of the

formation of sulphuric acid as

very obvious ; the nitre, they say, furnishes a

part of the oxygen to the sulpliur, and the

atmosphere supplies the

rest.

for this explanation, the

nitre, if

Unfortunately
it

were

all

oxygen, would not furnish above -^Vth of what

is wanted ; but nitre is
only 55 per cent, oxy-

gen

with

it

cannot, therefore, supply the sulphur

than V^th })art of wliat it

much more

wants, if all the oxygen were extricated ; but

not more than ~ or 4-d of this small portion is
disengaged from the potash ; for, the salt be-

comes a sulphate instead of a

nitrate,

and

re^

most of the oxygen it had, or acquires

oxygen again from some source. Several well
tains

informed manufacturers, aware of the fallacy of

the above explanation, have attempted to di-

minish the nitre (which

expence

is

an article of great

to them), or to discard

but they find

it

altogether

indispensibly necessary in some

or
other
;
for, without it they obtain
portion
little

it

but sulphurous acid, which

and not the

part incondensible,

want. The manner

for

in

which the

long time remained an

is

in great

acid

they

nitre operates,

aenigma.

At

OXYGEN WITH SULPHUR.

596
'length

Desormtrs and Clement, two French

chemists, have solved the difficulty, as may be

seen in an excellent essay in the Anna], de

Chimie, 180G, or
17.

in

Nicholson's Journal, vol.

These authors shew, that

in the

com-

bustion of the usual mixture of sulphur and

nitre, sulphurous acid is first formed, and nitrous acid or nitrous gas liberated, partly from
the heat, and partly perhaps from the action of
sulphurous acid ; the nitrous gas or acid becomes the agent in oxidizing the sulphurous

oxygen of the atmoand then leaving them in

acid, by transporting the

spheric air to

it,

union, which constitutes sulphuric acid. The

particle of nitrous gas thert attaches another of

oxygen to itself, and transports it to another

atom of sulphurous acid and so on till the
whole is oxidized.
Thus the nitrous acid
;

operates like a ferment, and without

it

no

sul-

phuric acid would be formed.

This theory of the formatioii of sulphuric
acid has so very imposing an aspect, that
to

it.

it

It

prove
requires experiment
however, very easily proved by a direct
and elegant experiment. Let 100 measures
of sulphurous acid be put into a dry tube over

scarcely
is,

mercury, to which add 60 of oxygen ; let then

10 or 20 measures of nitrous gas be added to
the mixture

in

a few seconds, the inside of

597

SULPHURIC ACID.

the tube beconnes covered with a crystalline

appearances like hoar frost, and the mixture is

reduced to ^d or ^th of its original volume.
If

a drop of water be admitted, the crysis

quickly dissolved into the wa-

now

talline matter
ter,

sparkling as

it

enters,

duum

of azote

and the gases en-

except a small

their elasticity,
tirely lose

and nitrous

gas.

resi-

If the tlibe

is

then washed out, the water tastes strongly acid,

It is
but has no smell of sulpharous acid.
evident, that in this process the nitrous gas
and transports it to the

unites to the oxygen,

sulphurous acid, which, receiving

nitrous,

becomes sulphuric

acid.

it

from the

It

appears,

moreover, that solid sulphuric acid is formed

when no water is present ; and consequently
this

is

the natural state of sulphuric acid en-

tirely free

from water.

It

must

bft

observed,

any water in substance is present when

the mixture of gases is made, the water seizes

that

if

the nitrous acid as

it

is

formed, and conse-

oxidizing the sulphurous

quently prevents
acid ; on the other hand, the presence of
it

water seems necessary in the sequel, to take

the new formed sulphuric acid away, in order
to facilitate the oxidizement of the remaining

The oxygen necessary to

sulphurous acid.
saturate 100 measures of sulphurous acid seems
to be about 50 measures ; but it is difficult to

OXYGEN WITH SULPHUR.

398

ascertain this with precision, because the nitrous gas takes

up the superfluous oxygen, and

begins to act upon the mercury.

Now, it has been shewn, that sulphurous
acid contains nearly its own bulk of oxygen,

and

1 atom of
sulphur and 2
appears from the above, that

constituted of

is

of oxygen

and

it

much oxygen more,

half as

converts

into sulphuric

it

sulphuric acid atom

is

that

acid

is,

atom,

hence, the

constituted of

atom of

sulphur and 3 of oxygen ; and if the atom of

sulphur be estimated at 13 in weight, and
the 3 of oxygen at 21, the whole compound
will weigh 34 times the weight of an
atom of hydrogen ; that is, pure sulphuric
acid consists of 38 sulphur and 62 oxygen per

atom

cent.

In the year 1806, by a careful comparison

of

all

the sulphates, the proportions of

which

deduced the weight of the

acid
to be 34 ; it now apof
atom
sulphuric
the
that
same
pears
weight is obtained synare well

known,

thetically,

without any

or

combinations

deductions, renders

weight

is

reference

to

its

agreement of these
beyond doubt that the

the perfect
it

nearly approximated, and confirms

the composition of the

atom which has

just

been stated.

There are scarcely any chemical

principles.

SULPHURIC ACID.
the proportions of
versely

determined

which have been so

di-

by experimentalists,

as

those of sulphuric acid

will

sufficiently

399

prove

the

following table
the observation j ac:

cording to
Berthollet

Tromsdorf

72

sulphur 4- 28
-f-

30

oxygen.

400

OXYGEN WITH SULPHUR.

and by th? generous invitation of Mr. Watkins,

of Darcy Lever, near Bolton, I had lately an
opportunity of gratifying myself by the inspection of his large and well-conducted acid

When opening
manufactory, near that place.
a small door of the leaden chambers, there issued a volume of red fumes into the
their colour

by
doubt of

and

left

smell,

their beinnr the

air,

which

no rooni to

fumes of nitrous acid.

There was scarcely any smell of sulphurous

From the nitrous fumes, one would
acid.
have been inclined

were

to think that the

chambers

I was
with nitrous gas.
particuof the
anxious
to
know
the
constitution
larly
air in the interior of the chambers, and Mr.
filled

Watkins was

number

so

of phials

obliging as to send me a
of air taken from thence.

examination, the

Upon

air

was found

to con-

oxygen and 84 azote.

There was no smell of sulphurous acid, and
of

sist

very

16 per

little

of nitrous acid,

fact,

it

this

last

having
through the water.
seems that the nitrous acid fumes

been condensed
In

cent,

in passing

never make more, perhaps, than 1 per cent,

upon the whole volume of air ; nor can the

oxygen be ever reduced much below 16 per

cent., because the combustion would instantly
cease.

A constant

the roof of the

dropping is observed from

chambers internally ; these drops

SULPHURIC ACID.

401

being collected, were found to be of the specific

gravity

.6

they had no sulphurous smell,

but one slightly nitrous.

It

is

not very easy to suggest any plausible

maaagement of a manufactory

alteration in the

of this article. Nitrou5 acid must be

present ;
but whether it is best obtained by exposing
nitre to the

burning sulphur, or by throwing

in the vapour of nitrous acid

by direct distilenquiry. Loss of nitrous

lation,

may be worth

acid

unavoidable, partly by

is

escape into

its

the air during the periods of ventilation,

its

and

condensation in the watery acid,

partly

by

on the

floors of the

chambers

must, therefore, be provided

ceed a certain quantity,

a regular
supply

but

if this

ex-

not only increases

injurious to the sulphuric
it

the expence, but is

acid in some of its
applications.

m all

probability, be

some

There must,
cham-

figure of the

bers better than any other, in

regard to their
proportions as to length, breadth, and height ;
this, perhaps, can be determined only by exAs water absorbs the nitrous acid
perience.

with avidity,

high chambers, and the com-

bustion carried on at a distance from the water,

must be circumstances favourable to economy
in regard to nitre.

Sulphuric acid has a strong attraction for

water j it even takes it from the
atmosphere

OXYGEN WITH SULPHUR.

402
in
is

the state of steam, with great avidity, and

therefore frequently used

what

called dryivg the

is

with water,

sulphuric

in

chemistry for

When mixed

air.

acid

produoes

heat, as has already been stated in

part of

this

When
formed

is

boiled

upon

sul-

sulphurous acid is
have not found this to be the case.

first

work.

sulphuric acid
has been said

it

phur,

much

the

But charcoal and phosphorus decompose the

acid by heat ; and the results are carbonic acid,
phosphoric acid, and sulphurous acid.
Sulphuric acid combines with the alkalies

and earths
salts

in

general,

with

forrhing

denominated sulphates.

On

acts variously, according to

this acid

centration

when

bulk of water,

it

them

the metals
its

con-

diluted with 5 or 6 times

acts violently

its

on iron and

zinc ; great quantities of hydrogen gas are

produced, which proceed from the decomposition of the water, and the oxygen of the
water unites with the metal, to which the acid
also joins itself, and a sulphate is thus formed.

When

the acid

metals

is

iieat,

it

is

concentrated,

its

action

on

but by the assistance of

;
oxidizes most of them, and gives ofF
less violent

sulphurous acid.
As the sulphuric acid exists in various degrees of concentration, it becomes a matter of

SULPHURIC ACID.
importance both to
those

who

use

bleachers, to

it

know

its

manufacturer, and to

the dyers and

the exact strength of it ;

largely, as

or in other words, to

combined with

403

know how much water

pure acid in any speThis subject engaged the particular

attention of Kirvvan some years ago, and he
is

tlie

cimen.

has furnished us with a table of the strengths

of sulphuric acid, of most

are

two things

table, the

one

densities.

requisite to

is

There

form an accurate

to ascertain the exact

quan-

of real acid in some specimen of a

given
specific gravity ; the other is to observe caretity

fully the effects

produced on the

specitic gra-

vity of such acid,

<]uantity

by diluting it with a given

of water. Mr, Kirwan has succeeded

very well in the former, but has been pecuThe errors of

Jiarly unfortunate in the latter.
his table

seem

to

have been

known

for the last

10 years to every one,

except the editors oF

works on chemistry.
exhibits the results of

The following table

my own experience on

this acid for several

years.

OXYGEN WITH SULPHUR.

404

Table of the quantity of

real

acid in 100 parts of liquid

sulphuric acid^ at the temperature 60".

Atomi.

Add.

Water.

1+

405

SULPHURIC ACID.
the acid and water

way

distil

together, in the

as nitric acid of 1.42 sp. gravity, or

riatic

of 1.094.

It

same

mu-

a mistai^en notion, that

is

common sulphuric acid of commerce is of

maximum strength, though it is of the
maximum density nearly. The fact is, acid
nearly of the maximum strength varies very
the

the

little in its specific

gravity,

by the addition or

subtraction of a small quantity of water.

Kirwan's principal error.

strength of 81 and 80, do not
1

in the third place of

cording to his table,

The

as great.

75

to

80 per

tlie

to

more than

whereas, ac-

difference

commerce

is

14 times

varies

trom

cent, of acid, or about 7 per cent.

in value, in the different

occasion

differ

decimals

acid of

Here

Acids of the

is

examine.

specimens I have had

This variation only

changes the second figure in decimals an unit i

the
though, according to Kirwan's table,

change

is

7 times as much.

The

specific gra-

be the criterion of strength

vity ought not to
in acids above 70 per cent. ; the temperature
at which they boil is a much better criterion,
admits of a range of 12 or 15 for 1
be
per cent, of acid. Or the strength may
water
of
found by determining what quantity
must be added to reduce the acid to some

because

it

known

acid,
strength, as that of the glacial

of 1.78 sp. gravity.

Oxygen with sulphur,

406
There

2.

table

of

stituted

nothing further striking In the

to the aci'd, which is con-

is

we come

till

atom

to 2 of

water

this

acid

possesses the remarkable property of congealing

above 32% and of

in a temperature at or

46
it,

its

specific

in

Trans. 1787), and

(Philos.

re-

any temperature below

gravity is 1.78, as Keir found

maining congealed

it

contains 68

per cent, of real acid, both by theory and experiment ; it is determined by theory thus
:

one atom of sulphuric acid weighs 34,

and

2 of water 16, together making 50 j hence, if

100 68 ; it is found experimen50 34
:

100 grain measures of glacial

sulphuric acid be saturated with carbonate of
tally thus

let

potashy

and the sulphate of potash be ob-

tained

it

weigh, after being heated

will

to a

moderate red, nearly 270 grains, of which

121 will be acid, and 149 alkali, according to
the analyses of

Kirwan and Wenzei.

If the

liquid acid be of greater or less specific gra-

kss

then

real acid,

1
per cent, more or
cannot be frozen in a

even

vity, so as to contain
it

temperature above 32% but

rature a

little

contain

glacial,

it

is

32.

a tempeliquid acid

in

may

If the

per cent, more or less than the

cannot be frozen without the cold

produced by
that

below

mixture of snow and

insufficient, if

it

deviate

salt

and

more than

407

SULPHURIC ACID.

per cent, from the glacial, as Mr. Keir determined. I find the frozen acid to be of the
It seems progravity 1.88 nearly.
bable that the difficulty of freezing would increase in both sides, till the acids of 1 and 1

specific

above, and

The

and

below.

below 30 per cent, may, without any material error, have their strength
estimated by the first and second figures of
3.

decimals

acids

in

the column of sp. gravity

thus

acid of 15 per cent, strength, will have the

specific gravity 1.15, Sec.

SECTION

3.

OXYGEN WITH PHOSPHORUS.

There

are only

two compounds of oxygen

and phosphorus yet known

the characters of acids
Tiated

they both have

the one

is

denomi-

phosphorous acid, the other phosphoric

extremely probable that the former,

though recognised as an acid, is yet in the
lowest degree of oxidation, and may therefore
acid.

It is

with equal propriety

be called phosphorous

oxide, phosphoric oxide, or, after the

of metals,

oxide of phosphorus.

however, adopt the

common name.

manner

We

shall,

OXYGEN WITH PHOSPHORUS,

108

1.

When

Phosphorous Acid.

phosphorus

to the atmosphere,

and

gen,

it

is

exposed

for

some days

gradually acquires oxyinto an acid liquid.

converted

is

This process may be effected by putting small

pieces of phosphorus on the sloping sides of a
glass funnel,

into a phial as

and suffering the liquid

it is

phosphorous acid,

formed.
is

The

to

drop

liquid, called

viscid, tastes sour,

and

is

capable of being diluted "with water to any

amount. It has the usual effect of acids on the
test

colours.

rated,

When

heated, water

is

evapo-

and afterwards phosphuretted hydrogen

gas ; finally, there remains phosphoric acid in

the vessel.
It should seem from this, that

heat gives the oxygen of one part of the phos-

phorous acid to another, by which the latter

is
changed into phosphoric acid, and the phosphorus of the former is liberated ; but at that
degree of heat the liberated phosphorus acts
one part of it takes the oxygen
;

on the water

form more phosphorous acid, and the other

the hydrogen to form phosphuretted
hydrogen ^ and thus the process is carried on

to

takes

till all the

phosphorus is in the state of phosIt
phoric acid, or phosphuretted hydrogen.

is

probable, that in this

way

the phosphorus

PHOSPHOROUS ACID.
is

divided, so that

two

thirds of

to oxygen, and one third

this has

to

409
it

are united

hydrogen

not been ascertained by

but

direct ex-

periment.

Phosphorous acid

acts

upon

several metals,

oxidizing them by the decomposition of water, and at the same time giving out phosphu-.
retted

hydrogen

the resulting

metallic salts

supposed, phosphates, the redundant

phosphorus being carried off by the hydrogen.
This acid combines with the alkalies, earths,

are,

it is

and metallic oxides, and forms with them a

class of salts called pJwsphitcs.

When

nitric acid

is

put to phosphorous acid,

nitric acid is decom-

and heat applied, the

posed, half of

phorous acid,
acid,

and the

its
oxygen unites to the phosand converts it into phosphoric

rest

of the nitric acid escapes in

the form of nitrous gas.

The proportion of the

two elements

consti-

tuting phosphorous acid has not hitherto been

ascertained ; I am inclined to believe, from the

experiments and observations about to be

re-

lated concerning phosphoric acid, that phos-

composed of 1 atom of phosphorus, weighing 9 nearly, and 1 of oxygen,

phorous acid

is

weighing 7 ; the compound weighing 16. If

be the case, it may appear singular that
none of the other elements exhibit acid prothis

OXYGEN WITH PHOSPHORUS.

410

when combined with

1 atom of
oxyshould be observed, that the phosphoric oxide is in a liquid form, and disposed

parties

gen

but

it

phosphorus and phosphoric

do not combine in

to separate into

acid, circumstances that

In fact, phosregard to the other oxides.

pherous acid may be considered as phosphoric
acid holding phosphorus in solution,
than as a distinct acid.

2.

Phosphoric Acid.

Though some
phoric acid,

rather

of the compounds of phos-

and the earths and

common enough,

yet

alkalies, are

acid, in

this

a pure

any considerable
a
both tedious and
process
requiring
quantity,
three
methods
There
are
by which
expensive.
state,

is

rarely obtained

in

1. If a small
phosphoric acid may be formed
5 to 20
from
of
phosphorus, namely,
portion
covered
be
and
immediately
ignited,
grains,
:

with a large bell glass, over water, the phosphorus burns with great brilliancy, and soon
fills

the vessel

with white fumes

time, the combustion ceases

after

in a short

which the

fumes gradually subside, or adhere to the side

of the glass in the form of dew ; these white
fumes are pure phosphoric

acid.

2. If

a small

411

PHOSPHORIC ACID.

into heated
piece of phosphorus be dropped
nitric acid in a phial or gas bottle, a brisk
effervescence ensues, occasioned by the escape

of nitrous gas, and the phosphorus gradually

disappears, being converted into phosphoric
acid,

acid

and mixed with the remaining

another small piece

into the liquid,

and

so

may

on

nitric

then be dropped
succession

in

till

almost wholly decomposed ;

the remaining liquid may then be gradually
increased in temperature, to drive off all the
the nitric acid

nitric acid

is

what

is left is

a liquid consisting

of phosphoric acid and water ; by increasing

the heat to a moderate red, the water is driven
off,

on

and

liquid phosphoric acid remains,

becomes

cooliflg

like glass.

rous acid be prepared

by

3.

which

If phospho-

the slow combustion

of phosphorus, as mentioned above, and then

a portion of nitric acid added to the liquid,
nitric acid gives
part

and heat be applied, the

of

its

oxygen

to

the phosphorous acid,

nitrous

gas escapes.

heated,

is

Of

What

remains,

and

when

pure phosphoric acid.

these three processes, the

first

may be

recommended when

the object is to find the

proportion of the elements of the acid ; but the
third, when the object is to procure a quantity of acid for the purposes of inOf these the third is preferable
vestigation.

second and

OXYGEN WITH PHOSPHORUS.

412
in

an economical point of view, because

requires only half as

calculation,

find

much

that

acid.

nitric

rt

By

20 grains of phos-

phorus will require '200 grains of

nitric

acid

of 1.35, by the second process, but only 100

grains by the third ; but a small excess

should always be allowed for

loss

by evapo-

ration, &:c.

Phosphoric acid,

in the state of
glass,

when exposed
comes oily, and may be

liquescent

to the

air

diluted

is

debe-

it

with any

This acid is not so corquantity of water.

rosive as some others ; but it has the other
acid properties of a sour taste, of reddening
vegetable blues, and of combining with the
alkalies, earths,
salts,

and metallic oxides,

which are called phosphates.

power

It

to

form

has the

of oxidizing certain metals, by decom-

posing water in the manner of sulphuric acid ;

the oxygen of the water unites to the metal,

and the hydrogen is liberated in the state of

Charcoal decomposes this acid, as well
gas.
as the phosphorous, in a red heat ; hence the
process for obtaining phosphorus form superphosphate of lime.

Nothing very certain has been determined

respecting the relation of the strength of this
acid to the specific gravity of the liquid solution.

Some experience

I have had,

makes

me

PHOSPHORIC ACID.

413

think the following table will be found nearly

at all events, it may have its use till
correct
:

a better can be formed.

Table of the quantity of

real acid In

of liquid phosphoric acid.

Acid per cent,

by weight.

100 parts

4l4

OXYGEN WITH PHOSPHORUS.

The

first contained
20| per
but
after
the combustion, it
oxygen j
contained only 16 or \6^ per cent., the temperature being about 40 at the time. Whence,

escape.

air

at

cent,

appears that in these inof

grains
phosphorus may be concluded to have united to 6 grains of oxygen.

by calculation,

stances

The

it

data, indeed,

would give a

proportion of ^oxygen

some phosphorous acid

but
is

it

is

rather less

probable that

formed near the con-

clusion of the combustion.

With respect

to the constitution

of the phos-

two opi1 atom

phoric acid atom, there can be but

nions entertained.

Either

it

must be

of phosphorus with 2 atoms of oxygen, or

with 3 of oxygen.
According to the former
opinion, the phosphoric atom will weigh 9,
and the phosphoric acid atom 23 ; according
to the latter opinion, the phosphoric

weigh

J-,

and the acid atom 35.

appeal to the phosphates

weight of the acid

to

atom

We

might

determine

but this class of

will

salts

the

has

been analyzed wiih sufficient precision.

Fortunately, there is another compound of

not

phosphorus which

is

subservient to our pur-

pose ; namely, phosphuretted hydrogen. As

the properties of this gas will be treated of in
the proper place, we shall only observe here
^hat the gas is a compound of phosphorus and

415

PHOSPHORIC ACID.

hydrogen

that

it

hydrogen

that

its

contains just

its

bulk of

is

about 10

specific gravity

times that of hydrogen ; and that when fired

in Volta's eudiometer along with oxygen, it is

converted into

water and phosphoric

acid,

requiring 150 percent, in volume of oxygen

for its complete combustion j but is, notwithstanding, burnt so far as to lose
with 100 measures of oxygen.

its

elasticity

These

facts

atom of phosphorus
the atom of phosphoric acid

leave no doubt that the

weighs 9

that

weighs 23, being a compound of 1 with 2 of

oxygen ; that the atom of phosphorous acid
is 1

with

of oxygen,

weighing

16,

and

that

are formed when

phosphorous acid and water
of
volumes
phosphuretted hydrogen and
equal

oxygen

are exploded together.

SECTION

<5.

HYDROGEN WITH AZOTK,

Only one compound of hydrogen and azote
has yet been discovered
known to chemists as an

it

has been long

important element,

and under various names, according to the

state in which it was exhibited, or to the arlicle from which it was derived j namely, vo-

HYDROGEN WITH AZOTE,

416
latilc alkaliy

niaCy

of sal ammo-

hartslwriiy spirit

&c. but authors

at present generally dis-

it
by the name of ammonia. Its nature
and properties we shall now describe.

tinguish

Ammonia.
In order to procure ammonia, let one ounce
of powdered sal ammoniac be well mixed with
two ounces of hydrate of lime (dry slaked
lime), and the mixture be put into a gas
bottle i apply the heat of a lamp or candle,
and a gas comes over, which must be received
li;
in jars over dry mercury,
is dmmoniacal

ammonia in a pure state.

This gas is unfit for respiration, and for supit has an
extremely punporting combustion

gaSy or

gent smell, but when diluted with common

air, it forms an useful and well-known stimu-

The

lant to prevent fainting.

specific gravity

of this gas has been found nearly the same

by

various authors,

which

able, as the experiment

difficulties that

cases.

of

is

is

the

do, not occur

According

to

more remark-

attended with some

in

many

other

Davy, 100 cubic inches

grains; according to Kirwan,

Allen
and Pepys, 18.7; and
grains
Biot, 19.6; the mean of these, 18.6 grains,
it

18.2

weigh

18.

AMMONIA.

417

may be

considered as a near approximation at

the temperature 60" and pressure 30 inches of

mercury

hence the

specific gravity

weight of atmospheric

Ammoniacal gas

air

is .6,

the

being one.

sent into water,

is

con-

densed almost with the same rapidity as steam ;

in this respect it corresponds with fluoric and

The
muriatic acid gases.
forms
the
and ammonia
monia sold by
niac

this

is

the

the

compound

common

of water

amname of spirit of sal ammoform in which ammonia is

the most frequently used.

It.

is

liquid

of great im-

portance to ascertain the quantity of gaseous

or real

ammonia

in given solutions of ammonia

This subject has been greatly nega very good attempt was made about

in water.

lected

10 years ago by Mr. Davy, to ascertain the

quantity of
different

table,

ammonia

specific

in

watery solutions, of
the result was a
;

gravities

which may be considered an excellent

first
approximation ; hut it is to be regretted
that so important an enquiry should not have

attracted attention since.

have instituted a

few experiments on this head, the results of

which will no doubt be acceptable.
phial, capable of holding 1400 grains ot

water, was partly

filled with mercury, and the

with 200 grains of water, and inverted in
mercury ; into this 6000 grain measures of am*

rest

HYDROGEN WITH AZOTE.

418

moniacal gas were transferred ; the liquid had

not diminished sensibly in specific gravity ;
it

required

2'!-^

grain

measures of muriatic

1.155, to saturate the water; by evapo-

acid,

rating in a heat

below boiling water, 12 grains

of dry muriate of ammonia were obtained.

!Novv, supposing 1400 measures of gas equal
to 1 grain in weight, there would be found in
the salt 5.7 grains of muriatic acid, 4.3 grains

of ammonia, and 2 grains of water.

this

method of proceeding not

upon

for,

been dried
yet the

found

to be relied

though the mercury had recently

an oven in the temperature 240",

in

ammoniacal gas could not be

trans-

from one graduated tube to another,

without a loss of 10 or 15 per cent. ; I had
terred

reason to conclude, then, that the

jn the

avoid

above
this

salt

was overrated.

ammonia

In order to

source of error, I adopted the method

used by Dr. Priestley, of putting muriatic

acid gas to the alkaline in the graduated tube ;
first

but here was

still an
objection, as the muriatic
acid gas must be measured previously to the
transfer, and it is equally absorbable by water

with alkaline gas.

Priestley had

However, I found, as Dr.

done before, that equal measures

of the two gases as nearly as possible saturated

For, when a measure of acid gas

each other.

was put

to

one of alkaline, there was a small

AMMONIA.
residuum of alkaline gas
line

was

419

and when the alka-

was a

transferred to the acid, there

small residuum of acid

before

Having

gas.

concluded (page 287) that muriatic acid gas

was of the specific gravity 1.61, 1 might have

adopted the ratio of acid and alkali in muriate

of ammonia to be 1.61 to .6 ; and hence have
inferred the quantity

and volume of ammonia

in a given solution,

from the quantity of mu-

riatic

acid

solution

But there was one

against this

the

requisite

to

saturate

it.

important circumstance

atom of muriatic acid

knew

weighed 22, and the ratio of .61 to .6, is the

same as 22 to 8.2 nearly hence, the weight
1

of an atom of
4.1,

ammonia must have been

8.2 or

which. I was aware was inconsistent with

the previous determinations concerning azote

and hydrogen. Observing in the 2d vol. of

of the Mcmoirta (TArcueiL that Biot and

l^ussac find the specific

gravity of

Gav

muriatic

acid gas to be so low as 1.278, and under-

standing from conversation with Mr. Davy,

had found the specific gravity of

that he also

the gas to be considerably-less than

had con-

cluded, I was induced to repeat the experiment of weighing it, taking every care to

avoid the introduction of liquid solution.

X
ient a streatn of acid gas, derived from comjnon

salt

and concentrated sulphuric

acid,

HYDROGEN WITH AZOTE.

420

through an intermediate vessel, into a dry flask

of common air, loosely corked, till it had expelled 4ths of the air, as appeared afterwards;
the inside of the glass had a very slight opacity

on

surface

its

weight

it

had gained

l-j-V

was then uncorked and

it

grain in
its

mouth

plunged into water, when |ths of the flask

were in a few moments occupied by the water.
Other trials gave similar results. The flask

common

held 6 grains of

Whence

air.

I de-

rive the specific gravity of muriatic acid gas to

be 1.23, and am induced to apprehend that
this

is

rather

more than

less

than the truth.

The weights of equal volumes of muriatic acid

will then be as 1.23
gas and ammoniacal gas
22
to
as
to .6; or
11, nearly; and if we assume

that 11 measures of acid gas are sufficient

for 12 of alkaline,

which

not unlikely from

is

we shall have 22 parts acid

experience
for the constitution of muof
ammonia
12
to
;

then

ammonia (exclusive of water), which

make the theory and experience har-

riate of

will

monize

according to

ammonia must

view, muriate of

this

consist of

atom of muriatic

ammonia, each atom of ammoa

compound of 1 atom of azote and
being

acid and 2 of
nia
1

of hydrogen.

that

22 parts of

and

Z'h

However

this

may

real muriatic acid,

be, I find

38 of

nitric,

of sulphuric, as determined by the re-

AMMONIA.

421

spectlve foregoing tables, will saturate equal

portions of any

ammoniacal solution

then, may be considered as

tity

of real

and

if

ammonia

in

tests

be incorrect,

test

solutions

different

the ratio of 22 to 12, above adopted,

it

cannot be greatly so

much

error will be general, being so

upon

these,

of the quan-

any table of

ammoniacal

and the

per cent,

The

solutions.

acids I prefer for use, are such as contain

half the

quantities

of acid above stated in 100

Thus, 100 grain measures

grain measures.
of muriatic acid, sp. gravity 1.074, contain
1 1
grains of real acid ; 100 measures of nitric
acid,

1.141, contain 19 grains; and 100

mea-

of sulphuric acid, 1.135, contain 17

Now, 100 measures of
grains of real acid.
ammoniacal solution of .97 sp. gravity, are
sures

just sufficient

to

saturate

adopt that solution as test

Whence

these.

ammonia, and con-

clude that 100 grain measures of

grains of real ammonia.

it

contain 6

It will be perceived, then, that the accuracy

of the ensuing table depends upon several
points: namely, whether 100 measures of muriatic acid of 1.074, really

of acid

whether the

riatic acid gas,

1.23 and

.6,

contain 11

grains

of
specific gravities

mu-

and ammoniacal

or in that ratio

gas, are really

and whether 11

measuxes of acid gas saturate 12 measures of

HYDRDGEN WITH AZOT.

422

ammoniacal

believe the errors in

gas.

any

of these particulars to be very small, and probably they may be such as partly to correct

each other.
I

Mr, Davy,

find, after

water being put

to a

that a measure of

measure of ammoniacal

so-

two occupy two measures, without

lution, the

any sensible condensation

ammonia

consequently,

if

the

measure of any given

be
as
determined ; then
.90,
specific gravity,
the quantity in a measure of .95, will be just half
quantity of

as

much

in a

Hence, a table

tor measures,

and one

for

is

easily constructed

weights

is

derivable

without much calculation.

Table of the

t]Manlitics

of real or gaseous ammonia in so-

lutions of different specific gravities.

Sprtific gr-

AMMONIA.

On

ihe above table,

it

423

jnay be oroper to re-

mark, that I have not had large quantities of

ammonlacal solution lower than ,94, so as to
find

their

specific

gravities

experinientally

but have had small quantities to the amount of

10 or 20 grains of the several solutions from

26 to 12 per cent. ; I have no reason to sus*

pcct any material deviation from the law of
descent observed in the specific gravity down
to 12 per cent.,

ber

when we go below

to .85, and

it

is

num-

that

cannot be great down

not of much importance, be-

at all events,

it

cause solutions of that strength arc never obtained in the large way.
The second column,

exhibiting the grains of

sures of the solution,

practice

than the

is

ammonia

in

100 mea-

more convenient

third,

which

gives

for

the

weight in 100 grains of solution. I'he fourth

column, vvhich shews the temperature at
which the several solutions boil, will be found
highly interesting. The ebullition of a liquid
well Icnown to take place, when the steam
or vapour from it is of the same force as the
is

In solutions down to
atmospheric pressure.
12 per cent., the experiments were performed

by inserting a thermometer into a phial con^

taining the solution, and plunging the phial
into hot water till the liquid boiled 5 but in
the

higher solutions a

small portion,

as

20

HYDROGEN WITH AZOTE.

424'

grains,

cury

was thrown up a tube filled with merwas then put into a phial of

the tube

mercury, and the whole plunged into warm

water ; the temperature was then ascertained
requisite to bring the

in the

mercury

The

the level of that in the phial.

lumn

is

from the

calculated

tube to
fifth

second,

co-

sup-

posing the specific gravity of ammoniacal gas

.6.

It

observed, that the above table

may be

of ammonia in different sogives the quantity

lutions, from 15 to 20 per cent, less than Mr.

Davy's table

the

also, that

common ammo-

niacal solutions of the shops usually contain

from 6

to 12 per cent, of

Before
fourth and

we can
fifth

columns of the

ascertain the force of

solutions at

found

in

ammonia.

estimate the

different

some one

value of the

table,

we must

vapour from ammoniacal

temperatures.

If

it

be

we may by anaAs the steam

others.

instance,

logy infer the results in

from water varies in force in geometrical progression to equal increments of temperature,

might be expected that the steam or gas

from liquid ammonia should do the same ; but

it

is a
compound, the simple law
of the force of aqueous steam does not obtain.
It appears, however, from the
following re-

as the liquid

sults,

that a near
approximation to this

law

is

AMMONIA.
observed.

a quantity

was by

cuum

425

Into a syphon barometer I threw

of .946 liquid ammonia, which

&c. transferred

agitation,

the va-

to

The vacuum was

over the mercury.

then immersed successively

in

water of different

temperatures, and the force of the gas observed

as under,
Temperaliire.

old scale,

new

diiFcrences.

scale.

Force of atnraonl*
acai gteani fiom
liquid .946.

140"

15 r

103'

115

30 inch,
J

31'

74"

84*"

7.5

50^

55

3.75

Hence

it

seems, that the intervals of tempe-

rature required to double the force of

ammo-

niacal steam, increase

no doubt but

this sort

mix with common

ticity

air,

in

ascendinp^.

had

of steam or gas, would

without having its elas-

affected, like as other steams

do

but 1

ascertained the fact by experiment

Thus I
mixed a given volume of air with steam of 15
:

inches force, and found that the air was doubled

in bulk.

These

shew

facts are curious

that

ammonia

is

and important. They

not retained in water

HYDROGEN WITH AZOTE.

426

without external force, and that the pressure

elastic fluid avails but that of ammo-

of no

niacal gas itself

thus establishing the truth of

the general law which I have so

on, that

710

elastic fluid is

much

sufficient

insisted

barrier

agai?ist the passage of another elastic fluid.

We

may now

upon what causes the

see

saturation of water with

They

are

two

ammonia depends.

the temperature of the liquid

end the pressure o^ihe incumbent ammoniacal

gas, exclusive of the air intermixed

For instance,
(old scale)

if

with

it.

the temperature be given, 50

then the strongest possible solu-

under atmospheric pressure, will be such,

that 100 measures will have the specific gravity
tion,

and contain 26 grains of ammonia, or

But if, in satugas.

.87,

419 times the volume of

rating the water by sending

common
cumbent

air, so

as

to

up

make

gas, there

gas, then the solution cannot

stronger than

.946,

be

|ths of the in-

of which

be made

100 measures

contain 11 grains of ammonia, or 162 times

I have obtained a satuthe volume of gas.
rated solution containing 26 per cent, ammonia, with TT^h common air in the incumbent

gas

and

at

the

same temperature, another

saturated solution, containing only 17 percent.

ammonia, with iths common

cumbent gas.

air

in

the

in-

AMMONIA.
With

respect to the constitution of ammonia,

and Bergman pointed out

Priestley, Scheele,

the

t'.vo

427

elements into whicii

Berthollet

settled

first

it is

decomposed.

the proportions of the

elements, and the quantity of each obtained

from a given volume of ammoniacal gas. It
is

highly

credit too, that

his

to

subsequent

repetitions of his experiments, under the improved state of knowledge, liave scarcely
amended his results. Priestley resolved 1 mea-

ammoniacal gas, by electricity, into 3

measures of gas not absorbable by water ; but
Berhis ammonia could not have been dry.
sure of

thollet resolved

same way

17 measures

this result

borated by various authors.

that the gas so produced,
parts of azote

33 in

into

tlie

has since been corro-

was

He

also

found

a mixture of 121

by weight, with 29 of hydrogen

azote with

of hydrogen.

or

4.^^

in

In 1800, Mr. Davy published his researches,

which were given several interesting results

Mr. Davy decomposed ammoby sending the gas through a red hot
after the common air was expo:celain tube

on ammonia,
nia,

pelled, the collected gas

was found

free from;

oxygen. To 140 measures of this gas were

added 120 of oxygen ; the mixture being exploded by electricity, 1 10 measures of gas were
left;

and of course 150 were cenverted

intv'

HYDROGEN WITH AZOTE.

42B
water

100 measures must have been

of this

Whence, 140 measures of

the ga$
hydrogen.
from decomposed ammonia, contained 100 hy-

drogen and 40 azote

or

100 measures con-

tained 71.4 hydrogen and 28.6 azote.

This

conclusion was so nearly agreeing with the

previous determination of Berthollet, that both

have

justly been held up as specimens of the

accuracy of modern chemical analysis.
In 1808, Mr. Davy published his celebrated

discoveries relating to

the decomposition of

the fixed alkalies.

Having ascertained that

these contained oxygen, he was led by analogy
to suspect the

same element

veral experiments

in

ammonia.

Se-

were made, which seemed

to countenance this idea

be considered conclusive,

but these could not

long as it was admitted that no oxygen appeared in the decomposition of ammonia by electricity, and yet
that the weight of the azote and hydrogen
as

to that of the ammonia

Mr. Davy re-examined the spe-

were together equal

decomposed.

ammoniacal gas, the quantity

evolved
by the decomposition of a
gaseii
volume
of
and the ratio of azote to
it,
given
cific

gravity of

of

hydrogen

in the

same.

the gases obtained

The

result

amounted only

was, that

to -j-Tths of

weight of the arhmonia ; the remaining

^Vth Mr. Davy thought must be oxygen.

the

AMMONIA.

429

which, uniting to hydrogen, formed a portion

of water. The way in which this ^[h was
saved, was principally by diminishing the absolute quantity of gases derived from a given

volume of ammonia, but partly by finding less

azote and more hydrogen than had been before
estimated.
niacal

mixed
and

Thus,

100 measures of ammo-

gas produced

only

180 measures of

though commonly estimated at 200;

gas was found to consist of 26 azote

gas,

this

and 74 hydrogen per cent.

These conclusions, so different from what
had been long adopted, and depending upon
experiments of s^me delicacy, were not likely
to

be received without a more general scrutiny.

Henry in England, and A. B. BerthoUet

Dr
in

France, seem both to have renewed the

component parts of ammonia with great care and assiduity. Dr.

Heniy's object was to determine whether any
investigation into the

oxygen, water, or any other compound containing oxygen, could be detected in the analysis

two

of

ammonia

tained from a
gas,

this

enquiry included the

others; aamely^ the quantity of gases ob-

given volume of ammoniacal

and the proportion of azore

in the same.

The

results

to

hydrogen

were, that neither

oxygen nor water could be found that for the

most part the bulk of ammonia was doubled
;

HYDROGEN WITH AZOTE.

430

by decomposition, even when the gas was

previously dried with extreme care 3 and that
the ratio of azote to hydrogen in the mixture,

from an average of

was

27:1:

Henry was

six careful

In

to 72i-.

this

last

experiments,
decision. Dr.

so fortunate as to discover a

easy and expeditious

had been known

mode

before

more

of analysis than

he found that am-

moniacal gas mixed with a due proportion of

oxygen, of nitrous oxide, or even of nitrous

would explode by an electric spark. He

found an under proportion of oxygen gas to
gas,

answer best (about 6 measures of oxygen

of ammonia)

the explosion produced a

pJete decomposition of the

partial

to

10

com-

ammonia, and a

combustion of the hydrogen

after

which more oxygen was put to the residuum,

and the remainder of the hydrogen consumed.

From one experiment, in which 100 measures

of ammonia were decomposed in a tube of
which the mercury had been previously boiled.
Dr. Henry only obtained 181 measures of gas j
and he seems to think that this experiment
may be the most correct in regard to that
object.

(Philos. Trans. 1809).

In the Memoires d'Arcueil, tom. 2, M. A.

B. BertholJet has a paper on the analysis of

ammonia.

He

Berthollet in

alludes to the experiments ot

the

memoirs of the academy.

AMMONIA.
1785

in

which the

431

ratio of 27.5 azote to 72.5

hydrogen, was found

in the

decomposed aav

tnonia, allowing 196 hydrogen for 100 oxygen.

He

repKDrts

several experiments

tions relative to the oxidation

of iron in ammoniacal gas.

and observa-

and deoxidation

He

then proceeds

to prove, that the weight of azote and hydro-

gen produced
monia,

the decomposition of amweight of the ammonia

in

equal to the

is

Biot and Arago determine the specific

of azote, hydrogen^ and ammonia,
gravities
itself.

to be .969, .078,

and .597

respectively,

which

A. B. Berthollet adopts. He finds that 100

measures of ammonia produce 205 of permanent gas ; which, by analysis^ gives 24.5 azote
and 75.5 hydrogen per cent. Like Dr. Henry,

A. B.

Berthollet

decomposed ammonia by ex-

with oxygen gas ; but unfortunately

ploding
he used an excess of oxygen, and then oeterit

mlned the residuary oxygen by the addition of

hydrogen he was aware, however, that part
:

of the azote
acid.
it

Upon

was thus converted

appear, that the gases

composition of ammonia
sible,

into nitric

collecting the results, he

equal to the

makes

produced by the deare, as nearly as pos-

weight of the ammonia.

Though the experiments of these two aumay be deemed satisfactory, with regard

thors

to the non-existence of

oxygen

in

ammonia.

HYDROGEN WITH AZOTE.

432

they would have been more so if they had

accorded in the quantity of gas derived from a
given volume of ammonia, and in the ratio of
azote to hydrogen.
Having made some experiments myself on these heads, I

lowed

to give

my

these differences.

Davy,

cury

al-

ammonia is not doubled by decomwhen due care is taken to prevent

that

position,

any

may be

opinion as to the causes of

1 am persuaded, with Mr.

liquid from adhering to the tube or mer;

the same time

but at

am

inclined to

experience, that 100 measures

will give not less than 185 or 190

believe, from

of

ammonia

measures of gas by dscomposition I took a

tube and filled it with dried mercury j then
:

transferred a portion of gas into

pushing

a glass rod

up

it,

and by

the tube several times,

displaced the mercury in the tube, so that no

liquid ammonia could exist in the renovated

mercury.
electricity,

100.

This gas, being decomposed by

produced after the rate of 1 87 for

With

hydrogen,

respect to the ratio of azote to

am

convinced
the

it is

to be obtained

ammonia

only by decomposing
previously
to the combustion of the
hydrogen, and this
may be done either by electricity or by heat ;
in these cases,

ammonia

28 measures of azotic

will

gas,

be resolved into

and 72 measures of

hydrogen gas, in the hundred.

have

re-

AMMONIA.

433

peatedly obtained it so by electricity, the re*

never deviating farther than from 27 to

suits

29 of azote.

This agrees su^ciently with

Berthollet's

original analysis by electricity,

and with Davy's analysis by heat in 1800;
both of them made without any theoretic
views as to quantity, wh'ch cannot be said of

any of the subsequent investigations on

this

subject.

We

now

are

how

to see

far these

results

will agree with the specific gravity of

ammo-

niacal gas

two

that

is,

whether the weights of the

gases are equal to the weight of the

am-

monia decomposed.

100 measures of ammonia, which

become
namely,

and

sp. gr. .6

5I. 8 azote,

which X
~ which X sp

gives

60

_^^_

185 measures of mixed gas,

sp- gr. .967 gives 50.09

133.* hydrogen,

gr. .0?

gives 10.65

69.7^

The excess of |ths of a giain upon 60, is too

small to merit notice, and may arise from an
inaccuracy

in

any of the data, which, if corno material influence on the

rected, could have

conclusions.
I shall

now make

few observations on the

other methods of analyzing ammonia.

Dr,
Henry's methods of burning ammonia in
Volta's eudiometer along with
oxygenous gas.

HYDROGEN WITH AZOTE.

43'1'

nitrous gas, and nitrous oxide, unite elegance

with expedition, and when well understood,
cannot but be valuable. It appears to me,

however, both from experience and analogy,

that a

monia,

compound combustible, such

as

am-

never decomposed and one of

is

its

elements burnt, to the entire exclusion of the

other.

Numerous

instances

may be found

in

the compounds of charcoal and hydrogen, of

phosphorus and hydrogen, &c. where one of
the elements seizes the oxygen with more rabut some portion of the
;
other is always burnt.
Even when the com-

pidity than the other

bustible gases are only

not combined,

we do not

mixed together, and

find that

one of them

precludes the other from taking a share of he

oxygen till it is saturated. Thus, in a mixture

of carbonic oxide with hydrogen, witn a deficiency of oxygen, part of both is burnt by an
electric spark.
Dr. Henry has, indeed, no-

ammonia fired with excess of oxygen, gives nitric acid as well as water. I have
reason to believe this is the case in some de-

ticed that

gree, in whatever proportion

they are

fired,

have seldom obtained so much as 27 per

cent, of azote by the combustion of ammonia
I

with oxygen 'the hydrogen being estimated by

doubling the oxygen spent), and in no inbut h will be manifest that all th
stance 28
:

AMMONIA.
is

oxygen
if

gen,

we

435

not consumed in burning the hydronote the ammoniacal gas expended,

and allow only 66 or 67 per

the hydrogen

gone

form

ammonia with

oxygen

for

which must have

greater expence of oxygen,

to

cent,

there will generally be fnund a

The combustion

nitric acid.

nitrous gas usually gives

of

from

25 to 27 per cent, of azote, allowing the conof nitrous gas to be what is stated at

stitution

page 331.

Upon

the whole,

fourtd nitrous

oxide to approximate nearest to the truth.

When 100 measures of ammonia are exploded

with 120 of nitrous oxide, the gases resulting

are azote with a very small portion of hydro-

gen

if

to this a little

hydrogen be added, and

then an excess of oxygen, another explosion

will determine the residuary hydrogen
which
;

being deducted, there remain about 172 azote,

120 of which come from the nitrous oxide,

and 52 from the ammonia, which gives after

the rate of 28 azotf per cent, on the evolved
gases.

When the decomposition

of arrmonia

attempted by oxymuriatic acid gas, a graduated tube is filled wi.:h the gas, and plunged
is

in this w^y, if we
liquid ammonia
reckon a measure of the acid gas to a measure
of hydrogen, we shall find the azote evolved

into

and

left in

cent,

the tube,

amount

upon both gases.

It

is

to 23 or 24 per
to

be presumed.

HYDROGEN WITH AZOTE.

436

then, tha oxymuriatic acid, like oxygen,

consumes part of both the elements of am-

monia.
the weight of azote with that

By comparing

of hydrogen in the above table, we find them

This evidently marks the
as 4.7 to 1 nearly.
constitution of

ammonia

to be that of

before

weigh

atom of

But

each of the elements combined.

we have

determined the element of azote

5.1,

when

treating of the

to

compounds

of

azote and oxygen.

This difference is probably
to be ascribed to our having over-rated the
specific gravity of nitrous gas, and perhaps

In the Memoires

nitrous oxide.

d'Arciceil^

observe Berard finds the specific gravity of nitrous gas to be 1.04, instead of 1.10, which
last I

have made

calculations from

my

if

the

former should prove true, it will reduce my

valuation of azote in nitric acid nearly to 4.7 ;
I have not had an opportunity of ascertaining
the specific gravity of nitrous gas ; but am inclined to believe that 1.10 may be too high.
Berthollet finds nitrous oxide to be 1.36, instead of 1.61

much

suspect the former

is

too

low.

Upon

the whole,

atom of ammonia
hydrogen and

Thc

is

we may

conclude that an

constituted of

atom of

of azote, and weighs nearly 6.

diameter of the elastic particle

is

.909,

OLEFIANT GAS.

437

that of hydrogen being 1.

Or, 300 measures
of ammoniacal gas contain as many atoms as
400 measures of hydrogen, or as 200 of

oxygen.

SECTION

7.

HYDROGEN WITH CARBONE.

There are two combinations of hydrogen
with carbone, now well known, easily disand from all other
tinguishable from each other
combinations.

They

are both elasHc fluids

one of them, called olcfiant gas, is a compound

of 1 atom of hydrogen and 1 of carbone ; the
other, which I call carburetted hydrogen, is
a compound of 2 atoms of hydrogen and I
of carbone, as will be

manifest

f'-om

what

follows.

Olefiafit

Gas.

The gas denominated oUfiant, was discovered and examined by t'ie Dutch chemists,
Bondt, Dieman,
ject

&:c.

was published

nal de Physique,

and a memoir on the sub-

in the loth vol. of the Jour-

1794.

JtYDROGEN WITH CARBONE.

438

defiant gas may be procured by mixing 2

measures of sulphuric acid witli 1 measure of
alcohal ; this mixture in a gas bottle must be
heated

to

about 300" by a lamp,

when

the

exhibits the appearance of ebuHitioa,

liquid

and the gas comes over

it

should be passed

through water, to absorb any sulphurous acid

which may be generated.

This gas is unfrt for respiration, and extinguishes flame, but it is highly combustible :
its
specific gravity, according to the Dutch
is .905 j
according to Dr. Henry,
Perhaps .95 is abaut the truth. Water
absorbs -^th of its bulk of this gas ; or the atoms

chemists,
.967.

of gas in the water are just twice the distance

without
and it may be expelled
again by the othe" gases. This property (of
they are

j.

being absorbed by' 8 times its bulk of water)

occurred to me in ISOi, in a course of experiments on the absorption of gases by water.
It

is

peculiar

distinguishes
is

it

to

this

from

all

gas,

and consequently

others.

When

mixed with oxymuriatie acid

gas
minution

takes place, like as

olefiant

gas, a di-

when oxygen

and nitrous gas are mixed ; but the result is

An oily which swims on the surface of the
water.

gas the

Hence the Dutch chemists gave this

name of olefiant. For this purpose,

they found 3 measures of olefiant gas required

439

OLEFIANT CAS.
4 measures of the acid gas

but Dr. Henry

finds 5 of olefiant require 6 of the acid.

difference

The

not great, considering the

As neither of these

diffi-

is

culty of the experiment.

will agree

results

with the other

two

perties of these

known

pro-

gases, I suspected that

in some degree incorrect;

be the case from the follow-

both would be found

which proved

to

Having taken two similar

ing experiments.
tubes graduated, containing each about 170
grains of water, I filled them, one immediately
from a bottle generating oxyacid
muriatic
copiously ; into one of these,
200 measures of olefiant gas were slowly transafter the other,

ferred

after

gas was

standing some time, the residuary

and noted then the other

transferred

tube with acid gas was taken, the gas passed

5 or 6 times through water, till no further di-

minution was observed, and the residuary gas

was noted and allowed for impurity in the first
tube.

By

this

procedure no acid gas was

lost,

and an excess of

olefiant

purity of this

did not enter into the calcu-

lation.

riatic acid

in

last

In one

trial,

gas being used, the

165 measures of oxymu-

gas condensed 168 of

another,

165

took

167.

olefiant gas

From

these, I

conclude that oxymuriatic acid requires a very

little more than its bulk of olefiant gas to be
saturated

perhaps 100 of the former

may

take

HYDROGEN WITH CARBONE.

440

102 measures of the

latter

but

if

we reckon

equal volumes, the error cannot in general

be

material.

defiant gas burns with a dense, white

It explodes with uncommon violence

flame.

when mixed with oxygen and

electrified

the

products resulting are various, according to the

When completely saturated

with ox-vgen, the results are, according to

circumstances.

c*rb. acid.

100 measures take 280 oxygen, produce 180

2S4.
179
Dr. Henry, 100

Berthollet,

The

of the produce is water. These

agreeing so well with each other, arc

rest

results,

can add that my

the more plausible ; but
own experience corroborates thepti, particuI

My

results have
regard to oxygen
less
than
but
more
than 270;
300,
always given
the acid, I apprehend, should be about 185

larly

in

190: unless a great excess of oxygen be

used, the charcoal is partly thrown down, and it
or

makes the gas

in

result

than

is

turbid after the explos'on

this case

affords

less

the

carbonic acid

due.

When

defiant gas a!one

is

subjected to con-

tinued electricity, either over mercury or water, the result is hydrogen gas, and a quantity
of charcoal is deposited.
very careful ex-

periment of this kind was

made by Dr. Henry

OLEFIANT GAS.
and myself,

in

which 42 measures of pure

defiant gas were electrified

82

these

found to
fiant

gas.

441

till

became

they

were exploded with oxygen, and

consist of 78
hydrogen, and 2 deMere 40 olefiant became 78 hy-

drogen, or very near double.

was thrown down.

The

charcoal

to this,

According

100

measures of olefiant gas will contain 195 of

hydrogen ; which require 98 oxygen for their

combustion
the

now

the

as

charcoal must take

or nearly 196 measures,

rest,

it

follows that

combustion of olefiant gas, 2 parts of

the oxygen are spent upon the charcoal, and 1
in the

part

upon the hydrogen, flence we obtain

an atom of olefiant gas

this conclusion, that

consists of

of charcoal and

No oxygen

united.

of hydrogen

can be present

in olefiant

gas; because during the elec'rification

be detected, either

in

it

would

the form of water

or

carbonic oxide.
It will

be proper

now

to see

how

far the

weights of the gases entering into combination,

An
agree with the previous determinations.

atom of charcoal weighs 6.4 (see page 382),

and 1 of hydrogen weighs 1, together
making
an atom of olefiant gas, 6.4. I'his atom will
require

of

oxygen

for

its

combustion

namely, 2 for the charcoal, to form carbonic

acid, and 1 for the hydrogen, to form water ;

HYDROGEN WITH CARRONE.

442
these 3

weigh 21

whence

6.4 parts of olefiant

should take 21 of oxygen.

Now supposing, according to Dr. Henry's result, that 100 measures of olefiant gas require
gas

by weight,

284

for

their

combustion

and

further, that

the specific gravity of oxygenous gas

is

1.10

(agreeably to Alien and Pepys, as also Biot

and Arago), we

shall

have 284

i.i

=312.4,

the weight of the oxygen j hence, if 21

:
6.4
312.4:95, the weight of 100 measures of
:

olefiant gas, corresponding to a specific gravity

of .95.

Hence, then, it appears that the

of
the
weight
gases combined, perfectly corro-

borates the above conclusions respecting the

constitution of olefiant gas.

There are some remarkable circumstances

combustion of

attending the
^^olta's

olefiant

eudiometer, which deserve

gas in

notice as

part of the history of the gas, but particularly

as they put the constitution of the gas beyopd
all

doubt.

100 measures of oxygen be put

and electrified, an ex-

If

to 100 of olefiant gas,

plosion ensues, not very violent

of a diminution,
increase of gas
will

as

usual, there

instead of

be found about 360

but instead
is

great

200 measures, there

some traces of car-

bonic acid are commonly observed, which disappear on passing two or three times through
lime water

there will then remain, perhaps.

OLEFIANT GAS.
550 measures of permanent

443

which

gas,

all

is

combustible, yielding by an additional dose of

oxygen, carbonic acid and water, the same as
if entirely

burnt in the

therefore,

is

state

this

new

The answer

first

instance.

What,

gas in the intermediate

is

clear.

It

carbonic

is

oxide and hydrogen mixed together, an equal

number of atoms of each. One third of the

oxygen

requisite for the

suffices

to convert the carbone into carbonic

complete combustion,

oxide, and the hydrogen at the instant is lihence the other two thirds are em;

berated

ployed, the one to convert the carbonic oxide

into acid, the other to convert the

In

into water.

fact, the

hydrogen
350 measures consist

of nearly 170 of each gas, which together re170 of oxygen for their com-

quire nearly
bustion.*

* M. Berthollet contends, that

gen

all

the combustible gases

whk'h carbone and hydrogen enter, contain

into
:

he calls them oxj/carburelted hydrogen.

also enters into his views in this respect.

to olefiant gas,

on

this opinion,

it

will

when

M.

gas, and

it

but which

when

tico

Berthollet has not

But there

far as relates

is

one circumstance

explained in regard to

turns upon a point which he and

is

oxy-

be time enough for animadversion

the accuracy of the above facts and

observations are questiofled.

which

As

also

Mr. Murray

not perhivps generally received

I
;

gases unite to form a third, this las^

heavier ikon the lighter of the two.

Now,

tliis

acknowledge,

namely, that
2v specifically

in

the above

HYDROGEN WITH CARBONE.

41-4

The
.81 to

diameter of an atom of olefiant

gas
J.
And 100 measures of

hydrogen

contain as

many atoms

is
it

as 188 of
hydrogen, or

94 of oxygen, or (probably) as 200 of

oxywhence the union of this last
;
with olefiant gas, must be 2 atoms of the

as

muridtic acid

gas

with

of the acid.

2.

The

Carhurettcd Hydrogen.

gas which

denominate carburetted

hydrogen, was known in a

to Dr.
Priestley ; he called

by the name of
voisier,
thollet,

vated

state of mixture,
all

such mixtures

injiammabk

lieaiij

air.

La-

Higgins, Austin, Cruickshanks, Ber-

Henry and
this

have since

others,

department of science.

shanks contributed

much

culti-

Cruick-

to unveil th.^
subject,

by pointing out carbonic oxide as an inflammable gas, sui generis, but often found mixed
with other gases.

No

correct notion of the

constitution of the gas about to be described,

seems

to

have been formed

instance, \\v find olefiant gas and

to term a third
(according to

fiis

by oue half nearly than the

this

the

oxygenous

opinion),

to

atomic

gas, uniting

vvljich. is

lighter of the two.

new oxycarburetted hydrogen

the above principle

till

lighter

How

is

be reconciled with

CARBU RETTED HYDKOGE^T.

44^

was introduced and applied in the inIt was in the summer of ISOI-,

ftieory

vestigation.

that I collected at various times,

the

places,

ponds;

this

and

in various

inflammable gas obtained from

gas I found always contained some

and a portion of azote;

when cleared of these, it was of a

traces of carbonic acid

but that

uniform constitution.
I

was

After due examination,

one half of the oxy-

convinced that just

gen expended in its combustion, in Volta's

eudiometer, was applied to the hydrogen, and
the other half to the charcoal.
fact afforded a clue to

its

This leading

constitution.

Carburetted hydrogen gas may be obtained

state, with the above exceptions,

in a pure

from certain ponds

in

warm

weather.

Clayey

ponds,
vicinity of a town, where soot
and other carbonaceous matter is deposited,
in the

abound with

this

gas.

The bottom

of the

with a stick, large bubbles

pond being
which
ascend,
may be caught by filling a
stirred

tumbler with water, and inverting it over the

ascending bubbles. This gas is obtained nearly
pure also by

distilling pitcoal

with a moderate

now

largely used as a substitute

for lamps and candles, under the name of coal
gas.
According to Dr. Henry's analysis, coal

red heat.

It is

gas does not usually contain more than 4 or 5

per cent, of carbonic acid, sulphuretted hydro-

HYDROGEN WITH CARBONE.

ii6

The rest is principally

gen, and defiant gas.
carburetted hydrogen, but mixed with some
atoms of carbonic oxide and hydrogen. The
last portion of gas driven off from pit-coal,
be entirely carbonic oxide and hydrodistillation of wood and of moist

seems

to

gen.

The

charcoal, and

many

other vegetable substances,

hydrogen, but highly

with
carbonic
acid, carbonic oxide
charged
carburetted

produces

and hydrogen

the

exclusively at the

The
1.

It

port

two

last

gases always appear

end of the process.

properties of carburetted hydrogen

unfit for respiration,

is

combustion.

of

2.

and

are,.

for the sup-

Its specific

gravity

when

pure, from my experience is very near

.6.
Dr. Henry finds the coal gas to vary from
.6 to .78 ; but then the heaviest contain 15

per cent, of the heavy gases, carbonic acid,

sulphuretted hydrogen, and olefiant gas.

Water absorbs ^V^^ of its bulk of this gas. If

100

measures

of

carburetted

hydrogen be

mixed with 100 measures of oxygen (the least

that can be used with effect), and a spark,
passed through the mixture, there
plosion, without

lume

water,

after passing a
it

is

reduced a

of carbonic acid.
possess

all

is

an ex-

any material change of vo-

few times through lime

little,

manifesting signs

This residue

is

found

to

the characters of a mixture of equal

447

CARBUllETTED HYDROGEN.

and

volames of carbonic oxide

Upon adding 100 measures

hydrogen.

of oxygen to this

residue and passing a spark, nearly 100 measures of carbonic acid are produced, and the

of the produce

rest

is

If 100 measures

water.

of carburetted hydrogen be put to upwards of

200 of oxygen, and. lired over mercury, the
result will be a diminution of near 200 measures,

found

and the residuary 100 measures

to be carbonic acid.

Though
in

be

carburetted hydrogen is naturally

many coal mines, and occasionally

produced
mixing with
ful

will

common
in

explosions

air,

exhibits

the large

mixed with common

air,

some dread-

;
yet when
Volta's eudio-

way
in

does not explode by a spark, unless

the gas be to the air, as 1 to 10 nearly, and
then feebly.
meter,

it

When
is

a portion of carburetted hydrogen gas

for

electrified

volume,

in

some time,

it

increases in

the end almost exactly doubling

same time a quantity of charcoal

The whole of the gas is then
deposited.
found to be pure hydrogen.

itself

at the

is

All these facts being compared, there canleast doubt as to the constitution

not remain the

It is a compound
of carburetted hydrogen.
of one atom of charcoal and two of hydrogen ;

the

compound atom occupies

the

same space

HYDROGEN WITH CARBONE,

448

an atom of hydrogen
and 4 atoms
(nearly) as
of oxygen are necessary to its complete combustion ; namely, 2 for the charcoal to form
;

carbonic acid, and 2 for the hydrogen to form

This conclusion derives a very elegant
water.
confirmation, from the facts observed by ex-

ploding the gas with one half of the oxygen

In this
requisite for complete combuslion.

atom of the gas requires onlv 2

case, each

atoms of oxygen^ the one joins to one of hydrogen and forms water the other joins to
;

the

carbone

to

same moment
springs

form carbonic oxide,

at

th6

atom of hydrogen
Thus there becomes 100 measures

off.

the remaining

of carbonic oxide and 100 of hydrogen, or the

same

As

bulk, as the original mixture.

atom of charcoal

the weight of an

is

5.4,

and 2 atoms of hydrogen arc 2, the compound

atom weighs 7.4
but as there are the same
;

number of atoms of hydrogen and

retted

hydrogen

sents

the

hydrogen

weight of

in the

number of
is

times that

air

is

about

repre-

carburetted

heavier than hydrogen.

common

of carbu-

same volume, 7.4

Now,

the

12 times as

as hydrogen
therefore, the relative
weights or specific gravities of the two gases,

great

are as 7.4 to 12, or as .6 to

agrees with experience

1,

hence

nearly,

we

which

derive this

conclusion, that carburetted hydrogen consists

CARBURETTED HYDROGEN.

449

entirely of hydrogen and carbone, the

whole

weight of the gas being accounted for in the

carbonic acid and water formed by its combustion.*
I think
to

my

of

this

it
proper to observe, that, according^
most careful experiments, 100 measures
gas require rather more than 200 mea-

*
According to M. Berthollet (IVJem. d'Arcueil, tome 2cl)
ihe gas from chrircoal is a triple compound of carbone,
oxygen, and bydiogen. Whatever our speculative chemists

believe, no practical chemist in Britain adopts

may

That

this idea.

no one disputes

it

always contains more or

but then the oxygen

the carbone forming carbonic oxide.

The

ture consists of carburetted hydrogen

never find any

Jlities

100

first

sp. gr.

gives 21

16

32

.08

23

.476 takes 81

raixt

Here

it

nppeais, that

gives53

20 measures of

carb. hyd. -f-

34

46 hydrogen, constitute a mixture of 100

of the sp. grav. .476, which being burned, take

carb. oxide
tripasures

For instance^

takes 42

r;irb.

JOG

quan

of Berthollel's nine specimens.

.9t

carb. byd. sp. gr. .6

34

46hyd.

mix-

.462 took 81 oxy. gave 56 carb. acid.

20

ox.

rest of the

the relative
difficulty in ascertaining

take the

gas,

of oxygen

and hydrogen.

of each* of the gases in such mixtures.

suppose we

less

united solely to

is

-f-

Hence this mixture

81 oxygon, and give 53 carb. acid.
may be considered as agreeing with Bert hoi let's gas from
charcoal above specified.

HYDROGEN WITH SULPHUR.

450

sures of oxygen, and give rather

100 carbonic acid

more

than 5 per cent, and

Hence,
neglected.

then,

hydrogen
but rather

is

not

may
general be
we may conclude
in

atom

that the diameter of an

ot'

nearly equal to that

is

more than

but the difference

carburetted

of hydrogen,

less.

SECTION

8.

HYDROGEN WITH SULPHUR.

There
sulphur

are

two compounds of hydrogen with

the one, a well

known

elastic fluid

denominated sulpJiuretted hydrogen, the other

a

vitjcid,

oily

compound,

retted hydrogen.

called supersulphii-

The former

of these consists

atom of each element,* the the latter probably of 1 atom of hydrogen united to 2 of

of

sulphur.

1.

The

best

Sulphuretted Hydrogen,

way

have found

to ob'ain sul-

phuretted hydrogen
pure state, is to heat
a piece of iron to a white or welding heat in a
in a

is

* The
figure

for

incorrect

ought to be

united to

it

sulphuretted hy<lrogen, plate 4, part

of suipiiur.

atom of hyiliogen instead

1,

ol i,

SULPHURETTED HYDROGEN.

451

suddenly drawing it from

apply arollof sulphur ; the two being
rubbed together, unite and run down in a
smith's forge, then

the

fire,

which soon

liquid form,

This compound

brittle.

to be granulated

and becomes

fixes

or sulphuret of iron,

and put

into a gas bottle,

is to be added,
acid
to which dilute sulphuric
after which the gas comes over plentifully.
is

When

the sulphuret of iron

cible from iron filings

answers well

it

is

made

and sulphur,

in a cruit

often gives hydrogen

seldom

mixed

with the sulphuretted hydrogen. The reason

seems to be, that several sulphurets of iron
exist

namely, the first, the second, the third,

it is the second only, or that which is

&c. and

constituted of

formed
is

atom of

in the process

iron

and 2 of sulphur,

above described, which

essential to the formation of sulphuretted

The

drogen.

no gas

others either give

at all.

Sulphuretted hydrogen

and

for

hy-

hydrogen or

is

unfit for respiration

supporting combustion

it

has a disa-

of rotten eggs ;
greeable smell, resembling
its specific gravity is 1.10 according to Kirwan,
and 1.23 according to Thenard. Mr. Davy,
that

understand, makes

ofmineafew

it

about 1.13.

years since,

Thenard's

obtained,

we may

but

till

Some

trials

gave a result near

more correct one can be

adopt the mean 1.16.

Wa-

HYDROGEN WITH SULPHUR.

452

ter absorbs just

therefore,

it

will be left
is

is

after

better, in

still

bulk of

its

this

gas

mixed with hydrogen,

in

washing

th:s last

Sulphure'tcd

When

hydrogen burns with a blue flame.

fective quantity),
spark.
sited,

water

100 mea-

in the ratio of

50 of oxygen (which

sures to

is

the least ef-

explodes by an

it

wha^

water, or

lime water.

mixed with oxygen,

when'y

electric

produced, sulphur is depoand the gases disappear. If 150 or more

;

is

measures of oxygen are used, then after the

explosion over mercurv, about 87 measures of
found

sulphurous acid are

in

and

the tube,

150 of oxygen disappear, or enter

into

com-

bination with both the elements of the gas.

From
&c.

it

the experiments of Austin, Henry,

has been established, that sulphuretted

hydrogen undergoes no change of volume by

electrification,

these

repeated

been able

but deposits sulphur.

experiments,

have
not

whether there was

to ascertain

crease or diminution.

and have

The

residue of gas

inIs

pure hydrogen.

From

these

facts, the
is

of sul-

clearly pointed out.

phuretted hydrogen
is 1 atom of
sulphur and

same volume

constitutian

It

of hydrogen, united

as 1 of pure hydrogen.
burned, 2 atoms of oxygen unite to 1
of sulphur to form sulphurous acid, and 1 of

in the

When

SUPZRSULPHURETTED HYDROGEN.

453

oxygen to 1 of hydrogen to form water. The

weights of the (flements confirm this constitution.
One atom of sulphur has been found
weigh 'S

to

page 393),

(see

to

which adding

hydrogen, we obtain the weight of an

atom of sulphuretted hydrogen =14; this
1

for

number

number of times

Irkewise expresses the

that sulphuretted hydrogen should exceed hy-

drogen in specific gravity. But common air

exceeds hydrogen 12 times
therefore, 12 :
;

14

specific gravity of

vity of sulphuretted

common

hydrogen

air

sp. gra-

1.16, agree-

Hence
ably to the preceding determination.
this gas is
wholly composed of sulphur and
hydrogen, as above.
Sulphuretted hydrogen unites, like the acids,
and metallic oxides, form-

to alkalies, earths,

ing with them

which
thes<*

are

salts

called

ot

definite

proportions,

Some of

hydrosulphyrrff;

are important chemical agents

but they

are apt to undergo changes by keeping, especially in solution.

2.

Supersulplmrctted Hydrogen.

This compound may be obtained as follows

Let half an ounce of flower of sulphur and as

much hydrate of lime, be gently boiled together in a

quart of rain water for one hour;.

HYDROGEN WITH

4bl.

SLaPHlTR.

more water may be added

as

it

evaporates.

After cooling,

clear yellow

which

is

a solution of sulphuret of

tained,

lime:

it

is

li-quid

will vary in specific gravity

ob-

from l.Ot

To 6
1.02, according
ounces of this liquid put half an ounce of mucircumstances.

to

to

riatic acid,

and

stir

In a short

mixture.

the

time, the mixture exhibits a milky appearance,.

and

this

becomes interspersed with brown

which

dots,

oily

gradu-ally subside into an adhesive

mass of a semiliqaid form at the bottom. The

liquid may then be poured off, and the brown

washed with water, which is to be

poured off. From 20 to 40 grains of this brown
mass

oily

substance will be obtained

it is

super-

sulphuretted hydrogen.
Scheele, Berthollet,

observations on

posed

this

to the ahr, or

and Proust, have made

compound.
even

in water,

When
it

ex-

exhales

hydrogen, especially if warm.

account of its viscidity and adhesiveness,

sulphuretted

On

very dif^cult to subject it to experience.

If a portion of it touch the skin, &c. it requires
a knife to scrape it off.
It may be poured
it is

from one

vessel to another

which prevents
"When a little of

its
it is

by means of water,

adhering

to

the

vessel.

appplied to the tongue,

sensation of great heat, and a bitter taste arc

felt ;
the saliva becomes white like milk.

SUPERSULPHURETTED HYDROGEN.

When

liquid alkali

is

455

poured upon supersul-

phurettcd hydrogen, heat

is
produced, hydroformed, and sulphur precipitated.
These fects have all been observed by mcj

sulphuret

is

though few if any of thera are new.

There is no doubt this substance
of sulphur and hydrogen.

and exposed them

to

glass capsule, over a candle,

flame, and
it

is

it

ignited,

The residuum

is

from

trie

moment

exhaling sulphuretted

wonder

like

clay 4

When

that supersulphuretted

considered,

drogen

soft

burned away with a blue

no sensible residuum.

left

formed

they ceased to

till

exhale sulphuretted hydrogen.

weighed 21 grains; it was

when

Is

took 30 grains,
a moderate h^at in a
I

that a portion

of

its

hyformation

hydrogen, we cannot
it should
give less

of

its
weight of this gas. But scarcely
be raised that the sulphur of
doubt
can
any
the gas is originally equal to that left behind ;

than half

or that supersulphuretted hydrogen

tuted of 2 atoms of sulphur and

is

consti-

of hydrogen,
and consequently weighs 27 times as much as
1

hydrogen.

Though

it

is

not our present business to ex-

plain the previous process by

which the

under discussion

yet, as

is

some time before

way,

it

obtained
it

it

comes regularly

may perhaps be

allowable.

article

will
in

be

our

Hydrate

HYDROGEN WITH PHOSPHORUS.

466
of lime,
united
it

is

is

atom of lime and

when

lime.

mixed with

The

it,

above,

When mu-

sidphurct of hijdrate of lime.

is

of water

The compound

takes 3 atoms of sulphur.

riatic acid

boiled with sulphur as

the acid seizes the

atoms of sulphur divide the atom

of water in such

sort, that

two of them take the

hydrogen to form supersulphnretled hydrogen,

and one takes the oxygen to form sitlphurous
oxide.
This last occasions the milkiness of
the liquid ; by long digestion
vanishes the sulphurous oxide

the

milkiness

changed into
sulphuric acid and sulphur, which last falls
down, and forms nearly one fourth of that
-,

which

is

originally existed in the sulphuret.

SECTION

9.

HYDROGEN WITH PHOSPHORUS.

There

is

only one combination of hydrogerj

with phosphorus yet known it is a gas denominated ])hnspJnirelted hydrogefi.

This gas
;

may be procured

as follows

Let an ounce or

two of hydrate of lime

(dry slacked lime) be

put into a gas bottle or retort, and then a few
small pieces of phosphorus, amounting to 40

or 50
grains.

If the materials are sufficient tq

457

PIIOSPHURETTED HYDROGEN.
the bottle, no precaution need

fill

but

if

be used

or retort should be pre-

not, the bottle

viously filled with azotic gas, or

some gas not

order to prevent an excontaining oxygen,

a
The
of
heat
lamp is then to be applosion.
and
a
which
comes
may be received
gas
plied,
in

This gas

over water.

drogen

is

phosphuretted hy-

mixed with hydrogen.

but sometimes

Liquid caustic potash may be used instead

of hydrate of lime, in order to prevent, the generation of hydrogen.

hydrogen gas has the following properties: 1. When bubbles of it

Phosphuretted

come
fire

into the atmosphere, they instantly take

an explosion is produced, and a ring of

white smoke ascends,

acid

2.

It

unfit

is

supporting combustion
is

.85,

ct>mmon

air

which

for
:

is

phosphoric

respiration,

Water absorbs

5.

If the gas be electrified, the

-^V^h of

thrown down, and there

phosphorus is
remains the

finally

bulk of the gas of pure hydrogen.

by

electricity,

to a

large

is

for

being denoted by unity :

its bulk of this
gas:

4.

the phosphorus

and

Its specific gravity

3.

easily

In fact,

thrown down,

either

by heat, or by being exposed

surface of water.

phosphuretted hydrogen

is

In this respect,

nearly related

to

sulphuretted hydrogen.

Though phosphuretted hydrogen explodes

HYDROGEN WITH PHOSPHORUS,

458

when
if

sent Into the atmosphere in bubbles, yet

sent into a tube of three tenths of an inch

it
may be mixed with pure oxygen,
without any explosion. In ail the experiments
I have made, which are more than 20, I never

diameter,

had an instance of a spontaneous explosion.

In this case, an electric spark produces a most
vivid light, with an explosion not very violent

phosphoric or phosphorous acid and wa-

ter are produced.

My

experiments on the combustion of

this

When

100
following
gas
measures of pure phosphuretted hydrogen are
mixed with 150 of oxygen, and exploded, the
give the

results

whole of both gases disappears

water and

phosphoric acid are formed i when 100 measures of the gas are mixed with 100 oxygen,

and

fired,

in

pears ;
acid are

the whole of both gases

this

case, water

formed

mixed with

when

still

disap-

and phosphorous
100 measures are

100 of oxygen, phosare

and
acid
water
formed, but part of
phorous
the combustible gas remains unburnt.

As

this

gas

less

is

than

liable to

be contaminated with

hydrogen, sometimes largely, on account of

the facility it poiisesses of depositing phosphorus,

it

is

expedient to ascertain the exact

proportion of phosphuretted hydrogen to hydrogen in any proposed mixture. This I find

PHOSPHURETTED HYDROGEN.

may

Whenever a

sufHcicnt

is

afforded, the

whole of

is

consumed

be done.

easily

quantity of

oxygen

the combustible gas

volume of oxygen and

noted

459

the quantity of

must also be noted.

its

The exact

must be

purity

oxygen

Then

in the residue

the

total

dimi-

nution after the explosion, being diminished

by the oxygen consumed, leaves the combus-

Now,

tible gas.

takes 14 times

gen takes t

its

as phosphuretted hydrogen
bulk of oxygen, and hydrobulk of oxygen ; we shall ob-

its

following equations, if P denote the

that of
volume of phosphuretted hydrogen,
tain the

hydrogen,

that of oxygen,

and

H
S= P 4- H,

the whole of the combustible gas.

P=
H=

From
gases
lysis

iS

i|S O

these equations, the ratio of the two'

any mixture is deduced.

may be corroborated as follows

The

in

ana-

To any

mixture containing a certain volume of phos-

volume

phuretted hydrogen, let the same

oxygen be added ; after the explosion, the
ot

diminution will be just twice the volume of

oxygen. In this case, the phosphuretted hy-

drogen

is

by the oxygen ; phosand water are formed, and the

preferred

phorous acid,

hydrogen remains

in the tube.

If

more oxy-

HYDROGEN WITH PHOSPHORUS.

460

gen is put than the phosphuretted hydrogen,

then the dinilnution after firing is more than
twice the oxygen.

The

investigation respecting the proportion

of hydrogen

mixed with phosphuretted hy-

drogen, was instituted chiefly in consequence

of a difference of opinion respecting the specific

gravity of the

latter gas.

had found

100 cubic inches to weigh about 26 grains ;

Mr. Davy infonned me he had found 109
inches to weigh only 10 grains
is

enormous.

the difference

requested Dr.

Henry wouki

We
assist me in repeating the experiment.
obtained a gas, such that 100 inches weighed
llgrains ; this result surprized me ; but upon
burning the gas with oxygen,
only to take

its

it

was found

bulk of that gas, and conse-

quently to be half hydrogen and half phosphuretted hydrogen, which satisfactorily ex-

Mr. Davy's gas, I

dilHculty.
have
beer
must
conceive,
f phosphuretted hydrogen and y hydrogen, at the time it was
plained the

weighed ; however this may be, it is evident,

from what is related above, that nothing certain
can be inferred

relative to the specific gravity

of this gas, unless a portion of the gas be ana-

lyzed previously to

its

cumstance of which
ently aware.

being weighed
I

was not

a cir-

at first suffici-

PHOSPHURETTED HYDROGEN.
I

461

have recently procured some phosphuretted

hydrogen gas from caustic potash and phosphorus an accident prevented me obtaining
;

a sufficient quantity to weigh ; but I got 5 or

6 cubic inches, which of course were mixed

with the azotic gas previously put into the

retort.
The pure combustible gas was of
such character, that 100 measures required
only 85 of oxygen for their combustion j it
was consequently 35 phosphuretted hydrogen
and 65 hydrogen per cent, and probably

would have weighed

aftei

the

rate

100 cubic inches.

11 grains for

of 10 of

expected

much purer gas.

As to the constitution

of phosphuretted hydrogen, it is clearly 1 atom of phosphorus

united to 1 of hydrogen, occupying the same
space as 1 of elastic hydrogen. In combustion,
the atom of hydrogen requires one of oxygen,
and the atom of phosphorus requires one or

two of oxygen, according

as

we

intend to

or

acid.
phosphoric
phosphorous
of
measures
100
that
Hence it is
phosphuretted hydrogen require 50 oxygen to burn the
to form phoshydrogen, 50 more of oxygen
to
form
more
50
and
phosphoric
phorous acid,

produce

acid.

The weight

conclusion

it

of the gas corroborates this

has been seen that the atom of

9 (page 415)
phosphorus weighs nearly

this

CARBONE WITH SULPHUR, &C.

462

would make

the specific graviry of phospbu-

hydrogen equal to 10 times that of hydrogen, which it actually is, or nearly so, from
retted

the foregoing experiments.

The

next compounds to be considered in

course, would be those of azote with carboTWf

with sulphur, and with phospJiorus ; but such

compounds either cannot be formed, or they
arc yet

unknown.

SECTION

iO.

CARBONE WITH SULPHUR, WITH

PHOSPHORUS, AND SULPHUR WITH
PHOSPHORUS.
1

Carbone with Sulphur.

In the 42d vol. of the An. de Chimie, page

136, Clement and Desormes have announced

a combination of carbone and sulphur, which

they

call

carburettcd sulphur.

They obtain

it

by sending the vapour of sulphur over red hot

charcoal ; it is collected in water in the form
of an oily liquid of the specific gravity 1.3.
This liquid is volatile, like ether, expanding

any gas into which

it i$

admitted, and forming

CAHBURETTED SULPHUR.
SL

permanent

elastic fluid

No

*6S

over the mercury of

gas
produced at the same
time as the liquid.
When too much sulphur is
driven through, instead of a liquid, a solid

a barometer.

is

compound is formed which crystallizes in the

They seem to have shewn that the
compound does not contain sulphuretted hytube.

drogen.

In

the 64th vol. of the Journal de

Physique, A. B. Berthollet endeavours to prove

that the liquid in question is a compound of

hydrogen and sulphur, and contains no charThe facts adduced are not sufficient to
coal.
decide the question either way. I should be
unwilling to admit, with Clement and Desormes, that the two inelastic elements, charcoal and sulphur,

would form an

elastic or vo-

latile compound ; yet, they have rendered it

a part of
highly probable that charcoal makes
the compound, as it disappears during the
I

process.
thollet

is

contains

think

it

most probable, that Ber-

correct in the idea that this liquid

hydrogen.

We

know

of no other

volatile liquid that does not contain hydrogen.

Perhaps

it

will be

found a

triple

compound of

hydrogen, sulphur, and charcoal.

CARBONL WITH SULPHUR, &C.

464

Carbone

2.

ivith

Phosphorus.

combination of carbone and pnosphorus

has been pointed out by Proust, in the 49th
volume of the Journal de Physique, which he

names

phosphuret. of carbone.

It is the

reddish

which remains when new

substance

phosphorus

is

strained through leather in

made

warm

The proportion of the two elements

has not been ascertained.

water.

3.

Sulphur with Phosphorus.

Melted phosphorus dissolves and combines

with sulphur, and that in various proportions,
which have not yet been accurately ascer-

The compounds may be denominated

The method of
of phosphorus.

tained.

sulphurets

forming these compounds,

is

to melt a given

weight of phosphorus in a tube nearly filled

with water, and then to add small pieces of
sulphur, keeping the tube in hot water, taking
care not to exceed 160% or 170% or 180% be-

cause the

water

new compound

Pelletier

at

begins to decompose

those

high temperatures.
has given us some facts towards a

rapidly

theory of these

various combinartions, in the

SULPHURETTED PHOSPHORUS.
4th vol. of the An. de

Chimie.

465

He

found

and phosphorus remuch lower temperature

that a mixture of sulphur

mained
than

fluid

either

at

of them individually

different proportions

gave

and that

different fusing or

congealing points. One part of phosphorus,

combined with 4th of sulphur, congealed at
77; one part with ^, at 59"; one part with 4,
at 50 ; one part with 1, at 41 ; one part with
2, at 544

and the

rest

but a certain portion was fluid,

solid

and one part with

3j

at

99. 5.

One would be apt to think, from these experiments, that sulphur and phosphorus might
be combined

in all

servation on the

proportions

5th led

me

but the ob-

to suspect that

it

might have been applied to some others if the

results had been carefully noted.
I mixed 18|-

grains of phosphorus ,nnd 13 of sulphur in a

graduated tube, put in water, and immersed

the whole into water of 160.
The phos-

phorus having been rendered fluid as usual, at

100, gradually reduced the sulphur, till the
whole assumed a liquid form of the specific
gravity 1.44.

It

remained uniformly

fluid at

was wholly congealed at 42. Here

were two atoms of phosphorus united to one of

45, but

I (hefi added 6t grains of

sulphur,
making the mixture 18t phosphorus, and 19t

sulphur.

CARBONE WITH SULPHUR, &C.

466
salphur

form

this'new mixture was reduced to uni-

170% and was of 1.47 specific

was fluid

fluidity at

gravity; reduced to 47, one part

and the other

solid, the

bottom of the tube.

latter

This

at the

being

solid part

was not

completely reduced to fluidity in the temperature 100.

This seems to indicate that two

combinations took place j the one,

two atoms of phosphorus and one of suiohur,
distinct

the other, one atom of phos;

and
one
of sulphur, solid under 100.
phorus
I next added 64- grains more of sulphur, making in the whole 18{ phosphorus and 26 sulJiquid at 47

phur, consequently in such proportion as to

afford a union of one atom of each ; the union

was completed

in a

temperature of 180

the

Cooled down to
specific gravity was 1.50
80, the whole was solid ; heated to 100, the
whole became a semi-liquid, uniform mass.

Being afterwards heated

became

to

140, the

whole

but upon cooling again, the

greatest part congealed at 100, but |d or ^^th
fiui-^

'emained

down

liquid

to

47.

From

these

most probable that one atom

experiments,
of each forms a combination which is solid at
it is

lOO" or below

but that being heated,

it

is

apt to run into the other mode of combination,

or that constituted of two atoms of phosphorus

and one of

svilphur.

The

properties of these

467

POTASH.

two

species of sulphuret of phosphorus I have

not had an opportunity to investigate.
The
water in the tube is evidently decomposed ia

part

it
becomes milky,
;
oxide of sulphur, and

by the compound

probably through the

both sulphuretted and phosphuretted hydrogen

seem to be formed in small quantities at temperatures above

60.

SECTION

1.

FIXED ALKALIES.
The

fate of the

two

fixed alkalies, potash

and soda, has been rather remarkable.

They

had long been suspected to be compound elements, but no satisfactory proof was given.

At length Mr. Davy, by his great skill and

address in the application of galvanism to produce chemical ciianges, seemed
lished the

compound

to

have estab-

nature of these elements,

both by analysis and synthesis. They appeared

to be metallic oxides y or peculiar metals united

with this idea, some

oxygen. Consistent
account of the metals, denominated potasium
and sodium, has been given in this work. (See
to

But from what follows, it appage 260).

that these metals are
pears most probable,

riXED ALKALIES.

468

co'npoaixds of potash and soda with hydrogen,

that the two fixed alkalies still remain

and

among

the iindecompounded bodies.

1.

Potash

wood.

is

Potash.

obtained from the ashes of burned

Water

the ashes, and

dissolves the

may

then

artificial

saline

matter of

be poured

heat

and

oflF

the salt called

evaporated by
If the
potash remains in the vessel.
obtained be exposed to a red heat,
:

salt
it

so

loses

combustible niaiter, becomes white, and is in

in commerce it is then called
part purified
:

pearl-ash.

This mass

rious salts, but

is

bonate of potash.

is still

a mixture of va-

In order to obtain the pot-

a quantity of peari-asli (or

better, salt of tartar of the shops,

ash separate,

what

is still

constituted chiefly of car-

let

almost to pure
is this
pearl-ash reduced
carbonate of potash) be mixed with its weight
of water, and the mixture be stirred ; after

which

the undissolved salt has subsided, pour

clear solution into an iron pan,

it

oflP

the

and mix with

a portion of hydrate of lime, half the weight

then add a quantity of water
j

of the liquid

the ingredient^, and

equal to the weight of
boil the mixture for several hours, occasionally

adding more water

to

supply the waste.

When

469

POTASH.
tVje

is

liquid

found not to effervesce with acids,

the ebullition

may be

After the

discontinued.

lime has subsided, the clear liquid

is

to

be de-

canted, and then boiled down in a clean iron

pan till it assumes a viscid form, and acquires

almost a red heat.

into

molds, &c. and

The
pure
tion
iron,

acid.

It

may then be poured

it

immediately congeals.

substance so obtained
;

but

it

still

of water,

is

potash nearly

contains a considerable por-

some foreign

salts,

oxide of

and frequently some unexpelled carbonic

The water may z\mount to 20 or 25 per

upon the whole weight, and the other

In this prosubstances to 5 or 10 per cent.
cess, the carbonic acid of the potash is trans-

cent,

ferred to the lime.

If potash of still greater purity be required,
the method practised by Berthollet may be purThe solid potash obtained as above
sued.

must be dissolved
will

to

fall

solution

in alcohol

the foreign salts

the bottom insoluble

may then be decanted

the liquid

into a

silver

bason, the alcohol be evaporated, and the fluid

It may be
potash exposed to a red heat.

poured out upon a clean polished surface,

where

of
instantly congeals into solid plates
into
and
be
broken
which are to
put

it

potash,
well stoppered bottles, to prevent the access of
This potash is a solid,
air and moisture.

470

FIXED ALKALIES.

brittle,

white mass,

parts potash
is

crystalline

may be

100

in

the purest that has ever yet

Potash

parts,

and

been obtained.

exhibited in a more regular

form by admitting more water to

If the solution be reduced to

it.

Si

consisting of about

and 16 water,

the specific

gravity of 1.6> or 1.5, upon cooling, crystals

will be formed, containing about 53
per cent,
of water, or more, if the air is cold. These

Hence
hydrate of potash.
of potash may be formed, containing from 84 per cent, of potash to 47, or
crystals are called

solid hydrate

under.

Potash has a very acrid taste

ingly corrosive

it

is

exceed-

applied to the skin, so as to

obtain the name of caustic.
The specific gravity of the common sticks of potash used by
if

surgeons, I find to be 2.

but these are a

mixture or potash and carbonate of potash,

with 20 or 30 per cent, of water. If pot-ash
were obtained pure, I apprehend its specific
gravity

would be about

When

2.4.

crystals of potash

(that

drate) are exposed to heat, they

the water

is.

the hy-

become

liquid,

gradually dissipated with a hissing

at length the fluid
acquires a red

is

noise,

till

heat.

It then remains
tranquil for some time ;
the heat be increased, white fumes be-

but

if

gin to arise copiously.

The

alkali

and water

471

POTASH.
both evaporate

in this case

therefore, the pro-

cess cannot be used to expel the last portion of

water from the

in

alkali.

If the hydrate be taken

the red hot and tranquil state,

it

contains

This

84 per cent, potash and 16 water.

is

ascertained by saturating a given weight of it

wiih sulphuric acid, when sulphate of potash
is

formed

from water, and 100 parts of

free

the hydrate give only 84 parts

the

to

new

compound.
Water has

If a
a strong affinity for potash.
be
into
84
cent,
of
the
hydrate
put
per
portion
as much water, great heat is immediately pro-

But it
duced, equal to that of boiling water.
is observable that the crystallized hydrate containino'

much

when mixed

water,

with snow,

When

potash is exattracts moisture and car-

produces excessive cold.

posed to the air, it

Potbonic acid, becoming a liquid carbonate.
ash dissolved in water, and kept in a stoppered
bottle, retains its causticity

kaline ley, and

and

may be had

it

is

called

al-

of various strengths

specific gravities.

Potash, and the other alkalies, change veinto green.

getable colours, particularly blues,
and maarts
the
in
is of great utility

Potash

nufactures,

printing,

particularly

soap and

in

glass

bleaching, dying,
It
manufactures.

unites with most acids to form

salts.

It

does

472

FIXED ALKALIES.

not unite with any of the simple substances,

as far as

is

yet

known, except hydrogen, and

that in a circuitous way, as will presently be

The hydrate of potash unites with
noticed.

sulphur
three or

but the compound, consisting of

principles, cannot yet be dis-

more

cussed.

The
ash

theory of the nature and origin of pot-

still

remains

in

The

great obscurity.

great

question, whether it is a constituent principle

of vegetables, or formed during their combustion,

is

One

not yet satisfactorily answered.

circumstance

favourable to the investigation

of the nature of potash, the weight of its ulti-

mate

particle

very

definite

is

is

easily

ascertained

with

compounds

it

forms

most of the

from which

it
appears to be 42 times
the weight of hydrogen.
The following proof
the
most
salts with base
common
portions

acids,

of potash, are deduced from my experience

they are such that good authorities may be

for greater and less proportions of

the different elements.

found both

per cent.

Carbonate of potash, 31.1, acid

42

^S.Q base, as 19

Sulphate

44.7

1-

55.^

3*

42

JNitrato

47.5

1-

52.5

'iS

42

Muriate

34.

65.6

22

[-

42

-j-

473

POTASH.

The above
be

free

capable of sustaining a

salts are

red heat, and

therefore be supposed to

may

from water

at all events, the

potash

must contain the same quantity of water in

combination with the respective acids, as apits
weight. The
22 represent.,
38
and
19, 34,
as the reader will recollect, the weights of the

pears from the uniformity of

above numbers,

atoms of the respective acids, except the nitric,

which is double. As water has so strong an
afTinity for potash, and as the weight of the
elementary particle of potash above deduced
is more than five times that of water, it
may
still

be supposed that water enters into the

constitution of potash, or that

it is

compounded

of some of the lighter earths with azote, oxyFrom present appearances, howgen, &c.
ever, the notion that potash

stance seems

From

is

a simple sub-

more probable than

the above observations,

ever.

appears that
be considered as a simple
substance, and would require to be placed

potash ought

among

still

it

to

such substances, but that

In

obtained alone.

that

it

state

cannot be

which

apa hydrate, con-

proaches nearest

to

taining at least

atom of water united

purity

it is

to

of

potash, amounting to 16 per cent, of water.

This hydrate

is

therefore a ternari)

compound,

or one of three elements, and ought to be

post-

FIXED ALKALIES,

474'

poned till the next chapter but, in the present state of chemical science, utility must be
:

allowed

some instances

in

thodical arrangements.

most

The

to

supersede me-

fixed alkalies are

chemical agents, and the sooner

useful

we become

acquainted with them the better ;

more especially, as some of the first chemists

of the present age have been led

into

consi-

derable mistakes, by presuming too much upon

their knowledge of the nature and properties

of these familiar

articles.

In the Memoires dc V Instilnt dc France^

1806, Berthollet published researches on the

Jaws of
given

afiinity,

from which some extracts are

Journal de Physique for March

these, it appears that he found sul-

in the

By

1807.;

phate of barytes to consist of 26 acid and 74

base, and sulphate of potash of 33 acid and 67

The

base.

former of these results was corro-

borated by the previous experience of Thenard but both are so remote from the uniform
;

results of other chemists,

that they could never

be generally adopted. At length Berthollet

discovered the error, and has announced it in
the

2d

vol.

of the Memoires d'Arcueil.

It

consisted in mistaking the hydrates of barytes

and potash
seems

to

for pure barytes and

It
potash.
have been generally adopted, but

certainly prematurely, that barytes

and potash,

HYDRATE OF POTASH.
in a state of fusion,

were pure, or

But upon due

water.

me

from

14 per eent. of wa-

as theory, leads
experience
of
16
water, which acpercent,
adopt
as well

my

free

investigaiion, he found

that fused potash contains

ter

475

to

cords with the position of

atom of each of

form the hydrate ;

uniting
42
of
by weight
namely,
potash with 8 of
water. This discovery reconciles the jarring

the elements

results
salts,

to

on the proportions of the above neutral

and throws

light

upon some other

inter-

esting subjects of chemical analysis.

2.

Upon

Hijdvate of Potash,

turning

my

I soon perceived the

attention to this subject,

table exhibit-

want of a

ing the relative quantities of potash and water

two element*.

in all the combinations of these

In a state of solution, the specific gravity may

be taken as a guide ; but this is not quite so
convenient

when

the

compound

is

in

a solid

found nothing of the kind in any

publication, and therefore undertook a course

form.

of experiments to determine the relative quantities of potash, &c. in the various solutions.

The
table,

results

which

are contained
I

would have

in

to

the following

be considered

FIXED ALKALIES.

47G

only as an approximation to truth

but

it

wili

certainly have its use till a more complete and

accurate one be obtained.
Dr. Henry was so

obliging as to facilitate
senting

me

my

progress,

by pre-

with portions of the fixed alkalies,

prepared after Berthollet's method.

Table of the ijuantity of

real

potash in watery solution*

of different specific gravities, &c.

Atoms.

HYDRATE OF POTASH.

477

binatlons to 10 atoms of water the weight of

an atom of potash is taken to be 42, and 1 of
water 8. From these data the second column
:

is

There did not appear any strikof distinction between the

calculated.

ing characteristic
first,

be so

second, third, &c. hydrates, (if they may

called) except that the first bears a red

heat in the liquid form, with tranquillity and

Before this, the wawithout loss of weight.
ter

gradually dissipated with a hissing noise

is

and fumes.

remarked, however, that when

a solution of potash

is

boiled

down

the

till

thermometer indicates upwards dF 300, the

evaporation of the water, and the rise of the
thermometer, are desultory
rations appear

somewhat

that

is,

the ope-

stationary for a time,

and then advance quickly

how

far

this

may

from the nature of the compound,

arise

or

from the imperfect conducting power of the

I could not
liquid in those high temperatures,

determine without more frequent repetitions

of the experiment.

The

third

column

Is,

as usual, obtained

by

multiplying the second column by the specific

convenient in praogravity ; it is often more
tice to estimate quantity

by measure than by

weight.

The
vity

fourth

column denotes the

below 1.60 the hydrate

is

specific gra-

completely

its

FIXED ALKALIES.

may be made so by a moderate heat

but above that temperature, I found some diffluid, or

ficulty in ascertaining the specific gravity,

tenor of the table.

and

it

from the

The common

sticks of

was obliged sometin^es

to infer

potash of the druggists are of the sp. gr. 2.1,

which I found by plunging them into a gra-

duated tube

filled

with mercury, and marking

These

sticks

and carbonate.

Real

the quantity that overflowed.

are a mixture of hydrate

conceive, be heavier than they

potash must,
of the second and fourth
relation
are.
The
I

columns was ascertained by taking a given

weight of the alkaline solution, saturating it
with test sulphuric acid (1.134), and allowing
21 grains of alkali for every 100 measures of
acid (containing 17 real)

which the

alkali re-

quired.

The

5th column denotes the temperatures at

different hydrates congeal or crys-

which the
tallize.

This part of the subject deserves

much

more accurate enquiry than I have been able

No doubt the diflPerent
to bestow upon it.
hydrates might be distinguished this way.
Proust talks of a crystallized hydrate of potash,

containing '30 per cent, of water ; and Lowitz

of one containing 43 per cent, of water. They
calculate, I presume, upon the supposition of
fused potash

being free from water

if so.

479

CARBONATE OF POTASH.
Proust*s hydrate

the fourth of our table, and

is

Lowitz's the sixth.

be put

trust to

marked

The

in this

This

is

would not have much

the temperatures

indicates the temperatures

different specific

easily ascertained,

which an

degrees, in

have

column.

column

sixth

which the

at

in

gravities boil.

except tor the high

analysis of the hydrate

was required upon every experiment. I believe

the results will be found tolerably accurate.

As

the range of temperature

is

large, this

may

be found a very convenient method of ascertaining the strength of alkaline solutions,

the specific gravities are unknown.

Carbonate of Potash.

3.

Though

when

be premature to enter into the

it

nature of carbonate of potash, a triple compound, yet its utility as a test is such as to

be noticed

require

it

to

Indeed

it

may

in the present section.

generally be a substitute for the

hydrate of potash, and it can

dily be procured in a state
purity.

The

consists of

carbonate

much more

rea-

of comparative

mean

is

one atom of acid united

that

which

to

one of

potash, which by

some

carboiiate.

of course, constituted of

It is,

writers

is

called a suhJ

480

FIXED ALKALIES.

parts of acid by weight united to 42 of potash.

This

salt is to

be had

druggists, under the

but when

it is

in tolerable purity of the

name

be used

to

of salt of tartar
in solution

for

pure
and a

carbonate, a large quantity of the salt,

small quantity of water, are to be mixed and
agitated ; then let the undissolved salt subside,

and pour

off the clear solution,

which may be

diluted with water, 8ic.

This

salt is

known

well

to be, like the dry

I took
hydrate of potash, very deliquescent.
of
that
had
of
carbonate
43 grains
just
potash

before been

made red

capsule exposed

glass

the weight

became 60

hot, put
to

them

into a

the air; in one day

grains

in

three days,

seven days, 75 grains; in II

grains;
in 21 days, 89+ grains ; in
89
days,
grains
61

in

The specific gravity was

All the water is, however, driven
1.54 nearly.
oft by a moderate heat ; namely, that of 280.
25 days, 90

grains.

It supports a high red heat before fusion,

when
out

sublimation,

ascertained that

it

and undecompounded.
I
was a perfect carbonate, by

dissolving 61 grains of pure dry

water,

and

fused loses no weigh!, remaining with-

when 42

were thrown down, corresponding

of carbonic acid.

salt

in

lime

grains of carbonate of lime

to 19 grains

CARBONATE OF POTASH.

Table of the quantity of

real carbonate of potash in

solutions of different specific

gravities,
Atoms.

481

watery

FIXED ALKALIES.

482

the nuawbers in the second and fourth columns

The

together.
gravities

the second

in

tities

fourth

the

contains

specific

the relations of these to the quan-

column were found, by

weight of the solution, arid sawith a certain number of measures

taking a given
turating

of

test

it

sulphuric acid (1.134), allowing 21 real

potash, or 30^ carbonate, for every 100 measures of acid required ; because such acid con-

by measure of

tains 17 per cent,

real sulphuric

acid, and that requires 21 of potash.

The

strongest solution of this salt that can

obtained

of the specific gravity 1.54.

is

consists of

atom of carbonate and

be

This

8 of water

but by putting dry carbonate into that solution,

various mixtures may be formed up to the specific gravity

vity

is

1.80

above

that the specific gra-

scarcely to be obtained but

by inference.

I could not obtain a solid stick of fused car-

bonate but what was spongy,

It

incipient decomposition.

that the specific gravity 1.25,

30 per

cent,

of carbonate,

prefer as a test for acids

contains 21

measures of

suppose from

may be
is

observed,

which contains
that

which I

because the solution

per cent, pure potash, and 100

it

consequently require 100 mea-

sures of the test acids.

I found a specimen of the pearl-ash of

merce

to contain

com-

54 parts carbonate of potash.

CARBONATE OF POTASH..
22 parts of other
in the hundred.

The

be found

the

temperature

This will

saline solutions boil.

generally a

^ood approximation to
observed the thermometer did not

truth,

and 24 parts of water

salts,

column denotes

fifth

which the

at

483

2W

above
as long as any visible moisture
remained; as soon as that vanished, the salt
assumed the character of a hard and perfectly
rise

dry substance.
In the course of these experiments, I took
a quantity of carbonate of potash, and heated
red hot

it

put to
1

salt

it

as

then weighed

>

much water

it

which I

after

as afforded

atom

namely, 8 parts water to 61 salt.

was then pulverized in a mortar ;

to

The
it

was

put out upon white paper, and appeared a

white, dry salt ; but upon pouring it back
into

the mortar,

some

particles of the salt ad-

hered to the paper.

The same

water was again put

to

them with a

whole mass assumed a

knife, the

it.

quantity of

Upon mixing

pasty consistence, and adhered to the knife in

the shape of a ball ; after being well rubbed
in the mortar,

it

again assumed a white, dry

Upon paper, it seemed like salt

appearance.
some
time
of tartar
exposed to the air. Several
to
the paper, but were easily
stuck
particles
removed by a

knife.

The

addition of another

484

FIXED ALKALIES.

atom

of water redueed the

consistence of bird-lime
it

cut like half dried clay.

water reduced

it

to

compound

to the

but after standing

The next atom of

the consistence of book-

binders paste.

The

duced

thick fluid, consisting of dis-

it

to

fifth

solved and undissolved

salt.

cessive application of like

became

atom of water

re-

This^ by the sucportions of water,

a perfect fluid with 8 atoms of water

Its specific graof carbonate of potash.

there
undissolved
was
some
1.5
but
;
vity
the
of
salt
of tartar
potash subsided,
sulphate

to

was

not having been previously purified.

4.

Potasium, or Hydriiret of Potash.

Since writing the articles on

Sodium (page 260 and

quent

articles

on

seq.),

fluoric

Potasium and

and the subse-

and muriatic acid

good deal more light

(page 277 and seq.),
has been thrown on these subjects. Two paa

pers on the subjects have been published by

a series of essays by Gay Lussac
;

Mr. Davy

and Thenard, are contained in the 2d vol. of

the Memoires d'Arcueil ; the same volume
also contains a paper by Berthollet, announcing an important discovery relating to the fixed
alkalies i namely, that in a state of fusion by

POTASIUM, OR KYDRURET OF POTASH. 485

they contain a

heat,

water

proportion of

definite

chemical combination.

in

them with the more recent ones,

re-

Upon

considering the former facts, and

I

comparing

am

obliged
of

new views respecting the nature

new metals. Mr. Davy still adheres

to adopt

these

to

and which indeed were the

his original views,

only rational ones that could be formed (supposing the fused alkalies to contain no water),

namely, that potash is ihe oxide of potasium ;

Gay Lussac and Thenard, on the contrary,
consider potash as undecompounded, and potasium a compound of hydrogen and potash,
analogous to the other known compounds of

This
hydrogen and elementary principles.
last is the only one, I think, that can be admitted either from synthetic or analytic experiments, so as to be reconcileable with the
facts

but

clusions

duced.

most

was

do not coincide with

289 and

seq.),

it

having adopted
tasium

the con-

Mr. Davy has furnished us with the

and precise facts and though I
to controvert some of them (see page

definite

led

all

which the French chemists have de-

was principally through

am now

persuaded those

more accurate than

Mr. Davy

first

fixed alkalies,

my

views of the nature of po-

his

results

were

imagined.

attempted

to

decompose the

by applying Voltaic electricity

rOTASH WITH HYDROGEN.

4S6

saturated

in this case,
watery solutions
and
were
eviobtained,
hydrogen
gas
oxygen
dently proceeding, as he concluded, from the

to

decomposition of the water.

But when any

potash that had previously been fused,

was

substituted for the watery solution, no hydro-

gen gas was given out at the negative pole,

but potasium was formed, and pure oxygen
was given out at the positive pole. The re-

was unaltered.

sidual potash

The

conclusion

he drew was, that the potash was decomposed

into potasium and oxygen.
But it now appears, that fused potash

of water and
operates

upon

is

composed of

of potash.

this

atom

he electricity
atom of water to se-

last

"1

parate its elements ; it succeeds in detaching

the atom of oxygen, but that of hydrogen

draws the atom of potash along with it, formThe atom of hying an atom of potasium.
drate weighing 50

(= 42 potash

into one

8 water) is
of potasium, weighing

decomposed
Hence
43, and one of oxygen weighing 7.
the atom of potasium is composed of 1 potash -f 1 hydrogen, weighing 4 3
and not of
1

potash

1,

oxygen, weighing 35, as stated

page 262.
The method of obtaining potasium, discovered by the French chemists, is to find the

at

first

hydrate of potash

in

a state of vapour over

POTASIUM, OR HVDRURET OF POTASH. 487

red hot iron turnings, in an iron tube intensely

heated
is

;
hydrogen gas is given out, potasium
formed and condensed in a cool part of the

tube, and part of the potash is found united

In this mode of producing pota-

to the iron.

sium,

constitution

its

the former.
gether,

shew

not so obvious as in

is

The two methods, however,

that

to-

fused potash contains both

oxygen and hydrogen, which

now

is

abun-

dantly confirmed by experiments of a different

It seems probable that in the latter
kinJ.

method the hydrate of potash

posed into potash

is

partly

decom-

and water, and partly

potasium and oxygen

into

both cases the iron

in

acquires the oxygen.

The

specific gravity of

.796, according to
to

Davy

potasium is .6, or
but .874 according

The

Gay Lussac and Thenard.

combined with

its

levity of

it,

low red heat,

being potash and

volatility at a

agrees with the notion of

its

Hydrogen, or pofassetted hydrogeiu resembling

the other

known compounds

of sulphur, phos-

combined with
phorus, charcoal, arsenic, &c.
hydrogen.
When burned in oxygen gas, potasium produces potash as dry as possible to be procured,
according to Mr. Davy
drate.
it

When

potasium

that
is

is,

the

thrown

first

into

hywater

burns rapidly, decomposing the water, and

POTASH WITH HYDROGEN.

488

Calculating the oxygen

giving off hydrogen.
from the quantity of hydrogen, Mr. Davy finds

100 (hydrate

oxygen

of) potash contain from 13 to 17

Lussac seems to make

Gay

14-.

it

2.284 grammes of potasium gave 649

cubic centimetres of hydrogen
reduced, 35,5
grains gave 34.5 cubic inches English measure,
For,

which correspond

= 5.9

grains of hydrate

But

17.25 inches of oxygen

41.2
5.9
35.3

and 41.2

5.9 :: 100

14.

exactly the quantity that theory

7 oxygen
assign ; for, 43 potasium

this

would

to

Hence

grains.

is

50 hydrate, which gives

the hundred.

just

Potasium burns spontaneously

acid gas

muriate of potash

probably water.

It

14 oxygen in
in

is

oxymuriatic
formed, and

decomposes sulphuretted,

phosphuretted, and arseniuretted hydrogen gas,

and
according to Gay Lussac and Thenard,
unites to the sulphur, &c.

with some of the

hydrogen. Mr. Davy finds tellurium to unite

with the hydrate of potash by Voltaic electri-

decomposing it. Potasium burns

nitrous gas and nitrous oxide, forming dry

city without

in

It
hydrate of potash, and evolving azote.
burns in sulphurous and carbonic acid, and in

carbonic oxide
to the sulphur

and charcoal.

is

hydrate of potash which unites

formed, or hydrate of potash

OTASIUM, OR HYDRURET OF POTASH. 489

The combustion of potaslum

gas

is

Davy

is

potasiura
riate

in muriatic acid

Both Mr.
particularly worthy of notice.
and the French chemists agree that when

burned

of potash

is

in muriatic acid

gas,

mu-

formed, and hydrogen evolved,

quantity with that evolved in

which agrees in
the decomposition of water by the same quanof metal.
But, what is most astonishing,
tity
they both adopt the same explanation, when
views of the constitution of po-

their different

tasium

require

them

count

fox

be opposite.

to

Mr.

which he might acthe phenomenon ; the one was to

Davy had two ways

in

suppose that a part of the acid was decomposed, and furnished the oxygen to the metal
fo form

the oxide

(potash),

which joined

to

the remainder of the acid, and the hydrogen

was an evolved elementary

principle of that

part of the acid decomposed ; and the other,

to suppose that the acid gas contained in a
state of

union just as

cient to oxidate

much water

the metal (this

as

was

suffi-

would have

been thought an extraordinary circumstance

a few years ago).
Either of these positions
was consistent ; but he adopted the latter,

and seemed

to confirm

it

by shewing that a

given quantity of muriatic acid gas afforded

the same quantity of muriate of silver, whether

combined previously with

potai)h or potaslun].

POTASH WITH HYDROGEN.

490

This explanation did not meet

well as the former,
for the facts (page

conspired

to

views as
account

289) on the notion of a de-

Two

composition of the acid.

to incline

my

endeavoured

me

to this

circumstances

view

The one

was, that hydrogen seemed on other accounts

to be a constituent of muriatic acid j the other

was, that water does not ap,.ear in any other

instance to be combined with any elastic fluid;
I mean in such

moved, the
along with

it

one respect
rated

the

way

that

the water be re-

if

of the molecule will carry

the character of the whole.
In

rest

mistook the data, having over-

weight of

muriatic

would now be understood

to

acid

gas.

abandon the ex-

planation founded on the decomposition of the

acid ; and to adopt the much more simple one
that the muriatic acid combines with the pot-

ash of the potasium, at the

same

instant

ex^

pelling the hydrogen; in this way there is no

occasion for any water either combined" or
It exceeds my comprehension how
Gay Lussac and Thenard should insist so

olherwise.

largely on the opinion that muriatic acid gas

contains

water,

should seem,

in

and

that

principally,

as

it

order to account for the hy-

drogen evolved during the combustion of potasium, and the supposed oxydation of the
metal.

FOTASIUM, OR HYDRURET OF POTASH. 491

It has

been stated that potasium burns ia

silicated fluoric acid gas

(page 283), the result

The

of potash and some hydrogen.

of
this is not obvious.
theory

is fluate

gas.

Mr.

8 grains of the

metal

Potasium acts upon ammoniacal

Davy found

that

when

in ammoniacal gas, between 12f

and 16 cubic inches of the gas were absorbed,
and hydrogen evolved corresponding to the

were fused

oxydation of the metal by water, that is, 1

atom of hydrogen for I atom of potasium.
The new compound becomes of a dark olive

By applying a greater degree of heat

ammonia is in part expelled again but

colour.

the

part

is

also

decomposed.

Gay Lussac and

Thenard

say, that by admitting a few drops

of water to the compound, the whole of the
elements of the ammonia are recoverable, and

nothing

Davy
to

but

affirms

caustic

potash

Mr.

remains,

the results of the decomposition

be somewhat

different.

evident, that in this process

It

seems pretty

two atoms of am-

monia

unite to one of potasium, expelling its

hydrogen at the same moment, For, 43 grains
,

of potasium would require 12 of ammonia

therefore 8 will require 2^ grains,

respond to 12x cubic inches.

and

which cor-

FIXED ALKALIES.

492

5.

Soda

is

Soda.

commonly obtained from

the ashes

of plants growing on the sea-shore, particularly

from a genus called salsola

in

Spain, where

called balargely prepared,

In Britain, the various species o( fucus

this article
rilla.

is

it is

and

or sea-weed are burnt,

their aslies

form a

mixture containing some carbonate of soda

Soda is found ii>
this mixture is called kelp.
;

some

parts of the earth

bonic acid, and

riatic acid, as

in others

minerals

combined with

car-

combined with mu-

and hence

it

has been

called the fossil or mineral alkali, to

distin-

from potash or the vegetable alkali.

guish
To obtain soda in as pure a state as possible,
recourse must be had to a process similar to
it

Pure carbonate of
that for obtaining potash.
soda must be treated with hydrate of lime and

water

the carbonate of soda

is

decomposed

the soda remains in solution in the liquid, the

carbonic acid unites to the lime, and the new

compound
clear

down

is

precipitated.

Afterwards

the

decanted and boiled

liquid must be
the water gradually goes off with a
;

hissing noise

till

the soda acquires a low red

when the alkali and remaining water

become a tranquil liquid. This liquid may be
heat,

493

SODA.

when

run out into molds, &c.

and

geals into a hard mass,

served in bottles for use.

If

it

is

instantly con-

then to be pre-

still

greater heat

be applied, the alkali and water are together

dissipated in white fumes.

Soda thus obtained

a solid, brittle, white

is

mass, consisting of about 78 parts pure soda

and 22 water per

cent,

(Annales de Chimie,
alkali is only 72
but
;

With more

according to d'Arcet

Tome
I

water, soda

68, p.

believe that

may be had

like potash, probably containing

182)
is

the

too low.

in crystals,

50 or 60 per

cent, of water.

caustic

when

it

is

Soda, like potash, is extremely

deliquescent, and produces heat
water.

dissolved in

vity of fused soda

find to

into a graduated

The
be

glass tube.

2,

specific

gra-

by pouring it
There is some

reason to apprehend that pure soda, could it

be obtained, would be specifically heavier than
potabh, though

ultimate particle

its

is

certainly

of less weight than that of the latter.

the
properties and uses of soda are much
as those of potash

The
same

indeed, the two alkalies

were long confounded, on account of their resemblances. The compounds into which they
enter are in

many

instances essentially difTerent,

atoms are very unin vegetables is

soda
of
origin
equal.
somewhat obscure, though it may be derived

and the weights of

The

their

FIXED ALKALIES.

494-

from the muriate of soda

in

water of

the

the sea.

The weight
rived from the
it

of an atom of soda

many

forms with the acids

limes that of hydrogen.

phate, nitrate

known

salts.

is

easily

de-

compounds which
It
appears to be 28

definite
;

The

carbonate, sul-

and muriate of soda,

From

are

a comparison of

well

all

my own

experiments with those of others on the proportions of these salts, free from water, 1 de-

duce the following

per cent.

59.6 base, as 19

28

4-^.2

34

28

,57.6

42.4

3S

2S

44

06.

22

28

Carbonate of soda 40.

Sulphate

34.S

Kitrate

Muriate

acid,

-}-

These proportions scarcely differ 1 per cent.

from those of Kirwan and other good autho"
The numbers 19, 34, 35 and 22 being
rities.
the weights of the respective atoms of acids,
number 28 must be the weight of an atom

the

of soda.

Hence we

find that soda

is

a peculiar

element, differing from every one we have yet

determined in weight. From the weight of
it
may be suspected to be a
of
water,
oxygen, or some of the
compound
from present appearbut
elements
j
lighter
ances, no such suspicion seems well founded.

the element soda,

Soda should thcn^ with propriety, be treated

HYDRATE OF

SODA.

as an elementary principle.

We

to the hydrate,

495
shall

proceed

and the hyreasons which have been

the carbonate,

druret of soda, for

given under the head of potash.

6.

Hydrate of Soda.

Soda, in what has

its

pure

state,

is

till

lately

been considered

The

combined with water.

smallest portion of water seems to be one atom

to one of soda ; that is, 8 parts of water by
to

weight

28 of soda, or 22 per cent, of wa-

have not obtained soda purer than that

of d'Arcet of 72 per cent. ; but it always conter.

some carbonic acid and other impuincline me to conclude that 78

tained
rities,

which

attainable puper cent, would be the highest

it is
called the first hydrate
rity ; this may be
hard and brittle, and twice the weight of wa:

The

ter.

second, third, fourth, and

fifth

hy-

drates are, I apprehend, crystalline ; but njy

experience does not warrant me to decide upon
their nature

the sixth,

and those with more

water, are all liquid at the ordinary

ture

their specific

gravity

is

temperaobtained in the

usual way, and the corresponding quantity of

real alkali is ascertained by the test acids.

The

following Table for soda, is constructed

manner of that for potash (page 476).

after the

496

FIXED ALKALIES.

It will

be found
moderately accurate

could

not

give

it

the attention

it

but I

deserves.

Nothing of the kind has been published to my

knowledge j yet, such tables appear to me so
necessary to the practice of chemical enquiries,
that I have wondered how the science could

be

so long cultivated without them.

That

solution

which

convenient for a

will

be

found most

of the specific gravity

test,
1.16 or 1.17, and contains 14
per cent, by

measure of

is

real alkali

sures require the

consequently, 100 mea-

same volume of acid

tests for

their saturation.
Table of the quantity of

real

soda

in

watery solutions of

diflerent specific graviiiti,

Atoms.

&c.

CARBONATE OF SODA.

Carbonate of Soda.

7.

The

salt I

497

call

carbonate of soda^

had of the druggists

name of purified

in great purity,

is

to

be

under the

sub-carbonate of soda.

It

is

obtained in the form oF large crystals, containing much water ; but when exposed to the air
for

some time,

these crystals lose most of their

water, arid becom.e like flour.

took 100

grains of fresh crystallized carbonate of soda,

and exposed it to the action of the air in a

saucer

In

in 2 days, to

day
6'1-

was reduced

it

grains

in 6 days, to 45 grains

and

in 9 days

was

it

in

to

80 grains

4 days, to 49 grains

44 grains ;
44 grains, had the

in 8 days, to

still

flour, and probably

no more weight. It was then
a red heat, after which it weighed

appearance of fine dry

would have

lost

exposed to
37 grains nearly.
fact, that the

red,

is

Now, it is a well established

common carbonate of soda, heated

constituted of 19 parts of acid and 28

of soda
nearly.

Kirwan

or 40.4 acid and b9.Q base, per cent,

Klaproth
says,

40.

says,
i

acid,

42 acid,

58

59,9 base.

base
It

is

equally well established that the crystallized

carbonate recently formed in a low tempe63 per cent, water, as

rature, contains about

above determined.

All experience confirms

FIXED ALKALIES.

493
this

Bergman and Kirwan

find

64 parts of

water, Klaproth 62, and d'Arcet 63.6. Hence

the constitution of the crystallized carbonate
is

ascertained

easily

(=

+ 28)

19

atoms of water unite

to form the
:

37

37

if

atom of the carbonate

to each

for,

to

common

6.3

63

47

80, the weight of water attached

that

10

is,

of carbonate of soda

Again,

crystals.

if

47

the weight of water attached

to 37 parts of carbonate of soda, to correspond

with

atom of water

but 37

6.3

43.3

appears that 100 parts of crystallized carbonate being reduced to 44 or 43.3,

from

this

it

indicates that

all

of water are

the 10 atoms

evaporated, except one. It should beem, then,

that the ordinary efflorescence of this salt is not

dry carbonate, but 1 atom of carbonate and 1

of water. This supposition is confirmed by experience ; for, in 5 days the above 37 grains of
heated carbonate became 44 grains by ex-

posure to the air.

There is another very remarkable character
of the carbonate of soda, which, however, I

apprehend
neral law

common

will be
in

found to

chemistry

crystallized

arise

when

carbonate

is

heat in a glass retort, as soon as

temperature about
but when

\^'ater;

150**,

it

this fluid

from a ge-

a quantity of

exposed to
attains a

it

becomes
is

fluid

as

heated to 212%

CARBONATE OF SODA.

49.9

and kept boiling a while, a hard, small grained,

salt

precipitated from

is

the

liquid,

which,

upon examination, I find to be {\\q fftli hydrate, or one atom of carbonate of soda united
to 5 atoms of water.

For, 100 grains of this

46 by a red heat ; but 1 atom of carbonate weighs 47, and 5 atoms of water weigh
40, together making 87 j now, if 87 of such

salt lose

salt

contain 40 water, 100 will contain 46.

The

>

clear liquid resting

has the specific

whole

upon the fifth hydrate

gravity 1.35; on cooling, the

liquid crystallizes into a fragile, icy mass,

which

with a very moderate heat.

dissolves

This appears by the test acid to be constituted

of 1 atom of carbonate and 15 atoms of water.

Thus the

tenth hydrate, by heat,

and converted
like

into the

fifth

manner, probably, the

transformed into the

When

drate.

gravity

hydrate

is

formed

residuary liquid
1.18,

By

fifteenth

resolved
;

in

might be

tenth and thirtieth hy1.35 sp.

is

it

to csystajlize, the fifteenth

in the liquid,

and

reduced to the

treating

the test acids,

is

fifteenth

any solution below

set aside

is

and

this

will be

atom of carbonate^

to

finally the

sp. gravity of

liquid solution

with

found to consist of

30 of water.

course that solution which the

It

common

is

of

crys-

of carbonate always form, when duly agior a saturated solution at

tated with water

tals

500
the

FIXED Alkalies,

mean ordinary temperature of

heat, other

By

sphere.

be obtained from 1.85

crystallize

such

the atmo-

liquid solutions

to 1.35

may be

may

but they soon

called supersaturated

solutions.

The
have

different species of hydrates in crystals

different

expected;

of the tenth

is

might be

gravities, as

specific

that of the fifteenth

1.42, and

is

1.35, that

that of the fifth 1.64.

These were found by dropping the

into solutions of carbonate of potash

were suspended,

or by

weighing them

turated solutions of the

ascertain
first

crystals
till

same.

that of the pure

they

in

sa-

could not

carbonate and the

hydrate.

AVhen carbonate of soda

is

alkali, the specific gravity 1.22

solution

used for a

test

would be

that

which contains 14 per cent, by meawhich 100 measures would

sure of alkali, of

of test acid for saturation

require 100

but, as

that solution cannot be preserved without partial crystallization, it will

be better to substitute

a solution of half the strength

1.11

;
namely, that of
then 200 measures of the solution will

require 100 of

The

test acid.

following Table contains the characters

of various combinations of carbonate of soda

and water,

resulting

from

my

investigations.

CARBONATE OF SODA.
Table of the quantit)' of

real

carbonate of soda

compounds of different

501

in

watery

specific graviiies.

Atoms.
point.

unknown.

FIXED ALKALIES.

502

this would probably wholly crysno very reduced temperature. The

'2d, 3d, 4th, 6th, &c.
hydrates, I have not
found to offer any remarkable discrimination.

perature

tallize at

Sodiumy or Ilydruret of Soda,

8.

to the present state of

According

our

know-

of sodium given at page

Jedge, the account
As the
262, will require some modification.
article

from which

obtained

the

is

first

sodium has always been

hydrate of soda, and as in

the electrization of fused hydrate of soda, no

given out, according to Mr. Davy, but

oxvgen ; it follows of course that sodium must
gas

is

be a compound of soda and hydrogen, which

may be called a hydruret of soda. Mr. Davy,
conceiving soda in a state of fusion to be pure
or free from water, as was the
at the time,

of

it

concluded that

the soda

and oxygen.

common

opinion

in the electrization

was decomposed

into

sodium

This conclusion does not

now

be tenable, though Mr. Davy still

appear
adheres to it, without having shewn what beto

comes of

the

water acknowledged to be pre-

sent in every instance of the formation of so-

dium and potasium

(Philos. Trans. 1809), to

SODIUM.
the

amount of IG per

503

upon the com-

cent,

pound.

Though Mr. Davy's

method of ob-

original

taining sodium by Voltaic electricity is the

most instructive, as to the nature of the new

product, yet, that of Gay Lussac and Thenard

is the most convenient when a quantity ot the

That is, to pass the vapour

article is required.
of red hot hydrate of soda over iron turnings
The
in a gun barrel, heated to whiteness.
hydrate seems to be decomposed
in part

it is

two ways

in

resolved into sodium, or hydruret

of soda, and oxygen, the former of which distils into a cooler receptacle of the barrel, and
the latter unites to the iron

in

part, the hy-

and soda, and

the former again into oxygen, which unites to
the iron, and hydrogen which escapes, whilst
drate

is

decomposed

into water

the soda unites to the iron or

its

oxide, forming

a white metallic compound.

The

specific gravity

Mr. Davy
mate

particle (being

of

sodium

The weight

at .9348.
I

is

stated

of

its

atom of soda and

by
ulti1

of

not 21, as stated

hydrogen) must be 29, and
of the
at page 263.
Consequently, 100 parts
contain
first hydrate of soda, or fused soda,
80.6 sodium and 19.4 oxygen per cent. This

agrees with that one of

Mr. Davy's

ments which gave the

portion of oxygen.

least

experi-

504

EARTHS.

Sodium amalgamates
cording

to

with

ac-

potasium,

Gay Lussac and Thenard,

in va-

are

more

fusible than either of the simple metals,

being

rious

in

proportions,

and the

some cases liquid

alloys

the freezing point of

at

In general, the properties of sodium

those of potasium so

water.

are found to agree with

nearly, as not to require distinct specification.

SECTION

12.

EARTHS.
The

class of bodies called earths

are nine in

Magnesitty
Argily

The

number

Yttria,

last

by chemists

names

Strontites,

Barijtes,

Silex,

three

their

are Lime,
Alumine or

Glucine and Zircone.

recently discovered

are

and

scarce.

The

earths constitute the bases of the fossil

Though they have frequently been

be compound bodies, and several
have
been made to decompose them,
attempts

kingdom.

suspected to

it

does not yet appear but that they are simple

Some of the earths

or elementary substances.

possess alkaline properties; others are without

such properties ; but they all partake of the

following characters

1.

They

are incombus-

LIME.

505

do not unite with oxygen

tible, or

2.

they

are inferior to the metals in lustre and opacity ;

3. they are sparingly soluble in water ; 4. they
are difficultly fusible, or resist great heat without alteration ; 5. they combine with acids j

thev combine

6.

with each other, and with

metallic oxides; and, 7. their specific gravities

are from

The
is

to 5

attempt to decompose the earths

Mr. Davy ; he seems to have shewn,
some of the earths are analogous to the
latest

that of

that

fixed alkalies, in respect to their properties of

forming metals

but these metals, like those of

the alkalies, are most probably compoijnds of

hydrogen and the respective

1.

This earth

found

is

earths.

L ime.

one of the most abundant

in all parts

it is

of the world, but in a state

generally with some acid.

united with carbonic acid, it exists in

of combination,

When

large strata or beds in the form of chalk, limestone, or marble ; and it is from some of these
that lime

is

usually obtained.

The common method

of obtaining lime,

is

expose pieces of chalk or limestone in a kiln

for a few days to a strong red or white heat ;
to

by

this

process, the carbonic acid

is

driven

off,

506

EARTHS.

and the lime remains

nearly the

same

in

stone, but with the loss

It

compact masses

of

and shape as the lime-

si^e

of

oF^lhs

its

weight.

probable, the intermixture of the lime-

is

stone and coal in the combustion of the latter

with the heat, to

contributes, along

The

lime from chalk

Composition.
pure but tiiat from

common

tains from 10 to

20 per

de-

the
is

nearly

limestone con-

cent, of foreign sub-

stances, particularly aluminc, silex,

and oxide

of iron.

Lime

thus obtained,

called (juicklinie,

but

is

2.3.

which

is

commonlv

white and moderately hard,

Its s[)ecific

brittle.

Kirwan,

is

gravity, according to

corrosive to animal

It is

and

vegetable substances ; and, like the alkalies,

converts coloured vegetable infusions, partiIt is infusible.
It
cularly blue, into green.
has a strong attraction lor water, so as to rob

the atmosphere of

its

to the atmosphere,

it

and

in a

few days

dry powder;
quires

begins

'i'i

to

in

vapour

down

falls

this

when exposed

its

into a fine white

process,

per cent, in

exchange

gradually iniblbes water,

if

pure,

it

ac-

after this,

it
weight ;
water for carbonic acid,

and carbonate of Jime

is
slowly regenerated.
of
water
is
thrown upon 2 of
part
the
lime
quicklime,
quickly falls to powder

When

with intense heat, calculated to be 800" (page

507

LIME.
89)

operation is called slaking the lime,

preparatory to most of its applications ;

this

and

is

new compound

the

limey and appears

denominated hydrale of
be the only proper com-

is

to

bination that subsists between lime and water.

a red heat the water

By

driven off and the

is

lime remains pure.

As lime combines with the principal acids
hitherto considered, and forms with them per
fectly neutral salts

and

as the proportions of

these salts have been experimentally ascertained

with precision,

we

enabled to determine

are

the weights of an atom of lime

Acict.

Carbonate of !ime, 44
Siiipliate

:Nilrale

Muriate

thus,

Base.

-4-56

percent

as

19:24

5S.5-f4l.4..

34:24,

6l.3-}-3S.7

38:24

47.S-fJ2.2

22:24,

Carbonate of lime

is,

believe, universally

allowed to contain either 44 or 45 per cent, of

acid ; and sulphate is mostly supposed to contain

58 per cent, acid, the extremes being 56

and 60.
salts

but

The

proportions of the other

two

have not been so carefully determined

it

is

easy to satisfy one's self that the pro-

portions assigned are not wide of the truth.

Let 43 grains of chalk be put into 200 grain

measures of the

test nitric acid (1.143), or

the

EARTHS.

508
test

the

muriatic (1.077), and

lime

it

will be found that

be wholly dissolved, and the

will

Hence

acids saturated.

it

follows that the

elementary atom of lime weighs 24.

have

supposing carbonate of
lime to be, according to Kirwan, 45 acid 4- 55

formerly stated

lime

it

at 23,

The

cent.

per

worth consideration

difference is scarcely
but experience seems to

warrant 24 rather than 23

the

for

atom of

lime.

When

a large quantify of water

upon a piece of quicklime,

it

thrown

is

sometimes re-

fuses to slake for a time

j
perhaps this is caused
by the water preventing the rise of temperaIn this case the water does not dissolve
ture.

the lime

-,

hence

perly speaking
hydrate of lime

small degree.

and

zvate?',

it

is

is

should seem that lime probut

;

not soluble in water

readily soluble, though in a

The

solution

is

called limc-

a very useful chemical agent.

is

Lime-water may be formed by agitating a

quantity of hydrate of lime in water; distilled
or rain water should be preferred.
One brisk
agitation

water

is

but

nearly sufficient
if

to saturate

complete saturation

the agitation should be repeated

the

required,

two

or three

After the lime has subsided the clear

times.
liquid

is

must be decanted and bottled

Authors

differ as to

for use.

the quantity of lime dis-

509

LIME.

solved by water some say that water takes

The
-5-^ of its weight of lime ; others, -g-i-^.
:

fact

that

is,

with due

few have

care.

the experiment

tried

Dr. Thomson,

in the 4th ed.

chemistry says, from his experience,

of his

-^l-j-.

much nearer the truth than the other

One author says, that water of 212

This

is

two.

takes up double the quantity of lime that v^ratcr

of 60 does, but deposits the excess on cooling

had

no experimental proof
said half instead

would have been nearly

some experiments on
sults are

When

is

given.

If

he

of double, the assertion

true.

this subject,

haye made

and the

re-

worth notice.
water of 60

hydrate of lime,

is

duly agitated with

but a
;

clears very slowly

it

soon be passed
quantity of the lime-water may
a
filter of blotting paper, when it bethrough

comes

clear

and

fit

for

use.

found 7000

75 grains of test
grains of this water require
its saturation.
for
acid
Consequently
sulphuric
If a quantity of
water, mixed with hydrate of
iime, be warmed to 130 and then agitated, it
it

contained 9 grains of lime.

this saturated

7000 grains of this water

only 60 grains of test sul-

soon becomes clear

decanted, require
saturation.
phuric acid in order to produce
The same saturated lime-water was boiled with
bvdrate of iime for two or three minutes, and

510

EARTHS.

set aside to cool

without agitation

it

very soon

and 7000 grains being decanted, required only 46 grains of test acid to be neucleared,

tralized, the

test

Hence we deduce
I

being as usual 1.134.

the following table.

takes

part

water of

60

acid

130

212

lip

511

LIME.

months with lime-water exposed

still

contained

-^-^r^

of

its

to the

air,

weight of lime.

Lime-water has an acrid

taste,

notwith-

It operates
standing the small quantity of lime.
on colours like the alkalies. Certain blue co-

lours, such

as syrup of violets, are

infusion

of litmus, which

green
converted from blue to red by a
;

has

its

changed to
has been
little

acid,

blue colour restored by lime-water,

archil solution,

reddened by an acid,

is

and

restored

When expurple colour by lime-water.

has a thin crust
lime-water
the
to
air,
posed
to

its

formed on

its

surface

this

is

carbonate of

lime, the acid being derived from the atmoit is insoluble, and falls to the bottom j
;

sphere
in time the whole of the lime
into carbonate,

is

thus converted

and the water remains pure.

If a person breathes through a tube into limewater, it is rendered milky through the formation of carbonate, or
l)onic

acid

if

water containing carit j but a double

be poured into

a supercarbonate of
quantity of the acid forms
lime, which is soluble in a considerable degree.

Though

lime

is

soluble in water in so small a

of distilled water may

quantity, yet a portion
be mixed with ^ |^ of its bulk of lime-water,

and the presence of lime

will

be shewn by the

test colours, or by nitrate of mercury, &c.

Lime combines Vv^ith sulphur and with phos-

512

EARTHS.

phorus these compounds will be considered

under the heads of sulphurets and phosphurets.
:

It

combines

with the acids, and forms

also

with them neutral

salts.

Lime

unites to certain

metallic oxides, particularly those of mercury

and lead

pounds

but the nature of these

not

is

last

com-

much known.

One

of the great uses of lime is in the formation of mortar. In order to form mortar,
the lime

slaked and mixed up with a quan-

is

tity of sand, and the whole well wrought up

into the consistence of paste with as little water

This cement, properly interposed

as possible.

amongst the bricks or stones of buildings, gradually hardens and

adheres to them so as to

bind the whole together.

This

is

partly, per-

to the regeneration of

haps principally, owing

the carbonate of lime from the carbonic acid
of the atmosphere.

The

best ingredients

and

their proportions to form mortar for different

purposes,

do not seem yet

to

be well un-

derstood.

2.

This earth

is

Magtiesia.

obtained from a

salt

now

called

sulphate of magnesia, which abounds in sea-

water and
to

the

in

bjest

some natural springs. According

analyses, crystallized sulphate of

MAGNESIA.

513

magnesia consists of 56 parts of pure dry sulphate, and 44 parts water in the hundred.

Some

authors find more water in this salt

namely, from 48 to 53 per cent. ; but Dr.

Henry, in his analysis of British and foreign
in the Philos. Trans. 1810, takes notice
of a crystallized sulphate of magnesia contain-

salt,

ing only 44 per cent, water; and the specimen

of sulphate which I have had for many years
bears the

same character.

am,

therefore,

inclined to adopt this as the true proportion of

water. Now, Dr. Henry found that 100 grains

of the above sulphate of magnesia produced

111 or 112 grains of sulphate of barytes; and
it

is

acid

well established that

;

4 of

this last salt is

hence, the sulphuric acid in

100

sul-

phate of magnesia (56 real) is equal to 37

grains ; consequently the magnesia is equal to
19 grains: but the weight of an atom of sulphuric acid is 34 ; therefore, 37 19 : 34 17,
:

nearly, which must be the weight of an atom

of magnesia, on the supposition that sulphate

of magnesia is constituted of one atom of acid

united to one of base, of which there is no
reason to doubt.

I have in the

first

part of

work, page 219, stated the weight of magnesia to be 20 ; it was deduced chiefly from

this

Kirwan's analysis of sulphate of magnesia

but

514

EARTHS.

from present experience

Though few of the

salts

I think it is too
high.
of magnesia have been

analyzed with great precision, yet the weight

of the atom of magnesia derived from different
analyses

above

would not

"20.

common

fall

below

17,

nor

rise

Dr. Henry and I analyzed the

carbonate of magnesia well dried in

and found it to lose 40 per cent, by acids,

57
and
per cent, by a moderate red heat. Hence
it should consist of 43 magnesia, 40 carbonic
found the carbonate
acid, and 17 water.
100",

We

water and some acid about

to give out

begin
430 ; but

it

supported a heat of 550 for an

hour without losing more than 16 per cent.

Hence the carbonate must be constituted of 1

atom of

acid,

of magnesia, and 1 of water,

20 ; for, 19 + 8 4- 20

stating the magnesia at

47

and

if

47

19, 8,

and 20

100

40,

17 and 43 respectively, according to the above

experirnents. 1 have reason to think, however,

weight of the atom of magnesia ought

deduced Irom the sulphate than
the carbonate ; because it is probable that this
that the

rather to be

always contains a small portion of sulphate

of lime, when prepared by the medium of
common spring water; this portion will be
last

found
will

in the result

be placed

to

of the analysis by

fire,

and

the account of magnesia.

515

MAGNESIA.

Wherefore

conclude the weight of an atom

of magnesia to be 17.
carbonate of magnesia

It
is

is

said that a super-

obtainable

but

when

sulphate of magnesia and supercarbonate of

soda in solution are mixed together, there is a
of cargreat effervescence and disengagement
bonic acid, and nothing but the common carbonate of magnesia is precipitated according
to my experience.
Dr. Henry, indeed, ob-

tained a crystallization by exposing a dilute

mixture for some time j the crystals were small

opake globules, about the

size

of small shot

but upon examination, they proved to be nothing but carbonate of magnesia united to 3

atoms of water instead of

lost

grains

whence

'iO

70 by

its

For, 100

atom.

and 30 by acids ;
constitution was 30 acid + 30 earth

water, or 19 acid

The

water.

a red heat,

constitution

19 earth

-f-

24 or 25

of crystallized

sul-

phate of magnesia must, therefore, be 1 atom

5 atoms of
1 atom of magnesia
of acid

91; this
weight 34-+17 + 40
19 base + 44 water,
+
37
acid
cent.
per
gives
agreeably to Dr. Henry's experience above-

water

in

mentioned.

The

constitution of the most

common

salts

of magnesia, in their dry state will, therefore,

be as under

516

EARTHS.
Base.

Acid.

Carbonate of magnesia 53
G6.7

Sulphate

17

percent, as 19

17

-f- 3:>.3

3-1-

17

17

Nitrate

69

4- 31

38

Muriate

5G.4

+ 43.6

22:17

The

nitrate of

in

magnesia

the above table

agrees with that of Kirwan, and Richter, and

the muriate with that of Wenzel.

To

obtain magnesia, the sulphate must be

dissolved in water, and a quantity of pure potash in solution must be added ; the magnesia

then thrown down, and

may be separated
carbonate of potash be put
into the solution of sulphate of magnesia, car-

is

by

filtration.

Or

if

bonate of magnesia will then be precipitated,

which may be separated by filtration ; this last
must be exposed to a red heat to drive off the
the former need only to be
;
dried in a gentle heat.
Magnesia is a white, soft powder, possessing
little taste and no smell ; its specific gravity is

carbonic acid

said to be 2.3.

lours like lime

It operates

and the

on vegetable co-

alkalies.

It

is

by heat, and very sparingly soluble

According

to KirV\'an,

it

requires

infusible

in water.

7000 times

weight of water to dissolve it ; I found it

require 16,000 times its weight of water in
its

one experiment.

When

exposed to the

air.

517

MAGNESIA.
luagnesia, like lime, attracts

atom of water

of magnesia, amounting to about 47 per

cent, by my experience ; it attracts carbonic
to

acid

but very slowly.

It

does not combine

with any ot the simple substances, except perhaps hydrogen and sulphur. With the acids it
forms neutral
to

salts,

which

combine wiih other

are found frequently

salts.

As the sulphate of magnesia is the ordinary

combination of this earth exhibited as a soluble
salt,

it

may be

of use to have

? table

shewing

the quantity of real dry sulphate, and of ordinary crystallized sulphate, in given weights or

measures of solutions of different specific gravities.

The table is founded on my own experience.
Table of sulphate of magnesia.
Atoms.

518

EARTHS.

lution obtained by boiling

and

the fi^eenth

is

a saturated solution at 60".

3.

The

Biijyles.

now denominated

earth

was

baryteSy

discovered by Scheele in IT?!.

Since then
the labour and experience of several distin-

guished chemists have

knowledge both

of

added much
and

the earth

the

to

com-

its

pounds so that now it may perhaps be said

to be the best understood of ail the earths.
It
;

occurs most frequently in combination with

sulphuric

acid,

the

compound being

called

sulphate of barytes^ formerly ponderous spar,

and

is

per.

found about mines, particularly of copoccurs in combination with car-

It also

bonic acid, though rarely ; the compound

denominated carbonate of barytes.

is

Barytes may be obtained either from the sulphate or the carbonate. The former must be
pulverized, mixed with charcoal, and exposed
in a crucible to a red heat for

sulphate

is

sulphuret

when

thus
is

to

changed
be

the sulphur

treated
is

some hours

into a sulphuret.
vvith

nitric

the

This
acid,

thrown down, and the

barytes combines with the acid

the acid

may

then be driven off by a red heat- and barytes

will remain in the crucible.
If the carbonar<*

519

BARYTES.

be used,

it

must be pulverized, mixed with

for some time in a cru-

charcoal, and exposed

cible to the heat of a smith's forge.

water
ing

Boiling

will then dissolve the pure barytes, leav-

the charcoal

and carbonate, and upon

of barytes are obcooling, crystals of hydrate

the water may
of
The
tained.
greatest part

be driven off by heat.

Pure barytes obtained by the former method
is a greyish white body,
easily reduced to

and
powder. It has a harsh and caustic taste,
Like lime,
if swallowed proves poisonous.

when exposed

to the

atmosphere,

water, and then parts with

acid.

It

green.

it

for

it

absorbs

carbonic

changes certain vegetable blues to

Its

is
nearly 4.
specific gravity

Ba-

with water,
rytes forms various combinations
called hydraUSy which will presently be menIt combines with sulphur and phosnot with the other simple subbut
phorus,

tioned.

stance.

The

sulphuret and phosphuret will

their respective heads.

be considered under

The weight

of the ultimate panicle of barytes

can be very nearly approximated, and appears

to be 68. or twice the weight of an atom of
This appears from the followsulphuric acid.
of the most
ing statement of the proportions

common

bcrytic salts,

cessfully investigated.

which have been

suc-

520

EARTHS.
Acid.

Btte.

Carbonate of barytes 22

78

19

68

3J-

6S

6i

38

68

75.6

22

68

is

percent

33.3 -f 66.7

Sulphate

+
24.4. +
36

Nitrate
Muriatft

The

-f-

following respectable authorities agree

22 per cent, acid to carbonate of

in assigning

barytes

cently

Clement, Desor-

Pelletier,

namely,

and Kirwan

jnes, Klaproth,

Mr. Aikin

finds 21.67,

and more

Thomson, 21.75

(Nicholson's Journal,

and 23, 1809).

The

last

vol.

22

mentioned chemist

finds sulphate of barytes to be 33 acid,

barytes.

re-

and Mr. James

and 67

His conclusion corroborates the pre-

vious ones

of Withering,

Black,

Klaproth,

Kirwan, Bucholz, and Berthier, who

all

fi:c

the acid at or near 33 per cent.

Vauquelin,
Rose, Berthollet and Thenard. and Clement

and Desormes

32 or more acid

find

croy and Aikin, 34.

It is

and Four-

very satisfactory to

see the near coincid<nce in regard to the constitution of this salt

made

because

it

is

frequently

a test of the quantity of sulphuric acid

and of sulphur.

Mr.

J.

Thomson

finds 59.3

barytes per cent, in nitrate of barytes,

Clement

and Desormes 60, Kirwan 58 and 55 at different trials, and Fourcroy and Vauquelin 50.

These

results

other,

and are

differ
all

considerably from

below

each

the proportion

as-r

BARYTES.
signed above

but

it

521

must be observed that

of barytes contains water,

perhaps various quantities of water ac-

crystallized nitrate

and

cording to the temperature in which it crystallize'". ; now, if the atom of nitrate be associ-

atom of water, then the proportion

of barytes per cent, will be 59.6, which nearly
agrees with Thomson, and Clement and Deated with

sormes
will

if

with 2 atoms of water, the barytes

j if with 3
atoms, then

be 55,7 percent,

52.3, 8ic.

Crystallized muriate

of barytes ap-

an atom of dry mu2 atoms of water , or 22 acid +- 68

pears clearly to consist of

rjate

barytes

acia

16 water; this reduced gives 20.8

64.1 barytes

For, Kirwan

water

finds

15.1 water per cent.

20 acid

Fourcroy, 24 acid

+ 60

64 base
base

+16

16 wa-

ter; and Aikin, 22.9 acid + 62.5 base + 14.6

water per cent., which agree with each other,

and with the theory

as nearly as can

be ex-

pected.
Rarytes combines with most acids, and forms
In many respects it
salts.

with them neutral

appears to be related to the fixed alkalies, only

in weight it is nearly the same as both of them

put together.

EARTHS.

522

Hydrate of Barytes.

When

from the
pure barytas, obtained
or

ni-

moist-

by heat, is exposed to the air,

ened by water, it combines with it, and that
trate

is

forming a number of Aj/drates, which have not been sufficiently attended to and discriminated ; much heat is

in various degrees,

evolved during the combination

it

was mis-

bahydrate of barytes for pure

taking the
that caused the uncertainty for some time
first

rytes

in regard to the proportions of the elements of

Now, if
sulphate of barytes (see page 474).
an atom of barytes weigh 68, the first hydrate
will weigh 76, to which if 34 sulphuric acid
be added, we shall have an atom of sulphate
of barytes = 102, (for the water is driven off

by the union of the acid and

base)

if

then

we

conceived the hydrate to be pure barytes, we

should conclude that 76 barytes united to 26

102 sulphate, which is

sulphuric acid to form
conclusion of
mistaken
former
the
near
very

Thenard and
is

Berthollet.

Hence, then, there

reason to conclude that their barytes, kept

some time
hydrate,
ter.

in a red heat,

or one

When

was

in reality the first

atom of barytes and one of

pure barytes

water, a solution

is

is

\n^-

dissolved in boiling

formed of

specific gravity

HYDRATE OF BARYTES.

52

<5

-xceeding 1.2; on cooling, great part of it

these crystals are the tzventietk
;

crystallizes

1 atom of
barytes and 20
of water, or 30 barytes and 70 water per cent. ;
if they are exposed to a heat about 400" or 5(X)%

hydrate, or consist of

they melt, great part of the water

and a dry whiie powder

iht Jifth hydrate.
(r=

6^

-f

20 X

In

8) are

is

is

dissipated,

obtained, which

is

223 parN
108 (= 68 -h

this operation,

reduced to

which is exactly the reduction obtained experimentally by Dr. Hope,

This dry powder melts below a red heat ; but
5

^), or 100 to 47,

I have not been able to find what

it

would be

reduced to by exposure to a red heat, because

it
acquires carbonic acid, even in a crucible,
as Benhollet has observed, almost as fast as

it

My experience on the crystals of

limited ; but from the followhas
been
barytes
I
conclude
they are the hvejitieth hydrate.
ing
loses water.

1 took

80

grains cf fresh crystallized barytes,

and dissolved them

the solution

in

was of the

1000 grains of water-,

specific gravity

.024

took 70 grain measures of test sulto saturate it, and afforded 36 grains
acid
phuric
this solution

of dried sulphate of barytes : of this 12 grain;?

were acid and 24 barytes. AVhence we learn,
1st, that

80 grains of

crystals are equal

real barytes, or 22.S equal to

20 X

68

to

but 228

68, which shews that 20 atoms

24

~
<:t

524

EARTHS.

water are united

decimals

in

to

of barytes; 2d^ that the

the second and third places of the

expression for the specific gravity, denote the

ouantity of real barytes in 1000 grain measures

This

of the solution.

last

must evidently hold

witViont anv material error in

all

the niferior

and hence the strength and value of

water
may be known by its specific
barytic
an
gravity,
advantage which does not practi-

solutions

cally appertain to lime-water.

trials,

however,

By subsequent
found the quantity of barytes

rather overrated.

The

following sketch of a table of the hymay have its use, till a more

drate of barytes

ample and correct one can be constructed.

Table oftlie Hydrate of Barytef;.
Atoms.

525

SrRONTITES.
its

distinguishing properties, were pointed out

in an essay read to the Royal

by Dr. Hope

Society of Edinburgh,
in

1792, and published

Several distin*

in

1794.

their Transactions,

guished chemists have since confirmed and ex*

tended these investigations. The Scotch mineral

a carbonate of strontites

is

has since been found

but the earth

combined

in various parts

with sulphuric acid.

Strontites is obtained from the sulphate or
carbonate of strontites, by the same processes
as barytes
it

in

from the like compounds

indeed,

bears so close a resemblance to barytes, both

its

free

and combined

confounded with

same acrid
sonous

taste

it is

state, as to

Strontites has

it.

as barytes

less soluble in

but

have been

much

it is

the

not poi-

water than barytes;

has the property of giving a red or purple

colour to flame, for which purpose the nitrate

it

or muriate

may be

])lied to the

dissolved in alcohol, or ap-

wick of a candle.

the atom of strontites

which
be 46.

it

is

of

salts

forms with the more comnion acids

to

Thus,
Acid.

Carbonate of

strontites

Sulphate
Nitrate
"Muriate

The weight

deducible from the

'

Baif.

P^f cent, as 19

29.2

-f-

"'^-^

42.5

57.5

45.2

+
+

54.8

38

67.6

22

32.4

46

34:46
:

46
46

52&

EARTHS.

Dr. Hope, Pelletier, and Klaproth find 30

per cent, of acid in the carbonate.
Clayfield,

Henry, and Kirwan

find

Kirwan

acid in the sulphate.

tallized nitrate to contain

Klaproth,

42 per cent,

finds the crys-

31.07 acid, 36.21

and 32.72 water; which I presume denotes 1 atom of acid, 1 of base, and 5 of wabase,

ter
this

that

is,

38 acid

46 base

40 water

reduced, would give 30.6 acid, 37.1 base,

and 32. S water per

cent, which very nearly

agrees with his experience.
Taking the dry
46.2
his
results
would
salt,
acid, and 53.8
give

A'auquelin finds the nitrate to contain

base.

48.4 acid, 47.6 base, and 4 water; but this

constitution cannot be

correct

Neither can

which gives 51.4 acid and

Richter's analysis,

water, and 48.6 base.'Dry muriate of strontites,

according to Kirwan, consists of 31 acid,

but Vauquelin states 39 acid,
;

and 69 base
and 61 base

the former, without doubt,

is

nearer the truth.

HydnUe

of

Stroiititcs.

to pure strontites,

it

When

water

becomes hot and

is

put

swells, like

lime and barytes, and falls into dry powder.

This powder seems to be the tirst hydrate ;
whence, 46 parts of strontites will take 8 of

water to form
water

These

be

this

added,

crystals

combination
the

hydrate

but

if

more

crystallizes.

appear to be the 12lh hydrate

521

ALUMINE.
they are constituted of

that

Is,

tites

and 12 of water

46

4-

atom of

96

stron-

142, or 32

68 water per cent, agreeably to

the experience of Dr. Hope. Water dissolves
about -r^Trtb of its weight of pure strontites in

strontites

the temperature of 60, or y^th of its weight

of the crystals ; the specific gravity of the solution

is

"Whence

it

But boiling water

1.008.

nearly

solves about half

weight of the

its

appears that strontites

soluble than barytes,

than lime.

The

of strontites

is

less

specific gravity of the crystals

rightly determined

for the

much

and much more soluble

Iratz to be nearly 1.46.

be used

is

dis-

crystals.

by Hassen-

Strontian water

may

same purposes as lime-water,

or barytic water.
Strontites

form neutral

combines with most of the acids to

salts.

It also

combines with

sul-

phur and phosphorus.

5.

The

Almnine^ or Jrgil.

earth denominated alumine, constitutes

a great portion of common c/aj/ ; but this last

is a mixture of two or more earths with iron,
&c., and therefore cannot be exhibited as pure
The earth may be obtained pure
from a common well known salt, called alum,
alumine.

EARTHS.

528

which is constituted of sulphate of potash and

sulphate of alumine combined together, with
a portion of water.
quantity of alum is to
be dissolved in 10 times its weight of water ;

ammonia

to this a quantity of liquid

added
and

the sulphuric acid seizes the

lets fall

the alumine, whicti

rated from the

exposed

may be

filtration

by

liquid

is

to

be

ammonia,
sepa-

and then

to a red heat.

Alumine thus obtained

is

a fine white earth,

spongy, and adhesive when moistened j it has

neither taste nor smell
it is said to have the
;

specific gravity, 2.

When mixed

forms a mass which

it

is

with water,

the basis of earthen

ware, and capable of receiving any figure, In

this case, by the application of great heat, it

becomes

excessively hard, and loses in part,

or wholly,

its

adhesive quality.

Pure alumine

bears the highest heat of a furnace without under^joinjr

anv change.

Alumine does not form any known combination with oxygen, hydrogen, charcoal, sulphur, or phosphorus ; but it combines with
the alkalies, with most of the earths,
several metallic oxides.

many

It

of the acids, but forms in most cases un-

crystallizable

salts.

It

possesses a strong

nity for vegetable colouring matter,

its

and with

combines too with

affi-

and hence

great importance in the arts of dyeing and

ALUMINE.
printing, in

which

it

is

.^29

to fix the

employed

colour on the cloth.

The weight
easily

earths and alkalies

which

aiom of alumine

of an

determined

as

that

partly

is

not so

of the

preceding
because ihe salts

forms with the acids are not crystal-

it

and partly because they have not had

a proportionate share of attention paid to them.

lizable,

The

with alumine which has been

salt

only

is

carefully analyzed

alum

and properties of
to
to

its

the triple

compound, or

an acquaintance with the constitution

this salt is of great

importance

manufacturer, and to the various

whom

it is

artists

of indispensible utility.

The experience of Chaptal, Vauquelln, and

of Thenard and Roard (An. de Chimie, vol.
22, 50, and
18)

shews

59, or Nicholson's Journal, vol.

that the

nearly the same in

alum of
its

all

countries

constitution

and

is

very

qualities,

it contains 33
percent, sulphuric acid, 11
or 12 alumine, 8 or 9 potash, and 47 water.

that

All the authors

it is tf-ue,

more

have mentioned do not agree,

in these

numbers

but the differences

appearance than reality. V^auquelin obtains 95 sulphate of barytcs from 100

alum, but Thenard and Roard obtain 100.

are

The

last

in

mentioned chemists adopt only 26

in sulphate of barytes
whereas

per cent, acid

it is

now

universally allowed there

are

about

EARTHS.

530
33

cent, acid

p)er

Thomson,

am

in

that

This

cent, sulphate of barytes.

most correct, and

as the

recent.
this

is

counts

Mr. James

salt.

informed, finds nearly

it

is

result

100 per
I

also the

adopt
most

Vauquelin finds 481- water in alum j

more than is generally found, and acin

some degree

for his obtaining less

Chaptal finds 47 per cent,

alum, with which my expe-

sulphate of barytes.

water

in English

rience accords.

Vauquelin finds 10.5 alumine,

Thenard and Hoard, 12.5 per cent.
Mr.
Tennant of Glasgow, who favoured mc with

an

analysis, finds

11.2 alumine in the alum

This

manufactured there.
1

last

chemist finds

which

per cent, sulphate of potash,

same

as

Thenard and Hoard's

nearly,

is

the

15.7.

42 potash, have been

shewn to constitute 76 sulphate, 15 must con-

Now,

as

34 acid

tain 6.7 acid

results then,

4-

and 8.3 potash. Collecting these

appears that alum may be said

it

to consist of,

33

sulphuric acid.

11.7 alumine.
8.3 potash.

47
lO^j

water.

ALUMINE.

Of

531

the 33 sulphuric acid^

it

must be recol-

lected that 6.7 parts beJong to the potash

that

yth of the whole ; the remainder, or ^tlis,

belong to the alumine. Hence, then, were

is,

there only

'>

atoms of sulphuric acid ui a mole1 atom

would appertain to an

cule of alum,

atom of potash, and the other 4 atoms to as

many of alumine, provided the acid and alumine
unite one to one,

which we

are to

presume

reason appear to the contrary.

It should seem, then, that an atom of alum is
sufficient

till

constituted of one of sulphate of potash in the

centre, and 4 atoms of sulphate

around

= 26.3
34

it,

alumine

(if

But S3

forminor a square.

acid to 11.7 alumine; and 26.3

6.7

11.7

weight of an atom of alumine.

Dry alum must, therefore, be 5 X 34 + 4'2 -f
4X15= 272 but as this is found combined
:

15, the

with water

in

the

of water are attached

for this

purpose,

common alum, it
know how many atoms

state of

will be satisfactory to

we

one atom of dry alum

have 53 47
272 24
to

the wcij^ht of water

gives the

number

of atoms

atom of common alum

this,

divided

30.

b)'

^,

Hence, an

consists of,

1 atom of
r= 76= per cent. 15
sulphate of potash
4 atoms of sulphate of alumine
I9e
38
30 atoms of water.
47

And

=240
5!2

100

532

EARTHS.

A saturated

solation of

alum

in water, at the

of the specific gravity 1.048,

temperature 60,
and is constituted of 1 atom of dry alum and
is

600 of water

or the

quantity of water

The

alum has 20 times the

the

that

crystals

specific gravity of alum itself

is

contain.

about

and by means of heat, solutions of

it

in

.7

water

be obtained of any inferior specific graat least, I have had a solution, which,
vity

may

when

was

hot,

1.57.

Alumine does not combine with carbonic

acid; but

it

combines with the

nitric

and mu-

would, therefore, be desirable

that the weight of an atom of alumine should
riatic acids

it

be investigated fiom these last combinations,

No author that
as well as from the sulphate.
I

in

know

has given the proportion of elements

of alumine ; and in muriate of

nitrate

alumine Bucholz determines equal parts of acid

and base, and Wenzel 28 acid to 72 base ; so
that no confidence can be placed in them.

determined the proportions of these salts as

follows
100 grains of alum were dissolved in
:

water; the alumine was precipitated by 150

measures, more or

less,

of

test

ammonia,

{.91),

care beinsT taken that the aluminous solution

was saturated with ammonia, and that none

v;as superabundant
the liquid was then well
;

agitated,

and immediatelv divided

into three

533

ALUMINE.

equal portions. It was then found that each

of these portions took 52 measures of the test
acids.;

namely, the sulphuric, the

nitric,

and

the muriatic respectively, to dissolve the floating alumvne, and to clear the solutions which

were afterwards found

bined acids.
salts are

be

to

from uncom-

free

Hence, the proportions of the

deduced

as

under

Acid.

Sulphate of alumine 69.4

71.7
Nitrate
59.5

Muriate

Base.

+ 30.6 per cent, as 34-:

38
+ 28.3
22

+40.5

15

15

15

be proper here to notice an opinion

It will

which Vauquelin supported in

1797, but which is not adverted

his

essay in

to in his suc-

of Theceeding essay in 1804, nor in the one

nard and Roard in 1806; I mean the opinion
that

alum

consists of the supersulphate of alu-

mine and sulphate of potash. If this be true,

then the atom of alumine must weigh 30, because 2 atoms of sulphuric acid unite to

The

alumine.
support.
the blue

opinion appears
a solution of alum

When

to red

of

me without

to

is

put to

but

this is
changes
not a proof of excess of acid where the base of
the salt has a strong affinity for colouring mat-

ter

the

test,

there
salt,

is

it

it

probably a true decomposition of

or perhaps the colouring matter forms

534

EARTHS.

Thai no
triple compound with the salt.
uncombined acid accompanies alum is certain,

because the
it.

least portion

of alkali decomposes

Besides, a red heat drives off half of the

acid at least from supersalts

but alum bears a

red heat without losing a sensible portion of

From the experiment related above, it
acid.

appears that the sulphuric, the

nitrfc,

and the

muriatic acid tests are of equal efficacy in satuAre thes^ all supersalts ? If
rating alumine.
so,

why

does not half the acid

rn

each case

neutralize the earth, and form a simple salt?

But

it is

said

if

alumine be boiled

in a solution

of alum, the alumine combines with the alum,

and

falls

down an

insoluble,

neutral

salt.

Vauquelin asserts he has made the experiment ; but he mentions no proportions, nor
does he point out the time requisite to produce
the effect.

With a view

cipitated the alumine

to this subject,

pre-

from a measure of satu-

alum at 60 (about 100 grains

of alum) by the necessary quantity of ammonia j
rated solution of

to this liquid,

which was found

containing the alumine

in

neutral,

still

suspension, I

put

another measure of the same solution of alum,

and boiled the whole for 10 minutes in a glass
vessel

tered

it

and

fil-

was not much diminished

in

was then

the liquid

specific gravity,

set aside

to

cool,

and required nearly the same

ALUMINE.

5.35

quantity of ammonia to saturate it, and afforded the same quantity of alumine as the first

measure.
Apprehending the sulphate of ammonia present might influence the result, I
next put the dry pulverized alumine from 100
grains of

alum

alum

in water,

into a solution of

and

in

100 grains of

another experiment the

moist recently filtered alumine, and boiled

whole

for

and the liquor

restored,

same

t\\e

10 minutes; the water evaporated was

filtered

specific gravity as at

it

was of the

tasted equally

first,

aluminous, and the precipitate collected and

dried, weighed just the same as before. These
facts lead

me

to

doubt concerning the existence

of this alum saturatedwith its earthy as the earlier

chemists called

it.

But supposing the existence

of a combination of sulphuric acid with twice

the quantity of alumine, I know no reason why
it

should not be constituted of

atom of acid

and 2 of alumine.
Hence, I conclude the
weight of an atom of alumine above slated is a
fair

deduction.

The French

chemists seem to have proved

that the presence of even a very small portion

of sulphate of iron in alum

some of

its

Hydrate of Alumine,

very injurious in

Saussure, in

the

52d

Journal de Physique, observes, that

is
precipitated from its solution, in

vol. of the

alumine

is

uses in dyeing, Sic.

536

EARTHS.

two

very different states, according to circum-

stances

the one he calls spongy, and the other

gelatinous alumine ; they both retain 58 parts

per cent, of water, when dried in common

summer
of

heat

the former parts with the

water at a red heat; but the

its

loses 48 per cent,

There may

whole

latter

only

at the

highest temperature.
be some doubt as to the accuracy of

but it would seem probable that

;
alumine, at the ordinary temperature, retains 2
atoms of water, or 15 parts alumine hold 16 of
these facts

water

by

this

would allow 52 per

a red heat.

The

cent,

loss

subject deserves further

attention.

6.

The

earth

denominated

dantly in a great

many

in Jlinty rock crystal,

in

Silex.

found abun-

is

silex,

stones

it is

and others

almost pure

but of stones

it only
constitutes a part, being
combination with one or more of the

general

found

in

other earths, or with metals, &c.

found
sand.

in small particles in the

The most

It

is

also

form of white

distinguishing feature of this

melting along with either of the

fixed alkalies, and forming with them that

earth

is

beaulifui

The

its

and well

known compound,

specific gravity of flint

usually about 2.65.

and rock

glass.

crystal

is

After being heated red

537

siLEX.

hot for some time,

flint

may be

pulverized in

an iron mortar, and forms a white earth, which

may be

regarded as silex

pure for

suflrtciently

It forms a harsh, gritty powmost purposes.

der, which does not cohere nor form a paste

with water
in

It

like clay.

is

insoluble in water

It is infusible

any sensible degree.

silex

by heat,

To

unless at an extremely high degree.

obtain

a pure state, a mixture of sulphuric

in

acid and fluate of lime must be distilled in glass

vessels, or

along with pulverized

superfluate of silex

is

produced

flint,

when

an

elastic

in

the gas may be received over water, on

;
the surface of which a crust of fluate of silex is
state

being removed by filtration

or otherwise, the clear liquor is to be saturated

formed

this crust

with ammonia,

down.
fine

When

when pure
dried in a

white powder.

silex

is

red heat,

it

thrown
forms a

The common mode

pre-

scribed to obtain pure silex gives pure glass, as

will presently be explained.

It

that sulphuric acid, poured on

is

remarkable,

fluate of silex,

expels the fluoric acid in fumes, though

not combine with the silex.
Silex combines with the

two

it

does

fixed alkalies,

with most of the earths, and with metallic

oxides ; but with few of the acids immediately,
alkali,

except the fluoric ; when joined to an

it
may be united to several of the acids,

538

EARTHS.

forming triple salts. It seems not to combine

with oxygen, hydrogen, or the other combusnor with ammonia.

tibles,

The
with

form

fixed alkalies

two

may each be combined

silex

in

glass,

one part of

proportions.
silex

In order to

and one of

fine

dry carbonate of soda may be mixed together ;

but if potash is used, then 1^- parts will be reIf the other or soluble

quired.

compound

iii

wanted, then double the quantities of alkali

must be used, or 2 parts of soda and 3 of potash.

strong red heat in each case

is

acces-

form a complete union of the principles ;

the fused mass gives out the carbonic acid of
sary to

when poured out immediately

when the double quantity

the alkalies, and

becomes

glass; but

of

is

alkali

used, the glass

is

deliquescent, and

may be completely dissolved in water. This

last may be caHed supersodiuretted or superpoand the former sodiurelted or

tasiuretled si/ex,

When

potasiurett^d silex.
into a solution

an acid

is

dropped

of superpotasiuretted silex,

white precipitate

is

immediately formed, which

potasiuretted silex, or common glass, and

not silex, as has hitherto been supposed.
For,

is

1.

The

heated precipitate,

I find,

weighs about

^ds of the red hot potasiuretted silex, whereas

the silex is only about -^d of the compound ; 2.
the acid requisite to

throw down the preci-

SILEX.

531;

the alkali in
phate, is only half of that which
the compound would require for its saturation ;
S.

the

precipitate,

heat,

is

and,

4.

dried in a moderate

fusible into glass

as the

acids

red

by the blow-pipe

do not take

-,

the alkali

not to take more alkali

glass, they ought
from superpotasiurettcd silex than what would
reduce it to common glass.

from

to find the weight of an

than that of any other of the previous earths, because it enters into combination
It

is

more

atom of

difficult

silex

with only one of the acids, and the proportions

have not yet been ascertained, i have, however, succeeded pretty well by investigating its
relations with potash, lime,

and barytes.

Hav-

of superpotaaiuretted
ing obtained a quantity
silex without any excess of alkali ; that is,

which afforded a

precipitate

with the

least por-

the alkali be in excess, acid

tion of acid (for

if

may be added

without any precipitation), 1

a given weight of the dried comin water, by sulphuric acid

previously
pound
in excess ; the precipitate was heavy and bulky ;
precipitated

remaining on the filter for some time, it

resembled a mass of over-boiled potatoe ; the

after

water being forced out by pressure, a white

subtance remained, which easily leff the filter,
and when dried in a low red heat, left a harsh
giitty

powder, nearly 4ds of the weight of the

EARTHS;

540

compound.
Again, test sulphuric acid was
added
to
the solution, of a given
slowly
weight
of the dry

compound

in

water

mixture manifested acid to the

was considered
weight of pure

to

test liquid, it

The whole

as saturated.

added was found

as soon as the

acid

be sufficient to saturate a

alkali nearly

equal to

-j-d

of that

These experiments
dry compound.
rendered it obvious that only one half of the
of the

alkali

was engaged by the

acid, the other half

remaining with the silex and the conversion

of the precipitate into, glass by the blow-pipe
It remainecf, then^
confirmed the conclusion.
;

to determine

which of the two combinations

As

of alkali and silex was the most simple.

part of the alkali

pound,

and

is

easily

difficultly

drawn from one comfrom

the

other,

the

former must be supposed two atoms of alkali

to one of silex, and the latter one to one.

From

this

it

should seem, that the weight of

is
nearly the same as that of an

an atom of silex

^tom of potash

and the near agreement of

is an

the specific gravities of these two bodies,

argument in favour of the conclusion.

Superpotasiuretted silex exhibited remarkOne hunable results with lime and barytes.

dred measures of the solution, containing 18

5000 grains of

grains dry, were saturated with

lime water, containing 6 grains of lime

-,

the

541

SILEXi
precipitate, filtered

was 19

heat,

and dried

quired 27 grains of
turate

it

The

grains.

test

whereas, the

water took 54

in

muriatic acid to sa*

like

quantity of lime

Here, then,

grains.

low red

residuary liquid re-

it

a[)pcars

atom of the superpotasiuretted silex

must have been decomposed into one atom of
that each

potash,

which remained

atom of potasiuretted
two atoms of lime, and
cipitated.

in the liquidj

silex,

the

and one

which united to

compound was

That the matter

in the liquid

pre-

was

potah, and not lime, was proved by carbonic

acid 9 and the test muriatic acid shewed that

every atom of potash in the liquid took the

The case was
place of two atoms of lime.
different

One hundred

with barytes.

measures

of the solution, containing 18 grains dry, were

saturated with 850 measures of 1.0115 barytic
water, containing 9 dry barytes. The residuary liquid took 28 test acid to saturate it,

and the precipitate dried in a red heat was 20

Here it is evident that one atom of
grains.
from the
barytes had detached one of potash

compound, and taken

its
place ; consequently,
the residue of liquid required the same quanof acid as the barytic water, and the pre-

tity

cipitate

ash,

was a

triple

and barytes

compound

of silex, pot-

one atom of each, consisting

EARTHS.

5i'2

probably ot 9 pans of barytes, 5|

and

silex,

5^ potash.

Upon

the whole, I

that one atom of

silex

am

inclined to believe

weighs nearly 45 times

that of hydrogen.

Silex combines with alumine by heat,

the

compound

and

forms hard infusible bodies, such

as porcelain, earthen ware, bricks, 8jc.

7.

This earth

is

Yttria.

found

at

Ytterby, in Sweden.

It constitutes a portion of tlie mineral

called

of
analyzed by Gadolin, and
gadolinite,
that called i/lirotajitalite, both found in the
first

same mine.

The

earth

may be obtained by

in a mixture
dissolving the pulverized mineral
of nitric and muriatic acids ; the liquor poured

off

is

then evaporated to dryness, the residuum

If ammonia be now added,

dissolved in water.

the earth

is

It is

precipitated.

obtained in the

form of a white powder, said to be of the speIt is infusible by heat, and

4. SI.
cific
gravity

insoluble in water
veral of the acids

but

it

forms

and these

salts

salts

with se-

have mostly

a sweet taste, and are in some instances coloured.

many

They resemble

particulars.

the m.

According

tallic

salts

in

to Klaproth, the

CLUCINE.

S4-3

hydrate of yttria, a dry powder, contains 31

per cent, water this would imply that the
;

atom of
as

it

is

yttria

the

weighs 18, 36, or 53, according

second, or third hydrate ; but

first,

he

finds the

55

yttria,

carbonate of yttria to be 18 acid,

and 27 water: now, supposing the

carbonate to be I atom of acjd, 1 of earth, and
3 of water, and that the acid and water weigh
45, then the atom of earth

53

and

deduced

is

to

be

conclusion agrees with tiie preceding one, which supposes the hydrate to be
the third.
The great specific gravity of the
;

this

earth countenances the notion of the

ing heavy

but

determination

we cannot

till it

is

atom be-

upon the above

supported by more varely

rious experiments.

8. Glucine.

The

earth called glucine (from the sweet-

tasted salts

which

it

tained chiefly from

and

the

emerald.

forms with acids) is obtwo minerals, the beryl

These minerals are consti-

tuted of silex, alumine, and glucine; the two

former being abstracted by the usual processes,
there remains the glucine, a soft white powder,

adhering to the tongue, but without

smell,
vity

is

and

infusible

by heat.

said to be 2.97.

It

is

taste

or

Its specific gra-

insoluble in

wa-

EARTHS.

5i4f

ter.

This earth combines with the acids, with

liquid fixed alkalies,

of ammonia.
yttria,

but

is

and with

In the

last

much more

in carbonate of

alumine and

We

resembles

it

soluble than that earth

ammonia.

derable resemblance in

liquid carbonate

case

its

Glucine has consiproperties both to

yttiia.

have not

data sufficient to

the

find

weight of an atom of glucine but from the

experiments of Vauquelin on the carbonate of
;

(Annal. de Chimie, torn. 26, pages

it should seem to
weigh nearly
or
twice
the
30,
weight of alumine. It is re-

glucine

160 and 172)

markable, too, that the analysis of the beryl,

and of the emerald, give nearly the same quanalumine and glucine, which indicates
tity of
thar the weight of an

atom of the

latter

is

ei-

ther equal to that of the former, or some multiple

of

it.

9.

The

Zircone.

zircon or jargon, and the hyacinfhy are

two precious

stones found chiefly

These contain

a peculiar earth
name of zircone.

ceived the
tained ihus

in

Ceylon.

which has
It

re-

may be ob-

Let one part of zircon in powder,

parts of potash ; then let the

be fused with 6

mass be diffused through a portion of water,

545

ZIRCONE.

which

will dissolve the potash

and

must be dissolved

in

It

somewhat

combi-

muriatic acid, and potash

must be added, which

cone.

its

This residuum

nations, and leave a residuum.

will precipitate the zir-

a fine white powder, insipid, and

When violently
harsh to the feel.

is

it is converted into a kind of

porcelain,
and of the specific gravity 4.35.
hard,
very
Zircone is not soluble in water, but it retains

heated,

.|.

or

air,

of its weight of water when dried in the

-^
and assumes the appearance of gum arable.

Zircone
is in

is

not soluble in liquid alkalies, but it

it adheres to se-

the alkaline carbonates;

veral of the metallic

Zircone unites

oxides.

with acids, and forms with them

of which are insoluble
very soluble.

in water,

They have an

salts,

many

but others are

astringent taste,

resernbling some of the metallic salts.

As tne salts of zircone have not yet been

formed with

sufficient

care

to ascertain the

ratio of their constituent principles,

we can

not

exactly determine the weight of an atom of this

Vauquelin finds 44 carbonic acid and

and
56 zircone in carbonate of zircone ;
water
but, unfortunately, he has not given the acid

earth.

separately from the water.

Allowing the ac-

curacy of the above, and supposing the carbonate to contain 1 atom of water, the weight
of an atom of zircone will be 34

but

if

wc

EARTHS.

546

suppose 2 atoms of water, then the atom of

This last I judge to be
earth comes out 45.
nearest the truth.

It

is

remarkable, that the

hyacinth contains 32 parts of silex and 64 of

zircone, which, according to the above conclusion, corresponds to 1 atom of silex and 2
of zircone, a constitution by no means impro-

bable.

Upon

this principle, the

drate above mentioned,

water and

of zircone,

may
or

gummy hybe 2 atoms of

16 water

45

zircone.

END OF PART SECOND.

EXPLANATION OF FLAXES.
PLATE 5.

Exhibits the various symbols devised to represent the simple and compound elements ; they are nearly
the same as in plate 4, only extended and corrected : they
will be found to agree with the results obtained in the pre-

ceding pages.
Fig.

Simple.

EXPLANATION OF PLATES.
Wt.

Fig.
23. Tungsten

5ti

25. Orium
26. Potash

40
45
42

27. Soda

28

28. Lime
29. MagMsia
30. Barytes
81. Strontites

24

32. Alumine
33. Silex
34. Yltria

15

Titanium

24-.

45
53
30
45

38- Fluoric acid

39. Muriatic acid
40. O.xymuriatic acid

12
17
19

26
31
12,4

47. Carbonic acid

IQ.-t
48. Sulphuroas oxidfe 20

46

Compound;
37. Water

Wt.

>'g.
41. Nitrons pas?
42. Nitrous oxide
43. Nitric acid

44. Oxj'oitric acid

45. Nitrous acid
46. Carbonic oxide

17

Olucine
36. Zircone

6.

68

35.

PLATE

547

8
15

22
29

49. Sulphurous acid

50. S'liphuric acid

27
34

51. Pliusphoronsarid
52. Phosphoric acid
53. Ammonia

32
23

54. Olefia;n gas

55. Carburett^d hyd.
56 Sulphuret. hydr,
57. Supersulph. hydr.
58. Phosphuret. hydr.
59. Phosphor, sulph.
60. Superphos. sulph.

6
6.4>

7.4
14
27
10

22
31

Symbols of compound elements (continued

from Plate 5.)

Wt.

Fig.

50
Hydrate of potash
2. Potasium, or hydro ret
43
of potash
61
3. Carbonate of potash
36
4. Hydrate of soda
1.

5. Sodium, or hydruret
of soda

6. Carbonate of soda
7. Hydrate of lime
8. Carbonate of lime
9. Sulphate of lime
10. Nitrate of lime
11. Muriate of lime
ot barytes

* The

Muriate of barytes
17. Sulphate of alumine

49

18. Nitrate of alun)ine

5,'?

19. IMuriate of

20.

Davy, &c.

ammoniacal

alumine

Alum

29
47
32
43
58

37

272

69,

46

76

or glass

ga?,

37

22. Superpotasiuretted

129

silex

23. Potash, silex, & lime 135

24. Pola^h, silex, & ba-

155

rytes

25. Fluate of silex

26. Subpotasiurelted *

ammonia

by Gay Lussac

60
54

27. Oxymuriate of olefiant gas

olive coloured substance obtained

in

90

16.

21. Potasiurctted silex,

)2. Hydrate
13. Carbonate of barytes 87
14. Sulphate of barytes J02
106
15. Nitrate of barytes

tasium

Wt.

Fig.

by heating
aiwl

41

po.-

Thenard,

EXPLANATION OF PLATES.

5*S

PLATE

Fig. 1, 2, and 3. represent profile views of the

disposition and arrangement oF panicles constituting elastic
fluids, both simple and compuund, but not mixed ; it would
7.

convey an adequate

idea ot the last case, agreeThe principle

maintained, page 1 90.
may, houever, be elucidated by the succeeding figures.
4particles of azote with
Fig. 4. is the representation of

bediflicult to

ably

to the principles

their elastic atmospheres, marked by rays emanating from

the solid central atom ; these ravs being exactly alike in all
the 4 particles, can meet each other, and maintain aa

equilibrium.
Fig, 5. represents 2 atoms of hydrogen drawn in due proportion to those of azote, and coming in contact with them ;
it is obvious that the atoms of hydrogen can apply one to
the other With facility, but can not apply to those of azote,
by reason of the rays not meeting each other in like circumstances ; henct, the cause of the intesine motion which
takes place on the mixture of elastic fluids, till the exterior
particles

come

PLATE

8.

to press

The

on something solid.
16 figures represent the atoms of

first

different elastic fluids, drawn in the centres of squares of

magnitude, so as to be proportionate to the diameters of the atoms as they have been herein determined.
dififerent

to
Fig. I. is the largest ; and they gradually decrease
which IS the srcallest ; namely, as under.

fig.

10,

Fig.

Fig.
1. Soperfliiate of
2. Muriatic acid

silex

3. Carbonic oxide

9.

Oxymurialic acid

10. Nitrous gas

11. Sulphurous acid

4. Carbonic acid

12.

Nitrous oxide

5. Sulphuretted hydrogen
6. Pliosphuretted hydrogen

13.

Ammonia

14.

defiant gaa

Oxygen

7.

Hydrogen

15.

8.

Carburetted hydrogen

16. Azote.

curve lines, by which the boiling point

Fig. 17. exhibits
of liquid solutions of nitric and muriatic acid, and of ammonia, of any strength, may be determined. They arc
results contained in the preceding
representations of the
It
tables relative to these articles.
any point be taken in
one of the curves, and a horizontal line be traced to the

margin, the strenglii per cent, by weight of the liquid will

and if a perpendicular line be traced to the top
be shewn
the temperature at which the liquid of that strength boila in
;

the opeQ

air will

bu found.

APPENDIX.

xJlS

it is
nearly two years since the printing
of this second part commenced, it may be exof chemical
pected that in the rapid progress

investigation,
terval,

some addition

been made

in

the in-

to the stock of facts

and ob-

servations relating to the

has,

more

early subjects

The ground upon which I

herein discussed.

determine the weights of the ultimate particles

of the metals, has not yet been entered upon.
This will occupy a leading place in a second

volume,

when

phurets come

the metallic

to

oxides and sul-

be considered.

It

will

be

observed, that I have seen reason to change

some of the metallic weights which were

and it is probable, that
given in the first part ;
in our future investigations these

may be again

changed ; this will depend upon the precision

with which the proportions of the elements of
the metallic oxides, sulphurets and salts, shall

be obtained.

The

identity of tantalium

and

columbium seems to have been ascertained by

550

APPENDIX,

Mr. Davy, and

Dr. Wollaston.

the French

Gay Lussac and Thenard, have fura number of facts and observations on

chemists
nished

various subjects, resulting from their application of the new metals, potasium and sodium,

and Voltaic

electricity, to

When

the

mind

chemical investiga-

ardently engaged in
prosecuting experimental enquiries., of a new
and extraordinary kind, it is not to be extions.

pected that

mined

new

is

theoretic views can be exa-

in all their relations,

to be consistent with

and formed so as

known and

the well

of chemistry

established facts
facts themselves

all

nor that the

can be ascertained with that

which long experience, an acquaintance with the instruments, and the defects to
precision

which they

are

like observations

liable,

and a comparison of

made by

are calculated to produce.

different

persons,

This may appear

to be a sufficient apology for the differences ob-

served in the results of the above celebrated

chemists, and for the opposition, and some-

times extravagance, of their views.

All the phenomena of combustion are exhi
bited by heating potasium in fluoric acid gas
(superfluate of silex)

though

this

would seem

to intimate that the gas contains oxygen, yet,

as

Mr. Davy properly

observes, heat

and

lighl

APPENDIX.
are merely the
combination.

551

results of the intense

agency of
remarkable that hydrogen
is
given out, yet not so much as would be
given by the action of potasium on water ; it is
variable, and amounts generally to less than
It is

Mr. Davy and tKe

decom-

4th of that quantity.

French chemists agree

position of the acid

the hydrogen

The

fact,

in the belief of a

but

it is

doubtful whether

from the potasium or the acid.

have observed, page 286, of the
is

diminution of a mixture of hydrgen and fluoric

acid gas by electricity, is one of the
strongest
in favour of the notion that the acid
gas contains

oxygen.
Muriatic acid has been a great
object of inMr. Davy's ideas on this subject^
vestigation.
in his Electrochemical Researches, 1808,
were,

that the acid gas contains water in a

state

or, to use

combined

my own

phraseology, that an
atom of real muriatic acid combined with one
;

of water, formed one of the acid gas

in

hence,

the gas, the

potasium
the water, the hydrogen was li-

burning potasium

in

decomposed
berated, and the oxygen joined to the potasium
to form potash, with which the real or
dry
acid immediately united.
plausible

but

it

was

the French chemists

This conclusion was

truly

astonishing to see

draw the same conclusion

552

APPENDIX.

from their views of the subject.

They should

have viewed muriatic acid gas as the pure acid,

which combined with the potash of the potaMr. Davy
sium, and liberated its hydrogen.
has recently written an essav on the oxymuand muriatic acids, with a copy of which
he has just favoured me ; in this, he discards
riatic

his former opinion of the gaseous combination

of acid and water, and adopts another, that

muriatic acid gas is a pure elastic fluid, resulting from the union of hydrogen with oxy muriatic acid,

which

simple substance.

last

he conceives to be a

This notion agrees so

far

with mine, as to make hydrogen the base of

muriatic acid ; but I cannot adopt his constitution of the acid.

Mr. Davy now

considers

the hydrogen liberated, by the combustion of

potasium in muriatic acid gas, as proceeding

from the decomposed acid, and the new compound an oxymuriate o^ potasium. The explanation I prefer

is,

that

from the potasium, and

the hydrogen proceeds

the

undecomposed acid

gas unites to the potash.

As

to

oxymuriatic acid.

Gay Lussac and

Thenard have reported some very striking and

unexpected properties of it which they have
discovered.

They

assert, that dry

oxymuriatic

acid gas was not decomposed by sulphurous

553

APPENDIX.

acid gas, nitrous oxide, carbonic oxide, nor even

nitrous gas, when these were dry ; but ihat it

was immediately decomposed by them if water

These inai) appear to them to
present.

was
be

tacts

but certainly they are too important:,

and some of them too

ditlicultly ascertained, to

be believed merely upon the assertion of any

one. By what means were they found ? What

was the

structure of the apparatus, the quantity

of gases operated upon, the time they were allowed to be in contact, the means employed to
investigate the results, &:c. &;c.
all

To answer

would require
and TheLussac
Gay

these enquiries satisfactorily,

a volume

in detail

yet,

nard have not said one word.

Now, we know

that the facts respecting the mixtures of these

gases over water, are not as above stated.

Mr.

250) that

Davy

observes, (Researches, page

oxygenated muriatic acid and nitrous oxide
" were
mingled in a water ap[ aratus there
" was a
slight appearance ot condensation ;
" but this was most
probably owing to absorp-

**

"

tion

by the water

on agitation, the oxy-

"

genated muriatic acid was absorbed, and the

"
greater part of the nitrous oxide remained un-

" altered."

have repeatedly mixed carbonic

oxide and nitrous gas with oxymuriatic acid in

a water apparatus ; the former mixture ex-

xirrr.NDix.

554-

hibits

no signs of chemical union

seconds

afterwards,

if

chemical action commences,

somewhat slower than

trous gas

dark,

it

but

\vill

the

if

remain

out any change.

that

and

several

upon

latter

it,

continues

of oxygen and ni-

mixture be put

for days, I

The

for

the sun shine

in

the

believe, with-

mixture, or nitrous

gas and oxymuiir.tic acid, in equal measures,

over water, produces an instantaneous union,

muc h more
trous gas,

rapid than that of oxygen and

and which

to all

ni-

appearance seems

independent upon the water.

Now,

if

these

simple experiments give such dilTerent results

in different hands,

what may we expect of the

coniplex experiments, where the gases are previously dried, and then mixed in vessels quite
free

from mercury and water, and lastly exafter such mixture has taken place,

amined

regard being still had to the effects which mercury and water have, or are supposed to have,

upon such mixtures ?

Mr. Davy has given

shew

several

experiments to

combines with hybut none of

produce muriatic acid

that oxymuriatic acid

drogen

to

them appears

to

mc

decisive.

When

equal

measures of hydrogen and oxymuriatic acid

were introduced into an exhausted vessel, and
fired

by an

electric spark, the

result

was a

'

APPENDIX.
slight vapour,

55i

and a condensation of

-^V to

of the volume, the gas remaining being

This

riatic acid.

fact, if

it

^V
mu-

can be relied upon,

it is to
support ; I

favourable to the notion

is

should have expected a condensation of 4 or 4of the total volume on the common hypothesis ;

had described the apparatus and

of
quantity
gases submitted to the experiment,
with the mode of determining the quantity
and quality of the residual gas, it would have

if

the author

assisted in
it is

any future enquiry on the subject ;

an important experiment. Mr.

certainly

Davy

allows the hyperoxymuriate of potash

He supposes the
be attracted by the potasium, or the
potash, rather than by the oxymuriatic acid.
The facts appear to me to draw the other way
to

abound with oxygen.

oxygen

to

much more

powerfully.

We

find

oxymuriatic

acid in conjunction with much oxygen, in several other salts, but potash no where, except

when joined to this acid.

Some observations on

nitric

acid,

and the

compounds of azote and oxygen, have

been made by Gay Lussac, in the 2d vol. of

other

the Memoires d'Arcueil.

He

contends that

one 7neasnre of oxygenous gas unites to two

vieasitres of nitrous gas to form nitric acid, and
to three

measures to form nitrous acid.

Now

556

APPENDIX.

have shewn, page 328, that

oxygen may be combined with
I

gas, or

with 3.5,

with

or

measure of

J.

of nitrous

any intermediate

quantity whatever, according fo circumstances,

which he seems to allow ; what, then, is the

nature of the combinations below

3, of nitrous gas

but the opinion

No

is

answer

<^ounded

that all elastic fluids

one

to another, as

in equal measures,

some simple

to 2,

to 3,

In fact, his notion of measures

relation

2 to

3,

&c.

analogous to
could be proved that
elastic fluids have the same number of atoms

mine of atoms
all

and above

given to this ;
an
upon
hypothesis

combine

or in measures that have

2,

is

in the saine

and

if

is

it

volume, or numbers that are as

I,

2, 3, &c. the two hypotheses would be the

same, except that mine is universal, and his

applies

only

to

elastic

Gay Lussac

fluids.

could not but see (page 188, Part

V7ork) that a similar hypothesis

1.

of this

had been enter-

tained by me, and abandoned as untenable;

however, as he has revived the notion, I shall
make a fev,- observations upon it, though I do
not doubt but he will soon see

its

inadequacy.

Nitrous gas is, according to Gay Lussac,

constituted of equal measures of azote and oxygen, which,

volume

as

when combined, occupy

when

free.

He

the same

quotes Davy,

who

APPENDIX.

found

44-.05

azote,

and

55.95

He

nitrous gas.

weight, in

them

into volumes,

and

100 azote

108.9 oxygen.

to

ever, a mistake
it

finds

in

this

557

if

oxygen by

converts

these

after the rate of

There

is,

how-

properly reduced,

100 azote to 112 oxygen, taking the

gives

specific gravities

according to Biot and Arago.

But that DaVy has overrated the oxygen 12

per cent, he shews by burning potasmm in ni-

when 100 measures afforded

The degree of purity of the

trous gas,

of azote.

just

50

nitrous

and the particulars of the experiment, are

Tiiis one result is to stand

gas,

not mentioned.

(see

mean of

three experiments of Davy,

and
may or may not be more
page 318)

against the

Dr. Henry's

correct, as hereafter shall appear.

analysis of

gas also

ammonia embraces

he

100 measures of ammonia

finds

require 120 of nitrous gas

Now

this will

that of nitrous

apply

to

a very direct manner ;

ammonia is formed of

for their saturation.

Gay

Lussac's theory in

according to him,
measure ot azote and

for,
1

3 of hydrogen, condensed into a volume of 2

it

follows, then, that 100

oxygen

to saturate

ammonia

the hydrogen

require

75

hence, 120

nitrous gas should contain 75 oxygen, or 100

Here
should contain 62.5, instead of 50.
either the theory of

Gay

Lussac, or the expe-

558

APPENDIX.

rience of Dr. Henry, must give results wide of

th truth.
In regard to ammonia too, it may
farther be added, that

azote to hydrogen

neither

nor

to 3,

is
Is

the rate

of

the volume of

ammonia doubled by decomposition, according

experiments of Berthollet, Davy, and
Henry, made with the most scrupulous atten-

to the

tion to accuracy, to

own.

There

which may be added

my

another point of view in

which this theory of Gay Lussac is unfortunate,
in regard to ammonia and nitrous
gas j 1 meais

sure of azote with 3 of hydrogen, forms 2 of

ammonia

and

measure of azote with

oxygen, forms 2 of nitrous gas

of

now, accord-

ing to a well established principle in chemistrv, 1 measure of oxv^en ought to combine

\vith 3 of

hydrogen, or with onehalf as much,

much ; but no one of these com-

or twice as

binations takes place.

my

If

Gay Lussac adopt

conclusions, namely, that 100 measures of

azote require about 250 hydrogen to form ammonia (page 433), and that 100 azote require

about 120 oxygen to form nitrous gas (page

331), he will perceive that the hydrogen of the
former would unite

to the oxygen of the latter,

and form water, leaving no excess of either,

further than the unavoidable errors of expe-

riments might produce

and thus the great

APPENDIX.

559

chemical law would be preserved.

is, I

believe, that gases

exact

measures

in

do not unite

The
in

any one instance

truth

equal or
;

when

do

to

so, it is owing to the inacthey appear

of
our
In no case, perexperiments.
curacy
is there a nearer
approach to mathemahaps,

tical exactness,

oxygen

to 2 of

than

in that

of

measure of

but here, the most

hydrogen ;
I have ever
made, gave 1.97

exact experiments

hydrogen
I shall

to

oxygen.

close this subject,

by presenting two

tables of the elements ot elastic fluids

they

are collected principally from the results

already-

given. in detail, with a few small alterations or

corrections

the utility

chemistry will

of them to practical

be readily recognised.

560

APPENDIX.

Tables of the elements of elastic fluids

rature and pressure.

(TABLE

1.)

at a

mean tempe-

J'U(/r

Siniple

O0(D#O

O0O
CD
o@
U

16

15

18

19.

13

SI

i'2

23

24-

25

Q7

?9

30

31

:,2

J.3

34

J!6

10

.21

19

98

17

(follllipOHIllci

r\

J.3

i9

oo ooo
'7/

(DO CDOCD 00)0

Oxvfe/i
c
-

It'////

^'arbr'y^g

r(U(^/ St^fp'^' ''

i8

-17

ili

"IS

o o#o o oo
(^A-ix'^'^/

ji

((v///

fj/tvs/j/i.

Kvolrcxi'ii

00

CD

/ivr/. \V(dt Sul/iJi.i^p/ii'Sph

66

->/

mt/i ayte kCarbofie

54

5d

f,9

.5

O0 0

.)0

^^^^Sb

Sul/jhur inilipUuspk
60
59

OiniO

r/u/.e.6.

yj

n
10

16

14

15

15

12

^
19

17

27

26

2J
21

2^

2X

25

Pfa/ej.

Hydro o'eii gas

I

Nitrous gas
2

(Carbonic acid e;as

3

JDIAMIETJKRS

OF

]BI.A S TIT
i

ATOMS

I'/^/r

Dalton, John
A new system of chemical

QD
28

philosophy-

v.l
Physical

8t

Applied

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