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T HE AI M this b o ok is to ex hi bit the scie nti c


c o nnex i o n o f the v ari o us s tep s by which o u r kno w

l edge o f the p h eno me na o f h e at has b e en e xt end ed
The rs t o ft h es e s te p s is the inventi o n o fthe th erm

mete r by which the regis tratio n and co mparis o n
o f t em

p e ra tu re s is re nde red p o ssi b l e T h e s e co n d

st ep is th e measu rement o f qu antiti es o f h eat o r

Cal o ri m

etry The wh o l e sci enc e o f heat is fo u nd ed

o n Th e rm o me try and Cal o ri met ry and wh en th es e

op erati o ns are u nd e rst ood we may p ro ce ed to th e


t hi rd s te p which is the i nv es t igati o n o f th ose relati o ns

bet wee n the t h e rmal and the mech ani cal p rop e rti es o f

su b stances which f o rmthe su bj ect o fThe rmo d y namics .

The wh o le o f thi s p art o f the su bj ect de p e nds o n the

c o nside rati o n o f the I ntri nsic Energy o f a s y ste m o f
b o di es as d ep e ndi ng o n th e te m p e ratu re and p h ysical
st at e as well as the fo rmmo ti o n and rel ativ e p o siti o n

, , ,

of th es e b o dies Of this e ne rgy h o wev e r o nl y a

, ,

a r t is a v ail ab l e f o r the p u rp o se o f ro duci n

p p g e

chani c al wo rk and th o u gh the ene rgy its el f is in de

struc ti ble the av ail abl e part is li ab le to di m

, inutio n by
the acti o n o f ce rtain natu ral p ro cess es such as c o n .

d u cti o n and radi ati o n o f h eat fric ti o n and visc osi ty

, , .

roc esses by which ene rgy is re nd ered u navail


a s o u rce o f wo rk are cl ass ed t ogeth er u nde r
e nam e o f the D i ssi pati o n o f Energy and to m th e:

vi P reface .

su bj ect s o f the nex t di visi o n o f the b ook Th e last .

c hapter is dev o te d to the e x p l anati o n o f v ari ous

p h e n o m e n a b y m ean s o f t h e h yp o th e s is t h a t b o d i es
c o nsi s t o f mo l ecules th e mo ti o n o f whi ch co ns t i tu tes

the h eat o f th o se b o dies .

I n o rd er to b ri ng the t re at m e nt o f th ese s u bj ects

wi th i n th e li m its o f this t ex t b ook it has b ee n fo und -


nece ss ary to o m it ev eryt h i ngwhich is no t an essenti al

p art o f th e i ntell e ctu al p ro ce ss b y w hich t he d o c t ri n e s
o f h e at h ave bee n d evel o p ed o r wh ich d o es not
mat eri all y assist the stu de nt in fo rmi ng his o wn j u dg

me nt o n th e se d oct ri ne s .

Fo r this re as o n no ac c o u nt is giv en o f sev e ral v ery

i mp o rtant exp e ri ments and many illust rati o ns o f the

th eo ry o f h eat by me ans o f natu ral p h e no mena are


om i tt e d The stud e nt howev e r will nd this p art of

, ,

th e s u bj ect t reat ed at great e r l e n th in s eve ral e x c el


l ent wo rks o n the same su bj ect which h ave l at ely

A full acc o u nt o f the mo st i mp o rtant expe ri ments

o n the e f fects o f h e at wi ll be fo u nd i n D ix o n 3
Treatis e o n H eat ( H o dges Sm

ith ,

P ro fess o rB al fo u r S tewart s t reati se c o ntains all that '

is nece ssary to b e k nown i n o rde r to mak e e xp eri o

ments o n h eat The st u dent may be als o referre d to


D esc hanel s N atu ral Phi l o s o p h y P art I I transl at ed

, .

by P ro fesso r Evere tt who has add e d a chap ter on

Th erm o d y namics ; to P ro fesso rRanki ne s wo rk o n the

S te amEngi ne i n which h e will nd th e rs t s yst e m a ti c

t reatis e o n th erm o d ynamics ; to P ro fess o r Tait s The r

mo d ynamics whic h co ntains an h is t o rical s k etch o f

the su bj e ct as we ll as the m athe m


, atical inv esti gati o ns ;

and to P rofe ss o r Ty nd all s wo rk o n H e at as a M ode

o f Mo ti o n} i n which the d o ct ri nes o f th e sci ence ar e

fo rc ibl y im p res se d o n th e m i nd b y w ell ch o s e n i lluS - o



M eaning ofthe wo rd Tem p erat ure

The M ercurial Therm om eter

H eat as a Quanti ty .

D iffusion of H eat by Condu cti o n and Radi ati on .

The three Physical States ofB odies



D eniti on ofH igher and Lower Temperatu re

Tem peratu res o f Re f
e re nce

D ifferent Therm om etri c S c ales

C onstruc tion o fa Ther om m eter

The Air Therm om eter

Other M ethods ofAsc ertaini ng Tem p eratures



t t
S elec i on o fa Uni o f H ea t
t m
All H ea is ofthe sa e K ind
I ce C alori e ers
Bunsen s Calori

Method ofM ixture
Deni tions o fThermal Capaci ty and

Latent H eat of Steam

Contents .



Measurement of Quanti ti es
The Uni ts ofL ength, M ass, and Ti me, and their D erived Units .

M easurem ent ofForce

Work and Energy

Principle ofthe Conservation ofEnergy



Longi tudinal Pressure and Tension

D eni tion ofa Fluid Hydrostati c Pressure

Work done by a Piston on a Flui d

W att 5 Indi cator and the Indi cator Diagram

Elasti ci ty ofa Flui d




Relati on b etween V olum e, Pressure, and Te mperature

Iso thermal L ines ofa G as

I so her mal L i nes ofa V apour mContac t with its Liquid
SteamL ine and W ater L ine
Co nti nui ty o f the Li q ui d and Gaseo us S tates Exp eriments of .

Cagniard de la Tour and Andrews



Proper i es o f3 Su
. bstance when heat is prevented fromentering o r
leaving i t
The Adi abatic L ines are S teep er than the Iso thermals
D iagra sho wi ng the Eec ts of H eat on Water
Contents .



Carac t s Engine

S ec o nd Law ofTher odyna i csm m

C arnot s Functi on and Thomson s Ab solute Scale o fTem t

p era ure

M axi u Efciency of a H eat Engine
Thermodynami c Scale of Temp eratu re
En tropy
Ficti ti ous Thermal Lines




F our Thermodynamic Relations

The two Modes o fD eni ng Specic H eat
Th e two M o des ofD ening Elasti city


L A T E N T H EA T , .

Relati on between the Latent Heat andthe Alterati on o fthe V olume

ofthe Substanc e during a Change of State

L o wering o f the Freezi ng Point by Pressure



Calculati on o fthe Speci c H eat ofAir



I n rinsi c Energy dened
Available Energy
Dissi pation o fEnergy
Mechanical and Therm al Analogies

Prof Gibbs Therm o dynam i c M odel

x Ca nto :25 .



Theory ofa Fluid rushing through a Po ro us Plug

Deter ination ofthe Absolute S cale o fTe perature m



Pri nciple o fthe Baro meter

The B arometer in a D iving Bell
H eight ofthe H om ogeneous Atm osphere

H eight ofa M ountain found by the B arometer



Waves of Permanent Type

V l
e oc i ty of Sound


RA I A I .

D enition of Radiation
I nterference
Dif ferent Kinds o fRadiati on
Prevost s Theo ry ofExchanges

Rate ofCooling
Effects ofRadiation on Ther om eters m
Contents . xl



How they are Produc ed 2 50

J oule

5 D etermi nati o n of th e Po int of M ammumD ensi ty of Water 2 52



t t
C onduc i on hrough a Plate
D ifferent M easures o f Cond ctivi ty

C o nd cti on in a S o lid

S ketch o fFo uriers Theory

H arm o ni c D istributions o fTem p eratu re

S teady and Peri odi c Flow o fH eat

D eterm i nati on ofthe Therm al C ondu cti vi ty ofBodies
A ppli cati ons ofthe Theo ry



ci ent of Diffusio n
Co ef
Researches o fG raha and L oschmidt



Super cial Energy and Sup erc ial Tensio n

Rise of a Liquid m a Tub e
Evapo rati on and C ondensati on as Affected by Capillarity
Table o f Supercial Tensio n


11 0m m M RY O F THE co m m
o n OF

Mah a b of a

Bo dy
Ki netie Theory of Gases
Dedu c tion o fthe l z v s of a ses

Limi tatio n of the Second Law a

The Properti es ofMo lec ula
r m

H E A T .



mCTION be twee n hot bodies and col d ones is

all and is ass oci at ed in o ur m inds wi th the

sensatio ns which we e xperience in touching

es acco rdi ng as they are ho t o r cold The
, .

these sensatio ns is s usceptible o fdegrees so that ,

timat e one body to be hott er o r colder than

the touch The words ho t warm cool cold
, , , ,

ou r mi nds wi th a series o fse nsatio ns which

indic at e a correspo nding series of s tates o f

respect to heat .

wo rds therefo re as the names o f these

, ,

states o f the obj ect o r i n scie ntic l angu age they are the
, , ,

names of Tempe rature s the wo rd ho t i ndicating a high


t empe ratu re col d a low temperature and the int ermediat e

, ,

t erms i ntermedi ate temperatures w hile the word t emperature


itselfis a ge neral t erm intended to apply t o any o ne o f these

sa tes o f the obj ect
2 I ntroducti on .

tempe ratures We may give names t o any nu mber of


particular degrees o f t emperature and exp res s any other ,

t empe rature by its relative plac e among these degrees .

The t emperatu re o fa bo dy th ere fo re i s a qu anti ty which

, ,

i ndicates how ho t or how co ld the body is .

Whe n we say that the temperat ure o f o ne body is higher

o r lower th an th at o fanothe r we mean that the rs t body is

ho tt er o r colder than th e seco nd bu t we al so imply that we


re fer the state o f both bodies to a ce rtai n scal e o f tempe

rature s . By the u se the refore of the wo rd t emperature
, , ,

we x in o ur minds the convictio n that it is po ssible not ,

only to feel bu t t o measure how ho t a body is

, , .

Words of this kind which express the same things as


the word s o f p rimi tive langu age b u t exp res s them in a way

susceptible o f accurate nume rical s tatement are called ,

scie ntic l te rms because they contribu t e t o the growth of


scie nc e .

We might suppose th at a perso n who has carefu lly cul

ti vated his senses would be able by simply touching an
obj ec t to assign its place i n a scale o f tempe ratures but i t is ,

fo und by expe riment that the es tim ate f ormed o ftemperature

by the touch depe nds upo n a great varie ty o fcircumstances ,

some of these relati ng to the texture or co nsiste ncy o f the

obj ect and some to the tempe rature o f the h and o r the

state ofheal th o fthe perso n who m akes the estimate .

For instance if the temperature of a piece o fwood were


the same as that o f a pi ece of iro n and m u ch higher than ,

that of the hand we should estimate the iro n to be hotter


an the wood because it parts wi th its heat m ore readily to


the hand where as if their tem peratures were equal and

, ,

much lower than that o f the h and we sho uld estimate the ,

iro n to be colder than the wo od .

There 1s anorer co m mo n expenmeng in whic h we plaoe

Ye eratu re '

ti me. If we then dip bo th h ands in the same basin o f

lukewarm water alt ernately or even at once it will appear
, ,

c old to the warmed h and and ho t t o the cooled hand .

I n fact o ur se nsations o f every kind depe nd upo n so


m any variable co ndi tio ns th at for all scie ntic purposes we


p refer to form o ur estimat e o f the s tate of bodies from their

observed actio n o n some apparatu s who se co ndi tio ns are
more simple and les s v ariable than those o f our own se nses .

The prope rties o f mo st substance s vary when their tem

p e ra ture v aries
. Some o f t hese v ari ati o ns are ab ru p t and ,

serve to i ndicate part icular t emperatures as points o f t e

fere nce ; othe rs are co nti nu ous and serve to meas ure othe r

tempe ratures by compariso n with the temperatures of refer

e nce .

Fo r instance the tempe rature at which ice melts is found


to be always the same u nde ro rdinary ci rcumstances tho ugh , ,

as we shall see it is slightly al te red by change o f p ressure

, .

The t empe rature o f s t eam which issues from boiling wate r

is al so constant when the pressure is constant .

These two phenome na therefo re the mel ting of ice and
o a r
the boiling w t e indicate in a visrh le manner two tempe
ratures which we m ay use as points ofrefe rence the positi on ,

o fwhich depends o n the prope rties o f water and no t o n the

c o ndi tions o f o ur sense s.

O ther ch anges of state which take place at t empe ratures

mo re o r less de ni t e such as the melti ng of wax o r o f

lead and the boiling o f liqu ids o f deni te compositi on are

, ,

o ccasio nally u sed to indicate when these temperatures are

attai ned, bu t the melti ng o f ice and the boili ng o f pure

water at a standard pressu re rem ai n the most important
t emperature s o fre f e re nce in mode rn sci enc e .

Th ese phenome na of ch ange of state serve to i ndicate

only a certain numbe r o f part icular temperatures In .

o rde r to meas u re t emperatu res in ge ne ral we mu st avail


ourselves o f some p roperty o f a s ubs t ance which alters

e ontinuo usly wi th the tempe rature .

a 3
4 I nt roduc tion .

The volume o f most s u bstances i ncreases continuo usly

as the t emp e ratu re rises the p ress u re remaining constant

There are exceptions to this rule and the di latations of ,

differe nt s ubstances are no t in ge neral in the same propor

tio n bu t any substance in which an increase o ftemperature ,

howeve r small p rodu ces an increase o fvolume m

, ay be u sed
to indicate change s o ftemperature .

For instance mercury and glass bo th expand whe n heated,


but the dilatatio n o f mercury is greate r than that o f glass .

Hence ifa col d glass vessel be lled wi th cold mercury and ,

if the vessel and the mercury in i t are then equally h eat ed ,

the gl ass vessel will expand bu t the mercury will expand


more so that the vessel will no longe r contai n the mercury

, .

If the vessel be provided with a lo ng neck the mercury ,

forced ou t o fthe vessel will rise in the neck and if the neck ,

is a narrow tube nely grad uat ed t he amount o f me rcury


forced out of the vessel m ay be accurat ely measured .

This is the principle o f the co mmo n mercurial therm o

me ter the co nstru ction o f which will be afterwards more

minu tely descri bed At prese nt we consider i t si mply as an


i nstrument the indications of which vary whe n the tempts

rature varies but are always the same when the t emperature

of the instrument is the same .

The dilatatio n ofo ther liquids as well as th at o f solids and


of gases m ,
ay be used f or the rmometric p urpo se s and the ,

thermo electric properties o fmetals and the variation oftheir


elec tric resis tance wi th tempe ratu re are also employed in ,

researches o n heat We m u s t rst however study the theory

, ,

o ftem pe ratu re in itsel f before we examine the properties of

th Ferent subst ames as rel at ed t o tempe rature and f o r this ,

p u rpose we sh all use t he particular mercurial the rmom eter

Tire Thermometer .


Thi s thermome te r co nsis ts o f a glass tube te rminating in

a b ulb the bulb and part o f the tube being lled with

mercury and the res t o f the tube being empty We shall

, .

suppose the tu be to he graduated in any manner so th at the

heigh t of the mercury in the tube may be obse rved and
reco rded We sh all no t however assume either that the
, ,

tu be is o f u ni fo rm sec tion o r that the degrees are of equal

size so th at t he scale ofthis p r
imitive the rmome te r must be
regarded as completely arbitr ary By means ofo ur thermo

meter we can ascertain whe ther one temperature is higheror

lowe r th an ano the r o r equal to it but we cannot asse rt that
, ,

the di ffere nce be tween two t empe ratures A and B is greater , ,

o r le ss th an the di fference between two other ternperatures .

C and D .

We shall supp ose that in eve ry o b servati on the tem perature

o f the mercu r y a n d the gl ass is eq u al and u nifo rm ove r the
who le thermomete r The reading o f the scale will then

depend o n the temperatu re o f the thermome t er and since , ,

we have no t yet es tablished any more perfec t thermometric

scale we sh all call thi s re adi ng p rovisio nally
the temperature

by the arbitrary scale o fthe thermometer .

Th e reading o fa thermometer i ndicates p rimarily its own

temperature but if we bring the thermomete r i nto intimate

co ntact wi th ano ther su bstance as for ins tance if we plunge


it into a liqui d fo r a s uf cie nt time we nd that the reading


of the the rmome te r beco mes highe r o r lowe r accordi ng as

the liqui d is hott er o r colde r than the thermome ter and th at ,

ifwe leave the thermome t erin co ntac t with the su bstance fo r

a suf cient time the readi ng becomes statio nary Let us .

call this u ltimate reading the temperature of the sub stance


We shall nd as we go o n that we h ave a right to d o 8 0 .

Let us no w take a vessel o f wate r which we shall suppose

to be at the t emperature o f the air so th at if le f , t to itsel f it
6 I ntroduc ti on

would rem ai n at the same t emperature Take ano the r .

smaller vessel o f thi n shee t copper or ti n plat e and ll i t ,

with water oil o r any o the r liqu id and immerse it in the

, , ,

larger ves sel o fwat er for a certai n time Then ifby means .

o f ou r the rmome t er we regi st er the t emperatures of the

liquids in the two vessels be fo re and aft er the immersio n of

the copper ve ssel we nd th at if they are originally at th e

same tempe rature the t emperature ofbot h remains the sam e ,

but th at ifo ne is at a hi ghe r tempe ratu re than the oth er that ,

which has the higher tempe rature becom es colder and that
which has the lowe r tempe rat ure beco mes hotter so that if ,

they co nti nu e in contact fo r a su f cient time they arrive at

last at the same temperatu re aft e r which no change o f term

p eratu re t akes pl ace .

The loss o ftemperature by the hot body is no t in general

equal to the gain of tempe ratu re by the cold body but i t is ,

m anifest that the two sim ultaneous phe nomena are due to
one cause and this cause m
ay be descr i bed as the passage
of Heat f rom the hot b ody to the cold o ne .

As this is the rst time we h ave u sed the word H eat let us ,

examine what we mean by it .

We nd the cooling o f a hot body and the heating of

a cold body h appe ni ng sim ultaneously as parts o f the same
phenomenon and we describe thi s phenome no n as the pos

sage ofheat from the hot body t o the cold o ne H eat then .
, ,

is someth ing which may be transferred from o ne body to

ano ther so as to diminish the qu an ti ty o f heat in t he rst

and incre ase th at in the seco nd by the same am o u nt .

When heat is comm unicated to a body the t emperatu re ,

of the body is gener ally incre ased bu t some time s o the r


effects are produ ced such as change o f s tate Whe n heat

leaves a body, there is ei ther a fall o f t em

perature o r a
o f sa te I f no
. he at e nte rs o r le aves a body and ,

or mechanical actio ns take place

H eat as a Q uanti t y
Heat there fo re may pass out o f o ne body into another
, ,

ju st as water m ay be poured f rom o ne vessel i nto ano ther ,

and i t m ay be retai ned in a body f o r any time jus t as wate r

may be kept in a vessel We have there fore a righ t to speak


ofheat as o f a m easurable q uanti ty and to treat i t m athem

, a
tically lik e o ther measu rable quanti ties so long as it co ntinues
t o exist as heat We sh all nd however th at we have no
, ,

right to treat heat as a substance fo r it m

ay be transf
into something w hich is not heat and is certa no t a

s ubstance at all namely mechanical work

, , .

We must remember the refore that though we admit heat

, ,

to the ti tle of a measurable qu antity we m ust no t g i ve i t ,

rank as a substance b u t must hold o ur mi nds i n su spense


till we have further evide nce as to the natu re o fheat .

Such evidence is furnished by expe rime nts on fric tion in ,

wh ich mechanical work inst ead o f being transmitted from


one p art ofa m achine t o anothe r is app arently lost while , ,

at the same time and in the same place , heat is ge ne rated ,


the amou nt o f heat being in an exact proportio n to the

am ou nt of work lo st We have there fore reaso n t o believe
, ,

that heat is o f the same nature as mechanical work that is , ,

it is o ne o fthe fo rms o f Energy .

In the eigh tee nth ce ntu ry whe n many new facts were

being discove red relating t o the actio n o f heat o n bodies ,

and when at the same time great p rogres s was being made
in the knowledge o f the chemical actio n o f substances the ,

word Caloric was introduced to signify heat as a measurable

quantity So l ong as the word de noted no thi ng more th an

this i t might be usefully employed bu t the form o f the wo rd

, ,

accommod at ed itself to the t endency o f the chemis ts o f that

time to seek for new imponderable subs tances so that ,

the word calo ric came t o connote no t merely heat bu t heat


as an indes tru c tible impo nde rable f l uid i nsinu ating i tself ,

into the po res o f bodies dilati ng and dissolving them and

, ,

A t tive termis one whi ch deno tes a subj ect and implies an
c onno a
8 I ntrodwt ion .

ultimately vapo ris ing them c ombining wi th bodi es in d enit e


quanti ties and so becoming l ate nt and reappearing when

, ,

th ese bodie s alter their condi t ion In fact the wo rd cal oric
, ,

when o nce introd uced soo n came to imply the rec ognwed

existence o fso methi ng m aterial though probably of a more


subtle nature than the then newly discovered gases Caloric


bled these gases in bei ng i nvisible and in i ts pro perty

o f becoming xed i n solid bodies It di ffe red from them .

because its weight could no t be detected by the nest

bal nces bu t there was no doubt in the minds o f many
a ,

emi ne nt men that calo ric was a uid pervading all bo dies ,
probably the cause o fall repulsion and possibly eve n o f the ,

exte nsion o f bodie s in space .

Si nce ideas o f t his ki nd have always been co nnecte d

with the word caloric and the word itself has been in no

slight degree the means o f embodying and propagating

these ideas and since all these ideas are now k nown to be

false we shall avoid as m uch as p o ssible the use o f the


word calo ric in treati ng o f heat We shall nd it useful .


however when we wish to refer to the e rroneous theory


which supposes heat to be a subs tance to ( a ll i t the ,

Caloric Theo ry o f Heat


The wo rd heat tho ugh a p rimitive word and no t a


scie ntic t erm will be fo und sufcie ntly free from ambigui ty

when we u se it to exp ress a measurable quanti ty because i t ,

will be associated wi th wo rds exp ressive o f quanti ty indi ,

cati ng how m u ch heat we are spe aking o f

We have no thi ng to do with the wo rd heat as an abstrac t

term si gnif ying the propert y o f hot th ings and when we ,

might say a certain heat as the heat o f new milk we shall

, ,

always use the more sci entic wo rd temperatu re and speak ,

o fthe temper ature ofnew milk .

We shall neve r u se the wo rd h eat to deno t e the sensati on

used in ordinary langu a e
g ,

3 unless whe n the sensation ,

c ause as
M easu rement of H eat .

in the ca se o f pai n 81 C The o nly name we h ave fo r this

, .

sensation is the sensatio n o fheat .

When we require an adj ec tive to de note th at a phe

no m eno n is related to heat we sh all call i t a Ma m a!
phe nomeno n as fo r i nstance we shall speak o fthe the rmal
, , ,

co ndu ctivity o f a su bstance o r o f thermal radiation to dis

tinguish the co nd uction and radiation o f heat f rom the

c ond uc tio n o f electrici ty o r the radiatio n o f light The .

science o fheat has bee n called ( by Dr Whewell and o thers )


Thermo tics and the theo ry of heat as a fo rm o f e ne rgy is


c alled Thermodynamics In the same way the theo ry o f the


equilibri um o fheat migh t be called Thermostatics and th at ,

o f the motio n of heat The rmokinematics .

The i nstru me nt by which the t empe rature o f b o dies is

regis t ered is called a The rmomet e r or measu rer o f warmth ,

and the me thod o fco nstructi ng and u si ng thermomet ers m ay

be called Thermome try .

The instrument by which quantities o f heat are measured

is ca lled a C alo rimeter probably bec ause it was invented at

a time when heat was called Calo ric The name however
, ,

is no w well es tabli shed and is a co nve nient o ne as i ts form

, ,

is suf ciently disti nct from that o f the wo rd Thermometer .

The m e thod o f measuring heat may be called Calo rimetry .

A c ertain quanti ty o f heat with which all other quanti ties


are compared is c alled a The rm al U ni t Thi s is the quanti ty



o f heat req u ired to produ c e a particular ef fec t such as to ,

mel t a pound of ice o r to raise a po und o f water from o ne


de ned tempe ratu re to another dened te mperatu re A par .

tic ulartherm al u nit has been call ed by some au thors a C alor

ie .

We have now ob tai ned two o f the fundame ntal ideas

of t he scie nce o f heat the idea o f temperatu re o r the ,

property o fa body co nsidered wi th re fe re nce to i ts powe r of

heating o ther bodies and the idea ofh eat as a meas urable
quantity which may be transferred from ho tt er bodies to

c o lder ones. We sh all co nsider the furthe r develOptnent o f

W e id eas in the chapters o n Thermome try and Calorimetry ,
o r physi cal mt e ot the

ho dy .

to a co lde r bo dy .

nised C o nduction C o nvectio n and Radiation
, , .

Co nduct i on is the ow ofheat throu gh an unequally s

b ody from place s o fhigher to places ofIowa tempm ure

Co nvectio n 13 the motion of the hot body im


v s

hea with 1t I fby this m onon it is brought new bodies co l der

t elt it will warm them faster than if it had no t been

m ore by the moon the ho t ana ce from o ne


pl ace to an o ther , tho ugh the ultimate tra der o f h eat may

y l oses heat, and the co lder

D zj
i mon qfH

eat . 1I

place tend to bec ome eq ual We sh all no t at prese nt discus s


the co nvec tio n of heat becau se it is no t a pu rely thermal


phenomenon since i t depe nds o n a ho t subs tance being


carried fro m o ne place t o another either by hum an effort

, ,

as when a ho t iro n is take n o u t o fthe re and p ut into the

o f the heated su bstance ,

er heated by co ntact with the bottom of a


o n the re exp and s as it b ecomes warmed

, ,

ascending current m aki ng way f

, o r colder and

e user water to descend and take its place I n .

case of convectio n the ultimate and o nly di rect

transfer o fheat is due to co ndu ctio n and the o nly e ffect o f

the motio n of the h ot substance is to bri ng the u nequ ally

er so as to f
, acilitate the
accept the cond uctio n o f heat

as a fact witho u t at present atte mpting to f

, orm any theory
the p rocess by which it takes place We .

fusi on of h eat by condue

rt that in the di f
o f heat is entirely from the hotte r to the
is th at the amou nt of heat

the hotter to the colder body is inv ariably

the amount, if any trans ferred fro m the colder


experime nts which we have described heat p asses ,

body into another through an i nte rve ning sub

el o fw ater through the gl ass bulb of a

me rc ury i nsi de the bulb .

This p roces s by which heat passes from hotter to colder


parts o f a body is c alled the c o ndu ction of bes t When


heat is passing thro ugh a body by co nductio n the tem ,

peratur e o f t he body m u st be g r eater in the p arts f

r om
which the heat comes than in those to which it tends ,

and the quantity o f heat whic h passes thro ugh any thin

layer of the substance depe nds on the differe nce of the

12 I ntroduc tio n .

if we put a silver spoo n i nto a cup of hot tea,

o f the spoo n in the tea soo n bec o m

in t.

A to B The h t h
. m
warms a a m
little , and so makes 3 warmer t han

end o f the Spoo n wl in co urse 01

The es sential
equisi t e to the con r

auc tion o f heat is ,

that i n every part
o f i ts course the heat

mu st p ass fro mhott er to colder parts o f the body N o .

heat c an be co nducted as far as 5: till A has bee n a

hotte r t han a 8 th an c 0 than n and D than 5 To d o

, , , .

this req ui re s a certain am ou nt o f heat to be ex pende d in

warming in successio n all these i nt ermediat e parts of the
spoo n so th at fo r some time afte r the spoo n is place d in

the cup no al teration o f temperature can be pe rceived at

the end o fthe spoo n .

H ence we m ay de ne co nductio n as the passage o f heat

th ro ugh a body depending o n ineq uali ty o f temperature in
adj acent p arts o fthe body .

When any part o f a bo dy is heated by

o f the body through which

be hott er than i tself md the parts higher up the s h a m o f


heat edil h ott er .

I f we no w try the expe rime nt o f the spoo n in the teacu p

wi th a German silver spoo n alo ng wi th the silver
shall nd that the end of the silver spoon bec omes
; and
be able to perceive any
Radi ati on . t3

il e
s v r, and Ge rm an sil ver q uicker th an bone or horn The .

reason why the end o f t he spoo n neve r gets as ho t as the

tea is that the i ntermediate part s o f the spoo n are coolingr

partly by giving their bes t t o the air in co ntac t with them ,

and partly by radiatio n ou t i nt o space .

To show th at the rst e ffect o f heat o n the the rmome te r

.s to warm the mat e rial o f which the b ulb is composed and ,

that the heat cannot reach the uid i nside till the bu lb has
bee n warmed take a therm ome te r wi th a large bulb w atch
, ,

the uid in the tube and dash a little hot water ove r the

bulb The uid will fall in the tu be befo re i t begi ns to


rise showing that the b u lb began t o expand bef

ore the uid
expanded .


On winte r we feel the s un s rays warm eve n

day in

whe n water is freezing and ice is h ard and dry .

If we mak e use o f a the rmome t er we nd that if t he ,

i t i t indicat e s a tempe ratu re far above


air immediately s urro undi ng the bu lb is

elow freezi ng The h eat therefore which
, ,

ich the the rmome te r also responds is no t ,

warmer than
heat reaches
which i t warms wi thou t warming the air through

p asses is called radi ation Substance s which

, .

radi atio n taking place th rough them are called

heat to pass
becomi ng themselves ho t are called
which passe s th rough the medium
is generally called Radiant He at ,

is radiant i t posses se s none o f th e

guish heat from o therfo rms of e nergy ,

which it passes .
14 I nt raducti m .

and the o ther physi cal prope rti es o fthe body are in no way ,

aected by the pas sage o f the radiatio n p rovided the body


is perfectly diatherm anous If the body is no t perfe ctly


diathe rm anous it stops mo re o r less o f t he radiation and ,

b ecomes heated itself instead o f transmitti ng the who le


radi atio n to bodies beyo nd i t .

The distinguishing ch arac teristic o f radi ant heat is that ,

i t travels in m y : like light whe nce t he,name radiant T hes e .

rays have all the physic al prope rtie s o frays o f ligh t and are ,

capable o freexi o n refractio n i nte rfe re nce and polari ation

, ,
s , .

Th ey m ay be divided into dif fere nt ki nds by the p rism as ,

light is divided into its compone nt colou rs and some o f the ,

heat rays are ide ntical wi th the rays o f ligh t while other

kinds of heat rays m ake no imp ressio n o n our eyes Fo r


i nstance ifwe take a glass co nve x le ns and place it in the

, ,

s un s rays a body placed at the focu s where a small i m

o f the sun i s fo rmed will be inte nsely h ea t ed while the le ns ,

itselfand the air through which the rays p ass remain quit e
cold I f we allow the rays before they reach the focus to

fall o n the surf ace o fwate r so that the ray s m eet i n a focu s

in the interio r o f the water then if the w at er is qui te cl ear


at the f ocus i t will remain tranqu il b ut ifwe make the focus


fall u po n a mo t e in the wat e r the rays will be stopped the

, ,

mote will be heated and wi ll cause the water nex t it to

expand and so an upward cu rre nt will be produced and the
, ,

more will begin to rise in the wate r Th is shows that it .

is only when the radiation is W ed that i t has any eec t in


heating what it falls o n .

By means o fany regular co ncave piece of metal such as ,

the scale of a bal ance pressed whe n ho t against a clear


sheet o fice rst on o ne si de and then o n the o ther i t is easy

, ,

to m ake a lens o fice which m ay be used o n a sunny day as

was fo r medy
e i nvented by
Radiati on . 15

at ice and make a at surface o n i t parallel to the origi nal ,

surface o f the lake o r to the layers o f bubbles gene rally


fou nd i n large blocks ; then let the co nverging rays o f the

su n from an ordinary burning glas s f all o n this surface and ,

come to a focus within the ice The ice no t bei ng per .


fectly diatherm

anous will be warmed by the rays bu t m uch

, ,

more at the focus than anywhere else Thus the ice will .

begin to melt at the foc us in the i nte rior o f its s ubstance ,

and as it does so the portio ns which melt rst are regu

, ,

larly fo rmed crystals and so we see in the path o f the beam


a nu mber o f six rayed stars which are hollows cut o u t of


the i c e and co ntaining water This w ater however does .

, ,

no t qu ite ll them becau se the wate r is o f less b ulk that:


t he ice o f which it was m ade so that p arts o f the s tars are


Experiments the heati ng effects o f radiation show


that not only the sun bu t all ho t bodies emit radiatio n When .

the b o dy is h ot enough its radi atio ns become visi ble and

, ,

the body is said to be red hot Whe n it is still hotte r it .

sends forth not o nly red rays but ray s o f every c olo ur and
, ,

i t is the n said to be white ho t Whe n a body is too cold .

to shine visibly i t still shines wi th i nvisible heati ng rays

, ,

which c an be perceived by a s u ffi c ie ntly de licate thermo

meter and it does no t appear that any body c an be so

co ld as no t to send forth radiati ons The reason why all .

bodi e s do no t appear to shine is that o ur eyes are se nsi tive ,

only to particular kinds o f rays and we o nly see by means ,

of r ays o f these ki nds coming f rom some very hot body

, ,

either directly or after reexio n or scatte ring at the surface

d ot her bodies .

We shall see that the phrases radiation o f heat and t a

diant heat are no t quite scientically correct and m u st be

used with caution Heat is c erta ly comm u nicat ed from


one body to ano ther by a process which we call ra

diatio n which takes place i n the regio n be twee n the

two bo di es .We have no right however to speak o f this , ,

16 I ntroducti on .

process o f radiation as heat We have de ned.

as i t exists in hot bodies and we have see n tha t all


is o f the same ki nd But the


diffe rs from heat as we have de ned ir rst in no t ,

the body hot through which i t passes ; and in being ,

many diffe rent kinds Hence we shall generally speak


radiatio n and whe n we speak o f rad iant heat w e do I


mean to imply the exis te nce o f a new kind o f heat but ,

co nsider radiation in its thermal aspect .


Bodies are found t o behave in diffe re nt w avs u nder I

actio n o ff orces Ifwe cause a lo ngitudinal pres sure to l

o n a body i n one directio n by means o f a pair o f pi ncer s

a vice the body be ing f

ree t o move in all o the r di re c tiom

we nd that if the body is a piece o fcold iron there is ve

li t tle effec t produ ced unless the pressure he very great

the body is a piece o f india rubber i t is compressed in tl


direc tion o f i ts le ngth and bulges o u t at the sides bu t ,

soon co mes int o a s tate o fequilibrium in which i t co ntinu ,


to su ppo rt the pressure ; bu t ifwe s ubs ti tu t e water fo r tl

india rubber we canno t pe rform the xperime nt for tl
e ,

water ows away late rally and the j aws o f the pince

come toge ther wi thou t havi ng exerted any apprec iab

pressure .

Bo dies which c an sustain a longitudinal pres sure howen ,

small t hat pressu re m ay be wi thout being supported by


lateral pre ssure are called solid bodies

Those whit .

canno t do so are called uids We shall see that in a u i


at rest the pressure at any point mus t be eq ual in all direr

tions and this p ressure is called the p ress ure o fthe ui d
S olids, L iquids, and Gases . 17

Fluids having thi s property are called liquids Water is a .

liq u id and ifwe p ut a li ttle wat e r into a bottle the water


will lie at the bottom ofthe bo t tle and will be separated by ,

a distinct surface from the air o r the gaseous water subs tance -

If, the contrary the uid which we put i nto the clo sed
on ,

vessel be o ne of the seco nd class then h owever small a , , .

portio n we introd uce i t will expand and ll the vessel o r at

, ,

least as much ofi t as is no t o ccu pied by a liquid .

g a
Fluids having this property are called gas es Air is a
, a n d if we rst exhaust the air f ro a vessel an

introduce the smallest quanti ty o fair the airwill immediately

d the n m .

expand till it lls the whole vessel so that there is as m uch

air in a cubic inc h in o ne part of the vessel as in another _

Hence a gas cannot like a liq ui d be kept in an ope n

, ,

mo u thed vessel .

The distinction therefore between a gas and a liquid is

, ,

that h oweverlarge the space m

ay be i nto which a porti on of

g a s is in troduced the,gas will exp and and exert p ress ure o n

every part ofits bo undary whereas a liquid will no t expand

more th an a ve ry sm all ac o n o f its bu lk eve n whe n the ,

pressure is red uced to ze ro ; and some liquids can even

sus tai n a hydros tatic tension or negative pressure with out , ,

their parts being sep arat ed .

The three principal states in which bodies are fo und are ,

therefo re the solid the liquid and the gaseou s states

, , , .

M ost su bstances are capable o f exist ing in all these states,

as, f o r ins tance wate r exists in the f
, orms o f ice water and , ,

steam . A few solids such as carbo n h ave no t yet been

, ,

melted and a few gases such as oxygen hydrogen and , , ,

nitrogen have no t yet been li queed or solidied but these

, ,

may be consi de red as exceptio nal cases arising from the ,

li mi te d range o f tempe rature and p ressure which we c an


comm and in our experiments .

The ordinary effec ts o f heat in m odifying the physical

stat e of bodies m ay be th us described We m ay take water .

18 I ntroduction .

as a f
a miliar example and e xplain when i t is m any, the
, ,

different phe nome na of o ther bodies .

At the lowest temperatures at which it has b een o bserved

water exists in the solid fo rm as ice When heat is c om .

municated t o very cold ice or to any othe r solid bo dy not


at its mel ti ng t emperatu re

1. The tempe rature ri ses .

z . The body ge nerally expands ( the o nly excepti o n am ong

solid bodiea as far as l am aware is the iodide of si lver , ,

which has bee n found by M F izeau to co ntract as the .

tempe rature rises) .

3 . T he rigidi ty o fthe body o r its resistance to chan ge o

form generally diminishes
This phe nomeno n is m ore

appare nt in some bodies than in o the rs It is very c on .

spicu ous in iro n w hich when heated bu t not melted be c om

, es

so ft and easily fo rged The co nsistency o fglass resins fats

, , ,

and f rozen oils alters very much with ch ange o ftemperature .

On the o the r hand it is beli eved that steel wi re is stier at


1 00 C than at 0 C and it has bee n sho wn by Joule and

. .

Thomso n that the l ongitudi nal elasticity o f caoutch o uc

i ncreases with the tempe ratu re between certain l imits of
t empe rature When ice is very near its melting point it

4 .A gre at m any solid b o di es are co nstantly i n a stat e o f

evaporati on o r transformatio n into the gaseous state at the ir
free surface Camph or, i odine, and carbo nate o f ammo nia

are well kno wn examples of this

These solid bodi es, ifno t .

kept in stoppered bo ttles grad ually disappear by evapora


ti on and the vapour which escapes from them m

ay b e
rec ognised by its smell and by its chemical actio n Ice .

too is co ntinually passi ng into a stat e of vapour at its


surface and in a dry clim ate d uri ng a long fros t large


beco me smaller and at las t disappear .

o ther so lid bodies which do no t seem to lose

s ubstance in this way ; at least we canno t ,
F us ion . 19

be detected by their smell are evaporating

c an

slowness Th us iro n and copper have each a


smell This however may ari se from chemical

, ,

the s urface which se ts free hydrogen o r so me


combined with a very small quantity o f the

F U S IO N .

Whe n the temperature o f a solid body is raised to a

su fcient height i t begins to mel t i nto a liquid Suppose a .

sm all po rtio n oft he solid t o be mel ted and th at no mo re heat ,

is applied t ill the temperatu re o f the remai ning solid and o f

the liquid has become equalised ; ifa little more heat is the n
applied and the t empe rature again equalised there will be
mo re liquid i natter and less solid matter bu t since the liquid ,

and the solid are at the same temperature th at temperature ,

mus t s till be the mel ting temperatu re .

Hence i f the partly mel ted m ass be kept well mixed


toge the r so that the solid and ui d parts are at the same

t empe rat ure th at t emperat ure m u st be the melti ng tempera


ture o fthe solid and no rise o f t empe rature will follow from

the addition o fheat till the whole o fthe solid has been co n
v ert ed int o liquid .

The heat which is required to melt a c ertain qu antity of

a solid at the melting poi nt into a liquid at the same

te m rature is ca lled the l ate nt heat o ff usio n .

I t is c alled Io tazt heat becau se the application o f this


heat to the body does not raise its temperature or warm the
body .

Those therefore who m aintained hcat to be a sub stance

, ,

suppose d that it existed in the uid in a co nceal ed o r l ate nt

state and in this way they disti nguished it from the heat

which when applied to a body m akes it hotter o r raises the

, , ,

tw p em ture This they called se nsible heat A body there

. .

fore was said to po ssess so much heat

, Part o f this heat was .

c alled sensi ble heat and to i t was ascribed the tem eratu re
, p
0 2
20 I ntroducti on .

of the body The o ther part was called latent h eat and

to it was ascribed the liquid or gas eo us form o f the b o dy .

The fact th at a certai n qu anti ty o f heat m u st be applie d

t o a pound o fmel ting ice to co nvert it into water is all that
we mean in this treatise whe n we speak o f this quanti ty
of heat as the latent heat o ff usio n o fa po u nd o f w ater .

We make no assertio n as t o the state in which the heat

exists in the wat er We do not eve n assert th at the heat

communicated to the ic e i s still in exi stence as heat .

Besides the change from soli d to l iq u id the re is generally ,

a change o fvolume in the ac t o ff usio n The wate r formed .

from the ic e is o f smaller b ulk than the ice as is shown by ,

ice oating in water so th at the t o tal vol ume o f the ice and

wate r dimini shes as the melti ng goes o n .

On the other hand many substances exp and i n the ac t o f


fu sio n so th at the solid p art s sink in the uid

, D uri ng the .

fusion of the mass the vol ume in these case s increases .

It has been shown by Pro f J Thoms on fro m the

. .

p rinciples o fthe dynamical theo ry o fheat that ifpressure is ,

applied to a mixture o fice and wat er it will no t o nly compress ,

bo th the ice and the water but some o f the ice will be,

mel t ed at the same time so that the total compressio n will


be increased by the co ntraction o fbulk due to this melting

The heat requ ired to mel t this ice b eing taken from the res t
of the mass the temperature o f the whole will dimini sh
, .

H ence the mel ting point is lowered by pressure in the

case of ice This ded uctio n from theo ry was experimental ly

veried by Sir W Thomson . .

If the substance had been one o f those which expand in

melting the e ec t ofp ressure w ould be to so lidify so m

e of
the mixt ure and to raise the t emperature o ffus i on
, Mo s t o f .

the su bstances of whic h the crus t of the earth is composed

act of melting H ence t hei r mel ti ng po ints

M ow e
r, 1 849.
us ion when the ext e rnal parts began t o soli dify

d sink in the molten m ass and whe n they had


solid u nder the

above the
I t does no t
the matter
state eve n if the t empe rature is far above that

o f ro ck s in o ur furnace s .

shown by Sir W Thom . so n that ifthe e arth as


no t mo re rigi d than a b all o fglass o f eq ual size ,

o f the moo n and sun wo uld pu ll i t o u t o fsh ape ,

much It i s .

o n would be so smoo th and regu lar that

be able to perceive i t in a d irect way bu t i ts


e t o diminish the apparent rise o f the tides of

as to m ake them m u ch sm alle r th an they

fore, from
wh at we know o f the tides of
earth as a whole is mo re rigid than glass ,

very l arge portio n o f i ts interio r can

of p ressure o n the melting poi nt of

reco ncile this co ncl u sio n with the

temperature as we descend in the

e tio ns as to the interior tempera

d o n thi s fact by the aid o f the theo ry of the

ofheat .

se w e r o r H EAT on mou rns .

he at is applied to a li qui d its eec ts are


.1 To warm the liquid . The qu anti ty o fheat required to

ra i se the liqui d o ne degree is ge nerally greater th an th at
requi red to raise the subs tance i n the solid fo rm one degree ,

and in general i t requires mo re heat at high than at low

t em peratu res t o warm the liquid one degree .

.a To alter its volume .M os t liqu ids expand as their

22 Int roducti on .

t empe ratu re rises ,

water co ntracts from 0 C to 4 C
b ut



and the n expands slowly at rst bu t afterwards more

, ,

rapidly .

3 To l e its physical state Liquids such as oil tar

. at r .
, , ,

&c which are sl uggish in their motio n are said to be

, ,

viscous Whe n they are heated their viscosity gen erally


diminishes and they become more mobile Thi s i s the case .

even with water as appears by the experiments o f M O E

, . .

Whe n sulphur is heated the melted sulphur undergo es


several rem arkable changes as its temperatu re ri ses, being

mob ile when rst melted the n becoming remark ably visco us

at a highe r tempe rat ure and again becoming mob ile whe n

still more heated .

4 T o co
. n vert the liquid o r solid into gas When a liqu id .

o r a solid ody is placed in a vessel the re st of which is

empty it gives of? part o f its o wn substance in the form of

g as .T his p rocess is ca lled eva po rati o n and the gas give n ,

06 i s commo nly called the vapo ur o f the soli d o r liquid sub

stance The process o f evapo ratio n goes o n till the de nsity


of the vapour in the vessel has reached a value which de

pends only o n the temperatu re .

Ifin any way as by the motio n o f a pis to n the vessel be

, ,

made larger then more vapour will be fo rmed till the de nsi ty

is the same as be fore I fthe pist on be pushed in and the


vessel made smalle r some o f the vapour is co ndensed in to


the liquid state, but the density of the remainde r of the

vapo ur still remains the same .

If the remainde r o f th e vessel ins tead o f co ntaining ,

nothing but the vapour o f the liquid co ntains any qu anti ty ,

of air o r som e other gas no t capable o f chemi cal actio n o n

the liquid then exac tly the same quanti ty of vapou r will be

e d but the time required f

, o r the vapour t o rea ch th e
be greater as i t has to ,

the vessel by a kind o f

discovered by Dalto n .
E 23

of the liquid int o vapo ur requires an

heat which is g enerally much greater

sion o f the same substance .

density p ressure and temperature

, ,

solids there is fo r each

or ,

nsity which is the g reatest


vapo ur can have at that temperature ,

ensed i nto the liqu id o r solid fo rm .

temperature there is als o a m aximum

vapour can exert .

i s at the great est de nsi ty and pressure

temperature is called a saturated vapour .

poi nt o fco ndensatio n and the slightes t ,

o r decre ase o f tempe r ature wi ll cause

to be co ndensed P rofesso r Ranki ne .

e word vapo ur by itselfto the case o fa

and when the vapo u r is no t at the point of
calls i t s upe rheated vapour or simply gas , .


Whe n a liqu id in an open vessel is heated to a tempera

ture such th at the p ressure o f its vapou r at that tempera
ture is greater th an the p ressure at a po int in the inte rior
of the liq uid , the li quid will begin to evapo rate at that
p oint, so that a b ubble o f vapo ur will be formed there .

This process in which bubbles o f vapour are formed in


e i nte rior o f the liquid is called boiling o r ebulli tio n

, .

Whe n water is heated in the ordi nary way by applying

heat to the bottom ofa vessel the lowest layer o f the water

bec omes ho t rs t and by its expans ion i t beco mes lighter


than the colder water above and gradually rises so that a

, ,

gw tle ci rc u latio n o f wate r is kept u p and the whole wate r ,

ie gradually warmed th ough the lo west layer is always the


ho ttest As the temperature i ncreases the ab sorbed ai r

, ,

24 I ntrodztotzo .

which is ge nerally fo u nd in ordinary water is expelled z , ,

rises in small bu bbles wi thou t noise At last the water.

co ntact with the heat ed m etal becomes so ho t that in s] ,

o f the p ressure o f the atm o sphere o n the su rf ace of

water the addi tional pressure du e t o the water in

vessel, and the cohesio n o f the water itself, some of 1

water at the bottom is transformed into steam form -
m! ,

b u bble adhering to the bo ttom of the vessel As soo n a .

b ubble is fo rmed evaporation goes on rapidly from the wa


all ro und it so t h at i t soo n grows large and rises orn t


, ,

bottom . I f the upper part o f the water into whi ch 1

bubble rises is still below the boiling temperatu re 1 ,

bubble is condensed and i ts sides co me together with


sharp rattling noise called simm ering But the rise of 1

, .

bubbles stirs the wate r abou t m uch more vigorously th

the mere expan sio n o f the water so that the water is so

h eated throughou t and brough t t o the boi l and then 1

, ,

bubbles enlarge rapi dly during t heir whole ascent a ,

burst into the air thro wing the water abou t and maki
, ,

the well known so tt erand more ro lling noise ofboiling


The s t eam as it bursts out o f the bubbles 15 an invisi

, ,

g ,s but whe n it comes i nto the colde r ai r it is cool ed bel
its condensi ng point and part o f it is formed i nto a do

consi sting of small drops o f wate r which o at in the a

As the cloud o f drops di sperses i t se lf and mixes wi th
air the quanti ty o f water i n each cubic foot diminishes
the volume of any part o f the cloud i ncrease s The lit .

dro ps o f water begin to evapo rate as soo n as there is su

cient room fo r the vapour t o be fo rmed at the tem
of the atmosphere and so the clo u d vanishes agai n ii

The te mm
rature to which water must be he ated befort
b oils depends i n the rst plac e on the pressure o f t
B oili ng . 2 5

that of the atmosphere fo r in o rder to fo rm bu bbles the


pressure o f the steam has to overcome no t only the p ressu re

du e to the atmo sphere and a certain depth o f water but that ,

cohesion between the parts o fthe water o f which the eec ts


are visible in the tenacity o f b u bbles and drops H ence i t .

is possible to heat wate r 2 0 F above i ts boiling point wi th


o u t ebullition
. If a small quantit y o f metal lings are now -

thrown into the water a li ttle air will be carried down o n


the surface o fthe lings, and the proces s o fevaporation will

take place at the interface be tween this air and the hot water
wi th such rapidi ty as t o pro duce a violent boiling almo st ,

amo u nti ng t o an explosio n .

I fa curre nt ofst eam from a boil er is passed into a vessel

o f col d wat er we h ave rst the co ndensatio n o f steam ,

ac co mpanied with a v ery lo u d si mmering o rratt ling noise and ,

a rapid h eating o fthe wat e r

. When the water is suf ciently

h eat ed, the steam is no t co ndensed bu t escapes in bu bbles

, ,

and the wat er is no w boiling .

As an instance o f a different kind let us su ppose that ,

pure but contai ns some sal t such as

, ,

t o r sulphate o f sod a o r any other substance

, ,

to combine with water and from which the ,

separate be fore i t c an evaporate Wate r c on .

int of pure
the other hand co n ,

t a lower t emperature

C is
. passed into a vessel co ntaini ng a
o ne of the salts we have mentioned ,

c y to combine wi th water t he c o nden ,

1 be promo ted by thi s tendency ,

the solution has been heated far

int so that by passing st eam

n o fnitrate o fsoda M r Pet er , .

1 8 69 . v 13 ~
26 I ntrodu cti on .

If water at a temp erature b el o w 1 00 C be pl aced in a


vessel and if by means o f an air pump we red uce the pres


s ure o fthe air on th e surface o f the water evaporati o n go es


o n and the sur face o f the water b eco m es c o ld er th an the

interio r parts . I f we go o n wo rking the air pu mp the -

pressure i s redu ced to th at ofvap our ofthe temp erature of the

interio r o fthe uid The water th en b egins to b o il exac tly

as in the o rdi nary way and as it b o i ls the temp erature


rapidly f alls the h eat b ei ng exp end ed in evap orati ng the


water .

Thi s exp erim ent m ay b e p erform ed wi th o ut an air pu mp -

in the fo ll o wing way B o il water in a ask o ver a gas

am e o r spirit l amp and whil e it is b o ili ng b riskly co rk the

ask and rem o v e it fro m the am e The b o iling will s o o n

, .

ceas e but if we no w d ash a li ttl e co ld water o ver the as k

, ,

so me of the steamin the u pp er part will be condensed the ,

pressure o f the rem aind er wi ll be dimi nish ed and the water ,

will b egin to b o il agai n The experim ent may b e mad e


m ore s tri king by p lunging the ask entirely u nder co ld

water The steam will b e co nd ensed as b efo re bu t the

wat er th ough it is co o l ed m ore rapidly than wh en the co ld


water was m erely p o ured o n the ask retains its h eat l o nger

than the steam and conti nu es to b o il for so me ti me

L aws of Gases . 27


The distingu ishing p roperty of gases is their powe r of

i ndenite exp ansio n As the p ressure is diminished the

volume of the gas no t o nly incre ases bu t before the p ressure ,

has bee n reduced t o zero the volume of the gas has become
greater than th at o fany ves sel we can pu t it in .

Thi s is the p rope rty wi thou t which a s u bstance cannot

be called a gas bu t it is fou nd th at actual gases full wi th

greater o r less degrees o f accu racy certai n numerical laws ,

which are commonly re ferred to as the G as eo u s Laws .


The rst o f these laws expres ses the relatio n betwee n the
pressure and the de nsi ty o f a gas the tempe rature bei ng ,

co nstant and is usually stated thu s The volume o f a


po rtio n o fgas varies inve rsely as the pressu re .

This law was discovered by Robert Boyle and p ublished ,

by him in 1 662 in an appendix to his N ew Experime nts

, ,

Physico mech anical 8:c touching the Spring ofthe Air


M ariotte abou t 1 67 6 in his treatise D e la N ature de

, ,

l Air enunciated the same law and carefully ve ried i t and i t

, , ,

is generally referred to by C onti nental writers as M ariotte s

law .

This law m ay also be sta ted thus

The p ressu re o fa gas is p roportional to its densi ty .

Anothe r stateme nt o fthe same law has bee n p roposed by

Professo r Rankine, which I think places the law in a very

I f we take
closed and exhausted vessel and i ntrod uce
a ,

into i t o ne grain o f air this air will as we k now e xe rt a

, , ,

certai n pressure o n every square i nch o f the surf ace o f the

vessel Ifwe no w introd uc e a seco nd grain o fair then this

se cond grain will exert exactly the same pressure o n the

sides of the vessel th at it woul d have exe rt ed if the rs t grain
had not bee n there before it so that the pressu re will now

be doubled He nce we may s tate as the pro pert y of a


pe rfect gas that any po rtio n o f i t e xerts th e sam

, e pre ssure

against the sides o f a vessel as if the other porti on s had not

bee n there .

D alton exte nded this law to mix tures of gases o f di rent

kinds .

We h ave already seen that if several di ere nt porti ons of

the same gas are pl aced together in a vessel the p ressure on,

any part of the side s o f the ve ssel is the sumo f the pres
sures which each portio n wo uld exert if plac ed by itself in
the vessel .

D alton s law asserts that the same is true fo r porti ons of

diere nt gases placed in the s ame vessel and that the


pressure o fthe mixture is the sumo f the pressures du e to the

several po rti ons of gas if introd u ced separately into the

vessel and b rought t o the same tempe rature .

This law o f D alto n is sometim es stated as if portions of

ga s o f differe nt ki nds beha ve t o ea ch othe r in a c1t

m anner from portio ns o f gas o f the same ki nd and we are ,

told that when gase s o f differe nt ki nds are placed in the

same vessel, each acts as i fthe othe r were a vacu u m .

This stateme nt p roperly u nderstood is correct but i t

, , ,

seems to c o nvey the impression that if the gases had been

of the same kind some other resul t would h ave happened ,

whereas there is no difference between the two cases .

Another law established by D alton is that the maximum

density of a vapo ur in contact with its liquid is no t affected
by the prese nce o f other gases It has been shown by

M Regnault that whe n the vapo ur o f the sub stance has a


tendency to combine wi th the gas the m aximum density


attainable by the vapour is somewhat increased .

time o fDal ton it was supposed that the cause

Gases and V ap ou rr . 29

D alton showed that the vapour water is a gas whi ch

of ,

just at the surface o f the water has a certain m aximum


density and which will gradually diuse itself through the


space above whether lled wi th air o r not till, i f the sp ace is

, ,

lim ited the density of the vapour is a maximu m th roughout

, ,

o r, if the space is large e no ugh till the wate r is all d ried up

, .

The prese nce of air is so far fro m bei ng essent ial t o this
process that the more air there is the slower it goes o n , ,

because the vapo ur has to penetrate throu gh the air by the

slow p rocess o fdiu si on

The phenomeno n discovered by Regnault that the density

of vapou r i s sligh tly i ncreased by the prese nce o f a g as
which has a t ende ncy to combine wit h it is the o nly instance ,

in which the re is any tru th in the doctri ne o f a liquid bei ng

held in sol u tio n by a gas .

The law of Boyle is no t perfectly fullled by any actual

g a.s It is ve ry nearly f
u llled by those gases which we are

no t able to c o nde nse i nto liquids and am o ng other gases it


is m os t nearly fu llled whe n their t emperatu re is m uch above

their point of co ndensation .

When a gas is near its point o f condensation i ts density

increases more rapidly than the pressu re When it is .

actually at the poi nt ofco ndensation t he slightest increase o f

pressure co ndenses the whole o f i t into a liquid and in the ,

liquid form the density increases very slowly with the

p r essu re .

The seco nd law o f gases was discovered by Charles but ,

is commonly re fe rred to as th at ofG ay Lussac o r o f Dalton -


It m ay be stated th us

Pro f esso r o fPhysi cs at th e Conservatoi re des Ar

t s et M etiers, Pans .

Born 1 746 Di ed r82 3 Celebrated as having rst e ployed hydroge n

. . m
in balloo ns
me m

Dalto n, in 1 80 1, rst pu blished this law . G ay L a-

pub h

3 0 I ntrodu cti on .

Thevol ume o f a gas under co nstant pressure expands

whe n raised from the freezing to the boiling temperature by
the same fraction o f itself whatever he the nature o f the gas , .

It has bee n found by the care ful expe rimen ts of M .

R egnau lt M Rudberg Prof B Ste wart and o thers that the

, . .

volume ofair at cons tant pre ssure expands fromr to r3 665

be tween 0 C and ro o C H ence 30 cu bic inch es of



air at 0 C would expand t o abo u t 41 cubic inches at


1 00 C .

I f we admit the truth o f Boyle s law at all temperatures


and if the law o f Ch arles is found to be true f or a partic ular

pressure say th at o fthe atmo sphere then i t is easy to show

, ,

th at the law o fCharles must be true for every othe r pressure .

Fo r if we call the volume v and the pressure P then we ,

may ( all the product o f the numerical val ue of the volume

and p ressure v r and Boyle s law asse rts that this pro


d uc t is co nstant p rovided the t emperature is co nstant If

, .

the n we are further informed that when P has a given

value v is i ncreas ed from r to r 3665 when the temperature

rises from the freezing point to the boili ng point the p ro duc t ,

v P will be i nc rease d in the sam e proportio n at that particular

p ressure But v P we know by Boyle s law does no t depend o n


the particularpressu re but remai ns the same for all p ressunes ,

whe n the temperature remai ns the same Hence whatever .


be the p ressure the product V P will be increased i n the ,

p ropo rti o n o f r to 1 3 665 whe n the t emperature rises f rom

C to 1 00 C

0 . .

The lawo fthe equality o f the dil atatio n o fgases which as , ,

origi nally stated, applied o nly to the dilatation from 0 C


to 1 00 C has been fou nd t o be true fo r all o ther tempera


tu res f o r whi ch it has hitherto been tested .

de a i nee, ai mp [ . he stat
.es th
157at C i t
1 802
ize n C harlD
es had


fte en years before the date of his e o ir, the equality of

the p ncipal gases ; b ut, as C harles never pnblished
TIn! Gaseous S tate .
3 t

there fo re th at gases are distinguished from


matt e r no t only by their power o f indenite


ll any vessel however large and by the

, ,

heat has in dil ating them bu t by the


p li c i ty o f the la ws which regu late these

s olid and liq uid stat es the e ffect o f a
o r o f tem perature in changing the

cd at the same temperature and

pressure ,

will rem ain equal ifwe afterwards bring them

other temperature and pressure and this ,

al together in chemi cal nature

are bo th in the perfectly gaseous

y remarkable properties which

of m atter as that in whi c h its

the physical properties o f bo dies as

esc riptio n o f

heat we have begun wi th solid bodies as those ,

c an most easily handle and have gone on to


in o pen vessels and h ave now


escape from open vessels and ,

c This is the order which is


are mu ch mo re imp erfectly known and concl udi ng


the little that has been hi therto discovered about the co n

sti tu ti o n o f so lid bodies

3 2 Tbe r momtry .



D e nition Tempe ratu re 7 7h: tem

of p eratu re f
o a body
is its tirer m m
al state co bi n ed with re ference to its power g

D enitio n o f Hi gher and Lower Tempe ra

ture If whe n

two bodies are p lac d

e i n tber mal oommumM on, one J ti re

out boat is

rard to bo w a lu /la te
g m
peratu re titan that se/1M t

mi v
ot es heat
f ro mit

Co r If swimtwo bodra

are p laced i n Ma ma! m u

tiorr noti fier of t/remloser ar go i m heat ,

Me two bodie s are

two bodi er are t/r m Ma ma! q u ilibrru m We


said to be in .

have he re a means o f comparing the t emperatu re o f any

two bodies so as to determine which has the higher

temperature and a test o f the equali ty of temperature


which is indepe nde nt o f the nature o f the bodies tested .

But we have no means of es tim ating nume rically the dier

ence between two temperatures so as to be able to assert,

are q ua! torat of tire so m e bod y bar

/e Memdws corral tan .

M atu res T his

. law is no t a truism , b u t exp resses t he f
a ct
that ifa piece o f iro n when plunged i nto a vessel o f water
is in thermal equilibrium wi th the wate r, and if the same
Ca m
i sole of Te peratu res .

equ ilibrium and the same woul d be true o f any other three

substances .

This law the re fo re exp resses much more than Eu clid s

, ,

axiom that Thi ngs which are equ al t o the same thing are

equal to o ne another and is the fo undati o n o f the whole


scie nce of the rmometry Fo r if we take a thermomet er


such as we have already described and b ring i t into ih,

timate contact with different bodies by plunging i t into ,

liqu ids o r i nserti ng i t into h oles made in solid bodies we

, ,

nd th at the mercury in the tu be rises or falls till i t has

reached a ce rtai n point at which i t rem ains statio nary We .

the n know th at the thermometer is neither becoming hotte r

no r colder but is in therm al equilib rium wi th the surround

ing body . It follows from this by the law o f equal tem


peratures that the temperature of the body is the same as


that o f the thermometer and the temperature o fthe thermo


me t er i tself is known from the height at which the mer

cu ry stands in the tube .

Hence the rm di ng as it is called o f the thermometer

, ,

that is the numbe r o f degrees indicated o n the scale by the


top of the mercury in the tube informs us of the tem

p era tu re o f t he s urro u ndi ng s u bstance as well as o f that of

the me rcury in the thermomete r I n this way the thermo


meter may be used to compare the t emperature of any

t wo bodi es at the same time o r at dif fere nt time s so as ,

to ascertain whethe r the temperature of o ne o f them is

higher or lower than that o f the o ther We may compare .

in this way the temperatures of the air o n diffe rent days

we m ay asce rtai n that wat er boils at a lowe r t emperature at
the to p ofa mou ntain th an it does at the sea sho re and that -

ice melts at the same temperature in all parts o f the world .

For this purpose it w ould be necessary to carry the same

thermometer to different pl aces and to preserve i t wi th

great care, for if it were destroyed and a new o ne mad ,

we shoul d have no certainty that the same t emperature is
indic at ed by the same reading tu the two the rmometers .

34 Tbermomeb
y .

Thus the obse rvations of temperature recorded during

si xtee n years by Rinieri at Florence lost their
value afte r the suppressio n o f the Accademia del C im e ntn ,

and the su pposed destructi on o f the thermome t ers with

which the observations were made But when Antinori in .

1 8 2 9 di scovered a nu mber of the very thermometers used

in the ancient observations Lib ri was able to comp are them


with Raumurs scale and thus to show that the cli mate of


Florence has no t been rendered sensibly colder in wi nter

by the cleari ng o fthe woods o f the Apennines .

I n the construc tio n ofarti ci al standards fo r the measure

ment ofquantities of any kind it is desirable t o have the
means o f compari ng the standards togethe r either directly , ,

or by means o f some natural object o r phenome no n which

is easily accessible and not liable to change Bo th methods .

are used in the p reparation o fthermometers .

We h ave already noticed two natural phe nome na which

take pl ace at denite temperat uresthe melting o f ice and
the boili ng o f water The advantage o f employi ng the se

t empe ratures to dete rmine two points o n t he scale o f the

thermometer was poi nted o u t by Sir Isaac N ewton Scale .

Graduam C aloris Phil Trans


. .

The rst of these points o f reference is commonly call ed

the Freezing Point To de te rmine i t the the rmometer is

placed in a vessel lled wi th pounded ice o r snow thoro ughly

moistened with water If the atmospheric temperature be

abo ve the f reezing point the melting o f the ice wi ll ensure


the prese nce o f water in the vessel As lo ng as every part .

o f the vessel contains a m ixtu re o f water and ice i ts t em

p e ra tu re rem ai ns u ni f
o rm f
o r i f heat e nters the vessel i t

c an o nly mel t some o f the ice and if heat escapes fr

the vessel some o fthe wat e r will freeze but the mixture can ,

be made nei ther hotter nor colder ti ll all the ice is melte d

Te peratures o R
f eferenee .

completely imme rsed in the mixture

suf cient time so that the me rcury

tati onary po int The position of the


Pi c. 3.

te mpemmle of

l y the W e

t of r eference is
The gem

pe nds on the pressure o f the atmo

sphere The greater the pressure of

the air o n the surface of the water ,

the higher is the t emperature to

whi ch the water must be raised
before it begins to boil
To detm

mi ne the Boiling Poi nt the stem o f the therm o

met er is passed through a hole in the lid of a tall veml

in the lower part o f which water is m ade to boil briskly so ,

that the whole of the upper part where the therm ometer is

placed is lled with s team When the therm

, . omete r has
ac quired t he temper a ture o f the current of steam the stem
is drawn up through the hole in the lid of the vessel ll the
m of the colu m n o f mercury bm m es visible A scratch
is then made o n the tube to indicate the bo iling point

In careful determinatio ns o f the boiling point no part of

the thermometer is allowed to dip into the boiling water ,

because it hmbeen found by Gay Lussac that the temperatu re


of the wate r is no t always the same b ut that i t boils at,

dierent tem peratures in dMerent kinds of ves se l s It hm


been sh owa however by Rudberg that the temperature of


n 2
36 m
T ay .

the steam which escapes from boiling water is the same in

every kind of vessel and depe nds o nly on the pressure at

the surfac e of the water H ence the thermom e ter is no t


dipped in the water but suspended in the issui ng steam To

, .

e nsu re that the temperature of the steam shall be the same

whe n it reaches the thermometer as when it issues fro m the
boiling water the sides o f the v essel are sometimes protected

is called a s team j acket A current of steam is


made to play ove r the out

s ide of the sides of the
vessel The vessel is thus .

raised to the same tem pe

rature as the steam i tself so ,

that the steam cannot be

cooled during its passage
fro m the boiling water to
the the rmometer .

For instance if we tak e ,

any tall narrow vess el as ,

a co ee pot and cover its mou th and part of i ts si des



with a wider vessel tu rned upside do wn taking care that ,

there sh all be plenty of room for the s team to esc ape, then
ifwe boil a small qu antity o fwaterin the c o ee pot atherm

o -

mete r placed in the s t eam above will be rai sed to the

exact temperature o fthe boiling point o fwater c orrespo ndmg
to the state o fthe barome t er at the time .

To mark the level o f the m ercury o n the tu be o f the

thermomet er withou t coo ling it we must draw it up thro ugh


a co rk o r a plug o fi ndi a rubbe r in the steam j acket through

- -

which the steam passes till we c an j ust see the to p o f the

column of mercury A mark must the n be scratched o n the

glass to register the boiling point This experiment o f .

exp osi ng a thermome ter t o the steam of bo iling water is an

s upplies a m eans of gradu
g them whe n they have been
S cale f
o te Thermometer .

depends on the pressure of the air we m

ay determi ne
pressure of the air by bo ili ng wate r when we are no t able to
measure i t by means o f the approp riate instrument the ,

barometer .

We hav e now ob tained two points ofre fe rence m arked by

scrat ches on the tube o f the the rmometer the freezi ng point

and the boiling point We shall suppose for the present


t h at whe n the boiling po int was marked the baro meter

h appe ned t o i ndicate the standard p ress ure o f 2 99 0 5
i nche s o f mercury at 0 C at the level o f the sea in the


l atitu de o f Lo ndon In this case the boiling point is


the stand ard boili ng point In any other case it must be


O ur therm o meter will now a r

g ee with any other pro perly
constructed thermomet er at these two temperatures .

In orde r t o indi cat e o the rtemperatu res we must construct ,

a sc ale that is a series o fm arks

, eithero n the tube itsel for

o n a co nve nie nt p art ofthe apparatu s cl o se to the tu be and

well fas tened to it .

Fo r this purpose having se t tled what val ues we are to give


to the freezi ng and the boiling points, we divide the space

be tween t hose points into as m any equal parts as there are
degrees between them and continue the series ofequal divi

sions u p and down the scale as far as the tube o fthe thermo
met er extend s .

Three di erent w ay s of doing this are still in use and,

as we o f t en nd temperatures stated according to a

different sca le from that which we adopt ours elves it is ,

necess ary to know the principles o n which th ese scales are

fo rmed .

The C entigrade scale was i ntroduced by Celsiu s l I n i t

the freezi ng point is marked 0 and called ze ro and the

bo iling po int is m arked

The obvio us simplici ty o fthis mode oi dividing the spac e
between the poi nts of reference into t o o equal parts and
Pro fesso r of Astro nomy in th e U ni ve rsity o f Upsala .
38 Thermo mtrye .

calling each o fthese a degree andreckoning all temperatures


in degree s from the freezing poi nt caused it to be very ,

generally adopted along wi th the Fre nch decimal sys t em of


measurement, by scientic men especially o n the C ontinent


of Europe .It is true that the advantage o f t he de cimal

syst em is no t so great in the measureme nt o ftemperatures as
in other cases, as it merely makes i t easier t o remember the
freezing and boiling temperatures but the gradu ati on is not

too ne for the roughes t purpo ses while fo r accu rate ,

measurements the degrees may be subdivided i nto tenths and

hundredths .

The o the r two scales are called by the names o fthose who
introduced them .

Fahrenhei t o f D antzig abo ut 1 7 1 4 rst c onstructed

, , ,

thermomete rs comparable wi th each o ther In Fahrenheit s .

sc ale the freezing po i nt is marked and the boiling point

the space betwee n bei ng divided into 1 80 equal parts,
and the graduatio n extended above and below the poi nts o f

reference . A point 3 2 degrees below the freezi ng point is

called zero or , and tempe ratures below this are indicated
by the number o fdegrees below zero .

This scal e is very generally u sed in English speaking -

countries for purposes o fo rdinary life and also for those o f ,

scie nce
th ough the Centigrade scale is co ming into use
am ong those who wish th eir res ults to be readily f oll owed by
foreigners .

The o nly advantages which can be ascribed t o Fahrenhei t s

scale, besides its early introduction its general di ffusion and

, ,

its actual employment by so many o f our cou ntrymen are ,

that mercury expand s almost exac tly o ne ten tho usand t h of -

i ts volume at 1 42 F for every degree o f Fahrenhei t s scale


and that the coldest tempe r atu re which we can get by

mixing snow and salt is near the zero of Fahrenhei t s

temperatures given in Fahrenhei t s sc ale wi th

sc ale we have only be


efrzc S cales .

r em ember that 0 C entigrade is 3 2 Fahrenheit and that ve


degrees C enti grade are equal to nine of Fahre nhei t .

The third thermometri c sc ale is that o fReau mur I n this .

sc ale the f reezing po int is marked 0 and the boiling point

I amnot aware of any advantage o f this scale It is .

used to some ext e nt on the Co ntinent o fEu rope for medical

and domestic purposes Four degrees o f Reaum ur co rre
. p

sp o nd to ve C entigrade and to nine o f Fah re nheit .

The existence o f th we three thermome tric sc ales furnishes

an example o fthe inco nvenience o f the want of unif o rm i ty in
systems o fm easurement The whole o f what we have said

abo u t the compariso n o f the di f ferent scales might have

bee n omitted ifany o ne o fthese scales had been adopted by
all who u se thermometers I nstead o fspe nding o ur time in

describing the arbitrary pr0posals o fdifferent m en we sh ould ,

have go ne on to inves tigate the laws o f heat and the pro ~

pet ties o fbodies .

We shall afterwards have occasi on to use a sc ale diffe ring

i n its zero poi nt from any oftho se we h ave co nsidered bu t

whe n we do so we shall bring forward reaso ns for its adoptio n

depe ndi ng on the nature of things and no t on the predilec '

tio ns o fmen .

Iftwo the rmomete rs are co nstructed of the same kind o f

glass with tu bes o funiform bore andare ll ed with the same
, ,

liquid and th en graduated i n the same way they may be co n ,

sidered f o r o rdi nary pu rposes as comparable ins truments ;

so that thou gh they may never have bee n actually com

p ar ed togethe r y et i n a
,sce rta i ning the tempe ratu re o f a ny
thing the re will be very li ttle di erence whe the r we use the

o ne therm o meter or the othe r .

Bu t if we desire great accuracy in the measurement o f

tem perature so that the observations made by dierent

observers wi th differe nt i nstru ments m ay be st ric tly co m

parable the only satis factory method is by agreeing to

choose o ne therruo m eteras a standard and compari ng all the

Ot hers with i t .
40 T/mmo
mtry t .

All thermomete rs ought to be m ade with tubes o f as

uniform bo re as can be f ou nd but fo ra standard therm o meter

the bo re sho uld be calibrated that is to sa , its size shoul d be y
me asured at short i ntervals al l alo ng its le ngth .

Fo r t his p urpo se be fore the b ulb is blown a small qu antity

, ,

o fmercury is introd uced i nt o the tube and moved along the

tube by forcing air i nto the tube behi nd it This is do ne by .

squeezing the air o u t o f a small indiar ubber ball whi ch is

fas te ned to the end o f the t ube .

If the length o f the col u m n o f mercury remains exactly

the same as it passes alo ng the tube the bore o f the tube ,

must be uniform bu t even i n the best tubes there is always

some want o funifo rmity .

B ut if we introdu ce a sho rt colum n of m erc ury into the

tube then mark both ends o fthe colum n, and m

ove it o n its
own length till o ne end comes exactly to the mark wh ere

the other end was originally, then mark the other end and ,

move it o n again we sh all have a seri es o f marks o n the tube


s u ch that the cap aci ty ofthe tube betwee n any two consecu
tive m arks will be the same being equal to that of the

col u mn o fmercu ry .

By this me thod which was invented by Gay Lussac a


number o f divi si o ns m ay be marked on the tube each of ,

which co ntains the same vol ume and though they will pro

bably no t co rresp ond to degrees when the tube is made u p

into a thermomet er i t will be easy to co nvert the reading o f

this instrume nt i nto degrees by multiplying it by a p roper

factor and i n the use ofa standard ins trument this trouble is

re ad ily unde rtaken f o r the sake o fa curacy


The tube aving been p repared i n this way o ne end i s

heated till it is mel ted and i t i s blown into a bu lb by forcing

air in at the other end o f the tube I n o rde r to avo id


introducing mois ture i nto the tube, thi s rs do ne not by the ,

hollow indra rubber ball, which ts~

Construc tion o f a Tkerm

o mten 4 1

The tube o f a therm omet er is generally so narrow th at

mercury will no t enter i t fo r a reaso n which we sh all explain

when we come to the p ro pe rti es o f liquids H ence the .

followi ng method is a dopt ed to ll the therm o met e r By .

rolling paper ro und the open end o f

the tube, and making the tube thus Fm
formed project a little beyo nd the
g lass tube a,
cavi ty is fo rmed int o ,

which a little mercury is poured .

The mercury however will no t ru n

, ,

do wn t he tube o f the thermome ter ,

partly because the bulb and tube are

alre ady fu ll o fair and partly because

the mercury requires a ce rtain pres

sure from witho ut to ent er so narrow
a tube The b ulb is therefore gently

heated so as to cause the air to e x

pand and s ome of the air escapes

through the mercury When the bulb .

c ools the p ress u re o f the air i n the


bulb becomes less than the pressure

o fthe air outside and the dif
, fere nce
of th ese pressures is sufcient to
make the mercu ry e nter the tu be ,

when i t runs down and partially lls

In o rde r to ge t rid of the remainder o fthe air and o fany ,

mo i sture in the thermometer the bulb is grad ually heated


t ill the mercu ry boils The air and s t e am escape along


wi th the v apour ofmercury and as the b oili ng continu e s the


las t remai ns of air are expell ed thro ugh the mercu ry at the
top of the tube Whe n the boiling ceases the mercu ry runs

back into the tube which is thu s perfectly lled wi th mercury

, .

While the the rm omete r is still hotter than any te mperature

at which it will afterward s be u sed and while the mercury or
42 M axi m .

its v apour co mpletely lls it a blo wpipe ame is made t o ,

play o n the top o fthe tube so as t o melt i t and c lose the end

of the tu be The tube t hus closed with its o wn su

is said to be hermetically sealed "

There is now nothing in the tube bu t me rcury and when ,

the mercury contracts so as to leave s space above it this .


space is either empty o f all gross matter o r contai ns only ,

the vapo ur ofmercury If in spite o f all our precautions

, ,

there is still so me airin the tube , this c an easily be asca tained


by invert ing the the rmome ter and letti ng some o f the mer
ury glide towards the end o f the tube If the i nstrume nt

i s perfect it will reach the end of the tube and completely


ll i t Ifthere is air in tne tube the air will forman elastic


cushi on which will p reve nt the mercury from reaching the


end o f the tu be, and wi ll be see n in the f o rmo f a small

We have next to determine the freezing and boiling points ,

as has bee n already descri bed, but certain p recauti o ns have

still to be o bserved In the rst pl ace glass is a substance

in which internal changes go o n fo r some time after i t

has been strongly heated, o r exposed to i nte nse fo rces .

In f act gl ass is in some degree a pl astic bo dy

I t is .

fo und th at aft er a thermomete r has bee n lled and sealed

the capacity of the bulb dimi nishes slightly and that this ,

change is comparatively rapid at rst and only gradually ,

become s inse ns ible as the bulb app roaches i ts u ltimate c on

ditio n It causes the freezing po int to rise in the tube to

or and if aft er the displacement o f the ze ro the

, ,

mercury be again boiled the zero re turns to its old pl ace


and gradually rises again .

This ch ange o f the zero point was discovered by M -


Flaugergu es
It may be considered complete in f
. rom f ourto

Fro mHermes or Merc ury , the imaghred m
vento r o f chemistry .

de md wy q , xxi .
p 333
Co mm f
o TImmatu r
e .

six months I n order to avoid the error which it would


introdu ce into the scale the i nstrument should if possible

, , ,

have its zero determined so me months after it has been

lled and since even the de te rm
ination of the boiling point
o f water produces a slight dep ressi on o f the f reezing point

( t hat is a n exp
an si o n o f the bulb ) the freezi ng poin t should

no t be de te rmined after the boiling point bu t rather ,

before it .

When the boiling po int is determined the barometer is ,

pro bably no t at the s tandard height The mark m ade on .

the thermometer mus t in graduating it be considered to

, ,

represe nt no t the stand ard bo iling point but the bo iling

, ,

point correspo ndi ng to the observed height of the baro

me ter which m,
ay be f ound from the tables .

To co ns truct a therm o meter in this elaborate way is by

no means an easy task and eve n when two therm ometer
, s have

been co ns tructed with the u tm o st care their readings at ,

po ints distant fro m the eezing and bo iling p oints m

ay no t
agree o n acco unt o f dif
, ferences in the law o f expansi on of
t he gl ass o f the two thermometers These differences ho w .

ever are sm all f

o r all thermometers are made of the same

desc ription o fglass .

B ut since the main obj ect o f th ermometry is that all

t hermometers shall be strictly comparable and since thermo ,

meters are easily carried om o ne place t o another the'

bes t method of obtai ni ng this object is by comparing all

therm ometers either directly o r indirectly with a si ngle
stan dard thermometer For this purpose the thermometers
, ,

a er being properly gradu ated are all pl aced alo ng with the ,

standard thermome te r in a vessel the temperature of which ,

c an be maintained u ni f orm fo r a co nsiderable time Each .

thermometeris then comp ared wi th the standard therm ometer .

Dr .
Joule,ho we ver, nd s th at th e rise of the eezing p oint of a

delica e t t m her o me er has t b or wen y -si x year

ee n go ing o n f t t
s, hough the t
changes are now exc eedi ngly m inu e Pkg Soc M e ncken , Feb 2 2 .
t . . .

t he
44 momtry
T/wr e .

A table o f correctio ns is made for each th erm om c tu

by e nteri ng the reading o f that thermomete r al ong with ,

the co rrection which m us t be applied to that reading to

reduce i t to the readi ng o f the standard ther mo me ter .

This is called the proper co rrection for that reading If .

it is posi tive it m ust be added to the reading and ifnegative ,

it mu st be sub tracted from it .

By bri nging the vessel to v arious temperatures the cor ,

rectio ns at these temperat ures for each thermome ter are

asce rtained and the ser
, i es o f corrections belongi ng to each
th ermome ter is m ade out and preserved along with that
thermo me t er .

Any thermomete r m ay be sent to the O bservato ry at

Kew and will be returned with a list o f co rrectio ns by the

, ,

applicatio n o f which observatio ns m ade with that thermo


meter become strictly comparable with those made by the

standard thermometerat K ew orwith any other thermometer

is very smal l compared with the expense o f making an

original standard the rmometer and the sci entic valu e of

observatio ns m ade with a thermometer thus compared is

greater than th at o fob servations m ade with the most elab o
rately prep ared the rmomete r which has no t bee n compared
wi th some exi sting and known standard instrument .

I h ave described at considerable length the proc esses by

which the therm ometric scale is constructed and th ose by ,

which copie s o f i t are m u ltiplied because the practic al


establishme nt of such a scale is an admirable instance o f

the method by which we must proceed in the scientic
observatio n o fa phenome no n su ch as temperature which for , ,

the p resent we regard rather as a quali ty capable o fgreate r

, ,

or less int ensity than as a q uanh b which m

ay be added to

or su b t ract ed o mothe r quanti ties ofthe same kind .

TW i nn considered as a Q uali ty .

the sum of its components When we are able to attach a


di stinct meaning to such an operatio n and determine its ,

resul t our conceptio n o f temperat ure will be raised to the


rank of a quantity Fo r the present however we m ust be

, ,

co ntent to regard tempe rature as a quali ty o fbodies and be ,

sati sed to know that the t emperatures o f all bodi es can be

referred to their proper places in the same scale .

For instance we have a right to say th at the t empe ratures


of f reezi ng and boiling dif fer by 1 8 0 Fahrenheit ; b ut we

h ave as yet no right to say that this dierence is the same

as that between the temper atu res 3 00 and 480 on the

same scale Still less can we assert that a tempe rature o f


2 44 F

3 a + z rz .

is equ al to the su mo f the t emperatures of freezing and

boi ling I n the same way if we had no thing by which to


measure time except the succession of our o wn tho ughts ,

we might be able to refer each eve nt within our o wn ex

p eri ence to its p rope r chro no l o gica l p lace in a se ries bu t ,

we should have no means o f comparing the interval of time

between o ne pair of eve nts wi th th at between ano ther pai r ,

unless it happened that o ne of these pairs was i ncl u ded

within the other pair in which case the interval between the

rst pair must be the smallest It rs only by obse rvation of


the uniform o r periodic moti ons o fbodies and by ascertain ,

ing the co ndi ti ons unde r which certain motions are always
accomplished in the same time that we h ave been e nabled ,

to measure time rst by days and years as indicated by

, ,

the heavenly motions and then by hours mi nutes and

, , ,

seco nd s as indicated by the pe nd ulums of o u r clock s till

, ,

we are now able no t o nly to calculate the time of vibration


o fdi erent kinds o f ligh t bu t to compare the time o f vibr


, a
tion ofa molecule of hydroge n set in mo tio n by an electri c
discharge thro ugh a gl ass tube with the time o f vibratio n

ofanothe r molecule of hydrogen i n the su n f o rming part o f ,

some great eruption o f rosy clo ud s and wi th the time o f ,

vibratio n o f ano ther molecule in Siri us which has no t

46 Tm m try
e .

transmitt ed its vibratio ns to o ur e arth but has simply ,

p revented vibrations arising in the body of that star fro m

In a subsequ e nt chapter we sh all consider the further

progress o fo u r knowledge o fTemperature as a Quantity .


The origi nal thermometer invented by Galileo was an

air thermo m eter It consisted o f a glass b ulb with a long

neck . The air in the bulb was heated and the n the neck ,

was pl unged into a colou red liquid As the air in the b ulb

co o led th e liquid rose in the neck and the highe r the

, ,

li quid the lower the tempe rature o f the air in the bulb .

By p utting the bulb into the mo uth o f a patient and noting ,

the point to which the liquid was drive n down in the tube a ,

physician might estimate whe the r the ailment was o f the

nature o f a fever o r no t Such a thermomete r has several

obvious merits It i s easily co nstructed and gives larger


indicatio ns fo r the same change o ftempe rature than a thermo

meter co ntaining any liq uid as the thermometri c sub
s tance Besides this the air requires less heat to warm i t

than an equal bulk o f any liquid so that the air thermo


me ter is ve ry rapid in its indicatio ns The great inc o n .

venienc e o f the instrument as a means o f m easuring tem

p eratur e is
th at the heigh t o f the liquid in the tu be depe nd s

o n the pressure o f the atmosphe re as well as o n the tem

p e ratu re of the air in the b ulb T h.e air ther mo m eter cann o t
therefore of i tself t ell u s any thi ng about t emperature We .

must cons ult the barome te r at the s ame time in orde r to ,

correc t the reading o f the air thermomete r Hence the air .

thermome ter to be o f any scie ntic val ue must be use d

, ,

along with the barome te r and its readi ngs are of no use

till after a process of calculation has been go ne through .

it at a great disadvantage comp ared with the

o f ascertai ning tem er a
Te A i r T/ mvn mt ro e e .

tures But if the researches o n which we are engaged are


o fso impo rtant a nature that we are willi ng to undergo the

labour of double observatio ns and numerous calculations ,

the n the advantages o f the air the rmometer m ay again p re

po nderate .

We have seen that i n xing a scale o f temperature afte r

m arki ng o n o ur thermometer two temperatures of reference
and lling u p the interval with equal divisio ns, two thermo
meters co ntaini ng differe nt liqu ids will no t in ge neral agree
except at the tempe ratures o freference .

I f on the other hand we cou ld secure a c onstant pressure

, ,

in the air thermomete r then i f we exch ange the air fo r any


other gas all the readings will be exactly the same provided

the readi ng at o ne o f the temperatures o f referenc e is the

same It appears there fore that the scale o f temperatures
, ,

as indic at ed by an air thermomete r has this advantage ove r

t he scale indicated by mercury o r any other liquid or sol id,
that whereas no two liquid orsolid substances can be made to
agree in thei r expansion throughou t the scale all the gases ,

agree with o ne another I n the abse nce o f any bette r


reaso ns f or choosi ng a scale the agreement o f so m any


su bstances is a reaso n why the scale of temperatures fur

h ished by the expansio n o fgases should be considered as o f

great scie ntic value I n the course of our s tu dy we


shall nd that there are scienti c reaso ns o f a m u ch higher

order which enable u s to x on a s cale of t emperature ,

based not o n a probability o f this kind but on a more inti ,

mate k nowledge of the properties o f heat Th is scale so .


far as it has been investigated is fou nd to agree ve ry closely


with that o fthe air thermometer .

There is ano ther reas on o f a practical kind in favou r of

, ,

the u se o f air as a thermome tric substance namely that air , ,

remains in the gaseo us state at the lowest as well as the

highest t empe ratu res which we can prod u ce and there are ,

no indicatio ns i n ei ther case of i ts app roachi ng t o a change

o f state .Hence air o r one o f the pe rmanent gases is o f

, ,
48 Ther mammy .

of the temperatures efe rence such for instance as the

of r , , ,

freezing po int o fmercury o r the melti ng point o f sil ve r .

We shall co nsi der the p ractical method o f using air as a

thermome tric substance whe n we come t o G asom etry In .

the meantime let u s consider the air thermome ter in its

simplest form that o fa long tu be o f uni form bo re closed at

o ne end and conta

i ning air o r some other gas which is
s epar ated from the outer air by a short colu mn o f m ercury ,

no 5 oil or some o ther l iquid which is

. .

Al l W cap able o f moving freely along the

7 mm
tub c while at the same time i t pre

vents all commu nication between the

co nned air and the atmosphere .

We shall also suppose that the pres

sure acti ng on the conned ai r is in
m .
some way m ai ntai ned co nstant dur

ing the course o f the ex periments

we are going to describe .

The air thermometer is rst sur

ro unded with ice and ice cold water -

Le t us suppo se that the uppe r su rface

o f the air no w stands at the point

marked Freezing} The thermome ter

is the n surrounded with the steam

risi ng from water boiling u nder an
atm ospheri c pressu re of2 9 90 5 inches

o fmercu ry Let the surface o fthe


enclosed air now stand at the poi nt

marked Boiling In this way the .


two temperatures o frefere nce are to

be marked o n the tube .

To complete the scale o f the

we must divide the distance between boi ling and
a selected nu mber of equal parts and carr y ,
A brolu te Z era .

O f cou me ,
c ar

ry the graduatio n far e n ough d own
the tube we shall at last come to the bottom o f the tube

What will be the reading at that point ? and what is meant

by it ?
To determine the reading at the botto m o f the tu be is a
very simple m atter We know that the distance o f the

freezi ng poi nt from the bottom o f the tube is to the dis tance
o f the boiling point f rom the botto m in the propo rtio n of

r to 1 3 665 since this is the dilatation of air be twee n the


freezing and the boiling temperatu res H ence i t follows by

. ,

an easy ari thmetical calcu lation that if as in Fahrenheit s

, ,

scale the freezing point is marked

and the boili ng

point the bo ttom of the tube must be marked

I f as in the C entigrade scale the freezing point
, ,

is marked and the boili ng point ro o the bott om of the


tube will be marked This then is the reading at , ,

t he bottom o f the scale .

The o the r questi on Wh at is meant by this reading ?


req u ires a mo re caref ul consideratio n We h ave begun by .

de ning the measure of the tempe ratu re as the reading

of the scale o fo ur thermome te r whe n i t is exposed to that

temperatu re . N ow if the readi ng co uld be observed at the
bo ttom of the tu be it would i m y that the vol ume o f the

air had bee n red u ced to no thi ng It is hardly necessary to


say that we have no expectatio n o f ever observing s u ch a

reading . Ifi t were possibl e to abstract from a subs tance all

the heat i t co ntai ns i t would probably still remain an

ext e nded su bs tance and would occupy a certain vol ume

, .

Such an abstrac tio n o fall i ts heat from a body has never

bee n e ffec t ed so that we k now no thing abou t the tem

ra t re which would be indi cated by an air thermometer

p e u

placed in co ntact wi t h a body absol u tely devoid o f heat .

Thi s m u ch we are sure o f however that the reading would

, ,

be above F .

I t is exce edingly co nve nient especially i n dealing with


questio ns relating t o gases t o recko n tempe ratures no t from

, ,

5 0 l rr momd ry .

the freezing point Fahrenheit s zero but fro m the

, or from

bottom of the tube o fthe air thermometer .

This poi nt is the n cal led the absol u te ze ro o f the arr

thermome ter and temperatures recko ned o m it are called

absol u te tempe ratures I t is probable that the dil atati o n of


a perf ect gas is a little less than 1 3 665 If we suppo se it .

1 3 66 the n ab sol te zero will be

u 46o o n F ahre nhe i t s

scale o r z 73 Ce ntigrade


I fwe add 460 to the ordinary re ading o n Fahre nh eit s

scal e we shall obtain the absol ute temperature in Fahren


heit s degree s


Ifwe add z 73 to the C e ntigrade reading we sh all obtain


the abso l ute tempe rature in Ce ntigrade degrees .

We shall o fte n have occasio n to speak o f absolute

tempe rature by the air thermometer When we do so we .

mean nothing more th an what we have j u st said namel .

temperature reckoned fro m the bottom of the tube of the air
thermomete r We assert no thing as to the state of a body

deprived o fall its heat abou t which we h ave no experim

, ental

knowledge .

One o fthe most hnpo rtant appli c atio ns o f the conception

o fab solute temperature is to simplif y the expressio n of the
two laws discovered re spectively by Boyle and by Charle s .

The laws m ay be comb ined into the stateme nt that t he

to Me absolute tem
peratu re


For ins nce, if we h ave to measure quantities o fa gas by

their vol um es under various conditions as to temperature
and pressure we c an red u ce these vol umes to what the y

would be at some standard temperature and pressure .

Thus ifv P T be the actual volume p ressure and abso lute

, , , ,

temperature and v0 the volu me at the sta nd ard p ressure Po

, ,

and the standard temperature To the n ,

7 T,
A bsolute Temperatures .
5 1

li e have only to compare the relative qu ntities of the

in di
ffe e nt me u em e ts in the s me se
ies f i
gas r as r n a r o exp er

ments we m ,
ay suppose Po and To both unity, and use the
quantity - wi thout always multiplying it by ,
which 18
T Po

a co nstant quantity .

The great scie nti c impo rtance of the scale o ftempe rature
as determined by means o fthe air o r gas thermom eter ari ses
from the f act establish ed by the expe riments of Jou le and

Thomso n th at the scale o f temperature derived from the


expansion o fthe mo re pe rmanent gases is almost exactly the

same as that f ounded u pon purely thermodynamic co nsidera ~

ti ons which are independe nt o fthe peculiarp rope rties ofthe


thermometric body This agreeme nt has been experimentally


veri ed o nly withi n a range o f temperature between 0 C


and 1 00 C I f howeve r we ac c ept the m olecular theory o f

, ,

gases the volume o f a perfect gas ought to be exactly pro


portional to the abs olute temperatu re o n the th erm odynamic

scal e and i t is probable th at as the temperature ri s es the

properties o f real gases approxim ate t o those o f the theo o

All the the rm ome ters which we have considered have

bee n constructed on the principle o fmeasuring the expansio n
o fa substance as the tempe rature rises In certain cases i t is .

convenient to estimate the te mperature o fa substance by the

heat which it gives ou t as i t cools to a standard temperature .

Thus if a piece o f platinum heated in a furnace is dropped

fo rm an es timate of the temperature o f
amou nt o f heat comm unicated to the

nticthan that fo unded o n expan

so if the same qu anti ty o f heat always

se o f tempe rature whatever the original


full methods o t measuring gu es the studc nt is

account o fthe

Bunsen s Garmd ry translat ed by Roscoe


8 2
5 2 The r momtry .

temperature of the body But the specic heat of m . ost

substances i ncreases as the temperature rises , and it in
creases in diffe rent degrees fo r dierent substances so that

this method cannot furnish an absolu te scale o ft emperature .

It is only in the case o fgase s that the specic heat o fa given

mas s of the su bstance remains the same at all t emperatures .

There are two methods o f estim ating tempe rature which

are f ounded o n the electrical properties o f bo di es We .

canno t wi thin the limi ts o f this treatise e nter into the

, ,

theory of these methods but must refer the stude nt to works


o n electr i ci ty One of these me thods depe nds o n the fact


that in a co nducti ng ci rcuit formed of two different metals ,

if one of the ju nc tio ns be warmer th an the o ther there will ,

be an electromotive force which will p rod u c e a current of

electricity in the circu it and this m ay be measured by

means o fa galvanomete r I n this way very minu te di fferences


o ftem pe rature between the ends o fa piece ofmetal m ay be

detected Thus ifa piece o f iro n wire is soldered at both


ends to a cop pe rwire and ifo ne of the j unctions is at a place


where we cannot introdu ce an ordinary thermom eter we m ay ,

ascertain its temperatu re by placing the othe r junctio n in a

vessel ofwater and adj us ting the temperature of the w ater

till no current passes The t emperatu re o f the water will

then be equal to that ofth e inaccessible junctio n .

Electric currents exci t ed by difference s of tempe rature in

dierent parts o fa metallic circuit are called thermoe lec tric

curre nts An arrangeme nt by which the electromo tive forces


arising f rom a number o f j unctio ns m ay be added together

is called a thermopile and is used in experime nts o n the


heating e ffect of radiati on becau se i t is mo re sensi tive to


changes of temperature caused by small quantities of heat

than any other instrume nt .

Professor Tai t has found th at if t, and 1, deno te the

tem p eratu r es o f the ho t and cold j unctio n o f two metals,

M q w
r qf Roy al /M
dy g M A 8
1 70 7 1
El ms xI m -
a a mM M .

the electro motive fo rce of the circui t formed by these two

metals is
4 fall
A (1
f [ T i 01

where A is a constant depending on the nature ofthe metal s ,

and r is a tem perature al so depending on the metals ,

such that when o ne j unction is as m uch hotter than T as the

other is colder no cu rrent is p roduced r may be called the

neutral tem rature f o r the two me tals Fo r coppe r and .

iro n i t is about 2 84 C

The other method of estimating the tem perature of a place

at which we cannot set a thermometer is f ounded on the
increase o f the elec tric resistance of metals as the tempe
rature rises This me thod has bee n success fully empl o yed

by M r Siemens Two coils o fthe same kind o fne platinum



wire are prepared so as t o have equal resi stance Their .

ends are co nnected with lo ng thick copper wires so that the ,

coils may be placed if necessary a long way from the gal va

no m eter These copper termi nals are al so adjusted so as to

be o f the s ame resistance fo r both coils The resistance o f .

the terminals should be sm all as compared wi th that o f the

coils One o f the coils is then sunk say to the bottom o f

the sea and the other is placed in a vessel o f water the

, ,

tempe ratu re o f which 13 adj us ted till the resistance of bo th

coils i s the same By asce rtaining wi th a therm o meter the

temperature of the vessel o fwater that o f the bottom ofthe ,

sea m ay be ded u ced .

M r Siem
. ens has found that the resistance of the me tals
may be exp res sed by a form ula o fthe form
R a V i z
1 T 7,
where a is the resistance r the absolu te temperature and , ,

a B y coe f cients Of these a is the largest and the re


sistance dep endi ng o n i t increases as the sq uare root of the

abs olute temperature so that the resistance i ncreases more


slowly as the temperature rises The second term [3 r is .
, ,

M nngs of Roya l S w ay, April


ea : 2 7, 3 8 7 1 .


HAVING explai ned the p rinciple s of Thermome try o r the ,

method of ascertaining temperatures we are able to under

stand what we m

ay call C alorimetry o r the m ethod of


measuri ng quantities ofheat .

Whe n heat is applied to a body it prod uces effec ts of

various kinds I n most ca se s i t raises the temperature of

the body ; it generally alte rs its vol ume o r its pressure and in ,

ce rtain cases it ch anges the state of the body fro m so lid to

liquid o r fro m liquid to gaseous.

Any eect o f heat m ay be used as a m eans o f measuring

quantities of heat by applying the p rinciple th at when two

equal p ortions o f the same substance in the same state are
act ed o n by heat in the same way so as to p roduce the
same effec t then the qu antities o fheat are equal
, .

We begin by choo sing a standard body and dening the ,

standard e ffect o f heat upo n it Thus we m

. ay ch oose a
pound ofice at the freezing point as the standard body and ,

we m ay dene as the unit o fheat that quantity o fheat which

must be applied to thi s pound o f ice to convert it into a
pound o f water sti ll at the freezing po int This is an .

example o f a certain change o f state being used to dene

what is meant by a quantity ofheat This u nit o f heat was

b ht into actual use in the expe rime nts o f Lavoisier and


Inthis system a quantity o f heat is meas ured by the

number of pounds (or of grammes ) of ice at the freezing
TIn Uni t o f H w t .

p o i nt which that quantity of heat would co nvert into wate r

at the freezing point .

We might also employ a dierent system o fmeasurem ent


by dening a quanti ty ofheat as m easured by the number o f

p ounds of water at the bo iling po int which it would c onvert
i nto steam at the same temperature .

This method is frequ ently used in determining the amount

o fheat generated by the combustio n of f uel .

N eitherof these methods requires the use of the thermo

meter .

Anothe r method depending o n the use of the thermo


meter is to dene as the unit o f h eat that quantity of h eat


which ifapplied to unit o fmass ( one pound or one gramme)

o f wate r at some standard temperature ( that o f greatest

density 39 F or 4 C , or occasi onally some temperature




m ore convenient for l aboratory work such as 62 F or 1 5 ,


will raise that water one degree (Fahrenheit o r Centigrade )

According to this metho d quantity of heat is me asured

by the quantity o fwater at a stand ard temperature which that
quantity ofheat would raise o ne degree .

All that 18 assumed 1n these methods of measuri ng heat i s

that 1f1t takes a certain quantity o fheat to produce a certai n
effect on o ne pound ofwater in a certain state then to prod uce ,

the same effect on another similar pound o f water will

require as much heat so th at twice the qu antity of heat

is required for two pounds three times for three pounds

, ,

and so on .

We have no right to assu me that bec ause a u nit of heat

raises a pound o f wate r at 3 9 F o ne degree there f

ore two

units o fheat will rai se the same pound two degrees for the
quantity of heat requ ired to raise the w ate r from 40 to 41

may be different from that which raised it from 3 9 to

Indeed it has been fo u nd by experiment that mo re he at


is requ ired to raise a pound o f water one degree at high

te mperatures than at low ones .
5 6 Calori metr
y .

But ifwe measure heat according to either of the metho ds

al ready described ei ther by t he quantity ofa particular ki nd

o f matt erwhich it c an ch ange f rom o ne easily obse rve d state

to another without altering its temperature or by the ,

quantity of a particular kind o f matter which it can raise

from o ne give n tempe ratu re to another give n t emperat ure ,

we may treat q uan tities of heat as mathematical quanti ties ,

and add o r subtract them as we please


We have howeve r in the rst place to es blish that the

, ,

heat which by entering o r leavi ng a body in any manner

p roduces a given ch ange in it is a quantity stri ctly com
parable with th at which melts a pound o f ice and diers ,

f rom it o nly by bei ng so m any times greate r o r less .

I n other words we have to show that heat o f all kind s


whe ther coming from the hand o r ho t water o r ste am o rred

, ,

ho t iro n o r a am

, e o rthe su n o rf
rom any othe r source c an
, ,

be measured i n the same way and that the qu antity o feach


requ i red to e ffect any given ch ange to mel t a po und o f ice

, ,

to boil away a pound ofwater, o r to warm the waterfrom one

temperature to another is the same from wh ateve rsource the

heat comes .

To nd whether these e ffects depend on anything excep t

the quantity of heat received for instance if they depend in ,

any way o n the temperatu re o f the source o f heat supp ose

two experiments tried I n the rs t a certain quanti ty o fheat


( y
sa the he at emitt ed by a c andle while a n i nch o f candle is
consumed ) is app lied directly to melt ice I n the second the

same quantity of heat is applied to a piece of iro n at the

f reezing point so as to warm i t and the n the heated iro n is

plac ed in ice so as to melt a certai n q uanti ty o fic e while the ,

iron itself is c ooled t o its o riginal temperature .

If the quantity o f ice melted depends o n the tempe rature

of the sou rce f rom whe nce the heat p roceed s o r o n any ,

the heat the quan ,

A ll H eat is of we same ki nd .

the second the same quantity of heat comes o '

It is found by experiment that no such difference exists ,

and theref ore heat co nsidered with respect to its power of


warming things and changing their sta te is a quantity stri ctly ,

capable o f m easurement and no t subj ect to any variations


i n quality or in kind .

Another p rinciple the tru th o f which is established by


c alo rim ric al experiments is that if a body in a give n state

, ,

i s rst heated so as to ake i t pass through a series o fstates
dened by the tempe rature and the volume o f the body

i n eac h state, and if it is then allo wed to coo l so as to

as in reverse o rder th ro ugh exactly the same series of
p s

states, the n the quantity o fheat which entered it d uring the

h eating process is equal to that which left it d uri ng the

cooling process By those who regarded heat as a sub

stance and c alled i t Calo ric this principle was regarded

, ,

as selfevident and was ge nerally tacitly assum ed

We shall .

show however that though it is true as we have s tated i t

, , ,

yet if the series o f states du ring the proces s o f heating is


different from that during the pro cess o f cooling the quan ,

tities o f h eat abso rbed and e mitt ed may be dierent In


fact heat m ay be gene rated o r destroyed by certain pro

cesses and this shows th at heat is no t a substance By
, .

nding what it is produced from and what it is reduced to, ,

we may hope to determi ne the nature ofh eat .

In m o st of the cases in which we measure quantities of

heat the heat which we measu re is p assing o u t o f o ne body

i nto another o ne of these bodies being the calorimeter


itself We assume th at the quantity of heat which leaves


t he o ne body is equal to th at which the o ther re ceives ,

provided rst that nei ther body receives o r parts with heat
, ,

to any third body ; and z ndly that no ac tio n takes place

, ,

among the bodies excep t the giving and receiving o fh eat .

The truth of t his assumptio n m ay be established ex

p erimen lly by taki m

ng a nu mbe r o f bodies at differe nt
5 8 Calori metr
y .

temperatu res and determini ng rst the quantity of heat re


quired t o be give n to or taken from each separately to bring

i t to a ce rtain standard temperature If the bo dies are .

no w brought to their origi nal temperatures and allo wed to ,

exch ange heat amo ng themselves in any way then the total ,

quanti ty ofheat required to be given to the system to bring

it to the standard temperature will be fou nd to be the same
as that which wo uld be deduced f rom the results in the rs t

We now proceed to dwcribe the experimental methods

by which these results may be veried and by which quanti ,

ties ofheat in general may be measured .

I n so me o f the earlie r exper

i me nts o f Black o n the heat
required to mel t ice and to boil water the he at was app lied ,

by means ofa ame and as the supply o fh eat was as sumed


t o be u niform the quantiti es o f heat supplied were i nferred


to be proportio nal to t he time d uring which the supply

conti nued A meth o d o f this kind is obvi ously very im

pe rfect and m order to make it at all accurate would need


nu m ero u s p recautio ns and auxiliary investigations with

respect to the laws o f the prod uctio n o f heat by the ame
and i ts appli c atio n t o the body which is h eated Another .

method also dependi ng on the observation of time is more

, ,

wo rthy o fcondence We shall descri be i t under the name


ofthe M ethod ofCooling .


M lcke, a Swede, was

the rst who employed the melting
of snow to meas ure the heat given off by bodies i n co o ling .

The principal diiculty m this meth od is to ensure that all

f by the body is em
the h eat given of ployed in melting the
ice and that no other heat re aches the i c e so as to melt it
, ,

o rqes mpe s o
mthe water so as to eeze it

. This co ndition
Tbe [ cc Calori meter .

the Frm c h Academy of Sciences for 1 7 80 The instrument .

itself is preserved in the Conservatoire des Arts et M tiers

Frc 6 . .

af e eived the

name of Calo rimeter c o n ,

sists o f three ves sels o ne ,

wi thin another .

The rst or i nnermost

the receiver is intended t o


hold the body from which

t he heat to be measured
escapes . It is m ade of
thin sheet co pper so that ,

the heat may readily pass

i nto the second vessel The .

sec ond vessel, or calo rimeter proper entirely surro unds the ,

rst The l ower p art o f the space betwee n the two vessels is

lled with broken ice at the freezing ( o r melting) po int and ,

the rst vessel is then covered by means o f a lid which is ,

i tselfa vessel full of broken ice When the ice m elts in this

vessel whether in the lower part or in the cove r o f the rst


vessel the water trickles down and passes through a drainer

, ,

which preve nts any ice from escaping and so runs out i nto a ,

b ottle set to catch i t The third vessel which we m

. ay call ,

the ice jacket entirely su rro und s the seco nd and is furnished
, , ,

like the second with an upp er lid to cover the second Both
, .

the vessel and the lid are full of broken ice at the freezing
poi nt, but the water formed by the melti ng of this ice is
carried o to a vessel distinct from that which contains the

water fro m the calorimeter p rope r .

Now, suppose that there is nothing in the receiver and


that the tem ture o f the surroundi ng air is above the

freezing p oint
wl m
Any heat whi ch enters tine Q \QX name

e lt so m e of the ICC in the ack et and w m W


j ? ,
60 Calori metr
y .

and no will be mel t ed in the calo rime ter As long as

ic e

there is ice in the j acket and in the calorimet er the term

p er a tu re o fbo th will be the same th at is, the f
r eezi,
ng poin t ,

and there f o re by the law of equilibri u m of heat no heat

, ,

will pass th ro ugh the seco nd vessel either outwards o r

inwards H ence if any ice is mel t ed in the calorimet er
, ,

the heat which mel ts i t must come from the receiver .

Le t u s next suppose the receive r at the free zing tempera

ture le t the two li ds be carefully lifte d o foran instant and

a body at some higher t emperature i ntroduc ed into the re


c ei ver then let the l ids be qui ckly repl aced H eat will pass .

from the body thro ugh the sides o f the receive r int o the
calorime ter ice will be melted and the body will be cooled,
, ,

and this process will go o n ti ll the body is cooled to the

freezin g point after which there will be no more ice

melt ed .

I f we measure the wate r p roduced by the melting of the

ice we m
ay estim ate the quantity o f heat which escapes
from the body w hile i t c ools from its original tempe rature to
the freezi ng point The recei ver is at the freezing poi nt at

the begi nning and at the end o f the operation 80 that the ,

heati ng and subsequ e nt cooling o f the receiver d oes not

in ue nce the res ult .

N o thing can be mo re perfect than the theory and design

o f this apparatus It is worthy o fLaplac e and ofLavoisier

and in thei r h ands i t f urnish ed good results .

The chief inco nve nience in using it arises fro m the fact
that the wat er adheres to the broke n ice instead o fdraining
away f rom it completely so that it is im p,o ssb
1 le to es tima te
acc u rat ely how m u ch ice has really bee n melted .

To avoid this source o f u ncertainty Sir John He rschel ,

proposed to ll the i nterst ice s o f the ice with wate r at the

freezing point and to estimat e the quantity o fice melted by

the contractio n which the volume of the whole u ndergoes ,

since as we shall a erwards see the volume of the water is

, ,

les s than that o f the ic e from wh ich it was fo rmed I am .

Hansen s Calori m
eter . 6r

no t aware that this suggestio n was ever developed into an

exp erimental meth o d .

Bunsen independently devised a cal orimeterfo unded o n


the same p rinciple but in the use of which the so urces


o f er ror are eliminated and the ph ysical constants deter ,

mined with a degree of precision seld om before attained

in researches o f this ki nd .

B unsen s calo rimeter as devised by its au thor is a small

, ,

instrument The body which is to

Pro 7 . .

give off the heat which is t o be

measured is heated in a test tube -

placed in a cu rre nt o f steam o f

known temperature It is then .

dropped as quickly as may be int o

, ,

the test tube T o f the calo rimeter


which co ntai ns w ater at 0 C The


body sinks to the bottom and gives

of fheat to the water The heated water do es no t rise in the

tube fo r the eect ofheat on water between 0 C and 4 C



i s t o increase i ts de nsity It therefore remains surrounding


the body at the bottomofthe tube and its h eat c an escape ,

only by conduction eithe r u pwards throu gh the wat er o r ,

through the sides o f the tube whi ch being thin afford a , , ,

be tt er channel The tube is surrounded by ice at 0 C in



the calo rimeter C so that as soo n as any part o f the water

, ,

in the tube is raised to a higher temperature co nd uc tion ,

takes place thro ugh the sides and part o fthe rec is mel ted ,

This wi ll go on till everything within t he tube is again

reduced to 0 C and the whole qu anti ty o f me mel ted by


heat mn wit/ti n is an accurate measure o fthe heat which

the heated body gives out as it cool s to 0 C

To p reve nt any exch ange ofhe at betwee n the calo ri meter

c and surro undi ng bodies it is pl aced i n a vessel 5 lled with,

snow gathered whe n new fallen and free from smoke This

Po . Amt Sep t . . 1 8 70, and F I511 . Mag . 1 871 .

Oz Calori metr
y .

subs tance unless the tempe rature o fthe room is below o C ,


soon acqu ires and lo ng maintains the t emperature of 0 C


I n preparing the calo rime t er i t is lled with distilled water , ,

from which every trace o fair mus t be expelled by a c a reful

process o fboiling If there is air i n the wat er the p roem

o ff reezi ng expels it and p roduces b ubbles o fai r the volume ,

o f w hich introd uces an erro r o f measurement The lo w .

part of the cal orimeter co ntains mercury and co mm uni cates ,

wi th a bent tube also containing mercury The upper part .

o f this tube is bent horizont ally and is caref ully calibrate d ,

and graduated As the m

. ercur y a nd the vessel are al ways
at the tempe ratu re 0 C they are o f constant volume and

, ,

any changes in the p ositio n o fthe mercury in the graduate d

tube are due t o the mel ting o f ice in the calo rime ter and ,

the co nseque nt diminu tion o fvolume o fthe mass o f ice and

water in it .

The moti o ns o fthe ex tre m ity o f the col umn of merc ury
being proporti onal to the quanti ties o f heat emitted from
the test tube i nto the calorimeter it is easy to see ho w

quantities o fheat m ay be compared In f act Bunsen has .


made satisfacto ry de t erminatio ns ofthe specic heat ofthose

rare metals such as indium of whi ch o nly a f
, ew gr ammes

have bee n obtai ned .

To p repare the calori meter for use ice m ust be formed ,

in the calo rime ter round the test tube Fo r thi s p urpose -

Bunsen causes a current o falcohol, cooled bel ow 0 C by a


freezing mixture t o ow to the bo ttom o f the tes t tube and


u p alo ng i ts sides In thi s way the greate r part o fthe water


in the cal o rimeter is soo n froze n When the apparatus has .

been le ft fo r a sufcient time in the vessel co ntaining snow ,

the temperature ofthis we rises to 0 C and the apparatus

ay be m

is ready fo r use A great many experime nts m

. ade
aft er o ne freezing o fthe wat er

See Peg . Arm S ept. . 1 8 70, or Phil M 03

. . 1 87 1.
Exfe mmts f r the S tud nt
o e . 63


The second col orim etric method is us ually called the

M ethod o fM ixture This name is give n to all the processes


i n which the quanti t o fheat whi ch escapes from o ne body

is measu red by the increase o f temperature it prod uce s in
another body i nto which it es capes The m ost perfect

meth od o fensuring that all the heat which escapes from the
o ne body pas ses i nto the o ther is to mix th em bu t in m any ,

cas es to which the method is no w applied this canno t be

done .

We shall illustrat e this method by a few experiments ,

which can be performed by the stude nt wi thout any special

apparatus . A few experiments o f this kind ac tually per
formed y himself will give the stude nt a mo re intellige nt
interest in the su bj ect and will give him a more lively faith

in th e exactness and uniformity of nature and in the m ac


curacy and u nce rtainty o four observatio ns than any reading ,

o fbo o ks o r eve n witnessing elabo r

ate experime nts perf
o rmed
by p ro fessed men of science .

I shall suppose the student to have a thermome ter the ,

bu lb o fwhich he can immerse in the liquids o fwhich the

temperature is to be measured and I shall s uppo se the

graduatio n of the thermometer to be that of Fahre nheit as ,

it is the most c o mmon in this co untry .

To co mpare the ef fects o fheat on water and on lead take ,

a strip o f sheet lead weighi ng say o ne pound and roll i t

, , , ,

into the form of a loose spiral so that whe n it is dropped


into wate r the watermay play round eve ry part o fit freely .

Take a vessel o fa convenient sh ape su ch th at the roll o f


lead when placed in the vessel wi ll be well covered with a

H ang up the lead by a ne string and dip it in a saucepan

of boi li ng water and co ntinu e to boil i t till i t is

heated While this is goi ng o n weigh

64 Calo ri metr
y .

water in your vessel and ascertain its temperature with


the thermome te r Then li ft the roll o f lead out o f the


bo ili ng water hold it i n the steam till the water is drained


o and i mmerse it as quickly as po ss1b le in the cold water


in the vessel By means o fthe stri ng you m

. ay sti r i t abo u t in
the water so as to bring it in co ntact wi th new portio ns o fthe
water and to prevent it from giving its heat directly to the

sides o fthe vessel .

From time to time obse rve the temperature of the water

as indicated by the thermometer I n a few mi nutes the .

temperature o f the water will cease to rise and the experi ,

me nt may the n be stopped and the calculatio n begun .

I shall su ppose (fo r the sake of xing o ur ideas) that the

t empe ratu re of the wat er before the hot lead was p ut in was

F. an
d tha t the nal tempe ratu re whe n the le a d cea sed ,

to impart heat to the wat er was 62 F If we take as our ,


unit o fheat that quantity o fheat which wo uld raise a pound

o f wate rat 60 F o ne degree, we have here ve uni ts o fheat


imparted to the water by the lead .

Since the lead was fo r some time in b o iling water and ,

was aft erwards held in the s team we m ay assume its o riginal ,

temperature to be 2 1 2 ( thi s however should be teste d by the

, ,

thermome ter) D uring the experime nt the l ead cooled 1 5 0


f om 1
r 2 2 to 6
and gave o u t as we h ave seen ve units , ,

of heat to the water Hence the difference o fthe heat of a


po und o flead at 2 1 2 and at 62 is ve u ni ts o r the same

quanti ty ofheat which will heat a po und ofwaterve degrees

from 5 7 to 62 will b eat a pound oflead 1 5 0 degrees f rom

62 to

I f we ass u me wh at is nearly th ough no t,

exac tly true th at the quantity o f heat requ ired to heat the

lead is the same for each degree of rise of temperature the n ,

we might say th at to raise a po und o f lead ve degrees

requires only one thirtieth part o fthe heat requ ired to raise

a p ound of water ve d egrees .


eec ts o fheat o n
TImmal Cap ac i ty o f a B ody .

raise a pou nd o flead thro ugh thi rty times as

as it would raise a pou nd o f w ate r and we ,

that to prod uce any mode rate ch ange o f

n a pound o flead requ ire s o ne thirtie th o f the -

to p rod uce the s ame change on an equal weight

in scie ntic language by

heat is o ne thirtieth o f

ard subs tance with

mo re co ncise manner
is $10 .

quicksilve r and water

ture is no t the mean o f
of the i ngredients was k nown t o Boe rhaave

D r Black howeve r was the rs t to explain

, ,

and m any o thers by the doctri ne which he

that the e ffect o f the sa me qu anti ty o f heat in
t emperature ofthe body depends no t only on the
matter in the body bu t o n the ki nd of m atte r o f

fo rmed Dr I rvi ne Bl ack s p upil and assistant

. .
, ,

is p roperty of bodies the name o f Capacity for

e expressio n Speci c H eat was aft erwards i ntro

sh all secu re acc uracy along wi t h the greatest


to established cu s tom by de ning these te rms



cap ac ity of a body for beat is Me mber qf write qf

mire flzat body dqone f p
ree o te m eratu re .

spe ak o f the he at o f a p articular

capaci ty fo r
as a coppe r vessel in which cas e the capacity

11 t he weight as well as o n the kind of matter .

stating the quantity ofwat e r which has the same c apaci ty .

We may also speak o f the capacity for h eat ofa su bstance ,

such as copper in which case we ref

, er to u ni t of m ass of the
substance .

D EF I N IT ION o r sp ac rrr
c H EAT .

7h Sp me H eat of a body is tire ratio o f tir

e q uanti ty q

Thespecic heat therefo re is a ratio o f two qu antities of

the same kind and is exp ressed by the same nu mber what
, ,

ever be the units employed by the observer and whatever


Om etric scale he adopts .

It is very important to be ar in mind that these phrasa

mean neither more no r less than wh at is stated in these de

I rvine wh o contri buted greatly t o establish the fact that


the quanti ty o f heat which e nters o r leaves a body depend s

on i ts capaci ty f
o r heat m u ltiplied by the number o fdegrees

throu gh which its t empe rature ri ses or falls we nt o n t o ,

assu me that the whole quan ti ty o fheat in a body is eq u al to

i ts capacity multiplied by the t o tal temperature o f the body ,

reckon ed f rom a point which he called the absolu t e zero .

This is equivale nt to the assumption that the c apacity o f the

body remai ns the same from the given temperature down
wards to this absolu te zero The truth of su ch an assu mp

ti on could never be proved by experiment and i ts falseh ood ,

is easily es tablished by showing that the specic heat o f

mo st liquid and solid subs tances is different at different
temperatu res .

The resul ts which I rvi ne and o thers lo ng after him

, ,

ded uced by calcul ations fou nd ed on this assu mptio n are no t

only of no val u e bu t are shown to be so by their i ncon

n o fthe experiment
Sp ecic H eat o f a S u bstance . 67

with the lead and water in orde r to show how i t can be


m ade mo re accurate by atte ndi ng to all the circumstances o f

the case I h ave p urposely avoided doing so at rst as my

objec t was t o illustrate the meani ng o f Specic Heat .

I n the fo rme r descriptio n o f the e xpe riment i t was

assumed no t o nly th at all t he heat which escapes f
rom the

lead e nte rs the water in the ve ssel bu t th at i t rem ains in


the wat er till the co nclu sio n o f th e experim ent, whe n the
t emperatures o f the lead and wat er have become equalised
The latter p art o f this assu mp tio n cannot be quite true ,

for the wat er m u st be co ntained i n a vessel o f some kind ,

and must communicate some o f i ts heat t o this vessel and ,

al so m u st lose heat at i ts u ppe r surf

ace by evaporation & c ,

I fwe could form the vessel o f a perfect no n co nd uc to r o f -

b eat this loss o f heat from the w ater would no t occ ur; bu t

no su bstance o f which a vessel c an be formed c an be c o n

si der ed eve n approxima a no n conduc to r o fheat ; and if


we use a vessel which is me rely a sl ow conductorofh eat it is ,

very dif cul t eve n by the mos t elaborate calculatio ns to

, ,

determi ne how much he at is tak en up by the vessel itself

d uring the expe rime nt
A bette r pl an is t o u se a ves sel which is a ve ry good
co nduct or o f heat b ut of which the capaci ty for heat is

small such as a t hin copper o r silver ves sel and t o p revent

, ,

this vessel from parting rapidly wi th its heat by poli shing

its outer surface and no t allowing i t to touch any large

mass of metal but rather givi ng it slender su ppo rts and


placing it within a me tal vessel having its inner surface

In this way
we shall e nsure that the heat shall be qu ickly
distributed betwee n the wate r and the vessel and may con ,

sider their temperatures at all times nearly equal while the ,

loss o fheat from the vessel will take pl ace sl owly and at a
rate w hich m ay be calculated when we know the temperature
of the vessel and o fthe air o u tside .

For this purpo se ifwe int e nded to m ake a very elabo rate

t 2
experimen t we should i n the rst place determi ne the

c apaci ty for he at o fthe ve ssel by a separ ate experim ent and ,

then we should put i nto the vessel about a pou nd of warm

wate r and dete rmine its tempe rature from mi nu te to mi nute ,

while at the same time we obse rve with ano ther th ermom eter
the t emperature o fthe air in the room I n this way we should .

obtai n a set o f ob servations from which we might d ed u ce the

rate of cooli ng f fere nt t emperatu re s and compute the
or di f ,

rate o f cooling whe n t he vessel is o ne two three &c , , , .


degrees ho t te r th an the air and then knowi ng the tempe ,


rat ure o f the ve ssel at vario us stage s o f the experiment f or

nding the specic heat o fle ad we sho uld be able to c alc u


lat e the loss ofheat from the vessel due to the cooling during
the co nti nu ance o fthe expe rime nt .

B ut a m u ch simple r method o f ge tti ng rid o f these dii ~

cu lties is by t he me thod o f maki ngtwo experim en ts the rst

wi th the lead which we have described and the second wi th ,

ho t wate r, in which we e ndeavou rto make the ci rcums tances

which cause the loss ofhe at as similar as we can to those in
the case o fthe lead .

Fo r ins tance ifwe su ppose th at the specic gravity o flead


is about eleven times th at o f water ifinstead o fa pound o f


lead we use o ne eleventh o fa po und o fwate r the bulk of the


water will be the same as th at of the le ad and the dep th of ,

the water in the vesse l will be equ ally i ncreased by the lead
and the water .

If we al so suppo se that the specic heat of lead is one

thirtieth o fthat o fwater the n the heat given ou t by a po un d

of l ead i n co oling 1 5 0 will be eq u al t o the heat gi ve n o ut

by one eleventh o fa p ou nd o fwat er i n c ool ing


Hence ifwe take o ne e leventh o fa pound o fw ate r at 5 5


above that is at and pour it into the vessel wi th

the water as before at we may expect th at the lev el o f
the water will rise as much as when the ho t lead was pu t in ,

t he temperature will also rise to abou t the same

The only dierenc e between the expe riments as


far as the l oss o f heat is conce rned is that the w arm wat er , ,

will rai se the t empe rat ure of the cold water in a m uch
sho rt er tim e than the ho t lead did so th at ifwe observe the ,

t empe ratu re at the same time aft er the mixture in bo th

cases the loss by cooling will be great er wi th the warm wat e r

th an wi th the hot lead .

In this way we m ay ge t rid o f the chie f part o f the di th

cu l ty o f m any e xpe rime nts o f compariso n I nstead o f .

m aking o ne experiment in which the cooli ng o f the lead is


c omp ared wi th the heati ng o f the wat e r and the ves sel ,

i ncluding an unk nown loss o f heat from the ou tside o f the

ve ssel we m ake two e xperiments in which the heating
, ,

o fthe vessel and the total lo ss o f heat sh all be as nearly as

possible the same but in which the heat is furnished in the


o ne c ase by hot lead and i n the other by warm wate r


The student m ay compare this method wi t h the method o f

double weighing i nve nted by P re Amiot bu t commonly ,

known as Bo rda s meth od in which rst the body to be


weighed and then the weights are placed in the same scale
, , ,

a nd weighed agai nst the same counterpoise .

We shall illu strate this method by nding the e ffect ofsteam

m heati ng water and comparing it wi th th at o f hot water
, .

Take a ke t tle and m ake the lid tight with a little our and

w ater and ad apt a short i ndia rubber tube to the spo u t and

a tin o rglass nozzle t o the t ube M ake the wat er in the kettle

boil and whe n the steam comes freely through the nozzle

dip i t in cold water and yo u will s atisfy yourself th at the


steam is rapidly co ndensed every bubble o f s team as it


issues coll apsi ng wi th a sharp rattling noise .

Having made yoursel f familiar with the general natu re o f

the expe rime nt o f the co ndensation o f steam yo u may ,

proceed to measu re the heat given o ut to the water Fo r .

this purpo se pu t so me cold wat e r in yo ur ves sel say about

, ,

three quart ers o f a pound

Weigh the ve ssel and wate r

carefully and observe the temperatu re o f the water ; then

, ,

w hile the s team ows freely from the nozzle, co nde nse steam
in the wate rfora sh ort time ,
and r emo ve the noz zle ob serve

taki ng no te of the time t he experiment

of .

Let us su pp o se the ori ginal weight

Weight after the co ndensation ofsteam
H ence the weight ofsteamco ndensed is
Tem p erat u re o f w at er at fi rs t
Tem pera tu re at the e nd o f ex p eriment
Rise o ftem p era ture

Let us no w make a second experimenh as like the rst

as we can o nly diering f rom i t by the use o f h o t water

ins t ead o fsteam to prod uce the rise of t emperature .

It is impo ssible in practice to ensu re that everythi ng shall

be exactly the same but afte r a few trials we m
ay sel ect a
me thod which will nearly if no t qui t e full the conditions
, ,

Thus it is easy to b ring the vessel and cold water to the

same weight as befo re namely 5 ooo grains but we shall
, , ,

suppose the temperature no w to be 5 6 F inst ead of


We now pour in water at 1 76 F gradually so as to make this


experime nt l ast about as lo ng as the rst and we nd that ,

the t emperature is now and the weigh t 6 ooo grai ns , .

Hence r o oo grai ns o f water cooling ro o raise the vessel


and its co nte nts

Assumi ng that the specic heat o f water is the same at

all tem peratures which is nearly tho ugh by no means
, ,

exactly true the quantity 05 heat given out by the water

, ,

i n the sec o nd experim ent is equal to what would rais e

t oo ooo gr
, ains ofwater o ne degree .

In the experiment with the s t eam the t emperatures m

nearly though no t exactly equal bu t the rise o f t emper
, a ture
was greater in the p roportio n o f 2 2 to s o Hence we may .

con lude that the quanti ty o f heat which prod uced this
L atent H eat f
o S tea m
7 1

This was done by the co nde nsati o n and su bsequ ent

cooling o f 1 00 grains o f s t eam Le t us begin wi th the heat

given ou t by the t oo grains o f wat er at 2 1 2 E i nt o which


the steam is co ndensed It is cooled from 2 1 2 to 7 7 o r

1 and gi ves o u t there f ore an amount o f heat which

would raise grains of water o ne degree But the .

whole effect was so th at the re is an amount of

heat whic h would raise grains of wat er o ne degree ,

which must be given out during the co ndensation o f the

steam and before the cooling begins H e nce each grain

o f steam in co ndensi ng gi ves o u t as mu ch he at as would

raise 965 grains o f w ate r r F o r 5 3 6 grains 1

C enti .

grade .

The fact th at steam at the boiling point gives o u t a large

quanti ty o f heat when i t is co nde nsed into w ate r which is
still at the same tempe rature and the converse fact that in

order to convert water at the boiling temperature i nto steam

o f the s ame temperature a large quantity o f heat must

be comm unicated to it was rst cle arly established by


Black in 1 7 5 7 .

H e e xpressed it by saying that the lat ent heat o f steam

is 96 5 F and thi s form o f exp re ssio n is still in u se and

, ,

we should take it to mean neithe r more nor less than what

we have j us t st ated .

Black however and many o f his followers supposed he at

, , ,

to be a subs tance which whe n it makes a thing ho t is

sensib le bu t which whe n it is not pe rceived by the hand

o r the thermome t er still exi sts in the body in a lat e nt o r

co nceal ed state Black s pposed th at the difference be tween


boili ng wate r and ste am is that steam contai ns a great deal


more calo ric than the hot wate r so that it may be co n ,

sider e d a compou nd o f wate r and calo ric ; b u t since this ,

additio nal caloric p roduces no ef fec t o n the temperature ,

but lurks co ncealed in the steam ready to appear whe n it is

c ondensed he called thi s part o f the heat lat ent heat
, .

I n consi de ring the sc ientic val ue o f Black s discovery o f

7 2 Calori metr
y .

late nt heat and of his mode o f expressi ng it we sho uld

, ,

recollec t th at Blac k him selfi n 1 7 5 4 was the discove rer o fthe

fact th at the b ubbles fo rmed when marble is put into an acid

co nsist o fa real subs tance different from air which wh en e,
e , ,

is similar to ai r in appearance but when xed may exist in


liquid s and in solids This substance which we no w call


carbonic acid Bl ack called xed air and t his was the rst
, ,

gaseous body distinctly recognised as su ch O ther airs or


g a s es we re afterwards discove red and the im i lse given to


chemistry was so great o n account of the exte nsion o f the


scie nce t o these atte nuated bodies th at most phil o sophers ,

o f the time were o fopi nio n that heat ligh t elec tr i ci ty and , , ,

magne tism ifno t the vi tal fo rce i tself would soo ner o r lat er
, ,

be added to the li st Observi ng however that the gases

, ,

could be weighed while the prese nce of these o ther agents


could no t be det ected by t he balance those who admitted ,

them to the rank of substances called them imponderable

substanc es and so metime s o n acco unt of their mobility
, , ,

imp onderable uids .

The analogy be tween the free and xed sta tes o fcarboni c
acid and the sensible and late nt states o f heat e ncouraged
the growth of m at erialis tic phras es as applied t o heat ; and
i t is evident that the same way ofthinking led electri cians to
the notion o f disguised o r dissimul ated electricity a notio n ,

which survives even yet and which 13 no t so easily stripped


o f its erro neous co nnotatio n as the phrase late nt heat


I t is worthy ofremark that Cave ndish though o ne o f th e ,

greatest chemi cal di scoverers of his ti me would no t acc ep t ,

the phrase latent he at

H e p re fers to spe ak of the

generatio n o f heat when steam is condensed a phrase ,

inco nsis tent with the notion that heat is m atter and ,

obj ects to Black s t erm as relating to an hypo th esis

depending o n the suppo sitio n th at the heat o f bodies i s

ntaini ng more o r less of a su bstance
Lat mt H eat .

on ,

bodie s m uch the most probable I ch ose to use
heat is ge nerated

no t no w be in dange r o f any erro r i f we use

expre ssio n meaning nei the r more nor less

a gi ven stale in order

ecognise the fact th at he at whe n applied t o a

ac t i n two ways by ch anging i ts state or by ,

tempe rature and that in ce rtai n cases it may ac t

g the s tate wi thou t i ncreasing the tempe ratu re .

rtant cas es i n which heat is th us employed

1 . The co nversion of solids i nto liquids This is called


the reverse p rocess o f freezing or

be all owed to escape fro m the body

liquids ( or solids ) into the gaseo us


called evaporation and its reve rse co nde nsa


3 . When a gas expands in o rde r to mai ntain the tem


cons tant heat must be commu nicated to i t and

, ,

n p rope rly de ned may be called the latent heat o f


are many chemi cal changes during which heat is

cases the quanti ty of heat which e nt ers o r

body may be measu re d and in orde r to exp ress

o f this measu rement i n a co nvenie nt f o rm we ,

the late nt heat required fo r a give n change in the

care fully remembe r that all that we know abou t

occurs when it pass es from o ne body to ano th er ,

q u o ted by Fo rbes Dissertation V

. I E ncyc B ri t
. . .
74 E lementar D
y y namic al P ri W Ier .

and th at we mus t no t assu me th at after heat has entered

a su bs tanc e i t exists in the f orm of h eat wi thi n that
su bstance .That we have no righ t to make su ch an
ass u mptio n will be abu ndantly shown by the dem onstration

th at heat may be transformed into and m ay be p rod u ced

from somethi ng which is no t heat .

Regnaul t s method of p ass ing l arge q uantities of the

substance through the calorimeter will be descri be d in

treating o f the p roperties o f gases and the M ethod of ,

Coo ling will be conside red in the ch apte r o n Radiatio n .



IN the rst part o f this tre at ise we h ave co nned ourselves

t o the explanation o f the method of ascertaining the tern
p e ratu re of
bodies which we call thermometry and the
, ,

method ofmeasuring the quanti ty o f he at whi ch e nters o r

leaves a body and this we call calorimetry
, Bo th o f these .

are requ ired in orde r to stu dy the eec ts o fhe at upo n bodies ;

bu t we cannot comple t e thi s s tudy without m aking measure

ments o f a mechanical kind because heat and mechani cal

fo rce m ay act o n the same body and the ac tual resul t ,

depe nds on bo th ac tio ns I propo se there fore t o recall to

, ,

the student s memo ry some o f th o se dynamical p rinciples

which he ought t o b ri ng wi th him to the study o fheat and ,

whi ch are necessary whe n he passes from purely therm al

phenomena s uch as we have considered to phenomena ia
, ,

volvi ng p ressu re expans io n & c , and which will enable him

, , .

aft erwards t o proceed to the stu dy o f thermodynamics

proper in which the rel ations o f thermal phe no mena among

themselves are deduced from purely dynamical pri nciples

o mi mportant s tep

The m in the p rogress of ev ery

M easurement of Quantiti es .

s cience is the measurement o f quantities Those who se .

curiosity is satised with observing what happens h ave

occ asionally done se rvice by directing the attention of others
to the phenomena they have seen but it is to those who
e ndeavo ur to nd ou t how mu ch the re is of anything th at
we owe all the great advances i n our knowledge .

Th us every science has so me instrument o f precisio n ,

which may be take n as a material type of that science which

i t has advanced by enabling observe rs t o express thei r

res ul ts as measured quantitie s I n astro nomy we have .

the divided circle in chemistry the balance in heat the

, ,

thermome t er while the whole system of civilised life may


be tly symbolised by a foot ru le a set o f weights and a , ,

clock. I shall therefo re m ake a few remarks o n the

, ,

measureme nt ofqu antitie s .

Every quantity i s expressed by a phrase consisti ng o f two

compo nents o ne o fthe se be ing the nam e of a number and
, ,

the other the name of a thi ng of the same k i nd as the

q uanti ty to be exp ressed but o f a certain magnitude agreed

o n amo ng m en as a standard or u nit .

Th u s we speak of two d ays o fforty eight hours ,


Each of t hese exp re ssio ns has a nu merical part and a

de nominational part the nu meri cal part being a number,

whole o r fractio nal and the de no m

, inational part being the
nam e of the thi ng which is to be taken as many times as is

indi cated by the number .

I fthe nu merical part is the number one then the quantity ,

is the s tandard quantity itself as whe n we say o ne po und , ,

or one inch o r o ne day

, A qu antity o fwhich the numeri cal

part is u nity is called a u ni t When the numerical part is .

so me o ther number the quantity is still said to be re ferred to

, ,

or to be exp ressed in te rms ofth at quantity which wo uld be

deno ted ifthe nu mber were one and which is called the uni t ,

In all cases the u nit is a qu antity of the same ki nd as the

quantity which is exp re ssed by means o fi t .

I n many cases several u ni ts o f the s ame ki nd are in use ,

7 6 E lementary Dy na i cal P n w
r i
p lt s m '

as miles yards, feet andinche s as measures of length cubic

, , ,

yards gallo ns and uid ou nces as meas ures of capacity ;

, , ,

besides the e ndles s varie ty o funits which have been adop ted
by differe nt natio ns and by diffe rent d istri cts and differe nt

trade s in the same nation .

Whe n a quanti ty given i n te rm s o f one unit has to be err

pressed in te rm s o f ano ther we nd the number o f t imes ,

the second uni t is co ntained in the rst and multiply this ,

by the given number .

He nce the nume rical part o fthe expression of t he same

quanti ty varies inversely as the u ni t in which it is to be ex
p ressed as in the example two d ays and fo rty ei ght hou rs
, ,

which mean the same thing .

There are many qu anti ties which can be de ned in t erm s

o fstandard quanti ties o f a dif ferent ki nd I n this case we .

make u se o f derived units Fo r instance as soon as we .


have xed o n a measure of le ngth we m ay dene by means ,

ofit no t o nly all le ngths but als o the area of any su rf

ace ,

and the co ntent o fany sp ace Fo r this purpose if the foot .


is the u nit o f length we construct by Euclid I 46 a square

, , .

whose side is a foo t and exp ress all areas in te rms o f thi s

sq uare foot and by constructing a cube whose edge is


af oot we have dened a cubic foot as a u nit o fcapacity .

We also exp ress velocitie s in miles an ho ur o r fee t in a ,

second & c,

In fac t all qu antities wi th wh ich we h ave to do in dynamics


may be expressed in terms ofunits derived by d eni ti on o m

the three fundamental uni ts o fLength M ass and Time , ,

S A .

It is so impo rtant to mank ind that the se units sho uld be

well dened th at in all civili sed nations th ey are dened by
the S tat e wit h ref
ere nce to m ate rial standards which are pre ,

served wi th the u tmo st me For instance in this country .


line or

18 8: r9 V ic t . c .
7 ,
2 J y 30
ul , 1 85 5 .
Uni ts o f L engt .

distance between the ce ntres of the transverse lines in the

t wo gold plugs i n the bronze b ar deposi t ed i n the o f
o f t he Excheq u er shall be the genu ine stand ard yard
at 62 F and if lo st i t shall be replaced by m eans o f i ts


The uthorised c opies he re referred to are those which are

p re se rved at the Royal M int the Royal So ciety o f London
, ,

the Royal Observatory at Greenwich and the N ew Palace ,

at Westminst er O ther copies h ave bee n m ade wi th great


care and with these all measu res o f length m u st be com


pared .

The length o fthe Parliame ntary s tandard was cho sen so

as to be as nearly as possible equ al to th at of the best
standard yards forme rly u sed in England The State there .

fore endeavou red to m aintai n the stand ard o f i ts ancie nt


m agni tude and by its autho rity it has dened the actual

magnitu de o f this standard wi th all the p recisi o n o f which

m odern science is capable .

The m etre derives i t s au tho ri ty as a stand ard o ma law

o f the F rench Republic in 1 79 5 .

I t is dened to be the distance between the e nds ofa ro d

o f platinum m ade by Bo rda l the ro d being at the t empera

ture o f melting ice This di stance was chose n withou t


reference t o any f orme r measures u sed in France It was .

int ended t o be a universal and no t a national measure and ,

was derived from D elambre and M ec hain s measurement of

the size o f the earth The distance measured al o ng the


earth s surface ho mthe pole to the equat or is nearly ten

etres I f howeve r in the p rogre ss o fgeodesy a

, , ,

ould be obtained from that o f D elamb re ,

will no t be altered b u t the new result will be


in the old metres The authorised standard o f


therefore no t the t erres tri al globe but Borda s ,


co nf r
la lo i du rS Ger ninnL an II I . Prsent le
7 3 E le mntary
e Dy na ical P ri m mpla .

plati num ro d which is m u c h mo re likely to be accu rate ly


measured .

Th e v alue o f the F rench system o f me asu res does not

depend so m uch o n the absolu t e val u es of the units adopted
as o n the f act that all t he u ni ts o f the same kind are

connected toge the r by a decim al syst em o f m ulti plicati on

and divisio n so th at the whole syst em u nder the name of
, ,

the metrical system is rapidly gai ni ng gro u nd even in


countri es whe re the old national syste mhas bee n carefully

dened .

The metre is 3 9 3 7 043 B ritish inches .

S A T ND ARD 0 1" M ASS .

By the Ac t above ci ted a weigh t o f platinum marked

P S 1 844 1
. . depo sited in the o fce o f the Exchequ er
, ,

shall be the legal and ge nu ine stand ard measure o fwei ght ,

and shall be and be de nom inated the Imperial S tandard

Pou nd Avoirdupois and shall be deemed to be the o nly


standard me asure ofweight from which all otherwe ights and

other me asures h aving re fere nce to weigh t sh all be derived ,

computed and asce rt ai ned and o ne equal seven thousand th

, ,

part o f such p ou nd avoirdupois shall be a grain and ve ,

th ousand seven h undred and sixty such grains shall be and

be deemed to be a pound troy Ifat any time herea er the .

said Imperial Standard Po und Avoirdupois be lost o r in any

manner destroyed defaced o r othe rwise inj ured the Com
, , ,

missioners o fHer M aj esty s Treasury may cause the same to

be restored by refere nce t o o r adoption ofany of the copies

aforesaid or such ofthem as may rem ain available fo r that


purp ose
The constructi on o f this stand ard was entrusted to Pro
fessor W H M iller who has given an account of the
. .

methods employed in a paper which may be here referred


to as a m odel of scientic accuracy .

I n the sam pla e

e c s as the S tandards o fIg mh
t .

PM} . ax-r . 1 856, p 75 3

. .
Uni ts f
o M ass .

The French standard o f mass is the Kilogramme des

Archives, made o f plati num by B o rda and is i ntended t o ,

rep rese nt t he mass o f a cubic d ecimetre o f distilled wat e r

at the t empe rat ure 4 C


The ac tu al dete rm ination of the density of wat er is an

ope ration which requi res great care and the differences ,

be twee n the res ul ts obtai ned by the mo st skilful observers ,

though smal l are a tho usand times greater th an the differ


enc es o f the resu l ts o fa comp ariso n o fstand ard s by weighi n

them The diffe rences o f the val u es of the densi ty ofwate r

as fo und by caref ul obse rve rs are as m uch as a th o usandth

part o fthe whole whereas the me thod o f weighi ng admi ts

o f an acc uracy of withi n o ne p art in ve millio ns .

Hence the French standards though originally fo rmed ,

to represent ce rtai n natu ral qu anti ties m ust be no w co n ,

si dered as arbitrary stand ards of which copies are to be ,

taken by direct comparison The French or metri c system


has the advantage of a uniform applicati on of the decimal

me thod and it is also in many case s conve nient to remembe r

that a cubic metre o fwat er is a tonne a cubic decimetre a ,

kilogramme a cubic ce ntimetre a gramme and a c ubic

, ,

millimetre a milligramme the wate r bei ng at i ts maximum


densi ty or at abo u t 4 C

I n 1 8 2 6 the B ri ti sh s tandard o f m ass was de ne d by

saying th at a cu bic inch o f water at 62 F co ntai ns 2 5 2 45 8

grains and tho ugh th is is no lo nge r a legal de nition we

, ,

may take i t as a rough s tatement o f a fact that a cubic i nch ,

of wate r weighs abou t grai ns a cubic foot about ,

o unces avoirdupois and a cubi c yard about three q uarters o f


a to n. Of the se estimat es the second is the furthe st from

the truth .

Professor M iller has compared the British and French

standards and nds the Kilogr
amme des Archives equ al to

x5 43 2 3 48 74 grains
From these legal deniti o ns i t will be see n that what is
generally called a standard of weight is a c ertain piece of
80 E lementary Dy na mi al P ri n iples
c c .

pl ati num
th at is a p articular body the q uant i ty

which is taken and dened by the State t o be a

The weight strictly so called th at is the tenden cy o fare


a r
body t o move do w w ds is not i nvariable for i t dc pe nrk
n ,

o n the part o f the wo rld where i t is placed i ts weight be in


great er at the poles th an at the equato r and greater at the


level o f the sea than at the top o fa mo untai n .

Wh at is really invariable is the quantity o f mat ter in the

body o r what is called in scientic language the m
, ass of the
body and even i n commercial transactio ns what is generally

aimed at in weighing good s is t o e st imate the quanti ty o f

m atter and no t t o de t e rmine the fo rce with which they tend

do wnwards .

I n fact the o nly occasio ns in co m

mo n life in whi ch it is
required to estimate weight c o nsidered as a force is whe n we

have to de termine the strength requi red to lift o r carry

thi ngs, o r when we h ave to make a structu re stro ng eno ugh
to suppo rt their weigh t I n all o ther cases the word weigh t

m ust be understood to mean tire Quantity 4 tire tiring as

determ ined by the process of wag /li ng agai nst standard

As a great deal co nfus io n p revails o n thi s subj ect in


o rdinary language and still great e r co nfusio n has been


i ntroduced into books o n mech ani cs by the no tio n that a

pou nd rs a certain force, i nst ead o fbeing as we have seen a
, ,

ce rtain piece o f pl ati num o r a piece o f any othe r kind o f


matter equal in mass to the piece o f platinu m , I have

tho ught it wort h while t o spe nd some t ime in dening
accu rat ely what i s meant by a po und and a kilogramme .


All na tions derive their measures of time from the

e heave nly bodi es The mo tio n o f .
Uni t f
o Ti me . St

to the time o frevol utio n o fthe earth about i ts axis or more ,

exactly to the interval betwee n s u ccessive transits o fthe rst

point o f Aries, is used by astro nome rs unde r the name of
sidereal time .

So lar time is that which is give n by a sun dial and is -


not u ni f orm A u niform meas ure o f time agreeing wi th


solar time in the lo ng run is called me an solar time and is

, ,

that which is given by a correct clock A solar day is lo nger .

than a sidereal day I n all physical researches mean solar


time is employed and one seco nd is generally take n as the


uni t o ftime.

The evi de nce upon which we form the co ncl usio n that
two di

erent po rtio ns of time are o r are no t equal c an o nly

be appreciated by those who h ave maste red the principles

o f dynamical reaso ning I c an o nly here assert that the

comparison for example o f the leng th o f a day at p rese nt

, ,

with the le ngth o f a day years ago is by no means

an unf ruitf
ul enquiry and that the rel ative length o f th ese

days m ay be de te rmined to wi thi n a small f ractio n o f a

second . This shows that time tho ugh we co nceive it ,

merely as the succession o f our states o f co nsciou sness is ,

capable o f measurement indepe ndently no t only o f o ur


mental states but ofany particular phenome non whatever


, .


In the measurement o f quantities differing in kind from

the three units we m ay eitherad o pt a newunit independently

for each new quantity o r we m ay endeavo ur to dene a unit


of the pro per kind from the f und am ental units I n the latt er .

Fo r instance it

c ase we are said to use a system of units .


we have ad op ted the foot as a unit of length, the systematic

unit ofcapac ity is the cubi c foot .

The gallon, which is a legal measure in this co untry, is

unsyst ematic considered as a measure of capacity, as it

82 mntary Dy narmbal P ri nc pl
E le e i es .

co ntains the awkward number of cubic inche s The .

gallon however is neve r tested by a direct measurem ent o f

, ,

i ts cubic co nte nts bu t by the co nditio n that i t must contain


ten pounds o fw ater at 62 F


D EF I N ITI ON o r D ansrrv H e damry qf a body i t

measured by tire number qf writ: cf mass in unit of volume

For instance i f the foot and the pound be taken as

fundame ntal u nits the n the de nsi ty o f anything is the


number o f pounds i n a cubic foot The densi ty of water .

is about 62 3 po u nds to the cubic foot I n the m etri c .

system the de nsity o f w at e r is o ne to nne to the s tere one

, ,

kilogramme to the litre o ne gramme to the cubic centi


metre and o ne milligramme to the cub ic millimetre


We shall sometimes h ave to use the word rarity to ,

signify the i nve rse o f densi ty that is the vol ume o f unit of
, ,

mass o fa substance .

Dsrm rr
r o s o r Sp sc rrrc G aavrrv ] 7ze sited/i: grmty .

qf a body is ti le rat io f
o i ts density to that of s om e stand ar d

Since the specic gravity o f a body is the ratio of two

things o f the same kind it is a numerical quantity and has
, ,

the same val ue whatever nati onal u nits are employed by


those who de te rmine it Thus if we say th at the spe ci c


g ra vi t y o f me rcu ry is about 1 35 we sta te t hat m ercu ry ,

i s abo ut thirt een and a halftimes heavier than an equal bu lk

o fwat er and this f
, act is i ndepe nde nt o f t he way in which
we measure either the m ass o r the vol ume o fthe liquids
m om

D EF I N ITI ON O F U mro ' '

a V s L rv I 7ze veloaty ey a .

body m ovi n g u ni
f orml
y is measu red by tire nu m ber qf uni t: f

lengt/z travelled over i n unit qf ti me .

Th u s
we speak of a veloci ty of so m any feet or metres

p er seco nd .

D sn t rou o s M OM ENTU M 27re m

o entu f
o a b ody i s . m m
m easured by tae p raduet qf tbe tfeloa v qf tlce bod
g y i s M e
M easu rement of F orce . 83

FORCE Forte is wizatener d anger or

di reetrbn i n uni t

o ti me.

The unit o fforce is that fo rce which if i t acted o n uni t of

mass fo r unit of time would produce in i t unit o fveloci ty .

For the Bri tish uni t o ffo rce the name o fPou nd al has been
propo sed by Pro f J ames Thom son I t is that force which,
. .

if it acted fo r a seco nd o n a pound would p rod uce in i t a


veloci ty o fo ne foot p er seco nd .

I n the centimetre gramme seco nd system adopted by the

- -

C ommittee o n U nits o f the Bri ti sh Associati on the unit o f ,

fo rce is the D yne A dyne acting for o ne seco nd o n a


gramme would give i t a veloci ty of o ne centimetre p er

The weight o f any body at Lo ndo n acti ng o n that body ,

for a seco nd would produce in it a vel ocity of3 3 1 8 89 feet


p er sec on d. He nce the we ight o f a poun d at Lo ndo n is

3 a r

8 8 9 poundals .

At P aris the vel ocity o fa body after falling freely fo r one

mes per seco nd Hence the weigh t .

dynes .

o ur experiments

in all countri es

by pe rsons in di ffere nt parts o f the wo rld had

ared th at it was f ound that the weigh t o f a
gramme is di fferent in diffe rent places and ,

the i ntensi ty of gravi tatio n o r the attraction of ,

o ve
ab . We shall distingu ish the measure by
6 2
To redu ce fo rc es mrpressed in gravi tation measure to abso
l ute m easure we must m u l tiply the number d eno ting the

force m gravi tatio n measure by the value of the i nte nsity of

gravity expressed in the same metrical system The value .

o fthe intensi ty o f gravi ty is a very imp ort ant number in all

scientic calcul ations and i t is generally denoted by the

le tter g The number g may be dened in any o f the


follo wing ways which are all equivalent :


g i ra namb er exp ressi ng tae ndm gp

r ro a hm i b r a fal


Thevalu e o f g is generally determined at any place by

experiments with the pend u lum These experiments re .

q uire great care and the descriptio n of them d o es not


belong to our p resent subject The value o f g m . ay be

found wi th sufcient accuracy for the present s tat e o fscience
by means o fthe formula ,

{ (
3 f
g G ( r 0 00 2 6
5 59 c o s z h) r a
37 P
In this formula, 0 is the inte nsi ty o fgravity a the m ean
level o fthe sea in latitu de 45

3 2 1 7 3
0 po undals to the pou nd o r 98 05 33 dynes to the

gramme .

x is the latitude of t he place The form ula shows th at the


force of gravity at the le vel o f the sea increases from the

equato r to the poles The last facto r o f the fo rm ula ex

presses according to the calculations o f Poisson the




ec t of t he height o f the place o f observatio n ab o ve

the level of the sea in dim inishing the force of gravity .

The symbo l p represents the mean density o f the whole

W 111, which is probably abo ut 5 } times that of wate r p .
Wag/l t i . 85

represents the mean density o f the ground j ust below the

place of owervatio n which may be take n at about 2 }

times the de nsi ty of water so that we may write ,


3 p r3 2 ne arly .

2 P
z is the height o f the place above the level o f the sea, in
feet or metres and r is the radiu s of the earth

r m etres
feet, or .

Fo r rough purp oses it is su fcie nt t o remember th at in

Britai n the inte nsity o fgravi ty is abou t poundals to the
po und and in France abo ut 980 dynes to the gramme

The reas o n why in all accu rate measurements, we h ave


to take account o fthe variati on o fthe intensi ty o fgravi ty in

diffe re nt places is that the absolute value o f any force such
, ,

as the p ress ure o f air o f a given density and temperature ,

depe nds entirely o n the p roperties o f air and no t o n ,

the f orce of gravity at the place o f observati on If .


therefore, this pressure has bee n observed in gravitati on

measu re that 18 in pounds o n the sq uare inch , or in inches
, ,

o f mercury o r i n any way in which the we ight of some


substance is made to furnish the measure ofthe pm ssure then

the resul ts so obtai ned will be true o nly as long as the

intensity o fgravi ty is the same and will no t be true withou t

co rrectio n at a place in a different latitude from the place o f

observation Hence the use o f reducing all measures of

force to abso l ute m easure .

In a rude age, before the i nventio n o f means for

o vercomi ng f riction the weight o f bo dies f
, o rmed the chief
o bstacle to setti ng them in mo tion It was o nly after .

some p rogres s had bee n m ade in the art o f throwing

missiles and in the use o f wheel carriages and oati ng

vess els that m en s minds became prac tically impressed


with the idea o f m ass as disti nguished from weight Ac .

c o rdingly while almost all th e metaphysici ans who dis


i ssed t he qualities o fm atter assigned a promine nt place to

perceived that the so le unal terable property ofmatter is its
mars At the revival of sci ence this prope rt y was exprwsed

by the phrase the ine rtia o f matter but while the men of


sc ience understo o d by this term the tendenc y of the bo dy

to persevere in its stat e o f motion (o r res t ) and considered ,

i t a measu rable quanti ty those phil os ophers who were nu


acquainted wi th science underst ood inertia i n i ts li t eral

sense as a quali ty me re want o factivi ty or lazi ness
Even t o this day th ose wh o are no t practically f amiliar
wi th the free m o ti o h of large m asses thou gh they all admit

the truth of dynamical pri nciples yet feel li ttle repugnance


i n accepting the theory known as Bo scovich s that su b


stances are c omposed of a sys tem of points which are ,

mere ce ntres o fforce attracting o r repelling each o ther I t

, .

is p robable that many quali ties o fbo dies might be exp lained
o n this suppositio n bu t no arrangem ent o f ce ntres o f f
, orce ,

h owever complicated could acco unt for the fact that a body

requires a certai n f orce t o produce in i t a certai n change

of mo tio n which f act we express by sayi ng that the body

has a ce rtai n measurable mass N o part of this mass a n


be due to the existence o f the supposed centres o f force .

I the refo re reco mmend to the s tude nt th at he shou ld

impress his mind with the idea o fm ass by a few experim ents ,

such as setting in m otion a grindsto ne or a well bal anced -

wheel and the n endeavouring to stop it twirling a long

, ,

pole, 8t e till he comes to associate a set o f acts and sensa


tio ns with the scie ntic doctri nes o f dynamics and he will ,

never af terwards be in any d ange r of loose ideas o n these

subj ec ts He should also read Faraday s essay o n M ental '


I nertia whic h will imp ress him with the p rope r me


p h o ric al use o f the phra se to exp ress ,

no t laziness, bu t
Work . 87


Work is do ne whe n resistance is overco me and the quantity ,

o f wo rk do ne is me asured by the product o f the resisti ng

fo rce and the dis tance through which that fo rce is ove r
come .

Th us ifo ne pound is lifted o ne foot high in oppo sition to


t he force o fgravity a certai n amount of work is done and

, ,

this quantity is known among engi nee rs as a foot pound -


If a body who se m ass is twe nty pounds is li fted ten feet , .

this might be do ne by taking o ne o fthe pounds and rais ing it

rst one foot and then another till it had risen ten feet, and
the n doing the same wi th each o f the remainin pounds so
g ,

th at the quanti ty o f wo rk ca lled a foot pound i s perfo rmed


z oo times in raising twe nty po unds ten f ee t Hence the .

wo rk do ne m lifti ng a body 18 fou nd by multiplying the weight


o f the bo dy in pou nds by the height in f eet The result

is the work in foot pounds -

The foot p ound is a grawtafzbn measu re depending o n


the intensity o fgravi ty at the pl ace To red uce i t to absol u t e


meas ure we mus t mul tiply the number o ffoot po unds by the -

intensity of gravi ty at the pl ace to get the number of foot ~

The work do ne whe n we raise a heavy body is done in

o verc oming the attrac tio n o f the e arth Wo rk is also do ne

when we draw asunde r two magnets which attract each

o ther whe n we d raw out an el astic co rd whe n we comp ress
, ,

air and in ge neral , whe n we apply f

, ,
orce to anyt hing which
moves in the directio n o f the fo rce .

There is one case o f the applicatio n o fforce to a m o vi ng

b ody which is o f great importance namely whe n the force
, ,

is employed in changi ng the veloci ty o fthe body .

Suppose a body who se m ass i s M (M pounds o r M grammes)

to be moving in a ce rtai n di rec tion with a velocity which
we shall call ti and let a force, which we shall call F be
, ,
88 E lmwtm D
jy y nami cal P ri nciple s .

a pplied to the body in the directio n o fits motio n Let us .

co nsider the e ffect o f thi s force acting on the bo dy fo r a

very sm all time T, during which the body mo ves thro ugh
the space 5 , and at the end o fwhich i ts ve loci ty is v

To ascertain the m agni tude o f the fo rce F let us c onsi der


the mome ntum which it p rod u ces in the body and the time ,

d uri ng which the mome ntu m is produced .

The mome ntu m o f the begi nning o f the time T was m r


andat the end o fthe time T it was m v so t hat the m o mentum


prod uced by the fo rce F acting for the time T is rw aw


B ut since forces are measured by the mome ntu m pro d uced

i n u ni t o f t ime the mome ntu m p rod uced by r in o ne u ni t

o f time is r and the momentu m p rod u ced by r i n T u ni ts of


time is FT Since the two v alues are equ al


Fr M (7/

Th is is o ne form o fthe fundame ntal

equation ofti
I fwe dene the imp ulse o f a force as the average val ue o f
the force mul ti plied by the time d uring which it acts then ,

thi s equation m ay be exp re ssed i n wo rds by saying that

the impul se o fa force is equal to the momentum p roduced
by it
We h ave next to nd r the sp ace de sc ribed by the body

d uri ng the time T If the veloci ty had bee n u niform the


sp ace described would have bee n the p rod uct o f the tim

by the veloci ty Whe n the veloci ty is no t u nifo rm the time

K inetic E rwrgy . 89

Hence the space described is

r v V ) T

This may be co nsidered ki nematical equati on si nce

as a ,

i t depends on the natu re o f motion o nly and no t o n that ,

o fthe moving body .

I fwe multiply together these two equations we get


and ifwe divide by T we nd

ge r m pu n!-

N ow is the wo rk done by the force F acti ng o n the


body while i t moves in the directio n o f r through a sp ace S .

I f we also denote rm, the m as s o f the body m ultiplied by

half the square o f its velocity by the exp re ssio n Me ki n e


ener gy q f M e bod y the n

, rst!
will be the ki ne t ic e ne rgy
aft e r the actio n o f the fo rce F th rough a space 5 .

We m ay now exp ress the equ atio n i n word s by saying

that the work d one by the force 1? in setting the body in
mo tio n is measured by the increase o fki netic ene rgy d u ring
the time that the force acts .

We have proved th at this is true when the inte rval of time

during which the force acts is so small that we may co nsider
the mean veloci ty during that time as equal to the arithme
tical m ean o f the velocities at the beginni ng and end o fthe
time Thi s assumption which is exac tly true when the

force is u niform is approximately true in every case whe n


the time considered is small e no ugh .

By dividing the whole time o f actio n o f the force i nto

small parts and provi ng that in each ofthese the work do ne

by the force is equal to the increase o f kinetic e nergy o f the

body we may by adding the different po rtio ns o f the wo rk
, ,

and the dif fere nt increme nts of energy arrive at the resul t ,

that the to tal work do ne by the fo rce is equal to the t otal

increase o fkinetic energy .

If the force acts on the bo dy i n the di rectio n O pposite to

the motion the kinetic ene rgy o fthe body will be diminished
90 Ela m tarjy Dy namical
i nstead o fincreased and the fo rce instead o fdoing work
, ,

the body, will be a resistance which the body in i ts mot

overcomes Hence a moving body c an do wo rk in c v

co mi ng resistance as long as i t is in motion and the we,

do ne by the movi ng body is equal to the di minuti on o f

ki netic e nergy till whe n the body is b ro ught to rest,
, ,

whole work it has do ne is eq ual t o the whole ki ne tic ene

which it bad at rs t .

We no w see the appropriat eness o f the nam e kins

the p roduct l aw
e ne rgy which we have hi the rt o u sed merely as a nam e

.Fo r the ene rgy o f a body m ay

de ned as the capaci ty which it has of do ing work and ,

meas ured by the qu anti ty o f wo rk which i t c an do 1


kinetic ene rgy of a body is the energy which i t has

virtue o f being in m oti on and we have just sho wn that

val ue may be fo und by mul tiplying the mass o fthe bo dy

h alfthe square o fthe veloci ty .

I n o ur investigatio n we h ave fo r the sake of sim

, pli e

s uppo sed the fo rce to ac t in the same directio n as

motio n To m ake the p roofpe rfectly ge neral as i t i s git

i n treatises o n dynamics we h ave only to resolve the ac t


fo rce i nto two parts o ne in the directio n o f the motio n a


the o ther at right angles to i t and to observe that the p


at righ t angles to the motion can nei the r do any work o n

body nor change the veloci ty or the kine tic e nergy so t ,

the whole effect whe ther o f work or o fal t e ration o fkint


e nergy depends o n the part of the fo rce which is in


direct ion ofthe motion .

The stude nt ifno t famili ar wi th this s ubj ect should rt

, ,

to some treatise o n dynamics and compare the investigat


there given with the outline o f the re aso ni ng given abo

Our obj ect at prese nt is to x in o ur minds what is me

impo rtance o f giving a name to the quant

Kinetic Energy seems to have been rst rec
K i netic and P o tent ial E nergy .
9 r

the sq uare o f the velocity the name o f V is V i va This is .

twice the kinetic ene rgy .

N ewto n in a scholiu m to his Third Law o f M otion has

, ,

stated the rel atio n betwee n wo rk and ki netic e ne rgy in a

manner so perfect th at it canno t be improved but at the ,

same time wi th so li tt le apparent e f fort o r de sire to at trac t

att e ntio n t hat no o ne seems to have bee n struck wi th the
great impo rtance o f the passage till it was pointed ou t
rece ntly by Thomso n and Tai t .

The u se o fthe te rm Energy in a scientic sense to exp re ss

, ,

the quanti ty o fwo rk a body can do was i ntrod uced by Dr ,


Yo ung Lec tures o n N atu ral Philosophy Lecture ,

The e nergy of a system o f bodie s act ing on o ne another

th f orces depe nding o n theirrel ative positi ons is due partly
o their mo tio n and partly to their relative positio n
, .

That part which is due to their motio n was called Actual

Ene rgy by Ranki ne and Ki ne tic Energy by Th o mso n and

Tait .

That part which is due to their rel ative posi t ion depe nds
u po n the work which the various f o rces would do if the
bodies were to yield to the actio n o f these forces This is .

called the Sumo f the Tensio ns by Helmholtz i n his cele ,

brated memoir o n the C o nse rvatio n o f Fo rce "

Thomso n .

called it Statical Energy and Rankine i ntrod uced the term


Pote ntial Ene rgy a very felici to u s name si nce it no t only

, ,

signies the e nergy which the sys tem has no t in possession ,

bu t o nly has the po we r to acqu i re but i t also indicate s th at


it is t o be found from what is called ( o n othe r grou nds ) the

P o tential Functio n .

Thu s whe n a heavy body has bee n lifted to a ce rtain

height above the earth s su rface the sys tem o ftwo bodies it

, ,

and the earth have pote ntial e nergy equal to the wo rk


which wou l d be done if the heavy body were allowed to

descend till it is s t opped by the surface o f the earth
I f the body we re allowed to fall freely it would em

pi re ,

Bedin 1 8 47 Translated in Taylo r s Scienti c M em i b V ES T

. . o rn t . ;
9 2 Elcmmtary Dy namical P ri nciple .

veloci ty and the ki netic energy acqu i red wou ld be exactly

equ al to the po t ential e nergy lost in the same ti m

e .

I t i s proved m tre atises o n dynamics th at if m any systetn ,

of bodies the f,
orce which acts be tween any two bodi es rs in
the li ne joining them and depends o nly on their di stance
, ,

and no t o n the way i n which they are moving at th e time ,

then if no other forces act on the system the sum of the ,

pote ntial and ki ne tic e nergy o f all the bodies of the system
will always rem ain the sam e .

Thi s p ri nciple is called the Principle o f the C onservation

o fEnergy it is o fgreat impo r tance in all branches o fscie nce ,

and the recent advanc es i n the scie nce o f heat h ave beer .

chiey due to the applicatio n o fth is principle .

We cannot i ndeed assume wi tho ut evidence o f a sans


factory natu re th at the mutu al actio n b etween any two pa


o fa re al body must always be in t he line j oi ning them and ,

must depe nd o nly o n their di stance We know that this is .

the case with respect to the attraction o fb odies at a d istance ,

bu t we c anno t m ake any s uch assumptio n co ncerni ng the

i nt ernal forces of bodies o f whose internal cons ti tutio n we
know next to nothing .

We cannot eve n assert that all energy must be either

po t e ntial o r ki netic though we m
, ay no t be able to co nceive
any other f o rm N eve rtheless the pri nciple has been de

monstrated by dynam ical reasoning to be absolu tely true for

sys t ems fullling certain co nditions and it has been proved ,

by experiment to be true wi thin the limits o f error o fc haer

vation in cases where the ene rgy takes the forms of h eat
, ,

magne tisatio n electri cation St e so that the followi ng state

, , ,

ment is o ne which if we cannot absolutely afrm its noces


sary tru th is wor ,

thy o f being care fully tested and traced ,

into all the co nclusio ns which are implied in i t .

Conserv at i on of E my .

m m
into any of Me for : a ref/rid: argy i s
If by the applicat io n o f mechanical fo rce, heat o r any ,

othe r ki nd o f ac tion to a body o r system o f bo dies it is

, ,

made to pass thro ugh any series o f changes and at las t t o


return i n all respects to its o riginal state then t he e ne rgy


c ommunic ated t o the sys tem d uring this cycle o f operatio ns

must be equal to the energy which the system comm unicates
to other bodies during the cycle .

Fo rthe system is in all respec ts the same at the beginning

and at the end o ft he cycle and in particular it has the same

amount o f energy i n it ; and the re f ore since no i nternal


act io n o f the sy st em can ei the r p rod u ce or des troy e ne rgy ,

the quantity o f energy which enters the sys tem m ust be

equal to that which leaves it d uri ng the cycle .

The reaso n fo r believing heat no t to be a su b stance

is that it can be ge nerated so th at the quantity o f i t m
be increased to any exte nt and it can also be destroyed
, ,

though this Ope ratio n requires ce rtai n co nditions to be

The e so n fo r believi ng heat to be a fo rm o f e nergy is

that heat m ay be generated by the app lication o fwo rk and ,

that for every u nit of heat whi ch is generated a ce rtai n

qu antity of mech anical e nergy di sappears Besides wo rk

may be done by the ac tion o f heat, and fo r every foot

po und ofwork so do ne a certai n qu antity o f heat is put out

Now whe n the appearance o f o ne thi ng is strictly c o n

nected with the di sappearance of another, so that the
am ount which exists of the o ne thing depends o n and can
be mlculated from the amo unt o f the other which has dis
as bee n fo rmed at the
ey are b oth f o rms o f the

that heat is energy in a peculiar

believing heat as it exists in a ho t
body t o be in the fo rm
ki of
n etic
e e gy that is, that the
n r

particles o f the ho t body a re i n actu al though in visible

m oti on wi ll be discu ssed aft erward s .




EVERY force cts between two bodies o r p arts o f bodhs

a .

If we are co nsideri ng a p articular body o r system o f b odi es,

then those forces which ac t between bodies belo nging to this
system and bodies no t belo nging to the systemare calle d

Exte rnal Forces and those which ac t between the d ifferent


parts o fthe sys tem i tselfare called I nternal Fo rces .

I fwe now su pp ose the system to be divided in imagina

tion i nt o two parts, we may consider the forces external to

o ne o f the parts to be rst those which ac t betwee n that
, ,

part and bodies external to the system and seco nd those , , ,

which ac t betwee n the two parts o f the system The com .

b ined ef fect o f these fo rces is known by the actual m o tio n

o r rest o f the part to w hich they are applied so that, if we ,

know the resultant o f the external forces o n each part we ,

c an nd th at o f the int ernal f orces ac ti ng between the two

Thu s, if we co nsider a pill ar su ppo rting a statue and ,

i magine the pill ar divided into two parts by a h orizontal

plane at any distance from the ground the i nternal force ,

between the two p arts o f the pillar may be found by con

si dering the weight o f the statue and that part o f the pillar

whi ch is above the plane The lower part o f the pillar


presses o n the u pper part wi th a force which exactly co unter

weigh t This force i s called a Pressure
. .

way we may nd the internal fo rc e ac ting

P ressu res and Tensi ons .

heavy b ody t o be a Tensio n equal to the weight o f the


heavy body and o fthe part o fth e rope below the imagi nary
sectio n.

The inte rnal force in the pillar is called Lo ngi tudinal

Pressure and th at in the rope is called Lo ngitudinal Te nsion
, .

I f this pres sure o r te nsio n is u nifo rm ove r the whole hori

zo ntal sectio n the amount o f i t p er square inch ca n be

found by dividing the whole fo rce by the number o f squ are

i nches in the section .

The int ernal fo rces in a body are called Stresses and ,

lo ngi tudinal pressure and t e nsion are examples o f particular

kinds o f stress I t is shown in treatises o n El asticity that

the m ost ge neral k ind o f stres s at any po int o fa body m ay

be represented by th ree lo ngi tu di nal p ress ures o r te nsions in
di rectio ns at right angles to each o ther .

Fo r instance a brick in a w all m

, ay suppo rt a ve rtical
pressure depending o n the height of the wall above it and ,

also a h oriz o ntal p ressure in the directi on o f the length of

the wall depending o n the th ru st o fan arch ab utting against

the wall while in the di rection pe rpe ndicular to the face o f


the wall the p ressu re is that of the atmosphere .

I n so lid bo dies s uch as a brick these th ree pressu res m

, , ay
t the ir magnit ude bei ng limited only by

o f the solid which wi ll b reak down if the f

, orce
e xceeds a ce rtai n amount .

the press ures in all direc tio ns must be equ al ,

very slightest diffe re nce betwee n the pressu res

di rec tions is sufcie nt to set the uid in moti on .

ect o f uid pres sure is so impo rtant t o wh at

I think it wo rth while at the ri sk o f repeati ng

to state what we mean by

that the p ressures in

or A FL U I D .
A uid is a body the M ig
rant s

r h taface w}:id:
ite r w
s mM a ose parts
96 S tresses and S trai ns .

Si nce the pressu re is enti rely perpend ic u lar to the sur

face there c an be no fric tio n be twee n the p art s o f a uid
i n co ntact


W rath The p ressu res in any two di re c ti on s at a poi

F a .
o f a u id are equal Fo r le t the plane

o f the p aper be that o f th e t wo given


direc tions and draw an is o scele s triangle


whose sides are pe rpe ndi c ular to the two

direc tions re spectively and c a the

equ ilibri u m o f a small triangular prim

of which this tr i angle is th e bas e Let .

P Q be the pressures perpe ndicul ar to the side s and a ,

that perpe nd icular t o the b ase The n si nce th ese three


forces are in equilibrium and since it make s equal anglu


wi th P and Q P and Q must be equal

But the fo rces on

wh ich P and Q ac t are also equal ; there fo re the p ressures

re fe rred to uni t ofarea o n the se face s are equal whi ch was ,

to be proved .

A gre at many substances may be found whi ch perfectly

full this denitio n ofa u id when they are at rest and they ,

are the re fore called uids But no existing uid fulH the

de nition whe n i t is in motion In a uid in motio n the


pressure s at a poi nt m ay be greater in o ne directio n than

in ano t her o r what is th e same thi ng the fo rce between
, , ,

two parts m ay no t be perpendicu lar to the inte rf ace which

separates those parts .

If a uid could be fo u nd which fullled the deni tion

when in motio n as well as when at rest it would be called a ,

Perfect Fl uid All actual uids are imperfect and exhibit


the phe nomeno n o f internal friction or viscosity by whi ch ,

their m o tion after being sti rred abo ut in a vessel is gradually

ste pped, and the ene rgy o f the moti o n is co nverte d into
P ressu re i n a Flui d

at any p oi nt o f a
uid is the rati o o f the
ace to t he area o fthat s urf
n a small su rf ace
m ade to diminish i ndenitely ,

o fthe su rf
ace always coincides

called hydros tatic p ressure to ,

essure Bo th kinds o f

fo rce in the

redu ce them t o absolute me asures .

also me asu red in terms of the height o f a

column o f wate r o r o fmercury which would prod uce by its

pressu re Thus a pressu re o f 1 6 feet o f


the squ are

foot, and a press ure o f4 i nche s o fwate r is more nearly equal

measure o f length the p ressure will be expressed i n tonnes


wei ght but ifwe u se the decimetre ce ntimetre ormillimetre

, , , ,

the pressure will be expressed in kilogrammes grammes , ,

o r milligramme s respec t ively i n gravi tatio n meas ure

, .

The de nsi ty o f mercury at 0 C is

times th at o f

ence the pressure due to a give n depth o f

ti mes that o fan equal dep th of water .

Th e pressure of the air is ge nerally

measu red by me ans o f the mercu rial barome ter This baro .

meter co nsists o f a glass tube closed at o ne end and lled

with me rcury fro m which all air and moi sture are expelled

by boiling it in the tube The tube is then plac ed wi th i ts


open end in a vessel o fmercury and i ts closed end raised


till the tube is vertical The mercury is fou nd to stand at


98 S tresses and S trai ns .

a certain level in the tube the height of which above t he


level o f the mercury in the vessel o r ciste rn is ca ll e d the

heigh t o fthe baromet e r .

The surface o f the mercu ry in the cis t ern is exp ose d to

the press ure of the air while the su rface o f t he m ercury in

the tube is exposed o nly to the press ure o f wh at e ver is in

the tube above it The o nly know n substance which can

be there is the vapour o f mercury the p ressure o f whi ch at ,

ordinary temperatures is so sm all that i t m ay be n eglected ,

so that the pressure o f the air may be measured by that

due to the dif ference o f level o f the mercu ry in t he tu be
and i n the cistern .

Th e p ress ure o f the atm o sphe re is as we k now very , ,

vari able and is dierent in differe nt places ; but fo r various


purposes i t is co nve nient to use as a l arge u nit o f p ressure

, ,

a p ress ure not very d if fe re nt from the ave rage atm ospheric
p ressure at the mean level o fthe sea This u nit o f pressure .

is called an atm osphe re and is used in measuring p ressures


in steam e ngines and boilers

I ts exac t value in the me tri cal

system is the press ure due to a dep th o f 7 60 m i llim htres of

me rcu ry at 0 C at Paris where the force o f gravi ty is


9 808 68 m tres This is equ al t o kilogramm es weight


o n the square c enti m tre I n absol ute me asure i t is equal


to the gramme the centi m tre and the second

, ,

being the fundamental u nits .

I n the British sys t em an atmosphe re is de ned as the

pressure due t o a depth o f 2 9 9 05 inche s o f mercury at
3 2

F a
.t Lo n do n whe r e
, t he fo rce o fgr a vi ty is 3 2 1 8 8 9 ee
f t ,

and is roughly r4 po u nd s weight o n t he square i nch I t is

, , .

therefore 0 9 9968 o fthe atmosphere o fthe me trical system .



the same kind in

S tra tus.

o fheat alo ne on these bodi es v i i o nt at the me


a t ra io n o f
le t

be elongated
if two p oints
lie in a li ne parallel to this direc tio n, their
be i ncreased o r diminished in a certai n ratio ,

e joi ning the points he perpendicular t o this

le ngth o f th e line will not be altered .

longitudi nal line

of the form of t he
o r successi vely in

o ther This syst em


in treatises o n the
mo st general kind of
in p articular .

in the three
to other are all equal, the
3 similar to itsel f, and i t expands
in all directio ns , as mo st solid bodi es do

three lo ngitudinal strains of which this

the volume by a fractio n
the longitudi nal strain i t ,

volume 18 equ al to the o riginal


by the algebraical sum ofthe th ee

r s tra ins .

a z
The ratio of the increment o fvol ume t o the original vo lume is
called the voluminal expansio n whe n posi tive o rthe voluminal ,

co ntraction when negative and i t appears from wh at we have


said that when the str

, ai ns are sm all the vol um i nal expansio n
is equal to the su mo f the lo ngi tu dinal ext ensio ns o r when , ,

the se are equal to th ree time s the lo ngi tudinal ex t e nsi o n

, .

and sw a .
g S tr ai n T h e o ther particu lar c ase i s wh en
the dimensions o fthe body are e xt e nded in o ne dire c ti on : in

the ratio o f a to 1 and co ntrac ted in a perpendicu l ar dirc e


tio n in the ratio o f t t o a I n thi s case there is no al tera


tio n o fvolume but the body is dis to rt ed

, .



We shall in the rst place su ppose that the stress c on

tinues co nstant duri ng the ch ange o ffo rm which we co nsider .

I f during conside rable change ofform the stress und ergoes


considerable change we m ay divide the whole o pe ratio n into


parts d u ri ng each o f which we m

, ay regard the stress as
co nstant and nd the total work by summatio n
, .

The ge neral rule is th at if the stress and the strain are o f


the same type the work do ne o n u ni t o f vol ume d uri ng any


strai n i s the product o f the strai n i nt o the ave rage v al u e of

the s tress .

I f howeve r the stress be o fa type conjugat e t o the s train

, , ,

no work i s do ne .

Thus ifthe s tress be a lo ngi tudi nal o ne we m

ust multiply ,

the average val ue o f the stress by the longitudi nal strai n in

the same di rec tion and t he resul t is no t affect ed by the

magni tude o f the lo ngi tu dinal strains in direc tio ns at right

angles to the s tress .

If the stress be a hydrost atic p re ss ure we m ust multiply ,

the average val ue o f this p ressure by the volum inal oom

work done o n the body per unit of

of the body .
Work done on a P laid . 10 1

Hence the wo rk do ne by exte rnal fo rces on a uid when

its volume is dimini shed is equal to the product o f the
ave rage p re ssu re i nto t he dimi nution o f volume and if ,

the uid expand s and overcome s the resi stance o f ext ernal
force s the wo rk done by the uid is measured by the pro

d uct o f the i ncrease of vol ume i nto the average pressure


during th at increase .

The co nsi deratio n o f t he work gained o r lost duri ng the

ch ange o f volu me o f a uid is so important th at we sh all
calcu late it from the beginni ng .


Le t us suppose that the uid is in commu nicatio n with a

cylinder in which a pist on is free rm 9 . .

t o slide .

Le t the area o f the face of the

pi ston be deno ted by A .

Let the p ressure o f the uid

be de no ted by p o n u ni t o f area .

The n the whole p ressure o f the ui d o n the face o f the

pisto n will be rip and if P i s the ext ernal force which keeps

t he pi ston in equ ilibri um P A)

N ow le t the pis ton be

pressed inwards agains t the uid th rough a distance x .

The volu me o f the cyli nder occ upied by the uid will be
di mi nished by a vol u me v Ax becau se the volume o f a

cyli nde r is equ al t o the area o f i ts base m ulti plied by its

height .

I f the fo rce P co nti nu es u nifo rm o r if P is the ave rage ,

value o f the external force d uring this motio n the wo rk ,

do ne by the external fo rce will be w me .

I fwe p u t fo r P i ts valu e in t e rm s o fp the p res sure of the ,

u id pe r u ni t o farea this become s


W w ;
and ifwe emembe r th at
r ax is equal to v, this becomes
o r co nve nie nce,we s uppose th at the area o f the piston
is u nity then putting A
r we sh all h ave P = p and v x ,

so that the linear distance travelled by the pis t o n is nw

merieally equal to the vol ume d isplaced .


shall no w desc ribe a

FI G . 1 0.
me thod o fstudying the actio n
i able volume
o f a uid o f var ,

which was i nvent ed by J ames

Watt as a prac ti cal meth od of

dete rmini ng the work do ne by

the s team e ngine ando fwhich

the co nstruc tion has been

gradually perfected till it is ,

no w capable o f tracing every

part o fthe actio n o f the steam
in the mos t rapidly wo rking e ngi nes .

At p rese nt however I sh all use this me th o d as a means

, ,

o f explai ni ng and repre senti ng t o the eye the wo rk ing o f a

uid This use o f the indicato r diagram which was i ntro


duced by C l apeyron has bee n grea tly developed by Rankine


1n his work on the st eam engine -


Let 0 a be a horizo ntal straigh t line and o p a vertic al


line On 0 0 (which we sh all call the line o f volumes ) take


distances o a o b o c to rep rese nt the volume occu pied by

, ,

times and at a b c e rect perpendiculars


ting on a co nve nie nt scale the pressure

, ,
I ndicator D i agra m
. 1 03

( Fo r instance, we may suppose that in the s cal e o fvolumes , ,

o ne i nch measu red ho rizo ntally rep res ents a vol ume equal
, ,

t o a cubic foo t and that in the scale ofp ressure s o ne inch , ,

measured vertically rep resents a p res sure o f

, pounds

weight o n the square foo t ) .

Let us no w s uppose that the volume incre ases from o a

to o 5 while the pressu re remains co ns tant so that a A b B
, , .

The n the increase o fvolume is me asured by a b and the ,

p ressure which is overcome by the expansio n of the uid by

a A o r b B so th at the work do ne by the uid is rep re se nted

by the p roduc t o f these quantities o r a b a A that is the , , , ,

are a o fthe rectangle A a b B .

O n the scale which we have assumed every square inch ,

o fthe area o f the gure A B b a represe nts foo t po unds -

o fwork .

We have s upposed the p ress ure to remain constant during

the change of vol ume I f this is no t the case bu t if the

p ressure changes from 5 B to c c while the volume changes


from o b to o c then if we take 5 c sm all e no ugh we m

, ay ,

suppose the p ressure to change unifo rmly from the o ne

value to the o ther so th at we may take the mean value o f

t o be MB 6 c c ) M ul tiplying this by b r .

c c) b c which is the well k nown exp ressio n


o f the strip B c 6 su pposi ng B c a s traight


do ne by the uid is therefore still equal t o the

by B c the two vertical lines from its extre

ho rizo ntal line 0 v .

fthe volume and p ressure of the uid are made

manne rwhatever and ifa point P be made at

to move so that its horizontal dis tance from the

vol ume which the u id occupies at
ertic al dis tance f rom o 2) repre se nts
o ft he u id at the same ins tant and ,

end o fthe path traced by P ve rtical ,

I f the path P returns into i tself so
of as to form a or

FM . r'r.

Ri chards s I ndicato r


clowd gure then the vertical line s at the beginning and e nd


o f the path will coincide so t hat it is unn

, to draw
them and the work will be represe nted by the area o f t he

circui t goes ro u nd the Ioop in t h e

then the represents


external fo rces but ifq P

t e direction the area o f ,
Actio n of Mr I ndic ator . 1 05

the l oop represents the wo rk done by the ext ernal forces on

th e uid .

I n the indi mt co nstructed by Watt and improved by

o r as

M c Naught and Rich ard s the st eam o r o the r uid is pu t in


co nnection with a small cyli nder co ntaini ng a pi sto n When .

the uid p resses this pis to n and rai se s it the pi st o n presses ,

against a spiral sp ri ng so co nstruct ed th at the distance


through which the spring is compressed is p roportional

to the p ressu re o n the pisto n I n thi s way the heigh t o f the

pisto n o fthe i ndicato ris at all time s a measure o fthe p res sure
o fthe uid .

The piston also carries a pe nc i l the po int o fwhich p res se s


ligh tly agai ns t a sheet o f paper which 15 wrapped ro und a

ve rtical cylinder capable o ftu rni ng rou nd its axis .

This cyli nde r 13 co nnec ted wi th the worki ng piston o f the

e ngi ne o r with some part o fthe e ngine which move s alo ng

wi th the pisto n in su ch a way th at the angle th rough which

t he cylinder tu m

s is al ways prop orti o nal to the distance

t hro ugh which the wo rki ng pist o n has mo ved .

If the indicato r is no t co nnect ed wi th the steam pipe ,

the cylinde r will tu rn beneat h the po int o f the pe ncil and ,

a ho rizo ntal line will be d rawn o n the pape r This line .

c o rrespo nds to o v and is called the li ne o fno pressure

, .

Bu t ifthe ste am be admi tt ed below the indi cato r pisto n ,

the pencil will move u p and down while the paper move s ,

ho rizontally be neath it and the combi ned mo tion will trace


o u t a line o n the pape r which is called an indi c ato r di agr

, am .

Whe n the engi ne wo rks regularly so that each stroke is ,

similar t o the last the pe ncil wi ll trace o u t the same curve


at every stroke and by examining this curve we m

, ay learn
much about the actio n of the engine I n particular the area .

o f the cu rve represents the amou nt o f wo rk do ne by the

s t eam at each s troke o f the e ngine .

If the indic at or had been co nnected wi th a pump in ,

which the external forces do wo rk o n the uid the trac ing ,

p o int wo uld move i n t he oppo site di rection r ou nd the

106 S tresses and S trai ns .

diagram and its area wo u ld indicate th e e manat e


done o n the u id d uri ng the stroke .

Hithe rto we have confi ned o ur attentio n to the wo r

by the p ressure o n the pisto n and have no t b e e n can

wi th the cau se o fthe al te ratio n o fvolu me o f th e u i d .

increase o fvol ume m ay f o r anyt hi ng we kn o w aria

, ,

an addi ti o nal s u pply bei ng introd uced int o t h e c ylin

when steam is i ntro duced from the boiler and the ,

nu ti o n of vol ume m ay aris e from the esm p e o f t h i

from the cyli nd er .

As we are no w going to use the di agram fo r t he p i

o fexplaining the p rope rties o fbodies when ac t e d o n b

and by mechanical f orce we shall suppose th at the


whe the r uid or partly solid is placed in a cylindel


o ne end closed and th at its vol ume is measure d t


di stance o fthe pisto n from the closed end of the c ylin

Ifat any i nstant the v
N e w
o fthe bo dy is a au d i ts

sure ) we represent thi


by means o fthe poi nt ?

the li ne o f volumes to
sent 71 and L P ve rtical

present p .

I n this way the posi t

a point in the diagram n

made to indicate t he v
and the p ressure o f a b<

any ins tant .

N ow let the p ress ure be i ncreased the temperate ,

m aining the same then the volume of the uid w


diminished ( It is manife st that an increase of presau


never p roduce an i ncrease of volume for in t hat c a ,

1 07

Let the pressure therefore i nc rease

, , t o 0 G, and
from o r
le t the co nsequent diminu tio n of volu me be fro m o L to
11 M and complet e the rec tangle o 0 Q M
, .

Then the point P i ndicates the o riginal and Q the nal

co ndi tio n o fthe uid wi th respec t to p ressure and volume ,

and all the inte rmediat e s tat es o f the uid will be repre
sented by poin ts in a li ne straight or curved which joins P
, ,

and Q .

The wo rk do ne by the press ure o n the uid is rep resented

by the area o f the fi gure P Q M L which is o n the left hand

o f the tracing poi nt as i t moves alo ng P Q .

I f P r and Q M i ntersect in R the n P R represents the


ac tual dimi nu tio n ofvol u me and R Q the actual i ncreas e o f


The ac tual volume is rep rese nte d by P P so that ,

nal compressi o n is rep rese nted by t he ratio o f P a

DE FI N IT IO N o r ru n Eu srxc mr or A FL U I D .

elastici ty o a u i d
o any s mall i ncrea e qfp ress ure to Me

lzereby produced .

Sincethe vol uminal comp ressio n is a numerical quantity ,

the elasticity is a quantity ofthe same kind as a pressure .

the uid by means of the

a straight line and p rod u c e it till it

o p in n ; then r s is a pressure equal

o f the uid in t he s tate r

epresented by P ,

iti ons which cause i ts state to vary in a

ted by the line P Q .

that r s is to a Q in the ratio o f P P tO P n,

ment of
1nc re
elasticity .

e relatio n betwee n the vol ume and the pres

u nde r ce rtain co ndi tio ns as f
o r i nstance at a

represented by a curve traced out by P ,

uid when i n the s tate rep resented by P

of rp essures the elas ticity of the uid

We h ave hitherto su ppo sed th at the temperature o f the

body remai ns the same during i ts compress ion from the
vol ume P F to the volu me Q o This is the m o st common

suppositio n when t he el astici ty o f a uid is to be m easured .

But in most bodies a compressio n p rod uces a rise o f te mp e

rature and ifthe heat is no t allowed t o escape t he c ec t of

, ,

thi s will be t o make the increme nt o f p ress ure great er than

in the case o fco ns tant t emperature H e nce every subs tance

has t wo el asticities o ne correspo ndi ng t o co nstant t em pera


t ure and the other co rrespo nding to the case where no hmt

is allowed to escape The rst value is applicable to stresses


and strai ns which are lo ng co nti nued so th at the subs tance


acq uire s the temperatu re o f su rroundi ng bodies The .

seco nd value is a plicable t o the case o f r apidly ch angin

p g
fo rces as i n the case o f the vibratio ns o f bodies which

prod u ce sound s in which the re is no t time for the tempe


ratu re to be equalised by co nduc tio n The elasticity in


these cases is always greate r than in the case o f un iform

t emperatu re.



E ,


Ir the pressure is made t o v ary while the t emperature re

mains constant the volume will dimi nish as the pressure

P will trace o u t a li ne in the diagram

eq ual t emperature o r an isothermal ,

Tlmr Co m

m ti o . 1 09

the substance u nde r vario us pressures at th at particular


t emperature .

By making experime nts o n the su bstance at othe r tem

p eratu res and d,
rawi ng t he iso the rm al li nes belo nging to

these temperature s we c an express all the relat io ns betwee n


the p ressure volume and tempe rature o fthe substance

, ,

In the diagram each iso therm al line sho uld be m arked


wi th the t empe rature to which it co rrespond s in degrees ,

and the lines should be d rawn fo r every degree o r f o r eve ry ,

ten o r eve ry hu nd red degrees according to the pu rpose fo r ,

which the diagram is inte nded .

When the volume and the p ress ure are known t he ,

t emperatu re is a dete rmi nate q u anti ty and it is easy to see ,

how from any two o f the se three quanti ties we c an deter

mine the thi rd Thus if the cu rved lines in the diagram

are the lines o f equ al temperatu re the tempe rature co r ,

respo nding t o each be ing indicated by the nu me ral at the

end of the li ne we can solve th ree p r

obl ems by means o f

1. G ive n the pressu re and the vol u me to ,

nd the t empe
t e
ra u r .

Lay f0
Of L on the line o f vol u mes to represe nt the gi ven
volume and 0 , r o n the li ne o f p ressure s t o rep rese nt the
given pres sure the n draw F P ho rizontal and L P ve rtical to
, ,

determi ne the po int P I f the po int P falls on o ne o f the


li nes of equal temperature the numeral attached to that line ,

indicates the temperatu re I fth e poi nt P falls be twee n two .

o f the lines we mus t e stimate i ts di stance f

, rom the two

nearest li nes and the n as the sum o fthe se distances is t o the


distance from the lower line o f t empe ratu re so is the dif ,

fere nce o f temperature o f the two li ne s to the excess o f the

tru e tempe ratu re above that of the lower li ne .

2 .Give n the vol ume and temperatu re t o nd the pres

Lay Of f0 t to . represe nt the volume anddraw L P

and le t P be the p oint wh ere this line cu ts th e Vi n e oi nae
1 10 m
I sot/zer al Curves .

given t emp erature Th en L P rep res ents the

. re quired
press ure .

3 .G iv en the p res su re and t emp eratu re to , nd the

vo l u me .

FI G . 1 3.

Lay p
f 0 F to re resen
Of t the pressure and d raw F P hori
z ontal till it meets the line of the given temp erature in P ,

th en F P rep res ent s the requ i re d v o lu m e .



w G aseous S tate .

ub stance is in the gaseou s state then it is easy to

I f th e s ,

draw the i so th erm al curves by taking acco u nt of the laws o f

Bo yl e and Charl es .

By B oyl e s law the p ro d uct o f the v o lum e and the pres


u e is always the same fo r the same t emperature H ence

s r . .

in the curve the area o f the rectangle 0 L P P wi ll be the

same provided P be a poi nt in the same i sotherm

al cu rve .

The cu rve which has this p rope rty i s k now n i n geometry

by the name o fthe rec tangul ar li yperbo la the lines 0 v and ,

o f bei ng the asymptotes o f the hyperbol as in g 1 3 The . .

asympto t e s are li ne s su ch that a po i nt travelli ng alo ng the

curve in ei the r di rectio n co ntinually appro ache s o ne o r

other o f the asymp to tes but neverreache s it The physical

i nt erpretatio n of this is th at if a gas fulls Boyle s law and


if the te mpe rature rem ain the same

1 . Suppose we travel alo ng the curve in the directio n
leadi ng toward 0 th at is t o say suppose the pres sure

is gradually i ncreased the n the vol ume will co nti nually


diminish but always slowe r and slower; for however much

, ,

we increase the pre ssure we can never redu ce the volume to


nothing so t hat the isotherm

al line will never reach the lin e

0 p though it c ontinu ally ap proaches it

At the sam e time

if Boyle s law is fullled we can always by do ubling the


pressure red uce the vol ume t o o ne half; so th at by a su i


cient increase o fpress ure the vol ume may be reduced till it
is smalle r than any p rescribed quantity .

2 . Suppose we travel in the o th er directio n along the

curve that is to say suppose we i ncrease the vol ume o f the
, ,

vessel which contai ns the gas the n the po int p approaches


d to no thing ,

ves sel may become .

P er/Ed G an Ano the r property o f the

if P s be drawn a tange nt to t he curve
t he asymp to t e , r s o No w P a
el asticit y of the s ub stance , and 0 P the pres
the el as tici ty of a perfect gas is numeri c ally
S atu rated V apou r . t t3

mo re inclined to the vertical and wider apart, bu t still very

nearly straight li nes Liquids however which are ne ar the
, ,

cri ti cal point descri bed at the end of this ch ap ter are more
compressib le th an even a gas .

In solid bodies the compressibili ty an d the expmsio n by

heat are in gene ral smaller th an in liquids Their indic ato r .

diagrams will therefore have t he same general charac t eri s tics

as those o fliquids .

mmcxroa D IAG RAM or A S U BSTA NC E PAR T 01? wmc n

s mou rn AN D PAR T vap o ua .

Let us suppose that a po und o f water is plac ed in a ves sel

and brough t to a given temperature say 2 1 2 F and that

, .

by means o f a pis to n the c apaci ty o f the vessel is made

larger or smaller the temperature rem aini ng the same If
, .

we suppose the vmel to be o riginally ve ry large say 1 0 0 cubic ,

fee t and to be maintai ned at 2 1 2 F then the whole of the


wate r will be co nverted i nto s t eam which will ll the vessel


and will e xe rt o n i t a p re ss ure o f abo u t 5 75 pounds weight

o n the square f oo t If we no w pres s down the piston and


so cause the capacity o f the vessel t o diminish the press ure ,

will i ncrease nearly in the same p ropo rtio n as the vol ume
dim ini shes so that the p rod uc t of the numbers represe nting

the press ure and vol u me will be nearly co nstant Whe n .


ho wever the vol ume is co nsiderably dimi nished this produc t

, ,

begins to dimi nish th at is to say the pressure does no t ia

, ,

crease so fast as i t o ugh t to do by Boyle s law if the steam

we re a perfec t gas I n the diag ram g 1 4 p rr4 the

, .
, .

relatio ns between the p ressu re and volume o f st eam at z rz

are i ndicat ed by the cu rve a b The p ressure in atmo


spheres is m arked o n the righ t hand o fthe diagram and the ,

volume o fo ne pound in cubic feet, at the bo ttom

, .

Wh en the volume is diminish e d to


cu ot c te et e .
1 14 [ sot/ter md Carms
e .

C bi
u c feet

lsother s fo r S ea t mand Water.
Water and S tea m . 1 15

pre ssure is lh so that the prod uct o f the vol ume


and p ressure i nstead o f

, is no w re d uced t o 5
Thi s dep artu re from the law o f Boyle though no t very l arge , ,

is q ui t e decided The p ressu re and volume o fthe steam in


thi s state are indicat ed by the point 6 in the diagram .

If we no w dimi nish the volume and s till m aintai n the

same temperatu re the press ure will no lo nger increase bu t
, ,

part o fthe steam will be co nverted i nto water ; and as the

vol ume conti nues to diminish more and more o f t he s team ,

will be conde nsed i nto the liqu id fo rm while the pressure ,

rem ai ns exac tly the same namely po unds weigh t o n '

, ,

the square foo t o r o ne atmo sphe re Thi s i s i ndicated by

. .

the horizontal line 6 c in the diagram .

This p ressu re will co ntinu e the s ame till all the st eam is
conde nsed int o wat er at the vol ume o f which will be
0 o r6 o f a cu bic f

oot 3 q uanti ty t oo small to be rep resented

, .

clearly in the di agram .

As s oo n as the volume there fore is reduced to this value , ,

there will be no mo re st eam to co ndense and any fu rthe r ,

re ductio n of vol ume is resi st ed by the el asticity o f water ,

which as we h ave see n is ve ry l arge compared wi th th at o f

, ,

a gas .

We are no w able to trace t he iso therm al li ne fo r wate r

correspo nding to the tempe ratu re When v is very
gr eat t he cu rve is nearly o f the o
f rm o f an hy p e rbol a f o r

which v P As v dimi nishes the c urve falls sligh tly ,

below the hyperbola so that whe n v 2 6 36 v p

, ,

H e re howeve r the li ne sudde nly and comple t ely al t e rs i ts

, ,

charac ter and becomes the ho rizo ntal straight li ne 5 c fo r

, ,

which P and th is s traigh t line e xtend s f rom

v to v o o r6 whe n ano ther equally su dde n

change takes place and the li ne from bei ng exact ly ho rizo n

, ,

tal ,becomes nearly but no t q uite vertical nearly in the ,

d irecti o n c p fo r the p ressure m ust be i ncreased beyo nd


the limi ts o f o ur expe rime ntal me thod s lo ng be f ore any

very co nsiderable ch ange is m ade in t he vol ume o fthe water .

1 s
S tea m1 i n
. s and Wu tar 1 . int .

seco nd is that the vol ume

, of the liquid when condensed is

The do tt ed line in the diagram indicates the pressures

and the vol u mes at which co ndensation begi ns at the
various tempe ratures m arked o n the horizo ntal parts o f the
iso thermal lines .

When the p ressu re and vol ume are those indicated by

points abo ve o r o n the righ t h and o f this curve the whole
substance is in the gaseo us state We m ay call this li ne the

st eam line . I t is no t an i so thermal line .

I f the scale c f the diagram had bee n large e nough to have

rep re sented the vol ume o f the co ndensed water we shou ld ,

h ave had ano ther do tted line near the line 0 p such that fo r ,

points o n the left hand o fthis li ne the whole substance i s in

the liq uid state We may call this the water l ine Fo r
. .

condi tio ns o f pressu re and vol ume i ndicat ed by points

be twee n the two do tted li nes the subs tance is partly in the

liquid and partly i n the gaseous state Ifwe draw a h ori .

z ontal li ne th ro ugh the give n po int till it meets the two

do tt ed li nes the n the w eigh t of s t eam is to the weight o f


water as the segment be tween the point and the wat er line
is to the segment between the point and the s t eam line In .

bo nic acid fi g 1 5 , .

consi st of a curved
righ t h and rep rese nting the gaseous
portio n representi ng the process o f c on
a nearly vertical portio n representi ng
The righ t hand b ranch o f the dotted

m ust here call the gas li ne corre spo nds ,

ne and the lef t hand branch o r liqui d line

, ,

the w at er li ne which was no t distingu is h


two lines which we h ave called the st eam li ne


l ine conti nually approach e ach othe r as the


is raised the qu es tio n natu rally arises D o they

, ,
Carbonic A ci d . 1 19

and in he greatly ex t ended o ur k nowled ge o f the

1 82 6

e ffec ts o f temperat ure and pressure o n gases H e co nsiders .

that above a certai n temperature which , in the langu age o f ,

D r Andrews we m
ay call the critical t emperature fo r the

substance no amou nt of pressure will p rod uce the pheno


me non which we call co ndensati o n and he supposes that the ,

temperature of 1 66 F belo w zero is probably above the


critical tem perature fo r oxyge n hydroge n and ni troge n , , .

D r Andrews has examined carbonic acid under varied


condi tions o ft emperature and press ure in o rde rto asce rtain ,

the relations o f the liquid and gaseous s tates and has ,

arrived at the co nclusi o n th at the gaseous and liquid s tat es

are only widely separated f o rms o f the same co ndi tion o f
matter and may be made to pass o ne into the other with

ou t any i nt errup tio n or breach of co ntinuity


Carbonic acid is a subs tance which at o rdinary tempe ra

tures and pressures is known as a gas The meas ureme nts .

of Regnault and o ther s sh ow that as the p ressure increases

the volume diminishes fast er than that of a gas which obeys

the law of Boyle and that as the temperature rises the ex

th e diagram of carbo nic aci d at

pressures are therefore somewhat
hat wide r apart than those o f the

1 20
) ca rb for
o nic acid is take n f
r om Dr .

wi th the exceptio n of the do tt ed line

n wi thi n which the substance c an exist
vapour The base line of the

s no t t o ze ro press ure but to a pressu re

, ,

eres .

o f the is o the rmal li nes is th at o f x3 xC



at a press ure o fabo ut 47 atmospheres

The substance is see n to become

PM . Tram 1 8 69, p 5 75
. . .
E xperi mnt: q
e ndrewr
. tzr

i n the s m f mp mm g s
te o o a and the lower i n the state o f

liquid . The upper surfac e o f th e liquid can be dis tinctly

seen, and where this surf ac e is c lose to the si des ofthe glass
co ntaini ng the su bstance i t is seen to be cur v ed, as t he

surfac e ofwater is in sm all tnbes .

As the vo i um e is dim inished, m

ore of the sub stanoe is

liqueed , till at las t the whole is c ompressed into the liquid

I have described th is iso thermal line at greater length ,

that the student m ay compare the p ropert ies of ca rbo nic acid
at F wi th those ofwater at 2 1 2 F


r The steam bef

. ore condensation begi ns has properties
agreeing nearly thou gh no t qu ite wi th those o fa perfect g
, , as .

In carbo nic acid the vol ume j ust before liquef ac t io n com
menc es is li ttle more than three fths of that of a perfec t

g as a t the sa me tempera t ur e and p ress ur e Th e correspo. n din g

iso thermal lines for air are give n in the diagram and it ,

will be see n how mu ch the c arbonic acid isotherm al has

fallen below th at ofair befo re liqu ef actio n begi ns .

2 . The steam when co ndensed into water occupies less

than the sixte en h undred th part o f the volume of the s t eam

The liquid carbo nic acid o n the other hand occupies nearly
, ,

a f th part o fits vo l ume just before condensation We are .

theref ore able to draw the dotted line o f co mplete co nden

satio n in thi s diagram though in the case o f water i t would

have required a microscope to dis tinguish i t from the line o f

no vol ume .

T t o w t h

3 . h e s eam whe n c n densed in to a er at 2 1 2 as

properties no t di eri ng greatly from those of cold water


Its dil atability by h eat and its comp ress ib ility by pressure
are probably so mewhat greater than when cold bu t no t ,

enough t o be noticed when the m easurements are no t very

p re ci se .

Liquid carbonic aci d as was rst observed b y M e es

, .

M es a the temp erat ure ri ses to a greater degre e t h an e v e n

a as
g , and, as D r Andrews has
shown it yields to pressure

m uch mo re th an any o rdinary liquid F rom D r Andre ws s . .

expe rime nts it also appears that its compressibili ty di m i o

nishes as the p re ssure inc reases The se resu l ts are apparent .

eve n in the diagram I t is therefore far mo re co mpreesble

, ,

t han any ordi nary liquid and i t appears from t he experi


me nts o f Andrews th at i ts compre ssibili ty dimi nishes as the

vol ume is red uced .

I t appears therefo re that the behaviouro fliquid carb onic

, ,

acid u nde r the ac tio n o f he at and p re ssure is ve ry different

from that o fordinary liquids and in some respects approac hes ,

to th at o fa gas .

I f we ex ami ne the nex t o fthe i so the rmals ofthe di agram ,

that fo r 2 1 5 C or

F the appro xi m atio n be t ween the

liquid and the gaseous s tat es is still mo re apparent H ere .

co nde nsatio n takes place at abou t 60 atmo spheres o f pres

sure and the liqu id occu pies nearly a third o f the volume of

the gas The exceedingly de nse gas is approachi ng in its


prope rties t o the exceedi ngly light liquid Still there is a .

disti nct separatio n be twee n the gaseous and liqu id s a tes .

though we are appro aching the critical tem pe ratu re This .

cri tical temperatu re has bee n determi ned by Dr Andrews to .

be C or . F At thi s t empe rature and at a


pressu re o ffrom 7 3 t o 7 5 atmo spheres c arbo nic acid appears ,

to be in the cri tical condi tio n No separation i nto liqu id and .

vapo ur can be de tected bu t at the same time very sm all


variatio ns o f pressure o r of t emperature produ ce su ch great

variations o fdensi ty th at ickeri ng movements are observ e d
in the tu be rese mbli ng i n an e xagge rated fo rm the appear

anc es exhibi t ed during the m ix ture o f liquids o f di erent


densities or when columns o f heated air ascend thro ugh


colder strata .

The iso thermal li ne for C o r 88 F passes above .


this critical point Du ring the whole compression the sub


two di stinct co nditio ns in different parts o f

the pressure is less than 73 atmosph e res
Contznui tj r of Me L iq u id a nd C arson: S tates

the si o thermal li ne though greatly atter than that o fa perfect


ga s
r e semble s it in ge neral e
f atures F rom 73 t
.o 75 atmo
sphe res the volu me dimi nishes very rapidly b ut by no means ,

suddenly, and above thi s pre ssure the vol ume diminishes
more grad ually than in the cas e o f a pe rfect gas bu t still ,

mo re rapidly than in most liquids .

I n the iso the rmals for C or . F andfor C . .

or F we can still observe a sligh t increase o fcompres


sibili ty near the same part o f the diagr am b u t in the ,

isothe rm al line for 48 1 C o r rr8 6 F the curve is c o n


cave upwards thro ughou t its whole co urse and diers from

the correspo nding isothermal li ne fo r a pe rfect gas o nly by

being so mewhat atter showing that fo r all ordi nary p res

sures the v ol ume is s omewhat less th an th at assigned by

Boyle s law


Still at the tempe rature o f F carbo nic acid has all


the properties o fa gas, and the effects o fheat and press ure o n
it differ from thei r effects on a pe rfect gas only by qu anti ties
requiring caref ul experiments t o detect them .

We have no reaso n t o believe that any phenome no n

similar to co ndensatio n wo uld occu r however great a ,

pressure we re applied t o carbonic aci d at this t emperature .

I n fac t by a proper management we can co nvert c ar


boni c acid gas into a liquid wi tho u t any sudde n ch ange

I f we begi n wi th carbonic acid gas at 5 0 F we may rst


above 88 F the cri tical poi nt

. .

to say 1 00 at mo , ,

iquefac tio n occ urs .

er the p r ess u re o f
process no sudden
0 F


p ro

At the t emperatu re F we canno t

of5 0


acid gas int o a liqu id wi thou t a sudden

by this process in which the press ure is
1 24 [ 5 0:11a m] CW .

applied at a high temperature we have c aused the su


t o pass from an u ndoubte dly gaseous to an u ndo

liquid state witho u t at any time undergoing an ab rup t
sim il ar to o rdinary liqu efact io n .

I have described the experiments o f Dr Andre ws .

bonic acid at gre ater le ngth because they furni sh t h

co mple te view hi the rt o given o f the relatio n berm
liq uid and the gaseo u s state and o f the mod e i n wlx

prope rties of a gas may be co ntinuously and impa le

c h anged i nto those o fa liqu id .

The criti cal temperatures o f m ost ordinary q ui

much higher than that of carbo nic acid and t heir p ,

in the critical state is very great so that experimen ts


cri tical state ofo rdi nary liquids are difcul t and da
M Cagniard de la Tour estim ated the temperature am

su re o fthe cri tical state to be

Al cohol
B isul phide b
o fCar o n

In the case of water the cri tical temperatu re a

high that the wate r began t o dissolve the glass tube
co ntai ned it .

The critical temperatu re o fwh at are called the pern

gases is p robably excee dingly low so that we canno t I ,

known me thod p rod uce a degree o f cold su i ci ent ,

whe n applied along wi th e normo us p ressu re to c o r , .

them into the liquid state .

I t has bee n sugge sted by P ro fessor J ames Thoms o n

the isothermal curves for temperatu res below the c
temperature are only appare ntly, and no t really d ,

tro u o ns and that their true f

orm is somewhat similar
i ndi ca ted by the horizo ntal li nes D r and D H any horizo n ,

tal line such as c E 0 cuts the curve in three di f ferent

points The li te ral int erp retatio n o f this geo metrical c ir

c um stanoe would be th at the uid at this p ressure and at ,

the temperature o f the isothe rmal li ne is capable ofexisting


i n three differe nt states

. One o f these indicated by c
, ,

evidently co rrespo nds to the liq uid state Ano ther indi

d by c corresponds t o the gaseous s tat e

, At the inter

mediate poi nt E the slope o f th e curve i ndicates th at the

and the p re ssure i ncrease and

FIG. 1 6.

eq uili

ush r
may therefo re

lained at p 303 , .

e rat e o fevapo
and the rate
H ence fo r
is a det ermi nate vapo ur d ensity, and -

det erminate pressu re represented by the horizon

, .

at whi ch the evapo ratio n exactly balances the c o n ~

1 26 I sother mal Cafte r .

densa ti on At the p res sure indic at ed by this ho riz ontal li


the liquid will be in eq uilibrium wi th i ts vapour At all great .

pressures the vapo ur ifin co ntact with the liq u id will be co

, ,

densed ; and at all smalle r p ressures the liquid if i n co ats ,

wi th i ts vapo ur will evapo rat e He nce the iso therm

, . al line ,

deduced from expe riments o f the ord inary kind will co nsist ,

the cu we n a q the straight line c c and the cu rve 0 it , .

B ut it has been poi nted ou t by P ro f J Tho m s on th . .

by su itable co ntrivances we may detect th e existe nc e

o ther parts of the iso therm al curve We know that tl .

portion o f the curve co rrespo nding to the li qui d stat e e

t e nds beyond the point c ; fo r if the liquid is w e fully fret
from air and o ther imp uri ties and is no t in con tac t wi,

anythi ng but the sides o f a vessel t o w hich it closely a

heres the p ressu re m
ay be reduce d co nsiderably be low th

indicated by the poi nt 0 till at las t at so me point betwec

, ,

c and D the phenome no n o f boiling wi

, w sa c o r
mences, as described at p 2 5 . .

Let u s next co nsider the subs tance wholly in the state

vapo ur as i ndicated by the point x and let i t be kept at ti
, ,

same tempe rature and grad ually compres sed ti ll it is in ti

state i ndicated by the point 0 If there are any d rops .

the li quid in the vessel o r if the vessel is capable o f beir


wetted by the liquid co ndens atio n will no w begin Bu t

, .

there are no facili ties fo r condensation the pre ssu re m ay ,

increased and the vol u me di m inished till the state of tl ~

vapou r is that which is represented by the point P At th .

point condensatio n must take pl ace if it has not begu

before .

The exis tence o f thi s variability in t he circumstance s

conde nsatio n tho ugh seemingly probable is no t as y
, ,

established by experime nt like th at o f the variabi li ty in tl

Adi abe tic Care rs . 1 27

of this part of the iso therm al

ep rese nted by the po rtio n

ver, r

o f the iso the rmal cu rve D E F c an neve r be realised in a


homogeneo us m ass for the su bs tance i s then i n an esse nti ally


u nstable co nditio n si nce the p ressure increases wi th the


vol ume We cannot therefo re e xpect any expe rime ntal

, ,

evide nce o fthe exi stence o fthis p art of the curve u nless as , ,

Pro f J Thomso n s uggests this state of things m

. .
, ay exist
o f the thi n supe rcial stratum of transitio n

uid to i ts own gas in which the phenome na o f


capillari ty take place .



Hr maaro we have con idered

properties of substance
s th e
o nly wi th respec t to the vol ume occu pied by a po und o fthe
the p ressu re acti ng o n every square foot o r inch ,

o fthe sub stance which we have assumed ,

peratu re measured by a
change the state of the

t req ui red in each case Fo r t he ac tual .

ch quanti ties o fhe at we must employ the

in o ur chap t er o n Calo rimetry or o thers ,

Be fo re e nt eri ng o n these consideratio ns ,

the very important case in which

pl ace are eec ted witho ut any

the su bstance from wi thout o r out

e into o the r bodies .

o fassociating the s tat eme nt o fscie nti c f

l 28 Adzabatic Cu rt/es .

wi th mental images which are easily fo rmed , and which pte

serve the s tate ments in a fo rm always ready for u se we shah ,

su ppo se that the subs tance is co ntained in a c ylinder tted

wi th a pis t on and that bo th the cylinde r and the p isto n are

absol utely imperme able t o he at so th at no t o nly is heat


preve nted from ge tti ng o ut or in by p assing co m pletely

thro ugh the cyli ndero rpis t o n bu t no heat a n pass between

the enclosed subs tance and the matte r o f the c ylindu a

pis to n i tself .

No su b stance m nature is absol u tely im pe rmeab le to heat ,

so that the i mage we h ave formed can neverbe fu lly realrseda

bu t i t is always pos si ble t o ascertain in e ach parti c ularm
, se ,

th at heat has no t ente red o r le ft the substance th o ugh the


me thods by which thi s is do ne and the arrangements by

which the co ndi tion is fullled are complic ated I n the

pre sent discussio n i t wo uld o nly distract o ur attentio n from

the most impo rtant facts to describe the details o f physical
experime nts We therefore rese rve any desc ript io n o factual

experime ntal method s till we can expl ain them in co nnexion

wi th the principles o n which they are founded In explain .

ing these principles we make use o f the most suitable illus

tratio ns wi thou t assuming that they are physically possible
, .

We therefore su ppose the substance placed in a cylinder ,

and i ts vol u me and p ress ure regul at ed and measu red by a

pis ton and we suppo se that during the changes o f volume


and pressure o f the subs tance no heat eithe r e nters i t or

leaves it .

I n order to rep resent the relatio n be twee n the volu me and

the pressu re we suppose a curve traced o n the indic at or

di agram during the mo tion of the pis to n exac tly as in the


c ase o f the isotherm al line s f o rmerly descri bed The only


differe nce is that where as in the case of the isothermal

lines the substance was m ai nt ai ned always at one and the
Yi wzr

1 29

The line drawn on the indicator di agram in the latter cas e

has been named by Professo r Rankine an Adiabatic line ,

because it is dened by the co nditio n that heat is no t allowed

to pm t hrough the vessel which co nnes the
substance .

Since the properties of the su bstance u nder thi s co ndition

are completely dened by its adiabatic lines it will assist u s ,

in understanding these prope rties if we associate them with

the correspo nding features o fthe adiabatic lines .

The rst thing to be observed i s that as the vol ume di mi

ni shes the p ressu re invariably i ncreases I n fact if u nderany

circumstances the p ressure were to dimini sh as the vol um e

diminishe s the sub stance would be m an unstable state and
, ,

would either collapse o r explode till it attained a co ndition

in whi ch the p ressu re increased as the vol ume diminished .

Hence the adiabatic lines slope downwards from left to

right in the indi cator diagram as we have drawn it .

If the pressure be continually increased up to the greatest,

pressure which we c an produ ce, the volu me continually

diminishes but always slower and slower so that we cannot
, ,

tell whether the re is o r is no t a limiting vol ume such that no

pre ssure however great can comp ress the substance to a
, ,

smaller volume .

We canno t in fact trace the lines u pward beyond a

, ,

certain distance and there fore we canno t assert anything of


the upper part o ftheir course except that they cannot rec ede

from the line of press ures becau se in that case the volume

wo uld increase o n account ofan increase o fpress ure .

If on the o ther h and we suppose the piston to be drawn

, ,

out so as to allow the volume to increase the pressure will ,

di minish
I f the substance is in the gaseous form or assu m es that ,

form during the p rocess the substance will co ntinue to exert


pressure o n the pisto n even though the volume i s e norm ou sly

increase d, and we have no experime ntal reason t o believe
that the p ressure would be reduc ed to no thing however much ,

the lines extend indenitely i n the directio n o f th e line
volumes conti nually approaching but never reac hi ng it
, .

With respect to substances which are no t ori i nally m l

gaseous form some of them when the pressure is suic ier
, ,

diminished are k nown to assume that form and i t is plausi

, ,

argued that we have no evide nce th at any substan c e hav e,

so lid and howeve r cold if entirely free from external pr


sure would no t sooner or l ater become dissipat ed throw


S pace by a kind o f evapo ration .

The smell by which s u ch metals as iron and c o pper m

be recognised is adduced as an i ndication that bodi
appare ntly ver xed are continually throwing o

e ctic
y ,
o f themselves i n some very attenuated f orm and if in the

c ases we h ave no means of detecting the e luviumexcept

the smell in o ther cases we m
ay be deprived o f th is ev iderl

by the circumstance that the efuviumdoes no t affect c

sense ofsme ll at all .

Be this as it may there are m any substances the press:


o f which seems to ceas e entirely when the vol um e 11

Tlmr R elation to tire I sotker

mal r . I 3r

This is an i llu stratio n o f the ge neral principle th at whe n

the s tate ofa body is changed in any way by the application
o ff orce in any form and if in o ne case the body is subjected

t o some co nstraint while i n ano ther case it is f

ree f rom this
co nstraint but similarly circu mstanced in all othe r respects ,

then ifduring the ch ange the body takes advantage o f this

freedom less force will be required to p rod uce the ch ange

th an whe n the body is su bj ected to co ns traint .

In the case before u s we m ay su ppo se the co ndi tio n o f

constant tempe ratu re to be obtained by making the cylinde r

o f a substance which is a pe rf ect condu ctor o f heat and ,

surrou nding i t wi th a ve ry large bath o fa uid which is also a

pe rfect conductor ofheat and which has so gre at a capacity

fo rheat that all the heat it receives from or gives o f f to the sub
stance in the cyli nder does no t sensibly alter its tempe ratu re .

The cylinder in this case i s capable o f constraining the

substance itsel f because it cannot get through the sides o f

the cylinder; but 1t is not capable o fco nstrai ning the heat o f
the s ubstance which can pass freely o ut or in through the

walls ofthe cylinder .

If we no w s uppose the walls o f the cylinder to beco me

pe rfect non co nducto rs o fheat every thi ng remains the same
, ,

except that the heat is no longer free to pass into o r out o f

the cylinder .

I f i n the rst case the moti o n o f the pisto n gives rise to

any motio n of the heat th ro ugh the w all s then in the ,

second case whe n thi s mo tion is preve nted , more fo rce will

be required to prod uce a given mo tion of the cylinder o n

acc ou nt o fthe greate r co ns trai nt o fthe system o n which the

From this we may ded uce the effect which the comp ression
of a substance has o n its tempe ratu re when heat is p reve nted
from entering o r leaving the s ubstance .

We have seen that in every case the p ressure incre ases

more than it does whe n the tempe rature remains co us ant o r ,

ifthe i ncrease ofpressure be su pposed given the diminu tion


x 2
Aazabatzc Cu w as

FIG . x8.

Therm o r Ai r
al L ines f .

I so ther als
Efeet f
o P ressu re on Temp emtu re . r3 3

of vol ume i s less whe n the heat is conned Hence the .

volume after the p ressure is appli ed is greater whe n the heat

is co n ned than when the temperature is constant .

Far the greater nu mber o f s ubstances expand when their

temperature is raised so that fo r the same pressure a greater

volume corresponds to a higher temperature I n these sub .

stances there fore compression produces a rise oftemperature

, ,

if heat is not allowed to escape ; but i f the w alls of the

cylinder permi t the passage o f heat as soo n as the tempe ,

ratu re has begu n to rise heat will begin to ow o u t so that ,

if th e compressio n is effect ed slowly the p ri ncipal thermal

e ffect of the compressio n wi ll be t o m ake the su bstance part
wi th some o f i ts heat The isothermal and adiabatic lines

o f air are given in g 1 8 p 1 3 2 The adi ab atic li nes are

. .

more incli ned to the horizo ntal th an t he iso the rmal lines .

The re are however certain substances which co ntract

, ,

instead of expanding when thei r temperature is raised .

When p ressure is applied to these substances the compression

produced is as in the former case less when heat is pre
, ,

vented from passi ng than when the temperature is m aintained

co nstant The volume afte r the application of p ressure is

there fo re as before greater than whe n the tempe rature is c o n

, ,

stant ; but since in these substances an increase o f volum e

indicates a fall oftemperature it follo ws that instead o fbeing, ,

heated they are cooled by compression and that ifthe walls

, , ,

o f t he cylinde r pe rmit the passage o f he at heat will ow in ,

fromwi thou t to resto re t he equ ilib rium o ftemperatu re .

During a change o f state when at a given p ress ure the

, , ,

vol ume alters considerably without change oftemperature as ,

succes sive portions of the subs tance pass from the o ne state
to the other the isothermal lines are as we have already
, ,

rem arked horizo ntal

The adiabatic lines however are
, ,

inclined downwards om left to right Any i ncrease o f .

pressure wi ll cause a po rtio n o f the substance to pass into

th at one o f the two states in which its vol ume is least I n .

so d o ing it will give o ut heat if as i n the case ofa liquid and ,

its vapour the substance gives o u t heat in passing into the

1 34

denser state ; but if as in the case o f ice and water the i r

orm of water, tim
, , ,

requi res heat to melt it i nto the denser f

an increas e of p ressure will cause some o f the ice to melt .

and the mixture will become col der .

The iso thermal and adiab atic lines for steamin presence
o fwater are given in g 1 9 p 1 3 5 .
The is ot h ermal lines
. .

are here ho rizo ntal .

The steam line v v which i ndicates the vol u me o f one


pou nd o fsaturate d steam is also drawn on the diagram I ts


incli nation to the horizo ntal li ne is less than that o f the

adiabatic lines H ence whe n no heat is allowed to escape ,

s sure cau ses some o f the water to becom


an increase o f pre e
ste am and a diminu tion o f p ressure causes som e of the

steam to be co ndensed int o water This was rst sho wn by .

Clausius and Ranki ne .

By means of di agrams o f the isothermal and adiabatic

lin es the thermal p ro perties o f a s ubstance c an be com
p letel y de ned , as we sh all show i n the subseque n t ch apters
As a scie ntic method , this mode o f representi g the pro
pet ties of the substance i s by far the best but in order to

interpret the di agrams some knowledge o f therm odynamics


is required As a mere aid to the student 1n rem e mberi ng


the prope rties of a substance the followi ng mode o f trac ing


the changes of volume and temperature at a constant pres

su re m ay be f ound use ful though it is quit e desti t ute of

those scie ntic merits which re nder the indicato r diagram

so valuable in the inves tigation o f physical phenom ena .

The di agram o n p 1 3 7 repre sents the effect o f the ap pli


cati on of heat to a pound o f ice at 0 F The quantity of


heat applied to the ice is indicated by the distance measu red

alo ng the base line marked units o f he at

Th e volume .

o f the substance is indicated by the length of the per


e nd ic ular from the b ase li n e c u t 013 by the lin e of

Adi abatze Carr/es

Fro . 1 9.

Thermal Li nes o f S tea mand Water


I so ther als
Adiab atic s
S tea L i ne v v
so th at its vol ume ,
as co mpared wi th water at
The ice no w begins to melt the temperature remains ,

constant at 3 2 E bu t the volu me o f ice d im ini she s and


the volu me of water increases as is repre sented by the ,

l ine m arked v ol ume o f ice The latent heat o f i c e is


1 44 F , so th at the process o f melti ng goes on ti ll 1 u

44 nits
o f h eat have been applied to the s ubstance, and the wh ole

is converted into wate r at 3 2 F


The vol ume o f the wat e r at 3 2 F is acc o rding to


M Desp retz
. Its specic heat is at this tem

pot ature a very li ttle greater than unity it is exactly unity

at F and as the temperature rises the specic hea t

increases so th at to heat the water from 3 2 F to 2 1 2 F

. .

requires 1 8 2 u nits i ns tead o f 1 8 0 The vol ume of the .

water diminishes as the tempe rature rises from 3 2 F to


E where it is exactly 1
I t the n expands slowly at .

rst but more rapidly as the tempe rature rise s till at 2 1 2 F

, ,

the volume of the water is

I f we co ntinue to apply heat to the water the p ressure ,

being still th at of the atmo sphere the water begins to boil , .

For eve ry u nit o f he at o ne nine hundred and sixty fth


part of the pound o f water i s boiled away and is converted

into s te am the volume o fwh ich is about
, times th at of
the water from which it was fo rmed The diagram might be .

extended o n a larger sheet o f paper to represent the wh ole

pro cess of bo iling the wate r away This process woul d t e .

quire 965 u ni ts of heat so th at the whole le ngth of the base


line fro m 0 w ould be i nches At this poi nt the water .

would be all b oiled away and the s team w ould occupy a ,

volume o f times th at o f the water The vertical line .

o n the diagram which wo uld represent the volume o f the

steam would be i nches o r more th an 2 8 6 feet lo ng

, .

would be s 2 1 2 F If we continue to

e steam still at the atmospheric pressure

, ,

Heat E ngi ne s
1 38 .

the rate of degrees fo r eve ry unit of hea t, the spec

heat of steam being
The volume o fthe s u pe rheated steam al s o in c reases ll
regul ar m anner being p roportional to its abso lu te tem

rom 460 F
ature recko ned f

r .



H rr
m ro the only u se we have m ade o f the indi w
diagram 18 to explain the relatio n betwee n the volu m e and
pressure o fa su bstance placed 1n certain t hermal co ndi tion
The co nditio n that the temperature is co nstant gave us
isothe rm al lines and the co ndi tion that no c o mmu ni cati

of heat takes pl ace gave us the adi abatic lines W e ha .

now to conside r the application of the same meth o d to

measurements of quantities o f heat and quanti ti es of m
chanic al wo rk .

At p 1 0 2 it was sh own that ifthe pe ncil of the indicat


moves from B to c this shows that the vol ume o f the eu


stance has i ncreased from o b to o e u nde r a pressu re W


was o riginally B b and nally 0 e .

The work done by the pressure o f the substanc e again

the piston during this mo tio n is rep resented by the an
B e c b and since the vol u me increase: d uring the p roc es

it is the substance which doe s the work o n the pi sto

and no t the pis t o n which does the work o n the substanc e .

In heat e ngines o f ordinary co nstruction such as s tea ,

engines and air engine s the form of the path described


the pencil depends on the mech anical arrangements of t]

engi ne, such as the O peni ng and shutting ofthe valves Whil
Carno t : E W M . 1 39

the wo rking o f an engine of a species e nti rely i maginary

o ne which it is impos sible t o co nstru ct, but very easy to

This engine was inve nted and described by Sadi Carno t ,

in his Rexio ns sur la P uissance motrice du Feu pub


lished in 1 8 2 4 '
It is called Carnot s Reve rsible Engine for

reaso ns which we shall explain .

All the arrangements connected with this e ngine are c on

tri ved fo r the sake of being explained and are no t intended

to rep rese nt anything in the working o freal engi nes .

Carnot himself was a believer in the mate rial nature o f

h eat and was in consequ ence led to an erro neo us statement

of the qu anti ties o f heat which must enter and l eave the

e ngine As o ur object is to understand the theo ry o f heat


and no t to give an historical acco unt of the theo ry we shall


avail ourselves o f the im rtant step which Carnot m ade ,

while we avoid the error into which he fell .

l ha zn


Let D be the worki ng sub stance which may be any sub


stance whateve r which is in any way affect ed by heat but , ,

for the sake o fp reci sio n we shall suppose i t to be ei ther air


or steam o r partly steam and p artly co ndensed wate r at the


same temperature .

The working subs tance is contained in a cyli nder tted

with a pist on The walls of the cyli nder and the pist on are
a m: as : e
1 5: 1 c . th e
m I m : 25 1

E 77 3 O l
drm We ne w p lac e

the C 1 22: i s: o n the non c o n du c ting


stan d e ,
w l at no h eat mn eecape ,

d we th en forc e the pist on d o wn,

so as to dim inish the v olume o fthe
sub stance As no h eat can esc ap e,

the t em p era tu r e ris es and the rela


tio n between vo lume and pressure

at any i nstant will be exp ressed by
the p e nc il t rac i ng the a d iabatic li ne A B .

We u mtimu: thi s pro cess till the temp erature has ris en to
u that o fthe ho t body A
, . D uri ng th is process we have ex
| mw | m | an am o u nt o f w o rk o n t h e s u bst a n c e whic h is re

p u m-
c cl b
y th e ar ea A 11 b a I.f wo r k is r eck o ne d ne g ativ e

Whe n it in up c ut o n the substance, we mu st regard that

em l
p yo ed i nthi s r t o ratio n a n g a tiv e
s pe s e .
Ca mt o e

F our Operat i ons . 1 41

Second Op We no w transfer the cylinder t o the

e a
r ti on
hot body A and allow the pist o n gradually to rise The
, .

immediat e e ffect o f the expansion o f the substance is t o

make its temperature fall but as soon as the t emperature ,

begins to fall heat ows in from the hot body A thro ugh the

perfectly co nd ucting bottom and keeps the temperature from ,

falling below the temperature 5 .

The substance will therefore expand at the tem perature 8 ,

and the pencil will trace out the line B c which is p art o fthe ,

isoth ermal line co rrespo nding t o the uppe r temperature 8 .

During this process the substance is doing work by its

press ure on the piston The amount of this work is re .

prese nted by the area B c e b and it is to be reckoned ,

positive .

At the same time a cert ain amount ofheat which we shall ,

call B has p assed from the ho t body A into the working


substance .

273137 1 Operatzbm The cylinderis nowtransferred fro m the

hot body A to the non conducti ng body c and the piston is

allowed to rise The indic ating pencil will trace out the

adiabatic line 0 D since there is no communicatio n o f heat

, ,

and the tempe rature will fall dur i ng the p rocess When .

the temperature has fallen to r that o f the cold b ody , ,

let the operatio n be s topped The pencil will the n have .

arrived at n a poi nt on the iso therm al line f

, or the lower

temperature T .

The wo rk do ne by the substance du ring this p ro cess is

represe nted by the area c D d e and is posi tive , .

Fourtk Operation The cylinder is placed o n the c old


body B It has the same temperature as B so t hat the re is no


transfer o fheat But as soo n as we begin to press d own the


piston he at ows from the working substance into B so th at ,

the temperature rem ains sensibly equal to r d uring the '

operation The piston must be forced down till it has


reached the po int at which it was at the beginning o f the

rst operati on and since the temperature is also the same,
, ,
H eat E ngi nes .

the pressure will be the same as at rst T h e w ith .

su bstance therefore after these four o peratio n s has return:

, , ,

exactly to its origi nal state as regards vol u m e p ressu ref ar


D uri ng the fourth operatio n in which the p en c il traces t]


po rtio n D A ofthe iso thermal li ne fo r the lower te m peratur

the pis ton does wo rk o n the substance the am o un t o f whic ,

is to be recko ned negative, and which is rep res e nted by ti

area D A a 11 .

At the same time a certain amou nt o fheat whi ch we sha ,

de note by It has owed from the working su b stance i nto tl


cold body B

Dsr mrrro x or A Crone A series o fp

o erations by wk
t/i e substance is nally brouglit to tile sa m
e state i n all ra n
Cy cle of operations
as at j irst is called a
Total Work done du ri ng t/ie Cy cle When the pis to n
rising the substance is giving out work ; this is th e cas e
the seco nd and third Op eratio ns When the piston is sinki ng

is pe rforming work on the s u bstance which is t o be reckrme

negative Hence to nd the wo rk pe rf
, ormed by the su bstanc
we must subtract the area D A B b ( 1 represe nti ng the negativ ,

work fro m the positive wo rk B c D d b The remainder

, , . .

A B c D represe nts t he use f

, ul work pe rfo rmed by the so
s tance during the cycle o foperations If we h ave any di .

cu lty in u nderstanding how this amo unt o f wo rk can b

obtai ned in a u se ful form during the worki ng of the engim
we h ave o nly to suppo se that the pisto n when it rises i
employed in lifti ng weights and th at a portio n o fthe weigl

lifted is employed to fo rce the piston down again As th .

pressure of the su bstance i s less when the pisto n is si nkin

than when it is rising i t is plai n that the e ngine can raise

g rea ter weight tha n that which 15 requ i red to comple t e th

Co parir m f Tlwrmal and M
o echanical E m . 1 43

heat, for i n the rst and thi rd the h eat is conned by the
n on co nducting stand

I n the second operatio n a quanti ty of heat rep rese nted by

H passes f rom the hot body a i nto the wo rking s u bs tance at
t he upper temperature 5 and i n the fo urth Operatio n a

quantity Of heat represented by a p asses fro m the worki ng

subs nce into the cold b ody B at the lower temperature T .

The worki ng s ubs tance is left after the cycle of O perations

in p recisely the same state as it was at rst so that the whole ,

p y sim l res u l t o f the cycle is
r A quantity H of he at take n f
, , rom A at the temperatu re 8 .

. The pe rform ance by the substance Of a quantity Of
work repre sented by A B c D .

3. A q ua n t ity
, ,
l l O f hea t commu nicated to B at the tem
p eratu re T .


It has lo ng bee n thought by tho se who study natural

forces th at in all Observed actio ns amo ng bo dies the wo rk
which is done is merely transferred from o ne body in which
there is a store of e nergy int o another so as t o increase the ,

s tore of e nergy in the latter body .

The wo rd e nergy is em ployed to denote the cap acity

which a body has Ofpe rforming work whether thi s capaci ty ,

arises from the motio n Of the body as in the case Ofa m

, u non

ball which is able to batt er down a wall before it can h e


step ped rom its positio n as i n the case o f the weigh t O fa

o rf ,

is able to keep the clock goi ng

r cause su ch as the el asticity of

work is measured and th at ifw e whole


were measured in this way the mutual

t 4-

ac tion of the pu ts of di e systa n m neit he r in m

di inish its total stoc k of ene lgy.

H enc e any increase o r

must be trace d to the

The belief in the doctrine of the c onsa va t i w

d a

made into the mechanical value Ofvari ous form s O f er

were all undertaken by m en who believed tlm t in so d

they were laying a foundation fora more ac curate kno wl
Ofphysi cal actio ns co nsidered as forms o f em ery The .

that so many form s Of ener gy c an b e m eas ured on

hypo thesis that they are all equivalent to m echanic al em
and that measurements conducted by dif ferent m m
e o da
c onsistent with each other sh ows that the do
, e

To estimate its truth fro m a demonstrative poi nt Of

we must co nsider as we have always to d o m making

estim ates, wh at 18 involved i n a direct co ntradiction of

d octri ne Ifthe doctri ne is not true then it is po ssihh

the parts o f a m aterial system by their m

utual aetio n al

and without bei ng themselves alte red i n any permanent 1

either to do work on external bodies o r to have work 6

o n them by external bo dies Since we have supp osed

sys tem alters cycle of Operations to be in exactly the s


an te as at rs t, we m ay suppose the cycle o f operation

be repeated an indeni te number Oftimes and therefore,

system is capable in the rst case Of doing an inde

quantity of work withou t any thing bei ng supplied to it ,

in the seco nd o f abso rbing an indenite quantity of I

That the doctrine Of the co nservation of energy is

Cb mma m f E n rgy
e o e . 1 45

themselves had repeatedly Observ ed the apparent loss of

ener i n f
r iction and other natu ral ac tions witho u t maki ng
g ,

any attemp t o r eve n showing any desi re to ascertain what

becomes Ofthi s energy .

The evidence however which we have Of the doctrine is

, ,

nearly ifno t qu i t e as complete as th at Ofthe co nservation o f

matterthe doctrine that in natural operations the quantity
Ofmatte rin a system always remai ns the same tho ugh it m ay
change its form .

N0 good evidence has been brought agai nst eitherofthese

doctrines and they are as certain as any other part Of our

knowledge o fnatu ral thi ngs .

The gre at meri t OfCarno t s method is th at he arranges his

operations in a cycle so as to leave the working su bstance


in precisely the same co ndition as he found i t We are .

therefore su re that the energy remaining in the working

su bstance is the same i n amount as at the beginni ng Of the
cycle If this conditi on is no t fullled we should have to

discover the e nergy required t o change the s ubstance from

i ts original to i ts nal state before we could make any
asse rtion b ased u pon the co nservation o fenergy .

We have the refore got ri d Of the co nside ratio n of the

called its

get fo r the resulting e nergy

Ofwork do ne represented by A B c D
, and
I: Of heat at the temperature r o f the cold

Of the conservatio n of energy tell s us th at

e heat H at the t empe rature 5 exceeds th at
emp e ratu re r by a q uanti ty o f me
epresented by A B c D which can be easily
r ,

in foo t po unds Thi s i s admitted by all



ot believed heat to be a m aterial subs tance,

H eat E ngi ne s:

ca e d mlorh which of cou rse cann o t be c reate d o r
He th erefore conclu ded that since the qu ant it y o f I

maimngin the su bstance is the same as at rst H the . , ,

O f heat commu nicated t o i t and ll the quantit y I , ,

abstr acted f rom it must be the same , .

These two po rtio ns Of heat however are as I

mm m
, , ,

0 in dif
, fe rent co ndi tio ns fo r a is at th e ,

o fthe ho t body and aat that ofthe co ld body and I

, ,

co ncluded that the work o f the e ngine was do n e

expense Of the fall Of temperatu re the energy I ,

distribu tion o f heat being great er the hotter th e b o dy

contai ns it .

He illustrat ed this theory ve ry clearly by the analog

water mill When water drives a mill the wat er whi ch

the mi ll leaves it again u nchanged in quantity but at a ,

level Comparing heat with wate r we must co mpare


at high tempe ratu re wi th water at a high level Water .

to ow from high ground t o low ground just as heat tel ,

ow h o mhot bodies to cold ones A water mill male: .


o fthis te nde ncy o fwat e r and a heat e ngine m

, akes use r

co rrespo nding property o fheat .

The measu reme nt Ofquantities Ofheat especially W] ,

has to be done in an engi ne at work is an op eration of ,

difculty and it was no t till 1 862 that i t was sh own 1:


mentally by H im that It the heat emitted is really less

, ,

8 , the heat received by the engine B ut it is easy t .

that the assumptio n that a is equal to a m ust be wrong

For ifwe were t o employ the engine in stirring a h
then the wo rk A B c n spent in this way wo uld genera
amou nt Ofheat which we m

ay denote by b m the liqui

The heat H at the high t emperature has therefore

un d and we nd instead Of it a q uantity a at ths

tem rr
e rature an d also 6
a t the tempe r ature o f the li
whatever it is .
H eat is no t a S u bstance .

created which is contrary to the hypothesis that i t


Besides this we migh t have allowed the heat H t o pass


fromthe hot body to the cold body by cond u ctio n ei ther ,

directly o r through o ne o r more conducti ng bodies and in ,

this case we know that the heat received by the cold body
wo u ld be equal to the heat taken from the hot body si nce ,

conductio n does no t alter the quanti ty o f h eat H e nce in .

this ( u se 8 It but no work is do ne d uring the transfer o f


heat When in addition to the trans fe r ofheat work is done

, ,

by the engine there ought to be some dif

, fere nce in the nal
re sult but there will be no dif
, ference ifI: is still equ al to a .

The hy pothesis o fcal o ric, or the theo ry that heat is a k ind

o f matt er is rendered unte nable rst by the p roo fgive n by
, ,

Rumford and mo re completely by D avy th at heat c an be

, ,

generated at the expense o f mechanical work and second , ,

by the measurements of H im which show that whe n heat ,

does work in an engine a p ortion ofthe h eat disappears

, .

The dete rminatio n ofthe mech anical eq uivalent o fheat by

Joule enables u s to asse rt that the heat which is required t o
raise a po und o fwate r from 39 F to 40 F is mech anically

. .

equivalent to 77 2 foot pounds o fwork -


It is to be observed that in thi s statement nothi ng is said

of the body in which the heat exi sts .

o f water from 39 F to


o f cold water at 5 0 F


mth srmat a

F, . or f
ro e

erminati n and o ,

whatev er be the
Whe n heat is measured as a
is paid to the temperature o f
xists any more than to the size
, ,

o f that body just as when we deter


a body we pay no attentio n to its o ther

a body in a certai n state ,

as to temperature , &c ,.
1 48 H eat E ngi nes .

is capable ofheating so many po unds o fwater fro m3 9 F


4 0

F be o
. re it is i tself cooled to a give n te mpe ra ture 5 : ,

F the if th t body i i ts o riginal stat e is sti rred abo

4 0 .n ,
a n , ,

and i ts parts ru bbed together so as to expend 7 7 2 f o o t poun -

o fwork in the p rocess it will be able t o h ea t o n e pour


more o fwater from 3 9 F to 40 F before it is c o o led to



given temperature .

Carnot the refore was wro ng in su pposing t hat

, ,

mechanical e nergy o f a given quantity of heat is great

when it exis ts in a ho t body than when it exists in a col
body We no w know that i ts mech anical energy is exact]

the same in bo th cases al tho ugh whe n in the ho t bo dy it


mo re available for the purpose of drivi ng an engine .

I n o urstateme nt ofthe four operatio ns of C arno t s engin

we arranged them so as to leave the result in a state i

which we can interpret it either as Carnot did o r ac c o rdin ,

to the dynamical theory o fheat Carno t hims elf began wil .

the Ope ration which we h ave placed second, the exp ansic
at the u pper temperature and he directs us to co ntinu e ti

fourth O peratio n compressi o n at the lower temp erature ti

, ,

exactly as m uch heat has left the substance as e ntered durir

the expansio n at the upper temperature The result o f th .

operatio n would be as we no w know to expel to o mu

, ,

h eat so that after the substance had b een compressed


the non conducting stand to its original volume i ts t emper


ture and p ressure would be too low It is easy to am end .

directions for the exte nt to which the outow o fheat is to

pe rmitted bu t it is still easier to avoid the di fcu lty

placing this Operation l ast as we h ave done , .

We are now able t o state preci sely the relatio n between

the quantity of heat which leaves the e ngine and 8 ti , ,

quanti ty received by i t B is exactly equal to the sumo f


heat to which the mechanical wo rk represe nted

Heat ex ressed
p i n F oot-pounds . 1 49

o nce i nstead o f rst expressing the m in


s at ,

and then red u ci ng the result to foot pounds by -

means of Joule s equ ivale nt o f heat In fact the the rmal


unit depe nds for its deni tion o n the choice o f a standard
substance to which heat is t o be applied o n the ,

choice o f a standard qu antity o f th at subs tance and ,

Oic e o f the e ec t t o be p rodu ced by the heat

as we choose wate r o r ice the grai n or the ,

of which have

void ambiguity and

a , ,

about the worki ng of

ss phraseol ogy .

h ave already sho wn how an area o n the indi cator

rep rese nts a qu anti ty o f wo rk we shall have no ,

in understanding th at it m ay also be taken to re

quantity o fheat equivale nt to the same quantity of
ofheat .

the relation betwee n H and ll

ofheat take n into the engi ne at th e

exceeds the quantity ll o f heat give n , ,

the lower t empe ratu re T by a quantity

by the area A B c D o n the indicato r

heat is as we have already shown

, ,
co n

mec hanical work by the engine .

as R V RSED AC I l ON o r cann ons s no w s


culiarity o f engine is that whether it is

Carno t s

heat from the ho t body o r giving it out to the


o f t he s ub stance i n the e ngine

fro m th at o f the body in thermal

By su pposing the co nductivity o f
1 50 H eat E ngi nes .

the bottom o f the cyli nder to be sufciently

s upposing the motio ns o f the pist on to b e
slow we may m
, ake the actual dif ference o f tem pa
which causes the ow o f h eat to take place as man3
please .

I fwe reverse the mo tio n o fthe piston when the su bs!

is in the rmal communicatio n with A or B, the rst effect
be to alter the temperature o f the working su bstance,
an exceedingly sm all al teratio n o f tem pe rature will be

ci ent to reve rse the o w Of heat if the m o ti o n is


eno ugh .

N ow let us sup o se the engine to be worked backw

by exactly reve rsi ng all the operations already desc ril
Beginning at the lower temperature and vo l u me 0 a la
be placed o n the cold body and expand fromvolum e 0

o d . I t will receive from the cold body a quanti ty of l

a The n let i t be comp ressed withou t loa ng heat t o

It will then have the upper tem perature 8 Let it ther .

placed o n the hot body and compressed to vol ume 0 6 .

will give ou t a qu antity o f heat a to the hot body Fins .

let i t be allowed to expand withou t receiving heat to volt

0 a and i t will re turn to its o rigi nal state The o nly di ere
, .

betwee n the di rect and the reverse ac tio n o f the engi ru

that in the direct act io n the working substance wust l
little cooler than A when i t receives i ts heat and a li ,

warme r than 8 when i t gives it out whereas in the 1 t

actio n it must be warmer t han a when it gives out he at a ,

cooler than a wh en it takes heat in B ut by working


e ngine su ciently slowly these diffe rences may be re du

within any limits we please to assign so that fo r tl ,

reti cul purposes we m ay regard C arac t s engine as stri


ty o f heat into which this wo rk 18 transformed

p rocess .

o f Carno t s engine shows us th at it is

heat from a cold body to a hot o ne ,

be do ne at the expense o f

t body to a cold o ne

s on o f itself b ut ,

of heat into work It appears .


pass from hot bodies to co ld o nes

One o f these in which a highly

u se o f is nearly
, bu t not quit e

by spending the work we

resto re almost the whole of the heat
the hot The o ther mode of trans

o f i tself whe never a hot and a cold

each oth er appears to be irreversible

, ,

o m a cold b ody to a hot one o f

o nly when the operatio n is effected by the articial

the expe nse o fmechanical work .

w come t o an impo rtant principle which is en ,

t o Carnot I f a given reversible engine working


u ppe r temperature 5 and the lowe r tempera

receivi ng a quanti ty H o f heat at the upper

prod u ces a quanti ty w of mechanical work ,

er engine what e ve r be its co nstructio n can

, ,

when supplied wi th
g betwee n the same

Darw rrxo rt or En rc ras c v

. 1f a is Me su l
pp y qf a m ,

is called tile M ake r

) f
o tile
H eat Engzrzer

I 5 2 .

principle then, is that the ei c i enc y o f a re

C arno t s


sible engi ne is the greatest th at c an be ob taine d wi th a i

range o ft empe rat ure .

Fo r suppose a ce rtain engi ne M has a greater alheit

, ,

between the tempe ratures 3 and r t han a rev ersible e


N then if we co nnec t the t wo e ngines so that M by

, ,

di re ct action drives N in the reverse direction at e ac h str ,

o f the co mpound engine N will take f rom the col d I)

B the heat It and by the expendi ture o f work w give to


ho t body A the heat H The engine M will recei ve r


heat 8 and by hypo the sis will do more work while tn


fe rring it to B than is required to drive the engine

H e nce at every stroke there will be an excess of u s
work do ne by the combined engine .

We must no t suppose howev er th at this i s a violation

, ,

the principle o f cons ervatio n o f e nergy for if M does m ,

wo rk than N would do it co nverts more heat into worl


eve ry stro ke and there fore M resto res to the co ld bod


smaller quantity o f heat than N takes from it Hence .


legi ti m ate conclusio n from the hypo thesis is , that the cc

b ined e ngine will by its u naided action, convert the h

Of the cold body B into m echanical wo rk and that 1 ,

p rocess may go o n till all the heat in the system is co nvex

into work .

This is manifestly co ntrary to experience and there! ,

we m ust adm it that no e ngin e can have an e f ciency grea

than that o fa reversible engine working between the 83
tempe ratures But before we conside r the results o f C
no t s p rinciple we m us t e ndeavo ur t o exp ress clearly

law which lies at the bottom o fthe reaso ning .

The pri nciple o fthe co nse rvation o fe nergy whe n appl ,

to heat is commonly called the Fi rst Law o f Them


to the quantity o f ea h t .
L aws o f l erm oa
y na mi cs . I 53

is no tdeduced from this law and ,

s tatem ent involved a violation of it .

Carno t s principle is ded uced has been
odyna mics .

form ofenergy the second law


by the unaided action ofnatural

p art o f the heat o f a body into
allowing he at t o pass from t hat
er temperatu re C lausius who

Carnot in a m anne r co nsistent

expresses this law as follows
from o ne body to another

sligh tly di fferent fo rm

means o f i nanimate material age ncy ,

effect from any portio n o f m atter by

o f t he coldest o f the su r

stat eme nts the student will


o f the f act w hich they em

b e o f mu ch greater import
words o n which a demo n
co nstru ct ed .

in the form o f he at ,

enby arranging our

movi ng part of the

parts o f the heated body to any

o f ordi nary motio n The heated

dered pe rfectly cold and all its,

co nvert ed into the vis ib le motio n

1 54 H eat E ngi nes .

Now this ppo si tio n i nvolves a direct con tradic tion to


the seco nd law of thermodynamics bu t is c o nsistent wi th ,

the rst law The second law is there fo re eq u ivalen t to a


denial o fo ur powe r to pe rfo rm the Ope ratio n j ust d escri bed,

ei ther by a train ofmechanism, o r by any o ther metho d yet
d iscovered H e nce i f the heat o f a body cons ists in the

moti on o f i ts parts the separat e parts which mo ve mu st


be so small o r so impalp able that we cannot in any way lay

hold o fthem to st op them .

I n fact he at in the fo rm o f heat neve r passes o u t o f a

, , ,

body excep t when it ows by co nduction or radiatio n i nto a

colde r body .

There are several p rocesses by which the tem perature o f

a body m ay be lowe red wi thout removi ng heat f rom it such ,

as expansio n evapo ration and lique f , actio n and certain , ,

chemical and electrical processes Eve ry o ne o f these .


howeve r is a reve rsible p rocess so th at when the bo dy is

, ,

b ro ught back by any se rie s o fope rations to i ts original state ,

wi tho ut any heat being allowed to e nter o r escape d uring

the process the tempe rature will be the same as before in
, ,

virtue o fthe reversal of the processes by which the temp e ra

t ure was lowered But i f during the operati ons h eat
, ,

has passed from hot parts o f the system to cold by c on

ductio n o r if anythi ng of the nature o f fri ctio n has taken

place then to bring the sys tem to its original s te wi ll


requ ire t e expe nditu re o fwo rk and the removal o f h eat


We m ust no w return to the important result dem


o nstrate d
by Carnot that a reve rsible engine working between two
, .

give n temperatures and receivi ng at the higher temperatu re


a given quantity o f heat perf o rms at l east as m uch work


as any other engi ne wh atever working under the same

co ndi tions It follows from this that all reversible engim ,


whatever be the working substance employed, have the

same e ci enc y, p rovided they wo rk between the same
te mperatu re o f the so urce o f heat A and the same tem pera
tu re of the refrigerator a .

Ce n ters F u nc ti on . I 55

c rs dif
ering very slightly say by run o f a degree the

e fcie ncy ofan engine wo rking betwee n these temperatures

will depe nd on the t empe rature only and no t o n the su b ,

stance employed and this efcie ncy divided by the dier


e nce oftemperatures is the quantity called Camot rfund rbn


a quantity depending on the tempe rature o nly .

Carnot of course u nderstood the temperature to be

, ,

estimated in the ordinary way by means o f a th ermometer

o f a selected substance gr ad uated acco rdi ng to one of the
established sc ales and hi s function is e xpressed in terms o f

the temperature so determined Bu t W Tho m so n in

. .

was the rst to point out th at Carno t s re sult leads to a

method of de ni ng tempe rature which is m uch mo re

scie ntic than any o f those derived from the beh avio ur o f
o ne selected substance o r class o f s ub stances and which ,

is pe rfectly indepe nde nt o f the nature o f the su bstance

emp loyed in de ning it .

rao m
so n s

asso w rs

s c ams o r T EM PERAT URE .

Le t r A B c rep rese nt the iso thermal li ne correspo nding

to temperature r for a certai n subs tance For the sake o f .

disti nctness i n the gure I have s upposed the substance t o


be partly in the liquid and partly in the gaseous state s o ,

that the isothermal lines are horiz ontal and easily di s ,


tinguished f rom the adiabatic li nes which slope downwards ,

to the right The i nves tigatio n howeve r is qui te indep en

, ,

de nt o fany such res trictio n as to the nature o f the worki ng

s ubs tance When the vol ume and pressure o fthe s ubs tance

are those i ndicated by the poi nt A let heat be applie d ,

and let the s u bs tance expand always at the t emperature T

, ,

till a quantity o f heat a has e ntered and let the stat e o f ,

the su bstance be the n indicat ed by the poi nt a Let .

the p rocess go o n till ano the r equal quantity H o fheat has , ,

entered , and let G indicate the re sul ti ng state The process .

may be carried on so as t o nd any number o fpoi nts on

[ 5 6 H eat Engi n .

the isothe rm al li ne su ch th at , eac h po int passed dun

the expansio n o fthe s ubstance a q uanti ty n o f h eat has be

communicated to it .

No w let A A A

, B
B s c c

be adiabati c line s dra
c i

F 3
through A B c t hat i s lit
rep rese nti ng the relati on 1
, ,

twee n volu me and pressi

whe n the substance is allo w
to exp and withou t rec ei vi
heat from without .

be isothermal li nes c o n
s o nding to the tem er m
r an
d p at

We have already fo llow

Carno t s p ro o f that in a

versible e ngi ne working f rt ,

the temperature T ofthe source ofheat to the temperature

rigerator the work w produced by the quanti ty
o f the re f ,

heat H drawn from the source depends o nly o n T and

He nce since A a and B c correspond t o equal q uantiti

o f heat H received f ro m the sou rce the areas A a s A a]


B c c B which represe nt the correspo ndi ng work perform:


m ust be equal .

The same is true ofthe areas c u t off by the adiabatic lin

from the space betwee n any other pair o f isotherm al lines

Hence ifa series o f adiabatic li nes be drawn so that t

poi nts at which they cut o ne o f the isothe rmal lines co n
spo nd to s uccessive equal additio ns o f heat to the s ubatan

at that temperature the n thi s series o fadiab atic lines will r


off a series o f equal areas from t he stri p bounded by any tr

isothermal lines .

No w Th omson s me thod o fgraduati ng a scale o ftemper


' "
ture is equivale nt to choosing the poi nts A A A fro m whi ,

to draw a series o fisotherm al lines so th at the M

A B n ,
A bsolu te S rule of Tem
p erature . I 57

be equ al to the area A B B A co nta ined between any other
' "

pair o fconsecutive isothe rmals T T "

It i s the s ame as sayi ng that the nu mberofdegrees betwee n

the temperature T and the tempe rature T is to be reckoned

proportional to the area A B B A "

Ofcourse two things rem ain arbitrary the standard tem ,

p era tur e which is t o be recko ned zero an d the size o f t he ,

degrees and these may be chose n so that the absol ute scale

correspo nds wi th o ne of the ordinary scales at the two

standard tempe r ature s bu t as soo n as these are de t ermi ned

the numerical measure o fevery other temperature is settled ,

in a m anne r i ndepende nt o f the law s o f expansio n o f any

one subs tance by a method in fac t which leads to the same
, ,

resul t wh atever be the substance emplo yed .

It is true that the experiments and measurements required

to graduate a thermometer o n the principle here pointed out
wo uld be far more difcul t th an those required by the
o rdi nary metho d described in the chapter o n Therm ometry .

Bu t we are no t in this chapter descri bing co nve ni ent method s

, ,

o r good worki ng engines Our obj ects are i ntellectual


no t practical and when we have es tablished theo retically


the scie ntic advantages o f this me thod of grad uatio n we ,

shall be better able to u nde r stand the practi cal methods by

which it can be realised .

We no w draw the series of isothermal and adiabatic lines

A particular iso thermal li ne th at of temperature , is cut T,

by the adiabatic lines so that the expansio n o f the subs tance

between co nsecutive adiabatic li nes co rrespo nds to successive

quanti ti es o fheat each equal to i t applied to the substance
, ,

This det ermines the serie s o fadiabatic li nes .

The iso therm al lines are drawn so th at the successive

isothermals cut off from the space betwee n the pair of
" ' ' "
adiabatic lines A A A and B B B equal areas A s B A ,
' '
A B B A &c .

The iso thermal lines so determined cut of

? equal areas
1 58 H earE ngi nes .

from eve ry other pair of adiabatic lines so that the two ,

systems o flines are such th at all the quadrila t erals fo rmed

by two pai rs o fco nsecutive lines are equ al in area


We have now graduated the isothermals o n the diagm

by a method fo unded on Carac t s princip le alo ne and in '

dependent ofthe nature o f the worki ng subs tanc e and it is ,

e asy to see how by al tering ifnecessary the inte rval between

, ,

the lines and the li ne cho sen for zero we c an make the ,

graduation agree at the two standard tempe ratures with

, ,


Let us now co nsider the rel ation betwee n the heat su pplied
t o an engine and the wo rk do ne by it as exp ressed i n terms
o fthe new scale of t emperature .

If the tem perature o fthe so urce of heat is T and if a is ,

the quanti ty o fheat supp lied to the engi ne at that t empera

ture then the work done by thi s heat depe nds e nti re ly on

the temperature o f the re frige rator Le t T be the t e mpera


ture o fthe re frige rator the n the work do ne by H is rep resented


by the area A B B A o r since all the areas betwe en the

, ,

isothermal s and the adi abatics are equal let H c be th e area ,

o fo ne of the quadrilaterals then the work done by H will be


H c (T The qu anti ty c depe nds o nly o n the tem

It i c lle d C F unc tio n o f the tem pera

p er atur e T . s a arno t s

ture We shall nd a simple expressio n for i t at page x6c


This therefore is a complete determination o f the work

, ,

done when t he temperature o f the source o f heat is T I t .

depends o nly o n Carnot s principle and is true wh ether we


admit the rst law o fthe rmodynam cs o r no t

Ifthe tempe rature o fthe so urce is no t T bu t we mu st

consider what quantity o f heat rs represented by the expan

sio n A B along the isotherm al T Calling this quantity o f

heat a the work do ne by an engine worki ng between the

T/mr E

akng '
. 1 59

N ow Carnot supposed that H

R, which would make

g ( whe re c

t he e f ciency of the engi ne simply c T

is Carno t s functio n,co ns tant quan ti ty o n this suppositio n

a .

B ut according t o the dynamical theo ry ofheat we get by the ,

rs t law ofthermodynamics

the heat being meas ured as mechanical work or ,

= H H C (T

Onthis theo ry there fore the e ffi cie ncy

, , of the e ngi ne
w orking be twee n T and T is



We have no w obtained a me th o d o fexpressing differences

o f temperatu re in such a way th at the di erenc e o f two

temperatures m ay be compare d with the ditference o f two

o ther t emperatures B ut we are able to go a step f

. arther
than this and to reckon t emperature from a zero point

dened on thermodynamic principles i ndependently of the

prope rties of a selected substance We must carefu lly .

distinguish between wh at we are doing no wo n really scientic

principles fro m what we did fo r the sake o f co nvenience in
d escribing the air thermome t er Absolute tempe rature o n

the air therm ometer is merely a co nvenient expression ofthe

laws of gases The absol ute temperature as now dened

is independent ofthe nature of the therm o metri c substance .

It so happe ns however that the difference betwee n these

, ,

two scal es of temperature is very small The reaso n ofthis .

1 60 Hm: E ngi nes .

It is plain th at the wo rk which

give n quan t ity o f he

a c an perfo rmin an engine c an never be greater than t

mechanical equivale nt o f that heat though th e col der t

refrigerato r the gre at er p ropo rtio n o f heat is co nverted in

work It is plai n there fore that if we determine T t
, ,

temperatu re o f the refrigerato r so as to make w th e we


mechanically equivalent to H the heat received by ti


engine we shall obtain an expressio n for a state o f things


which the e ngine would co nvert the whole heat into wo n

and no body can po ssi bly be at a lower tem pe rature thi
the value thus assigned to T "

This is th e lowest temperatu re any body can have . Ca
ing this tem perature zero we nd ,

or the tempe rature reck oned fro m absolute ze ro is t]
u nc tion c
reciprocal of C arno t s f


We have therefore arri ved at a complete denition o f ti

measure o f tempe rature in which nothing remains to 1

determined excep t the size o f the degrees Hitherto d .

size o fthe degrees has been c ho se n so as to be equal to

mean val u e of those o f the ordinary scales To co nvert .

ordinary expressions into abso lute tem p eratu

to the ordinary expressio n a co nstant number

which may be called the absolute temperatu re 0
the s cale There is also a co rrection varying at

part s o f the scale which is never very great when


pera tur e is meas u red hy the ai r thermometer We .

exp ress the ei ci ency o fa reversible heat e ngi ne in

the absolute temp eratu re s of the source o f heat ,
A brolu te Tem
p eratu re . 16r

The qu anti ty of heat whi c h is given o u t to the re frigerato r

at te mperat u re r is
b : a w H I ,
whenc e
tr b n s
s r Ir T
that is in a re ve rsible e ngi ne the ratio o f the heat received to

the heat rejected is that o fthe numbers exp ressing o n an abso

l u t e scale the temperatures o f the source and the re frigerat or .

This relation furni she s us with a method o f determi ni ng

the ratio o f two t emperatu res on the absolute scale It is .

indepe nde nt o fthe nature o f the substance employed in the

reversible e ngine and i s there f ,
ore a pe rfect me thod co n
sidered f rom a theore ti cal point o f view The prac tical .

difcul ties o f fu llli ng the requi red condi tio ns and maki ng
the necessary measurements have no t hi therto been over
come so that the comp ariso n o f the absolu t e scale o f tem

p e ra tu re wi th the o rdi nary scale m ust be made in a dif

fere nt

way .
(See p .

Let us no w re turn to the diagram g 2 3 (p on which . .

we have trac ed two systems o f lines the iso thermal s and ,

the adiabatics To draw an iso thermal line through a given


point requires o nly a series o fexperiments on the substance

at a given t emperature as shown by a thermometer o f any

ki nd To draw a series of these lines to represe nt su cces


sive degrees o ftemperature is eq uivalent to xi ng a s cale o f

temperatu re .

S uch a sc ale might be de ned in many differe nt ways ,

e ach o f which depe nds o n the propert ies o f some selecte d

s ubstance For instance the scale might be founde d o n the

e xpansion o fa particularsubs tance at some standard pressure .

I n thi s case if a horizontal line is drawn to represent the


standard pressure then the iso thermal li nes o f the selec ted

s ubstance will c ut this line at equal int ervals I f howeve r .

, ,

the nature o f the substance o r the standard pressure he

dierent the the rmome tric scale will be m eneral dif
The sc ale might also be founded o n the variation ofpressure

1 62 TM oldy/nu mb .

ofa s ubstanc e co nned in a giveu spac e as i n th e case of ,

certain applicati ons o fthe air thermometer .

It has also been proposed to dene t empe rature so tint

equal increme nts of heat applied to a standard s u bstance

will produce equal i ncrements o ft emperature T hi s method .

al so fails t o give results consi st e nt f

o rall s u bstanc e s beca use ,

the speci c heats of differe nt substances are no t in the same

ratio at di f ferent temperatures .

The o nly method whi ch is ce rtain t o give co nsistent re

sults whatever be the s ubs tance em
, ployed rs that whi ch rs ,

founded o n Camo t s Function and the m o st co nveni ent


form rn which this method can be applied rs that which dc

hu es the abso l u t e tempe ratu re as the reciprocal o f Carno t s

be made betwee n the absolute temperature on the thermo

dynamic scale and the t emperature as indicat ed by a
thermome ter ofa particular kind o fgas ( See p 2 1 . .


We have next to consider the seri es o f adiabatic lin es as

indicating a series o f degree s o f another p ropert y o f the
body xpressed as a measurable quantity such t hat when
e , ,

there i s no communication o f heat this quanti ty remains

co nstant but when heat enters or leaves the body the quan

ti ty increases or diminishes .

We shall adopt the name given by Clausiu s to this quan ~

ti ty and call it the entropy o fthe body Rankine i n wh o se

, .

investigations this quanti ty also plays an impo rtant part mi ls ,

i t the thermodynamic functio n This t erm however is no t

, ,

so approp riate as the name might have been assigned to any


o ne of sever al important qu antities in thermodynamics

We must regard the entrOpy o f a body li ke i ts volu m

e, ,

pressu re and temperature as a distinc t physical p ro perty o f

, ,

t h e body dep end ing o n i ts ac tual state .

The proper zero ofentropy is that o fthe body wh en ent irely

E s trap} . 1 63

The en tropy o f the body in any othe r condi tio n is then

measured thus Le t the body expand ( or co ntract) withou t

communication o fheat till it reaches the standard tempera

tu re the value o f which o n the thermodynamic scale is 1
, , , .

Then let the body be kept at the standard temperature and

brough t t o the standard pressure and le t H be the number

o funi ts o f heat given ou t d uring this process Then the .

entropy o f the body in its original stat e is g .

We shall use the symbol p t o d eno t e the entropy .

I f the body in o rder to arrive at the standard state

, ,

requires to abso rb heat then its o r

, i ginal e ntropy must be
reckoned negative wi th respec t t o the s tan dard stat e .

When heat e nte rs a body at the t emperature 6 and causes

the entropy to increase from 95 to ex the amo unt of heat
, ,

which ente rs the body is

The entro p y o fa body in a given state is p rop ortional to
the mass ofthe body, so th at the e ntropy o f two po unds of
wat er is do uble t hat o fo ne poun d in the same s tate .

We often however speak o f t he entropy o f a substance

, , ,

by which we mean the entropy o f u ni t o f mass ofthat sub

stance ih the given state .

The entropy o f a sys t em o f bodies in different s tates is

the sumofthe entmpies o fea ch ofthe bodies .

When a quantity H o fheat passes from a body at t empera

, ,

ture 6, t o a bo dy at t emperature 03 the entropy ofthe rst body


ed by while t hat of the second is increased by

3, so that the entropy
5 2
of the system increases by H

N ow it is the condition of the transfer o f heat that i t

passes from the hotter to the colder body and therefore 0 , ,

must be greater than 03 .

The transference o f heat therefo re from o ne body o fthe

, ,

system to anot heralways increases the entropy of the sys t em .

C lau si us exp resses this by saying th at the ent m

py o f the
Sys temalways t end s toward s a maxim u m v alue .

M 2
1 64 Yberm

ody m
r mzar .

change ofstate is represent ed as we have seen by

, ,

where 9 is the mean temperature o f the body d u ring the

process and n, and i nrepresent the e ntropy at t he b eginning

and the end o ft he p rocess .

l f we suppose the two isentropic lines p, and p, to be

co ntinu ed in the directio n o f decreas ing t emperatu res down
to the temperature T then the area incl uded between the

two isentropic lines betwee n the temperatu res 6 and T will

be ( 9 7 ) ( Ps
Ifwe co uld draw the isentropic and i so thermal lin es cor
rec tly f o r all t empe ratu re s down t o the absolute ze ro o f the
thermodynamic scale then the whole area in cl uded between

the isentropic lines and the isothermal s fo r0 and zero wou ld

be and this area would represe nt the heat which
ent ers the body during the process .

B ut though i t is impossible t o co nj ecture the p roperties

of a body at abs olute zero o r to draw o n a diagram the true

forms o f the thermal line s near that temperature i t is easy , ,

afte r we h ave co nstructed the thermodynamic diagram f or

that p art of the eld which is known by obse rvation ,

to draw lines in the u nknown part o fthe eld by me ans of ,

which we may still represe nt quantities o f heat by areas .

I f the known part o f the eld is bounded by the i so ther

mal T and if we draw from the extremi ties o f the kn own

p arts of the isentropi c li nes a series o f lines of any form 0

which do no t intersect each o ther and if we draw another


line z z so that the space includ ed be twee n this line two

, , ,

nei ghbouring isentm pic s e, an d a,nd t he i soth erm al lin e

T is we may in calculating quanti ties ofheat treat

, ,

the line z z as the c ti tious iso thermal o f absolute ze ro and


the series o fline s as a c ti tio us isentropic se ries .

For the area between the two isentropic l ines from tem
p e r ature 8 to temper atu re T is ( OT) ( )
a r
T his a rea is
within the known part of th e eld The co ntinuatio n of

this area i n the unkno wn part o f the eld down t o the eti ~

tions isothermal of absolute zero is The who le

F i cti tio us Tder mal L i n es . 1 65

and i t therefore represents the

in passi ng at the temperature 0

The whole heat bso rbed by a body in passing from a


stat e A to a state a through a de nite series of intermedi ate

steps represe nted by Fm 3
the path A B m
. 2 43 .

, ay be
lled the heat o f
the path A a By .

A B into a A

nu mbe r o f

small parts and co n


sidering the area re

p rese nting the hea t

absorbed duri ng the
passage o f the body
over each o f the se divisions we nd that the su mo f these

areas is the area included by the path As the isentropics ,

through A and 8 incl uding their ctitious parts and the cti ,

t ious iso thermal o f absol ute zero .




and T, T, r epresent two isothermal lines

be the quadrilateral which lies be tween bo th

If the line s are drawn clo se e nou gh to

t lines .

e may treat this quadrilat eral as a parall elogram .

o f this parallelogram is as we h ave already ,

1ty .

lines through A and D to meet the line

Q the n since the p arallelogram s
, ,

o n the same base and are be tween

1 66 Thermod
y namics .

lines A k and Km eet Q D pro du ced ifnec essary Then

P to , .

the rectangl e A K P k is equal to the p ar allelogramA K Q B,

b ecause they stand on the same bas e A K, and are b etween
the sam e paral l els A x and 15 Q H ence the rect angl e A K P k

FI G. 2 4.

is l
a so e qual parallelogramA B c D
to the If .

th eref ore we draw A K fro m A h orizontally to mee t the


i soth ermal T3 and A k vertical ly to m eet a h oriz o ntal line


thro ugh D we shall h ave the follo wing relation :


A K A k = A B C D . .

I n the sam e way, if the ho riz ontal line thro ugh A cu ts the
adiabatic line hz in L and the v erticals through D and B in
mand n ,
vertical line through A cu ts the i so th erm al
and ifthe
l ine T2 in M the adiabatic line 2 in N and the h oriz o ntal
, ,

li ne through B in l we shall get the followi ng fou r valu es o f


the area of A B c D inclu ding th at which we h ave already


ABCD A N A n r . .

We have next to i nterpret the physical m eaning of the

four pairs o fli nes which ent er i nto th ese products .

We must rem ember that the v olu me o f the s u bstance is

measured horizontally to the right and its pressure vertically ,
F our TIr m wdy nm
mical R lations e . 1 67

upwards ; that the i nt erval be tween the iso thermal lines

rep resents o ne degree of t emperature the grad uation of the ,

sc ale bei ng as muc h subdi vided as we please ; and that the

interv al betwee n the adiabatic lines represents the addi tio n

o f a qu anti ty o f heat whose nu me rical value is T the ,

( )
r A K r ep r ese nts the in cre a se o f vol u me fo r a rise o f
temperature equal to one degree the pressure being mai n ,

tained co nstant This is called the drlar abili ty o f the


su bstance per uni t of m as s and if we de no te the dilatabili ty


p er uni t o fv o l ume by a A 1: wi ll,be de noted by v a .

A k represe nts the d imi nutio n of p ressu re co rrespo nding

to the addition o fa quanti ty ofheat represent ed numeric al ly
by r the t empe rature being maintained co nstant
, .

If the p ressure is i ncreased by u nity the tem perature


aim ng co ns tant the quantity o fh eat which is emi tt ed by


the substance 15 - 1 . Sinc e A x . A k =r 3 ,

A b A k
Hence the foll owing relation between the di latation u nder
constant pressure and the heat developed by pressure .

stance be i ncreased by unity while the temperature is m ai n

tai ned co nstant the quanti ty o f heat emitted by t he sub

stance is eq ual to the produ ct o fthe absolu te temperature

int o the dilatatio n fo r o ne degree of temperature under
co nstant p ressure .

H ence i f the temperatu re is maintained co nstant those

, ,

sub stance s which incre ase in volume as the tempe r ature

rises give o u t he at when the p ressu re i s increased and ,

those which contract as the tempe rature rises absorb heat

when the p re ssure i s increased .

( )
2 ep
A 1 r
. resen ts the i ncreas e o f vol ume u nder co nstant
pressure whe n a quantity o f heat numeric ally equal to T is
communicated to the su bstance .

A 1 rep rese nts the incre ase o f pressure required to raise

1 68 Thermodynami cs .

the substance o ne degree of tempe rature whe n no heat is

allowed t o escape .

prese nts the heat which must be commu nicated to the sub
stance in order to increase i ts volume by u ni ty the pressure ,

bei ng constant This is equ al to the prod uct o f the ah


sol ute temperature into the i ncrease o f pressure required

to raise the tempe rature o ne d egree when no heat 18 all o wed
to e scape .

( 3) A M represe nts the increase

p ess ure co rresp o ndi ng of r

to a rise o f o ne degree o f temperature the volume being ,

co nstant (We m . ay suppose the su bstance e nclosed i n a

vessel the sides o fwhich are perfectly unyieldi ng ) .

A or represe nts the increas e o f vol u me prod u ced by the

communication of a quanti ty o f heat numerically equal to
T the temperature bei ng m ai ntained co nstant

The heat given o ut by the substance when the vol u me is

dimi nished by u ni ty the tem perature bei ng maintained c on

stant , is therefo re This quantity is called th e latent
A ,
heat of expansio n .

Sinc e A M A m r, we may express the relation between


these lines thus T A M , o r, in words

ird Thermod
y namic Relatzom The late nt hea t ex of

a n i n is equ al to the p roduct o f the ab ol u te temperat u e

p s o s r
and the increme nt o f p ressu re p er degree o f temperature at

co nstant volume .

( 4) e ese
A N r
p r nts the i ncrease o f the press ure whe n a
quanti ty T of heat is commu nicated t o the s ubstanc e the
, , ,

volume being co nstant .

A n rep resent s the dimi nu tion of volume when the sub

Speao H oax

. 1 69

eprese nts the

A a

r ise o f temperature due to a diminution o f the vol ume

by unity no heat being allowed t o escape and this is equ al
, ,

to A N the increase o f pressure at co nstant volume due to


a q u anti ty o fheat nu meric ally eq ual to T co m

m unicated to ,

the substance
We have th us ob tained four relations amo ng the physical
p roperties o f the subs tance These four relatio ns are no t .

i ndependent o f each other so as to rank as separate truths

, .

Any o ne might be ded uced fro m any o ther The equality .

o f the p ro ducts A a A k & c to the parallelogram A B c D

, , .

and to each othe r is a me rely g eom etr i cal tru th and does ,

no t depend u pon t hermodynamical pri ncip les Wh at we .

learn from the rmodynamics is that the parallelogram and

the four p rodu cts are each equal to u nity whatever he the ,

nature of the substance or its co ndi tio n as t o pressure and

tempe rature .


The q uantity o fheat required to raise unit o fmass o fthe

substance o ne degree o f temperatu re is called the specic
heat o fthe su bstance .

These fou r relations may be c o ncisely expressed in the language of

ferential Calculus as follo ws
the Dif

2 h ( 0 co ns t).

275 (11 co ns t)

Here 0 deno tes the vol me u .

p pre ssu re.

0 b l t temperature
a so u e .

0 the rmodynamic function ,

o r en rt
o py .
the rmal unit or the heat requ ired t o raise uni t o f mass of

water o ne degree To reduce this to dynamical measure we


mus t mul tiply by Joule s mechanical equivale nt o fthe thermal

unit The quantity thus found is no longer a m ere ratio, as


at p 66 but depends on t he thermometric scal e which we


select and al so o n the uni t o fwo rk .

Bu t the specic heat o fa s ubstance depe nds o n the m o de

in which the pressure and volume o f the substan ce vary
during the rise o ftempe ratu re .

There are therefore an indenite number of m odes o f

, ,

dening the specic heat Two o nly o f these are o f any


practical impo rtance The rst meth od is t o suppose the


volume t o re main co nstant during the rise o f t emperature .

The specic heat u nder this co nditio n is called the speci c

heat at co nstant vol ume We shall de note i t by x

I n the diagram t he line A M N represents the di erem

states of the substance whe n the v olume is constant, A at

represents the increase o f p ress ure du e to a rise o f o ne

degree o f tempe rature and A N that due to the applicati o n


o fa quantity o fheat nume ri cally eq ual to T Hence to nd .

the quanti ty o f heat K which mus t be commu nicated to

, .

the substance in orderto raise its temperature o ne d egree ,

and so incre ase the p ressure by A M we h ave ,

A N zA M

The seco nd me thod o fde ning specic he at is t o su p pose

the pressu re co nstant The specic heat under co nstant
pressure is denoted by xv
The li ne A L x in the diagram represe nts the dif
ferent stat es
of the substance at co nstant p ressu re A It represents the in

crease o fvolume due to a ri se ofone degree of temperature ,

and A L represent s the m erc ase o f vol u me due to a q uanti ty

( A third mode dening specic heat is sometimes

adopted in the case o f saturated steam I n thi s cas e the .

steam is su ppo sed t o rem ai n at the poi nt o f satu ration as

the temperature rises It appears from the experime nts o f

M Regnault as shown in the diagram at p 1 3 5 that heat


leaves the saturated st eam as i ts temperatu re rises so that ,

its specic heat is W r i te a res ul t poi nted o u t by C lausius


and Ranki ne ) .

E AS I I .

The elas tici ty o f a substance was de ned at p 1 0 7 to .

be the ratio of the increment o f p res sure to the com

pressi on p roduced by it the c ompressio n being dened

to be the ratio o f the dimi nutio n o fvolume to the o riginal

vol ume .

Bu t we require to know some thing abou t the thermal

co nditio ns unde r which the subs tance is placed be fore we
c an assign a denite value to the elas ticity The o nly two .

co ndi tions which are o f p ractical impo rtance are rst , ,

when the t empe rature remains co nstant and seco nd when , , ,

there is no comm u nicatio n of heat .

( )
1 T he e la st i c ity u nder the co ndi tio n th at the tempe ratu re
rem ai ns co nstant m ay be deno ted by as ,

I n this case the relation between volume and pressure is

de ned by the isotherm al line D A The i ncreme nt o f

pressure is k A and the dimi nu tion o f vol ume is mA


Calling the vol u me v the elast icity at co nstant tempe ra


ture is
A k A M
Eg V V
f .


( )2 The
elastici ty unde r t he co nditio n th at h eats m
a . m
enters nor leaves the substanc e 18 deno ted uy E s

I n th is case the re lati o n be tw e en v o\ume an d W

Tlzermod m '

1 72 y na zcs .

d ened by the adiabatic l ine A B The incre m ent o f p ressure .

is A l and the d ecrem ent o f vo l um e is A n H ence the

, .

el asticity wh en no h eat escap es i s

A l A N
= V
= V
AL A n

Th ere are sev eral imp o rtant rel ati ons among these
q u ant iti es I n th e
. rst pl ac e we nd for the rati o o f the ,

sp eci c h eats ,


i 3

o r the ra o o fthe
ti sp ecic h eat at co nstant pressure to that
at c o nstant v o l u m e i s equ al to the rati o o f the e lastici ty

wh en no h eat escap es to the el asticity at c o nstant t e mp era

t u re. Thi s rel ati o n is qui t e ind ep end ent o fthe p rinc ipl es of
th ermo dynamics b ei ng a direct co nsequ ence ofthe deni

t l o ns .

The ti , to E9, i s
ra o o f KD to RV , o r of E4 comm only deno ted
by the ymb o l y th u s K p
s K
7 and E4, y Eg ,

L et us next d et erm ine the difference b etween th e two

e l asticiti es
A 1A . m An . A k
A mA n
V .

The m erator o f the fractio n is evid ently by th e

nu , geo

metry o f the gure equal to the parall elogram A B

, c D.
M ul tiplyingby x we nd v,

K (E v
A m A N An .

si nc e A n A N A B c D as we h ave shown

Sinc e K E K p E9 we al so nd

x ) T V v
A !

Th ese l ti re a o ns are indep endent o f the pri nciples of

thermo dynam ics .
L atent H eat . 1 73

I fwe pply the thermodynami cal equatio n A M A m

no w a .

,1 each o f these qu antities becomes eq ual to

r v (A

N ow A M is the increment of p ressure at constant volume

p e r degree o f tempe rature a ve ry important quantity
Th e .

o mm

ay be wri tte n

results theref

r -
Ea A w Ma



A VERY impo rtant class cases is that in whi ch the sub


su nee is in two different s tate s at the same temperature and

pressure, as when part o fit is soli d and part liquid, o r part
s olid or liquid and part gaseous

I n such cases the vol ume occupied by the su bs nc e m u s t

be considered as consisti ng o ftwo parts, a, being th at of the
subs nc e in the rst s tate an d n, that o f the subs nc e in
, m
the seco nd state The quanti ty of he at necessary t o co nvert

u nit o f m ass o f the s ubs tance f rom the rst stat e to the

second wi thout altering i ts temperature is called the Latent

H eat o f the substance and is deno t ed by L
, .

D uring this process the volu me changes fro m v, t o a, at

the constant pressure p .

Let P s be an isothermal
li ne which in this case is hori

zo ntal and let it co rresp o nd to


the pressure P and the tempe P

ratu re S .

Let Q T be another 180
thermal line co rresp o nding to
the premure Q and the tempo
r ature T .
1 74 . L atent H eat .

L et B A and c D b e adi ab atic li nes cutting the iso th ermals

1n A B c n

Th en the sub stance, i n ex an ding at the t emp eratu re 5

from the v ol u m e P B to the vo lu m e P C, will abs o rb a
B c
quanti ty of h eat equ al to L wh ere L is th e latent

h eat at te p erature 8 .

Wh en the sub stance i s co mpressed from Q D to Q A at

t emp erature T i t will giv e ou t a quantity ofheat equ al to
7 2

wh ere quanti t ies refer to the temp erature T

the acc ent ed .

The quantity of work d o ne by an engi ne wh en th e indi

cating poi nt d escrib es the gure A B c D o n the diagram is
repres ented by the area o f thi s gu re and ifthe t e mp eratures ,

5 and T are so near e ach o th er that we m ay n egl ect the

curvature o fthe lines A B and c D this area is ,

I fthe difference o f p ressures P Q is very sm all B c ,

nearly so t h at we m
ay write the area thu s

B c (P Q) .

B u t we m ay calcu l ate the wo rk in ano th er way It is .

equ al to the h eat ab sorb ed at the high er tem perature

mu l tipli ed by the rati o o fthe difference o f the temp eratures

to the high er t emp erature Thi s is


Equati ng the two valu es of th e work, we nd the latent

h eat
L == )
2! r S
S _

wh ere it is to be re m emb ered that i n calculating the ne

5 g the difference o f the pressures P and Q and the

erenc c t emp eratures 3 and 1: are t o o e sw


( Ii ofthe oonsee .
v r mall
s . I n fact, this fractio n is that w hich in the lan
gu age of the differe ntial calcul us would be denoted by
The student m ay ded u ce the equation at o nce f rom the

d m
thi r ther od nam
y ic relatio n at p 1 68 . .

The os t impo rt ant case of a su b stance in two differe nt
states is th at in which the subs tance is p artly water and
partly steam at the same temperature .

The pressure of steam in a vessel contai ning wat er at the

same temperature is called the p res sure of saturated steam
o r aq u eous vapour at that temperatu re ~

The value of this pressure has bee n determined fora great

number o f t emperatures as measu red on the o rdi nary scales .

The mos t complete de terminatio ns o f this kind are those o f

Regnault . Regnau lt has also determined L the l atent heat ,

o funi t ofmass o f steam f o r m any di erent tempe ratures


, .

Hence if we also k new the val ue o f a,

, 24 o r the ,

differe nce of v olume between u nit ofm ass of wate r and the
same when conve rted int o steam we should h ave all the

da for dete rmining s the absol u t e t emperature o n the


U nfortu nately there is

co nsiderable dif culty in asoer
taining the volume o f steam at the poi nt o f saturation If .

we place a known weigh t o f wat e r i n a vessel the capacity ,

o f which we can adj us t and determine ei the r the cap aci ty


c orre sponding to a given t emperature at which the whole i s

j ust co nverted into s t eam o r t he t
, empe ratu re c o rresp ondi ng
to a gi ven capaci ty we may obtain data fo r determi ning

the density o f saturated s t eam bu t it is exceedingly dif cu lt


completion of the evaporation or the

and at the same time to

is to be hoped that these

then o ur knowledge ofthe

temperature wi th the thermodynamic

extendi ng from 3o F to 43 2 F

. .

au sius and R anki ne nave u s e QR

a . .
the fo rmula in o rder to calculate the densi ty o f saturated
steam assuming th at the absol u te t emperature is equal to the

temperature recko ned from 46o o fFahre nhei t s scale -


The same principle e nables us t o es tab lish relatic ns

between the physical p roperties o f a subs nc e at the point m
at w hich it changes f rom the solid to the liqu id state .

The tempe rature o fmelting ice was al ways supp o sed to be

absol ut ely co ns tant ti ll i t was poi nted o u t by P rofesso r James
Thomso n th at i t follows from Carno t s p ri nc iple that the

mel ting point m us t be lowe red when the pressure i ncreases ;

for if v , is the vol ume o f a pou nd o f ice and a, that o f a ,

po und of wate r bo th being at 3 2 R , we know t hat the


vo lume o fthe ice is greater than that o f the water H ence .

if s be the melti ng point at p ressure P, and r the melting

point at pressure Q we h ave as at p 1 74
, ,

S T 8

I f we m ake the pre ss ure o f o ne atmowhere and ,

s 3 3

F the n t he melti ng temperature at pressure Q is

F ( v, ) ( Q /i )

1 :
3 2 . r
) ,

N ow the volume pound o f ice at 3 2 F is o o r7 4

of a


c ubic feet and th at o f a pound o f wat er at th e same

temperature is 0 0 1 6 c ubic feet 03 s the absol ute te pe .


rature co rrespo ndi ng to

, 3 2 F is L

the late n
. t ,
hea t ,

required to co nvert a po und o f ice into a pou nd o f water ,

1 42 therm al u nits 1 42 x 7 2 f
7 o o t pou n ds H e n ce T ,

the te mpe rature o f melting co rrespo nding to a pressu re o f


Q pou nds weigh t per square foot is ,

T 3 2 o ooooo 6 3

x ( Q
) .

I f the pressu re he th at o fn atm osp heres each atmosph ere ,

bei ng pounds weigh t per square foot ,

T= =3 2 3 ( )
o o r3 n r .

g a
r m ma r
} ,
y Edi nbu m i, vol. xvi. p .
5 75
F exi ng P oi nt altere d by P remrre . l 77

H ence the melting point o f ice is lowered by abou t the

se ve nty fth part o f a degree of Fahre nhei t fo r eve ry

addi tio nal atmo sphe re o f pressure Thi s res ult of theory .

was ve ried by the di rec t experiments o f Professor W .

Thomso n)
Professor] Thomson has also pointed o u t the impo rtance

o f the unique co nditio n as to temper ature and p ressure under

which wat e r or any o ther substance can permanently exis t
in the solid liquid and gaseou s fo rms in the same vessel
, , .

This c an only be at the freezing temperatu re corresponding

t o the pressure o f vapo ur at this freezi ng point He calls .

this the triple point because three therm al lines meet in it


the s e m li e which divides the liqui d rom the gaseo us

( )
x t a n ,

s tate ; ( a) the ice line which divides the liquid fromthe s olid

s tat e ( 3 ) the boar fros t line which divide s the so lid from the

gaseous s tat e .

Wheneve r the vol ume o f the substance is like that o f ,

wate r less in the liquid than in the so lid state the e f

fect o f ,

p ress ure o n a vessel co ntaining the s ubstance partly in a

liquid and partly in a solid stat e is t o cause some o f the
solid portion to melt and to lowe r the temperature o f the

whole t o the mel ting point correspo nding to the pressure .

I f o n the co ntrary the volume o f the subs tance is greater in

, ,

the liq uid than in the solid s tate the effect o f press ure is to,

solidif y some ofthe liquid part and to raise the temperature ,

to the mel ting point correspo nding to the pressure To .

determi ne at o nce whe the r the volume o f the substance is

great er in the liquid o r the solid stat e we have o nly to ,

observe whe ther solid po rtio ns ofthe su bstance sink or swim

in the melted s ubs tance If like ice in wate r they swim
, , ,

the volume is gre ate r in the solid state and pressure causes ,

melting and lowers the melti ng poi nt I f like sulphur wax .

, , ,

and mos t ki nds o f st o ne the solid substance si nks in the


liq uid then pressure causes solidicatio n and raises the


melting point

y ou Royal S mdy '

o Edi nburgh , a ss .

1 78 Application f
o T/iermody na mmt

o G m
When two pieces o f ice at the meltin g p o in t are pn
toge ther the p ressure causes melting to tak e p lace a

portio ns of the surface in co ntac t The wat er so fo


escapes o ut o f the way and the temperatu re is low

Hence as soon as the p ressu re diminish e s th e two pan
froze n together wi th ice at a temperature b elo w
phenomenon is called Regelatio n .

It is well known that the temperature of th e eart h in cr

sa we descend so that at th e bo ttomof a dee p b o rin
, g
co nsiderably hotter than at the surface We sh all see
unless we suppo se the p rese nt state of things t o be c

great antiquity this increas e of t emperature m u s t go c


m u ch greater depths than any ofour borings I t is a s .

this supposi tion to c alculate at what depth th e temper:

would be equal to th at at which mo st kinds o f s to n e mt
our f urnace s and i t has bee n some times asse rted that at

dep th we should nd everything in a state o f Fus io n .

we must recollect that at such dep ths there is an arro w

pressure and therefore rocks which in o ur fu rnac es w

be melted at a certain temperature may remain s o li d 8

m uch greater temperatures i n the heart of the earth .



THE physical properties o f bodies in the gaseous state

mo re simple th an when they are in any other s te m .

then mo re or less accurately represented by the law

Boyle and Charles which we shall speak of for bre vig
, ,
Te mady nam

zcs o f Gases . 1 79

the m o s laws
e u . We may express them in the following
L et denote the vol ume o f u nit o f m ass 1) the pressure,
1: ,

1 t he temperature measured by an air thermometer and

recko ned from the absolu te zero o f that instrume nt, then

the quantity
aremains constant for the same gas

We here use the symbol 1! to denote the absol ut e tempe ra

ture as meas ured by the air th ermometer rese rvi ng the ,

symbol 8 t o de note the t emperature accordi ng to the

absolute thermodynamic scal e .

We h ave no righ t to assume without p roo f that these two

quantities are the same, al though we sh all be able t o show
by experiment that the one is nearly equal to the other .

I t is prob able that when the vol ume and the t emperature
are suf cie ntly great all gases full with great accuracy the
gaseous laws but whe n by comp ression and co oling, the

gas is b rough t n ear to i t

s po int o f condensatio n i nto the
liquid form, the quantity be com es less than it is for

the perfectly gaseo us stat e and the su bstance though s till

, ,

apparently gaseous no longe r f

, u lls with accuracy the
gaseou s l aws (Se
. e pp 1 16 .

The specic heat o f a gas can be determined only by a

course o fexperiments i nvolvi ng considerable difcu l ty and
requiring great delicacy i n the measurements The gas .

must be enclosed in a vessel and the de nsity o f the ,

ga s itsel f is so sm a ll th at its c apacity f

o r heat f
o rms b ut
a small part o f the total capaci t y o f the apparatus Any .

erro r therefore in the determination of the capacity either

, ,

o f the vessel i tself o r o f the vessel wi th the gas in it will

produce a m u ch l arger error i n the c alculated specic heat o f

the gas .

Hence th e determinatio ns of the speci c h eat of gases

were generally very inaccurate till M Regnault brought ,
But i fthe vessel in whic h the gas is containedis incapable
ofreceiving heat o
the gas or of co mmunic ating he at to

rise and the tn

essure will be great er than i t was in the
mer case
for . The elastici ty, therefore, will be grw er in the
case of no thermal co m municati ou than in the case of

To determine the elasticity under these circumstances in

this way would be impossible because we c annot obtain a

vessel which will not allow heat to m pe from the gas

there will be very li ttle me

ti for the heat to escape, but
then there will be very little time to measu re the pressure
in the ordinary way It is possible however afte r co m
, ,

pressing air into a large vessel at a known temperature to ,

open an aperture of co nsiderable size for a time which is

sui c ient to allo w the air to ru sh out till the pressure is th e
m e within and without the vessel but not sufcient to ,

allow much heat to be ab orbed by th

s e air o
mthe sides of
Cooli ng of Ai r by M ansi on . 181

the vessel Whe n the aperture is closed the ai r is somewh at


cooler than before and though i t receives heat fro m the


side s o f the vessel so fast th at its temperature in the cooled

state cannot be accu r ately observed with a thermometer the ,

amo unt o f cooling m ay be cal cul ated by observing the

p ressure ofthe air withi n the vessel after its temperature has
become equal to that o f the atmosphere Si nce at the

moment ofclosing the apert ure the airwith in was cooler than
the air without while its p ressure was the same it follows
, ,

that when the tem perature wi thin has risen so as to be

equal t o that o fthe atm osphere its pres sure will be great er .

Let p , be the ori ginal p ressure o f the air comp ressed in a

vessel whose volume is v let its t emperature be T equ al t o ,

that ofthe atmosphere .

Part o f the air is then allowed to escape, till the pressure

within the vessel is P equal to that o f the atmosphere ; let

the temperature o f the air remaini ng within the vessel be t .

No w let the ape rture be cl osed, and let the temperature of

the airwi thin become agai n r equal to that ofthe atmosphere
, ,

and let its p ressure be thenp g .

To determine 1 the absolute temperature o f the air when


cooled we h ave since the volume o f the enclosed air

, ,

is co nstant the p roportio n



This gives the cooling e ffect o f expansion from the
pressure p , to the pressure P To det erm
. ine the corre
f vol ume we m u st calc ulate the vol ume
ed by the air which remains in the vessel .

d o f the experiment it occupies a volume v at a ,

and a tem pe rature 7 At the beginning o f the


i ts pres sure was p , and i ts tempe rature T :

vol ume which i t the n occupied was v 8 3

a sudden i ncrease o f vol ume in the ratio of } , t o p , c orre
spo nd a to a diminu tio n o f pressure f rom p , to P Si nc e p, .

is greater th aa the rati o o f the pressures is greater t han


the ratio of the vol umes .

The elasticity o fthe air under the conditio n o f no therm al

co m mu nicatio n is the val ue o f the quantity

P p
V 7! | ] P

a v a -

whe n the expansio n is very small or when , v ery little

greater than P .

But we know that the elasticity at constant temperature

is numerically equal to the pressure (see p H ence we.

nd fo r the value o fy, the ratio o fthe two elasti cities ,

Pl P

Pl Pt
or, m ore exactly ,

108 492
Alth ough this method of determ i ning the elasticity i n the
case o fno therm al communicati on is a practicable o ne it is ,

by no means the m ost pe rfect method It is dif cult for .


instance to arrange the experiment so th at the pressure


may be comple tely equalised at the time the apertu re is

closed while at the same time no se nsible po rtio n o f h eat

has bee n commu nicat ed to the air f rom the side s o f the

vessel It is also necessary to e nsure th at no air has en


tered from wi tho u t and th at the moti o n withi n the vessel has

su bsided be f ore the ape rture is closed .

Bu t the veloci ty ofso und in air depends as we shall after ,

wards show ou the relatio n be tween the variatio ns o f i t s


densi ty and its pressu re during the rapid conde nsatio ns and
rarefact i ons which occu rduring the p ropagatio n o fso und As .
R atio E

f i

o las t a ttes . 1 83

t ime to travel by conduction t o parts cooled by expansion ,

even ifair were as go od a co nd uctor o f heat as c opper is .

Bu t we know that air is really a ve ry bad cond uctor o f heat ,

so that in the propagation o fsou nd we m ay be qui te certain

th at the changes o f volume take pl ace without any appreci
able commu ni c ation of heat and the ref ,
ore the elasticity as ,

deduced from measureme nts of the veloci ty of so und is ,

that corresponding to the co ndition o fno thermal communi

c atio n

The rati o o fthe elas ticitie s ofair as ded u ced f

rom exp eri
me nts on the velocity o fsound is ,

This is also as we have shown the ratio of t he specic

, ,

heat at constant press ure to the specic he at at co nstant

volume .

These relations we re point ed o ut by Lapl ace long befo re ,

the recent development o fthermodynamics .

We now proceed following Rankine to apply the thermo

, ,

dynami cal equation o fp r73 .

xv) T V (A M ?
In the cas e o f a uid fullling the gaseous laws and ,

also such that the absol ute zero o f its thermometric scale
coincides with the absolute zero o fthe thermodynam ic scale ,

we have

o s t t quantity
a c n an .

N ow at the freezing tempe rature which is ,

on Fahre nh ei t s sc a
l e from absolu te zero 1) 0

1 84 App lication of TM mdy namicr t
e o G ases .

foo t-pounds by Regnau lt s expe riments o n air so that n


is 5 3 z r foot pou nds per degree of Fahrenheit


Thi s is the work do ne by o ne pou nd o f air in ex pandi ng

u nde r co nstant p ressure while the tempe r ature is raised o ne
degree Fahrenheit .

N ow it is the mechanical equivalent of the h eat requi red


to rai se o ne pound of air one degree Fahre nheit wi thout

any ch ange o f volume and x, is the mechanical eq u ivalent

o fthe heat required to produ ce the s ame ch ange o ft em pera

ture when the gas exp ands under constant p ressure so that ,

a, K rep rese nts the additio nal heat requ ired f

, o r the ex

pe nsio n The equation therefore shows that this addi tional

, ,

heat is mechanically eq uivale nt to the work do ne by the

air duri ng its expansio n This i t must be remembered,

is not a selfe vident truth be cause the air is in a different


co nditio n at the end o f the operation fro m that in which

it was at the beginning It is a co nsequ ence o f the fact,

di scovered experimentally by Jo ule ( p that no ch ange .

o f t emperature occurs when air expands without doing

ext ernal work .

We h ave now obtained in dynamical me asure, the dier


ence betwee n the two specic heats ofair .

We also know the ratio o f rt , to it to be P 408 H ence , .

x' r3 o

4 f
po u nds per degree Fahrenh eit,
it , x,
zr p o unds p er degree Fah foot -

N ow the specic heat ofwater at its m aximum de nsi ty is

Joule s equivalent of heat : fo r o ne p ound it is 7 7 2 foot

po unds per degree Fahrenhei t .

Hence ifc, is the specic heat ofair at constant prc cstm e

erred to that o fwate r as u nity
re f ,


was publish ed by Rankine in 1 85 0 .

E nergy . 1 35

The value of the specic heat determined directly

o f air,

e mexperiment by M Regnault . and published in 1 8 5 3 is ,




THE e nergy of a body is its capacity fo r doing w ork, and

i s meas ured by the amou nt o f work which it can be made
t o do The I ntri nsic e nergy o fa body is the work which it

c an do in virtue o f its actual co ndi tio n, wi tho u t any sup ply

e e gy from wi tho ut
of n r .

Thus a body m ay do wo rk by expandi ng and ove rcomi ng

pressure o r it may give ou t heat and this he at m
, ,
ay be
converted into work in whole or in part I fwe possessed a .

pe rfec t reversi ble e ngine and a refrige rato r at the absolute


zero oftempe rature we might co nvert the whole of the heat


which escapes from the body into mechanical wo rk As we .

cannot obtai n a refrige rator absolutely cold it is impossible , ,

eve n by means o f pe rfect engines to convert all the heat ,

into mech anical work We know howeve r from Joule s

, ,


expe riments the mech anical val ue o f any quantity o f heat

, ,

so t hat if we know the wo rk do ne by expansio n and the ,

quantity ofheat give n o ut by the body duri ng any alteration

o f i ts co ndi tio n we c an calcu l ate the e nergy which has been

expe nded by the body during the alteratio n .

As we cannot in any case dep rive a body o f all its heat,

and as we canno t in the case of bodies which assu me the

gaseou s form increase the vol ume o f the contai ning vessel

suf ciently to obtai n all the mechanical energy o f the ex

p an s i ve o
f rce ,we c annot dete rm i ne experime ntally the wh ole
e nergy of the body I t is suf cient however, for all

practical purposes t o know how much the energy exceeds

or f alls short of the energy of th e b ody h as W u hM e .
1 86 Energy , E ntropy , and D iss ipati on.

conditio n fo r instance , at a standard temperature and a

In questi ons about the m u tual actio n o fbodies we are


co nc erned with the dierence between the e nergy o f eac h


bo dy in dierent stat es and no t with its ab solu te val u e so


, ,

that the method of comp aring the energy of the body at

any time wi th its energy at the stand ard temperature and

press ure is suf cient for o ur purpose I f the b ody in i ts .

actu al s tate has less e nergy than whe n it i s in the standard

state the expressio n for the rel ative e nergy will be nega

tive This however does no t imply that the ene rgy of

, ,

a b ody can ever be really negative f or thi s is imp ossible

, .

It only shows that in the standard s tat e it has more e nergy

than in the actual state .

Let us compare the energy o f a subs tance in two dierent


s tates Let the two states be indicat ed in the diagram by


the points a and B and let the intermedi ate states through

which it passes be indicated by the li ne, straight or curved,

whi ch is drawn from A to B .

The work of the path o r the wo rk which the body d oes


while passing from the s tat e A t o the stat e B along the path
A B is rep resented as we
Fro 6 . 3 .
, ,

have shown at p ro 3 by .

the area inclu ded between

the path a s the line of ,

eq ual volume ab the line , ,

o f ze ro p ressu re b e and , ,

the line o f equal volume ,

a x and it is to be rec ko ned


positive whe n this area is

descri bed in the direction
of the h ands ofa watch .

The heat o f the path or ,

the heat absorbed by the

body d uring i ts passage
arc s . i ncluded b etween the
A vai lable Energy . 1 87

path the isentro pic B B the c ti tiou s zero i so thermal

A B, , 6
, a ,

and the isentropic n A ( Se e page .

This e is to be reckoned posi tive when it li es o n the

ar a

right hand o f a B In the gure in which i t lies o n the left


hand o fA B it m us t be recko ned negative or in othe rwo rds

, , , ,

it represents heat give n ou t by the body .

The sum o f the work done and o f heat give n o u t by the

body both in dynami cal measure is the whole energy give n
, ,

o u t by the body during i ts pas sage f rom the stat e A to the

state B It is repre sented by the whole area a Aa BB ba and


this area therefore represents the dimi nution o f the energy

, ,

o f the body which is evidently indepe nde nt o f the f

orm of
the path be tween A and B N ow this area is the difference

betwee n the areas A a z ax and 8 432 68 which are bo unded ,

by the line o fzero pressure the c ti tious li ne o fzero tempe,

ratu re and the lines of equal volume and o f eq ual entropy


I fwe suppose the ctiti ous line o fzero t emperature joined

to the line of zero pressu re by a l ine of any form 132 we , ,

may consider the area bounded by these lines and by the

li nes of equal volume and o f equal entropy th rough A as
represe nting th at part o f the e ne rgy of the body i n the
stat e A the variations of which we are dealing with for if ,

the body passes into the state B by doing work and giving ,

out heat the energy give n o u t is represented by the excess


o f the area A a Z a A above B z b n and this there f ore re , , ,

p resents the excess o f the e nergy in the stat e A above that

in the s tate B .

H e nce in discussing t he variati ons o fthe energy we m

ay ,

consider them repre sent ed by the variations o f the area

A a l aA o r what is the same thing we m
, , ay suppo se the ,

ene rgy to be rep resented by this area together wi th an

unknown co nstant .


The sum o fthe work done by the body and the dynamical
equ ivalent of the heat which i t gives o u t during i ts W ,
1 88 E nergy , 5 am , and Di m
fmthe tat A to
ro s e the s mt e we have seen, the
B is, as

s e whatev r be th
e e path by whi ch the bo d
y passes fro m
the state A to the state s If, however, we su ppose that

the body is surrounded by a medium the temperature of


F ac ade .
whi ch is mai ntai ned c o n
stannso that the bo d can
give o ut heat only when its

the m ediu m and of ,

can take in hcat only whe n

its temperature is lower

than that of the medium ,

the n these conditions will

co nne the path within
certain limits .

D raw the isothermal T T

representing the constant temperature o f the surrounding

medium The n since the temperature o f the body at A and


at all po ints above the line T T is higher than th at o f the

medium the body cannot recei ve heat from the mediu m

, .

Hence its entropy cannot increase and the p ath cannot rise ,

abo ve the adiabatic o r ise ntropic A a drawn thro ugh A , .

Again when the body gives out heat to the medium i ts

, ,

temperatu re must be higher th an that o f the mediu m .

Hence the path m us t be above the iso the rmal r r '


The path formed by the isentro pic A r and the isothermal '

o re the limi ti ng fo rm o f the path and is that
1 B is the re f ,

wherei n the wo rk do ne by the body i s a maximum and the ,

heat give n out by it a minimum .

I fwe de no te the e nergy o fthe body in the stat e A by e ,

and i ts entropy by o and the ene rgy and entropy o f t he


body at the temperatu re and p ress ure o f the surroundi ng

medium ( rep resented by B) by e, and oa then the total
e ne rgy give n out as work and heat during the p assage from
re st ate A to the s tat e B is e eo -
Available Energy . 1 89

The am ou nt heat which the body gives out during the


process cannot be less th an th at corresponding to the path

A r B which is


where r is the a bsolute t emperature of the surrou nding

The done by the body during the process

amount of wo rk
cannot therefore be greater than
, ,

3 -
50 -
0 T )
This,there fo re is the part o f the energy which is available

for mechanical purposes unde r the circumstances in which

the body is placed namely whe n surro unded by a medi um
, ,

It appears there fo re that the greaterthe origi nal entropy

, , ,

the smaller is the avail able energy o fthe body 1


I fthe system unde r c onsiderati on c onsists ofa number o f

bodies at different p ressures and temperatures co ntained
within a vessel from which nei the r matter no r heat can
escape then the amount o f ene rgy converted into w ork will

be great est when the system is reduced to thermal and

mechanical equili brium by the following process .

rst Let each of the bodies be b ro ught to the same tem


p era ture by exp ansio n or co mp ressi o n with ou t c ommunica

tio n ofheat .

and The bodies being now at the same tempe rature let

tho se which exe rt the greatest pressure he allowed to expand

In f
ormer edi ti ns of this book th meaning of the t rmEntropy
o e e

as introduced by C lausius was erro neously stated t b e that part o fthe


e rgy whi ch canno t be co nverted into w rk The boo k then pro wed do . o

to use the termas eq u ivalent to the availabl e e nergy thus intro duc ing
gre at confusio n int o the language o f th rm dyn am i m I n th is e
edi ti on
o .

I have endeavou red to use the wo rd Entro py ac cording to i ts original

deni tion by Clausius .
[ 90 E nergy , E ntropy , and D issipati o n .

and t o compress those which e xert less press ure till the ,

press ures o fall the bodies i n the ve ssel are equal the pro cess ,

bei ng co ndu cted s o slowly that the t empe ratures o f all the
bodies remain sensibly equal t o each o ther thro ughou t the
process .

During the fi rst p art o f this p roce ss in which there i s no


comm unication o f heat between the bodies the e ntropy o f ,

each body remai ns co ns tant D u ri ng the second part the


bodies are all at the same temperatu re and therefo re the c o m


muni cation o f heat from one body to ano ther diminishes

the entro py ofthe o ne body as much as i t increases that of
the o ther so th at the su mo f the e ntropy re mains co nstant
, .

Hence the t o tal entropy o f the syst em remains the sarne

from the begi nning to the end o f the process The work .

done against mech anical re sistances during the establishment

o fthe rmal and mech anical equilib r i u m is greater when the
pro cess is co nduct ed in this way than whe n co nduction of
heat is all o wed to tak e place between b odies at sensibly
different temperatures .

Hence the nal state o fthe sys tem is determined by the

followi ng co nditio ns

Let n be the numbe r o fbodies formi ng the system .

Le t m, m be the mas se s o fthese bodies

, ,

v the vol ume o funit o f mas s o f each

, ,

o, a n the e ntropy o fu n i t o f m ass o f each ,

e, c the e ne rgy o fu ni t of mass o feach

, ,

p the
, p ressu re o f ea ch ,

0, On the temperature o feach .

The volume of the whole is

u g
1 ,

and since the system is contained in a vess el of v o lume v,

2( m) V

daring the wh ole pro cess

A vai lable E nergy . 19 !

Th e entropy of the whole is

m? l !

When there is no commu nication o f heat except betwee n

oo dies o f equ al temperature 0 rem ai ns co nstant, When .

the re is comm unication o f heat betwee n b odies ofdiffere nt

temperatu re 0 increase s
, .

I n the nal state o fthe system

6! 02 6 =

There are the refo re a 1 co nditions with respect to

pressure and n r condi tio ns wi th respect to temperature
, ,

t ogether with one condi tion wi th respect to volume and o ne

with respect to entropy o r in all z 7: co ndi tions to be sati s
, , ,

ed by the n bodies and si nce the s tat e o f each bo dy is a

m cti on o f two vari able s the co ndi tions are necessary and

su i c ient t o de t e rmi ne the nal state o feach ofthe n bodies .

The work d one against resistances external t o the system

may be determined by comparing the total energy at the
beginning o fthe process wi th the nal energy ; fo r si nce no ,

heat is allowed to escape any dimi nution o f energy must


arise f ro m work being do ne .

The total energy is

S hut ) B .

I f E be the o riginal and E the nal v alue o f this quantity


the energy available to produce mech anical work is

E E o

If d uri ng any part o f the process by which the sys tem

reaches i t s nal state o fthermal and mechanical equilibri u m
there takes pl ace a commu nicatio n o f a quanti ty H o fheat
t emperature 0, to a body at temperature 0
the total entropy o fthe system arising from
tion is as we have shown ( at p


32 0x
and the nal entropy ins tead , of being equal to the original
entropy d, becomes
+ H

This increase o fthe nal entropy involves a corresp o nding

increase in the nal temperature and the nal energy .

I fthe rise o f the nal temperature is small then since the , ,

volume is constant the increase o f the nal energy is


e w o _ L
and the available e nergy is therefore diminished by this
quantity o n ac count o f the p assage o f the quanti t y H o f
heat from a body at temperatu re 0, to a body at tem
p eratu re 02 .

Processes ofthis kind by which while the total energy

, ,

remains the same the available energy is diminished

, are ,

ins tances ofwhat Sir W Th omso n has ca lled the D issipa


tion of Energy The doctri ne o f the dissipation of energy


is closely co nnected with th at o f the grow th o f entropy but ,

is by no means identi c al wi th it .

The increment o f the total entropy o f a system arising

from the comm unication o f a give n amount o fheat a from , ,

a body at o ne given tw perature 6 1 to another give n tem , ,

parature , is as we have seen,


(a a)
1 r

a quantity completely determi ned by the state of the system

The energy dissi pated o r r nd r

e e ed una vailable as a so urce

o fmechanical work is

into which a new f

a ctor ,
6, ente rs , and this factor d eno te ,
D zlrrzlpatwn of E nergy . 1 93

the nal temperature o fthe system when i t has reached the

state ofthermal and mechanical equilibri um 6 the refore .
, ,

since it depends o n the nal s tat e o f the system can ,

o nly be cal cu lated whe n we k now no t only the relations

be tween the thermodynamic variables for all the bodies but ,

t he vol ume whi ch they occupy in their nal state .

Th e calculat io n o f the amount o f e nergy dissipated d uring

any p rocess is theref o re m uch more di fcult than that o fthe
increase o fthe total entropy .

I fthe system is allowed to reach its nal state o f thermal

and mechanical equ ilibri u m in such a manner that no ex

ternal work is done and no heat is allowed to leave o r enter


the syst em the condition is that the nal e nergy is equal to


the original e nergy .

Combining this with the othe r co ndi tions th at the vol u me is


unchanged and that the nal stat e wi th respec t to pressure


and temperatu re is co m mon to all the bodies we may de t er ,

mi ne the nal v alue of the tempe rature pressure and total

, ,

e ntropy

The t o tal entropy will now have the maximum val ue co n

sistent with the o riginal state o f the system The dissipatio n

o fthe available energy will be complete .


In s tudyi ng therm odynamics we m ay nd considerable

assistance f rom a comp ariso n betwee n the the rmal and the

mech anical phe nome na .

We have to do wi th energy in two fo rms work and heat , .

When energy is being tran sferred from one body t o ano ther
we can always tell whether the rst body is doing mechanical
work on the seco nd or communicating heat to it Work is .

do ne by mo tio n agains t resistance Heat is communicated


from a hotter to a colder body .

But as soon as the energy has entered the seco nd bo dy,

1 94 M echani cal and Tlzermal A nalogiar .

we can no longer dis tinguish by any legitim ate process

whetherit is in the fo rm o fwork o r o fheat I n fact we may .

remove i t f
rom the body under either o ft hese f o rm s .

Ifa uid at a pressure 10 increases in vo l ume from v to rz


it performs wo rk against external resistance the amou nt o f ,

which work is
p a w
body at temperature 6 increases in entropy from q to
I fa


n amount fheat must h ve ente ed it ep sented by
a o a r r re

uv = a -

If both these p rocesses take place , and if the energy

the body is thereby changed f
rom E to E, then
E = H
p( i
r r
) .

H ere then we have two sets of qu anti ties ,

el ting
o ne r a

work , the otherto heat .

Of these quanti ties Work and Heat are si mply two fo rms
o f En rg
e y .

The vol ume is a quantity su ch th at with ou t a change o f

i ts val ue no work can be done The am ou nt o fwork done.

however is measu red not by the change of vol ume alo ne

, , ,

bu t by that change m u ltiplied by anothe r quantity the

In the same A
t opy is a quantity such that
ay the en r

wi tho u t a change in i ts value no heat c an enter o r leave the

body The amount o f this heat however is no t measured
, ,

by the ch ange o f e ntropy but by that change mul tiplied by


an o the q
r uan tity the absolute tw perature .

Again the pressure is a quantity such that is equ ality in


t wo c o m m unica ting vessels dete rmines their mechanic al

M echanical and l r mal Aaalogi s e . 1 95

equ ilibrium while its excess in either determines a ow o f


uid fro m that vessel to the other .

I n like manner the temperature is a quantity su ch th at its

equ ality in two bo dies in contact determines their thermal
equ ilibrium while i ts excess in either determines a ow o f

h eat from that body t o the o ther .

Ifwe regard the ene rgy o f a body as de termined by its

volume and its e ntropy then the p res sure m
ay be dened as

the rate at which the energy diminishe s wi th increase of

volume while the entropy rem ains cons tant
, .

The t emperatu re m ay in like manne r be dened as the

rate at which the ene rgy increases with increase o fe ntropy ,

the volu me remaining cons tant .



Professo r] Willard Gibbs of Yale College, U S , to whom

, . .

we are indeb ted for a care fu l examinatio n of the different

me thods o frep resenting thermodynamic relations by plane
diagrams has introduced an exceedingly val uable method of

studying the prope rties o fa subs tance by means ofa surface


According to this method t he volume e ntropy and

, , ,

energy o fthe body in a given state are represented by the

three rec tangul ar coo rdinates o f a po int in the surface and ,

this point on the surf ace is said t o co rresp ond to the given

stat e ofthe body We sh all suppo se the volume measured


towards the east from the meridian plane correspo nding to

no volume the entropy measured t owards the north f
, rom a

the po si tion o fwhich

e we cannot measure
Tlwrmoay aami c S u rface

1 96 .

The sec ti on o f this su rface by a vertical plane p e rpen

dicular to the meridian repre sents the relati on b et m
vo lume and energy when the entro py is constant, that is,
when no h eat enters o r leaves the body .

I f the p ressure is p o sitive then th e bo dy by exp anding

, , ,

energy wo uld diminis h . The rate at whic h the energy

diminishes as the volume increases is represented by the
tangent ofthe angle whi ch the cu rve o fsection mak es with
the ho rizo n .

The pressure is the re fo re rep resented by the tangent oi

the angle o fslope o fthe curve o fsectio n The p res sure is .

po si tive whe n the curve slopes downwards t owards the west .

When the slope of the curve is t owards the east the c om

A tensi on or negative pressure cannot exist in a gas . It

may , however exist in a liquid such as mercury Thus if
, , .

a baro meter tube is well lled with clean mercu ry and ,

then placed in a vertical posi tio n wi th its close d end ,

uppermost the mercury somet imes does not fall in the


t ube t o the poi nt correspo nding to the atm ospheric pres

su re but remains su spe nded in the tube so as to ll it
, ,

completely .

The p ressure i n this case is negative in that part of the

me rc ury which is ab ove the level o f the o rdinary baro metric
co l umn .

In s olid b o dies as we know tensio ns o f considerab le

, ,

magnitu de m ay exist .

Hence in our therm o dynami c model the p ressure of the

substance is indicat ed by the tange nt of the sl ape o f the
curve o f constant entmpy and is reckoned positive whe n

h en e gy dimi nishes as the volume i ncreas es

t e r .
Represen tation of P ressu re and Te peratu re m . 1 97

energy increases as the e ntropy increases that is to say by , ,

the tangent o fthe slope ofthe curve .

Since the temperature recko ned from absolute zero is an

, ,

essentially positive quantity the curve o f co nstant volume


mus t be such that the e ntropy and energy al ways increase

together .

To ascertain the pressure and t emperature o fthe substance

in a given state , we m ay draw a tangent plane to the c or

respo nding poi nt of the s urf ace The no rm al to thi s plane


through the origi n will cu t a horizontal pl ane at u ni t o f dis

tance above the o rigin at a poi nt whose coordinat es rep rese nt
the p ressure and temperature the pre ssure being rep re sented

by the coo rdinate drawn towards the west and the tempera ,

ture by the coo rdinate drawn t owards the north .

The p ressure and t emperat ure are thus represented by

the direction o f this normal and if at any two points
, ,

o f the surf ace the direc tio ns o f the no rmal s are parallel
, ,

then in the tw o states of the su bstance corresp onding to

these two points the p ressu re and ternp erature mu st be the
same .

I fwe wish t o trace out o n a model o f the su rface a series

o flines of equal p ressu re we have o nly to pl ace i t in the

sunshine and to tu rn i t so th at t he s un s rays are parallel to


the plane ofvolume and ene rgy and make an angle wi th the

line of volume whose tangent is p roportional to the pressure .

Then if we trace o n the surface the boundary of light and


shadow the pressure at all po ints of this line will be the


same .

I n like manner ifwe place the model so th at the s un s


rays are parallel to the plane o f entropy and energy the ,

boundary o fligh t and shadow will be a line such th at the

t empe rature is the same at every point and proportional to ,

the tangent of the angle which the sun s rays make with the

li ne ofe ntropy .

I n this way we m ay trace o u t o n the model tw o se ries o f

li nes : lines of equal p res sure which Pro fessor G ib bs m
, lis
I sopies tics ; and lines o f equal temperature or Isoth ermals ,

Besides these we may trac e the three sys tems o f plane see

tions parallel t o the coordinate planes the isome tri cs o r lines


of equal volume the i sentrOp ic s o r lines o f equal en tropy,


whi ch we forme rly called after Ranki ne adiabati cs and

, , ,

the isenergi cs o r lines o f eq ual e nergy .

The network formed by these ve systems of lin es will

fo rm a complete represen tatio n o f the relations betwe en the
ve quanti ties volume e ntropy energy press ure and tern
, , , , ,

p eratu r,e fo r al l stat es o f the body .

The body itself need no t be homogeneou s either in

chemical nature o r in physi cal state All that is necessary

is that the whole sho uld be at the same p re ssu re and the
same tempe rature .

By m eans of thi s model Pro fessor Gibbs has solve dseveral

impo rtant problem s relating to the thermodynamic relati ons
between two p ortio ns ofa substance i n different physic al

states but at the same p ressure and tempe r

ature .

Let a su bs tance be capable o f existi ng in two d if ferent

stat es say liq uid and gaseo us at the same t empe r
, , at ure and
pressure We wish to determ ine whether the substance will

t end o fi tsel fto pass from o ne ofthese states to the o ther .

Le t the s ubs tance be placed in a cylinder under a pisto n, ,

and surrounded by a medium at the given tempe rature and

pressure the exte nt o f this medium being so great that its

pressure and temperature are no t sensi bly al t e red by the

changes o f volume o f the working substance o r by the ,

h eat which that body gives ou t o r tak es in .

The two physi cal states which are t o be compared are t e

presented by two points o n the surface o f the model ; and
since the pressure and temperature are the same the tangent ,

planes at these points are ei the r coincident o r parallel .

on a scale prop ortional to the amount o fthis medi um 3 and
as we assume th at there is a ve ry great mass o fthi s medium ,

the scale o fthe su rface will be so great that we m ay regard

the portio n of the surface wi th which we have to d o as
sensibly plane ; and since its p ressu re and tempe r ature are
those of the working substance in the give n state this plane

surface is p arallel t o the

tange nt plane at the
given point o f the
face o ft he m odel .

Let A B c be three
poi nts o f the model at
which the tange ntplanes
are parallel the e ne rgy

being recko ned down

Let a a a be the tange nt plane at A, and le t us co nsider it

as par t of the m odel rep resenting the exte rnal m edium this

model being so placed that vol u me entropy and energy

, ,

are recko ned i n the opposite directio ns f rom those in the

model ofthe working sub stance .

Now let us supp o se the subs tance to p ass from the state A
to the state B passing through the series o f states rept e

se nted by the points o n the isothermal l ine joining the points

ofequal tempe rature A and B .

Then since the wo rking substance and the external medi u m

are al ways at the same t emperatu re the entropy lost by the

in volume what is lo st by the other .

p assage o fthe working s ubstance from

te B the state o f the external medi um

by a point in the tange nt plane in the

the poi nt rep rese nting the stat e o f the

same horizo ntal mo tio n which represents a gain of

Therm wan? H
a lE -
al a l

o hu m o r e nt ro py o fthe o ne su bstanc e w an na!
humo t t py in the o ther

vo ltttt lt: o r en ro .

l h mr whe n the state o f the worki n g s u b stan ce is 3 ;


mo tml -
p o i nt B th at o f the ext ern al me di umwit h:
by the
v e rt i ca l li nt t mi

n pt rm u tu d b th p i nt a wh r th
y e o e e e ,

u lm :t:ts the t:u r g e n t p l a n e thro ugh A .

No w the: ( l i t:rgy is re c ko ned d o wnwards fo r t he I DfI ZI

ul l r t:m r and up ward s f

. u o r the exter nal m e di m n Hew .

th u wm g A t h o rizo ntal K B rep rese nts th e g ai n i n m a

, y if
t hv wo rki ng su bst anc e , and K a the lo ss o f e nergy o i i t

X l t l l lzt l m e di um
t .

l lu liuc u a o r the vertical height o f th e r a nge ) ! $ 2 !

' '

bo w to po i nt i t re pres ents the gai n o fe nergy i n th e -

.: .
, hole
s s tv m o n si sti ng o fthe wo rki ng s u bs tan c e an d the
y c

du ri ng tho passage fro mthe state A t o the sme lt


ltu litttu

ltu t t he e n rgy o fthe syste mc an be inc reas ed o nly b y doing


Wo rk on ll .

ltut the y
s ste m c an of its elf pass o m o ne state to

. o to thr r, the wo rk rc q tti rc d to p ro duc e th e c o rrespo nding

I l. -
. mgm sof co ngu ra ti o n must be drawn fro mth e energy d
thc s ys t y must th erefore di mini sh
e m and th
e e ne r
g .

Th u t the re fo re that in the case b efore us the energ

, y .

ittt trrztS s sho ws t hat the p assage f

ro m the sta te a to the

st ut u in p re se nc e o f a m ediu m o f co nstant t e m er ature

o u l pre ssu re c anno t be ef fec ted with o ut the exp endi ture of

wo rk by so me e xte rnal agent .

The wo rki ng su bstanc e th erefo re canno t o f i tself pas , ,

fro mthc state A to the state B if B li es below the plane ,

whi c h to uc h e s the surface at A .

We have su ppo sed the s ubstance to p ass fro mA t o n by a

r c e ss duri n w hi c h it is always at the sam e t em er at re
p o g p u
as the e x t e rnal m e dium I n this case the entro py of the .

systemrem ai ns co nstant .

If however the communication o fh eat b etwe e n th e sub


stances o ccu rs whc n th ey are not at the same tempera re


Condi tion f S tabilzty

o . 201

the entropy o f the sys t em will increase ; and if in the gure

the gain o f entropy o fthe working substance is represented
b y the ho rizo ntal compo nent o fA B the loss o f entropy o f ,

the external medium will be represent ed by a smaller

q uanti ty such as the ho rizontal compo nent o fA a H ence


a will be to the le f

t of a and therefore higher The gain
, .

o fe ntropy o f the system will t here fore be represented by the

ho rizontal part o fa a

N ow si nce temperatu re is esse ntially positive a gain o f ,

e ntropy at a given volume al ways implies a gain o f energy .

Hence the gain o f energy is greater whe n there is a gain o f

e ntropy than when the entropy remains cons tant
There is the refore no method by which the change from
, ,

A to B can be e ffected withou t a gain o f ene rgy and this ,

implies the expenditure o fwork by an external agent .

I f therefo re the tangent plane at A is everywhe re abo ve

, ,

the thermodynamic surface the conditio n of the working


substance represe nted by the p o int A is essentially stable ,

and the substance cannot o f itsel f pass into any other state

while exposed t o the same exte rnal inue nces of pres sure
and temperature .

This will be the case if the surface is co nvexo co nvex -

upwards .

If on the o ther h and the s urf

ace as at the p o int a is
, , ,

either co ncave upwards in all directio ns or co ncave in ,

o ne direction and co nvex in ano ther it will be po ssi ble to ,

draw on the surface a line from the point o f contact lying

entirely abo ve the tangent plane and therefore representing

a series o f states thro ugh which the substance c an p ass o f

this case the point o fcontact represents a state o fthe

substance which if physically p ossible for an instant is
, ,

essentially unstable and cannot be perman ent


There is a third case ho wever in which the surface as

, , ,

at the noint c is co nvexo co nvex so that a line drawn on

2 02

the surf
aee from the p oint o f contac t mn t slie b elo w
tangen t plan
e ; bu t the tangent plane ,
ifproduc ed
cu ts the surf
ace at c , so that the po int A lies
tangent pl ane In thi s c ase

through any continuo us series

any line d rawn on the e c to A begins by dip ;

below the tangent plane But ifa quanti ty howe v er sn


o fthe su bstance in the stat e A is in physi cal co n tact w

pas s aonce from the state 0 to the state A wi tho ut pass

through the intermediate amtes
The e nergy set at libe rty by this W omati o n 1

pro cess will be ofthe nature o fan u ph eion


Ins nc es of such a proc a s occur a liquid no

pre sence o f its vapour is h eated abo ve i n M i li ng p o i nt ,

also whe n a liquid is c ooled bel o w in po int o rw!


In the rs t of these u ses the conne t of the small

in the seco nd, the co t of ice will pro duce explo e

freezi ng ; in the third, a c rystnl o f the salt

p losive c r
y stallin tio n ; and in th e f
o m th, a a

Finally, whe n the W t plane to u cha the m

P ri mi ti v e and S st andb y S u rfaces . 2 03

H ence in additio n to the surface al ready considered which

, ,

we m ay c all the p rimi tive surface and which represents the


properti es o fthe s ubstance when h o moge neous all the points ,

of the line joining the two poi nts o f co ntact o f the same

tangent plane belo ng to a seco ndary su rf ace which repre ,

sents the properties o f the sub stance whe n part is i n o ne

state and part in another .

To trace o u t thi s secondary surface we m ay suppose the

d oubly tangent plane to be made t o roll u pon the surfac e ,

always touchi ng i t at t wo po ints called the node couple -


The two points o fcontact will thus trace o u t two curves

such that a po int in the one co rresponds t o a point in the
o ther These two curves are called in geometry the node

maple curves .

The seco ndary su rface i s generated by a line which move s

so as al ways to joi n correspo nding po ints o f contact I t ts .

a developable surf ace being the e nvelope o f the rolli ng


tangent plane .

To co nstruct it spread a lm o fgrease on a sheet o fglass


and cause the shee t o f gl ass t o roll wi thou t sli pping o n the
model always to uching it in two points at leas t
, .

The grease wi ll be partly trans ferre d from the glass t o the

model at the pom r a o f co ntact and there will be traces o n

the model of the node co u ple c urves and on the glass o f


co rresponding plane curves .

I fwe no w copy o n p aper the curve traced out o n the

glass and cut i t o u t we may be nd the pape r so that the c u t

edges shall coincide wi th the two node co uple curves and -


the paper between these cu rves will form the derived sur
face representing the s tat e o f t he body whe n part is in o ne

physi cal stat e and part i n ano ther .

There is o ne positio n o f the tangent pl ane in which it

t ouches the p rimitive surface in th ree poi nts These points .

represent the solid li q uid and gaseous s tate s o f the su b

, ,

stance wh en the temperatu re and the p ressure are such that

the three s tates can exist t o gether in eq uilibrium .
2 04 Tker mody nami c M odel .

Th e plane these points are th e zmgl

triangle, o fwhic h
represe nts all po ssible mixtures o f these thre e st ate s I .

instance if the re are 8 gramme s in the soli d state L gram

, ,

in the liqui d s tate and v grammes in the stat e o f vap0


this condi tion o f the substance will be rep resen te d by

point in the triangle which is the ce ntre o fgravity o f m ass
5 , L , and v placed at the corre spo nding angular p o i nts .

From this po sitio n o fthe tange nt plane i t m ay ro ll o n t


primitive s urface in three direc tio ns so as in each cas e t o to n

i t at two points We thu s ob tain three shee ts of th e de riv!

surface the rst co nnec ting the solid and liquid stat es ti
, ,

seco nd the liquid and gaseo us states and the third the g:

eo us and soli d states The se three develop able surfam


t ogether with the plane triangle 8 L V co ns ti tu t e what Pr


fesso r Gibbs calls the Surf ace o f D issip at ed Energy .

O fthe three developable su rface s the rst and third the ,

which co nnect the solid s tate wi th the liquid and gaseo v

h ave bee n experim m
en lly i nvestigated only to a sh ort di

tance from the triangle s L v ; but the sheet which co nnec

the liquid andgaseous stat es has bee n thoroughly ex plored
The experiments o fCagniard de la Tour and the ru nner

cal dete rmi nations o fAndrews show that the curves tracz

o ut by the two points o fco ntact o fthe doubly tangent la l

unite in a point which represe nts what Andrews cal ls tl
cri tical state At thi s point the two points o fco ntact of tl

rolling tange nt plane coalesce and if the plane co nt inu es


roll o n the surf ace i t will t o u ch it at o ne point o nly .

If the primitive surface fo rms a conti nu o us sheet be neal

the surface ofdissipated energy i t canno t be at all poin

n x
co ve o c o nve x upwards Ft .

let A D be the line j oi ning tn

correspo ndi ng points of c om a
o fthe doubly tangent plane at ,

let A B c n be the sectio n of t]

p rim itive sur m

by a ve rtic a l p lan e t hro ugh A D the n
, i t

manifest that the curve A B c n must i n so me part o f its

course be concave upwards .

N ow a po int o n the p rimi tive surface at which ei the ro fi ts

p rm c i pal c u rvatu res is concave u pward s rep rese nts a
, sta t e
of the body which is essentially u ns table Part o f the .

primitive surface therefo re if i t i s co ntinuous m ust repre

, , ,

sent states o f the body essentially u nstable I f therefo re

, ,

the primi tive surface is continuous there mus t be a regio n


representi ng states esse ntially u ns table because o ne o r bo th


o fthe principal curvatu res is co ncave u pwards This regio n


is bou nded by what is ca lled in geometry the i nor] : curve .

Beyond this curve the surface is convexo co nvex but the -


tangent plane still cuts the surface at some more or less

distant point till we come t o the curve o f the node co uple -

at which the tange nt plane t o u ches the surf ace at two poi nts .

Beyond this the tangent plane lies e ntirely above the surface ,

and the co rrespo nding state ofthe body is esse ntially s table .

The regi on betwee n the spinode curve and the node

couple curve represents stat es o f the body which though

ble when the whole su bstance is homogeneo us are liable ,

to sudden change if a portio n o f the same su bstance in

another state is p rese nt .

Since every vertical section through two co rrespond ing

points o f co ntact m us t cu t the spi node curve at the points
o finexi o n B and c the ch ord A D of the node couple curve

and the ch ord B C of the spinode curve must coincide at the

cri tical point so that at this point the spinode curve and the

two branches of the node-c ou ple curve coal esce and have a
common tange nt This point is called in geome try the

( a node! poi nt .

Nola For these geo metrical me

na s m ind bted
I a e to Pro fessor
2 06 TItermodj wmm:
z M odel


( Fl a

0 O rigin .

0 v Axis o fvol ume .

0 4 Axi s o fe ntropy .

o e Axis o fene rgy .

P5 Isopiestics or li nes of eq ual pres sure .

Of these ep rese ntsP, r egative pre ssure

a n , o r,in
word s a t ension su ch as
, ,
may exist in so li ds and in

T, reIsothe rmal s o r lines o f equal temp erat ure

, .

The curves T3 and T have branche s in the fo rm of c h

l oo ps .

aG H c . To the right
this line the su bstance is gas<

and ab solu tely st able To the left o f F 0 i t m

. ay co ndl
into the solid s tat e and to the le ft of o n c it m
, ay co nch
i nto the liquid state .

0E L M N Below this line the substance is liq ui d


absolutely stabl e To the righ t o fr K c i t m ay evapo r an .

the left ofL M N it may solidi fy .

QR S E To the left o fthis line the substance is solid


absol utely stable To the righ t of S R Q it m

. ay m e lt ,

above 8 E i t m ay evapo rate .

c is the cri t ical point o f the li quid and gaseous sta t es .

Below thi s point the re is no disco ntinu i ty ofstates .

c is ca lled i n geometry th e tac nodal po int .

The curves F G G H C K L L M N Q R s and a n , , , ,

branches o f wh at is called in geometry the node c m -

The curves x c x and W are b ranches of the sp in

Termoay nami c M odel


The plane tri angl e s L G rep resents that stat e o f unifo:

pressure and t emp erature at whi ch the sub stan c e c an
partly s olid partly liqu id and partly gas eo u s
, ,

The s traight li nes rep resent states o funiformp re ssu re at

temperature in which two dierent states are in e q u ilibriui

s G and E F b etween s olid and gaseo u s .

G L and K H b etw een liqu id an d gaseous .

s L, R M and Q N b etw een so lid and liqu id


The su rf
a e c di ssipated energy consists o f th e plat

triangl e s L G and the three devel o pable surfaces o f Whit

the generating lines are th o se abo ve m enti oned Thi s su

fac e li es ab o ve the prim i tive th erm o dynamic surfac e at

to uches i t al ong the nod e coup le curve
F m: E m mi . 2 09



M q a u ia o E d Work ir doe
du ri ng a Charge qfP ressure .

LET a uid be forced th rough a small hole o r one ormore ,

narrow tubes or a porous plug and let the work do ne by

, ,

the pressure from behind be entirely em ployed in over

coming the resis tance o f t he uid so that when the uid , ,

after passi ng thro ugh the plug has arrived at a ce rtai n poi nt

its vel oci ty is very sm all Let us also su ppose that no heat

e nt ers or leaves the uid and that no sound o r other


vibration the energy of which is comparable wi th that


which would sensibly alter the temperature o f the uid


pe s f
r o m the ap paratus .

We also suppose th t the m otio n is s teady that is t hat
a ,

the same qu anti ty o f the uid ente rs and issues f rom the
apparatus in ever y seco nd .

D uring the passage o funi t of mass through the app aratus

i f P and v are its p ressure and vo lum

e at the
h e 7 . 3 .

secti o n A be f ore reaching the plug andp v , ,

the same at the sectio n B after passing through

i t the work do ne in forcing the uid through

t he section A is p v and the work d one by the


ui d in issuing through the sectio n B is ) a so ,

that the amount o fwo rk communicated to the

uid in passing thro ugh the plug is P v p 21 .

mas s o f
the sec tio n A, and e the e nergy of
issui ng at the sectio n B ,

e B PV p r

I + P V
2 10 F ree Expans io n .

Th at is to say the sum o f the intrinsic energy and


product o f the vol ume and the pressure remain s th e s:

after passi ng through the plug pro vided no heat is l ost

gained from external sourc es

No w the i ntri nsic B is indicated on th e din :
by the area be tween A a
adiabatic li ne A a a vert ,

line and a 6 v the li ne of


pressure and p v is repres!


ed by the rectangl e A 19
Hence the area in cl ude d
a A p o n, the lines A a and '

bei ng p ro d uced till t ey run

represents the qu antity wh

remains the same af ter pass

throu gh the plug H ence .

the gure the area ap g 3

equal to the area c ontait
betwee n B a and the two adiabatic lines a a and B ,B .

We shall next examine th e relati ons be tween the dien


p p e rti es o f the su bstance i n o,rder to de t ermine the ri se

temperature corresp onding t o a passage through the pl

from a pressure P to a p ress ure p and we shall rst supp l

that P is no t m uch greater than p .

Le t A c be an isothe rm al line through A cu tt ing q B in ,

and let us su pp o se that the passage of the substanc e f rt

the state rep resented by A to the state represe nt ed by B

eec t ed by a passage along the iso ther al m hrte A g follo m
uy an increase me
o f volu fro mc to n The s aller l
. m
distance A n, the less will the r u es lts o f this pro cess di l

where a the dilatation o fu nit o f volume

18 at constant pres
per deg ree o f tempe ratu re .

The h eat eq uired to prod uce this rise

r of temperature is
it r,

where i t, de no t es the specic he at of the subs tance at co n

stant press ure.

The whole heat absorbed by the su bstance du ri ng the

passage from A to B is there fore
( P p)-
v 0 a + lg r,

and this is the value o f the area betwee n A B and the two
adiabatic line s A a B B
, .

No w this is eq ual to the area q B or ( P p) v .

Hence we have the equation

Kp r (P y) (
v I O u
where it, denotes the spec ic heat o f unit of m ass at c on
s tant pressu re exp ressed in dynami cal measure ;

r the rise o ft emperature af ter passi ng through the pl ug
P p the small differe nce ofp ressu re o n the two sides o f

the plug
v the volume o f unit o f mass ( whe n P p is so great as

t o cause considerable alt eratio n o f volume this qu antity ,

m ust be treated differently)

0 the tempe rature o n the ab solute dynamica l scale
a the dilatatio n o f unit o f volume at co nstant p ressure

p er deg ree o ftempe ratu re .

There are two cases in which observatio ns o f the rise ( o r

e quantities
212 F rx Exparzszlm .

vary so lit tle that t he effect o f i ts variatio n may

into acco unt as a correction requ ired only in G l e n
great accuracy The dilatati on a is also very small

so that the produ ct 6 ( I though no rto be abso lu t e l

, y r
my be found with su c ient accuracy withou t a v ery
kno wledge o ft he abmiute value o f0 .

If we su p pos e the w e to be du e t o a d e t]
eq ml to n o n one si de of th e l
p g
u and k o n th e o t

( p -

where p is the densi ty and g is ,

t e nu meri cal measu
o rce ofgravi ty Ne w .

Y a

so that equation ( 2 ) become

K. r = r ( H 9 u
) .

an e quati on ow which we can d etermine x, wh e n

r the rise o f temperat ure an dH ,

k the differe nc e
o f the liqu id ,
( 1 i ts c o c ient o f dilatatio n by h

( wi t hin a m o der a t e de g re e o f e xac tn es s) 0 th e ab so l

p er a tu re in r a m s o f t he de g ree s o f th e sa m e t h en
which is used t o det ermine
The qu anti ty x, i s the sp eci c h eat at co nstant 1
that is the quanti ty o f ha t wh ich will raise u nit o f
t he substance one degree o f the therm ometer I .

pressed here in dynamic al m easure o r foo t po undals -

If the spec ic heat is in gr:

be expressed


measure, as in o t pounds, we mus t divide by g the


o f gravi ty I f the spe cic h eat is to b e expressed


o f the specic heat o f a standard s ubstanc e, as, for i

water at i ts maximu m densi ty ,

we mus t divid e b

how by d irect erp et i


o f any s ub stanc e with

exp res sed in this way is

quanti ty expressed in d;
Dy namical E qu i valent of H eat . 2 13

measure , then the dynamical equivale nt of the thermal

unit is


The quantity J is called Joule s M echanical Equivale nt

o f Heat because Joule was the rst t o dete rmine i ts val u e

It m

by an accurate method ay b e dened as the specic


heat in dynamical measure o f water at its maximum

, ,

de nsity.

It is equal to 7 7 2 foo t po unds at Mancheste r per p ound


o fwater .If we al te r the standard o f m ass we at the same ,

time alter the u nit o f work in the same p roportion so that ,

we must still exp ress J by the s ame numbe r He nce we .

may express Joule s result by sayi ng th at the work done by

any quantity o f wat er i n f al ling 7 7 2 feet at M ancheste r is

c apable of raising that wate r o ne degree Fahre nhei t I fwe .

wish to rende r the deni tio n indepe nde nt o f the value of

gravity at a p articular pl ace we have only to calcul ate the

velocity ofa body after falling 7 7 2 feet at Manchest er The .

energy corresp onding to this veloci ty in any mass o f water

is capable when co nverted into heat o frais ing the wate r o ne
degree Fahrenheit .

There are co nsiderable difculties in obtaining the value of

J by this method eve n,wi th mercury { or which a pressure ,

of z 5 feet gives a rise of o ne degree Fahre nheit .

2 To re fut e Temperatu re: to ti re H er mody uamit Scale .

The most important pplicati on of the me thod is to

ascertain the t emperature 0 o n the thermodynamic scale,
, ,

which co rresponds to the reading t registered by any o rdi , ,

nary thermomete r eg a centigrade thermome te r

, . .

The su bstance employed is air o r any o ther gas which ,

satises approximately the gaseous laws exp ressed in the

r ( 4
not ) ,

where no, po, are the volume and press ure at the sero ofthe
2 14 Free E m issi on .

thermometer and no is the voluminal dilatati o n

, p e r dog
at th at t emperatu re .

The vol umi nal dilatation, a , at the tempe ratu re 1 is therei

so th at the expressio n fo r K ; becomes

; ( 0)
x + aof -

This exp ressio n is stri ctly true o nly fo r a very am

variatio n o f the p ressure Whe n as in the experiment s

Joule and Thomso n P is several times

, we must asc erta
the effec t o fthe grad ual dimi nution o fpressure by the proof
described at p s e x which is appli cable in this case b ea u
, ,

the variation of t emperature is found to be small Tl .

result is that instead of we must write log
} ,

the logarithm is Napierian , or 2

3 z6
o log where the log
ari th mis take n from the co mmo n tables . Hence we nd

9 f
(1 2/
0 o pe lo g P logp

an exp ression which gives the temperature 6 on the th em , ,

dynamic scale co rresponding to the readi ng t o fan o rdi nal , ,

th ermometer the degrees o fthe thermodynamic scale bein


equal to those o f the thermometer near the tem p ature c

the experiment .

I n the case o f most o f the gases exami ned by J on]

and Tho mson there was a slight co o ling e f fect o n the gs
a ssing throu gh the plug I n othe r words r was ne ati m
g ,

and the absolute tem rature was theref o re higher the

t empe ratures was greate r th an the true these tem ra tio of

t T e c oo li ng e ec t

p er at ures o n the hermody namic scale h .

was mu ch great er with carbo nic acid than with oxyge n ,

nitroge n or air as was t o be expected bec ause we kn ow

, , ,

fro m the experime nts o f Regnaul t th at the dil atation of

c arb onic acid is greater th an th at o f air o r its co nstitue nts .

It was also found for all these gases that the cooling e ffect
, ,

was less at high temperatures which shows th at as the ,

t emperature rises the dilatati o n o f the gas is more and

mo re ac cu rately propo rtio nal to the absolu te temperature
o fthe the rmodynamic scale .

The o nly gas which exhibited a co ntrary e f fect was

hydrogen i n which there was a slight heating e ffect afte r

p a ssin g the pl ug .

The resul t of the e xperiments of J o ule and Thomso n

was to show that the tempe rature o f melting ice i s
o n the thermodynamic scale the degrees being ,

such that th ere are t oo of them betwee n this tempe rature

and that o f the vapour o f boi ling wat e r at the stand ard

The absol u te zero o f the th ermodynamic scale is there

fore a7 3

7 C e ntigrade o r 46o 66 Fahrenheit


It appears , the refore that in the mo re perfect gase s the

, , ,

t accuracy by Joule who , ,

ic e nergy o f a gas is the same at

whatever be the v olume which it

e co mpres se d air
into a vessel till it co n
atmospheres and exh austed the air f
, rom

These vessels were then connected by

PM . M ar M ay 1 845
. .
2 t6 F m Expansi on .

means o fa pipe closed by a stopcock, and the whole place d

in a vessel o fwater .

After s su c ie nt time the water was tho ro ughly stirre d ,

and its t emperature tak e n by means o f a delicat e therm o o

me t er The stopcock was the n opened by means o fa p re pe r


key and the air allowed t o pass from the full into the e mp ty

vessel till equilib rium was es tablished between the two .

Las tly the water was again stirred and i ts temperature

carefully noted .

From a number o f experiments o f th is kind carefully ,

corrected fo r all sources o f erro r Joule was led to the ,

co nclusion that no change of M ature OW : 201m : ai r

W i mm . I

This esult as has been shown by the more accurate

r ,

experiments afterwards made by Joule and W Tho m s o n is .


o r there is a s light coo li ng e Thi s


no t qu ite co rrect f , ec t .

effect however is ve ry small in the case o fpermanent gase s

, , ,

and di mi nishes when the g as by rise o f temperature o r ,

diminution of pressure approaches nearer to the co ndi ti o n


o fa perf ect gas .

We m ay however asse rt as the res ul t o fthese experi m

. ent s ,

th at the amount of h eat absorbed by a gas expanding at

u niform tempe rature is nearly though no t exactly the thermal , ,

equivalent o f the mechani cal work done by the gas during

the expansion In fact we know that in the case of air the

heat absorbed is a little greater and in hydrogen a very littl e

less than this quantity .

This is a very impo rtant p roperty o fgases I fwe reverse .

the p rocess we nd that the heat developed by co mp ressing


air at co nstant tempe rature is the thermal equivalent of the

wo rk do ne i n compressing i t .

This is by no means a selfevide nt p ro positi on I n fact-


it is no t tru e in the cas e of substances w hich are no t in th e

gaseous state and eve n in the case of the more imperfect

gas es i t deviates from the truth He nce the calculation of .

M easu rement of Hagan by the B arometer . 2 17

the dynamical equivalent o f heat wh ich Maye r founded o n


this proposition at a time when its truth had not bee n


experimentally p ro ved canno t be regarded as legitimate

, .



TH E barometer is an ins trum ent by means o f which the

p ressure of the air at a particu lar place m ay be measu red .

I n the mercurial baromete r which is the most pe rfect fo rm of


the instrument the pressure of the air o n the free surface o f


the mercury in the cistern is equal to that of a column o f

me rcury whose height is the di ffe re nce betwee n the level o f
the mercu ry in the c istern which sustains the pressu re o fthe

air and that of the merc ury in the tube which has no air
, ,

above it . The pressure ofthe air is o ften exp ressed in te rms

o f the height o f this co lum n Th us we speak of a pressure

o f 3 0 inches o fmercury o ro fa p ressure o f760 millimetres o f


me rcury .

To express a p ressure in absolute measu re we mus t

co nside r the force exe rted against unit o f area For this .

purpose we must nd the weight o f a colum n o f mercury o f

the given height standing o n unit o farea as base .

If k is the height o f the c olum n the n s ince its secti on is

, ,

uni ty its v olume is exp ressed by It

, .

To nd the m ass of mercu ry co ntained in this vol ume we

mus t multiply the volume by t he de nsity o fme rcury I ftlus .

de nsity is de no ted by p the m ass o f the colum n is p A The

, .

pressure which we have to nd is the force wi th which this

, ,

mass is drawn d o wnwards by t he earth s attrac ti on If g


de notes the force o f the earth s attracti on on u nit o f mass


then t he force o n the col umn wi ll be g p It The pressure .

2 18 M easu rement of H ag
g ts b
y Me E m ma .

therefore of a co lumn of mercury of height ll is e xpres

sP ,

whe re l: is the height of the colum n p the densi t y of merct


and g the intensity o f gravi ty at the place T h e d ens ity .

mercu ry diminishes as the temperature increas es I t is us .

to redu ce all pressu res measured in this way to th e h eight

a colum n o fmercu ry at the f reezing t emperatu re o f water

If two barome t ers at the same pl ace are kept at di er

t empe ratures the heights o f the b arometers are in the p


po rtion ofthe vol umes o fme rcury at the two t e m pe rature

The inte nsi ty o fgravitatio n vari es at d iffe re nt plac e s be ,

less at the equato r than at the poles and le ss at the to p a,

mountain than at the level o fthe sea .

It is usual to reduce observed barome tric heigh ts to 1

height of a column o fme rcury at the freezing p oint and
the level o f the sea in latitude which would pro duce I
same pressure .

If there were no tides or wi nds and if the sea and the


were perfectly calm in the whole region betwee n two plac

then the actual pressure of the air at the level o f the a
must be the same in these two pl aces ; for th e su rface
the sea is ev erywhe re perpe ndicular to the force of gravi
I f the refore the pressu re o n its surface were dif
, , ferent
two places w ater would ow from the place o fgreate r pn

sure to the place o fless p ressure till equilib ri u m ensue d .

He nce, ifin calm weather the barometer is fo u nd to ate

at a dif ferent height in two dif fere nt pl aces at the level
the sea the reaso n mus t be that gravi ty is mo re intense

the place where the barometer is low .

Let us next consider the method of nding the de;

below the level of the sea by means of a b arometer c arri

If n is the depth of the surface of the water i n the din?

bell below the surfac e of the sea, and if is the press g m
the at o ephere on the surfac e o f the sea, then the p ress1
B aro meter i n a D i vi ng B ell . 2 19

of the air in the diving bell must exceed that o n the surface
o fthe sea by the p re ssu re due t o a colum n o fwater o fdepth

D. I f a is the de nsity o f seaw ater the pressure due to a ,

column o fdepth D is g a D .

Let the height of the baromete r at the surface o f the sea

be observed and let us suppose t hat in the divi ng bell it is

found to be higher by a height ll the n the addi ti onal p res ,

sure indic ated by this rise is g p lt, where p is the de nsity of

merc ury H ence

g v D =s p k

where s specic gravity of

The depth below the s urface o f the sea is the re fore equal
t o the prod u ct o fthe rise o fthe barometer m ul tiplied by the
specic gravity o f mercury I f the water is sal t we must

divide this resul t by the specic gravity of the salt wate r at

the place ofobservation .

The calc ul ation of depths u nder water by this meth o d is

comparatively easy becau se the densi ty of the wate r is not

very dierent at differe nt depths It is o nly at great depths


that the co mp ressio n o f the wate r would sensibly affect the

result .

Ifthe densi ty o fair had bee n as uniform as that of water ,

the measureme nt of heights in the atrnosph ere would have

been as easy For instance if the de nsity o f air had been

equal to a at all pressures, the n neglecting the variatio n of


gravity with height above the eart h we should nd the ,

height 0 of the atmosphere th u s : Let k be the height of

the barome t er and p the de nsity o fm
, errur
y then the pressure ,

indicated by the baro meter is

=rp ~
2 20 M easu rement of Hag/11: by Ike B a ro meter .

6 is the heigh t
If of an at mosph ere of

produces a pressure
p = g 6
a ~ .

= lz e .

This is the height o f the atm o sphere abo v e the ph ct

the fak e supposition th at its density is the same at all hei
as it is at that place This height is general ly referre dt

mo re briey and tec hnically as the height o ft h e W

Let us for a moment co nside r what this h eight (W4
evidently has no thing t o do with the real h ei gh t of
atm osphere ) really represe nts From the equ atio n

P g a 6 :

rememberi ng that a the de nsity o f air is the sam e thing

the reci procal ofv the vo lume ofu nit ofmass we get ,

or is simply the product p exp ressed in gravi tal

measure ins t ead o fabsolute meas ure .

N ow by Boyle s law the p roduct o f the pressure a


the vol ume at a constant temperature is co ns tant and ,

C harles s law this product is p ropo rtio nal to th e absol

tempe ratu re Fo r dry air at the temperature of mel ting ;


and whe n g 3 2 1 ,

Q feet,
or s o mewhat less th an ve s tatute miles .

It is we ll known that Mr G l aisher has ascend ed ii


balloo n to the he ight of seven miles This ballo o n 1 .

sup po rted by the air and though the air at this great h ei

was m ore than three times rarer than at the earth s suf c e

Heiglzt of a M omztazn

. 22 x

a tmo sphere must extend ab ove the heigh t 6 which we h ave


deduced from o ur f alse assump tion t h at the densi ty is

But though the de nsity o fthe atm osphere is by no me ans

u niform through great ranges of height, yet if we co n ne
ourselves to a very small range say the milli onth part o f6

th t is
a ,a bo u t o
o z 6 feet o rless th
,an the t hird o fan i nch the
density will o nly vary one millio nth part of itself from the

top to the bottom ofthis range so th at we m ay suppose the


pressure at the bottom to exceed th at at the top by exactly

Let us no w apply this method to determi ne the height o f

a mountain by the f oll o wing imaginary process t oo laborious ,

to be recommended except for the purp ose o f exp lai ning


the practical meth od

We shall suppose that we begi n at the top ofthe mountain ,

and that besides o ur barome t er we have o ne thermome te r

, ,

t o determ ine the tem peratu re of the mercury, and another to

d etermine the tempe ratu re o fthe air We are also p rovided .

with a hygrometer to det ermine the quanti ty o f aqueo us


v apour in the air so that by the thermometerand hygrom

ete r
we can calculate 6 the height o f the homo geneous atm o

s phere at every station o fo ur path

, .

On the to p ofthe mountai n then we obse rve the height o f

, ,

the baro meter to he p We now descend the mou ntain till


we o bserve the mercury in the barome t er to rise by o ne

millio nth part o f its o wn height The height of the barn.

meter at this rst station is


The distance we h ave descended is o ne milli onth of 0 -


the height ofthe homoge neous atmosphere for the observed

temperature at the rst s tage o f the descent Since it is .

at p rwent impo ssible to measure p ressu res &c to one , .


milli onth of their value it does not matter whether 6 be

2 22 M easu rement of H ab i ts b
y Me B a r m an .

measured at the to p ofthe m ou ntai n o r o ne t h ird o f an

lower down .

N ow le t us desce nd another s tage till th e p re ssu re 3,

increases one milli onth of itsel f so th at if p , is the


P2 Pl :

and the seco nd desce nt is through a he igh t eq ual t:

millionth o f 6 3 the height o f the h omoge ne o u s atmosp

i n the second stage .

Ifwe go o n in this way n ti m ee till we at l as t reach


bottom o f the mountain and if p is the p re ss ure at

, ,

bottom ,

P . PM

and the whole vertical height will be

6 1 + 62
k =

I fwe assu me that the temperature and h u m idi ty are

same at all heights between the to p and the b o tto m l


b, o,
t & c 6 .
6 and the height.o f,th e m
will be

I f we sn ow the number o f s tages we can det

n, ,

the height o f the mountain i n this way Bu t i t is .

nd a without go ing th rough the l aborious p

desce nding by distances o f the third o f an inch fo r l

p p i s the p ressu re at t he bottom andp t hat at the I ,

we have the equation

Taki ng the l ogarithm o f b Oth sides of this eq uation,

log ? n log ( r oo ooo r)
log y ,

a :
log ? log )

Now log r ooooo r

0 oooooo 4342 942 648

Substituting this value in the exp ressi o n fo ra, we get

5 10g
4342 94 !

where the l ogarithms are the co mm on logarithms to base

I: 2 3 02 585 0log

Fo r dry air at the tempe ratu re of melting ice 6

feet hence
It log
; { x 603 60 ( a

gives the he ight in feet fo r a tem perature 0 o n Fahre nheit s'

p urposes the dierenc e ofthe logarithms ofthe


For rough ,

heights o f the barometer mu ltiplied by ro oo o gives the .


dierence o fthe heights in fathoms of six feet .



THE foll owi ng me thod i vestigating the co nditi o ns o f the

of n

propagatio n o fwaves is due to Pro f Ranki ne

It involves .

only elementary p rinciples and operatio ns but leads to ,

results which have been hi therto ob tained o nly by op era

ti ons involving the higher branches o f mathematics .

P5 11 Tra
. m. 3 869 :

On the Ther mdynamic Theory
o of Waves ol
2 24 Waves .

The ki nd waves to which the investiganon appli es are


those i n which the motio n o f the parts o f the substance is

alo ng straight li nes parallel to the directi on in which the
wave is p ropagated and the wave is de ned to be one

which is propagated with co nstant velocity and the type o f ,

which d o es not alter during its propagatio n .

I n o ther w ords if we observe what go es o n in the


substance at a give n pl ace when the wave passes that place,

and if we su ddenly transport ourselves a certain distan ce
fo rward i n the di recti o n o f propagati o n o f the wave then ,

afte r a certain time we shall o bserve exactly the same thi ngs
occu rring in the same order in the new place whe n the wave ,

reaches i t If we travel wi th the velocity of the wave we


shall therefore obse rve no change i n the appearance pre

sented by the w ave as it travels along with us This is the .

characteris tic o fa wave o fperm anent type .

We shall rst co nsider the quantity of the su bstance

which p asses in u nit o ftime through u nit ofarea o fa plane
which we shall supp ose xed and perpe ndicular to the

direction ofmotion .

Let a be the velocity o f the s ubstance which we shall ,

suppose to be unifo rm then in unit of time a portion of the


subst ance whose le ngth is u p asses through any section

o fa pl ane perpe ndicular to the directi o n o fmotion H enc e .

the volume which passes t hrough unit ofarea is represent ed

by 11 .

N ow let Q be the quantity of the substance which passes

through and let 0 be t he volume o f u nit of m ass of the

substance, the n the wh ole vol ume is Q 0 and this by wh at

, ,

we have said is equal t o u, the velocity o f the substan ce


I f the pl ane i nst ead ofbeing xed is m oving forwards wit h

, ,

a vel o ci ty U the quantity which passes through it will


depend not on the absolute velocity u o f the substan ce

, , , ,

b ut o n the relative v el ocity u U and if Q is the quantity

, ,

w hich passes through the plane omrig/it t o lg?


q v = u u
Let A be an im aginary plane m o ving from lg}? to rig/i t
with velocity u and let this be the velocity o f propagation

F m . 3 9.

of the wave then as the plane A travels alo ng the values of

, , ,

u and all o the r quantities bel o nging to the wave at the

plane A rem ai n the same Ifu , is the absolute veloci ty of


the substance at A v, the vol ume o funit of mass, andp , the


eas ure all these quantities will be constant, and


l l
= U -

If a be other plane travelli ng wit h the same velo

an ,

city 0, and if Q2 11 , a, p , be the co rrespo nding values

Q3 (3) o o o o o

The distance between the planes a and 13 rem ains in

v ariable because they travel with the same veloci ty
, Also .

the quanti ty of t he substance intercepted be tween them

remains the same because t he de nsity of the substance at

co rresponding parts of the wave remai ns the same as the

wave travels along Hence the quantity o f m atter which

and B at A must be equ al to

Q z'l
(5 )
know u and Q and the volume of uni t o f
u , and 143 .

fo rces a cti ng on the m atter c on

p , is the pressure at te n e t s
2 26 Wat t s .

that at n the force aris ing from these pr ssu re s t end

i ncrease the momentum from left to right is p , p} .

This 18 the momentum ge nerated in u nit o f time 1

external p ressures o n the portio n o f the substanc e be
A and 3 .

N ow we must recollect th at though co rresp ondi ng ,

o f the substance in t his i nt e rval are al ways mo ving

same way the matter i tsel f betwee n A and B is c onti


changing a qu antity Q enteri ng at A and an e qual q u

, ,

Q le aving a t B .

N ow the portion Q which enters at A has a vel oc i

and theref ore a momentum Q u and that which ism
a has a veloci ty u and the re fore a mome ntu m Q a,
Hence the momentum o f the e ntering ui d exc eed
o fthe issu i ng uid by

Q( l

The o nly way in which this momentum can be p m

is by the acti on ofthe external pressures p , and p , ; I
mu tual actions of the parts o f the s ubstance canno t

momentum o fthe whole H ence we nd .


Pz Q( t 11 9
) ( )
Sub stituting the values o fa, and a, o
m equ
fr a i on t ( n

Q (vz

P1 P ( 7)


He nce
[ 1 + Q Q vg
( )
Now the only restri ction o n the position of the plan
that it must rem ain at a constant distance behind .
whatever he the dis tance betwee n A and B the ,

equation is always true .

Q 0 must continue

Hence the quantity p
during the whole process involved in the passage
wave Calling this qu anti ty 9 we have
Waves of P ermanent T m 2 27

or the pressure is eq ual to a co ns tant pressure P diminish ed , ,

by a quanti ty proportional t o the volume 11 .

This relatio n betwee n p ress ure and volume is no t fu llled

i n the case ofany actual subs tance In all s ubstances it is

true that as the volume diminishes the press ure increases ,

bu t the m crease o f pressure is never str i ctly prop ortio nal to

the diminu tion of vol me As soo n as the diminution o f

pressure we m ,
ay make u se of ou r fo rmer de ni tio n o f elas
ti c ity at p t o 7namely the ratio o f the nu m ber exp ressing

the increment of p ressure to th at express ing the vol uminal

compres sion o r calling the elas ticity n
, , ,

z a
H v Q by equation ( 7) ( ro )

where r) is the v olume o f u ni t o f mass and since a, and v, ,

are very nearly equal we m ay tak e eithe r f

or the value of a .

Again if rz is the vo lum

, e o funi t o fm ass in those parts of the
su bstance which are no t dis tu rbed by the w ave and f or ,

which therefore a
, o, ,

U = Qv

H enc e we nd


v =nv ( 1 27

which shows that the square of the velocity of propagation

o f a wave o f lo ngitu di nal displac ement in any substance is

equal to the produ ct o fthe elastici ty and the volume o funit

of mass .

I n c alculating the el astici ty we m ust take int o acc o unt the

conditions under which the compressio n of the substance
ac tually takes place If as i n t he cas e o f sound waves it is

very sudden so that any heat which is developed cannot be


condu cted away then we m ust calculate the elasticity on the


I n the case ofai r or any o thergas the elastic ity at constanx

2 28 Waves .

temp erature is nu merically equal to th e p re ssure If we

d eno t e as u sual the rati o of the sp ec i c h eat at c onstant
, ,

pressure to that at co nstant vo lume b y the symbo l 7 the ,

e lastici ty wh en no h eat escap es is

E 7 ?
H ence ifU is the v elocity ofsound ,

7 ? 7/
( 1 4)
We kno w that when the temp eratu re is th e sam e the

prod uct p v rem ains constant H ence the ve l o c i ty o f sound


is the sam e fo r the sam e temp erature whate ver he the ,

pressu re o f the air .

I f 55 i s the height o f the atm osphere su p p o se d hom o

g en eo us th at i s to say th e h eight o f a ,c o lu m n o f the

sam e densi ty as the actual density the weigh t o f which ,

wou l d produc e a pressure equ al to the actual p re ssure then ,

i fthe s ection o f th e column is u ni ty its vo lu m e i s 6 and if ,

mi s its mass 65 m0


Al so the w eight o fthis colu mn is p mg wh ere g is the ,

force o fgravi ty .

H ence
p v = g6

7 6
The v el o city of s ound may b e co mpare d with that of a
b o dy falling a certain distance u nder the actio n o f gravity .

Fo r if v i s the vel ocity o f a b o dy falling thro ugh a height s,

v z 2 g s .

I fwe make v U , then s =y 6 t .

At thetemperature o fm elti ng ic e 6
fee t if the
forc e o fgravity is 3 2 s

At the sam e t emp erature the v el o city of sound i n air is

feet p er second by exp erim ent .

The square o f thi s i s whereas the square of

the velo ci ty du e to h alf the h eigh t of the h o mogeneous
V eloci ty o f So md z . 229

atmosphe re is Hence by means of the known

veloc ity o fs
ound we can dete rmine 7 the ratio o f

to t o be
The height o fthe homoge neous atmosphere is p ropo rtional
to the temperature recko ned f rom absolu t e zero H e nce the .

veloci ty o f sound is propo rtio nal t o t he square root o fthe

absolute tempe rature I n several o f the mo re perfec t gases

the value o f7 seems t o be nearly the same as in air He nce .

in those gases the velocity o fsound is inversely as the square

root o fthei r specic gravity compared wi th air .

This investigation would be pe rfec tly accurate however ,

great the changes o fpressure and densi ty due to t he p assage

of the sou nd wave p rovided the su bstance is such th at in the

actual changes o fp ressure and volume the quanti ty

15 + n
remains co nstant Q bei ng the velocity o f prop agatio n I n
, .

all su bstances, as we have see n we m ay, when the values o f


p an d v are a lways very n ear th eir mean values ass u me a ,

value of Q which shall app roxi m ately satis fy this co ndi tion
but in the case o fvery violent so unds and other disturb ances
of the air the ch anges o fp and a m ay be so great that this

app roxim atio n ce ases t o be near the truth To und ers tand .

what takes place in these cases we mu st remember th at the

changes ofp and z) are not propo rtional to each oth er fo r in ,

almost all subs tances p increases f asterfo ra give n diminutio n

o fo as p incre ases and v diminishes .

Hence Q which represents the mas s o f the substance


traversed by the wave will be gre ater in those p arts o f the


wave where the pressure is great than in those parts where

is small ; that is the co ndensed po rtions o fthe

the rare ed po rtions The result .

2 30 Radiation .

way and f e ly the same reaso n as the waves o f

o r n ar

o n coming int o sh allow wate r becom e stee er in f

p rt
mo re gently slopi ng behind till at last th ey

sho re .

F m3a



WE have already noticed so me o f the phenomena o f

ti on and have shown that they do not prope rly be lo ng

science o f Heat and th at they should rather be tr


alo ng wi th so und and light as a branch o fthe great a


o fRadiation .

The phenomeno n of radiation consists in the trax

sion o f energy from o ne body to another by pro pa,
through the inte rvening medium in such a way the

progress o f the radiation may be traced after it has It ,

rst body and before it reaches the sec o nd travelli ng th ,

the medium wi th a certain velocity and leaving the m4


behind it in the co ndition in which it found it .

We h ave already considered one instance of radiati

the case ofwaves of sound In this c ase the energy

munic ated to the air by a vrh rati ng body is wo w

through the air and m
ay nally set s o me other body a ,
Radiati on . 2 31

fro , and partly in the form of condensatio n and rarefaction .

The energy due to sound in the air is distinct o mheat be


c ause it is propagated in a de ni te directio n so that in a ,

certain time it will have e ntirely left the portio n ofair unde r
co nsideration and will be fo und in another po rtion ofair to

which it has travelled N ow heat never passes out o f a hot


bo dy except to e nter a c older body so that the energy of ,

so und waves o r any other form of energy which is prop e


gated so as to pass wholly out ofone po rtio n ofthe mediu m

and into ano the r cannot be called heat
, .

There are, h owever important thermal effects p roduced


by radi atio n so that we cannot understand the science ofheat


without studying some o fthe phe nome na o fradiation .

When a body is raised t o a very high temperature it

becom es visible in the dark and is said to shine or to emit
, ,

light The vel ocity o f propagatio n o f the light emitted by


the sun and by very hot bodies has bee n approximately mea
s ured and is estimated to be between
, and
miles per second or abo ut , times faster than s ound

The time taken by the light in passing from o ne place to

anothe r wi thin the limited range which we h ave at o ur c o m
mand in a labo ratory is exceedingly short and it is only by ,

means of the most re ned experime ntal me thods that it has

been measured It is certain however th at there is an
, ,

interval of time between the emissio n o f ligh t by o ne body

and i ts receptio n by ano ther and that d uri ng this time the

energy transmi tted fro m the o ne body to the o ther has

existed in some form in the i ntervening mediu m .

The Opinions wi t h regard to the relation between light

and heat h ave s uf fe red several al ternatio ns acco rding as ,

these agents were regarded as su bstances or as accidents .

At one time light was regarded as a substance p roject ed

fro m the l u minou s body which if the lum , inou s body,

were hot might itself beco me ho t like any o ther substance

, .

Heat was th us regarded as an accident o fthe su mi t age

2 32 Radi a ti on .

When the r
p g
o r m of s ienc e had c rende re d the n

mnt of q anti ti of hcnt a acc

e u es s urace as th e measl
of q mnes o f gases ha Q n

pla c ed in th e lis t o f su A fte r w a rd s,

p go ress o f o p ti cs led to the r
e j e c ti o n o f
theo ry o f light, and the establi sh ent o f the m tmd

have exchanged places .

When the caloric theo ry of heat was at le ngth i

ated to
str be false, th e grou nds o f the argn ent wen m
independent of those whi ch had been used in the r
light .

We shall the refo re co nsider the nature o f rad

whether of light o r heat in an independen t m anm

same thi ng as what is called ligh t o nly perc eived ,

thro ugh a diffe rent channel The same radiation


whe n we become aware o f it by the eye we call light ,

we detect it by a thermometer or by the sensati on 0

we call radi ant heat .

I n the rst place radi ant h eat agrees with light i n :


m o ving in straight lines thro ugh any uniform medium .

no t, therefore propagated by dif

fusio n as in t he case ,

conductio n ofheat where the heat always trav els from


to colder parts o f the mediu m i n whatever di re c tio

condition m ay lead it


The medium thro ugh which radiant ha t

heated if pa fec dy diathemanoua any more than a
fectly transpar ent medium thro ugh which light a
p s
W huninous . But if any i mpurity or defec t o f
L ig/zt and H eat . 2 33

In the next place radiant heat is reected from the


oli shed s u rfac e s o f bo dies acco rdi ng to the same l aws as

ligh t
. A co ncave mirror collects the rays of the sun into a
brilliantly l u mi nous focus If these collected rays f
. all o n a

pi ece o fwood they will set it on re I fthe l u mi no us rays


are collect ed by means of a co nvex lens similar heati ng ,

effec ts are p roduced showi ng th at radi ant heat is refracted


whe n i t passes from one transpare nt medium to ano ther .

When light is refracted through a p rism so as to ch ange ,

its directio n thro ugh a considerable angle o f devi atio n it is ,

separat ed into a series o f kinds o f light which are easily

di s tingui shed from each o the r by their various colours .

The radiant heat which is refract ed through the pri sm is also

spread out thro ugh a conside rable angular range which shows ,

that i t al so consists o f radiatio ns of various kinds The .

lu minosi ty o f the different radiatio ns is evidently no t in the

same p ropo rtio n as their heat ing eec ts Fo r the bl u e and

green rays have very little heating po we r comp ared with the
ex treme red which are m uch less lu minous and the heating
, ,

rays are f o und far beyond the end of the red where no ligh t ,

at all is visible .

There are other me thods o f sep arating the dierent kinds


of li gh t which are sometimes mo re co nve nie nt than the use


o f a prism . M any subs t ances are more transpare nt t o

o ne kind o f light than ano ther, and are theref ore called
co l oured media Such medi a abso rb certain rays and

othe rs If the ligh t transmi tt ed by a stratum o fa


medium afte rwards passes thro ugh another stratum

be much less diminished i n
e kind o f ligh t whi ch is most
bee n already removed and ,

stratu m is th at which can pass

chromate o f po tash cuts o ff the whole o f

the mi ddle o f the gree n to the viole t but ,

the ligh t co nsis ti ng of the red, orange

, ,
2 34

yell ow and p art of the gre en is very slightly di mi nish e d in

, ,

i nte nsity by passing thro ugh anoth er stratum o f the sam e

medi um .

I f howe ve r the seco nd stratum be of a dif

, ,
ferent medium ,
which abs orbs most of the rays which the rst transmi ts i t ,

will cut off nearly the whole light thou gh i t may be itself ,

very transparent fo r other rays absorbed by the rst me dium .

Thus a stratum of sulph ate o f copper absorbs nearly all the

rays transmitted by the bich romate o fpo tash except a f ew ,

o fthe gree n rays .

M elloni found that dierent substances abs orb different


ki nds o f radiant heat and that the heat sifted by a screen


o f any su bstance will pass in greater propo rtio n thr o ugh

a screen o f the same su bstance than unsifted h eat while i t ,

may be stopped in greater prop ortion than unsifted heat by

a screen o fa dif fere nt substance .

These rem arks m ay illu strate the ge neral similarity betwe en

ligh t and radiant heat We m u st next conside r the reasons


which i nduce us to regard light as depending on a parti c ular

ki nd of mo tion in the medi um t hrough which it is pro

phe nomena o fthe i nterference of light They are explai ned .

m ore at l arge in treatis es on light bec ause i t is much easi er ,

to observe these pheno mena by the eye than by any kind

o fthermometer We sh all therefore be as briefas po ssi ble
. .

There are various me thods by which a beamo f ligh t fro m

a small lu m inous obj ect m ay be divided into two po rtio ns ,

which after travelling by slightly different paths nally fall

, ,

on a whi t e scree n Where the two portio ns oflight overlap


each other o n the screen a seri es of l ong narro w stri pes may

be seen alternately lighter and dark er than the average


brightness of the scree n near them and when white li ght is ,

us ed these s tripes are bordered wi th co l ours By usingli ght

, .

ofo ne kind o nly such as th at obtained f rom the salted wic lr


i t lam
ofa sp ir p, a gre a ter
num b e r of e o r f
ringes may
I nterference . 2 35

light and the dark bands If we sto p ei ther o f the portions


of light int o which the original be am was divided the whole ,

system of bands disappears showi ng th at they are due

, ,

no t to eithe r of the po rti ons alone b u t to both united

, .

I fwe no w x o u r atte ntio n o n one o fthe d ark band s and ,

the n cut off o ne o f the partial beams o f ligh t we shall ,

o bserve that instead ofappeari ng d arker it becomes actually

brighte r and ifwe again allow the ligh t to fall o n the screen

it becomes dark again He nce it is p o ssib le to p roduce


darkness by the addition o f two po rtions of light I f light .

is a substance there cannot be ano ther s ubstance which


when added to it shall prod u ce d arkness We are there fore .

c o mpelled to admit th at light is no t a substance .

N ow is there any other instance in which the additio n of

two apparently similar things dimi nishes the result ? We
know by experime nts wi th musical i nstruments th at a com
bi nation oftwo sounds m ay p rod u ce less audible eec t th an

either separately and it can be shown that this takes place


when the one is halfa wave le ngt h in advance o fthe other


H ere the mutual anni hilation o f the sounds arises from the
fact th at a motio n o f the air toward s the ear is the exact
opposite o fa motion away from the ear and if the two ih ,

strum ents are so arranged th at the motio ns which they te nd

to p ro duce 111 the air near the ear are i n oppo site drrec
ti ons and of equal m agnitude the res ult will be no motio n

at all . N ow there is nothing absurd in one mo tion being

the exact opposite of another though the supposi tion that

one substance is the exact opposite o fanother substance, as

in so me fo rms o fthe Two Fl u id theory o f Electricity is an


We may show the interference o f waves in a visible

manner by di pping a two p ro nged fork into waterormercury

The waves which dive rge from the tw o ce ntres where the
prongs ent er o r leave the uid are seen to produce a

on e gets ahead o f th e other .

Radi ati on .

N ow it is found by m easuri ng the p o siti o ns o f the brigl


and d ark b and s o n the screen that th e di e re nc e of tl


distances travell ed by the two porti o ns o f l igh t is for ti

bright bands always an exact multipl e o f a c ertai n vc .

s mall distance which we shall call a wave le ngth where: -


fo r the d ark b ands it is interm ediate b e twe e n t wo m ull

p l e s o f th e w av e l engt h-
b ei ng g }
I , & c ti mes, tlr , .

length .

We therefore co nclu d e that wh atev er e xi sts o r takt

pl ace at a certain point in a ray o f ligh t th e n at the sam , ,

i nstant at a p o int at 3, o r p } o f the wave l e ngth in advana

1 -

s o m ething exactly the o pp o si te exists o r tak e s p lace so tlu ,

i n goi ng alo ng a ray we nd an alternati o n o f c o ndi tion

which we may call p o siti ve and negative .

I n the o rdinary statem ent o f th e th eo ry o f u n dulation

th ese condi tio ns are d escribed as motion o f th e mediumir

Opp o si te directions The essential ch aract er o f the theon

w ou l d remai n the sam e if we were to sub sti tu t e fo r o rdinal)

m o ti o n to and fro any oth er successi o n o f o p p ositelj
direct ed c o ndi tio ns Professor Ranki ne has suggested 01)

p o si te ro tat i o ns o f m o l ecu l es ab o u t th ei r ax es and I hart ,

suggested opp o sitely direct ed m agnetizati o ns and electro

m o tive forces but the adoption o feith ero f th ese hypotheses
wo uld in no way al t er the essential charact er o f the undula
tory th eory .

N ow it is fo u nd that if a very narrow th ermo

. e l ectric pill

b e pl ac ed in the p o siti o n of the screen, and m o ved so that

so m eti m es a b r i ght b and and so m etim es a d ark o ne falls on

the pil e the galvanom eter i ndicat es th at the p i l e rec eives

mo re heat wh en in the bright th an when in the d ark band .

and th at wh en o ne po rti o n of the b eam is cut 05 th e heat in

the d ark band is i ncreas ed H ence in the i nterference d

radi ati o ns the h eating ef fect o beys the sam e laws as the
lu mino u s effect .

I nd eed it has b een fou nd th at even wh en th e som

, e!
o f radiation is a hot body which e mi t s no l u m i n o us m !
P olarzisatwn
. 2 37

the phenomena of i nte rfere nce can be trace d showi ng ,

th at two rays of dark heat c an i nterfere no less than two

ray s o flight. H e nce all th at we have said abou t the waves
o flight is applicable to the heat-radiatio n which is theref , ore
a serie s o fwaves .

I t is also known in the case o f l ight that aft er p assi ng

th rough a plate cut from a crys tal o f tou rmali ne parallel to
its axis the transmitted be am ca nnot p ass through a second
si milarly cu t pl at e o f tourm ali ne whose axis is perpendicul ar

to that o fthe rst th ough it can pass th rough it whe n the axis

is in any othe r positio n Such a beam of light which has


differe nt pro perties accordi ng as the seco nd plate is turned

into differe nt positions ro und the beam as an axis is called ,

a polarized beam There are m any o therways of polarizing


a beam o f light bu t the resul t is alway s of the same kind

, .

N ow thi s prope rty of polarized ligh t shows that the mo tio n

which consti tutes ligh t cannot be in the directio n o f the
ray, f or then there co uld be no di f ference betwee n dif
fere nt
sides of the ray The mo tion must be transverse t o the

direction o f the ray so that we m ,

ay now describe a ray of
polarized light as a condi tio n o f distu rbance i n a direction
at right angles to the ray propagat ed through a medium so ,

that the disturbance is in opposite directio ns at every half

wave length measured alo ng the ray Since Principal J D
. . .

F orbes showed that a ray o fdark heat can be pol arized we ,

c an m ake the same assertio n abou t the heat radiatio n .

Let us no w consider the co nsequ ences o f admitti ng th at

what we call radiation whether of heat light o r invisible
, , ,

rays which ac t o n chemi cal p reparatio ns, is o f the nature of

a transverse u ndulatio n in a medium .

A transve rse u ndulatio n is co mpletely de ned when we

1. Its wave leng th or t he distance between two places in

which the distu rbance is in the same phase .

2. Its amplitude as the great est exte nt of the disturb

means o fa p late o fto urmali ne , selec t t h o se vd u

p o larin tio n is the pri nc i pal plsne of the to u r mah

is unnece mary f r o o ur purpo se . We hav e no w g

ay and ofthe
o nly o n the nature o fthe r me di um ,

the mphmde of the dis mb nmmi

a n O m ar
intensi ty ofthe ray .

No w the ray ay be o bserve d in vari ou s n ys

ifit u c ires the senn non o fsighg reoei ve it i n ou

it ae as cha ni a l oo pounda v e u n y obs u v e i u

M u mm y r eoei ve e ray o m
n a t h a d m
no d de serr ne its hu thg eed


M all these ee bei ng eea s d one and

L gt and H eat.
2 39

and light is another seems t o be th at the arrangements

for operating o n radi atio ns of a selec t ed wave le ngth are -

trouble some and whe n mixed radi ations are employed in

, ,

which the luminous and the therm al effects are in differe nt

proportio ns anything which alt ers the proportion o f the

different radiatio ns in the mixtu re al ters also the proportion

o f the resulti ng therm al and lum inous e f fect as indeed it ,

g e ne rally alters the colo ur o f the mixed light .

We have seen that the exi stence o f the se radiations may .

be detected in vari ous ways by photographic prep aratio ns ,

by the eye and by the the rmomete r Th ere can be no

, .

doubt however as t o which o f these metho ds gives the true

, ,

measure of the energy transm itted by the radi ati on This .

i s exactly measu red by the heating ef fect of the ray when

c o mple t ely absorbed by any s ubs tance .

Whe n the wave le ngth is greate rthan 8 1 2 millionths o f a


m illimetre no lumi no us effect is produced on the eye though ,

the eect o n the thermome ter may be very great When


the wave length is 65 0 millio nths of a millimetre the ray is


visible as a red ligh t an d a co nside rable heating effect is


o bserved But when the wave le ngth is so o millionths o fa


mil limetre the ray which is see n as a brilliant green has

, , ,

much less he ating effect than the dark or the red rays, and
it is difcul t to obtain stro ng the rmal e ffects with rays o f
s maller wave le ngths even when concentrated
, .

But o n the other hand the photo graphic effect o f the

, ,

radiati o n o n sal ts of silver which is ve ry feeble i n the red


rays and even in the green rays becomes mo re p o werful

, ,

the smaller the wave length till for rays whose wave length

is 400 which have a feeble viole t luminosity and a still


feebler thermal cheer the photographic e f fec t is very


po werful ; and even far beyond the visible spec trum for wave ,

lengths of less than z oo millio nt hs o f a mill imetre which ,

are quite invisible to our eyes and qu ite undisc overable by

o ur thermomet ers the photograp hic ef , fect is still observe d .

This sho ws that nei ther the l u minous nor the ph otographic
2 40 Radi ation .

e ffect is in any way propo rt io nal to the enmgy o f the rs

tion when dierent kinds o f radiation are c o nc u rred

is probable that when the radiatio n prod u ce s the p h

graphic effect it is not by i ts energy doi ng wo rk o n
chemical compo u nd bu t ratherby a well M ed vib rarib

the molecules dislodging them from the posi ti o n o f all

indifferent equilibrium i nto which they had bee n thro wn
previou s chemical m anipul ations and enabling t h emt o 1

toge ther accordi ng to their mo re permanent a i n ines sc ,

to fo rm stabler compounds I n cases of this kin d the etl


is no more a dynamical measure ofthe cause th an the e!

o f the f all of a tree is a meas u re o f the energy o f t he n
which up rooted it .

It is true that in m any c ases the am ou nt o fth e radial

may be very ac curately estimated by means o f i ts chem

effects even when these chemical effe