Escolar Documentos
Profissional Documentos
Cultura Documentos
564
S.S.
[J. F. I.
has been evident that none of them fulfilled all of the purposes
for which attempts were made to use them. The rapidly
growing importance of physical constants in the study of
hydrocarbons has emphasized the weaknesses in the classical
methods of treating density and refractive index data and
justified a resurvey of the entire subject. At the same time
the increasing volume of experimental data becoming available
for pure hydrocarbons permits checking any equation against
experimental data to an extent that was impossible until
recently.
The present paper is a result of an extensive survey of the
classical methods of relating density and refractivity index
and of an intensive study of experimental data in an attempt
(I) to derive a refractivity equation that would be more
suitable and more convenient than any of the classical
equations for characterizing homologous series of hydrocarbons
by means of density and refractive index data determined at a
fixed reference temperature such as 2o C., (2) to interpret
homologous series relations in terms of the number and
frequency of dispersion electrons, and (3) to derive an equation
that would have theoretical significance and that would
express the effect of temperature on refractive index as accurately as the empirical equation of Eykman. In part I of
this paper item (I) only will be discussed.
Definition of Terms.
Nov., I936.]
REFRACTIVITY INTERCEPT
OF N E W T O N .
565
II. HISTORICAL.
566
S.S.
[J. F. I.
d i r e c t e d a t t e n t i o n to the c h a n g e of r e f r a c t i v e index a n d
d e n s i t y of a n y one c o m p o u n d w i t h c h a n g e in t e m p e r a t u r e s a n d
pressure.
TABLE I.
Newton's Specific Refraction Data Published in I717 .
i
The Propo/nan
of the Sines of
Incidence and
.The refra&ing B % RefraHion of
yellow Li[,ht.
dies.
A Pfeudo-Topaziu~,
being a natural,
l~e,lucid, britt e,
23 to
14125
l~aky Stone, of a
yellow Col:our.
Air.
3zor to 3,oooooo6z5
Glafs of Anti!nony.
~7 to
9[ 568
A Seleniris.
6~ to 4J, z3
61aff vulgar.
Cryltal of the Rock.
16 '445
z5 to
[fland Cry'ftal.
5 to
3 778
qal Gemnm:.
x7 to
1I 388
Mume.
35 to 24 ~z67
3orax.
zz to
151~ I5II
Nzter.
3z to zq, 345
Dantzick Vitri61.
303 to 2,001I z95
Otl of Vitriol.
~o to
7 'o4t
Rain Water.
5z9 to 396 7845
Faum Arab~ck.
31 to
2i ~79
;pirit" of Wine well
xoo
to
73
'87~$
re&ified.
Camphire.
3to
z z5
Oil Olive.
~ I tO
l I I5II
bin feed Oil.
4 to
27 I"I948
~,pirit of Turpentine.
zs.to
x7 :'I6z6
fimbar.
~4 tO
9 :'4zA Diamond.
tOO to ,4r 4'049
,J
t~e re,fratTiv,
Pozver
of the
Body h
of its
denfity.
t
"
'i
3979-
5zo~ ]
4864
5 ~8a
543e~
5450
6536
6477,
~57o
6716
7079
7~5t
6~Z4
784g'
8J74,
IOI~I
Iz55r
z z6o 7
rzSI 9
13zzz
~3654
Nov., I936.]
REFRACTIVITY
INTERCEPT
OF N E W T O N .
567
-t- etc.
T h e A in this
568
S.S.
KURTZ,
JR.,
AND A .
L.
WARD.
[J. F. I.
Brfihl . . . . . . . . . . . . . . . . .
Eisenlohr . . . . . . . . . . . . . .
Hulst . . . . . . . . . . . . . . . . . .
Carbon.
Hydrogen.
Double Bond.
2.5Ol
2.418
2.590
1.o51
I.IOO
I.O25
1.7o7
1.733
--
N o v . , 1936. ]
REFRACTIVITY
INTERCEPT
OF
569
NEWTON.
Assuming molecular refractivity to be an additive property, it follows that if the constitution and density of a
compound be known, the refractive index can be calculated.
Conversely, if the refractive index and constitution be known,
the density can be calculated.
If molecular refractivity is really an additive property it
should certainly be constant for a group of isomeric hydrocarbons. The excellent data that are available la, 16, 17 for the
isomeric heptanes offer an excellent opportunity for demonstrating whether molecular refraction is constant for a
relatively simple case such as a group of saturated, non-cyclic,
low molecular weight isomers. The data are shown in
Table I I I.
TABLE I I I .
Specific Refractions.
Compound.
d~.
4
Deviation of Observed
Refractive Index from
Curves I, II and I I I
in Fig. I.
20
n~-,
Lorent: Gladand
stone
Lorenz
and
Dale.
Newton.
Lorentz
and
Lorenz.
(C~ve
Average . . . . . . . . . . .
Gladstone
and
Dale.
(Curve
Newton.
(Curve
III.)
H.)
0.673;
0.674.'
o.6783
o.683~
0.687(
0.690(
o.693c
o.6951
o.698z
t.3822
1.3822
1.385c
r.3878
t.3887
t.3894
t.39Ii
t.392c
t.3937
o.3457
0.3453
o.3453
0.3449
0.3440
o,343I
o,3429
0.3426
0.3423
o.567.~
o.566~
0.5672
0.567(
3.565~
a.5642
3.5644
a.S63g
3-5637
1.3519
1.35o3
1.3528
x.3539
1.3515
1.3484
1.3491
1.349o
1.3493
+0.0022
j +0.ooi6
+o.oo16
+o.ooli
o.oooo
J--o.oo12
--o.oo14
I--o.oo18
--0.o022
+0.00:3
+0.o008
+o.ooli
+o.oolo
+o.oooi
--o.oo09
--o.ooo9
--o.oo12
--o.ool 4
+0.0003
--o.ooo1
+0.0005
+o.ooo8
+o.ooo2
--o.ooo6
--o.ooo3
--0.0005
--o.ooo 4
0.686(
t.388e
0.3440
3.865(
1.35o7
o.oo15
o.oolo
o.ooo4
(in p r e p a r a t i o n ) .
57
[J.
F. 1.
FIG. I .
L395
-
1.38'.
_
0.67
O.68
Dens/t,v
at
0.69
0.Z0
ZOE
shown in Table III. The curves were drawn from the mean
specific refractions for each of the three equations. The
points are the experimental data 1~ with densities plotted
against refractive indices. If the equations represented the
change in density and refractive index with change in structure, the points would fall on the curves. Curve I corresponds
to the average Lorentz-Lorenz specific refraction of 0.3440.
Curve II corresponds to the average Gladstone-Dale specific
refraction 0.5656. Curve III corresponds to the average
Newton specific refraction of 1.35o7.
571
c = constitution;
var. -- variable.
[ ~an0 Its"
]',
and
Dale
specific
refraction,
Curve
lI,
t,
222,
NO.
I33~--4o
572
S.S.
[J. F. I.
r A.c],,t, also
t,"
Cl '
......
Thus it is
the slope
Nov., i936. ]
573
----I~
~6
k
t~
-...z
c7
oe u
'.x',gpU/
,9/~!491o..,,~t,9,~
574
S.
S,
KURTZ,
JR.,
AND A.
L.
WARD.
[J.
F. I.
Series.
Paraffins.
Saturated monocyclic ......
S a t u r a t e d polycyclic.
Aromatics.
[]
I
M o n o olefines.
N o n c o n j u g a t e d diolefines . . . .
C o n j u g a t e d diolefmes.
2.O
I2
18
2.4
17
46
98
148
1.8
7.7
9.1
I6
32
47
] II0
IOI
2.9
21
i 80
53
13.6
36
63
81
5
49
1.0462
1.0396
1.0285
1.0629
14
I8
33
20
35
52
46
[53
51
lO8
89
57
79
I8
1.O521
1.O602
1.0819
20
43
60
53
i 93
97
55
I-O460
21
I.O6I 7
42
27
1.4
Cyclic u n s a t u r a t e s
O n e double b o n d . . . . . . . . .
I
Two conjugated double
bonds.
I
Nov., I936.]
REFRACTIVITY
INTERCEPT
575
OF N E W T O N .
TABLE V.
Series.
Deviatio~ from
Probable
Average X lO4.
Error X Io'.
No. of R~fracIndiuvity
vidual I Inter- [
J
Hydrocept
Single
Arit!l- [Maxi Maxicarbons./=n-- ~. m e t l c
muff
mum
Mean. ObservaM~an Plus Minus.
tion.
Paraffins . . . . . . . . . . . . . . . . . . . .
Saturated monocyclic ........
Aromatics ..................
I.O46I
I.O400
I.O627
M o n o olefines . . . . . . . . . . . . . . .
N o n c o n j u g a t e d diolefines . . . .
C o n j u g a t e d diolefines . . . . . . . .
1.0521
1.%92
Cyclic u n s a t u r a t e s
One double bond.
T w o c o n j u g a t e d ""clouiJle
bonds ................
1.0877
1.2
/ 3O
26
29
29
1.8
IO
I0
II
29
47
43
29
49
45
1.5
5.1
5.9
12
I9
23
1.8
13
7-5
I7
I2
I 24
II
] 29
I4
16
23
27
1.0461
1.0643
20
33 I
/
27
1.2
C H A N G E I N REFRACTIVITY I N T E R C E I ~ r W I T H C H A N G E I N T E M P E R A T U R E .
576
S.S.
~ J t
and L ~ J
[J. F. I.
of the curves
I-IYDROCARBONS.
577
578
S.S.
[J. F. I.
T h e average refractivity intercept of 8I saturated monocyclics was I.O396 with a mean deviation of 4- o.ooi8. T h e
probable errors of the mean and of an individual value were
0.00020 and o.ooi8 respectively. T h e deviations of three
hydrocarbons were greater than the statistical expectation.
All three were cyclopentane derivatives for which only one
investigator had reported values. Since density values published by reputable investigators for cyclopentane itself vary
in the second decimal place, it m u s t be concluded t h a t the
d a t a for five membered series are in an unsatisfactory state.
If unconfirmed values for three other hydrocarbons are
eliminated as being questionable, although within statistical
expectations, the average for 74 saturated monocyclics is
I.o4oo with a mean deviation of 4- o.ooII. The probable
errors of the mean and of an individual value are o.oooi2 and
o.ooIo respectively.
Saturated Di- and Polycyclics.
Because of the greater difficulty in preparing pure unsaturated hydrocarbons than saturated ones, it was to be
expected t h a t the deviations from the average would be
larger in the case of the unsaturated hydrocarbons. This
proved to be the case although the deviations were less than
might be expected under the circumstances.
Nov., I936.]
579
The average of 79 olefins was 1.o521 with a mean deviation of 4- 0.0020. The probable errors of the average and of
an individual value were o.oools and o.oo16 respectively.
The maximum deviation was 53. This is within statistical
expectations.
Of the 79 hydrocarbons, unsupported values for 4 showed
deviations of greater than 4 and for I2 showed greater than
30. Eliminating these, the following values are arrived at:
No. of
Olefins.
75
67
Average
Refractivity
ntercept.
Mean
Deviation
X ion,
1.o52o
1.o521
18
16
Maximum Deviation
X Io 4,
Probable Error
X xo4.
~-.
-.
Mean.
Individual
Value.
37
29
38
29
1.6
14
1. 5
I2
Because of the known difficulties in preparing pure diolefins, it was expected that this series would show relatively
wide deviations. This proved to be the case. It is particularly unfortunate, therefore, t h a t the number of hydrocarbons
available is so limited t h a t the values for any constant of this
character cannot be established with the accuracy of those
discussed above. Nineteen hydrocarbons were listed. Because of the uncertainties of the positions of the double bonds
in several of them, these may include several duplications.
Of the I9, one was eliminated on statistical grounds. This
left 18 with an average intercept of I.O6O2, a mean deviation
of o.oo43 and probable errors of o.ooo77 and 0.oo32 for the
580
S.S.
[J. F. I.
Nov., 1936.]
REFRACTIVITY INTERCEPT OF N E W T O N .
581
Aromatics.
RSF~C~VITY
~NTERCEPTS OF m G H
MOLECULAR W S m H T
COMPOUNDS.
582
S.S.
KURTZ,
JR., A N D A .
L.
WARD.
[J. F. I.
TABLE VI.
Cyclic Hydrocarbons.
Change X IO4.
Type.
Saturated . . . . . .
One double bond.
Two double
bonds...
Two eonjugate~l
bonds...
[ Refractivity
Intercept.
I.o461
1,o52I
Change X lO4.
For
Refractivity
For
For
For [ Two
Intercept.
For
For
Two
One
Two ' ConjuOne
Two ConjuDouble Double gated
Double Double gated
Bond. Bonds. Double
Bond. Bonds. Doubl(
' Bonds.
Bonds.
I.O4OO
I.o461
6o
1.0592
I.O877
Specific
Refractive
Dispersion
416
I.o643
Specific
Refractive
Dispersion
ng -- nC
d
X 104
I54
186
ng -- nC
d
X Ioi
Saturated . . . . . .
One double bond
Two double
bonds..
Two conjugated
bonds.
I53
187
216
61
I29
34
243
32
63
2oi
354
I4I
295
Compound.
Hydro-rubber
Hydrocyclo rubber
Cyclo r u b b e r .
RefracLittive
era- ] Temp. Density. Index
ture.
n D
ts
Is
Refractivity
Intercept.
I6 C.
20 C.
19
16
I6
16
is
16
20
20
20
20
20
20
Rubber.
Pur ified r u b b e r
Smoked sheet rubber
Synthetic methyl rubber
lS H. S t a u d i n g e r , " D i e H o c h M o l e k u l a r e n O r g a n i s c h e n V e r b i n d u n g e n , "
J u l i u s S p r i n g e r , Berlin, 1932.
ISH. L. Fisher, Chem. Rev., 7, 119 (193o).
20 I n t e r n a t i o n a l C r i t i c a l T a b l e s , M c G r a w - H i l l Co., N e w Y o r k , Vol. I I , 259
(1927).
Nov., 1936.]
REFRACTIVITY INTERCEPT
OF N E W T O N .
583
Average Refractivity Intercepts for Mixed Type Pure Hydrocarbons of High Molecular
Weight According to Mikeska. 2t
Type of Compound.
No. of
Compounds.
Approx. I InterAverage
cept at
Formula.
25 C.
C44 H82
1.o533
12
C29 H 4 3
C28 H56
1.o685
1.o442
C31 H6I
1.o442
584
S.S.
[J. F. I.
Nov., ]936.]
. . . . .
585
ooocoo
I
.......
<
o o o o o o
"a
~d~65d
~-
u~
~3
u~
~mmmm
4~
o o o o o o
66666d
......
66~65
0,
'2
I 6
+
5E66~d
oooooo
I+
65666~
o666d5
o ,-- ~-,.., o o
<
dS~gdd
~ o~~o,~.
N~N
I~
:..n
~'
S. S. Kt~g'rz, J~.,
586
A~D
A. L. WAgn.
'~-
oO
<5
000000
~ 0 ~ 0
OOO~O
~ 0 ~ 0
u~
o
6
d
0
xo
~o
q
o
o
5
e~
o
o
q
o
0 0 0 0 0 0
m
<
0 0 0 0 0 0
~
5
o
5
'0
I 6
0 0 0 0 0 0
Ol
0
,+
~e
0 0 0 0 0 0
uD
~
0
0
0
eO
0
0
c~
c~
~
eOeOO
U~r~
u~ u ~ o 0 t - ~ O x
<
~0
"~
<
0 0 0 0 0 0
0 0 0 0 0
[J.
F. I.
Nov., I936.]
587
20
d 4 '
o.7195
o.76oo
o.7944
o.8176
o.8146
0.834o
0.8455
(C4Hs)~ ...........
(C4Hs)3 ...........
(C4H8)4 ...........
(C,H0 ............
( C , H s ) ............
(C,H~)~) . . . . . . . . . . .
(C~Hs)~ . . . . . . . . . . .
n~O
'
1.4112
1.43o6
1.4482
1.46oi
1.4577
1.4684
1.4739
Refractivity
Intercept.
1.O515
1.o5o6
I.o5Io
I.O513
I.O5O4
1.o514
I.o512
sp~c~ic
FrT.DS OF U S E F ~ N S S S
OF CLASSICAL SQUATIONS.
or ~
t) m
C1
I331--4i
588
S.S.
KURTZ,
JR., AND A .
L.
WARD.
[J. F. I.
Nov., 1936.]
REFRACTIVITY INTERCEPT OF N E W T O N .
589
The refractivity intercepts of the lower alcohols, mercaptans, ethers, sulfides, ketones, organic halides, etc., are in
general less than I.ooo, whereas hydrocarbons, with the
possible exception of some high molecular weight polynuclear
naphthenes, are above I.OIO. Therefore, the refractivity
intercept provides a ready means for distinguishing between
hydrocarbons and compounds containing appreciable proportions of oxygen, sulfur, or halogen.
In the case of hydrocarbon mixtures, the refractivity
intercept may be used to distinguish between saturated cyclic
and aromatic compounds, both of which have relatively high
density and refractive index. As shown by Ward, Kurtz and
Fulweiler 17 a large number of naturally occurring naphthas of
high density have low refractivity intercepts. One may,
therefore, conclude that most natural naphthas which have a
high density contain much more saturated cyclic than
aromatic material.
Two examples of qualitative analysis follow:
Example No. I. A California gasoline 23 yielded a narrow
cut having the following properties:
Boiling point
Density, d l
Refractive index, n ~
Refractivity intercept
= 79.2 C.,
= o.7378,
= 1.4o9 r,
= I.o4o2.
~3j. B. Hill, L. M. Henderson, and S. W. Ferris, Ind. Eng. Chem., i9, 128
(1927).
590
S.S.
[J. F. I.
=
=
=
=
I85 C.,
o.8718 ,
1.5o2o,
I.o66I.
In the analysis of hydrocarbon mixtures physical properties such as density, refractive index, specific refraction,
aniline point, etc. have frequently been used to estimate the
proportion of two constituent types, such as paraffins and
naphthenes, in the binary mixture remaining after the removal
of aromatics and olefines. It is possible by means of the
refractivity intercept to determine graphically the proportion
of three constituent types such as paraffins, naphthenes and
aromatics in naturally occurring naphthas, or aromatics,
noncyclic olefins and cyclic olefines in cracked naphthas. The
method depends upon plotting refractivity intercept against
density for pure compounds, thus obtaining a physical
property triangle suitable for graphical analysis of the
unknown three component mixture. Master graphs of this
type are prepared for each of 7 cuts of fixed boiling range. A
direct plot of refractive index against density gives a physical
property triangle which is too elongated for practical use.
Dispersion plotted against density for such constituents also
yields a physical property triangle of approximately the
proper form, but the refractivity intercept-density triangle is
more convenient and more accurate.
A complete description of a method for analyzing naphtha
which uses (I) fractional distillation, (2) chemical treatment
and (3) physical property triangles will be given by Kurtz
and Headington3~
~4S. S. Kurtz, Jr., and C. E. Headington, Paper to appear soon in Ind. Eng.
Chem. or Ind. Eng. Chem., Anal. Ed.
Nov., I936.]
XI.
REFRACTIVITY INTERCEPT
OF N E W T O N .
591
592
[J. F. I.
SUMMARY.