Specific Heat Ratios for

Hvdrocarbons
W. C. EDMISTER, Standard Oil Company (Indiana), Whiting, Ind.
The second derivative was determined graphically from the

A chart is presented for estimating CJC,

a, correlation, Equation 3 was integrated, and values ' of

(7) ratios for methane, ethylene, ethane,

propylene, propane, isobutylene, isobutane,
2-butene, n-butane, isopentane, n-pentane, benzene, diisopropyl, n-hexane, nheptane, diisobutyl, and n-octane at reduced pressures up to 1.2 and at reduced
temperatures up to 2.5.

AC,/K2 were tabulated ( I ) . From these results the effect

of pressure on the isobaric specific heat can be computed.
The effect of temperature on the specific heat can be calculated by the correlation of atmospheric specific-heat data (1).
Upon the introduction of ar and reduced units, Equation 2
becomes:

HE ratio of isobaric to isometric specific heats, Cp/Cv=

y, is a n essential thermodynamic property in calculations involving the adiabatic compression or expansion

of a gas. It may be determined experimentally or computed
by thermodynamic relations from P-V-T and atmospheric
specific-heat data. There are few y data, either experimental
or calculated, for hydrocarbons, however. Some experimental
y data are available (3) a t atmospheric pressure for hydrocarbons of one to six carbon atoms. Values a t various pressures
have been computed and plotted only for methane (2).

The derivatives of CY? were determined graphically from the

arcorrelation and were tabulated (1).

Calculation and Correlation of C,/C,

The computation of C,/G ratios from these equations and
reduced thermodynamic functions were made for various reduced temperatures and pressures for seventeen hydrocarbons,
and the resulting C,/C, ratios were plotted against P, for
lines for constant T,. One of these plots (for propane) is
shown in Figure 1. Comparison of the plots showed that
they were very similar and that all of them could be made to
coincide by either expanding or condensing their C,/C, scales.
I n other words, Figure 1 for propane will hold equally well
for all the other hydrocarbons if different numerical values
are given the ordinate scale. This is done by the following
equation:

Basic Equations
The two fundamental thermodynamic equations used in
computing C,/C, ratios from P-V-T and atmospheric specific
heat data are:
=

--T

Y =

where 7s

C(Y8

- 1)

value of C,/C, for propane

C = constant for each hydrocarbon (Table 1)
y = Cp/Cvfor the hydrocarbon in question
=

The integration constant for Equation 1 must be found from

experimental isobaric specific heat data. Although data a t
any pressure could be used, data only a t atmospheric pressure
are available. The volume derivatives for the above equations can be determined graphically or analytically from P-VT data by means of graphic or algebraic equations of state.
I n a previous paper ( I ) a generalized reduced correlation of
P-V-T data for hydrocarbons was developed by using the
volume residual quantity, a, which is defined as the difference
in the ideal and the actual gas volumes. The resulting correlation gave the reduced volume residual quantity, a?, as a
function of reduced temperature T , and pressure P,.
When expressed in terms of a, and reduced units and integrated between the limits of P, and P,= 0 a t constant values
of T,, Equation 1 becomes:

where AC,

Kz =

increase in isobaric specific heat from 0 pressure to

any pressure P,
P , ac/Tcra constant for each hydrocarbon

FIQURE
1. PLOTFOR PROPANE
373

(5)

INDUSTRIAL AND ENGINEERING CHEMISTRY

374

FIGURE

2.

GRAPHICAL
METHOD FOR

By means of Figure 1, Table I, and Equation 5 the C,/C,

ratio can be estimated for all seventeen of the hydrocarbons
listed in Table I for the range of temperature and pressure
covered by Figure 1.
Figure 2 combines Figure 1, Table I, and Equation 5 to
present a rapid graphical method for estimating y . I n constructing Figure 2, the pressure and temperature ranges were
extrapolated. The solution of an example is shown by heavy
dashed lines and arrows; we find y = 1.525 for propylene a t
P, = 0.555 and T, = 0.95.
TABLEI. CONSTANTS
FOR SEVENTEEN
HYDROCARBONS
Value of
Constant
Hydrofor
Equation 5
carbon
Methane
3.5
Ethylene
2.1
Ethane
1.58
Propylene
1.17
Propane
1.00
Isobutylene
0.810

Value of
Constant
Hydrofor
carbon
Equation 5
Isobutane
0.778
2-Butene
0.737
n-Butane
0.705
Isopentane
0.590
n-Pentane
0.541
Benzene
0.525

Value of
Constant
Hydrofor
carbon
Equation 5
Diisopropyl
0.442
n-Hexane
0.442
n-Heutane
0.364
Diisobutyl
0.300
n-Octane
0,300

Accuracy of Correlation
Figure 2 gives values of y that check the values computed
from the original P-V-T correlation with a maximum deviation of *4 per cent. Most of the points are checked within 1
per cent by the correlation.

VOL. 32, NO. 3

ESTIYATING y

As a test of the above correlation, values of y from it were

compared with the atmospheric pressure experimental data
from the International Critical Tables (3). The maximum
deviation was 4 per cent. A comparison a t higher pressure
would be more severe and of more interest, but unfortunately
there are no high-pressure experimental y data.
Application of Results
The Cp/Cvratio is primarily of use in calculations of isentropic expansion and compression of gases. The following
equation for the theoretical horsepower required for single
stage adiabatic compression of gas is based upon the assumption of perfect gas behavior:

I n such processes neither pressure nor temperature remains

constant, but each necessarily varies. The conventional use
of Equation 6 is with a constant specific-heat ratio throughout
the process. For want of better data, the atmospheric pressure y or even the y for air is frequently used for hydrocarbons. Such a procedure will cause appreciable errors in
many cases. Figure 2 shows that y varies widely with temperature, pressure, and molecular weight. Although a rigorous solution of Equation 6 would require integration with y
as a variable, sufficient accuracy for engineering purposes is ob-

MARCH, 1940

INDUSTRIAL AND ENGINEERING CHEMISTRY

tained when y is considered constant at an average of the

values at the inlet and outlet conditions.
The use of Equation 6 with y values from Figure 2 is a step
in the right direction but does not correct for the fact that
Equation 6 is based on perfect gas law behavior. However,
the effect of deviation from ideal gas law behavior on Equation 6 is not so important as the effect on y; therefore the
use of Figure 2 should greatly improve the accuracy of such
computations.
I n engineering work the compression and expansion of
mixtures is frequently encountered. y for mixtures may be
determined by computing the molal average of y values of the
individual components, the y for each component being determined for the temperature and total pressure involved.

375

Acknowledgment
The author is indebted to the following Evening Division
graduate students in chemical engineering a t Armour Institute
of Technology for assistance in the thermodynamic computations: E. C. Berger, D. G. Debo, C. H. Deuter, W. E. Findling, C. Giuliani, W. A. Hoyer, E. B. Lund, A. H. Maack,
U. G. Naef, E. L. Niederhofer, N. C. Penfold, A. G. Petkus,
J. C. Reidel, J. D. Schulz, and G. Thodos.

Literature Cited

~2

&$ ~ ~~ :~(lg3). , ~ ~ ~~ ~; ~ , 3

(3) International Critical Tables, Vol. V, p. 80, New York, McGrswHill Book Co., 1929.

Infrared Absorption Spectra

of Drying Oils

D. L. GAMBLE AND C. E. BARNETT

The New Jersey Zinc Company, Palmerton, Penna.

The application of the methods of infrared

absorption spectra in the study of the drying oils is described. The discussion includes the following items : the spectra of
the drying oils and the effect of pigmentation on the spectra, the absorption spectra
of the pure esters of the drying oil fatty
acids, the effect of conjugation on the absorption, changes in the infrared absorption spectra caused by exposure of the esters
to ultraviolet light and oxygen, and the
effect of polymerization on the spectra.

HE economic importance of the physical and chemical

changes which take place during the formation and decomposition of films of the drying oils is such that these
reactions have been the subject of constant investigation for a
number of years. The purpose of this paper is to present
results indicative of the possibilities of the method of infrared
absorption spectra as applied to this general problem.
The peculiar efficacy of the infrared absorption technique
lies in the fact that it is a physical method with no chemical
effect on the paint film; therefore, it permits repeated examination of the specimen in which progressive changes are
taking place. Since many pigments are transparent in the
infrared, the measurements are unaffected by the presence of
pigments, and thus the method offers the possibility of studying the effects of pigments on the changes occurring in the
vehicle during drying and aging. Excellent discussions of
the theory and interpretation of infrared absorption spectra
as applied to organic compounds will be found in the literature
(1, 5 ) .

Apparatus and Procedure

The apparatus described in the previous paper (2) was
modified somewhat for this work:
A Nichrome glower was used as the source of radiation although it is weak at wave lengths beyond 10.0 microns; flters

(7) were used to remove contaminating radiation. Since glass is

opaque in the infrared beyond 6.0 microns, samples are examined
in rock salt cells, as films on rock salt plates, or often without any
backing. Thick cells may be made with rings of known thickness
as separators, while for thin cells thin tinfoil is a suitable material.
The cell is held together with clips or with any adhesive that is not
attacked by the sample. Pigmented films may contain from 20
to 40 per cent by weight of pigment and are usually prepared for
examination by brushing out the paint on a plate of polished rock
salt. The absorption spectra of such a film may be measured wet
or dry or after any desired period of exposure; the same film is
used throughout, and the absorption spectra are determined a t
various stages in its life. Films may be prepared on amalgamated
panels, and sections may be removed as desired and mounted directly without any backing. The thickness of the films should be
carefully controlled. The best way to do this is by measurement
of the transmission through the film a t some wave length where
there is a minimum of absorption.

As an indication of the sensitivity of the spectrometer,

Figure 1 (left) shows the absorption spectrum of linseed oil
compared with the published curve of Stair and Coblenta (8)
and with the results obtained with a grating spectrometer
which was set up t o study the region between 5.0 and 8.0
microns more closely. The agreement between the two
prism spectrometers is good, or at least the difference between the two is insignificant in view of the difference between either one and the grating spectrometer.

Absorption Spectra of China Wood and Linseed

Oils
Figure 1 (right) shows the absorption spectra of linseed oil,
China wood oil, and oiticica oil from 2 to 12 microns. Absorption bands are found in the first a t 3.4, 5.8, 6.9, and 8.4,
and 11.5 microns and in addition a t 10.0 microns in the China
wood and oiticica oils. The bands a t 3.4 and 6.9 microns are
due to the G - H vibration and that a t 5 3 to the C 4 ; the
band a t 8.4 microns has been variously ascribed to C = O (9),
C-C
(S), and (OH) (4). Lecompte (5) lists this as a characteristic absorption of esters which varies somewhat with the
composition of the ester: Our personal opinion is that these
changes are attributable to the acid radical which serves to
form the ester, rather than to the alcohol radical. For the
purpose of this paper it is enough to ascribe it to the presence