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A SemiEmpirical Equation for the Vapor Pressure of Liquids as a Function of

Temperature
Arthur A. Frost and Donald R. Kalkwarf

Citation: The Journal of Chemical Physics 21, 264 (1953); doi: 10.1063/1.1698871
View online: http://dx.doi.org/10.1063/1.1698871
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THE JOURNAL OF CHEMICAL PHVSICS VOLUME 21, NUMBER 2 FEBRUARV. 1953

A Semi-Empirical Equation for the Vapor Pressure of Liquids as a


Function of Temperature*
ARTHUR A. FROST AND DONALD R. KALKWARFt
Chemical Laboratory of Northwestern University, Evanston, Illinois
(Received August 27,1952)

The slight reverse curvature-in the plot of 10gP versus l/T (P, vapor pressure; T, absolute temperature)
may be explained on the basis of the nonideal behavior of the vapor together with the change in heat of
vaporization with temperature. If it is assumed that AH is linear with T and that the van der Waals a/V2
term is a first approximation to the deviation from the ideal, the following equation may be obtained by in-
tegration of the Clapeyron equation:
B P
logP=A+
1+C logT+np.
The last term is the nonideal gas correction with constant D=a/2.303R2. With constants A, B, and C de-
termined empirically, the equation reproduces experimental vapor pressures from the triple point to the
critical point with an average deviation of 0.3 percent.

N UMEROUS equations, both empirical and theo-


retical have been given relating vapor pressure P
with absolute temperature T.1 The simplest theoretical
where P is the vapor pressure in atmospheres, Tb is the
absolute boiling point and
A = A c1 OE(1- TTl (F- TTl.
relation is the familiar Clausius-Clapeyron equation:
10gP=A-(BIT), (1) Here Tr is the reduced temperature TITcrit and A c, E,
and F are constants. The quantity A was found to go
where A and B are empirical constants. This equation through a minimum at a reduced temperature of about
is derived from the thermodynamically exact Clapeyron 0.92. A graphical interpretation of Cox's A can be ob-
equation: tained by solving Eq. (3) for A in the following form:
dP/dT=ilHITilV, (2)
1 10gP
where ilH is the heat of vaporization and il V the corre- A= (4)
sponding increase in volume on converting liquid to Tb [(lIT b)-(lIT)]'
vapor. The derivation of (1) assumes: (a) constant ilH showing that A is proportional to the negative slope of
independent of T, (b) that the vapor is an ideal gas, and the chord joining the points on the 10gP versus liT
(c) that the liquid volume is negligible. Equation (1) plot corresponding to the boiling point (logP=O,
predicts linearity in a plot of logP versus liT. l/T= 1/T b) and an arbitrary point (logP, liT). It is
Thodos,2 in a careful survey of empirical vapor pres- seen that the reverse curvature of the 10gP versus liT
sures of saturated hydrocarbons, has shown that the plot then corresponds to Cox's A going through a
plot of 10gP versus liT is not quite linear but really mlmmum.
S shaped with a reversal of curvature between the
boiling point and the critical point. This is illustrated DERIVATION OF THE EQUATION
by Fig. 1 in which data for n heptane as selected by
Thodos have been graphed. The extra curve in the figure Over the greater part of the temperature range (lower
temperatures) the 10gP versus liT plot is convex up-
shows in exaggerated fashion the nature of the curva-
wards. This has been explained quite well as due to a
ture which may just be seen in the actual plot by careful decrease in ilH as T increases. In particular, if it is
inspection. assumed that ilH falls linearly as T increases but that
The S shaped form is inherent in the empirical equa- the other assumptions of the Clausius-Clapeyron equa-
tion of Cox3 which is as follows: tion are satisfied, the Rankine equation results: 1
10gP=A[1- (TbIT)], (3) 10gP=A - (B/T)+C 10gT. (5)
* Presented at the Cleveland meeting of the American Chemical Now the reversal in curvature being discussed in this
Society, April, 1951.
t Abstracted from the Ph.D thesis of Donald R. Kalkwarf. paper occurs at higher temperatures, between the boil-
Present address: General Electric Company, Hanford Works, ing point and the critical point. This is a region of high
Richland, Washington. vapor pressure where deviations of the vapor from the
1 For a review see G. W. Thomson, Chern. Revs. 38, 1 (1946),
also A. Weissberger, Physical Methods of Organic Chemistry (Inter- ideal gas law would be most noticeable. It is only logical,
science Publishers, Inc., New York, 1949), second edition, Vol. I, then, to consider the effect of such deviations. Being
Part 1, Chap. V by G. W. Thomson.
t G. Thodos, Ind. Eng. Chern. 42, 1514 (1950).
unable to integrate the equation in complete generality,
3 E. R. Cox, Ind. Eng. Chern. 28, 613 (1936). an approximate solution will be obtained which contains
264

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265

a first-order correction for the non ideal gas behavior


such that the resulting equation should be good up to a
reduced temperature of perhaps 0.8 or more.
n-HEPTANE
Van der Waals' equation,
[P+(a/V2)](V -b) =RT, (6)
a and b being van der Waals' constants, may be put in
the form:
RT
V=b+--- (7)
P+(a/P)
LOG P
If V in the correction term a/V2 is approximated by (MM)
RT/ P, and it is realized that the liquid volume is to a
first approximation equal to b, then the change in 3.0
volume on vaporization is approximately
RT
V=------ (8)
P[l + (aP / R2P)]
As in the Rankine Eq. (5), it will be assumed that
2.0
AH is linear in T; specifically,
AH=AHo-C'T, (9)
where AHo and C' are considered empirical constants.
Substitution of (8) and (9) in the Clapeyron Eq. (2)
yields
1.0 '--_ _"--_--:-'--::-_-L.. _ _...;;;...& _ _~
P( AHO-C'T)(l+ aP ) 2.0 ..lxla 3.0
dP R2P T
FIG. 1. Vapor pressure of n-heptane.
dT RP
or
the integrated result in (14), P has been reintroduced
dlnP = AHO(l_~T)(l+ ap) (11) using (13). RT/ AH is of the order .of magnitude of 0.1 ;
dT RP AH° R2p therefore, the last two terms of (14) will be neglected.
or Integration of the complete Eq. (12) then results in
AHO C' aPAH)
dlnP= ( ---+-- dT. (12)
AHo C' aP
RP RT R3T4
InP=A'----lnT+- (15)
RT R R2P
Equation (12) may be integrated if P in the small or
last term is given as a function of T. To a sufficient B DP
approximation, consistent with our previous assump- 10gP=A+-+C 10gT+-, (16)
tions, this P may be represented by T P
P=Poe-tJ.HIRT, (13) where A, B, and C are empirical constants, Band C
being negative, and D is related to van der Waals' a by
which is equivalent to the Clausius-Clapeyron equation.
D=a/2.303R2. (17)
With this substitution, the last term in (12) integrates
as follows: Alternatively, all four constants may be evaluated
empirically.4
aPAH aAHPoJe-tJ.HIRT Although Eq. (15) has been derived using only first-
--dT=-- dT
J R3T4 R3 T4 order corrections for the deviation of the vapor from
an ideal gas and for the temperature variation of AH,
aP [ 2RT 2R2P] and, therefore, presumably limited to temperatures not
= - 1 + - + - - +const, (14) too near the critical, it is found as shown in the next
R2p t:.H (t:.H)2
section that the equation quite accurately reproduces
where it has been assumed that the t:.H of Eqs. (14), vapor pressure data right up to the critical point. This
(13), and the last term of (12) is constant, this being situation may be partially understood by the following
permissible because this is a first-order correction. In 4 R. E. Perry and G. Thodos, Ind. Eng. Chern. 44, 1649 (1952).

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266 A. A. FROST AND D. R. KALKWARF

TABLE 1. Numerical values of the constants used in the equation If the proposed equation is correct, a plot of the quantity
10gP=A+(B/T)+C 10gT+(DP/1'2) (P in rnrn Hg)
10g(P/P f )- D[(P/'J'2)- (Pf/T/)]
A -B -c D
a=
Methane" 13.44740 567.5868 2.681065 0.191423 (l/T) - (l/Tf )
Ethane 16.74451 1068.273 3.566685 0.457881 10g(T/Tf )
Propane 19.05446 1429.728 4.227769 0.736275 versus f3
n-Butane 21.68560 1793.194 5.024486 1.22954
n-Pentane 22.92307 2098.332 5.328139 1.61495
(l/T)- (lITf)
n-Hexane 25.08480 2436.187 5.955353 2.07240
n-Heptane 26.86378 2750.888 6.458216 2.67736 should be a straight line of slope C and intercept B.
n-Octane 29.02343 3087.966 7.080892 3.17191 As an example, the data for n-heptane are plotted in
Carbon dioxide b 23.06810 1374.064 5.634143 0.305254
Water" 22.75017 2908.894 4.695517 0.424676 Fig. 2 using the critical point as the reference point
(Ph Tf). A straight line is determined by the data when
• Experimental data for hydrocarbons as selected by Thodos (reference 2). the value 2.67 for D is used as calculated from van der
b Data from C. H. Meyers and M. S. van Dusen, Nat!. Bur. Standards
J. Research 10, 381 (1933). Waals' constant a for n-heptane. When other values of
, Data from N. S. Osborne and C. H. Meyers, Nat!. Bur. Standards J. D such as zero or one are used, the other curves shown
Research 13, 1 (1934).
in Fig. 2 are obtained. Thus, it is seen that data plotted
argument: As the critical temperature is approached, in this way are very sensitive to changes in the value of
~ V actually approaches zero rather than the finite D and that the correct value is that obtained from the
value given by Eq. (8). Also ~H approaches zero at an van der Waals' constant a.
increasing rate rather than linearly as Eq. (9) would By visual inspection of the plot with D= 2.67 it is
indicate. More explicitly, both ~ V and ~H have as a possible to pick two points which lie on the "best"
limiting form near the critical point (Tc-T)n, where T straight line through the experimental data, and from
is the critical temperature and the exponent n is ap- them determine the slope C and intercept B. Knowing
proximately 0.3 to 0.4." If n is not the same in expres- B, C, and D, the constant A may be evaluated by sub-
sions for ~ V and ~H for the same substance, the ratio stituting in the general equation for any of the three
~HI ~ V would become zero or infinite at the critical points thus far used.
point and result, according to the Clapeyron Eq. (2), Although evaluation of the constants A, B, and C
in a zero or infinite slope in a vapor pressure-tempera-
ture plot. This latter is not observed; therefore, the
same n must apply to both ~ V and ~H, and as a result
~HI ~ V is to this approximation independent of tem-
"-HEPTANE
perature. This argument shows that the first-order cor-
rections used in deriving (15) are better than first ex-
pected owing to a cancellation of higher-order correc-
tions as the critical temperature is approached. 6 1400

EVALUATION OF THE CONSTANTS AND


TEST OF THE EQUATION
Use of the equation 10gP=A+(B/T)+C 10gT
+ (DP/'J'2) requires the determination of the constants 1600
A, B, and C for the substance involved. As was shown
in the preceding section, the constant D is simply
related to the van der Waals constant a which in turn -c{
is derived from data at the critical point of the sub-
stance. The method used to determine the other con-
stants is as follows: A reference point (Ph T f ) is taken
where the experimental data are felt to be particularly
accurate. These data may be put into the equation to
give 10gPf=A+(B/Tf)+C 10gTf+(DPf/T/). Sub-
tracting this expression from the general equation for 1700
10gP eliminates the constant A and leaves

10gP =B(~-~)+CIOg~+D(P _ Pf).


0=0

Pf T Tf T , . 'J'2 T/
----
6 AV is related to the orthobaric density difference. For this
latter see S. Sugden, J. Chern. Soc. 1927, 1780. For AH see K. M.
Watson, Ind. Eng. Chern. 35, 398 (1943). 200 -(I
• For other qualitative considerations see O. L. 1. Brown, J.
Chern. Educ. 28, 428 (1951). FIG. 2. Evaluation of constants of Eq. 16 for n-heptane.

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LIQUID VAPOR PRESSURES 267

by the method of least squares would undoubtedly TABLE II. Average deviation. a
improve the fit of the equation to the experimental
Eq.l Eq.2 Eq.3 Eq.4
data, it was felt that this simpler procedure was suffi-
cient to indicate the accuracy of an equation of this Methane 0.44 percent 1.43 percent 0.15 percent ... percent
Ethane 0.20 1.00 0.08
type. Propane
n-Butane
0.36
0.38
9.33
1.26
0.10
0.17
2.08
1.61
Table I shows the constants as evaluated for eight n-Pentane 0.25 1.13 0.42 1.15
n-Hexane 0.25 0.67 0.24 0.60
hydrocarbons together with carbon dioxide and water. n.Heptane 0.34 1.35 0.07 0.51
n-Octane 0.31 0.85 0.14 0.89
For the hydrocarbons the reference point was the Carbon dioxide 0.05
Water 0.41
critical point; for carbon dioxide, the triple point; for Average 0.31 2.11 0.17 1.16
water, the normal boiling point.
A summary of the average deviations between vapor • Data for Eqs. 2. 3. and 4 as calculated by Thodos (see reference 2).
b Equation 1: This paper.
pressures calculated from various equations and ex- • Equation 2: Gamson and Watson (see reference 2).
d Equation 3: Thodos (see reference 2).
perimental values, utilizing data over the complete • Equation 4: Cox (see reference 3).
liquid range, is shown in Table II. Although the Thodos
equation shows an average deviation of only 0.17 per- correction. It suffices to carry out a calculation by suc-
cent, somewhat less than the 0.31 percent of the present cessive approximation, placing successively better
equation, it should be realized that the former has six values of P in the last term to obtain still better values
empirical constants as compared with only three here. of P from 10gP. Even in the most unfavorable case,
The presence of P on both sides of the equation would at temperatures near the critical point, not more than
make it difficult to solve for P as a function of T if it three or four cycles are necessary to obtain a value of
were not for the fact that the last term DP/Tl is a small P accurate within half a percent.

THE JOURNAL OF·CHEMICAL PHYSICS VOLUME 21. NUMBER 2 FEBRUARY. 1953

The Effect of Pressure on Self-Diffusion in Carbon Disulfide*


R. C. KOELLER AND H. G. DRICKAMER
Department of Chemistry, University of Illinois, Urbana Illinois
(Received September 3, 1952)

A method has been developed for measuring diffusion coefficients in liquids to 10000 atmospheres pres-
sure. Measurements have been made over this pressure range atO°, 20°, and 40°C for the system CS 2 -CSS36.
The results are interpreted in terms of the enthalpy, entropy, and volume of activation as a function of tem-
perature and pressure.

INTRODUCTION in the diffusing component and a scintillation counting


technique was employed to give a continuous account of
IlarTtinguishing
is evident that one of the most important dis-
characteristics of liquids is their molecu-
motion. The difference between a liquid and an
the concentration of tracer element at one end of the
diffusion cell. Knowing the concentration at one end of
isotropic solid lies in the immensely shorter residence the cell to be a function of time, it was possible to cal-
time in the liquid phase. This comes about as a result culate the diffusion coefficient.
of the free volume in liquids (about 10 percent of the Results are presented in this paper for self-diffusion
molal volume) which considerably reduces cohesive in carbon disulfide at 0°, 20°, and 40°C to 10000
forces and permits increased molecular motion. It is atmospheres pressure. The sa. tagged CS 2was obtained
clear then that any understanding of this motion must from Tracerlab.
be obtained through a comparison of diffusivity with Further results on organic mixtures, on water, and on
free volume. When one realizes that many organic aqueous solutions will be reported in the near future.
liquids may lose 20 to 30 percent of their molal volume THEORY
in being compressed to 10000 atmos, it is obvious that
a study of diffusion over this pressure range will give Various approaches to a kinetic theory for liquids
information about the nature of motion in liquids which have been made by Frenkel,! Eyring,2 Wirtz,a Prigo-
is not obtainable from any other approach. gine,4 and others. While the methods differ, they all
A suitable cell was developed so that it was possible
1 J.
Frenkel, Z. Physik 35, 652 (1926).
to determine diffusion coefficients in liquids under pres- 2 Eyring, Laidler, and Glasstone, Theory of Rate Processes (Mc-
sures up to 10000 atmos. Radioactive tracers were used Graw-Hill Book Company, Inc., New York, 1941).
3 Wirtz, Physik Z. 44, 221, 309 (1944).
* This work was supported in part by the AEC. 4 Prigogine, de Broukere, and Amand, Physica 16, 577 (1950).

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