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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
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/21/2?ver=pdfcov
Published by the AIP Publishing
Application of the semi-empirical method to determine the spatial distribution function for thermalized
photoelectrons created by vacuum ultraviolet or high-energy irradiation of some nonpolar dielectric liquids
J. Chem. Phys. 106, 9497 (1997); 10.1063/1.473851
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THE JOURNAL OF CHEMICAL PHVSICS VOLUME 21, NUMBER 2 FEBRUARV. 1953
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.
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265
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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
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.
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.
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