Problem Set 4

Due:
10/01/2021

Problem 1:
Consider a gas for which the intermolecular potential U (r ) is given by

 ∞ r ≤σ

U (r ) =  A
− r n r >σ

where A (positive) and n are constants.

(a). Obtain an expression for the second virial coefficient of this gas at high temperature.

(b). Determine allowable values of n in this expression and the relationship of dB / dT

with the attractive part of the potential.

Problem 2:
Supercritical extraction is used to decaffeinate coffee beans before roasting. If the solvent
is carbon dioxide at 40ºC, caffeine obeys the following empirical relation:

− ( P −40) 2
RT
∞
v =
2 − 10000e 20 +101
P
∞
where v 2 is the partial molar volume of caffeine in carbon dioxide at infinite dilution, in
cm3/mol, R is the gas constant, T is the absolute temperature, and P is the pressure in
bar. For solid caffeine at 40 ºC the vapor pressure is 10.5 Pa and the molar volume is
157.9 cm3/mol. Calculate (a) the solubility of caffeine in carbon dioxide at 40 ºC and 60
bar. (b) the enhancement factor at these conditions. If the caffeine-saturated solvent is
removed and its pressure is then reduced isothermally to 25 bar, calculate (c) the fraction
of caffeine that precipitates.
Problem 3:
Consider a liquid mixture of components 1, 2, 3, and 4. The molar excess Gibbs energies
of all the binaries formed by these components obey relations of the form

gijE = Aij xi x j

where Aij is the constant characteristic of the i-j binary and xi is the mole fraction of
component i. The total molar excess Gibbs free energy is given by

g E = ∑∑ gijE
i j>i

Derive an expression for the activity coefficient of component 1, γ 1 ,in the quaternary
solution, in terms of { Aij } , x2, x3, x4, R and T.
Problem 4:
Plot the P-x1-y1 diagram at 70◦C for the binary system ethanol(1)-toluene(2) using (a) Scatchard-
Hildebrand (regular solution) theory, (b) the original van Laar equation, where
A0 B0
lnγ1 =  2 and lnγ2 =  2 with
A 0 x1 B 0 x2
1+ B 0 x2
1+ A 0 x1

√ √ 2 √ √ 2
0b1 a1 a2 0 b2 a1 a2
A = − and B = −
RT b1 b2 RT b1 b2
and (c) the van Laar equation using experimental infinite dilution activity coefficients γ1∞ = 7.69
and γ2∞ = 5.58. Comment on (d) the major sources of error (e) the main benefits of each. Which
of these (f) predicts an azeotrope and what is (g) the azeotropic composition? Relevant data are
presented in Table 1 and vapor-liquid equilibrium data are given in Table 2 for reference. Recall
27R2 T 2
that for the van der Waals equation, a = 64PCC and b = RT C
8PC
. Clearly state all assumptions.

Table 1: Data for ethanol and toluene at 70◦ C

Ethanol Toluene
Psat (bar) 0.722 0.272
∆Uvap (J/mol) 39250 49030
ρ (g/cm3 ) 0.737 0.822
TC (K) 513.9 591.8
PC (bar) 61.4 41.0

Table 2: The VLE data of Wright (1933) for the ethanol(1)-toluene(2) system at 70◦ C.

x1 y1 P (mmHg)
0.107 0.62 367
0.231 0.686 557
0.352 0.703 569
0.443 0.71 572
0.543 0.724 584
0.625 0.739 590
0.726 0.76 592
0.767 0.774 598
0.845 0.814 598
0.904 0.861 591
0.957 0.924 575