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10.213 Chemical Engineering Thermodynamics Spring 2002 Problem Set I

This document contains a problem set for a chemical engineering thermodynamics class due on April 24, 2002. It includes 5 multi-part problems involving the Redlich-Kwong equation of state, excess Gibbs free energy of binary liquid mixtures, experimental data for heat of mixing binary liquid mixtures, heat capacities and heat of vaporization of steam.

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108 views2 pages

10.213 Chemical Engineering Thermodynamics Spring 2002 Problem Set I

This document contains a problem set for a chemical engineering thermodynamics class due on April 24, 2002. It includes 5 multi-part problems involving the Redlich-Kwong equation of state, excess Gibbs free energy of binary liquid mixtures, experimental data for heat of mixing binary liquid mixtures, heat capacities and heat of vaporization of steam.

Uploaded by

Daniel García
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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10.

213 Chemical Engineering Thermodynamics


Spring 2002

Problem Set I
Due Wednesday, April 24, 2002 in lecture

Problem 29
The Redlich-Kwong equation can be written as:
RT a
P= − and manipulated to provide that
V − b T 0.5 V(V + b)

b a 0.42748R 2 Tc2.5 0.08664RTc


Z = 1+ − , where a = and b = .
V − b RT1.5 (V + b) Pc Pc

b
a ln(1 + )
b V + Z − 1 − ln Z . As a hint, consider the use of either
a) Show that ln φ = − ln(1 − )−
V bRT1.5
GR dP GR dρ 1
= ∫oP( Z − 1) (eq 6.46) or = ∫oρ( Z − 1) + Z − 1 − ln Z (eq 6.57) where ρ = .
RT P RT ρ V
b) Determine the fugacity of n-butane gas at 500 K and 50 bar using the equation derived in a).
c) Determine the fugacity of n-butane gas at 500 K and 50 bar using the values of HR = -4.51
kJ/mol and SR = -6.55 J/mol-K determined in Example 6.4 for n-butane under these
conditions (pp 215-216 in SVN&A).
d) Determine the fugacity of n-butane gas at 500 K and 50 bar using generalized correlations.

Problem 30
The excess Gibbs free energy of a binary liquid mixture at T and P is given by:
GE
= (−2.6 x1 − 1.8 x 2 ) x1 x 2
RT
a) Find expression of ln γ1 and ln γ2 at T and P.
b) Show that when these expressions are combined in accord with Eq 11.95 that the given
equation for GE/RT is recovered.
c) Show that the expressions in a) satisfy the Gibbs-Duhem equation.
d) Show that (d ln γ1/dx1)x1=1 = (d ln γ2/dx1)x1=0=0.
e) Plot GE/RT, ln γ1, and ln γ2 as calculated by the given equation for GE/RT and by the
equations developed in a) vs. x1. Label points ln γ1∞ and ln γ2∞ and show their values.
f) Plot ∆G/RT vs x1.
g) Does Σ(xi d γi) = 0? Should it? Hint: consider the definition of the Gibbs-Duhem equation.
Problem 31
The data tabulated below are experimental values of HE for binary liquid mixtures of
1,2-dichloroethane (1) and dimethyl carbonate (2) at 313.15 K and 1 atm

(from R. Francesconi et al. Int. DATA Ser. A, Vol. 25, No. 3, p. 225, 1997).
x1 HE (J/mol) x1 HE (J/mol)
0.0426 -23.3 0.5163 -204.2
0.0817 -45.7 0.6156 -191.7
0.1177 -66.5 0.6810 -174.1
0.1510 -86.6 0.7621 -141.0
0.2107 -118.2 0.8181 -116.8
0.2624 -144.6 0.8650 -85.6
0.3472 -176.6 0.9276 -43.5
0.4158 -195.7 0.9624 -22.6

a) Determine from the data numerical values of the parameters a, b, and c in the correlating
equation:
HE = x1 x2 (a + b x1 + c x12)
(Hint: consider plotting HE/(x1x2) vs. x1 as a way to determine values of a, b, and c.)
b) Determine the minimum value of HE from the results in part a). At what value of x1 does this
occur?
c) Determine expressions for H 1E and H 2E from the results of part a). Prepare a plot of H 1E
and H 2E vs. x1 and discuss its features.
d) Plot ∆H vs. x1. What is the relationship between ∆H and HE?
e) Determine values of HE, H 1E , and H 2E for x1 = 0 and x1 = 1. For cases where HE = 0 and
either H 1E or H 2E ≠ 0, explain how HE can equal 0 while either H 1E or H 2E do not.

Problem 32.
Steam undergoes an isothermal change in state from 9000 kPa and 400 ºC to 300 kPa and 400 ºC.
Determine using steam tables, the ratio of the fugacity in the final state to that in the initial state.
(Hint: this question requires only a little bit of calculation, so think first about how to connect
fugacities (or rather, fugacity ratios) given the type of data in a steam table.)

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