Test 3 Solution 2014 PDF
Test 3 Solution 2014 PDF
Test 3 Solution 2014 PDF
(1) Read carefully and determine whether the following statements are true or false and
indicate your thermodynamic reasoning. If you claim that a statement is false, you may
state that it violates a law of thermodynamics, or you may employ a physical counter-
example or any plausible reason. You may wish to amend any false statement with a
clarifying phrase that makes the statement true. If you claim that a statement is true, please
indicate your thermodynamic reasoning.
a) It is correct to represent excess Gibbs energy as GE = Σ xiµi – Gid .
(3 marks)
TRUE
ME = M – Mid
Summability relations: M = ∑ xi M i
Thus, M E = ∑ xi M i − M id
G E = ∑ xi Gi − G id
but µ i ≡ Gi
∴ G E = ∑ xi µi − G id
c) If a mixture of chemical species is not in chemical equilibrium, any reaction that occurs at
constant T and P must lead to a decrease in the total Gibbs energy of the system.
(2 marks)
TRUE
The total Gibbs energy of a system at constant T and P must decrease until the condition for
equilibrium is reach when Gt attains its minimum value. At this equilibrium state, its
differential is zero or (dGt)T,P = 0.
(2) The molar entropy (J mol-1 K-1) of a binary liquid system of species 1 and 2 at constant T
and P is given by the equation S = 120x1 + 70x2 + (15x1 + 8x2) x1x2. Determine expressions as
(8 marks)
dS
Using Eq. (11.15), S1 = S + x2
dx1
S1 = −7 x13 − x12 + 58 x1 + 70 + (1 − x1 )(−21x12 − 2 x1 + 58)
Reagreement and simplification of equation will lead to:
S1 = 14 x13 − 20 x12 − 2 x1 + 128
dS
Using Eq. (11.16), S 2 = S − x1
dx1
(3) Consider the following set of vapor-liquid equilibrium (VLE) data for system of species
1 and species 2 at 120 oC as shown in Table 1:
b) A student found that the activity coefficients of species 1 and species 2 follow
Redlich/Kister expansion, namely
GE
= Ax1 x2
RT
where A is a constant. Using the data calculated in Table 1, determine the expressions
of both ln γ1 and ln γ2.
(5 marks)
According to Redlich/Kister expansion,
GE
= A , whereby ln γ 1 = Ax22 ; ln γ 2 = Ax12
x1 x2 RT
Thus, A is the average values of GE/x1x2RT which are calculated in (3a).
(−0.228) + (−0.243) + (−0.270) − 0.741
A= = = −0.247
3 3