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) For an ideal gas mixture, the following statement is a consequence of Gibbs Theorem:
H iig = H ig (2 marks)
False. The enthalpy of an ideal gas is independent of pressure, thus the partial molar
enthalpy is equal to pure-species enthalpy (or H iig = H iig ) and not its solution property. Hig
could be found using summability relation, in which case H ig = ∑ y i H iig = ∑ y i H iig .
i i
(b) The relationship between partial residual Gibbs energy and chemical potential could be
written as:
Gi R = µ i − µ iig (2 marks)
True. The chemical potential and the partial molar Gibbs energy are identical, i.e. µ i = Gi .
Seeing that the residual Gibbs energy could be written as Gi R = Gi − Giig ,
thus Gi R = µ i − µ iig .
(c) According to Lewis/Randall rule, the fugacity of each species in an ideal solution is
proportional to its mole fraction in liquid phase either at low or high pressure. (2 marks)
True. Lewis/Randall rule applies to each species in an ideal solution at all conditions of
temperature, pressure and composition. The proportionality constant is the fugacity of pure
species i in the same physical state as the solution and at the same temperature and pressure.
(d) For a pure species coexisting liquid and vapor phases are in equilibrium, the corresponding
fugacity coefficients φi could be expressed as:
φiv = φil = 1 (2 marks)
False. When the system is in equilibrium, φ iv = φil . However, φ iv = φil = 1 is only applicable
when the vapor phase (in equilibrium) is an ideal gas because φ iv = 1 .
(e) For a system initially contains n1 moles CH4 and n2 moles H2O and undergoing the
following reaction with ε as a reaction coordinate,
ni0 + vi ε 3ε
False. Using yi = , the mole fraction of H2 should be y H 2 = , in which
n0 + vε n1 + n 2 + 2ε
case v = ∑vi = -1-1+1+3 = 2, n0 = ∑nio = n1 + n2 and nio for H2 should be 0.
where H is in J mol-1.
Determine:
− −
a) expressions for H 1 and H 2 . (7 marks)
dM
Use M 1 = M + x2
dx1
H1 = (−20 x13 − 180 x1 + 600) + (1 − x1 )(−60 x12 − 180)
H1 = 40 x13 − 60 x12 + 420
dM
Use M 2 = M − x1
dx1
H 2 = (−20 x13 − 180 x1 + 600) − x1 (−60 x12 − 180)
H 2 = 40 x13 + 600
b) numerical values for the pure-species enthalpies H1 and H2, using the expressions you
have determined from 2a. (4 marks)
H1 = H1 when x1 = 1
H1 = 40(1) 3 − 60(1) 2 + 420
H1 = 400 J mol −1
H 2 = H 2 when x2 = 1 or x1 = 0
H 2 = 40(0) 3 + 600
H 2 = 600 J mol −1
− ∞ − ∞
c) numerical values for the partial enthalpies at infinite dilution H 1 and H 2 . , using the
expressions you have determined from 2a. (4 marks)
H 1∞ = H 1 when x1 = 0
H 1∞ = 40(0)3 − 60(0) 2 + 420
H 1∞ = 420 J mol −1
H 2∞ = H 2 when x2 = 0 or x1 = 1
H 2∞ = 40(1) 3 + 600
H 2∞ = 640 J mol −1