Complete Course on Solution Thermodynamics

Q.2. A system of unite mass at equilibrium consists of two phases, a and b of extent x
and (1-x) respectively. Write down expressions for the pressure and the specific
enthalpy of the system as a whole in terms of the properties Pα , Pβ ,hα , hβ. GATE – 1990
Q.12. At 318 K at total pressure of 24.4 kPa, the composition of system ethanol (1)
and toluene (2) at equilibrium x1 = 0.3 and y1 = 0.634. The saturation pressure at the
given temperature for pure components is, P1 = 23.08 kPa and P2 = 10.05 kPa,
respectively. Calculate:
(a) The liquid phase activity coefficients.
(b) The value of GE/RT for the liquid phase. GATE – 1991
Q.15. The necessary and sufficient condition for equilibrium between two phases is,
(A) Condition of each component should be same in the two phases
(B) The temperature of each phase should be same
(C) The pressure should be same in the two phases
(D) The chemical potential of each component should be same in the two phases
GATE – 1992
Q.16. For a single component, two-phase mixture the number of independent variable
properties are,
(A) Two
(B) One
(C) Zero
(D) Three GATE – 1992
Q.26. An experimental determination of a vapor liquid equilibrium state of ether (1) and
acetone (2) binary system gave the following result:
x1 = 0.3, T = 40°C,
y2 = 0.42, P = 105 Pa.
The saturation vapor pressures of the pure components at 40°C are,
Ether (1) = 1.21 x 105 Pa
Acetone (2) = 0.56 x 105 Pa
The vapor phase can be assumed to be ideal.
(a) Calculate the liquid phase activities coefficients
(b) What is the value of excess Gibbs free energy GE/RT for the liquid phase? GATE – 1994
Q.36. The activity coefficients of benzene (A)–cyclohexane (B) mixtures at 40 0C, are
given by RT lngA = bxB2 and RT lngB = bxA2 . At 40 0C. A and B form an azeotrope
containing 49.4 mol % A at a total pressure of 202.5 mm Hg. If the vapour pressures of
pure A and pure B are 182.6 and 183.5 mm Hg respectively, calculate the total pressure
of the vapour at temperature 40 0C in equilibrium with a liquid mixture containing 12.6
mol % A. GATE – 1996
Q.43. The molar excess Gibbs free energy, gE , for a binary liquid mixture at T and P is
given by (gE/RT = Ax1x2 , where A is a constant. The corresponding equation for ln γ1 ,
where γ1 is the activity coefficient of component 1, is
(A) Ax22
(B) Ax1
(C) Ax2
(D) Ax12 GATE – 1997
Q.44. An equimolar mixture of benzene and toluene is contained in a piston/cylinder
arrangement at a temperature T.
What is the maximum pressure below which this mixture will exist as a vapour phase
alone?
At the given T, the vapour pressures of benzene and toluene are 1530 and 640 mm Hg,
respectively. Assume that Raoult’s law is valid. GATE – 1997
Q.45. Determine the mol fraction of methane, x1 , dissolved in a light oil at 200 K and 20
bar. Henry’s law is valid for the liquid phase, and the gas phase may be assumed to be an
ideal solution.
At these conditions,
Henry’s law constant for methane in oil = 200 bar
Fugacity coefficient of pure methane gas = 0.90 Mol.
fraction of methane in the gas phase, y1 = 0.95 GATE – 1997
Q.46. Ethanol is manufactured by the vapour phase hydration of ethylene according to the
reaction :
C2H4 (g) + H2O (g) C2 H5 OH (g)
The reactor operates at 400 K and 2 bar and the feed is a gas mixture of ethylene and steam
in the mol ratio 1:3. The equilibrium constant is 0.25.
Estimate the composition (mol%) of the equilibrium mixture. Assume ideal gas behaviour
and take f10= 1 bar, where f10 is the standard state fugacity of component 1. GATE – 1997
Q.52. A mixture of A and B conforms closely to Raoult’s law. The pure component
vapour pressures PA sat and PB sat in kPa are given by (t in 0C)

If the bubble point of a certain mixture of A and B is 76 0C at a total pressure of 80 kPa,

find the composition of the first vapour that forms. GATE – 1998
Q.56. Saturated solution of benzene in water is in equilibrium with a mixture of air
and vapours of benzene and water at room temperature and pressure. Mole fraction
of benzene in liquid is xB and the vapour pressures of benzene and water at these
conditions are pvn and pvw respectively. The partial pressure of benzene in air-vapour
mixture is
(A) pvB (B) xB pvB (C) (patm – pvw) xB (D) xB patm GATE – 1999
Q.57. Maxwell’s relation corresponding to the identity,

GATE – 1999
Q.58. The vapour pressures of benzene and toluene are 3 and 4/3 atmospheres
respectively. A liquid feed of 0.4 moles of benzene and 0.6 moles of toluene is
vapourized. Assuming that the products are in equilibrium, the vapour phase mole
fraction of benzene is
(A) 0.4 (B) 0.6 (C) 0.8 (D) 0.2 GATE – 1999
Q.59. For the binary system methanol (1) and benzene (2), the recommended values
of the Wilson parameters at 68 0C are A12 = 0.1751 and A21 = 0.3456. The vapour
pressure of pure species at 68 0C are p1sat = 68.75 kPa and p2sat = 115.89 kPa. Show
that the given system can form an azeotrope at 68 C. Assume that the vapour
behaves like an ideal gas. GATE – 1999
Q.60. In a binary liquid solution of components A and B, if component A exhibits
positive deviation from Raoult’s law, then components B,
(A) exhibits positive deviation from Raoult’s law
(B) exhibits negative deviation from Raoult’s law
(C) obeys Raoult’s law
(D) may exhibit either positive or negative deviation from Raoult’s law GATE – 2000
Q.61. Assume that benzene is insoluble in water. The normal boiling points of
benzene and water are 80.1 0C and 100 0C, respectively. At a pressure of 1 atm, the
boiling point of a mixture of benzene and water is
(A) 80.1 0C
(B) less than 80.1 0C
(C) 100 0C
(D) greater than 80.1 0C but less than 100 0C GATE – 2000
Q.66. In a binary mixture the activity coefficient y1 of component 1, in the entire
range of composition, is given by

where R, A and B are constants. Derive the expression for the activity coefficient of
component 2. GATE – 2000
Q.67. A reasonably general expression for vapour-liquid phase equilibrium at low to
moderate pressures is Where fi is a vapour fugacity coefficient, γi is the
liquid activity coefficient, and fi is the fugacity of pure component i. The Ki value (yi =
Ki xi) is therefore in general, a function of
(A) temperature only
(B) temperature and pressure only
(C) temperature, pressure, and liquid composition xi only
(D) temperature pressure, liquid composition xi, and vapour composition yi GATE – 2001
Q.70. At 100 0C, water and methylcyclohexane both have vapour pressures of 1.0 atm.
Also at 100 0C, the latent heats of vapourization of these compounds are 40.63 kJ/mol
for water and 31.55 kJ/mol for methylcyclohexane. The vapour pressure of water at
150 0C is 4.69 atm. At 150 0C, the vapour pressure of methycyclohexane would be
expected to be :
(A) significantly less than 4.69 atm
(B) nearly equal to 4.69 atm
(C) significantly more than 4.69 atm
(D) indeterminate due to a lack of data GATE – 2001
Q.76. The partial molar enthalpy of a component in an ideal binary gas mixture of
composition z, at a temperature T and pressure P, is a function only of
(A) T
(B) T and P
(C) T, P and z
(D) T and z GATE – 2002
Q.80. The Excess Gibbs free energy for cyclohexanone (1)/ phenol (2) is given by
(GE/RT) = -2.1 x1 x2 ; where, x1 and x2 are the mole fractions of components 1 and 2 in
the liquid phase. The vapour pressures of components at 417 K are P1sat = 75.2 kPa
and P2sat = 31.66 kPa.
(a) Derive the expressions for activity coefficient of each component as a function of
composition.
(b) Verify whether the expressions derived in (a) satisfy the Gibbs – Dubem equation.
(c) Determine the equilibrium pressure P and vapour composition for a liquid phase
composition x1 = 0.8 and 417 K. Assume vapour phase to be ideal gas. GATE – 2002
Q.84. When dilute aqueous solutions of two salts are mixed, the process is associated with
(A) decrease in temperature
(B) increase in temperature
(C) no change in temperature
(D) change in temperature which is a function of composition GATE – 2003
Q.87. For water at 300 0C, it has a vapour pressure 8592.7 kPa and fugacity 6738.9 kPa.
Under these conditions, one mole of water in liquid phase has a volume 25.28 cm3 , and
that in vapour phase 391.1 cm3 . Fugacity of water (in kPa) at 9000 kPa will be
(A) 6738.9 (B) 6753.5 (C) 7058.3 (D) 9000 GATE – 2003
Q.91. At 60 0C, vapour pressure of methanol and water are 84.562 kPa and 19.953 kPa
respectively. An aqueous solution of methanol at 60 0C exerts a pressure of 39.223 kPa;
the liquid phase and vapour phase mole fractions of methanol are 0.1686 and 0.5714
respectively. Activity coefficient of methanol is
(A) 1.572 (B) 1.9398 (C) 3.389 (D) 4.238 GATE – 2003
Q.94. As pressure approaches zero, the ratio of fugacity to pressure (f/P) for a gas
approaches
(A) Zero (B) Unity (C) Infinity (D) an indeterminate value GATE – 2004
Q.105. The van Laar activity coefficient model for a binary mixture is given by the form

Given γ1 = 1.40, γ2 = 1.25, x1 = 0.25, x2 = 0.75, determine the constants A* and B*,
(A) A* = 0.5, B* = 0.3
(B) A* = 3, B* = 0.5
(C) A* = 0.333, B* = 0.2
(D) A* = 2, B* = 0.333 GATE – 2005
Q.112. For a reversible exothermic gas phase reaction, A + B ↔ C, the equilibrium
conversion will increase with
(A) increase in pressure and increase in temperature
(B) decrease in pressure and increase in temperature
(C) increase in pressure and decrease in temperature
(D) decrease in pressure and decrease in temperature GATE – 2006
Q.113. For a binary mixture of A and B at 400 K and 1 atm, which ONE of the following
equilibrium states deviates significantly from ideality ?
Given : where
PAsat = vapor pressure of A, atm
T = temperature, K
PA = partial pressure of A, atm
xA = mole fraction of A in liquid
yA = mole fraction of A in vapor

(A) xA = 0.5; yA = 0.25

(B) xA = 0.5; PA = 0.25
(C) xA = 0.5; PA = 0.5
(D) xA = 0.6; yA = 0.3 GATE – 2006
Q.116. If TA and TB are the boiling points of pure A and pure B respectively and TAB is that
of a non-homogeneous immiscible mixture of A and B, then
(A) TAB < TA and TB
(B) TAB > TA and TB
(C) TA > TAB > TB
(D) TB > TAB > TA GATE – 2007
Q.120. If mi ,mi, miR , miE are molar, partial molar, residual and excess properties
respectively for a pure species “i” , the mixture property M of a binary non-ideal mixture of
components 1 and 2, is given by
(A) x1 + x2
(B) x1 m1R + x2 m2R
(C) x1 m1 + x2 m2
(D) x1 m1E + x2 m2 GATE – 2007
Q.126. A methanol-water vapor liquid system is at equilibrium at 60°C and 60 kPa. The
mole fraction of methanol in liquid is 0.5 and in vapor is 0.8. Vapor pressure of
methanol and water at 60°C are 85 kPa and 20 kPa respectively. Assuming vapor phase
to be an ideal gas mixture, what is the activity coefficient of water in the liquid phase ?
(A) 0.3 (B) 1.2 (C) 1.6 (D) 7.5 GATE – 2007

Q.127. What is the excess Gibbs free energy (gE , in J/mol) of the liquid mixture ?
(A) 9.7 (B) 388 (C) 422 (D) 3227 GATE – 2007
Q.132. The molar volume (v) of a binary mixture, of species 1 and 2 having mole
fractions x1 and x2 respectively is given by v = 220 x1 + 180 x2 + x1 x2 (90 x1 + 50 x2 ).
The partial molar volume of species 2 at x2 = 0.3 is
(A) 183.06 (B) 212.34 (C) 229.54 (D) 256.26 GATE – 2008
Q.134. A binary mixture containing species 1 and 2 forms an azeotrope at 105.4°C and
1.013 bar. The liquid phase mole fraction of component 1 (x1) of this azeotrope is 0.62.
At 105.4°C, the pure component vapor pressures for species 1 and 2 are 0.878 bar and
0.665 bar, respectively. Assume that the vapour phase is an ideal gas mixture. The van
Laar constants, A and B, are given by the expressions :

(i). The activity coefficients ( γ1 , γ2 ) under these conditions are

(A) (0.88, 0.66) (B) (1.15, 1.52) (C) (1.52, 1.15) (D) (1.52, 0.88)

(ii).The van Laar constants (A, B) are

(A) (0.92, 0.87) (B) (1.00, 1.21) (C) (1.12, 1.00) (D) (1.52, 1.15) GATE – 2008
Q.136. For a binary mixture at constant temperature and pressure, which ONE of the
following relations between activity coefficient (γi) and mole fraction (xi) is
thermodynamically consistent ?

GATE – 2009
Q.138. An equimolar liquid mixture of species 1 and 2 is in equilibrium with its vapour
at 400 K. At this temperature, the vapour pressures of the species are P1sat = 180 kPa and
P2sat = 120 kPa. Assuming that Raoult’s law is valid, the value of y1 is
(A) 0.30 (B) 0.41 (C) 0.50 (D) 0.60 GATE – 2010
Q.141. At constant T and P, the molar density of a binary mixture is given by ρ = 1 + x2
, where x2 is the mole fraction of component 2. The partial molar volume at infinite
dilution for component 1, V1∞, is
(A) 0.75 (B) 1.0 (C) 2.0 (D) 4.0 GATE – 2010
Q.142. Minimum work (W) required to separate a binary gas mixture at a temperature
T0 and pressure P0

is where y1 and y2 are mole fractions. fpure.1 and fpure.2 are fugacities of pure species at T0
and P0 and f1 and f2 are fugacities of species in the mixture at T0 , P0 and y1 . If the
mixture is ideal then W is
(A) 0 (B) – RT0 [y1 ln y1 + y2 ln y2 ]
(C) RT0 [y1 ln y1 + y2 ln y2 ] (D) RT0 GATE – 2011
Q.143. The partial molar enthalpies of mixing (in J/mol) for benzene (component 1) and
cyclohexane (component 2) at 300 K and 1 bar are given by and ,
where x1 and x2 are the mole fractions. When ONE mole of benzene is added to TWO
moles of cyclohexane, the enthalpy change (in J) is
(A) 3600 (B) 2400 (C) 2000 (D) 800 GATE – 2011
Q.146. Consider a binary mixture of methyl ethyl ketone (component 1) and toluene
(component 2). At 323 K the activity coefficients γ1 and γ2 are given by

where x1 and x2 are the mole fractions in the liquid mixture, and Ψ1 and Ψ2 are
parameters independent of composition. At the same temperature, the infinite dilution
activity coefficients γ1 ∞ and γ2 ∞ are given by ln γ1 ∞ =0.4 and ln γ1 ∞ =0.2 The vapour
pressure of methyl ethyl ketone and toluene at 323 K are 36.9 and 12.3 kPa
respectively. Assuming that the vapour phase is ideal, the equilibrium pressure (in kPa)
of a liquid mixture containing 90 mol % toluene is
(A) 19 (B) 18 (C) 16 (D) 15 GATE – 2011
Q.147. In a throttling process, the pressure of an ideal gas reduces by 50 %. If CP and
CV are the heat capacities at constant pressure and constant volume, respectively (γ =
CP /CV), the specific volume will change by a factor of
(A) 2 (B) 2 1/γ (C) 2 (γ–1) /γ (D) 0.5 GATE – 2012
Q.150. For an exothermic reversible reaction, which one of the following correctly
describes the dependence of the equilibrium constant (K) with temperature (T) and
pressure (P) ?
(A) K is independent of T and P
(B) K increases with an increase in T and P
(C) K increases with T and decreases with P
(D) K decreases with an increase in T and is independent of P GATE – 2012
Q.152. Consider a binary liquid mixture at constant temperature T and pressure P. If the
enthalpy change of mixing, ΔH = 5 x1 x2 where x1 and x2 . are the mole fraction of species
1 and 2 respectively and the entropy change of mixing
ΔS = – R [x1 ln x1 + x2 ln x2 ] (with R = 8.314 J/mol.K),
then the minimum value of the Gibbs free energy change of mixing at 300 K occurs when
(A) x1 = 0 (B) x1 = 0.2 (C) x1 = 0.4 (D) x1 = 0.5 GATE – 2012
Q.158. A binary; liquid mixture is in equilibrium with its vapor at a temperature T =
300K. The liquid mole fraction x1 of species 1 is 0.4 and the molar excess Gibbs free
energy is 200 J/mol. The value of the universal gas constant is 8.314 J/mol-K, and γi
denotes the liquid-phase activity coefficient of species i. If ln(γ1) = 0.09, then the value of
ln(γ2 ), up to 2 digits after the decimal point, is _______ GATE – 2013
Q.162. Match the following:

(A) Q─III, R─I, S─II

(B) Q─III, R─II, S─IV
(C) P─III, R─II, S─IV
(D) P─III, R─IV, S─I GATE – 2014
Q.164. Consider a binary liquid mixture at equilibrium with its vapour at 25 °C. Antoine
equation for this system is given as
where t is in C and p in Torr. The Antoine constants (A, B, and C) for the system are given in
the following table

The vapour phase is assumed to be ideal and the activity coefficients ( γi) for the non-ideal
liquid phase are given by

If the mole fraction of component 1 in liquid phase (x1) is 0.11, then the mole fraction of
component 1 in vapour phase y1 ) is
(A) 0.50 (B) 0.60 (C) 0.70 (D) 0.80 GATE – 2014
Q.165. For a pure liquid, the rate of change of vapour pressure with temperature is 0.1
bar/K in the temperature range of 300 to 350 K. If the boiling point of the liquid at 2 bar is
320 K, the temperature (in K) at which it will boil at 1 bar (up to one decimal place) is
____________ . GATE – 2015
Q.170. Given that molar residual Gibbs free energy, gR , and molar residual volume, vR ,
are related as
, find gR at T = 27 ºC and P = 0.2 MPa. The gas may be
assumed to follow the virial equation of state, z = 1 + BP/RT, where B = –10-4 m3/mol at
the given conditions (R = 8.314 J/mol.K). The value of gR in J/mol is:
(A) 0.008 (B) –2.4 (C) 20 (D) –20 GATE – 2015
Q.171. A binary mixture of components (1) and (2) forms an azeotrope at 130ºC and x1 =
0.3. The liquid phase non-ideality is described by ln γ1 = Ax22 and ln γ2 = Ax12 , where γ1 ,
γ2 are the activity coefficients, and x1 , x2 are the liquid phase mole fractions. For both
components, the fugacity coefficients are 0.9 at the azeotropic composition. Saturated
vapor pressures at 130 ºC are P1sat = 70 bar and P2sat = 30 bar. The total pressure in bars
for the above azeotropic system (up to two decimal places) is _____________. GATE – 2015
Q.172. The partial molar enthalpy (in kJ/mol) of species 1 in a binary mixture is given by
where x1 and x2 are the mole fractions of species 1 and 2, respectively.
The partial molar enthalpy (in kJ/mol, rounded off to the first decimal place) of species 1
at infinite dilution is ______. GATE – 2016
Q.175. A binary system at a constant pressure with species ‘1’ and ‘2’ is described by the
two-suffix Margules equation, , where g E is the molar excess Gibbs free energy, R
in the universal gas constant, T is the temperature and x1 , x2 are the mole fractions of
species 1 and 2, respectively. At a temperature T, and , where g1 and g2 are the
molar Gibbs free energies of pure species 1 and 2, respectively. At the same temperature,
g represents the molar Gibbs free energy of the mixture. For a binary mixture with 40
mole % of species 1, the value (rounded off to the second decimal place) of is
_______. GATE – 2016
Q.180. The vapour pressure of a pure substance at a temperature T is 30 bar. The actual
and ideal gas values of g/RT for the saturated vapour at this temperature T and 30 bar are
7.0 and 7.7, respectively. Here g is the molar Gibbs free energy; and R is the universal gas
constant. The fugacity of the saturated liquid at these conditions, rounded to 1 decimal
place, is ______bar. GATE – 2017
Q.182. G denotes the Gibbs free energy of a binary mixture, nT denotes the total number
of moles present in the system, µi is the chemical potential of the ith component (µ1≠ 0
and µ1 >µ2 ) and xi is the mole fraction of the i component. The correct variation of G/nT
(in J/mol) at constant temperature and pressure is given by

(A) (B) (C) (D)

GATE – 2018
Q. 186.

GATE – 2019
Q. 187.

GATE – 2019
Q. 190.

GATE – 2019
Q. 192.

GATE – 2019
Q. 193. Mole fraction and activity coefficient of component 1 in a binary liquid mixture
are x1 and γ1 respectively. GE is excess molar Gibbs energy of the mixture. R is
universal gas constant and T is absolute temperature of the mixture. Which one of the
following is always true?

GATE – 2020
Q. 195.

GATE – 2020