Thermodynamics
Thermodynamics
Q.1 Assume that benzene is insoluble in water. The normal boiling points of benzene and water are 80.10 C
and 1000 C respectively. At a pressure of l atm, the boiling point of a mixture of benzene and water is
(A) 80.1 0C
(C) 1000 C
Q.2 On a p-V diagram of an ideal gas, suppose a reversible adiabatic line intersects reversible isothermal
P
line at point A. Then at point A, the slope of the reversible adiabatic line and the slope of the
V S
P
reversible isothermal line are related as
V T
Where Cp / Cv
P P P P
(A) (B)
V S V T V S V T
P P P 1 P
(C) (D)
V S V T V S V T
Q.3 The thermal efficiency of reversible heat engine operating between two given thermal reservoirs is 0.4.
The device is used either as a refrigerator or as a heat pump between the same reservoirs. Then the
coefficient of performance as a refrigerator (COP)R and the coefficient of performance as a heat pump
(COP)HP are
and 3 respectively
CH4 (g) 2H2O(g) CO2 (g) 4H 2 (g) Then K1 , K 2 and K 3 are related as
K1 K 2
(C) K 3 (D) K3 (K1K 2 )2
2
Q.5 A reasonably general expression for vapour-liquid phase equilibrium at low moderate pressures is
i YP
i i Xi f i .
0
Where i is a vapour fugacity coefficient i is the liquid activity coefficient, and f i is the fugacity of pure
component i.
Q.6 High pressure stream is expanded adiabatically and reversibly through a well insulated turbine, which
produces some shaft work. If the enthalpy change and entropy change across the turbine are
represented by H and S , respectively, for this process
Q.7 The Maxwell relation derived from the differential expression for the Helmholtz free energy ( dA ) is
T P S V
(A) (B)
V S S V P T T P
V T S P
(C) (D)
S P P S V T T V
cyclohexane. The vapour pressure of water at 1500 C is 4.69 atm. At 1500 C , the vapour pressure of
methyl cyclohexane 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
Q.9 Air enters an adiabatic compressor at 300 K. The exit temperature for a compression ratio of 3, assuming
air to be an ideal gas ( CP / CV 7 / 5 ) and the process to be reversible, is
Q.10 Which of the following conditions are satisfied at the critical point by the p-V-T relation of a real fluid?
2 P P 2P P
(A) 2 0 (B) 2 0; 0
V T V T V T V T
2P P 2P P
(C) 2 0; 0 (D) 2 0; 0
V T V T V T V T
Q.11 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
Q.12 Which of the following identities can be most easily used to verify stream table data for superheated
steam?
T P T V
(A) (B)
V S S V P S S P
P S V S
(C) (D)
T V V T T P P T
Q.13 The number of degree of freedom for an azeotropic mixture of ethanol and water in vapour-liquid
equilibrium is
Q.14 A rigid vessel, containing three moles of nitrogen at 300 C is heated to 2500 C . Assume the average heat
capacities of nitrogen to be Cp 29.1J / mol 0C and Cv 20.8 J / mol- 0C . The heat required neglecting the
Q.16 1m3 of an ideal gas at 500 K and 1000 kPa expands reversibly to 5 times its initial volume in an insultaed
container. If the specific heat capacity (at constant pressure) of the gas is 21 J /mol-K, the final
temperature will be
Q.17 For estimation of hear capacity of a solid compound, one can use
Q.18 For organic compounds, Group Contribution Method can be used for estimation of
Q.19 When dilute aqueous solution of two salts are mixed, the process is associated with
Q.20 In Joule’s experiments, an insulated container contains 20 kg of water initially at 250 C . It is stirred by
an agitator, which is made to turn by a slowly falling body weighing 40 kg through a height of 4 m.
The process is repeated 500 times. The acceleration due to gravity is 9.8m/s2 . Neglecting the heat
Q.21 One mole of nitrogen at 8 bar and 600 K is contained in a piston –cylinder arrangement. It is brought
to 1 bar isothermally against a resisting pressure of 1 bar. The work done (in joule) by the gas is
Q.23 Heat capacity of air can be approximately expresses as Cp 26.693 27.365 103 T , where C p is in
J/mol- K and T is in kelvin. The heat given off by 1 mol of air, when cooled at 1 atmospheric pressure
Q.24 A solid metallic block weighning 5 kg has an initial temperature of 5000 C , 40 kg of water initially at
250 C is contained in a perfectly insulated tank. The metallic block is brought into contact with water.
Both of them come to equilibrium. Specific heat of block material is 0.4 kJ/kg K. Ignoring the effect of
expansion and contraction and also the heat capacity of tank, the total entropy change in kJ / kg K is
(A) 1.87 (B) zero (C) 1.26 (D) 3.91
Q.25 The following heat engine produces power of 100,000 kW. The heat engine operates between 800 K and
300 K. It has a thermal efficiency equal to 50% of that of the Carnot engine for the same temperatures.
The rate at which heat is absorbed from the hot reservoir is
(A) 100,000 kW (B) 160,000 kW (C) 200,000 kW (D) 320,000 kW
Q.26 A steam turbine operates with a superheated steam flowing at 1 kg/s. This steam is supplied at 44 bar
At 41 bar, 1000 C
Enthalpy of saturated steam 2799.9 kJ/ kg
Entropy of saturated steam 6.0583 kJ /kg K
aqueous solution of methanol at 600 C exerts a pressure of 39.223 kPa, the liquid phase and vapour
phase mole fraction of methanol are 0.1686 and 0.5714 respectively. Activity coefficient of methanol is
1 kg of saturated steam at 1000 C and 1.01325 bar is contained in a rigid walled vessel. It has a volume
1.673m3 . It cools to 980 C , the saturation pressure is 0.943 bar; 1 kg of water vapour under these
Q.30 For an ideal gas mixture undergoing a reversible gaseous phase chemical reaction, the equilibrium
constant
Q.31 As pressure approaches zero, the ratio of fugacity to pressure (f/p) for a gas approaches
(A) Zero (B) Unity
Q.33 A car tyre of volume 0.057 m3 is inflated to 300 kPa at 300 K. After the car is driven forten hours, the
pressure in the tyre increases to 330 kPa. Assume air is an ideal gas and CV for air is 21 J/mol-K. The
V V b V V b
(A) RT ln f (B) RT ln f (C) RT ln f (D) RT ln f
Vi Vi Vi b Vi b
Q.35 A cyclic engine exchanges heat with two reservoirs maintained at 100 and 3000 C respectively. The
maximum work (in joule) that can be obtained from 1000 J of heat extracted from the hot reservoir is
1
NO O2 NO2 , G0 35kJ/mol
2
The boiling points for pure water and pure toluene are 1000 C and 110.60 C respectively. Toluene and
water are completely immiscible in each other. A well-agitated equimolar mixture of toluene and water
is prepared.
Q.37 The temperature at which the above mixture will exert a pressure of one standard atm is
Q.38 At a total pressure of one standard an exerted by the vapours of water and toluene, the mole fraction
of water x w , in the vapour phase satisfies
Q.39 In Vander Waals equation of state, what are the criteria applied at the critical point to determine the
parameters a and b?
P 2P V 2V
(A) 0; 2 0 (B) 0; 2 0
V T V T P T P T
P 2P V 2V
(C) 0; 2 0 (D) 0; 2 0
V V T V T P T P
(C) The efficiency of heat engine increases as the temperature of the heat source is increased while
keeping the temperature of the heat sink fixed
(D) A cyclic process can be devised whose sole effect is to transfer heat from a lower temperature to
higher temperature
Q.41 A process flow sheet analysis results in the degree of freedom having a value of 2-. Which one of the
following steps must be next carried out?
(A) Identify and add two new independent equations from process model
(B) Remove two equations that have been wrongly assumed to be independent
(D) Assign value to one variable and remove one equation that was wrongly assumed to be
independent
Q.42 A Carnot heat engine cycle is working with an ideal gas. The work performed by the gas during the
adiabatic expansion and compression steps W1 and W2 respectively, are related as
Q.43 The van Laar activity coefficient model for a binary mixture is given by the form
A* B*
ln 1 2
;ln 2 2
A * x1 B* x 2
1 1
B* x 2 A * x2
Q.44 What is the actual power required to drive a reciprocating air compressor which has to compress 34 m3
of air per minute from 1.013 105 N/m2 to 4.052 105 N/m2 ?
Assume that pVl.25 is constant, where, P is the pressure and V is the volume, and the efficiency of the
compressor is 85%
A frictionless cylinder piston assembly contains an ideal gas. Initially pressure (p1 ) 100 kPa ,
Temperature (T1 ) 500 K and volume (V1 ) 700 106 m3 . This system is supplied with 100 J of heat and
pressure is maintained constant at 100 kPa. The enthalpy variation is given by H (J/mol)
3000 50T; where, T is the temperature in kelvin and the universal gas constant R 8.314
J/mol-K
(A) 700 106 (B) 866.32 106 (C) 934.29 106 (D) 1000.23 106
Q.46 The change in interval energy of the gas in joule is
(A) Zero (B) 100 (C) 23.43 (D) 83.37
Q.47 A heat engine operates at 75% of the maximum possible efficiency. The ratio of the heat source
temperature (in kelvin) to the heat sink temp (in kelvin) is 5/3. The fraction of the heat supplied that is
converted to work is
(A) 0.2 (B) 0.3 (C) 0.4 (D) 0.6
Q.48 For the isentropic expansion of an ideal gas from the initial conditions P1 , T1 to the final conditions
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
Q.52 Pure A at 200 0C is fed to a steady state adiabatic continuous reactor at the rate of 100 kg/h, where it
undergoes an exothermic reaction to give its isomer B. The product stream is at temperature 500 0C .
The heat of reaction is 21kJ/mol of A and the specific heat of the reaction mixture is constant at
Q.53 The molar density of water vapour at the normal boiling point of water is 33mol/m3 . The
compressibility factor under these conditions is close to which one of the following? R 8.314 J / mol-K
(A) 0.75 (B) 1 (C) 1.25 (D) 1.5
Q.54 If TA and TB are the boiling points of pure A and B respectively, and TAB is that of a non-homogeneous
Q.55 The state of an ideal gas is changed from (T1 , P1 ) to (T2 , P2 ) in a constant volume process. To calculate
Q.56 The change in entropy of the system undergoing a cyclic irreversible process is
(A) Greater than zero (B) Less than zero
(C) Equal to zero (D) Equal to the S surrounding
Q.57 Parameters a and b in the van der Waals and other cubic equations of state represent
(A) A-molecular weight, b-molecular polarity
(B) A-molecular size, b-molecular attraction
(C) A-molecular size, b-molecular speed
(D) A-molecular attraction, b-molecular size
"i" , the mixture property M of a binary non-ideal mixture of components 1 and 2, is given by
(A) x1m1 x 2 m2 (B) x1m1R x 2 m2R (C) x1m1 x 2 m2 (D) x1m1E x 2 m2E
Q.59 For the two paths as shown in the figure, one reversible and one irreversible, to change the state of the
system from a to b,
(A) (T / V)S (p / S)V (B) (p / T)V (S / V)T
(C) (T / p)S (V / S)p (D) (V / T)p (S / p)T
Q.61 Which of the following represents the Carnot cycle (ideal engine)?
Q.62 2 kg of steam in a piston-cylinder device at 400 kPa and 1750 C undergoes a mechanically reversible,
isothermal compression to a final pressure such that the steam becomes just saturated. What is the
work W, required for the process.
Data
V 0.216 m3 /kg
U 2579kJ/kg, S 6.622kJ/kg-K
(A) zero (B) 230 kJ (C) 334 kJ (D) 388kJ
attains equilibrium at 400 K and 3 bar. The standard Gibbs free energy change of reaction at these
conditions is G0 4000 J/mol . For 2 mol of an equimolar feed of ethylene and steam, the equation in
terms of the extent of reaction (in mol) at equilibrium is
(2 ) (1 ) 2
(A) 0.3 0 (B) 0.9 0
(1 )2 (2 )
(2 )
(C) 0.3 0 (D) 0.9 0
(1 )2 (1 )2
Q.64 A methanol-water vapour liquid system is equilibrium at 600 C and 60 kPa . The mole fraction of
methanol in liquid is 0.5 and in vapour is 0.8. Vapour pressure of methanol and water at 600 C are 85
kPa and 20 kPa respectively. Assuming vapour 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
Q.65 What is excess Gibbs free energy (G E ,in / J/mol) of the liquid mixture?
Q.66 A perfectly insulated cylinder of volume 0.6 m3 is initially divided into two parts by a thin, frictionless
piston, as shown in the figure. The smaller part of volume 0.2 m3 has ideal gas at 6 bar pressure at 1000 C
At certain instant of time t, the stopper is removed and the piston moves out freely to the other end.
The final temperature is
Q.67 The cylinder insulation is now removed and the piston is pushed back to restore the system to its initial
state. If this is to be achieved only by doing work on the system (no heat addition, only heat removal
allowed), what is the minimum work required?
(A) 3.4 kJ (B) 107 kJ (C) 132 kJ (D) 240 KJ
Q.68 For a Carnot refrigerator operating between 400 C and 250 C , the coefficient of performance is
(A) 1 (B) 1.67 (C) 19.88 (D) 39.74
Q.69 The work done by one mole of a Vander walls fluid undergoing reversible isothermal expansion from
initial volume Vi to final volume Vf is
V V b
(A) RT ln f (B) RT ln f
Vi Vi b
V b 1 1 V b 1 1
(C) RT ln f a (D) RT ln f a
Vi b Vf Vi Vi b Vf Vi
Q.70 The standard Gibbs free energy change and enthalpy change at 250 C for the liquid phase reaction
CH3COOH (l) C2 H 5OH(l)
CH3COOC2 H 5 (l) H 2O(l)
are given as G0298 - 4650 J/mol and H0298 -3640 J/mol . If the solution is ideal and enthalpy change
A binary mixture containing species 1 and 2 forms an azeotrope at 105.40 C and 1.013 bar. The liquid
phase mode fraction of component 1 (x1 ) of this azeotrope is 0.62. At 105.40 C , the pure component
vaport 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
2
x ln 2
A 1 2 ln 1 ,
x1 ln 1
2
x ln 1
B 1 1 ln 2 ,
x 2 ln 2
Q.71 The activity coefficients ( 1 , 2 ) under these conditions are
(A) (0.88, 0.66) (B) (1.15, 1.52) (C) (1.52, 1.15) (D) (1.52, 0.88)
Q.72 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)
Q.73 The molar volume of (V) a binary mixture of species 1 and 2 having mole fractions x1 and x 2
closed system. Which one of the following is true for internal energy (U) and Gibbs free energy (G) of
the gas at the two states?
Q.75 For a binary mixture at constant temperature and pressure, which one of the following relations
between activity coefficient ( i ) mole fraction (x i ) is thermodynamically consistent?
1 2
(A) ln 1 1 2x1 x12 , ln 2 x1 (B) ln 1 1 2x1 x12 , ln 2 x12
2
1
(C) ln 1 1 2x1 x12 , ln 2 x12 (D) ln 1 1 2x1 x12 , ln 2 x12
2
5
An ideal gas with molar heat capacity CP R
2
(Where, R 8.314 j/mol-K ) is compressed adiabatically from 1 bar and 300 K to pressure P2 in closed
system.
The final temperature after compression is 600 K and the mechanical efficiency of compression is 50%.
Q.78 An equimolar liquid mixture of species 1 and 2 is in equilibrium with its vapour at 400 K. At this
temperature, the vapour pressure of the species are P1sat 180 kPa and P2sat 120 kPa. Assuming that
Q.79 A new linear temperature scale, denoted by 0 S , has been developed, where the freezing point of water
is 2000 S and the boiling point is 4000 S . On this scale, 5000 S corresponds, in degree Celsius to
mixture at 150 kPa and 300 K . At the exit condition the enthalpy of the saturated liquid is 500kJ/kg and
the enthalpy of the saturated vapour is 2500 kJ/kg. The percentage of the original liquid, which
vaporize is
(A) 87.5% (B) 67 % (C) 12.5% (D) 10%
Q.81 At constant T and P, the molar density of a binary mixture is given by 1 x 2 where x 2 is the mole
fraction of component 2. The partial molar volume at infinite dilution for component 1. V1 is
Q.82 Minimum work (W) required to separate a binary gas mixture at a temperature T0 and pressure P0 is
fˆ fˆ
W RT0 Y1 ln 1 Y2 ln 2
f f
pure,1 pure,2
Where, y1 and y 2 are mole fractions, f pure,1 and f pure 2 are fugactities of pure species at T0 and P0 and f̂1
and f̂ 2 are fugactites of species in the mixture at T0 , P0 . If the mixture is ideal then W is
Q.83 1 mol of methane is contained in a leak proof piston –cylinder assembly at 8 bar and 1000K. The gas
undergoes isothermal expansion to 4 bar under reversible conditions. Methane can be considered as an
ideal gas under these conditions. The value of universal gas constant is 8.314 J/mol-K . The heat
transferred (in kJ) during the process is
(A) 11.52 (B) 5.76 (C) 4.15 (D) 2.38
Q.84 Consider a binary mixture of methyl of methyl ethyl ketone (component 1) and toluene (component 2).
At 323 K, the activity coefficients 1 and 2 are given by
ln 1 x 22 (1 2 42 x1 )
ln 2 x12 (1 2 4 2 x 2 )
Where, x1 and x 2 are the mole fractions is the liquid, mixture and 1 and 2 are parameters independent
of composition. At the same temperature, the infinite dilution activity coefficients 1 and 2 are given
by ln 1 0.4 and 2 0.2 . The vapour pressures of methyl ethyl ketone and toluene at 323 K are 36.9
kPa 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
(Component 2) at 300 K and 1 bar are given by H1 3600x 22 H2 3600x12 where x1 and x 2 the mole
fractions. When 1 mol of benzene is added to 2 mol of cyclohexane, the enthalpy change (in joule) is
(A) 3600 (B) 2400 (C) 2000 (D) 800
Q.86 In a throttling process, the pressure of an ideal gas reduces by 50%. If C P and CV are the heat capacities
CP
at constant pressure and constant volume respectively and , then the specific volume will
CV
change by a factor of
1
temperature Tc,out .
Neglect any heat loss from the heat exchanger to the surrounding. If Th,in Tc,in , then for a given time
temperature Ts and specific volume Vs . The container is filled with the gas until the pressure in the
container reaches Ps .
There is no heat transfer between the supply line to the container and kinetic and potential energies are
negligible. If C P and CV are the heat capacities at constant pressure and constant volume respectively
CP
and , then the final temperature of the gas in the container is
CV
( 1)Ts
(A) Ts (B) Ts (C) ( 1)Ts (D)
change of mixing is S R[x1 ln x1 x 2 ln x 2 ] (with R 8.314J/mol-K ), then the minimum value of the
Q.91 A gaseous system contains H 2 , I2 and HI, which participate in the gas-phase reaction
2HI H2 I2
Q.92 The thermodynamic state of a closed system containing a pure fluid changes from (T1 , p1 ) to (T2 , p2 ) ,
where T and p denote the temperature and pressure, respectively. Let Q denote the heat adsorbed (> 0
if absorbed by the system) and W the work done (> 0 if done by the system). Neglect changes in kinetic
and potential energies. Which one of the following is correct?
(C) (Q - W) is path-independent
(D) (Q W) is path-independent
Q.93 An equation of state is explicit in pressure p and cubic in the specific volume V .At the critical point C,
the isotherm passing through C satisfies
P 2p P 2P
(A) 0, 2 0 (B) 0, 2 0
V V V V
P 2P P 2P
(C) 0, 2 0 (D) 0, 2 0
V V V V
Q.94 The units of the isothermal compressibility are
Q.95 In a process occurring in a closed system F, the heat transferred from F to the surroundings E, is 600J.
If the temperature of E is 300K and that of F is in the range 380-400 K, the entropy changes of the
surroundings (SE ) and system (SF ) , in J/K, are given by
(A) (B)
(C) (D)
Group 1 Group 2
(P) G (I) Arrhenius equation
n i T,P,n ji
(Q) G (II) Reaction equilibrium constant
n i S,V,n ji
(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
U U H H
(A) V nR (B) P nR
V S S V P S S P
U H H U
(C) V nR (D) P nR
P S S P P S S V
Q.101 Consider a binary liquid mixture at equilibrium with its vapour at 250 C . Antoine equation for this
B
system is given as log10 P1sat A
tC
Where t is in 0 C and p in Torr. The Antoine constants (A, B and C) for the system are given in the
following table.
Component A B C
1 7.0 1210 230
2 6.5 1206 223
The vapour phase is assumed to be ideal and the activity coefficients ( i ) for the non-ideal liquid phase
are given by
ln ( 1 ) x 22 [2 0.6x1 ]
If the mole fraction of component 1 in liquid phase (x1 ) is 0.11, then the mole fraction of component in
Q.102 If v, u, s and g represent respectively the molar volume, molar internal energy, molar entropy and
molar Gibbs free energy, then match the entries in the left and right columns below and choose the
correct option.
g
(Q) (II) Pressure
P T
g
(R) (III) V
T p
u
(S) (IV) S
s v
(A) P-II, Q-III, R-IV, S-I (B) P-II, Q-IV, R-III, S-I
(C) P-I, Q-IV, R-II, S-III (D) P-III, Q-II, R-IV, S-I
Q.104 Three identical closed systems of a pure gas are taken from an initial temperature and pressure (T1 , P1 )
to a final state (T2 , P2 ) , each by a different path. Which of the following is always true for the three
systems? ( represents the change between the initial and final states: U,S,G,Q and W are internal
energy, entropy, Gibbs free energy, heat added and work done, respectively.)
(C) S, W,Q are same (D) G, U, S are same
Q.105 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 ______.
Q.106 An ideal gas is initially at a pressure of 0.1 MPa and a total volume of 2 m3 .It is first compressed to 1
MPa by a reversible adiabatic process and then cooled at constant pressure to a final volume of 0.2 m3 .
The total work done (in kJ) on the gas for the entire process (up to one decimal place) is Data: R = 8.314
J/mol K; heat capacity at constant pressure (Cp ) 2.5R
Q.107 Given that molar residual Gibbs free energy, g R and molar residual volume V R , are related as
gR P V
R
dP , find g at T 27 C and P 0.2MPa . The gas may be assumed to follow the vital
R 0
RT 0
RT
BP
equation of state, Z 1 , where B 104 m3 / mol at the given conditions (R 8.314J/mol.K).
RT
J
The value of g R in is :
mol
(A) 0.08 (B) –2.4 (C) 20 (D) –20
Q.108 A binary mixture of components (1) and (2) forms an azeotrope at 1300 C and x1 0.3 . The liquid phase
non-ideality is described by ln 1 Ax 22 and ln 2 Ax12 , where 1 , 2 are the activity coefficients, and
x1 , x 2 , are the liquid phase mole fractions. For both components, the fugacity coefficients are 0.9 at the
The total pressure in bars for the above azeotopic system (up to two decimal piaces) is
Q.109 The partial molar enthalpy (in kJ/mol) of species 1 in a binary is given by h1 2 60x 22 100x1x 22 , where
x1 and x 2 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 _______.
Q.110 An ideal gas in adiabatically and irreversibly compressed from 3 bar and 300 K to 6 bar in a closed
system. The work required for the irreversible compression is 1.5 times the work that is required for
reversible compression from the same initial temperature and pressure to the same final pressure.
The molar heat capacity of the gas at constant volume is 30 J mol1K 1 (assumed to be independent of
temperature): universal gas constant R is 8.314 J mol1K 1 ; ratio of molar heat capacities is 1.277.
The temperature (in K, rounded off to the first decimal place) of the gas at the final state in the
irreversible compression case is______
Q.111 A gas obeying the Clausius equation of state is isothermally compressed from 5 MPa to 15 MPa in a
RT
closed system at 400 K. The Clausius equation of state is P where P is the pressure, T is the
v b(T)
temperature, v is the molar volume and R is the universal gas constant. The parameter b in the above
equation varies with temperature as b(T) b0 b1T with b0 4 105 m3 mol-1 and
b1 1.35 107 m3 mol1K 1 . The effect of pressure on the molar enthalpy (h) at a constant temperature is
h v
given by v T .
P T T P
Let h i and h f denote the initial and final molar enthalpies, respectively. The change in the molar
enthalpy h f h i (in J mol1 , rounded off to the first decimal place) for this process is_______.
Q.112 A binary system at a constant pressure with species ‘1’ and ‘2’ is described by the two-suffix Margules
gE
equation, 3x1x 2 where g E is the molar excess Gibbs free energy, R is the Universal gas constant, T
RT
is the temperature and x1 , x 2 are the mole fractions of species 1 and 2, respectively.
g1 g
At a temperature T, 1 and 2 2 , where g1 and g 2 are the molar Gibbs free energies of pure
RT RT
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
g
decimal place) of is________.
RT
Q.113 Water is heated at atmospheric pressure from 400 C to 800 C using two different processes. In process-I,
the heating is done by source at 800 C . In process-II, the water is first heated from 400 C to 600 C by a
source at 600C and then from 600 C to 800 C by another source of 800 C . Identify correct statement.
(A) Enthalpy change of water in process-I is greater than the enthalpy change in process-II
(B) Enthalpy change of water in process-II is greater than the enthalpy change in process-I
(C) Process-I is closer to reversibility
(D) Process-II is closer to reversibility
Q.114 The volumetric properties of two gases M and N described by the generalized compressibility chart
which expresses the compressibility factor (Z) as a function of reduced pressure and reduced
temperature only. The operating pressure (P) and temperature (T) of two gases M and N along with
their critical properties (PC,Tc) are given in the table below.
Gas P (bar) T (K) PC (bar) PC (bar)
M 25 300 75 150
N 75 1000 225 500
ZM and ZN are the compressibility factor of the gases M and N under the given operating conditions
respectively. The relation between ZM and ZN is
(A) ZM 8 ZN (B) ZM 3ZN
Q.115 A sparingly soluble gas (solute) is in equilibrium with a solvent at 10 bar. The mole fraction of the
solvent. In the gas phase is 0.01. At the operating temperature and pressure the fugacity coefficient of
the solute in the gas phase and Henry’s law constant are 0.92 and 1000 bar respectively. Assume that
liquid phase obey Henry law. The mole% of solute in the liquid phase. Rounded to 2 decimal place, is
_______.
Q.116 The pressure of liquid is increased isothermally The molar volume of liquid decrease from
50.45 106 m3 /mol to 48 10 6 m3 /mol during the process. The isothermal compressibility of the liquid
is 109 Pa 1 which can be assumed to be independent of pressure. The change in the molar gibbs free
energy of the liquid, rounded to nearest integer is ______s/mol
Q.117 The vapor pressure of a pure substance at a temperature T is 30 bar The actual and ideal gas values of
g/RT for the saturated vapor at this temperature T and 30 bar are 7.0 and 7.7 respectively. Here g is the
molar gibbs free energy by and R is the universal gas constant the fugacity of the saturated liquid at
these conditions rounded to a decimal place is _______ bar.
ETBE Water
TBA EtOH
The equilibrium constant for this reaction is K c 1 . Initially, 74g of TBA is mixed with 100 g for aqueous
solution containing 46 weight% ethanol. The molecular weights are 74 g/mol for TBA, 46 g/mol for
EtOH, 102 g/mol for ETBE, and 18 g/mol for water.
Q.120 G denotes the Gibbs free energy of a binary mixture, n T denotes the total number of moles present in
the system, i is the chemical potential of the i th component ( i 0 and 1 2 ) and x i is the mole
G
fraction of the i th component. The correct variation of (in J / mol ) at constant temperature and
nT
pressure is given by
(A) (B)
(C) (D)
equal to 60. The pressure and temperature at the top of the tube are 100 kPa and 200C respectively.
Consider the universal gas constant and acceleration due to gravity as 8.314 J mol1K 1 and 9.81 m s 2
respectively. If the gas is ideal, the pressure (in kPa) at the bottom of the tube will be ____________
(rounded off to third decimal place).
Q.122 In a closed piston-cylinder system, methane was observed to obey the following equation of state
P(V nb) nRT
where b = 0.029 m3 /mol . The temperature and volume are 500 0 C and 5 m3 respectively for 100 moles of
methane. At this state of the system, the isobaric rate of change of temperature with volume (in 0 C / m3
Q.124 For a single component system, vapor (subscript g) and liquid (subscript f) coexist in mechanical,
thermal and phase equilibrium when
(A) u g u f (Equality of specific internal energy)
Q.125 Consider a rigid, perfectly insulated, container partitioned into two unequal parts by a thin membrane
(see figure). One part contains one mole of an ideal gas at pressure Pi and temperature Ti while the
other part is evacuated. The membrane ruptures, the gas fills the entire volume and the equilibrium
Pi
pressure is Pf . If C p (molar specific heat capacity at constant pressure), C v (molar specific heat
4
capacity at constant volume) and R (universal gas constant) have the same units as molar entropy, the
change in molar entropy Sr Si is
(C) R ln 4 (D) Cp ln 2
The Gibbs free energy of the reaction g0rxn 22972.3 J/mol and universal gas constant
R 8.314 J/(mol K) . Both the reactants and products can be assumed to be ideal gases. If initially only
4 mol of H 2S and 1 mol of CO are present, the extent of the reaction (in mol) at equilibrium is ______
(rounded off to two decimal places).
Q.128 Consider a vessel containing steam at 180 0C . The initial steam quality is 0.5 and the initial volume of
the vessel is 1 m3 . The vessel loses heat at a constant rate q under isobaric conditions so that the quality
of steam reduces to 0.1 after 10 hours. The thermodynamic properties of water at 180 0C are (subscript
g : vapor phase, subscript f : liquid phase) :
Specific volume :
vg 0.19405 m3 /kg, vf 0.001127 m3 /kg,
Specific enthalpy :
h g 2778.2 kJ/kg, h f 763.21 kJ/kg
The rate of heat loss q (in kJ/hour) is _______ (rounded off to the nearest integer).
Q.129 For a given binary system at constant temperature and pressure, the molar volume (in m3 /mol ) is given
by : 30x A 20x B x A x B (15x A 7x B ) , where x A and x B are the mole fractions of components A and
B, respectively. The volume change of mixing mix (in m3 /mol ) at x A 0.5 is ________ (rounded off to
one decimal places).
Q.130 A fractionator recovers 95 mol % n – propane as the distillate from an equimolar mixture of n – propane
and n – butane. The condensate is a saturated liquid at 55 0C . The Antoine equation is of the form,
Assuming Raoult’s law, the condenser pressure (in bar) is ________ (rounded off to one decimal place).
GE
(C) lim 0.5 (D) lim 1 0
x1 1 RT x1 1
The efficiencies of the engines C1 and C2 are 0.40 and 0.35, respectively. If the temperature of Reservoir
R 1 is 800 K, then the temperature (in K) of Reservoir R 3 is _____(round off to nearest integer).
Q.133 Consider the gas phase reaction N2O4 2NO2 occurring in an isothermal and isobaric reactor
maintained at 298 K and 1.0 bar. The standard Gibbs energy change of the reaction at 298 K is
G0298 5253 J mol1 .The standard states are those of pure ideal gases at 1.0 bar. The equilibrium
mixture in the reactor behaves as in the ideal gas. The value of the universal gas constant is
8.314 J mol1K 1 . If one mole of pure N 2O4 is initially charged to the reactor, the fraction of N 2O4 that
decomposes into NO2 at equilibrium is
(A) 0 (B) 0.17 (C) 0.38 (D) 1
Q.134 A pure gas obeys the equation of state given by
PV BP
1
RT RT
Where P is the pressure, T is the absolute temperature, V is the molar volume of the gas, R is the
universal gas constant, and B is a parameter independent of T and P. The residual molar Gibbs energy,
G R , of the gas is given by the relation
P
GR dP
(Z 1)
RT 0 P
Where Z is the compressibility factor and the integral is evaluated at constant T. If the value of B is
1104 m3mol1 , the residual molar enthalpy (in J mol1 ) of the gas at 1000 kPa and 300 K is
(A) 100 (B) 300 (C) 2494 (D) 30000
The net heat flowing into the system for process I is Q I and that for process II is Q II . The value of
QI QII (in J) is
1 B 2 C 3 C 4 A 5 C
6 B 7 B 8 A 9 A 10 A
11 A 12 D 13 B 14 A 15 A
16 B 17 C 18 A 19 B 20 B
21 B 22 B 23 C 24 B 25 D
26 C 27 A 28 B 29 C 30 D
31 B 32 B 33 B 34 D 35 A
36 C 37 A 38 C 39 A 40 C
41 B 42 D 43 B 44 A 45 B
46 D 47 B 48 B 49 A 50 D
51 C 52 B 53 B 54 A 55 B
56 B 57 D 58 A 59 B 60 A
61 C 62 D 63 D 64 B 65 C
66 D 67 C 68 C 69 D 70 B
71 B 72 C 73 B 74 B 75 D
76 D 77 C 78 D 79 C 80 C
81 C 82 B 83 B 84 C 85 B
86 A 87 B 88 A 89 A 90 D
91 B 92 C 93 D 94 B 95 D
96 B 97 B 98 D 99 C 100 D