CEN 3309 ENGINEERING THERMODYNAMICS
PROBLEM SET
P1: Saturated-vapour steam at 100 kPa (tsat = 93.63 °C) is compressed adiabatically to 300 kPa.
If the compressor efficiency is 0.75, what is the work required and what are the properties of the
discharge stream?
P2: Saturated water vapour enters the turbine of a Carnot cycle at 300 °C and the efficiency of
the cycle is 0.3.
Show the cycle on T-S diagram.
a) Calculate the temperature and the steam quality of the exhaust steam from the turbine.
b) Calculate the steam quality of the stream entering the pump.
P3: Steam generated in a power plant at a pressure of 8600 kPa and at a temperature of 500 °C is
fed to a turbine. Exhaust from the turbine enters a condenser at 10 kPa, where it is condensed to
saturated liquid, which is then pumped to the boiler.
a) Determine the thermal efficiency of a Rankine cycle operating at these conditions.
b) Determine the thermal efficiency of a practical cycle operating at these conditions if the
turbine efficiency and pump efficiency are both 0.75.
c) If the rating of the power cycle of part (b) is 80 000 kW, what is the steam rate and what
are the heat-transfer rates in the boiler and condenser?
P4: Refrigerant-134a enters the compressor of a refrigerator at 140 kPa and –10 °C at a rate of
0.2 m3/min and leaves at 1 MPa. Assume the isentropic efficiency of the compressor is 100
percent. The refrigerant enters the throttling valve at 0.95 MPa and 30 °C and leaves the
evaporator as saturated vapor at –18.5 °C.
Show the cycle on a T-s diagram with respect to saturation lines and determine,
a) the power input to the compressor
b) the rate of heat removal from the refrigerated space
c) the pressure drop and rate of heat gain in the lines between the evaporator and the
compressor.
P5: A heat pump using refrigerant-134a heats a house by using under-ground water at 8 °C as
the heat source. The house is losing heat at a rate of 60000 kJ/h. The refrigerant enters the
compressor at 280 kPa and 0 °C, and it leaves at 1 MPa and 60 °C.
Determine,
a) The power input to the heat pump
b) The rate of heat absorption from the water
c) The increase in electric power input if an electric resistance heater is used instead of a
heat pump.
P6: An absorption refrigeration system receives heat from a source at 110 °C and maintains the
refrigerated space at -20 °C. If the temperature of the environment is 25 °C, what is the
maximum coefficient of performance (COP) this absorption refrigeration system can have?
P7: Refrigerant-134a enters the compressor of a refrigerator as superheated vapor at 0.14 MPa
and -10 °C at a rate of 0.05 kg/s and leaves at 0.8 MPa and 50 °C. The refrigerant is cooled in the
condenser to 26 °C and 0.72 MPa and is throttled to 0.15 MPa. Disregarding any heat transfer
andpressure drops in the connecting lines between the components, determine;
a) The rate of heat removal from the refrigerated space and the power input to the
compressor
b) The adiabatic efficiency of the compressor
c) The coefficient of performance of the refrigerator
P8: Natural gas, assumed here to be pure methane, is liquefied in a simple Linde process.
Compression is to 60 bar and precooling is to 300 K. The separator is maintained at a pressure of
1 bar, and unliquefied gas at this pressure leaves the cooler at 295 K. What fraction of the gas is
liquefied in the process, and what is the temperature of the high-pressure gas entering the throttle
valve?
P9: Describe a graphical interpretation of equations given below:
=
=
P10: The experimental molar enthalpy data of mixing for a binary liquid mixture consist of ethyl
alcohol (1) and benzene (2) are given below:
x2 0 0.1 0.2 0.3 0.4 0.5 0.6 0.8 1.0
ΔH, J/mol 0 111.7 204.3 287.7 365.2 432.8 479.8 433.6 0
Determine graphically partial molar enthalpies of benzene for mole fraction of 0.4, 0.6 and 0.7.
P11: The enthalpy of a binary liquid system of species 1 and 2 at fixed T and P is represented by
the equation
H = 400x1 + 600x2 + x1x2(40x1 + 20x2)
Where H is in J/mol. Determine expressions for and as functions of x1, numerical values
for the pure species enthalpies H1 and H2, and numerical values for the partial enthalpies at
̅1∞ and 𝐻
infinite dilution 𝐻 ̅2∞ .
P12: 2 moles of SnCl4 and 3 moles of CCl4 are mixed at 298 K and 1 atm to form an ideal gas
mixture. For given conditions the entropy values of SnCl4 and CCl4 are 258.3 J/mol K and
214.14 J/molK respectively. Calculate;
a) Δv, Δh, Δu, Δg, Δa, Δs changes of mixing
b) The entropy of the mixture
c) The partial molar entropy of SnCl4 in mixture
P13: The Kammerlingh-Ones equation for 1 mole methane at 20 oC is given as;
PV = 24.055− 4.8678*10−2 P + 8.956*10−5 P2 +10.486*10−10 P4
Calculate the fugacity and the fugacity coefficient of CH4 at 300 atm.
P14: The compressibility factor (z) of a gas at 0 oC is given in terms of P;
z = 1.0 − 5.314*10−4 P + 4.276*10−6 P2 − 3.292*10−9 P3
Calculate the fugacity and the fugacity coefficient of the gas at 300 atm.
P15: 5 dm3 of O2, 10 dm3 of CO2 and 15 dm3 of N2 are mixed reversely at 27 oC and 1 atm to
form an ideal gas mixture. For given conditions calculate Δv, Δh, Δu, Δg, Δa, Δs, q, w changes
of mixing.
P16: Calculate the fugacity of 1-butene at 138 oC and 30.6 atm using the following data:
P, atm z
1 0.991
6.8 0.936
13.61 0.865
20.41 0.781
27.21 0.675
30.61 0.603
34.01 0.496
40.82 0.177
54.42 0.221
68.03 0.267
P17: 1 mole of O2 gas at 1 bar and 0 oC was compressed from 22.71 L to 2.25 L under
isothermal conditions.
a) Calculate ΔG for this compression process by using ideal gas equation
b) Calculate ΔG for this compression process by using Van der waals equation
c) Calculate ΔGR
P18: a) Calculate fugacity and fugacity coefficient for water at 300 oC and 40 bar
b) Calculate fugacity and fugacity coefficient for saturated vapor at 300 oC
P19: A ternary gas mixture contains 20 mole percent A, 35 mole percent B, 45 mole percent C.
At a pressure of 60 atm and temperature of 75 oC, the fugacity coefficients of components A.B
and C in this mixture are 0.7, 0.6 and 0.9 respectively. What is the fugacity of the mixture?
P20: In a mixture of ethylene (C2H4) and oxygen (O2), the fugacities of pure species are 20.7 atm
and 24.4 atm respectively. If the mole fraction of C2H4 in the mixture is 67%, calculate the
partial fugacity of C2H4 and O2 by using the Lewis-Randall’s rule.
P21: Calculate the activity coefficients and excess chemical potential values of C2H4 and O2, by
using the fugacities of pure species at 0 oC and 25 atm, given in the previous problem. The
partial fugacities of C2H4 and O2 are given as 14.4 atm and 8.1 atm respectively, for the mixture
containing 67% C2H4.
P22: At 25 oC and 20 atm the fugacity ( of component (1) in a binary liquid mixture is given
by
x1 – 80x12 + 40x13
Where x1 is the mole fraction of (1) and is in atm. For the stated T and P, determine,
a) The fugacity of pure component (1), f1
b) The fugacity coefficients of pure component (1), φ1
c) An expression for the activity coefficient γ1, as a function of x1 (consider the standard
state for component (1) on the Lewis Randall rule)
P23: Variation of activity coefficient of n-butanol with mole fraction in the water (1) – n-
butanol (2) system is given below:
x1 x2 γ2
1 0 12.5
0.99 0.01 12.3
0.98 0.02 11.6
0.95 0.05 9.92
0.90 0.10 6.05
0.80 0.20 3.12
Determine the activity coefficient of water in the mixture consisting of 10% n-butanol.
P24: An experimental determination of a vapor-liquid equilibrium state for the ethanol (1) –
toluene (2) binary system gave the following results: t = 45 oC, P = 183 mmHg, x1 = 0.3,
y1 = 0.634. In addition, saturation pressures at 45 oC for the pure components are known; P1sat =
173 mmHg, P2sat = 75.4 mmHg. Making the usual assumptions for low-pressure VLE determine
for the given state:
a) The liquid phase activity coefficients: γ1, γ2
b) The value of GE/RT for the liquid phase
c) The value of ΔG/RT for the liquid phase. Note the sign to your answer. How do you
know what this sign must be?
d) Does the liquid phase exhibit positive or negative deviations from ideal solution
behaviour? Does the VLE exhibit positive or negative deviations from Roult’s law?
e) In addition to the data given above, we have for the same conditions a value for the best
of mixing for the liquid phase: ΔH/RT = HE/RT = 0.437. What will be the value of
GE/RT for the liquid phase at 60 oC? Can you determine γ1 and γ2 at 60 oC from this
value? Why or Why not?
P25: VLE in the benzene (1) – toluene (2) system is well represented by Roult’s law and
moderate pressure
t, oC P1, atm P2, atm
88 1.268 0.501
90 1.343 0.535
94 1.506 0.608
98 1.683 0.689
100 1.777 0.732
104 1.978 0.825
a) What are the compositions of the equilibrium liquid and vapour phases for the benzene-
toluene system at 90 oC and 1 atm?
b) Determine the temperature and pressure at which the equilibrium liquid and vapour
phases for this system contain 55 mole percent of benzene and 75 mole percent of
benzene, respectively.
P26: The binary system, acetonitrile (1) – nitromethane (2) can forms closely to Roult’s law. The
relation between the vapour pressure of pure species with temperature are given by Antoine
equations below:
2945.47 2972.64
ln P1sat , kPa = 14.2724− ln P2sat , kPa = 14.2043−
t, C + 224
o
t, C + 209
o
a) Show P-x1 and P-y1 diagrams at 75 oC.
b) Show t-x1 and t-y1 diagrams at 70 kPa.
P27: For a system in which the following reaction occurs,
CH 4(g) + H 2O(g) → CO(g) + 3H 2(g)
assume that 2 mol CH4, 1 mol H2O, 1 mol CO, and 4 mol H2 are present initially. Determine the
expressions for the mole fractions yi as function of ɛ.
P28: Consider a vessel which initially contains only no moles of water vapor. If decomposition
occurs according to the reaction
H 2O(g) →(g) + H2(g)
find the expressions which relate the number of moles and the mole fraction of each chemical
species to the reaction coordinate ɛ.
P29: Consider a system in which the following reactions occur:
CH 4(g) + H 2O(g) → CO(g) + 3H 2(g)
CH 4(g) + 2H 2O(g) → CO2(g) + 4H 2(g)
where the numbers (1) and (2) indicate the value of j, the reaction index. If the system contains
initially 2 mol CH4 and 3 mol H2O, determine expressions for the yi as functions of ɛ1 and ɛ2.
P30: In a bomb calorimeter 0.02 moles of propane (C3H8) is completely oxidized to CO2 and
water vapor on burning with 0.6 moles of air. What is the final composition of the system? Air
contains 21 mole % oxygen and 79 mole % nitrogen. The oxidation reaction is written in
conventional chemical reaction as;
C3 H8 (g) + 5O2 (g) → 3CO2 (g) + 4H2O(g)
P31: The equilibrium constants for the following reaction at 25oC and 45 oC are 0.143 and 0.193,
respectively. Calculate ΔGo at 25 oC and ΔHo.
Note: Assume ΔHo is independent of the temperature.
cyclohexane(s)⎯⎯ ⎯→methylcyclopentan(s)
AlCl3
P32: The equilibrium constants for the given reaction at 700oC and 1000 oC are respectively 0.63
and 1.66.
CO2( g ) + H 2( g )
⎯→CO(g) + H 2O( g )
Calculate
a) The average ΔH value between 700oC and 1000 oC
b) The equilibrium constant at 800oC
P33: Calculate the equilibrium constant for the vapor-phase hydration of ethylene at 145 oC.
C2 H4 ( g ) + H2O( g ) → C2 H5OH( g )
P34: Acetic acid is esterified in the liquid phase with ethanol at 100 oC and atmospheric pressure
to produce ethyl acetate and water according to the reaction
CH3COOH(l) + C2 H5OH(l) → CH3COOC2 H5 (l) + H2O(l)
If initially there is one mole each of acetic acid and ethanol, estimate the mole fraction of ethyl
acetate in the reacting mixture at equilibrium.
P35: The equilibrium pressures for the following reaction at 178 oC and 183 oC are 509 mmHg
and 605 mmHg respectively. Calculate the reaction heat, reaction entropy, reaction free enthalpy
and equilibrium pressure at 298 K
2Ag2O(s) ⎯
⎯→4Ag(s) + O2( g )
Note: Heat capacities (J/molK) of the components: Cp (Ag2O(s)) = 57.98 + 37.20*10-3T
Cp (Ag(s)) = 23.41 + 6.27*10-3T
Cp (O2(g)) = 27.17 + 4.18*10-3T
P36: An elementary nuclear-powered gas-turbine power plant operates as shown in figure. Air
entering at point 1 is compressed adiabatically to point 2, is heated at constant pressure between
points 2 and 3, and is expanded adiabatically from point 3 to point 4. Specified conditions of
each stream are given in the figure The temperature of surroundings is Tσ = 293 K. Make a
thermodynamic analysis for the compressor, nuclear reactor and turbine. Calculate the
thermodynamic efficiency of the system and evaluate the results. Assume air is an ideal gas for
which CP=(7/2)R.
ΔHreactor= - 8995.96kJ/kmol
ΔSreactor= + 9.75 kJ/kmol K
Nuclear
Reactor
650q°C
T2 = 538.85 K T3 = 848K
P2 = 5 atm /\/\/\/\/\/\/\/\/\/\/ P3 = 5 atm
2 3
Turbine
Compressor Ws
= 0.85 = 0.80
Wc
4
1
T1 = 303K T4 = 597.94K
P1 = 1atm P4 = 1atm
