Thermodynamics (16CH33)

Question bank for UNIT I

1 Define the following: System/surrounding, State/Path functions,

Intensive/extensive properties, Reversible/irreversible process, Open
system/closed system/isolated system, state/properties.

2 Classify the following into intensive and extensive properties:

Internal energy, entropy, temperature, pressure, viscosity, refractive index,
density, specific volume, specific internal energy

3 Define: Equilibrium, Mechanical/thermal/phase and chemical equilibrium

4 Reversible and irreversible process

5 Mathematical representation of state and path function

6 Define energy, work, Classification of energy, power, work of expansion on PV

diagram

7 Define force, pressure, units of pressure

8 Units of universal gas constant R with pressure

9 RT
For an ideal gas, show that the specific volume v= , is a state function.
P

1 RT
Show that dW =PdV , is a path function where v= ,
0 P
1 1kgmole of an ideal gas at pressure of 700x10 4 N/m2 and at 300k is confined to a
1 piston and cylinder arrangement as shown in fig. The piston is held in position
by latches. The weight of the piston and piston rod together is 20 kg and that of
the weight W, 45 kg.The space behind the piston is evacuated. The cylinder is
immersed in a constant temperature bath maintained at 300 k.
W

Evacuated
space

The latches holding the piston are removed and the piston is allowed to expand
rapidly through a distance of 40 sm and once again held by latches. If the c/s
area of the cylinder is 1 cm2. Calculate the work obtained if
(i) Gas alone is the system
(ii) Gas + Piston rod is system
(iii) Gas + piston rod + weight is system

1 If the gas taken as system in the above problem is expanded reversibly from
2 700x104 N/m2 to 638 x 104 at a constant temperature of 300 k. Calculate the
work. R = 8.314 Nm/kgmolek.

1 A spherical balloon of diameter 0.5 m contains a gas at 1 bar and 300 k. The gas
3 is heated and the balloon is allowed to expand. The pressure inside the balloon is
found to expand. The pressure inside the balloon is found to vary linearly with
the diameter. What would be the work done by the gas when the pressure inside
reaches 5 bar.

1 Nitrogen gas is confined in a cylinder and the pressure of the gas is maintained
4 by a weight placed on the piston. The mass of the piston and the weight together
is 50 kg. The acceleration due to gravity 9.81 m/s 2 and the atmospheric pressure
is 1.01325 bar. Assume frictionless piston, determine
(i) The force exerted by the atmosphere, the piston and the weight on
the gas if the piston is 100 mm in diameter.
(ii) The pressure of the gas
(iii) If the gas is allowed to expand pushing up the piston and weight by
400 mm, what is the work done by the gas in kJ.
(iv) What is the change in potential energy of the piston and the weight
after the expansion in part C

1 One mole of a gas which obeys the relation PV = RT, where R = 8.314 J/molK
5 is initially at 300 k and 0.1 MPa. The gas is heated at constant volume till the
pressure rises to 0.5 MPa and then allowed to expand at constant temperature till
the pressure reduces to 0.1 MPa. Finally the gas is returned to its original state
 by compressing at constant pressure. Calculate the work done by the gas in each
of the processes and also estimate the net work done by the gas.

1 An elevator with a mass of 2500 kg rests at a level 10 m above the base of the
6 shaft. It is raised to 100 m above the base of the shaft, where the cable holding it
breaks. The elevator falls freely to the base of the shaft, and strikes a strong
spring. The spring is designed to bring the elevator to rest and by means of a
catch arrangement to hold the elevator at the position of maximum spring
compression. Assuming the entire process to be frictionless and taking 9.81
m/s2. Calculate
(i) The potential energy of the elevator in its position relative to the base
of the shaft
(ii) The work done in raising the elevator
(iii) The potential energy of the elevator in its highest position relative to
the base of the shaft
(iv) The velocity and kinetic energy of the elevator just before it strikes
the spring

1 What is Phase rule. 01

7

1 What do you understand by degrees of freedom

8

1 Derive the first law for steady state flow process.

9

2 State the laws of thermodynamics:

0

2 A man whose weight is 700 N takes 25min for climbing up the staircase. What 01
1 is the power developed in him if the staircase is made up of 20 stairs each 0.18
m in height

The potential energy of a body of mass 20 kg is 3.5 kJ. What is the height of the 01
body from the ground? If a body of mass 20 kg is moving at a velocity of 50 m/s
what is the kinetic energy.

2 A mercury manometer used to measure pressure inside a vessel indicates 400 01

2 mm. One end of the manometer is exposed to the atmosphere. The atmospheric
pressure is 1.01325 bar. Density of mercury 13.56 x 103 kg/m3. What is the
absolute pressure in the vessel in N/m2.

2 Energy: Is it a property of the system explain

3

2 What is STP/NTP
4

2 What is Internal energy, Enthalpy and Entropy?

5
2 Sign conventions
6

2 First law of thermodynamics for

7
(i) First law for a closed system undergoing a cycle
(ii) First law for a closed system undergoing a change of state
(iii) First law for applied to Flow process (Open system & Steady flow
process

2 Flow Calorimeter, Ideal Gas temperature scale

8

2 A tank comprising a fluid is stirred by a paddle driven by a 2 Hp motor. Heat

9 losses from the tank are 1576 kJ/hr. Does the internal energy of the system
consisting of 10 kg of fluid in the tank increase or decrease.

3 1kgmole of a gas of specific heat 20 kJ/kgmoleK is heated in a closed chamber

0 of negligible specific heat. If the gas temperature rises by 15 0C, what is the
change in internal energy

3 A cylinder containing 1 gmole of liquid water at 100 0C is heated until all the
1 cylinder is converted to saturated vapor. The cylinder is fitted with a piston
which just resets the pressure of 1 atm.
(i) How much work is done by the expanding gas
(ii) What is the internal energy change during this vaporization process
Neglect the volume of liquid water. 1 gm mole of gas at 1 atm and 0 0C occupies
22.414 litres. The heat of vaporization at 1000C is 40.4 kJ/gmol

3 A closed rigid container has 2.5 kg of an ideal gas at 1 atm and 25 0C. If the gas
2 is heated at 5.4 kJ/min, how long will it take for the gas to attain 10 atm. Given
CV = 0.96kJ/kgK

3 A turbine operating under steady state conditions receives 5000 kg of steam per
3 hour. The steam enters the turbine at a velocity of 3000m/min at an elevation of
5m and specific enthalpy of 2777kJ/kg. It leaves the turbine at a velocity of
600m/min, at an elevation of 1m and specific enthalpy of 2252kJ/kg. Heat losses
for the turbine to surroundings amounts to 16680kJ/hr. Determine the HP output
of the turbine

3 Water at 950C is pumped from a storage tank 1 to a second storage tank 15 m

4 above by a 2 HP motor. 42117 kJ/min of heat is extracted from this water in a
heat exchanger. If the flow rate is 183 kg/min, what is the temperature of water
in the second tank.

3 Water flowing at 50C is heated to 650C by bleeding a small amount of steam

5 from a main line at 5 bar and 200 0C into the water. The steam is throttled to 1
bar before entering the water line. What is the mass of steam required to heat
 100 kg of water. Neglect PE, KE and heat loss.
Note: Throttling is a constant enthalpy process

3 Water at 368K is pumped from a storage tank at the rate of 25m 3/hr. The motion
6 for the pump supplies work at the rate of 2 hp. The water passes through a heat
exchanger where it gives up heat at a rate 42,000kJ/min and is delivered to a
second storage tank at an elevation of 20 m above the first tank. What is the
temperature of the water delivered to the II tank?
Assume the enthalpy of water as 0 at 273K. and the specific heat of water is
constant at 4.2 kJ/KgK

3 Calculate ∆U, ∆H for 1 kmol of water as it is vaporized at constant temperature

7 of 373K and constant pressure of 101.325 kPa. The specific volumes of liquid
and vapor at these conditions are 1.04 x 10 -3 and 1.675 m3/kmol respectively.
Heat of 1030 kJ is added to water for this change.

3 Show that for an ideal gas dU=CVdT for all the processes (Constant Volume,
8 pressure, adiabatic process).

3 Show that for an ideal gas dH = CPdT for all the processes (Constant Volume,
9 pressure, adiabatic process).

4 A stationary mass of gas is compressed without friction from an initial state of

0 0.3 m3 and 0.105 MPa to a final state of 0.15 m 3 and 0.105MPa. The pressure
remaining constant during the process during the process. There is a transfer of
37.6 kJ of heat from the gas during the process. How much does the internal
energy of the gas change.

4 Derive the equations to determine the Q, ∆U, ∆H and work done for Isothermal,
1 Isobaric, Isochoric and Adiabatic process.

4 When a system is taken from state a to state b as shown in fig along path acb,
2 84kJ of heat flows into the system and the system does 32 kJ of work.
(i) How much will the heat that flows into the system along path adb be,
if the work done is 10.5 kJ?
(ii) When the system is returned from b to a along the curved path, the
work done on the system is 21kJ. Does the system absorb or liberate
heat, and how much of heat is absorbed or liberated?
(iii) If Ua=0 and Ud=42kJ, find the heat absorbed in the process ad and
db.
4 A fluid is confined in a cylinder by a spring loaded frictionless piston so that the
3 pressure in the fluid is a linear function of volume (p = a + bv). The internal
energy of the fluid is given by the following equation U = 34 + 3.15 pv. Where
U is in kJ, p in kPa and v in m 3. If the fluid changes from an initial state of 170
kPa, 0.03 m3 to a final state of 400 kPa, 0.06 m 3 with no work other than that
done on the piston, find the direction and magnitude of the work and heat
transfer.

4 An inventor claims to have designed a process which takes in only sat steam at
4 100 oC and which by a complicated series of steps makes heat continuously
available at a temperature level of 200oC. The inventor claims further that for
every kilogram of steam taken into the process, 2000 kJ of energy as heat is
liberated at the temperature level of 200OC. Show whether or not the process is
possible.
4 An ideal gas undergoes the following sequence of mechanically reversible
5 process in a closed system (Cv = 3/2 R, CP = 5/2 R).
i) From an initial state of 343.15K and 1 bar it is compressed
adiabatically to 423.15K
ii) It is then cooled from 423.15K to 343.15K at constant pressure.
iii) Finally it is expanded isothermally to its original state.
Calculate W, Q, ∆U, ∆H for each three process and for the entire process.
If these changes are carried out irreversibly but to accomplish exactly the same
changes of state, Find Q and W if each step is carried on with an efficiency of
80%.

4 The internal energy of a certain substance is given by the following equation

6 U =3.56 pv +84 where U is given in kJ/kg, P is in kPa and V in m 3/kg. A system
composed of 3 kg of this substance expande from an initial pressure of 500 kPa
and a volume of 0.22 m3 to a final pressure of 100 kPa in a process in which
pressure and volume are related by p v 1.2=constant .

(i) If the expansion is quasistatic find Q, ∆ U , W for the process

(ii) In another process the same system expands according to the same
pr-vol relationship as in part (a), and from the same initial state to the
same final state as in part (a) but the heat transfer in this case is 30
kJ. Find the work transfer for this process
 (iii) Explain the difference in work transfer in part (a) and part (b)

4 An electric current of 0.5 A from a 12 V supply is passed for 5min through a

7 resistance in thermal contact with saturated water at 1 atm. As a result, 0.798 g
of water is vaporized. Assuming that water vapor behaves ideally, Calculate the
molar internal energy change and enthalpy change during the process

4 pv
An ideal gas is one for which is a constant regardless of the changes it
8 T
undergoes. Such a gas has a volume of 0.02271 m 3/mol at 00C and 1 bar. In the
following problem air may be considered an ideal gas with the constant heat
capacities Cv = 5/2 R, CP = 7/2 R where R = 8.314 J/molK. The initial conditions
of the air are 1 bar and 25oC. It is compressed to 5 bar and 250C by two different
mechanically reversible processes. Calculate the heat and work requirements
and ∆ U , ∆ H of the air for each path.
(i) Cooling at constant pressure followed by heating at constant volume
(ii) Heating at constant volume followed by cooling at constant pressure

4 When a system is taken from state a to state b along path acb, 100 J heat flows
9 into the system and the system does 40 J of work. How much heat flows into the
system along path aeb if the work done by the system is 20 J? The system
returns from b to a along path bda. If the work done on the system is 30 J, does
the system absorb or liberate heat

5 Calculate ∆ U , ∆ H for 1 kg vapor of water when it is vaporized at a cnnstant

0 temperature of 100 0C and the constant pressure of 101.325 kPa. The specific
volume of liquid and at these conditions are 0.00104 and 1.673 m 3/kg.For this
change 2256.9 kJ of heat is added to the water

5 Suppose a particular gas which obeys the relation PV = RT expands reversibly

1 from P1 to P2, During the expansion process it is found that p v ᵧ =constant .
Determine the work done by the gas.

5 A cylinder of volume 0.1 m3 is filled with nitrogen at 15 MPa and 300 K. The
2 cylinder valve has developed a leak and after some time the gas pressure in the
 cylinder has reduced to 5MPa. Assume that the cylinder is always at 300 K
which is ambient temperature and the gas obeys the relation pv = RT where R =
8.314 J/molK, Calculate the work done by the gas. Specify the assumptions
made in estimating the work done. The atm pressure is 101.325 kPa.

5 Suppose 1 Kg ice at 00C and 101.325 kPa is completely converted to steam at

3 1000C and at same pressure. Calculate the work done during melting and during
vaporization. It is given that the density of ice at 0 0C is 916.23 kg/m3 and the
specific volume of steam at 1000C and 101.325kPa is 1.673m3/kg. The specific
volume of liquid water at 00C ia 1 x 10-3 m3/kg

Tutorials
1 5 moles of N2 at 800C is contained in a rigid vessel. How much heat must be
added to system to raise the temperature to 3000C. If the vessel has a negligible
heat capacity? If the mass of vessel is 10 kg & if its heat capacity is 0.5 J/gm 0C,
how much heat is required?
3 moles of N2 at 230 0C is contained in a piston – cylinder arrangement. How
much heat must be extracted from this system to reduce the temperature of the
system to 800C and Cv = 20.85 J/mol 0C for N2.
2 The following data are recorded in a flow calorimeter in which water is the test
fluid. Flow rate = 4.15 g/sec. T1 = 00C, T2 = 3600C, P2 = 3 bar, Rate of heat
addition from the heater = 12740 Watts. It is observed that water is completely
vaporized in the process. Calculate the enthalpy of steam at 300 0C and 3 bar.

J
12740
s
Ans: m[H2] = Q = = 3069.87 J/g
g
4.15
s
3 Water flows through a horizontal coil heated from outside by high temperature
flue gases. As it passes through the coil, the water changes state from 230 kPa
and 820C to 101.33 kPa and 121 0C. Its entering velocity is 3.05 m/sec and exit
velocity is 182.9 m/s. Determine the heat transferred through the coil by unit
mass of water
4 A steam turbine receives steam at a rate of 54 tons/hr and as per the following
data, The turbine entrance is at 3.048 m above the exit level. The heat losses are
14 kW. Find the work output of the turbine.
Data Inlet Outlet
Pressure 6205 kPa 9859 kPa
Temp 811 K 319 K
Velocity 3.048 m/sec 274.3 m/sec
Internal energy 3150 kJ/kg 2212 kJ/kg
Sp vol 0.058 m3/kg 13.36 m3/kg
5 Steam flows at steady state through a converging insulated nozzle 25.4 cm long
and 5.08 cm in dia. At the nozzle entrance temperature is 313 0C, pressure = 690
kPa. Velocity is 30.5 m/sec. at the nozzle exit 2320C, 345 kPa. What is the
velocity at exit. Find the dia at the exit.
6 Steam at 1378 kPa and 3160c enters a turbine through a standard 76 mm pipe line
with a velocity of 3.048 m/s. The exhaust in the turbine is carried through a
standard 254 mm pipeline and is at 28 kPa and 710C. Assuming no heat losses
from the turbine determine the power out put.
7 Water at 900C is pumped fro storage tank 1 to storage tank 2 15 m above by 1.5
HP motor. 9000 kCal /min of heat is extracted from water in a heat exchanger.
The flow rate of water is 180 kg/min. What is the temperature of water delivered
to the second tank.
8 A balloon which is initially collapsed and flat is slowly filled with hydrogen at
100 kPa so as to form it into a sphere of radius 1 m. Determine the work done by
the gas in the balloon during the filling process.
9 A 12 V storage battery is charged by supplying a current of 2 A for 3 Hrs.
Determine the work done on the battery and the quantity of electric charge
transferred.
TUTORIALS 2

1 A balloon which is initially collapsed and flat is slowly filled with hydrogen at 100
kPa so as to form it into a sphere of radius 1 m. Determine the work done by the
gas in the balloon during the filling process.
2 An electric potential difference of 230 V is maintained across a 470 ohm resistor
for a period of 10 min. Determine the electric work done and the power
3 A 12 V storage battery is charged by supplying a current of 2 A for 3 Hrs.
Determine the work done on the battery and the quantity of electric charge
transferred.
4 It is desired to store 28 kg of nitrogen at 14 MPa pressure and 27oC in a cylinder.
Assuming that nitrogen behaves like an ideal gas determine the size of cylinder
5 One mole nitrogen contained in a rigid and insulated tank at 300 K is stirred at
300K by a paddle wheel, which is operated by 60 W electric motor for 2 min. If
the molar heat capacity at constant volume for nitrogen is given by CV =
18.956+4.93x10-3T where CV is in J/molK and T is in Kelvin. Calculate the change
in entropy of nitrogen
6 120kJ work was fone on a car in accelerating is from an initial speed of 10 km/h to
100 km/h.(i) Determine the mass of the car (ii) What could be the final speed of
the car if the work done on the car is 200 kJ.

UNIT II (II Law of Thermodynamics)

1 Clausius Statement of II Law
2 Kelvin Planck statement for II Law
3 Violation of Clausius and Kelvin Planck statement
4 Heat pump, Refrigerator, COP.
5 Carnot Cycle, PV diagram for Carnot cycle
6 Work done in a Carnot cycle
7 Absolute Thermodynamic temperature scale
8 Efficiency of a reversible heat engine
9 Entropy change of an ideal gas
10 Calculate the entropy change when 1 kg nitrogen is changed from 300 K and 1
bar to 500 K and 3 bar. For nitrogen CP = 1.0416 kJ/kgK. Assume that nitrogen
behaves like an ideal gas
11 A reversible engine absorbs 1040 kJ of heat at 260oC and discards heat at 40oC.
What is (i) the work output of the engine
(iii) The heat rejected
(iv) The entropy change of the system, surrounding and the total change in
entropy
(v) The efficiency of the heat engine
12 1 kg of saturated steam at 100oC is condensed to saturated water at 100oC. Is the
process reversible if the surrounding temperature is 25oC
13 A metal block of specific heat 0.37 kJ/kg and mass 10 kg is initially at 50oC in a
room where air temperature is 25oC. The pressure is constant at 1 atm. Compute
(i) Entropy change of block
(ii) Entropy change of air
(iii) Total entropy change.
If the block in the above example is cooled with 50 kg water initially at 25oC,
What is the total entropy change
14 A cyclic engine operates between a source temperature of 800oC and sink
temperature of 30oC. What is the heat least rate of heat rejection per kW net
output of the engine
15 A domestic food freezer maintains a temperature of -15oC. The ambient air
temperature is 30oC. If heat leaks into the freezer at a rate of 1.75kJ/s, What is the
least power necessary to pump this heat continuously.
16 A reversible engine operates between two reservoirs at temperatures of 600oC
and 40oC. The engine drives a refrigerator which operates between reservoirs at
temperatures of 40oC and – 20oC. The heat transfer to the engine is 2000 kJ and
the net work output of the plant if 360 kJ.
(i) Evaluate the heat transfer to the refrigerator and the net heat transfer
at 40oC.
(ii) Reconsider (a) given that efficiency of the heat engine and COP of the
refrigerator are each 40% of the maximum values
17 It is proposed to device a refrigeration plant to convert 100 tonnes/tonne of water
at 0oC into ice at 0oC in a day in summer while the ambient atmosphere is at
37oC. The latent heat of fusion of water at 0oC is 334.92 kJ/Kg. estimate the
minimum power required to operate the refrigerator plant in kWatts.
18 The normal boiling point of helium is 4.2 K and the latent heat of vaporization of
helium is 20.83 kJ/kg. It is required to produce 5 kg/hr liquid helium from helium
vapor at 4.2 K. The surrounding temperature is 27oC. Calculate the COP of the
unit and the power needed to operate the plant
19 It is proposed to use a heat engine which absorbs energy as heat at 127oC with the
surrounding atmosphere at 27oC as the sink to operate a refrigerator to produce
ice at 0oC. The refrigerator rejects energy to the surrounding atmosphere.
Calculate
(i) The ratio of the energy removed from the cold body by the
refrigerator to the energy absorbed by the heat engine.
(ii) The ratio of the energy rejected to the surrounding atmosphere to the
energy absorbed by the engine.
20 A reversible heat engine with an efficiency of 0.4 drives a reversible refrigerator
with a COP of 5. If both the heat engine and the refrigerator rejects energy to the
surrounding atmosphere at 27oC, Determine the temperatures of the reservoir
from which the engine absorbs energy and the reservoir from which the
refrigerator extracts energy.
21 A reservoir engine shown in the figure operates between three thermal reservoirs
at 600K, 400K and 300 K. The engine receives 2400 kJ of energy as heat from
the reservoir at 600K and does 1500 kJ of work. Determine the heat interactions
with the other two thermal reservoirs.

Thermal Reservoir 600K Thermal Reservoir 400K Thermal Reservoir 300K

Q2 = ?

Q3 = ?
Q1 = 2400 kJ

W = 1500 kJ

22 Calculate the entropy change if 1 kg of water at 30oC is heated to 80oC at a

pressure of 1 bar. The specific heat of water is 4.2 kJ/kgK
23 At 0oC, ice melts with a latent heat of fusion of 334.93 kJ/Kg. Calculate the
entropy change if 1 kg ice melts into water at 0oC.
24 A lump of steel of mass 30 kg at 427oC is dropped into 100 kg of oil at 27oC. The
specific heat of steel and oil are 0.5 kJ/kgK and 3.0 kJ/kgK respectively.
Calculate the entropy change of steel, oil and universe.
25 Calculate the entropy change when 1 kg of nitrogen is changed from 300 K and 1
bar to 500 K and 3 bar. For nitrogen CP=1.0416kJ/kgK. Assume that nitrogen
behaves ideally.
26 An inventor claims to have designed a heat engine which absorbs 1 kJ of energy
as heat at 727oC and delivers 0.6 kJ of work. When the ambient temperature is
27oC. Would you agree with his claim.
27 A reversible heat engine delivers 0.65kW and rejects energy at the rate of 0.4 kJ/s
to a reservoir at 27oC. Determine the efficiency of the engine and the temperature
at which energy is absorbed by the engine.
28 Two Carnot engines I and II operate in series between a high temperature
reservoir at 1027 oC and a low temperature reservoir at 27oC. The engine I
absorbs energy from the high temperature reservoir and rejects to a reservoir at
temperature T. The engine II receives energy from the reservoir at T and rejects it
to the low temperature reservoir. The amount of energy absorbed by engine II
from the reservoir at T is same as that rejected by engine I to the reservoir at T. If
engines I and II are found to have the same efficiency, determine the temperature
T. If engine I receives 100 kJ energy as heat from the high temperature reservoir
calculate the work delivered by engine I and engine II.
29 An inventor claims to have designed a process which takes in only sat steam at
100 oC and which by a complicated series of steps makes heat continuously
available at a temperature level of 200oC. The inventor claims further that for
every kilogram of steam taken into the process, 2000 kJ of energy as heat is
liberated at the temperature level of 200OC. Show whether or not the process is
possible.

Heat Reservoir = 200oC

= -2000kJ
Sat steam (100oC) Liquid water at 0OC

Apparatus
H1 = 2676.0 kJ/kg , H2 = 0, S2 = 0
S1 = 7.3554 kJ/kgK
=

Heat Reservoir = 0oC

(cooling water)

30 An inventor claims to have designed a heat engine which absorbs 1000 kJ and
400 kJ energy as heat from reservoirs at 800 K and 400K respectively and
delivers 1000 kJ energy as work. He also claims that engine uses a reservoir at
300 K as sink. Judge whether the engine is theoretically possible or not
31 It is desired to maintain an auditorium at 25oC throughout the year. Hence it is
planned to use a reversible device which can be used as a refrigerator in summer
and as a heat pump in winter. The ambient temperature in summer is expected to
reach 45oC and in winter the minimum temperature may touch 3oC. The energy
loss through the walls, roofs and doors is estimated at 50 kJ/s. Determine the
minimum power required to operate the device in summer and winter.
32 An inventor claims to have designed a heat engine which absorbs 260 kJ of
energy as heat from a reservoir at 52oC and delivers 72 kJ of work. He also states
that the engine rejects 100 kJ and 88 kJ of energy to the reservoirs at 27oC and
2oC respectively. Judge whether the claim is acceptable or not.

Equations of state:

1 Express Vander Waals equation in terms of reduced parameters

Estimate the Vander Waals constants for Ethane (C2H6) and Freon-12 (CCl2F2) assuming
that the critical constants of the substance are known

Substance Tc(K) PC(bar)

Ethane (C2H6) 305.43 48.84
 Freon-12 (CCl2F2) 384.70 40.12
2 It is desired to store 28 kg of nitrogen at 14 MPa pressure and 27oC in a cylinder.
Assuming that nitrogen behaves like an ideal gas determine the size of cylinder
3 If a cylinder of volume 0.1 m3 is filled with 1.373 kg of ammonia at 1.95 MPa. Determine
the temperature at which ammonia exist in the cylinder. Assume that ammonia obeys the
Vanderwaals equation of state. The Vanderwaals constants a and b are 422.546x10-
3
Pa(m3/mol)2 and 37x10-6 m3/mol, respectively.
4 A 0.1 m3 cylinder is charged with ethane to a pressure of 120 bar at 27oC. assuming that
ethane behaves like an ideal gas, Estimate the mass of ethane in the cylinder.
5 Suppose it is desired to charge 15 kg of ethane at 300 K into a cylinder of volume 0.08
m3, determine the pressure to which the cylinder is to be charged
6 If 20 kg of ethane is charged into a cylinder of capacity 0.15m3 and the cylinder is held at
a pressure of 15 MPa, determine the temperature of the gas in the cylinder assuming
ethane is an ideal gas
7 A cylinder 0.01 m3 volume is filled with 0.727 kg of n-octane (C8H18) at 427.85K.
Assuming that n-octane obeys the Vander Waals equation of state, calculate the pressure
of the gas in the cylinder. The Vanderwaals constants a and b are 3.789 Pa(m3/mol)2 and
2.37x10-4 m3/mol, respectively.
8 Assuming that ammonia obeys the Vander Waals equation of state, calculate the molar
volumes of ammonia vapor and liquid ammonia at 1.95MPa and 321.55K. The
Vanderwaals constants a and b are 422.546x10-3Pa(m3/mol)2 and 37x10-6 m3/mol,
respectively.

Maxwells equations
1 Derive Maxwells Equations for all energies
2 Chain rule:

( ) ( )( )
∂x
=
∂x ∂a
∂ y z ∂a z ∂ y z
3 Reciprocal Relation:

( )
∂x
=
1
∂y Z ∂y
( )
∂x z
4 Cyclic relation:

( )( )( )
∂x ∂ y ∂ z
∂ y Z ∂ z x ∂x y
=−1

5
( ) ( )
∂u
=
∂u
∂ x∂ y ❑ ∂ y ∂x ❑

( )
∂ ∂u
=
∂ ∂u
∂ x ∂ y ∂ y ∂x ( )
6 Prove the relation
k CP
TdS= C v dP+ dv
β vβ

β= ( )
1 ∂v
v ∂T P
 k= ( )
−1 ∂ v
v ∂P T
Internal Energy Relations
7
( )
∂u
∂P T
=Pvk−Tvβ

( ∂∂ uv ) = Tβk −P
T

8
du=C v dT + T
[( ) ]
∂P
∂P v
−P dv

[ ]
9

du=C dT − P+T
v
( ∂T )
∂v
P
dv
( ∂∂ Pv ) T

1 du=( C P −Pvα ) dT + v [ Pβ−Tα ] dP

0 where
α=
1 ∂v
v ∂T( ) P

β= ( )
−1 ∂ v
v ∂P T
1
1
du=−T ( ∂T∂ v ) dP−Pdv +C dT
P
p

1 Show that internal energy is a function of temperature only for an ideal gas.
2 To show:

( ) ( ) ( )
∂u
=
∂u
=
∂ P T ∂v T ∂ s T
∂u
=0

1 Show that du=C v dT for all processes

3 To show that

( ) ( ) ( )
∂u
=
∂u
=
∂ T s ∂T P ∂T v
∂u
=C v

1
4 Show that for an ideal gas ( )
∂T
∂P u
=0

Enthalpy Relations
1
5 [ ( )]
dH =C P dT + V −T
∂v
∂T P
dP

1
6 [ ( )]
dH =vdP+ C v dT + T
∂P
∂T v
dv
 [ ]
1
7
dH =C v dT + vdP− T
∂v
∂T P
dv
( )
∂v
∂P T ( )
1 α
dH =vdP+ C v dT +T dv
8 β
α=
1 ∂v
v ∂T P ( )
β=
−1 ∂ v
v ∂P T ( )
1 Show that dH =C P dT for all processes
9 To show that

( ) ( ) ( )
∂H
=
∂H
=
∂T s ∂ T P ∂ T v
∂H
=C P

2 Show that internal energy is a function of temperature only for an ideal gas.
0 To show:

( ) ( ) ( )
∂H
∂P T
=
∂H
∂v T
=
∂H
∂s T
=0

2 Joule Thomson co-efficient

1
μ=( )
∂T
∂ P H CP
v
= ( Tα−1 )

α=
1 ∂v
v ∂T ( ) P

2 Show that Gibbs Hemholtz relations:

2 Show that

[ ] ∂ ( GT )
∂T P
=
−H
T2

[ ]
( )∆G
∂
T −∆ H
=
∂T P T2

2 Derive Gibbs relation

3
3 2 CT
G=H −aTlnT −b T − +¿
2

Specific heat relations

2 Show that
4

( )
∂ CP
( )
2
∂ v
=−T 2
∂P T ∂T
2
5 Find the variation of Cv with v at constant temperature, ie to prove that ( ∂∂Cv ) =0
P

T
2
6 Find ( ) for Vander waals gas
∂ CP
∂P T
2
7 Find ( ) for Vander waals gas
∂ Cv
∂v T

( )( )
2
2 ∂v ∂P α
8 Show that C P −C v =T =Tv
∂ T P ∂T v β
2 Show that C P −C v =R for an ideal gas
9
3 Find C P −C v for Vander Waals gas
0
3 Prove
1
( )( )( )
∂P
∂T v
∂T ∂v
∂v P ∂P T
=−1

3
2 Show that ( ∂u
∂v T)=0 for virial equation of state

Show that ( ) ( )
3 ∂u ∂ lnT
=C v
3 ∂T s ∂ lnP v

Show that ( )
3 ∂u Cv P
4 = for an ideal gas
∂v P R

Show that ( )
3 ∂u
=v ( Pβ−kT )
5 ∂P T

Show that ( )
3 ∂T TR
= for ideal gas
6 ∂ P S P CP
3 Show that

[ ]
7

dS=− T
∂v
( )
∂T P
dv +C v
dT
∂v
( )
∂P T
T

3 Clausius equation

( ) [ ]
8 P2 ∆ H 1 1
ln = −
P1 R T1 T 2

Clausius Clapeyron equation

ln
T2
( )
=
∆v
T1 ∆ H 2
[ P −P1 ]

3 Calculate the vapour pressure of water at 363 k, if the vapour pressure at 373 k is
9 101.3 kPa. The mean heat of vaporisation in this temperature range is 2275kJ/kg
4 Mercury has a density of 13.69 x 103 in the liquid state and 14.193 x 103 kg/m3 in
0 the solid state both measured at the melting point of 234.33 K at 1 bar. If the heat
of fusion of mercury is 9.7876 kJ/kg. What is the melting point of mercury at 10
bar
4 Determine the increase in entropy of solid magnesium when the temperature is
1 increased from 300K to 800K at atmospheric pressure. The heat capacity is given
by the following relation
−3 4 −2
C P =26.04+5.586 x 10 T +28.476 x 10 T
4 Reported values for the virial coefficients of isopropanol vapour at 200oC are
2 B = -388 cm3/mol-1
C = -26,000 cm6/mol2.
Calculate V and Z for isopropanol vapour at 200oC and 10 bar by
(1) Ideal gas equation
Pv BP
( 2 ) Z= =1+
RT RT
(3) Truncated to three terms (virial equation)
4 One mole nitrogen contained in a rigid and insulated tank at 300 K is stirred at
3 300K by a paddle wheel, which is operated by 60 W electric motor for 2 min. If
the molar heat capacity at constant volume for nitrogen is given by CV =
18.956+4.93x10-3T where CV is in J/molK and T is in Kelvin. Calculate the
change in entropy of nitrogen
4 Residual Property, Fugacity, fugacity coefficient
4
4 Determination of fugacity of pure gas by different methods
5
4 Derive an expression for the fugacity coefficient of a gas obeying the equation of
6 state P(v-b) = RT and estimate the fugacity of ammonia at 10 bar and 298 K,
given that
b = 3.707 x 10-5 m3/mol.
50
4 J
7 From the P-v-T data for a gas it is found that ∫ αdP=−556.61 . Find the
0 mol
fugacity of the gas at 50 bar and 300 K.
4 Find the fugacity coefficient at 1 bar, 5 bar and 10 bar for a gas that follows, the
8 equation of state . PV= RT(1-0.00513P) where P is in bar
4 From the following data, Calculate the fugacity coefficient of carbon monoxide
9 (CO) at 100 atm and 400 K.

P, atm 1 4 7 10 40 70 100
Z 1.0002 1.0002 1.0017 1.0025 1.0042 1.0112 1.0216
5 Show that the fugacity of a gas obeying the Vander Waals equation of state is
0 given by
b 2a RT
lnf = − + ln
v−b RTv v−b
5 Determine the fugacity and fugacity coefficient of steam at 623 K and 1000kPa.
1 Using enthalpy and entropy values from steam tables. Assume that steam behaves
ideally.
 VAPOR LIQUID EQUILIBRIA
1 Theory: Raoults Law, Duhems theorem, Explain p-x-y, t-x-y diagrams
x1 = 1, y1 = 0 at t To start with the experiment, x1 =1, means pure liquid at
❑ ❑ ❑
¿t1 t=t 1 . The temperature is then increased to t 2 where x1 = 0
means liquid is completely vaporised therefore y1 = 1

vapor
t vs y Tie line vapour and liquid coexist

t vs x
liquid

x1=0 y1=1 x1=1 y1=0

x1, y1
2 Hints to plot p-x-y diagram
x1 = 1, y1 = 0 at To start with the experiment, x1 =1, means pure liquid at
s s s
p= p 1 p= p 1. The pressure is then reduced to p2 where x1 = 0 means
liquid is completely vaporised therefore y1 = 1

liquid
P vs x Tie line vapour and liquid coexist

P vs y

vapor

x1=0 y1=1 x1=1 y1=0

x1, y1

Problems

1 Binary system acetonitrile(1)/nitromethane conforms closely to Raoults law, Vapor

pressures for the pure species are given by Antoine equation
 s 2945.47 s 2972.46
ln p1=14.2724− , ln p2=14.2043− T ∈ K , p ∈kPa
T −49.15 T −64.15
(a) Prepare a graph showing p vs x1, pvs y1 for a temperature of 348.15K
(b) Prepare a graph showing T vs x1, T vs y1 for a pressure of 70 kPa

So s 2945.47 s 2972.46
ln p1=14.2724− = 83.21, ln p2=14.2043− = 41.98
l 348.15−49.15 348.15−64.15
(a)

s s s
Assum P=x 1 p 1+ x 2 p 2 x 1 p1
e x1 y 1=
P

0 41.98 0
0.2 50.226 0.331342
0.4 58.472 0.56923
0.6 66.718 0.748314
0.8 74.964 0.888
1 83.21 1

(b) s B s 2945.47
At 70 kPa , T 1= + C T1= + 49.15=342.991
s
A−ln p1 14.2724−ln70
 s B s 2972.64
T 2= +C T 1= +64.15=362.73
s
A−ln p2 14.2043−ln 70

Assume T between 342.991 to 362.73, Find ps1 , p2s using the equations below for
assumed values of T

s 2945.47 s 2972.46
ln p1=14.2724− , ln p2=14.2043− T ∈ K , p ∈kPa
T −49.15 T −64.15
s
P− p2 x 1 p1
s
x 1= s s y 1=
p 1 − p2 P

s s
T p1 p2 P given x y
362.73 0.000 0.000
359.15 0.1424 0.2401
355.15 0.3184 0.4742
70 kPa
351.15 91.76 46.84 0.5156 0.6759
347.15 0.7378 0.8484
342.99 1.000 1.000

GRAPH
2 The binary system acetone (1) / acetonitrile (2) conforms closely to Raoults
law. Using the vapour pressure data given
Prepare a graph showing p vs x1, pvs y1 for a temperature of 50oC.
ToC 38.45 42 46 50 54 58 62.33
s
p1mm 400 458.3 532 615 707.9 811.0 937.4
Hg
s
p2mm 159.4 184.6 216.8 253.5 295.2 342.3 400
Hg
(a) Plot P-x-y at 50oC
(b) Plot T-x-y at 480 mmHg.

s 2940.46 s 2945.47
ln p1=14.5463− , ln p2=14.2724− T ∈ K , p∈kPa
T +237.22 T + 224
(a)
At 50oC,
ToC 50 Calculate α,
s s
p1mm 615 p1 615
α= s = =2.426
Hg p 2 253.5
s
p2mm 253.5
Hg

Assume s s
P=x 1 p 1+ x 2 p 2 x1 α
x1 y 1=
1+(α−1) x1

0 253.5 0
0.2 325.8 0.377
0.4 398.28 0.617
0.6 470.5 0.784
 0.8 542.5 0.9065
1 615 1.0

Graph

(b) At 480 mm Hg, (760 mm Hg = 101.325 kPa)

480 mm Hg = 63.99 kPa

s B s 2940.46
T 1= −C T 1= −237.22=45.85
s
A−ln p1 14.5463−ln 63.99

s B s 2945.47
T 2= −C T 1= −224=67.236
s
A−ln p2 14.2724−ln 63.99

Assume T between 342.991 to 362.73, Find ps1 , p2s using the equations below
for assumed values of T

s 2940.46 s 2945.47
ln p1=14.5463− , ln p2=14.2724− T ∈ K , p∈kPa
T +237.22 T + 224
s s
P− p2 x 1 p1
x 1= s s y 1=
p 1 − p2 P

s s
T p1 p2 P given x y
45.85 63.97 28.24 63.99 1 1
49.414 72.78 33.09 0.778 0.885
52.978 82.55 38.007 0.582 0.75
56.543 93.33 43.49 0.4109 0.599
63.107 118.29 56.4 0.122 0.225
 67.2 132.21 63.9 0 0

GRAPH

3 Mixture of n-heptane (A)/ n-octane (B) are expected to behave ideally. The
total pressure over the system is 101.3 kPa. Using the vapour-pressure data
below,
Construct the boiling point diagram
The equilibrium diagram
Derive a general equation between y, x and α.
TK 371.4 378 383 388 393 398.6
s
p1 , kPa 101.3 125.3 140 160 179.9 205.3
s
p2 , kPa 44.4 55.6 64.5 74.8 86.6 101.3

s s
So p1 P−p 2
l α= s
x 1= s s
, where P=101.3 kPa
p2 p1 −p 2

x 1 α avg
y 1=
1+ ( α avg−1 ) x 1

From table α avg=2 .16

TK 371.4 378 383 388 393 398.6
s
p1 , kPa 101.3 125.3 140 160 179.9 205.3
s
p2 , kPa 44.4 55.6 64.5 74.8 86.6 101.3
α 2.28 2.25 2.17 2.14 2.08 2.02
 x1 1 0.656 0.487 0.312 0.157 0.0
y1 1 0.811 0.674 0.492 0.279 0.0

2.16 α avg
y 1=
1+1.16 x 1

GRAPH

4 Construct p-x-y diagram for cyclohexane (1) / benzene (2) system at 40oC.
Use the following expression for the liquid phase activity coefficient.
2 2 s s
ln γ 1=0.458 x 2 ln γ 2=0.1458 x 1 .At 40oC p1=0.243 atm, p2=0.240 atm

Given: At 40oC ps1=0.243 atm, ps2=0.240 atm

s
p1
Calculate α = s
p2

Assume γ1 γ2 s s
P=x 1 γ 1 p1 + x 2 γ 2 p 2
s
x 1 γ 1 p1
x1 y 1=
P

1 0.24 0
0 1.581
1.018 0.2606286 0.250059
0.2 1.341
1.076 0.268668 0.423288
0.4 1.17
1.17 0.2692008 0.582765
0.6 1.076
0.8 1.018 1.341 0.2622672 0.754571
 1.581 0.243 1
1 1
5 From the following vapour-pressure data, construct the temperature- comp
diagram at 1 atm, for the system benzene-toluene assuming ideal solution
behaviour
ToC 80 92 100 110.4
s
p1 mm Hg 76 1078 1344 1748
0
s
p2 mm Hg 30 432 552 760
0
s s
So p1 P−p 2 x 1 α avg
l Calculateα = x
s 1
= , y 1=
p2
s
p1 −p 2
s
1+(α avg−1)x 1

where P=1 atm∨760 mm Hg

or
s
P− p 2
s
x1 p
x 1= s s y 1=
1
p −p
1 2 P

ToC 80 92 100 110.4

s
p1mm Hg 760 1078 1344 1748
s
p2mm Hg 300 432 552 760
x1 1.00 0.508 0.256 0.000
y1 1.00 0.720 0.453 0.00

6 Generate p-x-y data for a binary system at a temperature at which

s s
p1=84.562 kPa , and p2=19.953 kPa . Assume system obeys Raoults law.
sol
Given: ps1=84.562 kPa , and ps2=19.953 kPa .

s s s
Assum P=x 1 p 1+ x 2 p 2 x 1 p1
e x1 y 1=
P

0.2 32.875 0.514

0.4 45.797 0.739

0.6 58.718 0.864

 0.8 71.640 0.944

7 State and explain Henrys Law

Henrys Law: For a species present as a very dilute solute in liquid phase,
Henrys law states that the partial pressure of the species in the vapour phase
(y1P) is directly proportional to its liquid phase mole fraction(x1).
Or
When a gas is in contact with tha surface of a liquid, the amount of gas which
will go into the solution is proportional to the partial pressure of that gas

y 1 P α x1
❑
y 1 P=x 1 H 1

Do the below sum to get clear idea of this law.

8 Assuming that carbonated water contains only CO2 and H2O, determine the
 compositions of the vapour and liquid phases in a sealed can of soda and the
pressure exerted on the can at 283.15 K. Henrys constant for CO2 in water at
283.15 K is about 990 bar.
Critical temperature of: CO2 = 312oC, H2O = 374oC
Pressure of: CO2 = 730 atm, H2O = 217.7 atm
❑
sol CO2 (1) Henrys y 1 P=x 1 H 1 As CO2 is present as a very dilute
law solute in liquid phase (H2O)
s
H2O (2) Raoults y 2 P=x 2 p2 From steam tables, at 283.15 K,
p2=0.01227 ¯¿
s
law

Learn this before solving the sum:

y1 Mole fraction of CO2 (1) in vapour phase (assumed to be pure CO2

and therefore y1 = 1)
y2 Mole fraction of H2O (2) in vapour phase (assumed to be pure CO2
and therefore y2 = 0)
x1 Mole fraction of CO2 (1) in liquid phase (negligible quantity
diffuses into water therefore it is assumed that x1 = 0.01)
x2 Mole fraction of H2O (2) in liquid phase (It should be pure water or
x2 = 1)

Assume x1 = 0.01, and y1= 1.0

(CO2 is present as a very dilute solute in liquid phase ie x1 = 0.01 and Vapor
phase does not have any water ie y1 = 1, or y2=0), We will later prove
assumption is correct)
❑ s
P=x 1 H 1 + x2 p 2 =(0.01 x 990)+¿

y 1 p1 9.912
x 1= = =0.0100 conforms theoriginal assumption
H1 990

s
x 2 p2 0.99 x 0.01227
y 2= = = 0.0012
P 9

y 1=( 1− y 2 )=( 1−0.0012 )=0.998 ie nearly pure CO2

Modified Raoults Law:

For low to moderate pressures a much more realistic equation for VLE results when the
second major assumption of Raoults law is abandoned and account is taken of deviation from
solution ideality in the liquid phase by a factor inserted into Raoults law and modified to read
s
y 1 P=x 1 γ 1 p 1

γ 1=activity coefficient , function of temperature∧liquid pHase composition

s s
P=x 1 γ 1 p1 + x 2 γ 2 p 2

UNIT III

1 Write the different methods used to find fugacity

50
2 J
From the P-v-T data for a gas it is found that ∫ αdP=−556.61 . Find the fugacity of
0 mol
the gas at 50 bar and 300 K.
3 Find the fugacity coefficient at 5 bar for a gas that follows, the equation of state.
PV= RT(1-0.00513P) where P is in bar
4 The fugacity of component A in binary liquid mixture of components A and B 298 K and
20 bar is given by f A=50 x A −80 x 2A +40 x 3A , where fA is in bar and xA is the mole fraction
of component A, Determine the fugacity fA of pure component xA and hence the fugacity
coefficient A.
5 Derive an expression for the fugacity coefficient of a gas obeying the equation of state
P(V-b) = RT and estimate the fugacity coefficient of ammonia at 10 bar and 298 K given
that b = 3.707 x 10-5 m3/mol.
6 The activity coefficient of component(1) in a binary system is given by
2 3 4
lnγ 1=a x 2 +b x 2+ c x 2 here a,b,c are constants. Obtain an expression for γ 2 in terms of x 1.
7 At 30oC and 1 atm, the volumetric data for a liquid mixture of benzene(b) and
cyclobenzene(c) are represented by the equation
V (cm3/gmol) = 109.4 - 16.8 xb – 2.64 xb2. Where xb is the mole fraction of benzene. Find
an expression for the partial molal volumes of the two components V b and V c .
8 The enthalpy of a binary liquid system of species 1 and 2 at fixed T and P is represented
by the equation:
H=400 x 1+600 x 2 + x 1 x 2 ( 40 x 1+20 x 2 ) where H is in J/mol. Determine the expression for
H 1 and H 2 as function of x1 , numerical values for the pure species enthalpies H1 and H2
and numerical values for the partial enthalpies at infinite dilution H 1∞ , H 2∞ .
9 Calculate from the following data, the fugacity coefficient of carbonmonoxide at 100 atm
and 400 K.
P, 1 4 7 10 40 70 100
atm
Z 1.0002 1.0002 1.0017 1.0025 1.0042 1.0112 1.0216
PV
Where Z is compressibility factor such that Z= .
RT
 Derive the equation used.
10 Define fugacity and activity coefficient. Differentiate excess property and residual
property and hence derive an equation to find fugacity coefficient by compressibility
factor method.
11 Estimate the fugacity of gaseous propane at 310K and 12 bar
P bar 1.7 3.4 6.8 10.2 11.7 13.6 34

V m3/kg 14.5772 7.0796 3.3176 2.0592 1.6808 0,021 0.00207

12 When a carbon monoxide gas is compressed at temperature 273 K , the variation in

pressure and volume is listed below
P1 atm 1 25 50 75 100 150 200 300 400 500 600

V1lit/ 22.40 0.88 0.43 0.29 0.21 0.14 0.11 0.08 0.07 0.06 0.05
mol 1 4 7 0 7 7 4 4 0 2 7

Calculate the fugacity and fugacity co-efficient of cabon monoxide gas at 100 atm and
500 atm.
13 Derive Gibbs relation
3
2 CT
G=H −aTlnT −b T − +¿
2
14 Show that the fugacity of a gas obeying the Vander Waals equation of state is given by
b 2 a lnRT
lnf = − +
v−b RTv v−b
15 The fugacity of component A in binary liquid mixture of components A and B 298 K and
20 bar is given by f A=50 x A −80 x 2A +40 x 3A , where fA is in bar and xA is the mole fraction
of component A, Determine the fugacity fA of pure component xA and hence the fugacity
coefficient A.
16 The partial molar volume of ethanol in 60 mol% ethanol water solution is
−6 m
3
kg
57.5 ×10 The density of the mixture is 849.4 3 . Calculate the partial molar
mol m
volume of water in the mixture
17 Calculate the fugacity of CO gas at 100 atm pressure and 75oC assuming that the gas
2
obeys Vander Waals equation of state. The constants for this equation of state are: a =
3.606 x 106 atm CC/gmol2 b = 42.88 cc/gmol.
18 Laboratory alcohol containing 96% alcohol and 4% of water is to be diluted to a solution
containing 56% alcohol and 44% water. All percentages are on weight basis. The partial
specific volumes are as follows:
3 3
m −3 m
In 96% alcohol solution v w =0.816 ×10−3 , v E =1.273× 10 .
kg kg
3 3
m −3 m
In 56% alcohol solution v w =0.953 ×10−3 , v E =1.243× 10 .
kg kg
density of water is 998kg/m3.How much water should be to 2 ×10−3 m3 of the laboratory
alcohol. What is the volume of the dilute alcohol obtained.
19 The need arises in a laboratory for 2000 cm 3 of an anti freeze solution consisting of 30
mol% methanol in water. What volumes of pure methanol and of pure water at 298.15K
 must be mixed to form 2000cm3 of anti freeze, at 298.15K ? Partial molar volumes of
methanol and water in a 30 mol% methanol solution and their pure species molar
volumes, both at 298.15 K are (1) Methanol V 1=¿ 38.632 cm3/mol, V1 = 40.727 cm3/mol
(2) Water V 2=¿ 17.765 cm3/mol, V2 = 18.068 cm3/mol
20 It is required to prepare 1 m 3 of methanol (1) Water (2) solution at 25 oC with x1 = 0.3881.
Determine the volumes of methanol and water to be mixed at 25 oC. Given density of
methanol at 25oC is 786.846 kg/m3.
Partial molar volume of methanol: 39.176 x 10 -6 m3/mol, Molar mass of methanol: 32 x
10-3 kg/mol, Partial molar volume of water 17.453 x 10 -6. and Molar mass of water 18 x
10-3 kg/mol
21 It is required to prepare 2 lt of 30 mole% methanol(1)- water(2) solution at 25 0C. What
volumes of pure methanol and water are to be mixed to prepare the solution.
Data: At 25oC, Partial molar volumes of 1 and 2 are 38.632 cm3/mol, 17.765 cm3/mol.
Pure component molar volumes of 1 and 2 are 40.727cm3/mol, 18.068cm3/mol.
22 The Vanlaar constants A and B for the system ethanol/benzene at 45 oC. The activity
coefficients at 450C are 1.910 and 1.3285 respectively. Calculate the activity coefficients
of the components in a solution containing 10 mol % ethanol.
23 Plot x-y diagram for the azeotrope ethanol – water system using vanlaar equation.
If azeotrope composition is 89 mole% of ethanol, Bubble point of the mixture is 750 C at
760 mm Hg, Vapor pressure of water: 329 mm Hg at 750 C and Vapor pressure of
ethanol: 755 mm Hg at 750 C.
24 The Vanlaar constants A and B for the system nitromethane/Carbon tetrachloride at 45 oC
are 2.230 and 1.959 respectively. Calculate the activity coefficients of the components in a
solution containing 30 mol % nitromethane.
25 The VLE data for the system methanol(1) - nitromethane(2) at 760 Torr is given below.
Determine the Vanlaar constants for the system.
t oC 96.90 68.20 65.10 64.50
x1 0.0150 0.4260 0.7470 0.9140
y1 0.1330 0.7470 0.8380 0.9210
The Antoine constants are given as
A B C
Methanol (1) 8.08097 1582.271 239.726
Nitromethane (2) 7.28166 1446.937 227.600
B
logP= A− t in oC
t +C

26 The following VLE data for the system benzene (1) – heptane(2) at 60 oC has been
reported. Assuming that the three suffix Margules equation adequately represent the VLE
data of this system determine the Margules parameters.
s s
p1=391.635Torr, p2=227.98 Torr
P Torr 237.60 265.20 317.50 333.00 368.70 387.20
x1 0.0870 0.1800 0.4040 0.4790 0.7130 0.9070
y1 0.1870 0.3400 0.5780 0.6420 0.7960 0.9070
27 The Vanlaar constants A and B for the system nitromethane (1) /Carbontetrachloride (2)
at 45OC are 2.230 and 1.959 respectively. Calculate the activity coefficient of
nitromethane in a solution containing 30 mole% nitromethane.
How is the thermodynamic consistency tested
28 The following isothermal VLE data for I-Propanol (1) / Chlorobenzene (2) at 95 0C was
reported. Test whether the data is thermodynamically consistent or not.
P 350 446 518 574 609 632 665 681 691
Torr
x1 0.055 0.12 0.212 0.313 0.430 0.520 0.63 0.749 0.872
9 8
y1 0.35 0.51 0.599 0.650 0.697 0.726 0.75 0.813 0.883
1 9
s s
Given p1=681.77 Torr , p 2=248.48 Torr
Write three suffix Margules equation, Vanlaar equations show them graphically

29 Calculate the VLE data for chloroform (1) / 1,4 dioxane (2) at 323.15 K and hence reduce
the VLE data to a simple mathematical equation for dimensionless excess Gibbs energy.
P 15.79 17.51 18.15 21.37 24.95 29.82 60.38 65.39 69.36
kP
a
x1 0.00 0.0932 0.1248 0.2626 0.3615 0.4750 0.8780 0.9398 1.0
y1 0.00 0.1794 0.2383 0.4628 0.6184 0.7552 0.9860 0.9945 1.0
UNIT V

30 Derive Gibbs relation

3
2 CT
G=H −aTlnT −b T − +¿
2
31 State and explain the criteria for chemical reaction equilibrium.

32 Calculate the decomposition pressure, that is the equilibrium pressure of gaseous species
that result from the decomposition of calcium carbonate at 1200 K. The isobaric molar
heat capacities of CaCO3 (s) and CaO (s) are given by
5
−3 12.87 x 10
C p CaC 0 =82.34 +49.75 x 10 T − 2
3
T
5
−3 4.51 x 10
C pCaO=41.84+20.25 x 10 T − 2
T
Where CP is in J/molK and T in K. ∆a = 4.869, ∆b = -20.812 x 10-3, ∆c = 0,
∆d = 0, ∆e = -1.259 x 105 .
33 Develop a relation between equilibrium constant K & temperature T for the ammonia
synthesis process
Given reaction 1/2N2 + 3/2H2 ------> NH3
Data : DH o 298 K = - 46,190 joules/g moles
DF o 298 K = - 16,635 joules/g moles
DCp = - 31.780 + 35.517 * 10-3 T – 9316* 10-6T2
Cp in joules/g moles K, T in K
34 The standard heat of formation and standard free energy of formation of ammonia at 298
K are -46,100J/mol and -16,500 J/mol respectively. Calculate the equilibrium constant for
the reaction N2 + 3H2 2NH3. At 500 K assuming that the standard heat of reaction is
constant in the temperature range 298 to 500 K.
Explain the parameters affecting the equilibrium constant
35 Estimate the standard free energy change and equilibrium constant at 700 K for the
reaction N2 + 3H2 ------> 2NH3
Data :The standard heat of reaction and free energy of reaction at 298 K are DH o = -
92,200 J/mol; DG o = - 33,000 J/mol and the constants are Da = - 48.8 ;
Db = 34.76 x 10-3
36 Develop a relation between equilibrium constant K and temperature T for the ammonia
synthesis reaction.
o J o J
N2+ H2→ 2 N H 3 Data: ∆ H 298 =−46,190 mol, ∆ G298 =−16,635 mol ,
g g
o −3 −6 2 J
∆ C P 298=−31.78+ 35.52 X 10 T −9.32 X 10 T molK .
g
37 Develop an expression to determine the rate constant in terms of Gibbs free energy change
and discuss the effect of temperature on the equilibrium constant.
38 The equilibrium constant Ka for the water-gas shift reaction
CO2(g) + H2(g) CO(g) + H 2O(g) at 298.15 K is 8.685 x 10 -6. Estimate
the value of ka at 1000K assuming that ∆Ho is constant in the temperature range 298.15K
to 1000K.
What are the factors that affect the equilibrium conversion. Discuss.

39 Industrial methanol is produced according to the reaction

CO(g) + 2H2(g) CH3OH(l). Assuming that the reaction attains a steady state of
equilibrium, estimate the degree of conversion at 500K and 5 bar pressure. If the reactor is fed
with a stoichiometric mixture of CO(g) and H2(g), Determine the composition of the equilibrium
mixture at 500K and 5 bar pressure. The enthalpy of vaporization of CH3OH at 298.15K is 37.988
kJ/mol.
o
Given: Sat pressure of CH3OH at 298.15K is 0.16716 bar.∆ G f 298(CO)=−137.327 kJ , ∆ G f 298¿ ¿,
o
∆ H f 298(CO)=−110.532kJ , ∆ H f 298¿ ¿ , ∆a = -63.710, ∆b = 89.915 x 10-3, ∆c = -28.683 x 10-6, ∆d
= 0, ∆e = -1.122 x 105.
40 Estimate the equilibrium composition if CO (g) H 2(g) and A(g) are fed to a reactor in the
mole ratio 1:2:5 for the production of methanol. The reactor is maintained at 500 K and 5
bar pressure. Assume that the gas phase behaves like an ideal gas. Take ka= 4.973 x 10-3.
41 Calculate the decomposition pressure, that is the equilibrium pressure of gaseous species
that result from the decomposition of calcium carbonate at 1200 K. The isobaric molar
heat capacities of CaCO3 (s) and CaO (s) are given by
5
−3 12.87 x 10
C p CaC 0 =82.34 +49.75 x 10 T − 2
3
T
5
−3 4.51 x 10
C pCaO=41.84+20.25 x 10 T − 2
T
Where CP is in J/molK and T in K. ∆a = 4.869, ∆b = -20.812 x 10-3, ∆c = 0, ∆d = 0, ∆e = -
1.259 x 105 .
42 The reaction N2 + O2 2NO takes place in the gas phase at 2700 oC and
2025 kPa. The reaction mixture initially comprises 15 mol% oxygen, 77 mol% nitrogen
and the rest inerts. ∆Go = 113.83 kJ/mol at this temperature. Assuming ideal gas behavior,
calculate the partial pressures of all species at equilibrium.
Calculate the value of K at 25oC and 800oC for the water gas reaction
CO+ H 2 O →C O2+ H 2 using the following data:
Substance H2 CO H2O CO2
o
∆ H f (kJ) 0 -110.52 -241.83 -392.51
o
∆ G f (kJ) 0 -137.27 -228.60 -394.40
Where ∆ H of ∧¿ ∆ G of refer to standard state of enthalpy and free energy change
respectively at 25oC