SVS COLLEGE OF ENGINEERING

COIMBATORE 642 109

DEPARTMENT OF PETROCHEMICAL ENGINEERING

QUESTION BANK

Name of the Faculty : Mrs. G. Sarojini

Subject : Chemical Engineering Thermodynamics

Regulations : R2017

Course Code : PE8491

Branch : Petrochemical Engineering

Year & Semester : II Y ear & IV Semester

Academic Year : 2018-19

 UNIT-I
ZEROTH AND FIRST LAWS, PROPERTIES OF PURE SUBSTANCES
Part-A
1. What is the difference between the classical and the statistical approaches to
thermodynamics?
The properties of matter such as velocity, kinetic energy and energy of the individual
molecule at a given instant or at a particular time are studied. This approach is known as
statistical thermodynamics. It is also called as microscopic approach.

Instead of studying parameters at molecular level, the behavior of the total system in terms
of properties such as pressure, volume, temperatures are studied. These properties at every
instant can easily be measured called thermodynamics. It is also as called as macroscopic
approach.

Classical thermodynamics deals with the effects of many molecules.

2. Explain the following terms. (a) Process (b) Cycle

Process: It is defined as the change of state undergone by a gas due to energy flow.

Ex: Constant volume process, Polytropic process etc.,

Cycle: When a system undergoes a series of processes and return to its initial condition, it
is known as cycle. Ex: Air standard cycle, Diesel cycle etc.,

3. What is heat?
Heat is defines as the energy crossing the boundary of a system due to the temperature
difference between system and surrounding. It is usually represented by ‘Q’ and expressed
in kJ or J.

4. Define a thermodynamic system. Classify the following systems as

open/closed/isolated: (a) Mixture of ice and water in a metal container, (b) A wind
mill.
Thermodynamic system is defined as the any space or matter or group of mater where the
energy transfer or energy conversions are studied.

Mixture of ice and water in a metal container is a closed system

A wind mill is an open system

5. Define heat and thermodynamic definition of work.

Heat:

Heat is defined as the energy crossing the boundary of a system due to the temperature
difference between system and surrounding.
 Thermodynamic Work:

It is the work done by the system when the energy transferred across the boundary of the
system. It is mainly due to intensive property difference between the system and
surrounding.

6. What is meant by point and path functions? Give some examples.

The quantity which is independent on the process or path followed by the system is known
as point function.

Ex: Pressure, Volume, Temperature etc..,

The quantity which is dependent on the process or path followed by the system is known as
path function.

Ex: Heat transfer, Work transfer

7. What is meant by thermodynamic equilibrium? Mention its types.

When a system is in the thermodynamic equilibrium, it should satisfy the following three
conditions

a. Mechanical Equilibrium – Pressure remains constant

b. Thermal Equilibrium - Temperature remains constant

c. Chemical Equilibrium - There is no chemical reaction

8. Define thermodynamic properties.

Thermodynamic properties are the observable characteristics of the thermodynamic
system. Pressure, temperature, volume, viscosity, modulus of elasticity etc. are the
examples of property.

9. What is the difference between a closed system and an open system?

S.No Closed system Open System
 1. There is no mass transfer Mass transfer will take place

In addition to the heat and work, mass

2. Only heat and work will transfer
transfer also takes place

3. System boundary is fixed System boundary may or may change

Ex: Piston & cylinder arrangement,

4. Ex: Air compressor, Boiler
Thermal power plant

10. What are intensive and extensive properties?

S.No Intensive Properties Extensive Properties

Independent on the mass of the

1. Dependent on the mass of the system
system

If we consider part of these properties

remain same. If we consider part of the system, it
2. will have a lesser value. Ex: Total
Ex: Pressure, Temperature, Density, energy, Total volume, weight etc..,
etc..,

11. Distinguish between the terms “change of state”, “path” and “Process”.
State: It is the condition of the system at any particular moment. The state is identified by
the properties of the system such as pressure, volume, temperature etc.,

Path: The succession of states crossed through the control volume during change of state
in the thermodynamic system is called path.

State 2

State 1
 Process: It is the change of state undergone by a system from one equilibrium state to
another. To describe a process completely, one should specify the initial and final state of
the process as well as path if follows.

12. What is the qualitative difference between heat and work?

Heat is considered as an input to perform the desired work either on the system or by the
system.

Work is considered as output done on the system or by the system.

13. Define quasi-static process.

The process is said to be quasi-static, it should proceed infinitesimally slow and follow
continuous series of equilibrium states. Therefore, the quasi-static process may be a
reversible process.

14. What is meant by hyperbolic process?

The hyperbolic process follows the law PV=C. This process is identical to isothermal
process. But, Isothermal process is applicable to gases only. Hyperbolic process is
applicable to vapors.All properties like work done; heat transfer, change in enthalpy and
change in internal energy are same as isothermal process.

15. Define Zeroth law of thermodynamics.

It states that when a body ‘A’ is in thermal equilibrium with a body ‘B’ and also separately
with a body ‘C’ then ‘B’ and ‘C’ will be in thermal equilibrium with each other.

16. Differentiate microscopic and macroscopic approach.

Microscopic approach is one having fragmented the system under consideration and
analysing the different constituent subsystem.
Macroscopic approach is the one in which complete system as a whole is considered and
studied without caring what constitute the system at microscopic level.
17. What is pure substance? Give examples.
A substance that has fixed chemical composition throughout is called pure substance. It
does not have to be of a single chemical element or compound. A mixture of various
chemical elements or compounds also qualifies as a pure substance as long as the mixture
is homogenous.
Example: Mixture of liquid water and water vapor; carbon dioxide, CO2.
18. Define compressibility factor.
It measures the deviation of a real gas from ideal behavior. It is represented by Z=PV/RT
19. Define generalized compressibility chart.
It is constructed based on the principle of corresponding states. It is one of the best means
of expressing the deviation from ideal behavior. The compressibility factor Z is plotted
against the reduced temperature and reduced pressure.
20. Define law of corresponding states.
It states that all gases when compared at the same reduced temperature and reduced
pressure has approximately the same compressibility factor and all deviate from the ideal
behavior to the same extent.
21. Define Mollier diagram.
An enthalpy–entropy chart, also known as the h–s chart or Mollier diagram, plots the total
heat against entropy, describing the enthalpy of a thermodynamic system.
22. What are the corollaries to the first law of thermodynamics?
Corollary - 1 There exists a property of a closed system such that a change in its value is
equal to the difference between the heat supplied and the work done during any change of
state.

Corollary - 2 The internal energy of a closed system remains unchanged if the system is
isolated from its surroundings.

23. Define thermodynamic temperature scale.

A scale widely used to measure temperature; it is also a useful tool that also helps in
calculating the thermodynamic quantities and possesses some degree of universality.

Part-B

1. 0.3 kg of air at 1.5bar pressure and 870C temperature at condition 1 is compressed

polytropically to condition 2 at pressure 7.5 bar, index of compression being 1.2. it is then
cooled at constant pressure to condition3 and then finally heated at constant temperature to
its original condition1. Find the net work done and the heat transferred. Take R= 0.287
KJ/Kg K, CP =1.005 KJ/Kg K, =1.4.

2. 0.2 kg of air at 1.5 bar and 270C is compressed to a pressure of 15 bar according to the law
PV1.25= Constant. Determine the work done on or by air, heat flow to or from the air,
increase or decrease in entropy.

3. A three process cycle operating with nitrogen as the working substance has constant
temperature compression at 340C with initial pressure 100 KPa. The gas then undergoes a
constant volume heating and then polytrophic expansion with 1.35 as index of compression.
The isothermal compression requires -67 kJ/kg of work. Determine
 i) P,V and T around the cycle
ii) Heat in and out
Net work done. For nitrogen CV=0.74 kJ/kg K.

4. 0.3 kg of air is at 1.5 bar pressure and 87oC temperature at condition 1 is compressed
polytropically to condition 2 at pressure 7.5 bar, index of compression being 1.2. It is cooled at
constant pressure to condition 3 and then finally heated at constant temperature to its original
condition 1. Evaluate the net work done and heat transferred.
Take R=0.287 kJ/kgK, CP = 1.004 kJ/kgK and γ = 1.4.

5. A fluid undergoes a adiabatic compression from 5 MPa, 2m3 to 0.05 m3 according to the law,
pv1.3= constant. Determine the change in enthalpy, internal energy, entropy, heat and work
transfer during the process.
 UNIT-II

APPLICATION OF I LAW TO STEADY STATEPROCESSES, II LAW

PART-A
1. Explain first law of thermodynamics.
First law of thermodynamics states that when system undergoes a cyclic process net heat
transfer is equal to work transfer. ∫Q = ∫W

2. What is meant by enthalpy?

The sum of internal energy and flow energy is known as enthalpy of the system.

Mathematically, enthalpy H = U + PV (kJ)

Where U = Internal energy (kJ)

P = Pressure (kN/m2)

V=Volume (m3)

3. Define flow energy.

Work is needed to push the fluid into or out of the boundaries of a control volume if mass
flow is involved. This work is called the flow work (flow energy). Flow work is necessary
for maintaining a continuous flow through a control volume.

4. What are the conditions for steady flow process?

When a flow process is satisfying the following conditions, it is known as a steady flow
process.

The mass and energy content of the control volume remains constant with time.

The state and energy of the fluid at inlet, at the exit and at every point within the control
volume are time independent.

The rate of energy transfer in the form of work and heat across the control surface is
constant with time.

5. Define reversible process.

Thermodynamic system that is capable of restoring its original state by reversing the
factors responsible for occurrence of the process is called reversible system and the
thermodynamic process involved is called reversible process.
6. Define irreversibility.
The irreversibility is the characteristics of the system which forbids system from retracing
the same path upon reversal of the factors causing the state change. Thus, irreversible
systems are those which do not maintain equilibrium during the occurrence of a process.
7. Limitations of I law of thermodynamics.
The first law of thermodynamics has the inability to deal with the direction of the process
and the extent of change. It also fails to recognize the qualitative difference between
various forms of energy.
8. Define internal energy. Give its unit and symbol.
The energy stored within the body is called internal energy. Its unit is kJ. It is denoted by
‘U’. ΔU = Q - W

9. State the Kelvin – Plank statement of second law of thermodynamics.

Kelvin – Plank states that it is impossible to construct a heat engine working on cyclic
process, whose only purpose is to convert all the heat energy given to it into an equal
amount of work.

10. What is PMM-I? Why is it impossible?

PMM of the first kind delivers work continuously without any input. It violates first law of
thermodynamics. It is impossible to construct an engine working with this principle.

11. State Clausius statement of second law of thermodynamics.

It states that heat can flow from hot body to cold without any external aid but heat cannot
flow from cold body to hot body without any external aid.
12. State Carnot’s theorem.
No heat engine operating in a cyclic process between two fixed temperature, can be more
efficient than a reversible engine operating between the same temperature limits.

13. What is the Corollaries of Carnot theorem?

(i) In the entire reversible engine operating between the two given thermal reservoirs with
fixed temperature, have the same efficiency.

(ii) The efficiency of any reversible heat engine operating between two reservoirs is
independent of the nature of the working fluid and depends only on the temperature of the
reservoirs.

14. Define – PMM of second kind.

Perpetual motion machine of second kind draws heat continuously from single reservoir
and converts it into equivalent amount of work. Thus it gives 100% efficiency.

15. Write the expression for COP of a heat pump and a refrigerator?
COP of heat pump
 Heat supplied T2
COPHP = =
Work input T2 − T1

COP of Refrigerator

Heat extracted T1
COPHP = =
Work input T2 − T1

16. What is the relation between COPHP and COPref?

COPHP = COPref +1

17. Why Carnot cycle cannot be realized in practical?

In a Carnot cycle all the four processes are reversible but in actual practice there is no
process is reversible. There are two processes to be carried out during compression and
expansion. For isothermal process the piston moves very slowly and for adiabatic process
the piston moves as fast as possible. This speed variation during the same stroke of the
piston is not possible. It is not possible to avoid friction moving parts completely.

18. Name two alternative methods by which the efficiency of a Carnot cycle can be
increased.
Efficiency can be increased as the higher temperature T2 increases.

Efficiency can be increased as the lower temperature T1 decreases.

19. Why a heat engine cannot have 100% efficiency?

For all the heat engines there will be a heat loss between system and surroundings.
Therefore we can’t convert all the heat input into useful work.

20. Is the second law independent of the first law?

Yes, the second law of thermodynamics independent of the first law. The second law
speaks about quality of energy.

21. Define Entropy.

The entropy of an assembly in a state of thermal equilibrium is a thermodynamic property,
in principle related through equations of state to other thermodynamic properties. The
change of entropy is defined only for reversible processes stated as
22. Define the terms source sink and heat reservoir.
Source is the part from where heat is rejected to a colder body for doing work, or the part
from where heat is generated for doing work is called as the source,

Sink is the part which receives heat from work absorbing or work developing device is
called sink.

Reservoir is the part which supplies or receives heat continuously without change in its
temperature is called a reservoir.
23. What is meant by principle of increase of entropy?
For any infinitesimal process undergone by a system, change in entropy, dS=dQR/T

For a reversible, dQ= 0 and hence dS= 0

For irreversible, dS> 0

So the entropy of a system would never decrease, it will always increase and remains
constant if the pressure is reversible and is called as principle increase of entropy.

24. What is meant by Clausius inequality?

It is impossible for a self acting machine working in a cyclic process unaided by any
external agency to convey heat from a body at a lower temperature to a body at a higher
temperature,

25. Explain the term reversibility.

If the process traces the same path during the process when reversed is called as
reversibility. And the entropy change is zero.
26. Can the entropy of the universe decreases? Why?
Entropy of the universe cannot decrease. It will be constant or will increase due to
irreversibility.

27. What is the essence of the second law of thermodynamics?

1 To know the feasibility of process.

2 To know about the quality of energy.

28. Define the term absolute entropy.
The change in entropy of the system with respect to ambient conditions or any other
standard reference condition is known as absolute entropy.

29. Give the criterion of irreversibility.

If the conditions of a given reversible process lead to the violation of the second law of
thermodynamics then the process is said to be irreversible.

PART-B

1. An ice plant working on a reversed Carnot cycle heat pump produces 15 tons of ice per
day. The ice is formed from water at 00C and the heat is rejected to the atmosphere at
250C. The heat pump used to run the ice plant is coupled to a Carnot engine which
absorbs heat from a source which is maintained at 2200C by burning liquid fuel of 41500
kJ/kg of calorific value and rejects the heat to the atmosphere. Determine
(1) Power developed by the engine
(2) Fuel consumed per hour. Take enthalpy of fusion of ice =334.5 kJ/kg
 2. A reversible heat engine operates two reservoirs at 8200C and 27oC. Engine drives a
reversible refrigerator which operates between reservoirs at temperature of 270C and -
150C. The heat transfer to the engine is 2000kJ and the network available for the
combined cycle is 300kJ.

iii) How much heat is transferred to the refrigerant and also determine the total heat
rejected to the reservoir at 270C.
If the efficiency of the heat engine of the heat engine and COP of the refrigerator are each 40%
of their maximum values, determine heat transfer to the refrigerator and also heat rejected to the
reservoir at 270C.

3. Develop the energy conversion efficiency of the Carnot cycle in terms of temperature.
 UNIT-III

THERMODYNAMIC POTENTIALS, EQUILIBRIA AND STABILITY

PART-A
1. What is refrigeration?
The term refrigeration means maintenance of temperature below that of surroundings.
2. How the low temperature is achieved?
Allowing a phase change to take place in a such a way to extract heat, e.g., evaporation of
liquid. Expanding a compressed gas or vapor so that it does external work. Desorption of
gas. Expanding a gas in Joule Thomson way
3. Define Capacity of Refrigeration or Ton of refrigeration
The one ton of refrigeration is equivalent of heat removal at the rate of 200 BTU/min or
12000 BTU/h or 3024 kcal/h necessary to freeze 1 ton of water at 320F.
4. Define the coefficient of performance.
It is the ratio of refrigeration produced and work supplied.
5. Mention a few common refrigerators.
Anhydrous ammonia, Halogenated hydrocarbons commonly known as Freon – 12 ,Methyl
chloride, Carbon dioxide and Sulphur dioxide.
6. What is Heat pump?
It is a device used to absorb heat from the low temperature region and rejects into high
temperature region.
7. What are the different methods for the liquefaction of gases?
Cooling at constant pressure, Cooling by expansion in an engine and Cooling by throttling.
8. What is the difference between a heat pump and a refrigerator?
Heat pump is a device which operating in cyclic process, maintains the temperature of a
hot body at a temperature higher than the temperature of surroundings.
A refrigerator is a device which operating in a cyclic process, maintains the temperature of
a cold body at a temperature lower than the temperature of the surroundings.
9. What is meant by heat engine?
A heat engine is a device which is used to convert the thermal energy into mechanical
energy.
10. Define the term COP?
Co-efficient of performance is defined as the ratio of heat extracted or rejected to work
input.
Heat extracted or rejected
COP =
Work input
 11. Define refrigerant.
A refrigerant is a substance or mixture, usually a fluid, used in a heat pump and
refrigeration cycle. In most cycles it undergoes phase transitions from a liquid to a gas and
back again.
12. What is the purpose of sub-cooling the refrigerant in vapour compression
refrigeration cycle?
It results in increase of C.O.P provided that no further energy has to be spent to obtain the
extra cold coolant required. It is used to increase the refrigerating effect.
13. State the methods to increase the thermal efficiency of a Rankine cycle
By regenerating feed heating, By reheating of stream, By water extraction & By
using binary vapour.
14. Define Clapeyron equation.
It predicts the dependence of equilibrium pressure on temperature when two phases of a
given substance coexist. It is given by, dP/dT=∆H/T∆V

15. What is Joule-Thomson coefficient (µ)?

It is the fall in temperature associated with a unit decrease in pressure under this condition.
µ=(∂T/∂P)H
16. What is Gibbs phase rule?
There exists a definite relationship between the number of degrees of freedom (F), the
number of distinct chemical species constituting the system (C), and the number of phases
present at equilibrium (Π). This is given by Gibbs phase rule, F=C-Π+2
17. Write the clausius clapeyronequation ?
P2s H  1 1 
n    
P1s R  T1 T2 
P1s & P2s are vapour pressures
T1 & T2 are temperatures

PART-B
1. Derive the Clapeyron equation

2. An ice skate is able to glide over the ice because the skate blade exerts sufficient pressure on
the ice that a thin layer of ice is melted. The skate blade then glides over this thin melted water
layer. Determine the pressure an ice skate must exert to allow smooth ice skate at -100C. The
following data is given for the range of temperature and pressure involved.

Hfg(ice) = 334kJ/kg; vliq= 1*10-3 m3/kg; vice= 1.01*103 m3/kg. .

3. Derive the Maxwell relations connecting thermodynamic properties.

4. Derive the first and second form of entropy equations.

5. A two stage vapour compression refrigeration system with a direct contact heat exchangers
operates with ammonia as a refrigerant. The evaporator and condenser temperatures are -30C
and 40C respectively. If the capacity of the plant is 30 tonnes of refrigeration, estimate the total
work of compression and theCOP. Had the compression been done in a single stage, what would
have been the percentage increase in the COP owing to the staging of the compression process?

6. A vessel of volume of 0.04 m3 contains a mixture of saturated water and saturated steam at a
temperature of 2500C. The mass of the liquid present is 9 kg. Estimate the pressure, the mass, the
specific volume, the enthalpy, the entropy and the internal energy.
 UNIT-IV

PROPERTIES OF PURE COMPONENTS AND MIXTURE

PART-A
1. What is Gibbs duhem equation?
 ni d i  0 is known as Gibbs Duhem equation
 T 1 p
2. What is partial molar property?
The partial molar property of a particular component in a mixture measures the
contribution of that component to the mixture property.

 (nm) 
Mi   
 ni  P ,T ,nj

3. Define Lewis – Randall role

id
f 1  Xifi This equation is known as Lewis Randal rule

4. What is the equation for fundamental excess property relation?

The equation for fundamental excess property relation is
E
 nG E  nV E nH E Gi
d   dP  2
dT   dni
 RT  RT RT i RT

5. What is partial molar volume for Vi ?

 (nV ) 
The Partial molar volume for Vi is Vi  
 ni  P ,T ,nj

6. Why  xidmi  0 ?
i

The equation  xidmi  0

i
is satisfied for all Changes in P, T and Mi caused by changes

of state in a homogenous state.

7. What is the fugacity coefficient?
fi
The fugacity coefficient is denoted by i 
pi
Fi Fugacity of species i
Pressure of species i
8. Define activity.
It is the ratio of fugacity of a component in the solution in a given condition to the fugacity
of that component in the standard state. ai=fi/fi
9. What is activity coefficient?
It measures the extent to which the real solution departs from ideality. It is
denoted by γi and fi=γixifi°

10. Define residual volumes.

The residual volume α is defined as the difference between V and the volume occupied by
one mole of an ideal gas at same temperature and pressure. α= V-(RT/P)
11. What is departure function?
It is the difference between the thermodynamic property at the specified temperature and
pressure and the property that the substance would have exhibited at same temperature and
pressure, had it been an ideal gas.
12. Define chemical potential.
The term chemical potential is equivalent to free energy for one mole. Gibb’s defined the
chemical potential as, μ = F = H – TS
Where, F, H and S are based on single mole of material. Obviously chemical potential is an
intensive property.
13. Define fugacity.
It is used solution thermodynamics to represents the behavior of real gases. In chemical
thermodynamics, the fugacity of a real gas is an effective partial pressure which replaces
the mechanical partial pressure in an accurate computation of the chemical equilibrium
constant. It is equal to the pressure of an ideal gas which has the same chemical potential
as the real gas.
14. What are thermodynamic diagrams?
Thermodynamic diagrams are diagrams used to represent the thermodynamic states of a
material (typically fluid) and the consequences of manipulating this material. For instance,
a temperature-entropy diagram (T-S diagram) may be used to demonstrate the behavior of
a fluid as it is changed by a compressor.
15. Define Lewis-Randall rule.

It applies to each species in an ideal solution at all conditions of temperature,

pressure, and composition. It shows that the fugacity of each species in an ideal solution is
proportional to its mole fraction; the proportionality constant is the fugacity of pure
species i in the same physical state as the solution and at the same T and P.
16. Define Raoult’s law.
It states that the partial vapor pressure of each component of an ideal mixture of liquids is
equal to the vapor pressure of the pure component multiplied by its mole fraction in the
mixture.
For single component,
where is the partial vapor pressure of the component in the gaseous mixture,
is the vapor pressure of the pure component ,
is the mole fraction of the component in the mixture .
17. Define Henry’s law.
The law states that the mass of a dissolved gas in a given volume of solvent at equilibrium
is proportional to the partial pressure of the gas. pi = xiKi, Where pi = partial pressure of the
solute over the solution
xi = mole fraction in the solution
Ki = proportionality constant (Henry’s law constant)
18. Define Gibbs Duhem equations.
It tells how the partial molar properties change with compositions at constant temperature
and pressure. Σ ni dMi = 0
19. What are property changes of mixing?
ΔM = M-Σxi Mi
ΔM is the correction term used when thermodynamic properties of the solution whether
ideal or real are evaluated from the pure component.
20. Define excess property.
The excess property ME is defined as the difference between the actual property and the
property that would be calculated for the temperature, pressure and composition. M E=M-
Mid

PART-B
1. A closed rigid cylinder is divided by a diaphragm into equal compartments, each of
volume 0.1m3. Each compartment contains air at a temperature of 200C. The pressure in
one compartment is 2.5MPa and in the other compartment is 1 MPa. The diaphragm is
ruptured so that the air in both the compartments mixes to bring the pressure to a
uniform value throughout the cylinder which is insulated. Find the net change of entropy
for the mixing process. (M/J 2015)

2. A mixture of ideal gases consists of 5kg nitrogen and 10kg of carbon dioxide at a pressure
of 250kPa and at a temperature of 250C. Find

(i) The mole fraction of each component

(ii) The equivalent molecular weight of the mixture
(iii) The equivalent gas constant of the mixture
(iv) The volume and density of the mixture
 (v) The CP and CV of the mixture.
If the mixture is heated at constant volume to 500C, find the change in internal energy,
enthalpy and entropy of the mixture. Find the same properties of the mixture, if the heating is
carried at constant pressure to 600C. Take  for N2 and CO2. (N/D 2014)

3. Methane at 1 bar and 250C enters an insulated chamber at a rate of 2.5 kg/s. It is mixed
with air in an air/ methane mass ratio of 18. The flow is steady and the kinetic energy
changes are negligible. Ambient pressure and temperature are 1 bar and 250C, determine
(a) the temperature of the mixture leaving the chamber
(b) the irreversibility of the mixing per kilogram of the methane. (Take CV and CP of
methane as 1.7354kJ/kg K and 2.2537 kJ/kg K )

4. Propane (g) at 25C and 100 kPa is burned with 40% theoretical air at 25C and 100 kPa. The
reaction occurs reversibly at 25C. The oxygen and nitrogen gases are separated before the
reaction takes place ( each at 100 kPa, 25C). The constituents in the products are separated and
each is at 25C, 100 kPa. Determine

(i) The reversible work for this process

(ii) If the above reaction occurs adiabatically and each constituent in the products is at
100 kPa pressure and at the adiabatic flame temperature, compute the increase in entropy,
the irreversibility of the process and the the availability of the products of combustion.

5. Derive the expression for fugacity and fugacity coefficient.

6. Formulate the Gibb’s –Duhem relation for mixture and give its applications
 UNIT – V

PHASE EQUILIBRIA AND CHEMICAL REACTION EQUILIBRIA

PART-A

1. What are the criteria of Phase equilibrium?

The criteria for the phases to be in equilibrium is that temperature, pressure and chemical
potential must have the same values for a given component in each phase at equilibrium.
2. What are the criteria of equilibrium in terms of fugacity?
According to criteria of equilibrium, the temperature and chemical potential must be same
for a component in all phases. Therefore, the fugacity of the component must also be same
in all phases.
3. Define equilibrium constant.
The equilibrium constant is defined as the ratio of the mole fraction of a component in the
gas phase and liquid phase.
4. What is the significance of ‘van Laar equations’?
The Van Laar equations are used to evaluate activity coefficients. The equations are
written as,

Where ‘A’ and ‘B’ are constants.

5. What are the criteria for stability?
The criteria for stability is that at constant temperature and pressure the free energy change
on mixing ΔG, its first and second derivatives are all conditions functions of the
concentration term x and
6. Define the degrees of freedom (F)?
The number of degrees of freedom denoted by F which, the number of independent
variables that must be arbitrarily fixed as to establish uniquely the intensive state of the
system.
7. State Duhem theorem.
For any closed systems formed initially from the given masses of prescribed chemical
species, the equilibrium state is completely determined when any two independent
variables are fixed.
8. Give the importance of Vapor liquid equilibria data.
The vapor-liquid equilibrium data are essential for many engineering calculations,
especially in the design and analysis of separation operations like distillation, absorption
etc.
9. What are boiling point diagrams?
The boiling point diagrams are plot of temperatures as ordinates against composition of,
liquid and vapor as abscissa. The boiling point diagrams are known as T – x,y diagrams.
10. What you meant by Dew point curve and bubble point curve?
Dew point is the condition where first drop of condensed liquid is appearing while cooling
the super heated vapor. The upper curve of T – x,y which connect all the dew point is
known as dew point curve. Similarly bubble point is the one where first bubble originates.
11. What is sub cooled liquid and super heated vapor?
The liquid present below the bubbles point curve in the boiling point curve is known as sub
cooled liquid and vapor present above the dew point curve is known as super heated vapor.
12. What is a tie line?
The line joining the point where liquid and vapor are at equilibrium at the system pressure
and temperature is known as tie line.
13. Define relative volatility.
The relative volatility of a system is the ratio of vapor pressure of our component to
another

14. What are called azeotropes?

Azeotropes are constant boiling mixtures. They are the mixtures having constant boiling
point.
15. Explain minimum boiling azeotropes with examples.
The minimum boiling azeotropes are having their boiling point less than of the pure
components and such azeotropes have maximum pressure. E.g, Isopropyl ether – Isopropyl
alcohol, CS2 – Acetone, Benzene – cyclohexane, Water – ethanol.
16. Explain maximum boiling azeotropes with examples.
The maximum boiling azeoyropes are having their boiling point greater than that of the
pure component and such azeotropes have minimum pressures. E.g, Acetone –
Chloroform, Water – Acids (HCl, H2SO4).
17. What are the applications of Equilibrium Constants?
The K values are to decide,
Dew point and Bubble point temperatures and pressure, Composition of phase in
equilibrium, Distribution of mixture between liquid and vapor.
18. Give Duhem – Margules equation.
The form of Gibb’s Duhem equation in terms of Fugacity

Is referred a Duhem – margules equation.

19. What are called Kellong charts?
Kellon charts are K vs T, P charts. Equilibrium constant at particular temperature and
pressure can be calculated for different substance using Kellong charts.
20. Define activity.
It is defined as the ratio of the fugacity of the component in the solution to the fugacity in
the standard state. ai=fi/fi°
21. Define bubble point and dew point temperature.
A bubble point temperature is the one at which the first bubble of vapor is produced from
liquid on heating at constant pressure. The dew temperature is the one at which first drop
of condensate is formed on cooling a vapor at constant pressure.

22. Define Azeotropes.

Azeotropes are the constant boiling mixture. When azeotrope is boiled the resulting vapor
will have the same composition as the liquid from which it is produced.

23. How is equilibrium constant determined by standard free energy change and the
temperature?
The equilibrium constant is determined by standard free energy change and the
temperature by, ΔG° = -RT ln K

24. Define Le Chaterlier’s principle.

It states that a system at equilibrium when subjected to disturbances respond in away that
tends to minimize the effect of the disturbance.
25. Define Van’t Hoff equation.
It predicts the effect of temperature on the equilibrium constant and hence on the
𝑑 ln 𝐾𝑒𝑞 ∆𝐻 𝜃
equilibrium yield. =
𝑑𝑇 𝑅𝑇 2

PART-B

1. Using the Gibbs function data, determine the equilibrium constant for the reaction
H2 +O2H2O at 298K and 1800K.

2. Create the expression for fugacity and fugacity coefficient at temperature T and pressure
P.

3. Develop an expression for vapour-liquid equilibrium for a multicomponent system.

4. Ammonia dissociates into N2 and H2 gases according to the equation N2 + H2 NH3.
Determine the relation between the equilibrium constant and the degree of reaction at
equilibrium for this reaction.