GATEFLIX Chemical Thermodynamics

THERMODYNAMICS
For
CHEMICAL ENGINEERING
Chapter 1: Basic Concepts
1.1.1 What is thermodynamics?
“Thermodynamics is a basic science that deals with energy conversion feasibility of a
Process, and its effect on the properties of the system, surrounding.
 How does thermodynamics differ from heat transfer?

Let’s consider the following example
A metal rod which is maintained at 800C, is immersed in water bath (200C). Heat is
transferred from metal rod to water bath due to temperature gradient. The final
equilibrium temperature can be calculated from thermodynamics. But, it doesn’t tell
about the time to achieve the final temperature. The time can be calculated from the rate
of heat transfer.
Thermodynamics deals with the amount of energy in form of heat or work and considers
only equilibrium state while Heat transfer deals with the rate of energy transfer.
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Basic Concepts
1.2.1 Definitions:
(1) System: The part of the universe that we choose to study
Eg. A reaction vessel, a distillation column or a heat engine
(2) Surroundings: The part of the universe except the system
(3) Boundary: The surface dividing the system from the surroundings
(4) Process: The changes taking place within the system is referred to as a process e.g.
Hydrocarbon fuel and oxygen in a combustion chamber constitute the system and the
combustion of fuel to form water and carbon dioxide constitutes a process.
(5) Control Volume: Fixed volume over which mass can pass in and out of its boundary.
1.2.2 Homogeneous and Heterogeneous systems:
(1) Homogeneous System:
- This system is also called a phase
- The properties are the same throughout properties vary smoothly without showing
any surface of discontinuity eg. Liquid water in a beaker
(2) Heterogeneous system:
- This is a system which consists of more distinct homogeneous regions or phases
- There is a sudden change in properties the phase boundaries eg. A liquid mixture of
benzene and water forms a heterogeneous system made up of two immiscible liquid
phases.
1.2.3 Closed and Open system:
(1) Closed system: Energy can transfer between system and the surroundings, but not
mass. eg. Batch reactor
(2) Open System: Mass and energy can transfer between the system and surroundings.
eg. Heating in open vessel
(3) Isolated system: Neither Mass nor energy can transfer between the system and
surroundings. Eg. Ideal isolated system is not actually possible
Basic Concepts
1.2.4 State and Properties:

- Certain specifications such as pressure, volume and temperature are necessary to
define the conditions of a given system. The condition defined by such specifications
is called the state of the system.
- The variables used to define the state are called the properties
- The essential features of a property are
(1) A property should have a definite value when the system is in a particular state
(2) The value of the property should be determined irrespective of how the system is
brought to that particular state.
State function and path function:
- Some properties do not depend on the past history of the substance nor on the means
by which it reaches a given state. They depend only on present conditions, however
reached. Such quantities are known as state function.
- Eg. Pressure, volume, internal energy.
- Properties those depend on initial and final state as well as the means by which it
reaches a given state are known as path functions.
- Eg. Heat and work
- The differential of a state function represents an infinitesimal change in its value and
the differentials of path function are not changes, but are infinitesimal amounts.
P2 V2
 dP  P  P  P
P1
2 1 and  dV  V
V1
2  V1  V (State functions)
 dQ  Q and  dW  W (Path functions)

1.2.5 Extensive and Intensive properties:
(1) Extensive property:
- The property which depends on the quantity of matter specified in the system is
known as extensive property. Eg. Mass and volume.
- The total value of any extensive property is the sum of the values of the property of
individual components into which the system can be subdivided.
Basic Concepts
(2) Intensive property:

- The property which is independent of the quantity of matter of the system is known
as intensive properly. Eg. Pressure, Temperature, density, etc.
- Some intensive properties are delivering from the extensive properties by specifying
the unit amount of the substance concerned eg. Specific volume, molar volume
1.2.6 Specific and Molar Properties:
Extensive property
Specific property (is an intensive property) =
mass of the substance
 
Eg. Specific volume m3 / kg , V  Vt / m where V t is total volume of the system. The
reciprocal of specific volume is density.
Specific Internal Energy  kJ / kg  = Total internal energy/mass of the system
Extensive property
Molar property (is an intensive property) =
moles of the substance
Eg. Molar volume  kg / kmol  , V  Vt / n . The reciprocal of molar volume is molar

density.
Molar enthalpy  kJ / kg  =Total enthalpy/moles of the system
1.2.7 Force (F):

- The SI unit of force is the Newton
- The Newton is defined as the force which when applied to a mass of 1 kg produces an
acceleration of 1 ms2 .
- 1 kg f = 9.8 N
1.2.8 Temperature (T):
- 10C  1 K  27315
.
- In addition to Kelvin and Celsius scale there are other two scales: The Rankine scale
and the Fahrenheit scale
T R   1.8 * T K 
T  0 F  T R   459.67
T  0 F  1.8 * T  O C  32
Basic Concepts
1.2.9 Pressure (P):

- The normal force exerted by the fluid per unit area of the surface is known as pressure
- The unit of pressure is N / m2 (pascal)
- Other units of pressure are atm, bar, mmHg etc.
1.2.10 Work (W):
- Work W is performed whenever a force acts through a distance.
dW  F*dl (1)
Where F is component of force acting along the line of the displacement dl.
A common example is the compression or expansion of a fluid in a cylinder resulting

from the movement of a piston. The force exerted by the piston on the fluid is equal
to the product of the piston area and the pressure of the fluid.
F  pext *A (2)
dW   (pext *A)dl   pext dV (3)
Integrating the equation (3)

2
W   pext dV
1
The equation indicates that the work depends on the path.
1.2.11 Heat:
Heat is the quantity flowing between the system and the surroundings that can be
used to change the temperature of the system and/or the surroundings. If heat
enters the system, then it is positive. Heat (q), like W, is a function of path; not a state
function. The modern unit of heat is Joule (1 calorie = 4.184 J)
Basic Concepts
1.3.1 Heat Capacity (C):
- Connects heat with temperature

 dq 
dq  CpathdT C path   
 dT  path
Constant volume: CV
Constant Pressure: Cp
q C
path
path dT
1.3.2 Energy:
(1) Kinetic energy:
When a body of mass m, acted upon by a force F, is displaced a distance dl during a
differential interval of time dt, the work done is given by
dW  F*dl (4)
According to newton’s law F  m*a (5)
dW  m*a*dl (6)
The acceleration a  du / dt where u is the velocity of the body.
du dl
dW  m dl  m du
dt dt
dl
Now, u
dt
dW  m*u*du (7)
This equation is integrated for a finite change in velocities from u1 to u2
u
2
 u2 u2 
W  m  udu  m  2  1 
u1  2 2
Basic Concepts
mu22 mu12  mu 2 
or W      (8)
2 2  2 
Each of the quantities ½ mu2 in equation (8) is a kinetic energy.
Ek  ½ mu2 (9)
Unit of kinetic energy is kg m2s2 .
(2) Potential energy:

If a body of mass m is raised from an initial elevation z1 to a final elevation z2 , an
upward force at least equal to the weight of body must be exerted on it, and this force
must move through the distance z2  z1 . As the weight of the body is the force of
gravity on it, the minimum force required is given by Newton’s law
F  ma  mg (10)
The minimum work required to raise the body is the product of this force and the
change in elevation.
W  F  z2  z1   mg  z2  z1   mz2g  mz1g    mzg  (11)
Each of the quantities mzg in equation (11) is a potential energy.
Ep  mzg (12)
1.3.3 Steady state:

Assume that copper rod is connected with heat source (maintained at 1000 C ) and
heat sink (maintained at 300 C ). Heat will transfer from source to sink through copper
rod. After sufficient time, the temperature will be constant at any location on the rod
and does not vary with time.
- Steady state means that properties of the system (copper rod) at any specified
location, are independent of time.
Basic Concepts
1.3.4 Equilibrium state:

- If the copper rod is separated from heat source and heat sink, and it is allowed to cool
 
in atmosphere 250C , the temperature will be constant as well as uniform 250C at  
any location the copper rod. It means the copper rod is in equilibrium with
atmosphere.
- A system is said to be in a state of equilibrium if the properties are uniform throughout
and they do not vary with time.
- In a state of equilibrium. The properties of the system are uniform and only one value
can be assigned to it.
1.3.5 Thermodynamic Equilibrium:
- In thermodynamic, equilibrium refers to a state of equilibrium with respect to all
possible changes-thermal, mechanical and chemical. The criteria for thermal
equilibrium, mechanical equilibrium and chemical equilibrium are presented below.
1.3.6 Thermal Equilibrium- Characterized by equal temperature
1.3.7 Mechanical Equilibrium- Characterized by equal pressure
1.3.8 Chemical Equilibrium- Characterized by equal chemical potential
1.3.9 Zeroth law of thermodynamics:

- It states that if body A is in thermal equilibrium with B and B is in thermal equilibrium
with C, then C is also in thermal equilibrium with A.
- Let body A be brought in thermal contact with another body B. Heat flows from one
to the other and eventually thermal equilibrium is established between A and B. If
another body C is also in thermal equilibrium with B, then it is experimentally
observed that A and C are also in thermal equilibrium.
1.4.1 Reversible Process:
- A process is reversible when its direction can be reversed at any point by an
infinitesimal change in external conditions.
- All spontaneous processes occurring in nature are irreversible. They cannot be
reversed without the use of external energy.
Basic Concepts
- The system as well as surroundings comes back to the same initial state while
following the same path.
1.4.2 The Characteristics of Reversible Process:
(1) In a reversible process, the driving and opposing forces are in exact balance, and in
infinitesimal change and the external conditions would cause a reversal in the
direction of the process.
(2) For reversible process to occur, friction, turbulence and other dissipative effects
would be absent.
(3) It takes an infinite time for its completion.
(4) A reversible process occurring in a work-producing machine delivers the maximum
amount of work and that occurring in a work- requiring machine requires the
minimum amount of work.
(5) A reversible process is an idealized and imaginary concept and may be used for the
comparison of the performance of actual systems and for indicating the efficiency of
processes.
1.4.3 Internally reversible process: If only the reversibility of the system is considered,
not external surroundings, the system is called internally reversible process. The
system changes very slowly, without friction, through a series of equilibrium states in
the case of internally reversible process.
Basic Concepts
1.4.4 Cyclic Process: A series of processes, which returns to its original state. The cycle is
thermodynamic “round trip”.
1.4.5 Irreversible Process: An irreversible process is a process that cannot return both
the system and the surroundings to their original conditions.
1.4.6 Adiabatic Process: The process in which there is no heat transfer into or out of the
system. The system can be considered to be perfectly insulated.
Chapter 2: First law of thermodynamics
One important concept in thermodynamics is the relationship between heat and work.
However, there is no logical relationship between heat and work and so it had to be found
experimentally. The experiments were carried out by J P Joule between 1840 to 1849. The
important experiment involved a system consisting of a well-lagged cylinder containing
water going through a cycle composed of two processes. In the first process, shear work was
done on the system when a paddle turned as a weight was lowered, as shown below.
As a result, the water temperature was found to rise steadily. When the temperature reached
a certain value, the paddle wheel was stopped and the work done noted (historically in foot
pounds-force).In the second process the system was brought into contact with a cold body
so that heat was transferred from the system.
This process was then cut-off when the system reached its original state and again the
amount of heat transfer was noted down (in British Thermal units or calorie).
After making the measurements for a variety of systems and for various amounts of work
and heat, it was found that the amounts of work and heat were always proportional. These
observations were then formalized into the first law of thermodynamics which is stated as:
"If any system is carried through a cycle (the end state being precisely the same as the initial
state) then the net work is proportional to the net heat transfer".
Or,
∮ 𝑑𝑊 = 𝐽 ∮ 𝑑𝑄
Where J is a constant known as the Mechanical Equivalent of Heat. In British units J is 778 ft
lbf per Btu and in SI units it’s 1 Nm or Joules i.e.
First Law of Thermodynamics
∮ 𝑑𝑊 = ∮ 𝑑𝑄 in SI units
2.1.1 First law For non-cyclic process:

Let us now take up a system undergoing a non-cyclic process where transfer of heat
and work take place and there is some change in the state of system i.e. initial and
final states are different. Figure shows the non-cyclic process occurring between 1
and 2. If we assume the system to have the heat interaction ΔQ and work interaction
ΔW, then from the basic principles it can be said that:
Energy lost = Energy gained
Therefore, between states 1-2, the energy balance can be written as
𝑄1−2 − 𝑊1−2 = 𝑈1−2
where, 𝑄1−2 , 𝑊1−2 and 𝑈1−2 are the heat, work and stored energy values. This stored
energy is called as internal energy for a system having negligible electrical, magnetic,
solid distortion and surface tension effects.
General expression based on above can be given as follows:
∆𝑄 − ∆𝑊 = ∆𝑈
Or,
2 2 2
∫ 𝑑𝑄 − ∫ 𝑑𝑊 = ∫ 𝑑𝑈
1 1 1
or, for elemental interactions; 𝑑𝑄 − 𝑑𝑊 = 𝑑𝑈
𝑑𝑄 = 𝑑𝑈 + 𝑑𝑊
Thus the first law of thermodynamics for non-cyclic processes can be given by
∫ 𝑑𝑄 = ∫ 𝑑𝑈 + ∫ 𝑑𝑊
Mathematically, it can be shown that the internal energy is a thermodynamic

property. Let us consider the non-cyclic process following oaths A, B and C in the
directions as shown in the figure.
As the processes A &B and A &C constitute a thermodynamic cycle starting and
finishing at state 1, the first law of thermodynamics for cyclic process can be
employed,
∮ 𝛿𝑄 ∝ ∮ 𝛿 𝑊
∮(𝛿𝑄 − 𝛿 𝑊) = 0
For the cycle following path 1–A–2–B–1, the first law of thermodynamics says,
∮(𝛿𝑄 − 𝛿 𝑊) = 0
2 1 2 1
or ∫ (𝛿𝑄)𝐴 + ∫ (𝛿𝑄)𝐵 = ∫ (𝛿𝑊)𝐴 + ∫ (𝛿𝑊)𝐵
1 2 1 2
Which can be rewritten as,
2 2
∫ (𝛿𝑄 − 𝛿𝑊)𝐴 = ∫ (𝛿𝑄 − 𝛿𝑊)𝐵 (𝑖)
1 1
Also, for the cycle following path 1–A–2–C–1, the first law of thermodynamics can be
applied as,
2 2
∫ (𝛿𝑄 − 𝛿𝑊)𝐴 = ∫ (𝛿𝑄 − 𝛿𝑊)𝐶 (𝑖𝑖)
1 1
From equations (i) & (ii) it is obvious that
2 2 2
∫ (𝛿𝑄 − 𝛿𝑊)𝐴 = ∫ (𝛿𝑄 − 𝛿𝑊)𝐵 = ∫ (𝛿𝑄 − 𝛿𝑊)𝐶
1 1 1
Which shows that (𝛿𝑄 − 𝛿𝑊) is some property as it is independent of the path being
followed. In addition, it can be rewritten as,
2 2 2
∫ (𝛿𝑈)𝐴 = ∫ (𝛿𝑈)𝐵 = ∫ (𝛿𝑈)𝐶
1 1 1
∆𝑈1−2,𝐴 = ∆𝑈1−2,𝐵 = ∆𝑈1−2,𝐶
2.2 Thermodynamic Process:

There are five basic thermodynamic processes:
1. Isothermal Process
2. Isochoric Process
3. Isobaric Process
4. Adiabatic Process
5. Polytropic Process
6. Free expansion Process
2.2.1 Isothermal Process: (Externally slow process): Thermodynamic process in which

the temperature remains constant is called constant temperature or isothermal
process. For a perfect gas during isothermal process;
The relation between different thermodynamic properties can be given as

𝑝1 𝑉1
𝑝1 𝑉1 = 𝑝2 𝑉2 = Constant, or, 𝑃 =
𝑉
Work done in isothermal process can be given as
𝑉2
So work involved 𝑊1−2 = ∫ 𝑃 ∙ 𝑑𝑉
𝑉1
𝑉2
𝑝1 𝑉1 𝑉2
𝑊1−2 = ∫ ∙ 𝑑𝑉 = 𝑃1 𝑉1 ln ( )
𝑉1 𝑉 𝑉1
𝑊1−2 = 𝑃1 𝑉1 ln 𝑟
Where r = ratio of final and initial volumes
By first law of thermodynamics,
2 2 2
∫ 𝑑𝑄 = ∫ 𝑑𝑊 + ∫ 𝑑𝑈
1 1 1
𝑄1−2 = 𝑊1−2 + (𝑈2 − 𝑈1 ) = 𝑊1−2 + 0
𝑈2 − 𝑈1 = 𝑀𝑐𝑣 (𝑇2 − 𝑇1 ) = 0
because 𝑇1 = 𝑇2
2.2.2 Isochoric Process: When a fluid undergoes a thermodynamic process in a fixed

enclosed space such that the process occurs at constant volume, then the process is
called constant volume process or isochoric process or isometric process. Let us
consider heating of a gas in fixed enclosure at constant volume. On p–V diagram this
process is represented by a vertical line as shown in Fig.
Area under the process line is zero which indicates that there is rise in pressure but
there is no work done as there is no change in volume.
Work involved shall be,

𝑉2 =𝑉
𝑊1−2 = ∫ 𝑃 ∙ 𝑑𝑉 = 0
𝑉1 =𝑉
From first law of thermodynamics for process,

2 2 2 2
∫ 𝑑𝑄 = ∫ 𝑑𝑈 + ∫ 𝑑𝑊 = ∫ 𝑑𝑈 + 0
1 1 1 1
𝑄1−2 = 𝑈2 − 𝑈1 = 𝑚𝑐𝑣 (𝑇2 − 𝑇1 )
2.2.3 Isobaric process: It refers to the thermodynamic process in which there is no change
in pressure during the process. To understand let us take a cylindrical vessel having
gas in it. It has a piston above it. Piston is free to reciprocate in the cylinder. Under
normal situation piston shall be subjected to atmospheric pressure. Now, let heat be
added to cylinder from bottom of cylinder. Due to heat addition, presuming energy
transfer taking place reversibly and system always remaining in equilibrium, the gas
shall try to expand. Expansion of gas results in raising up of the piston and it attains a
new state say 2. Process is shown on p-V diagram in Fig.
The work involved in the raising of piston shall be given by,

𝑉2
𝑊1−2 = ∫ 𝑃 ∙ 𝑑𝑉 = 𝑃 ∙ (𝑉2 − 𝑉1 )
𝑉1
Mathematically from the first law of thermodynamics, it can be given that,
2 2 2
∫ 𝑑𝑄 = ∫ 𝑑𝑈 + ∫ 𝑑𝑊
1 1 1
𝑄1−2 = 𝑚𝑐𝑣 (𝑇2 − 𝑇1 ) + 𝑃(𝑉2 − 𝑉1 )
= 𝑚𝑐𝑣 (𝑇2 − 𝑇1 ) + 𝑚𝑅(𝑇2 − 𝑇1 )
𝑅
Substituting forcv , i.e.𝑐𝑣 =
𝛾−1
1 𝛾𝑅
𝑄1−2 = 𝑚𝑅(𝑇2 − 𝑇1 ) { + 1} = 𝑚(𝑇2 − 𝑇1 ) { } = 𝑚𝑐𝑃 (𝑇2 − 𝑇1 )
𝛾−1 𝛾−1
2.2.4 Adiabatic Process: An adiabatic process is the thermodynamic process in which

there is no heat interaction during the process, i.e. during the process, Q = 0. The
adiabatic process follows the law 𝑃𝑉 𝛾 = constant where γ is called adiabatic index and
is given by the ratio of specific heats at constant pressure and constant volume. Thus,
it is obvious that adiabatic expansion shall be accompanied by the fall in temperature
while temperature will rise during adiabatic compression. The adiabatic expansion
process is shown on Fig.
Work done during adiabatic expansion process can be given as,

𝑉2
𝑊1−2 = ∫ 𝑃 ∙ 𝑑𝑉
𝑉1
For the adiabatic process,

𝑃𝑉 𝛾 = 𝑃1 𝑉1 𝛾 = 𝑃2 𝑉2 𝛾 = C
𝑠𝑢𝑏𝑠𝑡𝑢𝑡𝑖𝑛𝑔 𝑡ℎ𝑒 𝑣𝑎𝑙𝑢𝑒 𝑜𝑓 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑖𝑛 𝑤𝑜𝑟𝑘 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛, 𝑤𝑒 𝑔𝑒𝑡
𝑝1 𝑉1 − 𝑝2 𝑉2
𝑊1−2 =
𝛾−1
2 2 2
From first law of thermodynamics ∫ 𝑑𝑄 = ∫ 𝑑𝑈 + ∫ 𝑑𝑊
1 1 1
𝑝1 𝑉1 − 𝑝2 𝑉2
𝑄1−2 = (𝑈2 − 𝑈1 ) +
𝛾−1
𝑝1 𝑉1 − 𝑝2 𝑉2
0 = 𝑚𝑐𝑣 (𝑇2 − 𝑇1 ) +
𝛾−1
𝑊1−2 = 𝑚𝑐𝑣 (𝑇1 − 𝑇2 )
2.2.5 Polytropic Process: Polytropic process is the most commonly used process in practice. In
this, the thermodynamic process is said to be governed by the law 𝑃𝑉 𝑛 = constant where n
is the index which can vary from – ∞ to + ∞. The given figure shows some typical cases in
which the value of n is varied and the type of process indicated for different values of n.
Thus the various thermodynamics processes discussed above are special cases of polytropic
process. Work interaction in case of polytropic process can be given as,
𝑉2
𝑊1−2 = ∫ 𝑝 ∙ 𝑑𝑉, where𝑃1 𝑉1𝑛 = 𝑃2 𝑉2𝑛 = constant . On solving, we get
𝑉1
𝑝1 𝑉1 − 𝑝2 𝑉2
𝑊1−2 =
𝑛−1
2 2 2
From first law of thermodynamics ∫ 𝑑𝑄 = ∫ 𝑑𝑈 + ∫ 𝑑𝑊
1 1 1
𝑝1 𝑉1 − 𝑝2 𝑉2
𝑄1−2 = (𝑈2 − 𝑈1 ) +
𝑛−1
𝑚𝑅(𝑇1 − 𝑇2 )
or, 𝑄1−2 = 𝑚𝑐𝑣 (𝑇2 − 𝑇1 ) +
𝑛−1
𝑅
also,𝑐𝑣 = or 𝑅 = 𝑐𝑣 (𝛾 − 1)
𝛾−1
(𝛾 − 1)
𝑄1−2 = 𝑚𝑐𝑣 {(𝑇2 − 𝑇1 ) + ∙ (𝑇1 − 𝑇2 )}
(𝑛 − 1)
Thus heat transfer during a polytropic process for a perfect gas;
𝑚𝑅(𝑇1 − 𝑇2 ) (𝛾 − 𝑛)
𝑄1−2 = ×
𝑛−1 (𝛾 − 1)
So heat transfer can be given as
(𝛾 − 𝑛)
𝑄1−2 = × (𝑊)𝑃𝑜𝑙𝑦
(𝛾 − 1)
2.3 Enthalpy:
Enthalpy of a Substance is defined as H = P.V+ U
Enthalpy is an extensive property and its unit is KJ. Hence, Enthalpy is total energy by
virtue all 3 fundamental properties.Enthalpy of an ideal gas is given by H  mCpT
H = U + PV
H1 = U1 + P1V1
H2 = U2 + P2V2
H2 – H1 = (U2 –U1) + (P2V2 –P1V1)= Cv +R (T2 –T1)
H2 –H1 = Cp (T2 –T1)
dH = CpdT
2.4 Steady Flow:

Steady flow means the rate of flow of mass and energy across the control volume are
constant. At steady state of a System, any thermodynamic property will have a fixed value
at the same state and does not change with respect to time.
2.4.1 Mass balance:
M1  M '  M 2  M ''
2.4.2 Energy balance:
 v2   v '2   v2   v ''2 
Q2  m  h1  1  gz1   m '  u   gz '   W2  m2  h2  2  gz2   m  u   gz2'' 
 2   2   2   2 
Sometime in equation that neglecting internal energy.
Q2  m1h1  m ' u '  Ws  m2h2  m '' u ''
 v2   v2 
Q  m  u1  p1v1  1  gz1   ws  m  u2  p2v2  h2  2  gz2 
 2   2 
 v12   v22 
Q  m  h1   gz1   ws  m  h2   gz2 
 2   2 
1
Q  ws  m(h2  h1 )  (v22  v12 )  g ( z2  z1 )
2
2.5 Flow Devices:
Thermodynamics does provide equations that interrelates the changes occurring in

pressure, velocity, cross-sectional area, enthalpy, entropy, and specific volume of a
following stream. We consider here the adiabatic, steady-state, one-dimensional flow of a
compressible fluid in the absence of shaft work and of changes in potential energy. The
thermodynamic equations are derived from different fundamentals equations.
2.5.1 Continuity equation:
For control volume, the law of conservation of mass can be written as
Rate of accumulation of mass within the control volume + Net rate of mass out by
the flowing streams = 0
dm
 ( uA)  0 (1)
dt
For steady state flow process, there is no accumulation of mass within the control volume
and equation (1) is reduces to
(uA)  0
1u1 A1  2u2 A2 (2)
2.5.2 Energy equation:
The total energy balance equation is
 u2 
   gZ  H   Q  Ws (3)
2 
If Q, WS and changes in potential energy are set to zero,
u 2
H  0 (4)
2
dH  udu
(5)
u22  u12  2( H 2  H1 )
2.5.3 Bernoulli’s equation:
It is a special form of the mechanical energy balance applicable only to non-viscous

incompressible fluids, which do not exchange shaft work with the surroundings.
 u2 P
  gZ    constant (6)
2 
Using above fundamental equations, following two equations are derived for duct flow of
compressible fluids.
dP  u 2  dS u 2 dA
V (1  M )  T 1 
2
  0 (7)
dx  C P  dx A dx
 u 2 
  M2  2
du  CP  dS  1  u dA
u T   0 (8)
dx 1 - M 2  dx  1  M 2  A Adx
 
 
Where
V= Specific volume
P= Pressure
T=Temperature
X = length in the direction of flow
u = velocity of the fluid
S = Entropy
CP = Specific heat capacity at constant pressure
A = Cross section area of the duct
M = Mach number = u/c
It is defined as the ratio of the speed of the fluid in the duct to the speed of the sound in the
fluid.
2.5.4 Flow in pipe:
For the case of steady-state adiabatic flow in a horizontal pipe of constant cross-sectional
area, dA/dx=0, and Eqs. (7) and (8) reduce to:
 u 2   u 2 
1    M2 
dP T CP  dS du  C  dS
   dx u  T P (9)
dx V 1- M2 dx 1  M  dx
2
   
   
For subsonic flow, M2 < 1, and all quantities on the right sides of these equations are
positive;
dP du
 0 and 0
dx dx
Thus, the pressure decreases and the velocity increases in the direction of flow. However,
the velocity cannot increase indefinitely. If the velocity were to exceed the sonic value,
then the above inequalities would reverse. Such a transition is not possible in a pipe of
constant cross sectional area. For subsonic flow, the maximum fluid velocity obtainable in
a pipe of constant cross section is the speed of sound, and this value is reached at the exit
of the pipe. At this point dS/dx reaches its limiting value of zero. Given a discharge pressure
low enough for the flow to become sonic, lengthening the pipe does not alter this result;
the mass rate of flow decreases so that the sonic velocity is still obtained at the lengthened
pipe.
The equations for pipe flow indicate that when flow is supersonic the pressure increases
and the velocity decreases in the direction of flow. However, such a flow regime is unstable
and when supersonic stream enters a pipe of constant cross section, a compression shock
occurs, the result of which is an abrupt and finite increase in pressure and decrease in
velocity to a subsonic value.
2.5.5 Flow in Nozzle:
The limitations observed for flow in pipes do not extend to properly designed nozzles,
which bring about the interchange of internal and kinetic energy of a fluid as the result of
a changing cross-sectional area available for flow. In a properly designed nozzle the area
changes with length in such a way as to make the flow nearly frictionless. In limit of
reversible flow, the rate of entropy increase approaches zero, and dS/dx=0. In this event
Eqs. (7) and (8) become:
dP u 2  1  dA du u  1  dA
   and    (10)
dx VA  1  M 2  dx dx A  1  M 2  dx
The characteristics of flow depend on whether the flow is subsonic (M < 1) or supersonic
(M > 1). The various cases are summarized as below.
Subsonic: M<1 Supersonic: M>1
Converging Diverging Converging Diverging
dA - + - +
dx
dP - + + -
dx
du + - - +
dx
Thus, for subsonic flow in a converging nozzle, the velocity increases and the pressure
decreases as the cross-sectional area diminishes. The maximum obtainable fluid velocity is
the speed of sound, reached at the throat. A further increase in velocity and decrease in
pressure requires an increase in cross-sectional area, a diverging section. Because of this, a
converging subsonic nozzle can be used to deliver a constant flow rate into a region of
variable pressure.
Suppose a compressible fluid enters a converging nozzle at pressure P1 and discharges from
the nozzle into a chamber of variable pressure P2. As this discharge pressure decrease below
P1, the flow rate and velocity increase. Ultimately, the pressure ratio P2/P1 reaches a critical
value at which the velocity in the throat is sonic. Further reduction in P2 has no effect on
the condition in the nozzle. The flow remains constant, and the velocity in the throat is
sonic regardless of the value of P2/P1.provided it is always less than the critical value. For
steam, the critical value of this ratio is about 0.55 at moderate temperatures and pressures.
 /( 1)
P2  2 
  (11)
P1    1 
Supersonic velocities are readily attained in the diverging section of a properly designed
converging/diverging nozzle. With sonic velocity reached at the throat, a further decrease
in pressure requires an increase in cross-sectional area, a diverging section in which the
velocity continues to increase. The transition occurs at the throat, where dA/dx=0.
The speed of sound is attained at the throat of a converging/diverging nozzle only when the
pressure at the throat is low enough that the critical value of P2/P1 is reached. If insufficient
pressure drop is available in the nozzle for the velocity to become sonic, the diverging
section of nozzle acts as a diffuser. That is, after the throat is reached the pressure rises and
the velocity decreases; this is the conventional behavior for subsonic flow in diverging
section.
2P1V1   P2  
( 1) / 
u 
2
1     (12)
  1   P1  
u 22  c 2  PV (13)
2.5.6 Throttling Process:
When a fluid flows through a restriction, such as an orifice, a partly closed valve, or a
porous plug, without any appreciable change in kinetic or potential energy, the primary
result of the process is a pressure drop in the fluid. Such a throttling process produces no
shaft work, and in the absence of heat transfer, the first law can be reduced to
H  0 or H 2  H1
The process therefore occurs at constant enthalpy. Since the enthalpy of an ideal gas
depends on temperature only, a throttling process does not change the temperature of an
ideal gas. For most real gases at moderate conditions of temperature and pressure, a
reduction in pressure at constant enthalpy results in a decrease in temperature. For example,
if steam at 1000 kPa and 573.15 K (300 0C) is throttled to 101.325 kPa (atmospheric
pressure), H2=H1=3052.1 kJ kg -1
2.5.7 Turbines (Expanders):
Principle: “The expansion of a gas in nozzle to produce a high-velocity stream is a process

that converts internal energy into kinetic energy”.
This kinetic energy is in turn converted into shaft work when the stream impinges on blades
attached to a rotating shaft. Thus a turbine (or expander) consists of alternate sets of nozzles
and rotating blades through which vapor or gas flows in a steady-state expansion process
whose overall effect is the efficient conversion of the internal energy of a high-pressure
steam into shaft work. When steam provides the motive force as in a power plant, the device
is called a turbine; when a high-pressure gas, such as ammonia or ethylene in chemical or
petrochemical plant; is the working fluid, the device is often called an expander.
However, the potential energy term can be omitted, because there is little change in
elevation. Moreover, in any properly designed turbine, heat transfer is negligible and the
inlet and exit pipes are size to make fluid velocities roughly equal. So, first law reduces to:
Ws  mH  m( H 2  H1 ) (14)
Ws  H  H 2  H1 (15)
Normally, the inlet conditions T1 and P1 and the discharge pressureP2 are known. Thus in
Equation (15) only H1 is known, and bothH2and Ws remain as unknowns. The energy
equation alone does not allow ay calculations to be made. However, if the fluid in the
turbine undergoes an expansion process that is reversible as well as adiabatic, then the
process is isentropic, and S2=S1. This second equation allows determination of the final
state of the fluid and hence of H2. For this special case, Ws given by Eq. (15), written:
Ws(isentropic) = (H) S (16)
The shaft work WS (isentropic )  (H ) S is the maximum that can be obtained from an
adiabatic turbine with given inlet conditions and given discharge pressure. Actual turbines
produce less work, because the actual expansion process is irreversible. We therefore define
a turbine efficiency as:
Wa
 (17)
WS (isentropic )
Where Wa is the actual shaft work. By Eqs. (15) and (16),
H
 (18)
(H ) S
Values of  for properly designed turbines or expanders usually range from 0.7 to 0.8.
2.5.8 Ejectors
Ejectors remove gases or vapors from an evacuated space and compress them for discharge
at a higher pressure. These devices employ the momentum and kinetic energy of a high
velocity stream to entrain and compress a second gas or vapor stream. Steam jet-ejectors
are used for pumping large volumes of vapor and gas at low pressures.
Working:
Steam (primary fluid) is first expanded by passing through a nozzle, where it attains
supersonic velocity. Due to the high velocity of the steam entering the mixing space, a low
pressure region is created there and as a result the steam transfers some of its momentum
to the gas or vapor (secondary fluid) entering through the gas inlet. In the diffuser section,
the mixed stream is decelerated and it gets compressed, the work of compression being
derived at the expense its kinetic energy. The compressed gas leaving the ejector is
discharged directly to atmosphere or it can be sent to a water-cooled condenser.
Questions
1. A 2 kW, 40 liters water heater is switched on for 20 minutes. The heat capacity CP for
water is 4.2 kJ/Kg K . Assuming all the electrical energy has gone into heating the water,
increase of water temperature in 0C is?
Solution
Energy supplied = m x Cpw x ∆ T
2 KJ/S x 60 x 20 = 40 kg x 4.2 KJ/Kg K x ∆ T K
∆ T K = (2 x 60 x 20) / (40 x 0.2) = 14.285 K = 14.285 0C
2. Nitrogen gas (28) N2 is enclosed in a cylinder by a piston at the initial condition of 2 bar,
298 K, 1 m3 in a particular process. The gas slowly expands under isothermal condition
until the volume becomes 2 m3. Heat exchange occurs with the atmosphere at 298 K
during the process. Determine the work interaction for the gas 1W2?
Solution:
P1 = 2 bar, V1 = 1 m3, V2 = 2m3, T1 = 298 K = T2
W = P1V1 ln V2/V1 = mRT1 ln V2/V1
= (2 x 100) x 1 ln x 2/1 [(P1V1) / (RT1)] = m= (200 x 1) / (8.374 x 298)
= 138. 63 KJ
3. A gas contain in a cylinder is compressed. The work required for the compression is 5000
KJ. During the process heat interaction of 2000 KJ causes the surrounding to be heated.
The change in internal energy during the process is (U2 – U1)?
Solution:
Work required W = - 5000 KJ
Q = -2000 KJ
Q – W = (U2 – U1)
-2000 + 5000 = (U2 – U1)
(U2 – U1) = 3000 KJ
4. Nitrogen at an initial state of 10 bar, 1 m3& 300 K is expanded isothermally to the volume of
2m3. The PVT relation is given by
(P + a/V2) V = RT a> 0
The final pressure will be
a. < 5 bar
b. > 5 bar
c. 5 bar
d. Cannot ascertained in the absence of value of a
Solution:
P1 = 10 bar, T1 = 300 K
V1 = 1 m3, V2 = 2 m3
𝑎 𝑎
[𝑃 1 + 2 ] 𝑉1 = [𝑃 2 + 2 ] 𝑉2
𝑣1 𝑣2
𝑎
10 + 𝑎 = [𝑃 2 + ] 2
4
𝑎 𝑎
5+ = [𝑃 2 + ]
2 4
𝑎
5+ = 𝑃2
4
So, the answer is (d) cannot ascertained in the absence of value of a
5. A monoatomic ideal gas with γ= 1.67, molecular weight = 40 is compressed adiabatically

from 0.1 MPa, 300 K to 0.2 MPa. The work of compression of the gas in kJ/Kg (W) is
________
Solution:
W = (P2V2 – P1 V1) /(γ-1)
= m R (T2 – T1) / γ -1
 1

 P  
R  T2  T2  2  
  P1  
W  
 1
=22.59 kJ/kg
6. 1mol of methanol is contained in a leak proof piston cylinder 8bar and 100 K The gas
under isothermal evaporation to 4 bars. Methane can be considered as an ideal gas. The value
of the universal gas constant R = 8.314 Jmol-1k-1. The H.T in KJ during the process is
a. 11.52
b. 5.76
c. 4.15
d. 2.38
Solution: Q= W
𝑝1
= RT ln 𝑝2
8
= 8.314 ×1000 ln4
= 5.71 J/mol
7. A perfectly insulated cylinder of volume 0.6m3is initially divided into two parts by
frictionless piston as shown in figure.
The small part of volume 0.2m3 has the ideal gas and a pressure of 6bar & 1000C, and the
other part is evacuated. At certain instant of time the stopper is removed and the piston
moves out freely to the other end. The final temperature is:
a. 140°C
b. -33°C
c. 100°C
Answer: This is a case of free expansion. Therefore temperature remains the same i.e.100°C.
ii) The cylinder insulated is now removed and a piston is pushed back to restore the system
to its initial state. If this is to be achieved only by doing work on the system (no heat addition,
only heat removed allowed) what is the minimum work required?
a. 3.4 kJ
b. 0.7 kJ
c. 132 kJ
d. 240 kJ
𝑣2
Solution: W2 = PV ln
𝑣1
𝑣2
=P2V1 ln𝑣1
=6 ×100 × 0.2 × ln (0.2/0.6)
= -131.83 kJ
(-ve sign indicate work will be required to be done on the system)
8. A fluid flowing alone a pipe line undergoes a throttling process from 10bar to 1bar. i.e.
passing through a partially open valve. Before the throttling the specific volume of fluid is
0.5 m3/kg & after throttling 2m3/kg. What is the change in specific initial energy?
Solution: V1 = 0.5m3/Kg
V2 = 2m3/Kg
In throttling process,
H1 = H2
P1V1 – P2V2 = U2- U1
10×100×0.5 - 100×2 = U2- U1
ΔU = 200 KJ/Kg
9. The mass flow rate in air compressor is 1kg/sec. the condition that the inlet is 0.1MPa,
300K. The pressure at the exit of the compressor is 1MPa. Assuming the compressing process
to be adiabatic and air as an ideal gas the power input to compressor in kW is
(a) 25.2 (b) 113.2 (c) 280 (d)1257.2.
Solution: M1 = 1kg/sec.
P1 = 0.1 MPa.
Compressor is an open system
𝛾
W = 𝛾−1 (P1V1 - P2V2)
𝛾
= 𝛾−1 𝑚𝑅 (T1 - T2)
1.4
WΔ = 0.4 × 1 × 0.287 (300 - T2)
For adiabatic:
𝑇1 𝑇2
𝛾−1 = 𝑃2 𝛾−1
𝑃1 𝛾 𝛾
𝑃 𝛾−1
T2 = T1 ( 𝑃2 )
1 𝛾
1
= 300× (0.1) 0.4/1.4
=
300 × 10 (0.4/1.4)
1.4
W = 0.4 × 0.287
= -280.46KW
10. Water is flowing out and more water is entering back to back. Develop the expression for
variation in temperature of H2O with respect to time. Neglect the effect of change in KE &
PE. Take Cpw = 4.2kJ/Kg.
Solution: M1 = M2 =M (say)
M’ = M’’ = M (say)
Q2 + m1h1 + m’v’ = Ws2 + m2h2 + m’’v’’
Q2 - Ws2 = m (h2 – h1) + M (U’’ - U’)
𝑑𝑡
[-7.6 – (0.6)] × 3600 = 270 × 4.2 × (T -318) + 45 × 4.2 × 𝑑τ
𝑑𝑡
=22 + (T-318) + 6𝑑𝜏 = 0
𝑑𝑡
= (T-296) + 6𝑑τ = 0
𝑑𝑡
6𝑑τ + 𝑇−296= 0
Integrating,
ln (T -296) + 6τ =C
Initially,τ = 0,T= 318K
ln (318 -296) =C = ln22
ln (T -296)+6τ = ln22
𝑇−296
ln( )= -6 τ
22
𝑇−296
( ) = e-6τ
22
T-296 = 22 e-6τ
T= 296+22 e-6τ
= (318-22) + 22 e-6τ
T=318-22 (1- e-6z)
Chapter 3 Second Law of thermodynamics
Limitation of first law of thermodynamics:
 It helps to determine the energy changes involved in a process but it cannot tell us whether
a proposed change would actually occur or not.
 It doesn’t tell the direction of change.
 It doesn’t tell about conditions of equilibrium.
 It doesn’t recognize the qualitative differences between various forms of energy like heat
and work.
3.1 Second law of thermodynamics:
The observations just described suggest a general restriction on processes beyond that
imposed by the first law. The second law is equally well expressed in two statements that
describe this restriction:
 Statement 1: No apparatus can operate in such a way that its only effect (in system and
surroundings) is to convert heat absorbed by a system completely into work done by the
system.
 Statement 2: No process is possible which consists solely in the transfer of heat from one
temperature level to a higher one.
 Statement 3: It is impossible by a cycle process to convert the heat absorbed by a system
completely into work done by the system.
Statement 1 does not say that heat cannot be converted into work; only that the process
cannot leave both the system and its surroundings unchanged. Consider a system consisting
of an ideal gas in a piston/cylinder assembly expanding reversibly at constant temperature.
According to the first law, ΔU = Q + W
At constant temperature, ΔU = 0 and therefore, Q= -W. The heat absorbed by the reversible
expansion of the gas. At first this might seem a contradiction of statement 1. Since in the
surroundings the result is the complete conversion of heat into work. However, this
statement requires in addition that no change occurs in the system, a requirement that is not
met.
Second Law of Thermodynamics
This process is limited in another way because the pressure of the gas soon reaches that of
the surroundings, and expansion ceases. Therefore, the continuous production of work from
heat by this method is impossible. If the original state of the system is restored in order to
comply with the requirements of statement 1. Energy from the surroundings in the form of
work is needed to compress the gas back to its original pressure. At the same time energy
as heat is transferred to the surroundings to maintain constant temperature. This reverse
process requires at least the amount of work gained from the expansion; hence no net work
is produced. Evidently, statement 1 may be expressed in an alternative as statement 3.
3.2 Heat engine:
The classical approach to the second law is based on the study of heat engines, devices or
machines that produce work from heat in a cyclic process. An example is a steam power
plant in which the working fluid (steam) periodically returns to its original state.
In such power plant the cycle (in its simplest form) consists of the following steps:
 Liquid water at ambient temperature is pumped into a boiler at high pressure.
 Heat from a fuel (heat of combustion of a fossil fuel or heat from a nuclear reaction) is
transferred in the boiler to the water, converting it to high- temperature steam at the boiler
pressure.
 Energy is transferred as shaft work from the steam to the surroundings by a device such as
a turbine, in which the steam expands to reduced pressure and temperature.
 Exhaust steam from the turbine is condensed by transfer of heat to the surroundings,
producing liquid water for return to the boiler, thus completing the cycle.
Essential to all heat-engine cycles are absorption of heat into the system at a high
temperature, rejection of heat to the surroundings at a lower temperature, and production
of work. In the theoretical treatment of heat engines, the two temperature levels which
characterize their operation are maintained by heat reservoirs, bodies imagined capable of
absorbing or rejecting an infinite quantity of heat without temperature change.
In operation, the working fluid of a heat engine absorbs heat

W = QH-QC
where, QH = heat transformation hot reservoir at TH
QC = heat transformation cold reservoir at TC
The thermal efficiency of the engine is defined as:

= net work output/ heat absorbed
∴ = W/QH= (QH-QC)/QH
∴ = 1- QC/QH …………….(1)
Absolute-value signs are used to make the equations independent of the sign conventions
for Q and W. For to be unity (100% thermal efficiency), QC must be zero. No engine has
ever been built for which this is true; some heat is always rejected to the cold reservoir.
3.3 Carnot Engine:
The thermal efficiency of a heat engine depends on the degree of reversibility of its
operation. Indeed, a heat engine operating in a completely reversible manner is very special,
and is called a Carnot engine. The characteristics of such an ideal engine were first
described by N.L.S. Carnot in1824. The four steps that make up a Carnot cycle are
performed in the following order:
 Step 1: A system at the temperature of the cold reservoir TC undergoes a reversible

adiabatic heat absorption process that causes its temperature to rise to that of a hot reservoir
at TH
 Step 2: The system maintains contact with the hot reservoir at TH, and undergoes a
reversible isothermal process during which heat QH is absorbed from the hot reservoir.
 Step 3: The system undergoes a reversible adiabatic heat rejection process in the opposite
direction of step 1 that brings its temperature back to that of the cold reservoir at TC
 Step 4: The system maintains contact with the reservoir at TC and undergoes a reversible
isothermal process in the opposite direction of step 2 that returns it to its initial state with
rejection of heat QC to the cold reservoir.
 A Carnot engine operates between two heat reservoirs in such a way that all heat absorbed
is absorbed at the constant temperature of the hot reservoir and all heat rejected is rejected
at the constant temperature of the cold reservoir. Any reversible engine operating between
two heat reservoirs is a Carnot engine; an engine operating on a different cycle must
necessarily transfer heat across finite temperature differences and therefore cannot be
reversible
3.3.1 PV diagram of Carnot Cycle
Efficiency of Carnot cycle,
“The thermal efficiency of a Carnot engine depends only on the temperature levels and not
upon the working substance of the engine”.
3.4 Entropy:
If the heat quantities refer to the engine (rather than to the heat reservoirs), the numerical
value of QH is positive and that of QCis negative.
The equivalent equation written without absolute-value signs is therefore
Thus for a complete cycle of a Carnot engine, the two quantities Q/T associated with the
absorption and rejection of heat by the working fluid of the engine sum to zero. The
working fluid of a cyclic engine periodically returns to its initial state, and its properties,
e.g temperature, pressure, and internal energy, return to their initial values. Indeed, a
primary characteristic of a property is that the sum of its changes is zero for any complete
cycle. Thus for a Carnot cycle suggests the existence of a property whose changes are given
by the quantities Q/T.
Each Carnot cycle has its own pair of isotherms THand TCand associated heat quantities
QHand QC. When the adiabatic curves are so closely spaced that the isothermal steps are
infinitesimal, the heat quantities become dQH and dQC and for each Carnot cycle is written
as
In this equation TH and TC absolute temperatures of the working fluid of the Carnot engines,
are also the temperatures traversed by the working fluid of the arbitrary cycle. Summation
of all quantities dQ/T for the Carnot engines leads to the integral:
Where the circle in the integral sign signifies integration over the arbitrary cycle, and the
subscript “rev” indicates that the cycle is reversible.
Thus the quantities dQrev/T sum to zero for the arbitrary cycle, exhibiting the characteristics
of a property. We therefore infer the existence of a property whose differential changes for
the arbitrary cycle are given by these quantities.
The property is called entropy and the differential changes are:
(1)
where St is the total (rather than molar) entropy of the system.
Alternatively,
dQrev = T d St
Paths ACB and ADB show two arbitrary reversible processes connecting these points.
Integration for each path gives:
(2)
Where in view of Equation (15) the two integrals must be equal.
We therefore conclude that is independent of path and is a property change given by

StB - StA.
If the fluid is change from state A to state B by an irreversible process, the entropy change
must still be
but experiment shows that this result is not given by
evaluated for the irreversible process itself, because the calculation of entropy changes by
this integral must in general be along reversible paths.
If a process is reversible and adiabatic, dQrev = 0; then by Equation (16), dSt = 0. Thus the
entropy of a system is constant is constant during a reversible adiabatic process, and process
is said to be isentropic.
 Entropy owes its existence to the second law, from which it arises in much the same way
as internal energy does from the first law. Equation (1) is the ultimate source of all
equations that relate the entropy to measurable quantities. There exists a property called
entropy S, which is an intrinsic property of a system, functionally related to the measurable
coordinates which characterize the system. For a reversible process, changes in this
property are given by Equation (1).
 The change in entropy of any system undergoing a finite reversible process is:
(2)
 When a system undergoes an irreversible process between two equilibrium states, the
entropy change of the system ∆S t is evaluated by application of Equation (2) to an
arbitrarily chosen reversible process that accomplishes the same change of state as the
actual process. Integration is not carried out for the irreversible path. Since entropy is a
state function, the entropy changes of the irreversible and reversible processes are identical.
 The entropy change of a systemcaused by the transfer of heatcan always be calculated by
Whether the heat transfer is accomplished reversibly or irreversibly.
3.5 Mathematical Statement of Second Law:
Consider two heat reservoirs, one at temperature TH and a second at the lower temperature
TC. Let a quantity of heat be transferred from the hotter to the cooler reservoir. The
entropy changes of the reservoirs at TH and at TC are:
These two entropy changes are added to give:
Since TH >TC , the total entropy change as a result of this irreversible process is positive.
Also becomes smaller as the difference TH - TC gets smaller. When TH is only
infinitesimally higher than TC, the heat transfer is reversible, and approaching zero
as the process becomes reversible.
is always positive, approaching zero as a limit when the process becomes reversible.
This same conclusion can be demonstrated for any process whatever, leading to the general
equation:
This mathematical statement of the second law affirms that every process proceeds in such
a direction that the total entropy change associated with it is positive, the limiting value of
zero being attained only by a reversible process. No process is possible for which the total
entropy decreases.
3.6 Third law of thermodynamics:
(1)
Measurements of heat capacities at very low temperatures provide data for the calculation
from Equation (1) of entropy changes down to 0.K. When these calculations are made for
different crystalline forms of the same chemical species, the entropy at 0 K appears to be
the same for all entropy of the more random form is greater than that of the crystalline
form.
Such calculations, which are summarized elsewhere, lead to the postulate that “the absolute
entropy is zero for all perfect crystalline substances at absolute zero temperature” which
now accepted as the third law.
If the entropy is zero at T = 0 K, then Equation. (1) lends itself to the calculation of absolute
entropies. With T = 0 as the lower limit of integration, the absolute entropy of a gas at
temperature T based on calorimetric data is:
This equationis based on the supposition that no solid- state transitions take place and thus
no heats of transition need appear. The only constant-temperature heat effects are those of
fusion at Tf and vaporization TV. When a solid-phase transition occurs, a term is

added.
3.6 Refrigeration:
The maintenance of a temperature below that of the surroundings by continuous absorption

of heat at a low temperature level is known as refrigeration. It is usually accomplished by
evaporation of a liquid in a steady-state flow process. The vapor formed may be returned
to its original liquid state for re-evaporation in either of two ways. Most commonly, it is
simply compressed and the condensed. Alternatively, it may be absorbed by a treating these
practical refrigeration cycles.
Applications:
 It is used in the air-conditioning of buildings and in domestic refrigerators.

 It is used in the treatment, transportation, preservation of food and beverages.
 It is used in the manufacturing of synthetic rubber, textiles, chlorine, plastics, hydrogen
fluoride etc.
 It is used to remove heat of reactions and to liquefy process gases for gas separation by
distillation and condensation.
 It is used in lubricating oil purification, separation of volatile hydrocarbons, and
separation of gasoline from natural gas, solvent recovery and crystallization of salts
from solutions.
3.7 The Carnot refrigerator:
 In a continuous refrigeration process, the heat absorbed at a low temperature is

continuously rejected to the surroundings at a higher temperature.
 Basically, a refrigeration cycle is a reversed heat-engine cycle. Heat is transferred from
a low temperature level to a higher one; according to the second law this requires an
external source of energy.
 The ideal refrigerator, like the ideal heat engine, operates on a Carnot cycle, consisting
in this case of two isothermal steps in which heat QH is rejected at the higher
temperature TH, and two adiabatic steps. The cycle requires the addition of net work W
to the system.
 It consists of the following steps:
1. Reversible adiabatic compression
2. Isothermal heat rejection
3. Reversible adiabatic Expansion
4. Isothermal heat absorption
 Since U of the working fluid is zero for the cycle, the first law is written
W  QH  QC (1)
 The measure of the effectiveness of a refrigerator is its coefficient of performance 

defined as:
heat absorbed at the lower temp erature QC

  (2)
net work W
Equation (1) may be divided by QC
W Q
 H 1
QC QC
W T T  TC
 H 1  H (3)
QC TC TC
TC
 (4)
TH  TC
This equation applies only to a refrigerator operating on a Carnot cycle, and it gives the maximum
possible value of  for any refrigerator operating between given values of TH and TC.
 It shows clearly that the refrigeration effect per unit of work decreases as the temperature of
heat absorption TC decreases and as the temperature of heat rejection TH increases.
 For example, for refrigeration at a temperature level of 278.15 K (5 0C) in a surroundings at
303.15 K (30 0C), the value of  for a Carnot refrigerator is:
278.15
  11.13
(303.15  278.15)
Limitations:
1. Carnot cycle demands reversible operation, and it is difficult to eliminate all reversibility’s in
an actual operation.
2. Isothermal heat interactions at the heat absorption and the heat rejection stages, which proceed
at very slow rates necessitate large heat transfer areas.
3. If the heat absorption is achieved by the evaporation of a refrigerant then the possibility of the
input stream to the compressor containing liquid cannot be overruled. This may lead to severe
erosion problems in the compressor.
4. The work output of an expansion engine or turbine used for reversible expansion is normally
very small whereas their costs are prohibitively high.
3.8 The vapor compression cycle:
 The actual refrigeration cycles are less efficient than the ideal Carnot cycle, because of
the presence of the irreversible effects, such as friction and imperfect heat insulation
etc.
 As shown in figure, it consists of the following steps:
1. Reversible adiabatic compression
2. Isothermal heat rejection
3. Reversible adiabatic Expansion
4. Isothermal heat absorption
 A liquid evaporating at constant pressure (line2) provides a means for heat absorption
at a low constant temperature. The vapor produced is compressed to a higher pressure,
and is then cooled and condensed with rejection of heat at a higher temperature level.
 Liquid from the condenser returns to its original pressure by an expansion process. In
principle, this can be carried out in an expander from which work is obtained, but for
practical reasons is accomplished by throttling through a partly open valve.
 The pressure drop in this irreversible process results from fluid friction in the valve, the
throttling process occurs at constant enthalpy. Line 4 1 represents this throttling
process.
 The dashed line 23’ is the path of isentropic compression while Line 23,
representing the actual compression process, slopes in the direction of increasing
entropy reflecting inherent irreversibility.
 On the basis of a unit mass of fluid, the equations for the heat absorbed in the evaporator
and the heat rejected in the condenser are:
QC  H 2  H1 and QH  H 3  H 4 (5)
 These equations follow from Equation of second law for flow system when the small
changes in potential and kinetic energy are neglected.
 The work of compression is
W  H3  H2 (6)
H 2  H1
From equations (2) and (6),  (7)
H3  H4
 To design the evaporator, compressor, condenser, and auxiliary equipment one must
know the rate of circulation of refrigerant m. This is determined from the rate of heat
absorption in the evaporator by the equation:
QC
m (8)
H 2  H1
 For given values of Tc and TH, the highest possible value of  is attained for Carnot
cycle refrigeration. The lower values for the vapor-compression cycle result from
irreversible expansion in a throttle valve and irreversible compression.
3.9 Heat Pump:
 The heat pump, a reversed heat engine, is a device for heating houses and commercial
buildings during the winter and cooling them during the summer.
 In the winter it operates so as to absorb heat from the surroundings and reject heat into
the building. Refrigerant evaporates in coils placed underground or in the outside air;
vapor compression is followed by condensation, heat being transferred to air or water,
which is used to heat the building.
 Compression must be to a pressure such that the condensation temperature of the

refrigerant is higher than the required temperature level of the building.
 The operating cost of the installation is the cost of electric power to run the compressor.
If the unit has a coefficient of performance, QC / W  4, the heat available to heat the
house QH is equal to five times the energy input to the compressor.
 Any economic advantage of the heat pump as a heating device depends on the cost of
electricity in comparison with the cost of fuels such as oil and natural gas.
 The heat pump also serves for air conditioning during the summer. The flow of
refrigerant is simply reversed, and heat is absorbed from the building and rejected
through underground coils or to the outside air.
Questions
1. A refrigerator operates on reversed Carnot cycle. Determine the power required to drive
refrigerator between temperatures of 42ºC and 4ºC if heat at the rate of 2 kJ/s is extracted
from the low temperature region.
Solution:
To find out, W=?

Given: T1 = 315 K, T2= 277 K and Q2 = 2 kJ/s
From thermodynamic temperature scale;
𝑄1 𝑇1
=
𝑄2 𝑇2
𝑄1 315
=
2 277
Q1 = 2.274 kJ/s
Power/Work input required = Q1 – Q2
= 2.274 – 2
Power required = 0.274 kJ/s
Power required for driving refrigerator = 0.274 kW Ans.
2. A heat pump working on a reversed Carnot cycle takes in energy from a reservoir
maintained at 3ºCand delivers it to another reservoir where temperature is 77ºC. The
heat pump drives power for its operation from a reversible engine operating within the
higher and lower temperature limits of 1077ºC and 77ºC. For 100 kJ/s of energy supplied
to the reservoir at 77ºC, estimate the energy taken from the reservoir at 1077ºC.
Solution: Arrangement for heat pump and heat engine operating together is shown in fig. Engine
and pump bothreject heat to the reservoir at 77ºC (350 K).
For heat engine,

350 𝑊
𝜂𝐸 = 1 − =
1350 𝑄1
𝑄1 − 𝑄2
0.7407 =
𝑄1
𝑄2
0.7407 = 1 −
𝑄1
𝑄2 = 0.2593𝑄2
For heat pump,
𝑄4
𝐶𝑂𝑃𝐻𝑃 =
𝑄4 − 𝑄3
350 𝑄4
𝐶𝑂𝑃𝐻𝑃 = =
350 − 276 𝑄4 − 𝑄3
𝑄4 = 1.27𝑄3
Work output from engine = Work input to pump

𝑄4
𝑄1 − 𝑄2 = 𝑄4 − 𝑄3 ⇒ 𝑄1 − 0.2593 𝑄1 = 𝑄4 −
1.27
Also it is given that Q2 + Q4 = 100
Substituting Q2 and Q4 as function of Q1 in following expression,
Q2 + Q4 = 100
𝑄1
0.2593𝑄1 + = 100
0.287
𝑄1 = 26.71 𝑘𝐽
Energy taken by engine from reservoir at 1077ºC= 26.71 kJ Ans.
3. A reversible heat engine operates between two reservoirs at 827ºC and 27ºC. Engine
drives a Carnot refrigerator maintaining –13ºC and rejecting heat to reservoir at 27ºC.
Heat input to the engine is 2000 kJ and the net work available is 300 kJ. How much heat
is transferred to refrigerant and total heat rejected to reservoir at 27ºC?
Solution: Block diagram based on the arrangement stated;
𝑄1 𝑇1
we can write, for heat engine, =
𝑄2 𝑇2
𝑄1 1100
=
𝑄2 300
Substituting Q1 = 2000 kJ, we get Q2 = 545.45 kJ
Also WE= Q1 – Q2 = 1454.55 kJ
𝑄3 260
For refrigerator, = (1)
𝑄4 300
Also, WR= Q4 – Q3(2)
andWE – WR = 300
orWR = 1154.55 kJ
Equations (1) & (2) result in,
Q4 – Q3 = 1154.55 (3)
From equations (1) & (3),
Q3 = 7504.58 kJ
Q4 = 8659.13 kJ
Total heat transferred to low temperature reservoir
= Q2 + Q4 = 9204.68 kJ
Heat transferred to refrigerant = 7504.58 kJ
Total heat transferred to low temperature reservoir = 9204.68 kJ Ans.
4. In a winter season when outside temperature is –1ºC, the inside of house is to be

maintained at 25ºC.Estimate the minimum power required to run the heat pump of
maintaining the temperature. Assume heating load as 125 MJ/h.
Solution:
𝑄1 𝑄1
𝐶𝑂𝑃𝐻𝑃 = =
𝑊 𝑄1 − 𝑄2
1
= 𝑄
(1 − 𝑄2 )
1
Also we know
𝑄1 298.15
=
𝑄2 272.15
Thus, 𝐶𝑂𝑃𝐻𝑃 = 11.47
𝑄1
Also, 𝐶𝑂𝑃𝐻𝑃 = , substituting Q1
𝑊
Therefore, 𝑊 = 10.89 MJ/h
or, 𝑊 = 3.02 kW
Minimum power required = 3.02 kW Ans.
Chapter 4 Pure Substance
4.1 The pure substance
We define a
• Pure substance: a material with homogeneous and invariable composition.
To elaborate,
• Pure substances can have multiple phases: an ice-water mixture is still a pure substance.
• An air-steam mixture is not a pure substance.
• Air, being composed of a mixture of N 2 , O2 , and other gases, is formally not a pure substance.
However, experience shows that we can often treat air as a pure substance with little error.
4.1.1 Vapor-liquid-solid phase equilibrium
Pure Substance
Pure Substance
Pure Substance
Pure Substance
Pure Substance
4.1.2 Independent properties
Pure Substance
4.1.3 Thermal equations of state
4.1.4 Ideal gas law
Pure Substance
4.1.5 Dryness fraction (X)

𝑀𝑎𝑠𝑠 𝑜𝑓 𝑑𝑟𝑦 &𝑆𝑎𝑡𝑢𝑟𝑎𝑡𝑒𝑑 𝑠𝑡𝑒𝑎𝑚
𝑋=
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑑𝑟𝑦 & 𝑠𝑎𝑡𝑢𝑟𝑎𝑡𝑒𝑑 𝑠𝑡𝑒𝑎𝑚 + 𝑀𝑎𝑠𝑠 𝑜𝑓 𝑠𝑎𝑡𝑢𝑟𝑎𝑡𝑒𝑑 𝑤𝑎𝑡𝑒𝑟
Quality of Steam = 𝑥 × 100 = 𝑥%
𝑇𝑠𝑢𝑝 – 𝑇𝑠 = 𝐷𝑒𝑔𝑟𝑒𝑒 𝑜𝑓 𝑠𝑢𝑝𝑒𝑟ℎ𝑒𝑎𝑡
 Gases cannot condense at their own pressure but they can be condensed only when they are
brought below their pressure.
4.1.6 Isothermal Compressibility  κT 
A very important property of a substance is how compressible it is. Gases are very compressible,
so when subjected to high pressures, their volumes decrease significantly (think Boyle’s Law!)
Solids and liquids however are not as compressible. However, they are not entirely incompressible!
High pressure will lead to a decrease in volume, even if it is only slight. In addition, of course,
different substances are more compressible than others.
To quantify just how compressible substances are, it is necessary to define the property. The
isothermal compressibility is defined by the fractional differential change in volume due to a
change in pressure.
(1)
4.1.7 Isobaric Thermal Expansivity ( α )
Another very important property of a substance is how its volume will respond to changes in
temperature. Again, gases respond profoundly to changes in temperature (think Charles’ Law!)
whereas solids and liquid will have more modest (but not negligible) responses to changes in
temperature. (For example, if mercury or alcohol did not expand with increasing temperature, we
would not be able to use those substances in thermometers.)
The definition of the isobaric thermal expansivity (or sometimes called the expansion coefficient)
is
(2)
Pure Substance
On combining equations (1) and (2);
Questions
1. 1 kg of saturated steam at 100ºC, 1.01325 bar is contained in a rigid walled vessel. It has
a volume of 1.673 m3. It cools to 98ºC. The saturation pressure is 0.943 bar. 1 kg of water
vapor under these conditions have a volume of 1.789 m3. The amount of water vapor
condensed in kg is:
(a) 0 (b) 0.065 (c) 1.1 (d) 1.0
Solution:
𝑉𝑤𝑒𝑡 = 𝑥 𝑘𝑔 𝑑𝑟𝑦 𝑠𝑡𝑒𝑎𝑚 + (1 − 𝑥) 𝑘𝑔 𝑤𝑎𝑡𝑒𝑟
𝑉𝑤𝑒𝑡 = 𝑥𝑉𝑔 + (1 − 𝑥) 𝑉𝑔 (negligibly small)
𝑉𝑤𝑒𝑡 = 𝑥𝑉𝑔 + 𝑉𝑔 = 1
𝑉1 = 𝑉2
(Vg1) = (Vwet)2 = (x Vg)2
1.673 = x2 + 1.789
x2 = 0.935
Water pressure = 1 – 0.955 = 0.065 kg of steam got cooled
2. Water has a critical specific volume of 0.003155m3/kg. A closed and a rigid steel tank of
volume V=0.025m3 contains a mixer of water and steam at 0.1 MPa. The mass of mixer is
10kg. The tank is now slowly heated. The liquid level inside the tank
a) Will rise
b) Will fall
c) Will remain constant
d) May rise or fall depending on the amount of heat added.
Answer: The liquid level will rise
Pure Substance
3. The following table of properties is printed out for saturated liquid and saturated vapors
of NH3. The titles for only the 1st two columns are available. All we know is that the other
column contains data from specific property namely enthalpy and entropy.
2 8
1 3 4 5 6 7
P
T(0C)
1418.0
-20 190.2 88.76 0.3657 8.05 5.6155 1299.5
1442.2
0 429.6 179.69 0.7114 180.36 5.3309 1318.0
1460.2
20 587.5 272.89 1.0408 274.30 5.0880 1332.2
1470.2
40 1554.9 368.74 1.3574 371.43 4.8662 1341.0
i) h data are in column.

a) 3 & 7
b) 3 & 8
c) 5 & 7
d) 5 & 8
ii) When saturated liquid at 400c is throttled to -200 c ,the quality at exit will be
a) 0.189
b) 0.212
c) 0.231
d) 0.788
Solution: smaller values are of entropy
4th column= sf 6th column= sg
3rd column = uf 5th column = hf
h = u + pv
The lower value is for ug = 7th column and the rest one is hg = 8th column
Pure Substance
ii) during throttling h remains constant

h1 = h2
(hf)1 = (hwet)2
(hf)1 = (hf + xhfg)2
= [hf + x(hg – hf )] 2
371.43 = [89.05 + x(1418.0 – 89.05)]
X = 0.2124
4. A saturated liquid at 1500KPa and 500Kpa with enthalpy of 750KJ/Kg is throttled to a

liquid vapor mixer at 150Kpa & 350K. At exit condition, enthalpy of saturated liquid is
500KJ/Kg. and enthalpy of saturated vapor is 2500KJ/Kg. percentage of saturated liquid,
which vaporized, is
a) 87.5%
b) 67%
c) 12.5%
d) 1%
Solution:
hf1 = [hf + x (hg – hf )]
250
750 = 500+ x(2500-500) ; = x; x = 12.5%
2000
5. Steam undergoes isentropic expansion in a turbine from 5000Kpa, 400 0C & S =

6.65KJ/KgK, Sf = 1.4336kJ/kgK , Sg = 7.2234’’
The exit condition of steam is A?
a) Superheated vapor
b) Partially condensed vapor with quality of 0.9
c) Saturated vapor
d) Partially condensed vapor with quality 0.1
Solution:
6.65 = S2 – Swet
6.65 = 1.4336 + x(7.2234 – 1.4336)
x = 0.9
Therefore, answer (b) is correct.
Chapter 5 Mixture Properties
5.1 Mixture
Any state of material where two or more pure substances are mixed together but not chemically
combined.
Any mixture is a combination of two or more pure substances which are separable physically.
There are two types of mixtures:
1. Homogenous Mixture: Single phase exists. (saturated solution of salt in water)
2. Heterogeneous Mixture: Different phases exist. (water + oil); colloidal solution (milk)
Potentials:
1. Mechanical Equilibrium: Pressure change (ΔP) = 0

2. Thermal Equilibrium: Temperature change (ΔT)=0
3. Chemical Equilibrium: (μ) It is a partial molar free energy and is equal to the change in
total Gibbs free energy per unit change of moles of any component. Chemical Potential (Δµ)=0
𝜕𝐺 𝑡
𝜇=( )
𝜕𝑛𝑖 𝑃,𝑇,𝑛
𝑗≠𝑖
5.2 Reversible (ideal case):
- ΔSSystem = Q/T ; ΔSUniverse = ΔSSystem + ΔSSurrounding
- ΔSSurrounding = -Q/T ; ∴ΔSUniverse = Q/T – Q/T = 0

- ΔSSystem– Q/T= 0
∴ Q - T ΔSSystem = 0
Now, At Constant Pressure, Q = ΔH
∴ ΔG =ΔH - TΔSSystem = 0
Mixture Properties
5.3 Irreversible (spontaneous):

𝑄1 +𝑄2 𝑄
- ∆𝑆𝑠𝑦𝑠𝑡𝑒𝑚 = ( )=𝑇
𝑇
𝑄2
- ∆𝑆𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔 = − 𝑇
𝑄 𝑄2
- ∆𝑆𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑒 = 𝑇 − >0
𝑇
𝑄2
∴ ∆𝑆𝑠𝑦𝑠𝑡𝑒𝑚 − >0
𝑇
𝑄2
∴ − ∆𝑆𝑠𝑦𝑠𝑡𝑒𝑚 < 0
𝑇
∴ Q2 - TΔSsystem< 0
∴ ΔH - TΔS< 0
∴ ΔG <0
 If G <0, process is spontaneous in forward direction.
 If G >0, process is spontaneous in backward direction (Not possible)
 If G =0, process is reversible and net change in chemical potential is zero. (in equilibrium)
5.4 Helmholtz free energy:
A = U - TS
where, A = Helmoltz free energy
U = Internal energy of the system
T = Absolute temperature
S = Entropy
5.5 Fundamental Properties Relation: (P, V, T)
Mixture Properties
These are the relations of four thermodynamics potentials or properties (U, H, A, G) with canonical
variables (T, P, V, S) for pure homogenous fluids at constant composition in a closed system.
From first law: dU = δQrev - δWrev
From second law: δQrev = TdS ; δWrev = PdV
∴ dU = TdS - PdV (1)
Now U = U(S,V)
𝜕𝑈 𝜕𝑈
∴ 𝑑𝑈 = ( 𝜕𝑆 ) 𝑑𝑉 + (𝜕𝑉 ) 𝑑𝑆 (2)
𝑉 𝑆
Comparing and equating equation (1) and (2)

𝜕𝑈 𝜕𝑈
𝑇 = (𝜕𝑉 ) 𝑎𝑛𝑑 𝑃 = − ( 𝜕𝑆 )
𝑆 𝑉
Now H = U + PV
∴ dH = dU + d (PV)
∴ dH = dU + PdV + VdP
∴ dH = (TdS - PdV) + (PdV + VdP)
∴ dH = TdS + VdP (3)
Now dH = H(S,P)
𝜕𝐻 𝜕𝐻
∴ 𝑑𝐻 = ( 𝜕𝑆 ) 𝑑𝑆 + ( 𝜕𝑃 ) 𝑑𝑃 (4)
𝑃 𝑆
From equations (3) and (4),

𝜕𝐻 𝜕𝐻
Hence, 𝑇 = ( 𝜕𝑆 ) 𝑎𝑛𝑑 𝑉 = ( 𝜕𝑃 )
𝑃 𝑆
Helmoltz energy A = U - TS
∴ dA = dU - TdS - SdT
∴ dA = (TdS - PdV) - (TdS + SdT)
∴ dA = - PdV - SdT
Mixture Properties
Gibbs Free Energy, G = H -TS

∴ dG = dH - TdS - SdT
∴ dG = TdS + VdP - TdS - SdT
∴ dG = VdP – SdT
5.6 Maxwell’s Relations

If F = F (x,y), then the total differential of F is defined as
𝜕𝐹 𝜕𝐹
𝑑𝐹 = (𝜕𝑥 ) 𝑦 𝑑𝑥 + (𝜕𝑦) 𝑥 𝑑𝑦
dF = M dx + N dy
𝜕𝑀 𝜕2 𝐹 𝜕𝑁 𝜕2 𝐹
Then ( 𝜕𝑦 ) = and ( 𝜕𝑥 ) =
𝑥 𝜕𝑥𝜕𝑦 𝑦 𝜕𝑥𝜕𝑦
So
𝜕𝑀 𝜕𝑁
( 𝜕𝑦 ) = ( 𝜕𝑥 ) (This is the criteria for exactness)
𝑥 𝑦
The Maxwell’s relations derived from fundamental property relations are

𝜕𝑇 𝜕𝑃
(𝜕𝑉) = − ( 𝜕𝑆 )
𝑆 𝑉
𝜕𝑇 𝜕𝑉
(𝜕𝑃) = ( 𝜕𝑆 )
𝑆 𝑃
𝜕𝑃 𝜕𝑆
(𝜕𝑇 ) = (𝜕𝑉)
𝑉 𝑇
𝜕𝑉 𝜕𝑆
(𝜕𝑇 ) = − (𝜕𝑃)
𝑃 𝑇
5.7 Open System
For open system:

G = G(P, T, nA, nB, nC,…………)
 (nG)   (nG)   (nG) 

d (nG)  
 P T ,n
dP   T  dT    
i  ni T , P , n
dni
P,n
j i
d (nG)  (nV )dP  (nS )dT   i dni

i 1
 (nG) 
i   
 ni  P,T ,n j i
Mixture Properties
Where chemical potential is,
5.8 Phase Equilibrium:
For phases α and β:

d (nG )  (nV  )dP  (nS  )dT   i dni
i 1
d (nG )  (nV  )dP  (nS  )dT   i dni

i 1
Adding these equations
d (nG)  (nV )dP  (nS )dT   i dni   i dni

i 1 i 1
The each phase is open to other phase, but the combined system of two phases is closed with
respect to the surroundings.
Therefore,
  dn     dn  0
i 1
i i
i 1
i i
But dni  dni
 (    )dn  0
i 1
i i i
Hence,
i  i (Phase Equilibrium)
5.9 Partial Molar Property:
For pure substance:

M t = ni * Mi
where, ni = change in moles; Mi = Molar property of pure component i, M t is the molar

property of the solution.
For mixture:
M t ≠ ni * Mi
But,
Mixture Properties
M   xi M i where M i is the partial property.

i
Partial Property is defined by

 (nM ) 
Mi   
 ni  P,T ,n ji
Notations:
Pure-species property= Vi , Ui ,Si, Hi , Gi
Mixture property= V, U, S, H, G
__ __ __ __ __
Partial Property= V i , U i, H i,Gi, S i
Gibbs-Duhem Equation
 x dM
i
i i = 0 (Constant T and P)
Partial Property relations for binary mixture:
dM
M1  M  x2
dx1
dM
M 2  M  x1
dx1
5.10 Effect of temperature and pressure on Chemical Potential (μi):
 (nG) 
i   
 ni  P,T ,n j i
 i    2 (nG)   i    2 (nG) 

 P    n P  and  T    n T 
   i T ,n ji    i  P,n ji
d(nG) = (nV)dP - (nS)dT
 (nG)   (nG) 
 P   nV and  T   nS
 T ,n   P ,n
  2 (nG)   (nV )  __   2 (nG)   (nS )  __

      Vi and         Si
 Pni T ,n ji  ni T ,n ji  T ni P,n ji  ni P,n ji
 i  __  i  __
 P   Vi and  T    Si
   
Mixture Properties
5.11 Fugacity (f)
It shows the deviation of real gas from ideal gas.

For homogenous pure fluid in a closed system,
dG = VdP - SdT
At isothermal conditions: dG = VdP
𝑑𝑃
𝑑𝐺 = 𝑅𝑇 (for an ideal gas)
𝑃
dG =RTd(ln P)
Real gases:
dG =RTd(ln f)
where, f = P , for ideal gases
f = effective pressure extorted in case of real gas.
Integrating above equation,
𝑓
𝛥𝐺 = 𝑅𝑇𝑙𝑛 𝑓2
1
Standard state fugacity,

𝑓
𝐺 − 𝐺 0 = 𝑅𝑇𝑙𝑛 𝑓0
5.12 Fugacity Coefficient (Φ)
fugacity of real gas

Fugacity coefficient 
pressure of ideal gas
f

P
When P  0, f  P, It indicates real gas  ideal gas.
Fugacity coefficient from Compressibility factor:

At constant temperature,
dG =RT d(ln f) and dG=VdP
So, RT d(ln f) = V dP
Mixture Properties
d(ln f) = (V/RT) dP
But, the compressibility factor,
Vreal
Z
Videal
V
Z
RT
P
V Z
 
RT P
dP
 d (ln f )  Z
P
dP dP dP
d (ln f )  Z 
P P P
dP
d (ln f / P)  (Z 1)
P
dP
  d (ln f / P)   (Z 1)
P
P
dP
ln    (Z 1)
0 P
Fugacity coefficient from molar residual volume:
Residual volume,
VR = V- Vig
So, V=VR+Vig
dG = VdP (Constant T)
dG =RT d(ln f)
V
 d (ln f )  dP
RT
1 RT
 d (ln f )  (V R  )dP
RT P
VR
 d (ln f )  dP  d (ln P)
RT
VR
 d (ln f / P)  dP
RT
Mixture Properties
P
VR
ln( f / P)   dP
0 RT
P
  V R dP  RT ln 
0
5.13 Calculations using enthalpy and entropy of the system
dG  RTd (ln f )
G f
 dG   RTd (ln f )
G0 f0
G  G0  RT ln( f / f 0 )
G = H - TS
G0 = H0 - TS0
( H  TS )  ( H 0  TS 0 )  RT ln( f / f 0 )
( H  H 0 ) (S  S 0 )
 ln( f / f )  0

RT R
Fugacity in solids and liquids:
At equilibrium, ΔG = 0
GS - GV = 0
GS = GV
 fs 
G  G S  GV  RT ln  V 
f 
So at equilibrium, f S = f V, similarly f L = f V
5.14 Activity
It is the ratio of fugacity-to-fugacity at standard state for pure substance.
fi
a
fi 0
G  RT ln a
Effect of Temperature:
Mixture Properties
 ln a H 0  H

T RT 2
Effect of Pressure:
V
ln a 
RT
 P  P0 
5.15 Lewis Randall Rule

The fugacity of a component in an ideal solution is directly proportional to the molar fraction of the
component in the solution. It is applicable at low pressure and the concentration of the component is in
excess. It is not valid at high pressure.
^
f i  xi fi
Where
^
f i = fugacity of component i in ideal solution
xi = Mole fraction of component i in the solution
fi = fugacity of pure component i
5.16 Raoult’s Law
Ideal solution
 PMP of the solution is equal to molar property of the solution

 When there is not intermolecular interaction between the molecules
 When there is no volume change, when components mixed together
𝑉̅𝑖 = 𝑉𝑖
𝑓̂𝑖 = 𝑥𝑖 𝑓𝑖
For ideal solution,

̂ = 𝑝̅𝑖
𝑓𝑖
𝑓𝑖 = 𝑝𝑖𝑠
𝒑̅𝒊 = 𝒙𝒊 𝒑𝒔𝒊
The partial pressure of the component in the ideal solution is directly proportional to mole fraction in the
liquid solution
𝑝̅𝑖 = 𝑦𝑖 𝑝
𝑝̅𝑖 = 𝑦𝑖 𝑝 = 𝑥𝑖 𝑝𝑖𝑠
Valid for concentrated solutions.
Mixture Properties
5.17 Henry’s law
For dilute ideal solution, the fugacity of component is directly proportional to the mole fraction of the
component in the solution.
̂ α 𝑥𝑖
𝑓𝑖
̂ = 𝑥𝑖 𝐻𝑖
𝑓𝑖
For dilute solution
̂ = 𝑥𝑖 𝐻𝑖 for 𝑥𝑖 → 0
𝑓𝑖
̂ = 𝑥𝑖 𝑓𝑖
For 𝑥𝑖 → 1, 𝑓𝑖 Lewis Randall rule (Raoult’s law)
̂ = 𝑓𝑖
At 𝑥𝑖 = 1, 𝑓𝑖
5.18 Activity in solution
Ratio of fugacity of the component in solution to the fugacity of component in the standard state.
𝒇̂𝒊
𝒂𝒊 =
𝒇𝒐
𝝁𝒊 𝒇̂𝒊
∫ 𝒅𝝁𝒊 = ∫ 𝑹𝑻 𝒅(𝐥𝐧 𝒇̂𝒊 )
𝝁𝒊𝒅
𝒊 𝒇𝒐𝒊
𝑓̂𝑖
⇒ 𝜇𝑖 = 𝜇𝑖𝑖𝑑 = 𝑅𝑇 𝑙𝑛 ( )
𝑓𝑖𝑜
𝝁𝒊 = 𝝁𝒊𝒅
𝒊 + 𝑹𝑻 𝐥𝐧 𝒂𝒊
𝑓̂𝑖
𝑎𝑖 =
𝑓𝑖𝑜
For ideal solution
̂ = 𝑥𝑖 𝑓𝑖
𝑓𝑖
Mixture Properties
𝑓𝑖 = 𝑓𝑖𝑜
𝒂𝒊 = 𝒙𝒊
For real solution
𝑓𝑖 ≠ 𝑓𝑖𝑜
𝒂𝒊 = 𝜸𝒊 𝒙𝒊
𝛾𝑖 = activity coefficient, ‘i’ indicates the extent to which the solution is non-ideal
̂ = 𝜸𝒊 𝒙𝒊 𝒇𝒊
For real solution, 𝒇𝒊
For ideal solution, 𝜸𝒊 = 𝟏
‘i’ & ‘j’
If 𝑥𝑖 → 1, 𝛾𝑖 → 1
If 𝑥𝑖 → 0, 𝑥𝑗 → 1, 𝛾𝑗 → 1
# Effect of temperature on 𝛾𝑖
𝛿 ln 𝑓𝑖 𝐻𝑖𝑜 − 𝐻𝑖 (1)
=
𝛿𝑇 𝑅𝑇 2
𝛿 ln 𝑓̂𝑖 ̅̅̅̅
𝐻𝑖𝑜 − ̅̅̅
𝐻𝑖 (2)
= 2
𝛿𝑇 𝑅𝑇
̂ = 𝛾𝑖 𝑥𝑖 𝑓𝑖
𝑓𝑖
Equation (2) - (1)
𝛿 𝑓̂𝑖 ̅̅̅̅ 𝐻𝑖 𝐻𝑖𝑜 − 𝐻𝑖

𝐻𝑖𝑜 − ̅̅̅
𝑙𝑛 = −
𝛿𝑇 𝑓𝑖 𝑅𝑇 2 𝑅𝑇 2
𝛿 ̅̅̅̅
(𝐻 𝑜 ̅̅̅
𝑖 − 𝐻𝑖 ) 𝐻𝑖𝑜 − 𝐻𝑖
ln(𝛾𝑖 𝑥𝑖 ) = −
𝛿𝑇 𝑅𝑇 2 𝑅𝑇 2
𝛿 ̅̅̅
𝐻𝑖 − 𝐻𝑖
ln(𝛾𝑖 𝑥𝑖 ) =
𝛿𝑇 𝑅𝑇 2
5.19 Property Change of Mixing
For ideal solution, 𝜇 = ∑ 𝑥𝑖 𝜇𝑖
For ideal solution, 𝜇 = ∑ 𝑥𝑖 𝜇𝑖 + ∆𝜇
Mixture Properties
Property of change of mixing, ∆𝜇 = 𝜇 − ∑ 𝑥𝑖 𝜇𝑖
∆𝜇 = ∑ 𝑥𝑖 𝜇̅𝑖 − ∑ 𝑥𝑖 𝜇𝑖
∆𝜇 = ∑ 𝑥𝑖 (𝜇̅𝑖 − 𝜇𝑖 )
# Free Energy Change of Mixing

̅̅̅
𝐺𝑖 𝑓̂𝑖
∫ 𝑑𝐺𝑖 = ∫ 𝑅𝑇 𝑑 ln 𝑓𝑖
𝐺𝑖𝑜 𝑓𝑖𝑜
𝑓̂𝑖
𝐺̅𝑖 − 𝐺𝑖𝑜 = 𝑅𝑇 ln
𝑓𝑖𝑜
𝐺̅𝑖 − 𝐺𝑖𝑜 = 𝑅𝑇 ln 𝑎𝑖
∆𝐺 = 𝑅𝑇 ln 𝑎𝑖
∆𝐺 = 𝑅𝑇 ∑ 𝑥𝑖 ln 𝑎𝑖
∆𝐺 = ∑ 𝑥𝑖 (𝐺̅𝑖 − 𝐺𝑖𝑜 )
For ideal solution, 𝑎𝑖 = 𝑥𝑖
∆𝑮 = 𝑹𝑻 ∑ 𝒙𝒊 𝐥𝐧 𝒙𝒊
For pure solution, 𝑥𝑖 → 1
∆𝑮 = 𝟎
Mixture Properties
#Volume Change of Mixing
𝛿𝐺𝑖
( ) = 𝑉𝑖
𝛿𝑃 𝑇, 𝑥
𝛿𝐺̅𝑖
( ) = 𝑉̅𝑖
𝛿𝑃 𝑇, 𝑥
𝛿𝐺̅𝑖 𝛿𝐺𝑖 𝛿
𝑉̅𝑖 − 𝑉𝑖 = ( ) − ( ) = (𝐺̅ − 𝐺𝑖 )
𝛿𝑃 𝑇, 𝑥
𝛿𝑃 𝑇, 𝑥 𝛿𝑃 𝑖
∵ [(𝐺̅𝑖 − 𝐺𝑖 ) = 𝑅𝑇 ln 𝑎𝑖 ]
𝛿
̅𝑖 − 𝑉𝑖 ) = 𝑅𝑇
(𝑉 (ln 𝑎𝑖 )
𝛿𝑃
𝛿
̅𝑖 − 𝑉𝑖 ) = ∑ 𝑥𝑖 (𝑅𝑇
∆𝑉 = ∑ 𝑥𝑖 (𝑉 ln 𝑎𝑖 )
𝛿𝑃
𝜹
∆𝑽 = 𝑹𝑻 ∑ 𝒙𝒊 ( 𝐥𝐧 𝒂𝒊 )
𝜹𝑷
For ideal solution, 𝒂𝒊 = 𝒙𝒊
𝜹
∆𝑽 = 𝑹𝑻 ∑ 𝒙𝒊 ( 𝐥𝐧 𝒙𝒊 )
𝜹𝑷
For pure system, ∆𝑽 = 𝟎
# Enthalpy Change of Mixing
𝛿 𝐺𝑖 −𝐻𝑖
( ) = 2
𝛿𝑇 𝑇 𝑃,𝑥 𝑇
𝛿 𝐺̅𝑖 ̅̅̅𝑖
−𝐻
( ) = 2
𝛿𝑇 𝑇 𝑃,𝑥 𝑇
̅̅̅𝑖 − 𝐻𝑖 )
∆𝐻 = ∑ 𝑥𝑖 (𝐻
𝛿 𝐺̅𝑖 𝛿 𝐺𝑖
̅̅̅𝑖 − 𝐻𝑖 ) = 𝑇 2 [−
(𝐻 ( )]𝑃,𝑥 − 𝑇 2 [− ( )]𝑃,𝑥
𝛿𝑇 𝑇 𝛿𝑇 𝑇
𝛿 𝐺̅𝑖 − 𝐺𝑖
∆𝐻 = ∑ 𝑥𝑖 [𝑇 2 {− ( )}]𝑃,𝑥
𝛿𝑇 𝑇
𝛿 𝑅𝑇 ln 𝑎𝑖
∆𝐻 = 𝑇 2 ∑ 𝑥𝑖 [− { }]𝑃,𝑥
𝛿𝑇 𝑇
Mixture Properties
𝜹
∆𝑯 = −𝑹𝑻𝟐 ∑ 𝒙𝒊 [ 𝐥𝐧 𝒂𝒊 ]𝑷,𝒙
𝜹𝑻
For ideal solution,

𝜹
∆𝑯 = −𝑹𝑻𝟐 ∑ 𝒙𝒊 𝐥𝐧 𝒙𝒊
𝜹𝑻
For pure solution,
∆𝑯 = 𝟎
#Entropy Change of Mixing
∆𝑺 = ∑ 𝒙𝒊 (𝑆̅𝑖 − 𝑆𝑖 )
𝛿𝐺̅𝑖
= −𝑆𝑖̅
𝛿𝑇 𝑃,𝑥
𝛿𝐺𝑖
= −𝑆𝑖
𝛿𝑇 𝑃,𝑥
𝛿𝐺̅𝑖 𝛿𝐺𝑖
∆𝑆 = ∑ 𝒙𝒊 (− + )
𝛿𝑇 𝛿𝑇 𝑷,𝒙
𝛿
= ∑ 𝒙𝒊 − (𝐺̅𝑖 − 𝐺𝑖 )
𝛿𝑇
𝛿
= ∑ 𝑥𝑖 [− 𝑅𝑇 ln 𝑎𝑖 ]
𝛿𝑇
𝛿
= − ∑ 𝑥𝑖 [𝑅𝑇 ln 𝑎𝑖 + 𝑅 ln 𝑎𝑖 ]
𝛿𝑇
𝛿 𝑙𝑛 𝑎
= −𝑅 ∑ 𝑥𝑖 [ 𝛿 𝑙𝑛 𝑇𝑖 + 𝑙𝑛 𝑎𝑖 ]
𝜹 𝒍𝒏 𝒂𝒊
∆𝑺 = −𝑹 ∑ 𝒙𝒊 − 𝑹 ∑ 𝒙𝒊 𝒍𝒏 𝒂𝒊 ]
𝜹 𝒍𝒏 𝑻
For ideal and pure solution,
∆𝑺 = 𝟎
For ideal solution,
𝜹 𝒍𝒏 𝒙𝒊
∆𝑺 = −𝑹 ∑ 𝒙𝒊 − 𝑹 ∑ 𝒙𝒊 𝒍𝒏 𝒙𝒊
𝜹 𝒍𝒏 𝑻
Mixture Properties
𝛿 𝑙𝑛 𝑥𝑖
As 𝑥𝑖 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡, 𝛿 𝑙𝑛 𝑇
=0
∆𝑺 = −𝑹 ∑ 𝒙𝒊 𝒍𝒏 𝒙𝒊
5.20 Excess property
𝜇𝐸 = 𝜇𝑟𝑒𝑎𝑙 − 𝜇𝑖𝑑
𝜇𝐸 > 0 + 𝑣𝑒 𝑑𝑒𝑣𝑖𝑎𝑡𝑖𝑜𝑛 𝑓𝑟𝑜𝑚 𝑖𝑑𝑒𝑎𝑙𝑖𝑡𝑦
𝜇𝐸 < 0 − 𝑣𝑒 𝑑𝑒𝑣𝑖𝑎𝑡𝑖𝑜𝑛 𝑓𝑟𝑜𝑚 𝑖𝑑𝑒𝑎𝑙𝑖𝑡𝑦
# Excess Change of Mixing
∆𝜇𝐸 = ∆𝜇𝑟𝑒𝑎𝑙 − ∆𝜇𝑖𝑑
∆𝜇𝑟𝑒𝑎𝑙 = 𝜇𝑟𝑒𝑎𝑙 − ∑ 𝑥𝑖 𝜇𝑖
∆𝜇𝑖𝑑 = 𝜇𝑖𝑑 − ∑ 𝑥𝑖 𝜇𝑖
∆𝜇𝐸 = {𝜇𝑟𝑒𝑎𝑙 − ∑ 𝑥𝑖 𝜇𝑖 } − {𝜇𝑖𝑑 − ∑ 𝑥𝑖 𝜇𝑖 }
∆𝝁𝑬 = 𝝁𝒓𝒆𝒂𝒍 − 𝝁𝒊𝒅 = 𝝁𝑬
#Excess Gibb’s free energy
𝐺 𝐸 = ∆𝐺𝑖𝐸 = ∆𝐺 − ∆𝐺 𝑖𝑑
∆𝐺𝑖𝐸 = ∆𝐺𝑖 − ∆𝐺 𝑖𝑑
𝑓̂𝑖
∆𝐺𝑖 = 𝑅𝑇 ln
𝑓𝑖𝑜
𝑓̂
𝑖
𝑖𝑑
∆𝐺𝑖 = 𝑅𝑇 ln 𝑜
𝑓
For real solution, 𝑓̂

𝑖
𝑟𝑒𝑎𝑙
= 𝛾𝑖 𝑥𝑖 𝑓𝑖𝑜
For ideal solution, 𝑓̂𝑖𝑑

𝑖 = 𝑥𝑖 𝑓𝑖
𝑜
∆𝐺𝑖 = 𝑅𝑇 ln 𝛾𝑖 𝑥𝑖
∆𝐺𝑖𝑖𝑑 = 𝑅𝑇 ln 𝑥𝑖
∆𝐺𝑖𝐸 = 𝑅𝑇 ln 𝛾𝑖 𝑥𝑖 − 𝑅𝑇 ln 𝑥𝑖
∆𝑮𝑬𝒊 = 𝑹𝑻 𝐥𝐧 𝜸𝒊
Mixture Properties
5.21 Calculations for activity coefficient
Wohl’s Equation
𝒒𝟏
𝐥𝐧 𝜸𝟏 = 𝒛𝟐𝟏 [𝑨 + 𝟐(𝑩 − 𝑨)𝒛𝟏 ]
𝒒𝟐
𝒒𝟐
𝐥𝐧 𝜸𝟐 = 𝒛𝟐𝟐 [𝑩 + 𝟐(𝑨 − 𝑩)𝒛𝟐 ]
𝒒𝟏
𝒙𝟏 𝒙𝟐
𝒛𝟏 = 𝒒 𝒛𝟐 = 𝒒
𝒙𝟏 + 𝒙𝟐 ( 𝟐) 𝒙𝟐 + 𝒙𝟏 ( 𝟏)
𝒒𝟏 𝒒𝟐
𝑞1 & 𝑞2 = molar volume fraction of 1 & 2
𝑧1 &𝑧2 = effective molar fraction of 1 & 2
A & B = arbitrary constants
Murgulus Equation
3 suffix equation
−𝑞1 = 𝑞2
𝐥𝐧 𝜸𝟏 = 𝒛𝟐𝟏 [𝑨 + 𝟐(𝑩 − 𝑨)𝒛𝟏 ]
𝐥𝐧 𝜸𝟐 = 𝒛𝟐𝟐 [𝑩 + 𝟐(𝑨 − 𝑩)𝒛𝟐 ]

𝒙𝟏 𝒙𝟐
𝒛𝟏 = 𝒛𝟐 =
𝒙𝟏 + 𝒙𝟐 𝒙𝟏 + 𝒙𝟐
2 suffix equation
A = B , 𝑞1 = 𝑞2
𝐥𝐧 𝜸𝟏 = 𝒛𝟐𝟏 𝑨
𝐥𝐧 𝜸𝟐 = 𝒛𝟐𝟐 𝑩
𝒙𝟏 𝒙𝟐
𝒛𝟏 = 𝒛𝟐 =
𝒙𝟏 + 𝒙𝟐 𝒙𝟏 + 𝒙𝟐
Van Laar Equation

𝒒𝟏
𝐥𝐧 𝜸𝟏 = 𝒛𝟐𝟏 [𝑨 + 𝟐(𝑩 − 𝑨)𝒛𝟏 ]
𝒒𝟐
𝒒𝟐
𝐥𝐧 𝜸𝟐 = 𝒛𝟐𝟐 [𝑩 + 𝟐(𝑨 − 𝑩)𝒛𝟐 ]
𝒒𝟏
Mixture Properties
𝒒𝟏 𝑨
=
𝒒𝟐 𝑩
𝐥𝐧 𝜸𝟏 = 𝒛𝟐𝟏 𝑨
𝐥𝐧 𝜸𝟐 = 𝒛𝟐𝟐 𝑩
𝒙𝟏 𝒙𝟐
𝒛𝟏 = 𝑩 𝒛𝟐 = 𝑨
𝒙𝟏 + 𝒙𝟐 (𝑨) 𝒙𝟐 + 𝒙𝟏 (𝑩)
Questions
1. Determine the electric work required to produce 1 mol of H in the electrolysis of liquid
water at 298 K and 1 atm.
H2O  H2(g) + O2(g)
Data given: At 298 K and 1 atm
ΔH = 286 kJ H2
SH2 = 131 J/K
SH2O = 70 J/K
SO2 = 205 J/K
ΔS = Sf - Si = SH2 + ½ So2 - SH2O
ΔG = 237.27 kJ
2. Find: Reaction is spontaneous or not at 25oC and 500oC. At what temperature it will
achieve the equilibrium?
N2  g   3H2  g   2NH3  g 
ΔHio (kJ/mol) ΔSo (J/K. mol) at std (25oC, 1 atm)
N2 0 191.6
H2 0 130.6
NH3 -46.11 192.6
Solution: ΔGo = ΔHo - TΔSo
- ΔHo =nHoproduct - n Horeactant
ΔHo = 2 * (-46.11) - 0 - 0
ΔHo = -92.22 kJ
- ΔSo = n Soproduct - n Soreactant
Mixture Properties
ΔSo = (2 * 192.6) - (1 * 191.6) - (3 * 130.6)
ΔSo = -198.75 J/K
i) ΔGo = -92.22 - [298 * (-198.75) * 10-3 ]
ΔGo = 66.91 kJ (not spontaneous; spontaneous in backward direction)
ii) ΔGo = -92.22 - [773 * (-198.75) * 10-3 ]
ΔGo = 66.91 kJ (not spontaneous; spontaneous in backward direction)
iii) ΔGo = 0
0 = -92.22 - [ T* (-198.75) * 10-3 ]
T = 465.3 K
4. The molar volume of binary mixture is given as V = 220 x1 + 180 x2 + x1x2 (90x1+ 50x2).
Find out the part molar volume of component 2 at x2 = 0.3.
Solution:
V = 220 x1 + 180 x2 + x1x2 (90x1+ 50x2)
V=220 x1 + 180 x2 + 9 x12x2 + 50 x1x22 -x1(220 + 18x1x2+50x22)
V=180 x2 - 9 x12x2
V=180 x2
Mixture Properties
5. At 300 K, 1 bar, the volumetric data of liquid mixture of benzene and cyclohexane are
given as V = (109.4 * 10-6) - (16.8 * 10-6)x - (2.64 * 10-6)x2, where x is the mole fraction of
cyclohexane. What is the partial molar volume of cyclohexane at x = 0.4.
Solution:
V = (109.4 * 10-6) - (16.8 * 10-6 )x - (2.64 * 10-6)x2
V1 =v + (1 - x1) V1x1 ; x1 = Mole of cyclohexane
V1 = [(109.4 * 10-6) - (16.8 * 10-6 )(0.4) - (2.64 * 10-6)(0.4)2 ]+ (1 - 0.4) [- (16.8*10-6 ) - (2.64 *
10-6)(0.4)]
V1 = (109.4 * 10-6) - (6.72 * 10-6) - (0.4224 * 10-6)
V1 = 90.91 * 10-6
6. The molar enthalpy of binary solution H = 400 x1 + 600 x2 + x1x2 (40 x1 + 20 x2). Find the
H1 at x2 = 0.7.
Solution:
H1= 400 (0.3) + (600 * 0.7) + (0.7 * 0.3) [(40*0.3) + (20 * 0.7)] - [0.7 (600 +
40 (0.32)+2(20*0.3*0.7))]
H1 = 117.06.
7. From the PVT data for a gas it is found that 050 dP = -556.611 /mol. Find the fugacity at
50 bar and 300 K?
Solution:
RT ln (fP) = - 556.61
∴ 8.314 * 300 * (ln f - ln 50) = -556.61
∴ f = 40 bar
Chapter 6 Chemical Reaction Equilibria
6.1 The reaction coordinate
The general chemical reaction as written
|𝑉1 | + 𝐴1 + |𝑉2 |𝐴2 + ⋯ … … … … . . → |𝑉3 |𝐴3 + |𝑉4 |𝐴4 + ⋯ … … ….
Where |𝑉𝑖 | is a stoichiometric coefficient and Ai stands for a chemical formula. The symbol Vi itself is called
a stoichiometric number and by the sign conversion, it is
+ve for a product and –ve for a reactant
e.g. CH4 + H2O  CO + 3H2
VCH4 = -1 , VH20 = -1 VCO = 1 VH2 =3
The stoichiometric number for an inlet species is zero.
The changes in the numbers of moles of species present are in direct proportion to the stoichiometric
number.
e.g. if 0.5 mol of CH4 disappears by reaction, 0.5 mol of H2Oalso disappears. Simultaneously 0.5 mol of CO
and 1.5 mol of H2 are formed.
𝑑𝑛2 𝑑𝑛1 𝑑𝑛3 𝑑𝑛1

𝑣2
= 𝑣1 𝑣3
= 𝑣1
etc.
𝑑𝑛3 𝑑𝑛2 𝑑𝑛3 𝑑𝑛4

= = =
𝑣1 𝑣2 𝑣3 𝑣4
All terms are being equal, they can be identified collectively by a single quantity representing an amount
of reaction.
Thus a definition of dƐ
𝑑𝑛1 𝑑𝑛2 𝑑𝑛3
= = = − − − − − = 𝑑Ɛ
𝑣1 𝑣2 𝑣3
𝑑𝑛𝑖 = 𝑣𝑖 𝑑Ɛ (i = 1, 2 , M)
Ɛ is called reaction coordinate ( or extent of reaction), characteristics the extent or degree to which a
reaction has taken place.
Chemical Reaction Equilibria
For initial unreacted state, Ɛ = 0 and ni = nio
𝑛𝑖 Ɛ
∫ 𝑑𝑛𝑖 = 𝑣𝑖 ∫ 𝑑Ɛ
𝑛𝑖𝑜 0
ni = ni0 + ViƐ
Summation over all species yields
𝑛 = ∑ 𝑛𝑖 = ∑ 𝑛𝑖0 + Ɛ ∑ 𝑣𝑖
𝑖 𝑖
n = no + V Ɛ
e.g H2 O - H2 + ½ O2 (no moles of water)
Find expressions which relate the no. of moles
6.2 Multi reaction equilibrium:
When two or more independent reactions proceed simultaneously, subscript j serves as the reaction index
Ɛj for each reaction
Vij designates the stoichiometric number of species i in reaction j.
dni= ∑𝑗 𝑣𝑖𝑗 dƩ𝑗
Integrating from ni = ni0 and Ʃ𝑗 = 0 to ni and Ʃ𝑗
ni = ni0 + ∑𝑗 𝑣𝑖𝑗 Ʃ𝑗
n= ∑𝑖 𝑛𝑖0 + Ʃ𝑖 Ʃ𝑗 𝑣𝑖𝑗 Ʃ𝑗 =𝑛𝑜 +Ʃ𝑗 (Ʃ𝑖𝑣𝑖𝑗 )Ʃ𝑗
where, 𝑣𝑗 =Ʃ𝑣𝑖𝑗 n= no + Ʃ𝑣𝑗 Ʃ𝑗
𝑛𝑖0+Ʃ
𝑗𝑣𝑖𝑗 Ʃ
𝑗
𝑦𝑖 =
𝑛0+Ʃ 𝑣𝑖 Ʃ
𝑗 𝑗
6.3 Application of equation criteria to chemical reactions
The total Gibbs energy of a closed system at constant T and P must because during an irreversible process
and the condition for equilibrium is reached when at attains its minimum value.
At this equilibrium state
(𝑑𝑢 )T,P =0
This it a mixer of chemical species is not in chemical equilibrium and reaction that occurs at constant T
and P must lead to a decrease in total Gibbs energy of the system.
At equilibrium,
The total Gibbs energy is zero
The standard Gibbs- energy change and the equilibrium constant
D (n k ) = (n v) dp – (ns) dT + Ʃµi dni
Changes in the mole numbers ni replaced by Vi dƐ
d (n k) = (n v) dp – (n s) dT + Ʃ viµi dƐ
Taking the differentiation with respect to dƐ at constant T, P
Ə(nu) Ə(G t)
∑ 𝑣𝑖 = [ ] = [ ]
ƏƐ 𝑇1𝑃 ƏƐ 𝑇1𝑃
At equilibrium the quantity on the right hand side will be zero
Now,
∑ 𝑣𝑖 µ𝑖 = 0
µ𝑖 = [𝑖 (𝑇)] + 𝑅 𝑇 𝑙𝑛 𝑓̂𝑖
G𝑖 = [𝑖 (𝑇)] + 𝑅 𝑇 𝑙𝑛 𝑓̂𝑖 (For pure species at standard state)
0
𝑓̂
µ𝑖 − µ0𝑖 = RTln ̂𝑖0
𝑓𝑖
0
𝑓̂
Ʃ𝑣𝑖 [𝐺𝑖0 + 𝑅𝑇𝑙𝑛 ( 𝑖0 )]=0
𝑓̂𝑖
̂𝑖 0
𝑓
Ʃ𝑣𝑖 𝐺𝑖0 + 𝑅𝑇 Ʃln (
̂𝑖 0
)𝑣𝑖 =0
𝑓
0 Ʃ𝑣𝑖𝐺0
𝑓̂
lnП( ̂𝑖0)Vi = - 𝑅𝑇
𝑖
𝑓𝑖
Where, П Signifies the product over all species I,
̂𝑖 0
𝑓
Пi( ̂ 0 ) Vi =K = П(ai) Vi
𝑓𝑖
−𝛥𝐺 0
Where K= exp( )
𝑅𝑇
−𝛥𝐺 0
lnk =
𝑅𝑇
K is called equilibrium constant.
𝛥𝐺 0 =Ʃ𝑖𝑣𝑖𝐺 0 = standard Gibbs free energy at equilibrium.

𝑖
−𝛥𝐺 0 −𝛥𝐺 0
K = exp ( ) and lnk =
𝑅𝑇 𝑅𝑇
𝛥𝐺 0 =Ʃ𝑣𝑖𝐺 0
𝑖
6.4 Gas phase reaction:
𝑝
̂ 𝒊) Vi = ( 0 )-vk
П𝒊 (𝒚𝒊 𝝓 𝑝
Here yi may be the elemental in favor of the equilibrium value of the reaction coordinate Ɛ𝑒 . Then for a
fixed temperature equilibrium relates Ɛ𝑒 to P.
If the equilibrium mixer is an ideal solution 𝜙̂𝑖 the fugacity coefficient of pure species i at T and P.
̂ 𝒊) Vi = ( 𝑝0 )-vk
П𝒊 (𝒚𝒊 𝝓 𝑝
Each ϕ𝑖 for a pure species can be evaluated from a generalized correlation once the equilibrium T and P
are specified.
High the equilibrium mixture behaves essentially as an ideal gas. So, 𝜙̂𝑖 = 1
𝑝
П𝒊 (𝒚𝒊 ) Vi = (𝑝0 )-vk
6.5 Liquid phase reaction:
(𝑝0 −𝑝)
П𝒊 (𝒙𝒊 𝒚𝒊)Vi = k exp[ 𝑅𝑇
Ʃ𝑖 𝑣𝑖 𝑣𝑖 ]
Except for high pressure, the exponential form is close to unity and may be omitted
П𝒊 (𝒙𝒊 𝒚𝒊) Vi = k
The activity coefficient can be calculated by Wilson or UNIFAC method.
If the equilibrium mixer is an ideal solution yi is unity.
П𝒊 (𝒙𝒊 ) Vi = k (law of mass action)
GATE QUESTIONS
GATE-2009
1. An ideal gas at temperature T1 and pressure p1 is compressed isothermally to pressure p2 (>p1) in a
closed system. Which one of the following is true for internal energy (U) and Gibbs free energy (G) of
the gas at the two states?
(A) U1 = U2, G1 > G2 (B) U1 = U2, G1 < G2
(C) U1 > U2, G1 = G2 (D) U1 < U2, G1 = G2
Ans: B
5
2. An ideal gas with molar heat capacity Cp = 2 R (where R = 8 314 J/mol K) is compressed adiabatically
from 1 bar and 300 K to pressure P2 in a closed system. The final temperature after compression is 600
K and the mechanical efficiency of compression is 50%.
(i) The final pressure P2 (in bar) is
(A) 23/4 (B) 25/4 (C) 23/2 (D) 25/2
Ans: D
(ii) The work required for compression (in kJ/mol) is
(A) 3.74 (B) 6.24 (C) 7.48 (D) 12.48
Ans: C
GATE-2010
1. A new linear temperature scale, denoted by S, has been developed, where the freezing point of water
is 200S and the boiling point is 400S. On this scale, 500S corresponds, in degree Celsius to
(A) 100C (B) 125C (C) 150C (D) 300C
Ans. C
2. A saturated liquid at 1500 kPa and 500 K, with an enthalpy of 750 kJ/kg is throttled to a liquid-vapour
mixture at 150 kPa and 300 K. At the exit conditions, the enthalpy of the saturated liquid is 500 kJ/kg
and the enthalpy of the saturated vapour is 2500 kJ/kg. The percentage of the original liquid, which
vaporizes, is
(A) 87.5% (B) 67% (C) 12.5% (D) 10%
Ans: C
3. For a binary mixture at constant temperature and pressure, which one of the following relations between
activity coefficient (γi) and mole fraction (xi) is thermodynamically consistent?
Gate Questions
1
(A) ln γ1 = − 1 + 2x1 − x12, ln γ2 = x12 (B) ln γ1 = − 1 + 2x1 − x12, ln γ2 = x12 (C)
2
1
ln γ1 = − 1 + 2x1 − x12, ln γ2 = − x12 (D) ln γ1 = − 1 + 2x1 − x12, ln γ2 = − x12
2
Ans: D
GATE-2011
1. The partial molar enthalpies of mixing (in J/mol) for benzene (component 1) and
cyclohexane(component 2) at 300 K and 1 bar are given by ∆H̅1 = 3600 x22 and ∆H̅2 = 3600 x12,
where x1 and x2 are the mole fractions. When ONE mole of benzene is added to TWO moles of
cyclohexane, the enthalpy change (in J) is
(A) 3600 (B) 2400 (C) 2000 (D) 800
Ans: D
2. Consider a binary mixture of methyl ethyl ketone (component 1) and toluene (component 2). At 323 K
the activity coefficients γ 1 and γ 2 are given by
Where x1 and x2 are the mole fractions in the liquid mixture, and Ψ1 and Ψ2 are parameters
independent of composition. At the same temperature, the infinite dilution activity coefficients, γ1∞
and γ2∞ are given by ln γ1∞ = 0.3 and ln γ2∞ = 0.2. The vapour pressures of methyl ethyl ketone and
toluene at 323 K are 36.9 and 12.3 kPa respectively. Assuming that the vapour phase is ideal, the
equilibrium pressure (in kPa) of a liquid mixture containing 90 mol % toluene is
(A) 19 (B) 18 (C) 16 (D) 15

Ans. C
3. Minimum work (W) required to separate a binary gas mixture at a temperature T0 and pressure P0
is
Where y1 and y2 are mole fractions, fpure1 and fpure2 are fugacities of pure species at T0 and P0, and
f̂1and f̂2are fugacities of species in the mixture at T0, P0 and y1. If the mixture is ideal then W is
(A) 0 (B) -RT0 [y1 ln y1 + y2 ln y2]
(C) RT0 [y1 ln y1 + y2 ln y2] (D) RT0
Ans. B
4. One mole of methane is contained in a leak proof piston-cylinder assembly at 8 bar and 1000 K.
The gas undergoes isothermal expansion to 4 bar under reversible conditions. Methane can be
considered as an ideal gas under these conditions. The value of universal gas constant is 8.314
J/mol K. The heat transferred (in kJ) during the process is
Gate Questions
(A) 11.52 (B) 5.76 (C) 4.15 (D) 2.38
Ans. B
GATE-2012
1. In a throttling process, the pressure of an ideal gas reduces by 50%. If CP and CV are the heat capacities
at constant pressure and constant volume, respectively (γ = CP/CV), the specific volume will change by
a factor of
(A) 2 (B) 21/γ (C) 2(γ −1)/γ (D) 0.5
Ans. B
2. If the temperature of saturated water is increased infinitesimally at constant entropy, the resulting state
of water will be
(A) Liquid (B) Liquid-vapor coexistence
(C) Saturated vapor (D) Solid
Ans. A
3. In a parallel flow heat exchanger operating under steady state, hot liquid enters at a temperature Th-in,
and leaves at a temperature Th-out. Cold liquid enters at a temperature Tc-in, and leaves at a
temperature Tc-out. Neglect any heat loss from the heat exchanger to the surrounding. If Th-in ˃ Tc-in,
then for a given time interval, which ONE of the following statements is true?
(A) Entropy gained by the cold stream is GREATER than entropy lost by the hot stream
(B) Entropy gained by the cold stream is EQUAL to the entropy lost by the hot stream
(C) Entropy gained by the cold stream is LESS than the entropy lost by the hot stream
(D) Entropy gained by the cold stream is ZERO
Ans. A
4. For an exothermic reversible reaction, which one of the following correctly describes the dependence
of the equilibrium constant (K) with temperature (T) and pressure (P)?
(A) K is independent of T and P
(B) K increases with an increase in T and P
(C) K increases with T and decreases with P
(D) K decreases with an increase in T and is independent of P
Ans. D
Gate Questions
5. An insulated, evacuated container is connected to a supply line of an ideal gas at pressure Ps,
temperature Ts and specific volume Vs. The container is filled with the gas until the pressure in the
container reaches Ps. There is no heat transfer between the supply line to the container, and kinetic and
potential energies are negligible. If CP and CV are the heat capacities at constant pressure and constant
volume, respectively (γ = CP/CV), then the final temperature of the gas in the container is
(A) γ Ts (B) Ts (C) (γ – 1) Ts (D) (γ – 1) Ts/ γ
Ans. A
6. Consider a binary liquid mixture at constant temperature T and pressure P. If the enthalpy change of
mixing, ∆H = 5x1x2, where x1 and x2 are the mole fraction of species 1 and 2 respectively, and the
entropy change of mixing ∆S = -R[x1 lnx1 + x2 lnx2] (with R = 8.314 J/mol K), then the minimum value
of the Gibbs free energy change of mixing at 300 K occurs when
(A) x1 = 0 (B) x1 = 0.2 (C) x1 = 0.4 (D) x1 = 0.5

Ans. D
GATE-2013
1. A gaseous system contains H2, I2, and HI, which participate in the gas-phase reaction
At a state of reaction equilibrium, the number of thermodynamic degrees of
freedom is _______
Ans. 3
2. The thermodynamic state of a closed system containing a pure fluid changes from (T1, p1) to (T2, p2),
where T and p denote the temperature and pressure, respectively. Let Q denote the heat absorbed (> 0
if absorbed by the system) and W the work done (> 0 if done by the system). Neglect changes in kinetic
and potential energies. Which one of the following is CORRECT?
(A) Q is path-independent and W is path-dependent
(B) Q is path-dependent and W is path-independent
(C) (Q –W) is path-independent
(D) (Q +W) is path-independent
Ans. C
3. An equation of state is explicit in pressure p and cubic in the specific volume v. At the critical point ‘c’,
the isotherm passing through ‘c’ satisfies
Ans. D
4. The units of the isothermal compressibility are

(A) m−3 (B) Pa−1 (C) m3Pa−1 (D) m−3Pa−1
Gate Questions
Ans. B
5. In a process occurring in a closed system F, the heat transferred from F to the surroundings E is 600J.
If the temperature of E is 300 K and that of F is in the range 380-400 K, the entropy changes of the
surroundings (∆SE) and system (∆SF), in J/K, are given by
(A) ∆SE = 2, ∆SF = -2 (B) ∆SE = -2, ∆SF = 2

(C) ∆SE = 2, ∆SF < -2 (D) ∆SE = 2, ∆SF > -2
Ans. D
6. A binary liquid mixture is in equilibrium with its vapor at a temperature T = 300 K. The liquid mole
fraction x1 of species 1 is 0.4 and the molar excess Gibbs free energy is 200 J/mol. The value of the
universal gas constant is 8.314 J/mol K, and γidenotes the liquid-phase activity coefficient of species i.
If ln(γ1) = 0.09 , then the value of ln(γ2), up to 2 digits after the decimal point, is _______
Ans. 0.06 to 0.08
GATE-2014
1. From the following list, identify the properties which are equal in both vapour and liquid phases at
equilibrium
P. Density Q. Temperature R. Chemical potential S. Enthalpy
(A) P and Q only (B) Q and R only

(C) R and S only (D) P and S only
Ans. B
2. In a Closed system, the isentropic expansion of an ideal gas with constant specific heats is represented
by
Ans: D
Gate Questions
3.
(A) Q-III, R-I, S-II (B) Q-III, R-II, S-IV (C) P-III, R-II, S-IV (D) P-III, R-IV, S-I
Ans. C
4. Which ONE of the following is CORRECT for an ideal gas in a closed system?
Ans. D
5. Consider a binary liquid mixture at equilibrium with its vapour at 25C. Antoine equation for this
system is given as log10pisat = A – (B/t + C), where t is in C and p in Torr. The Antoine constants (A,
B and C) for the system are given in the following table.
Component A B C
1 7 1210 230
2 6.5 1206 223
The vapour phase is assumed to be ideal and the activity coefficients (γi) for the non-ideal liquid
phase are given by
ln (γ1) = x22 [2 - 0.6 x1]
ln (γ2) = x12 [1.7 + 0.6 x2]
If the mole fraction of component 1 in liquid phase (x1) is 0.11, then the mole fraction of
component 1 in vapour phase (y1) is _______.
Gate Questions
Ans. 0.65 to 0.75
GATE-2015
1. For a pure liquid, the rate of change of vapour pressure with temperature is 0.1 bar/K in the temperature
range of 300 to 350 K. If the boiling point of the liquid at 2 bar is 320 K, the temperature (in K) at
which it will boil at 1 bar (up to one decimal place) is _______.
Ans. 310
2. Three identical closed systems of a pure gas taken from an initial temperature and pressure (T1, P1) to
a final state (T2, P2), each by a different path. Which of the following is ALWAYS TRUE for the three
systems? (T represents the change between the initial and final states; U, S, G, Q and W are internal
energy, entropy, Gibbs free energy, heat added and work done, respectively.)
(A) ∆U, ∆S, Q are same

(B) W, ∆U, ∆G are same
(C) ∆S, W, Q are same
(D) ∆G, ∆U, ∆S are same
Ans. D
3. For a gas phase cracking reaction A B + C at 300C, the Gibbs free energy of the reaction at this
temperature is ∆G = − 2750 J/mol. The pressure is 1 bar and the gas phase can be assumed to be ideal.
The universal gas constant R = 8.314 J/mol K. The fractional molar conversion of A at equilibrium is:
(A) 0.44 (B) 0.50 (C) 0.64 (D) 0.80
Ans. D
4. If v, u, s and g represent respectively the molar volume, molar internal energy, molar entropy and molar
Gibbs free energy, then match the entries in the left and right columns below and choose the correct
option.
P. – (u/v)s (I) Temperature
Q. – (g/P)T (II) Pressure
R. – (g/T)P (III) V
S. (u/s)v (IV) S
(A) P-II, Q-III, R-IV, S-I (B) P-II, Q-IV, R-III, S-I
(C) P-I, Q-IV, R-II, S-III (D) P-III, Q-II, R-IV, S-I
Ans. A
5. Which of the following can change if only the catalyst is changed for a reaction system?
(A) Enthalpy of reaction
Gate Questions
(B) Activation energy

(C) Free energy of the reaction
(D) Equilibrium constant
Ans. B
6. An ideal gas is initially at a pressure of 0.1 MPa and a total volume of 2m3. It is first compressed to 1
MPa by a reversible adiabatic process and then cooled at constant pressure to a final volume of 0.2m3.
The total work done (in kJ) on the gas for the entire process (up to one decimal place) is _______.
Data: R = 8.314 J/mol K; heat capacity at constant pressure (Cp) = 2.5R
Ans. 750 kJ
7. Given that molar residual Gibbs free energy, gR, and molar residual volume, vR, are related as,
Find gRat T = 27C and P = 0.2MPa. The gas may be assumed to follow the virial equation of state,
z = 1 + BP/RT, where B =− 10−4m3/mol at the given conditions (R = 8.314 J/mol K). The value of
gRin J/mol is:
(A) 0.008 (B) -2.4 (C) 20 (D) -20
Ans. D
GATE-2016
1. The partial molar enthalpy (in kJ/mol) of species 1 in a binary mixture is given by h1 = 2 - 60x22 + 100
x1 x22, where x2 and x2 are the mole fractions of species 1 and 2, respectively. The partial molar
enthalpy (in kJ/mol, rounded off to the first decimal place) of species 1 at infinite dilution is _______.
Ans. -58
2. A binary liquid mixture of benzene and toluene contains 20 mol% of benzene. At 350 K the vapour
pressures of pure benzene and pure toluene are 92 kPa and 35 kPa, respectively. The mixture follows
Raoult’s law. The equilibrium vapour phase mole fraction (rounded off to the second decimal place) of
benzene in contact with this liquid mixture at 350 K is _______.
Ans. 0.4
3. An ideal gas is adiabatically and irreversibly compressed from 3 bar and 300 K to 6 bar in a closed
system. The work required for the irreversible compression is 1.5 times the work that is required for
reversible compression from the same initial temperature and pressure to the same final pressure. The
molar heat capacity of the gas at constant volume is 30 J mol‒1K‒1 (assumed to be independent of
temperature); universal gas constant, R is 8.314 J mol‒1 K‒1; ratio of molar heat capacities is 1.277. The
temperature (in K, rounded off to the first decimal place) of the gas at the final state in the irreversible
compression case is _______.
Ans. 371 to 375
Gate Questions
4. A gas obeying the Clausius equation of state is isothermally compressed from 5 MPa to 15 MPa in a
closed system at 400 K. The Clausius equation of state is where P is the pressure, T is the
temperature, v is the molar volume and R is the universal gas constant. The parameter b in the above
equation varies with temperature as b(T) = b0 + b1T withb0 = 4 * 10-5 m3mol-1and b1 = 1.35 * 10-7
m3mol-1K-1. The effect of pressure on the molar enthalpy (h) at a constant temperature is given by
. Let hi and hf denote the initial and final molar enthalpies, respectively. The change
in the molar enthalpy hi - hf (in J mol‒1, rounded off to the first decimal place) for this process is
_______.
Ans. 400
5. A binary system at a constant pressure with species ‘1’ and ‘2’ is described by the two-suffix Margules
equation, , where gE is the molar excess Gibbs free energy, R is the universal gas constant,
T is the temperature and x1, x2 are the mole fractions of species 1 and 2, respectively. At a temperature
T, where g1and g2are the molar Gibbs free energies of pure species 1 and 2,
respectively. At the same temperature, g represents the molar Gibbs free energy of the mixture. For a
binary mixture with 40 mole % of species 1, the value (rounded off to the second decimal place) of
is _______.
Ans. 1.64
GATE-2017
1. The volumetric properties of two gases M and N are described by the generalized compressibility chart
which expresses the compressibility factor (Z) as a function of reduced pressure and reduced
temperature only. The operating temperature (T) and pressure (P) of two gases M and N along with
their critical properties (Pc, Tc) are given in the table below.
Gas P (bar) T (K) Pc(bar) Tc(K)
M 25 300 75 150
N 75 1000 225 500
Zm and Zn are the compressibility factor of the gases M and N under given operating conditions,
respectively.
The relation between Zm and Zn is
(A) Zm = 8 Zn (B) Zm = 3 Zn (C) Zm = Zn (D) Zm = 0.333 Zn
Ans. C
2. Water is heated at atmospheric pressure from 40C to 80C using two different processes. In process I,
the heating is done by a source at 80C. in process II, the water is first heated from 40C to 60C by a
source at 60and then from 60c to 80C by another source at 80C.
Identify the correct statement.
(A) Enthalpy change of water in process I is greater than enthalpy change in process II
Gate Questions
(B) Enthalpy change of water in process II is greater than enthalpy change in process I
(C) process I is closer to reversibility
(D) process II is closer to reversibility
Ans. D
3. The pressure of a liquid is increased isothermally. The molar volume of the liquid decreases from 50.45
* 10-6 m3/mol to 48 * 10-6m3/mol during this process. The isothermal compressibility of the liquid is
10-9 Pa-1. Which can be assumed to be independent of pressure.
The change in the molar Gibbs free energy of the liquid, rounded to nearest integer is
Ans. 2511.4
4. A sparingly soluble gas (solute) is in equilibrium with a solvent at 10 bar. The mole fraction of the
solvent in the gas phase is 0.01. At the operating temperature and pressure, the fugacity coefficient of
the solute in the gas phase and the Henry’s law constant are 0.92 and 1000 bar, respectively. Assume
that the liquid phase obeys henry’s law.
The mole percentage of the solute in the liquid phase, rounded to 2 decimal places is
Ans. 0.90 to 0.92
5. The vapour pressure of a pure substance at a temperature T is 30 bar. The actual and ideal gas values
of g/RT for the saturated vapour at this temperature T and 30 bar are 7 and 7.7, respectively. Here, g is
molar Gibbs energy and R is the universal gas constant.
The fugacity of the saturated liquid at these conditions, rounded to 1 decimal place, is
Ans. 14.7 to 15.1
GATE-2018
1. Consider the following properties:
(P) Temperature (Q) specific gravity (R) chemical potential (S) volume
The option which lists ALL the intensive properties is
(A) P (B) P and Q (C) P, Q and R (D) P, Q, R and S
Ans. C
2. G denotes the Gibbs free energy of a binary mixture, nT denotes the total number of moles present in
the system, i is the chemical potential of the ith component (i 0 and 1 > 2) and xi is the mole
fraction of the ith component. The correct variation of G/nT (in J/mol) at constant temperature and
pressure is given by
Gate Questions
Ans. C
GATE-2019
1.
Ans. C
2. For a single component system, vapor (subscript g) and liquid (subscript f) coexist in
mechanical, thermal and phase equilibrium when
(A) ug = uf (equality of specific internal energy)
(B) hg = hf (equality of specific enthalpy)
(C) sg = sf (equality of specific entropy)
(D) gg = gf (equality of specific Gibbs free energy)
Ans. D
Gate Questions
3.
Ans. A
4.
Ans. 0.009 to 0.011
5.
Ans. 17.5 to 18.5
6.
Ans. 0.9 to 1.1
Gate Questions
7.
Ans. 0.27 to 0.3
Gate Questions
Solutions
(2009)
1.
(i) T1 = 300 K, P1 = 1 bar, T2 = 600 K
Cp – Cv = R
Cv = Cp – R
Cv = (3/2) R
Cp/Cv = 
 = 5/3
For, adiabatic process T and P relation is
/-1
PT
So,
P2/P1 = (T2/T1)/-1
After putting all the values in above equation

P2 = (2)5/2 P
(ii) For, adiabatic process work that is required is calculated by
𝑃1𝑉1−𝑃2𝑉2
W=
(−1)
𝑅 (𝑇1− 𝑇2)
W=
(−1)
Put values in equation

Where = efficiency
W = 7.48 kJ/mol
(2010) 1.
𝐶−0 𝑆 − 200
=
100 − 0 400 − 200
𝑆 = 100
𝐶 500 − 200
= = 1.5
100 400 − 200
𝐶 = 150℃
Gate Questions
2.
V Hv
Feed (F)
L Hl
F = 1 kg
PF = 1500 kPa
TF = 500 K
V = x kg
Hv = 2500 kJ/kg
Tv = 300 K
Pv = 150 kPa
Hl = 500 kJ/kg
Take energy balance,
𝐹 ∗ 𝐻𝐹 = 𝑉 ∗ 𝐻𝑣 + 𝐿 ∗ 𝐻𝐹
750 = x*2500 + (1 – x)*500

X = 0.125 = 12.5%
3. The thermodynamics consistency of activity coefficients for a binary mixture can be cheeked
by Gibbs equation
𝑑 ln 𝛾1 𝑑 ln 𝛾2
x1 𝑑𝑥1
+ x2 𝑑𝑥1
=0
Check for all options

Option D satisfied the condition.
2011
1. Liquid mixture = 1 mole benzene + 2 moles of cyclo-hexane = 3 mole

x1 = 0.33, x2 = 0.66
∆H = x1*∆H1 + x2*∆H2
= x1*3600*x22 + x2* 3600* x12
= 800 J/mol
2. At x2 = 0 and x2 = 1
ln γ1∞ = 0.3 and ln γ2∞ = 0.2
Put in given formula,
Gate Questions
1 - 2 = 0.4, 1 + 2 = 0.2
1 = 0.3, 2 = -0.1
Then x2 = 0.9, x1 = 0.1
P = γ1 x1 p1 + γ2 x2 p2
P = 16 kPa
3. For ideal mixture
According to Randall rule for an ideal gas
f̂ = y fpure put this for two component into given equation

Answer is B
4. Isothermal expansion
Q = W = nRT ln (p1/P2)
= 1*8.14*100* ln (2)
= 5762.8 J
= 5.762 kJ
2012
1 For throttling process,
P1*V1 = P2*V2
P2 = P1*0.5
V1 = 1
Put the values in above equation,
V2 = 2
5. 1𝑄2 + 𝑚1 ℎ1 + 𝑚′ 𝑢′ = 1𝑤𝑆2 + 𝑚2 ℎ2 + 𝑚" 𝑢"

1𝑄2 = 0, 𝑚′ = 0, 𝑤𝑆2 = 0
𝑚1 ℎ1 = 𝑚" 𝑢"
𝑚1 = 𝑚"
ℎ1 = 𝑢"
𝐶𝑝 𝑇𝑠 = 𝐶𝑣
𝑇 " = 𝛾𝑇𝑠
6. ∆G = ∆H - T∆S
∆G = 5*x1*x2 + RT [x1 lnx1 + x2 lnx2]

∆G = 5x1-5x2+RT {x1lnx1+ (1-x1) ln(1-x1)}
For minimum free energy change, differentiate above equation w.r.t. x 1 or check by
putting option values in equation
And option D gives minimum value of ∆G = -1727.6
Answer is D, x1 = 0.5
Gate Questions
2013
1 The degree of freedom
F=C–P+2–R–S
F=3–1+2–1–0
F=3
2 From First Law of Thermodynamics, Q-W=ΔU

ΔU= internal energy which solely depends only on initial and final temperature. It is
independent of path.
3 We know that, at critical point

𝜕 2𝑃 𝜕𝑃 −𝑏 ± √𝑏 2 − 4𝑎𝑐
( 2 ) =( ) =0
𝜕 𝑉 𝑇 𝜕𝑉 𝑇 2𝑎
Hence answer (D) is correct
5 Tsurr = 300K,
Heat transferred from system to surrounding
Q = 600 J
Entropy charge of surrounding, ∆SE =Q/Tsurr = 600/300 = 2 J/K
As we know ∆Suniverse > 0 or
∆SE + ∆SF > 0
∆SF > - ∆SE
∆SF > -2 J/K
6 We know that
Ge / RT = x1* ln1 + x2* ln2
x2 = 1 – x1 = 1 – 0.4 = 0.6
200 / (8.314)*(300) = (0.4)* (0.09) + (0.6)* ln2
ln2 = 0.0736
2014
1. Answer (B)
2. Answer (D)
3. Answer (C)
4. Answer (D)
𝐵
5. From given Antoine equation, 𝑙𝑜𝑔10 = 𝐴 − 𝑡+𝐶 , calculate vapor pressure of both
component
Gate Questions
1210
log10 𝑃1𝑠𝑎𝑡 = 7 −
25 + 230
𝑃1𝑠𝑎𝑡 = 177.8 𝑡𝑜𝑟𝑟
For component 2
1206
log10 𝑃2𝑠𝑎𝑡 = 6.5 −
25 + 22.3
𝑃2𝑠𝑎𝑡 = 43.35 𝑡𝑜𝑟𝑟
Given x1=0.11 and x2=0.89

ln 𝑦1 = 𝑥22 [2 − 0.6𝑥1 ] = 1.53
𝑦1 = 4.63
ln 𝑦2 = 𝑥12 [1.7 + 0.6𝑥2 ] = 0.027
𝑦2 = 1.02
From modified Raoult’s law component 1 and 2
𝑦1 𝑃 = 𝑥1 𝑦1 𝑃1𝑠 𝑎𝑛𝑑 𝑦2 𝑃 = 𝑥2 𝑦2 𝑃2𝑠
𝑦1 𝑃 𝑥1 𝑦1 𝑃1𝑠
=
𝑦2 𝑃 𝑥2 𝑦2 𝑃2𝑠
𝑦1
= 0.693
1 − 𝑦1
2015
1 Given dP/dT = 0.1

dP = 0.1*dT
P = 0.1T + C
Given at T = 320K, P = 2 bar
2= 0.1*320 + C
C = -30
Equation becomes
P = -30 + 0.1T
Putting P = 1 bar
T = 310K
2. We have, U, S and G are state variables (point functions). So, ΔU, ΔS and ΔG remain
same between two states 1 and 2.
Gate Questions
3 We have
A B + C
At t = 0 1 0 0
At t = t 1 -    where,  = fraction converted
Equilibrium constant
K = (YB * YC * P)/ YA
 
.
1+  1+ 
K= 1−
1+ 
2
K = 1− 2
Also
ln k = [ -∆G/ RT]
K = exp[ 2750/8.314*573]
K = 1.78
So,  = 0.8
4 Answer (A)
5 Answer (B)
6 1 to 2: reversible adiabatic process
2 to 3: reversible isobaric process
Given,
P1 = 0.1 MPa = 106 Pa
V1 = 2 m3
P2 = 106 Pa
V3 = 0.2 m3
Cp = 2.5 R so Cv = 1.5 R
 = Cp/Cv = 1.667
For process 1 to 2
V2/V1 = (P1/P2) 1/

V2 = 0.5 m3
Work done for process 1 to 2
𝑃1𝑉1−𝑃2𝑉2
W= (−1)
Gate Questions
W = -450 kJ
Work done for process 2 to 3
W =P∆V
= 106 * (0.2 – 0.5)
= -300 kJ
Net work done
Wnet = 450+300 = 750 kJ
7 Given,
We know, VR = V - Vig = (Z – 1) RT/P
And Z = 1 + BP/RT
(Z – 1)/P = B/RT
Put this value in above equation,
gR = B(P – 0) = - 10-4 * 0.2*106
gR = - 20 J/mol
2016
1 For infinitely dilute solution of component (1)
x1 0 & x2 1
So, h1 = 2 – 60(1)2 + 100(0)(1)2
h1 = - 58 kJ/mol
2 From Raoult’s Law

pi = partial pressure
piv = vapour pressure
p = total pressure
pi = x1* piv
Gate Questions
and yi =pi / p
yB = (0.2*92)/(0.2*92 + 0.8*35)
yB = 0.4
3 We know that
Wirr = 1.5 Wrev
Cv (T2’ – T1) = 1.5 Cv (T2 – T1)
T2’ – T1 = 1.5 Cv (T2 – T1)
T2’ – T1 = 1.5 {T1 (P2/P1) ( - 1)/- T1}
T2’ = 373 K
4 We know that
𝑅𝑇
P = (v−b)
v = (RT/P) + b
= (R/P + b1) T + b0
𝜕𝑣
= R/P + b1
𝜕𝑇
𝜕ℎ 𝜕𝑣
= v – T 𝜕𝑇
𝜕𝑇
= [(R/P + h1)T + b0] – T(R/P + b1)

= b0
dhT = b0*dPT
(hf – hi)T = b0 (Pf – Pi)T
= 4*10-5 *(15 – 5) * 106
= 400 J/mol
5 Answer is 1.647
we know that
gE = g – gid
gE /RT = g /RT – gid /RT
Gate Questions
g/RT = gE /RT + gid /RT

g/RT = gE /RT + {x1g1 + x2g2 + RT (x1lnx1 + x2 ln x2)}/RT
g/RT = 3x1x2 + (x1g1 + x2g2)/RT + x1lnx1 + x2 ln x2
g/RT = 3*0.4*0.6 + 0.4*1 + 0.6*2 + 0.4*ln(0.4) + 0.6*ln(0.6)
g/RT = 1.647
2017
1. For gas M; P= 25 bar, Pc=75 bar
𝑃 25 1
𝑃𝑟 = = =
𝑃𝑐 75 3
For gas N; P= 75 bar, Pc=225 bar

𝑃 75 1
𝑃𝑟 = = =
𝑃𝑐 225 3
For gas M; T= 300 K, Tc=150 K, Tr = T/Tc =2
For gas N; T= 1000 K, Tc=500 K, Tr = T/Tc =2
Compressibility Factor, Z = k (Pr/Tr)
1
𝑘 (3) 𝑘
𝑍𝑚 = =
2 6
1
𝑘( ) 𝑘
3
𝑍𝑛 = = ⇒ 𝑍𝑚 = 𝑍𝑛
2 6
2. Answer (D)
3.
4. H= 1000 bar, Ø =0.92 for dilute solution

We can use Henry law for solute Hx = Ø yP
1000 x = 0.92 (1-0.01) (10)
Here, y and x are mole fraction of solute in gas liquid respectively x = 9.108 x 10-3
Mole percentage of solute in liquid phase = 100 (9.108 x 10-3) = 0.91
5. g/RT = 7
(g/RT)ig = 7.7
Gate Questions
As we know
𝑓𝑖 𝑔𝑅
∅𝑥 = exp ( )
𝑃 𝑅𝑇
𝑔𝑅 𝑔 𝑔
= − ( ) = 7 − 7.7 = −0.7
𝑅𝑇 𝑅𝑇 𝑅𝑇 𝑖𝑔
𝑔𝑅 𝑓𝑖
= −0.7 = = 𝜌 × 𝑝(−0.7)
𝑅𝑇 𝑃
𝑓𝑖 = 30 exp(−0.7) = 14.9 𝑏𝑎𝑟
2018
1. Answer (C)
2. Answer (D)
2019
1. Answer (C)
Insulator container
No heat transfer
T = 0 for vacuum expansion
𝑃1 𝑉2
= =4
𝑃2 𝑉1
For no temperature change
𝑉2
∆𝑆 = 𝑅 ln = 𝑅 ln 4
𝑉1
2. Answer (D)
3. Answer (A)
4. Answer 0.01
PCO2= 10 bar
PCO2= x1H
H= 1000 bar
x1= 0.01
5. Answer 17.9
𝐵
ln 𝑃 𝑠𝑎𝑡 = 𝐴 −
𝑇+𝐶
1872.46
ln 𝑃1𝑠𝑎𝑡 = 9.1058 −
328 − 25.16
𝑃1𝑠𝑎𝑡 = 18.59
2154.90
ln 𝑃2𝑠𝑎𝑡 = 9.0580 −
328 − 34.42
𝑃1𝑠𝑎𝑡 = 5.572
𝑃𝑡𝑜𝑡𝑎𝑙 = 𝑃1𝑠𝑎𝑡 𝑥1 + 𝑃2𝑠𝑎𝑡 𝑥2 = 17.887
6. Answer 1
At const temperature and pressure, molar volume of a binary system is given by:
V =30xA + 20xB + xA xB (15xA- 7xB)
Volume change of mixing
 V V-1 (Vi xi )
 V = V – V1x1 – V2x2
V1= 30, V2= 20
V =30x1 + 20x2 + x1 x2 (15x1- 7x2) – (30x1 + 20x2)
V = x1 x2 (15x1- 7x2)
On putting the values and solving, we get
V =1 m3/mol
7. Answer 0.29
T = 800 K, P = 2 bar
Co + H2 S ⇆ COS + H2
∆𝐺° = 22972.3 𝑇/𝑚𝑜𝑙
𝑅 = 8.314 𝐽/𝑚𝑜𝑙 𝐾
∆𝐺° 22972.3
ln 𝑘 = = = 0.03162
𝑅𝑇 8.314 × 800
For ideal gas mix, standard state to be J bar
K= Ka = KP = 0.03162
KP=Ky.PV
1−𝜉
𝑦𝐶𝑂 =
𝜉
𝜉
𝑦𝐻2 =
5
𝜉
𝑦𝐶𝑂𝑆 =
5
4−𝜉
𝑦𝐻2 𝑆 =
5
Putting the values, we get
𝜉 = 0.2889

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THERMODYNAMICS

 How does thermodynamics differ from heat transfer?

1.2.4 State and Properties:

 dQ  Q and  dW  W (Path functions)

(2) Intensive property:

Eg. Molar volume  kg / kmol  , V  Vt / n . The reciprocal of molar volume is molar

1.2.7 Force (F):

1.2.9 Pressure (P):

A common example is the compression or expansion of a fluid in a cylinder resulting

dW   (pext *A)dl   pext dV (3)

Integrating the equation (3)

The equation indicates that the work depends on the path.

1.3.1 Heat Capacity (C):

- Connects heat with temperature

According to newton’s law F  m*a (5)

The acceleration a  du / dt where u is the velocity of the body.

This equation is integrated for a finite change in velocities from u1 to u2

Each of the quantities ½ mu2 in equation (8) is a kinetic energy.

Unit of kinetic energy is kg m2s2 .

(2) Potential energy:

gravity on it, the minimum force required is given by Newton’s law

W  F  z2  z1   mg  z2  z1   mz2g  mz1g    mzg  (11)

Each of the quantities mzg in equation (11) is a potential energy.

1.3.3 Steady state:

1.3.4 Equilibrium state:

1.3.7 Mechanical Equilibrium- Characterized by equal pressure

1.3.8 Chemical Equilibrium- Characterized by equal chemical potential

1.3.9 Zeroth law of thermodynamics:

2.1.1 First law For non-cyclic process:

Energy lost = Energy gained

Therefore, between states 1-2, the energy balance can be written as

𝑄1−2 − 𝑊1−2 = 𝑈1−2

General expression based on above can be given as follows:

or, for elemental interactions; 𝑑𝑄 − 𝑑𝑊 = 𝑑𝑈

Mathematically, it can be shown that the internal energy is a thermodynamic

Which can be rewritten as,

From equations (i) & (ii) it is obvious that

∆𝑈1−2,𝐴 = ∆𝑈1−2,𝐵 = ∆𝑈1−2,𝐶

2.2 Thermodynamic Process:

2.2.1 Isothermal Process: (Externally slow process): Thermodynamic process in which

The relation between different thermodynamic properties can be given as

Work done in isothermal process can be given as

Where r = ratio of final and initial volumes

By first law of thermodynamics,

𝑄1−2 = 𝑊1−2 + (𝑈2 − 𝑈1 ) = 𝑊1−2 + 0

2.2.2 Isochoric Process: When a fluid undergoes a thermodynamic process in a fixed

Work involved shall be,

From first law of thermodynamics for process,

𝑄1−2 = 𝑈2 − 𝑈1 = 𝑚𝑐𝑣 (𝑇2 − 𝑇1 )

The work involved in the raising of piston shall be given by,

Mathematically from the first law of thermodynamics, it can be given that,

𝑄1−2 = 𝑚𝑐𝑣 (𝑇2 − 𝑇1 ) + 𝑃(𝑉2 − 𝑉1 )

= 𝑚𝑐𝑣 (𝑇2 − 𝑇1 ) + 𝑚𝑅(𝑇2 − 𝑇1 )

2.2.4 Adiabatic Process: An adiabatic process is the thermodynamic process in which

Work done during adiabatic expansion process can be given as,

For the adiabatic process,

𝑊1−2 = 𝑚𝑐𝑣 (𝑇1 − 𝑇2 )

Thus heat transfer during a polytropic process for a perfect gas;

So heat transfer can be given as

H2 – H1 = (U2 –U1) + (P2V2 –P1V1)= Cv +R (T2 –T1)