CH6503 – CHEMICAL ENGINEERING THERMODYNAMICS II

UNIT 1 – PROPERTIES OF SOLUTIONS

PART A

1. What are Partial Molar properties? Explain with an example. (May 2009,2016) (Nov/Dec 2014)
(Nov/Dec 2015,2016)
The Partial molar property of a particular component in a mixture measures the contribution of that
component to the mixture property. It is the property of a component when it is in admixture with one
or many components.

2. How do you define the term Chemical Potential? (Dec 2008, May 2009,2016, May 2011,
Nov/Dec 2014)
Chemical Potential μi of a component i in a solution is the partial molar free energy in the solution G i. It is
used as an index of Chemical equilibrium.

3. Give the classification of non-ideal solutions. (May 2011)

Non ideal solutions are broadly classified into two types, those positively deviating from ideality and
those negatively deviating from ideality. Excess functions indicate the deviations from ideal solution
behavior.

4. Give the Physical meaning of Partial Molar Properties.

It is the rate of change of the total solution property with respect to number of moles of a particular,
component at constant T and P. The partial molar properties of the components of the mixture vary
with composition because the environment of each type of molecule, changes as the composition
changes. The intermolecular forces also get changed resulting in the changes in thermodynamic
properties.

5. State Henry’s law. (May 2011)

Fugacity of a component in a solution is directly proportional to the concentration.
fi x i Ki
6. Mention the characteristics of ideal solutions (May/June 2013,16)
An ideal solution is one in which all molecules are of same size and all forces between molecules are
equal obey ideal gas equations are called ideal solutions.

7. What is the condition for the Phases to be in equilibrium in a multiple phase system?
For the multiple phase system at the same T and P to be in equilibrium, the chemical potential of each
species should be same in all phases.

8. What are the methods available for determining Partial Molar Properties? (May2014)
(1). Analytical Method
(2). Graphical Method.
(3). Tangent intercept Method.
9. Clearly distinguish between ideal and non-ideal solutions? (May 2011)
A solution in which the partial molar volumes of the components are the same as their molar volumes in
the pure state is called an ideal solution. In non-ideal solution molecules do interact and they occupy some
space.

10. Explain the Graphical Method of determining Partial Molar Property.

When the data of variation of Vt with respect to ni is available a plot of Vt versus ni is constructed.
Taking slope of the tangent at the point under consideration, gives partial molar property.

11. Explain the Tangent intercept method used to determine the Partial Molar Property.
Molar property is plotted against mole fraction of one component and the tangent drawn to the curve at
the desired point gives partial molar property.

12. What are ideal gas mixtures?

Ideal gas mixtures are those whose molecules have no influence on one another. Each molecule in the
mixture exists independent to the others, its properties are unaffected by the presence of different
molecules.

13. Explain the analytical method of determining the partial Molar Property.
Analytical method: If the volume of a solution is known of its composition, the partial molar volume of a
constituent may be found by partial differentiation with respect to the amount of the constituent.

14. Define fugacity and Fugacity coefficient.(May 2016)

Fugacity is the term equivalent to pressure applicable to non ideal solution and is a measure of effective
pressure. The ratio of fugacity to the pressure is referred to as fugacity coefficient.

15. What is Lewis Randall Rule?

The fugacity of each species in an ideal solution is proportional to its mole fraction, the proportionality
constant is the fugacity of pure species i in the same physical state as the solution and at the same T and
P.

16. What are excess properties?(May 2016)

Mathematical formalism of excess properties ME is analogous to that of the residual properties. It is the
difference between actual property value of a solution and the value it would have as an ideal solution at
the same T, P and composition.

17. Give Gibb’s Duhem’s equation.

18. What is standard state?

A Standard state is a particular state of a species at Temperature T and at specified conditions of
Pressure, composition and physical condition as gas, liquid or solid.

19. State Henry’s Law.

The Partial pressure/fugacity of a solute over the solution is proportional to its mole fraction in the
solution.

20. State Raoult’s law.

The partial pressure of a solute over the solution is the product of its liquid phase mole fraction and its
 pure component vapor pressure. This is true for ideal solutions.

21. Which is the standard state for gasses?

For gases two standard states are common.
(i). The pure component gas in its ideal state at 1 bar. a i = fi (ii).
The pure component gas at the pressure of the system. ai = fi/fo =
i
xifi/fi =xi

22. Which is the standard state for liquids?

(i). The pure component liquid at a pressure of 1 bar. (ii).
The pure liquid at the pressure of the system

23. Gibb’s free energy function is referred to as generating function. Explain.

When Gibb’s energy as a function of T and P is known, one can estimate all other thermodynamic
properties. Gibbs energy function implicitly represents complete property information and hence
referred to as a generating function.

24. What is the phase rule variable for non reacting system? Mention its application. (Nov 2015)
F = C-P + 2
where F is degrees of freedom, C is number components and P is number of Phases.

25. Differentiate between molar volume and partial molar volume?

Molar volume of a pure compound is the volume occupied by one mole of the chemical, partial molar
volume is the term referred to the volume occupied by one mole of the chemical is solution, which is in
association with other solutes.

PART B

1. Derive the Gibbs Duhem equation with the assumptions. Derive the various forms of Gibbs
Duhem equation (NOV 2014,2016)(May 2016) (May 2011) (May/ June 2014)

Consider a binary solution made up of components 1 and 2 whose mole fractions in the solution are x 1
and x2 respectively. Equation can be written as
𝑥1 𝑑1 + 𝑥2 𝑑2 = 0

where 1 and 2 are the chemical potentials of components 1 and 2 respectively. This can be rearranged as

x1d1 = -x2 d2

Dividing by dx1 and noting that dx1 = -dx2 in binary mixtures, the above result gives

Introducing the relationship between chemical potential and the fugacity Equation into the above, we get

Since activity ai =fi / fi o ,fugacities in Equation may be replaced in terms of activity as

 0
Since f i , the fugacity in the standard state, is independent of the composition of the solutions,

Thus the Gibbs – Duhem equation in terms of activity is

By Equation, ai = ixi. Substitute this into Equation and thus the most important and widely used form of the
Gibbs-Duhem equation that involving the activity coefficients, is obtained.

The second terms on both sides of the above equation vanish, as they are equal to unity. Therefore

As the activity coefficients directly measure the departure from the ideal solution behavior, Equation is the
most useful form of the Gibbs-Duhem equation.
The various forms of Gibbs-Duhem equations are rigorous thermodynamic relations that are valid for
conditions of constant temperature and pressure. They tell us that the partial molar properties of a mixture
cannot change independently; in a binary mixture, if the partial molar property of one of the component
increases, the partial molar properties of the other should decrease.

These include:
a) In the absence of complete experimental data on the properties of the solution, Gibbs-Duhem
equations may be used to calculate additional properties. For example, if experimental data are
available for the activity coefficient of one of the components in a binary solution over certain
concentration range, the activity coefficient of the other component over the same composition range
can be estimated using Gibbs-Duhem equations. This is particularly useful wherever the volalities of
the two components differ markedly. The measurements usually give the activity coefficient of the
more volatile component whereas that of the less volatile component is calculated using Equation.
Thermodynamics properties of some high boiling liquids (e.g. polymers) dissolved in a volatile liquid
(say, benzene) can be computed by measuring the partial pressure of the latter in the solution.
b) Thermodynamics consistency of experimental data can be tested using Gibbs-Duhem equations. If
the data on the partial molar property of each component measured directly in experiments satisfy
the Gibbs-Duhem equations, it is likely that they are reliable, but if they do not satisfy the Gibbs-
Duhem equation, it is certain that they are incorrect.
c) Gibbs-Duhem equations can be used for the calculation of partial pressure from isothermal total
pressure data. Suppose that in an experimental investigation of vapour-liquid equilibrium, the total
 pressures are measured. The Gibbs-Duhem equation facilitates the calculation of the composition of
other phase thereby reducing the experimental work considerably.
d) Partial pressure data can be obtained from isobaric boiling point data using Gibbs-Duhem equations.
The isobaric T-x data can be easily converted to x-y data

These equations find application in various other situations such as in the derivation of the
relationship between Henry’s law and Raoult’s law for a real solution, in proving the essential criterion that
the vapour and liquid composition are the same for an azeotropic mixture etc.

2. Calculate the partial molar volumes of methanol and water in a 40% (mol) method solution
given the following data at 1 bar and 298 K. (May 2013)

X 0 0.114 0.197 0.249 0.495 0.692 0.785 0.892 1.0

V x 103 m3/mol 0.0181 0.0203 0.0219 0.023 0.0283 0.0329 0.0352 0.0379 0.0407

where x (mole fraction of methanol)

X-mole fraction of methanol

Y - V X103 m3/mol Thus

Partial molar volume of methanol = 0.0407 x 10-6 m3/mol

Partial molar volume of water = 0.0162 x 10-6 m3/mol

3. At 300K and 1 bar the volumetric data for a liquid mixture of benzene and cyclohexane are
represented by V = 109.4 x 10-6 – 16.8 x 10-6 X – 2.64 x 10-6 X2 where X is the mole fraction of the
benzene and V has the units of m3/mol. Find the expressions for the partial molar volumes of
benzene and cyclohexane. (MAY 2011, NOV 2015)

The molar volume of the solution as a function of composition is given:

2
V = 109.4 × 10-6 -16.8 × 10-6 x1 – 2.64 × 10-6 x 1

Where xi = mole fraction of component 1 (in this case, benzene). By Equation,

Differentiating Equation we get

Using Equation V 2 can be found out.

The partial molar volume of benzene:

The partial molar volume of cyclohexane:

4. Discuss the Methods for the determination of partial molar properties.

Method 1 (Analytical): If the volume of a solution is known as a function of its composition, the partial molar
volume of a constituent may be found by partial differentiation with respect to the amount of that constituent.
j

Method 2 (Graphical): Let Vt, the volume of the solution containing a fixed amount of one of the
constituents (say, n1) is known for several values of the amount of other constituent (say, n2). We may
plot Vt against n2. See Fig. 7.2. The slope of the tangent to the curve is
Which, by definition is V 2 , thepartial molar volume of component 2. The volume of solution is
assumed, so large that no significant change in composition occurs when n2 is changed. This method has
limitation of not yielding values of V 1 directly. Also, it is not advisable to use this method for
determination of V2 when n2 is large compared to n1. The method of tangent intercepts is free from
such limitations and is therefore preferred for the determination of partial molar properties.

Method 3 (The tangent-intercept method): This is a graphical method widely used for the
determination of partial molar properties of both components in a binary solution. The molar volume v is
plotted against mole fraction of one of the components (say, x2, the mole fraction of component 2). To
determine the partial molar volumes, draw the tangent to the curve at the desired mole fraction. The
intercept that this tangent makes with the vertical axis at x2 = 1 gives and the intercept on the vertical
V2
To prove this result, consider a binary solution containing n1 moles of component 1 and n2 moles of
component 2. Let the total volume be Vt and let V be the molar volume. Then
Vt = nV = (n1 + n2) V

Differentiating Equation with respect to n1, keeping n2, T and P constant

The mole fraction x2 is given by

Differentiating Equation with respect to n1 keeping n2 constant, we get

which can be rearranged as

Equation can be substituted into Equation to yield the following:

Similarly it can be shown that

 In Figure, the length BD=BE+ED, where BE is the slope of the tangent at P times the
length PE. That is,

And ED = V, the molar volume at the molar fraction x2, Thus

Which, by Equation is V 2, similarly, the length

The above methods are applicable for the determination of various other partial molar
properties also. Of the various mixture properties, only the volume can be determined
absolutely. For the determination of other properties like Gi , H i, etc., it becomes
necessary to work with property changes on mixing like ∆G, ∆H, etc

5. The volume of an aqueous solution of NaCl at 298Kwas measured for a series of

molalities (moles of solute per kg of solvent) and it was found that the volume varies with
molality according to the following expression. V=1.003X10-3+ 0.1662 X10-4 m + 0.177
X10-5 m1.5 + 0.12 X10-6 m2. Where m is the molality and V is in m3. Calculate the partial
molar volumes of components at m=0.1 mol/Kg. (MAY 2014)

The partial molar volume of NaCl:

V=1.003X10-3+ 0.1662 X10-4 m + 0.177 X10-5 m1.5 + 0.12 X10-6 m2

Substituting m=0.1 in the above equation we get, V = 1.0047 x 10 -4 m3/mol

Differentiating the above equation,

Substituting m=0.1 in the above equation we get, V1 = 0.1748 x 10-4 m3/mol. Therefore,

Partial molar volume of water = 18.05 x 10-6 m3/mol

Partial molar volume of NaCl = 17.48 x 10-6 m3/mol
 6. (a) The Henry’s law constant oxygen in water at 298 K is 4.4 x 104 bars. Estimate
the solubility of oxygen in water at 298 K for a partial pressure of oxygen at 0.25
bars. (MAY 2011)
(b) What is excess property? Explain (MAY 2011)

(a) We know that,

Substituting K = 4.4 x 104 bar and pi = 0.25 bar, we get xi = 0.0568 x 10-4. For very dilute

solution,
Therefore, the solubility of oxygen is 0.0568 x 10-4 moles per mole of water. Or,

0.0568 x 10-4 x 32 x 1/18 = 0.101 x 10-4 kg oxygen per kg water.

(b) Excess properties:

The difference between the property of a real solution and that of an ideal solution is important in
chemical thermodynamics, especially in the treatment of phase equilibria. The excess property, M E, is
defined as the difference between an actual property and the property that would be calculated for the
same temperature, pressure and composition by the equations for an ideal solution.

ME=M-Mid -------------------------------1

M is the maolar property of the solution and Mid is the property of a n ideal solution under the same
conditions. The excess property change of mixing is defined in a similar manner.

∆ME=∆M-∆Mid ----------------------------2

∆ME is the excess property change of mixing, =∆M and ∆Mid are the property changes of mixing for
a real solution and an ideal solution respectively, both under the same conditions. As

∆M=M-ΣxiMiº --------------------------- 3

Eqn 2 can be written as ∆ME=M-Mid---------------------------------------- 4

Comparing above equations ∆ME=ME --------------------------- 5

Let us consider the excess volume VE of

a solution. VE=∆VE=∆V-∆Vid

Since ideal solution involves no volume change of mixing, ∆Vid=0

7. What is the effect of temperature and pressure on activity coefficient? (MAY 2009)

Effect of pressure:
The effect of pressure on fugacity is given by

The fugacity of I, fi, is written as

Combining both equations, we get,

But,

So,

As mole fraction xi is independent of pressure, i.e.

we get,

Effect of temperature:
The effect of temperature on fugacity is given by
For a substance i,

Combining both equations, and

xi is independent of temperature, we get

8. “Chemical potential as a criterion for phase equilibrium” - Explain. (MAY 2009,

DEC 2008)

The chemical potential of component I, is same as partial molar free energy Gi. It is
denoted by i. It is defined as,

The total Gibb's free energy of a solution is

The total differential,

For a closed system,

At constant pressure and temperature,

Therefore,

At constant temperature and pressure,

The change in free energy, is because of the change in number of moles,

Thus, for a binary solution,

The chemical potential is the contribution to Gibb's free energy and is an important
property used in phase and chemical equilibria.
 UNIT 2 – PHASE EQUILIBRIA

PART – A

1. State Duhem’s theorem. (JUNE 2009, Nov/Dec 2014)

It states that for any closed system formed initially from the given masses of prescribed chemical
species, the equilibrium state is completely determined when any two independent variables are
fixed.

2. Define the terms Phase and component.

Phase is that part of the system which is physically distinct, chemically homogeneous and
mechanically separable.
Component is nothing but chemical species that is present in different phases of the system.

3. What is phase rule as applicable to a reacting system?

The criterion of phase equilibrium is valid even when chemical reactions occur within the
system. However, the phase rule needs modification for it to be applicable for reacting systems.
This is because for each independent reaction occurring, and additional constraint is imposed
on the system. Thus the number of degrees of freedom will be reduced by one for each
independent chemical reaction. If r independent reactions occur in the system, then the phase
rule becomes F = C - π - r +2
For example, considering a system containing five components distributed between two phases.
If the number of independent chemical reactions occurring is one, then the number of degrees
of freedom will be 5-2-1+2 =4

4. Define Gibb’s Phase rule. (Nov 2013)

Gibbs phase rule is one which gives the number of variables that must be arbitrarily specified to
fix all remaining phase rule variables.
F = 2 - ∏ + N where F is degrees of freedom, ∏ is number of phases and N is the number of
chemical species.

5. Define Bubble point and dew point temperatures. (May/June 2014, 2013, 2012)
Bubble point is the temperature at which first bubble of the vapor is produced, that is when the
saturated liquid is further heated. Dew point is the temperature at which first drop of liquid
condenses from a saturated vapor upon cooling.

6. For a heterogeneous multicomponent system, what is the general criterion of phase

equilibrium? (May/June 2013)
A heterogeneous closed system is made up of two or more phases with each phase behaving as
open system within the overall closed system. Because each phase consists of two or more
components in different proportions, it is necessary that the criterion of multicomponent phase
equilibrium be developed in terms of partial molar free energies or the chemical potentials of
the components.

7. Define relative volatility? (May 2011,Nov 2016)

Relative volatility of a binary mixture is the ratio of pure component vapor pressure of volatile
component to the pure component vapor mixture of second component.
 8. Give Clausius Clapayron equation and explain the terms.

where ΔH is heat of vaporization assumed to be constant, in the temperature range of T 1 to T2.

P1s and P2s are the saturation pressures at temperatures at T1 to T2 respectively.

9. Give the importance of Vapor liquid equilibrium.

The most commonly encountered coexisting phases in industrial practice are vapor and liquid.
To quantify the mass transfer between them, the departure of the system form equilibrium is
very important and hence VLE data.

10. Write Clapayron equation and explain the terms involved.

Where ∆H and ∆V are the enthalpy and volume changes accompanying a process. It predicts
the dependence of equilibrium pressure on temperature when two phases of a given substance
coexist.

11. What is the criterion applicable for low pressure VLE problems?
At low pressures fugacity coefficient is assumed to be one since the vapor phase behaves ideally.
𝒚𝒊 𝑷 = 𝜸𝒊 𝒙𝒊 𝑷𝒔𝒂𝒕
𝒊

12. What is Boiling point diagram? (May/ June 2014)

The boiling point diagrams are plots of temperature as ordinate against composition of liquid and
vapor as abscissa.

13. What is equilibrium diagram?

Equilibrium diagram is a plot in which equilibrium vapor composition is taken as the ordinate
and corresponding liquid phase composition is taken as abscissa.
14. Differentiate between minimum boiling and maximum boiling azeotropes?
Minimum boiling azeotropes are those showing positive deviation from ideality and maximum
boiling azeotropes are those showing negative deviation from ideality.

15. What are azeotropes? Give examples.

Azeotropes are constant boiling mixtures. They are formed by solution showing large
positive or negative deviation from ideality.
Ex: Benzene – Ethanol mixture. Alcohol – water mixture.

16. What is the effect of pressure on azeotropes? (May/ June 2014)

The azeotropic composition shifts continuously with change is pressure. In some cases changing
in pressure may eliminate azeotropism from the system.
17. Give the fundamental relationship in the study of VLE.

18. What are partially miscible and immiscible systems? Give an example each.
Partially miscible systems are those in which the components are miscible only within a
temperature range either above or below or in between two temperatures. Ex: Phenol water
system.
Immiscible systems are those in which components are not at all miscible irrespective of
temperatures of the system. Ex: Benzene – Water.

19. What are the applications of Ternary liquid equilibrium?

Ternary liquid equilibrium finds application in three component systems like extraction,
leaching.

20. Write any two activity composition models.

Margules Model and Vanlaar Model.

21. What do you mean by saying a system is in equilibrium?

When a system of multiple phases is in equilibrium, then there should not be energy,
momentum and mass transfer between the phases. That is all phase must have same T and P
and each species in all phases must have same chemical potential.

22. Write down the condition of Criteria for liquid/liquid equilibrium.

Two liquids will be in equilibrium when they are in thermal, chemical and mechanical
equilibrium.
That is when the chemical potential of the chemicals present in both the liquids are same and
the system is at same Temperature and pressure.

23. What are partially miscible systems? Give examples.

Partially miscible systems are those in which the solubility of one liquid in another liquid is seen
only under certain conditions are temperature.

24. Give the applications of Clausius Clapayron equation

Clausius Clapayron equation is extensively used in mass transfer operations, to quantify the
energy requirements.

25. What is the criterion for Phase equilibrium in terms of fugacity and chemical
potential?
i

26. What is assumption with which Clapayron equation yields Clausius – Clapayron
equation?
Clausius assumed that the vapor behaves ideally and introduced ideal gas equation in to
Clapeyron equation, which resulted in Clausius-Clapeyron equation.

27. What are azeotropes? How do you categorize an azeotrope?(Nov 2015,2016)

Azeotropes are constant boiling mixtures.They are formed by solution showing large
positive or negative deviation from ideality.Ex: Benzene – Ethanol mixture. Alcohol – water
mixture.
Minimum boiling azeotropes are those showing positive deviation from ideality and maximum
boiling azeotropes are those showing negative deviation from ideality.

28. What is Poyting correction?

For high pressure VLE problems, the equation employed is,

The exponential term in the above equation is called the Poyting correction.

PART B

1. Prove that if Raoult’s law is valid for one constituent of a binary mixture over the whole
concentration range it must also apply to the other component. (MAY 2011, 2013, NOV
2014)

Assume that Raoult’s Law is obeyed by component 1 in a binary mixture. Then

P1  x1P1S
Raoult’s law is obeyed by ideal solution when the vapour phase behaves as an ideal gas whereas
Lewis – Randall rule is obeyed by ideal solutions irrespective of whether the gas phase is ideal or
not.
So for component 1, we can write
f1  x1f1
d ln f1   d  ln x1 
d  ln F1 
1 --- 1
d  ln x1 
Gibbs – Duhem equation relates fugacities of components in a binary mixture as
x1d  ln F1  d  ln F2 
 x2
dx1 dx2
Rearranging this equation
d  ln F1  d  ln F2 
 ---  2 
d  ln x1  d  ln x2 
This equation is sometimes referred to as Duhem – Margules equation comparing equation (1)
with (2) we see that
d  ln F2 
1
d  ln x 2 
d(ln f2 ) = d(ln x2)
Nothing that F2 = F2 when x2 = 1 the above equation can be integrated
 f2 x2

 d ln f2    d ln x2 
f2 1

ln f2 ln x2

f2 1
 or 
F2
 x2
f2
(i.e) f2  x2f2, which is the Lewis – Randal rule for component 2. If the vapour is an ideal gas,
this can be equally written as
P2  x2P2S
This is Raoult’s law for component 2. The conclusion to be drawn from the above
derivation is that if Raoult’s law is applicable to one of the constituents of a liquid mixture at all
concentrations it must be applicable to be other constituent as well.

2. The azeotrope of the ethanol benzene system has a composition of 44.8% ethanol with
a boiling point of 341.4 K at 101.3 KPa. At this temperature the vapor pressure of
ethanol is 68.9 KPa and the vapor pressure of Benzene is 67.4 KPa. What are the
activity coefficients in a solution containing 10% alcohol? (MAY 2011)
Let benzene be component 1 and alcohol component 2.For the azeotrope

P 1013 P 1013
1  S
  1.4702 1  S   15030
P1 68.9 P1 67.4
X1=0.552 and x2 =0.448. Substituting these values in Eq. the constants A and B in the van Laar
equation can be evaluated.

2
 x In  2   1+ 0.448  In 15030   1.3305
2

A  In  1  1  2   In 1.4702  
 x1 In  1   0.552  In 1.4702 
2
 x In  l   0.552  In 1.4702   1.9106
B  In  2  1  1   In 15030  1+ 
 x2 In  2   0.448  In 1.5030 

For a solution containing 10% alcohol x1 = 0.90 and x2 = 0.1. For calculating the activity
coefficient at this concentration, van Laar equations, Equation are used.
 Ax22 1.3305  0.12
In  1    0.02519
 A / B  x1  x2  1.3305 / 1.9106  0.9  0.1
2 2

Bx12 1.9106  0.9 2

In  2    1.4210
 x1   B / A  x2  0.9   9106 / 13305  0.1
2 2

Therefore ,  1  1.0255 and  2  4.1412 `

3. Explain the different methods to check the consistency of VLE data. (MAY 2011,
JUNE 2012)

Consistency tests for VLE data are based on Gibb’s Duhem equations. They are
i) Using slope of ln γ curves
The Gibb’s Duhem equations in terms of activity coefficient is

When ln γ is plotted against x1, and the slopes of the tangent is measured at any selected
composition of x1. If both slopes have the opposite sign – data consistent; else inconsistent.
ii) Using data at mid point
The van Laar equation is

By putting x1=x2=0.5, we get

When ln γ is plotted against x1, the data is consistent if

 Both curves are at same level in the end point
 The curve lowest at the mid point is highest at the end point
Otherwise, the data is inconsistent.

iii) Redlich-Kister method:

Also known as the zero area method. It can be used for testing data, when the activity coefficient
is available over the entire range.
The excess free energy is ∆𝐺 𝐸 = 𝑅𝑇 𝛴 𝑥𝑖 𝑙𝑛𝛾𝑖
For a binary solution, it can be written as, ∆𝐺 𝐸 = 𝑅𝑇 ( 𝑥1 𝑙𝑛𝛾1 + 𝑥2 𝑙𝑛𝛾2 )
Differentiating with respect to x1,

Also, substituting the following solution into the above equation

We get

When the above equation is integrated between x1 =0 to x1=1 (∆GE=0 at both points), we get

Thus, when ln (γ1/γ2) is plotted against x1, the net area of the curve should be zero. Then the data
is consistent. Else it is inconsistent.

iv) Using co existence equation:

The activity coefficients can be written as

Substituting the above in Gibb’s-Duhem equation, we get,

As the saturation pressures are constant at constant temperature, we get,

On rearranging ,we arrive at the co-existence equation which can be used to test the consistency
of VLE data.
v) Using partial pressure data:
Gibb’s duhem equation in term of fugacity can be re written as

The partial pressure of both components are plotted against mole fraction and slopes are
determined at selected composition.
Data consistent if the absolute values of these slopes are the same. Else the data is cinconsistent.

4. Show that for a stable liquid phase, the fugacity of each component in a binary mixture
always increases with increase in concentration at constant temperature and pressure.(May
2016)
The excess free energy of mixing was defined in chapter. It was shown there that
G E  G  G id
G E  G E  RT  xi In  i
G id  RT  xi In xi
Combining these there equations we find that
G  RT  xi In  i xi 
G
  xi I n  i xi   x1 In  1 x1   x2 In  2 x2 
RT
Differentiating this with respect to x1,
d  G  d In 1 In 2
   x1 In  1 x1   x2 In  2 x2    In  x1 1   In  x2 2   x1  x2
dx1  RT  dx1 x1 x1
By Gibbs – Duhem equation
In  1 In  2 In  2
x1  x2   x2
x1 x 2 x1
When this is substituted into equation we get
d  G 
   In  1 x1   In  2 x2 
dx1  RT 
Activity coefficients are defined as
f f
1  1 , 2  2
x1 f1 x2 f 2
Where f 1 and f 2 are the fugacities of components in solution and f1 and f2 are the fugacities of
pure components. Substituting these into equation we get
d  G  f1 f
   In  In 2
dx1  RT  f1 f2
Differentiating equation again with respect to x1 and noting that fugacities of pure components
are independent of concentration, we get
d2  G  d d
2   In f 1  In f 2
dx1  RT  dx1 dx1
According to Gibbs – Duhem equations, the fugacities in a binary mixture are interrelated as
indicated below.
In f 1 In f 2 In f 2
x1  x2   x2
x1 x2 x1
Therefore,
d x d In f 1
In f 2   1
dx1 x2 dx1
Using this equation can be written as
d2  G  d x d 1 d
2   In f 1  1 In f 1  In f 1
dx1  RT  dx1 x2 dx1 x2 dx1
d2 G RT d
 In f 1
dx12 x2 dx1
Equation reveals that the left – hand side of the above equation is greater than zero. Therefore,
RT d
In f 1  0
x2 dx1
d
In f 1  0
dx1
In a similar way, we can show that
d
In f 2  0
dx2
The last two equations imply that fugacity of components in a stable solution always increase
with increase in concentration.

5. Applying the criterion for equilibrium, Derive Clausius Clapayron equation.(Nov 2015)
The Clapeyron equation using Maxwell’s relations can be written as
 dP H

dT T V
The criterion of equilibrium provides an alternate route for its derivation. Consider any
two phases a and be of the same substance under equilibrium. Since G a and Gb are both
functions of temperature and pressure, and these functional relationships are different for
different phases, the two phases can coexist only at such values of the temperature and pressure
that Ga = Gb. If the temperature and pressure are altered infinitesimally without disturbing the
equilibrium, the change in the free energy must be the same in each phase.

dGa = dGb

In a phase change there is no work other than the work of expansion, so that
dG= V dP – S dT

Using this in equation

Va dP – Sa dT = Vb dP – Sb dT

V and S are the molar volume and molar entropy of the fluid with the superscript
representing the phase for which the properties correspond to. Equation can be rearranged to the
following form.
dP Sa  Sb S
 a 
dT V  V b
V
In the above equation, S and V are the entropy change and volume change
respectively, accompanying the phase change. Since the transition between phases is occurring
reversibly, the entropy change can be evaluated if the latent heat of phase change is known.
H
S 
T
Where H is the latent heat for the phase change. Substituting equation into equation the
Clapeyron equation results.
dP H

dT T V
This relation gives the increase in pressure that is necessary to maintain the equilibrium
between phase for a pure substance when the temperature is increased. By using the following
simplifications can be modified to yield the Clausis – Clapeyron equation applicable for vapour –
liquid equilibria.
1. The latent heat of vaporization is constant and independent of temperature.
2. The molar volume of liquid is negligible compared to that of vapour.
3. The vapour behaves as ideal gas.
The Clausius – Clapeyron equation was derived in chapter and is reproduced below.
PS H  1 1 
In 2S    
P1 R  T1 T2 
Where P1S and P2S are the vapour pressures at temperatures T1 and T2 respectively.
6. Using criterion of phase equilibrium, show that the change in entropy during phase
changes can be calculated from the latent heat of and the absolute temperature as
∆S=∆H/T. (June 2014)
Suppose that two phase a and b are in equilibrium. Using the definition of free energy

Ga = Ha – TSa and Gb = Hb - TSb

Here, H and S denote the enthalpy and entropy of the substance. Substituting these results, in
equation,

Ha – TSa = Hb - TSb

This equation can be rearranged as,

Hb  Ha
Sb  S a 
T
The Left – hand side of the above equation is the entropy change accompanying the phase
change of one mole of the substance (S), and the numerator on the right – hand side represents
the enthalpy change for the phase change of one mole of the substance or the latent heat of phase
change (H). That is,
H
S 
T

7. The activity coefficients for component 1 in a binary solution can be represented by, lnγ1
= ax22+ bx23+cx24, where a, b and c are concentration independent parameters. Derive an
expression for γ2. (May2014)
Equation may be written as
x1
In 2    0x1 d( In 1 )
x2

For the present case, differentiating the given equation,

𝑑 ln 𝛾2 = (2𝑎𝑥2 + 3𝑏𝑥22 + 4𝑐𝑥23 )𝑑𝑥2

Substituting this in the above equation we get
𝑥1
𝑙𝑛𝛾2 = − ∫ (2𝑎𝑥1 + 3𝑏𝑥1 𝑥2 + 4𝑐𝑥1 𝑥22 )𝑑𝑥2
0
𝑥1
= − ∫ (2𝑎𝑥1 + 3𝑏𝑥1 (1 − 𝑥1 ) + 4𝑐𝑥1 (1 − 𝑥1 )2 )𝑑𝑥2
0

3𝑏 4𝑐
𝑙𝑛𝛾2 = (𝑎 + + 4𝑐) 𝑥12 − (𝑏 + ) 𝑥13 + 4𝑐𝑥1
2 3
8. Explain the triangular diagram for ternary liquid liquid phase equilibria (May 2016)
 Involving three components.
 A binary mixture of components A and C is brought in contact with a solvent B.
 The solvent B is either partially soluble in liquid A or is immiscible with it.
 The component C gets distributed in different proportions between the two insoluble
phases - ‘raffinate’ and the ‘extract’.
 The A-rich phase is known as the raffinate and the B-rich phase is known as the extract.
 The ternary liquid–liquid equilibrium diagrams are usually represented on equilateral
triangular coordinates.
 On the equilateral triangle the length of the altitude is allowed to represent 100%
composition and the length of the perpendiculars from any point to the bases represent
the percentages of the three components. The apexes of the triangle represent the pure
components A, B, and C and points on the sides represent binary mixtures.
 Type-I systems - one pair is partially soluble.
The pairs A-C and B-C are miscible in all proportions and the pair A-B is miscible only
partially.
Examples: water (A)–chloroform (B)–acetone (C)
water (A)–benzene (B)–acetic acid (C)
Liquid C dissolves completely in A and B whereas A and B dissolve only to a limited
extent in each other.
 In the region below the mutual solubility curves the two liquid phases exist under
equilibrium. The mixture, whose combined composition is represented by point M
separates into a raffinate R and an extract E at equilibrium. Thus, RE is a tie line for the
system
 The curve DRPF is the binodal solubility curve, which shows the change in the solubility
of A-rich and B-rich phases upon addition of C at a fixed temperature. Any mixture
outside this curve will be a homogeneous solution of a single liquid phase. There is one
point on the binodal curve P, which will represent the last of the tie lines where the A-rich
and B-rich phases become identical. It is known as the plait point. With increase in
temperature the mutual solubilities of A and B increase and extraction is not possible
under this condition.

 Type II systems - two pairs are partially soluble

Examples: chlorobenzene(A) – water(B) – Methylethylketone(C)
n-heptane (A) – aniline (B) – methylcyclohexane(C)
  Here A and C are completely miscible while A-B and B-C pairs show only limited
solubility
 Points D and F represent the mutual solubility of A and B and points H and G those of B
and C at the prevailing temperature. Curves DRH and FEG are the ternary solubility
curves.
 As temperature is increased the mutual solubilities increase and above the critical
solution temperature of the binary pair B-C, the system becomes identical to type I
system

9. Write note on azeotropes, high boiling and low boiling azeotropes. Discuss the effect of
Temperature for pressure on Azeotropic composition. (May 2012)
 Azeotropes are constant boiling mixtures.
 When an azeotrope is boiled, the resulting vapour will have the same composition as the
liquid from which it is produced.
 The boiling point of an azeotrope remains constant till the entire liquid is vaporised.
 The azeotropes are formed by solution showing large positive or negative deviation from
ideality.
 If the vapour pressures of the constituents of a solution are very close, then any
appreciable positive deviation from ideality will lead to a maximum in the vapour
pressure curve and negative deviations from ideality under the same conditions leads to a
minimum in the vapour pressure curve
 At the composition at which there exists a maximum or minimum in the vapour pressure
curve, the same exists in the boiling point diagrams. The mixture is said to form an
azeotrope at this composition under the given temperature and pressure.
 Minimum-boiling azeotropes. Solutions showing positive deviation from ideality.
 In the boiling point diagram, the liquid and vapour curves are tangent at point M,
the point of azeotropism at this pressure. The temperature at M is the minimum
temperature of boiling for the system.
 For all mixtures of composition less than M, the equilibrium vapour is richer than
the liquid in the more volatile component. For all mixtures richer than M, the
vapour is less rich than the liquid in the more volatile component.
 If solutions either at P or Q are boiled in an open vessel with continuous escape of
vapours, and solutions like these cannot be distilled by usual distillation methods.
Examples:
 ethanol–water which forms azeotrope at 89.4% (mol) ethanol at 351.4 K and
101.3 kPa.
 benzene–ethanol (341.2 K and 101.3 kPa., 55%benzene),
 isopropyl ether–isopropyl alcohol (345.1 K and 101.3 kPa, 39.3% alcohol)
 Maximum-boiling azeotropes
When the total pressure of the system at equilibrium is less than
the ideal value, the system is said to exhibit negative deviation from ideality.
 Solution on either side of the azeotrope, if boiled in an open vessel with escape of
vapours will ultimately leave a residual liquid of the azeotropic composition in the vessel.
 Maximum-boiling azeotropes are less common than the minimum-boiling type.

 Examples:
Hydrochloric acid–water system forms an azeotrope at 11.1% (mol) HCl at 383 K and
101.3 kPa.
Chloroform–acetone (337.7 K and 65.5% acetone),

10. Water (1) – hydrazine (2) system forms an azeotrope containing 58.5% (mol) hydrazine
at 393 K and 101.3 kPa. Calculate the equilibrium vapour composition for a solution
containing 20% (mol) hydrazine. The relative volatility of water with reference to
hydrazine is 1.6 and may be assumed to remain constant in the temperature range
involved. The vapour pressure of hydrazine at 393 K is 124.76 kPa.
The vapour pressure of water at 393 K =1.6 × vapour pressure of hydrazine at 393 K= 1.6
×124.76 =199.62 kPa.

P1s  199.62kPa; P2S  124.76 kPa

For the azeotrope, x1 = 0.415 and x2 = 0.585
P 101.3 P 101.3
1  S   0.5075 2  S   0.8120
P1 199.62 P2 124.76
Using these in Eq. we obtain
2
0.585   0.2083 
2
 x In  
A  In  1  1  2 2   0.6783  1    1.3927
 x1 In  1   0.415   0.6783 
0.415   0.6783 
2
 x In  1  
B  In  2  1  1   0.2083  1    2.2822
 x2 In 2   0.585   0.2083 

Fro the solution containing 20% (mol) hydrazine, x1 = 0.8 and x2 =0.2. The activity coefficients
are evaluated using Eq.
Ax 22 -13927×0.2 2
In γ 1 = 2 = 2 =0.1176
 A/B  x1 +x2  0.8  -1.3927  /  -22822  +0.2
Bx12 -2.2822×0.8 2
In γ 2 = = =1.1485
 x1  B/A  x2  0.8+0.2  -2.2822  -1.3927 
2 2

 1  0.8891;  2  0.3171

From Eq, we see that yiP =  i xi PiS . That is,

P1S Ps
y1   1x1 , y2   2 x2 2
P P
To evaluate the vapour compositions using these equations, we should know the vapour pressure
values at the new equilibrium temperature. Taking the ratio of the last two equations, we get

y2 1  y1  2 x2 P2S  2 x2 1
  
y1 y1  1x1P15  1 x1 12
This can be rearranged to give
1 1
y1  5   0.9472
 2 x2 P2 1  0.3171  0.2  1
1
 1 x1 P1S 0.8891 0.8 1.6
Y2=1- 0.9472 = 0.0528
The composition of the vapour in equilibrium with the liquid containing 20% hydrazine is 5.28%
hydrazine and 94.72% water.
 .UNIT – 3 – CORRELATION AND PREDICTION OF PHASE EQUILIBRIA

PART A
1. What do you mean by Activity? Give the importance of activity. (May 2011) (Nov 2014) (Nov
2015)
Activity is the ratio of fugacity to the fugacity in standard state. It is relative fugacity. The concentration
of a species to the overall property value is dependent on its activity in the solution.

2. What is co-existence equation? (May/June 2013)

3. Give the importance of Gibbs-Duhem’s equation. (May/June 2013) (May/ June 2014)
 In the absence of complete experimental data on the properties of the solution, Gibbs Duhem’s
equation may be used to calculate additional properties.
 It can be used to test thermodynamic consistency of experimental data.

4. What do you mean by activity coefficients? (May 2011) (Nov 2015)

Activity coefficients are a measure of the extent to which the real solution departs from ideality.
Activity coefficient of the component γi is defined by the following relation:

5. What is the effect of pressure on activity coefficients? (DEC 2009) (May/ June 2014)

6. Explain zero area method for testing the consistency of VLE data? (JUNE 2009, 2012)
A plot of ln versus x1 is prepared and if the net area under the curve obtained is zero, then it is assumed
that the data is consistent. This is also called as Redlich-Kister method.

7. What do you mean by excess property? (Nov 2011)

Excess property is defined as the difference between actual property value of a solution and the value it
would have as an ideal solution at the same Temperature, pressure and composition.
8. Define Activity coefficient (May/June 2012)
By definition, activity coefficient is the ratio of activity to the number of moles or mole fractions of
component i in a solution. The numerical value of the activity coefficient is dependent on both the standard
state and the units of expression for composition. For an ideal solution, activity coefficient is considered to
be unity, i.e., γ1=1. It can be expressed as

𝑓𝑖
𝑎𝑖 𝑓𝑖 ̂𝑖
𝑓
𝛾𝑖 = = 0 = 0𝑛 = 0
𝑛𝑖 𝑓𝑖 𝑛𝑖 𝑓𝑖 𝑛𝑖 𝑓𝑖 𝑥𝑖
𝑛

9. Discuss the significance of co-existence equation. (Nov/Dec 2012)

The co existence equation can be used for testing the consistency of vapor liquid equilibrium data. It can be
used to calculate any one of three variables P, x or y if experimentally measured values of the other two
variables are available. If all the three variables are experimentally determined then the co-existence
equation can be used to test the consistency of the measured data.

10. What do you mean by Consistency tests?

Consistency tests are ways and means of validating experimentally obtained VLE data which are prone
to inaccuracies. Almost all these tests are based on Gibbs – Duhem’s equations written in terms of activity
coefficients.

11. What is the effect of pressure of activity? (May 2014)

 12. How do you define the activity of a component in a solution?
Activity of a component in a solution is the ratio of the fugacity of the component in the solution to that of
the fugacity of the component in standard state.

13. Give NRTC equation.

14. What are UNIQUAC and UNIFAC method?

Uniquac is Universal quaci chemical equation and Unifac is Universal functional activity coefficient
method. These two are local composition models which account for the short range order and non random
molecular orientations that result from differences in molecular size and intermolecular sizes.

15. Name local composition models for activity coefficients.

1) Non Random Two Liquid (NRTL) model.
2) UNIQUAC model.
3) UNIFAC model.

16. Which is the most reliable method for testing the consistency of experimental VLE data?
Local composition models are considered as them most reliable method for testing the consistency of
experimental VLE data.

17. How can you test the consistency data using partial pressure data?
Using Gibbs- Duhem’s equation.

18. How can you calculate the activity coefficient using Gibbs-Duhem’s equation?

19. How would you estimate the composition of the vapor phase in equilibrium with two
immiscible liquid phases?
For immiscible binary systems
𝑦𝐴 𝑃𝐴0
=
𝑦𝐵 𝑃𝐵0
The relative proportions of two liquids in the distillate can be calculated remembering that the number of
mole of each component present in the vapor phase is proportional to its Vapor Pressure.

20. List out the different tests available for testing the consistency of VLE data of binary system.
(Nov 2015)
Different methods of testing the consistency of VLE data are
(i) Using slope of ln curves.
(ii) Using data of mid point
(iii) Redlich-Kister method
(iv)Using the coexistence equation.
(v) Using the Partial pressure data.

21. What are activity coefficient equations? Give an example.

Activity coefficients equations are those which relate activity coefficient and concentration of the solution.
Eg: Margules Equation, VanLaar Equation.

22. What is the difference between Activity Composition models and Local composition models?
Activity composition models consider the solution is under investigation is of uniform concentration and it
will not take in to consideration the variation in the composition the sample at different points. Whereas the
local composition models considered various parameters that will account for the variation in the
concentration at different points in the solution.

23. Write down any two activity composition models.

Margules and Van laar models are most used two activity composition models.
 24. Explain the importance of GE/RT term.
GE/RT ar the ratio of energies and is a dimensionless quantity which specifies the ratio of energy
deviation from that of the ideal value.

25. What is the effect of Temperature on activity coefficients?

26. Give Wilson’s equation.

27. What is a coexistence equation?(May 2016)

Coexistence equation is uses to test the consistency of VLE data.

.
28. Give Margules equation and Van Laar equation. (May 2011,Nov 2016)

Margules equation

Van Laar equation

 PART B

1. For the system n- pentane (1) n-heptane (2), the vapor pressures are given by the Antoine
equation ln P= A-(B/(T-C)) where P is in kPa and T is in K. the constants are as follows

System A B C
n-pentane 13.8183 2477.07 40.00
n-heptane 13.8587 2911.32 56.56
Assuming that the solution formed is ideal, calculate
i) The composition of the liquid and vapor in equilibrium at 95 kPa and 336.2 K
ii) The composition of the vapor in equilibrium with a liquid containing 34% (mol)
pentane and the equilibrium temperature at P = 95kPa.
iii) The total pressure and the vapor composition in equilibrium with a liquid of
composition x1=0.44 at T=333.2K (May 2013), (Nov 2014)
From Antoine equation, at 336.2 K
2477.07
𝑙𝑛𝑃1𝑆 = 13.8183 −
(𝑇 − 40.00)
2477.07
𝑙𝑛𝑃1𝑆 = 13.8183 −
(336.2 − 40.00)

ln 𝑃1𝑆 = 5.4554 𝑃1𝑆 = 234.02 𝐾𝑃𝑎

2911.32
𝑙𝑛𝑃1𝑆 = 13.8587 −
(𝑇 − 56.56)
2911.32
𝑙𝑛𝑃1𝑆 = 13.8587 −
(336.2 − 56.56)

ln 𝑃2𝑆 = 3.4477 𝑃2𝑆 = 31.43 𝐾𝑃𝑎

We know that, P= P 2 S + (P 1 S -P 2 S)x1

95=31.43+ x1(234.02 − 31.43)

X1 = 0.3137

We know that, y 1 = x1 P1 S /P from this we can obtain

y1 =0.7727

i) P= P 2 S + (P 1 S -
P 2 S) x1
95= P2S + 0.34 (P1S -P2 S)

Assume T=335 K, by using Antoine equations we get,

P1S = 226.207 kPa P2S = 30.050

kPa
Thus, P2S + 0.34 (P1S -P2S) = 96.743> 95 kPa
 Assume T=334 K, by using Antoine equations we get,
P1 S = 219.837 kPa P2S = 28.938
kPa
Thus, P2S + 0.34 (P1S -P2S) = 93.844< 95 kPa

Assume T=334.7 K, by using Antoine equations we get,

P1S = 224.282 kPa P2S = 29.713
kPa
Thus, P2S + 0.34 (P1S -P2S) = 95.866> 95 kPa
So
Assume T=334.6 K, by using Antoine equations we get,
P1S & P2S at 334.6K, we get y1= 0.80

ii) At 333.2 K we have P1S = 214.842 kPa P2 S

= 28.0739 kPa by using Antoine equations, we
know that,
P= P 2 S + (P 1 S -P 2 S) X1
P=110.25 kPa
Also, y1 = x 1 P1 S /P
y1= 0.8574
2. Explain the following activity coefficient models. (May 2013,2016)
i) Wilson Model ii) NRTL model iii) UNIQUAC model iv) UNIFAC model
Wilson equation

 Based on the concept of local compositions

 recommended only for liquid systems that are completely miscible, or for partially miscible
systems
 2 adjustable positive parameters L12 and L21.

 The differences in the characteristic energies(aij) are assumed to be temperature independent

 Wilson equation provides a good representation of VLE of a variety of miscible
mixtures
 suitable for solutions of polar or associating components like alcohols in
non-polar solvents for which the Margules and van Laar equations are generally inadequate.
Disadvantages
 It is not suitable for systems showing maxima or minima on the ln g versus x curves.
Not useful for systems exhibiting limited miscibility.
NRTL Model – Non Random Two Liquid Operation

The adjustable parameters

 The constants b12 and b21 and a12 are independent of composition and temperature.
 The parameter a12 is related to the non-randomness in the mixture.
 If a12 is zero, the mixture is completely random and the NRTL equation reduces to the Margules
equation.
 It is found from fitting of experimental data that a12 varies from about 0.20 to 0.47. In the
absence of the experimental data, the value of a12 is arbitrarily set, a typical choice being a12 =
0.3. When a12 is arbitrarily fixed, NRTL equation becomes a two-parameter model.
 NRTL equation is applicable to partially miscible as well as totally miscible systems. For
moderately non-ideal systems, it offers no advantage over the van Laar and Margules equations.
But, for strongly non-ideal solutions and especially partially miscible systems, the NRTL
equations provide a good representation.

UNIQUAC model

 Consists of two parts – combinational and residual

 Combinational part describes the prominent entropic contribution and is determined by the sizes
and shape of the molecules and requires only pure component data.
 Residual part - which is due primarily to the intermolecular forces that are responsible for the
enthalpy of mixing and depends on the intermolecular forces and involves two adjustable binary
parameters.

Where
z is the coordination number, r, q and q’ are pure-component molecular structure constants. The molecular
size and surface area are given by r and q respectively. For fluids other than water or lower alcohols,
q = q’. For alcohols, the surface of interaction q’ is smaller than the geometric surface q. The adjustable
binary parameters t12 and t21 are related to the characteristic energies ∆u as follows.

The segments and area fractions are obtained as follows

 The UNIQUAC equation satisfies a large number of non-electrolyte mixtures containing non-
polar fluids such as hydrocarbons, alcohols, etc., and water,including partially miscible mixtures.
 The main advantages of this equation are its wide applicability and simplicity.

UNIFAC model

The activity coefficients are estimated through group contributions. The liquid is treated as a
solution of different structural groups from which the molecules are formed, rather than a
solution of molecules themselves. This method is based on and similar to the UNIQUAC model.

3. The following data were reported for the vapor - liquid equilibrium for the ethanol water system
at 298
K. Test whether the data are thermodynamically consistent or not.

Xi 0.122 0.163 0.226 0.320 0.337 0.437 0.440 0.579 0.830

Yi 0.474 0.531 0.562 0.582 0.589 0.620 0.619 0.685 0.849
P 5.57 6.02 6.38 6.76 6.80 7.02 7.04 7.30 7.78

The vapor pressure of ethanol and water are 7.86 and 3.17 KPa. (MAY 2011), (Nov 2015)
𝑦1 𝑃
Assuming that the gas phase behaves ideally, the activity coefficients are calculated as, 𝛾1 = and
𝑥1 𝑃1𝑆
𝑦2 𝑃
𝛾2 =
𝑥2 𝑃2𝑆

Thus the values are calculated and listed below:

X1 0.122 0.163 0.226 0.320 0.337 0.437 0.440 0.519 0.830

γ1 2.95 2.49 2.018 1.56 1.51 1.26 1.26 1.09 1.01

γ2 1.05 1.06 1.13 1.31 1.33 1.49 1.51 1.72 2.18

 ln(γ 1/ γ 2) 0.96 0.85 0.43 0.12 0.12 -0.16 -0.18 -0.45 -0.76

ln(γ 1/ γ 2)) is plotted against x1 and the net area is not equal to zero. Thus, the data doesn’t satisfy Redlich
Kister criteria for consistency.

4. Water (1) - Hydrazine (2) system forms an azeotrope containing 58.5 mole% hydrazine at
393K and 101.3KPa. Calculate the equilibrium vapor composition for a solution containing
20mole% hydrazine. The relative volatility of water with reference to hydrazine is 1.6 and may be
assumed to remain constant in the temperature range involved. The vapor pressure of hydrazine
at 393K is 124.76Kpa. (May 2013, Nov 2012, Nov 2013)

The VP of water at 373 K = 1.6 x VP of hydrazine at 373 K = 1.6 x 124.76 = 199.62 KPa

𝑃1𝑆 = 199.62 𝐾𝑃𝑎 𝑎𝑛𝑑 𝑃2𝑆 = 124.76 𝐾𝑃𝑎 x1 = 0.415 and x2 = 0.585
𝑃1 101.3 𝑃2 101.3
𝛾1 = 𝑆 = = 0.5075 𝑎𝑛𝑑 𝛾2 = 𝑆 = = 0.812
𝑃1 199.62 𝑃2 124.76

Substituting in Van Laar equations we get,

A= - 1.3927 and B= - 2.2822. Here, x1=0.8 and x2=0.2. Substituting these in the following equation,

We get γ1=0.8891 and γ2= 0.3171

Also,

Rearranging, we get,
 Thus, 5.28% hydrazine and 94.72% water.

5. (i) Explain the criteria for phase equilibrium

(ii) Discuss vapor liquid equilibrium. (MAY 2011)
(i) Consider a closed system consisting of two phases of a binary solution, for example, the vapour
and liquid phases of an alcohol–water solution. If the system is in thermodynamic equilibrium,
mass, temperature and pressure are uniform throughout.
We know that, ‘Clausius inequality’,

𝑑𝑄 = 𝑑𝑈 + 𝑑𝑊

𝑇𝑑𝑆 ≥ 𝑑𝑈 + 𝑑𝑊

𝑑𝑈 ≤ 𝑇𝑑𝑆 − 𝑑𝑊

𝑑𝑈 ≤ 𝑇𝑑𝑆 − 𝑃𝑑𝑉

Constant U and V - For an isolated system, dQ=0, dW=0 and thus dU=0. Also the volume is constant.
dV=0. Thus

Thus, the entropy must be maximum at equilibrium.

Constant T and V - We know that, 𝐴 = 𝑈 − 𝑇𝑆 and 𝑈 = 𝐴 + 𝑇𝑆

𝑑𝑈 = 𝑑𝐴 + 𝑇𝑑𝑆 + 𝑆𝑑𝑇

Also, 𝑑𝑈 ≤ 𝑇𝑑𝑆 − 𝑃𝑑𝑉 and thus, 𝑑𝐴 ≤ −𝑃𝑑𝑉 − 𝑆𝑑𝑇

At constant temperature and volume, we get

Thus, the Helmholtz free energy must be minimum at equilibrium

Constant T and V - We know that, 𝐺 = 𝐻 − 𝑇𝑆 and 𝐻 = 𝑈 + 𝑃𝑉

Therefore,𝐺 = 𝑈 + 𝑃𝑉 − 𝑇𝑆

𝑑𝐺 = 𝑑𝑈 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇

𝑑𝑈 = 𝑑𝐺 − 𝑃𝑑𝑉 − 𝑉𝑑𝑃 + 𝑇𝑑𝑆 + 𝑆𝑑𝑇

Also, 𝑑𝑈 ≤ 𝑇𝑑𝑆 − 𝑃𝑑𝑉 Thus, 𝑑𝐺 ≤ 𝑉𝑑𝑃 − 𝑆𝑑𝑇

Therefore,

Thus, the free energy must be minimum at equilibrium.

ii) The vapour-liquid equilibrium (VLE) data are essential for many engineering
calculations.The conditions of equilibrium require that the fugacity of a component in the
liquid phase be equal to that in the vapour phase. That is,

Also, for the vapour phase

The fugacity of a component in gas mixture can be written as

Where Φi is the fugacity coefficient. For the liquid phase,

Also, rearranging using activity coefficient

Equating the fugacities of the vapour and the liquid phase,

Rearranging,

This is called the activity coefficient approach. Using this, the VLE problem can be
solved. by dividing them into the following grouping for convenience.

Case 1: IDEAL GAS – PHASE, IDEAL LIQUID SOLUTION:

For ideal gases, the fugacity coefficient is equal to 1 and for ideal solutions the activity coefficient is 1
and the fugacity at low pressure, is equal to saturation pressure of pure liquid. Then,

Case 2: LOW – PRESSURE VLE PROBLEMS:

If the pressure is low enough that the assumption of ideal gas behaviour for the gas phase
would not introduce any significant errors in practical calculations. The above equation can
be modified as follows.

Case 3: HIGH – PRESSURE VLE PROBLEMS:

The fugacity and activity coefficient are complex functions of temperature, pressure and
compositions and can be written as

Also, we know that,

𝑅𝑇 = ln 𝑉𝑑𝑃

the volume does not change appreciably with pressure, we get,

Therefore, substituting we get,

This is the general equation for vapour – liquid equilibria. The exponential in the above
equation is known as the poynting correction and it is approximately unity when pressure is
low.
 UNIT 4 – CHEMICAL REACTION EQUILIBRIA
PART A
1. Explain the criterion of Chemical reaction equilibrium (May/June 2012, Nov/Dec 2012, Nov/Dec
2014, 2016)
At equilibrium the total Gibbs Energy at Gt is minimum. Its differential is zero at equilibrium.

2. Explain the term “Reaction co-ordinate” (May 2011, Nov 2014)

The reaction coordinate measures the progress of a reaction and is defined as the degree to which a
reaction has advanced. It is denoted by .

3. Define Standard Free Energy and how it is related to equilibrium constant? (May 2011)
Standard free energy is the change in the energy content observed in the system before and after the
reaction.
G  RT ln K

4. What is the effect of Pressure on Reaction Equilibrium constant? (Nov/Dec 2012) (May/ June
2014)
The equilibrium constant defined in terms of activities of reactants and products is independent of
pressure.

5. Explain the activities of reactants and products.

The activities of reactants and products correspondingly decides the rate of forward and backward
reactions and hence the overall rate.
6. What reaction conditions affect the equilibrium conversion in chemical reactions? (May/June
2013)
Temperature and activities of the reactants and products affects the equilibrium conversion in chemical
reaction.

7. Write a note on the choice of Standard State in the study of Chemical reactions. (May2014)
The temperature in the standard state is the same as that of the reaction, and the pressure of 1 bar (or std
1 atm) is used.
For gases the std state chosen is the pure component at the temperature of the reaction and at unit
fugacity.

8. Explain Equilibrium constant

Equilibrium constant for a reaction is the ratio of product of activities of all products raised to their
stoichiometric coefficients to that of the product of all activities raised to their stoichiometric
coefficients.

9. What are the various methods to compute equilibrium constant?

Equilibrium constant can be computed from experimental data using std. heat of reaction or employing
thermal data.

10. What are the applications of equilibrium constant?

Equilibrium constant is the most necessary data for the design of reactor systems.

11. What is the effect of temperature on equilibrium constant?

K H o  1 1 
ln    
K1 R  T T1 


12. What is meant by Set of Primary reactions?

Primary reactions are first step of intermediate reactions that altogether constitutes, microscopically
observed overall chemical reaction.

13. What is the relation between Ka, Ky and K?

K  Ky KP
a

14. What are Single and Multiple reactions?
The reactants reacting in only one manner and yielding specific products are called single reactions.
The reactants reacting in different ways yielding different types of products are called multiple
reactions.

15. Is the Gibbs free energy change of a chemical reaction related to the work done by the
system? Give an example.
The Gibbs free energy change of a chemical reaction is related to temperature.

16. Explain the term “Equilibrium Conversion”

Equilibrium conversion is the conversion obtained in the reactor system with its ΔG minimum.

17. What are Homogeneous and Heterogeneous reactions?

Homogeneous reactions are those in which all the chemicals involved in a reaction are in the
same physical phase. If not they are called Heterogeneous reactions.

18. What is the effect of Pressure on the Degree of conversion at equilibrium, for a gas phase
reaction?
Though the equilibrium constant is unaffected by pressure it does affect the equilibrium composition
in gas phase reactions according to the Le chtellier’s principle.

19. How does the addition of Inert gases affect the degree of conversion on chemical reaction?
(Nov 2015)

Inert affects the equilibrium conversion as per the above equation. The presence of inerts will decrease
conversion if reaction is accompanied by a decrease in the number of moles and inerts present in the
system will have no influence on the degree conversion if γ is zero.

20. Write the relation between Equilibrium constant and standard free energy change.

G  RT ln K

21. What do you mean by the term “feasibility of a reaction”

Feasibility of a reaction is indicated the numerical figure obtained by adding the standard free energy
of all the chemicals involved in the chemical reaction. If the value is negative then the reaction is
thermodynamically feasible and if the value is negative then the reaction is thermodynamically not
feasible.
22. How will you estimate the standard heat of reaction at temperature T given the standard
heat of reaction?
By considering the energy requirements for decreasing the reacting system to the reference standard
temperature and energy requirements for increasing the reacting system to the original temperature
Standard heat of reaction at temperature T is determined.

23. What is the effect of Pressure on Equilibrium composition?

Pressure affects the equilibrium composition is gas phase reactions. According to Le Chatelier’s
principle when pressure is applied the system responds in such a way as to minimize the effect of
increase in pressure.

24. List out the factors affecting Equilibrium Conversion

The reaction conditions that influence the extent of reaction under equilibrium are Temperature,
Pressure, and presence of inert materials, presence of Excess reactants and presence of the products of
the reaction in the initial mixture.

25. In what type of reactions, is the equilibrium constant independent of temperature?

For the reactions in which the heat of reaction is negligible then their equilibrium constant is
independent of temperature.

26. Explain the term “Reaction co-ordinate” ?What is its significance in chemical reaction. (Nov
2015)
The reaction coordinate measures the progress of a reaction and is defined as the degree to which a
reaction has advanced. It is denoted by .
1. What is the effect of temperature on equilibrium constant? Define van’t Hoff equation (Nov
2015)(May 2016)
The effect of temperature on equilibrium constant is quantitatively expressed equation, which is developed
below. The relationship of equilibrium constant to the energy of reaction is given by
∆G0 = -RT ln K ------ (1).
The standard state is identified by specify pressure (or fugacity), but the temperature is always the same as that
of the reaction equilibrium. G0 and hence K will vary with this temperature.
For a single species the effect of temperature on its free energy is predicted by Git equation

For the substance in its standard state,

The partial derivative notation is dropped from the above equation, as the energy, by virtue of the definition of
the standard state, depends on the equilibrium but not on the equilibrium pressure. Multiplying the above
equation by vi and sums species present in the system, we get

The standard free energy of the reaction and standard heat of reaction are related to the and enthalpy of
individual species respectively as given below.

Using these in Eq. 3 and dividing both sides by R, we get

Substitute Eq. 3 into Eq. 4 we get

Equation 5 known as van’t Hoff equation, predicts the effect of temperature ont the constants and hence on
the equilibrium yield. H0 in Eq. 5 is the standard heat of is apparent that if H0 is negative. i.e. if the reaction is
exothermic, the equilibrium eases as the reaction temperature increases. Alternatively, for an endothermic
reaction, the equilibrium constant will increases with increase in temperature.
If H0, the standard heat of reaction, is constant, Eq. 5 on integration yields

And K1 are the equilibrium constant values at temperatures T and T1 respectively. Equation (6) can be
used to evaluate the equilibrium constant with good results over small temperature ranges. Equation is exact if H0
is independent of temperature. A reasonably accurate method of interpolation or extrapolation of equilibrium
constant is provided by plotting In K versus reciprocal temperature, which leads to a straight line according to Eq.
(6).
2. The standard heat of formation and standard free energy of formation of ammonia at 298 K
are – 46,100 J/mol and -16,500 J/mol respectively. Calculate the equilibrium constant for the
reaction. (MAY 2011,NOV 2016)
 The standard free energy of reaction is estimated from Equation

The second summation yields zero as the free energy of formation of the elements are zero

Using Equation

Therefore,

The standard heat of reaction at 298 K = 2 × -46,100 = -92,200 J/mol. This is assumed constant within the
temperature range involved. Now use Equation to evaluate the equilibrium constant.

Therefore, the equilibrium constant at 500 K = 0.18

3.Explain reactions coordinate. What are the criteria of chemical reaction equilibrium? (MAY 2011)

 Also called extent of reaction

 It is denoted by ɛ
 The reaction coordinate measures the progress of a reaction and is defined as the degree to which a
reaction has advanced.
 Change in the extent of reaction dɛ is the same for each component, whereas the changes in the
number of moles are different for different species taking part in the reaction.

 Before the reaction starts, ɛ=0

Criteria for chemical reaction equilibrium

At constant temperature and pressure, the transfer of materials from one phase to another under equilibrium is
found to occur with no change in the free energy. Stated mathematically, the total Gibbs free energy is
𝑡
𝑑𝐺𝑇,𝑃 =0
There is no change in the Gibbs free energy of the system, provided the change is taking place at constant
temperature and pressure.
Consider a closed system in which a chemical reaction represented by the following general equation has
been allowed to reach a state of equilibrium at a given temperature and pressure.
𝑎𝐴 + 𝑏𝐵 → 𝑙𝐿 + 𝑚𝑀
The free energy change of the process in term of chemical potential, is given by
Also,

Then,

where –a,-b, l, m are stoichiometric constants ɛ is the extent of the reaction. For an infinitesimal change in a
reacting system

Since the process is at equilibrium,

This is the criterion of equilibrium for chemical reactions

Since the reaction proceeds in the direction of decreasing Gibbs free energy G, the forward reaction (A B)
takes place if mA > mB and the backward reaction (A B) proceeds if mA < mB. When mA = mB, the
slope of the curve is zero. This occurs at the minimum of the curve and corresponds to the position of
chemical equilibrium.

4. Derive the expression relating equilibrium constant and standard free energy change from the
fundamentals of thermodynamics. Develop the expression giving the reaction equilibrium
constant (K) in terms of the reactants and products in the case of a homogeneous chemical
reaction. (May 2012)

Consider a closed system in which a chemical reaction represented by the following general equation has
been allowed to reach a state of equilibrium at a given temperature and pressure.
𝑎𝐴 + 𝑏𝐵 → 𝑙𝐿 + 𝑚𝑀
The criterion of equilibrium for the above chemical reaction can be written as,

The chemical potential and fugacity are related as

At standard state,

Combining the above two equation we get,

Writng the above equation for all 4 species and substituting in

We get,

Using the definition of K and ∆G0, we arrive at

5. Show that the equilibrium constant in the decomposition of calcium carbonate into CO2 and
lime is equal to the partial pressure of CO2. Explain how would you estimate the decomposition
pressure? What would happen if the CO2 pressure is reduced below this value? (May 2013)
The overall reaction can be represented as
𝐶𝑎𝐶𝑂3 (𝑠) → 𝐶𝑎𝑂(𝑠) + 𝐶𝑂2 (𝑔)
The equilibrium constant for the reaction is

The activities of the solid components present at equilibrium are close to unity provided the pressure is
moderate and both solids are present at equilibrium. Since the standard state for gases is the ideal gas state at
1 bar, the standard state fugacity is equal to unity and therefore, the activity of CO2 in the equilibrium
mixture is equal to its fugacity. But fugacity of a component is equal to its partial pressures at low
temperature, then

This is the equilibrium partial pressure exerted by CO2 and its value depends only on temperature. If the
partial pressure is lowered below this equilibrium value, CaCO3 will decompose and will eventually
disappear
6. Derive the relationship between mole fraction of species in multiple reactions and the
extent of reactions. (MAY 2017)
When two or more reactions occur simultaneously, the number of moles of each component changes
because of several reactions. Equations can be modified as

Here, vij is the stoichiometric number of species I in the jth reaction and ɛj is the extent of this
reaction. When the equation is modified to hold multiple reactions, the number of moles of I after the
reaction is,

The total number of moles is obtained by summing the number of moles of individual species.

If

Then,

The mole fraction of component I in the mixture is

7. A gas mixture containing 3 mol CO2, 5 mol H2 and 1 mol water is undergoing the following
reactions
CO2+3H2  CH3OH+H2 O CO2+3H2
 CO+H2O

Develop expressions for the mole fraction of the species in terms of the extent of reaction.
(MAY 2017)
The total moles initially present,
n0  3  5  1  9
For the first reaction, For the second reaction,

V1 = -1-3+1+1= -2
V2 = -1-1+1+1 = 0
The mole fractions are calculated using Equation
 Similarly,

8. n-Butane is isomerised to i-butane by the action of catalyst at moderate temperatures. It is

found that the equilibrium is attained at the following composition.

Temperature, K Mol %, n-butane

317 31.00
391 43.00

Assuming that activities are equal to the mole fractions, calculate the standard free energy of the
reaction at 317 K and average value of heat of reaction over this temperature range. (NOV 2016)

Since activities are equal to mole fractions

where yib is the mole fraction of i-butane and ynb of n-butane in equilibrium mixture. Therefore,

Also,

Also,

Therefore,

9. Estimate the standard free energy change and equilibrium constant at 700 K for the reaction
N2 (g) + 3H2 (g) 2NH3 (g)

Given that the standard heat of formation and standard free energy of formation of ammonia at 298
K to be -46,100 J/mol and -16,500 J/mol respectively. The specific heat (J/mol K) data are given below
as function of temperature (K): (DEC 2016)
 The standard heat of reaction and standard free energy of reaction at 298 K were estimated in Example
0  92, 200 J/mol; G0  33,000 J/mol
Also,
  2  29.75  27.27  3 27.01  48.8
  (2  25.11  49.3  3 3.51)10  34.76 10
3 3

  7.920110 4
By equation,

Therefore, A=14.169. Substitute ∆H´ and A into Equation, we get

Putting T=700 K in the above equation, we get

10. In the synthesis of ammonia, stoichiometric amounts of nitrogen and hydrogen are sent to a
reactor where the following reaction occurs

N2 + 3H2 2NH3

The equilibrium constant for the reaction at 675 K may be taken equal to 2 × 10 -4.
(a) Determine the per cent conversion of nitrogen to ammonia at 675 K and 20 bar.
(b) What would be the conversion at 675 K and 200 bar?

Basis: 1 mol nitrogen and 3 mol hydrogen are in the reactant mixture. Let ɛ be the extent of reaction. Then
the number of moles of various species at equilibrium is calculated by ni  ni0   i 
Thus the moles of nitrogen, hydrogen and ammonia are 1-, 3-3 and 2. Total moles at equilibrium is =
4-2. The moles fractions of nitrogen, hydrogen and ammonia are, respectively
The sum of stoichiometric numbers, v = 2 – 1 – 3 = -2. Equation gives
Ky  (K / K )P-v  KP2

In arriving at this result ideal behaviour is assumed, so that K  1

Thus we have the necessary relation connecting the equilibrium composition and
pressure.

When P = 20 bar

Solving this,  = 0.1448. Fractional conversion of nitrogen,

That is, conversion of nitrogen = 14.48%.

When P = 200 bar

Therefore,  = 0.5375. So, conversion of nitrogen = 53.75%.

 UNIT – 5 – REFRIGERATION AND LIQUEFACTION
PART A

1. What is Heat engine and a Heat pump? (MAY 2011, Nov 2014)
A heat engine is a energy conversion devise, which converts heat energy into work. A heat
pump is a thermodynamic system operating in a cycle that removes heat from a low
temperature body and delivers it to a high temperature body. External work is required to
accomplish this.

2. What do you mean by capacity of a refrigerator? (May/June 2013, Nov/Dec 2012)

The refrigerator capacity determines the rate of circulation of the refrigerant, which in turn,
decides the design and size of the various units such a s condenser, compressor, evaporator,
and the expansion devices. The capacity is sometimes measured in ton of refrigeration. One
ton is defined as the heat of absorption at the rate of 12000 BTU per hour. This rate
corresponds to the rate of heat removal that is required to freeze 1 ton of water in a day
originally at 273 K. One ton of refrigeration rate of 12600 KJ/h in SI units.

3. Why the efficiency of actual refrigeration cycles is less than Carnot’s cycle?
(May/June 2013) The COP of real refrigeration cycles is always less than the carnot
efficiency. It is usually about 0.6 times the Carnot efficiency for a simple refrigeration cycle,
but can be as high as 0.9 times the carnot efficiency if complex cycles are used. If the
temperature range is too large then it may be more economical to use a cascaded refrigeration
system, in which a low- temperature cycle rejects heat to a higher temperature cycle that
rejects heat to cooling water or ambient air.

4. What is joule- Thomson effect? (May/June 2012)

When a compressed gas below its temperature of inversion is expanded through a fine
orifice or nozzle, it gets cooled. This phenomenon is known as joule Thomson effect.

5. Why is throttling used in practical refrigerators in place of turbine? (May/June 2012)

Domestic compressor refrigerators usually operate on a rankine cycle. The actual device-
whose schematic diagram is shown in figure operates almost in an identical cycle to the
rankine engine, except for its reverse direction. The most striking difference is the throttling
valve between states E and D in place of the turbine. (The throttling valve may be small
orifice on a plate, a porous ceramic filter, or a capillary within the tube. The gas expands
across the throttle and its pressure drops.) The reason for this change is clear from the T-S
diagram; the liquid expanding from state D partly evaporates. This would lead to the
technical problems mentioned above in the operation of the turbine, and the liquid part of the
mixture would produce much less work while expanding than the vapour. In this case, it is
not worth recycling; it will take the form of losses. Another difference is that, having
reversed the direction of the engine cycle, it is not the liquid to be pumped but the vapor to be
compressed.

6. What are the limitations of refrigeration system operating in a Carnot cycle? (Nov/Dec
2012)
A refrigeration machine operating on the Carnot cycle cannot be achieved in practice. Carnot
cycle demands reversible operation, and it is difficult to eliminate all irreversibility in an
actual operation. Isothermal heat interactions at the heat absorption and the heat rejection
stages, which proceed at very slow rates necessities large heat transfer areas. A temperature
difference between the refrigerant and the reservoirs in the heat absorption and heat injection
stages is necessary, in order to have a finite rate of heat transfer. If the heat absorption is
achieved by the evaporation of a refrigerant then the possibility of input stream to the
compressor containing liquid cannot be overruled. This may lead to severe corrosion
problems in the compressor. Apart from these, the work output of an expansion engine or a
turbine used for reversible expansion is normally very small whereas their costs are
prohibitively high.

7. Explain one ton of refrigeration (Dec 2009)(Nov 2015)

One ton of refrigeration is defined as the heat absorption at the rate of 12000BTU per hour.
This rate corresponds to the rate of heat removal that is required to freeze one ton of water in
a day originally at 273 K. One ton of refrigeration is equal to a refrigeration rate of 12660
KJ/hr in SI units.

8. Explain C.O.P. and refrigeration capacity (MAY 2011) (May/ June 2014)(Nov
2015,2016)
COP, the Coefficient of Performance is the ratio of desired effect to the work input.
Refrigeration capacity determines the rate of circulation of the refrigerant and is measured in
ton of refrigeration.
𝑄𝑐
𝐶𝑂𝑃 =
𝑊

9. Explain the principle of Refrigeration

Refrigeration is the continuous absorption of heat at a low temperature level, usually
accomplished by evaporation of a liquid in a steady state flow process. The vapor formed is
returned to its original state by either compression and condensing or absorbing by a liquid of
low volatility, from which it is subsequently evaporated at higher pressure.

10. What are the requirements for a good refrigerant?

Toxicity, Flammability, cost, corrosion properties and vapor pressure in relation to
temperature are of greater importance in the choice of refrigerant.

11. Name few refrigerants and their relative advantages.

Halogenated hydrocarbons like Freon – 12, Genetron, Mafron are non toxic, non flammable
and non explosive refrigerants. Less halogenated hydrocarbon are preferred but refrigerants
like Ammonia, Carbon dioxide are eco friendly.
12. Name different components of an air-refrigeration cycle.
Refrigerator, Compressor, Water cooler and expansion engine are different components of an
air refrigeration cycle.

13. Define compressor efficiency

Compressor efficiency is defined as the ratio of isentropic work to the actual work required for
compression.

14. Why is throttling used in practical refrigerators in place of turbine?

Flow through a partly closed valve is known as throttling process, this results in the partial
vaporization of the liquid accompanied with reduction in pressure.

15. What is a vapor-compression refrigeration cycle?

In vapor compression cycle, the vapor formed due to the absorption of heat in the refrigerated
area, is compressed using a compressor followed by condensing and returning it to its original
state.

16. What is meant by absorption refrigeration?

An absorption refrigeration unit uses the heat absorbed from a high temperature source directly
for achieving the necessary refrigeration.

17. What are the various Liquefaction processes?

1). Linde process.
2). Claude Process.

18. Name various methods with which liquefaction can be accomplished.

1). Vaporization of liquid.
2). Joule Thomson expansion.
3). Expansion of gas in an engine delivering external work.

19. Define Joule-Thomson expansion

Joule Thomson expansion is a steady state flow process across a restriction

20. Explain Linde liquefaction process

The Linde process for gas liquefaction works on the joule Thomson expansion, and gases with
positive joule Thomson co efficient are liquefied using Linde’s Process.

21. Explain Claude liquefaction process

The Claude process for gas liquefaction utilizes isentropic expansion of a compressed gas in
which an expansion turbine is used in place of a throttle valve.

22. Define Cycle efficiency

Cycle efficiency is the ratio of reversible work for the process to that of theoretical

23. Define Practical efficiency

Practical efficiency is the ratio of theoretical work for an ideal operation to that of the actual
work for the cycle.
24. What is an Air standard diesel dual cycle?
In diesel engines the temperature at the end of compression, exceeds the final ignition
temperature and the combustion of fuel occur spontaneously.

25. What are Otto and Diesel cycles?

Otto and Diesel cycles are the two important air standard cycles used for the analysis of
internal combustion engines.

26. What is the advantage of Claude liquefaction process over Linde Liquefaction
process?
Claude process in more efficient in the sense some amount of work is derived from the
cooling vapors, by replacing the throttle valve by an expander.

27. What are the factors that are to be considered for selecting a refrigerant?
Toxicity, Flammability, cost, corrosion properties and vapor pressure in relation to
temperature are of greater importance in the choice of refrigerant.

28. What are the methods to accomplish cooling?

Cooling of Vapors and there by liquefaction can be obtained (i) by heat exchange at constant
pressure. (ii). by an expansion process for which work is obtained (iii) by a throttling
process.
PART B
1. Discuss the desirable properties of refrigerant in detail. (May /June 2014)
 Boiling temperature: it is necessary that the operating pressure be maintained above
atmospheric o avoid air and moisture leaks into the system. The normal boiling point of
the refrigerant should, therefore be lower than the desired temperature levels in the
refrigerator.
 Freezing point: the freezing point of the refrigerant should be well below the minimum
temperature at which the system is opened.
 Critical temperature and pressure: the critical temperature and pressure of the refrigerant
should be above the operating system temperature and pressure. If the operating
temperature is above the critical temperature, it is impossible to condense the gas by
compressing it to high.
 Condenser and evaporator pressures: the condenser pressure should not be very high. If
pressure is very high, the cost of equipment and the cost of operation would be excessive.
If the evaporator pressure is excessively low, the compression ratio would be abnormally
high. If the refrigerant has sub atmospheric vapor pressures at the temperature in the
refrigerator coil, the possibility of contamination by leaks cannot be overruled.
 Specific volume: specific volume of the vapor determines the size of the compressor. Low
suction volumes are desirable for reciprocating compressors and high suction volumes for
centrifugal compressors
 Latent heat: a high latent heat of vaporization of the refrigerant is desired, because it
results in high refrigerant effect per unit weight of the refrigerant and low rate of
circulation of the refrigerant.
 Specific heat of liquid : If the specific heat of the refrigerant liquid is unduly high, large
quantity of heat would have to be removed to cool the hot liquid entering the evaporator to
bring its temperature down to the saturation valve. Therefore, low specific heat of the
liquid refrigerant is preferred.
 Molecular weight: molecular weight of the refrigerant affects the compressor size because
the specific volume of the vapor is directly related to it. A high molecular weight
refrigerant gives high specific volumes for the vapor, which is preferred for centrifugal
compressors, where as for reciprocating compressors a low molecular weight for the
refrigerant is advantageous.
 Safety aspects: refrigerants are grouped according to toxicity an flammability.
Halogenated hydrocarbons are relatively nonflammable, nontoxic and nonexplosive.
These belongs to group 1. Group 2 refrigerants are either toxic or flammable. Examples
are methyl chloride and sulphur dioxide
 Other desirable properties: normally, a refrigerant would be in use for a very long period.
Consequently, the chemical stability of the refrigerant is another importan criterion in the
choice of a proper refrigerant. They should also be non-corrosive, should have low
viscosity and high thermal conductivity,
 2. Explain the Air- refrigeration cycle in detail with a neat flow diagram. (May 2012) (Nov
2013)
 Working fluid – air
 Air does not undergo any phase change
 Air is compressed adiabatically to pressure P1 and temperature T1 in the compressor
(AB)
 It is then cooled at constant pressure in the cooler (BC)

Q2

Q1
Fig.Air Cycle.
`

 Air is then expanded in the turbine to pressure P 2, which is equal to the pressure at
compressor intake (CD)
 The air leaving the turbine is passed through a refrigerator, where it absorbs heat at
constant pressure P2(DA)
 The gas leaving the refrigerator enters the compressor and the cycle is repeated.

Let the rate of air circulation be . Assume that the heat capacity of air remains constant during
the cycle. Then, heat absorbed is

and the heat rejected is

The net work required is

The coefficient of performance of an air-refrigeration machine is

For an adiabatic process

Substituting in the COP equation, we get

 Advantage – air is available at no cost

 Disadvantages:
i. Low efficiencies
ii. Large heat transfer surfaces required
iii. Large quantity of air is to be handled

3. Explain with neat sketch of Vapor - Compression refrigeration process. (May 2011) (Nov
2013,2016)

During this cycle, the fluid is evaporated in the refrigerator for absorbing heat at a constant
temperature. The vapors are then compressed to a higher pressure. These vapors at a higher
pressure are taken to a condenser whereby condensation the heat is rejected at some higher
constant temperature. The cycle is completed by bringing the fluid to its original state through
an expansion step. The compression and expansion process are made reversible as much as
possible by taking care to eliminate irreversibility.

(a) The expansion step is carried in two ways. By using an expansion engine shown in Figure
which operates more or less reversibly. When drawn on a T – S diagram (Figure) the
cycle resembles a Carnot cycle with a little difference of cooling of superheated vapor to
saturation temperature before the commencement of condensation step.
 (b) The expansion may also be carried out by using an expansion valve which makes the
expansion step of cycle isenthalpic and consequently an irreversible process. The
expansion valve is used, being less expensive as compared to expansion engines, in
household refrigerators and air conditioners.

Performance parameters
i. Coefficient of Performance

ii. Carnot’s Coefficient of Performance

𝑇𝑐
𝛽𝑚𝑎𝑥 =
𝑇𝐻 − 𝑇𝑐
This equation represents the maximum theoretical coefficient of performance of any refrigeration
cycle operating between cold and hot regions at TC and TH, respectively.
Features of Actual Vapor-Compression Cycle
► Heat transfers between refrigerant and cold and warm regions are not reversible.
► Refrigerant temperature in evaporator is less than TC.
► Refrigerant temperature in condenser is greater than TH.
► Irreversible heat transfers have negative effect on performance.

► The COP decreases – primarily due to increasing compressor work input – as the
► temperature of the refrigerant passing through the evaporator is reduced relative
to the temperature of the cold region, TC.
 ► temperature of the refrigerant passing through the condenser is increased relative
to the temperature of the warm region, TH.
Irreversibility during the compression process are suggested by dashed line from state 1 to 2.
► An increase in specific entropy accompanies an adiabatic irreversible
compression process. The work input for compression process 1-2 is greater than
for the counterpart isentropic compression process 1-2s.
► Since process 4-1, and thus the refrigeration capacity, is the same for cycles 1-2-
3-4-1 and 1-2s-3-4-1, cycle 1-2-3-4-1 has the lower COP.
Isentropic Compressor Efficiency
► The isentropic compressor efficiency is the ratio of the minimum theoretical work input
to the actual work input, each per unit of mass flowing:
► The isentropic compressor efficiency is the ratio of the minimum theoretical work input
to the actual work input, each per unit of mass flowing:
(−𝑊̇𝑐𝑣 /𝑚)̇𝑠 ℎ2𝑠 − ℎ1
ɳ𝑐 = =
(−𝑊̇𝑐𝑣 /𝑚)̇ ℎ2 − ℎ1

4) Explain in detail about the Absorption refrigeration process. (DEC 2009, Nov 2011)(May 2016)

Another form of refrigeration that becomes economically attractive when there is a source of
inexpensive heat energy at a temperature of 100 to 200oC is absorption refrigeration, where the
refrigerant is absorbed by a transport medium and compressed in liquid form. The most widely
used absorption refrigeration system is the ammonia-water system, where ammonia serves as the
refrigerant and water as the transport medium. The work input to the pump is usually very small,
and the COP of absorption refrigeration systems is defined as
Desired output Cooling effect QL Q
COPR     L
Required input Work input Qgen  Wpump ,in Qgen
• Absorption refrigeration systems (ARS) involve the absorption of a refrigerant by a
transport medium.
 • The most widely used system is the ammonia–water system, where ammonia (NH3)
serves as the refrigerant and water (H2O) as the transport medium.
• Other systems include water–lithium bromide and water–lithium chloride systems, where
water serves as the refrigerant. These systems are limited to applications such as A-C
where the minimum temperature is above the freezing point of water.
• Compared with vapor-compression systems, ARS have one major advantage: A liquid is
compressed instead of a vapor and as a result the work input is very small (on the order of
one percent of the heat supplied to the generator) and often neglected in the cycle
analysis.
• ARS are often classified as heat-driven systems.
• ARS are much more expensive than the vapor-compression refrigeration systems. They
are more complex and occupy more space, they are much less efficient thus requiring
much larger cooling towers to reject the waste heat, and they are more difficult to service
since they are less common.
• Therefore, ARS should be considered only when the unit cost of thermal energy is low
and is projected to remain low relative to electricity.
• ARS are primarily used in large commercial and industrial installations.

For a refrigeration rate of Q2 kJ/h, the minimum work required when the refrigerator and the
condenser are at temperatures T2 and T1 respectively is given by
In order to deliver a work equal to W, a heat engine operating between a high-temperature source
at T3 and the surroundings at T1 should absorb a quantity of heat Q3, where

Substituting we get,

The above ratio is the refrigeration obtainer per unit quantity of high temperature heat. It is the
efficiency if the cycle.

5) With necessary diagram explain the Claude liquefaction system. (MAY 2010, Nov 2012)
 It is expansion of gas in an engine which delivers external work
 Utilizes isentropic expansion of compressed gas
An energy balance around the heat exchanger, turbine, and the separator giveswhere

WS is the work delivered by the turbine. If the turbine operates adiabatically, the shaft work WS
is equal to the decrease in enthalpy of the gas during expansion.

The thermodynamic efficiency of the process is defined as the ratio of the minimum reversible
work for the given process to the actual work. This can be evaluated as the product of two other
efficiencies, viz., the cycle efficiency and practical efficiency.

6) Give a comparative study between vapor compression and vapor absorption system.
(MAY 2010, Nov 2012)

S.no Aspect Vapor Absorption Vapor Compression System

System

1 Quality of the Low grade energy Vapor compression system needs

Energy Input sources are more than high grade energy. It needs electrical
capable of running a or mechanical energy for operating
vapor absorption compressor which is an essential
system. These sources part of VC refrigeration system.
can be waste heat from
furnaces, exhaust steam
etc. Solar power can
also be used for running
it.

2 Moving part The only moving part of In Vapor compression the moving
in the system Vapor absorption part is the compressor which
refrigeration system is
 the pump. operated by electric motor or engine

3 Effect of Very little effect is seen The refrigerating effect or

Evaporator in the refrigeration refrigeration capacity decreases with
pressure capacity with the the lowering evaporator pressure.
lowering evaporator
pressure.

4 Workability Load Variation does not Vapor compression system does not
at Load have any effect on the work well at partial load. The
varying load performance of the performance is very poor.
vapor absorption system

5 Evaporator In vapor absorption Liquid refrigerant entering

exit system, if the liquid compressor is not desirable in Vapor
refrigerant leaves the compression system. It could
evaporator, the damage the compressor. So the
refrigerating effect is refrigerant is superheated before
reduced but the system leaving the evaporator.
functions well without
any problem.

6 Lowest When water is used as -150 degree Celsius or even lower

temperature refrigeration the can be achieved with the cascading
temperature attained is system.
above 0 degree Celsius

7 Coefficient of The COP of absorption The COP of Vapor compression

Performance refrigeration system is system is very good.
poor.

8 Capacity Capacity above 1000 TR It is difficult to capacity above 1000

is easily achievable. TR with single compression system.

9 Refrigerant Ammonia or water can Hydrocarbons, Chlorofluorocarbons

be used as refrigerant and Hydrochlorofluorocarbons are
with a proper absorber. used as refrigerations.

7) Write about Carnot cycle with T S diagram and discuss its limitation. (May 2011)
Carnot cycle. The carnot cycle is an ideal cycle consisting of two isothermal processes during
which Q2 is absorbed at the lower temperature T 2 and the heat Q1 is rejected at higher
temperature T1 and two adiabatics, the result of which is the addition of the network W to the
system. The carnot cycle (on T-S) is shown in FigureFig. Carnot cycle.
 • Idealized thermodynamic cycle consisting of four reversible processes (any
substance):
 Reversible isothermal expansion (1-2, TH=constant)
 Reversible adiabatic expansion (2-3, Q=0, THTL)
 Reversible isothermal compression (3-4, TL=constant)
 Reversible adiabatic compression (4-1, Q=0, TLTH)
• Work done by gas = PdV, area under the process curve 1-2-3.

The Carnot Principles

• The efficiency of an irreversible heat engine is always less than the efficiency of a
reversible one operating between the same two reservoirs. hth, irrev < hth, rev
• The efficiencies of all reversible heat engines operating between the same two reservoirs
are the same. (hth, rev)A= (hth, rev)B
• Both Can be demonstrated using the second law (K-P statement and C-statement).
Therefore, the Carnot heat engine defines the maximum efficiency any practical heat
engine can reach up to.
• Thermal efficiency th=Wnet/QH=1-(QL/QH)=f(TL,TH) and it can be shown that th=1-
(QL/QH)=1-(TL/TH). This is called the Carnot efficiency.
• For a typical steam power plant operating between T H=800 K (boiler) and TL=300
K(cooling tower), the maximum achievable efficiency is 62.5%.
8) A vapor compression refrigeration system with ammonia as the working fluid is to
operate between 266 K and 300 K. Determine the following.
(i) COP given that the enthalpy of saturated vapor at 266 K = 656 KJ/Kg and the
enthalpy of superheated vapor leaving the compressor is 724 KJ/Kg, enthalpy of
saturated liquid at 300 K is 144 KJ/Kg.
(ii) COP if a temperature approach of 5 K is necessary in the evaporator and condenser,
and the efficiency of the compressor is 75%. Enthalpy of saturated vapor entering the
condenser is 758 KJ/Kg, enthalpy saturated liquid at 305 K is 159 KJ/Kg.
(iii) The COP of an ideal Carnot refrigerator. (MAY 2011, MAY 2017)

9) An air-refrigeration machine rated at 10ton is used to maintain the temperature of a

cold room at 261K, when the cooling water is available at 293K. The machine operates
between pressures of 1.013bar and 4.052bar. Assume a 5-K approach in the cooler and
the refrigerator. If the specific heat of air may be taken as 1.008 KJ / Kg K and  = 1.4,
calculate the COP and air circulation rate. (JUNE 2013)
The temperature of the air leaving the refrigerator is

The temperature of the air leaving the cooler is

𝑇𝐴
𝐶𝑂𝑃 =
𝑇𝐵 − 𝑇𝐴
Considering energy balance in the rerigerator, we get