Pe3451 Cet Notes

JCT COLLEGE OF ENGINEERING AND TECHNOLOGY
UNIT – III
PROPERTIES OF SOLUTIONS
PART-A
1. Define chemical potential?
The definition of chemical potential is the fundamental new property is called

chemical potential.
2. Define ideal solution?
Based on an idealization of solution behavior called the ideal solution
3. What is fundamental property for single phase fluid system?
d(nG)  nvdp  nsdt    i dni is the fundamental property for single phase fluid
i
system.
4. What is multiple phases?
Multiple phases at the same T and P are in equilibrium when the chemical potential
of each space is the same in all phases.
5. What is partial molar property of spaces I in the solution?
The partial molar property of spaces in the solution is

 (nm) 
Mi   
 ni  P ,T ,nj
6. What are summability relations?
M   Xi Mi
i
nM   ni Mi
i
7. What is molar property of spaces?
The molar property of spaces I is  Xi dMi  0 Where Mi  molar property of

i
spaces i as it exist in solution.

8. What are the partial properties for binary system?
dM
M1  M  X2
dXi
dM
M 2  M  X1
dXi
Are the partial properties for binary system
9. What is partial molar property ?
A partial molar property of a constituent spaces in an ideal – gas mixture is equal to

the corresponding molar property of the spaces as a pure ideal gas at the mixture
temperature but at a pressure equate to it partial pressure in the mixture.
10. Give the expression for independent of pressure ?
H ig   yiH iig is the expression for independent of pressure.

i
11. What is fugacity coefficient for pure gases ?
The fugacity coefficient for pure gases is

P
dP
In1   (Z1  1)
o
P
12. How the fugacity of a pure liquid is calculated ?
1. The fugacity coefficient of star saturated vapour 1sat  1V is determined from an
integrated form at P  P1sat .
2. The fugacity change resulting from the pressure increase P1sat .to P that changes the
state from saturated liquid to compressed liquid.
13. Write the exponential form for pointing factor ?
sat sat
Vi1  P  Pisat 
fi   P exp
1
RT
14. What is partial residual property ?

R R ig
The partial residual property is denoted by M 1 is M 1  Mi  Mi
15. What is partial residual Gibbs energy ?
R R ig
The partial residual Gibbs energy is denoted by G 1 is G1  Gi  Gi
16. What is fugacity coefficient of spaces i is the solution ?
fi 
 1  i is called fugacity coefficient of spaces I in the solution.
yi P
17. Develop a general equation for calculation of In i values from compressibility
factor data ?
Solution :
P
nG R dP
  (nz  n)
RT O P
   nz  n  
P
dP
Ini    
o 
ni  P ,T ,n , P
Since
( nz ) and
ni  Zi
P
dP
Ini    zi  1
o
P
18. What is fugacity coefficient from the viral equation of state ?
BP
The fugacity coefficient from the viral equation of state is Z  1 
RT
19. Determine the fugacity coefficient for nitrogen and methane in N 2 (1) / CH 4 (2)
mixture at 200K and 30 bar if the mixture contains 40 mol % N 2 experimental Viral
coefficient data are as follows.
cm3
B11  35.2, B22  105.0, B12  59.8
mol
Solution :
 12  2 B12  B11  B22
 12  2( 59.8)  35.2   105.0 
3
 20.6 cm mol
30
Ini   35.2  0.6 2 (20.6) 
83.14(200) 
 0.0501
30
Ini   105.0  0.4 2 (20.6) 
83.14(200) 
 0.1835
1  0.9511  2  0.8324
1
20. Estimate the value for fugacity of 1-butane vapor at 2000 c and 70 bars.
Solution:
Tr  1.127
Pr  1.731
  0.191
 o  0.627 and  1  1.096
0.191
   0.627  1.096   0.638
f   P  (0.638)(70)  44.7 bars
21. Define Lewis – Randall role

id
f 1  Xifi This equation is known as Lewis Randal rule
22. What is the equation for fundamental excess property relation ?
The equation for fundamental excess property relation is

E
 nG E  nV E nH E Gi
d  dP  2
dT   dni
 RT  RT RT i RT
23. What happen if the fugacity of spaces I is in the physical state ?
The fugacity coefficient of spaces I in an ideal solution is equal to the fugacity

coefficient of pure spaces I in the physical state at same T & P
id
   i
i
24. What excess property ?
The excess property ME is defined as the difference between the actual property
values of a
solution.
M E  M  M id
25. What is generalized correlation for the fugacity coefficient ?
P  Pi Pr dP=PidPr
Pr
dPr
Ini    Z  1
o
i
Pr
Pr Pr
dP dP
In    Z  1 rr    Z1 r
o
o
P o
Pr
In  In o   In 1
Pr Pr
dP dP
In    Z  1 rr , In 1   Z1 r
o o
o
P o
Pr
26. Give the equation for In  o is a partial property with respects to G P / RT .
The equation for In  o is a partial property with respect to G P / RT is

  nG R

Ini  


RT  
ni 
  P ,T ,n ,
27. What is the fugacity coefficient for vapour & liquid ?
iV  1I  isat

fisat
isat 
P1sat
28. What is equation for ideal – gas state fugacity of pure spaces I ?
The equation for ideal gas state fugacity of pure spaces I is

fi
i 
P
Where P  Pressure
fi fugacity for pure spaces i
29. What is the symbol for solution properties partial properties and pure spaces
property ?
Solution property is denoted by M

Partial property is denoted by Mi
Pure – spaces Property is denoted by Mi
30. What is partial pressure of spaces I ?
yip P  xi Pisat
Where
Yi Vapour phase mole fraction
Pisat  Vapor pressure of pure spaces
The product yip on the left side is known as partial pressure of spaces i.
31. Give some examples for solution properties ?
U, H, S, G are some of the examples for solution property
32. Give some examples for partial properties ?
Ui , Hi , Si and Gi are some of the examples for partial property.
33. Give some examples for pure spaces property ?
Ui, Hi, Si, Gi are some of the examples for pure spaces property.
34. If n moles of ideal gas mixture occupy a total volume V t then what is the
pressure ?
The n mole of ideal gas mixture occupy a total volume V t at temperature T, then the
nRT
pressure is P  t
V
P  Pressure,
N  no. of moles,
T  Temp,
V t  total volume
35. Evaluate the fugacity coefficient through cubic equation ?

P
dP
In1   (Zi  1)
o
P
Bii P
(Zi  1) 
RT
P
Bii
RT o
Ini  dP
Bii P
Ini   Ini  Zi  1  In(Zi   i )  q1 I1
RT
36. What is the fugacity coefficient from viral equation of state ?
BP
The fugacity coefficient from Viral equation of state is Z  1 
RT
Where
P  Pressure,
R Gas constant
T  Temperature
37. What is the result of  phase ?
More than two phases the equality of chemical potentials the result of  phase
is
1  1  ................  1 ( i  1, 2..........N )
38. What is partial molar volume for Vi ?
(nV ) 
The Partial molar volume for Vi is Vi  
 ni  P ,T ,nj
39. Why  xidmi  0 ?

i
The equation  xidmi  0 is satisfied for all Changes in P, T and

i
Mi caused by
changes of state in a homogenous state.
40. What is M value for binary solution ?
The M value for binary solution is

M  X1 M1  X2 M 2
Where M is a function of X1 at constant T and P
41. What is the pressure value for I species in the mixture ?
The pressure value for is species in the mixture is

n RT
Pi i
VT
ni no of moles of species i
42. What is total pressure ?
Pi ni
  y1( or )P1  yi P
P n
Where
Yi  mole fraction of species i
Pi  Partial pressure of species i
The sum of partial pressure equals the total pressure
43. Derive the pointing factor ?
P
Infi 1
fisat RT P1sat
 Vi dP
Infi ViI ( P  Pisat )


fisat RT
( P  Pisat )ViI
fi  isat Pisat exp
RT
44. What is residual Gibbs energy ?
R ig
The residual Gibbs energy is G i  Gi  G i is called partial residual Gibbs energy.
45. Write the equation for fundamental excess property relation ?
E
 nG E  nV E nH E Gi
d   dP  2
dT   dn is the equation for fundamental excess
 RT  RT RT 1 RT
property relation.
(PART-B)
1. A 30 percent by mole methanol-water solution is to be prepared. How many

cubic meters of pure methanol (molar volume, 40.72710-6 m3/mol) and pure water
6
(molar volume, 18.068 10 m3 / mol) are to be mixed to prepare 2 m3 of the desired
solution? The partial molar volumes of methanol and water in a 30 per cent
6 6
solution are 38.632 10 m3/ mol and 17.765 10 m3/mol, respectively.
Solution: Molar volume of the desired solution is
V  x1V 1  x2V 2  (0.3  38.632 106  0.7 17.765 10 6 ) = 24.0251106 m3/mol
Therefore, 2 m3 of the desired solution contains
2 / (24.0251 ×10-6) = 83.2463×103 mol
Number of moles of methanol in 2 m3 of solution = 83.2463 × 103 × 0.3 = 24.9739 × 103
mol
Number of moles of water in 2 m3 of solution = 83.2463 × 103 × 0.7 = 58.2724 × 103 mol
Volume of methanol to be taken = 24.9739 × 103 × 40.727 × 10-6 m3 = 1.0171 m3
Volume of water to be taken = 58.2724 × 103 × 18.068 × 10-6 m3 =1.0529 m3
2. Laboratory alcohol containing 96% alcohol and 4% water is to be diluted to a

solution containing 56% alcohol and 44% water. All percentages are on weight
basis. The partial specific volumes are as follows: In 96% alcohol solution,
Vw = 0.816 × 10 -3 m3/kg, V e = 1.243 × 10 -3 m 3 /kg .In 56% alcohol solution,
V w = 0.953 × 10 -3 m 3 /kg, V E = 1.273 × 10 -3 m 3 /kg . The density of water may be taken
as 0.997×103 kg/m3.
(a) How much water should be added to 2 × 10-3 m3 of the laboratory alcohol?
(b) What is the volume of the dilute alcohol obtained?
Solution: Basis: 2 × 10-3 m3 laboratory alcohol.
1 kg laboratory alcohol (0.96 × 1.273 + 0.04 × 0.816) × 10 -3 =1.255 × 10-3 m3

2 × 10-3 m3 of laboratory alcohol  2 ×10-3 / (1.255 × 10-3) = 1.594kg
(a) Let the mass of water added be m kg. Taking an alcohol balance, we get
1.594 × 0.96 = (m + 1.594) 0.56
Thus mass of water added is,
m = (1.594 × 0.96) / 0.56 -1.594=1.1386 kg
And volume of water added is
1.1386 / (0.997 × 103) = 1.142 × 10-3 m3
(b) Mass of dilute alcohol obtained = 1.594 + 1.1386 = 2.7326 kg
Specific volume of 56% alcohol = (0.56 × 1.243 + 0.44 × 0.953) × 10 -3 =1.115 × 10-3
m3/kg
Therefore,
Volume of dilute alcohol obtained = 1.115 × 10-3 × 2.7326 = 3.0468 × 10-3 m3
3. At 300 K and1 bar, the volumetric data for a liquid mixture of benzene and
cyclohexane are represented by V= 109.4 × 10 -6 -16.8 × 10-6 x – 2.64 × 10-6 x2, where x is
the mole fraction of benzene and V has the units of m 3/ mol. Find expressions for
the partial molar volumes of benzene and cyclohexane.
Solution: The molar volume of the solution as a function of composition is given:

V = 109.4 × 10-6 -16.8 × 10-6 x1 – 2.64 × 10-6 x12
Where x1 = mole fraction of component 1 (in this case, benzene). By Equation,
v
V1  V  x2
x2
V
V 1  V  (1  x1 )
x1
Differentiating Equation we get
V 1 =109.4 × 10-6 -16.8 × 10-6 x1 – 2.64  10-6 x12 + (1-x1) (-16.8 × 10-6 – 5.28 × 10-6x1)
=92 .6 × 10-6 -5.28 × 10-6x1 + 2.64 × 10-6 x12
Using Equation V 2 can be found out.
V
V 2  V  x1
x1
V2 = 109.4 × 10-6 -16.8 ×10-6x1 – 2.64 x12 – x1 (-16.8 × 10-6 – 5.28 × 10-6x1)
2
=109.4 × 10-6 + 2.64 × 10-6 x1
The partial molar volume of benzene:

V1 =92.6 × 10-6 -5.28 × 10-6 x1 + 2.64 × 10-6 x12
The partial molar volume of cyclohexane:
V 2 = 109.4 × 10-6 + 2.64 ×10-6 x12
4. The volume of an aqueous solution of NaCl at 298 K was 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=1.003 × 10-3 + 0.1662 × 10-4 m + 0.177 × 10-5 m1.5 + 0.12 × 10-6 m2

Where m is the molality and V is in m3. Calculate the partial molar volumes of the
components at m = 0.1 mol / kg.
Solution: The partial molar volume of NaCl

 V   V 
V1     
 n1 n  m n2
2
V=1.003 × 10 + 0.1662 × 10-4 m + 0.177 × 10-5 m1.5 + 0.12 × 10-6 m2

-3
Differentiating Equation with reference to m,

V 1 = 0.1662 × 10-4 + 0.177 × 1.5 × 10-5 m0.5 + 0.12 × 2 ×10-6 m
= 0.1662 × 10-4 +0.2655 × 10-5 m0.5 + 0.24 × 10-6 m
Substituting m = 0.1, this equation gives V 1 = 0.1748 × 10-4 m3/mol. Substituting m =
0.1 in Equation+, V=1.0047 × 10-3 m3. But,
1000
V  n1 V 1  n2 V2  mV1  V2
18
Rearranging this equation and substituting the values, we find
18
V2  (1.0047  10 3  0.1  0.1478  10 4 )
 18.05  10 6 m3 / mol
1000
Partial molar volume of water = 18.05 × 10-6 m3 / mol
Partial molar volume of NaCl = 17.48 × 10-6 m3 / mol.
5. 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.
 V t 
V1   
 ni  P ,T ,n 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 (V / n2 ) P ,T ,n1
t
Which, by definition is V 2 , the partial 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.
Figure: Determination of partial molar properties by method 2.

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 V2 and the
intercept on the vertical axis at x2 = 0 (or x1 = 1) gives V1 . In Fig BD  V2 and AC=V1 .
Figure: The method of tangent – intercepts for the determination of partial molar
properties
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

 V t   V 
   V  V   n1  n2   
 n1  P ,T ,n
2
 n1 n
2
The mole fraction x2 is given by

n2
x2 
n1  n2
Differentiating Equation with respect to n1 keeping n2 constant, we get
 x2  n2 x2
   
 n1  n2 (n1  n2 ) n1  n2
2
Which can be rearranged as

n1  n2 x
 2
dn1 dx2
Equation can be substituted into Equation to yield the following:
V
V 1  V  x2
x2
Similarly it can be shown that
V
V 2  V  x1
x1
Since, for a binary solution, x1 = 1 - x2 and dx1 = -dx2, Equation can be put in another
form:
V
V 2  V  1  x2 
x2
In Figure, the length BD=BE+ED, where BE is the slope of the tangent at P times the
length PE. That is,
BE =  1  x2  V / x2 
And ED = V, the molar volume at the molar fraction x2, Thus
BD = V + (1-x2)  V / x2 
Which, by Equation is V 2, similarly, the length
AC = FC – FA = V – x2  V / x2   V 1
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 G i , H i , etc., it
becomes necessary to work with property changes on mixing like ∆G, ∆H, etc. The
methods of tangent intercepts for the determination of say G 1 and G 2 , requires the
plot of ∆G per mole versus x2.
6. Derive Gibbs – Duhem equation and other forms?
Consider a binary solution made up of components 1 and 2 whose mole fractions in

the solution are x1 and x2 respectively. Equation can be written as
x1d 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
1 
x1  x2 2
x1 x2
Introducing the relationship between chemical potential and the fugacity Equation
into the above, we get
In f1 In f 2
x1  x2
x1 x2
Since activity ai  f i / f i , fugacities in Equation may be replaced in terms of activity
o
as
In(a1 f10 ) In  a2 f 2 0


x1  x2
xi x2
Since f i , the fugacity in the standard state, is independent of the composition of the
0
solutions,
In( fi 0 )
0
xi
Thus the Gibbs – Duhem equation in terms of activity is
1na1 1na1
x1  x2
x1 x2
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.
1n 1 x1 1n 2 x2
x1  x2
x1 x2
1n 1 1nx1 1n 2 1nx2

x1  x1  x2  x2
x1 x1 x2 x2
The second terms on both sides of the above equation vanish, as they are equal to
unity. Therefore,
1n 1 1n 2
x1  x2
x1 x2
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.
Gibbs-Duhem equations find wide applications in solution thermodynamics. 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.
UNIT – II
PHASE EQULIBRIUM
PART – A
1. State duhrem’s theorem ?
It states that for any closed system formed initially from the given masses of
prescribed chemical spaces, the equilibrium state is completely determined when any
two indepent variables are fixed.
2. Write the wohl’s three – suffix equation ?
x1
Z1 
x1  x2 (Q2 / Q1 )
x2
Z2 
x2  x1 (Q2 / Q1 )
3. Write margules equation ?
n  1  x22  A  2( B  A)x1 
n  2  x12  B  2( A  B)x2  are the margules equation
n  1  Ax22  n  2  x12
4. Write the van laar equation for A & B ?
2
 x n 
A  n  1 1  2 2 
 x1n 1 
2
 x n 
B  n  2 1  1 1 
 x2 n 2 
5. Write the Wilson equation ?
V2  
12  exp  12 11 
V1  RT 
V 
 2 exp  12 
V1  RT 
V1  N12  22 
 21  exp  
V2  RT
V 
 1 exp  21 
V2  RT 
6. Define Azeotrope ?
Azeotropes are constant boiling mixtures. When an Azeotrope is boiled the

resulting vapour will have the same composition as the liquid form which it is
produced whereas the equilibrium temp of an ordinary soln varies from the bubble
point to dew point, the boiling point of an azeotropes remains constant till the entire
liquid vapourised.
7. Write the clausius clapeyron equation ?
P2s H  1 1 
n    
P1s R  T1 T2 
P1s & P2s are vapour pressure
T1 & T2 are temperature
8. What are the phase equilibrium problems ?
a) The determination of composition of phases exist in equilibrium at a known

temperature and pressure.
b) The determination of conditions of temperature and pressure required to obtain
equilibrium between phases of specified compositions
9. Write the Gibbs free energy equ ?
The Gibbs free energy equation and it is denoted by G G =H – Ts
10. Write the Helmholtz free energy ?
The Helmholtz free energy equation and it

A= U – Ts
Is denoted by (A)
11. What is criterion of stability ?
At constant T & P the free energy change on mixing DG, its first and second
derivative are all continuous functions of the concentration x.
12. What is the equation for ideal gas – phase and ideal solution ?
For mixtures of ideal gases 1  1 for ideal liquid solutions at low pressure  1  1 and
fugacity fio is equal to saturation pressure of pure liquid Pis at the t Yi P=xi Pis
13. What as the equation for low pressure VLE ?
If the pressure is low enough that the assumption of ideal gas behavior for the gas
phase would not introduce any significant errors in practical Yi P=xi Pis
14. What is the equation for VLE or pointing correction ?
 V ( P  Pis ) 
Yi 1 P   ixiis Pis exp  i 
 RT 
This equation is known as pointing correction or vapour liquate equilibrium equation
15. What is tie line ?
The mixtures at point B and c U) L + V at equilibrium at the system pressure & temp
T1 since both are at the same temperature, they can be joined by a line it is called tie
line.
16. Write the three differential equation
du = Tds – pdv
dA= -pdv sdT
dG= vdp – sdT
17. Draw the diagram T x y for maximum boiling azeotropes
T – x – y diagram
18. How consistency test for VLE data can be find ?
a) Using slope of n  curves

b) Using data at mid point
c) Redlich kister method
d) Using coexistence method
e) Using partial pressure data
19. Why minimum boiling Azeotrope occurs ?
Solution showing positive deviation from ideality in certain cases may lead to
the formation of azeotropes of the minimum boiling types
20. Why maximum boiling azeotrope occurs ?
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.
21. What is consistent diagram for slope of n ?
22. Draw the inconsistent diagram ?

23. What is the other name for Redlich kister method and why it is used ?
The other name for redlich kister method is zero area method. It is used to find the
consistency test for VLE data.
24. Draw the diagram for thermodynamics consistency by Redlich – Kister method ?
25. What is the equation for coexistence method ?
y i -x I
dn P= dy1
y I (1  y I )
dP P  y i -x I 

dy1 y I (1  y I )
26. What are the cases used in the data at mid port ?
Cases 1 : if A = B then n 1  B / 4 & n 2  A / 4

Cases 2 : if A =2B then n 1  2 / 9 B & n 2  2 / 9 A
Cases 3 : if A = 3B then n 1  3 / 16 B & n 2  3 / 16 A
27. Draw the equilibrium diagram for constant pressure ?

28. Draw the P – xy diagram for constant temperature
29. What are the cases used in slopes of n curves ?
If one of the n curves has a maximum at a certain concentration the other curve
should have a minimum at the same composition
30. What is the equation for partial pressure data ?
dnP1 dnP2
X1   x2
dx1 dx1
x1 dP 1 x dP 2
 2
P1 dx1 P2 dx1
33. What is the condition for VLE data ?
The conditions of equilibrium requires that the fugacity of a component in the liquid
phase be equal to that in the vapour phase.
34. Write the relation in which the model free energies are related to the fugacity of
the substance ?
The molar free energies are related to the fugacity of the substance by G = RT n F+c
G – Gibbs free Energy
R – Gas constant
T – Temp
F – Fugacity
35. In which way the first law of thermodynamic expressed
The first law of thermodynamics expressed as dQ = du + dw

36. What is the criteria of phase equilibrium ?
The irreversible process in contract occurs with a finite driving force and they cannot
be reversed by infinitesimal change on the external conditions.
37. What is single component system ?
The thermodynamic equilibrium in a system consisting of two or more phases of a

single substance we can treat the equilibrium between vapour and liquid phase of a
single substance at a constant T & P.
38. How the chemical potential is related to fugacity ?
The chemical potential is related to fugacity by

Mi = RT n f i  c
R – Gas constant, T – Temp, f i - fugacity
39. Write the equation for fugacity of a substance in vapour phase?
fi v  i p
yi - mole fraction
 i ' Fugacity coefficient
40. Write the equation for fugacity of substance in liquid phase?
f i L  xi iL f i 0
 i  activity coefficient
x i  mole fraction
f i  fugacity of the component in the standard state
41. What are the two types of azeotropes?
a) Maximum boiling azeotrope

b) Minimum boiling azeotrope
42. What is the equation for criterica of phase equilibrium at constant u & v?
du=Tds-pdv
if U & V is constant then
dsu,v =0
43. What is the equation for criterica of phase equilibrium at const T & V?
dA =-pdv –sdT
if T & V are constant then dAT,V =0
44. What is the equation for criterica of phase equilibrium at constant P & T?
dG = du + pdv + vdp - Tds – sdT

at if P & T are constant then dGT,P =0
45. What is the reason for minimum and maximum boiling azeotropes?
Minimum boiling – positive deviation

Maximum boiling – negative deviation
PART – B
1. 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.
Solution:
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 x i
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
d 2  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
d 2  G  d x d 1 d
2   In f 1  1 In f 1  In f 1
dx1  RT  dx1 x2 dx1 x2 dx1
d 2 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.
2. Using the criterion of phase equilibrium, show that the change in entropy during
phase changes can be calculated from the latent heat of phase change and the
absolute temperature as S = H/T.
Solution:
Suppose that two phase a and b are in equilibrium. Using the definition of free
energy
Ga = Ha – TSa, 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
3. Deduce the Clapeyron equation using the criterion of equilibrium, equation
Solution:
In chapter we have derived the Clapeyron equation using Maxwell’s relations.
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 Ga
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 b

dT V  V 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.
P2S H  1 1 
In    
P1S R  T1 T2 
Where P1S and P2S are the vapour pressures at temperatures T1 and T2 respectively.
4. Using the criterion of phase equilibrium show that the osmotic pressure over an
ideal solution can be evaluated as
RTx A
Posmotic =
VB
Where xA is the mole fraction of solute and VB is the molar volume of the solvent.
Solution:
Consider a vessel which is divided into two compartments by a semi-permeable

membrane. Pure solvent (say, water) is taken in one of the compartments and a
solution (say, sucrose in water) is taken in the other. Let T be the temperatures on
both sides of the membrane and P be the pressure. While the membrane is
impermeable to the flow of the solute, it permits the flow of solvent into the solution.
This phenomenon of a solvent diffusing through a membrane which is permeable to
it, but is impermeable to the solute, is known as osmosis.
Osmosis is caused by the difference in the chemical potentials of the solvent on the
two sides of the membrane. At a given pressure, the chemical potentials of the solvent
is greater than that of the solvent in the solution. By increasing the pressure at the
solution side of the membrane, the chemical potential of the solvent in the solution
can be increased. When the pressure is increased to P’ keeping the temperature
constant, the chemical potential of the solvent in the solution would become equal to
that of the pure solvent at pressure P, and the diffusion would stop. If the pressure is
increased above P’, the direction of diffusion would be reversed. In that event, the
solvent would diffuse from the solution to the pure solvent. This process is known as
reverse osmosis. The excess pressure P’ – P to be applied over the solution at constant
temperature to arrest the process of osmosis is known as the osmotic pressure. Thus,
osmotic pressure is
Posmotic = P’ – P
Let the mole fraction of the solutes constituting the solution be represented by xA
and the mole fraction of the solvent be represented by xB. Let ’B denotes the chemical
potential of the solvent at pressure P’. equation relates the chemical potential of a
component in a solution to its fugacity. Thus.
 B'  RT In f B  C
The chemical potential of the pure solvent at pressure P’ is given by
 B'  RT In fB  C
Combining the preceding two equation, we get
fB
 B'   B' *  RT In
fB
In this equation,  B' is the chemical potential of pure solvent at pressure P’, fB is
its fugacity and f B is its fugacity in the solution. Since the solution is ideal, the above
equation may be simplified utilizing the Lewis-Randall rule which relates fB as f B = xB
fB. Now we get the following result for the chemical potential of the solvent in the
solution at pressure P’.
 B'   B'  RT In x B
Under equilibrium this should be equal to the chemical potential of the solvent
in the pure state at pressure P which may be denoted by  B' . That is
 B'  RT In x B   B*
Re arranging this, we obtain
 B' *   B*   RT In x B
The left-hand-side of this equation involves the chemical potentials of pure B at
pressure P and P’. since the temperature is constant, we can use Eq. to replace the
chemical potential in terms of the pressure and volume. Equation leads to dG=d =V
dP, Thus
P'
P
VdP   RT In x B
Since volume of a liquid is not affected by change in pressure, the integral in
this equation can be easily determined in terms of the molar volume VB. Thus
VB  P '  P    RT in x B
Noting the definition of the osmotic pressure, the preceding equation may be written
as
RT In x B RT In  1-x A 
Posmotic   
VB VB
For small values of xA, we can use the approximation In(1-xA) =-xA. Thus we get
 RT x A
Posmotic 
VB
5. n-Heptane and toluene form ideal solution. At 373 K, their vapour pressures are
106 and 74 kPa respectively. Determine the composition of the liquid and vapour in
equilibrium at 373 K and 101.3 kPa.
Solution:
P1s  106; P2s  74, P =101.3
101.3 =74 +  106-74  x
Where x is the mole fraction of heptane in the liquid. On solving this, we get x =0.853
From Equation.
Y=0.853 × 106/101.3 =0.893
The liquid and the vapour at the given conditions contain respectively 85.3% (mol)
and 89.3% (mol) helptane.
6. An equimolar solution of benzene and toluene is totally evaporated at a constant

temperature of 363 K. At this temperature, the vapour pressures of benzene and
toluene are 135.4 and 54kPa respectively. What are the pressure at the beginning
and at the end of the vaporization process?
Solution: Put x = 0.5 in Eq. then P=94.7 kPa. This is the pressure at the beginning of
vaporization. Equation can be written as
P  Ps
x  5 25
P1  P2
Substitute this in Equation. Then,
P  Ps Ps
y  s 2s  1
P1  P2 P
On rearranging this equation, we get
P1s PsS
P s
P1  y  P1s  P2s 
Put y = 0.5 in this. Thus, we get P = 77.2 kPa. (This is the pressure at the end of
vaporization).
7. The vapour pressure of acetone (1) and acetonitrile (2) can be evaluated by the
Antoine equations.
294046
In P1s  14.5463 
T  35.93
2945.47
In P2s  14.2724 
T -49.15
Where T is in K and P is in kPa. Assuming that the solutions formed by these are
ideal, calculate.
(a) x1 and y1 at 327 K and 65 kPa
(b) T and y1 at 65 kPa and x1 = 0.4
(c) P and y1 at 327 K and x1 = 0.4
(d) T and x1 at 65 kPa and y1 = 0.4
(e) P and x1 at 327 K and y1 = 0.4
(f) The fraction of the system that is liquid and the composition of the liquid and
vapour in equilibrium at 327 K and 65 kPa when the overall compositon of the
system is 70 mole per cent acetone.
Solution (a) From the Antoine equations, at 327 K,

2940.46
In P1s  14.5463   4.4441 P1s  85.12 kPa
327  35.93
2945.47
In P2s  14.2724   3.6715, P25  39.31 kPa
327  49.15
Using Equation
65=39.31 + x1(85.12 -39.31) x1 = 0.5608
Using Equation
Y1 = 0.5608 × 85.12/65 = 0.7344
(b) Equation can be written as
65 = P2s  0.4  P1s  P2s 
The temperature is to be determined by trial so that this equation is satisfied. Assume
T = 340 K. Antoine equations give P1s  131.1kPa and P2s  63.14 kPa. Therefore,
P2s  0.4  P1s  P2s   90.32 kPa  65 kPa
Assume T = 330 K. At this temperature P1s  94.36 kPa and P2s  44.02 kPa. Thus,
P2s  0.4  P1s  P2s   64.15 kPa < 65 kPa
Assume T= 330.4 K. P1s  95.65 kPa and P2s  44.68 kPa. Thus,
P2s  0.4  P1s  P2s   65.07 kPa
Thus, equilibrium temperature, T = 330.4 K. Using Eq.
Y1 = 0.4 × 95.65/65 = 0.5886

(c) At 327 K, we have P1s  85.12 kPa and P2s  39.31 kPa. Here x1 = 0.4. Using these
values in Eq. We get P = 57.63 kPa. Using Eq.
y1 = 0.4 × 85.12/57.63 = 0.5908

(d) Equation can be written as
P  Ps
x1  s 2 s
P1  P2
When this is substituted into Equation We get
Ps P  Ps
y1  1  s 2 s
P P1  P2
Here y1 = 0.4 and P= 65. therefore,
P1s 65  P2s
  0.4
65 P1s  P2s
Assume a temperature and calculate the vapour pressures using Antoine Equations.
Substitute the vapour pressure values in the above equation. See whether the Left-
hand side = 0.4. This is repeated till the left-hand side of the above equation becomes
equal to 0.4.
At T =334 K, P1s  107.91 kPa and P25  51.01kPa.
P1s 65  P2s
  0.408
65 P1s  P2s
As this is very close to the required value of 0.4.T=334 K
Using Equation we get
y P 0.4  65
x1  1 s   0.241
P1 107.91
(e) At 327 K, we have P1s  85.12 kPa and P2s  39.31kPa. Here y 1  0.4
Equation relates y to x. When P in Equation is eliminated using Equation we get
x1 P1s
y1  s
P2  x1  P1s  P2s 
This can be rearranged to the following form.
y1 P2s
x1  s
P1  y1  P1s  P2s 
Substituting the given values, we get x1 = 0.2354.
From Equation
x P s 0.2354  85.12
P 1 1   50.09 kPa
y1 0.4
(f) The composition of the vapour and liquid in equilibrium at P= 65 kPa and T =327 K
were determined in part (a). They are x1 = 0.5608 and y1 = 0.7344. let f be the fraction of
the mixture that is liquid. Then an acetone balance gives
1  0.7  f  0.5608 + (1-f)  0.7344
Solving this, we get f= 0.1982. That is, 19.82 % (mol) of the given mixture is liquid.
8. Example: Mixtures of n-Heptane (A) and n-Octane (B) are expected to behave
ideally. The total pressure over the system is 101.3 kPa. Using the vapour pressure
data given below.
(a) Construct the boiling point diagram and

(b) The equilibrium diagram and
(c)Deduce an equation for the equilibrium diagram using an arithmetic average 
value.
T,K 371.4 378 383 388 393 398.6
Pa,kPa 101.3 125.3 140.0 160.0 179.9 205.3
PB,kPa 44.4 55.6 64.5 74.8 86.6 101.3
Solution Sample calculation: Consider the second set of data T= 378 K; PA =125.3 kPa;
PB =55.6 kPa.
Using Equation
101.3 =55.6 +xA (125.3 -55.6)
Therefore, xA = 0.656
Using Equation we see
yA =0.656 × 125.3 /101.3 = 0.811
Relative volatility is
  PA / PB  125.3 / 55.6  2.25
These calculations are repeated for other temperatures. The results are tabulated
below:
T, 371. 378 383 388 393 398.

K 4 6
xA 1.00 0.65 0.48 0.31 0.15 0
0 6 7 2 7
yA 1.00 0.81 0.74 0.49 0.27 0
0 1 2 9
 2.28 2.25 2.17 2.14 2.08 2.02
(a) Plot, of T versus x and y gives the boiling point diagram

(b) Plot of y against x gives the equilibrium diagram
(c) The average of the last row gives  =2.16. Use this value of  in Equation to get the
equation for the equilibrium curve.
 xA 216 x A
YA  
1    1 x A 1  1.16 x A
9. Prove that at the azeotropic composition, the vapour and liquid have the same
composition.
Solution: Refer the Duhem-Margules equation , Equation


d In f 1   d  In f 
2
d  In x1  d  In x 2 
Assuming the vapour to behave ideally, it can be written as
d  In p1  d  In p2 

d  In x1  d  In x 2 
Figure: Activity coefficient versus concentration.
Nothing that d In z = dz/z, the above result can be written as
x1 dp1 x2 dp 2

p1 dx1 p2 dx2
In binary mixtures, dx1 =- dx2 , so that Equation, can be written as
dp1 p1 x2 dp 2

dx1 x1 p2 dx1
The total pressure, P = p1  p2 . Differentiating this with respect to x1, we get
dp dp1 dp 2
 
dx1 dx1 dx1
Eliminating  dp1 / dx1  in Equation using Equation and rearranging we get
dp dp 2  x2 p 1 
 1 
dx1 dx1  x1 p2 
For a maximum or minimum on the total pressure curve, (dP/dx1) is zero. Then
Equation necessitates that either the terms in the parenthesis should be zero or
 dp2 / dx1  is zero. If the later term is zero the partial pressure would be unaffected by
concentration changes, which is not true. Hence, at the point of azeotropism, we have,
the following relation.
x p x p y
1  2 1  0 or 1  1  1
x1 p2 x 2 p2 y 2
Since x2 =1 –x1 and y2 = 1-y1, the above result means that at azerotropic conditions, x1=y1
or the vapour composition and liquid composition are the same.
10. The azeotrope of the ethanol-benzene system has a composition of 44.8% (mol)
ethanol with a boiling point of 341.4 K at 101.3 kPa. At this temperature the vapour
pressure of benzene is 68.9 kPa and the vapour pressure of ethanol is 67.4 kPa.
What are the activity coefficients in a solution containing 10% alcohol?
Solution: Lot benzene be component 1 and alcohol component 2.For the azeotrope
P 1013 P 1013
1    1.4702 1    15030
P1S 68.9 P1S 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 2
 x In  2   1+ 0.448  In 15030   1.3305
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  2  2  0.02519
 A / B  x1  x2  1.3305 / 1.9106  0.9  0.1
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
11. 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.
Solution: 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  199.62 kPa; 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 2
 x In   0.585   0.2083 
A  In  1  1  2 2   0.6783  1    1.3927
 x1 In  1   0.415   0.6783 
2
 x In  1   0.415   0.6783 
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 =0.1176
 A/B  x1 +x2  0.8  -1.3927  /  -22822  +0.2
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   1 x1 , y 2   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  1 x1 P15  1 x1  12
This can be rearranged to give
1 1
y1    0.9472
 2 x2 P25 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.
12. A stream of isopropanal-water is mixture is flashed into a separation chamber at

353 K and 91.2 kPa. A particular analysis of the liquid product showed an
isoproponal content of 4.7 % (mol), a value that deviated from the norm. It is
suspected that an air leak into the separator might have caused this. Do you agree?
The vapour pressures of the pure propanol and water are 91.11 kPa and 47.36 kPa
respectively, and the van Laar constants are A = 2.470 and B = 1.094.
Solution: For x1 = 0.047, x2 = 0.953, A = 2.47 and B = 1.094, Equitation gives

 1  7.388 and  2  1.011
The total pressure corresponding to this equilibrium composition is
P   1 x1 P1s   2 x2 P2s  0.047  7.388  91.11  0.953  1.011  47.36  77.27 kPa
This is less than the total pressure. This error must have been caused by an air-leak.
13. The following values refer to the Wilson parameters for the system acetone (1) –
water (2):
A12 = 1225.31 J/mol, a21 = 6051.01 J/mol, V1 = 74.05 × 10-6 m3/mol, V2 = 18.07 × 10-6
m3/mol.
The vapour pressures are given by
2795.817 3799.887
In P1s  14.39155  , In P2s  16.26205 
T  43.198 T  46.854
Where P is in kPa and T is in K. Calculate the equilibrium pressure and composition
of
(a) Vapour in equilibrium with a liquid of composition x1 = 0.43 at 349 K.
(b) The liquid in equilibrium with a vapour of concentration y1 = 0.8 at 349K.
Solution:
Using the Antoine equations ,at 349 K, the vapour pressures are calculated as
P1s  190.37 kPa , P2s  39.87 kPa

The parameters in the Wilson equation A12 and A21 are calculated using
Thus,
V2 a 18.07 1225.31 
A12  exp   12   exp     0.1600
V1  RT  74.05  8.134  349 
V a 74.05 6051.01 
A21  1 exp   21   exp     0.5092
V2  RT  18.07  8.314  349 
(a) Now from Eq.(8.72), we obtain
0.16 0.5092
1n  1  1n(0.43  0.16  0.57)  0.57   
 0.43  0.16  0.57 0.5092  0.43  0.57 
 1n(0.5212)  0.57( 0.33843)  0.4587
0.16 0.5092
1n  2  1n(0.5092  0.43  0.57)  0.43   
 0.43  0.16  0.57 0.5092  0.43  0.57 
=-1n(0.7890)-0.43(-0.33843)=0.3826
Thus γ1 = 1.5820 and γ2 = 1.4661.

The pressure is calculated as
P   1 x1 P1s   2 x2 P2s  1.5820  0.43  190.37  1.4661  0.57  39.87  162.82 kPa
The vapour composition is found out from the relation y1 P   1 x1 P1s

 1 x1 P1s 1.5820  0.43  190.37
y1    0.7954
P 162.82
(b) Since the liquid composition is not known, the activity coefficients cannot be
calculated. Assume γ1 = γ2 =1. The relation Pyi  xi P1s can be written for component 1
and component 2, which on rearrangement gives
x1  ( Py1 / P1s ) and x 2  ( Py 2 / P2s )
Since x1+x2=1,
Py1 Py 2
 s 1
P1s P2
Therefore,
1
P
( y1 / P )  ( y2 / P2s )
1
s
Using this, the pressure is found out.

1
0.80 0.20 
P      108.48 kPa
 190.37 39.87 
Use this pressure to calculate x1.
y P 0.80  108.48
x1  1 S   0.4559, x 2  0.5441
P1 190.37
Activity coefficients can now be determined for this composition using Wilson
equations.
 A12 A21 
In  1   In  x1  A12 x2   x2   
 x1  A12 x2 A21 x1  x2 
 A12 A21 
In  2   In  x2  A21 x1   x1   
 x1  A12 x2 A21 x1  x2 
In 1 = - In (0.4559 + 0.16  0.5441) + 0.5441
 0.16 0.5092 
 0.4559  0.16  0.5441  0.5092  0.4559  0.5441 
= - In (0.5430) + 0.5441 ( - 0.3613) = 0.4141
In 2 = - In (0.5092 0.4559+0.5441) – 0.4559
 0.16 0.5092 
 0.4559  0.16  0.5441  0.5092  0.4559  0.5441 
= - In (0.7762) – 0.4559 ( - 0.3613) = 0.4181
Therefore, 1 = 1.513 and 2 = 1.5191.
Now the pressure is recalculated incorporating the activity coefficient values. The
equation
1
P
 y1 / P    y2 / P2S 
1
S
Become
1
P
 y1 /  P     y2 /  2 P2S  
S
   1 1 
Substituting the values, we get P = 164.48 kPa. Liquid compositions are now
recalculated.
y1 P 0.80  164.48
x1    0.4568
 1 P1S
1.513  190.37
So that x2 = 0.5432. Activity coefficients under this condition are
0.16 0.5092
In  1   In  0.4568+0.16  0.5432   0.5432   
 0.4568  0.16  0.5432 0.5092  0.4568  0.5432 
I
= - In (0.5437) + 0.5432 (-0.3621) = 0.4127
In
0.16 0.5092
 2  1n(0.5092  0.4568  0.5432)  0.4568   
 0.4568  0.16  0.5432 0.5092  0.4568  0.5432 
= - 1n (0.7758)-0.4568 (-0.3621) = 0.4193
These give γ1 =1.5109 and γ2 = 1.5208.

1
P  164.48
 yi /( 1 P1 )   y2 /( 2 P2s )
s
This is same as the previous value calculated for P. Therefore, P = 164.48 kPa and x 1 =
0.4568.
14. The system methanol-methyl ethyl ketone forms an azeotrope containing 84.2%
(mol) methanol at 337.5 K and 101.3 kPa. The vapour pressures of the pure species
are given by the Antoine equation
B
1n P = A -
T-C
Where P is in kPa and T in K. The constants of the Antoine equation are given below:
A B C
Methanol 16.12609 3394.286 43.2
Methyl ethyl ketone 14.04357 2785.225 57.2
Determine the parameters in the Wilson equation.
Solution: The vapour pressures at 337.5 K are calculated using Antoine equations.
P1s  98.76 kPa , P2s  60.76 kPa
At the azeotropic composition (x1 = 0.842, x2 = 0.158) the activity coefficients are:
P 101.3 P 101.3
1  s
  1.026,  2  s   1.667
P1 98.76 P2 60.76
Equation can be rearranged as
x2 / x1
  2 x2 
   1  x1  A12 x2   1
 1   A12 x1 /( x1  A12 x2)   ( x1 / x2 )1n  1 ( x1  A12 x2 ) 
A12 is calculated by substituting the known values in the above equation.
0.158 / 0.842
 1.667  0.158 
 
 1   0.842 A12 /(0.842  0.158 A12 )  (0.842 / 0.158)1n 1.026(0.842  0.158 A12 ) 
 1.026(0.842  0.158 A12 )  1
0.1876
 0.2634 
 
 1   0.842 A12 /(0.842  0.158 A12 )  5.3291n[(0.8639  0.1621A12 )] 
 (0.8639  0.1621A12 )  1
A12 = 0.935. Substitute this value in equation and calculate A21. So, A12 = 0.467
15. A mixture contains 45% (mol) methanol (A), 30% (mol) ethanol (B) and the rest
n-propanol(C). Liquid solution may be assumed to be an ideal and perfect gas law
is valid for the vapour phase. Calculate at a total pressure of 101.3 kPa.
(a) The bubble point and the vapour composition

(b) The dew point and the liquid composition.
The vapour pressures of the pure liquids are given below:
Temperature,
333 343 353 363
K
PA, kPa 81.97 133.29 186.61 266.58
PB, kPa 49.32 73.31 106.63 166.61
PC, kPa 39.32 62.65 93.30 133.29
Solution: The vapour pressure of the components are plotted against temperature so
that interpolation of vapour pressure can be done easily.
(a) If the vapour phase can be treated as an ideal gas and liquid phase, an ideal
solution, the K-values can be written as K i  yi / xi  Pis / P . Equation can be written as
xi Pis
y  K x  
i i i
P
1
Now temperature are assumed till the above equality is satisfied. It is seen that at344
K,
x P i i
s
 0.98
P
And at 345 K,
xi Pis
 P
 1.015
The bubble-point lies between 344 and 345 K. By interpolation, the bubble-point is
obtained as 344.6 K. At this temperature the vapour pressures are obtained from the P
vs T plots. PAS  137.3 kPa , PBS  76.20 kPa and PCS  65.40 kPa .
Component Xi PiS K i  PiS / P yi  Ki xi

Methanol 0.45 137.30 1.355 0.610
Ethanol 0.30 76.20 0.752 0.226
Propanol 0.25 65.40 0.646 0.162
 Ki xi 0.998
The equilibrium vapour contains 61% methanol, 22.6% ethanol and 16.2% propanol.
(c) Equation (8.85) for the present case becomes
yi yi P
x   K
i 
PiS
 1.00
i
The dew-point temperature is to be determined by trial such that the above relation is
satisfied. By trial, it can be seen that at 347.5 K,
PA  153.28 kPa, PB  85.25 kPa and PC  73.31kPa .
S S S
Component yi PiS K i  PiS / P xi  yi / Ki

Methanol 0.45 153.28 1.5131 0.2974
Ethanol 0.30 85.25 0.8416 0.3565
Propanol 0.25 73.31 0.7237 0.3454
 yi / K i 0.9993
The values in the last column are the liquid composition at the dew point. Thus,
liquid contains 29.7% methanol, 35.7% ethanol, and 34.5% propanol.
16. A hydrocarbon mixture contains 25% (mol) propane, 40% (mol) n- butane and
35% (mol) n-pentane at 1447.14 kPa. Assume ideal solution behaviour and
calculate
(a) The bubble-point temperature and composition of the vapour

(b) The dew-point temperature and the composition of the liquid
(c) The temperature and the composition of the liquid and vapour in equilibrium
when 45% (mol) of the initial mixture is vapourised. (The values of K i can be
obtained from Figure
Of Chemical Engineer’s Handbook,5th ed.)
Solution:
(a) Assume temperature, say 355.4 K, and the Ki values are found out from the
nomograph [Fig.(b) in Chemical Engineer’s Handbook]. The products of Ki and xi are
calculated and their sum  xi Ki is found out. The results for two temperatures 355.4
K and 366.5 K are shown below.
T= 355.4 K T= 366.5 K
Component Ki kixi Ki kixi
xi
Propane 0.25 2.000 0.500 2.30 0.575

n-Butane 0.40 0.780 0.312 0.90 0.360
n-pentane 0.35 0.330 0.116 0.40 0.140
 Ki xi 0.928 1.075
The bubble-point temperature lies between 355.4 K and 366.5 K. By interpolation, the
temperature is found out to be 361 K. The calculations are carried out at this
temperature and the results are as follows:
Component xi Ki Ki xi
Propane 0.25 2.12 0.530
n-Butane 0.40 0.85 0.340
n-Pentane 0.35 0.37 0.130
 Ki xi 1.000
Since x K
i i is approximately 1.00, the bubble-point temperature is 361 K. The
values in the last column are the mole fraction of various components in the vapour.
At the bubble-point, the vapour contains 53% propane, 34% butane and 13% pentane.
(b) At the dew-point temperature, y /K

i i  1 . At 377.6 K, this value is 1.1598 and at
388.8 K and it is 0.9677.
T= 377.6 K T= 388.8 K
Component yi Ki Ki yi/ki
yi/ki
Propane 0.25 2.6 0.0962 2.9 0.00862
n-butane 0.40 1.1 0.3636 1.3 0.3077
n-pentane 0.35 0.5 0.7000 0.61 0.5738
 yi / K i 1.1598 0.9677
By interpolation, the dew-point temperature is found to be 387 K. The calculations for

this temperature is given below.
Component yi Ki yi / K i
Propane 0.25 2.85 0.0877
n-Butane 0.40 1.25 0.3200
n-Pentane 0.35 0.59 0.5932
 yi / K i 1.0009
The last column in the above table is the liquid compositions. The equilibrium liquid
at the dew point contains 8.77% propane, 32% butane and 59.32% pentane.
© In the following calculations, temperature is assumed so as to satisfy Equation .
For a basis of 100 mol of the initial mixture, F = 100 mol, V = 45 mol and L = 55 mol.
Equation becomes
zi
  0.45
1  L /(VKi )
T= 366.5 K T= 377.6 K
z
Component Ki Ki
i
zi / 1  L /(VKi ) zi / 1  L /(VKi )
Propane 0 2.3 0.1632 2. 0.1701
. 0 6
2
5
n-Butane 0 0.9 0.1696 1. 0.1895
. 0 1
4
0
n-Pentane 0 0.4 0.0863 0. 0.1016
. 0 5
3
5
zi / 1  L /(VKi )
0.4191 0.4612
From the calculation given above, we see that the equilibrium temperature is
between 366.5 K and 377.6 K. By interpolation, T= 374.6 K.
T= 374.6K
Component Zi Ki
zi / 1  L /(VKi )
Propane 0.25 2.50 0.1679
n-Butane 0.40 1.08 0.1876
n-Pentane 0.35 0.48 0.0987
zi / 1  L /(VKi ) 0.4542
Comparing Equations (1) and (2), we can see that
zi / 1  L /(VKi )
yi 
zi / 1  L /(VKi )
These are calculated using the values in the last column. Corresponding xi values are
found out using the material balance Equation.
Fzi = Vyi + Lxi
The results of the calculation are given below:
Component yi xi
Propane 0.3697 0.1521
n-Butane 0.4130 0.3894
n-Pentane 0.2173 0.4586
17. The activity coefficients for component 1 in a binary solution can be represented
2 3 4
by InY1  ax2  bx2  cx2 , where a, b and c are concentration independent
parameters. Derive an expression for In Y 2.
Solution:
Equation may be written as

x1
In 2    0x1 d( In 1 )
x2
For the present case,
d In  1 (2 ax2  3bx22  4cx23 )dx2
Substituting this in the above equation we get
x1
In  2    ( ax1  3bx1 x2  4cx1 x22 )dx2
0
x1
=   2 ax1  3bx1 (1  x)  4cx1 (1  x)2  dx1
0
3 8
=  a+ b  2c  x12   b  c  x13  cx14
 2   3 
UNIT – III
CORRELATION AND PREDICTION OF PHASE EQUILIBRIA
PART - A
1. What is Gibbs duhem equation?
  ni d i  0 is known as Gibbs Duhem equation

 T 1 p
2. Draw the diagram for activity coefficients for carbon disulfide acetone solution?
Activity coefficient for carbon disulfide acetone.
3. What is Henry law?
L
f 2  k2 x2
Where k2 is a characteristic constant for component 2 and depends only on I & p is

called Henry’s law
4. What is activity coefficient for margules equation?
n 1  x22  A12  2  A21  A12  x1 

n 2  x12  A21  2  A12  A21  x2 
5. What is activity coefficient for van laar equation?
B12 B21
n  1  n  2 
1   B12 x1 / B21 x2  1   B21 x2 / B12 x1 
2 2
6. What is the activity coefficient for Wilson equation?
G12 G21
n 1  n  x1  x2G12   x2
x1  x2G12 x2  x1G21
G12 G21
n 2  n  x2  x1G21   x1
x1  x2G12 x2  x1G21
7. What is the linear form of margules equation?
n 1
  A12  2  A21  A12  x1 
x22
n 2
  A21  2  A12  A12  x2 
x12
8. What is the linear form of van laar equation?
1 1 B12 x1
 
n 1 B12 B21 x2
1 1 B21 x2
 
n 2 B21 B12 x1
9. How can you express the margules equation in Q linear form.

 A12   A21  A12  x1 is the expression for margules equation.
x1 x2
10. How can express the vaan laar equation in Q linear form
x1 x2 1 B12  B21
  x1
Q B12 B12 B21
Is the expression for van laar equation
11. What is the advantage of activity coefficient.
i. It provides a framework for viewing and analyzing phase equilibrium

ii. It facilitates experimentation by a reducing the amount of data required.
12. What is the expression for fugacity of Gas liquid?
The expression for fugacity of Gas and liquid is
iG   T1 PY
1 i s
1
ic   T1 P1 xi1s 
13. How can we determine the phase equilibrium via an equation of state?
The phase equilibrium via an equation of state is determined by a) single component

equilibrium b) multicomponent equilibrium.
14. Explain the ideal liquid solution?
L
The ideal liquid solution equation model is f i  f i L xi i
15. What is the fugacity coefficient?

f
The fugacity coeffienct is denoted by i  i
pi
Fi  Fugacity of species i
  pressure of species i
16. What are the guidelines for ideal solution model?
1. It is always a good approximation at low pressure

2. It is always a good approximation at any pressure whenever I is present in large
excess and becomes exact in the limit as yi
17. What is equilibrium ratio?
The equilibrium ratio is denoted by k and it is defined as
Yi=Jixi
18. Draw the diagram for partial and total pressure of carbon and acetone?
This is the partial and total pressure of carbone disulfide and acetone.
19. Draw the diagram for activity coefficient for chloroform acetone?
Activity coeffeicnt for chloroform acetone solution at 37.17C
20. What is PR equation of State?
 
 
c
i 2  xiAij  Z  1  2 B
A  Bi j 1 Bi
n i    n   Z  1  n  Z  B 
2 2B  B

A 


1 2 B B
Is the PR equation of state
21. What is relative volatility?
The relative volatility is defined as

Y /x
 1 1
Y2 / x2
22. Vapour liquid equilibrium data for the n hexane chlorobenzene system at a
constant pressure of 759.8 mm Hg. The Antoine equation of liquid densities at 25C
Solution:
86.17
V1   130.8cc / gmol
0.659
112.56
V2   101.7cc / gmol
1.107
23. What is the expression for total pressure?
The expression for total pressure is
P  x1 p1 *  1  x2 p2 *  2
24. What are Azeotropes?
Azeotropes always occur at a maximum or minimum in either the pn or Tx curves.
25. What is the equation for single data point the simultaneous solution?
The equation for single data point the simultaneous solution CS

x2
  x1
 
  2 x2 
  G12 x2   x1  
1       n  1 x1  G12 X 2  
  x  G12 x2   x2  
 1  x1G12 x2   1
26. What is the condition applied for azeotrope?
The condition applied for azeotrope is
PA  B

PB   A
27. What is the equation for binary system at low pressure?
The equation for binary system at low pressure is

d np1 d np2
x1  x2 0
dx1 dx1
28. Draw the diagram for thermodynamic consistency test. With activity coefficient
The thermodynamic consistency test will activity coefficient is

29. What is the area thermodynamic test for the system chloroform ethanol?
A)Area thermodynamic test system chloroform ethanol
30. Draw the diagram fro constant pressure for partially miscible binary system?
The diagram for constant pressure for partially miscible binary system.
31. What is the diagram for constant temperature for partially miscible binary
system?
The diagram for constant temperature for partially miscible binary sytem.
32. Draw the diagram for liquid liquid solubility envelope for a binary system
The diagram for liquid solubility envelope for a binary system.
33. Write the equation for excess Gibbs free energy of mixing?
The equation for excess Gibbs free energy of mixing is
g  g ' h '
34. VLE data at 25 are available for the three binary systems and the ternary system
comprised of cyclohrane n-heptane and toluence.
Solution:
P1= 97.58, P2 = 45.72 P3 =28.45
 1  1.085,  2  1.072  3  1.224
P1 = 35.26 mm Hg
P2 = 16.32 mm Hg
P3 = 11.63 mm Hg
P= 35.26 +16.32 +11.63 = 63.21 mm Hg
35.26
1   0.558
63.21
16.32
2   0.258
63.21
35. What is the two different approaches?
The two different approaches are activity coefficient approach and equation of state
approach.
36. What is the equation relating the internal energy and entropy?
The equation relating the internal energy and entropy is
dT  p 
ds  CV   , dv
T  T 
37. What is the ideal gas value for entropy?
The ideal gas value for entropy is
dT dp
ds ig  C igpR
T p
Ig denotes the ideal gas value
38. Define the residual Gibbs energy?
The residual Gibbs energy is GR = G-Gig where G × Gig are actual and the ideal gas
value of Gibbs energy.
39. What is the equation for Gibbs energy at const T?
The equation for Gibbs energy at constant T is
GR V R
d  dp at constant T
RT RT
40. What is the equation for residual properties by cubic equation of state?
The equation for residual properties by cubic equation of state is
RT a T 
p
V  b V   b V   b 
41. What are the two cases used in the cubic equation of state?
The two cases are used in the cubic equation of state is    and  = 
42. What is the two phase  &  in pure spaces?
The two phases  &  in pure spaces is G  G  where G and G  are molar or
specific Gibbs energes of individual phases.
43. What is pseudo reduced parameter for Tc & Pc
T P
Tor  and Ppx 
TPc Ppc
44. What is coefficient of volume expansion?
change of volume w.r.t temp at constant p


original volums
45. What is thermal compressibility?
Change of volume w.r.t pressure at constant T

k
original volums
46. What is the significance of deriving the thermodynamic relation?
1. Directly measurable properties like P, T & V

2. properties which cannot be measured directly like S1 & U.
PART – B
1.Construct the P - x - y diagram for the cyclohexane (1) –benzene (2) system at 313
K given that at 313 K the vapour pressures are P1 = 24.62 kpa and P2 =24.41. kpa.
s s
The liquid-phase activity coefficients are given by

In y1  0.458 x2 , In y2  0.458 x1
2 2
Solution:
Assume x1  0.4, then x 2  0.6. Therefore
In  1  0.458  0.6  0.16488;  1  1.1793.
2
Similarly,
In  2  0.458  0.4  0.0733;  2  1.0760.
2
The total pressure is determined as:

P   1 x1 p1s   2 x2 p2s  1.1793  0.4  24.62  1.0760  0.6  24.41  27.37 kpa
The vapour composition y1 is found out from
 1 x1 P1s
y1 
P
1.1793  0.4  24.62
=  0.4243
27.37
The above calculation is repeated for various x1 values. The results are tabulated
below:
x1 0 0.2 0.4 0.6 0.8 1.0

1 1.5809 1.3406 1.1793 1.0760 1.0185 1.000
2 1.000 1.0185 1.0760 1.1793 1.3406 1.5809
P 24.41 26.49 27.37 27.41 26.61 24.62
y1 0 0.2492 0.4243 0.5799 0.7540 1.0
The results are plotted taking P on the y-axis and x1 and y1 on the x –axis.
2. From vapour-liquid equilibrium measurements for ethanol-benzene system at

318 k and 40.25 kpa it is found that the vapour in equilibrium with a liquid
containing 38.4% (mol) benzene contained 56.6% (mol) benzene. The system forms
an azeotrope at 318 K. At this temperature, the vapour pressures of ethanol and
benzene are 22.9 and 29.6 kpa respectively. Determine the composition and total
pressure of the azeotrope. Assume that van Laar equation is applicable for the
system.
Solution:
Let benzene be component 1 and ethanol component 2. Using Equation the activity
coefficients are determined.
0.566  40.25 0.434  40.25

1   2.0043,  2   1.2383
0.384  29.6 0.616  22.9
Using these values in Equation the van Laar constants are evaluated.
2
 x In  2   0.616  0.2137 
2
A=In  1 1  2   0.6953 1   1.5499

 x1 In  1   0.384  0.6953 
2
 x In  1   0.384  0.6953 
2
B=In  2 1  1   0.2137 1   1.9597

 x2 In  2   0.616  0.2137 
The van Laar45 equations, Equation can now be written as
1.5499 x22 1.9597 x12
In  1 = 2
, In  2  2
 1.5499   1.9597 
 x1  x2   x1  x2 
 1.9597   1.5499 
For any liquid composition, the activity coefficients are calculated using these
equations. If the mixture forms an azeotrope at any composition, then as per
Equation, the following relations also give the activity coefficients.
P P
1  , 2
P1s P2s
Thus, activity coefficients calculated using the van Laar equations should also satisfy
the relation P   1 p1s   2 p2s at the azecotropic composition. The azeotropic
composition is obtained by trial assuming values of x. For X 1=0.6, 1=1.3830 and
2=1.7806.
P=  1 P1 =1.383029.6=40.937 kPa
s
P=  2P2 =1.7806 22.9=40.775 kPa

s
These values are so close that it can be assumed that the composition corresponds to
an azeotrope. Thus, the liquid mixture forms an azeotrope containing 60% benzene
which boils at 318k and approximately 40.86 kPa, (mean of 40.937 and 40.775 kPa).
3. The activity coefficients in a binary system are givenby In 1= A x22 , In y2=Ax12.
Show that if the system forms an azeotrope, then A   In( P1 / P2 )1 and the
s s
azeotropic composition is given by

1  1 Ps 
x1  1  In 1s 
2  A P2 
Solution: The activity coefficients are:

 1 = exp (A x22 ),  2 = exp (A x12 ),
The total pressure over the system is given by
2

P   1 x1 P1   2 x2 P2   exp( Ax2 )  x1 P1
s s s
  exp( Ax )   x P 
2
1 2 2
s
Differentiation this with respect to x1, we get
At the azeotropic composition, the P-x curve has a maximum or minimum. Therefore,
the above result is equated to zero and after rearrangement, we get
 ps 
(1  2 Ax1 x2 )  1s  exp  A  x12  x22     0
 P2 
The roots of this equation are given by
P1s
A( x  x )  In s
2
1
2
2
P2
And 2 Ax1 x2  1
The first root can be rearranged as

1  1 Ps 
x1  1  In 1s 
2  A P2 
Since the value of x1 lies between 0 and 1 it is essential that  A  1 In ( P1 / P2 )I.
s s
Nothing that x1x2 for a binary mixture is less than or equal to 0.25, the second root
leads to A 2. This condition usually results in partial miscibility. Thus, condition for
homogeneous azeotropy is  A  1 In ( P1 / P2 ) and A 2.
s s
4. The following results were obtained by experimental VLE

measurements on the system, ethanol (1)-benzene (2) at 101.3 kPa. Test whether the
data are thermodynamically consistent or not.
X1 0.003 0.449 0.700 0.900
Y1 0.432 0.449 0.520 0.719
P1s 65.31 63.98 66.64 81.31
,kPa
P2s 68.64 68.64 69.31 72.24
,kPa
Figure: Test for thermodynamic consistency with partial pressure data.
Solution Assuming that the gas phase behaves ideally, the activity coefficients are calculated
as
y1P y2 P
1  , 2
x1P1s x2 P2s
The values so calculated are listed below:
X1 0.00 0.44 0.70 0.90

3 9 0 0
1 223.3 1.58 1.13 0.99
2 0.841 1.475 2.34 2.92
In 5.58 0.068 - -
( 1 /  2 ) 0.734 1.082
In (  1 /  2  values are plotted against x1. The net area is found out. Since is not equal to
zero, the given experimental measurements so not satisfy the Redlich - Kister criterion Eq.
(8.97) for consistency.
5. The following data gives the composition versus total pressure for the system chloroform
(1) – ethy I alcohol (2) at 328 K are:
X1 0.0331 0.9652
P,kPa 40.84 84.88
Vapour pressures of chloroform and acetone at 328 K are 82.35 and 37.30 KPa respectively.
Estimate the constants in the Margules equation.
Solution:
The Margules equations are:

In  1 = x2 A + 2(B – A)x1
2
In  2 = x1 B + 2( A– A)x2
2
A  In y1 and B  In y 2 , where  1 , and y2 are the activity coefficient values when
the respective mole fractions tend to= zero. Assuming that the vapour behaves as
ideal ges, P1  P  P2 . That is,
 1 x1P1s  P   2 x2 P2s
Or
P   2 x2 P2s
1 
x1P2s
As x2 approaches 1,  2 , becomes unity and the above equation become
 P  x2 P2s
 
1 … (1)
x1P1s
Similarly
P  x1P1s
 2  … (2)
x2 P2s
(Note: Equations(1) and (2) are known as Carlson and Colburn relations for activity
coefficient.) Substitute the given data into Eq. (1) and Eq.(2), we get
40.84  (1  0.0331)37.30
 1   1.752
0.0331 82.35
84.88  0.9652  82.35

 2   4.157
(1  0.9652)37.30
Therefore, A=In 1.752=0.561 and B=In 4.157=1.424.

6. The following table gives the partial pressure of acetone versus liquid
composition for acetone (1)-water (2) system at 333 K.
X1 0 0.0 0.1 0.3 0.5 0.7 1.00

33 17 18 54 36 0
P1 0 25. 59. 78. 89. 94. 114.
, 33 05 37 58 77 63
k
P
a
The vapour pressure of water at 333 K is 19.91 kPa. Calculate the partial pressure of
water in the vapour phase.
Solution: Equation is the Gibbs-Duhem equation in terms of partial pressures

x1 d P1 x d p1
 2
p1 dx1 p2 dx1
It can be put in the following form:
d p2 x1 d P1

P2 (1  x1 ) P1
For pure water, x1=o, p 1=0 and p2 = P2 . For getting the partial pressure of water at
s
any composition, integrate the above equation between P1 and 0.
P2 P1 x1 d P1
In  
P2s 0 (1  x1 ) P1
Using the given data calculate x1/(1-x1) P 1 and this is plotted against P1 . The area
under the curve between the limits 0 and P1 gives the integral in Equation from which
the partial pressure P2 can be calculated. The results are given below:
X1 0.03 0.11 0.31 0.55 0.73 1.00

0
3 7 8 4 6 0
P1 ,
19.9 19.3 18.2 16.9 15.4 13.9
kP 0
1 1 7 9 2 0
a
7. A high boiling organic liquid is purified from non-volatile impurities by

allowing it to mix with steam directly at a total pressure of 93.30 kPa. The vapour
pressure data are given as follows:
Temperature, k 353 373

Vapour pressure of water, kPa 47.98 101.3
Vapour pressure of liquid, kPa 2.67 5.33
Assume that water and the organic liquid are immiscible and the impurities do not
affect the vaporization characteristics. The vapour pressures vary linearly with
temperature. Calculate under three-phases equilibrium
(a) The equilibrium temperature and

(b) The composition of the resulting vapour.
Solution (a) At 353 K, sum of the vapour pressures is 50.65 kPa and at 373 K it is
106.63 kPa. Since the vapour pressures vary linearly, the temperature at which the
sum of vapour pressures is 93.3 kPa is obtained by interpolation.
373  353
T *  353  (93.3  50.65)  368.2 K
106.63  50.65
At 368.2 K, the vapour pressure of water is 88.50kPa and that of the liquid is 4.80 kPa.
Since at three-phase equilibrium, the partial pressure is equal to the vapour pressure,
the ratio of mole fractions of the components will be same as the ration of vapour
pressures. Let y be the mole fraction of water in the vapour. Than
88.5
y= =0.9
93.30
The vapour contains 94.86% (mol) water vapour.
8. Assuming that benzene is immiscible with water, prepare a temperature-

composition diagram for benzene (1)- water (2) system at 101.3 kPa using the
following vapour pressure data:
T, 32 33 34 34 353 363 373

K 3 3 3 8
P2s 12. 19. 31. 37. 47.3 70.1 101.
40 86 06 99 2 1 3
,
k
P
a
P1s 35. 51. 72. 85. 100. 135. 179.
, 85 85 91 31 50 42 14
k
P
a
The boiling point of pure benzene at 101.3 kPa is 353.1 K.
Solution:
The three-phase temperature is first found out. At T*, P  P1  P2 .P1  P2 is
s s s s
calculated for each given temperature, and this is plotted against temperature. T* Is
the temperature at which P is equal to 101.3 kPa. This is found out to be 342 K. The
horizontal line CD in fig.8.23 is drawn at this temperature. The vapour pressures at
this temperature are P1 =71.18 kPa and
s
P2s =30.12 Kpa. The mole fraction of benzene
in the vapour represented by point E in Fig. 8.23 is 71.18/101.3 = 0.70
Figure: Temperature composition diagram for Example
The dew-point curve BE is plotted by choosing a temperature lying between 373 K

(boiling point of water ) and 342 K (the three-phase temperature). For example, take
T=353 K. The partial pressure of water at the dew point is equal to the vapour
pressure. For the dew-point temperature of 353 K, the partial pressure of water is
47.32 = (1-y)  P
Where y is the mole fraction of benzene in the vapour. We get, y = 0.5329.
This calculation is repeated for various temperature and the entire curve BE is
drawn. For getting the curve AE the procedure is the same. Here temperatures are
assumed between 342K and 353.1 K, the latter being the boiling point of pure benzene.
On the curve Ae, the partial pressure of benzene in the vapour equals its vapour
pressure. For example, for a dew-point temperature of 348. K,
85.31 = P y, or y = 0.8422
The following table gives the results of a few such calculations:
T,K 3 3 3 3 3 3
4 4 5 5 6 7
2 8 3 3 3 3
.
1
Y 0 0 0 1 - -
(curve . . . .
AE) 7 8 9 0
0 4 9 0
Y 0 - 0 - 0 0
(curve . . .
BE) 7 5 3
0 3 1
UNIT-IV
CHEMICAL REACTION EQUILIBRIA

PART-A
1. What are the criteria for chemical equation?
The criteria for a chemical reaction to occur at equilibrium is that the free energy
charge is zero. Similar to criteria for phase equilibria, the temperature and pressure of
all the components be identical when two or more chemical species are in equilibrium.
Thus the criteria for chemical equilibria may be stated as
F=0 at constant temperature and pressure
2. What is the relation between standard free energy change and equilibrium
constant?
Consider a chemical reaction.

a.A +b.B  c.C +d.D
According to criteria for chemical equilibria state by (A)
   
F  cFc  d FD  aF A  bFB  0  (1)
For any component
F  F 0  RTInF / F 0   2 
Sub (2) in (1)
 f/f   f / f 
d
0 c 0
F   RT In
0 c D
f / f  f / f 
a b
0 0
n B
acad
=RT In cb Da
aB a A
a  f / f 0  activity of any component
acc aDd
K b a
 F   RT In k
aS a A
3. What is effect of temperature on the equilibrium constant?
The effect of temperature T on equilibrium constant k I studied from the equation.

d H 
 Ink  
dT RT 2
Where H 0 is standard heat of reaction?
4. How is the equilibrium constant K determined at any temp T?
The equilibrium constant k at temperature T is determined by the equation (H) , the

use of equation (H) decrease the value of H0 at temperature T which may be
evaluated from the the equation.
 2 
H  H 0     
0
T3
2 3
5. What is standard stats are chosen for solids liquids and gases?
The standard states chosen are
solids  pure solids at latm and temp of reaction

For liquids pure liquid at latm and temp of reaction
For gases pure component at the temp of unit fugacity
6. Write the definition of d  is given by the equation.
d n1 d n 2 d n 3 d n 4
    ........d 
V1 V2 V3 V4
Is the definition of d  is given by the equation.
7. How the mole fraction yi of the species are related to  ?

The mole fraction yi of the species are related to  by
ni nio nio  Vi

yi   
n n no  V
8. For a system in which the following reaction occurs.
CH 4  H 2O  CO  3H 2
Assume there a present initially 2mol CH4 1mol H2). 1mol CO and 4 mol H2.
Determine expression for the mole fractions yi as function of .
Solution:
For the given r × n

V   Vi  1  1  3  2
1
For the given numbers of moles of species initially present
n0   nio  2  1  14  8
1
2 1 
YCH 4  YH 20 
8  2 8  2
1  4  3
YC0  YH 2 
8  2 8  2
9. Consider a vessel which initially contains only no mol of water vapour. If

decomposition occurs according to the reaction.
H2O  H2 +Y2O2
Find expression which relate the no of moles and the mole fraction of each chemical
species to the reaction coordinate.
Solution:
1 1
V  1  1 
2 2
n0  
nH 2 0  n0   YH 2O 
1
n0  
2

nH 2   YH 2 
1
n0  
2
1

no2  y2 YO 2  2
1
n0  
2
The fractional decomposition of water vapour is
n0   n0   n0    
 
n0 n0 n0
10. Consider a system in which the following reaction occurs.

CH4 +H2O  CO +3H2  (1)
CH4 +2H2O  CO2 +4H2  (2)
Where the no(1) and (2) indicate the value of I the reaction index. If there are
present initially 2 mol CH4 and 3 mol H2O determine expressions for the yi as
function of 1 and  2
Solution
The stochrometric number Vi,j
I CH 4 H 2O CO CO2 H2
J Vj
1 -1 -1 1 0 3 2
2 -1 -2 0 1 4 2
2  1   2 1
yCH 4  Yco 
5  21  2 2 5  21  2 2
3  1  2 2 2
y H 2O  Yco2 
5  21  2 2 5  21  2 2
31  4 2
yH 2 =
5  21  2 2
11. Define standard gibbs energy change of reaction?
In spite of its depends on temperature K is called the equilibrium constant for the
reaction 1Vi Gi0 represented by G0 is called the standard Gibbs-energy change of
reaction.
12. What is the standard properly change of reaction for m.

The standard properly change of reaction. For (x) is
M    Vi M i
i
13. What is law of mass action.
i  Xi  i  K
v
This simple relation is known as law of mass action.
14. What is the phase rule of reacting systems.
The phase rule for reacting system is

F=2 – Π+N-r.
15. What is the equation if the equilibrium mixture is an ideal gas.
 vj
 P
 i  yi   
VD ,i
Kj
P 
16. Give some examples of fuel.
Hydrogen methane, butane, methanol are some examples of fuel.
17. What is the reaction in Heterogeneous system
When liquid and gas phases are both present in an equilibrium mixture of reacting
spices. Then it must satisfied along with the equation of chemical reaction
equilibrium.
18. Express the heavy law in the form of equation.
The Henry law is expressed as
Fi=kimi
19. Draw the diagram for standard state for dilute aqueous solutions.
Fig:
20. What is the fugacity ratio
The fugacity ratio can be expressed as

fi  i X i fi  f 
0
 0
  i X i  i0 
fi fi  fi 
21. Draw the diagram for total gibbs energy in relation to the reaction co ordinate.
Fig:
Total Gibbs energy in relation to the reaction co ordinate.
22. Write the expression for general relation between dni and d?
The general relation between a differential change dni in the no of moles of a

reacting species and d is Dni = Vid (i=1,2, N)
23. What is the expression if any equilibrium mixture is an ideal solution and r i is
unity?
The expression for the equilibrium mixture in an ideal solution and ri and ideal
solution and ri is unity
 i  xi  i  k
V
24. Explain the steps for V 

i
i i is zero.
 mG   r  sG ' 
v 
i
i i  
 r Tip  r Tip

Since the rate of change of total Gibb’s energy of the system with the system with the
reaction coordinate is constant T and P so
v 
i
i i 0
25. Explain the express the equation for property of pure species
AG0 = -  G
i
i
0
AG0  property of pure species

This is the equation for property of pure species
26. Express the equation for H0
The equation for H0 is
H 0   H 60
i
27. Express the equation for C p0
The equation for C p0   Vi C pi0

i
28. Find the value of equilibrium constant for NH3 syntheses reaction at 600K.
1 3
N 2  H 2  NH 3
2 2
4596
Ink   3.822 In T +2.136  10-6T 2  1244
T
At 600 k
4596
Ink   3.822 In 600+2.136  10-3  600 
600
-0.18T 10-6  600   12.44
2
=-3.134
k=0.0435  4.35 10-2
29. Find the value of equilibrium constant for NH3 synthesis reaction at 800k.
Solution:
Given T= 800 k
1 3
N 2  H 2  NH 3
2 2
4596
Ink   3.822 In T +2.136  10-3T  0.187  106 T 2  12.44
T
4596
 3.822 In 800+2.136  10-3 800  0.187  106  800   12.44
c
800
 5.774  3.1058  103
30. What is the sensible heat required to heat sulphur diaoxide from 25 c to 450c
the specific of sulphur diaoxide is given by the relation.
Solution:
1 kg mol of sulphurdioxide
723
Sensible heat 
298
723
 29.6  39.6 10

3
T  14.6 106 T 2 dT
298
 16529kg / kjmol
31. What is the driving force for chemical reactions?
The free energy is the driving force for chemical reactions.
32. What is the driving fore for thermal and mechanical processes?
Temperature and pressure are the during force for thermal and mechanical process.
33. Benzene is nitrated in the liqud phase to give nitro benzene. What is the
conversion of benzene at 25C and 1 bar.
Component H 0f S 0f
C6H6 48864 172.2
HNO3 172.658 155.1
H2O 22251 69.7
C6H5NO2 158146 223.5
Solution:
C6 H 6  HNO3  C6 H 5 NO2  H 2O
2
ka = kn =
1  x 
2
FD 298   F     F 
 69.7 15846  298  2225   172658  298 1555  1
-  488864-298 172.2 
 135700
34. Find the stachrometric number for this equation.
CH4 +H2O  CO+3H2
Solution:
The stachrometric number is
Vc H 4  1, VH 2O  1, Vco  1VH 2  3
35. Find the stochrometric number for this equation
Solution:
1 3
N 2  H 2  NH 2
2 2
The stochrometric number is
VN 2   1 VH 2   3 VNH 3  1
2 2
36. For a system in which the following reaction occurs.
CH4 +H2O CO2 +4H2

2mol of CH4, 1 mol of H2O , 1 mol CO2 and 4 mol H2 determine expressins for the mole
fractins yi as function of 
V   Vi  1  2  1  4  2
i
n0 = n i
io  2 11 4  8
2 1 
YCH 4  YCO 2 
8  2 8  2
2 4
YH 2O  YH 2 
8  2 8  2
37. What is the total stochrometric number V and mole fraction yi?
The total stochcometic number and mole fraction is
V1   Vi , j
i
ni o   j V1 , j  j
yi   i  1, 2....N 
n0   j V j ,  j
38. What are the conditions applied for (dGt)Tip =0
 Total Gibbs energy Gt is a minimum

 It’s differential is zero
39. Give the equation k factor and their three terms?
K=K0K1K2
 G0 
K 0  exp  
 TT 0 
 H 00  T0  
K1  exp  1   
 R T0  T  
  1
2
   -1   1
K 2  exp  In  -     BT0
    2 
  1   2   1 D  t  1
2 2
1
+ CT02
6  2 T02 
40. What is the stoichrometric number for the equation.
C3COOH+C2H5OH  CH3 H5 COOC2H5 +H2O

V1 =-1+1+1=0
41. Assume that 2 mol CH3COOH, 1 mol of C2 H5 OH 1 mol of CH3 COOC2H5 and 4
mol of H2O expression for yi CH3COOH+C2 YH5 OH  CH3COOC2H5 +H2O
V=0 n0   nio  2  1  1  4  8
1
2 1 
YCH 3COOH  YC 2 H 5OH 
8  2 8  2
2 4
YCH 3COOH  YC 2 H 5OH 
8  2 8  2
42. What is the n0 value for
CH 3COOH  C2 H 5OH  CH 3COOC2 H 5  H 2O

nCH 2COOH  n0   nCH 2COOC2 H 5  
nC2 H 5OH  n0   nH 2O  
43. What is the n0 value for
CH4 +H2O  CO +3H2

nCH4 = n0 -  nco = 
nH2O = n0 -  nH2 = 3
44. What is expression for fundamental property for single phase system?
The expression for fundamental properly for total differential gobb’s energy is
dnG=nvdp-nsdt + idni
45. What is the symbol (or) for the standard gibbs energy?
The standard Gibb’s energy denoted by G0.

PART - B
1. Derive the relationship between mole fraction of species in multiple reactions

and the extent of reactions.
Solution:
When two or more reactions occur simultaneously, the number of moles of

each component changes because of several reactions. Equations can be modified as
dni   i , j j
j
Here vi , j is the stoichiometric number for species I in the jth reaction and  j is the
extent of this reaction. Equation is modified to account for the multiple reactions, and
the number of moles of I after the reaction is
ni  nio   i , j j .
j
The total number of moles is obtained by summing the number of moles of individual
species.
 
n   nio   i , j j  n0     i , j  j .
i i j j  j 
Let v
i
i ,j  v j , the sum of the stoichiometric numbers in the jth reaction. Then the
above equation can be written as

n  n0   j j
j
The mole fraction of component I in the mixture is
ni 0   i , j j
ni j
yi  
n n0   j j
j
2. 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.
Solution:
The total moles initially present,
n0  3  5  1  9
For the first reaction,
V1 = -1-3+1+1= -2
For the second reaction,
V2 = -1-1+1+1 = 0
The mole fractions are calculated using Equation
3  ( 1)   1  ( 1)   2 3   1   2
yco2  
9  ( 2)   1  (0)   2 9  2 1
Similarly,
5  3 1   2 1
y H2  , y CH3OH 
9  2 1 9  2 1
1  1   2 2
y H 2O  , y CO 
9  2 1 9  2 1
3. The standard heat of formation and standard free energy of formation of

ammonia at 298 K are -46,100 J/mol respectively. Calculate the equilibrium constant
for the reaction
N 2 ( g )  3H 2 ( g )  2 NH 3 ( g )
At 500 K assuming that the standard heat of reaction is constant in the temperature
range 298 to 500 K.
Solution:
The standard free energy of reaction is estimated from Equation
G 0  
Products
 i Gio, f  
Reac tan ts
 i Gi0, f
The second summation yields zero as the free energy of formation of the elements are
zero.
G 0  
Products
 i Gi0, f  2  16, 500  33,000 J / mol
Using Equation
G 0 33,000
In K     13.3195
RT 8.314  298
Therefore,
K at 298 K = 6.0895 × 105
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.
K  0  1 1 
1n    
K1 R  T T1 
K 92, 200  1 1 
1n 5
     15.0344
6.0895  10 8.314  500 298 
Therefore, the equilibrium constant at 500 K,K = 0.18
4. 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, Mol %, n-butane

K
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.
Solution Since activities are equal to mole fractions, K  yib / ynb , where yib is the
mole fraction of i- butane and ynb the mole fraction of n-butane in the equilibrium
mixture. Therefore,
0.69
At 317 K, K   2.2258
0.31
0.57
At 391 K, K   1.3255
0.43
Equation gives
G 0   RT 1n K
G 0317  8.314  317 In 2.2258= -2108.74 J/mol
G 0319  8.314  391 In 1.3255= -916.03 J/mol
Assuming that the heat of reaction is independent of temperature we can use

Equation for calculating it.
K2 H 0  1 1 
In   2  1
K1 R T T 
2.2258 H 0  1 1 
1n    
1.3255 8.314  317 391 
Therefore, ∆H0 = -7218.02 J/mol.
5. 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):
C P  27.27  4.93  10 3 T for N 2

C P  27.01  3.51  10 3 T for H 2
3
C P  29.75  25.11  10 T for NH 3
Solution The standard heat of reaction and standard free energy of reaction at 298 K
were estimated in Example
 0  92, 200 J/mol; G 0  33,000 J/mol
Also,
  2  29.75  27.27  3  27.01  48.8
  (2  25.11  49.3  3  3.51)  10 3  34.76  10 3
Equation gives
92, 200  H   48.8T  17.38  10 3 T 2
=    48.8  298  17.38  10 3  (298) 2
=    1.3  10 4
Therefore,    7.9201  10 4. Equation gives
 2
33,000      1n T   R
2
=-7.9201  10 4  48.8  298  1n 298-17.38  10-3  298 2    8.314  298
=2105 - 2477.57
Therefore, A = 14.169. Substitute ∆H´ and A into Equation and Equation, we get
79,201 48.8 17.38  10 -3

1n K=  1n T + T  14.169
RT R R
G 0  79, 201  48.8 In T-17.38  10 -3T 2  14.169 RT
Put T=700 K in the above equations. Equation gives K = 1× 10-4; Equation gives
∆G0 = 53,607 J/mol.
6. 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?
Solution Basis: 1 mol nitrogen and 3 mol hydrogen are in the reactant mixture. Let 
be the extent of reaction. Then the number of moles of various species at equilibrium
are calculated using Equation as ni  ni 0   i . Thus the moles of nitrogen, hydrogen
and ammonia at equilibrium are respectively,
1-, 3-3 and 2. Total moles at equilibrium is = 4-2. The moles fractions of nitrogen,
hydrogen and ammonia are, respectively,
1 3(1- ) 2
, ,
4  2 4-2 4-2
The sum of stoichiometric numbers, v = 2 – 1 – 3 = -2. Equation gives
K y  ( K / K )P   KP 2
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.
 2 /  4  2 
2
4 2
3  2  10 P
1    /  4  2   3 1    /  4  2 
That is,
2
4 2  4  2 
4  2  10 4 P 2
27  1   
  4  2 
2
 3.6742  10 2 P
(1   )
(a) When P = 20 bar,
  4  2 
 0.73485
 1   2
2.73485 2  5.4697  0.73485  0
Solving this,  = 0.1448. Fractional conversion of nitrogen,

 
z  i    0.1448
nio
That is, conversion of nitrogen = 14.48%.

(b) When P = 200 bar,
 (4  2 )
 7.3485
(1   )2
9.3485 2  18.697  7.3485  0
Therefore,  = 0.5375. So, conversion of nitrogen = 53.75%.
We see that the increase in pressure favours the formation of ammonia as this reaction is
accompanied by a decrease in the number of moles.
7. A mixture of 1 mol CO, and 1 mol water vapour is undergoing the water-gas shift
reaction at a temperature of 1100 K and a pressure of 1 bar.
CO (g) + H2O (g)  CO2 (g) + H2 (g)
The equilibrium constant for the reaction is K = 1. Assume that the gas mixture
behaves as ideal gas. Calculate
(a) The fractional dissociation of steam.

(b) The fractional dissociation of steam if the reactant stream is diluted with 2 mol
nitrogen.
Solution: The mole fraction of the species at equilibrium are related to the equilibrium
Constant which is given by
K v
Ky  P
K
Where v is the sum of stoichiometric numbers. Here, v = 1 + 1 - 1 - 1= 0. As the gas
mixture behaves as an ideal gas, K  1 . Equation gives K y  k  1. Ky is related to the
mole fractions of various components as K y  yi i . Equation gives the relationship
between mole fractions and extent of reaction at equilibrium as
nio   i
yi 
n0   v
(a) The mole fractions of the constituents in the equilibrium mixture are expressed in
terms of the extent of reaction as given in the table below:
yC 02 y H2   / 2  / 2  2
Ky  1   
yCO yH2O  1    / 2   1    / 2  (1   )2
Solving the above,  = 0.5.

Conversion of steam z is obtained from Equation
Component vi nio , mol yi

CO -1 1 (1 -
)/2
H2O -1 1 (1 -
)/2
CO2 +1 0 /2
H2 +1 0 /2
n0 2
i 
z  0.5
nio
This means that 50% of steam is converted in the reaction.
(b)
CO -1 1 (1 - )/4
H2O -1 1 (1 - )/4
CO2 +1 0 /4
H2 +1 0 /4
N2 2
n0 4
8. A gas mixture consisting of 60% H2, 20% N2 and the rest inert gas is passed over a
suitable catalyst for the production of ammonia.
1 3
N 2  H 2  NH 3
2 2
The equilibrium constant KP = 1.25 × 10-2, The pressure is maintained at 50 bar.
Assume ideal gas behaviour for the gas mixture. Determine the composition of the
gases leaving the reactor.
Solution Basis: 100 moles of the reactant gases.

1 3
     1  1
2 2

N2 - 20  20  ( / 2) /(100   )
1/2
H2 - 60 [60 – (3/2)]/(100 - )
3/2
NH3 +1 0 /(100 - )
Inert gas - 20 -
n0 100
Since,
Ky  KP P  v
Then,
 /(100   )
1/ 2 3/ 2  (1.25  10 2 )50  0.625
20    / 2  /  100     60   3 / 2  / 100   
 /  100   
3 / 2  0.625
 20   / 2  60   3 / 2 
1/ 2
Solving this, we get  = 8.71. Mole fraction of nitrogen is obtained as
 20   / 2  / 100     0.1714
And mole fraction of hydrogen is
60   3 / 2  / 100     0.5141
Mole fraction of ammonia:
 /(100   )  0.0954
Mole fraction of inert gas:
1  0.1714  0.5141  0.0954  0.2191

Analysis of exit gases from the reactor:
N2 = 17.14%, H2 = 51.41%, NH3 = 9.54% and inert gas = 21.91%
9. Five moles of steam reacts with one mole methane according to the following
reaction at 850 K and 1 bar.
CH4 + H2O  CO +3H2 ; K1 = 0.574
CO + H2O  CO2 + H2; K2 = 2.21

Calculate the composition at equilibrium assuming ideal gas behaviour.

Solution Number of moles of a component at equilibrium = n1  nio   vi , j j
j
Let 1 and 2 be the extent of reactions for reaction respectively. Thus at equilibrium
the number of moles are,
CH4: 1 - 1, H2O: 5 - 1 - 2, CO: 1 - 2, H2: 31 + 2, CO2: 2
Total number of moles at equilibrium = 6 + 21. The mole fractions of various

components in the equilibrium mixture are:
CH 4 :  1   1  /  6  2 1  , H 2O :  5   1   2  /  6  2 1 
CO :   1   2  /  6  2 1  , H 2 :  3 1   2  /  6  2 1  , CO2 :  2 /  6  2 1 
 1   2  3 1   2 
3
YCOYH32
KY ,1  
1   1  5   1   2  /  6  2 1 
2
YCH4 YH2O
YCO2 YH2  2 (3 1   2 )
KY ,2  
YCOYH2O ( 1   2 )  5   1   2 
V1  1  3  1  1  2; V2  1  1  1  1  0
Substitute these into the following relationships

K y ,1  K1 p  V1 , K Y,2  K2 P  V2
Note that K1 = 0.574, K2 =2.21 and P = 1 bar. The resulting equations are solved for 1
and 2. Assume a value for 1 and calculate 2 by each equation. These two 2 values
are plotted against 1. This is repeated for various assumed 1 values. The intersection
of the two curves gives the solution. 1 = 0.9124; and 2 = 0.623. The mole fractions are
evaluated by supplying the values of 1 and 2. The results are:
CH4: 0.0112, H2O: 0.4415, CO:0.0357, H2: 0.4307 and CO2: 0.0804
UNIT-V
REFRIGERATION
PART-A
1. What is Refrigeration?
It is a continous absorption of heat at a low temperature level, usually

accompolished by evaporation of a liquid in a steady – state flow process.
2. What is the application of Refrigeration?
 Petroleum industry includes lubricating oil purification

 Low temperature reactions
 Separation of volatile hydrocarbons
 Gas liquefaction
3. What are the methods of producing refrigeration?
The methods of producing refrigeration are

 Cannot refrigeration
 Absorption refrigeration
4. Define coefficient of performance
The coefficient of performance (w) is defined as ratio of heat absorbed at the lower
temperature to the net work.
Heat absorbed at the lower temperature


network
Qc

W
5. Mention some of the refrigerants?
Ammonia, methyl chloride carbon dioxide, propane and other hydrocarbons are
some of the refrigerants
6. Draw the vapour-compression refrigeration cycle.
7. Draw the PH diagram for vapour compression refrigeration cycle?

8. Draw the diagram for Absorption refrigeration unit?
9. What are the uses of Liquefaction process?
 Liquid propane in cylinders serves as domestic fuel

 Liquid oxygen is carried in rockets
 Natural gas is liquefied for ocean transport
 Liquid Nitrogen is used for low-temperature refrigeration.
10. What are the methods for Liquefaction process?
There are two methods for Liquefaction process

 Linde Liquefaction process
 Claude Liquefaction process
11. What is the result of Liquefaction when a gas is cooled to a temperature in the
two-phase region?
(i) By heat exchange at constant pressure.

(ii) By an expansion process from which work is obtained.
(iii) By a throttling process
12. What is the Ts diagram for cooling process
13. Define Carnot theorem?
The thermal efficiency of a cannot engine depends only on the temperature levels
and not upon the working susbstance substance of the engines.
14. What is the coefficient of performance for cannot refrigerator and vapour
compression cycle.
The COP value for cannot refrigerant is
Tc

TH  Tc
And for vapour compression cycle is
H 2  H1

H3  H2
15. Draw a diagram for a two- stage cascade refrigeration system?
16. Draw the diagram for Linde liquefaction process.
17. Draw the diagram for Claude liquefaction process

18. Assess the thermodynamics efficiency of the liquefaction process and Assume
that reversible adiabatic compression and expression.
19. Define Capacity of refrigeration or ton of refrigeration?
The capacity of refrigeration is defined in terms of ton of refrigeration. The one ton
of refrigeration is equivalent of heat removal at the rate of 200 BTU/ min or 12000
BTU/hr necessary to freeze 1 ton water at 32F
20. Define circulation rate.
The circulation rate is defined in relation with refrigeration capacity e.g. for vapour
compression cycle. For one ton of refrigeration the circulation rate m is defined as
12000
m
HA  HD
21. What is Heat pump?
It is a device used for the heating of building and houses in winters and cooling
them in summers. In winger it absorbs heat from the surroundings and rejects into
the building while in summer it absorb heat from building and rejects to
surroundings.
22. What are the characteristics of an ideal refrigerant which are considered for its
choice and why?
The refrigerant chosen for a particular refrigeration operation should be such that it
has.
(i) Low vapour pressure in the condenser giving low design and maintenance cost
(ii) Low cost
(iii) Non-explosive nature
(iv) Constant entropy of saturated vapour
23. What is Refrigeration cycle?
Since the temperature below the surrounding is not only to be reached but
maintained so it necessitates the absorption of heat continuously at low level.
24. Describe various refrigeration cycles
i. Cannot cycle
ii. Air refrigeration cycle
iii. Vapour compression cycle
25. Mention a few common refrigerants
1. Anhydrous ammonia
2. Carbon diozid
3. Methyl chloride
4. Sulphur dioxide
26. What are the different methods for the liquefaction of gases?
The common features of all liquefaction processes is to cool the gas unit it reaches
the two phase region.
(i) Cooling at constant pressure
(ii) Cooling by expansion in an engine
(iii) Cooling by throttling
27. What is the process is most widely used in commercial plants?
The process is most widely used in commercial plants is the method of cooling is
known as Claude liquefaction process.
28. Define the word refrigeration
It implies the maintenance of a temperature below that of surroundings.
29. What is the refrigerant used in these cycles 2?
The tetra fluro ethane is the refrigerant used in these cycle 2.
30. What is the refrigerant used in the cyle 1?
The propylene is the refrigerant used in the cycle 1
31. Write the formula for trichloro fluro methane and dischlorodifluro methane.
Trichloro fluro methane  CCl3 F

Dichlorodifluro methane  CCl2 F2
32. Write the formula for dichlorotrifluro ethane.
The formula for dichlorotrifluro ethane is CHCl2CF3
33. Write the formula for tetra fluro ethane?
The formula for tetra fluro ethane is CF3CH2F
34. What is the formula for pentafluroethane?
The formula for pentafluroethane is CHF2 CF3
35. How can we overcome the operation of two or more refrigeration cycle?
The operation of two or more refrigeration cycles employing different refrigerants in

a cascade.
36. What is cascade process?
The 2 cycles operate so that the heat absorbed in the interchange by the refrigerant of
the higher temperature cycle 2 serves to condense the refrigerant in the lower
temperature cycle 1.
37. What is the pressure range used in cycle 2?

The pressure i.e. intake and discharge in the compressor is 21 and 112 psia
38. What is the pressure ratio in cycle 2?
The pressure ratio in cycle 2 is 5:3
39. What is the pressure range used in cycle 1?
The pressure that is intake and discharge in the compressor is 16 and 58 (psia)
40. What is the pressure ratio in cycle 1?
If we use-50F & 86 F with HFC – 134 a then the pressure ration in cycle 1 is 3:6
41. What is the intake pressure range?
If we use - 50F and 86F with HFC – 1349 then the intake pressure range is 5:6 (psia)
42. If we use -50F & 86F with HFC- 134a than what is the discharge pressure range?
If we use - 50F & 86F with HFC – 134a then the discharge pressure range is 112
psia
43. What is the pressure ratio for HFC-134a between 50F & 86F
The pressure ratio is 20 for the single stage compressor .
44. What is efficiency of a system?
w work
n 
QH Heat Absorbed
1-Ts
=
TH
45. What is the value for an actual absorption refrigerator?
Three times of the original value that is 3(0.81)

PART - B
1. An industrial unit wishes to install a conventional vapour compression type

refrigeration unit of capacity of 10 tons. The refrigeration unit employs water as
refrigerant. The temperature in the evaporator and condenser are 40 oF and 700F
respectively. The vapour leaving the evaporator is saturated and compression
process is isentropic, compute.
(i) C.O.P. and circulation rate.
(ii) Will there be any difference in C.O.P. and circulation rate if unit is
operating according to carnot cycle. If so how much ? Take necessary data
from the table.
Given : (As per Fig. 11.10)

Capacity of unit = 10 tons.
T2= 400F=4.40C
T1=700F=21.10C
From tables
HA=1078.6 BTU/Ib=2.508106 joules/kg
HC=38.05 BTU/Ib=0.088108 joules/kg
HD=38.05 BTU/Ib=2.538106 joules/kg
HE=1091.5 BTU/Ib=2.538106 joules/kg
SA=2.1585 BTU/Ib0R=9037.2 joules/kg0K
SE=2.0632 BTU/Ib0R =8638.205 joules/kg0K
To find : Circulation rate and C.O.P.
H  HD
(i) C.O.P.= A
HB  HA
HB=HE+CP(Tsup-Tsat)
Fig:
Tsup is obtained from SA and SB
TSup
SA=SB=SE+CP In
TSat
Refrigeration effect
Circulation rate =
HA  HD
Sol.in S.I.
Tsat=21.1+273=294.1 0K
Tsup
9037.2=8638.205+0.54.1868103 In
294.1
Tsup = 356 K
0
HB = HE + CP (Tsup-Tsat)
= 2.538  106 + 0.5  4186.8 (35.6-294.1)
= 2.667  106 joules/kg
2.508  106  0.088  106
C.O.P . =  15.2
2.667  106  2.508  106
Q2
Circulation rate m =
HA  HD
Q2 = 120002524.1868 10
=1.266108 joules/hr.
1.266  108
So circulation rate =
2.508  106  0.088  106
= 52.3 kg/hr.
Sol.in F.P.S.
Tsat = 460 + 70 = 530 0K
Tsup
2.1585 = 2.0632 +0.5 In
530
Tsup = 641 0R
HB = 1091.5 + 0.5 (641.0 – 530)
BTU
= 1147.0
Ibm
1078.6  38.05
C.O.P. =  15.18
1147  1078.6
12,000  10
Circulation rate =
HA  HD
12,000  10
=
1078.6  38.05
= 115.3 Ib/hr.
(i) Based on carnot cycle C.O.P.
T2 460  70
= 
T1  T2 (460  70)  (460  40)
= 16.67
Circulation rate will remain same.
(i) The C.O.P. is 15.2 and circulation rate is 52.3 kg/hr or 115.3 Ib/hr.
(ii) Based on carnot cycle the C.O.P. is 16.67 while circulation rate will remain the
same.
2.The specification for a unit employing Freon-12 as refrigerant are :
Temperature in evaporator =-100F.

Temperature in condenser = 600F
Find C.O.P. and rate of circulation of Freon –12 for each ton of refrigeration
effect if
(a) Expansion is reversible adiabatic.
(b) Expansion is adiabatic but not reversible.
Data : Cp = 0.14 BTU / Ib 0R
Temperature Enthalpy Entropy

and state BTU/Ib0R Joules/kg BTU/Ib0R Joules/kg0K
- 100F(sat. 77.5 1.802105 0.174 728.50
vapour)
60 0F (sat. 22.0 0.5118  - -
liquid) 105
60 0F (sat 85.0 1.976  0.17 711.756
vapour) 10 5
Given : T2 = - 100F = - 23.30C

T1 = - 600F =15.50C
Capacity of refrigeration unit = 1 ton
Enthalpy and entropy as given in the table.
To find : C.O.P. and circulation rate.
(i) With reference to Figure
Fig.
Q2 HA  HD
C.O.P. = 
W ( H B  HC )  ( H A  H D )
HA = Enthalpy of saturated vapour at – 100F

HD = ?
HC = Enthalpy of saturated liquid at – 600F
HB = ?
HA and HC are given in table.
Refrigeration effect
m = circulation rate =
HA  HD
Sol. in S.I
HA = 1.802  105 joules / kg

Given in the table.
HC = 0.51158 105 joules / kg
HB is enthalpy of vapour at condenser pressure and SA since (SB = SA).

HB = HE + CP (Tsup - Tsat)
TSup
SA = SB = SE + CP In
TSat
TSup
728.5 = 711.756 + CP In
TSat
BTU Joules
CP = O.14 o  0.14  4.1868  1000 In
Ib R kg o K
Tsat = 373 + 15.5 = 288.5 oK
TSup
728.5 = 711.756 + 0.14  4.1868  103 In
TSat
TSup
728.5 = 711.750 + 0.14  4.1868  103 In
288.5
Tsup = 296.8 K
o
HB = 1.976  105 + 0.14  4.1868  103 (293.8 – 288.5)

= 20.25  105 joules/kg
= 87.08 BTU/ Ib
HD = HA – (∆H) x
But SD = SA – (∆S) x
H
∆S =
T2
So (∆H) x = (SA - SD) T2
So HD = HA –(SA-SD)T2
= 1.802 105 – (728.50 – SD)T2
 H   H 
SD = SC = SSat -   = SE -  
 T1   T1 
 H   H E  HC 
Where   =(∆S)vaporization =  
 T1   T1 
 H  HC 
SC = SD = SE -  E 
 T1 
(1.976  10 5  0.51158  10 5 )
= 711.756 -
273  15.5
= 204.11 joules/kg 0 k
HD = 1.802  105 + (728.50 – 204.11) (273 – 23.3)
= 49259.8 joules/kg = 21.2 BTU/ Ib
1.802  10 5  0.49259  105
C.O.P. =
(2.025  10 5  0.51158  10 5 )  (1.802  105  0.49259  105 )
12000  1 252  4.1868
m = = 96.7 kg/hr.
1.802  105  0.49259  105
Sol. In. F.P.S.
(77.5  21.2) 56.3
C.O.P. =   6.41
(87.08  22)  (77.5  21.2) 65.08  56.3
12,000
m= = 213.0 Ib/hr.
77.5  21.2
(ii) When expansion is adiabatic but not reversible, Figure
i.e. expansion is through throtting
HC = HD’
H  HD '
C.O.P. = A
HB  HA
12000
m=
HA  HD '
Fig
Sol. In S.I.
(1.802  10 5  0.51158  105 )
C.O.P. =  5.8
(2.025  10 5  1.802  10 5 )
12,000  1  252  4.1868
m= = 97.8 kg/hr.
(2.025  10 5  0.51158  10 5 )
Sol . in F.P.S.
77.5  22 55.5
C.O.P. =   5.8247
87.08  77.5 9.58
= 5.8
12,000 12,000
m=   216.2 Ib/hr.
H A  H D ' 77.5  22
(i) When expansion is reversible adiabatic C.O.P. is 6.4 and circulation rate is 96.7 kg/hr or
213 Ib/hr.
(ii) When expansion is adiabatic but not reversible C.O.P. is 5.8, and circulation rate is 97.8
kg/hr
or 216.2 Ib/hr.
3. A liquid effluent is cooled in a chemical industry by a conventional vapour
compression machine using ammonia as refrigerant. The condenser and evaporator
pressures are 166.4 psia and 38.5 psia respectively. The temperature of vapour
entering the compression is increased to 200F by means of a heat exchanger through
the saturated liquid from condenser. The compression step is adiabatic but not
reversible, the efficiency being 80% as compared to isentropic operation. The heat
load in the refrigerator coils is 185,000BTU/min. Compute the power requirement of
the compressor and C.O.P. The heat capacity of superheated ammonia is 0.7.
Data:
ENTHALPY ENTROPY
Press Joules/kg0
BTU/Ib Joules/kg BTU/Ib0R
ure K
(Satur l l v l v
ation i va i a i a
Temp q p liq vap q p q p
.) u o uid our u o u o
i ur i u i u
d d r d r
0 5 5
1.
5 . 0 0
38.5 56 1
3 1.25 1.3 1 5 0
psia(1 1. 9
. 105 106 2 . 2.
00F) 1 4
8 0 7 8
9
8 6 0
0 1
1 0. 3
. 1
166.4 3 49 3.20 114 9 7
2 9
Psia 7 3. 41 78 0 9
8 4
(850F) . 6 05 106 6 4.
5 .
8 4 9
4 9
The schematic diagram of the unit is shown in Fig.

Given : Pressure in refrigerator = 38.5 psia
Pressure in condenser = 166.4 psia
Temperature of vapour at A’ = 200F
Temperature of liquid at C = 850F
HA = 561.1 BTU / Ib = 1.3  106 joules/kg
HA’ = ?
HE ‘ (Assuming A’B’ to be isentropic) = enthalpy
at 38.5 psia and SA’ = ?
HC = 137.8 BTU / Ib = 3.204  106 joules/kg.
Heat load in refrigerator coils = 185,000 BTU / min
= 1.95 108 joules/min.
Efficiency of adiabatic compression = 80%
To find : C.O.P. and H.P

Calculation of enthalpies at various points
HA’ = HA + CP (Tsup - Tsat).
= HA + CP (TA’ - TA)
= 561.10  0.7 + 10 = 561.1 + 7 = 56.8.1 BTU/Ibm.
= 1.32  106 joules/kg
Tsup 460  20
SA’ = SA + CP In = 1.1949 + 0.7 In
Tsat 460  10
= 1.2096 BTU/Ib m 0R
= 5042.5 joules/kg 0K
Had the compression been isentropic say A’ B’ than
SA ‘ = SB’
HB’ = h + L + CP (Tsup - Tsat)
= h + L + CP (TB’ - Tsat)
Since SA ‘ = SB’
Hence SA’ = 1.2096 = Total entropy of saturated vapour at B’

Tsup
+ Cp In
Tsat
Tsup
= 0.2854 + 0.9064 + 0.7 In
0.545
Tsup = TB’ = 559 R = 311 K
0 0
HB’ = 137.8 + 493.6 + 0.7 (559 – 545)

= 641.2 BTU /Ib-m = 1.49  106 joules/kg.
The actual compression is not reversible having 80% efficiency
So
( H )isentropic
 0.80
( H )actual
H B ' H A ' 641.2  568.1

 0.80 
HB  H A ' H B  568.1
1
HB = (641.2 – 568.1) +568.1
0.80
= 659.5 BTU/Ib-m.
=1.5335  106 joules/kg.
Since expansion is done through throttling so
HC’ = HD
Heat lost by the saturated liquid = Heat gained by vapour.
So (HC – Hc) = (HA’ – HA)
= 137.8 – (568.1 – 561.10)
= 137.8 – 7.0 = 130.8 BTU/Ibm.
=3.0229  105 joules/kg.
( H A ' H D ) H ' H D
C.O.P. =  A
( H B  HC ')  ( H A ' H D ) H B  H A '
Q Heat load in refrigerator
C.O.P. = 2 
W W
So Q
W  2
C .O . P .
W
H.P. = F is the factor to convert work in H.P.
F
Sol. In S.I.
(1.32  106  3.0229  10 5 )
C.O.P. =  4.76
1.5335  106  1.32  106
Q2 = 1.95  108 joules / min
1.95  108
So W= =682,773 joules / sec or watt
4.76  60
= 916 H.P.
Sol. In F.P.S.
568.1  130.8
C.O.P. =  4.76
659.5  568.1
Q2 = 185,000 BTU / min
185,000
W= BTU / min
4.76
= 916 H.P.
Power requirement = 916 H.P.
C.O.P. = 4.76
4. Dry ice is manufactured using Joule – Thomson process as shown in Figure

Fig
Data for various streams are:
Stream Pressure Temperature Enthalpy

No. in 0C
BTU / Joules/kg
bar Ibm
3 55.0 37.7 146 3.395  105
6 1.0135 Sat. solid -113 -2.6278 
10 5
8 1.0135 15.50C 168 3.90664 

105
7 1.0135 Sat. vapour 133 3.09275
105
Find the temperature of the stream (4) assuming no heat losses. What is the production
of dry ice per kilogram of carbondioxide compressed ?
Given : (As per Figure)
H3 = 146 BTU / Ib-m = 3.395  105 joules/kg
H6 = 113 BTU/Ib-m = - 2.62768  105 joules/kg
H8 = 168 BTU/Ib-m = 3.90664  106 joules/kg
H17 = 133 BTU/Ib-m = 3.09275 105 joules/kg.
To find : Temperature and state of (4) and production of dry ice/kg of CO2.
Let z be the kg of dry ice produced per kg of CO2 compressed then
H3 = H6Z + H8 (1 – z) …(1)
From this equation z may be computed.
A heat balance z may be computed.
H3 + (1-z)H7 = H4 + (1-z)H8 ...(2)
Assuming H6 and H7 are equilibrium so H7 is the enthalpy of saturated vapour at
1.0135 bar.
The temperature and state corresponding H4 is obtained from P- H chart (Appendix
11.3).
Sol. In S.I.
From equation (1)
( H3  H8 ) (3.395  10 5  3.90  10 5 )
Z= 
( H6  H 8 ) ( 2.6278  10 5  3.90664  10 5 )
= 0.078 kg of dry ice/kg of CO2
From (3)
H4 = 3.90664  10 5 - (1- 0.077) (3.90664  10 5 - 3.09275  10 5 )
= 3.1554  10 5 joules/kg
= 135.69 BTU/Ibm
From appendix 11.3 temperature is = 750F.
Sol. In F.P.S.
146  168
Z= = 0.078 Ib of dry ice/Ib of CO2
113  168
H4 =168- (1- 0.078) (168 – 133)
= 135.79 BTU/Ib-m
From appendix 11.3 temperature is = 750F.
5. Describe various refrigeration cycles and show each on T-s diagram.

Various refrigeration cycles are
(i) Carnot cycle.
(ii) Air refrigeration cycle.
(iii) Vapour compression cycle
a. with expansion engine.
b. Conventional.
(i) Carnot cycle. The carnot cycle is an ideal cycle consisting of two
isothermal processes during which Q2 is absorbed at the lower temperature T2 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
Figure
Fig. Carnot cycle.
(ii)Air refrigeration cycle. In the air machine shown in Fig.11.2, air absorbs heat at
the essentially constant pressure P1 in the refrigerator and rejects heat to the
surroundings in the cooler at a higher constant pressure P2. The air is compressed
isentropically from A to B. The expansion from C to D is at constant entropy.
The work produced during CD is utilized as energy required for compression step
AB.
The air cycle is shown on T – S diagram in Figure
Fig.Air Cycle.
(ii)Vapour Compression Cycle. During this cycle, the fluid is evaporated in the
refrigerator for absorbing heat at a constant temperature. The vapours are then
compressed to a higher pressure. These vapours 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 irreversibilities.
The expansion step is carried in two ways :
(a) 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 vapour 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. The cycle is shown in Fig.(1) and Fig.(2)
Fig.(1) Fig.(2)
6. Show by a sketch, the Joule-Thomson liquefaction process. What is energy

balance equation to calculate the fraction of gas liquefied ?
The Joule- Thomson liquefaction process is shown in Figure
An energy balance equation across cooler, valve and separator is
H6z + H8 (1 - z) = H3
Where z = fraction of gas which is liquefied.

And H3,H6, and H8 are sp. Enthalpies of streams (3), (6) and (8).
Fig.
H 292
B.E. / B.Tech. DEGREE EXAMINATION, APRIL/MAY 2004
Sixth Semester
Chemical Engineering
CH 338 – CHEMICAL ENGINEERING THERMODYNAMICS – II
PART-A
1. Give the statement of Gibbs’s theorem.
2. Define the fugacity coefficient of species in solution.
3. Explain the terms: positive and negative deviations from ideal-solution behaviour.
4. Draw the pxy diagram and locate the bubble point and dew point.
5. What are the activity- coefficient models? Give examples.
6. Name the important chemical processes of the application of phase equilibria.
7. How is the mole fraction of the components related to reaction coordinate?
8. Write down the effect of temperature on the equilibrium constant.
9. Why is throttling used in practical refrigerators in place of turbine?
10. What is the basic principle of the vapor-compression cycle?
PART-B
11. The azeotrope of the water-n-propanol system has a composition of 56.83% mol water
with boiling point of 360.9 K at a pressure of 101.3 kPa. At this temperature, the vapor
pressures of water and n-propanol are 64.25 kPa and 69.71 kPa respectively. Evaluate
the activity coefficients for a solution containing 20% mol water through the van Laar
equations.
12. (a) (i) Derive the equation for partial properties from an equation of solution
property as a function of composition.
(ii) Describe the tangent-intercept method to determine the partial molar
property.
(Or)
(b) (i) Define ideal and non-ideal solutions.
(ii) What are the characteristics of an ideal solutions.
(iii) A vessel is divided into two compartments. One contains 100 moles of
nitrogen and the other contains 100 moles of oxygen at 298 K and 1 bar. The barrier
separating them is removed and the gases are allowed to reach equilibrium under
adiabatic conditions. What is the change of entropy of the contents of the vessel.
13. (a) For the system ethyl ethanoate (i)/n-heptane (ii) at 343.15 K,
P 1
sat
 79.8 kPa
P2sat  40.5 kPa
GE
 0.95 x1 x2
RT
Assuming the modified Raoult’s law, yi P  x i vi Pi is applicable, determine the
sat
Bubble point, y1 calculation for x1 = 0.005.

Or
(b) (i) What are azeotropes ?
(ii) With proper phase diagrams Pxy,,Txy and y-x distinguish between minimum
and maximum boiling azeotropes?
(iii) What are the effects of temperature and pressure on azeotrope
composition
14. (a) Ethanol is manufactured by the vapor phase hydration of ethylene according
to the reaction :
C2 H 4 ( g )  H 2O ( g )  C2 H 5OH ( g ).
The reactor operators at 400 K and 2 bar and the feed is a gas mixture of Ethylene
and steam in the mole ratio 1:3. The equilibrium constants is 0.25. Estimate the
composition (mol %) of the equilibrium mixture. Assume ideal gas behaviour.
Or
(b) (i) Derive the relation between the mole fraction of the species present in
the reaction and the reaction coordinate.
(ii) Develop expressions for the mole fractions of reacting species as functions of
the reaction coordinate for a system initially containing 2 mol NH3 and 5 mol O2 and
undergoing the reaction :
4 NH 3 ( g )  5 O 2 ( g )  4 NO( g )  6 H 2O( g ).
15. (a) (i) With the help of pH diagram, deduce expression for the COP of the
vapor-compression cycles.
(ii) A vapour compression refrigeration system with ammonia as the working
fluid is to operate between 266 K and 300 K. Determine the COP, given that the
enthalpy of saturated vapour at 266 K = 656 kJ/kg and enthalpy of superheated vapour
leaving the compressor = 724 kJ/kg enthalpy of saturated liquid at 300 K = 144 kJ/kg.
Or
(b) Write short notes on the following:
(i) Poynting factor
(ii) Application of Gibbs-Duhen equation
(iii) Factors affecting the equilibrium constants
(iv) Consistency test of VLE data.
CHEMICAL ENGINEERING THERMODYNAMICS – II
PART A
1. Define free energy.
2. Define excess property.
3. Write the Gibbs-Duhem equation.
4. What is an azeotrope?
5. State the modified Raoult’s law.
6. Draw the equilibrium diagram (x vs y) for a maximum boiling mixture.
7. Write down the val-Laar equation.
8. Define residual properties.
9. Define C.O.P.
10. Define the term ton of refrigerator.
PART B
11. Calculate the fugacity of isobutene at 373,16 K and a pressure of 10,25 and 80
atmosphere by using the following experimental data :
12. (a) Write short notes on the following :

(i) Ideal solution.
(ii) Positive deviations from ideality.
(iii) Negative deviations from ideality.
Or
(b) (i) Explain the terms fugacity and chemical potential.
(ii) Discuss the significance of Lewis and Randall rule.
13. (a) (i) Discuss in detail a method of testing the thermodynamic consistency of
the VLE data for a binary system.
(ii) Discuss in detail the activity coefficient models.
Or
(b) Ethanol (1) and benzene (2) system forms an azeotrope with 44.8 mol%

ethanol with a boiling point at 68.24 C at 760 mmHg. The saturation pressures of
ethanol (1) and benzene (2) at 68.24 C are 506 mmHg and 517 mmHg respectively.
Estimate the van Laar constant for the system and evaluate the activity coefficients for
a solution containing 10 mol% ethanol.
14. (a) (i) Discuss the relationship between free energy change and equilibrium
constant. Explain how do you estimate equilibrium constant K.
(ii) The standard free energy change for a reaction at 25 C is -3375 cal/mol. 2030
kJ/kmol. The heat of reaction at 25 C is -18000 cal/mol. Estimate the equilibrium
constant for this reaction at 600 K.
Or
(b) (i) write a note on reaction co-ordinate or extent of reaction.
(ii) For the reaction CH4 + H2O = CO +3H2 assume that there are present initially 2
moles CH4, 1 mole of H2O and 1 mole of CO and 4 moles of H2. Determine the
expression for the mole fractions as a function of the reaction coordinate?
15. (a) (i) Describe the Carnot refrigeration cycle and its limitations.
(ii) Derive an equation for C.O.P. of an ordinary vapour compression refrigeration
system.
Or
(b) (i) what are the requirements for refrigerants?
(ii) Classify the refrigerant.
R 178
PART A
1. What are the different methods of determining partial molar properties?
2. What is the non-ideality of a solution? What is Henry’s law?
3. What is the condition of criteria for phase equilibrium?
4. What is phase rule? Give its equation.
5. Name any four method of consistency tests for VLE data.
6. What is Bubble-point equilibria?
7. What is the criteria for chemical reaction equilibrium?
8. How feasibility of a reaction related to ∆G?
9. What is COP?
10. What are the methods to accomplish cooling?
PART B
11. (i) What is the effect of temperature on activity coefficients?

(ii) The partial pressure of acetone (A) and chloroform (B) were measured at 298 K and
are as follows:
XA : 0 0.2 0.4
P A bar: 0 0.049 0.134
PB bar: 0.386 0.288 0.187
Calculate the activity coefficient of chloroform in acetone at 298 K based on std. State
as per Lewis - Randall rule.
Data: kB = 0.217 bar

s
Vapour pressure of pure chloroform P B
= 0.386 bars.
12. (a) Mixture of n-Heptane (A) and n-Octane (B) in ideal. The total pressure is 1
atm. Using the vapour pressure data given construct
(i) Boiling point diagram
(ii) Equilibrium diagram and
(iii) Deduce equation for the equilibrium diagram using average  values.
T,K : 371.4 378 383 388 393 398.6
PA, KP : 101.3 125.3 140 160 179.9 205.3
PB, KP : 44.4 55.6 64.5 74.8 86.6 101.3
Or
(b) (i) What are azeotropes?
(ii) Write about different azeotropes with the help of diagram’s and
examples.
  1n  1  
13. (a) Show that x 
i

 0
 x 1 T ,P
Where x = mole fraction
 = activity coefficient.
Or
(b) Using following data for acetone and water mixture calculate partial pr if
 
water, using Gibbs-Duhem equation at 60 C vapour pressure of water at 60 C is
149.4 mm.
Liquid composition mole % acetone : 0.0 3.3 11.7 31.8 55.4 73.6
100
Partial pressure of acetone mm Hg : 0 190 443 588 672 711

860
14. (a) (i) For a reaction show that dni = Vi dE

Where n = no. of moles
V = stoichiometric no
E = extent of reaction.
(ii) Derive an equation relating equilibrium constant and standard free energy
change.
Or
(b) (i) Derive Van’t Hoffs equation relating T and K.
(ii) Write about phase rule for reacting systems.
15. (a) (i) What are the properties of refrigerant?

(ii) Write about Carnot cycle with T.S. diagram.
PART-A
1. Define partial molar properties.
2. Define excess properties.
3. Define dew point and bubble point of phase equilibria.
4. Differentiate between positive and negative deviations on non-ideality.
5. How the feasibility of a chemical reaction is checked?
6. What is the criterion for chemical equilibrium for a two phase system?
7. State the Wilson’s equation for the estimation of vapor liquid equilibrium data.
8. Define the reaction coordinate of the chemical reaction.
9. Name the important refrigerants.
10. Define C.O.P.
PART B
11. (i) Define partial molar properties.

(ii) It is required to prepare 3 m3 of a 60 mol% ethanol – water mixture. It is the volumes
of ethanol and water to be mixed in order to get the saturated solution. The partial
molar volumes of ethanol and the mole of ethanol – water mixture are :
Vbar 1 = 57.5 * 10-6 m3/mol

Vbar 2 = 16*10-6 m3/mol (water)
The molar volumes of pure compound are:
Ethanol = 57.9*10-6 m3/mol
Water = 18*10-6 m3/mol
12. (a) Using the residual volume method compute the fugacity of propane at 11.87
bar and 37.7  C .
Pressure (bar)  1.72 3.44 6.39 10.32 12.04

Specific volume (m3/kg)  0.33 0.16 0.075 0.046 0.032
(b) (i) State the Lewis and Randall rule and explain the application of it.
(ii) A binary mixture contains 25 mole% A and 75 mole% B. At 50 bar total
pressure and 100 deg C the fugacity coefficients of A and B in the mixture are,
respectively, 0.65 and 0.9. What is the fugacity of the gaseous mixture/
13. (i) For the system of acetone (1) and n-hexane (2) at 20C the following
data are
Available :
Ge/RT = X1 * X2 * (1.7448 * X1 + 1.8012 * X2)

P sat = 24.20 Kpa
1
P
2
sat
= 15.95 Kpa
At 20C calculate the total pressure and vapour composition which would be in
Equilibrium with liquid mixtures at each of the following composition :
x1 = 0.10, 0.63, and 0.90. Assume that the vapour phase behaves ideally.
(ii) Based on these calculations how would you characterize this binary system.
Or
(b) Ethanol (1) and benzene (2) system forms an azeotrope with 44.8 mol%
ethanol With a boiling point of 68.24 C at 760 torr. The saturation pressures of ethanol
(1) and benzene (2) at 68.24 C are 506 torr and 517 torr respectively. Estimate the
vanlaar constant for the system and evaluate the activity coefficients for a solution
containing 10 mol % ethanol.
(i) What is the effect of temperature and pressure on equilibrium
constant?
(ii) Obtain a relationship between standard free energy change and equilibrium
constant.
Or
(i) Derive the relationship between equilibrium constant and temperature.
(ii) Explain how will you determine the equilibrium constant for heterogeneous systems.
(i) Define refrigeration capacity.
(ii) Explain vapour compression refrigeration. Derive the COP equation for it.
Or
(i) What are the requirements for refrigerators?
(ii) Describe about the absorption refrigeration cycle with a neat T-S diagram.
PART A
1. Differentiate between molar volume and partial molar volume.
2. Write Gibb’s Duhem equation.
3. Define chemical potential.
4. Draw P-T –x-y diagram for low boiling azeotrope.
5. Write any two activity composition models.
6. Define thermodynamic consistency test for VLE date.
7. Define reaction coordinate or extent of reaction.
8. What is the criterion of chemical reaction equilibrium?
9. Define the COP in refrigeration.
10. Write the name of any four refrigerants.
PART B
11. (a) What are the methods used to determine the partial molar property
and explain it.
Or
(b) Derive the different forms of Gibbs-Duhem equation and give its application.
12. (a) Mixtures of n- Heptane (A) and n- Octane (B) are expected to behave ideally.
The total pressure over the system is 101.3 kPa. Using the vapour pressure. Data
given below,
(i) Construct T - x1 – y1 diagram at P = 101.3 kPa
(ii) Construct P – x1- y1 diagram at T = 388 k.
T,K 371.4 378 383 388 393 398.6
PA,kPa 101.3 125.3 140 160 179.9 205.3
PB,kPa 44.4 55.6 64.5 74.8

86.6 101.3
Or
(b) An equimolar solution of benzene and toluene is totally evaporated at a
Constant temperature, the vapour pressure of benzene and toluene are 135.4 and 54
kPa respectively. What are the pressure at the beginning and at the end of the
vaporization process?
13. (a) The azeotrope of the benzene (1) – ethanol(2) system has a composition of
44.8% (mol) ethanol with a boiling point of 341.4 K at 101.3 kPa. At this temperature
the vapour pressure of benzene is 68.9 kPa and the vapour Pressure of ethanol is 67.4
kPa. What are the activity co-efficients in a solution containing 10% alcohol? Use Van
Laar equation.
(or)
(b) The following results were obtained by experimental VLE measurements on
the system, ethanol (1) – benzene(2) at 101.3 kPa. Test whether the data are
thermodynamically consistent or not.
X1 0.003 0.449 0.7 0.9

Y1 0.432 0.449 0.52 0.719
s
P , kPa
1
65.31 63.98 66.64 81.31
s
P , kPa
2
68.64 68.64 69.31 72.24
14. (a) Obtain the relationship between standard free energy and equilibrium
constant.
Or
(b) A gas mixture containing 2 moles N2, 7 moles of H2 and 1 mole NH3 Initially,
is undergoing the following reaction:
N2 + 3H2 – 2NH3.
(i) Derive the expression for the mole fractions of various components in
the reaction mixture in terms of extent of reaction.
(ii) Explain how the conversion of the limiting reactant is related to the extent of reaction.
15. (a) Explain the working of an absorption refrigeration cycle with a neat
diagram.
Or
(b) A vapour compression cycle using ammonia as refrigerant is employed in
manufacturing plant. Cooling water at 288 K enters the condenser at a rate of 0.25
kg/s and leaves at 300 K. Ammonia at 294 K condenses at a rate of 0.5 kg/minute.
Enthalpy of liquid ammonia at 294 K is 281.5 kJ/kg. The compressor efficiency is 90 %.
Saturated ammonia vapour at 258 K and enthalpy of 1426 kJ/kg enters the compressor
and refrigeration capacity in tons
B.TECH CHEMICAL ENGINEERING

PART –A
Define chemical potential. What is its physical significance?
What is the characteristics of an ideal solutions? State Lewis – Randall rule.
Give the condition of criteria for phase equilibrium.
Explain the maximum and minimum boiling azeotropes.
Name the activity coefficient – composition models of phase – equilibrium.
Explain Wilson equation.
What is the modified equation of Raoult’s Law?
State the standard Gibbs energy change of reaction.
How the equilibrium constant is related to gas phase compositions?
9. Define the coefficient of performance of a refrigerator.
10. Name the refrigeration cycles.
PART – B
11. For the binary mixture of A and B, the activity coefficients are given by.
1n  1  AX12 and 1n 2  AX12
The vapour pressure of A and B at 353 K are 119.96 kPa and 79.97 kPa respectively.
Does an azeotrope exist at 353 k? If so, what is the azeotropic pressure and
composition for A = 0.6. knowledge of partial properties.
12. (b) Define exceed properties of mixture and obtain the equation for
activitycoefficients.
13. (a) The following data were reported got VLE for ethanol – water system at 298 k.
Test whether the data are thermodynamically consistent.
X 0 0 0 0 0 0 0 0 1
1 . . . . . . . .
1 1 2 3 4 5 8 0
2 6 2 2 3 7 3
2 3 6 0 7 9 0
Y 0 0 0 0 0 0 0 0 1
1 . . . . . . . .
4 5 5 5 6 6 8 0
7 3 6 8 2 8 4
4 1 2 2 0 5 9
P 3 5 6 6 6 7 7 7 7
k . . . . . . . . .
P 1 5 0 3 7 0 3 7 8
a 7 7 2 8 4 2 0 8 6
Or
13. (b) A mixture of A and B conforms closely to Raoult’s row. The pure
component vapor
Pressure P A and P B in kpa are given by (tc)
sat sat
2945 2973
Ln P A = 14.27- ; Ln P B  14.20 
sat sat
t t 224 tt 209
If the bubble point of a certain mixture of A and B is at 76C at a total pressure of 80
Kpa, find the composition of then first vapor that forms,
14. (a) Derive the relation ∆G = - RT1nk

(b) What are the effects of P,T and the total strichiometric number V on the
equilibrium Compositions for the gas – phase reactions?
Or
15. (b) Industrial trade methanol can be produced according to the reaction.
CO(g) + 2H2(g)  CH3OH(g)
<Some text not clear> -1.3484 KJ. If an equi molar mixture of Co and H2 is <Some text
not clear> contained at 100 K and 1 bar, determine the fraction of Co that is <Some text
not clear> OH at equilibrium. Assume that the reaction mixture behaves the remain .
15 (a) (i) <Some text not clear> the coefficient of performance of the our not
refrigerator.
(ii) What are the important properties of a refrigerant.

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JCT COLLEGE OF ENGINEERING AND TECHNOLOGY

The definition of chemical potential is the fundamental new property is called

2. Define ideal solution?

Based on an idealization of solution behavior called the ideal solution

3. What is fundamental property for single phase fluid system?

4. What is multiple phases?

5. What is partial molar property of spaces I in the solution?

The partial molar property of spaces in the solution is

6. What are summability relations?

7. What is molar property of spaces?

The molar property of spaces I is  Xi dMi  0 Where Mi  molar property of

spaces i as it exist in solution.

9. What is partial molar property ?

A partial molar property of a constituent spaces in an ideal – gas mixture is equal to

10. Give the expression for independent of pressure ?

H ig   yiH iig is the expression for independent of pressure.

11. What is fugacity coefficient for pure gases ?

The fugacity coefficient for pure gases is

12. How the fugacity of a pure liquid is calculated ?

13. Write the exponential form for pointing factor ?

14. What is partial residual property ?

16. What is fugacity coefficient of spaces i is the solution ?

18. What is fugacity coefficient from the viral equation of state ?

21. Define Lewis – Randall role

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

The equation for fundamental excess property relation is

23. What happen if the fugacity of spaces I is in the physical state ?

The fugacity coefficient of spaces I in an ideal solution is equal to the fugacity

24. What excess property ?

26. Give the equation for In  o is a partial property with respects to G P / RT .

The equation for In  o is a partial property with respect to G P / RT is

27. What is the fugacity coefficient for vapour & liquid ?

iV  1I  isat

The equation for ideal gas state fugacity of pure spaces I is

fi fugacity for pure spaces i

Solution property is denoted by M

31. Give some examples for solution properties ?

U, H, S, G are some of the examples for solution property

32. Give some examples for partial properties ?

Ui , Hi , Si and Gi are some of the examples for partial property.

33. Give some examples for pure spaces property ?

35. Evaluate the fugacity coefficient through cubic equation ?

37. What is the result of  phase ?

1  1  ................  1 ( i  1, 2..........N )

38. What is partial molar volume for Vi ?

39. Why  xidmi  0 ?

The equation  xidmi  0 is satisfied for all Changes in P, T and

changes of state in a homogenous state.

40. What is M value for binary solution ?

The M value for binary solution is

41. What is the pressure value for I species in the mixture ?

The pressure value for is species in the mixture is

43. Derive the pointing factor ?

Infi ViI ( P  Pisat )

44. What is residual Gibbs energy ?

45. Write the equation for fundamental excess property relation ?

1. A 30 percent by mole methanol-water solution is to be prepared. How many

Solution: Molar volume of the desired solution is

2. Laboratory alcohol containing 96% alcohol and 4% water is to be diluted to a