Date post: | 07-Apr-2018 |
Category: |
Documents |
Upload: | raazia-mir |
View: | 223 times |
Download: | 0 times |
of 66
8/6/2019 Thermodyn Compiled Gmmadhu
1/66
e-Notes by G.M.Madhu, RVCE, Bangalore
Fugacity: It is derived from Latin, expressed as fleetness or escaping tendency. It is used
to study extensively phase and chemical reaction equilibrium.We know thatSdTVdPdG = -(1)
For isothermal conditionVdPdG =
For ideal gases
P
RTV =
= dPP
RTdG .
PRTddG ln=
To find Gibbs free energy for an real gases. True pressure is related by effective
pressure. Which we call fugacity(f).
fRTddG ln= -------(2)Applicable for all gases (ideal or real)
On differentiation+= fRTG ln
Is an constant depends on temperature and nature of gas.
fugacity has same units as pressure for an ideal gas.
For ideal GasesSdTVdPdG =
For Isothermal conditionsVdPdG =
from equation (2)VdPfRTd =ln
dPRT
Vfd =ln
p
dpfd =ln
pdfd lnln =pf = Fugacity = Pressure for Ideal gases
8/6/2019 Thermodyn Compiled Gmmadhu
2/66
Fugacity coefficient )( : Fugacity coefficient ids defined as the ratio of fugacity of acomponent to its pressure.
P
f=
Is the measure of non ideal behavior of the gas.
Standard State: Pure gases, solids and liquids at temperature of 298k at 1 atmosphere are
said to exist at standard condition. The property at this condition are known as standardstate property and is denoted by subscripto.
oG = Standard Gibbs free energy
of = Standard fugacity
Estimation of fugacity for gases
I methodSdTVdPdG =
For Isothermal conditionsVdPdG =
from equation (2)VdPfRTd =ln
dPRT
Vfd =ln
Integrating the above equation with the limits 0 to f and pressure 1 to P
=P
dPRT
Vfd
1
ln
Lower limit is taken as P =1 atm
At 1 atm assuming the gases expected to behave ideally
=P
VdPRT
f1
1ln
if PVT relations are known , we can find fugacity at any temperature and pressure
8/6/2019 Thermodyn Compiled Gmmadhu
3/66
II method
Using compressibility factorVdPdG =
VdPfRTd =ln --------------(2)
V in terms of compressibility terms it is given as
P
ZRTV =
Substitute V in equation 2
dPp
ZRTfRTd =ln
pZdfd lnln =subtracting both sides by dlnP
PdPZdPdfd lnlnlnln =
PdzP
fd ln)1(ln =
PdZd ln)1(ln =Integrating the equation from 1 to and 0 to P
=P
PdZd01
ln)1(ln
=P
P
dPZ
0
)1(ln
Using generalized charts: using reduced properties a similar chart as compressibility chart
is predicted for fugacity.
r
r
dPP
ZPf = 1ln
Fugacity is plotted against various reduced pressure at various reduced temperature
8/6/2019 Thermodyn Compiled Gmmadhu
4/66
Using Residual Volume( ): The residual volume is the difference between actualvolume (V) and the volume occupied by one mole of gas under same temperature and
pressureP
RTV = ,
P
RTV +=
fRTddPP
RTdG ln=
+=
fRTdP
dPdP
RTRT ln=
+
=
P
fddP
RTln
= dPRTPf
ln
Problem
For isopropanol vapor at 200oC the following equation is available
Z=1- 9.86 x 10-3P-11.45 x 10-5P2
Where P is in bars. Estimate the fugacity at 50 bars and 200oC
253 1041.111086.91 PPRT
PVZ
==
)1041.111086.91( 253 PPP
RT
p
ZRTV ==
=P
VdPRT
f1
1ln
=P
dPPPP
RT
RTf
1
253)1041.111086.91(
1ln
=50
1
50
1
53
50
1
1041.111086.9ln PdPdPpdpf
( )2
)150(1041.111501086.9
1
50lnln
2253
= f
f=26.744 bar
8/6/2019 Thermodyn Compiled Gmmadhu
5/66
5348.050
744.26 ===P
f
Fugacity for liquids and solids
General expression for fugacity is
=P
VdPRT
f1
1ln
For solids and liquids at constant temperature the specific volume does not change
appreciably with pressure, therefore the above equation is integrated by taking volume
constant. Integrating the above equation from condition 1 to 2
=2
1
2
1
lnP
P
f
f
dPRT
Vf
( )121
2ln PPRT
V
f
f=
Problem:
Liquid chlorine at 25oC has a vapour pressure of 0.77Mpa, fugacity 0.7Mpa and Molarvolume 5.1x 10-2 m3/kg mole. What is the fugacity at 10 Mpa and 25oC
PaP
PaP
6
2
6
1
1010
1077.0
=
=
Paf6
1 107.0 = KT 298= KgmoleJ
R 8314=
( )12
1
2ln PPRT
V
f
f=
f=0.846Mpa
Activity(a):
It is defined as the fugacity of the existing condition to the standard state fugacity
of
fa =
Effect of pressure on activity
8/6/2019 Thermodyn Compiled Gmmadhu
6/66
The change in Gibbs free energy for a process accompanying change of state from
standard state at given condition at constant temperature can be predicted as
fRTG ln= oo fRTG ln=
aRT
f
fRTGGG
o
o lnln =
==
at constant temperature VdPdG =
=G
G
P
PO o
dPVdG
)( oPPVG = )(ln oPPVaRT =
)(ln oPPRT
Va = This equation predicts the effect of pressure on activity
Effect of Temperature on Activity
aRTGGG o ln==
T
G
T
GaR
o
=ln
Differentiating the above equation with T at constant P
P
o
P
P T
T
G
T
T
G
dT
adR
=
ln
22
ln
RT
H
RT
H
dT
adR
o
P
+=
2
ln
RT
HH
dT
adR
o
P
=
This equation predicts the effect of temperature on activity.
8/6/2019 Thermodyn Compiled Gmmadhu
7/66
Properties of solutionsThe relationships for pure component are not applicable to solutions. Which needs
modification because of the change in thermodynamic properties of solution. The
pressure temperature and amount of various constituents determines an extensive state.The pressure, temperature and composition determine intensive state of a system.
Partial Molar properties:
8/6/2019 Thermodyn Compiled Gmmadhu
8/66
The properties of a solution are not additive properties, it means volume of solution is not
the sum of pure components volume. When a substance becomes a part of a solution it
looses its identity but it still contributes to the property of the solution.
The term partial molar property is used to designate the component property when it is
admixture with one or more component solution.
A mole of component i is a particular solution at specified temperature and pressure has
got a set of properties associated with it like etcSV iP, . These properties are partially
responsible for the properties of solution and it is known as partial molar property
It is defined as
( )ij
n
nMM
jnPTi
i
=
,,
iM = Partial molar property of component i.
M= Any thermodynamic property of the solutionn = Total number moles in a solutionni=Number of moles of component I in the solution
This equation defines how the solution property is distributed among the components.
Thus the partial molar properties can be treated exactly as if they represented the molarproperty of component in the solution.
The above expression is applicable only for an extensive property using
We can write
= ii MnnM ii xn
n=
= ii MxM
xi=Mole fraction of component i in the solution.
Measuring of partial molar properties
To understand the meaning of physical molar properties consider a open beaker
containing huge volume of water in one mole of water is added to it, the volume increaseis 18x 10-6m3 If the same amount of water is added to pure ethanol the volume increased
is approximately 14 x 10-6m3 this is the partial molar volume of H2Oin pure ethanol. The
difference in volume can explain the volume applied by water molecules depending onwater molecules surrounding to them. When water is added to large amount of ethanol,
ethanol molecules hence volume occupied surround all the water molecules will be
different in ethanol.
8/6/2019 Thermodyn Compiled Gmmadhu
9/66
If same quantity of water is added to an equimolar mixture of H 2O and ethanol, the
volume change will be different. Therefore Partial molar property change with
composition. The intermolecular forces also changes with change in thermodynamicproperty.
Let wV = Partial molar volume of the water in ethanol water solution
wV = Molar volume of pure water at same temperature and pressuret
V =Total volume of solution when water added to ethanol water mixture and
allowedfor sufficient time so that the temperature remains constant
ww
t VnV =
w
t
wn
VV
=
In a process a finite quantity of water is added which causes finite change in composition.
wV = property of solution for all infinitely small amount of water.
=
= w
t
w
t
vwn
V
n
VV
0lim
Temperature pressure an number of moles of ethanol remains constant during addition of
water.
EnPTw
t
wn
VV
,,
= nE-no of moles of ethanol
The partial molar volume of component i
inPTi
t
i
j
n
VV
=
,,
Partial molar properties and properties of the solution
Consider any thermodynamic extensive property (Vi, Gi etc) for homogenous system can be
determined by knowing the temperature, pressure and various amount of constituents.
Let total property of the solution
nMMt =+++= 321 nnnn
1,2,3 represents no of constituents
Thermodynamic property is a )jnnnnPTf 321 ,,,,For small change in the pressure and temperature and amount of various constituents can
be written as
8/6/2019 Thermodyn Compiled Gmmadhu
10/66
+
+
+
+
=
i
inTP
t
nnpT
t
np
t
nT
tt dn
P
Mdn
P
MdT
P
MdP
P
MdM
j,,
1
,,,,, 32
At constant temperature and pressure dPand dTare equal to zero.The above equation reduces to
dnin
MdM
ijnTP
ni
i i
tt
=
=
=,.1
dMt in terms of partial molar property
i
n
i
i
t dnMdM =
=1
iM is an extensive property depends on composition and relative amount of
constituents.
All constituent properties at constant temperature and pressure are added to give the
property of the solution.
+++= 332211dnMdnMdnMdM
t
( )dnxMxMxMdM t +++= 332211( )
332211332211nMnMnMnxMxMxMM t ++=+++=
= iit MnM
ProblemA 30% mole by methanol water solution is to be prepared. How many m 3 of puremethanol (molar volume =40.7x10-3m3/mol) and pure water (molar volume =
18.068x10-6m3/mol) are to be mixed to prepare 2m3 of desired solution. The partial molar
volume of methanol and water in 30% solution are 38.36x10-6 m3/mol and 17.765x10-6
m3/mol respectively.
Methanol =0.3 mole fraction
Water=0.7 mole fraction
Vt=0.3 x38.36x10-6+0.7x17.765x10-6
=24.025x10
-6
m
3
/molFor 2 m3soolution
mol36
10246.8310025.24
2=
=
Number of moles of methanol in 2m3solution
=83.246x103x0.3= 24.97x103mol
8/6/2019 Thermodyn Compiled Gmmadhu
11/66
Number of moles of water in 2m3solution
=83.246x103x07= 58.272x103mol
Volume of pure methanol to be taken
= 24.97x103
x 40.7x10-3
=1.0717 m3
Volume of pure water to be taken
= 58.272x103 x 18.068x10-6 =1.0529 m3
Estimation of Partial molar properties for a binary mixture :Two methods for estimation
Analytical Method and Graphical Method(Tangent Intercept method)
Analytical Method: The general relation between partial molar property and molar
property of the solution is given by
knPTK
kixMxMM
,, = ik x1
For binary mixture2,1 == ki
PTx
MxMM
,2
21
= 112 =+ xx , 12 1 xx = , 12 xx =
At constant Temperature and pressure
+=
1
11 )1(
x
MxMM ------(a)
=
1
2 1 x
MxMM -----------(b)
The partial molar property (extensive property) for a binary mixture can be estimated
from the property of solution using above equations (a) and (b).
8/6/2019 Thermodyn Compiled Gmmadhu
12/66
Tangent Intercept method:
This is the graphical method to estimate partial molar properties. If the partial molar
property (M) is plotted against the composition we get the curve as shown in the figure.
Suppose partial molar properties of components required at any composition, and then
draw a tangent to this point to the curve. The intercept of the tangent with two axis x1=1
and x1=0 are I1 and I2.
Slope of the tangent 1
2
1 x
IM
dx
dM =
1
12dx
dMxIM =
1
12dx
dMxMI =
Comparing I2 with equation (b) 22 MI =
and also (right hand side)1
1
1 1 x
MI
dx
dM
=
1
11 1dx
dMxMI =
8/6/2019 Thermodyn Compiled Gmmadhu
13/66
1
11 1dx
dMxMI += Comparing with equation(a) 11 MI =
The intercept of the tangent gives the partial molar properties.
Limiting cases: For infinite dilution of component when at x1=0 a tangent is drawn atx1=0 will give the partial molar property of component 1 at infinite dilution )( 1
M and
tangent is drawn at x2=0 or x1=1 will give infinite dilution )( 2
M of component 2
2
M
Problem
The Gibbs free energy of a binary solution is given by
mol
calxxxxxxG )10(150100 212121 +++=
(a) Finnd the partial molar free energies of the components at x2=0.8 and also at infinitedilution.
(b) Find the pure component properties
Sol:mol
calxxxxxxG )10(150100
212121+++=
Substitute 12 1 xx = and simplifying
15049891
2
1
3
1++= xxxG
+=1
11 )1(x
GxGG
491627 12
1
1
=
xxx
G
101163518 12
13
11 ++= xxxG
=1
12x
GxGG
1508182
1
3
12+= xxG
8/6/2019 Thermodyn Compiled Gmmadhu
14/66
To find the partial molar properties of components 1 and 2
x2=0.8, x1=1-0.8 = 0.2
1011635181
2
1
3
11++= xxxG
mol
calG 944.1021 =
1508182
1
3
12+= xxG
mol
calG 824.1492 =
At infinite dilution
0111 ==
atxGG
mol
calG 1011 =
1122 ==
atxGG orx2=0
mol
calG 1602 =
To find the pure component property
1111 == atxGG
mol
calG 1001 =
0122 == atxGG
mol
calG 1501 =
Chemical Potential:
8/6/2019 Thermodyn Compiled Gmmadhu
15/66
It is widely used as a thermodynamic property. It is used as a index in chemical
equilibrium, same as pressure and temperature. The chemical potential i of component
i in a solution is same as its partial molar free energy in the solution iG
The chemical potential of component i
jnPTi
t
in
GGi
,,
==
[ ]= 21,,, nnTPfGt
= + + =ni
1i
i
n,Ti
t
n,P
t
n,T
tt
dnn
GdT
T
GdP
P
GdG
j
+
+
= ii
nP
t
nT
tt dndT
T
GdP
P
GdG
,,
For closed system there will be no exchange of constituents (n is constant)
dTSdPVdG ttt =
at constant temperature
t
T
VP
G =
at constant pressure
t
P
ST
G=
+= ii
tttdndTSdPVdG
At constant temperature and pressure
= iiPTt dndG ,
For binary solution 2211 xxG +=
8/6/2019 Thermodyn Compiled Gmmadhu
16/66
Effect of temperature and pressure on chemical potential
Effect of temperature:
We know that
jnPTi
t
in
GGi
,,
== -------------------(1)
differentiating equation (1) with respect to T at constant P
inP
i
Tdn
G
T
=
2
,
---------------------(2)
SdTVdPdG = ---------(3)
differentiating equation (3) with respect to T at constant P
ST
G
P
=
differentiating again w r t ni
i
nPi
t
i
Sn
S
nT
G
j
=
=
,
2
iS is partial molar entropy of component I
2
,
T
TT
T
Ti
i
nP
i
=
2T
ST ii =
TSHG =
In terms of partial molar properties
iii STHG =
8/6/2019 Thermodyn Compiled Gmmadhu
17/66
iii
iii
STH
STH
=
=
2
, T
H
T
i
nP
i =
This equation represents the effect of temperature on chemical potential.
Effect of Pressure:
We know that
jnPTi
t
in
GGi
,,
== -------------------(4)
differentiating equation (4) with respect to T at constant P
inT
i
Pdn
G
P
=
2
,
---------------------(5)
SdTVdPdG = ---------(3)
differentiating equation (3) with respect to P at constant T
VP
G
T
=
differentiating again w r t ni
i
nTii
V
n
V
nP
G
j
=
=
,
2
,
i
nT
i VP
=
,
This equation represents the effect of pressure on chemical potential
8/6/2019 Thermodyn Compiled Gmmadhu
18/66
Fugacity in solutions
For pure fluids fugacity is explained as
fRTddG ln=
1lim 0 =P
fP
The fugacity of the component i in the solution is defined as analogously by
ii fRTdd ln=
1P
flim
i
i
0P =
i is Chemical potential
if is partial molar fugacity
For ideal gases Tii PyP =
PT Total pressure.
Fugacity in Gaseous solutions
We know that
jnPTi
t
in
GGi
,,
== ------(1)
differentiating equation (1) with respect to T at constant P
inT
i
Pdn
G
P
=
2
,
-----(2)
SdTVdPdG = -----(3)
differentiating equation (3) with respect to P at constant T
VP
G
T
=
differentiating again w r t ni
8/6/2019 Thermodyn Compiled Gmmadhu
19/66
i
nTii
Vn
V
nP
G
j
=
=
,
2
,
i
nT
i VP
=
,
PVii =
dPVfRTd ii =ln
Subtracting both sides by iPd ln
ii ydPdPd lnlnln +=
Composition is constant dlnyi=0
The above equation can be written as
P
dP
PdPd i == lnln
Modifying equation (a)
i- Represents fugacity of the component i in the solution.
Ideal solutions
An ideal mixture is one, which there is no change in volume due to mixing. In other
words for an ideal gaseous mixture partial molar volume of each component will be equal
to its pure component volume at same temperature and pressure.
dPRT
Vfd ii =ln
ii
ii PddPRT
VPdfd lnlnln =
ii
i
i PddPRT
V
P
fd lnln =
[ ] dPP
RTV
RTd ii
= 1ln
8/6/2019 Thermodyn Compiled Gmmadhu
20/66
iiVV = and == iiii VxxVV --- Raoults law
Ideal solutins are formed when similar components or adjacent groups of group are
mixed ii VV =
Eg: Benzene-Toluene
Methanol- Ethanol
Hexane- HeptaneSolutin undergo change in volume due to mixing are known as non ideal solutions
iiVV
Eg: Methanol-Water
Ethanol-water.Ideal solutions formed when the intermolecular force between like molecules and unlike
molecules are of the same magnitude.
Non-ideal solutions are formed when intermolecular forces between like molecules andunlike molecules of different magnitude.
For ideal solutions
ii
t VnV
= -------------------(1)
Vi is the molar volume of pure component I
ij
i
t
iVn,P,T
n
VV =
= ----------------- (2)
The residual volume for the pure component is
p
RTVi =
Therefore we know from reduced properties
=
P
ii dP
P
RTV
RTP
f
0
1ln ----(3)
For component i in terms of partial molar properties
=
P
i
i
i dPP
RTV
RTP
f
0
1ln ----(4)
Subtracting equation (3) from (4)
( ) =P
ii
ii
i dPVVRTPf
Pf
0
1ln ----(5)
we know that PyP ii =equation (5) reduces to
( ) =P
ii
ii
i dPVVRTyf
f
0
1ln
8/6/2019 Thermodyn Compiled Gmmadhu
21/66
comparing equation (2)
1=ii
i
yf
f
iii yff = --Lewis Randal rule
Lewis Randal rule is applicable for evaluating fugacity of components in gas mixture.Lewis Randal rule is valid for
1. At low pressure when gas behaves ideally.2. When Physical properties are nearly same.
3. At any pressure if component present in exess.
Henrys LawThis law is applicable for small concentration ranges. For ideal solution Henrys law is
given as
iii kxf =
iii kxP =
ki- HenrysConstant, if -Partial molar fugacity,
iP -Partial pressure of component i.
Non Ideal solutions
For ideal solutions iii kxf = ------------(a)For non ideal solutions iiii kxf = ----------(b)
Where i is an activity coefficient of component i.
Comparing equation (a) and (b)
==i
ii
f
f Non ideal solution / Ideal solution
For both ideal and Non ideal solutions the fugacity of solution is given by
equation
=i
i
i
x
fxf lnln
= iix lnln
Problem:A terinary gas mixture contains 20mole% A 35mole% B and 45mole% C at 60 atm and
75oC. The fugacity coefficients of A,B and C in this mixture are 0.7,, 0.6 and 0.9.
Calculate the fugacity of the mixture.
8/6/2019 Thermodyn Compiled Gmmadhu
22/66
Solution:
ccBBAA xxx lnlnlnln ++=
)9.0ln(45.0)6.0ln(35.0)7.0ln(2.0ln ++=
2975.0ln =7426.0=
P
f= , f =44.558atm
Gibbs Duhem Equation
Consider a multi component solution having ni moles of component I the property of
solution be M in terms of partial molar properties
i
t
MnnMM -----------------------(1).Where n is the total no of moles of solution
Differentiating eq (1) we get
iiii dnMMdnnmd +=)( ----------------------------(2)We know that
= 21 ,,, nnPTfnM
+
+
+
= ,,,2
1
,,1,,,, 313.212121
)()()()()( dn
n
nMdn
n
nMdP
P
nMdT
T
nMnM
nnPTnnPTnnTnnP
+
+
=
i
nPTinnTnnP
dnn
nMdP
P
MndT
T
MnnM
j,,,,,,
)()()()(
2121
From the definition of partial molar properties
+
+
=
ii
nnTnnP
dnMdPP
MndT
T
MnnM
2121 ,,,,
)()()( ----------(3)
Subtracting equation (2) from equation (3)
=
+
0)()(
2121 ,,,,
ii
nnTnnP
MdndPP
MndT
T
Mn------------------(4)
Equatin (4) is the fundamental form of Gibbs Duhem equation
8/6/2019 Thermodyn Compiled Gmmadhu
23/66
Special Case
At constant temperature and pressure dT and dP are equal to zero. The equation becomes
=0ii Mdx
For binary solution at constant temperature and pressure the equation becomes
02211 =+ MdxMdx
0)1( 2111 =+ MdxMdx ------------(5)
dividing equation(5) by dx1
0)1(1
21
1
11 =+
dx
Mdx
dx
Mdx
The above equation is Gibbs Duhem equation for binary solution at constant temperature
and pressure in terms of Partial molar properties.
Any Data or equation on Partial molar properties must satisfy Gibbs Duhemequation.
Problem:
Find weather the equation given below is thermodynamically consistent
)10(150100 212121 xxxxxxG +++=
1
11 )1(
x
GxGG
+=
1
12x
GxGG
=
1011635181
2
1
3
11+++= xxxG
1508182
1
3
12+= xxG
167054 12
1
1
1 += xxdx
Gd
1
2
1
1
2 1654 xx
dx
Gd=
G D equation
0)1(1
21
1
11 =+
dx
Mdx
dx
Mdx
0)x16x54)(x1()16x70x54(x1
2
111
2
11=
8/6/2019 Thermodyn Compiled Gmmadhu
24/66
It satisfies the GD equation, the above equation is consistent.
Phase Equilibrium
Criteria for phase equilibrium: If a system says to be in thermodynamic equilibrium,Temperature, pressure must be constant and there should not be any mass transfer.
The different criteria for phase equilibrium are
At Constant U and V: An isolated system do not exchange mass or heat or work with
surroundings. Therefore dQ=0, dW=0 hence dU=0. A perfectly insulated vessel at
constant volume dU=0 and dV=0.0
,VUdS
At Constant T and V: Helmoltz free energy is given by the expressionTSUA =TSAU +=
on differentiatingSdTTdSdAdU ++=
we know thatPdVTdSdU =
SdTTdSdAPdVTdS ++=
SdTPdVdA =
Under the restriction of constant temperature and volume the equation simplifies to
0, VTdA
At Constant P and T
8/6/2019 Thermodyn Compiled Gmmadhu
25/66
The equation defines Gibbs free energy TSHG =
TSPVUG +=SdTTdSVdPPdVdUdG ++=
SdTTdSVdPPdVdGdU
++= TdSPdVdGdGdU +=Under the restriction of constant Pressure and Temperature the equation simplifies to
0,
PTdG
This means the Gibbs free energy decreases or remains un altered depending on the
reversibility and the irreversibility of the process. It implies that for a system at
equilibrium at given temperature and pressure the free energy must be minimum.
Phase Equilibrium in single component system
Consider a thermodynamic equilibrium system consisting of two or more phases of a
single substance. Though the individual phases can exchange mass with each other.
Consider equilibrium between vapor and liquid phases for a single substance at constanttemperature and pressure. Appling the criteria of equilibrium
0=dG
0=+ ba dGdG adG and bdG are chane in free energies of the phases a and b respectively.
We know that
ii dnGSdTVdPdG +=For phase a
aaaaaaa dnGdTSdPVdG +=For phase b
bbbbbbbdnGdTSdPVdG +=
At constant temperature and pressureaaa
dnGdG = , bbb dnGdG =
For a whole system to be at equilibrium
ba
ba
dndn
or
dndn
=
=+ 0
[ ] 0= aba dnGG
8/6/2019 Thermodyn Compiled Gmmadhu
26/66
ba GG =When two phases are in equilibrium at constant temperature and pressure, Gibbs free
energies must be same in each phase for equilibrium.CfRTCfRT ba +=+ lnln
ba
ff =
Clapeyron Clausius Equation
Clapeyron Clausius Equation are developed two phases when they are in equilibrium
(a) Solid- liquid
(b) Liquid-Vapor
(c) Solid Vapor
Consider any two phases are in equilibrium with each other at given temperature and
pressure. It is possible to transfer some amount of substance from one phase to otherin a thermodynamically reversible manner(infinitely slow).The equal amount of
substance will have same free energies at equilibrium .
Consider GA is Gibbs free energy in phase A and GB is Gibbs free energy in phase Bat equilibrium.
GA=GB ------(1)
G = GA -GB =0 ------(2)
At new temperature and pressure the free energy / mole of substance in phase A isAA dGG + for Phase B BB dGG +
From basic equationSdTVdPdG -----(3)
dTSdPVdG AAA dTSdPVdG BBB
dTSdPVdTSdPV BBAA [ ] [ ]
ABAB SSdTVVdP
V
S
dT
dP
=
8/6/2019 Thermodyn Compiled Gmmadhu
27/66
V represents the change in volume when one mole of substance pases from
phase A to Phase B
T
QS=
VTQ
dTdP =
[ ]AB VVT
Q
dT
dP
----(4)This is a basic equation of Clapeyorn Clasius equation.
BVapor state A- Liquid state
Q=molar heat of vaporization = VH
VB is molar volume in vapor state, VA is molar volume in liquid state,
[ ]lg
VVT
Q
dT
dP
=
Vg>>>Vl (Gas volume is very high when compared to liquid volume)
g
V
TV
H
dT
dP =
=VH (Latent heat of vaporization),P
RTVg =
TRT
P
dT
dP =
2T
dT
RP
dP =Integrating the above equation from T1to T2 and pressure from P1 to P2.
211
2
T
1
T
1
RP
Pln
This equation is used to calculate the vapor pressure at any desired temperature.
= 21
2
1
T
T
P
PT
dT
RP
dP
8/6/2019 Thermodyn Compiled Gmmadhu
28/66
Problem:
The vapor pressure of water at 100oC is 760mmHg. What will be the vapor pressure
at 95oC. The latent heat of vaporization of water at this temperature range is
41.27KJ/mole.
=
2
1
P
mmHg760P
K36827395T
K373273100T
2
1 ==
211
2
T
1
T
1
RP
Pln
= 36813731314.8 1027.41760Pln3
2
mmHg3.634P2 =
Phase Equilibrium in Multi component system
An heterogeneous system contains two or more phases and each phase contains two ormore components in different proportions. Therefore it is necessary to develop phase
equilibrium for multi component system in terms of chemical potential.
The partial molar free energy or chemical potential is given as
jnPTi
iin
GG
,,
==
For a system to be in equilibrium with respect to mass transfer the driving force for
mass transfer( Chemical potential) must have uniform values for each component inall phases.
Consider a heterogeneous system consists of phase ,, andcontaining various components 1,2,3-------C , that constitutes the system.
The symbolk
i represents chemical potential of component iin phase k.
At constant temperature and pressure, for the criterion for equilibrium is
dG=0 ----(1)
Free energy for multi component system given by the expression
+= ii dnSdTVdPdG ------(2)At constant Temperature and pressure
ii dndG ----(3)
8/6/2019 Thermodyn Compiled Gmmadhu
29/66
Comparing equation 1 and 3
= ii dn0For multi component system
= =
=C
i k
k
i
k
i dn1
0
Expanding the above equation
0
22222222
11111111
=+++
++++
++++
cccccccc dndndndn
dndndndn
dndndndn
-----(4)
Since the whole system is closed it should satisfy the mass conservation equation
0
222
111
=++
+++
+++
CCC dndndn
dndndn
dndndn
----(5)
The variation in number of moles dni is independent of each other. However the sum of
change in mole in all the phases must be zero. For the criterion of equilibrium is that the
chemical potential of each component must be equal in all phases.
CCC ==
==
==
222
111
At constant temperature and pressure the general criterion for thermodynamic
equilibrium in closed system for heterogeneous multi component system
At constant T and P
iii == for i=1,2,3--------C
Since +== iii fRTG ln
The above equation is also satisfied in terms of fugacity
iii fff == for i=1,2,3--------C
8/6/2019 Thermodyn Compiled Gmmadhu
30/66
Phase Diagram for Binary solution
Constant pressure equilibrium
Consider a Binary system made up of component A and B. Where it is assumed to bemore volatile than B where vapour pressure A is more than B. When the pressure is
fixed at the liquid composition can be changed the properities such as temperature and
vapour compositions get quickly determined VLE at constant pressure is represented onT-xy diagram.
Boiling point diagrams
When temperature is plotted against liquid(x) and vapour(y) phase composition. The
upper curve gives and lower curve gives. The lower curve is called as bubble point
curve and upper curve is called as Dew point curve. The mixture below bubble point is
sub cooled liquid and above the Dew point is super heated vapour. The region betweenbubble point and Dew point is called mixture of liquid and vapour phase.
Consider a liquid mixture whose composition and temperature is represented bypoint A. When the mixture is heated slowly temperature rises and reach to point B,
where the liquid starts boiling, temperature at that point is called boiling point of whether
heating mixture reaches to point G when all liquids converts to vapour the temperature
at that point is called as Dew point. Further heating results in super heated vapour. Thenumber of tic lies connects between vapour and liquid phase. For a solution the term
boiling point has no meaning because temperature varies from boiling point to Dew point
at constant pressure.
8/6/2019 Thermodyn Compiled Gmmadhu
31/66
Effect of pressure on VLEThe boiling point diagram is drawn from composition x=0 to x=1, boiling point of pure
substances increases with increase in pressure. The variation of boiling point diagrams
with pressure is as shown in diagram. The high pressure diagrams are above lowpressure.
8/6/2019 Thermodyn Compiled Gmmadhu
32/66
Equilibrium diagram
Vapor composition is drawn against liquid comp at constant pressure. Vapour is always
rich in more volatile component the curve lies above the diagonal line.
Constant temperature Equilibrium
VLE diagram is drawn against composition at constant temperature. The upper curve is
and lower curve is drawn at vapour comp(y). Consider a liquid at known pressure andcomposition at point A as the pressure is decreases and reaches to point B where it
starts boiling further decreases in pressure reaches to point C when all the liquid
converts to vapour, further decreases in pressure leads to formation of super heatedvapour. In between B to C both liquid and vapour exists together
8/6/2019 Thermodyn Compiled Gmmadhu
33/66
Non ideal solution
An ideal solution obeys Raoults law and p-x line will be straight. Non ideal solution do
not obey Raoults law. The total pressure for non ideal solutions may be greater or lower
than that for ideal solution. When total pressure is greater than pressure given by Raoultslaw, the system shows positive deviation from Raoults law.
Eg: Ethanol-toluene
When the total pressure at equilibrium is less than the pressure given by Roults law thesystem shows negative deviation from Raoults law.
Eg: Tetrahydrofuron-ccl4
Azeotropes
Azeotropes are constant boiling mixtures. When the deviation from Raoults law is verylarge p-x and p-y curve meets at this point y1=x1 and y2=x2A mixture of this composition is known as Azeotrope. Azeotrope is a vapour liquid
equilibrium mixture having the same composition in both the phases.
Types of Azeotropes
Azeotropes are classified into two types
1. Maximum curve pressure, minimum boiling azeotropes
2. Minimum pressure maximum boiling azeotrope
The azeotrope formed when negative deviation is very large will exhibit minimum
pressure or maximum boiling point, this is known as minimum pressure Azeotrope.Eg : Ethanol water, benzene-ethanol
The azeotrope formed when ue deviation is very large will exhibit minimum pressure or
maximum boiling point, this is known as minimum pressure azeotrope.
Phase diagram for both types of AzeotropesMinimum Temperature azeotropes
8/6/2019 Thermodyn Compiled Gmmadhu
34/66
8/6/2019 Thermodyn Compiled Gmmadhu
35/66
Maximum Tem Min pressure Azeotropes
Calculation of VLE for ideal solution
Ideal solution: Ideal solution is one which obeys Raoults law. Raoults law states that the
partial pressure is equal to product of vapor pressure and mole fraction in liquid phase.
AVAA xPP =
PA- Partial pressurePVA- Vapor pressure
8/6/2019 Thermodyn Compiled Gmmadhu
36/66
xA- Mole fraction of component A
For binary solution (For component A and B)
We know that BAT PPP += -------(1)
AVAA xPP = , BVBB xPP =Substitute PA and PB in equation 1
BVBAVAT xPxPP +=
BA xx +=1 , BA xx =1)1( AVBAVAT xPxPP +=
( ) VBAVBVAT PxPPP += --------(2)
VBVA
VBTA
PP
PPx
=
Assuming the vapor phase is also ideal
T
AVA
T
AA
P
xP
P
Py ==
Substituting PT from equation (2)
( ) VBAVBVA
AVA
APxPP
xPy
+=
Dividing numerator and denominator by PVB
11 +
=
A
VB
VA
A
VB
VA
A
xP
P
xP
P
y
( ) 11 +=
A
AA
x
xy
The above equation relates x and y
is known as relative volatility of component A with respect to component B
8/6/2019 Thermodyn Compiled Gmmadhu
37/66
Problem: The binary system acetone and acetone nitrile form an ideal solution. Using the
following data prepare
P-x-y diagram at 50oC T-x-y diagram at 400mm Hg x-y diagram at 400 mm Hg
T PV1 PV238.4
5
400 159.4
42 458.3 184.6
46 532 216.8
50 615 253.5
54 707.9 295.2
58 811.8 342.3
62.3 937.4 400
Solution: ( ) 2121 VVVT PxPPP += ,T
VA
P
xPy 11= , PV1= 615, PV2 = 253.5
x1 PT y10.0 253.5 0.0
0.2 325.8 0.377
0.4 398.1 0.6179
0.6 470.4 0.784
0.8 542.7 0.906
1.0 615 1
T-x-y diagram at 400 mm Hg , PT=400mmHg21
21
VV
VT
PP
PPx
= ,T
VA
P
xPy 11=
T PV1 PV2 x1 y138.45
400 159.4 1 1
42 458.3 184.6 0.7869 0.9015
46 532 216.8 0.5812 0.7729
50 615 253.5 0.405 0.6226
54 707.9 295.2 0.2539 0.44958 811.8 342.3 0.122 0.2475
62.3 937.4 400 0 0
Calculation of VLE for non Ideal solution
For non ideal solution
Partial pressure is given by Viiii PxP =
i- Activity coefficient
8/6/2019 Thermodyn Compiled Gmmadhu
38/66
xi- Mole fractionPVi vapor pressure
For binary mixture
1111 VPxP =2222 VPxP =
21PPPT +=
222111 VVT PxPxP +=
111
222222111
11111
1
1
V
VVV
V
T
Px
PxPxPx
Px
P
Py
+=
+==
The above equation relates x and y for non ideal solution
Activity coefficients are functions of liquid composition x, many equations are available
to estimate them. The important equations areVanlaar equation
Wilson equation
Margules Equation
Vanlaar Equation:Estimation of activity coefficient
2
21
2
2
1ln
+
=
xxB
A
Ax
2
21
2
1
2ln
+
=
xA
Bx
Bx
Where A and b are known as vanlaar constants, if the constants are known theactivity coefficients can be estimated.
Estimation of Vanlaar constants1st Method: If the activity coefficients are known at any one composition, then vanlaar
constants A and B can be estimated by rearranging the equation
8/6/2019 Thermodyn Compiled Gmmadhu
39/66
2
11
22
1ln
ln1ln
+=
x
xA
2
22
11
2
ln
ln1ln
+=
x
xB
2nd Method
For a systems forming azeotrope, if the temperature and pressure s are known atazeotropic composition then activity coefficients can be calculated as shown below.
1111 VPxP =
1111 VT PxyP =
At azeotrpic compositionx1=y1
1
1
=V
T
P
P, 2
2=
V
T
P
P
Van laar constants A and B can calculated using the above equations.
Problem: The azeotope of ethanol and benzene has composition of 44.8mol% C 2H5OH at
68oC and 760mmHg.At 68oC the vapor pressure of benzene and ethanol are 517 and 506mmHg.
Calculate
Vanlaar constants
Prepare the graph of activity coefficients Vs composition Assuming the ratio of vapor pressure remains constant, prepare equilibrium
diagram at 760mmHg.
Solution: At azeotropic composition x1=y1=0.448, x2=y2=0.552, PV1=506mmHg,
PV2 =517mmHg
11
=V
T
P
P, 2
2
=V
T
P
P
501.1506
7601 == , 47.1
517
7602 ==
2
11
22
1ln
ln1ln
+=
x
xA
8/6/2019 Thermodyn Compiled Gmmadhu
40/66
2
)501.1ln()448.0(
)47.1ln()552.0(1)501.1ln(
+=A
A=0.829
2
22
11
2ln
ln1ln
+=
x
xB
2
)47.1ln()552.0(
)501.1ln()448.0(1)47.1ln(
+=B
B=0.576
Make use of the equations given below for plotting graph of activity coefficients Vs
composition.
2
21
2
2
1ln
+
=
xxB
A
Ax
,2
21
2
1
2ln
+
=
xA
Bx
Bx
111
222222111
1111
1
1
1
V
VVV
V
T
Px
PxPxPx
Px
P
Py
+=
+==
x1 x2 1 2 y1
0 1 6.745 1 0
0.2 0.8 2.4 1.095 0.384
0.4 0.6 1.644 1.374 0.4384
0.6 0.4 1.21 1.721 0.5077
0.8 0.2 1.0112 2.618 0.609
1.0 0 1 3.723 1
Margules equation
Eetimation of activity coefficients
[ ][ ]12
21
2lnxABAx +=
[ ][ ]2
2
122ln xBABx +=
The constant A in the above equation is terminal value of ln 1 at x1=0 and constant B isthe terminal value of ln 2 at x2=0
8/6/2019 Thermodyn Compiled Gmmadhu
41/66
When A=B2
21ln Ax= , 2
12ln Ax=
The above equations are known as Margules suffix equation.
Wilson Equation:Wilson proposed the following equation for activity coefficients in binary solution
[ ]
+
+
++=2121
21
2121
12221211 lnln
xxxxxxx
[ ]
+
+
+=2121
21
2121
12112122 lnln
xxxxxxx
Wilson equation have two adjustable parameters 12 and 21 . These are related to pure
component molar volumes.
=
=RT
a
V
V
RTV
V 12
1
21112
1
2
12 expexp
=
RT
aexp
V
V
RTexp
V
V 21
2
12212
2
1
21
V1 and V2 molar volumes of pure liquids - Energies of interaction between molecule
Wilson equation suffers main disadvantages which is not suitable for maxima or minima
onln
versus x curves.Consistency of VLE data
Gibbs duhem equation in terms of thermal consistency
0ln
)1(ln
1
21
1
11 =+
dx
dx
dx
dx
Plot of logarithmic activity coefficients Vs x1 of component in binary solution
8/6/2019 Thermodyn Compiled Gmmadhu
42/66
According to Gibbs Duhem equation both slopes must have oppsite sign then only thedata is consistent, otherwise it is inconsistent.
For the data to be consistent it has satisfy the following condition.
1. If one of ln curves has maximum at certain concentration and the other curveshould be minimum at same composition.
2. If there is no maximum or minimum point both must have + ue or ue on entire
range.
Co-existence equation
The general form of Gibbs duhem equation at constant temperature and pressure
=0ii Mdx ---(1)In terms of partial molar free energies
=0ii Gdx ------(2)dividing equation (2) by dx1
=01dx
Gdx ii -----(3)
+= ii fRTG ln
at constant temperature
11
ln
dx
fRT
dx
Gd ii = ----(4)
substituting equation (4) in equation (3)
0ln
1
=dx
fRTx ii
8/6/2019 Thermodyn Compiled Gmmadhu
43/66
0ln
1
=dx
fdx ii ------(5)
For binary system
0
lnln
1
2
21
1
1 =+ dxfd
xdx
fd
x ----(6)
0lnln 2211 =+ fdxfdx -----(7)
Equation (5) (6) and (7) are Gibbs Duhem equation in terms of fugacites and thus
applicable for both liquid and vapor phase
For liquids
iiii fxf =
iiii fxf lnlnlnln ++=
differentiating with respect to x1
1111
lnlnlnln
dx
fd
dx
xd
dx
d
dx
fdiiii ++=
-------(8)
fi is a pure component ffugacity it does not vary withx1
Substituting equation (8) in equation (5)
0lnln
11
=+dx
xdx
dx
dx ii
i
i
0ln
1
=dx
dx ii
----------------(9)
For binary system
0lnln
1
2
2
1
1
1=+
dx
dx
dx
dx
---------(10)
0lnln 2211 =+ dxdx -----------(11)
Equation (9) (10) and (11) are Gibbs Duhem equation in terms of activity coefficients
For ideal vapor
ii Pf =
From equation 5
=0
=0
8/6/2019 Thermodyn Compiled Gmmadhu
44/66
0ln
1
=dx
Pdx ii ------------(13)
For binary system
0lnln
1
22
1
11 =+
dx
Pdx
dx
Pdx ----------(14)
0lnln 2211 =+ PdxPdx ---------------(15)
Equation (13) (14) and (15) are Gibbs Duhem equation in terms Partial pressure.
For ideal vapor
TPyP 11 = , TPyP 22 =0)ln()ln( 2211 =+ TT PydxPydx
0ln)(lnln 212111 =+++ TPdxxydxydx121 =+ xx
0lnlnln 2111 =++ TPdydxydx
2211 lnln ydxydxP
dP=
2
22
1
11
y
dyx
y
dyx
P
dP=
012 =+ yy , 12 dydy =
on simplification
+
=)1(
)1(
1
1
1
11
y
x
y
xdy
P
dP
Further simplification
=)1( 1
11
1 yy
xyP
dy
dP
This is known as coexistence equation. It relates P,x,y for binary VLE system. This
equation is used to rest consistency of VLE data.
8/6/2019 Thermodyn Compiled Gmmadhu
45/66
Consistency test for VLE data
0lnln 2211 =+ dxdx
2
112
lnlnx
dxd =
)1(
lnln
1
112
x
dxd
=
= )1(ln
ln1
112
x
dxd
Redlich Kister Test
The excess free energy of mixing for a solution is given as
Nonidealideal
e GGG =
= iie xRTG ln
For binary system
[ ]2211
lnln xxRTGe +=
differentiating with respect tox1
+++=
1
2
2
1
2
21
1
1
1
1
lnln
lnln
dx
dx
dx
dx
dx
dxRT
dx
dG e
From Gibbs Duhem Equation
0lnln
1
2
2
1
1
1=+
dx
dx
dx
dx
+=
1
2
21
1
lnlndx
dxRT
dx
dG e
12 dxdx =
[ ]211
lnln = RTdx
dG e
8/6/2019 Thermodyn Compiled Gmmadhu
46/66
=
2
1
1
ln
RT
dx
dGe
=
=
=
=
=
1
0
1
2
1
1
0
1
1
1
1
ln
x
x
x
x
edxRTdG
The two limits indicates pure component for which 0=eG , where LHS is zero for bothlimits.
We can write
=
==
1
0
1
2
1
1
1
ln0
x
x
dx
This can be checked graphically. Net area should be equal to zero forconsistency(Area=0).
Problem
Verify whether the following data is consistent
X1 1 20 0.576 1.00
0.2 0.655 0.985
0.4 0.748 0.930
0.6 0.856 0.814
0.8 0.950 0.626
1.0 1.00 0.379Solution:
We know that the Redlich kister test is
=
=
=
1
0
1
2
1
1
1
ln0
x
x
dx
8/6/2019 Thermodyn Compiled Gmmadhu
47/66
2
1
2
1ln
0.57
6
-0.552
0.66
5
-0.408
0.80
4
-0.218
1.05
2
0.051
1.518
0.417
2.639
0.97
Plot2
1
ln
Vs x1
Area under the curve is zero. Data is consistent.
8/6/2019 Thermodyn Compiled Gmmadhu
48/66
CHEMICAL REACTION EQUILIBRIUM
Energy change accompanies all chemical reactions. Because of this energy
change the temperature of the products may increase or decrease depending on
the exothermic or endothermic nature of the reaction. The energy change may
be expressed in terms of heat of reaction, heat of combustion and heat of
formation.
Heat of reaction is the change in enthalpy of a reaction under pressure of 1.0
atmosphere, starting & ending with all materials at a constant temperature T
Heat of combustion is the heat of reaction of a combustion reaction.
Heat of formation is the heat of reaction of a formation reaction. A formation
reaction is one which results in the formation of one mole of a compound from
the elements.
Eq. H2 + O2 H2OC +O2 CO2
C + H2 + 1/2 Cl2 CHCl3
The standard heat of reaction, standard heat of formation, and standard heat of
formation are respectively the heat of reaction, heat of combustion and heat of formation
under 1 atmosphere starting and ending with all materials at constant temperature of
250C.
In chemical industries, processes are carried out under isothermal conditions
and this requires the addition or removal of heat from the reactor. Heat of
reaction values will give the amount of heat to be removed or added. Knowing
of this heat value helps to design the heat exchange equipment.
Standard heat of reaction
Calculation of H298 form heats of formation data:
The standard heat of reaction accompanying any chemical change is equal to
the algebraic sum of the standard heats of formation of products minus the
algebraic sum of the standard heat of formation of reactants.
Hr = Hf 298 products - Hf 298 reactants
8/6/2019 Thermodyn Compiled Gmmadhu
49/66
Heat of formation of any clement is zero
8/6/2019 Thermodyn Compiled Gmmadhu
50/66
Heat effects of chemical Reaction:
For the reaction, aA + bB cC + dD
Let heat capacity be Cp = + T + T2 then we have CpA = A + AT + AT
2
CpB = B + BT + BT2
CpC = C + CT + CT2
CpD = D + DT + DT2
And H0298 be standard heat of reaction at 298 K and standard heat of reaction at any
other temperature can be found byKirchoffs rule( )o
p
d H
CdT
= where
= [c(C + CT + CT2) + d( D + DT + DT
2 ) ] - [a (A + AT +
AT2 ) + b (B + BT + BT
2 )]
= [(c C +d D ) (a A + b B ) ]+ [ (c C + d DT) (a A + b B)]T + [ c C + dD) (a
A+ b B)] T2
or
( ) ( )Pr Re tan
Pr Re tan
Pr Re tan
oducts ac ts
C D A B
oducts ac ts
oducts ac ts
cC dC aC bC
=
= + +
=
=
Substituting in Kirchoffs rule
( )0
298
0 2
0 2
298
2 3
2 3
H T
H
o
H T T T
dH T T
dT
H T T T I
= + +
= + +
= + + +
, , , pC pD pA pBC C and C C
Cp = + T + T2
tan
substituting the values of
p p p products reac ts
p pC pD pA pB
C C C
C cC dC aC bC then
=
= + +
8/6/2019 Thermodyn Compiled Gmmadhu
51/66
OR in general
( )0 2
2 3= 2 3
PH C dT T T dT
T T T I
= = + +
+ + +
A chemical reaction proceeds in the direction of decreasing free energy.The sum of the
free energies of the reactants should be more than the sum of energies of products. For a
reaction to take place
Re Reor 0action action products reaction
G G G G =
8/6/2019 Thermodyn Compiled Gmmadhu
52/66
( ) ( )
( ) ( )
( ) ( )
( )
ReRe tan
0 0
0 0
= c ln ln
ln ln
action products ac ts
D BC A
C C D D
A A B B
C D A B
G G G
cG dG aG bG
G RT a d G RT a
a G RT a b G RT a
cG dG aG bG
=
= + +
+ + +
+ + +
= +
( )
0
Re
ln ln ln ln
ln
C
C D A B
c d
D
actiona b
A B
RT a a a a
a aG G RT
a a
+ +
= +
At equilibrium G = 0 andC
c d
D
a b
A B
a aK
a a
=
K is equilibrium constant of the reaction
[ ]0 0
0 ln ln
C
c d
D
a b
A B
a aG RT G RT K
a a
= + = +
at equilibrium
EFFECT OF TEMPERATURE ON EQUILIBRIUM CONSTANT K
8/6/2019 Thermodyn Compiled Gmmadhu
53/66
Gibbs - Helmoholtz equation at constant pressure is given
( )
( )
2
2 2
2
but ln K
ln K
ln KTor
ln KVan't Hoff equation.
This may be integrated to find the effect of temperature on K
When is
o
o
Gd
T HG RT
dT TRT
dd RH H
dT dT T T
d H
dT RT
H
= =
= =
=
2 2
1 1
K
2
K
2
1 2 1
1 1
contant d lnK
K 1 1ln
K
if K at T ,t
T
T
HdT
RT
H
R T T
is known
=
=
( )
( )
2
0
2
2
hen K can be calculated at other
ln KWhen H varies with T
ln K2 3
d H
dT RT
T Id dT
RT R R RT
=
= + + +
2ln Tln K=
2 6
T T IM
R R R RT
+ + +
Where M is a consatnt of integration
8/6/2019 Thermodyn Compiled Gmmadhu
54/66
0
20
2 30
ln
ln T
2 6
ln T 2 6
=
= + + +
= +
G RT K
T T IG RT M
R R R RT
T T
G T I MRT
For the reasction C2H4 + O2 C2H4O, develop equations for H0, K, and G0, find
G
0
at 550 KCp (Cal / mol K) Data: C 2H4 = 3.68 + 0.0224 T
O2 = 6.39 + 0.0021 T
C2H4O = 1.59 + .00332 T
Standard heat of reaction H0298
C2H4O = - 12 190 and C2H4 = - 12 500, Cal / mol
And G0298 = -19070 Cal / mol
= 1(-12190) 1(
-12500) = 310 Cal / mol
( )
p
Pr Re tan
In this problem C
1= 1.59 3.68 6.39 5.285
2oducts ac ts
T
= +
= + =
( )Pr Re tan
1= 0.0332 0.0224 0.0021 0.00975
2oducts ac ts
= + =
Then the variation of standard heat of reaction with temperature is
Re 298
Pr Re tan
actionoducts ac ts
H H H =
8/6/2019 Thermodyn Compiled Gmmadhu
55/66
( )
( )
2 3 2
0 2
298
2 0
298
0.009755.285
2 3 2
0.00975Given =310 = 5.285 then I =1452
2
0.00975
5.285 1452 This is variationof with temparatu2
lnK =
o
o
H T T T I T T I
H T T I
H T T H
= + + + = + +
+ +
= + + 2
0
0 298
298 298 298
5.285 0.00975 1452ln = ln
2 6 2 2(2) 2
G 19070G ln or lnK 32
2(298)
5.285 0.00975 145232 = ln 298 298 therefore M = 48.76
2 2(2) 2(298)
IT T T M T T M
R R R RT T
but RT K RT
M
+ + + +
= = = =
+ +
0
0 3 2
0 3 2
550
3
5.285 0.00975 1452lnK = ln 48.763
2 4 2
G ln 2 ln5.285 0.00975 1452
2 ln 2 ln 48.7632 4 2
G 5.285 ln 4.875(10 )( ) 1452 97.526( )
G 5.285(550) ln 550 4.875(10 )(550) 1452 97
T TT
RT K T K
T K T T T T
T T T T
+ +
= = = + +
= + +
= + + 0
550
.526(550)
G 35320.62 /Cal m ol =
50 mol% each of SO2 and O2 is fed to a converter to form SO3.
Show the variation of i) Standard heat of reaction with T ii) Equilibrium constant
with T. The Hfand Gf at 298 K are
Componen
t
Hf
k Cal / k
mol
Gf
k Cal / k
mol
SO2 -70960 -71680
O2 0 0
SO3 -94450 -88590
CPdata:
Componen
ta b(103)
SO2 7.116 9.512
O2 6.148 3.102
SO36.037
7
23.53
7
8/6/2019 Thermodyn Compiled Gmmadhu
56/66
Feed contains 50 mole% SO2 and O2.This means for every one mole SO2 there will be
one mole O2 in the reactant side and mole O2 in the product side, according to SO2 +
O2 SO3
Reactants: 1 mol SO2 + 1 mol O2 Products: 1 mol SO3 + mol O2 (excess)
[ ]Pr tan
-3 3 -3 -3 -3
Pr tan
0 2 3
1= 6.0377 + 6.148 7.116 6.148 - 4.152
2
1= 23.53(10 ) + 3.102(10 ) - 9.512 (10 ) + 3.102 (10 ) =12.474 x10
2
2 3
=
oducts reac ts
oducts reac ts
H T T T I
= +
=
= + + +
[ ]
-3 2
0 0 0 0
298
Re tan
-3 2
0
12.474x10-4.152T+2
298 is given by 94450 70960 23490 k Cal/ k mol
-23490=-4.152 (298 ) + 6.237 x 10 (298)
I = -22818.19
4.152 6.237 1
products ac ts
T I
But H at H H H
I
H T x
+
= = =
+
= +
3 2
2
3
0 22818.19
for K we have
lnK= lnR 2 6
4.152 12.474 10 22818.19lnK= ln2 2 2
T
Next
IT T T M
R R RT
xT T M xR T
+ + +
+ + +
00 298
298 298 298
0
298Products Reactants
298
3
GWe have G = -RTln or lnK =
2(298)
G = G - G = - 88590 - (- 71680) = - 16910 k Cal / k mol
16910lnK = 28.372
2(298)
4.152 12474 1028.372 ln2982 2
K
x
=
= +
3
22818.192982 2 298
0.9842
11409.09ln 2.076ln 3.1185 10 0.9842
Mx x
M
K T x T T
+ + =
= + + +
8/6/2019 Thermodyn Compiled Gmmadhu
57/66
Derive the general equation for the standard free energy formation for N2 + 3/2
H2 NH3The absolute entropies in ideal gas state at 298 K and 1.0 atm are
NH3 = 46.01 g Cal / g mol K
N2 = 45.77
H2 = 31.21
H0298 (g Cal / g mol) = - 11040
Heat capacity Data is given by Cp= a + bT + cT2 the values are
Component a bx102 cx105
NH3 6.505 0.613 0.236
N2 6.903 - 0.038 0.193
H2 6.952 - 0.46 0.096
Compute the free energy change at 1500K. Is reaction feasible?
0 0
298
Pr Re tan
0
298
We have G and
1 3=46.01 (45.77) + (31.21)= 23.69 g Cal / g mol K
2 2
G 11040 298( 23.69) 39
o
oducts ac ts
H S S S S = =
= =
Pr Re tan
2 2
Pr Re tan
80.38 g Cal / g mol K
1 3
6.505 (6.903) 6.952 7.37452 2
1 30.613 10 ( 0.038 10 )( 0.046 10
2 2
oducts ac ts
oducts ac ts
a a a
b b b x x x
= = + =
= = +
2 3
5 5 5
Pr Re tan
0 2 3
298
3 62
) 7.01 10
1 30.236 10 (0.193 10) (0.096 10 ) 0.045 10
2 2
2 3
7.01 10 0.045 1011040 ( 7.3745)298 298 (
2 3
oducts ac ts
x
c c c x x x
b cH aT T T I
X X
= = = + =
= + + +
= + +
3
2
298) OR I = -9153.26
ln ln and R =2 gCal / g mol K2 6
I
a b c I K T T T M R R R RT
+
= + + +
8/6/2019 Thermodyn Compiled Gmmadhu
58/66
0
298 298 298
3 62
-3980.38ln or ln K = = 6.6784
-(2x298)
7.3745 7.01 10 0.045 10 9153.266.6784 ln 298 298 (298)
2 2 2 6 2 2 298
11.798
G RT K
x xM
x x x
M
=
= + + + +
=0
3 60 2
3 60 2
1500
7
var with T is given by, = - RT lnK
-7.3745 7.01 10 0.045 10 9153.26= -2T ln 11.7987
2 2 2 6x2 2T
-7.3745 7.01 10 0.045 10= -2x1500 ln1500 1500 1500
2 2 2 6x2
The iation of G G
x xG T T T
x
x xG
x
+ + + +
+ + +
0
1500
Pr Re tan
9153.2611.7987
2x1500
g Cal28488.81
g moloducts ac tsG G G
+
= =
The reaction is not feasible G is highly +ve: For feasibility it should equal to zero
The hydration of Ethylene to alcohol is given by C2H2 + H2O C2H5OH
The heat capacity data for the component can be
represented by Cp = a + bT where T is in kelvin and Cp is
in cal / g mol0C
Develop general expression for the equilibrium constant and standard Gibbs free
energy change as function of temperature.
Temperature0
C 145 6.8 x 10-2
Equilibrium Constant 320 1.9 x 10-3
Componen
ta bx103
C2H4 2.83 28.601
H2O 7.3 2.46
C2H5OH 6.99 39.741
8/6/2019 Thermodyn Compiled Gmmadhu
59/66
Pr Re tan
3 3 3 3
Pr Re tan
2
3
= 6.99 (2.83 7.3) 3.14
39.741 10 (28.6 10 2.46 10 ) 8.68 10
lnK = lnR 2 6
3.14 8.68 10lnK = ln
2 2 2 2
At 418 K
oducts ac ts
oducts ac ts
a a a
b b b x x x x
a b c I T T T M R R RT
x IT T M
x T
= + =
= = + =
+ + +
+ +
3-2
3-3
3
3.14 8.68 10, ln 6.8x10 = ln 418 418
2 2 2 2 418
, I = -9655.807 & M = -5.667
3.14 8.68 10593 K, ln 1.9x10 ln593 593
2 2 2 2 593
3.14 8.68 10 -9655.80
lnK = ln2 2 2
x IM
x x
Solving
x I At M
x x
x
T Tx
+ + = + +
+ 3
-3 2
7
-5.6672
3.14 8.68 10 -9655.807But G = -2T ln -5.667
2 2 2 2
G = 3.14T ln T - 4.34x10 9655.807 11.334
T
xT T
x T
T T
+
+ +
+
THERMODYNAMIC FEASIBILITY OF REACTIONS The equilibrium constant K is a measure of the concentration of the products
formed at equilibrium. It is related by the equation G0 = - RT ln K. The more the value
of K, more will be the equilibrium conversion of products. When the value of G < 0,
means the value of K should be very large. Hence G is the measure of feasibility of a
chemical reaction.
i) If G0 < 0, there can be appreciable conversion of reactants in to products.
The more the ve value, more will be the feasibility of the reaction
ii) If G0 is +ve but less than 10 000 k Cal / mol, the reaction is not feasible,
at atmosphere , may be feasible at any other pressure
iii) If G0 is greater than 10 000 kCal / mol the reaction is not at all feasible
under any condition.
Equilibrium Calculations ( Homogeneous gas Phase reactions):
8/6/2019 Thermodyn Compiled Gmmadhu
60/66
aA (g) + bB (g) cC (g) + dD (g)
We haveC
c d
D
a b
A B
a aK
a a
=
for gases,
[ ]
0
0
c c c c c c c c
D D D D
A A A A
B B B B
c c c
as = p = 1 atmosphere: a = f
f = y but a p = y p
a y p
a y p
a y p
y pK =
c
c
f Activity a E f
f
f x
=
=
=
=
=
[ ][ ][ ]
[ ][ ]
[ ][ ]
[ ][ ]
[ ][ ]
[ ][ ]
[ ][ ]
[ ][ ]
[ ][ ]
D D D c D c D c D
A A A B B B A B A B A B
c + d - (a + b) n
y p y y p px xy p y p y y p p
( )( )( )(P ) =( )( )( )(P ) where = activit y co efficient for gas phase
d c d c d c d c d
a b a b a b a b a b
y y
x
K k k k k k k
=
=
y = mole fraction
= Fugacity Co efficient for gas phase
P = Total p ressure
Effect of variables on equilibrium :Effect of temperature:
0
298 298lnG RT K = since G depends only on temperature as the
pressure is fixed at 1.0 atmosphere, K value varies with temperature. It is not affected by
Pressure, Concentration, etc,. Variation of K with T is given by
( )2
ln KVan't Hoff equation.
d H
dT RT
=
For endothermic reactions H0 is + ve as T increases K also increases. This
means that the equilibrium conversion is more at higher pressure.
For exothermic reactions H0is ve. Therefore K increases with T. Hence the
equilibrium conversion decreases as T increases. Eg. SO2 + 1/2 O2 SO3
Effect of pressure: Consider a reaction of ideal gases, then K = KyPn or Ky = K / P
n
Whenn > 0. An increase in pressure decreases Ky. Hence equilibrium product
yield is less at high pressures
8/6/2019 Thermodyn Compiled Gmmadhu
61/66
When n< 0. An increase in pressure increases Ky and equilibrium product
yield
C2H4 + H2O C2H5OH n = 1 (1+1) = -1, n < 0
N2 + 3H2 2NH3 n = 2 4 = 2 n < 0 Here high
pressure is required
Whenn = 0 Here pressure has no effect on reaction. For ideal gases the effect
of pressure depends on the variation of and with pressure
Effect of Inert: Presence of inert has the opposite effect of increase of pressure.
Therefore whenn > 0,addition of inert increases Ky and equilibrium conversion
Andn < 0, addition of inert decreases equilibrium conversion.
Effect of excess reactants: Presence of excess reactants increases equilibrium
conversion of the limiting reactant
Presence of products in feed: decreases the equilibrium conversion of reactants.
Eg. CH3COOH + C2H5OHCH3COOC2H5 + H2O
If water is added by 1.0 mole to the feed, equilibrium conversion of CH3COOH
reduces from 30% to 15%
HCN is produced by the reaction N2 (g)+ C2H2 (g) 2HCN (g). The reactants are
taken in stoichiometric ratio at 1.0 atmosphere and 3000C. At this temperature G0=
-30100 k J / k mol. Calculate equilibrium composition of product stream and
maximum conversion of C2H2
n=2 (1+1) = 00 330100we have ln or lnK = or K = 1.8029x10
8.314(573)G RT K
=
Component
Moles
in feed
Moles
reacted
Moles
present
Mole
fraction
N2 1 X 1 X (1 X) / 2
C2H2 1 X 1 X (1 X) / 2
HCN -- 2X 2X(2X) / X =
X
8/6/2019 Thermodyn Compiled Gmmadhu
62/66
2 2 2
0
2 23
1 1
Assume 1 and 1
1.8029(10) , X = 0.01 1
2 2
Equilibrium Composition:
n n
y
HCN
y
N C H
K K K K P K K P P
y XK K Solving for X
X Xy y
= = = = =
= = = =
2
2 2
1 1 0.0207N 100 100 48.965%
2 2
1 1 0.0207100 100 48.965%
2 2
( )100 2.007%
X
XC H
HCN X
Equilibrium Conversi
= = =
= = = = =
2 2
2 2
2 2
2 2
max for reversible reaction
of 0.0207Max. Conversion of 100 100 100 2
of in feed 1 1
on of C H
Equilibrium conversion is imum
Moles C H reacted XC H
Moles C H = = =
Workout the problem, when the pressure is changed to 203 bar. Fugacity co efficients
of N2,,C2H2 and HCN are 1.1, 0.928, and 0.54 Assume K= 1
c c
0C C
a b a
A B A
2 2-3
y= (1) 203 where a,b, and c are stoichiometric co efficients
y
0.54 Xand K is known already = 1.8029x10 = .(1)
(1.1)(0928) 1-X 1-X
2 2
solving
n
y b
B
K K K K P y
=
2 2
2 2
2 2
X = 0.0382then equilibrium Composion of C H is ( Max reversible reaction)
moles C H 0.0382= x 100 = 3.82%
moles of C H in feed 1
reacted
Calculate the K at 673K & 1.0 bar for N2 (g) + 3 H2 (g) 2NH3 (g). Assume heat of reaction remains constant. Take standard heat of formation and
standard free energy of formation of NH3 at 298 K to be - 46110 J / mol and 16450 J
/ mol respectively.
8/6/2019 Thermodyn Compiled Gmmadhu
63/66
0
298 0
298 2980
298
0
298 1
2( 16450) 32900 Jln
2 (-46110) = -92 220 J
ln
GG RT K
H
G RT K
= = = =
=
1
10
2
1 2 1
2
- 32900 = - 8.314 (298) ln K
K 564861.1
K 1 1have ln
K
K 92220 1 1ln
584861.1 8.314 673 298
Hwe
R T T
=
=
=
4
2
K 5.75 10X =
Acetic acid is esterified in the liquid phase with ethanol at 373 K and 1.0 bar according
to
CH3COOH (L) + C2H5OH (L) CH3COOC2H5(L) + H2O (L)
The feed consists of 1.0 mol each of acetic acid & ethanol, estimate the mole fraction
of ethyl acetate in the reacting mixture at equilibrium. The standard heat of formation
and standard free energy of formation at 298 K are given below.
Assume that the heat of reaction is independent of T and liquid mixture behaves as
ideal solution.
CH3COOH
(L)
C2H5OH
(L)CH3COOC2H5(L) H 2O (L)
f0f
(J)- 484500 - 277690 - 463250 - 285830
G0f
(J)- 389900 -174780 - 318218 - 237130
8/6/2019 Thermodyn Compiled Gmmadhu
64/66
G0298 = 318218 237130 + 389900 + 174780 = 9332 J
H0298 = 463250 285830 + 277690 + 484500 = 13110 J
We have, G0298 = RT ln K
9332 = 8.314 (298) ln K1 or K1 = 0.02313
and for K2 at 373K we have
ComponentMoles
in feed
Moles
reacted
Moles
present
Mole
fraction
CH3COOH 1 X 1 X (1 X) / 2
C2H5OH 1 X 1 X (1 X) / 2
CH3COOC2H5 -- X X X / 2
H2O -- X X X / 2
2
2
20
2 2 2
3 2 5
x
20.067= solving, x = 0.252
(1 )1
2
0.252mole fraction of CH 0.126
2 2
y
xK K P
xx
xCOOC H
= =
= = =
1
2 1 2
2
2
1 1ln
0.02313 12110 1 1ln OR K 0.067
8.314 298 373
K H
K R T T
K
=
= =
8/6/2019 Thermodyn Compiled Gmmadhu
65/66
The standard free energy change for the reaction C4H8 (g) C4H6(g) + H2 (g)is given by GT
0 =1.03665 X 105 20.9759T ln T 12.9372 T, where range of GT0 in J /
mol and T in K
a) Over what range of T, is the reaction promising from thermodynamic view
point?
b) For a reaction of pure butene at 800K, calculate equilibrium conversion at 1.0
bar & 5.0 bar
c) Repeat part (b) for the feed with the 50 mol% butene and the rest inerts
a. For the reaction at G= 0, T 812.4 K, above this temperature G 0, reaction is unfavorable,
b. At 800K, G0 = 1842.16 J / mol
G0 = - RT ln K, or 1842.16 = - 8.314 ( 800 ) ln K or
K = 1.3191
K = ky Pn = ky P
( 2- 1 ) = ky P
Therefore at 1.0 bar K = kyP 1.3191 = ky ( 1 )
ky = 1.31910At 5 bar, 1.3191 = k y ( 5 )ky = 0.26382
Moles in
feed
Moles in product streamyi
C4H8 1 1 - X(1 X ) / (1 +
X)
C4H6 X X / (1 + X)
H2 X X / (1 + X)1 + X
8/6/2019 Thermodyn Compiled Gmmadhu
66/66
4 6
4
' ' 2C H H2
Y ' 2
C H8
2
y 2
x x
Y Y x1 x 1 xk or 1.3191 = or x = 0.7541
1 xY 1 x
1 x
Conversion of betene = 75.41%
xAt 5.0 bar, k = 0.26382 = , x = 0.4569, Conversion of b
1 x
+ + = =
+
etene = 45.69 %
C.
Moles in
feed
Moles in product streamyi
C4H8 1 1 - X (1 X ) / (2 + X)
C4H6 X X / (2 + X)
H2 X X / (2 + X)Inerts 1.0 1 1 / (2 + X)
2 + x
( )
( )
2
Y 2
2
Y 2
x 2 xat 1.0 bar, k K 1.3191
1 x2 x
x = 0.8194
K x 2 xat 5.0 bar k 0.26382
5 1 x2 x
x = 0.5501
+ = = == +
+ = = = +