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CHBE 346
REVIEW NOTES
Introductory Concepts
Definitions of System
Property, State, Equilibrium, Phase Rule
Criteria for Equilibrium
Clausius Clapeyron Equation
G U PV TS H TS
and
dG SdT VdP
dG SdT VdP 0
G n LG L nV GV dG n L dG L G L dn L nV dGV GV dnV
Since:
n n L nV dn 0 dn L dn L dn L dnV
Then:
G L GV
GV H V TS V H L TS L G L
We can derive:
S S S
Substituting for
entropy:
vap
( H V H L ) H vap
T
T
dP sat
H vap
dT
T (V V V L )
sat
H vap
1 Z stands for compressibility factor in
d
R( Z V Z L ) T ZPV/RT.
d ln P
sat
H vap 1
d
R
T
Clausius-Clapeyron equation
sat
r
ln P
H vap Tc Tc
H vap
RZ vapTc T Tc RZ vapTc
1
1
Tr
In terms of log10:
log10 Prsat
1
H
1
1
2.303 RZTc Tr
1
A 1
Tr
log10 Prsat
Tr 0.7
1
3
7
(w 1) A 1
(1 w )
0.7
7
3
sat
r
log10 P
7
1
1 w 1
3
Tr
5
Note: This approximation is good above P=0.5 bar. The estimations are based on
the critical pressure which is generally 40-50 bar and acentric factor at Tr=0.7.
log10 P sat A B / (T C )
Where T is in Celsius. Constants A, B and C are available for a wide range
of vapor-liquid equilibrium data. The Psat is given in mmHg.
Note: This equation should be only applied over the range recommended
and it should not be extrapolated.
Engineering Thermodynamics
CHBE 346
Phase Equilibrium in a Pure Fluid
Gibbs Free Energy and Fugacity
7
RT
Equations of State
ig 1 and
Ideal Gas
f ig P
ln
0
B
BP
dP
RT
RT
which becomes when you write the virial coefficient in reduced T and P :
ln
Pr 0
B w B1
Tr
Z (1 2) B
ln ln( Z B)
ln
Z 1
B 8 Z (1 2) B
A
Any of the methods discussed for gases can be used to calculate fB. The method
to calculate fD defers. Note A: gas, B: sat gas, C: sat liquid, D: liquid
D
fD
Apply the following equation: dG VdP RTd ln f RT ln sat VdP
f
P sat
f sat
RT
RT
where:
V satL VC Z C(1Tr )
0.2857
f sat P sat
or
f P sat
Engineering Thermodynamics
CHBE 346
Introduction to Multicomponent Systems
Phase diagrams
Vapor-Liquid Equilibrium (LVE) Calculations
Principles of Calculations
Standard approaches utilize the ratio of vapor mole fraction to liquid mole fraction,
known as the VLE K-ratio:
K i yi / xi
K x 1
1 or
i i
x 1
y /K
or
x y
i
11
Engineering Thermodynamics
CHBE 346
Vapor-Liquid Equilibrium (LVE) Calculations
using Raoults Law
Pi sat
Ki
P
or yi P xi Pi sat
1
Note that for such mixtures:
7
(1w )1
T
3
r ,i
(i) K-ratio depends only on T and P (independent of xi)
Pi sat Pc ,i 10
Ki
13
Engineering Thermodynamics
CHBE 346
General Flash Calculations
Adiabatic Flash Calculations
General Flash
To perform flash calculations (zi, F and the outlet T and P must be known).
L / F 1 V / F and zi xi ( L / F ) yi (V / F )
Using
yi xi Ki where K i Pi sat / P
Rearranging
xi
zi
and
1 (V / F )( K i 1)
yi
zi Ki
1 (V / F )( K i 1)
15
Engineering Thermodynamics
CHBE 346
Introduction to Mixture Properties
Property Changes of Mixing
Multicomponent VLE Raoults Law Calculations
V ig RT ni / P
i
H ig yi H iig
i
Therefore, we can add the component enthalpies and internal energies for ideal
gas mixtures using the mole fractions as the weighting factors:
ig
U mix
0
ig
Vmix
0
ig
H mix
0
17
U is xU
i i
or U is nU
i i
V is xV
i i
or V is nV
i i
Since
H is U is PV is xi U i PVi xH i
i
H is ni H i
We can add the component enthalpies and internal energies for ideal solution
mixtures using the mole fractions as the weighting factors.
Therefore, an ideal solution has a zero energy of mixing, volume of mixing and
enthalpy of mixing (heat of mixing).
is
U mix
0
is
Vmix
0
is
H mix
0
Examples of ideal solutions are all ideal gases mixtures and liquid mixtures of
family member pairs of similar size such as benzene+toluene, n-butanol+npentanol and n-pentane+n-hexane (n stands for normal to distinguish from isomers).
18
Engineering Thermodynamics
CHBE 346
Phase diagrams of Nonideal Systems
Concepts for Generalized Phase Equilibria
-
Explain nonidealities
Explain deviations from Raoults law
Nonideal Systems
20
Engineering Thermodynamics
CHBE 346
Equilibrium Criteria
Chemical Potential
fiV
RT ln
fi
iV iL RT ln fiV / fi L 0
fiV fi L
At equilibrium
This equation does not look like Raoults equation (we will prove it next).
22
Engineering Thermodynamics
CHBE 346
Introduction to Activity Models
Modified Raoults Law
Excess Gibbs Energy
The One-Parameter Margules Equation
GE
A 12 x1 x2
RT
Where A12 is a constant. This equation is symmetrical and it has an extremum at
x1=0.5 and becomes zero at purity of either component. The activity coefficient for
this model is (derive later):
ln i A 12(1 xi )2
Lets fit the model to experimental data.
24
yi i Pi sat
Ki
xi
P
Then the bubble, dew and flash calculations can be executed. Because the activity
coefficient depends on xi, the algorithms where xi is unknown require an initial guess
to calculate a value for i and an iterative procedure to converge.
The method for bubble pressure does not require iteration because the activity
coefficient depends on the temperature and liquid composition (both are inputs).
25
Engineering Thermodynamics
CHBE 346
Derivation of the Modified Raoults Law
Excess Gibbs Energy
Excess Properties
The Two-Parameter Margules Equation
fiV fi L
The Venn diagram below explains the deviations from ideality, going from ideal gas
model to ideal solution model to finally real solution model and the various
equations that hold in each case.
Ideal gas model
fiV yi P
Ideal solution model
fiV i yi P, i 1,
fi L xi fi o
fiV i yi P, i 1,
fi L i xi fi o
27
is
G E G G is G xi Gi G is xiGi Gmix Gmix
Gmix RT xi ln( xi )
i
i
i
Recall that: G xi i
fi
i RT ln o
fi
o
i
fi
ai o xi i
fi
fi
G xi Gi xi ( i Gi ) RT xi ln
f
i
i
i
i
Gmix RT xi ln ai RT xi ln xi i
i
Finally
28
G E xi GiE
E
E
Compare the above with: G RT xi ln( i ) or G / RT xi ln( i )
i
We get:
G E
GiE iE RT ln i
ni T , P ,n j ni
GE
n
n ( A12 x1 x2 ) (A12 n2 ) 1
RT
n
n2
1
G
1 n1
For i=1:
ln
A
n
1
12 2
12
2
RT n1 T , P ,n
n
n n
2
n1
1 n A12 x2 (1 x1 )
29
GE
x1 x2 ( B12 C12 ( x1 x2 ) D12 ( x1 x2 ) 2 ...)
RT
The two-parameter Margules equation is:
GE
x1 x2 (A 21 x1 A12 x2 )
RT
1 ln 2ln 2
A12 2 1
x1
x2 x2
and
1 ln 2ln 1
A21 2 2
x2
x1 x1
30
Engineering Thermodynamics
CHBE 346
Gibbs-Duhem Equation
Lewis-Randall Rule and Henrys Law
Osmotic Pressure
Gibbs-Duhem Equation
An expression known as the Gibbs-Duhem equation is useful
(i) Testing data for experimental errors
(ii) Generating the activity coefficients in a binary for a second component based
on the bahavior of the first component
(iii) Development of theories for G of mixture (models should follow this)
Start with
G ni i or dG ni d i i dni
Using
Combining
0 SdT VdP ni d i
n d
i
0 or
n d
i
E
i
0 at T , P constant
Inserting the relation between excess chemical potential and activity coefficient
n d
i
E
i
RT ni d ln i 0
i
ln 1
ln 2
x1
0
2
xi T , P
xi T , P
32
fi is xi fi or fi xi i fi
The problem is what if one of the components does not exist in these conditions at
pure form to calculate fi . For example for liquid-phase hydrogenation reactions or
oxygenation of water, hydrogen and oxygen are above their critical temperatures As
seen above the Lewis Randal rule requires the fugacity of the pure liquid/component.
In such cases (gases dissolved in liquids at infinite dilutions, Henrys law is used
(outlines the behavior of an ideal solution):
fi is xi hi
The Henry constant, hi is determined
experimentally and depends on P, T and solvent.
The slope in the graph is the Henry constant.
At high concentrations Henrys law breaks
down, however for gases with very low
solubility provides an acceptable approximation.
33
Osmotic Pressure
Consider a membrane separating W from W+C (water or blood purification in dialysis).
If both sides at same pressure, P, W runs from left to right (C cannot permeate) due to higher
potential due to higher mole fraction.
If pressure on the right increases to a level, , where flow stops (osmotic pressure)
If pressure is increased more, a condition of reverse osmosis occur, where flow reverses and W
runs from right to left.
RT
ln W
VW
34
Engineering Thermodynamics
CHBE 346
The Van der Waals for Mixtures
The Van Laar Model
Scatchard-Hildebarnd Theory
35
or
1
a
1 b RT
with
PV
RT
; b
RTc
8 Pc
Z 1 Z rep Z att 1
b
a
1 b RT
Where 1 denotes the ideal gas law, Zrep denotes deviations from ideal gas law
due to repulsive interactions between the molecules and Zatt denotes
deviations from ideal gas law due to attractive interactions between the
molecules.
36
The van der Waals equation of state for mixtures should have the same form.
The key quantities to be considered are van der Waals a and b.
If we know a=a(x) and b=b(x), then we could solve for Z for a mixture and
calculate other functions (departure functions).
The equations to be developed for the compositional dependence into the
mixture constants are termed mixing rules.
The parameter b represents the finite size of the molecules. Thus for similar molecules:
b xi bi
i
For the parameter a we must relate it to the departure function for U, resulting:
U U ig a a / V
In a binary mixtures there are three types of interactions (1+1) and (2+2) between
similar molecules and (1+2) or (2+1) between dissimilar molecules. Thus,
Where a11 and a22 are the a in the van der Wall equation of each component and a12
1/2
Where k12 is an adjustable parameter. The default k12=0 gives an estimate of a12.
37
GE U E
The energetics of a of the mixture are given by the equations presented in the previous page.
ig
Assuming zero excess volume, V xiVi then ( remember that U U a a / V :
i
U U ig
xi x j aij
i
xV
i i
U U ig
U U
ig
is
aii
Vi
( xi aii / Vi )
i
38
U E U U is
For binary mixtures, we
subtract the ideal solution
result
For
(U U ) a / V
ig
We get
Rearranging
U E (U U ig ) (U U ig )is
Thus,
U U
ig
x1V1 x2V2
a11
a22 x12 a11 2 x1 x2 a12 x22 a22
U x1
x2
V1
V2
x1V1 x2V2
UE
39
a
x1 x2V1V2
a
a
Q where Q 112 222 2 12
x1V1 x2V2
V1V2
V1 V2
It appears that this equation contains three parameters (V1, V2 and Q), however van Laar
recognized that these can be rearranged to result only two adjustable parameters.
QV1
QV2
A12 V1
A12
; A21
;
RT
RT
A21 V2
The final results are:
Activity
coefficients
A12 A21 x1 x2
GE U E
RT RT x1 A12 x2 A21
ln 1
A12
A12 x1
1 A x
21 2
and
ln 2
A21
A21 x2
1 A x
12 1
The parameters of the model can be fitted by using a single pair of experimental data (see E. 12.1)
x ln 2
A12 (ln 1 ) 1 2
x1 ln 1
and
x ln 1
A21 (ln 2 ) 1 1
x2 ln 2
40
Scatchard-Hildebrand Theory
This is the theory for nonpolar fluids. Setting a12 (a11a22 )1/2 that is k12 0
a22
x1 x2V1V2 a11 a22
a12
x1 x2V1V2 a11
E
U
Scatchard and Hilderbrand recognized the unknown parameters in terms of volume fractions
and disperse attraction energies that could be related to the pure component values.
U E 1 2 (1 2 ) 2 ( x1V1 x2V2 )
where
i xiVi / xiVi
is volume fraction
To calculate these, Scatchard and Hildebrand suggested to use experimental data such that
U ivap
H ivap RT
i
Vi
Vi
Table 12.1 gives values of the solubility parameters and molar volumes.
G E U E 1 2 (1 2 ) 2 ( x1V1 x2V2 )
RT ln 1 V1 22 (1 2 ) 2
and
RT ln 2 V2 12 (1 2 ) 2
41
Engineering Thermodynamics
CHBE 346
The Flory-Huggins Model
The Wilson Model
THE NRTL Model
42
Also
c V1 (1 2 ) 2 / RT
Activity
coefficients
ln 1 ln 1 / x1 (1 1 / x1 )
V1 2
2 (1 2 ) 2
RT
ln 2 ln 2 / x2 (1 2 / x2 )
V2 2
1 (1 2 ) 2
RT
43
Wilson Equation
This theory is based on local composition theory and accounts for intermolecular
interactions between a molecule and its immediate neighbors. Local composition
might differ from bulk composition as molecules might form clusters and not
evenly distributed at a local level. These effects are taken into account using local
composition theories such as the Wilson theory. The excess Gibbs energy is:
GE
x1 ln x1 x2 12 x2 ln x1 21 x2
RT
Activity
coefficients
where
12
21
ln 1 ln x1 x2 12 x2
x1 x2 12 x1 21 x2
12
21
ln 2 ln x1 21 x2 x1
x
1
2
12
1
21
2
12
V2
A
exp 12 and
V1
RT
21
V1
A
exp 21
V2
RT
Where Vi are the molar volume and A12 and A21 are related to the interaction energies
between the components. These are not known and they are treated as adjustable
parameters.
One limitation of the Wilson equation is that it is unable to model liquid-liquid equilibria,
but it is reasonably accurate for modeling the liquid phase when correlating the vapor
liquid equilibria.
44
Activity
coefficients
2
G
G21
12 12
ln 1 x
21
2
x
x
G
x1G12 x2
1 2 21
2
2
2
G
G
2
21 21
21
ln 2 x1
12
2
x
G
x
x1 x2G21
2
1 12
where
gij
RT
g12 g 22
RT
g g
G21 exp(a 21 ) and 12 21 11
RT
G12 exp( a 12 ) and 12
The NRTL is not appealing from a theoretical perspective, but it is flexibility has led to a
number of applications including elecrolyte models.
45
Engineering Thermodynamics
CHBE 346
The UNIQUAC
The UNIFAC
Project Not for the Final Exam
46
Engineering Thermodynamics
CHBE 346
Engineering Equations of State
for PVT Properties
Phase Equilibria in Mixtures by an
Equation of State
47
B xi x j Bij
i
Tc12 (Tc1Tc 2 ) (1 k )
1/2
'
12
Vc12
1/3
Vc1/3
1 Vc 2
Z c12 12 (Zc1 Z c 2 )
w12 12 (w1 w2 )
Then these are used in the correlations below to obtain B12 (B of the mixture). If Zc is not
available use: Zc=0.291-0.08w
Z 1 ( B 0 w B1 ) Pr / Tr
or
Z 1 B ( P / RT )
48
The tool for LVE is the K-ratio and an expression for the component fugacity
The EOS is capable of representing liquid phases by using the smaller root , we
show both vapor and liquid phases.
Note that for VLE
f L f V
i
i (T , P) iig (T , P)
RT
G / RT
G ig / RT
(G G ig ) / RT
n
ni
i
i
T , P ,ni j
T , P ,ni j
T , P ,ni j
G G ig BP
RT
RT
fi ( i iig ) (G G ig ) / RT
ln
y P
RT
n
i
i
T , P ,ni j
Define the ratio of the component fugacity to the partial pressure (ideal gas component
fugacity) as the component fugacity coefficient:
fi
i
or fi i yi P
yi P
Differentiation of the Gibbs departure function leads to (binary system):
49
i iig
RT
( A Aig )T ,V / RT
ni
ln Z
T ,V,ni j
To apply this consider the Peng-Robinson equation as an example. Using the above
relationship, the following equation can be derived:
fiV Bi V
Z V (1 2) BV 2( y1 Ai1 y2 Ai 2 ) Bi
AV
V
V
ln
( Z 1) ln( Z B ) V
ln V
V
V
V
y P BV
A
B
B 8 Z (1 2) B
i
where
AV yi y j Aij
i
BV yi Bi
i
The EOS approach encompasses both liquids and vapors. We replace the vapor phase mole
fractions with liquid mole fractions in all formulas.
fi L Bi
Z L (1 2) B L 2(x1 Ai1 x2 Ai 2 ) Bi
AL
L
L
L
ln
( Z 1) ln( Z B ) L
ln L
L
L
L
x P B L
A
B
B
8
Z
(1
2)
B
Recall:
fi L fiV
or
yiiV P xiiL P
or
K i iV / iL
Given Ki for all i, it is straightforward to solve VLE problems using the same procedures as for
ideal solutions.
50
i iig
RT
( A Aig )T ,V / RT
ni
ln Z
T ,V,ni j
To apply this consider the van der Waals equation. Using the above relationship,
the following equation can be derived:
B
ln k ln( Z B) k
Z B
where
B
a
A
;
;
Z
bRT B
a jk
a
2 x j Akj
j
Ajk
A
bk Bk
b
B
ln i ln( Z B)
Bi
2( x1 Ai1 x2 Ai 2 )
Z B
Z
Note that this equation applied for both liquid and vapor phases.
51
Bubble-Pressure Method
For bubble calculations (BP), all xi are known and we need to find yi so that:
1 or
K x 1
i i
xiiL
i V P i Ki xi 1
i
Unlike the activity model calculations, we cannot explicitly solve for pressure
because both fugacities, iL and iV depend on pressure. Additionally, iV
depends on the composition of the vapor phase which is not exactly known.
Typically, we use Raoults law with the shortcut vapor pressure equation for
the first guess of yi and P.
Then we determine all Ki and check the sum of yi.
If the sum is greater than 1 , the pressure is increased in the second guess.
If the sum is less than 1 , the pressure is decreased in the second guess.
Complete flow charts on performing these calculations for BP, BT, DP and DT as
well as flash calculations can be found in Appendix C (principles same as before)
52
Engineering Thermodynamics
CHBE 346
Partially Miscible Liquids
Ternary Systems
53
54
Ternary Systems
When a soluble third component is added to two partially miscible liquids we obtain a
ternary system in which the third component (solute) is partitioned between the two liquid
phases (solvents). The phase diagram of such a system is a triangular.
Discussion of Figure 8-13 (Matsoukas).
The three components are placed on the vertices of
the equilateral triangle.
The concentration of a component at any point
inside the triangle is measured by the fractional
distance of that point from the side opposite to the
vertex of the component (explain point A).
Point A lies at 44% of max distance above the
horizontal axis which makes the conc. Acetic acid
44wt%. This can be read from the grid lines placed
on the sides of the triangle (point B). Point C shows
the wt% water and D the wt%of MIBK. These should
add to 100%.
The shaded area represents two liquid system with
the rest one liquid phase.
Point E represents a two phase liquid (L1 which is
mostly water and L2 which contains mostly
methylisobutyl ketone. The lever rule applies (tie
lines are not horizontal).
55
Engineering Thermodynamics
CHBE 346
Energy Balance for Reacting Systems
Stoichiometry
Standard State Heat of Reaction
56
CH 4 H 2O CO 3H 2
1 1; 2 1; 3 1; 4 3
Consider a certain amount of C1 reacts with C2, to produce C3 and C4, we can prove that:
dn1
dn2
dn3
dn4
dni represent differential amount reacted and produced and is the reaction coordinate
and is related to the conversion.
Integrating
d
0
dn
ni
ni
57
nif nii i
In a flowing system
niout niin i
Where
Moles are not conserved in a chemical reaction. Adding all components in and out.
n out nin i
or
n out n in i
i
nif 0
for
all i
or
nif 0
for
all i
58
We select the standard state which is the reference state at the T of the system, 1 bar. We can write:
H To i H To,i i H ofT ,i
i H ofT ,i
products
i H ofT ,i
reactants
H ofT ,i is the standard heat (or enthalpy) of formation Appendix E.1. (T=298.15 K)
When we know the heat of reaction at a reference temperature we can calculate the heat of reaction
at any temperature.
T
T
H H C P dT H i C P ,i dT
TR
TR i
o
T
o
R
o
R
A reaction with negative heat is called exothermic and one with positive is called endothermic.
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Engineering Thermodynamics
CHBE 346
Energy Balance for Reactions
(a) Heat of Reaction Method
(b) Heat of Formation Method
60
0 H in n in H out n out Q W S
61
components
components
niin H iin
niout H iout
components
niin ( H in H Ro )i
components
niout ( H out H Ro )i
components
(n
in
i
niout ) H io, R
components
i
components
o
i,R
(H Ro )
in
i
components
( H in H Ro ) i
out
i
components
( H out H Ro ) i Q W S H Ro
The enthalpies of the streams should be calculated relative to the reference temperature
where HoR is known. The temperature of 298.15 is almost always the reference
temperature. is calculated on the basis of molar flows.
62
n [( H H
i
small
) H of ,TR ] n H mix
o
R i
o
ni CP dT H f ,TR
T
i
R
i
When phase change is involved an additional term is needed as discussed before (Example).
The energy balance can be written as:
components
niout ( H out H R0 ) H f , R
i
components
niin ( H in H R0 ) H f , R
out
in
ni C p ,i dT H f , R ni C p ,i dT H f , R
T
components T
components
R
R
i
out
in
If the reference state is gas and reaction is in liquid state, H vap should be taken into
account. See below example problem.
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Engineering Thermodynamics
CHBE 346
Equilibrium Constant
Reaction Equilibrium Constraint
The Standard State Gibbs Energy of Reaction
64
Reaction Equilibria
Equilibrium thermodynamics tells us the direction and extend to which a reaction will go.
The constraint of minimum Gibbs energy dictates the equilibrium results at fixed T and P.
Select the following reaction:
CH 3OH ( g )
CO( g ) 2 H 2( g )
or
The Cs represent the species and reactants have negative s, while products have positive.
The s are called the stoichiometric numbers.
If we consider ideal gases, then the equilibrium constant (P always in bars, prove that later):
K a yi P i
65
Example:
GTo i Gio
products
i G of ,i
i G of ,i
CH 4( g ) H 2O( g ) CO( g ) 3H 2( g )
GTo i G of ,i
i
The Gibbs energies of formation are tabulated at 298.15 K and 1 bar (E.1). This energy is taken
as zero for elements that naturally exist at 298.15 and 1 bar (similar to enthalpies of formation).
The standard state Gibbs energy of reaction is related to the equilibrium constant through:
exp(GTo / RT ) K a
The standard state is at fixed pressure Po. Thus GTo is independent of pressure. The
standard states are also at fixed composition (pure state) and therefore independent of
equilibrium composition. Looking at the above equation we can conclude that Ka is
independent of equilibrium composition and pressure.
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Engineering Thermodynamics
CHBE 346
Effects of P, Inerts and Feed Ratios
Temperature Dependence of Ka
Estimation of Temperature Effects
67
Pressure Effects
Pressure has important effects when both 1) gas species are involved in reactions and 2) the
stoichiometric numbers of gas species are different for reactants and products.
To see this, we can write the equilibrium constant for ideal gases using partial pressures as:
K a yi P i yi i P
When the stoichiometry is the same then Si=0 and the pressure drops out.
When Si<0 an increase in pressure will drive the reaction to higher conversions.
When Si>0 a decrease in pressure will drive the reaction to higher conversions.
Essentially the pressure squeezes the reaction towards the side with fewer moles.
68
Temperature Dependence of Ka
o
Always remember that GT depends on the standard state, which changes with
temperature. To calculate this change the Gibbs-Helmholtz relation is used.
(G / RT )
1 G
G
S H S
2
2
T
RT T P RT
RT RT
RT
RT 2
(GTo / RT ) ( ln K a ) H To
T
T
RT 2
GTo
H To
GRo
H To
dT
ln K a
dT ln K aR
2
2
RT
RT
RTR
RT
TR
TR
T
To calculate this, we take into account the heat capacities of the reactants and products (full
calculation) and substitute into the vant Hoff equation (see example below).
GTo J 1 1 a T b
GRo
c 2
d 3
2
3
ln
(T TR )
(T TR )
(T TR )
RT
R T TR R TR 2 R
6R
12 R
RTR
or
GTo
J
a
bT cT 2 dT 3
ln K a
ln T
I
RT
RT R
2R
6R
12 R
o
Where I may be evaluated from a knowledge of G298 by plugging in T=298.15 on the righthand side as illustrated below (example). J can be found from the corresponding eqn of H To
69
Ka
ln
K aR
GRo GTo H Ro
RT
RT
R
R
1 1
T TR
Ka
70
Engineering Thermodynamics
CHBE 346
Liquid Components in Reactions
Solid Components in Reactions
71
72