Chemical Equilibrium Constants

Chapter 6
Chemical Equilibrium
Nguyen Quang Long
T
Liquid phase reaction Gas phase reaction

2
Today’s Quiz
3
Contents
1. Introduction
2. Factors affect chemical equilibrium
3. Determination of Equilibrium constant
4. Ideal solutions and real solutions
5. Chemical equilibrium in real gases
6. Chemical equilibrium in real solutions
7. Chemical equilibrium in heterogeneous systems
4
1. Introduction
Equilibrium state
G
• T= constant
• P= constant
dG=0
Equilibrium State
(Keq)
dG < 0 dG =0
5
1. Introduction
Equilibrium constant
• For a reaction in gas phase: aA + bB = dD
G=ni i
GT = dD - aA - bB
Since: i = 0i(T) + RTlnPi (assume ideal gases)

[ or fully: i = 0i(T) + RTln(Pi atm /1atm) ]
 PD 
d
GT  (d D  a A  b B )  RT ln a b 
0 0 0
 PA .PB 
[ Note: Pi unit: atm]
6
1. Introduction
 P d

GT  (d D  a A  b B )  RT ln a b 
0 0 0 D
 PA .PB 
GT  GT0  RT ln  P (Van’t Hoff’s equation)
G0T : Gibbs energy change of the reaction at 1 atm,

depending only on temperature (= GT when  =1)
• At equilibrium (GT =0): GT0   RT ln( P ) eq
7
1. Introduction
• Equilibrium constant:
 PDd 
K P  ( P ) eq   a b GT0   RT ln K P
 PA .PB eq
• Since G0T depends only on T

 Kp depends only on T
P
GT  G  RT ln  P
0
T GT  RT ln
KP
8
1. Introduction
P
• Determination of reaction direction: GT  RT ln
KP
T,P = constant
Forward reaction
Kp > P GT < 0 occurs
Reverse reaction
Kp < P GT > 0 occurs
Kp = P GT = 0 Equilibrium
9
1. Introduction
Equilibrium constants
• For reaction in gas phase: aA + bB = dD
 P d  CDd 
KP   a b 
D KC   a b 
 PA .PB eq  C A .CB eq
 xDd   nDd 
Kx   a b  Kn   a b 
 x A .xB eq
 nA .nB eq
• Note:
Pi is actually Pi(atm)/1(atm);
Ci is actually Ci(M)/1(M);
ni is actually ni(mol)/1(mol);
 Unit of Kp, KC, Kx, Kn is [ ] (no unit)
10
1. Introduction
• For reaction in gas phase: aA + bB = dD
• Relationships:
 PDd   CDd   xDd   nDd 
KP   a b  KC   a b  Kx   a b  Kn   a b 
 PA .PB eq  C A .CB eq  x A .xB eq  nA .nB eq
n
n n  P 
K P  K C .( RT )  K x .P  Kn . 

 i eq
n
n= mole change of gaseous substances = d-a-b
P (atm): Reaction pressure
T (K) : Reaction temperature
R = 0.082 11
1. Introduction
n
 P 
K P  K C .( RT ) n  K x .P n  Kn . 

 i eq
n
Since KP depends only on Temperature then:

- Kc depends only on T
- Kx depends on T and P
- Kn depends on T, P and total of moles (ni)
- If n = 0 then KP = Kc = Kx = Kn
12
1. Introduction
Example
a. Determine Kp , KC of following reaction at 400 0C,

1atm:
COCl2 = CO + Cl2
Given: 0,1 mol COCl2 occupies 6,73L (at equilibrium).
b. Which reaction direction of the following mixtures:
1/ 0,5 mol COCl2 ; 0,3 mol CO ; và 0,2 mol Cl2
2/ 0,8 mol COCl2 ; 0,1 mol CO ; và 0,1 mol Cl2
13
1. Introduction
Example
• Solution:
COCl2 = CO + Cl2 (n=1+1-1= 1)
Initial 0,1 mol 0 0
Reacted y mol y y
Equil. (0,1-y) mol y y
ni = 0,1+y (mol)
14
1. Introduction
Example
− Ideal gas EOS: ni = 0,1 + y = PV/(RT)

 y = 0,022 mol
n n
 P   nCO .nCl 2   P 
K P  K n      . 
 ni  eq  nCOCl 2  eq  ni 
n 1
 nCO .nCl 2   P   y2  1 
K P   .    .   0,0509
 nCOCl 2   ni  cb  0,1  y   0,1  y
KP 0,0509 4
KC    9, 23. 10
( RT ) n 0,082.673
15
1. Introduction
Example
b. Reaction direction: comparing KP and P
n n
 P   nCO .nCl 2   P 
 P   n     . 
 ni   nCOCl 2   ni 
Mixture 1: 0.5 mol COCl2 ; 0,3 mol CO ; and 0,2 mol Cl2
1
 0,3.0,2   1  Reverse reaction
P   .   0,12  0,0509  K P
 0,5   1  occurs
16
1. Introduction
Example
b. Reaction direction: comparing KP and P
n n
 P   n .n   P 
 P   n     CO Cl 2 . 
 ni   nCOCl 2   ni 
Mixture 2: 0,8 mol COCl2 ; 0,1 mol CO ; and 0,1 mol Cl2
1
 0,1.0,1   1  Forward reaction
P   .   0,0125  0,0509  K P occurs
 0,8   1 
17
1. Introduction
Comments on equilibrium constants
i. A reaction can proceed in the forward direction or reverse
direction depending on the initial composition.
ii. All reactions are reversible. A reaction is considered
completion when its equilibrium constant is very large 
reactants’ concentration is negligible in the equilibrium
mixture.
iii. A reaction can proceed to completion if a product is
removed from the equilibrium mixture (in precipitation,
evaporation, or weak electrolyte).
18
∆G 0
298 KP (298)
  G  H
   
T  T  P T2
(PT G-H)
∆G 0
T KP (T) ?
d ln K P H

dT RT 2
19
Effect of temperature
  G  H
– Gibbs-Helmholtz equation:    2
T  T  P T
– Van’t Hoff equation: GT0   RT ln K P

   RT ln K P  H 0   ln K P  H 0
   2   
T  T P T  T  P RT
2
– Because of insignificant effect of pressure on H

and KP:
d ln K P H H
dT

RT 2  ln K P   RT 2 dT  I
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d ln K P H
 2
dT RT
–Endothermic reactions ?
–Exothermic reactions ?
21
d ln K P H

dT RT 2
– Endothermic reactions: H >0  d ln K P
0
dT
T increases  KP increases  Reaction shifts to
FORWARD direction (Endothermic direction)
(Le Chatelier principle)
– Exothermic reactions : H <0
T increases  KP decreases  Reaction shifts to

REVERSE direction (Endothermic direction)
(Le Chatelier principle)
22
d ln K P H
 2
dT RT
– For a small temperature change (H=const):
K P ,T2 H  1 1 
ln    
K P ,T1 R  T2 T1 
23
• Example: C (r) + CO2 (k) = 2CO (k)

– Given: KP (1000K) = 1,85, H (averg)= 41130 cal/mol,
Total pressure: P=1atm
Determine equilibrium compositions of gas phase

at 1000K and 1200K
24
• Solution:
– Gas phase consists of CO and CO2 :
Mole fraction of CO : x  Mole fraction of CO2 : (1-x)
– Equilibrium constant: 2 2 2
PCO n xCO 1 x
KP   K x .P  .1 
PCO2 xCO2 1 x
– At 1000 K: KP,1000 =1,85  x= 0,72
– At 1200 K:
K P ,T2 H  1 1  K P ,1200 41.130  1 1 

ln     ln    
K P ,T1 R  T2 T1  K P ,1000 1,987  1200 1000 
KP,1200 = 58,28 x = 0,98
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Effect of total pressure
– For condense phase reaction (liquid/ solid):

negligible effects
– For gas phase reaction: At specific T, KP = const
K P  K x .P n
?
26
Effect of total pressure
K P  K x .P n
 IF n > 0: When P increases Kx decreases

Equil. Shifts to REVERSE side
(reduce number of moles)
 IF n < 0: When P increases Kx increases
Equil. Shifts to FORWARD side
(reduce number of moles)
 IF n = 0: KP = Kx  no effect
27
Effect of inert components
– In solution: At a specific temperature
K C  K n .V  n  const
Adding inert/solvent  V increase:
• IF n > 0: Kn increases Equil. shifts to FORWARD side
(increase number of moles)
• IF n < 0: Kn decreases Equil. shifts to REVERSE side
• IF n = 0: KC = Kx  no effect
28
– Ideal gases: At a specific temperature, pressure

n
 P  P RT
K P  K n .   const 
 ni  eq ni eq V
(because: PV = RT.(ni)eq)
n
 RT 
K P  K n .   const
 V  eq
29
n
 RT 
K P  K n .   const
 V  eq
Adding inert/solvent at constant pressure V increase:
• IF n > 0: Kn increases Equil. Shifts to FORWARD side
• IF n < 0: Kn decreases Equil. Shifts to REVERSE side
• IF n = 0: Kp = Kx  no effect
30
Ex: C (s) + CO2 (g) = 2CO (g)
Given KP (1000K) = 1,85. Determine equilibrium

compositions at 1000 K, 0,1atm:
a. Pure CO2 reacts with excess C.
b. Equi-molar mixture (CO2 + N2) react with
excess C.
31
Solution: a. C (r) + CO2 (k) = 2CO (k) (n= 2-1=1)

Initial (mol) 1 0
Equilibrium (mol) 1-y 2y
(ni = 1-y+2y=1+y)
n 1
 P  2
(2 y )  0,1 
K P  K n .  1,85  .  y= 0,906
 ni  eq 1 y 1 y 
At equilibrium: CO/CO2 = 2y/(1-y) = 19,3
32
Solution : b. C (r) + CO2 (k) = 2CO (k) (n= 2-1=1)
Initial (mol) 1 0
Equil. (mol) 1-y 2y
ni = 1-y+2y+1=2+y
n 1
 P  2
(2 y )  0,1  y= 0,953
K P  K n .  1,85  . 
 ni  eq 1 y 2 y 
At equilibrium: CO/CO2 = 2y/(1-y) = 40,6
33
Effect of initial composition
– Yield (h%): mole fraction of products in the
equilibrium mixture.
– Conversion (): A= nA reacted/nAinitial
 Maximum equilibrium yield is obtained at stoichiometric

compositions.
 Equilibrium conversion of a reactant will increase if the

concentrations of the other reactants increase.
34
– Ex:
N2 + 3H2 = 2NH3
Initial: a b 0 (mol)
Equilibrium: a-y b-3y 2y (mol)
2y 2y
Yield: h%  100%  100%
(a  y )  (b  3 y )  2 y a  b  2y
y 3y
Conversion: N  và H 
2
a 2
b
35
– Ex: O2 + N2 = 2NO KP = 1 at 1500K.
Initial composition h (%) O2 N2
3 mol O2 + 3 mol N2 33,33 0,33 0,33
5 mol O2 + 2 mol N2 28,57 0,20 0,50
2 mol O2 + 5 mol N2 28,57 0,50 0,20
36
Direct method
Determine (Pi) or (Ci) at equilibrium state.
– Note:
• Determine (Pi) or (Ci) at equilibrium state: check
forward and reverse direction.
• Quench (rapid cooling) or inhibitor addition may be
used to make sure that the equilibrium is stable.
37
Indirect method
(i) Measure the change of physicochemical
parameters such as pressure, volume,
density, color, conductivity, …which
change due to the reaction.
38
Indirect method
(ii) Via equilibrium constant of other related
reactions.
example: (1) C (r) + O2 = CO2

(2) 2CO + O2 = 2CO2
(3) 2C (r) + O2 = 2CO
Rx(3) = 2* Rx(1) – Rx(2)
Kp (3) = KP2(1) . KP-1(2)
39
Thermodynamic method
G   RT ln K P
0
T
– Calculate G0T :
GT2 GT1 T2 T
dT
• Gibbs-Helmholtz equation:    (H T1   C P dT )
T2 T1 T1 T1
T2
• Chomkin-Svartsman equation:
GT  H 298  T .S298  T .ai M i
• Reduced Gibbs energy:
GT0  H 00  T .g p.u
40
Electrochemical method
• From measurement of electromotive force
(E)
0
nFE
G  nFE
0 0
ln K P 
RT
Where: E0 : Standard electromotive force of the battery

F : Faraday constant
n : number of exchanged electrons
41
Solution??
• Solution: A solution is a homogeneous
mixture; that is, a solution is a one-phase
system with more than one component. The
phase may be solid, liquid, or gas:
– Solid solution
– Liquid solution (or solution)
– Gas solution (gas mixture)
42
Solution??
• Solvent - Solutes
• Solution types:
– Ideal solutions
– Ideally (infinite) dilute solutions
– Real solutions
• Non-electrolyte solutions
• Electrolyte solutions (will be discussed in course
“Physical Chemistry 2”)
43
Solution composition
• (molar) concentration (Ci)

• Molarity (mi): moles solute/ 1 kg
solvent
• Weight percent (wi)
• Volume percent (vi)
• Mole fraction (xi): mole percent the
solvent mole fraction is greater than
the mole fraction of each solute.
44
Solution composition
• Example: A solution is prepared by dissolving 555.5 g
of sucrose, C12H22O11, in 750 mL of water and diluting
with water to a final volume of 1.0000 L. The density of
the final solution is found to be 1.2079 g/cm3. Find the
sucrose mole fraction, molality, and weight percent
in this solution.
(Answers: 0.04289, 2.488 mol/kg, 45.99%.)
45
Mixing quantities
• Mixing volume change:
V ≠ V*=xi.Vi
mixV = V- V*
• Similarly:
mixH = H- H*
mixS = S- S*
mixG = G- G*
(20°C and 1 atm) 46
Mixing quantities
(Similar)
Others:
47
Mixing quantities
Integral Heats of Solution
For a two-component solution, the

quantity mixH/nB is called the
integral heat of solution per mole
of B in the solvent A
Hint,B is numerically equal to the heat absorbed by the

system when 1 mole of pure B is added at constant T
and P to enough pure A to produce a solution of the
desired mole fraction xB
48
Ideal solution (ideal mixture)
• A solution where the molecules
of the various species are so mixV = 0
similar to one another that
replacing molecules of one mixU = 0
species with molecules of another
species will not change the spatial
structure or the intermolecular mixH = 0
interaction energy in the solution.
mixG = RT(n1lnx1+ n2lnx2)
• Examples:
benzene–toluene,
n-C7H16–n-C8H18,
C2H5Cl–C2H5Br,
C(CH3)4–Si(CH3)4.
*i (T, P) : chemical potential of pure

substance i at T, P of the solution.
49
Ideal solution (ideal mixture)
mixH - mixG - mixS

50
Ideally (infinite) dilute solution
• Solvent: x1  1 ; Solutes: xj  0
• solute molecules interact essentially only
with solvent molecules.
• Chemical potential:
Solvent: 1 = *i (T, P) + RT.lnx1
Solutes: j = f(T, P) + RT.lnxj
51
Ideally (infinite) dilute solution
Chemical potential i plotted

versus ln (xi ) for a typical
nonelectrolyte solute. The dashed
line extrapolates the ideally dilute
behavior to the limit xi → 1.
52
Real solutions
Activity (a): A function of mole fraction (x ) or concentration (C ).
i i
The ideal solution relation can be used for real solutions by replacing the (xi)
or (Ci) by the activity (ai) of that component.
iid = i0(T) + RTlnxi (ideal solutions)

i = i0(T) + RTlnai (real solutions)
ai
Activity coefficient: γi 
xi
Note: in electrolyte solution: i = ai/Ci (in Phy.Che. 2) 53

Real solutions
Determine activity coefficients:

• By experimental works
• By activity coefficient models: Margules, Van Laar,
UNQUAC, NRTL, Wilson, UNIFAC,…
54
Real solutions
• Margules model (simple):
(A: constant from

experiments)
(Application: 2-component system: non-polar or weakly polar compounds)
55
Real solutions
• Van Laar model (more accurate):
(: available for some

common solutions)
(Application: 2-component system: non-polar or weakly polar compounds)

56
Real solutions
• Example:
Using the Van Laar model, determine the water activity
coefficient of the water-acetone mixture containing 25
mol% water at 25 °C.
Given : For solution acetone (1) – water (2) at 25 oC:
 = 1.89
 = 1.66
57
– Ideal gas relation:

PV = RT (n=1 mol)
– Real gas relations:

2
RT  a  (PT Van der Walls)
P  
V  b V  a, b: constants
– Fugacity – Pressure
i = i0(T) + RTlnPi (ideal gas)
i = i0(T) + RTlnfi (real gas)
58
Real gases
– Fugacity coefficient: γ  f
• Ideal gases :  = 1 P
• Real gases:   1 (Depend on T, P and gases)
• (High pressure, low temperature)  big difference between f
and P
• (Low pressure, high temperature)  small difference between
f and P
– Equilibrium const:
fi = i.Pi Kf = K.KP
59
=Pr = P/Pc : reduced pressure
=Tr = T/Tc : reduced temperature
(f/P)
60
– Equilibrium constant:
G   RT ln K f
0
T
Exactly!!! (Accept, Proving is complicated)
– Fugacity coefficient:
fi
γi  K f  K γ .K P
Pi
Kf : Depend on Temperature : Kf= exp(-G0T /RT)
 : Depend on Temperature and Partial Pressure (Pi)
Require iterative calculation to obtain the equilibrium composition
61
Given data: T, P, ni0
Calculating Kf
Guesting K ni(eq)
Y
N
K = K(new) K  (new)/K  -1
Calculating Kp
=0
Calculating equilibrium Pi
Calculating (i) Calculating K(new)
62
– Equilibrium constant: G   RT ln K a
0
T
Exactly!!! (Accept, Proving is complicated)
– Activity coefficient:
ai
γi  K a  K γ .K x
xi
Ka : Depend on Temperature : Ka= exp(-G0T /RT)
 : Depend on Temperature and concentration

 K, Kx: Depend on Temperature and concentration.
Require iterative calculation to obtain the equilibrium composition
63
Given data: T, P, ni0
Calculating Ka
Guesting K ni(eq)
Y
N
K = K(new) K  (new)/K  -1
Calculating Kx
=0
Calculating equilibrium xi
Calculating (i) Calculating K(new)
64
• Chemical equilibrium:
– Chemical potentials in gas phase: i = 0i(T) + RTlnPi
– Chemical potentials in liquid/solid phase : i = *i(T) + RTlnxi
Chemical equilibrium: KP,x = (P,x)eq
• Example: Fe2 O3 (s) + 3CO (g) = 2Fe (s) + 3 CO2 (g)
 xFe
2 3
PCO 
K P,x  2 
 xFe O .PCO
3 
 2 3  eq
65
• If the substances in liquid, solid phase are insoluble

in each other (not form a solution), then xi = 1
 their value does not affect Keq: KP,x = (P)eq
• Ex: Fe2 O3 (s) + 3CO (g) = 2Fe (s) + 3 CO2 (g)
 xFe
2 3
PCO   PCO
3

K P,x  2  KP   3 2
P


 xFe O .PCO 
3
 2 3  eq  CO  eq
66
• Ex: CaCO3 (s) = CaO (s) + CO2 (g)
– Equil. Const.: KP = (PCO2)eq  depend only on T.

– When T increases, (PCO2)eq increases.
– When (PCO2)eq = (PCO2)atmosphere  Dissociation temperature
(CaCO3 Tdis = 512oC)
– When (PCO2)eq = 1 atm  Decomposition temperature
(CaCO3 Tdecomp. = 880oC)
67
END
68
Quiz
Explain
your
choice
69
Margules equations
– One constant:
(Applicable to: liquid mixture containing constituents of similar

size, shape and chemical nature)
– Two constants (read more in textbook)
70
Van Laar equations
(: from table)
71
72
One – constant
Magules
Benzen & 2,2,4- trimetyl pentane
73
Van Laar
Benzen & 2,2,4- trimetyl pentane
74
Others
• Wilson equations:
(12, 21: (lamda) constants)

• Nonrandom two liquid (NRTL) equations:
(,12,21: constants)
• ….
75
Others
• Universal Quasichemical (UNIQUAC ) equations
From table
12, 21: from

experimental data
z = 10
76
• Predictive activity coefficient models:
Regular Solution model UNIFAC

(RSM) (UNIQUAC Functional-
(Van Laar) group Activity Coefficient)
77
1. Introduction
n
 P 
K P  K C .( RT ) n
 K x .P n
 K n . 
 ni cb
Effect of T, P, ni on K?
78
2. Chemical equilibrium in various systems
In ideal solutions
• Ex: CH3COOC2H5 + H2O  CH3COOH + C2H5OH

– Initial: 1 mol 1 mol 0 mol 0 mol
– Equil: 2/3 mol 2/3 mol 1/3 mol 1/3 mol
a. Determine equilibrium constant

b. Calculate % ester reacted if at beginning
nH2O = 10 nCH3COOC2H5
c. Calculate nH2O / nCH3COOC2H5 if 99% ester reacted at
equilibrium.
79
2. Chemical equilibrium in various systems
In ideal solutions
• Solution:
y2
a. Kn = KX = KC = 0,25 Kn   0,25
(1  y ).(n  y )
b. Assume at beginning: 1 mol ester, n mol H2O :

3 y 2  (n  1) y  n  0
with n=10  y= 0,759  75,9% ester reacted.
c. y=0,99  n= 393
80
– Using reduced Gibbs energy (g):
G  H  T .g rxn
0
T
0
0
1  H 0

ln K P     g rxn 
0
R T 
81

Chemical Equilibrium Constants

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Chemical Equilibrium Constants

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Chapter 6

Liquid phase reaction Gas phase reaction

Since: i = 0i(T) + RTlnPi (assume ideal gases)

G0T : Gibbs energy change of the reaction at 1 atm,

• At equilibrium (GT =0): GT0   RT ln( P ) eq

• Since G0T depends only on T

Since KP depends only on Temperature then:

a. Determine Kp , KC of following reaction at 400 0C,

ni = 0,1+y (mol)

− Ideal gas EOS: ni = 0,1 + y = PV/(RT)

– Van’t Hoff equation: GT0   RT ln K P

– Because of insignificant effect of pressure on H

– Exothermic reactions : H <0

T increases  KP decreases  Reaction shifts to

• Example: C (r) + CO2 (k) = 2CO (k)

Determine equilibrium compositions of gas phase

K P ,T2 H  1 1  K P ,1200 41.130  1 1 

KP,1200 = 58,28 x = 0,98

– For condense phase reaction (liquid/ solid):

– For gas phase reaction: At specific T, KP = const

 IF n > 0: When P increases Kx decreases

– Ideal gases: At a specific temperature, pressure

Ex: C (s) + CO2 (g) = 2CO (g)

Given KP (1000K) = 1,85. Determine equilibrium

Solution: a. C (r) + CO2 (k) = 2CO (k) (n= 2-1=1)

At equilibrium: CO/CO2 = 2y/(1-y) = 19,3

At equilibrium: CO/CO2 = 2y/(1-y) = 40,6

 Maximum equilibrium yield is obtained at stoichiometric

 Equilibrium conversion of a reactant will increase if the

Initial composition h (%) O2 N2

3 mol O2 + 3 mol N2 33,33 0,33 0,33

5 mol O2 + 2 mol N2 28,57 0,20 0,50

2 mol O2 + 5 mol N2 28,57 0,50 0,20

example: (1) C (r) + O2 = CO2

Rx(3) = 2* Rx(1) – Rx(2)

Kp (3) = KP2(1) . KP-1(2)

Where: E0 : Standard electromotive force of the battery

• (molar) concentration (Ci)

(Answers: 0.04289, 2.488 mol/kg, 45.99%.)

• Mixing volume change:

For a two-component solution, the

Hint,B is numerically equal to the heat absorbed by the

*i (T, P) : chemical potential of pure

mixH - mixG - mixS

Chemical potential i plotted

iid = i0(T) + RTlnxi (ideal solutions)

Note: in electrolyte solution: i = ai/Ci (in Phy.Che. 2) 53

Determine activity coefficients:

(A: constant from

(Application: 2-component system: non-polar or weakly polar compounds)

(: available for some

(Application: 2-component system: non-polar or weakly polar compounds)

– Ideal gas relation:

– Real gas relations:

=Pr = P/Pc : reduced pressure

=Tr = T/Tc : reduced temperature

Exactly!!! (Accept, Proving is complicated)

Kf : Depend on Temperature : Kf= exp(-G0T /RT)

 : Depend on Temperature and Partial Pressure (Pi)

Require iterative calculation to obtain the equilibrium composition

Calculating (i) Calculating K(new)

Exactly!!! (Accept, Proving is complicated)

Ka : Depend on Temperature : Ka= exp(-G0T /RT)