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CH 6 - (New) Chemical Equilibrium-Nguyen Quang Long
CH 6 - (New) Chemical Equilibrium-Nguyen Quang Long
Chemical Equilibrium
Nguyen Quang Long
T
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 = dD - aA - bB
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
Equilibrium constant
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)
7
1. Introduction
Equilibrium constant
• Equilibrium constant:
PDd
K P ( P ) eq a b GT0 RT ln K P
PA .PB eq
P
GT G RT ln P
0
T GT RT ln
KP
8
1. Introduction
Equilibrium constant
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
Equilibrium constants
• 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
Equilibrium constants
n
P
K P K C .( RT ) n K x .P n Kn .
i eq
n
- If n = 0 then KP = Kc = Kx = Kn
12
1. Introduction
Example
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
14
1. Introduction
Example
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
2. Factors affect chemical equilibrium
Effect of temperature
G H
– Gibbs-Helmholtz equation: 2
T T P T
d ln K P H
2
dT RT
–Endothermic reactions ?
–Exothermic reactions ?
21
2. Factors affect chemical equilibrium
Effect of temperature
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)
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
2. Factors affect chemical equilibrium
Effect of temperature
24
2. Factors affect chemical equilibrium
Effect of temperature
• 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:
25
2. Factors affect chemical equilibrium
Effect of total pressure
K P K x .P n
?
26
2. Factors affect chemical equilibrium
Effect of total pressure
K P K x .P n
27
2. Factors affect chemical equilibrium
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
(increase number of moles)
• IF n = 0: KC = Kx no effect
28
2. Factors affect chemical equilibrium
Effect of inert components
n
RT
K P K n . const
V eq
29
2. Factors affect chemical equilibrium
Effect of inert components
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
(increase number of moles)
• IF n < 0: Kn decreases Equil. Shifts to REVERSE side
(increase number of moles)
• IF n = 0: Kp = Kx no effect
30
2. Factors affect chemical equilibrium
Effect of inert components
31
2. Factors affect chemical equilibrium
Effect of inert components
32
2. Factors affect chemical equilibrium
Effect of inert components
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
33
2. Factors affect chemical equilibrium
Effect of initial composition
– Yield (h%): mole fraction of products in the
equilibrium mixture.
– Conversion (): A= nA reacted/nAinitial
34
2. Factors affect chemical equilibrium
Effect of initial composition
– 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
2. Factors affect chemical equilibrium
Effect of initial composition
– Ex: O2 + N2 = 2NO KP = 1 at 1500K.
36
3. Determination of Equilibrium constant
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
3. Determination of Equilibrium constant
Indirect method
(i) Measure the change of physicochemical
parameters such as pressure, volume,
density, color, conductivity, …which
change due to the reaction.
38
3. Determination of Equilibrium constant
Indirect method
(ii) Via equilibrium constant of other related
reactions.
39
3. Determination of Equilibrium constant
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
3. Determination of Equilibrium constant
Electrochemical method
• From measurement of electromotive force
(E)
0
nFE
G nFE
0 0
ln K P
RT
41
4. Ideal solutions and real solutions
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
4. Ideal solutions and real solutions
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
4. Ideal solutions and real solutions
Solution composition
44
4. Ideal solutions and real solutions
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.
45
4. Ideal solutions and real solutions
Mixing quantities
V ≠ V*=xi.Vi
mixV = V- V*
• Similarly:
mixH = H- H*
mixS = S- S*
mixG = G- G*
(20°C and 1 atm) 46
4. Ideal solutions and real solutions
Mixing quantities
(Similar)
Others:
47
4. Ideal solutions and real solutions
Mixing quantities
Integral Heats of Solution
48
4. Ideal solutions and real solutions
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.
• 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
4. Ideal solutions and real solutions
Ideally (infinite) dilute solution
52
4. Ideal solutions and real solutions
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.
ai
Activity coefficient: γi
xi
54
4. Ideal solutions and real solutions
Real solutions
• Margules model (simple):
55
4. Ideal solutions and real solutions
Real solutions
• Van Laar model (more accurate):
57
5. Chemical equilibrium in real gases
– Fugacity – Pressure
i = i0(T) + RTlnPi (ideal gas)
i = i0(T) + RTlnfi (real gas)
58
5. Chemical equilibrium in real gases
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
5. Chemical equilibrium in real gases
(f/P)
60
5. Chemical equilibrium in real gases
– Equilibrium constant:
G RT ln K f
0
T
– Fugacity coefficient:
fi
γi K f K γ .K P
Pi
61
5. Chemical equilibrium in real gases
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
62
6. Chemical equilibrium in real solutions
– Equilibrium constant: G RT ln K a
0
T
– Activity coefficient:
ai
γi K a K γ .K x
xi
Calculating Ka
Guesting K ni(eq)
Y
N
K = K(new) K (new)/K -1
Calculating Kx
=0
Calculating equilibrium xi
64
7. Chemical equilibrium in heterogeneous systems
• Chemical equilibrium:
– Chemical potentials in gas phase: i = 0i(T) + RTlnPi
– Chemical potentials in liquid/solid phase : i = *i(T) + RTlnxi
xFe
2 3
PCO
K P,x 2
xFe O .PCO
3
2 3 eq
65
7. Chemical equilibrium in heterogeneous systems
xFe
2 3
PCO PCO
3
K P,x 2 KP 3 2
P
xFe O .PCO
3
2 3 eq CO eq
66
7. Chemical equilibrium in heterogeneous systems
67
END
68
Quiz
Explain
your
choice
69
Margules equations
– One constant:
70
Van Laar equations
71
72
One – constant
Magules
73
Van Laar
74
Others
• Wilson equations:
(,12,21: constants)
• ….
75
Others
• Universal Quasichemical (UNIQUAC ) equations
From table
z = 10
76
• Predictive activity coefficient models:
77
1. Introduction
Equilibrium constants
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
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 )
c. y=0,99 n= 393
80
3. Factors affect chemical equilibrium
Effect of temperature
– 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