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Chapter Scopes
Chemical Equilibria
Equilibrium constant (Kc and Kp)
Reaction quotient (Qc)
Solubility product (Ksp)
Le Chateliers Principle
I. C. E. Table
Chapter 7
Equilibria
1
Equilibrium
Chemical Equilibrium
Dynamic
Reversible
3
Meaning of K
Equilibrium Constant, K
Equilibrium Will
aA + bB
cC + dD
K >> 1
Favor products
K << 1
Favor reactants
Homogeneous
Equilibrium
Product- or ReactantFavored
2NO2 (g)
Kc =
Kp =
In most cases
Kc Kp
aA(g) + bB(g)
Calculation
cC(g) + dD(g)
Kp = Kc(RT)n
n = Total moles of gaseous products
Total moles of gaseous reactants
= (c + d) (a + b)
CO(g) + Cl2(g)
COCl2(g)
CO(g) + Cl2(g)
10
Heterogeneous
Equilibrium
COCl2(g)
Kp = Kc(RT)n
CaCO3(s)
n =
R = 0.082057
Kc =
T = 273.2 + 74 = 347.2 K
Kp =
11
Kc =
[CaO][CO2]
[CaCO3]
CaO(s) + CO2(g)
[CaCO3] = constant
[CaO] = constant
Kp =
12
CaCO3(s)
CaO(s) + CO2(g)
Calculation
Consider the following equilibrium at 295 K:
NH4HS (s)
NH3 (g) + H2S (g)
The partial pressure of each gas is 0.265
atm. Calculate Kp and Kc for the reaction?
Kp = PNH3 PH2S = 0.265 x 0.265 = 0.0702
Kp = Kc(RT)n
Kp = PCO 2
Kc = Kp(RT)-n
n =
13
T = 295 K
Kc =
14
15
SO3(g)
2S(s) + 3O2(g)
2SO3(g)
[SO3 ]
Knew
[O2 ]3/2
Knew
[SO3 ]2
[O2 ]3
[SO3 ]2
[O2 ]3
Q c = Kc
= (Kold )2
Q c < Kc
17
16
to reach equilibrium
(reactants product)
The system is ___________
(no net change)
The system proceeds from __________
to reach equilibrium
18
(reactants products)
[NO2] = 0.015M
[N2O4] = 0.025M
Qc =
2NO2(g)
N2O4(g)
K = 170, T = 298 K
x =
-b
(x)(x)
[A]0 - x
b2 - 4ac
2a
23
A(g)
B(g)
[A]0
-x
[A]0 - x
0
+x
x
Kc =
Kc =
[B][C]
[A]
[B][C]
[A]
(x)(x)
[A]0 - x
C(g)
0
+x
x
(x)(x)
[A]0
1. The reaction:
N2(g) + O2(g)
2NO(g)
contributes to air pollution whenever a fuel is
burned in air at high temperature, as in a
gasoline engine. At 1500 K, Kc = 1.0 x 10-5.
Suppose a sample of air has [N2] = 0.80 mol/L
and [O2] = 0.20 mol/L before any reaction
occurs. Calculate the equilibrium concentrations
of reactants and products after the mixture has
been heated to 1500 K.
[A]
Equation
Initial (M)
Change (M)
Equilibrium (M)
Exercise
[B][C]
20
Calculating Equilibrium
Concentrations
Kc =
Answer:
[N2] 0.80 M ; [O2] 0.20 M ;
[NO] 1.3 x 10-3 M
24
Kc = 0.0059 =
2 NO2(g)
[NO2 ]2
= 0.0059 at 298 K
[N2O4 ]
Concentration
Initial (M)
Change (M)
Equilibrium (M)
x =
0.0059
-b
[N2O4]
0.50
-x
0.50 - x
[NO2]
0
+ 2x
2x
25
b2 - 4ac
2a
2( 4)
27
0.00592 4( 4) ( 0.00295)
x = 0.026 or - 0.028
But a negative value is not reasonable.
Conclusion: x = 0.026 M
[N2O4] = 0.50 - x = 0.474 M
[NO2] = 2x = 0.052 M
[NO2 ]2
(2x)2
=
[N2O 4 ]
(0.50 - x)
28
Questions
The Ksp for AgCl is 1.8 x 10-10. If Ag+ and
Cl- are both in solution and in equilibrium
with AgCl. What is [Ag+] if [Cl-] = 0.020 M
Answer: [Ag+] = __________ M
Le Chateliers
Principle
Le Chateliers
Principle
When a system at
equilibrium is disturbed,
the equilibrium position
will shift in the direction
which tends to minimize
or counteract, the effect
of the disturbance.
31
Changes in
Concentration
Changes in
Concentration
aA + bB
Haber Process
N2 (g) + 3H2 (g)
Equilibrium
shifts left to
offset stress
32
2NH3
(g)
Add
NH3
Change
[product/s]
[product/s]
[reactant/s]
[reactant/s]
cC + dD
Shifts the Equilibrium
left
right
right
left
33
34
Changes in
Temperature
Changes in Volume
& Pressure
aA (g) + bB (g)
Change
cC (g)
Exothermic Reaction
T
Shifts the Equilibrium
shifts to the
K Equilibrium
left
pressure
pressure
shifts to the
K Equilibrium
right
volume
volume
Change
Change
35
T
T
Endothermic Reaction
Equilibrium shifts to the
K right
shifts to the
K Equilibrium
left
36
Le Chateliers Principle
(adding a catalyst)
aA + bB
Le Chateliers Principle
(adding a catalyst)
cC + dD
Adding a Catalyst
does not change K
does not shift the position of an
equilibrium system
system will reach equilibrium sooner
Lowers Ea for both forward and
reverse reactions
37
Le Chateliers
Principle
catalyzed
38
Summary
Change
Shift
Equilibrium
Concentration
yes
Change
Equilibrium
Constant
no
Pressure
yes
no
Volume
yes
no
Temperature
yes
yes
Catalyst
no
no
uncatalyzed
39