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Chapter 6
AgCl + NO3
6.1.2
Reversible Reaction
Example 2
H2(g) + I2(g)
2HI(g)
H2O (g)
concentration
[N2O4] at equilibrium
t1
time
cC (g) + dD (g)
[C]c[D]d
[A]a[B]b
Table 6.1
N2O4 (g)
K=
[NO2]2
[N2O4]
2NO2 (g)
= 4.63 x 10-3
constant
Kc =
Example 6
CH3COOH (aq) CH3COO- (aq) + H+ (aq)
Kc=
(PA)a (PB)b
Example 7
Write the equilibrium law in the form of Kp
and Kc for the following reactions:
a) N2(g) + 3H2(g) NH3(g)
b) 2NO(g) + O2(g) N2O4(g)
Answer:
Kp =
Kc =
Expression of Kc
Expression of Kc depends on the equilibrium
equation given
Example 8
2SO3 (g) 2SO2 (g) + O2 (g)
Kc = [SO2]2 [O2]
[SO3]2
Kc2 =
[SO3]2
[SO2]2 [O2]
Example 9
Find the relationship between Kc1 and Kc2 for the
following equilibrium equations.
1. SO3 (g) SO2 (g) + O2 (g)
Kc2 =
[SO3]2
[SO2]2 [O2]
Example 10
Consider the following reaction:
A(g) + B(g) 2C(g)
If 5 moles of A are allowed to mix and react
with 3 moles of B in 1dm3 container, 2 moles
of C are produced at equilibrium. What is the
value of Kc for this reaction?
(Ans: 0.5 )
Example 11
Consider the reaction:
CO(g) + 2H2(g) CH3OH(g)
The following equilibrium concentrations are
achieved at 400K:
[CO]
= 1.03M
[H2]
= 0.332M
[CH3OH]
= 1.56M
Example 12
Nitrogen gas reacts with oxygen gas at high
temperature to form nitrogen monoxide gas,
NO. The equilibrium constant for the reaction is
4.1 x 10-4 at 200oC.
If the concentration for both N2(g) and O2(g) at
equilibrium are 0.40 moldm -3 and 1.3 moldm-3
respectively, calculate the concentration of NO
gas at equilibrium?
(Ans: 0.0146 M)
Example 13
The equilibrium constant Kp for the reaction;
2NO2 (g) 2NO (g) + O2 (g)
is 158 at 1000K. What is the equilibrium pressure
of O2 if the P NO2 = 0.400 atm and PNO = 0.270
atm?
Answer;
Kp =
2
PNO
PO
PNO
2
2
PO
= Kp
PNO
PNO
cC (g) + dD (g)
[C]c[D]d
[A]a[B]b
Thus,
Kc =
Since P = nRT
V
[ ]=
P
RT
cC (g) + dD (g)
Kc = Kp (RT) (a + b) (c+d)
Kp = Kc (RT) (c + d) (a+b)
Kp = Kc (RT)n
COCl2 (g)
Answer;
0.14
[COCl2]
=
Kc =
0.012 x 0.054
[CO][Cl2]
= 220 M -1
Kp = Kc(RT)n
n = 1 2 = -1
[CH3COO-][H3O+]
Kc =
[CH3COOH][H2O]
H2O a pure liquid, has a constant concentration
and thus is not included in the expression.
Therefore, the equilibrium constant is written as,
[CH3COO-][H3O+]
Kc =
[CH3COOH]
Unit : M
2.
Carboxylic
Ester
acid
Kc =
[CH3COOC2H5]
[CH3COOH] [C2H5OH]
3.
CaCO3 (s)
[CaO][CO2]
Kc =
[CaCO3]
[CaCO3] = constant
[CaO] = constant
Kc = [CO2]
Kp = PCO2
CaCO3 (s)
PCO 2 = Kp
PCO 2 does not depend on the amount of CaCO3 or CaO
5.
Answer
;
Kp = PNH PH S = 0.265 atm x 0.265 atm
2
3
= 0.0702 atm2
n = 2 0 = 2
Kp = Kc(RT)n
T = 295 K
Kc =
0.0702 atm2
(0.08206 atm L mol1 K1 x 295 K )2
1.2 x 104 M2
Answer;
Kc = [NO]2 [Br2]
Kc =
[NOBr]2
1 =
Kc
1
[NO]2 [Br2]
[NOBr]2
1
Kc
[NOBr]
[Br2]1/2 [NO]
[NOBr]2
[NO]2 [Br2]
[NOBr]
= Kc
[NO] [Br2]
Kc =
1
Kc
Kc =
1
1.0 x 103 M
= 31.6 M-
= 31.6 dm3/2 mol
2HI(g)
Answer;
[H2]0 = 0.200 /10.0 = 0.0200 M
[I2]0 = 0.200 /10.0 = 0.0200 M
H2 (g)
[ ]0 / M
[ ] / M
[ ] / M
0.0200
-x
0.0200 - x
+ I2 (g)
2HI (g)
0.0200
-x
0.0200 - x
+2x
+2x
Kc =
[HI]2
[H2] [I2]
49.5 =
7.036 =
(2x)2
(0.0200 x) (0.0200 x)
2x
0.0200 - x
x = 0.0156
H2 (g)
I2 (g)
2HI (g)
[ ]0 / M
0.0200
[ ] / M
-x
[ ] / M
0.0200 - x
0.0200 - x
+2x
= 0.0044
= 0.0044
= 0.0312
0.0200
-x
0
+2x
Answer;
Initial pressures of H2 and I2.
PH = nH2 RT = (1.000)(0.08206)(721)
2
1.000
= 59.19 atm
PI = nI2 RT
2
= (2.000)(0.08206)(721)
1.000
= 118.4 atm
H2 (g)
P0
59.19
-x
59.19 - x
50.5 =
Kp
= PHI
PH P I
2
+ I2 (g)
2HI (g)
118.4
-x
118.4 - x
+2x
+2x
(2x)2
(59.19 x) (118.4 x)
I2
6.2.6
Degree of Dissociation,
C = changes in concentration
C0 = initial concentration
AB
C0 / M
C / M
C / M
A+
-x
+x
+x
a-x
+x
+x
x
=
a
C0 / M
HCOOH
0.5
H+
0
C / M
-0.0089
+0.0089
C / M
0.5-0.0089
0.0089
HCOO
0
+0.0089
0.0089
= 0.4911
x
a
0.0089
=
= 0.0178 = 1.78%
0.5
cC (g) + dD (g)
[C]c[D]d
[A]a[B]b
If Q = K
If Q < K
If Q > K
Reaction is reversed
- more products are present in the
mixture at t
reaction
Br2 (g)
2Br (g)
Br2 (g)
C0/M
[Br]2
Qc =
[Br2]
Q c > Kc
0.063
=
2Br (g)
0.012
Br2 (g)
C0/M
0.063
C/M
+x
C/M
0.063 + x
2Br (g)
0.012
- 2x
0.012 - 2x
[Br]2
Kc =
[Br2]
1.1x10-3
(0.012 2x)2
=
0.063 + x
x = 1.78x10-3
[Br] = 0.012 2x
[Br2] = 0.063 + x
If x = 0.0105
= -0.009 M
= 0.0735 M
If x = 1.78x10-3
= 0.00844 M
= 0.0648 M
11.
[HI]2
[H2] [I2]
(1.47 + 0.5)2
(0.200) (0.200)
= 97.0
H2 (g)
+ I2 (g)
2HI (g)
C0/M
0.200
0.200
1.47 + 0.500
C/M
C/M
+x
0.200 + x
+x
0.200 + x
-2x
1.97 2x
= 0.2535
= 0.2535
= 1.863
Kc =
54.0 =
Kc = 54
Qc = 97
[HI]2
[H2] [I2]
(1.97 2x)2
(0.200 + x) (0.200 + x)
7.35 =
1.97 2x
0.200 + x
x = 0.0535M
6.3.1
Le Chteliers Principle
A) Effect of Concentration:
Changing the concentration of the reactants or
products causes the equilibrium to shift to the
direction that will reduce the effect .
Example:
Increasing the concentration of reactant/s causes
the equilibrium position to shift forward in order to
reduce the disturbance (to eliminate the additional
concentration of reactant/s)
more products will be formed until the equilibrium is
reached again (i.e: composition of equilibrium
reaches Kc value which remains the same at a
fixed temperature).
Example ;
N2 (g) + 3H2 (g)
2NH3 (g)
Change
Equilibrium Shift
To the left
To the right
To the right
To the left
Example :
Consider the reaction below:
Fe 3+(aq)
+ SCN-(aq)
(Yellowish)
Fe(SCN)2+(aq)
(Blood red)
Answer;
Consider the reaction below:
Fe 3+(aq)
(Yellowish)
+ SCN-(aq)
Fe(SCN)2+(aq)
(Blood red)
Fe(SCN)2+(aq)
(Blood red)
B) Effect of Temperature:
The effect of temperature on an equilibrium
depends on the type of reactions, whether it
is:
i) an endothermic reaction
or
ii) an exothermic reaction
Temperature is the only factor that affects the
value of Kc
i) Endothermic reaction
An endothermic reaction is a reaction that
absorbs heat to form products.
Example:
Consider the following system:
N2O4(g)
2NO2(g)
H = +57 kJ
N2O4(g)
2NO2(g)
H = +57 kJ
N2O4(g)
2NO2(g)
H = +57 kJ
[ NO2 ]
[ N 2O4 ]
Concentration of
N2O4 increases, thus
Kc value decreases
Example:
Consider the reaction:
Co(H2O)62+(aq)+ 4HCl(aq)
pink
To overcome the
low temperature
reaction should
release heat
Disturbance:
Low temperature
High
temperature
C) Effect of Pressure
The pressure of a system may be changed by:
i) changing the moles of reactant or product
ii) changing the volume
iii) adding inert gas to the system
Affects only the reversible reaction involving
gaseous reactants/products
Example
N2(g) + 3H2(g)
2NH3(g)
Example
Consider the reaction:
2SO2(g) + O2(g)
2SO3(g)
Example:
For the following chemical equation,
N2 (g) + O2 (g) 2NO (g)
[NO]2
[N2] [O2]
Kc
[NO]
Equilibrium position
shifts from LEFT to the RIGHT
D)
Le Chteliers Principle
Change
Equilibrium shift
Change Equilibrium
Constant, K
Concentration
yes
no
Pressure
yes
no
Volume
yes
no
Temperature
yes
yes
Catalyst
no
no
Example :
Consider the chemical reaction at equilibrium given below
CaCO3 (s) CaO (s) + CO2 (g)
H =+ve
(a)
(b)
Kp = PCO2
= 0.220 atm
Kp = Kc(RT)n
n = 1 0 = 1
Kp= Kc(RT)
Kc =
Kp
(RT)
0.220 atm
0.08206 atm L mol 1 K 1 x 798 K
= 3.36 x 103 M
(b)(i)
(ii)
(iii)
(iv)
(v)
HABER PROCESS
A process that produces ammonia from
H2 and N2
The process is introduced by German
scientists Fritz Haber and Karl Bosch.
(sometimes called Haber-Bosch) in 1912.
Main objectives of the industry are to obtain a
high yield of the product while keeping the cost
down
Consider
N2(g) + 3H(g)
2NH3(g)
H = -92.6 kJ