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Equilibria
Learning outcome
Describe and explain the conditions used in the Haber process and the
Contact process, as examples of the importance of an understanding of
chemical equilibrium in the chemical industry
Show understanding of, and use the Bronsted-Lowry theory of acids and
bases
Learning outcome
Reversible Reaction
A+BC+D
The reaction is complete and will stop when
one of the reactants is used up.
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Reversible Reaction
Reversible Reaction
A+BC+D
The reaction is incomplete.
The products can react to form reactants.
A mixture of products and reactants is produced.
This is known as reversible reactions;
represented by
Reversible Reactions
Example:
http://www.youtube.com/watch?v=br8lKynV1Hc
Dynamic Equilibrium
Characteristics of an equilibrium (under constant
conditions):
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Dynamic Equilibrium
Dynamic Equilibrium
[A] & [C] plotted against time at constant T:
t1
Dynamic Equilibrium
Equilibrium Constant
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Equilibrium Constant
Equilibrium Constant
[I2(g)]eqm
[HI(g)]eqm
1.14 x 10-2
0.12 x 10-2
2.52 x 10-2
[H2(g)]eqm
[I2(g)]eqm
[HI(g)]eqm
0.92 x 10-2
0.20 x 10-2
2.96 x 10-2
1.14 x 10-2
0.12 x 10-2
2.52 x 10-2
46.4
10-2
10-2
10-2
10-2
10-2
10-2
47.6
0.34 x
0.86 x 10-2
0.34 x
0.86 x 10-2
2.35 x
5.86 x 10-2
0.92 x
0.20 x
2.96 x
0.34 x 10-2
0.34 x 10-2
2.35 x 10-2
47.8
10-2
10-2
10-2
46.4
0.86 x
0.86 x
5.86 x
Average
Equilibrium Constant
47.1
Equilibrium Constant
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Equilibrium Constant, Kc
For a system in equilibrium:
aA(g) + bB(g) cC(g) + dD(g)
Equilibrium Constant, Kp
Kp is the equilbirum constant in terms of partial
pressures.
Only applies on to gas reactions.
aA(g) + bB(g) cC(g) + dD(g)
Kc =
[C]c[D]d
[A]a[B]b
Equilibrium Constants
The actual value and units of Kc or Kp will depend on the
balanced equation.
Kc or Kp is a constant and is not affected by changes in
concentration, pressure, surface area or the presence of
catalyst.
Kc or Kp is affected by temperature and its value changes with
temperature.
Kp =
(PC)c(PD)d
(PA)a(PB)b
Equilibria
Two different types of equilibria:
A homogeneous equilibrium has everything present in the
same phase. The usual examples include reactions where
everything is a gas, or everything is present in the same
solution.
A heterogeneous equilibrium has things present in more than
one phase. The usual examples include reactions involving
solids and gases, or solids and liquids.
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Homogenous Equilibrium
Heterogenous Equilibrium
Example:
Kc =
2. Copper shake with silver nitrate solution:
Cu(s) + 2Ag+(aq) Cu2+(aq) + 2Ag(s)
Kc =
Equilibrium Constants
Example 1
Equilibrium Constants
CH3COOH(l) + C2H5OH(l) CH3COOC2H5(l) + H2O(l)
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Equilibrium Constants
Example 2
Equilibrium Constants
CH3COCH3 + HCN CH3C(OH)(CN)CH3
Equilibrium Constants
Equilibrium Constants
Example 3
Ethyl ethanoate is hydrolysed by water:
CH3COOC2H5(l) + H2O(l) CH3COOH(l) + C2H5OH(l)
0.1000 mol of ethyl ethanoate are added to 0.1000 mol of
water. A little acid catalyst is added and the mixture made up
to 1 dm3 with an inert solvent.
At equilibrium, 0.0654 mol of water are present. Calculate Kc
for this reaction.
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Equilibrium Constants
Equilibrium Constants
Example 4
When 1.0 mol of HI is heated to 460C in a 1.0 dm3 container,
0.78 mol of HI remained at equilibrium. Calculate the Kc for the
following equilibrium:
2HI(g) H2(g) + I2(g)
Equilibrium Constants
Equilibrium Constants
Example 5
At a total pressure of 1.0 atm, N2O4 is 50% dissociated at a
temperature of 60C :
N2O4(g) 2NO2(g)
Determine the value of the equilibrium constant, Kp for this
reaction at 60C.
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Equilibrium Constants
Equilibrium Constants
Example 6
N2(g) + 3H2(g) 2NH3(g)
The pressure exerted by these gases at constant T is 2.000 x 107
Pa. Under these conditions, partial pressure of N2 & H2 is 1.490 x
107 Pa and 0.400 x 107 Pa respectively.
Calculate the value of Kp for this reaction.
Equilibrium Constants
Equilibrium Constants
Example 7
2SO2(g) + O2(g) 2SO3(g)
2SO2(g) and O2(g) at partial pressures of 1.00 atm and 0.50 atm
respectively, are allowed to reach equilibrium at 675 K. When
equilibrium is attained, the total pressure in the container is
found to be 1.01 atm.
Calculate the Kp for this reaction.
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Le Chteliers Principle
When a system in dynamic
equilibrium is subjected to a
disturbance that upsets the
equilibrium, the system changes
in a way to reduce the
disturbance.
Le Chteliers Principle
This principle is the basis of explaining the
changes of equilibrium positions.
The equilibrium positions are affected by:
concentration (of reactants and products)
pressure
temperature
Effect of Concentration
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Effect of Concentration
B
concentration
equilibrium
achieved
disturbance
new equilibrium
position reached
A
[A]
C
D
time
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Question
CH3COOH(l) + C2H5OH(l) CH3COOC2H5(l) + H2O(l)
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Effect of Pressure
When a system in dynamic equilibrium is
subjected to a disturbance that upsets the
equilibrium, the system changes in a way to
reduce the disturbance.
disturbance = K or L of pressure
change = shifting of equilibrium position
Question
Question
13
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Question
Question
Effect of Temperature
Temperature is the only factor that alters the value of
Kc or Kp.
The direction of the change depends on whether the
forward reaction is endothermic or exothermic.
disturbance = K or L of temperature
change = shifting of equilibrium position
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H = -92.4 kJmol-1
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Industrial Application
It is of great practical importance to be able to predict,
and to control, the equilibrium composition of a
chemical reaction.
In an industrial process it may be desirable to convert
as much as possible of reactants to products as well as
fast as possible.
Contact Process
3 steps process:
1. Production of SO2(g)
2. Production of SO3(g) reversible reaction
Contact Process
Step 2 Production of SO3
Sulfur dioxide gas is oxidized to sulfur trioxide gas by
oxygen.
2SO2(g) + O2(g) 2SO3(g)
H = -197kJmol-1
Conditions:
- Temperature 450C
- Atmospheric pressure
- Vanadium (V) oxide as catalyst; V2O5
3. Production of H2SO4(aq)
Contact Process
Using Le Chateliers Principles to predict for a high
yield of sulfur trioxide.
2SO2(g) + O2(g) 2SO3(g)
H = -197kJmol-1
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Contact Process
Contact Process
Haber Process
N2(g) + 3H2(g) 2NH3(g)
H = -46kJmol-1
Typical conditions:
temperature: 450C
pressure: 200 atm
catalyst: porous iron catalyst (Fe3O4)
ammonia is removed by condensing it into liquid.
Acid-base Equilibria
Arrhenius Theory
Acids are substances which produce hydrogen ions in
solution.
Bases are substances which produce hydroxide ions
in solution.
Neutralisation happens because hydrogen ions and
hydroxide ions react to produce water.
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Arrhenius Theory
Arrhenius Theory
Brnsted-Lowry Theory
Brnsted-Lowry Theory
Species that
donates H+ is
an acid.
Species that
accepts H+ is
a base.
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Brnsted-Lowry Theory
Brnsted-Lowry Theory
Water is amphoteric can be acid or base.
Brnsted-Lowry acids and bases do not need
to involve solutions.
Species that
accepts H+ is
a base.
Species that
donates H+ is
an acid.
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Forward reaction:
NH3 is a base because it accepts a H+ to NH4+.
H2O is an acid because it donates a H+ to NH3.
NH3 and NH4+ are acid-base conjugate pair.
Backward reaction:
NH4+ donates H+ to form OH-, so it is conjugate
acid
OH- accepts H+ from NH4+, so it is conjugate base.
H2O and OH- are acid-base conjugate pair.
Strong base:
NaOH(s) + aq Na+(aq) + OH-(aq)
Strong acid:
HCl(aq) + H2O(l) H3O+(aq) + Cl-(aq)
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1.0
pH
0.1
0.01
HCl
(strong)
CH3COOH
(weak)
NaOH
(strong)
2.4
2.9
3.4
14
13
12
11.6
11.1
10.6
NH3
(weak)
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