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Chemical Equilibrium Part 2
Chemical Equilibrium Part 2
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Changes in Concentration
PCl5 y PCl3 + Cl2 Kc = 0.030
At equilibrium:
⚫ Adding reactants shifts the reaction toward products
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Le Châtelier Sample Problem
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Changes in Pressure and Volume
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Pre-solved Example
N2 (g) + 3 H2 (g) y 2 NH3 (g)
A system with 2.5 atm of N2 and 7.5 atm of H2 is allowed to equilibrate at 500°C,
then the overall pressure is increased by a factor of 10. What happens?
Before After
compression compression
2.0% of total 9.2% of total
PNH3 = 0.2 atm PNH3 = 8.4 atm
pressure pressure
PN2 = 2.4 atm PN2 = 21 atm
PH2 = 7.2 PH2 = 62
atm atm
⚫ The reaction shifts toward products because this minimizes
the total number of molecules in the system
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Further Examples
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Changes in Temperature
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Sample Question
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Adding a Catalyst
A catalyst is a substance that increases the rate of a reaction
without itself being consumed in the reaction
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Question
Which of the following equilibria would not be
affected by changes in overall pressure?
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New Question
What would happen if O2 were removed from the
following system at equilibrium at 25°C?
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Yet Another
Question
The following chemical reaction has reached
equilibrium. Which of the changes listed below
would cause the equilibrium to shift back toward the
reactants?
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Le Châtelier’s Principle Summary
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The Haber-Bosch Process
⚫ Artificial nitrogen fixation process to produce ammonia
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The Haber-Bosch Process
3) Use a catalyst to speed up the reaction
‐ Catalysts do not change Kc
‐ Catalysts lower the activation energy of a reaction, increasing its rate
⚫ Most Haber reactors use a porous iron catalyst made from Fe3O4
N 2 + 3 H2
2 NH3
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‐ forces the reaction toward products
Adding a Catalyst
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A Haber-Bosch
Plant
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Equilibrium Thermodynamics
∆G° measures the difference between the free energies of the reactants and
products when all species are present at 1 atm (gases) and 1 M (solutes)
Reactants y Products
∆G° < 0 → spontaneous → products favored → K>1
∆G° > 0 → not spontaneous → reactants favored → K<1
exponential relationship
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Standard Free Energy and Equilibrium
1 atm for gases
signifies standard conditions:
1 M for solutes
∆G°
at the standard state, Qc = Qp = 1
∆G° tells us how far the standard state is from equilibrium and
which direction the reaction must shift to reach equilibrium
∆G° K
large + << 1
small + <1
0 =1
small - >1
82 large - >> 1
Free Energy at Non-standard Conditions
What is the value of the free energy change when we are not at
standard conditions?
(i.e., ≠ 1 atm for all gases and 1 M for all solutes)
∆G at any Q:
when Q = 1, ∆G = ∆G° not
when Q = K, ∆G = 0 100 spontaneous spontaneous
50
∆G (kJ/mol)
G 0
For a rxn with a -50
equilibrium
∆G° = -100 kJ/mol: de -100
lt
-150 ∆G = ∆G°
-200
-40 -20 0 20 60
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40
ln Q
Temperature Dependence of Keq
Equilibrium constants change with temperature
- Predictable based on ∆H° of the reaction
We know:
and
So:
∆H° K
+ exp. increases with T
(endo) exp. decreases with T
- (exo)
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Temperature Dependence of Keq
Exothermic
ln K
Endothermic
1/T
higher temp
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Temperature Take-Homes
The value of the equilibrium constant changes with temperature for a
given reaction.
Master Equations:
A + B + heat y C+D
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A+B y C + D + heat
Temperature Dependence Example
The dimerization of NO2 is exothermic (b/c of bond making):
2 NO2 ° y N2O4
∆H= -
∆H° K
57.2 kJ/mol
- decreases with T
(exo)
Temperature Kc Kp
°C
‐78 400,000,000 25,000,000
0 1400 62.5
25 170 6.95
100 2.1 0.069
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Sample Problem
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