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Chemical
Equilibrium
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Contents and Concepts
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Changing Reaction Conditions:
Le Châtelier’s Principle
7. Removing Products or Adding Reactants
8. Changing the Pressure and Temperature
9. Effect of a Catalyst
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Learning Objectives
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2. The Equilibrium Constant
a. Define equilibrium-constant expression
and equilibrium constant.
b. State the law of mass action.
c. Write equilibrium-constant expressions.
d. Describe the kinetics argument for the
approach to chemical equilibrium.
e. Obtain an equilibrium constant from
reaction composition.
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2. The Equilibrium Constant (cont)
f. Describe the equilibrium constant Kp;
indicate how Kp and Kc are related.State
the law of mass action.
g. Obtain Kc for a reaction that can be written
as a sum of other reactions of known Kc
values.
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3. Heterogeneous Equilibria; Solvents in
Homogeneous Equilibria
a. Define homogeneous equilibrium and
heterogeneous equilibrium.
b. Write Kc for a reaction with pure solids or
liquids.
Using the Equilibrium Constant
4. Qualitatively Interpreting the Equilibrium
Constant
a. Give a qualitative interpretation of the
equilibrium constant based on its value.
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5. Predicting the Direction of Reaction
a. Define reaction quotient, Q.
b. Describe the direction of reaction after
comparing Q with Kc.
c. Use the reaction quotient.
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6. Calculating Equilibrium Concentrations
a. Obtain one equilibrium concentration given
the others.
b. Solve an equilibrium problem (involving a
linear equation in x).
c. Solve an equilibrium problem (involving a
quadratic equation in x).
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Changing the Reaction Conditions;
Le Châtelier’s Principle
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8. Changing the Pressure and Temperature
a. Describe the effect of a pressure change
on chemical equilibrium.
b. Apply Le Châtelier’s principle when the
pressure is altered.
c. Describe the effect of a temperature
change on chemical equilibrium.
d. Apply Le Châtelier’s principle when the
temperature is altered.
e. Describe how the optimum conditions for a
reaction are chosen.
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9. Effect of a Catalyst
a. Define catalyst.
b. Compare the effect of a catalyst on rate of
reaction with its effect on equilibrium.
c. Describe how a catalyst can affect the
product formed.
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Chemical reactions often seem to stop before they
are complete.
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CO(g) + 3H2(g) CH4(g) + H2O(g)
The graph
shows how the
amounts of
reactants and
products
change as the
reaction
approaches
equilibrium.
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CO(g) + 3H2(g) CH4(g) + H2O(g)
This graph
shows how
the rates of
the forward
reaction and
the reverse
reaction
change as the
reaction
approaches
equilibrium.
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Chemical equilibrium is the state reached by a
reaction mixture when the rates of the forward and
reverse reactions have become equal.
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We can apply stoichiometry to compute the
content of the reaction mixture at equilibrium.
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When heated PCl5, phosphorus
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We will organize this problem by using the
chemical reaction to set up a table of initial,
change, and equilibrium amounts.
Change –x +x +x
Equilibrium 1.00 – x x x
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The Equilibrium Constant, Kc
The equilibrium constant expression for a
reaction is obtained by multiplying the
concentrations of products, dividing by the
concentrations of reactants, and raising each
concentration term to a power equal to its
coefficient in the balanced chemical equation.
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For the reaction
aA + bB cC + dD
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Methanol (also called wood alcohol) is made
Kc
CH3OH
H2 CO
2
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When we are given some information about
equilibrium amounts, we are able to calculate the
value of Kc.
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Carbon dioxide decomposes at elevated
?
temperatures to carbon monoxide and oxygen:
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2CO2(g) 2CO(g) + O2(g)
Equilibrium 2.00 – 2x 2x x
0.90 mol 1.10 mol 0.55 mol
Kc
CO O 2
2
CO2 2
Kc
1.10 0.55
2
0.90 2
K c 0.82
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In a heterogeneous equilibrium, in the Kc expression, the
concentrations of solids and pure liquids are constant (due
to these substances’ constant density).
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? Write the Kc expression for the following
reaction:
Kc
COH2
H2O
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Given:
aA + bB cC + dD; K1
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Given:
aA + bB cC + dD; K1
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For the reaction
aA(g) + bB(g) cC(g) + dD(g)
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How are these related?
nA
We know [A]
VA
nA
So, PA RT
VA
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When you express an equilibrium constant for a
gaseous reaction in terms of partial pressures, you
call it the equilibrium constant, Kp.
a
P P
A B
b
A RT B RT
a a b b
Kp
C D
c
RT
d
c d - a - b
A a Bb
Kp
C D
c
RT n
d
A B
a b
Kp = Kc (RT)n
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For catalytic methanation,
CO(g) + 3H2(g) CH4(g) + H2O(g)
the equilibrium expression in terms of partial
pressures becomes
PCH4 PH2O
Kp
PCO PH32
and Kc
K p K c RT
2
RT 2
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The value of Kc at 227°C is 0.0952 for the
? following reaction:
CH3OH(g) CO(g) + 2H2(g)
What is Kp at this temperature?
Kp = 0.0952(RT)n
where
T = 227 + 273 = 500. K
R = 0.08206 L atm/(mol
K)
n = 2
Kp = 1.60 × 102
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We can use the value of the equilibrium constant
in several ways.
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Finally, we can determine equilibrium
concentrations given the initial concentrations and
the value of Kc.
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When Kc is very large (>102), the equilibrium
mixture is mostly products.
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?
Kc = 0.82 for a reaction. Describe the
composition of the equilibrium mixture.
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Reaction Quotient, Q
The reaction quotient has the same form as the
equilibrium constant, but uses initial concentrations
for its value.
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Qc must move toward Kc.
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Nickel(II) oxide can be reduced to the metal
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PCO 100. mmHg
PCO2 660. mmHg
PCO2 660
Qp 6.6
PCO 100
K p Qp
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Nitrogen and oxygen form nitric oxide.
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N2(g) + O2(g) 2NO(g)
Kc
NO
2
N2 O2
30
1.0 10
NO
2
0.040 0.010
NO
2
1.0 10-30 0.0400.010
NO 2
4.0 10 34
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Hydrogen iodide decomposes to hydrogen
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0.50 mol
HI0 0.10 M
5.0 L
Initial 0.10 M 0 0
Change –2x +x +x
Equilibrium 0.10 – 2x x x
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H2 I2
The Kc expression is, Kc =
HI2
Substituting:
0.016
x x
x 2
0.10 2x 2
0.10 2x 2
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x2
0.016
0.10 2x 2
x
0.126
0.10 2x
ax2 + bx + c = 0
b b 2 4ac
The solution is x
2a
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N2O4 decomposes to NO2. The equilibrium
N2O4(g) 2NO2(g)
At 100°C, Kc = 0.36.
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Again, we begin with the table:
N2O4(g) 2NO2(g)
Initial 0.100 M 0
Change –x +2x
Equilibrium 0.100 – x 2x
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NO 2 2
The Kc expression is, Kc =
N2 O 4
2x 2
4x 2
Substitute: 0.36
0.100 x 0.100 x
Rearrange: 4x 2 0.36 x 0.036 0
ax 2 bx c 0
a4 b 0.36 c 0.036
0.36 0.36 44 0.036
2
Substitute: x
24
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Solve: - 0.36 0.7056
x
8
x 0.045 0.105
x 0.06 x 0.15
Change –x –x +2x
Kc
HF
2
H2 F2
1.15 10 2
2.000 2 x
2
2.000 - x 2
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2
1.15 10
2.000 2x 2
2.000 - x 2
10.72
2.000 2 x
2.000 - x
10.722.000 - x 2.000 2 x
Kc
HF
2
(5.06)2
1.16 10 2
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The value of Kc at 227°C is 0.0952 for the
? following reaction:
CH3OH(g) CO(g) + 2H2(g)
What is Kp at this temperature?
Kp = 0.0952(RT)n
Kp = 1.60 × 102
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Le Châtelier’s Principle
When a system in chemical equilibrium is
disturbed by a change in
• temperature,
• pressure, or
• concentration,
the system shifts in equilibrium composition in a
way that tends to counteract this change of
variable.
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When a substance that is part of the equilibrium is
added to the mixture, the equilibrium shifts to use it
(in a direction that makes the substance a
reactant).
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Changes in the partial pressure of substances that
are part of the equilibrium are handled in the same
way as adding or removing a substance.
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The following reaction is at equilibrium:
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COCl2(g) CO(g) + Cl2(g)
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A change in the total pressure occurs because of a
change in the volume of the reaction container.
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When the size of the container increases, the
overall pressure decreases. The reaction will shift
to increase the pressure—that is, it will shift toward
the side with more gas molecules.
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In which direction will each reaction shift
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When the container volume is increased, the total
pressure is decreased. Each system will shift to
produce more gas by shifting toward the side with
more moles of gas.
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For an endothermic reaction, Ho > 0 (positive), we
consider that heat is a reactant.
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For an endothermic reaction, increasing the
temperature increases the value of Kc.
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In addition to the value of Kc, we can consider the
direction in which the equilibrium will shift.
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Given:
?
2H2O(g) 2H2(g) + O2(g); Ho = 484 kJ
?
synthesis of gasoline consists of passing a
mixture of carbon monoxide and hydrogen
over an iron–cobalt catalyst.
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A typical reaction that occurs in the Fischer–
? Tropsch process is
8CO(g) + 17H2(g) C8H18(g) + 8H2O(g)
In which direction will the equilibrium shift
when the pressure is increased?
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