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GENERAL CHEMISTRY
Chapter 5
Chemical Equilibrium
OUTLINE
Basic concepts
The equilibrium constant
LeChatelier’s Principle
Relationship between Kp &Kc
Relationship between G0rxn and K
Evaluation of K at difference temperature.
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Basic concepts
Reversible reactions:
Reactions that do not go to completion and that can occur
in either direction.
Both the forward and reverse reactions occur
simultaneously.
aA+bB cC+ dD
In the balanced equation:
“a, b, c, d” represent the stoichiometric coefficients
A, B are called the “reactants”
C, D are called the “products.”
The double arrow ( ) indicates that the reaction is
reversible
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Basic concepts
Chemical equilibrium exists when two opposing reactions
occur simultaneously at the same rate.
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The equilibrium constant
For a general reaction in the gas phase:
aA (g)+bB (g) cC (g)+ dD (g)
The equilibrium constant expression is:
PCc PDd
K eq a
PA PBb
Keq is the equilibrium constant.
The subscript “eq” to emphasize that partial pressure in
the equilibrium constant expression are those at
equilibrium.
The equilibrium constant
For a general reaction:
Kc values always involve equilibrium values of concentrations.
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The equilibrium constant
The equilibrium constant Keq has no units.
The value of Keq:
Is constant at a given temperature,
Changes if the temperature changes,
Does not depend on the initial concentrations.
Kc>1: most of the reactants would be converted into
products, we called a reaction “product-favored.”
Kc<1: most of the reactants remain and only small
amounts of products are formed.
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The equilibrium constant
Example:
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The equilibrium constant
Variation of Kc
The value of Kc depends on the form of the balanced equation
for the reaction.
If an equation for a reaction is multiplied by any factor, n,
then the original value of Kc is raised to the nth power.
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Variation of Kc
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Calculating Keq
In one of their experiments, Harber and co-workers
introduced a mixture of hydrogen and nitrogen into a
reaction vessel and allowed the system to attain
chemical equilibrium at 472oC. The equilibrium mixture
of gases was analyzed and found to contain 0.1207 M H2,
0.0402 M N2, and 0.00272 M NH3. From these data,
calculate the equilibrium constant, Keq, for
N2(g) + 3H2(g) 2NH3(g)
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Calculating Keq
Gaseous Hydrogen iodide is placed in a closed container
at 425 oC, where it partially decomposes to hydrogen and
iodine: 2HI (g) H2(g) + I2(g). At equilibrium, it is
found that [HI] = 3.3510-3M; [H2] = 4.79 10-4M; [I2]
= 4.79 10-4M. What is the value of Keq at this
temperature.
A mixture of 0.100 mole of NO, 0.050 mole of H2, and
0.050 mole of H2O is placed in a 1.00-L vessel. The
following equilibrium is established:
2NO(g) + 2H2(g) N2(g) + 2H2O(g)
Calculate the Keq for the reaction.
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Calculating Keq
Enough ammonia is dissolved in 5.00 liters of water at
25oC to produce a solution that is 0.0124 M in ammonia.
The solution is then allowed to come to equilibrium.
Analysis of the equilibrium mixture shows that the
concentration of OH- is 4.64 x 10-4M. Calculate Keq at 25
oC for the reaction.
NH3(aq) + H2O(l) NH4+(aq) + OH-(aq)
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Calculating Keq
A mixture of 5.00 x 10-3 mol of H2 and 1.00 x 10-2 mol of
I2 is placed in a 5.00 L container at 448 oC and allowed to
come to equilibrium. Analysis of the equilibrium mixture
shows that the concentration of HI is 1.87 x 10-3 M.
Calculate the Kc at 448 oC for the reaction.
H2(g) + I2(g) 2HI(g)
Keq=50.51
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Calculating Keq
Sulfur trioxide decomposes at high temperature in a
sealed container:
2SO3(g) 2SO2(g) + O2(g).
Initially the vessel is charged at 1000K with SO3(g) at a
concentration of 6.09 x 10-3 M. At equilibrium, the SO3
concentration is 2.44 x 10-3 M. Calculate the value for
Keq at 1000 K.
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The reaction quotient
The reaction quotient, Q, for the general reaction is given as
follows:
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The reaction quotient
Q < Kc: Forward reaction predominates until
equilibrium is established.
Q = Kc: System is at equilibrium.
Q > Kc: Reverse reaction predominates until
equilibrium is established.
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The reaction quotient
Q < Kc
The system is not at equilibrium the forward reaction must
occur to a greater extent than the reverse reaction;
Some HI must react to form more H2 and I2 to reach equilibrium 19
The reaction quotient
At 448 oC the equilibrium constant, Keq, for the reaction:
H2(g) + I2(g) 2HI (g) is 50.5. Predict how the reaction
will proceed to reach equilibrium at 448 oC if we start
with 2.0 x 10-2 mol of HI, 1.0 x 10-2 mol of H2, and
3.010-2 mol of I2 in a 2.0L container.
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LeChatelier’s Principle
LeChatelier’s Principle:
If a change of conditions (stress) is applied to a system at
equilibrium, the system shifts in the direction that reduces the
stress to move toward a new state of equilibrium.
Three types of changes can disturb the equilibrium of a
reaction:
1.Changes in concentration
2.Changes in pressure or volume (for reactions that involve gases)
3.Changes in temperature.
LeChatelier’s Principle (is pronounced “le-SHOT-lee-ay.”)
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FACTORS THAT AFFECT EQUILIBRIA
Changes in Concentration:
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FACTORS THAT AFFECT EQUILIBRIA
Changes in Concentration:
Adding a reactant or product shifts the equilibrium away
from the increase.
Removing a reactant or product shifts the equilibrium
towards the decrease.
To optimize the amount of product at equilibrium, we
need to flood the reaction vessel with reactant and
continuously remove product (LeChatelier’s Principle).
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FACTORS THAT AFFECT EQUILIBRIA
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FACTORS THAT AFFECT EQUILIBRIA
Changes in Volume and Pressure:
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FACTORS THAT AFFECT EQUILIBRIA
Changes in Volume and Pressure:
If there is no change in the total number of moles of gases, a
volume (pressure) change does not affect the position of
equilibrium.
If changing in the total number of moles of gases:
A decrease in volume (increase in pressure) shifts a
reaction in the direction that produces the smaller total
number of moles of gas.
An increase in volume (decrease in pressure) shifts a
reaction in the direction that produces the larger total
number of moles of gas.
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FACTORS THAT AFFECT EQUILIBRIA
Changes in Temperature:
Adding heat (i.e. heating the vessel) favors away from
the increase:
if H > 0, adding heat favors the forward reaction.
if H < 0, adding heat favors the reverse reaction.
Removing heat (i.e. cooling the vessel), favors towards
the decrease:
if H > 0, cooling favors the reverse reaction.
if H < 0, cooling favors the forward reaction.
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FACTORS THAT AFFECT EQUILIBRIA
Addition of a Catalyst:
A catalyst lowers the activation energy barrier for the reaction.
Therefore, a catalyst will decrease the time taken to reach
equilibrium.
A catalyst does not effect the composition of the equilibrium
mixture.
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RELATIONSHIP BETWEEN Kp & Kc
In general, the relationship between Kc and KP is:
Be Careful About the Value of R
L.atm
R 0.082
mol.K
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HETEROGENEOUS EQUILIBRIA
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HETEROGENEOUS EQUILIBRIA
Heterogeneous equilibria involve species in more than one phase.
Example:
Pureliquids and pure solids do not appear in the K expressions
for heterogeneous equilibria.
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RELATIONSHIP BETWEEN G0rxn & K
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RELATIONSHIP BETWEEN G0rxn & K
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RELATIONSHIP BETWEEN G0rxn & K
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Evaluation of K at difference temperature
The van’t Hoff equation
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Evaluation of K at difference temperature
Example:
We found that Kp =4.410-31 at 25°C (298 K) for the following
reaction, H0=180.5 kJ/mol for this reaction. Evaluate Kp at
2400K.
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