CHEMICAL EQUILIBRIA for the reaction,
4NH3(g) + 5O2(g)  4NO(g) + 6H2O(g)
Reversible Reaction
 reaction wherein the reactants disappear to form the
products (forward reaction) & after some time,
products begin to react to form the original reactants
(reverse reaction).
 Example of a reversible reaction is the synthesis of
methanol, CH3OH(g). It means that at the same time
CH3OH(g) is being formed, it decomposes to produce
CO(g) & 2H2(g).
CO(g) + 2H2(g)  CH3OH(g)
forward reaction is CO(g) + 2H2(g)  CH3OH(g)
reverse reaction is CH3OH(g)  CO (g) + 2H2(g)
Irreversible Reaction
 reaction wherein reactants disappear and converted
to products completely.
 Example of an irreversible reaction is the
decomposition of H2O2(l) to H2O(l) & O2(g)
H2O2(l)  H2O(l) & O2(g)
Chemical Equilibrium
 the state at which opposing reactions are proceeding
at equal rates
 the rate of the forward reaction (products formed
from reactants) is equal to the rate of reverse
reaction (reactants are formed form the products)
 involves different substances as reactants & products
N2O4(g)  NO2(g)
Physical Equilibrium
 equilibrium between the reactant & product of the
same substance but of different phase.
H2O(l)  H2O(g)
The Equilibrium Constant Expression, Keq
 the ratio of the equilibrium concentrations of the
product to the equilibrium concentrations of the
reactants raised to a certain power equal to their
stoichiometric coefficients at a certain temperature.
In the reaction,
aA + bB  cC + dD
the equilibrium constant expression is written as,
Keq = [C]c[D]d
[A]a[B]b
Chemical Equilibria
Gen Chem 213
Kc = [NO]4[H2O]6
[NH3]4[O2]5
or
Kp = (PNO)4(PH2O)6
(PNH3)4(PO2)5
notes:
 equilibrium constant expressions can be expressed
either in terms of equilibrium molar concentrations
(the expression is Kc), or in terms of equilibrium
partial pressures (the expression is Kp)
 in writing equilibrium constant expressions, we do
not include the concentrations of pure liquids or pure
solids.
 if K >>> 1; equilibrium favors the formation of
product (forward reaction)
if K <<< 1; equilibrium favors the formation of
reactants (reverse reaction)
Homogeneous & Heterogeneous Equilibria
 when the equilibrium system involves substances all
in the same phase, it is called homogeneous
equilibria
 when the equilibrium system involves substances in
different phases, it is called heterogeneous
equilibria
Exercises:
Write the Kc & Kp expressions for the following & classify
them as homogeneous or heterogeneous equilibria:
1. SO2(g) + 2H2S(g)  2H2O(g) + 3S(s)
2. NH3(g) + 5/4O2(g)  NO(g) + 3/2H2O(g)
3. 2HNO3(aq) + Ba(OH)2(aq)  Ba(NO3)2(aq) + 2H2O(l)
4. Mg(OH)2(s) + CO32-(aq)  MgCO3(s) + 2OH-(aq)
Relationship between Kc & Kp
 consider the reaction involving gases only,
aA(g) + bB(g)  cC(g) + dD(g)
assuming ideal gas behavior, PV = nRT
n/V = P/RT
 for systems involving gases only,
Kp = Kc(RT)n
where:
n = [d+c] – [a+b]
Mike Filomeno
Page 1 of 3

Exercises:
Calculations involving Kc & KP
1. In the reaction CO(g) + 2H2(g)  CH3OH(g) carried out at
483 K, the following equilibrium concentrations are
measured: [CO] = 1.03 M; [CH 3OH] = 1.56 M; [H2]=
0.332 M. Calculate the Kc & Kp of this reaction.
2. At a certain temperature, Kc= 1.8 x 104 for the
reaction N2(g) + 3H2(g)  2NH3(g). If the equilibrium
concentrations of N2 & NH3 are 0.015 M & 2.00 M
respectively, what is the equilibrium concentration of
H2?
Relationships Involving Equilibrium Constants &
Combining Equilibrium Expressions
 We invert (take the reciprocal) the value of K when
we reverse a chemical equation
ex:
at 298 K,
H2(g) + I2(g)  2HI(g) Keq = 794
2HI(g)  H2(g) + I2(g) K’eq = 1/794
 When we multiply the coefficients in a balanced
equation by a common factor (2, 3, ½, etc…), we
raise the equilibrium constant to the corresponding
power (2, 3, ½ , etc…)
ex:
at 298 K,
H2(g) + I2(g)  2HI(g) Keq = 794
2H2(g) + 2I2(g)  4HI(g) K’eq = (794)2
 When individual reactions are added to obtain a net
reaction, the individual equilibrium constants are
multiplied to obtain the equilibrium constant for the
net reaction
ex:
at 100 C,
step 1: 2NOBr(g)  2NO(g) + Br2(g) Keq = 0.42
step 2: Br2(g) + Cl2  2BrCl(g) Keq = 7.2
net rxn:2NOBr(g) + Cl2(g)  2NO(g) + 2BrCl(g)
K’eq = 0.42 x 7.2 = 3.0
Exercises:
1. The Kc for the reaction CO(g) + 2H2(g)  CH3OH(g) is
14.5. What is the Kc for the reverse reaction?
2. The following Kc value is given at 298 K for the
synthesis of NH3(g) from its elements.
N2(g) + 3H2(g)  2NH3(g) Kc = 3.6 x 108
What is the value of K c at the same temperature for
the reaction:
NH3(g)  ½N2(g) + 3/2H2(g)
3. For the reaction NO(g) + ½O2(g) at 184 C, KC = 7.5 x
102. What is the value of Kc and Kp at 184184C for the
reaction 2NO2(g)  2NO(g) + O2(g)?
4. Given the following equilibria,
N2(g) + ½O2(g)  N2O(g) Kc = 2.7 x 10-18
N2(g) + O2(g)  2NO(g) Kc = 4.7 x 10-31
Chemical Equilibria
Gen Chem 213
Find Kc for the reaction,
N2O(g) + ½O2(g)  2NO(g)
5. Given the following equilibrium constant values,
N2(g) + ½O2(g)  N2O(g) Kc = 2.7 x 10-18
N2O4(g)  2NO2(g) Kc = 4.6 x 10-3
½N2(g) + O2(g)  NO2(g) Kc = 4.1 x 10-9
Determine a value of Kp for the reaction at 298 K,
2N2O(g) + 3O2(g)  2N2O4(g)
The Reaction Quotient, Q
 the ratio of the initial concentrations of the product
to the initial concentrations of the reactants raised to
a certain power equal to their stoichiometric
coefficients at a certain temperature.
Predicting the Direction of Equilibrium
Qc = Kc reaction is at equilibrium
Qc < Kc reaction favors the forward reaction
Qc > Kc reaction favors the reverse reaction
Exercises:
1. At the start of a reaction, there are 0.249 mol N 2,
3.21 x 10-2 mol H2 & 6.42 x 10-4 mol NH3 in a 3.0 L
reaction vessel at 200 C. If the equilibrium constant
for the reaction N2(g) + 3H2(g)  2NH3(g) is 0.65 at this
temperature, determine whether the system is at
equilibrium. If not, determine the direction at which
the reaction will proceed.
2. Consider the following equilibrium process at 686 C,
CO2(g) + H2(g)  CO(g) + H2O(g)
The equilibrium concentrations of the reacting
species are [CO] = 0.050 M, [H 2] = 0.045 M, [CO2] =
0.086 M and [H2O] = 0.040 M.
a. Calculate the equilibrium constant for the reaction
at 686 C.
b. If the concentration of CO2 was raised to 0.75
mol/L by the addition of CO2, what would be the
favored reaction of the system so as to establish
equilibrium again.
3. A 5.00 L evacuated flask is filled with 1.86 mol NOBr.
After equilibrium is established at 25 25C, it is found
that there is 0.082 mol of Br 2 present. Determine Kc
& Kp for the reaction: 2NOBr(g)  2NO(g) + Br2(g).
4. 1.00 x 10-3 mol PCl5 is introduced into a 250.0 mL
flask, and equilibrium is established at 284284C: PCl5(g) 
PCl3(g) + Cl2(g). The quantity of Cl 2(g) present at
equilibrium is found to be 9.65 x 10 -4 mol. What is
the value of Kc & Kp for the dissociation reaction at
284 C?
5. Equilibrium involving SO2(g), O2(g) & SO3(g) is important
in sulfuric acid production. When a 0.0200 mol
sample of SO3 is introduced into an evacuated 1.52 L
vessel at 900 K, 0.0142 mol, SO 3 is found to be
present at equilibrium. What is the value of K p for
the dissociation of SO3(g) at 900 K?
6. A 0.0240 mol sample of N 2O4(g) is allowed to come to
equilibrium with NO2(g) in a 0.372 L flask at 25 25C.
Calculate the amount of N2O4 present at equilibrium.
N2O4(g)  2NO2(g) Kc = 4.61 x 10-3 at 25 C
Mike Filomeno
Page 2 of 3
 7. Solid silver is added to a solution with these initial a. increase the temperature of the mixture
concentrations: [Ag+] = 0.200 M, [Fe2+] = 0.100 M & b. introduce more H2O(g)
[Fe3+] = 0.300 M. The following reversible reactions c. double the volume of the container
occur: d. add an appropriate catalyst
Ag+(aq) + Fe2+(aq)  Ag(s) + Fe3+(aq) Kc = 2.98
What are the ion concentrations when equilibrium is 2. Consider the reaction,
established? 2SO3(g)  2SO2(g) + O2(g) H = 198.2 kJ
8. A solution is prepared with [V 3+] = [Cr2+] = 0.0100 M What would be the effect on the position of the
and [V2+] = [Cr3+] = 0.150 M. The following reaction equilibrium if:
occurs: a. the total pressure on the system is increased
V3+(aq) + Cr2+(aq)  V2+(aq) + Cr3+(aq) Kc = 7.2 x 102 b. oxygen gas was added to the reaction
Determine the ion concentrations when equilibrium is mixture
established. c. the temperature of the system was lowered
d. an inert gas, He, is added to the mixture
Le Chatelier’s Principle
 when an equilibrium system is subjected to a change
in temperature, pressure or concentration of a
reacting species, the system responds by attaining a
new equilibrium that partially offsets the impact of
the change.

Factors Affecting the State of Equilibrium:

1. Changes in Concentration
- an increase in the concentrations of the reactants
will cause the equilibrium to favor the forward
reaction; an increase in the concentration of the
products will cause the equilibrium to favor the
backward reaction.

2. Changes in Temperature
- raising the temperature of an equilibrium mixture
shifts the equilibrium condition in the direction of
endothermic reaction; lowering the temperature
causes a shift in the direction of the exothermic
reaction. Only changes in temperature can affect the
value of the equilibrium constant, K.

3. Changes in Pressure & Volume

- a decrease in the volume (hence an increase in
pressure) of the equilibrium mixture of gases causes
a net reaction in the direction producing fewer moles
of gases; an increase in the volume (hence a
decrease in pressure) of the equilibrium mixture of
gases causes a net reaction in the direction
producing more moles of gases

4. Effect of Catalysts
-the function of a catalyst is to change the
mechanism of a reaction to one having a lower
activation energy, hence it has no effect on the
condition of equilibrium.

Exercises:
1. Explain how each of the following factors affects the
amount of H2 present in an equilibrium mixture in the
reaction
3Fe(s) + 4H2O(g)  Fe3O4(s) + 4H2(g) H = -150 J

Chemical Equilibria Mike Filomeno

Gen Chem 213 Page 3 of 3