Chemical Equilibrium What is Equilibrium?

• What is equilibrium?
• Expressions for equilibrium constants, Kc;
• Calculating Kc using equilibrium concentrations;
• Calculating equilibrium concentrations using initial
concentration and Kc value;
• Relationship between Kc and Kp;
• Factors that affect equilibrium;
• Le Chatelier’s Principle

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This is not Equilibrium? Chemical Equilibrium in Nature:


(The formation of stalagmites and Stalactites)

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 Chemical Equilibrium Expression for Equilibrium Constant

• Consider the following reactions: Consider the following equilibrium system:

-(aq) ..(1)
CaCO3(s) + CO2(aq) + H2O(l) → Ca2+(aq) + 2HCO3 wA + xB ⇄ yC + zD
and [C] y [D] z
Ca2+(aq) + 2HCO3-(aq) → CaCO3(s) + CO2(aq) + H2O(l) ..(2) Kc = [A]w [B] x

Reaction (2) is the reverse of reaction (1). • The numerical value of Kc is calculated using the
At equilibrium the two opposing reactions occur at the same
concentrations of reactants and products that exist at
rate.
equilibrium.
Concentrations of chemical species do not change once
equilibrium is established.

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Expressions for Equilibrium Constants Calculating Equilibrium Constant

• Examples: • Example-1:
[NH 3 ] 2 1.000 mole of H2 gas and 1.000 mole of I2 vapor are
N2(g) + 3H2(g) ⇄ 2NH3(g); Kc =
[N 2 ][H 2 ]3 introduced into a 5.00-liter sealed flask. The mixture is heated
to a certain temperature and the following reaction occurs until
[PCl 3 ][Cl 2 ] equilibrium is established.
PCl5(g) ⇄ PCl3(g) + Cl2(g); Kc = [PCl 5 ]
H2(g) + I2(g) ⇄ 2HI(g)

At equilibrium, the mixture is found to contain 1.580 mole of

CH4(g) + H2(g) ⇄ CO(g) + 3H2(g); HI per L solution. (a) What are the concentrations of H2, I2 and
[CO][H 2 ]3 HI at equilibrium? (b) Calculate the equilibrium constant Kc.
[CH 4 ][H 2 O]
Kc =

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 Calculating Equilibrium Constant

for reaction: H2(g) + I2(g) ⇄ 2HI(g) Calculating Equilibrium Constant
• ———————————————————————————— • Example-2:
• H2(g) + I2(g) ⇄ 2 HI(g)
0.500 mole of HI is introduced into a 1.00 liter sealed flask
• ———————————————————————————— and heated to a certain temperature. Under this condition HI
• Initial [ ], M: 0.200 0.200 0.000 decomposes to produce H2 and I2 until an equilibrium is
• Change in [ ], M: -0.158 -0.158 + 0.316 established. An analysis of the equilibrium mixture shows
• Equilibrium [ ], M 0.042 0.042 0.316 that 0.105 mole of HI has decomposed. Calculate the
• ———————————————————————————— equilibrium concentrations of H2, I2 and HI, and the
[HI]2 (0.316) 2 equilibrium constant Kc for the following reaction:
[H 2 ][I 2 ] (0.042) 2 H2(g) + I2(g) ⇄ 2HI(g),
Kc = = = 57

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Calculating Equilibrium Constant Expression and Value of 


Equilibrium Constant for a Reaction
• The reaction: H2(g) + I2(g) ⇄ 2HI(g), proceeds from
right to left. • The expression for K depends on the equation;
• ———————————————————————————— • The value of K applies to that equation; it does
• H2(g) + I2(g) ⇄ 2HI(g) not depend on how the reaction occurs;
• ———————————————————————————— • Concentrations used to calculate the value of K
• Initial [ ], M: 0.000 0.000 0.500
• Change in [ ], M: +0.0525 +0.0525 -0.105 are those measured at equilibrium.
• Equil’m [ ], M 0.0525 0.0525 0.395
2
• (0.395)
————————————————————————————
(0.0525) 2
Kc = = 56.6

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 Relationships between chemical equations and Expression and Values of

the expressions of equilibrium constants Equilibrium Constant Using Partial Pressures
• The expression of equilibrium constant depends on how the • Consider the following reaction involving
equilibrium equation is written. For example, for the following
equilibrium: gases:
[HI]2
• H2(g) + I2(g) ⇄ 2 HI(g); K c = 2SO2(g) + O2(g) ⇄ 2SO3(g)
[H 2 ][I 2 ]
• For the reverse reaction: (PSO3 ) 2
[H ][I ] 2
Kp = (PSO2 ) (PO2 )
2 2
• 2HI(g) ⇄ H2(g) + I2(g); K c ' = [HI]2 = 1/K c

• And for the reaction: HI(g) ⇄ ½H2(g) + ½I2(g);

[H 2 ][ I 2 ]
Kc " = = Kc ' = 1
[HI]2 Kc

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The Relationship between Kc and Kp Relationship between Kc and Kp

• Consider the reaction: 2SO2(g) + O2(g) ⇄ 2SO3(g) • For reaction: PCl5(g) → PCl3(g) + Cl2(g);
[SO]2 (PSO3 ) 2
• Kc = [SO 2 ]2 [O 2 ] and Kp = (PSO2 ) 2 (PO2 ) (PPCl3 )( PCl2 ) [PCl 3 ]( RT) x [Cl 2 ]( RT)
Kp = =
( PPCl5 ) [PCl 5 ]( RT)
• Assuming ideal behavior, [PCl 3 ][Cl 2 ]
• where PV = nRT and P = (n/V)RT = [M]RT
= ( RT)1 = K C ( RT)1
[ PCl 5 ]
• and PSO3 = [SO3]RT; PSO2 = [SO2]RT; PO2 = [O2]RT
[SO 3 ]2 ( RT) 2 [SO 3 ]2
Kp = 2 2
= 2
( RT) -1 = K c ( RT) -1
[SO 2 ] ( RT) [O 2 ]( RT) [SO 2 ] [O 2 ]

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 Relationship between Kc and Kp Relationship between Kc and Kp
• In general, for reactions involving gases such that, • For other reactions:
• 1. 2NO2(g) ⇄ N2O4(g); Kp = Kc(RT)-1
• aA + bB ⇄ cC + dD
where A, B, C, and D are all gases, and a, b, • 2. H2(g) + I2(g) ⇄ 2 HI(g); Kp = Kc
c, and d are their respective coefficients,
• 3. N2(g) + 3H2(g) ⇄ 2 NH3(g); Kp = Kc(RT)-2
• Kp = Kc (RT)Δn
and Δn = (c + d) – (a + b)
(In heterogeneous systems, only the coefficients
of the gaseous species are counted.)

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Equilibrium Constant Expressions for

Homogeneous & Heterogeneous Equilibria
Heterogeneous System
Homogeneous equilibria: • Examples:
CH4(g) + H2O(g) ⇄ CO(g) + 3H2(g); CaCO3(s) ⇄ CaO(s) + CO2(g);
CO(g) + H2O(g) ⇄ CO2(g) + H2(g); Kc = [CO2] Kp = PCO2; Kp = Kc(RT)

Heterogeneous equilibria:
• HF(aq) + H2O(l) ⇄ H3O+(aq) + F-(aq);
CaCO3(s) ⇄ CaO(s) + CO2(g);
[H O + ][ F - ]
Ka = 3
HF(aq) + H2O(l) ⇄ H3O+(aq) + F-(aq); [HF]
PbCl2(s) ⇄ Pb2+(aq) + 2 Cl-(aq);

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 Solubility Eqilibrium
PbCl2(s) ⇄ Pb2+(aq) + 2Cl-(aq);
Ksp = [Pb2+][Cl-]2
(Ksp is called solubility product)
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Combining Equations and Equilibrium Constants
• Net equation: A + E ⇄ D + F;
[D][F]
K net = = K1 x K2
[A][E]
• If Eqn(1) + Eqn(2) = Net equation,
then K1 x K2 = Knet
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Combining Equations and Equilibrium Constants
• when two or more equations are added to yield a net
equation, the equilibrium constant for the net
equation, Knet, is equal to the product of equilibrium
constants of individual equations.
• For example,
[C][D]
Eqn(1): A + B ⇄ C + D; K1 =
[A][D]
[B][F]
Eqn(2): C + E ⇄ B + F; K 2 =
[C][E]
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Equilibrium Exercise #1
A flask is charged with 2.00 atm of nitrogen dioxide and 1.00
atm of dinitrogen tetroxide at 25 oC and allowed to reach
equilibrium. When equilibrium is established, the partial
pressure of NO2 has decreased by 1.24 atm. (a) What are the
partial pressures of NO2 and N2O4 at equilibrium?
(b) Calculate Kp and Kc for following reaction at 25 oC.
2 NO2(g) ⇄ N2O4(g)
(Answer: Kp = 2.80; Kc = 68.6)
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 Equilibrium Exercise #2a
• Methanol is produced according to the following equation:
• CO(g) + 2H2(g) ⇄ CH3OH(g)
• In an experiment, 1.000 mol each of CO and H2 were allowed to
react in a sealed 10.0-L reaction vessel at 500 K. When the
equilibrium was established, the mixture was found to contain
0.0892 mole of CH3OH. What are the equilibrium concentrations
of CO, H2 and CH3OH? Calculate the equilibrium constants Kc
and Kp for this reaction at 500 K?
(R = 0.0821 L.atm/Mol.K)
(Answer: [CO] = 0.0911 M; [H2] = 0.0822 M; [CH3OH] = 0.00892 M;
(b) Kc = 14.5; Kp = 8.60 x 10-3)
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Equilibrium Exercise #3
1. The reaction: N2(g) + 3H2(g) ⇄ 2NH3(g), If
has equilibrium constant, Kc = 0.0602 at 500oC. and N2(g) + O2(g) ⇄ 2 NO(g);
What is the equilibrium constant for the following reaction?
NH3(g) ⇄ ½N2(g) + 3/2H2(g)
2. For the reaction: 2SO2(g) + O2(g) ⇄ 2 SO3(g),
Kc = 280 at 1000 K.
What is the equilibrium constant for the decomposition of SO3 at
1000 K according to the following equation?
SO3(g) ⇄ SO2(g) + ½ O2(g).
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Equilibrium Exercise #2b
For the reaction: CO(g) + 2H2(g) ⇄ CH3OH(g)
Kc = 15.0 at a certain temperature. Is a reaction
mixture that contains 0.40 M CO, 0.80 M H2, and 0.10
M CH3OH at equilibrium? If not, in which direction
will the net reaction occur? What will be their
concentrations when equilibrium is established?
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Equilibrium Exercise #4
N2(g) + ½ O2(g) ⇄ N2O(g); Kc(1) = 2.4 x 10-18
Kc(2) = 4.1 x 10-31
What is the equilibrium constant for the reaction?
N2O(g) + ½ O2(g) ⇄ 2NO(g)
(Answer: Knet = 1.7 x 10-13)
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Applications of Equilibrium Constant
For any system or reaction:
1. Knowing the equilibrium constant, we can predict
whether or not a reaction mixture is at equilibrium,
and we can predict the direction of net reaction.
• Qc = Kc ➔ equilibrium (no net reaction)
• Qc < Kc ➔ a net forward reaction;
• Qc > Kc ➔ a net reverse reaction
2. The value of K tells us whether a reaction favors
the products or the reactants.
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What does the reaction quotient tell us?
If Qc = Kc, ➔ the reaction is at equilibrium;
If Qc < Kc, ➔ the reaction is not at equilibrium and there’s a
net forward reaction;
If Qc > Kc, ➔ the reaction is not at equilibrium and there’s a
net reaction in the opposite direction.
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Equilibrium constant is used to predict the
direction of net reaction
• For a reaction of known Kc value, the direction of net reaction
can be predicted by calculating the reaction quotient, Qc.
• Qc is called the reaction quotient, where for a reaction such as:
• aA + bB ⇄ cC + dD;
[C]c [ D]d
Qc =
[A]a [ B]b
• Qc has the same expression as Kc , but
• Qc is calculated using concentrations that are not necessarily at
equilibrium.
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Why is Equilibrium Constant Important?
• Knowing Kc and the initial concentrations, we can
determine the concentrations of components at
equilibrium.
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 Equilibrium Exercise #5 Calculating equilibrium concentrations using
initial concentrations and value of Kc
• For the reaction:
CO(g) + 2 H2(g) ⇄ CH3OH(g), Kc = 14.5 at 500 K. • Consider the reaction:
• Predict whether a mixture that contains 1.50 mol of H2, 1.00 • H2(g) + I2(g) ⇄ 2 HI(g),
mol of CO, and 0.50 mol of CH3OH in a 10.0-L vessel at 500 • where Kc = 55.6 at 425oC.
Kc is at equilibrium.
• If [H2]0 = [I2]0 = 0.1000 M, and [HI]0 = 0.0 M, what
• If not, indicate the direction in which the net reaction will occur
to reach equilibrium. are their concentrations at equilibrium?

(Answer: Qc = 22.2 > Kc; net reaction is to the left)

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Using the ICE table to calculate equilibrium

Calculation of equilibrium concentrations
concentrations
• Equation: H2(g) + I2(g) ⇄ 2 HI(g),
2x
• ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ = 55.6 = 7.46
• Initial [ ], M 0.1000 0.1000 0.0000 (0.100 - x
• Change [ ], M -x -x +2x 2 x = 0.746 - 7.46 x; => 9.46 x = 0.746
• Equilibrium [ ], M (0.1000 - x) (0.1000 - x) 2x
• ⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯ ⎯⎯⎯⎯⎯⎯⎯ x = 0.0789 ;
[HI]2 (2 x ) 2 [H 2 ] = [I 2 ] = 0.0211 M; [HI] = 0.158 M
Kc = = = 55.6
[H 2 ][ I 2 ] (0.100 - x ) 2

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 Equilibrium Exercise #6
For the reaction:
2 NO2(g) ⇄ N2O4(g); Kp = 1.27 at 353 K.
If the initial pressure of NO2 was 3.92 atm, and
initially there was no N2O4, what are the partial
pressures of the gases at equilibrium at 353 K? What
is the total gas pressure at equilibrium?
(Answer: PNO2 = 1.06 atm; PN2O4 = 1.43 atm; Ptotal = 2.49 atm)
37
Le Châtelier’s Principle
• The Le Châtelier's principle states that:
when factors that influence an equilibrium are altered, the
equilibrium will shift to a new position that tends to
minimize those changes.
• Factors that influence equilibrium:
Concentration, temperature, and partial pressure (for
gaseous)
39
Equilibrium Exercise #7
The reaction:
PCl5(g) ⇄ PCl3(g) + Cl2(g) has Kc = 0.0900.
A 0.1000-mol sample of PCl5 is placed in an empty
1.00-L flask and the above reaction is allowed to come
to equilibrium at a certain temperature. How many
moles of PCl5, PCl3, and Cl2, respectively, are present
at equilibrium?
(Answer: PCl5 = 0.0400 mol; PCl3 = Cl2 = 0.0600 mol)
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The Effect of Changes in Concentration
• Consider the reaction: N2(g) + 3H2(g) ⇄ 2 NH3(g);
[NH]2
Kc =
[N 2 ][H 2 ]3
• If [N2] and/or [H2] is increased, Qc < Kc
• ➔ a net forward reaction will occur to reach new equilibrium
position.
• If [NH3] is increased, Qc > Kc, and a net reverse reaction
will occur to come to new equilibrium position.
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 Effects of Pressure Change on Equilibrium
• If the volume of a gas mixture is compressed, the
overall gas pressure will increase. In which direction
the equilibrium will shift in either direction depends
on the reaction stoichiometry.
• However, there will be no effect to equilibrium if the
total gas pressure is increased by adding an inert gas
that is not part of the equilibrium system.
41
Reaction that shifts left when pressure increases,
but shifts right when pressure decreases
Consider the reaction: PCl5(g) ⇄ PCl3(g) + Cl2(g);
1. Forward reaction results in more gas molecules.
2. Pressure increases as reaction proceeds towards
equilibrium.
3. If mixture is compressed, pressure increases, and
reverse reaction occurs to reduce pressure;
4. If volume expands and pressure drops, forward
reaction occurs to compensate.
5. This type of reactions favors low pressure condition
43
Reactions that shift right when pressure increases
and shift left when pressure decreases
Consider the reaction:
2SO2(g) + O2(g) ⇄ 2SO3(g),
1. The total moles of gas decreases as reaction
proceeds in the forward direction.
2. If pressure is increased by decreasing the volume
(compression), a forward reaction occurs to reduce
the stress.
3. Reactions that result in fewer moles of gas favor
high pressure conditions.
42
Reactions not affected by pressure changes
Consider the following reactions:
1. CO(g) + H2O(g) ⇄ CO2(g) + H2(g);
2. H2(g) + Cl2(g) ⇄ 2HCl(g);
1. Reactions have same number of gas molecules in
reactants and products.
2. Reducing or increasing the volume will cause equal
effect on both sides – no net reaction will occur.
3. Equilibrium is not affected by change in pressure.
44
 The Effect Temperature on Equilibrium The Effect Temperature on Equilibrium

• Consider the following exothermic reaction: Consider the following endothermic reaction:
N2(g) + 3H2(g) ⇄ 2NH3(g); ΔHo = -92 kJ, CH4(g) + H2O(g) ⇄ CO(g) + 3H2(g), ΔHo = 205 kJ

• The forward reaction produces heat => heat is a product. 1. Endothermic reaction absorbs heat ➔ heat is a reactant;
• When heat is added to increase temperature, reverse reaction 2. If heat is added to increasing the temperature, it will cause a
will take place to absorb the heat; net forward reaction.
• If heat is removed to reduce temperature, a net forward reaction 3. If heat is removed to reduce the temperature, it will cause a
will occur to produce heat. net reverse reaction.
• Exothermic reactions favor low temperature conditions. 4. Endothermic reactions favor high temperature condition.

45 46

Equilibrium Exercise #8 Equilibrium Exercise #9

Determine shift in equilibrium if you have high • Determine shift if temp is increased:
pressure conditions:
1. 2SO2(g) + O2(g) ⇄ 2 SO3(g); 1. 2SO2(g) + O2(g) ⇄ 2 SO3(g); ΔHo = -180 kJ

2. PCl5(g) ⇄ PCl3(g) + Cl2(g); 2. CO(g) + H2O(g) ⇄ CO2(g) + H2(g); ΔHo = -46 kJ

3. CO(g) + Cl2(g) ⇄ COCl2(g); ΔHo = -108 kJ

3. CO(g) + 2H2(g) ⇄ CH3OH(g);
4. N2O4(g) ⇄ 2 NO2(g); ΔHo = +57 kJ
4. N2O4(g) ⇄ 2 NO2(g);
5. CO(g) + 2H2(g) ⇄ CH3OH(g); ΔHo = -270 kJ
5. H2(g) + F2(g) ⇄ 2 HF(g);

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 Chemical Equilibria in Industrial Processes Chemical Equilibria in Industrial Processes
Production of Sulfuric Acid, H2SO4;
1. S8(s) + 8 O2(g) → 8SO2(g) The production of ammonia by the Haber-Bosch
2. 2SO2(g) + O2(g) ⇄ 2SO3(g); ΔH = -198 kJ process:
3. SO3(g) + H2SO4(l) → H2S2O7(l) N2(g) + 3H2(g) ⇄ 2NH3(g); ΔH = -92 kJ
4. H2S2O7(l) + H2O(l) → 2H2SO4(l)
• This reaction is exothermic and very slow at low temperature.
• The second reaction is exothermic and has high activation
energy; • Increasing the temperature will increase reaction rate, but will
lower the yield.
• though thermodynamically favored the reaction is very slow
at low temperature,. • An optimum condition is achieved at moderate temperature of
• At high temperature reaction goes faster, but the yield would 250 to 300oC with catalyst added to increase the reaction rate.
be very low. • Increasing the pressure will favor product formation.
• An optimum condition is achieved at moderate temperatures • Reaction favors low temperature and high pressure conditions.
and using catalysts to speed up the reaction. Reaction also
favors high pressure.

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Chemical Equilibria in Industrial Processes

The production of hydrogen gas:

• Reaction: CH4(g) + H2O(g) ⇄ CO(g) + 3H2(g);

• This reaction is endothermic with ΔH = 206 kJ

• Increasing the reaction temperature will increase both
the rate and the yield.
• This reaction favors high temperature and low
pressure conditions.

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