GENERAL CHEMISTRY

P R ı N C ı P L E S A N D M O D E R N A P P L ı C AT ı O N S
ELEVENTH EDITION

PETRUCCI HERRING MADURA BISSONNETTE

Principles of Chemical
Equilibrium 15
PHILIP DUTTON
UNIVERSITY OF WINDSOR
DEPARTMENT OF CHEMISTRY AND BIOCHEMISTRY

Slide 15 - 1 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.

 CONTENTS
Principles of Chemical
15-1 The Nature of the Equilibrium
Equilibrium State
15-2 The Equilibrium Constant
Expression
15-3 Relationships Involving
Equilibrium Constants

15-4 The Magnitude of an Equilibrium

Constant
15-5 Predicting the Direction of Net
Chemical Change

15-6 Altering Equilibrium Conditions:

Le Châtelier’s Principle
15-7 Equilibrium Calculations: Some
Illustrative Examples

Slide 15 - 2 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.

 15-1 The Nature of the Equilibrium State
A system at equilibrium is in a state of balance.
Both forward and reverse reactions occur at exactly same rate.

In a closed reaction vessel at constant temperature, a reaction proceeds

spontaneously toward equilibrium. At equilibrium, the reaction quotient Q
attains the same constant value, K, irrespective of the starting amounts of
reactants and products.

2 Cu2+(aq) + Sn2+(aq) 2 Cu+(aq) + Sn4+(aq) (15.1)

Slide 15 - 3 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.

 2 Cu2+(aq) + Sn2+(aq) 2 Cu+(aq) + Sn4+(aq)

1. The reaction quotient Q has the same value at equilibrium

no matter what the starting concentrations are.
2. The equilibrium value of Q is represented by the symbol
K and is called the equilibrium constant

Slide 15 - 4 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.

Slide 15 - 5 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.
1B. At 25C, K = 9.14 × 10-6 for the reaction:
2Fe3+(aq)+Hg22+(aq) ⇌ 2Fe2+(aq) + 2Hg2+(aq).

If the equilibrium concentrations of Fe3+, Fe2+ and Hg2+ are 0.015 M, 0.0025 M
and 0.0018 M, respectively, what is the equilibrium concentration of Hg22+?

Slide 15 - 6 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.

 15-2 The Equilibrium Constant Expression
aA + bB + … cC + dD + …

A, B, C, D, etc. refer to chemical substances and

a, b, c, d represent the coefficients required to balance the equation.

If concentrations of substances are measured:

At any time: aCc ´ aDd ´ ...

Q= a
aA ´ aBb ´ ...

c
aC, ´ aD, eq ´ ...
d
At equilibrium: K=
eq

aA,a eq ´ aB,b eq ´ ...

Slide 15 - 7 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.
Equilibria Involving Gases
∆u
(PC / P°) (PD / P°) ... P ´ P .. æ 1 ö
c d c d
K= = ´ç ÷ C D
(PA / P°) (PB / P°) ... P ´ P .. è P° ø
a b
A
a b
B

∆ν = (c + d +…) − (a + b +…)

The sum of coefficients The sum of coefficients

for the products for the reactants

PCc ´ PDd ..
KP = a
PA ´ PBb ..

Kp is equilibrium constant expression written in terms of pressures.

Slide 15 - 8 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.

 Equilibria in Aqueous Solution
∆u
([C] / c°)c ([D] / c°)d ... [C]c ´ [D]d ... æ 1 ö
K= = ´ç ÷
([A] / c°) ([B] / c°) ... [A] ´ [B] ... è c° ø
a b a b

[C]c ´ [D]d ...

Kc =
[A]a ´ [B]b ...

Kc is equilibrium constant expression written in terms of

concentrations.

Remember that, Pure solids and liquids are not included in equilibrium constant
expressions

Slide 15 - 9 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.

 Equilibria Involving Pure Liquids and Solids

Remember that, Pure solids and liquids are not included in equilibrium constant
expressions

C(s) + H2O(g) CO(g) + H2(l)

æ 1ö æ 1ö
K = PCO(g) ´ çè P° ÷ø = K P ´ çè P° ÷ø

Slide 15 - 10 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.

 15-3 Relationships Involving the
Equilibrium Constant
Relationship of K to the Balanced
Chemical Equation
• When we reverse an equation, we invert the value of K.
• When we multiply the coefficients in a balanced equation
by a common factor we raise the equilibrium constant to
the corresponding power.
• When we divide the coefficients in a balanced equation by
a common factor we take the corresponding root of the
equilibrium constant.

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• When individual equations are combined (that is, added),
their equilibrium constants are multiplied to obtain the
equilibrium constant for the overall reaction.

N2O(g) + ½O2(g) 2 NO(g) Kc= ?

N2(g) + ½O2(g) N2O(g) K= 5.4×10−19 (a)

N2(g) + O2(g) 2 NO(g) Kc(3)= 4.6×10−31 (b)

Slide 15 - 12 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.

 N2(g) + ½O2(g) N2O(g) K= 5.410−19

(a)’ N2O(g) N2(g) + ½O2(g) K’(a) = 1/ 5.410−19 = 1.9 1018

(b) N2(g) + O2(g) 2 NO(g) K(b)= 4.610−31

Overall: N2O(g) + ½O2(g) 2 NO(g) Koverall= ?

Koverall = Ka’ x Kb

= 1.9×1018 × 4.6×10−31 = 8.5×10−13

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Relationship Between KP and Kc for Reactions
Involving Gases
The composition of a gas mixture can be specified by giving the
concentrations, in moles per liter, of the component gases.
Suppose we have nA moles of gas A, nB moles of gas B, nC moles
of gas C, and nD moles of gas D in container of volume V at
temperature T. Assuming ideal gas behavior, the partial pressure of
gas A is

nA RT
PA = = [A]RT
V

Slide 15 - 14 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.

 Relationship Between KP and Kc for Reactions
Involving Gases
Te equilibrium constant expression Kp for the following reaction
may also be written in terms of concentrations
aA(g) + bB(g) + … cC(g) + dD(g) + …

PCc ´ PDd .. ([C]RT)c ([D]RT)d ... [C]c ´ [D]d ... ∆ u gas

KP = a = = ´ (RT)
PA ´ PB .. ([A]RT ) ([B]RT) ... [A] ´ [B] ...
b a b a b

Δvgas is the sum of coefficients for gaseous products minus the sum
of coefficients for gaseous reactants.
∆ u gas
K P = Kc ´ (RT)
we must use R = 0.08314472 bar L K-1 mol-1 if partial pressures
are expressed in bar and concentrations in mol/L.

Slide 15 - 15 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.

4A. For the reaction
2NH3(g) ⇌ N2(g) + 3H2(g) at 298 K Kc=2.8×10-9.
What is the value of Kp for this reaction?

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 15-4 The Magnitude of the Equilibrium
Constant.
A very large value of K signifies that the reaction, as written, exhibits a
strong tendency to go to completion. An equilibrium mixture contains
about as much product as can be formed from the given initial amounts
of reactants.

A very small value of K signifies that the reaction, as written, exhibits very
little tendency to occur. An equilibrium mixture contains reactants, in
essentially their initial amounts, and very small amounts of products.

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A reaction goes essentially to completion if K =1010 and not at all if K =10−10.

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15-5 Predicting the Direction of Net Change.

2 Cu2+(aq) + Sn2+(aq) 2 Cu+(aq) + Sn4+(aq) (15.1)

[Cu+ ]2 [Sn4+ ]
Q= 2+ 2
K = 1.48
[Cu ][Sn2+ ]
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 Ex: PCl5(g) ⇌ PCl3(g) + Cl2(g), Kc = 0.0454 at 261C.
If a vessel is filled with these gases such that the initial partial
pressures are PPCl3 = 2.19 atm, PCl2 = 0.88 atm, PPCl5 = 19.7 atm,
in which direction will a net change occur?

Because Q<K net reaction will proceed to te right (forward)

Slide 15 - 20 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.

 15-6 Altering Equilibrium Conditions:
Le Châtelier’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.
This is known as Le Châtelier’s principle.

Slide 15 - 21 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.

 Effect of Changing the Amounts of Reacting
Species on Equilibrium

Suppose we start with certain equilibrium amounts of SO2, O2, SO3.

Now let s create a disturbance in the equilibrium mixture by forcing
an additional 1.00 mol SO3 into the 10.0 L flask.

Slide 15 - 22 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.

Reverse reaction proceed to attain new equilibrium.

FIGURE 15-5
Changing equilibrium conditions by changing the amount of a reacting species
2 SO2(g) + O2(g) 2 SO3(g), Kc= 2.8102 at 1000 K
Slide 15 - 23 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.
 Original equilibrium Immediately following disturbance

[SO3]2
Q= 2
= Kc Q > Kc
[SO2] [O2]

k1
2 SO2(g) + O2(g) 2 SO3(g)
k−1

Slide 15 - 24 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.

 Effect of Changes in Pressure or Volume
on Equilibrium
Change the pressure by changing the volume of the system.
Decreasing the volume of the system increases the pressure, and
increasing the system volume decreases the pressure. Thus, the effect
of this type of pressure change is simply that of a volume change.

When the volume of an equilibrium mixture of gases is reduced, a net change

occurs in the direction that produces fewer moles of gas.

When the volume is increased, a net change occurs in the direction that produces
more moles of gas.

Slide 15 - 25 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.

7A. The reaction N2O4(g) ⇌ 2NO2(g), is at equilibrium in a
3.00 L cylinder. What would be the effect on the
concentrations of N2O4(g) and NO2(g) if the pressure were
doubled (that is, cylinder volume decreased to 1.50 L)?

There is 1 mol gas in reactant and 2 mol in product site.. So

decreasing volume because shift to fewer gas..

In question, that direction is to the left (reverse rxn).

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Effect of Temperature on Equilibrium

Raising the temperature of an equilibrium mixture shifts the equilibrium

condition in the direction of the endothermic reaction. Lowering the
temperature causes a shift in the direction of the exothermic reaction.

Effect of a Catalyst on Equilibrium

A catalyst has no effect on the condition of equilibrium in a reversible
reaction.

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15-7 Equilibrium Calculations:
Some Illustrative Examples.
Numerical examples are given in the text that illustrate
ideas that have been presented in this chapter.
Refer to the “comments” which describe the
methodology. These will help in subsequent chapters.
Exercise your understanding by working through the
examples with a pencil and paper.

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9A. Equilibrium is established in a 3.00 L flask at 1405 K for the
reaction
2H2S(g) ⇌ 2H2(g) + S2(g).

At equilibrium, there is 0.11 mol S2(g), 0.22 mol H2(g), and 2.78
mol H2S(g). What is the value of Kc for this reaction?

Slide 15 - 29 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.

10A. A 5.00 L evacuated flask is filled with 1.86 mol NOBr. At equilibrium
at 25 C, there is 0.082 mol of Br2 present. Determine Kc and Kp for the
reaction
2NOBr(g) ⇌ 2NO(g) + Br2(g).
[R = 0.08314 L bar / (mol K)]

Reaction: 2NOBr(g) ⇌ 2NO(g) + Br2(g)

Initial: 1.86 mol 0.00 mol 0.00 mol
Any time: -2X 2X X (X=0.082 mol)
Change: -0.164 mol +0.164 mol +0.082 mol
Equil.: (1.86-0.164)mol 0.164 mol 0.082 mol

Slide 15 - 30 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.

12A. If 0.15 mol H2(g) and 0.20 mol I2(g) are introduced into a 15 L flask at
445 C and allowed to come to equilibrium, how many moles of HI(g)
will be present?
H2(g) + I2(g) ⇌ 2HI(g) Kc = 50.2 at 445 °C

Slide 15 - 31 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.

Slide 15 - 32 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.
13B. A solution is prepared with [V3+]=[Cr2+]=0.010 M and [V2+]=[Cr3+]=0.150
M. The following reaction occurs.
V3+(aq) + Cr2+ (aq) ⇌ V2+(aq) + Cr3+ (aq) Kc = 7.2×102
What are the ion concentrations when equilibrium is established?

Slide 15 - 33 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.

Slide 15 - 34 General Chemistry: Chapter 15 Copyright © 2017 Pearson Canada Inc.