Chemistry

The Molecular Nature of Matter and Change Eighth

Edition

Martin S. Silberberg and Patricia G. Amateis

©McGraw-Hill Education. All rights reserved. Authorized only for instructor use in the classroom.  No reproduction or further distribution permitted without the prior written consent of McGraw-Hill Education.
 Equilibrium: The Extent of Chemical Reactions
17.1 The Equilibrium State and the Equilibrium
Constant
17.2 The Reaction Quotient and the Equilibrium
Constant
17.3 Expressing Equilibria with Pressure Terms:
Relation Between Kc and Kp
17.4 Comparing Q and K to Determine Reaction
Direction
17.5 How to Solve Equilibrium Problems
17.6 Reaction Conditions and Equilibrium: Le
Châtelier’s Principle

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 The Equilibrium State
All reactions are reversible and under suitable
conditions will reach a state of equilibrium.

At equilibrium, the concentrations of products and

reactants no longer change because the rates of the
forward and reverse reactions are equal.

At equilibrium: rateforward = ratereverse

Chemical equilibrium is a dynamic state because

reactions continue to occur, but because they occur at
the same rate, no net change is observed on the
macroscopic level.

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 Equilibrium concept
 Equilibrium is a state where there is no observable changes

 Only occur in closed system where the rxn is reversible

 Ex:

At one time, evaporation

occurs as fast as
1 Evaporation will happen condensation. Thus the
system is said to be at
2 Condensation happen
“equilibrium”
at the walls
3 Liquid will return to the
source

Rate forward = Rate reverse

H2O (l) ⇌ H2O (g)

Conc. of reactants &
products are constant
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 Reaching Equilibrium on the Macroscopic and Molecular Levels
 

N2O4(g) 2NO2(g).
Figure 17.1Colorless Brown
©McGraw-Hill Education. © McGraw-Hill Education/Stephen Frisch, photographer
 The Equilibrium Constant

If rateforward = ratereverse then

kforward[reactants]m = kreverse[products]n
kforward [products]n
= = K the equilibrium constant
kreverse [reactants]m

Kc expression;

aA + bB ⇌ cC + dD
[C]c[D]d
Kc=
[A]a[B]b

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 K and the Extent of Reaction
K reflects a particular ratio of product concentrations
to reactant concentrations for a reaction.

K therefore indicates the extent of a reaction, i.e., how

far a reaction proceeds toward the products at a given
temperature.

A small value for K indicates that the reaction yields

little product before reaching equilibrium. The reaction
favors the reactants.

A large value for K indicates that the reaction reaches

equilibrium with very little reactant remaining. The
reaction favors the products.

©McGraw-Hill Education.
 Magnitude of Equilibrium constant(K)
 According to equilibrium law, K is expressed in terms of ratio products to
reactants
Kc = [Products]p
K = Products [Reactants]r
Reactants
Kp =(Pproducts)p
(Preactants)r

K is used to measure/know how rxn proceeds toward products.

Magnitude of K can tell us whether a rxn favors the products or reactants

formation at equilibrium.
K is unitless.

©McGraw-Hill Education.
 Magnitude of Equilibrium
constant(K)

<10
<10-3
-3

Small
Small K
K Rxn
Rxn yield
yield little
little product
product
”no
”no rxn”
rxn”

>10
>103
3

Rxn
Rxn yield
yield more
more
Magnitude
Magnitude Large
Large K
K product
product
of
of K
K
”rxn
”rxn goes
goes almost
almost to
to
the
the completion”
completion”

10 <x
10-3< x<10
-3 3
<103
Intermediate
Intermediate K
K Rxn
Rxn yield
yield significance
significance
reactant
reactant & product
& product

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 The Range of Equilibrium Constants

Figure 17.2
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 The Reaction Quotient Q
For the general reaction

the reaction quotient Qc = [D]d[C]c/[A]a[B]b

Q gives the ratio of product concentrations to reactant

concentrations at any point in a reaction.

At equilibrium: Q = K

For a particular system and temperature, the same

equilibrium state is attained regardless of starting
concentrations. The value of Q indicates how close the
reaction is to equilibrium, and in which direction it must
proceed to reach equilibrium.

©McGraw-Hill Education.
The Change in Q During the N2O4-NO2
Reaction

Figure 17.3
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 TYPES OF EQUILIBRIUM

Equilibrium

Homogenous Heterogenous
Equilibrium Equilibrium

- Equilibrium in which all reactants Equilibrium in which reactants &

& products are in the same phase products are in diff phase
- Consider all substances in K - Pure solid & liquid are excluded
expression form K expression

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 Homogenous equilibrium
Write equilibrium constant expression in terms of Kc

N2(g) + 3H2(g)⇌ 2NH3(g)

 CH3OH(l) + CH3COOH(l) ⇌ CH3OCOCH3(l) + H2O(l)

©McGraw-Hill Education.
 K and Q for Heterogeneous Equilibrium
A heterogeneous equilibrium involves reactants and/or
products in different phases.

CaCO3(s) CaO(s) + CO2(g)

A pure solid or liquid always has the same “concentration”,

i.e., the same number of moles per liter of solid or liquid.

The expressions for Q and K include only species whose

concentrations change as the reaction approaches
equilibrium.
 Pure solids and liquids are omitted from the expression for Q or K..

For the above reaction, Q = [CO2]

©McGraw-Hill Education.
 The Reaction Quotient For a Heterogeneous System
Depends Only on Concentrations that Change
CaCO3(s)⇌ CaO(s) + CO2(g)

 Since we only concern

on [ ] that changes as
they approach eq, thus
term of SOLID and
LIQUID are neglected
from K expression
 Kc = [CO2]
Figure 17.4
©McGraw-Hill Education.
 Heterogenous equilibrium
Write equilibrium constant expression in terms of Kc

 AgCl(s) ⇌ Ag+(aq) + Cl- (aq)

Ni(s) + 4CO(g)⇌ Ni(CO)4(s)

©McGraw-Hill Education.
 Sample Problem 17.1 – Problem and Plan
Writing the Reaction Quotient from the Balanced Equation

PROBLEM: Write the reaction quotient, Qc, for each of the

following reactions:

(a) N2O5(g) ⇌ NO2(g) + O2(g)

(b) Na(s) + H2O(l) ⇌ NaOH(aq) + H2(g)

(c) C3H8(g) + O2(g) ⇌ CO2(g) + H2O(g)

PLAN: We balance the equations and then construct the

reaction quotient.
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 Forms of K and Q
 For an overall reaction that is the sum of two more
individual reactions:
 Qoverall = Q1 x Q2 x Q3 x …..

 Koverall = K1 x K2 x K3 x ……

The form of Q and K depend on the direction in which

the balanced equation is written:

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 Forms of K and Q, Cont’d
 If the coefficients of a balanced equation are multiplied
by a common factor:

and K' = Kn

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 Sample Problem 17.2 – Problem
Finding K for Reactions Multiplied by a Common Factor
or Reversed and for an Overall Reaction 

PROBLEM: A chemist wants to find Kc for the following

reaction at 700 K:

2NH3(g) + 2I2(g) ⇌ 6HI(g) + N2(g) Kc= ?

Use the following data at 700 K to find the unknown Kc:

1) N2(g) + 3H2(g) ⇌ 2NH3(g) Kc1= 0.343

2) H2(g) + I2(g) ⇌ 2HI(g) Kc2= 54 

©McGraw-Hill Education.
 Sample Problem 17.2 – Plan
PLAN: We must manipulate reactions (1) and (2) so that
they add together to give the target reaction.  Reaction
(1) must be reversed; the new equilibrium constant (​​) is
the reciprocal of Kc1. Reaction (2) must be multiplied
by 3; the new equilibrium constant (​​) is Kc2 raised to the
third power. We then add the two manipulated
reactions and multiply their Kc values to obtain the
overall Kc.

©McGraw-Hill Education.
 Ways of Expressing Q and Calculating K

©McGraw-Hill Education.
 Variation forms of K
Form of Q/K for a forward and a reverse reaction

2SO2(g) + O2(g) ⇌ 2 SO3(g) Kc= [SO3]2/[SO2]2[O2] = 261

Eg: 2SO3(g) ⇌ 2SO2(g) + O2(g)

Thus the Qc and Kc for a forward reaction is the reciprocal of

the Qc and Kc for a reverse reaction

Qc(fwd) = 1/Qc(rev) and Kc(fwd) = 1/Kc(rev)

=1/261

= 3.83 x 10-3

©McGraw-Hill Education.
 VARIATION FORMS OF K

Rxn with Different Coefficient

 When an equation is multiplied by a factor, that factor will be

raised as “power” for the K
2SO2(g) + O2(g) ⇌ 2 SO3(g) Kc= [SO3]2/[SO2]2[O2] = 261

x 1/2
 Ex: 2SO2(g) + O2(g) ⇌ 2 SO3(g) Kc =261
1/2
Kc
SO2(g) + ½O2(g) ⇌ SO3(g) Kc =?
’

Kc =√261 = 16.2

©McGraw-Hill Education.
 Additional practice:Finding the Equilibrium Constant for an Equation
Multiplied by a Common Factor

PROBLEM: For the ammonia formation reaction N2(g) + 3H2(g) 2NH3(g)

the equilibrium constant, Kc, is 2.4x10-3 at 1000 K. If we change the
coefficients of the equation, which we’ll call the reference (ref) equation, what
are the values of Kc for the following balanced equations?
(a) 1/3N2(g) + H2(g) 2/3NH3(g) (b) NH3(g) 1/2N2(g) + 3/2H2(g)

PLAN: Compare each equation to the reference. Keep in mind that

changing the coefficients will be reflected in a power change in Kc
and a reversal of the equation will show up as an inversion of Kc.
SOLUTION:

(a) The reference equation is multiplied by 1/3, so Kc(ref) will be to the 1/3 power.
Kc = [Kc(ref)]1/3 = (2.4x10-3)1/3 = 0.13

(b) The reference equation is reversed and halved, so Kc(ref) is to the -1/2 power.

Kc = [Kc(ref)]-1/2 = (2.4x10-3)-1/2 = 20.

©McGraw-Hill Education.
 Expressing Equilibria with Pressure Terms Kc and Kp

K for a reaction may be expressed using partial

pressures of gaseous reactants instead of molarity.
 The partial pressure of each gas is directly proportional to its
molarity.
2NO(g) + O2(g) ⇌ 2NO2(g)

Qp= PNO22/ PNO2 .PO2 Qc= [NO2]2/[NO]2[O2]

Kp = Kc (RT)n

If the amount (mol) of gas does not change in the

reaction, ngas = 0 and Kp=Kc

©McGraw-Hill Education.
 RELATIONSHIP BETWEEN KC AND KP
 Generally, Kc is not equal to Kp

 Relationship between Kc and Kp can be derived

using ideal gas law

PV=nRT
P=(n/V)RT
Kp = Kc (RT)n
n (gas
(gas only!!)
only!!)

n=
n= mol
mol of
of gaseous
gaseous product
product –– mol
mol of
of gaseous
gaseous reactant
reactant

If the amount (mol) of gas does not

change in the reaction, Dngas = 0 and Kp =
Kc.

©McGraw-Hill Education.
 Sample Problem 17.3 – Problem and Plan
Converting Between Kc and Kp

PROBLEM: Ammonium hydrosulfide decomposes to

ammonia and hydrogen sulfide gases. Find Kc for the
decomposition reaction:

NH4SH(s) ⇌ NH3(g) + H2S (g) Kp= 0.19 (at 2180C)

PLAN: We know Kp, so to convert between Kp and Kc, we

must first determine Dngas from the balanced equation.
Since pressure is in atmospheres, R = 0.0821
L·atm/mol·K.
©McGraw-Hill Education.
 Determining the Direction of Reaction
The value of Q indicates the direction in which a
reaction must proceed to reach equilibrium.

If Q < K, the reactants must decrease and the products

increase; the reaction proceeds toward the products;
reactants → products until equilibrium is reached.

If Q > K, the reactants must increase and the products

decrease; the reaction proceeds toward the reactants;
reactants ← products until equilibrium is reached.

If Q = K, the system is at equilibrium and no further net

change takes place.

©McGraw-Hill Education.
 Reaction Direction and the Relative Sizes of
Q and K

Figure 17.5
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 Solving Equilibrium Problems
If equilibrium quantities are given, we simply substitute
these into the expression for Kc to calculate its value.

If only some equilibrium quantities are given, we use a

reaction table to calculate them and find Kc.

A reaction table shows

 the balanced equation,
 the initial quantities of reactants and products,
 the changes in these quantities during the reaction, and
 the equilibrium quantities.

©McGraw-Hill Education.
 Using a Reaction Table to Find Equilibrium Quantities
 Example: In a study of carbon oxidation, an evacuated vessel
containing a small amount of powdered graphite is heated to 1080
K. Gaseous CO2 is added to a pressure of 0.458 atm and CO forms.
At equilibrium, the total pressure is 0.757 atm. Calculate Kp.

Pressure
CO2(g) + C(graphite) ⇌ 2CO(g)
(atm)
Initial 0.458 — 0
Change –x — +2x
Equilibrium 0.458 – x —  2x

 The amount of CO2 will decrease and the amount of CO will

increase. If we let the change in CO2 equal -x, then the change in
CO will be +2x.
 Equilibrium amounts are calculated by adding the change to the
initial amount.
©McGraw-Hill Education.
 Using a Reaction Table to Find K
Once we have the equilibrium amounts expressed in terms of x,
we use the other information given in the problem to solve for x.

The total pressure at equilibrium is

PT(eq) = 0.757 atm= PCO2(eq) + PCO(eq)= (0.458atm-x)+ 2x

0.757 atm= 0.458 +x x= 0.757-0.458=0.299 atm

At equilibrium:

PCO2(eq) = 0.458-x=0.458-0.299=0.159 atm

PCO(eq)= 2x=2(0.299)=0.598 atm

Qp= PCO22(eq)/PCO(eq) = 0.5982/0.159= 2.25=Kp

©McGraw-Hill Education.
 Sample Problem 17.6 – Problem and Plan
Calculating Kc from Concentration Data

PROBLEM: In order to study hydrogen halide decomposition, a

researcher fills an evacuated 2.00-L flask with 0.200 mol of HI
gas and allows the reaction to proceed at 453°C.

2HI(g) ⇌ H2(g) + I2(g)

At equilibrium, [HI] = 0.078 M. Calculate Kc.

PLAN: To calculate Kc we need equilibrium concentrations. We

can find the initial [HI] from the amount and the flask volume,
and we are given [HI] at equilibrium. From the balanced
equation, when 2x mol of HI reacts, x mol of H2 and x mol of I2
form. We use this information to set up a reaction table.

©McGraw-Hill Education.
 Sample Problem 17.6 – Solution
SOLUTION: Calculating initial [HI]:[HI]=0.200mol/2.00L

= 0.100M

Concentratio
2HI(g) ↔ H2(g) + I2(g)
n (M)
Initial 0.100 0 0
Change –2x +x +x
0.100 –
Equilibrium x x
2x

[HI] = 0.078 = 0.100-2x; x=0.011 M

Qc= [H2][I2]/[HI]2= (0.011)(0.011)/(0.078)2= 0.020= Kc

©McGraw-Hill Education.
 Sample Problem 17.7 – Problem and Plan
Determining Equilibrium Concentrations from Kc

PROBLEM: In a study of the conversion of methane to

other fuels, a chemical engineer mixes gaseous CH4 and
H2O in a 0.32-L flask at 1200 K. At equilibrium the flask
contains 0.028 mol of CO, 0.084 mol of H2, and 0.045
mol of CH4. What is [H2O] at equilibrium? Kc = 0.26 for
this process at 1200 K.

PLAN: First we write the balanced equation and the

expression for Qc. We calculate the equilibrium
concentrations from the given numbers of moles and the
flask volume. We then use the value of Kc to solve for
[H2O].
©McGraw-Hill Education.
 Sample Problem 17.7 – Solution
SOLUTION: Writing the balanced equation and reaction
quotient:

CH4(g) H2O(g) ⇌ CO(g) + 3H2(g)

Qc= [CO][H2]3/[CH4][H2O]

Determining the equilibrium concentrations:

Similarly, [CO] = 0.088 M and [H2] = 0.26 M

©McGraw-Hill Education.
 Sample Problem 17.7 – Solution, Cont’d
SOLUTION: Calculating [H2O] at equilibrium:

Qc= [CO][H2]3/[CH4][H2O] and [H2O]= [CO][H2]3/[CH4] Kc

=(0.088)(0.26)3/(0.14)(0.26) = 0.042 M

©McGraw-Hill Education.
 Sample Problem 17.8 – Problem and Plan
Determining Equilibrium Concentrations from Initial
Concentrations and Kc

PROBLEM: Fuel engineers use the extent of the change

from CO and H2O to CO2 and H2 to regulate the
proportions of synthetic fuel mixtures. If 0.250 mol of
CO and 0.250 mol of H2O gases are placed in a 125-mL
flask at 900 K, what is the composition of the
equilibrium mixture? At this temperature, Kc is 1.56.

PLAN: We have to find the concentrations of all species

at equilibrium and then substitute into a Kc expression.
First we write a balanced equation, calculate initial
concentrations and set up a reaction table.
©McGraw-Hill Education.
 Sample Problem 17.8 – Solution
 SOLUTION: Writing the balanced equation and reaction quotient:

CO(g) + H2O(g) ⇌ CO2(g) + H2(g) Qc= [CO2][H2]/[CO][H2O]

Calculating initial reactant concentrations:

[CO] = [H2O]=0.250 mol/0.125L= 2.00M

Concentratio
CO(g) + H2O(g) ↔ CO2(g) + H2(g)
n (M)
Initial 2.00 2.00 0 0
Change –x –x +x +x
2.00
Equilibrium 2.00 – x x x
– x

©McGraw-Hill Education.
 Sample Problem 17.8 – Solution, Cont’d
 Substituting into the reaction quotient and solving for x:

At equilibrium, we have:

only the positive root has any chemical meaning, so we

ignore the negative root:

©McGraw-Hill Education.
 Sample Problem 17.8 – Solution, Final
 

©McGraw-Hill Education.
 The Simplifying Assumption
If a reaction has a relatively small K and a relatively
large initial reactant concentration, the concentration
change (x) can often be neglected. 

If the assumption results in a change that is less than 5%

of the initial concentration, the error is not significant,
and the assumption is justified. 
 If [A]i/Kc > 400, the assumption is justified; neglecting x
introduces an error of < 5%
 If [A]i/Kc < 400, the assumption is not justified; neglecting x
introduces an error of > 5%.

©McGraw-Hill Education.
 Sample Problem 17.9 – Problem and Plan
Making a Simplifying Assumption to Calculate Equilibrium Concentrations

 PROBLEM: Phosgene is a potent chemical warfare agent that is now

outlawed by international agreement. It decomposes by the reaction

COCl2(g) ↔ CO(g) + Cl2(g); Kc = 8.3x10–4 at 360°C

Calculate [CO], [Cl2], and [COCl2] when the following amounts of

phosgene decompose and reach equilibrium in a 10.0-L flask.

(a) 5.00 mol COCl2 (b) 0.100 mol COCl 2

 PLAN: We know from the balanced equation that when x mol of COCl2
decomposes, x mol of CO and x mol of Cl2 form. We calculate initial
concentrations, define x, set up a reaction table, and substituted the
values into the expression for Qc. Since Kc is very small, we can assume
that x is negligible, which simplifies the expression. We must check this
assumption when we have solved for x.

©McGraw-Hill Education.
 Sample Problem 17.9 – Solution (a)
 SOLUTION: (a) Calculating initial concentrations:

Concentratio
COCl2(g) ↔ CO(g) + Cl2(g)
n (M)
Initial 0.500 0 0
Change –x +x +x
Equilibrium 0.500 – x x x

©McGraw-Hill Education.
 Sample Problem 17.9 – Solution (a), Cont’d
 Because Kc is small, the reaction does not proceed very
far to the right, so let’s assume that x can be
neglected.

Solving for the equilibrium concentrations:

©McGraw-Hill Education.
 Sample Problem 17.9 – Solution (b)
(b) For 0.100
   mol of COCl2. The calculation in this case is the same
as the calculation in part (a), except that [COCl2]init = 0.100
mol/10.0L = 0.0100 M. Thus, at equilibrium

Making the assumption that 0.0100 M −x ≈ 0.0100 M and solving

for x:

Checking the assumption:

, the assumption is not justified

(from quadratic equation)

©McGraw-Hill Education.
 Sample Problem 17.9 – Solution (b),
Cont’d
Solving for the equilibrium concentrations:

[CO] = [Cl2] = x = 2.5×10−3 M

[COCl2] = 1.00×10−2 M − x = 7.5×10−3 M       

©McGraw-Hill Education.
 Sample Problem 17.10 – Problem and Plan
Predicting Reaction Direction and Calculating Equilibrium
Concentrations
 PROBLEM: The research and development unit of a chemical company
is studying the reaction of CH4 and H2S, two components of natural gas:

H4(g) + 2H2S(g) ↔ CS2(g) + 4H2(g)

In one experiment, 1.00 mol of CH4, 1.00 mol of CS2, 2.00 mol of H2S,
and 2.00 mol of H2 are mixed in a 250-mL vessel at 960°C. At this
temperature, Kc = 0.036.
(a) In which direction will the reaction proceed to reach equilibrium?
(b) If [CH4] = 5.56 M at equilibrium, what are the equilibrium
concentrations of the other substances?
 PLAN: To find the direction of reaction we determine the initial
concentrations from the given amounts and volume, calculate Qc, and
compare it with Kc. Based on this information, we determine the sign of
each concentration change for the reaction table and hence calculate
equilibrium concentrations.
©McGraw-Hill Education.
Sample Problem 17.10 – Solution (a)
SOLUTION:
   (a) Calculating the initial concentrations:

Similarly, [H2S] = 8.00 M, [CS2] = 4.00 M, and [H2] = 8.00 M

Calculating the value of Qc:

Comparing Qc and Kc: Qc > Kc (64.0 > 0.036), so the reaction

proceeds to the left. Therefore, concentrations of reactants
increase (+x) and those of products decrease (–x).

©McGraw-Hill Education.
 Sample Problem 17.10 – Solution (b)
(b)
   Setting up a reaction table, with x = [CS2] that reacts, which
equals [CH4] that forms:
Concentration
CH4(g) + 2H2S(g) ↔ CS2(g) + 4H2(g)
(M)
Initial 4.00 8.00 4.00 8.00
Change +x +2x –x –4x
4.00
Equilibrium 8.00 + 2x 4.00 – x 8.00 – 4x
+ x
Solving for x: At equilibrium [CH4] = 5.56 M = 4.00 M + x  so   x
= 1.56 M

©McGraw-Hill Education.
 Steps in Solving Equilibrium Problems

Figure 17.6
©McGraw-Hill Education.
 Le Châtelier’s Principle
When a chemical system at equilibrium is disturbed, it
re-attains equilibrium by undergoing a net reaction
that reduces the effect of the disturbance.

A system is disturbed when a change in conditions

forces it temporarily out of equilibrium.

The system responds to a disturbance by a shift in the

equilibrium position.
 A shift to the left is a net reaction from product to reactant.
 A shift to the right is a net reaction from reactant to product.

©McGraw-Hill Education.
The Effect of a Change in Concentration
If the concentration of A increases, the system reacts to
consume some of it.
 If a reactant is added, the equilibrium position shifts to the right.
 If a product is added, the equilibrium position shifts to the left.

If the concentration of B decreases, the system reacts to

consume some of it.
 If a reactant is removed, the equilibrium position shifts to the left.
 If a product is removed, the equilibrium position shifts to the right.

Only substances that appear in the expression for Q can

have an effect.
A change in concentration has no effect on the value of
K.

©McGraw-Hill Education.
 The Effect of a Change in Concentration
on a System at Equilibrium

Figure 17.7

©McGraw-Hill Education.
 The Effect of Added Cl2 on the PCl3-Cl2-
PCl5 System
Concentration (M) PCl3(g) + Cl2(g) PCl3(g)
↔

Original 0.200 0.125 0.600

equilibrium

Disturbance +0.075

New initial 0.200 0.200 0.600

Change –x –x +x

New equilibrium 0.200 – x 0.200 – x 0.600 + x

©McGraw-Hill Education.
 When Cl2 (yellow curve) is added, its
concentration increases instantly
(vertical part of yellow curve) and
then falls gradually as it reacts with
PCl3 to form more PCl5. Equilibrium is
re-established at new concentrations
but with the same value of K.

PCl3 + Cl2 ↔ PCl5

Figure 17.8

©McGraw-Hill Education.
 Sample Problem 17.11 – Problem and Plan
Predicting the Effect of a Change in Concentration on the
Equilibrium Position
 PROBLEM: To improve air quality and obtain a useful product,
chemists often remove sulfur from coal and natural gas by treating
the contaminant hydrogen sulfide with O2:
2H2S(g) + O2(g) ↔ 2S(s) + 2H2O(g)
What happens to
(a) [H2O] if O2 is added?
(b) [H2S] if O2 is added?
(c) [O2] if H2S is removed?
(d) [H2S] if sulfur is added?

 PLAN: We write the reaction quotient expression to see how Qc is

affected by each disturbance, relative to Kc. This effect tells us the
direction in which the reaction proceeds for the system to reattain
equilibrium and how each concentration changes.

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 Sample Problem 17.11 - Solution
SOLUTION:
  

(a) When O2 is added, Q decreases and the reaction proceeds to

the right until Qc = Kc again, so [H2O] increases.

(b) When O2 is added, Q decreases and the reaction proceeds to

the right until Qc = Kc again, so [H2S] decreases.

(c) When H2S is removed, Q increases and the reaction proceeds to

the left until Qc = Kc again, so [O2] increases.

(d) The concentration of solid S is unchanged as long as some is

present, so it does not appear in the reaction quotient. Adding
more S has no effect on the equilibrium position, so [H2S] is
unchanged.

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 The Effect of a Change in Pressure (Volume)

Changes in pressure affect equilibrium systems

containing gaseous components.
Changing the concentration of a gaseous component
causes the equilibrium to shift accordingly.
Adding an inert gas has no effect on the equilibrium
position, as long as the volume does not change.
 This is because all concentrations and partial pressures remain
unchanged.
Changing the volume of the reaction vessel will cause
equilibrium to shift if Dngas ≠ 0.
Changes in pressure (volume) have no effect on the
value of K.

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 The Effect of a Change in Pressure (Volume) on a System at
Equilibrium

Figure 17.9
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 Sample Problem 17.12 – Problem and
Plan
Predicting the Effect of a Change in Volume (Pressure) on the
Equilibrium Position
 PROBLEM: How would you change the volume of each of the
following reactions to increase the yield of the products?
(a) CaCO3(s) ↔ CaO(s) + CO2(g)
(b) S(s) + 3F2(g) ↔ SF6(g)
(c) Cl2(g) + I2(g) ↔ 2ICl(g)

 PLAN: Whenever gases are present, a change in volume causes a

change in concentration. For reactions in which the number of
moles of gas changes, a decrease in volume (pressure increase)
causes an equilibrium shift to lower the pressure by producing
fewer moles of gas. A volume increase (pressure decrease) has the
opposite effect.

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 Sample Problem 17.12 - Solution
SOLUTION: (a) CO2 is the only gas present. To increase
its yield, we should increase the volume (decrease
the pressure).

(b) There are more moles of gaseous reactants than

products
(Dngas > 0), so we should decrease the volume
(increase the pressure) to shift the equilibrium to the
right.

(c) The number of moles of gas is the same in both the

reactants and the products (Dngas = 0); therefore a
change in volume will have no effect.

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 The Effect of a Change in Temperature
To determine the effect of a change in temperature on
equilibrium, heat is considered a component of the
system.
 Heat is a product in an exothermic reaction (DH°rxn < 0).

 Heat is a reactant in an endothermic reaction (DH°rxn > 0).

An increase in temperature adds heat, which favors the

endothermic reaction.

A decrease in temperature removes heat, which favors

the exothermic reaction.

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 Sample Problem 17.13 – Problem and Plan
Predicting the Effect of a Change in Temperature on the
Equilibrium Position
 PROBLEM: How does an increase in temperature affect the
equilibrium concentration of the underlined substance and K for
each of the following reactions?
(a) CaO(s) + H2O(l) ↔ Ca(OH)2(aq) DH° = -82 kJ
(b) CaCO3(s) ↔ CaO(s) + CO2(g) DH° = 178 kJ
(c) SO2(g) ↔ S(s) + O2(g) DH° = 297 kJ

 PLAN: We write each equation to show heat as a reactant or

product. The temperature increases when we add heat, so the
system shifts to absorb the heat; that is, the endothermic reaction
is favored. Thus, K will increase if the forward reaction is
endothermic and decrease if it is exothermic.

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 Sample Problem 17.13 - Solution
SOLUTION: (a) CaO(s) + H2O(l) ↔ Ca(OH)2(aq) + heat
An increase in temperature will shift the reaction to
the left, so [Ca(OH)2] and K will decrease.

(b) CaCO3(s) + heat ↔ CaO(s) + CO2(g)

An increase in temperature will shift the reaction to
the right, so [CO2] and K will increase.

(c) SO2(g) + heat ↔ S(s) + O2(g)

An increase in temperature will shift the reaction to
the right, so [SO2] will decrease and K will increase.

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 Temperature and K
The only factor that affects the value of K for a given
equilibrium system is temperature.

 For a reaction with ΔH0rxn >0, an increase in temperature

will cause K to increase.

 For a reaction with ΔH0rxn <0, an increase in temperature

will cause K to decrease.

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 Catalysts and Equilibrium
A catalyst speeds up a reaction by lowering its
activation energy. A catalyst therefore speeds up the
forward and reverse reactions to the same extent.

A catalyst causes a reaction to reach equilibrium more

quickly, but has no effect on the equilibrium position.

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 Effects of Various Disturbances on a System at Equilibrium
Disturbance Effect on Equilibrium Position Effect on Value of K
Concentration
•Increase [reactant] •Toward formation of product None
•Decrease [reactant] •Toward formation of reactant None
•Increase [product] •Toward formation of reactant None
•Decrease [product] •Toward formation of product None
Pressure
•Increase P  (decrease V) •Toward formation of fewer moles of gas None
•Decrease P  (increase V) •Toward formation of more moles of gas None
•Increase P 
(add inert gas, no •None; concentrations unchanged None
change in V)
Temperature
•Increase T •Toward absorption of heat Increases if ​​ΔH°rxn > 0
Decreases if ​​ΔH°rxn < 0
•Decrease T •Toward release of heat Increases if ​​ΔH°rxn < 0
Decreases if ​​ΔH°rxn > 0
•None; forward and reverse rates increase
Catalyst added None
equally, and equilibrium is reached sooner

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