Chemistry, The Central Science, 10th edition

Theodore L. Brown; H. Eugene LeMay, Jr.; and

Bruce E. Bursten

Chemical Equilibrium

Equilibrium
 Fast Initial Step

• Because Ratef = Rater ,

Solving for [NOBr2] gives us

Can also write as:

Equilibrium
 The Concept of Equilibrium

Chemical equilibrium occurs when a

reaction and its reverse reaction proceed at Equilibrium
the same rate.
The Concept of Equilibrium
• As a system
approaches equilibrium,
both the forward and
reverse reactions are
occurring.
• At equilibrium, the
forward and reverse
reactions are
proceeding at the same
rate.
Equilibrium
 A System at Equilibrium

Once equilibrium is
achieved, the
amount of each
reactant and product
remains constant.

Equilibrium
 A System at Equilibrium
Rates become equal Concentrations become constant

Equilibrium
 Depicting Equilibrium

In a system at equilibrium, both the

forward and reverse reactions are
running simultaneously. We write the
chemical equation with a double arrow:

Equilibrium
The Equilibrium
Constant

Equilibrium
 The Equilibrium Constant

Forward reaction: Reverse reaction:

Rate law Rate Law

Equilibrium
 The Equilibrium Constant
At equilibrium

Rearranging gives:

Equilibrium
 The Equilibrium Constant
The ratio of the rate constants is a
constant (as long as T is constant).
The expression becomes

Equilibrium
 The Equilibrium Constant
To generalize, the reaction:

Has the equilibrium expression:

This expression is true even if you don’t know the elementary

reaction mechanism. Equilibrium
SAMPLE EXERCISE 15.1 Writing Equilibrium-Constant Expressions

Write the equilibrium expression for Kc for the following reactions:

Equilibrium
SAMPLE EXERCISE 15.1 Writing Equilibrium-Constant Expressions
Write the equilibrium expression for Kc for the following reactions:

Solution
Analyze: We are given three equations and are asked to write an equilibrium-constant expression for each.
Plan: Using the law of mass action, we write each expression as a quotient having the product concentration
terms in the numerator and the reactant concentration terms in the denominator. Each term is raised to the
power of its coefficient in the balanced chemical equation.
Solve:

PRACTICE EXERCISE
Write the equilibrium-constant expression, Kc for

Equilibrium
Equilibrium Can Be Reached from Either
Direction

Kc, the final ratio of [NO2]2 to [N2O4], reaches a

constant no matter what the initial concentrations
of NO2 and N2O4 are (with const T).
Equilibrium
Equilibrium Can Be Reached from
Either Direction
This graph shows data
from the last two trials
from the table.

QuickTime™ and
TIFF (LZW) decompre
e needed to see this
pi

Equilibrium
Equilibrium Can Be Reached from Either
Direction

It does not matter whether we start with N2 and H2 or

whether we start with NH3. We will have the same
proportions of all three substances at equilibrium.
What is the equilibrium expression? Equilibrium
What Does the Value of K Mean?
• If K >> 1, the reaction
is product-favored;
product predominates
at equilibrium.

Equilibrium
What Does the Value of K Mean?
• If K >> 1, the reaction
is product-favored;
product predominates
at equilibrium.

• If K << 1, the reaction is

reactant-favored;
reactant predominates
at equilibrium.
Equilibrium
Manipulating Equilibrium Constants
The equilibrium constant of a reaction in the
reverse reaction is the reciprocal of the
equilibrium constant of the forward reaction.

Equilibrium
Manipulating Equilibrium Constants
The equilibrium constant of a reaction that has been
multiplied by a number is the equilibrium constant
raised to a power that is equal to that number.

Equilibrium
Manipulating Equilibrium Constants
The equilibrium constant for a net reaction made up
of two or more steps can be found from the
equilibrium constants for the individual steps.`
At 1565 K we have these equilibrium constants:

ans=2.9 Equilibrium
 The Equilibrium Constant
Because pressure is proportional to
concentration for gases, the equilibrium
expression can also be written in terms of
partial pressures (instead of concentration):

Mixed versions are also used sometimes:

Equilibrium
Relationship between Kc and Kp
• From the ideal gas law we know that

= Pressure in terms of concentration

Equilibrium
 Relationship between Kc and Kp
Substituting P=[A]RT into the expression for
Kp for each substance, the relationship
between Kc and Kp becomes

Kp = Kc (RT)n
Where:
n = (moles of gaseous product) – (moles of gaseous
reactant)

Hint: ‗products–reactants‘ and ‗products over reactants‘ Equilibrium

is a common theme in chemistry.
Heterogeneou
s
Equilibrium
Equilibrium
The Concentrations of Solids and
Liquids Are Essentially Constant
Concentrations of liquids and solids can be
obtained by dividing the density of the
substance by its molar mass—and both of
these are constants at constant temperature.

Equilibrium
The Concentrations of Solids and
Liquids Are Essentially Constant

Therefore, the concentrations of solids

and liquids do not appear in the
equilibrium expression

PbCl2 (s)
Pb2+ (aq) + 2 Cl−(aq)

Kc = [Pb2+] [Cl−]2
Equilibrium
CaCO3 (s)
CO2 (g) + CaO(s)
As long as some CaCO3 or CaO remain in
the system, the amount of CO2 above the
solid will remain the same.

Equilibrium
 What Are the Equilibrium
Expressions for These Equilibria?

Equilibrium
The real scoop: units of equilibrium constants

Equilibrium constants are really defined in terms

of activity, not concentration.

becomes:

Activity is unitless, so K is unitless.

Equilibrium
Equilibrium

Calculations
Equilibrium
 Equilibrium Calculations
A closed system initially containing
1.000 x 10-3 M H2 and 2.000 x 10-3 M I2
At 448C is allowed to reach equilibrium.
Analysis of the equilibrium mixture shows
that the concentration of HI is 1.87 x 10-3 M.
Calculate Kc at 448C for the reaction:

2 HI (g)
H2 (g) + I2 (g)

Equilibrium
 What Do We Know?
ICE method:

[H2], M [I2], M [HI], M

Initially 1.000 x 10-3 2.000 x 10-3 0

Change

At 1.87 x 10-3
Equilibrium

Equilibrium
 [HI] Increases by 1.87 x 10-3 M

[H2], M [I2], M [HI], M

Initially 1.000 x 10-3 2.000 x 10-3 0

Change +1.87 x 10-3

At 1.87 x 10-3
equilibrium

Equilibrium
 Stoichiometry tells us [H2] and [I2]
decrease by half as much

[H2], M [I2], M [HI], M

Initially 1.000 x 10-3 2.000 x 10-3 0

Change -9.35 x 10-4 -9.35 x 10-4 +1.87 x 10-3

At 1.87 x 10-3
equilibrium

Equilibrium
 We can now calculate the equilibrium
concentrations of all three compounds…

[H2], M [I2], M [HI], M

Initially 1.000 x 10-3 2.000 x 10-3 0

Change -9.35 x 10-4 -9.35 x 10-4 +1.87 x 10-3

At 6.5 x 10-5 1.065 x 10-3 1.87 x 10-3

equilibrium

Equilibrium
…and, therefore, the equilibrium constant

[HI]2
Kc =
[H2] [I2]
(1.87 x 10-3)2
=
(6.5 x 10-5)(1.065 x 10-3)
= 51
Equilibrium
 The Reaction Quotient (Q)

• To calculate Q, one substitutes the

initial concentrations on reactants and
products into the equilibrium
expression.
• Q gives the same ratio the equilibrium
expression gives, but for a system that
is not at equilibrium.
Equilibrium
 If Q = K,
the system is at equilibrium.

Equilibrium
 If Q > K,
there is too much product and the
equilibrium shifts to the left.

Equilibrium
 If Q < K,
there is too much reactant, and the
equilibrium shifts to the right.

Equilibrium
Le Châtelier‘s
Principle
Equilibrium
 Le Châtelier‘s Principle

―If a system at equilibrium is disturbed by

a change in temperature, pressure, or the
concentration of one of the components,
the system will shift its equilibrium
position so as to counteract the effect of
the disturbance.‖

Systems shift from ―Q‖ towards ―K‖.

Equilibrium
What Happens When More of a
Reactant Is Added to a
System?

Equilibrium
 The Haber Process
The transformation of nitrogen and hydrogen into
ammonia (NH3) is of tremendous significance in
agriculture, where ammonia-based fertilizers are of
utmost importance.

Equilibrium
The Haber Process

If H2 is added to the
system, N2 will be
consumed and the
two reagents will
form more NH3.

Equilibrium
The Haber Process

This apparatus
helps push the
equilibrium to the
right by removing
the ammonia (NH3)
from the system
as a liquid.

Equilibrium
The Effect of Changes in Pressure

Equilibrium
 The Effect of Changes in
Temperature
Co(H2O)6 (aq) + 4 Cl(aq)
2+
CoCl4 (aq) + 6 H2O (l)

Equilibrium
The Effect of Changes in
Temperature

Equilibrium
Catalysts increase the rate of both the
forward and reverse reactions.

Equilibrium
 Equilibrium is achieved faster, but the
equilibrium composition remains unaltered.

Equilibrium
Equilibrium