6 - Systems at Equilibrium (Keq)

Chapter 14 Section 2 Systems at Equilibrium
The Equilibrium Constant, Keq

Limestone caverns form as rainwater, slightly acidified
by H3O+, dissolves calcium carbonate.
The reverse reaction also takes place, depositing

calcium carbonate and forming stalactites and
stalagmites.

CaCO3 (s ) 2H3O (aq ) Ca2 (aq ) CO2 (g ) 3H2O(l )

When the rates of the forward and reverse reactions

become equal, the reaction reaches chemical
equilibrium.
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The Equilibrium Constant, Keq, continued

There is a mathematical relationship between product
and reactant concentrations at equilibrium.
For limestone reacting with acidified water at 25C:

[Ca2 ][CO2 ]
Keq 1.4 10 -9
[H3O ]2
Keq is the equilibrium constant of the reaction.
Keq for a reaction is unitless, applies only to systems

in equilibrium, and depends on temperature and
must be found experimentally or from tables.


Determining Keq for Reactions at Chemical
Equilibrium
1. Write a balanced chemical equation.
Make sure that the reaction is at equilibrium
before you write a chemical equation.
2. Write an equilibrium expression.
To write the expression, place the product
concentrations in the numerator and the reactant
concentrations in the denominator.


Determining Keq for Reactions at Chemical
Equilibrium, continued
The concentration of any solid or a pure liquid that
takes part in the reaction is left out.
For a reaction occurring in aqueous solution,
water is omitted.
3. Complete the equilibrium expression.

Finally, raise each substances concentration to
the power equal to the substances coefficient
in the balanced chemical equation.

Calculating Keq from Concentrations of

Reactants and Products
Sample Problem A
An aqueous solution of carbonic acid reacts to reach
equilibrium as described below.

H2CO3 (aq ) H2O(l )
HCO3

(aq ) H3 O
(aq )
The solution contains the following solution

concentrations: carbonic acid, 3.3 102 mol/L;
bicarbonate ion, 1.19 104 mol/L; and hydronium ion,
1.19 104 mol/L. Determine the Keq.

Calculating Keq from Concentrations of

Reactants and Products
Sample Problem A Solution
[H2CO3 ] 3.3 10-2 [HCO3 ] [H3O ] 1.19 10-4
For this reaction, the equilibrium constant expression is
[HCO3 ][H3O ]
K eq
[H2CO3 ]
Substitute the concentrations into the expression.
[HCO3 ][H3O ] (1.19 10-4 ) (1.19 10-4 )
Keq 4.3 10 -7
[H2CO3 ] (3.3 10-2 )


Keq Shows If the Reaction Is Favorable
When Keq is large, the numerator of the equilibrium
constant expression is larger than the denominator.
Thus, the concentrations of the products will

usually be greater than those of the reactants.
In other words, when a reaction that has a large Keq

reaches equilibrium, there will be mostly products.
Reactions in which more products form than reactants

form are said to be favorable.


Keq Shows If the Reaction Is Favorable, continued
The synthesis of ammonia is very favorable at 25C
and has a large Keq value.

N2 (g ) 3H2 (g ) 2NH3 (g )

[NH3 ]2
K eq 3.3 10 8
at 25 C
[N2 ][H2 ]3


However, the reaction of oxygen and nitrogen to give
nitrogen monoxide is not favorable at 25C.

N2 (g ) O2 (g )
2NO(g )
[NO2 ]2
K eq 4.5 10 31 at 25 C
[N2 ][O2 ]


When Keq is small, the denominator of the equilibrium
constant expression is larger than the numerator.
The larger denominator shows that the concentrations

of reactants at chemical equilibrium may be greater
than those of products.
A reaction that has larger concentrations of reactants

than concentrations of products is an unfavorable
reaction.


These pie charts show the relative amounts of reactants
and products for three Keq values of a reaction.

Calculating Concentrations of Products

from Keq and Concentrations of Reactants
Sample Problem B
Keq for the equilibrium below is 1.8 105 at a
temperature of 25C. Calculate [NH4 ] when
[NH3] = 6.82 103.

NH3 (aq ) H2O(l )
NH
4 (aq ) OH
(aq )


from Keq and Concentrations of Reactants,
continued
Sample Problem B Solution
The equilibrium expression is
NH4and OH ions are produced in equal numbers, so

[OH ] [NH4 ].
So, the numerator can be written as x2.


continued
Sample Problem B Solution, continued
Keq and [NH3] are known and can be put into the
expression.
[NH4 ][OH ] x2
1.8 10 5 Keq
[NH3 ] 6.82 10-3
x2 = (1.8 105) (6.82 103) = 1.2 107


continued
Sample Problem B Solution, continued
Take the square root of x2.
[NH4 ] 1.2 10-7 3.5 10-4

The Solubility Product Constant, Ksp

The maximum concentration of a salt in an aqueous
solution is called the solubility of the salt in water.
Solubilities can be expressed in moles of solute per
liter of solution (mol/L or M).
For example, the solubility of calcium fluoride in
water is 3.4 104 mol/L.
So, 0.00034 mol of CaF2 will dissolve in 1 L of
water to give a saturated solution.
If you try to dissolve 0.00100 mol of CaF2 in 1 L
of water, 0.00066 mol of CaF2 will remain
undissolved.

The Solubility Product Constant, Ksp, continued
Calcium fluoride is one of a large class of salts that are

said to be slightly soluble in water.
The ions in solution and any solid salt are at

equilibrium.

CaF2 (s )
Ca 2
( aq ) 2F
(aq )
Solids are not a part of equilibrium constant
expressions, so Keq for this reaction is the product
of [Ca2+] and [F]2, which is equal to a constant.

The Solubility Product Constant, Ksp,

continued
Equilibrium constants for the dissolution of slightly
soluble salts are called solubility product
constants, Ksp, and have no units.
The Ksp for calcium fluoride at 25C is 1.6 1010.
Ksp = [Ca2+][F]2 = 1.6 1010
This relationship is true whenever calcium ions and

fluoride ions are in equilibrium with calcium fluoride,
not just when the salt dissolves.

The Solubility Product Constant, Ksp,

continued
For example, if you mix solutions of calcium nitrate
and sodium fluoride, calcium fluoride precipitates.
The net ionic equation for this precipitation is the

reverse of the dissolution.

Ca2 (aq ) 2F (aq ) CaF2 (s )

This equation is the same equilibrium. So, the Ksp for
the dissolution of CaF2 in this system is the same and
is 1.6 1010.



Determining Ksp for Reactions at Chemical Equilibrium
1. Write a balanced chemical equation.

Solubility product is only for salts that have low
solubility. Soluble salts do not have Ksp values.
Make sure that the reaction is at equilibrium.
Equations are always written so that the solid salt
is the reactant and the ions are products.


Determining Ksp for Reactions at Chemical Equilibrium
2. Write a solubility product expression.
Write the product of the ion concentrations.
Concentrations of solids or liquids are omitted.
3. Complete the solubility product expression.

Raise each concentration to a power equal to
the substances coefficient in the balanced
chemical equation.

Calculating Ksp from Solubility

Sample Problem C
Most parts of the oceans are nearly saturated with
CaF2.The mineral fluorite, CaF2, may precipitate when
ocean water evaporates. A saturated solution of CaF2
at 25C has a solubility of 3.4 104 M. Calculate the
solubility product constant for CaF2.

Calculating Ksp from Solubility, continued

Sample Problem C Solution

CaF2 (s )
Ca 2
( aq ) 2F
(aq )
[CaF2] = 3.4 104, [F] = 2[Ca2+]
Ksp = [Ca2+][F]2
Because 3.4 104 mol CaF2 dissolves in each liter of
solution, you know from the balanced equation that
every liter of solution will contain 3.4 104 mol Ca2+
and 6.8 104 mol F. Thus, the Ksp is:
[Ca2+][F]2 = (3.4 104)(6.8 104)2 =

1.6 1010

Calculating Ionic Concentrations Using Ksp,

Sample Problem D
Copper(I) chloride has a solubility product constant of
1.2 106 and dissolves according to the equation
below. Calculate the solubility of this salt in ocean
water in which the [Cl] = 0.55.

CuCl(s )
Cu
(aq ) Cl
(aq )

Calculating Ionic Concentrations Using Ksp,

continued
Sample Problem D Solution
The product of [Cu+][Cl] must equal Ksp = 1.2 106.

[Cl] = 0.55
Ksp = [Cu+][Cl] = 1.2 106
K 1.2 10 6
[Cu ] sp 2.2 106
[Cl ] 0.55
This is the solubility of copper(I) chloride because the
dissolution of 1 mol of CuCl produces 1 mol of Cu+.
Therefore, the solubility of CuCl is 2.2 106 mol/L.


Using Ksp to Make Magnesium
Though slightly soluble hydroxides are not salts, they

have solubility product constants.
Magnesium hydroxide is an example.

Mg(OH)2 (s )
Mg2
( aq ) 2OH
(aq )
[Mg2+][OH]2 = Ksp = 1.8 1011
This equilibrium is the basis for obtaining

magnesium.


Using Ksp to Make Magnesium, continued
The table at right lists

the most abundant ions
in ocean water and
their concentrations.
Mg2+ is the third most

abundant ion in the
ocean.


To get magnesium, calcium hydroxide is added to sea

water, which raises the hydroxide ion concentration to a
large value so that [Mg2+][OH]2 would be greater than
1.8 1011.
Magnesium hydroxide precipitates.
Magnesium hydroxide is treated with hydrochloric acid

to make magnesium chloride, MgCl2.


Finally, magnesium is obtained by the electrolysis of

MgCl2 in the molten state.
One cubic meter of sea water yields 1 kg of

magnesium metal.
Because of magnesiums low density and rigidity,

alloys of magnesium are used when light weight and
strength are needed.


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Chapter 14 Section 2 Systems at Equilibrium

The Equilibrium Constant, Keq

The reverse reaction also takes place, depositing

When the rates of the forward and reverse reactions

Copyright by Holt, Rinehart and Winston. All rights reserved.

The Equilibrium Constant, Keq, continued

For limestone reacting with acidified water at 25C:

Keq for a reaction is unitless, applies only to systems

Copyright by Holt, Rinehart and Winston. All rights reserved.

The Equilibrium Constant, Keq, continued

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Copyright by Holt, Rinehart and Winston. All rights reserved.

The Equilibrium Constant, Keq, continued

3. Complete the equilibrium expression.

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Calculating Keq from Concentrations of

The solution contains the following solution

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Calculating Keq from Concentrations of

[H2CO3 ] (3.3 10-2 )

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The Equilibrium Constant, Keq, continued

Thus, the concentrations of the products will

In other words, when a reaction that has a large Keq

Reactions in which more products form than reactants

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The Equilibrium Constant, Keq, continued

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The Equilibrium Constant, Keq, continued

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The Equilibrium Constant, Keq, continued

The larger denominator shows that the concentrations

A reaction that has larger concentrations of reactants

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The Equilibrium Constant, Keq, continued

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Calculating Concentrations of Products

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Calculating Concentrations of Products

The equilibrium expression is

NH4and OH ions are produced in equal numbers, so

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Calculating Concentrations of Products

x2 = (1.8 105) (6.82 103) = 1.2 107

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Calculating Concentrations of Products

Take the square root of x2.

[NH4 ] 1.2 10-7 3.5 10-4

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The Solubility Product Constant, Ksp

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The Solubility Product Constant, Ksp, continued

Calcium fluoride is one of a large class of salts that are