Ionic Equilibria in Aqueous Systems

Equilibria of Slightly Soluble Ionic Compounds

Any “insoluble” ionic compound is actually slightly soluble in aqueous solution.
We assume that the very small amount of such a compound that dissolves will dissociate
completely.

For a slightly soluble ionic compound in water, equilibrium exists between

solid solute and aqueous ions.

Writing Ion-Product Expressions

Write the ion-product expression at equilibrium for each

compound:
(a) magnesium carbonate (b) iron(II) hydroxide
(c) calcium phosphate (d) silver sulfide

We write an equation for a saturated solution of each compound,

and then write the ion-product expression at equilibrium, Ksp.
(a) MgCO3(s) Mg2+(aq) + CO32–(aq) Ksp = [Mg2+][CO32–]

(b) Fe(OH)2(s) Fe2+(aq) + 2OH–(aq) Ksp = [Fe2+][OH–]2

2+ 3 3– 2
(c) Ca3(PO4)2(s) 3Ca2+(aq) + 2PO43–(aq) Ksp = [Ca ] [PO4 ]

Table 19.2 Solubility-Product Constants (Ksp) of Selected Ionic

Compounds at 25°C

Name, Formula Ksp

Aluminum hydroxide, Al(OH)3 3x10–34
Cobalt(II) carbonate, CoCO3 1.0x10–10
Iron(II) hydroxide, Fe(OH)2 4.1x10–15
Lead(II) fluoride, PbF2 3.6x10–8
Lead(II) sulfate, PbSO4 1.6x10–8
Mercury(I) iodide, Hg2I2 4.7x10–29
Silver sulfide, Ag2S 8x10–48
Zinc iodate, Zn(IO3)2 3.9x10–6
 Determining Solubility from Ksp

Calcium hydroxide (slaked lime) is a major component of mortar,

plaster, and cement, and solutions of Ca(OH)2 are used in industry as a
strong, inexpensive base. Calculate the molar solubility of Ca(OH)2 in
water if the Ksp is 6.5x10–6.

We write the dissolution equation and the expression for Ksp. We know
the value of Ksp, so we set up a reaction table that expresses [Ca2+] and
[OH–] in terms of S, the molar solubility. We then substitute these
expressions into the Ksp expression and solve for S.
SOLUTION:

Ca(OH)2(s) Ca2+(aq) + 2OH–(aq) Ksp = [Ca2+][OH–]2 = 6.5x10–6

Concentration (M) Ca(OH)2(s) Ca2+(aq) + 2OH–(aq)
Initial - 0 0
Change - +S + 2S
Equilibrium - S 2S

Ksp = [Ca2+][OH–]2 = (S)(2S)2 = 4S3 = 6.5x10–6

S= Ksp/4 (6.5x10–6)/4 = 1.2x10–2 M

Table 19.3 Relationship Between Ksp and Solubility at 25°C

The higher the Ksp value, the greater the solubility, as long as we
compare compounds that have the same total number of ions in
their formulas.
 Common Ion Effects on Solubility

The presence of a common ion decreases the solubility of a

slightly soluble ionic compound.

PbCrO4(s) Pb2+(aq) + CrO42-(aq)

Add Na2CrO4 (a very soluble salt; a strong electrolyte)

Result: equilibrium shifts to the left (LeChâtelier’s principle)

 The effect of a common ion on solubility

CrO42- added
PbCrO4(s) Pb2+(aq) + CrO42-(aq) PbCrO4(s) Pb2+(aq) + CrO42-(aq)
 Calculating the Effect of a Common Ion on Solubility

PROBLEM: we have calculated the solubility of Ca(OH)2 in water.

What is its solubility in 0.10 M Ca(NO3)2? Ksp of
Ca(OH)2 is 6.5x10–6.

PLAN: The addition of Ca2+, an ion common to both solutions, should

lower the solubility of Ca(OH)2. We write the equation and Ksp
expression for the dissolution and set up a reaction table in
terms of S, the molar solubility of Ca(OH)2. We make the
assumption that S is small relative to [Ca2+]init because Ksp is low.
We can then solve for S .

SOLUTION:
Ca(OH)2(s) Ca2+(aq) + 2OH–(aq) Ksp = [Ca2+][OH–]2 = 6.5x10–6
[Ca2+]init = 0.10 M because Ca(NO3)2 is a soluble salt, and
dissociates completely in solution.
Concentration (M) Ca(OH)2(s) Ca2+(aq) + 2OH–(aq)
Initial - 0.10 0
Change - +S + 2S
Equilibrium - 0.10 + S 2S

Ksp = [Ca2+][OH–]2 = 6.5x10–6 ≈ (0.10)(2S)2 =

(0.10)(4S2)
6.5x10–6
4S2 ≈ so S ≈ √ (6.5x10-5)/4 = 4.0x10–3 M
0.10
 Ksp and Solubilities

Ksp values are used to determine relative solubilities provided that comparisons
are made between compounds whose formulas contain the same total
number of ions. The compound having the higher Ksp is more soluble.

Predicting the Formation of a Precipitate

For a saturated solution of a slightly soluble ionic salt,

Qsp = Ksp.

When two solutions containing the ions of slightly soluble

salts are mixed:
If Qsp = Ksp,
the solution is saturated and no change will occur.
 If Qsp > Ksp,
a precipitate will form until the remaining solution is saturated.

If Qsp < Ksp,

no precipitate will form because the solution is unsaturated.
 Selective Precipitation

Selective precipitation is used to separate a solution

containing a mixture of ions.

A precipitating ion is added to the solution until the Qsp

of the more soluble compound is almost equal to its Ksp.

The less soluble compound will precipitate in as large a

quantity as possible, leaving behind the ion of the more
soluble compound.
 Selective Precipitation

Selection of an ion in solution by precipitation; achieved by

adding a precipitating agent (ion) to the solution until the
Qsp of the more soluble compound is almost equal to its
Ksp (but Qsp < Ksp). This ion remains in solution, whereas
the other ion(s) having Qsp > Ksp precipitate.

Separating ions by selective precipitation

A solution consists of 0.20 M MgCl2 and 0.10 M CuCl2. Calculate

the [OH-] that would separate the metal ions as their hydroxides.
Ksp of Mg(OH)2 = is 6.3 x 10-10; Ksp of Cu(OH)2 = 2.2 x 10-20.

Both precipitates have the same ion ratio, 1:2, so we can compare
their Ksp values to determine which has the greater solubility.

Cu(OH)2 will precipitate first (it has the smaller Ksp) so we calculate
the [OH-] needed for a saturated solution of Mg(OH)2. This will
ensure that we do not precipitate Mg(OH)2. We can then check how
much Cu2+ remains in solution.
 Mg(OH)2(s) Mg2+(aq) + 2OH-(aq) Ksp = 6.3 x 10-10

Cu(OH)2(s) Cu2+(aq) + 2OH-(aq) Ksp = 2.2 x 10-20

[OH–] = √Ksp/[Mg2+] = √6.3x10-10/0.20 = 5.6x10–5 M

This is the maximum [OH–] that will not precipitate Mg2+ ion.

Calculating the [Cu2+] remaining in solution with this [OH–]

Ksp 2.2x10–20
[Cu2+] = = = 7.0x10–12 M
–
[OH ] 2 (5.6x10–5)2

Since the initial [Cu2+] is 0.10 M, virtually all the Cu2+ ion is
precipitated.
PLAN: Both compounds have 1/2 ratios of cation/anion, so we
can compare their solubilities by comparing their Ksp
values. Mg(OH)2 is 1010 times more soluble than Cu(OH)2,
so Cu(OH)2 will precipitate first. We write the dissolution
equations and Ksp expressions. Using the given cation
concentrations, we solve for the [OH–] that gives a
saturated solution of Mg(OH)2. Then we calculate the
[Cu2+] remaining to see if the separation was successful.
Arrhenius acids and bases
 Acid: Substance that, when dissolved in water, increases the
concentration of hydrogen ions (protons, H+).
 Base: Substance that, when dissolved in water, increases the
concentration of hydroxide ions.
Arrhenius Acids
• Acids that contain one ionizable hydrogen, such as nitric acid (HNO3), are
called monoprotic acids.

• Acids that contain two ionizable hydrogens, such as sulfuric acid (H2SO4),
are called diprotic acids.

• Acids that contain three ionizable hydrogens, such as phosphoric acid

(H3PO4) are called triprotic acids.
Limitations of the Arrhenius definition

The Arrhenius theory is limited in that it can only describe acid-base chemistry in
aqueous solutions. Similar reactions can also occur in non-aqueous solvents,
however, as well as between molecules in the gas phase. As a result, modern
chemists usually prefer the Brønsted-Lowry theory, which is useful in a broader
range of chemical reactions.
The Brønsted-Lowry theory defines an acid as a hydrogen-ion donor,
and a base as a hydrogen-ion acceptor.
• A conjugate acid-base pair are formed from each other by the loss or gain of
a single hydrogen ion.

• A substance that can act as both an acid and a base is said to be amphoteric.
• A Lewis acid is a substance that can accept a pair of electrons to form
a covalent bond.

• A Lewis base is a substance that can donate a pair of electrons to

form a covalent bond.
 Autoionization of Water
As we have seen, water is amphoteric.
• In pure water, a few molecules act as bases and a few act
as acids.

This process is called autoionization.

Ion-Product Constant
• This special equilibrium constant is referred to as the
ion-product constant for water, Kw.
• At 25°C, Kw = 1.0  10-14

• Kw = [H+][OH-] = 1.0 x 10-14

• If [H+] goes up, [OH-] decreases

• Inverse relationship
pH is defined as the negative base-10 logarithm of the hydrogen (hydronium) ion
concentration. pH = –log [H+]
• In pure water,
Kw = [H+] [OH–] = 1.0  10-14
• Because in pure water [H+] = [OH-],
[H3O+] = (1.0  10-14)1/2 = 1.0  10-7

• Therefore, in pure water,

pH = –log [H3O+]
= –log (1.0  10-7) = 7.00
• An acid has a higher [H3O+] than pure water, so its pH is <7
• A base has a lower [H3O+] than pure water, so its pH is >7.
• The “p” in pH tells us to take the negative log of the quantity (in this case,
hydronium ions).
• Some similar examples are
 pOH –log [OH-]

Because,
[H+] [OH−] = Kw = 1.0  10-14,
we know that
–log [H+] + – log [OH−] = 14.00
or, in other words,
pH + pOH = 14.00
 Acid-Base Properties of Salt Solutions

Hydrolysis may be defined as the interactions of ions of the salt with water resulting in
the formation of a weak acid or weak base or both.

Hydrolysis of Salts
• All salts are strong electrolytes – this means that they are fully ionized in
dilute aqueous solution
NaCl(s) Na+(aq) + Cl-(aq)
CH3COONa(s) CH3COO-(aq) + Na+(aq)
NH4Cl(s) NH4+(aq) + Cl-(aq)
• If the salts are formed from either weak acids or bases, then their ions may
react with water (hydrolysis)
– NaCl is the salt of a strong acid and strong base
– CH3COONa is the salt of a weak acid and a strong base
– NH4Cl is the salt of a strong acid and a weak base
• CH3COONa is the salt of a weak acid (acetic acid)
and a strong base (sodium hydroxide).
• The CH3COO- ions will react with water:
CH3COO-(aq) + H2O(aq) = CH3COOH(aq) + OH- (aq)
• The CH3COO- ion is a Bronsted-Lowry base. The
solution will be basic.
Kb = [CH3COOH] x[OH-] = 5.6 x 10-10
[CH3COO-]
• Any anion derived from a weak acid will be a
weak base
• NH4Cl is the salt of a strong acid (hydrochloric acid)
and a weak base (ammonia)
• The NH4+ ions will react with water:
NH4+(aq) + H2O(aq) = NH3(aq) + H3O+ (aq)
• The NH4+ ion is a Bronsted-Lowry acid. The solution
will be acidic.
Ka = [NH3] x[H3O+] = 5.6 x 10-10
[NH4+]
• Any cation derived from a weak base will be a weak
acid
 Anions as Weak Bases
Base Kb pKb
PO43- 2.2 x 10-2 1.66
CO32- 2.1 x 10-4 3.68
HPO42- 1.6 x 10-7 6.80
The larger the value of Kb, the stronger the base
PO43-(aq) + H2O(aq) = HPO42-(aq) + OH- (aq)
• The PO43- ion is a Bronsted-Lowry base. The solution
will be basic.
Kb = [HPO42-] x[OH-] = 2.2 x 10-2
[PO43-]
 Relation between Ka and Kb
• Ammonia in aqueous solution is basic:
NH3(aq) + H2O(aq) = NH4+(aq) + OH-(aq)
Kb = [NH4+] x[OH-] = 1.8 x 10-5
[NH3]
• The ammonium ion is its conjugate acid
• We can write an equation for NH4+ acting as an
acid as:
NH4+(aq) + H2O(aq) = NH3(aq) + H3O+ (aq)
Ka = [NH3] x[H3O+] = 5.6 x 10-10
[NH4+]
• Add the two equations:
H2O(aq) + H2O(aq) = H3O+(aq) + OH-(aq)
• The equilibrium constant of the resulting
equation is the product of the two equilibrium
constants:
Kw = [H3O+] x [OH-] = Ka x Kb
= (5.6 x 10-10) x (1.8 x 10-5)
= 1.0 x 10-14
• This relationship can be used to determine Kb for
a weak acid from a measurement of Ka for its
conjugate acid, and vice versa
 Relative Strengths of Bronsted-
Lowry Acids and Bases
Ka Conjugate Acid Conjugate Base Kb
very large HCl (strong acid) Cl- very small
H3O+ H2O
6.9 x 10- 4 HF F- 1.4 x 10- 11

1.8 x 10- 5 CH3COOH CH3COO - 5.6 x 10-

10

5.6 x 10- 10 NH4+ NH3 1.8x 10- 5

H2O OH-
very small OH- (strong base) O2- very large
Relative Strengths of Acids and Bases
• Bronsted-Lowry acids:
– Strong acids - stronger proton donors than H3O+
– Weak acids - weaker proton donors than H3O+ but stronger
than H2O
– Species that do not form acidic aqueous solutions

• Bronsted-Lowry bases:
– Strong bases - stronger proton acceptors than OH-
– Weak bases - weaker proton acceptors than OH- but
stronger than H2O
– Species that do not form basic aqueous solutions
 Predicting Acid-Base Properties
of Salts
• What will be the effect of the cation on the pH of
water?
• Will the cation act as a weak acid or will it be a
“spectator ion”
– If this is a salt of a weak base, the cation will be a weak acid
– If this is a salt of a strong base, the cation will be a “spectator
ion”
– If the cation is a hydrated metal ion, the solution will be a
weak acid
– If the cation is a group 1 or 2 metal ion, the cation will be a
“spectator ion”
 Predicting Acid-Base Properties
of Salts
• What will be the effect of the anion on the pH of
water?
• Will the anion act as a weak base or will it be a
“spectator ion”
– If this is a salt of a weak acid, the anion will be a weak
base
– If this is a salt of a strong acid, the anion will be a
“spectator ion”
Salts Formed by Reacting a Weak
Acid with a Weak Base
• To determine whether a salt of a weak acid and
weak base will be basic or acidic, it is necessary to
compare the values of Ka and Kb to determine
relative strength
– If Ka > Kb salt will be acidic
– If Ka < Kb salt will be basic
• eg: NH4F
– KaNH4+ = 5.6 x 10-10
– KaF- = 1.4 x 10 -11
– Solution has pH 6.2
Dividing equaion 3 by 2
 Buffer Solution

An acid-base buffer is a solution that lessens the impact of pH from the

addition of small amount of strong acid or strong base.

Buffers function by reducing changes in [H3O+] that result from additions of

acid or base to the solution.

An acid-base buffer usually consists of a conjugate acid-base pair where

both species are present in appreciable quantities in solution.

An acid-base buffer is therefore a solution of a weak acid and its conjugate

base, or a weak base and its conjugate acid.
The effect of adding acid or base to an unbuffered solution.

A 100-mL sample of dilute The addition of 1 mL of strong acid (left) or strong

HCl is adjusted to pH 5.00. base (right) changes the pH by several units.
 The effect of adding acid or base to a buffered solution.

A 100-mL sample of an acetate The addition of 1 mL of strong acid (left) or strong base (right)
buffer is adjusted to pH 5.00. changes the pH very little.

The acetate buffer is made by mixing 1 M CH3COOH ( a weak acid) with 1 M CH3COONa
(which provides the conjugate base, CH3COO-).
 Buffers and the Common-ion Effect
A buffer works through the common-ion effect and based on Lechateliar’s principle

Acetic acid in water dissociates slightly to produce some acetate ion:

CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+(aq)

acetic acid acetate ion

If NaCH3COO is added, it provides a source of CH3COO- ion,

and the equilibrium shifts to the left.

The addition of CH3COO- reduces the % dissociation of the acid.

 Table 19.1 The Effect of Added Acetate Ion on the Dissociation
of Acetic Acid

[CH3COOH]init [CH3COO-]added % Dissociation* [H3O+] pH

0.10 0.00 1.3 1.3x10-3 2.89

0.10 0.050 0.036 3.6x10-5 4.44

0.10 0.10 0.018 1.8x10-5 4.74

0.10 0.15 0.012 1.2x1015 4.92

 How a Buffer Works

The buffer components (HA and A-) are able to consume small amounts of
added OH- or H3O+ by a shift in equilibrium position.

CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+(aq)

The shift in equilibrium position absorbs the change in [H3O+] or [OH-],

and the pH changes only slightly.
 How an acetic acid/acetate buffer works
Buffer has more HA after Buffer has equal concentrations Buffer has more A- after
addition of H3O+. of A- and HA. addition of OH-.

H3O+ OH-

H2O + CH3COOH ← H3O+ + CH3COO- CH3COOH + OH- → CH3COO- + H2O

HA scavenges OH-, A- scavenges H+

 Some Details

CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+(aq)

[CH3COO-][H3O+]
Ka =
[CH3COOH]

[CH3COOH]
[H3O+] = Ka x
[CH3COO-]

Since Ka is constant, [H3O+] depends directly on the ratio

of the concentrations of HA and its conjugate base, A-.
 The Henderson-Hasselbalch Equation

An equation that relates pH, pKa and the ratio of

weak acid to its conjugate base for a buffer solution.

HA + H2O H3O+ + A-

Ka = [H3O+] [A- ] / [HA]

[H3O+] = Ka x [HA ] / [A-]

-log [H3O+] = -log Ka - log ([HA] / [A-])

pH = pKa + log ([A- ] / [HA])

pH = pKa + log ([base] / [acid])

Special case: when [base] = [acid], the pH of the buffer

solution equals the pKa of the weak acid.
 Calculating the effect of added H3O+ and OH- on
buffer pH
PROBLEM: Calculate the pH of the following solutions.
(a) A buffer solution consisting of 0.50 M CH3COOH and 0.50 M CH3COONa
(b) After adding 0.020 mol of solid NaOH to 1.0 L of the buffer solution in part (a)
(c) After adding 0.020 mol of HCl to 1.0 L of the buffer solution in part (a)

Ka of CH3COOH = 1.8 x 10-5

PLAN:

We can calculate [CH3COOH]init and [CH3COO-]init from the given information. From
this we can find the starting pH. For (b) and (c) we assume that the added OH- or
H3O+ reacts completely with the buffer components. We write a balanced equation
in each case, set up a reaction table, and calculate the new [H3O+]. Make
assumptions about the amount of acid dissociating relative to its initial
concentration

___________________________________________________________
SOLUTION: (a)
Concentration (M) CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+(aq)
Initial 0.50 - 0.50 0
Change −x - +x +x
Equilibrium 0.50 - x - 0.50 + x x
Since Ka is small, x is small, so we assume
[CH3COOH] = 0.50 – x ≈ 0.50 M and [CH3COO-] = 0.50 + x ≈ 0.50 M
[CH3COOH]
x = [H3O+] = Ka x ≈ 1.8x10-5 x 0.50 = 1.8x10-5 M
[CH3COO-] 0.50
pH = -log(1.8x10-5) = 4.74
 0.020 mol
(b) [OH−]added = = 0.020 M OH−
1.0 L soln
Setting up a reaction table for the stoichiometry:
Concentration (M) CH3COOH(aq) + OH-(aq) → CH3COO-(aq) + H2O(l)

Initial 0.50 0.020 0.50 -

Change -0.020 -0.020 +0.020 -
Equilibrium 0.48 0 0.52 -

Setting up a reaction table for the acid dissociation, using new initial concentration

Concentration (M) CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+(aq)

Initial 0.48 - 0.52 0
Change −x - +x +x
Equilibrium 0.48 - x - 0.52 + x x
Since Ka is small, x is small, so we assume
[CH3COOH] = 0.48 – x ≈ 0.48 M and [CH3COO-] = 0.52 + x ≈ 0.52 M

[CH3COOH]
x = [H3O+] = Ka x ≈ 1.8x10-5 x 0.48 = 1.7x10-5 M
[CH3COO-] 0.52

pH = -log(1.7x10-5) = 4.77
 0.020 mol
(c) [H3O+]added = = 0.020 M H3O+
1.0 L soln
Setting up a reaction table for the stoichiometry:
Concentration (M) CH3COO-(aq) + H3O+(aq) → CH3COOH(aq) + H2O(l)

Initial 0.50 0.020 0.50 -

Change -0.020 -0.020 +0.020 -

Equilibrium 0.48 0 0.52 -

Setting up a reaction table for the acid dissociation, using new initial concentration

Concentration (M) CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+(aq)

Initial 0.52 - 0.48 0

Change −x - +x +x
Equilibrium 0.52 - x - 0.48 + x x
Since Ka is small, x is small, so we assume
[CH3COOH] = 0.52 – x ≈ 0.52 M and [CH3COO-] = 0.48 + x ≈ 0.48 M

[CH3COOH] 0.52 = 2.0x10-5 M

x = [H3O+] = Ka x ≈ 1.8x10-5 x
[CH3COO-] 0.48

pH = -log(2.0x10-5) = 4.70
 Acid-Base Indicators

An acid-base indicator is a weak organic acid (HIn) whose color

differs from that of its conjugate base (In-).

The ratio [HIn] / [In-] is governed by the [H3O+] of the solution. Indicators can
therefore be used to monitor the pH change during an acid-base reaction.

The color of an indicator changes over a specific, narrow pH range, a

range of about 2 pH units.
Colors and approximate pH range of some common acid-base indicators.

pH
The color change of the indicator bromthymol blue.

pH < 6.0 pH = 6.0-7.5 pH > 7.5

CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+(aq)