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First page of chapter Acid-Base

Equilibria

1
 PRE-TEST
1. The products of neutralization are
always water and salts.
2. An acid is a proton donor.
3. Strong bases dissociate slightly in water.
4. Weak bases dissociate almost
completely when dissolved in water.

2
• 5. An acid produces H3O+ when dissolved in
water.
• 6. Basic substances have pH below 7.
• 7. Strong acids ionize completely in water.
• 8. Water can act both as an acid and as a base.
• 9. Acids are electron pair acceptors.
• 10. If there are a lot of H+, the pH is very
high.

3
 Arrhenius Acids and Bases
In 1884, Svante Arrhenius
proposed these definitions:
• Acid: A substance that produces
H3O+ ions in aqueous solution.
• Base: A substance that produces OH-
ions in aqueous solution.
• When HCl, for example, dissolves in
water, it reacts with water to give
hydronium ion and chloride ion.
With bases, the situation is slightly different:
• Many bases are metal hydroxides such as NaOH, KOH,
Mg(OH)2, and Ca(OH)2.
• These compounds are ionic solids and when they
dissolve in water, their ions become hydrated and
separate:

• Not all bases initially contain hydroxide ions. Some

bases produce OH- by reacting with water molecules,
here shown for ammonia:
We use curved arrows to show the transfer
of a proton from water to ammonia. The
first arrow shows the formation of an N-H
bond, the second shows breaking of an H-O
bond.
 Brønsted Acids and Bases
• Acid – proton donor
• Base – proton acceptor
• Conjugate base – what remains of the
acid after the donation of a proton
• Conjugate acid – newly formed
protonated species (base)

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Conjugate Acid-Base Pairs

9
10
 Lewis Acids and Bases
• Lewis base as a substance that can donate a
pair of electrons.
• Lewis acid is a substance that can accept a pair
of electrons.
• A Lewis acid-base reaction is one that
involves the donation of a pair of electrons
from one species to another.
• Most general definition of acids and bases

11
A Lewis Acid-Base Reaction

coordinate covalent bond

12
The Acid-Base Properties of Water
• Autoionization of water – water is
amphoteric, can act as an acid or base

or
13
For pure water at 25 oC
 
K w  [H3O ][OH ]
7 7 14
K w  (1 x 10 ) x (1 x 10 )  1 x 10

Relative amounts determine if the solution is

acid, base, or neutral.

• When [H3O+] = [OH], the solution is neutral.

• When [H3O+] > [OH], the solution is acidic.
• When [H3O+] < [OH], the solution is basic.
14
 The pH Scale

pH  log[H ]
or
pH  log[H3O  ]

or
 pH
[H3O ]  10
pH Meter: Laboratory
Measurement of pH
15
Relative amounts determine if the solution is
acid, base, or neutral.

• When pH = 7, the solution is neutral.

• When pH < 7.00, the solution is acidic.
• When pH > 7.00, the solution is basic.

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17
18
 Strong Acids and Bases
• Ionization or dissociation goes to completion – not
considered an equilibrium process
• Concentration of ions in solution is determined by the
stoichiometry of the reaction only
– [H3O+] is equal to starting concentration of the acid
– [OH] is equal to starting concentration of the base
(stoichiometry must be considered)
• Only a few acids and bases are strong

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20
21
1.What is the pH of a solution that has a
hydronium ion concentration of 6.5 x 10 5M?

2. What is the hydronium ion concentration of a

solution with pH 3.65?

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1.
pH  log[H3O  ]
5
pH  log[6.5 x 10 ]

pH  4.19

2. 
[H3O ]  10 pH

 3.65
[H3O ]  10
[H3O  ]  2.2x10 4

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Relations among pH, [OH], pOH, and Kw

pOH  log[OH ]

 pOH
[OH ]  10

K w  [H3O  ][OH ]

pK w  pH  pOH  14.00

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1. What is the pOH of a solution that has a
hydroxide ion concentration of 4.3 x 10 2M?

2. What is the hydroxide ion concentration of a

solution with pOH 8.35?

25
1.
pOH  log[OH ]
2
pOH  log[4.3 x 10 ]

pOH  1.37

2.
[OH ]  4.5x10 9

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 What is the pH of a 0.057 M solution of HBr?

HBr completely ionizes, and the [H3O+] is

equal to the initial concentration of HBr.
HBr (aq) + H2O (l) H3O (aq) + Br (aq)

pH  log[H3O  ]
pH  log[0.057]
pH  1.24
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What is the pOH of a solution of 0.034 M
solution of Ca(OH)2?
Ca(OH)2 completely ionizes, and the [OH] is equal
to twice the initial concentration of Ca(OH)2.
2+
Ca(OH)2 (aq) Ca (aq) + 2OH (aq)

2 mol OH
[OH ]  0.034 M Ca(OH) 2 x
1 mol Ca(OH)2
[OH ]  0.068 M
pOH  log[OH ]
pOH  log[0.068]
pOH  1.17 28
 Practice Problem

What are the concentrations of Hydronium

Ions (H3O+) and Hydroxide (OH-) ions in
0.085 M Ba(OH)2?
Ba(OH)2  Ba+2 + 2OH-
 Practice Problem

What is the pH of the following solution:?

[OH-] = 5.6 x 10-10 M
 Practice Problem

What is the pOH of the following solution:?

[H3O+] = 9.3 x 10-4 M
 Practice Problem

What is [H3O+] in a solution with a pOH of

5.89?
 Weak Acids and Acid Ionization
Constants
• Weak acids ionize only to a limited extent in
water.
• The degree to which a weak acid ionizes
depends on
– the concentration of the acid
– the equilibrium constant for the ionization
called the acid ionization constant, Ka.

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For a generic weak monoprotic acid

[H3O  ][A  ]
Ka 
[HA]

or

[H ][A  ]
Ka 
[HA]

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35
Format for solving problems of weak acids using an
equilibrium table

• Fill in initial concentrations

• Determine concentration changes in terms of x
• Determine equilibrium concentrations in terms of initial
concentrations (Ci) and x
• Substitute into the Ka expression and solve for x
36
 ( x )( x )
Ka 
Ci  x

which produces a quadratic expression of the form:

x  K a x  K aCi  0
2

If the initial concentration and Ka allow, the expression can

be simplified by assuming that x is insignificant when
compared to Ci.
Ci  x  Ci
( x )( x ) x 2
Ka  
Ci Ci
37
Testing the approximation – it is acceptable to
use this shortcut if the calculated value of x is
less than 5 percent of the initial acid
concentration.

x
5%  x100
Ci

38
Calculate the pH at 25°C of a 0.18 M
solution of a weak acid that has
Ka = 9.2 x 106.

39
 0.18 M 0 0

−x +x +x

0.18 M − x x x

6 ( x )( x )
9.2 x 10 
0.18 M  x
Use the approximation since Ka is small compared to Ci.
2
6 x
9.2 x 10 
0.18 M
40
 x2
9.2 x 10 6 
0.18 M
1.3 x 10 3 M  x
Check the approximation:
1.3 x 10 3 M
x100  0.72%
0.18 M
0.72%  5%
Approximation is valid.
3
pH  log(1.3 x 10 M )  2.89

41
 Weak Bases and Base Ionization
Constants
• Weak bases ionize only to a limited extent in
water.
• The degree to which a weak base ionizes
depends on
– the concentration of the base
– the equilibrium constant for the ionization
called the base ionization constant, Kb.

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 For a generic weak base

[HB  ][OH ]
Kb 
[B]

Solving problems involving weak bases requires the same

approach as for weak acids. Solving for x in a typical weak
base problem gives the hydroxide ion concentration rather
than the hydronium ion concentration.

43
44
Determine the Kb of a weak base if a 0.50 M
solution of the base has a pH of 9.59 at
25°C.

45
 pH  pOH  14.00
9.59  pOH  14.00
pOH  4.41

[OH ]  10 pOH
 4.41 5
[OH ]  10  3.89 x 10 M

46
 0.050 M 0M 0M

− 3.89x10-5 M +3.89x10-5 M+3.89x10-5 M

0.050 M* 3.89x10-5 M 3.89x10-5 M

* 0.050 M - (3.89 x 10 -5 M )  0.050 M

[HB  ][OH ]
Kb 
[B]

(3.89x10 5 M )2
Kb   3.0 x 10 9
0.50 M

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What is the Ka of a 0.12 M solution of
Phenylacetic acid (HPAc) with a pH
of 2.62
 Practice Problem
What is the Ka of a 0.12 M solution of Phenylacetic acid (HPAc)
with a pH of 2.62
HPAc(aq) + H2O(l)  [H3O+](aq) + PAc-(aq)
[H3O+]from HPAc + [H3O+]from H2O ≈ [H3O+]from HPAc
pH = - log[H3O+]
[H3O+] = 10-pH = 10-2.62 = 2.4 x 10-3 M
Concentration HPAc(aq) + H2O(l)  H3O+ + PAc-
Initial Ci 0.12 - 0 0
 -X - +X +X
Equilibrium Cf 0.12 - X - X X
Final Cf 0.12 2.4x10-3 2.4x10-3
[H3O+] = x = 2.4 x 10-3 M = [PAc]
HPAc is weak acid  HPAc = 0.12 M – x ≈ 0.12
M
[H 3O + ][PAc- ] (2.4 x 10-3 )(2.4 x 10-3 )
Ka =  = 4.8×10 -5
[HPAc] 0.12
 Practice Problem
What is the [H3O+] of a 0.10 M solution of
Propanoic Acid (HPr)? Ka = 1.3 x 10-5
HPr(aq) + H 2O  H 3O + (aq) + Pr - (Aq)
[H 3O + ][Pr - ]
Ka = = 1.3 x 10-5
[HPr]
HPr is a weak acid = [HPr]init = 0.10 M
Let x = [HPr]diss = [H3O+]from HPr = [Pr-]from HPr
Concentration HPr(aq) + H2O(l)  H3O+ + Pr-
Initial Ci 0.10 - 0 0
 -X - +X +X
Equilibrium Cf 0.10- X - X X
Final Cf 0.10 X X

Assumption: Ka is very small and x is small compared to

[HPr]init  HPr = 0.10 M – x ≈ 0.10 M Con’t
 Practice Problem (con’t)
Substituting into the Ka expression and solving for x
[H 3O + ][Pr - ] (x)(x)
Ka = = 1.3  10 -5 
[HPr] 0.10


x = 0.10  1.3  10-5 
x = 1.1 x 10-3 M = [H 3O+ ] = [Pr - ] = [HPr]diss

Checking the Assumption: [HBr]diss < 5% [HBr]init

[HPr]diss 1.1  10-3 M
For [HPr]diss : = x 100 = 1.1%
[HPr]init 0.10M

1.1% < 5%  Assumption Valid

 Conjugate Acid-Base Pairs
• The conjugate base of a strong acid, is an
example of a weak conjugate base.
• The conjugate base of a weak acid, is an
example of a strong conjugate base.
• Conversely, a strong base has a weak
conjugate acid and a weak base has a strong
conjugate acid.

52
Reciprocal Relationship Between the Strength of an Acid or
Base and the Strength of its Conjugate

Quantitative Relationship Between Ka and Kb

Kb  Ka  K w
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Determine Kb of the benzoate ion (C6H5COO).
5
K a  6.5 x 10

54
 Benzoate ion is the conjugate base of benzoic acid.

C6H5COOH (aq) + H2O (l) H3O (aq) + C6H5COO (aq)

K a  6.5 x 10 5

C6H5COO (aq) + H2O (l) OH (aq) + C6H5COOH (aq)

Kw
Kb 
Ka

1.0 x 10 14 10

Kb   1.5 x 10
6.5 x 10 5
55
 REVIEW
• Determine whether the solution is a
strong acid/base or weak acid/base
• 1. HCl
• 2. NaOH
• 3. Acetic acid
• 4. NH3
• 5. HNO3
• Determine the conjugate acid or conjugate
base:
• 6. HCl (CB)
• 7. HSO4- (CB)
• 8. NH3 (CA)
• 9. HPO4-2 (CB)
• 10. F- (CA)
• Boric acid is frequently used as an
eyewash to treat eye infections. The pH
of a 0.050 M solution of boric acid is
5.28. What is the value of the boric acid
ionization constant, Ka?
• 5.51 × 10–10
• What is the pH of a 0.100 M solution
of acetic acid
• (Ka = 1.8x10-5)?
 Diprotic and Polyprotic Acids
• Diprotic and polyprotic acids undergo successive
ionizations, losing one proton at a time
• The conjugate base in the first ionization is the
acid in the second ionization.
• Each ionization has a Ka associated with it.
• Ionization constants are designated by the step in
the ionization involved.

K a1 , K a2 , etc.
60
 Weak Acid Equilibria
• Polyprotic Acids
– Acids with more than one ionizable proton are polyprotic
acids
– One proton at a time dissociates from the acid molecule
– Each dissociation step has a different Ka
H3PO4(aq) + H2O(l)  H2PO4- + H3O+(aq)
[H 2 PO 4- ][H 3O + ]
K a1 = = 7.2 x 10-3
[H 3 PO 4 ]
H2PO4-(aq) + H2O(l)  HPO4-2 + H3O+(aq)
[HPO 4-2 ][H 3O + ] -8
K a2 = -
= 6.3 x 10
HPO4 -2(aq) +[H PO
H2 O(l)4 ]  PO -3 + H3O+(aq)
2 4

[PO4-3 ][H 3O + ] -13

K a3 = = 4.2 x 10
[HPO 4- ]
K a1 >> K a2 >> K a3
62
Calculate the concentrations of H2C2O4,
HC2O4 , C2O42 and H+ ions in a 0.20 M
oxalic acid solution at 25°C.
K a 1  6.5 x 10 -2

K a2  6.1 x 10 -5

63
• Calculate the following for 0.05 M Ascorbic
Acid (H2Asc):
[H2Asc], [HAsc-], [Asc2-], pH
Ka1 = 1.0 x 10-5 Ka2 = 5 x 10-12
Types of Acids
• Hydrohalic Acids – binary acids formed
between hydrogen and the halogens
– the predominant factor in determining
the strength of the hydrohalic acids is
bond strength

HF << HCl < HBr < HI

65
66
• Oxoacids - contain hydrogen, oxygen, and a
central, nonmetal atom
– contain one or more O H bonds
– an electronegative or a high oxidation state
central atom, will attract electrons, causing
the bond to be more O polar
H
– high electronegativity and oxidation result
in stronger acids

67
To compare oxyacid strengths
• Oxoacids having different central atoms that
are from the same group of the periodic table
and that have the same oxidation number.
– acid strength increases with increasing
electronegativity of the central atom

Example:

68
• Oxoacids having the same central atom but
different numbers of oxygen atoms
– strength increases with increasing oxidation
number of the central atom

Example:

69
• Carboxylic acids – organic acids with the
structure
O
R C O H

– Ionize to produce a carboxylate anion

O O
R C O R C O
– Increasing stability of the carboxylate
anion increases acidity

70
• Stability increases with the number of
electronegative groups in the R group

• CF3COOH > CCl3COOH > CHCl2COOH

> NO2CH2COOH > NC-CH2COOH
Indicate which is the stronger acid:
(a)HBrO3or HBrO4;
(b)H2SeO4 or H2SO4.

72
a) These two acids have the same central atom but differ in
the number of attached oxygen atoms. In a group such as
this, the greater the number of attached oxygen atoms,
the higher the oxidation number of the central atom and
the stronger the acid.
HBrO4 > HBrO3

b) In a group with different central atoms, we must

compare electronegativities. The
electronegativities of the central atoms in this
group decrease as follows:
S>Se.
H2SO4 > H2SeO4
73
The common ion effect is the shift in equilibrium caused by
the addition of a compound having an ion in common with
the dissolved substance.

The presence of a common ion suppresses

the ionization of a weak acid or a weak
base.
Consider mixture of CH3COONa (strong electrolyte) and
CH3COOH (weak acid).
CH3COONa (s) Na+ (aq) + CH3COO- (aq)
common
ion
CH3COOH (aq) H+ (aq) + CH3COO- (aq)
Consider mixture of salt NaA and weak acid HA.

NaA (s) Na+ (aq) + A- (aq)

Ka = [H+][A-]
[HA]
HA (aq) H+ (aq) + A- (aq)

Ka [HA]
[H ] =
+

Henderson-Hasselbalch equation
[A-]
[HA]
-log [H ] = -log Ka - log
+

[A-] [conjugate base]

pH = pKa + log
-log [H+] = -log Ka + log [A-] [acid]
[HA]

pH = pKa + log [A-] pKa = -log Ka

[HA]
 What is the pH of a solution containing 0.30 M
HCOOH and 0.52 M HCOO?
HCOOH pKa = 3.77
Mixture of weak acid and conjugate base!
HCOOH (aq) H+ (aq) + HCOO- (aq)
Initial (M) 0.30 0.00 0.52

Change (M) -x +x +x

Equilibrium (M) 0.30 - x x 0.52 + x

Common ion effect pH = pKa + log [HCOO-]

[HCOOH]
0.30 – x  0.30
[0.52]
0.52 + x  0.52 pH = 3.77 + log = 4.01
[0.30]

HCOOH pKa = 3.77

A buffer solution is a solution of:
1. A weak acid or a weak base and
2. The salt of the weak acid or weak base
Both must be present!

A buffer solution has the ability to resist changes in pH upon the

addition of small amounts of either acid or base.

Consider an equal molar mixture of CH3COOH and CH3COONa

Add strong acid

H+ (aq) + CH3COO- (aq) CH3COOH (aq)

Add strong base

OH- (aq) + CH3COOH (aq) CH3COO- (aq) + H2O (l)
 EXAMPLES
• Acetic acid/sodium acetate
• Ammonium chloride/ammonia
• Bicarbonate/carbon dioxide (carbonic
acid)
• dihydrogen phosphate/biphosphate
• Citric acid/citrate
 Solubility Equilibria

AgCl (s) Ag+ (aq) + Cl- (aq)

Ksp = [Ag+][Cl-] Ksp is the solubility product constant

MgF2 (s) Mg2+ (aq) + 2F- (aq) Ksp = [Mg2+][F-]2

Ag2CO3 (s) 2Ag+ (aq) + CO32- (aq) Ksp = [Ag+]2[CO32-]

Ca3(PO4)2 (s) 3Ca2+ (aq) + 2PO43- (aq) Ksp = [Ca2+]3[PO43-]2

Dissolution of an ionic solid in aqueous solution:

Q < Ksp Unsaturated solution No precipitate

Q = Ksp Saturated solution

Q > Ksp Supersaturated solution Precipitate will form

Molar solubility (mol/L) is the number of moles of solute dissolved
in 1 L of a saturated solution.

Solubility (g/L) is the number of grams of solute dissolved in 1 L of

a saturated solution.
 What is the solubility of silver chloride in g/L ?

- Ksp = 1.6 x 10-10

AgCl (s) Ag (aq) + Cl (aq)
+

Initial (M) 0.00 0.00

Ksp = [Ag+][Cl-]
Change (M) +s +s Ksp = s2

Equilibrium (M) s s 
s = Ksp

s = 1.3 x 10-5
[Ag+] = 1.3 x 10-5 M [Cl-] = 1.3 x 10-5 M

1.3 x 10-5 mol AgCl 143 g AgCl

Solubility of AgCl = x = 1.86 x 10-3 g/L
1 L soln 1 mol AgCl
Calculate the solubility of silver phosphate
in water. MM = 419g/mol
Ksp = 1.8 × 10–18
• Calculate the solubility of copper (II)
hydroxide. MM = 98 g/mol
• Ksp = 2.2 × 10–20
• Estimate the molar solubility of
La(IO3)3 and calculate the concentration
of iodate in equilibrium with solid
lanthanum iodate, for which Ks = 6.2 ×
10–12.
• X = 6.92 × 10–4 M
• [IO3–] = 2.08 × 10–3 (M)
• Calculate the molar solubility of PbCl2 at 25
oC in 0.100 M solution of KCl.

PbCl2(s) <--> Pb2+(aq) + 2Cl-(aq)

Ksp = 1.6 x 10-5

87
• Calculate the solubility of strontium
sulfate (Ks = 2.8 × 10–7) in (a) pure water
and (b) in a 0.10 M solution of Na2SO4.
• Estimate the solubility of barium sulfate
in a 0.020 M sodium sulfate solution. The
solubility product constant for barium
sulfate is 1.1 x 10-10.
• x = 5.5 x 10-9 M
• The Ksp of AgBr is 5.4 x 10¯13 at 25 °C.
Calculate the molar solubility of AgBr in
0.050 M AgNO3(aq) at 25 °C.
• s = 1.08 x 10¯11 M