Acid-Base Equilibria

18-1
 Etching with acids

The inside surfaces of these light Acids are used to wash away
bulbs are etched with HF. oxides of silicon and metals during
the production of computer chips.

18-2 Figure 18.1

 The Classical (Arrhenius) Definition of Acids and Bases

An acid is a substance that has H in its formula and dissociates in water

to yield H3O+.

A base is a substance that has OH in its formula and dissociates in water

to yield OH-.

Arrhenius acids contain covalently bonded H atoms

that ionize in water.

Neutralization occurs when the H+ ion from the acid and the OH- ion
from the base combine to form water.

H+(aq) + OH- (aq) H2O(l) ∆Horxn = -55.9 kJ

18-3
 Strong acids dissociate completely into ions in water.

HA(g or l) + H2O(l) H3O+ (aq) + A- (aq) Kc >> 1

Weak acids dissociate very slightly into ions in water.

HA(aq) + H2O(l) H3O+ (aq) + A- (aq) Kc << 1

Defining the acid dissociation constant

[H3O+][A-]
Kc =
[H2O][HA] stronger acid, higher [H3O+],
larger Ka
[H3O+][A-]
Kc[H2O] = Ka = weaker acid, lower [H3O+],
[HA] smaller Ka

18-4
 The extent of dissociation of strong acids

strong acid: HA(g or l) + H2O(l) H3O+(aq) + A-(aq)

Figure 18.3
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

18-5
 The extent of dissociation of weak acids

weak acid: HA(aq) + H2O(l) H3O+(aq) + A-(aq)

Figure 18.3 Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

18-6
 Reaction of zinc with a strong and a weak acid

Zn(s) + 2H3O+(aq) Zn+2(aq)

+ 2H2O(l) + H2(g)

1 M HCl(aq) 1 M CH3COOH(aq)
Figure 18.4

18-7
 Acid strength
decreases down
the table (smaller
Ka values)

18-8
 SAMPLE PROBLEM 18.1 Classifying acid and base strength from the
chemical formula

PROBLEM: Classify each of the following compounds as a strong acid,

weak acid, strong base or weak base.
(a) H2SeO4 (b) (CH3)2CHCOOH (c) KOH (d) (CH3)2CHNH2

PLAN: Pay attention to the text definitions of acids and bases. Look at O for
acids and for the -COOH group; watch for amine groups and cations
in bases.

SOLUTION: (a) strong acid - H2SeO4 - the number of oxygen atoms

exceeds the number of ionizable protons by a factor of 2.
(b) weak acid - (CH3)2CHCOOH is an organic acid having a -COOH group
(a carboxylic acid).
(c) strong base - KOH is a Group 1A hydroxide.

(d) weak base - (CH3)2CHNH2 has a lone pair of electrons on the

nitrogen and is an amine.

18-9
 The auto-ionization of water and the pH scale

H2O(l) H2O(l)

H3O +(aq OH-(aq)

)
18-10
 H2O(l) + H2O(l) H3O+(aq) + OH-(aq)

[H3O+][OH-]
Kc =
[H2O]2

Defining the ion-product constant of water

Kc[H2O]2 = Kw = [H3O+][OH-] = 1.0 x 10-14 at 25 oC

A change in [H3O+] causes an inverse change in [OH-].

In an acidic solution, [H3O+] > [OH-]

In a basic solution, [H3O+] < [OH-]
In a neutral solution, [H3O+] = [OH-]

18-11
 The relationship between [H3O+] and [OH-] and the
relative acidity of solutions

Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

[H3O+] divide into Kw [OH-]

[H3O+] > [OH-] [H3O+] = [OH-] [H3O+] < [OH-]

acidic neutral basic

solution solution solution

Figure 18.5

18-12
 SAMPLE PROBLEM 18.2 Calculating [H3O+] and [OH-] in an aqueous
solution

PROBLEM: A research chemist adds a measured amount of HCl gas to pure

water at 25 oC and obtains a solution with [H3O+] = 3.0 x 10-4 M.
Calculate [OH-]. Is the solution neutral, acidic or basic?

PLAN: Use the Kw at 25 oC and the [H3O+] to find the corresponding [OH-].

SOLUTION: Kw = 1.0 x 10-14 = [H3O+] [OH-]

[OH-] = Kw/ [H3O+] = 1.0 x 10-14/3.0 x 10-4 = 3.3 x 10-11 M

[H3O+] > [OH-]; the solution is acidic.

18-13
 The pH values of
some familiar
aqueous solutions

pH = -log [H3O+]

Related Expressions

pOH = -log [OH-]

pK = -log K

Figure 18.6
18-14
 A low pK corresponds to a high K.

18-15
 Relationships
between
[H3O+], QuickTime™ and a
Photo - JPEG decompressor
pH, [OH-] and are needed to see this picture.

pOH

Figure 18.7

18-16
 SAMPLE PROBLEM 18.3 Calculating [H3O+], pH, [OH-], and pOH

PROBLEM: In a restoration project, a conservator prepares copper-plate etching

solutions by diluting concentrated nitric acid, HNO3, to 2.0 M, 0.30 M,
and 0.0063 M HNO3. Calculate [H3O+], pH, [OH-], and pOH of the
three solutions at 25 oC.

PLAN: HNO3 is a strong acid so [H3O+] = [HNO3]. Use Kw to find the [OH-]
and then convert to pH and pOH.

SOLUTION: For 2.0 M HNO3, [H3O+] = 2.0 M and -log [H3O+] = -0.30 = pH
[OH-] = Kw/ [H3O+] = 1.0 x 10-14/2.0 = 5.0 x 10-15 M; pOH =
14.30
For 0.3 M HNO3, [H3O+] = 0.30 M and -log [H3O+] = 0.52 = pH
[OH-] = Kw/ [H3O+] = 1.0 x 10-14/0.30 = 3.3 x 10-14 M; pOH = 13.48

For 0.0063 M HNO3, [H3O+] = 0.0063 M and -log [H3O+] = 2.20 = pH

[OH-] = Kw/ [H3O+] = 1.0 x 10-14/6.3 x 10-3 = 1.6 x 10-12 M; pOH = 11.80

18-17
 Methods for measuring the pH of an aqueous solution

Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

pH (indicator) paper pH meter

Figure 18.8

18-18
 The Brønsted-Lowry Definition of Acids and Bases

An acid is a proton donor, that is, any species that donates an H+ ion.
All Arrhenius acids are Brønsted-Lowry acids.

A base is a proton acceptor, that is, any species

that accepts an H+ ion.

In the Brønsted-Lowry definition, an acid-base reaction is a proton

transfer process.

18-19
 Proton transfer is the essential feature of a Brønsted-
Lowry acid-base reaction

lone pair
binds H+

+
+

HCl H 2O Cl- H 3 O+
(acid, H+ donor) (base, H+ acceptor)

lone pair
binds H+

+
+

NH3 H 2O NH4+ OH-

(base, H+ acceptor) (acid, H+ donor)
Figure 18.9
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
18-20
 The Conjugate Acid-Base Pair

H2S + NH3 HS- + NH4+

H2S and HS- are a conjugate acid-base pair.

HS- is the conjugate base of the acid H2S.

NH3 and NH4+ are a conjugate acid-base pair.

NH4+ is the conjugate acid of the base NH3.

An acid reactant produces a base product and the two constitute

an acid-base conjugate pair.

Every acid has a conjugate base, and every base has a conjugate acid.

18-21
 The conjugate base of the pair has one fewer H and one more
negative charge than the acid.

The conjugate acid of the pair has one more H and one less
negative charge than the base.

A Bronsted-Lowry acid-base reaction occurs when an acid and a base

react to form their conjugate base and conjugate acid, respectively.

acid1 + base2 base1 + acid2

18-22
 Table 18.4 Conjugate Pairs in Some Acid-Base Reactions

conjugate pair

acid1 + base2 base1 + acid2

conjugate pair

reaction 1 HF + H2O F- + H3O+

reaction 2 HCOOH + CN- HCOO- + HCN

reaction 3 NH4+ + CO32- NH3 + HCO3-

reaction 4 H2PO4- + OH- HPO42- + H2O

reaction 5 H2SO4 + N2H5+ HSO4- + N2H62+

reaction 6 HPO42- + SO32- PO43- + HSO3-

Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

18-23
 SAMPLE PROBLEM 18.4 Identifying conjugate acid-base pairs

PROBLEM: The following reactions are important environmental processes.

Identify the conjugate acid-base pairs.
(a) H2PO4-(aq) + CO32-(aq) HPO42-(aq) + HCO3-(aq)
(b) H2O(l) + SO32-(aq) OH-(aq) + HSO3-(aq)

PLAN: Identify proton donors (acids) and proton acceptors (bases).

conjugate pair1 conjugate pair2

SOLUTION: (a) H2PO4-(aq) + CO32-(aq) HPO42-(aq) + HCO3-(aq)

proton proton proton proton
donor acceptor acceptor donor

conjugate pair1 conjugate pair2

(b) H2O(l) + SO32-(aq) OH-(aq) + HSO3-(aq)

proton proton proton proton
donor acceptor acceptor donor

18-24
 Relative Acid-Base Strength and Reaction Direction

General Rule: An acid-base reaction proceeds to the greater extent

in the direction in which a stronger acid and stronger base form a
weaker acid and a weaker base.

a b b a
H2S + NH3 HS- + NH4+ Kc > 1

A competition for the proton between the two bases!

a b b a
HF + H2O F - + H3 O + Kc < 1

18-25
 Strengths of
conjugate acid-
base pairs

A weaker acid has a stronger

conjugate base.

An acid-base reaction proceeds to

the right if the acid reacts with a
base that is lower on the list because
this combination produces a weaker
conjugate base and a weaker
conjugate acid.

Figure 18.10
18-26
 SAMPLE PROBLEM 18.5 Predicting the net direction of an acid-base
reaction

PROBLEM: Predict the net direction and whether Ka is greater or less than 1
for each of the following reactions (assume equal initial
concentrations of all species):
(a) H2PO4-(aq) + NH3(aq) HPO42-(aq) + NH4+(aq)

(b) H2O(l) + HS-(aq) OH-(aq) + H2S(aq)

PLAN: Identify the conjugate acid-base pairs and then consult Figure 18.10
to determine the relative strength of each. The stronger the species,
the more preponderant will be its conjugate.

SOLUTION: (a) H2PO4-(aq) + NH3(aq) HPO42-(aq) + NH4+(aq)

stronger acid stronger base weaker base weaker acid
Net direction is to the right; Kc > 1.

(b) H2O(l) + HS-(aq) OH-(aq) + H2S(aq)

weaker acid weaker base stronger base stronger acid
Net direction is to the left; Kc < 1.
18-27
 Weak Acid Equilibrium Problems

Two Key Assumptions

[H3O+] from the auto-ionization of water is negligible.

[HA]eq = [HA]init - [HA]dissoc ≈ [HA]init

(because a weak acid has a small Ka)
[HA]dissoc is very small

18-28
 Find the Ka of a weak acid from the pH of its
SAMPLE PROBLEM 18.6
solution

PROBLEM: Phenylacetic acid (C6H5CH2COOH, denoted as HPAc) builds up

in the blood of people afflicted with phenylketonuria, an inherited
genetic disorder that, if left untreated, causes mental retardation
and death. A study of the acid shows that the pH of a 0.12 M
solution of HPAc is 2.60. What is the Ka of phenylacetic acid?

PLAN: Write the dissociation equation. Use pH and solution concentration to

find Ka.

Assumptions: At a pH of 2.60, [H3O+]HPAc >> [H3O+]water

[PAc-]eq ≈ [H3O+]eq, and since HPAc is weak, [HPAc]eq ≈
[HPAc]initial = [HPAc]initial - [HPAc]dissociation
SOLUTION: HPAc(aq) + H2O(l) H3O+(aq) + PAc-(aq)

Ka = [H3O+][PAc-]
[HPAc]

18-29
 SAMPLE PROBLEM 18.6 (continued)

concentration (M) HPAc(aq) + H2O(l) H3O+(aq) + PAc-(aq)

initial 0.12 - 1 x 10-7 0

change -x - +x +x
equilibrium 0.12 - x - x +(<1 x 10-7) x

[H3O+] = 10-pH = 2.5 x 10-3 M, which is >> 10-7 ([H3O+] from water)

x ≈ 2.5 x 10-3 M ≈ [H3O+] ≈ [PAc-] [HPAc]eq = 0.12 - x ≈ 0.12 M

(2.5 x 10-3) (2.5 x 10-3)

Ka = = 5.2 x 10-5
0.12
1 x 10-7 M
[H3O+]water: x100 = 4 x 10-3 %
2.5 x10-3 M
Testing the assumptions: [HPAc]dissn: 2.5 x 10-3 M
x 100 = 2.1 %
0.12 M
(the 5% rule is not violated in either case)
18-30
 SAMPLE PROBLEM 18.7 Determining concentrations from Ka and
initial [HA]

PROBLEM: Propanoic acid (CH3CH2COOH, simplified as HPr) is an organic

acid whose salts are used to retard mold growth in foods. What is
the [H3O+] of a 0.10 M aqueous solution of HPr (Ka = 1.3 x 10-5)?
PLAN: Write the dissociation equation and Ka expression; make
assumptions about concentration that are valid; substitute.

Assumptions: For: HPr(aq) + H2O(l) H3O+(aq) + Pr-(aq)

x = [HPr]diss = [H3O+]from HPr = [Pr-] Ka = [H3O+][Pr-]

SOLUTION: [HPr]

concentration (M) HPr(aq) + H2O(l) H3O+(aq) + Pr-(aq)

initial 0.10 - 0 0
change -x - +x +x
equilibrium 0.10 - x - x x

Since Ka is small, we assume that x << 0.10

18-31
 SAMPLE PROBLEM 18.7 (continued)

[H3O+][Pr-] (x)2
Ka = 1.3 x 10-5 = =
[HPr] 0.10
5 = 1.1 x 10-3 M = [H3O+]
x  (0.10)(1.3x10 )

Checking assumptions:
[HPr]diss: 1.1 x 10-3 M / 0.10 M x 100 = 1.1%

18-32
 As the initial concentration of a weak acid decreases, the
percent dissociation of the acid increases!

[HA]dissociated
percent HA dissociation = x 100
[HA]initial

In the prior problem: for 0.10 M HPr, 1.1% dissociation

for 0.010 M HPr, 3.6% dissociation

Rationale: larger solution volume accommodates more ions

(analogous to pressure effects on gas equilibria when ∆ngas is non-zero)

18-33
 Polyprotic Acids that contain more
acids than one ionizable proton

phosphoric acid, H3PO4

[H3O+] [H2PO4-]
H3PO4(aq) + H2O(l) H2PO4-(aq) + H3O+(aq) Ka1 =
[H3PO4]
= 7.2 x 10-3
[H O +] [HPO 2-]
H2PO4-(aq) + H2O(l) HPO4 2-(aq) +
+ H3O (aq) Ka2 = 3 4
[H2PO4-]
= 6.3 x 10-8
HPO42-(aq) + H2O(l) PO43-(aq) + H3O+(aq) [H3O+] [PO43-]
Ka3 =
[HPO42-]
= 4.2 x 10-13
Ka1 > Ka2 > Ka3

18-34
 Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

18-35
 Why are the Ka values successively smaller as more H+ ions
dissociate from a polyprotic acid like phosphoric acid?

Since successive acid dissociation constants typically differ

by several orders of magnitude, pH calculations for aqueous
solutions of the free acids can be simplified
by neglecting H3O+ generated by subsequent dissociations.

18-36
 SAMPLE PROBLEM 18.8 Calculating equilibrium concentrations for a
polyprotic acid

PROBLEM: Ascorbic acid (H2C6H6O6; abbreviated H2Asc), known as

vitamin C, is a diprotic acid (Ka1 = 1.0 x 10-5 and Ka2 = 5 x 10-12)
found in citrus fruit. Calculate [H2Asc], [HAsc-], [Asc2-], and the
pH of a 0.050 M aqueous solution of H2Asc.
PLAN: Write out expressions for both dissociations and make assumptions.
Ka1 >> Ka2 so the first dissociation produces virtually all of the H3O+.
Ka1 is small, thus [H2Asc]initial ≈ [H2Asc]eq
After finding concentrations of the various species for the first dissociation,
use them as initial concentrations for the second dissociation.

[HAsc-][H3O +]
SOLUTION:
Ka1 =
H2Asc(aq) + H2O(l) HAsc-(aq) + H3O+(aq) [H2Asc]
= 1.0 x 10-5
[Asc2-][H3O +]
HAsc-(aq) + H2O(l) Asc2-(aq) + H3O+(aq) Ka2 =
[HAsc-]
= 5 x 10-12
18-37
 SAMPLE PROBLEM 18.8 (continued)

concentration (M) H2Asc(aq) + H2O(l) HAsc-(aq) + H3O+(aq)

initial 0.050 - 0 0
change -x - +x +x
equilibrium 0.050 - x - x x

Ka1 = [HAsc-][H3O+]/[H2Asc] = 1.0 x 10-5 = (x)(x)/0.050 M

5 x = 7.1 x 10-4 M = [HAsc-] pH = -log(7.1 x 10-4) = 3.15
x  (0.050)(1.0x10 )

concentration (M) HAsc-(aq) + H2O(l) Asc2-(aq) + H3O+(aq)

initial 7.1 x 10-4 - 0 0

change -x - +x +x
equilibrium 7.1 x 10-4 - x - x x

+
x = [(7.1 x 10-4)(5 x 10-12)]0.5 = 6 x 10-8 M = [H3O ]
18-38
 We can ignore the hydronium ion generated by second ionization.

[Asc-2] = (Ka2 x HAsc-)/[H3O+] = 5 x 10-12 M

Also: 7.1 x 10-4/0.050 x 100 = 1.4%

This value is < 5%, thus the assumption made in the analysis of the first
dissociation reaction is justified.

18-39
 Weak Bases: Their Relationship to Weak Acids

B(aq) + H2O(l) BH+(aq) + OH-(aq)

[BH+][OH-]
Kc =
[B][H2O]

Base-dissociation constant, Kb

[BH+][OH-]
Kb =
[B]

pKb decreases with increasing Kb (i.e., increasing base strength)

18-40
 Main Classes of Weak Bases: nitrogen-containing molecules (ammonia
and amines) and anions of weak acids.

Ammonia:

NH3(aq) + H2O(l) NH4+(aq) + OH-(aq) Kb = 1.76 x 10-5 (25 oC)

Amines:
RNH2, R2NH and R3N: all have a lone pair of electrons that
can bind a proton donated by an acid

18-41
 Abstraction of a proton from water by methylamine

lone pair
binds H+

CH3NH2 H2O
methylamine

OH-
CH3NH3+
Figure 18.11
methylammonium ion
18-42 Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
 Base strength
decreases
down
the table
(smaller
Kb values)

18-43
 SAMPLE PROBLEM 18.9 Determining pH from Kb and initial [B]

PROBLEM: Dimethylamine, (CH3)2NH, a key intermediate in detergent

manufacture, has a Kb = 5.9 x 10-4. What is the pH of a 1.5 M
aqueous solution of (CH3)2NH?
PLAN: Perform this calculation as done for acids. Keep in mind that you are
working with Kb and a base.

(CH3)2NH(aq) + H2O(l) (CH3)2NH2+(aq) + OH-(aq)

Assumptions: Kb >> Kw so [OH-]water is negligible

[(CH3)2NH2+] = [OH-] = x [(CH3)2NH]eq≈ [(CH3)2NH]initial

SOLUTION:
concentration (CH3)2NH(aq) + H2O(l) (CH3)2NH2+(aq) + OH-(aq)
initial 1.50 - 0 0
change -x - +x +x
equilibrium 1.50 - x - x x

18-44
 SAMPLE PROBLEM 18.9 (continued)

[(CH3)2NH2+][OH-]
Kb = 5.9 x 10-4 =
[(CH3)2NH]

(x) (x)
5.9 x 10-4 = x = 3.0 x 10-2 M = [OH-]
1.5 M

Check assumption: [3.0 x 10-2 M / 1.5 M] x 100 = 2% (error is

< 5%; thus, assumption is justified)

[H3O+] = Kw/[OH-] = 1.0 x 10-14/3.0 x 10-2 = 3.3 x 10-13 M

pH = -log (3.3 x 10-13) = 12.48

18-45
 Anions of Weak Acids as Weak
Bases
A-(aq) + H2O(l) HA(aq) + OH-(aq)

F-(aq) + H2O(l) HF(aq) + OH-(aq)

Kb = ([HF][OH-]) / [F-]

Rationale for the basicity of A-(aq): e.g., 1 M NaF

Acidity is determined by [OH-] generated from the F- reaction and

[H3O+] generated from the auto-ionization of water; since
[OH-] >> [H3O+], the solution is basic.

For a conjugate acid-base pair:

Ka x Kb = Kw

18-46
 SAMPLE PROBLEM 18.10 Determining the pH of a solution of A-

PROBLEM: Sodium acetate (CH3COONa, abbreviated NaAc) has

applications in photographic development and textile dyeing.
What is the pH of a 0.25 M aqueous solution of NaAc? Ka of
acetic acid (HAc) is 1.8 x 10-5.
PLAN: Sodium salts are soluble in water so [Ac-] = 0.25 M.
Use Ka to find Kb.

SOLUTION:
concentration Ac-(aq) + H2O(l) HAc(aq) + OH-(aq)
initial 0.25 - 0 0
change -x - +x +x
equilibrium 0.25 - x - x x

[HAc][OH-] Kw 1.0 x 10-14

Kb = = Kb = = 5.6 x 10-10
[Ac-] Ka 1.8 x 10-5

18-47
 SAMPLE PROBLEM 18.10 (continued)

[Ac-] = 0.25 M - x ≈ 0.25 M (since Kb is small)

[HAc][OH-]
Kb = 5.6 x 10-10 ≈ x2/0.25 M
[Ac-]

x ≈ 1.2 x 10-5 M = [OH-]

Check assumption: [1.2 x 10-5 M / 0.25 M] x 100 = 4.8 x 10-3 %

[H3O+] = Kw/[OH-] = 1.0 x 10-14/1.2 x 10-5 = 8.3 x 10-10 M

pH = -log (8.3 x 10-10 M) = 9.08

18-48
 Molecular Properties and Acid Strength

Non-metal hydrides: two factors determine acid strength, namely,

the electronegativity of the central non-metal atom E and the strength
of the E-H bond

Non-metal hydride acid strength increases across a period

(E electronegativity effect)

Non-metal hydride acid strength increases down a group

(E-H bond strength effect)

18-49
 The effect of atomic and molecular properties on
non-metal hydride acidity

electronegativity
6A(16) 7A(17) increases, acidity
increases
bond strength decreases,

H 2O HF
acidity increases

H 2S HCl

H2Se HBr

H2Te HI

Figure 18.12

18-50 Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
 The relative strengths of oxoacids

Electronegativity increases, acidity increases

H O I > H O Br > H O Cl
     

H O Cl << H O Cl O
 
 
number of O atoms increases, O
acidity increases

Figure 18.13 Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

18-51
 Acidity of Hydrated Metal Ions

Aqueous solutions of certain metal ions are acidic because the hydrated
metal ion transfers an H+ ion to water.

Generalized Reactions

M(NO3)n(s) + xH2O(l) M(H2O)xn+(aq) + nNO3-(aq)

M(H2O)xn+(aq) + H2O(l) M(H2O)x-1OH(n-1)+(aq) + H3O+(aq)

18-52
 The acidic behavior of the hydrated Al3+ ion

electron density solvent H2O acts

drawn toward Al3+ as base

H 2O H 3 O+

Al(H2O)63+ Al(H2O)5OH2+

Figure 18.14
18-53 Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
 high charge
QuickTime™ and a
Photo - JPEG decompressor
are needed to see this picture.
and small size
enhance acidity

18-54
 Acid-Base Properties of Salt Solutions

A. Salts That Yield Neutral Solutions: the anion of a strong acid and
the cation of a strong base (the ions do not react with water)

The anion of a strong acid is a much weaker base than water (HNO3).
The cation of a strong base only becomes hydrated (NaOH).

HNO3(l) + H2O(l) NO3-(aq) + H3O+(aq)

NaOH(s) Na+(aq) + OH-(aq)

18-55
 B. Salts That Yield Acidic Solutions: (1) the anion of a strong acid
and the cation of a weak base (the cation acts as a weak acid); (2) small,
highly charged metal ions; (3) cations of strong bases and anions of
polyprotic acids with another ionizable proton.

NH4Cl(s) NH4+ (aq) + Cl-(aq)

Case 1
NH4+(aq) + H2O(l) NH3(aq) + H3O+ (aq)

Fe(NO3)3(s) + 6H2O(l) Fe(H2O)63+(aq) + 3NO3-(aq)

Case 2
Fe(H2O)63+(aq) + H2O(l) Fe(H2O)5OH2+(aq) + H3O+(aq)

NaH2PO4(s) Na+(aq) + H2PO4- (aq)

Case 3
H2PO4-(aq) + H2O(l) HPO4 2-(aq) + H3O+(aq)

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 C. Salts That Yield Basic Solutions: the anion of a weak acid and the
cation of a strong base (the anion acts as a weak base)

CH3COONa(s) Na+(aq) + CH3COO-(aq)

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

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18-58
 SAMPLE PROBLEM 18.11 Predicting the relative acidity of salt solutions

PROBLEM: Predict whether aqueous solutions of the following compounds

are acidic, basic, or neutral (write an equation for the reaction of
the appropriate ion with water to explain pH effect).
(a) potassium perchlorate, KClO4 (b) sodium benzoate, C6H5COONa
(c) chromium trichloride, CrCl3 (d) sodium hydrogen sulfate, NaHSO4
PLAN: Consider the acid-base nature of the anions and cations. Strong
acid-strong base combinations produce a neutral solution; strong
acid-weak base, acidic; weak acid-strong base, basic.
SOLUTION: (a) The ions are K+ and ClO4-, which come from a strong base
(KOH) and a strong acid (HClO4). The salt solution will be neutral.
(b) Na+ comes from the strong base NaOH while C6H5COO- is the anion of a
weak organic acid. The salt solution will be basic.
(c) Cr3+ is a small cation with a large + charge, so its hydrated form will react
with water to produce H3O+. Cl- comes from the strong acid HCl. The
salt solution will be acidic.
(d) Na+ comes from a strong base. HSO4- can react with water to form H3O+.
The salt solution will be acidic.

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 Salts of Weakly Acidic Cations and Weakly Basic Anions

Both components react with water!

Acidity is determined by the relative acid strength

and base strength of the separated ions.

example: NH4HS

NH4+(aq) + H2O(l) NH3(aq) + H3O+(aq)

HS-(aq) + H2O(l) H2S(aq) + OH-(aq)

Ka(NH4+) = 5.7 x 10-10 Kb(HS-) = 1 x 10-7

Since Kb > Ka, the solution is basic.

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 SAMPLE PROBLEM 18.12 Predicting the relative acidity of salt solutions
from Ka and Kb of the ions

PROBLEM: Determine whether an aqueous solution of zinc formate,

Zn(HCOO)2, is acidic, basic, or neutral.
PLAN: Both Zn2+ and HCOO- come from weak conjugates. In order to find
the relatively acidity, write the dissociation reactions and use the
information in Tables 18.2 and 18.7.

SOLUTION:
Zn(H2O)62+(aq) + H2O(l) Zn(H2O)5OH+(aq) + H3O+(aq)

HCOO-(aq) + H2O(l) HCOOH(aq) + OH-(aq)

Ka Zn(H2O)62+ = 1 x 10-9

Ka HCOOH = 1.8 x 10-4 ; Kb = Kw/Ka = 1.0 x 10-14/1.8 x 10-4 = 5.6 x 10-11

Ka for Zn(H2O)62+ > Kb HCOO-; the solution is acidic.

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 The Leveling Effect

In water, the strongest acid possible is H3O+ and the

strongest base possible is OH-.

Any acid stronger than H3O+ donates its proton to H2O, and
any base stronger than OH- accepts a proton from H2O; thus,
water exerts a leveling effect (levels the strengths of all strong
acids and bases).

To rank strong acids: must dissolve in a solvent that is a weaker

base than water (i.e., one that accepts their protons less readily).

HCl(g) + CH3COOH(l) Cl-(acet) + CH3COOH2+(acet)

HBr(g) + CH3COOH(l) Br-(acet) + CH3COOH2+(acet)
HI(g) + CH3COOH(l) I-(acet) + CH3COOH2+(acet)

KHI > KHBr > KHCl

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 Three Definitions of Acids and Bases

The Arrhenius Definition

The Brønsted-Lowry Definition

The Lewis Definition

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 The Lewis Acid-Base Definition

An acid is an electron-pair acceptor. A base is an electron-pair donor.

F The adduct
H F
H contains a
B + N new covalent
B N bond.
F HH F
F F HH

acid base adduct

M(H2O)42+(aq)

M2 +
H2O(l) adduct

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 Lewis Acids with Electron-Deficient Atoms

Lewis acids
ROR’ + AlCl3 R-O-R’ contain (or can
adduct
base acid generate) a
AlCl3 vacant orbital.

Lewis Acids with Polar Multiple Bonds

SO2 + H2O H2SO3

acid base adduct

Metal Cations as Lewis Acids

Metal ions act
as Lewis acids
M2+ + 4H2O M(H2O)42+ when dissolved
acid base adduct in water.

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 Figure
18.15

Mg2+ ion as a Lewis acid in the

chlorophyll molecule

The ion accepts electron pairs from

four nitrogen atoms comprising part
of the chlorophyll molecule

Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
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 SAMPLE PROBLEM 18.13 Identifying Lewis acids and bases

PROBLEM: Identify the Lewis acids and Lewis bases in the following reactions:

(a) H+ + OH- H2O

(b) Cl- + BCl3 BCl4-

(c) K+ + 6H2O K(H2O)6+
PLAN: Look for electron pair acceptors (acids) and donors (bases).

SOLUTION: acceptor
(a) H+ + OH- H2O
donor

donor
(b) Cl- + BCl3 BCl4-
acceptor
acceptor

(c) K+ + 6H2O K(H2O)6+

donor

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