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Chapter 10

Acid-Base Equilibria

18-1
Acid-Base Equilibria
10.1 Acids and Bases in Water

10.2 Autoionization of Water and the pH Scale

10.3 Proton Transfer and the Brønsted-Lowry Acid-Base Definition

10.4 Solving Problems Involving Weak-Acid Equilibria

10.5 Weak Bases and Their Relation to Weak Acids

18-2
Table 18.1 Some Common Acids and Bases and their
Household Uses.

18-3
10.1 Acids and Bases in Water

Arrhenius Acid-Base Definition :


This is the earliest acid-base definition, which classifies
these substances in terms of their behavior in water.
An acid is a substance with H in its formula that dissociates
to yield H3O+.
A base is a substance with OH in its formula that
dissociates to yield OH-.
When an acid reacts with a base, they undergo
neutralization:
H+(aq) + OH-(aq) → H2O(l) DH°rxn = -55.9 kJ

18-4
Strong and Weak Acids

A strong acid dissociates completely into ions in water:


HA(g or l) + H2O(l) → H3O+(aq) + A-(aq)

A dilute solution of a strong acid contains no HA molecules.

A weak acid dissociates slightly to form ions in water:


HA(aq) + H2O(l) H3O+(aq) + A-(aq)
In a dilute solution of a weak acid, most HA molecules are
undissociated.
[H3O+][A-]
Kc = has a very small value.
[HA][H2O]

18-5
Figure 18.1A The extent of dissociation for strong acids.

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

There are no HA molecules in solution.

18-6
Figure 18.1B The extent of dissociation for weak acids.

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

Most HA molecules are undissociated.

18-7
The Acid Dissociation Constant, Ka

HA(aq) + H2O(l) H3O+(aq) + A-(aq)

[H3O+][A-] [H3O+][A-]
Kc = Kc[H2O] = Ka =
[HA][H2O] [HA]

The value of Ka is an indication of acid strength.

Stronger acid higher [H3O+] larger Ka

Weaker acid lower % dissociation of HA smaller Ka

18-8
Table 18.2 Ka Values for some Monoprotic Acids at 25°C

18-9
Classifying the Relative Strengths of Acids
• Strong acids include
– the hydrohalic acids (HCl, HBr, and HI) and
– oxoacids in which the number of O atoms exceeds the number
of ionizable protons by two or more (eg., HNO3, H2SO4, HClO4.)
• Weak acids include
– the hydrohalic acid HF,
– acids in which H is not bonded to O or to a halogen (eg., HCN),
– oxoacids in which the number of O atoms equals or exceeds
the number of ionizable protons by one (eg., HClO, HNO2), and
– carboxylic acids, which have the general formula RCOOH (eg.,
CH3COOH and C6H5COOH.)

18-10
Classifying the Relative Strengths of Bases

• Strong bases include


– water-soluble compounds containing O2- or OH- ions.
– The cations are usually those of the most active metals:
• M2O or MOH, where M = Group 1A(1) metal (Li, Na, K, Rb, Cs)
• MO or M(OH)2 where M = group 2A(2) metal (Ca, Sr, Ba).
• Weak bases include
– ammonia (NH3),
– amines, which have the general formula
– The common structural feature is an N atom with a lone
electron pair.

18-11
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) KOH (b) (CH3)2CHCOOH
(c) H2SeO4 (d) (CH3)2CHNH2
PLAN: We examine the formula and classify each acid or base, using
the text descriptions. Particular points to note for acids are the
numbers of O atoms relative to ionizable H atoms and the
presence of the –COOH group. For bases, note the nature of
the cation or the presence of an N atom that has a lone pair.

SOLUTION:
(a) Strong base: KOH is one of the group 1A(1) hydroxides.

18-12
Sample Problem 18.1

(b) Weak acid: (CH3)2CHCOOH is a carboxylic acid, as indicated by


the –COOH group. The –COOH proton is the only ionizable
proton in this compound.

(c) Strong acid: H2SeO4 is an oxoacid in which the number of atoms


exceeds the number of ionizable protons by two.

(d) Weak base: (CH3)2CHNH2 has a lone pair of electrons on the N


and is an amine.

18-13
10.2 Autoionization of Water and the pH Scale

The Ion-Product Constant for Water (Kw)


2H2O (l) H3O+ (aq) + OH- (aq)
[H3O+][OH-]
Kc =
[H2O]2

Kc[H2O]2 = Kw = [H3O+][OH-] = 1.0x10-14 (at 25°C)


In pure water,
[H3O+] = [OH-] = = 1.0x10-7 (at 25°C)

Both ions are present in all aqueous systems.

18-14
A change in [H3O+] causes an inverse change in [OH-],
and vice versa.
Higher [H3O+] lower [OH-]
Higher [OH-] lower [H3O+]

We can define the terms “acidic” and “basic” in terms of


the relative concentrations of H3O+ and OH- ions:

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


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

18-15
Figure 18.3 The relationship between [H3O+] and [OH-] and the
relative acidity of solutions.

18-16
Sample Problem 18.2 Calculating [H3O+] or [OH-] in an Aqueous
Solution
PROBLEM: A research chemist adds a measured amount of HCl gas
to pure water at 25°C and obtains a solution with [H3O+] =
3.0x10-4 M. Calculate [OH-]. Is the solution neutral,
acidic, or basic?

PLAN: We use the known value of Kw at 25°C (1.0x10-14) and the


given [H3O+] to solve for [OH-]. We can then compare [H3O+]
with [OH-] to determine whether the solution is acidic, basic,
or neutral.
SOLUTION:
Kw = 1.0x10-14 = [H3O+] [OH-] so

-
Kw 1.0x10-14
[OH ] = = = 3.3x10-11 M
[H3O+] 3.0x10-4

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

18-17
The pH Scale

pH = -log[H3O+]

The pH of a solution indicates its relative acidity:

In an acidic solution, pH < 7.00


In a neutral solution, pH = 7.00
In basic solution, pH > 7.00

The higher the pH, the lower the [H3O+] and the less
acidic the solution.

18-18
Figure 18.4

The pH values of some


familiar aqueous
solutions.

pH = -log [H3O+]

18-19
Table 18.3 The Relationship between Ka and pKa

Acid Name (Formula) Ka at 25°C pKa


Hydrogen sulfate ion (HSO4-) 1.0x10-2 1.99
Nitrous acid (HNO2) 7.1x10-4 3.15
Acetic acid (CH3COOH) 1.8x10-5 4.75
Hypobromous acid (HBrO) 2.3x10-9 8.64
Phenol (C6H5OH) 1.0x10-10 10.00

pKa = -logKa

A low pKa corresponds to a high Ka.

18-20
pH, pOH, and pKw

Kw = [H3O+][OH-] = 1.0x10-14 at 25°C

pH = -log[H3O+]
pKw = pH + pOH = 14.00 at 25°C
pOH = -log[OH-]

pH + pOH = pKw for any aqueous solution at any temperature.

Since Kw is a constant, the values of pH, pOH, [H3O+],


and [OH-] are interrelated:
• If [H3O+] increases, [OH-] decreases (and vice versa).
• If pH increases, pOH decreases (and vice versa).

18-21
Figure 18.5 The relations among [H3O+], pH, [OH-], and pOH.

18-22
Sample Problem 18.3 Calculating [H3O+], pH, [OH-], and pOH

PROBLEM: In an art restoration project, a conservator prepares


copper-plate etching solutions by diluting concentrated
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°C.

PLAN: HNO3 is a strong acid so it dissociates completely, and [H3O+]


= [HNO3]init. We use the given concentrations and the value
of Kw at 25°C to find [H3O+] and [OH-]. We can then calculate
pH and pOH.
SOLUTION:
Calculating the values for 2.0 M HNO3:
[H3O+] = 2.0 M pH = -log[H3O+] = -log(2.0) = -0.30
Kw 1.0x10-14 -15 M
[OH-] = = = 5.0x10
[H3O+] 2.0
pOH = -log[OH-] = -log(5.0x10-15) = 14.30

18-23
Sample Problem 18.3

Calculating the values for 0.30 M HNO3:


[H3O+] = 0.30 M pH = -log[H3O+] = -log(0.30) = 0.52
Kw 1.0x10-14 -14 M
[OH-] = = = 3.3x10
[H3O+] 0.30
pOH = -log[OH-] = -log(3.3x10-14) = 13.48

Calculating the values for 0.0063 M HNO3:


[H3O+] = 0.0063 M pH = -log[H3O+] = -log(0.30) = 2.20
Kw 1.0x10-14
[OH-] = = = 1.6x10 -12 M
[H3O+] 0.0063
pOH = -log[OH-] = -log(1.6x10-12) = 11.80

18-24
Figure 18.6 Methods for measuring the pH of an aqueous solution.

pH paper

pH meter

18-25
10.3 Brønsted-Lowry Acid-Base Definition

An acid is a proton donor, any species that donates an


H+ ion.
• An acid must contain H in its formula.

A base is a proton acceptor, any species that accepts


an H+ ion.
• A base must contain a lone pair of electrons to bond
to H+.

An acid-base reaction is a proton-transfer process.

18-26
Conjugate Acid-Base Pairs
In the forward reaction:
NH3 accepts a H+ to form NH4+.

H2S + NH3 HS- + NH4+

H2S donates a H+ to form HS-.


In the reverse reaction:
NH4+ donates a H+ to form NH3.

H2S + NH3 HS- + NH4+

HS- accepts a H+ to form H2S.


18-27
Conjugate Acid-Base Pairs

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.
A Brønsted-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

18-28
Table 18.4 The Conjugate Pairs in some Acid-Base Reactions
Conjugate Pair

Acid + Base Base + Acid

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-

18-29
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: To find the conjugate pairs, we find the species that donated
an H+ (acid) and the species that accepted it (base). The acid
donates an H+ to becomes its conjugate base, and the base
accepts an H+ to becomes it conjugate acid.

SOLUTION:

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


acid1 base2 base1 acid2
The conjugate acid-base pairs are H2PO4-/HPO42- and CO32-/HCO3-.

18-30
Sample Problem 18.4

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


acid1 base2 base1 acid2

The conjugate acid-base pairs are H2O/OH- and SO32-/HSO3-.

18-31
Net Direction of Reaction

The net direction of an acid-base reaction depends on


the relative strength of the acids and bases involved.

A reaction will favor the formation of the weaker acid


and base.
H2S + NH3 HS- + NH4+

stronger acid weaker base


stronger base weaker acid

This reaction favors the formation of the products.

18-32
Figure 18.8 Strengths of conjugate acid-base pairs.

The stronger the acid is, the


weaker its conjugate base.
When an acid reacts with a
base that is farther down the
list, the reaction proceeds to
the right (Kc > 1).

18-33
Sample Problem 18.5 Predicting the Net Direction of an Acid-
Base Reaction
PROBLEM: Predict the net direction and whether Kc 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: We identify the conjugate acid-base pairs and consult figure


18.8 to see which acid and base are stronger. The reaction
favors the formation of the weaker acid and base.

SOLUTION:
(a) H2PO4-(aq) + NH3(aq) HPO42-(aq) + NH4+(aq)
stronger acid stronger base weaker base weaker acid

The net direction for this reaction is to the right, so Kc > 1.

18-34
Sample Problem 18.5

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


weaker acid weaker base stronger base stronger acid

The net direction for this reaction is to the left, so Kc < 1.

18-35
10.4 Solving Problems Involving
Weak-Acid Equilibria

Problem-solving approach
1. Write a balanced equation.
2. Write an expression for Ka.
3. Define x as the change in concentration that
occurs during the reaction.
4. Construct a reaction table in terms of x.
5. Make assumptions that simplify the calculation.
6. Substitute values into the Ka expression and
solve for x.
7. Check that the assumptions are justified.

18-36
Solving Problems Involving
Weak-Acid Equilibria

The notation system


• Molar concentrations are indicated by [ ].
• A bracketed formula with no subscript
indicates an equilibrium concentration.

The assumptions
• [H3O+] from the autoionization of H2O
is negligible.
• A weak acid has a small Ka and its
dissociation is negligible. [HA] ≈ [HA]init.

18-37
Sample Problem 18.7 Finding Ka of a Weak Acid from the
Solution pH
PROBLEM: Phenylacetic acid (C6H5CH2COOH, simplified here as
HPAc) builds up in the blood of persons with
phenylketonuria, an inherited disorder that, if untreated,
causes mental retardation and death. A study of the acid
shows that the pH of 0.12 M HPAc is 2.62. What is the Ka
of phenylacetic acid?
PLAN: We start with the balanced dissociation equation and write
the expression for Ka. We assume that [H3O+] from H2 is
negligible and use the given pH to find [H3O+], which equals
[PAc-] and [HPAc]dissoc. We assume that [HPAc] ≈ [HPAc]init
because HPAc is a weak acid.

SOLUTION: HPAc(aq) + H2O(l) H3O+(aq) + PAc-(aq)

Ka = [H3O+][PAc-]
[HPAc]
18-38
Sample Problem 18.7
Concentration (M) HPAc(aq) + H2O(l) H3O+(aq) + PAc-(aq)

Initial 0.12 - 0 0
Change -x - +x +x
Equilibrium 0.12 - x - x x
[H3O+] = 10-pH = 2.4x10-3 M which is >> 10-7 (the [H3O+] from water)

x ≈ 2.4x10-3 M ≈ [H3O+] ≈ [PAc-] [HPAc] = 0.12 - x ≈ 0.12 M


(2.4x10-3) (2.4x10-3)
So Ka = = 4.8x10-5
0.12
Checking the assumptions by finding the percent error in concentration:
+ 1x10-7 M
[H3O ]from H2O = x 100= 4x10-3 % (<5%; assumption is justified).
2.4x10-3 M
-3
[HPAc]dissoc = 2.4x10 M x 100 = 2.0 % (<5%; assumption is justified).
0.12 M

18-39
Sample Problem 18.8 Determining Concentration from Ka and
Initial [HA]
PROBLEM: Propanoic acid (CH3CH2COOH, which we simplify as
HPr) is a carboxylic acid whose salts are used to retard
mold growth in foods. What is the [H3O+] of 0.10 M HPr
(Ka = 1.3x10−5)?

PLAN: We write a balanced equation and the expression for Ka. We


know [HPr]init but not [HPr] (i.e., the concentration at
equilibrium). We define x as [HPr]dissoc and set up a reaction
table. We assume that, since HPr has a small Ka value, it
dissociates very little and therefore [HPr] ≈ [HPr]init.

SOLUTION: HPr(aq) + H2O(l) H3O+(aq) + Pr−(aq)

Ka = [H3O+][Pr−]
[HPr]

18-40
Sample Problem 18.8

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 will assume that x << 0.10 and [HPr] ≈ 0.10 M.
[H3O+][Pr-] x2
Ka = 1.3x10-5 = =
[HPr] 0.10

x= = 1.1x10-3 M = [H3O+]

1.1x10-3 M
Check: [HPr]diss = x 100 = 1.1% (< 5%; assumption is justified.)
0.10 M

18-41
Concentration and Extent of Dissociation
[HA]dissoc
Percent HA dissociated = x 100
[HA]init
As the initial acid concentration decreases, the percent
dissociation of the acid increases.

HA(aq) + H2O(l) H3O+(aq) + A-(aq)

A decrease in [HA]init means a


decrease in [HA]dissoc = [H3O+] = [A-],
causing a shift towards the products.

The fraction of ions present increases, even though the


actual [HA]dissoc decreases.

18-42
Sample Problem 18.9 Using Molecular Scenes to Determine the
Extent of HA Dissociation

PROBLEM: A 0.15 M solution of acid HA (blue and green) is 33%


dissociated. Which scene best represents a sample of the
solution after it is diluted with water?

PLAN: We are given the percent dissociation of the original HA solution


(33%), and we know that the percent dissociation increases as
the acid is diluted. Thus, we calculate the percent dissociation of
each diluted sample and see which is greater than 33%.

18-43
Sample Problem 18.9

SOLUTION:

In each case, remember that each unit of H3O+ is produced from one unit
of HA, so [HA]init = [HA] + [H3O+].
[H3O+] x 100
% dissociation =
[HA] + [H3O+]

Solution 1. % dissociated = 4/(5 + 4) x 100 = 44%


Solution 2. % dissociated = 2/(7 + 2) x 100 = 22%
Solution 3. % dissociated = 3/(6 + 3) x 100 = 33%

Scene 1 represents the diluted solution.

18-44
10.5 Weak Bases and Their
Relation to Weak Acids
A Brønsted-Lowry base is a species that accepts an H+.
For a weak base that dissolves in water:
B(aq) + H2O(l) BH+(aq) + OH-(aq)

The base-dissociation or base-ionization constant is


given by:
[BH+][OH-]
Kb =
[B]

Note that no base actually dissociates in solution, but ions are


produced when the base reacts with H2O.

18-45
Table 18.6 Kb Values for Some Molecular (Amine) Bases at 25°C

18-46
Sample Problem 18.11 Determining pH from Kb and Initial [B]

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


detergent manufacture, has a Kb of 5.9x10-4. What is the
pH of 1.5 M (CH3)2NH?
PLAN: We start with the balanced equation for the reaction of the
amine with H2O, remembering that it is a weak base. We then
write the expression for Kb, set up a reaction table and solve
for [OH-]. From [OH-] we can calculate [H3O+] and pH.
We make similar assumptions to those made for weak acids.
Since Kb >> Kw, the [OH-] from H2O is neglible. Since Kb is
small, we can assume that the amount of amine reacting is
also small, so [(CH3)2NH] ≈ [(CH3)2NH]init.

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


[(CH3)2NH2+][OH-]
Kb =
[(CH3)2NH]

18-47
Sample Problem 18.11

Concentration (M) (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

Since Kb is small, x << 1.50 and 1.50 – x ≈ 1.50


[(CH3)2NH2+][OH-] x 2
Kb = = 5.9x10-4 ≈
[(CH3)2NH] 1.5

x = [OH-] = 3.0x10-2 M

Check assumption:
3.0x10-2 M x 100 = 2.0% (< 5%; assumption is justified).
1.5 M

18-48
Sample Problem 18.11

K 1.0x10 -14
w
[H3O+] = = = 3.3x10-13 M
[OH-] 3.0x10-2

pH = -log (3.3x10-13) = 12.48

18-49
Ka and Kb for a Conjugate Acid-Base Pair

HA + H2O H3O+ + A-
A- + H2O HA + OH-
2H2O H3O+ + OH-

Kc for the overall equation = K1 x K2, so

[H3O+][A-] x [HA][OH-] = [H3O+][OH-]


[HA] [A-]
Ka x Kb = Kw

This relationship is true for any conjugate acid-base pair.

18-50
Sample Problem 18.12 Determining the pH of a Solution of A-

PROBLEM: Sodium acetate (CH3COONa, or NaAc for this problem)


has applications in photographic development and textile
dyeing. What is the pH of 0.25 M NaAc? Ka of acetic
acid (HAc) is 1.8x10-5.

PLAN: Sodium salts are soluble in water and acetate is the anion of
HAc so it acts as a weak base. We write the base dissociation
equation and the expression for Kb, and solve for [OH-]. We
recall that any soluble ionic salt dissociates completely in
solution, so [Ac-]init = 0.25 M.

SOLUTION: Ac-(aq) + H2O(l) HAc(aq) + OH-(aq)

[HAc][OH-]
Kb =
[Ac-]

18-51
Sample Problem 18.12

Concentration (M) Ac-(aq) + H2O(l) HAc(aq) + OH-(aq)


Initial 0.25 - 0 0
Change -x - +x +x
Equilibrium 0.25 - x - x x

Kw 1.0x10-14
Kb = = = 5.6x10 -10 M
Ka 1.8x10-5

[HAc][OH-] x2
Kb = 5.6x10-10 = ≈ so x = [OH-] = 1.2x10-5 M
-
[Ac ] 0.25

Checking the assumption:

1.2x10-5 x 100 = 4.8x10-3% (<5%; assumption is justified)


0.25

18-52
Sample Problem 18.12

K 1.0x10 -14
w
[H3O+] = = = 8.3x10-10 M
[OH-] 1.2x10-5

pH = -log (8.3x10-10) = 9.08

18-53