Chapter 8

Chemical equilibrium:
equilibria in solution

Proton transfer equilibria

In this chapter we examine some consequences of
8.1 Brønsted–Lowry theory dynamic chemical equilibria. We concentrate on
the equilibria that exist in solutions of acids, bases,
8.2 Protonation and deprotonation
and their salts in water, where rapid proton
8.3 Polyprotic acids transfer between species ensures that equilibrium is
8.4 Amphiprotic systems maintained at all times. The link between Chapter 7
and the dis- cussion here is that, provided the
Salts in water temperature is held constant, an equilibrium
constant retains its value even though the individual
8.5 Acid–base titrations activities may change. So, if one substance is added
8.6 Buffer action to a mixture at equilibrium, the other substances
adjust their abundances to re- store the value of K.
Box 8.1 Buffer action in blood

8.7 Indicators
Proton transfer equilibria
Solubility equilibria

8.8 The solubility constant

The reaction of acids and bases are central to
chem- istry and its applications, such as chemical
8.9 The common-ion effect analysis and synthesis. One particularly important
8.10 The effect of added salts on applica- tion of proton transfer equilibrium is in
solubility living cells, for even small drifts in the equilibrium
concentration of hydrogen ions can result in
CHECKLIST OF KEY IDEAS disease, cell damage, and death. Throughout this
TABLE OF KEY EQUATIONS chapter, keep in mind that a free hydrogen ion
QUESTIONS AND EXERCISES (H, a proton) does not exist in water: it is always
attached to a water molecule and exists as H 3O, a
hydronium ion.

8.1 Brønsted–Lowry theory

According to the Brønsted–Lowry theory of acids
and bases, an acid is a proton donor and a base is a
proton acceptor. The proton, which in this context
means a hydrogen ion, H, is highly mobile and
acids and bases in water are always in equilibrium
with their deprotonated and protonated counterparts
and hydronium ions (H3O). Thus, an acid HA,
such as HCN, immediately establishes the
equilibrium
 PROTON TRANSFER EQUILIBRIA 173

HA(aq)  H2O(l) f H3O(aq)  8.2 Protonation and deprotonation

A(aq) All the solutions we consider are so dilute that we
aH O aA
  (8.1a)
can regard the water present as being a nearly pure
K a 3 a liquid
HA H O 2

A base B2 (such as and therefore as

NH3) immediately having unit activity
establishes the (see Table 6.2).
equilibrium When we set aH O  1
for all the solutions
we con-

B(aq)  sider, the resulting equilibrium

H2O(l) f K constant is called the
aBH acidity constant, Ka, of the acid
BH(aq)  

HA:
OH(aq) aOH 

a
B
a
H

O
)([A ]/c )
2
a  a ([
H 
O
]/
c
(8.1b) H 3O A (8.4a)
K3

In these equilibria, a
([HA]/c )
A is the conjugate
base of the a
H
A

acid HA and BH is This rather
the conjugate acid of cumbersome
the base B. Even in expression is
the absence of normally written
added acids and [H3O ][A ]
bases, proton
transfer occurs
between water
molecules and the
auto-
pro K (8
toly a a [H .4
sis
equ 
ilib O
a A] b
)
riu
m H
2 H2O(l)
K with ‘[ J]’
2 f 3
interpreted as [
a
H3O(aq) H
J]/c (that is, as
O
 (8.2) the numer- ical

OH (aq) value of the molar
concentration of
J with the units
mol dm3 struck
out). Acidity
constants are
is always present. chemistry, the
Autoprotolysis is hydronium ion
also called concentration is
autoionization. commonly expressed in
As will be familiar terms of the pH, which
from introductory is defined formally as
 174 CHAPTER 8: CHEMICAL EQUILIBRIUM: EQUILIBRIA IN SOLUTION
a r
pH  log also 2.0 Howev ln 10  2.303. equilibrium in
aH O 3
called mmoler, ............................. aqueous solution.
acid dm should Therefore, manipulations of The smaller the
where the (where
ionization neverpKa value of Ka, and
logarithm is 1 mmol
constants  be and related therefore the
to base 10.
and, less mol), forgott
quantities are larger the value of
In
appro- then en actually pK , the lower is
elementary a
priately the manipulations the concentration
work, the pH
(because replace
of standard of deprotonated
hydronium 
deproton mentreaction Gibbs molecules. In
ion activity 
ation is of energies in short, the higher
is replaced 2.70
not a activiti
disguise. the value of pKa,
by the If the
simple es the weaker the
numer- ical molarmolar
frag- Self-test 8.2
value of its concen
mentatio concen Show that pK a  D rG -/(RT ln 10). Hint: ln x  ln 10  log x.
molar tration
n into tration
concentratio were
atoms), is
n, [H3O], ten acid. Most acids
which is
dissociati timesinvaria have Ka  1 (and
on bly
less, at The value of
the acidity usually much less
constants. 0.20 hazard
than 1), with pKa
Data are mmolous. constant
 0, indicating
widely dm Becaus indicates the
only a small
reported then e extent to which
extent of
in terms the interac proton transfer
deprotona-
of the wouldt occurs at
negative be long t
common
by more than 0.4 from its normal value 3.70.ofdistanc
of 7.4. What is the approximate range molar concentrations of hydro- gen ions for which life can be sustained? i
logarithm Notice es, o
of this that replace n
quantity: the ment
pKa  log Ka higheris i
the pH,unre- n
It follows the liable
from eqn lower for w
7.8 (ΔrG the but a
 RT ln concentmost t
K) that rationdilute e
pK a is solutio r
of
proportio ns .
hydroni
nal to (less
um ions
ΔrG for than T
in the
the about h
solution
proton and 10 e
transfer that mol a s
reac- tion. change dm e
More in pH
explicitly, by 1 a
pK  Δ unit c
G /(RT corresp i
ln 10), onds to d
with a 10- s
equivalent to [H3O]/c with fold
setting the c  1 mol
activity change a
dm3. For
coeAcient  in their r
equal to 1 example, if the
molar molar e
and writing concentration concen
aH O   3
of H3O is tration. c
 PROTON TRANSFER EQUILIBRIA 175
lassified
weak
few
most
in
solution,
HBr,
HNO
and
classified
strong acids
and are
commonly
regarded as
being
completely
deprotonated
in aqueous
solution.
A brief
comment 4
Sulfuric acid,
H
with re- spect
only to its first
deprotonation;
HSO
 The corresponding expression for a base is
we can infer that the basicity constant of methylamine
called the basicity constant, Kb: itself, the equilibrium constant for
aBH aOH
 
[BH ][OH CH3NH2(aq)  H2O(l) f CH3NH 
(aq)  OH(aq)
K  pKb  log Kb
3
b
aB ] [B] is
(8.6)
pKb  pKw  pKa  14.00  10.56  3.44
where we have used the same convention for inter-
preting ‘[ J]’ as in eqn 8.5. A strong base is fully Another useful relation is obtained by taking the
pro- tonated in solution in the sense that Kb  1. negative common logarithm of both sides of the
One example is the oxide ion, O2, which cannot definition of Kw in eqn 8.5, which gives
survive in water but is immediately and fully log aH O aOH   (log aH O  log aOH )
converted into
its conjugate acid OH. A weak base is not fully 3 3

pro- tonated in water in the sense that Kb  1 (and  log aH 3O  log aOH   log Kw
usually much less than 1). Ammonia, NH 3, and its and therefore
organic
derivatives the amines are all weak bases in water,
pH  pOH  pKw (8.9)
and only a small proportion of their molecules
where pOH  log aOH . This enormously important
exist as the conjugate acid4 (NH or 3RNH).
The autoprotolysis constant for water, Kw, is relation means that the activities (in elementary

Kw  aH O work, the molar concentrations) of hydronium and

aOH  pKw  log Kw (8.7)
3 hydroxide ions are related by a seesaw relation: as
At 25°C, the only temperature we consider in this one goes up, the other goes down to preserve the
chapter, Kw  1.0  1014 and pKw  14.00. As may value of pKw.
be confirmed by multiplying the two constants
together, the acidity constant of the conjugate Self-test 8.3
The molar concentration of OH ions in a certain solution is 0.010 mmol dm3
acid, BH, of a base B (the equilibrium constant for [Answer: 9.00]
the reaction BH  H2O f H3O  B) is related to
the basicity constant of B (the equilibrium
constant for the reaction B  H2O f BH  OH)
a H3 O a B  a a The extent of deprotonation of a weak acid in
KaKb  BH OH  a H3Oa K
OHw solution depends on the acidity constant and the
aBH aB
for- mal concentration of the acid, F, its
by
concentration as prepared. The fraction
(8.8a)
deprotonated, , the fraction of acid molecules HA
The implication of this relation is that Ka increases that have donated a proton, is
as Kb decreases to maintain a product equal to the
con- stant K w. That is, as the strength of a base Fraction deprotonated
decreases, the strength of its conjugate acid increases,
equilibrium molar concentration of conjugate base
and vice versa. On taking the negative common  formal concentration of acid
logarithm of both sides of eqn 8.8a, we obtain [A ]equilibrium

log KaKb  (log Ka  log Kb)  log Ka  log Kb F(HA) (8.10a)
 log Kw
The extent to which a weak base B is protonated is
and therefore reported in terms of the fraction protonated:
pKa  pKb  pKw (8.8b) Fraction protonated
The great advantage of this relation is that the pKb equilibrium molar concentration of conjugate acid
values of bases may be expressed as the pKa of  formal concentration of base
their conjugate acids, so the strengths of all weak [BH ]
acids
and bases may be listed in a single table (Table equilibrium (8.10b)
8.1).  F(B)
A brief illustration If the acidity constant of the con- We can estimate the pH of a solution of a weak acid
jugate acid (CH3NH3) of the base methylamine (CH3NH 2)
or a weak base and calculate either of these fractions
is reported as pKa  10.56,
 by using the equilibrium-table technique described in
CH3NH3(aq)  H2 O(l) f 3 H O(aq) 3CH 2NH (aq) a pK  10.56 Section 7.5.
Table 8.1
Acidity and basicity constants at 298.15 K

Acid /Base Kb pKb Ka pKa

Strongest weak acids

Trichloroacetic acid, CCl3COOH 3.3  1014 13.48 3.0  101 0.52
Benzenesulfonic acid, C6H5SO3H 5.0  10 14
13.30 2  101 0.70
Iodic acid, HIO3 5.9  1014 13.23 1.7  101 0.77
Sulfurous acid, H2SO3 6.3  1013 12.19 1.6  102 1.81
Chlorous acid, HClO2 1.0  10 12
12.00 1.0  10 2
2.00
Phosphoric acid, H3PO4 1.3  1012 11.88 7.6  103 2.12
Chloroacetic acid, CH2ClCOOH 7.1  1012 11.15 1.4  103 2.85
Lactic acid, CH3CH(OH)COOH 1.2  1011 10.92 8.4  10 4 3.08
Nitrous acid, HNO2 2.3  1011 10.63 4.3  10 4 3.37
Hydrofluoric acid, HF 2.9  1011 10.55 3.5  10 4 3.45
Formic acid, HCOOH 5.6  1011 10.25 1.8  10 4 3.75
Benzoic acid, C6H5COOH 1.5  1010 9.81 6.5  105 4.19
Acetic acid, CH3COOH 5.6  10 10
9.25 5.6  10 5
4.75
Carbonic acid, H2CO3 2.3  10 8 7.63 4.3  107 6.37
Hypochlorous acid, HClO 3.3  107 6.47 3.0  10 8 7.53
Hypobromous acid, HBrO 5.0  10 6 5.31 2.0  109 8.69
Boric acid, B(OH)3† 1.4  105 4.86 7.2  1010 9.14
Hydrocyanic acid, HCN 2.0  105 4.69 4.9  1010 9.31
Phenol, C6H5OH 7.7  105 4.11 1.3  1010 9.89
Hypoiodous acid, HIO 4.3  10 4 3.36 2.3  1011 10.64
Weakest weak acids

Weakest weak bases

Urea, CO(NH2)2 1.3  1014 13.90 7.7  101 0.10
Aniline, C6H5NH2 4.3  10 10
9.37 2.3  105 4.63
Pyridine, C5H5N 1.8  109 8.75 5.6  10 6 5.35
Hydroxylamine, NH2OH 1.1  10  8
7.97 9.1  10 7
6.03
Nicotine, C10H11N2 1.0  10  6
5.98 1.0  10  8
8.02
Morphine, C17H19O3N 1.6  10 6 5.79 6.3  109 8.21
Hydrazine, NH2NH2 1.7  10 6 5.77 5.9  109 8.23
Ammonia, NH3 1.8  105 4.75 5.6  1010 9.25
Trimethylamine, (CH3)3N 6.5  105 4.19 1.5  1010 9.81
Methylamine, CH3NH2 3.6  10 4 3.44 2.8  1011 10.56
Dimethylamine, (CH3)2NH 5.4  10 4 3.27 1.9  1011 10.73
Ethylamine, C2H5NH2 6.5  10 4 3.19 1.5  1011 10.81
Triethylamine, (C2H5)3N 1.0  10 3
2.99 1.0  10 11
11.01
Strongest weak bases

* Values for polyprotic acids—those capable of donating more than one proton—refer to the first deprotonation.
† The proton-transfer equilibrium is B(OH) 3(aq)  2 H2O(l) f H3O(aq)  4B(OH)(aq).
Example 8.1 A note on good practice When an approximation
has been assumed, verify at the end of the calculation
Assessing the extent of deprotonation of
that the approximation is consistent with the result
a weak acid
obtained. In this case, we assumed that x  0.15 and
Estimate the pH and the fraction of CH 3COOH mole- have found that x  0.011, which is consistent.
cules deprotonated in 0.15 M CH3COOH(aq).
Another note on good practice Acetic acid
Strategy The aim is to calculate the equilibrium com-
(ethanoic acid) is written CH3COOH because the two O
position of the solution. To do so, we use the
atoms are inequivalent; its conjugate base, the
technique illustrated in Example 7.3, with x the
acetate ion (ethanoate ion) is written
2
CH3CO because
change in molar concentration of H3O ions required to
the two O atoms are now equivalent (by resonance).
reach equilibrium. We ignore the tiny concentration
of hydronium ions present in pure water. Once x has
been found, calculate pH  log x. Because we can Self-test 8.4
anticipate that the extent of deprotonation is small Estimate the pH of 0.010 M CH3CH(OH)COOH(aq)
(the acid is weak), use the appro- ximation that x is (lactic acid) from the data in Table 8.1. Before
very small to simplify the equations. carry- ing out the numerical calculation, decide
Solution We draw up the following equilibrium table: whether you expect the pH to be higher or lower
than that calcu- lated for the same concentration
of acetic acid.
Species CH3COOH H3O CH3CO2 [Answer: 2.5]


Initial concentration/ 0.15 0 0

(mol dm3)
Change to reach x x x
equilibrium/
(mol dm3)
Equilibrium 0.15  x x x
concentration/ Example 8.2
(mol dm3) Assessing the extent of protonation
of a weak base
The conjugate acid of the base quinoline (1) has pKa 
The value of x is found by inserting the equilibrium
con- centrations into the expression for the acidity
constant:

[H3O][CH3CO] xx 4.88. Estimate the pH and the fraction of molecules pro-
K  tonated in a 0.010 M aqueous solution of quinoline.
2
a
[CH3COOH] 0.15  x
We could arrange the expression into a quadratic
equa- tion and use the solution in Example 7.4.
However, it is more instructive to make use of the
smallness of x to re- place 0.15  x by 0.15 (this
N
approximation is valid if x  0.15, which is likely
because the acid is weak, but should be verified at Quinoline
the end of the calculation once x has been
calculated). Then the simplified equation Ka  x 2/0.15 Strategy The calculation of the pH of a solution of a
rearranges first to 0.15  Ka  x 2 and then to base involves one more step than that for the pH of a
x  (0.15  Ka)1/2  (0.15  1.8  105)1/2  1.6  103 solution of an acid. The first step is to calculate the
concentration of OH ions in the solution by using the
Therefore,
equilibrium-table technique, and to express it as the
pH  log(1.6  103)  2.80 pOH of the solution. The additional step is to convert
Calculations of this kind are rarely accurate to more that pOH into a pH by using the water autoprotolysis
than one decimal place in the pH (and even that may equilibrium, eqn 8.6, in the form pH  pKw  pOH,
be too optimistic) because the effects of ion–ion with pK w  14.00 at 25°C. We also need to compute
interactions have been ignored, so this answer would pK b  pK w  pKa.
be reported as pH  2.8. The fraction deprotonated, Solution First, we write
a, is
 0.15
[CH3CO ]2 equilibrium x 1.6  10
a  3 
F(CH3COOH) 
0.15
0.011
pKb  14.00  4.88  9.12, correspo K b  109.12  7.6  1010
nding to
That is, only 1.1 per cent of the acetic acid molecules
Now draw up the following equilibrium table, denoting
have donated a proton.
quinoline by Q and its conjugate acid by QH:
 8.3 Polyprotic acids
Species Q OH QH A polyprotic acid is a molecular compound that
can donate more than one proton. Two examples
Initial concentration/(mol dm3) 0.010 00
are sulfuric acid, H2SO4, which can donate up to
Change to reach equilibrium/ (mol dm3)
Equilibrium concentration/ (mol dm3) x x x two protons, and phosphoric acid, H3PO4, which
can donate up to three. A polyprotic acid is best
0.010  x x x con- sidered to be a molecular species that can
give rise to a series of Brønsted acids as it donates
ue of x is found by inserting the equilibrium con- centrations into the expression for theits succession
basicity constant: of protons. Thus, sulfuric acid is the
parent of two Brønsted acids, H2SO44 itself and
[OH ][QH ]x  x HSO, and phos- phoric acid is the parent of three
Kb   2
[Q]0.010  x Brønsted acids, namely 4 H 3PO4, H 4 2PO , and HPO

We suppose that x  0.010. Then the simplified equa- tion K b  x 2/0.010 rearranges . to
For a species H2A with two acidic protons (such
x  (0.010  K b)1/2  (0.010  7.6  1010)1/2  2.8  106
asx 
This value is consistent with the assumption that H2 SO4), the successive equilibria we need to
0.010. Therefore, con- sider are
pOH  log(2.8  106)  5.55
 
is 2A(aq)  H2O(l) f H3O (aq)  HA (aq)
and consequently pH  14.00  5.55  8.45, or about 8.4. The fraction protonated, a, H
 aH O aHA
+ 

Ka1  3
aH A
2
 
HA (aq)  H O(l) f H O (aq)  A (aq) 2

 2.8  106  2.8  104 2 3

a
[QHequilibrium
]

x a a
F(Q) 0.0100.010 Ka2  Ha3O A2 +

HA

In the first of these equilibria, HA is the conjugate
base of H2A. In the second, HA acts as the acid
n of nicotine (2) is 8.02. What is the pH and the fraction of molecules proto- nated in a 0.015 M2aqueous solution of nicotine?
and A is its conjugate base. Values are given in
Table 8.2. In all cases, Ka2 is smaller than Ka1,
typically by three orders of magnitude for small
molecular species, because the second proton is
more diAcult to remove, partly on account of the
negative charge on HA. Enzymes are polyprotic
acids, for they possess many protons that can be
donated to a substrate molecule or to the
surrounding aqueous medium of the cell. For
them, successive acidity constants vary much less
because the molecules are so large that the loss of
a proton from one part of the molecule has little
effect on the ease with which another some
distance away may be lost.

Table 8.2
Successive acidity constants of polyprotic acids at 298.15 K

Acid Ka1 pKa1 Ka2 pKa2 Ka3 pKa3

Carbonic acid, H2CO3 4.3  107 6.37 5.6  1011 10.25

Hydrosulfuric acid,2 H2S
Oxalic acid, (COOH) 1.3 102
5.9 107 6.88
1.23 6.5  105
7.1 1015 14.15
4.19

Phosphoric acid, H3PO4 7.6  103 2.12 6.2  10 8 7.21 2.1  1013 12.67
Phosphorous acid, H2PO3 1.0  102 2.00 2.6  107 6.59
Sulfuric acid, H2SO4 Strong 1.2  102 1.92
Sulfurous acid, H2SO3 1.5  102 1.81 1.2  107 6.91
Tartaric acid, C2H4O2(COOH)2 6.0  10 4 3.22 1.5  105 4.82
178 CHAPTER 8: CHEMICAL EQUILIBRIUM: EQUILIBRIA IN SOLUTION

Example 8.3 equilibrium has in fact been achieved, that the molar
Calculating the concentration of carbonate ion concentration of CO2 ions is 5.6  1011 mol dm3 and
in carbonic acid (within the approximations
3 we have made)
independent of the concentration of H2CO3 present
Ground water contains dissolved carbon dioxide, initially.
carbonic acid, hydrogencarbonate ions, and a very low
concentra- tion of carbonate ions. Estimate the molar
concentration of CO2 ions in a solution in which water Self-test 8.6
2
and CO (g) are
3 2
S Calculate the molar concentration of ions in
in equilibrium.
H2S(aq).
Strategy We must be very cautious in the [Answer: 7.1  1015 mol dm3]
interpretation of calculations involving carbonic acid
because equilib- rium between dissolved CO2 and
H2CO3 is achieved only very slowly. In organisms,
attainment of equilibrium is facilitated by the enzyme
carbonic anhydrase. We start with the equilibrium
that produces the ion of interest (such as A2) and
write its activity in terms of the acidity constant for
its formation (Ka2). That expression will con- tain the Example
8.4
activity of the conjugate acid (HA), which we
can express in terms of the activity of its conjugate Calculating the fractional composition of
acid (H2A) by using the appropriate acidity constant a solution
(Ka1). This equilibrium dominates all the rest provided Oxalic acid, H2C2O4 (ethandioic acid, HOOC—COOH),
the molecule is small and there are marked exists in solution in equilibrium with HC 2O4 and C2 O42.
differences between its acidity constants, so it may Show how the composition of an aqueous solution that
be possible to make an approximation at this stage. contains 0.010 mol dm3 of oxalic acid varies with pH.
Solution The CO23 ion, the conjugate base of the acid Strategy We expect the fully protonated species
HCO3, is produced in the equilibrium (H C O ) at low pH, the partially protonated species
2 2 4
 
2 (HC 2O ) at intermediate pH, and the fully deprotonated
HCO3 (aq)  H2O(l) f H3O (aq)  CO3 4

(aq) species (C2O24) at high pH. Set up the expressions for

the two acidity constants, treating H C O as the parent
a
H3O CO 
a 2
3
K a2 22 4
aHCO acid, and an expression for the total concentration of
3

oxalic acid. Solve the resulting expressions for the

Hence,
frac- tion of each species in terms of the hydronium
aHCOKa2
ion concentration.
a 2 3
CO3 a Solution The two acidity constants are
H3 O


The HCO ions are produced in the
H2C2O4(aq)  H2O(l) f H3O(aq)  HC2O(aq)
equilibrium
3
4
  [H3O][HC O]
H2CO3(aq)  H2O(l) f H3O (aq)  HCO3(aq) Ka1  24

One H 3O ion is produced for each HCO 3ion produced. [H2C2O4]
HC O(aq)  H O(l) f H O(aq)  C O2(aq)
These two concentrations are not exactly the same, 2 4 2 3 2 4
because a little HCO is lost in the second [H O][C O2]
deprotonation
3 3 2 4
K a2 
and the amount of H3O  has been increased by it. Also, [HC 2O4]
HCO3 is a weak base and abstracts a proton from
We also know that the total concentration of oxalic
water to generate H2CO3 (see Section 8.4). However,
acid in all its forms, its formal concentration F(H2C2O4),
those secondary changes can safely be ignored in an
approxi- is
mate calculation. Because the molar concentrations [H2C2O4]  [HC2O]4  [C2O24]  F(H2C2O4)

of HCO
3 and H O are approximately the same, we can We now have three equations for three unknown
suppose that their activities are also approximately concentrations. To solve the equations, we2proceed
the same, and set aHCO  aH O. When this equality is systematically by using to express [C O ] in terms
K
3 3 a2 2 4
substituted into the expression for aCO2 and we make of [HC O ], then K to express [HC O] in terms of

3 Because we know from Table 8.2 that pK  10.25, it
the approximation that aCO23  [CO 2]/c -, then we
obtain

[CO32]  Ka2c -
 2 4 a1 2 4
[H2C2O4]:
Ka2[HC O] K K [HC O ]
24
a2 24
[C O2]   a1 a2 2 2 4  2
follows that [CO 23 ]  5.6  1011 c-, and therefore, if [H3O] [H3O ]

K
a1 [H
22 C
O]
[HC 2O4 ]  4
[H3O]
 PROTON TRANSFER EQUILIBRIA 179

The expression for the total concentration F(H2C2O4)

A note on good practice Be ready to take
can now be written in terms of [H2C2O4] and [H3O]:
advantage of symmetries in the expressions:
K a1[H2C2O4 ] K a1K a2[H2C2O4] inspection of the three expressions for the fractions of
F(H2 C2 O4 )  [H2 C O ]
2 4

the species pre- sent shows a symmetry in the
appearance of [H3O] and
⎧
 ⎪ [H3O] [H3O]2
the Ks. By noting this symmetry, it is possible to write
Ka1 K a1K a2
⎫⎪ down the expression for the species present in a solu-
⎨1 
 2⎬
[H2C2O4]
⎩⎪ [H3O ] [H3O ] ⎪⎭ tion of a triprotic acid without further calculation (see
1 Self-test 8.7).
 {[H O]2  [H K }[H C O ]
O]K K
3 3 a1 a1 a2 224
[H3O]2
It follows that the fractions of each species present in Self-test 8.7
the solution are
Construct the diagram for the fraction of protonated
species in an aqueous solution of phosphoric acid.
F (H2C2O4) [ H2C2O4
] [Answer: Fig. 8.2]
 Ftotal
[H2C2O4]

(1/[H3O ]) {[H3O ]  [H3O ]K
 2  2
a1  K a1K a2} [ H PO H PO– HPO2– PO3–
H2C2O4]

[H3O]2 3 4 2 4 4 4
 1
[H 3O]2  [H O
3

]K a1
 K a1K

12.68
2.12

7.21
a2
0.8
(8.11a)
Fraction of species, f

and similarly
[HC O] 0.6
[Ha1O]K
a(HC O) 2 4 3
2 4
F(H2C2O4) [H3O ]2  [H3O ]K a1  K a1K a2 0.4
(8.11b)
[C O2] KK 0.2
a(C O2) 2 4 a1 a2
2 4
F(H2C2O4) [H3O ]2  [H3O ]K a1  K a1K a2
(8.11c)
0 2 4 8 10 12 14
6 pH
0
These fractions are plotted against pH  log[H3O] in
Fig. 8.1. Note how H2C2O4 is dominant for pH  pKa1,
that H2C2O4 and HC2O 4have the same concentration at Fig. 8.2 The fractional composition of the pro-
pH  pK a1, and that HC2O is dominant for pH  pKa1, tonated and deprotonated forms of phosphoric
2 4 acid in aqueous solution as a function of pH.
until C2O4 becomes dominant.

(COOH)2 HOOCCO– (CO )2–

2 2
1
We can summarize the behaviour found in
Example 8.4 and illustrated in Figs. 8.1 and 8.2
4.19
1.23

0.8 as follows. Consider each conjugate acid–base

Fraction of species, f

pair, with acidity constant Ka; then:

0.6
• The acid form is dominant for pH  pKa
• The conjugate pair have equal concentrations at
0.4
pH  pKa
• The base form is dominant for pH  pKa
0.2
In each case, the other possible forms of a
0
polyprotic system can be ignored, provided the
0 2 4 8 10 12 14 pKa values are not too close together.
6 pH
180 CHAPTER 8: CHEMICAL EQUILIBRIUM: EQUILIBRIA IN SOLUTION

Fig. 8.1 The fractional composition of the pro-

tonated and deprotonated forms of oxalic acid in 8.4 Amphiprotic systems
aqueous solution as a function of pH. Note that con-
jugate pairs are present at equal concentrations when An amphiprotic species is a molecule or ion that can

the pH is equal to the pKa of the acid member of the pair. both accept and donate protons. For instance, HCO 3
2
can act as an acid (to form CO3 ) and as a base (to
form H2CO3). The question we need to tackle is the
of these two expressions, noting from the equilibrium table that at equilibrium y  x  [H3O
pH of a solution of a salt with anMultiplication amphiprotic
anion, such as a solution of NaHCO3. Is the
solution acidic on account of the acid character of (y  x)2y y
3 Ka1Ka2  [H3 O]2
 x x
HCO , or is it basic on account of the anion’s basic
character? As that,
Next, we show we show in approximation,
to a good Derivation 8.1,y/x the pHtherefore
1 and of that [H3O]  (Ka1Ka2)1/2. For this step we rearrange the expression for Ka1 as foll
xKa1a solution
such Fy  y 2  Fx
isgiven
x2 by
Because xKa1, x 2, and y 2 are all very small compared with terms that have F in them, and for typical (but by no means all) formal concentrations F/c -
 Fy 1Fx
0pH
 pK ) (8.12)
(pK
We 2
conclude
a1 that x  y,a2and therefore that y/x  1, as re- quired. Equation 8.12 now follows by taking the negative common logarithm of both sides o

This expression is valid provided the molar

concentra- tion of the salt is high in the sense
(using the notation in Derivation 8.1) that F /c 
Kw /Ka2 and F/c  Ka1, where F is the formal
concentration of the salt. If these conditions are
not satisfied, a much more com- plicated
expression must be used (see the website).

A brief illustration If the dissolved salt is sodium

hydrogencarbonate, we can immediately conclude that
the pH of the solution of any concentration (provided
the approximations remain valid) is
pH  12 (6.37  10.25)  8.31
The solution is basic. This result is reliable provided F/c-
Salts in water
 2  104. We can treat a solution of potassium
dihydro- genphosphate in the same way, taking into The ions present when a salt is added to water may
account only the second and third acidity constants of themselves be either acids or bases and
H3PO4 because protonation as far as H3PO4 is negligible: consequently affect the pH of the solution. For
example, when ammonium chloride is added to
pH  12 (7.21  12.67)  9.94
water, it provides 
- both an acid (NH ) and a base (Cl). The solution
This expression is reliable provided F/c  0.05. 4

consists of a weak acid (NH4) and a very weak base
(Cl). The net effect is that the solution is acidic.
Similarly, a solution of sodium acetate consists of
Derivation 8.1
a neutral ion (the Na ion) and a base (CH23CO).
The pH of an amphiprotic salt solution
The net effect is that the solution is basic, and its
Let’s suppose that we make up a solution of the salt pH is greater than 7.
MHA with formal concentration F, where HA is the
amphiprotic anion (such as HCO3) and M is a cation
(such as Na). The equilibrium table is as follows: Self-test 8.8
Is an aqueous solution of potassium lactate likely to be
Species H2A HA A2 H3O acidic or basic?
[Answer: basic]
Initial molar 0 F 0 0
concentration/
(mol dm3) To estimate the pH of the solution, we proceed in
Change to reach x (x  y) y (y 
equilibrium/(mol
exactly the same way as for the addition of a ‘con-
3
) x)
dm ventional’ acid or base, for in the Brønsted–Lowry
Equilibrium x Fxy y y
x theory, there is no distinction between
concentration/
(mol dm3) ‘conventional’ acids like acetic acid and the
conjugate acids of bases (like NH). For example,
to calculate
4 the pH of
The two acidity constants are
0.010 M NH4Cl(aq) at 25°C, we proceed exactly as
[H3O[H
][HA 
A] ] (y  x)(F x x  y) in Example 8.1, taking the initial concentration of
K a  the acid (NH) to be 0.010 mol dm3. The K to use
1 2 4 a

[H O][A2] is the acidity constant of the acid NH 4, which is
Ka2  3 (y  x)y
 Fxy listed in Table 8.1. Alternatively, we use Kb for the
[HA]
c
o
n
j
u
g
a
t
e

b
a
s
e

(
N
H
3
)

o
f

t
h
e

a
c
i
d

a
n
d

c
o
n
v
e
r
t

t
h
a
t
 SALTS IN WATER 181

quantity to Ka by using eqn 8.6 (KaKb  Kw). We find 14

pH  5.63, which is on the acid side of neutral.
Exactly the same procedure is used to find the pH of 12
a solution of a salt of a weak acid, such as sodium
10
acetate. The equilibrium table is set up by treating
the anion CH3CO as a base (which it is), and using 8
for K 2 K for its 7 SB

pH
b the value obtained from the value of a

conjugate acid (CH3COOH). 6

4
Self-test 8.9 Stoichiometric point
Estimate the pH of 0.0025 M NH(CH3)3Cl(aq) at 25°C. 2
[Answer: 6.2]
SA
0
Volume of titrant added, V

8.5 Acid–base titrations means that we can expect pH  7. In a titration of a

weak
Acidity constants play an important role in acid–
base titrations, for we can use them to decide the
value of the pH that signals the stoichiometric
point, the stage at which a stoichiometrically
equivalent amount of acid has been added to a
given amount of base. The plot of the pH of the
analyte, the solution being ana- lysed, against the
volume of titrant, the solution in the burette,
added is called the pH curve. It shows a number of
features that are still of interest even nowadays
when many titrations are carried out in automatic
titrators with the pH monitored electronic- ally:
automatic titration equipment is built to make use
of the concepts we describe here.
A brief comment For historical reasons, the
stoichiometric point is widely called the equivalence point
of a titration. The meaning of end point is explained in
Section 8.6.

First, consider the titration of a strong acid with

a strong base, such as the titration of hydrochloric
acid with aqueous sodium hydroxide. The reaction
is
HCl(aq)  NaOH(aq)  NaCl(aq)  H2O(l)
Initially, the analyte (hydrochloric acid) has a low
pH. The ions present at the stoichiometric point
(the Na ions from the strong base and the Cl ions
from the strong acid) barely affect the pH, so the
pH is that of almost pure water, namely pH  7.
After the stoi- chiometric point, when base is
added to a neutral solution, the pH rises sharply to
a high value. The pH curve for such a titration is
shown in Fig. 8.3.
Figure 8.4 shows the pH curve for the titration
of a weak acid (such as CH3COOH) with a strong
base (NaOH). At the stoichiometric point the
solution
contains CH3CO2 ions and Na ions together with
any ions stemming from autoprotolysis. The presence
of the Brønsted base CH32CO in the solution
 182 CHAPTER 8: CHEMICAL EQUILIBRIUM: EQUILIBRIA IN SOLUTION

Fig. 8.3 The pH curve for the titration of a

strong acid (SA, the analyte) with a strong
base (SB, the titrant).
There is an abrupt change in pH near the
stoichiometric point at pH  7. The final pH of the
medium approaches that of the titrant.

14

12

10

8
SB

pH
6

4
Stoichiometric point
2
WA
0
Volume of titrant added, V

Fig. 8.4 The pH curve for the titration of a

weak acid (WA, the analyte) with a strong
base (WB, the titrant).
Note that the stoichiometric point occurs at pH  7 and
that
the change in pH near the stoichiometric point is
less abrupt than in Fig. 8.3. The pKa of the acid is
equal to the pH half-way to the stoichiometric point.

base (such as NH3) and a strong acid (HCl),

the solution contains NH ions and Cl ions 4
at the stoichiometric point. Because Cl is
only a very weak Brønsted base and NH is a 4
weak Brønsted acid the solution is acidic and
its pH will be less than 7.
Now we consider the shape of the pH curve
in Fig. 8.4 in terms of the acidity constants of
the species involved. The approximations we
make are based on the fact that the acid is
weak, and therefore that HA is more
abundant than any A ions in the solution.
Furthermore, when HA is present, it provides
so many H3O ions, even though it is a weak
acid, that they greatly outnumber any H3O
ions that come from
 the very feeble autoprotolysis of water. Finally,
when excess that because the ratio of acid to base molar concentra- tions occurs in eqn 8.13, the volume of solution cancels, and we can equate
base is present after the
ratio of amounts:
stoichiometric point has been passed, the OH ions
it provides dominate any that come from the water
autoprotolysis.
[acid]  nacid / V  nacid
To be specific, let’s suppose that we are titrating
3 [base] nbase / Vnbase
25.00 cm of 0.10 M CH3COOH(aq) with 0.20
M NaOH(aq) at 25°C. We can calculate Solution Thethe pH at
addition of 5.00 cm3, or 5.00  103 dm3 (because 1 cm3  103 dm3), of titrant corresponds to
the start of a titration of a weaknacid OH  (5.00
with a103 dm3)  (0.200 mol dm3)
strong
base as explained in Example 8.1,and  103
1.00 find pHmol 2.9.
This amount of OH (1.00 mmol) converts 1.00 mmol
The addition of titrant converts some of the acid
to its conjugate base in the reaction
CH COOH(aq)  OH(aq)  H O(l)  CH CO(aq)
3 2 3 2
CH3COOH to the base CH3CO.2 The initial amount of
Suppose we add enough titrant CH3COOH toin the
produce
analyte isa
concen- tration [base] of the nconjugate base
CH COOH  (25.00 and
 103 dm3)  (0.200 mol dm3)
simultan- eously reduce the concentration
3
of acid
 2.50  103 mol
to [acid]. Then, because the acid
so theand its conjugate
amount remaining after the addition of titrant is 1.50 mmol. It then follows from the Henderson– Hasselba
base remain at equilibrium:
CH3COOH(aq)  H2O(l)
f H3O(aq)  CH3CO 
2 (aq) pH  4.75  log 1.50  103  4.6
we can write 1.00  103
a a As expected, the addition of base has resulted in an increase in pH from 2.9. You should not take the value
a [base]
4.6 too seriously because we have already pointed out that such calculations are approximate. However, it is important to note th
H O CH3CO initial H O
K 3  2 acidic3 value.
a aCH3COOH [acid]
This expression rearranges first to

aH O Ka[acid]
3
+
 [base]
Self-test 8.10
and then, by taking negative common logarithms, we
Calculate the pH after the addition of a further
obtain 5.00 cm3 of titrant.
Use log xy  log x  log y [Answer: 5.4]
K [acid]
 log a   log a   log Ka  log [acid]
H3O [base] [base]
which can be written as the Henderson–Hasselbalch
equation

pH  pKa  log [acid] (8.13) Half-way to the stoichiometric point, when

[base] enough base has been added to neutralize half the
acid, the concentrations of acid and base are equal
and because log 1  0 the Henderson–Hasselbalch
equa- tion gives

ntermediate stage in a titration pH  pKa (8.14)

fter the addition of
yte in the titration described above. In the present titration, we see that at this stage of
the the
ciding the amount of OH ions added in the titrant, and then to use that amount to calculate titration, pH
amount of CH 4.75.remaining.
3COOH Note from the pH curve in
Notice
Fig. 8.4 how much more slowly the pH is changing
compared with initially: this point will prove
import- ant shortly. Equation 8.14 implies that we
can deter- mine the pKa of the acid directly from
the pH of the mixture. Indeed, an approximate
value of the pKa
may be calculated by recording the pH during a 14

titration and then examining the record for the pH

12
half-way to the stoichiometric point.
At the stoichiometric point, enough base has been 10
added to convert all the acid to its base, so the solu-
8
tion consists—nominally—only of CH3CO2 ions.

pH
These ions are Brønsted bases, so we can expect the WB
6
solution to be basic with a pH of well above 7. We
have already seen how to estimate the pH of a solu- 4
tion of a weak base in terms of its concentration B Stoichiometric
2
(Example 8.2), so all that remains to be done is to point
calculate the concentration of CH3CO 2at the stoi- 0 SA
chiometric point.
Volume of titrant added, V

A brief illustration Because the analyte initially con-

Fig. 8.5 The pH curve for the titration of a weak base (the
tained 2.50 mmol CH3COOH, the volume of titrant analyte) with a strong acid (the titrant). The
needed to neutralize it is the volume that contains the stoichiometric point occurs at pH  7. The final pH of the
same amount of base: solution approaches that of the titrant.

2.50  103 mol

Vbase   1.25  102
dm3 rapidly through the value calculated in the illustra-
3
0.200 mol dm
or 12.5 cm3. The total volume of the solution at this tion at the beginning of this section.
stage is therefore 37.5 cm3, so the concentration of A similar sequence of changes occurs when the
base is analyte is a weak base (such as ammonia) and the
2.50 10 mol titrant is a strong acid (such as hydrochloric acid).
[CH3CO2]  3  6.67 102 mol dm3
37.5 103 dm3 In this case the pH curve is like that shown in Fig.
It then follows from a calculation similar to that in 8.5: the pH falls as acid is added, plunges through
Example 8.2 (with pKb  9.25 for CH3CO2) that the pH of the pH corresponding to a solution of a weak acid
the solution at the stoichiometric point is 8.8. (the con- jugate acid of the original base, such
4
as
NH ), and then slowly approaches the pH of the
It is very important to note that the pH at the original strong acid. The pH of the stoichiometric
stoichiometric point of a weak-acid–strong-base point is that of a solution of a weak acid, and is
titration is on the basic side of neutrality (pH  7). calculated as illus- trated in Example 8.2.
At the stoichiometric point, the solution consists
of a weak base (the conjugate base of the weak
 8.6 Buffer action
acid, here the CH 2 3CO ions) and neutral cations

(the Na ions from the titrant). The slow variation of the pH when the
The general form of the pH curve suggested by concentrations of the conjugate acid and base are
these estimates throughout a weak-acid–strong-base nearly equal, when pH  pKa, is the basis of buffer
titration is illustrated in Fig. 8.4. The pH rises action, the ability of a solution to oppose changes
slowly from its initial value, passing through the in pH when small amounts of strong acids and
values given by the Henderson–Hasselbalch bases are added (Fig. 8.6). An acid buffer solution,
equation when the acid and its conjugate base are one that stabilizes the solu- tion at a pH below 7, is
both present, until the stoichiometric point is typically prepared by making a solution of a weak
approached. It then changes rapidly to and through acid (such as acetic acid) and a salt that supplies
the value characteristic of a solution of a salt, its conjugate base (such as sodium acetate). A base
which takes into account the effect on the pH of a buffer, one that stabilizes a solution at a pH above
solution of a weak base, the conjugate base of the 7, is prepared by making a solution of a weak base
original acid. The pH then climbs less rapidly (such as ammonia) and a salt that supplies its
towards the value corresponding to a solu- tion conjugate acid (such as ammonium chloride).
consisting of excess base, and finally approaches Physiological buffers are responsible for maintaining
the pH of the original base solution when so much the pH of blood within a narrow range of 7.37 to
titrant has been added that the solution is virtually 7.43, thereby stabilizing the active conformations
the same as the titrant itself. The stoichiometric of biological macromolecules and optimizing the
point is detected by observing where the pH rates of biochemical reactions (Box 8.1).
changes
 14 A brief illustration Suppose we need to estimate the
pH of a buffer formed from equal amounts of KH2PO4(aq)
12
and K2HPO 4(aq). We note that the two anions present
are H2PO and HPO2. The former is the conjugate acid of
10 4 4
the latter:
8
H PO(aq)  H O(l) f H O(aq)  HPO2(aq)
SB 2 4 2 3 4
pH

6
pKa so we need the pKa of the acid form, H2PO4. In this case
4 we can take it from Table 8.1, or recognize it as the
pKa2 of phosphoric acid, and take it from Table 8.2
2 instead. In either case, pKa  7.21. Hence, the solution
SP/2 SP
should buffer close to pH  7.
0 WA
Volume of titrant added,
Self-test 8.11
V
Calculate the pH of an aqueous buffer solution that con- tains equal amounts of NH3 and NH4Cl.
[Answer: 9.25; more realistically: 9]
Fig. 8.6 The pH of a solution changes only slowly in the
region of half-way to the stoichiometric point (SP). In this
re- gion the solution is buffered to a pH close to pK a.

Box 8.1 Buffer action in blood

The pH of blood in a healthy human being varies from

by hyperventilation, or excessive respiration. The
7.37 to 7.43. There are two buffer systems that help
simplest remedy consists of breathing into a paper bag in
maintain the pH of blood relatively constant: one arising
order to increase the levels of inhaled CO2. Metabolic
from a car- bonic acid/bicarbonate (hydrogencarbonate)
alkalosis may result from illness, poisoning, repeated
ion equilibrium and another involving protonated and
vomiting, and overuse of diuretics. The body may
deprotonated forms of haemoglobin, the protein
compensate for the increase in the pH of blood by
responsible for the transport of O2 in blood (Box 7.1).
decreasing the rate of respiration.
Carbonic acid forms in blood from the reaction
between Acidosis occurs when the pH of blood falls below about
water and CO2 gas, which comes from inhaled air and is 7.35. In respiratory acidosis, impaired respiration
also a by-product of metabolism: increases the concentration of dissolved CO2 and lowers
the blood’s pH. The condition is common in victims of
CO2(g)  H2O(l) f H2CO3(aq)
smoke inhalation and patients with asthma, pneumonia,
In red blood cells, this reaction is catalysed by the
and emphysema. The most efficient treatment consists
enzyme carbonic anhydrase. Aqueous carbonic acid then
of placing the patient in a ventilator. Metabolic acidosis
deproto- nates to form a bicarbonate
is caused by the release of large amounts of lactic acid
(hydrogencarbonate) ion:
or other acidic by-products of metabolism, which react
H2CO3(aq) f H(aq)  HCO
3

(aq) with hydrogencarbonate ion to form carbonic acid, thus
The fact that the pH of normal blood is approximately lowering the blood’s pH. The condition is common in
7.4 implies that [HCO]/[H CO ]  20. The body’s patients with diabetes and severe burns.
control of 3 2 3
the pH of blood is an example of homeostasis, the ability The concentration of hydronium ions in blood is also
of an organism to counteract environmental changes con- trolled by haemoglobin, which can exist in
with physiological responses. For instance, the deprotonated (basic) or protonated (acidic) forms,
concentration of carbonic acid can be controlled by depending on the state of protonation of several amino
respiration: exhaling air depletes the system of CO2(g) acid residues on the protein’s surface. The carbonic
and H2CO3(aq) so the pH of acid/bicarbonate ion equilibrium and proton equilibria in
blood rises when air is exhaled. Conversely, inhalation haemoglobin also regulate the oxygena- tion of blood.
increases the concentration of carbonic acid in blood and The key to this regulatory mechanism is the Bohr effect,
lowers its pH. The kidneys also play a role in the control the observation that haemoglobin binds O2
of the concentration of hydronium ions. There, ammonia strongly when it is deprotonated and releases O2 when it is
formed by the release of nitrogen from some aminoacids protonated. It follows that when dissolved CO 2 levels
(such as glutamine) combines with excess hydronium ions are high and the pH of blood falls slightly, haemoglobin
and the ammonium ion is excreted through urine. becomes protonated and releases bound O2 to tissue.
The condition known as alkalosis occurs when the pH Conversely, when CO2 is exhaled and the pH rises slightly,
of blood rises above about 7.45. Respiratory alkalosis is haemoglobin becomes deprotonated and binds O2.
caused
 An acid buffer stabilizes the pH of a solution
concentrations become 0.032 mol dm3 NaCH CO (aq)
because the abundant supply of A ions (from the 3
3 2

salt) can remove any H O ions brought by and 0.088 mol dm CH3COOH(aq). It then follows from
additional
3 the Henderson–Hasselbalch equation that
acid; furthermore, the abundant supply of HA
0.088
molecules can provide H3O ions to react with any pH  4.75  log  4.31
0.032
base that is added. Similarly, in a base buffer the
weak base B can accept protons when an acid is The change in pH is from 4.45 to 4.31, far smaller than
added and its conjugate acid BH can supply in the absence of the buffer.
protons
if a base is added. Self-test 8.12
These abilities can be expressed quantitatively
Estimate the change in pH when 0.20 cm3 of 1.5
by considering the changes in equilibrium
mol dm3 NaOH(aq) is added to 30 cm3 of (a) pure
composi- tion of hydronium ions in the presence water and (b) a phosphate buffer that is 0.20 mol
of a buffer. This behaviour is best illustrated with a dm3 KH2PO4(aq) and 0.30 mol dm3 K2HPO4(aq).
specific example. [Answer: (a) 7.00 to 9.00; (b) 7.39 to 4.42]

Example 8.6
Illustrating the effect of a buffer
When 1 drop (0.20 cm3, say) of 1.0 mol dm3 HCl(aq) is
added to 25 cm3 of pure water, the resulting
8.7 Indicators
hydronium ion concentration rises to 0.0080 mol dm3
The rapid change of pH near the stoichiometric
and so the pH changes from 7.0 to 2.1, a big change.
point of an acid–base titration is the basis of
Now suppose the drop is added to 25 cm3 of an
indicator detection. An acid–base indicator is a
acetate buffer solution that is 0.040 mol dm3
NaCH3CO2(aq) and 0.080 mol dm3 CH3COOH(aq). What
water-soluble organic molecule with acid (HIn)
will be the change in pH? and conjugate base (In) forms that differ in
colour. The two forms are in equilibrium in
Strategy The presence of the acid tells us that this solution:
mixture will be an acid buffer. Use the Henderson–
Hasselbalch equation (or, better, first principles), to HIn(aq)  H2O(l) f H3O(aq)  In(aq)
estimate the initial pH. Then calculate the amount of aH O aIn
 
H3O added in the drop and the consequent changes KIn  3

to the amounts of acetic acid and acetate ions in the aHIn

solution. Use the Henderson–Hasselbalch equation to
estimate the pH of the resulting solution. The pKIn of some indicators are listed in Table 8.3.
Solution The initial pH of the buffer solution is The ratio of the concentrations of the conjugate
acid and base forms of the indicator is
0.080
pH  4.75  log  [In ] KIn
4.45
0.040  aH O 
[HIn]
The drop of HCl(aq) contains
3

n(H3O)  (0.20  103 dm3)  (1.0 mol This expression can be rearranged (after taking com-
dm3) mon logarithms) to
 0.20 mmol pKIn pH

The buffer solution contains KIn

[In ]
n(CH CO)  (25  103 dm3)  (0.040 mol dm3) log [HIn]  log a  log  log aH3O 
H3O KIn 

3 2
Use log(x/y)  log x  log y
 1.0 mmol

n(CH3COOH)  (25  103 dm3)  (0.080 mol dm3)

and written as
 2.0 mmol
[In ]
The acetate ion is protonated by the incoming acid, log   pH  pKIn (8.15)
[HIn]
and
so its amount is reduced to 0.8 mmol. As a result, the We see that as the pH swings from higher than pK
amount of CH3COOH rises from 2.0 mmol to 2.2 mmol. In
The volume of the solution barely changes, so the two to lower than pK In as acid is added to the solution,
the ratio of In to HIn swings from well above 1 to
 Table 8.3
Indicator colour changes

Indicator Acid colour pH range of colour change pKIn Base colour

Thymol blue Red 1.2 to 2.8 1.7 Yellow

Methyl orange Red 3.2 to 4.4 3.4 Yellow
Bromophenol blue Yellow 3.0 to 4.6 3.9 Blue
Bromocresol green Yellow 4.0 to 5.6 4.7 Blue
Methyl red Red 4.8 to 6.0 5.0 Yellow
Bromothymol blue Yellow 6.0 to 7.6 7.1 Blue
Litmus Red 5.0 to 8.0 6.5 Blue
Phenol red Yellow 6.6 to 8.0 7.9 Red
Thymol blue Yellow 9.0 to 9.6 8.9 Blue
Phenolphthalein Colorless 8.2 to 10.0 9.4 Pink
Alizarin yellow Yellow 10.1 to 12.0 11.2 Red
Alizarin Red 11.0 to 12.4 11.7 Purple

14
At the stoichiometric point, the pH changes
sharply through several pH units, so the molar
12 con- centration of H3O changes through several
orders of magnitude. The indicator equilibrium
10
changes so as to accommodate the change of pH,
8 with HIn the dominant species on the acid side of
SB the stoichio- metric point, when H3O ions are
pH

6 abundant, and In dominant on the basic side,

when the base can re- move protons from HIn.
4
The accompanying colour change signals the
2 stoichiometric point of the titra- tion. The colour
SP
in fact changes over a range of pH, typically from
0 SA pH  pKIn  1, when HIn is ten times as abundant
Volume of titrant added, V as In, to pH  pKIn  1, when In is ten times as
abundant as HIn. The pH half-way through a
Fig. 8.7 The range of pH over which an indicator changes
colour is depicted by the tinted band. For a strong acid– colour change, when pH  pKIn and the two forms,
strong base titration, the stoichiometric point is indicated HIn and In, are in equal abundance, is the end
accurately by an indicator that changes colour at pH  7 point of the indicator. With a well-chosen
(such as bro- mothymol blue). However, the change in pH indicator, the end point of the indicator coincides
is so sharp that accurate results are also obtained even if
with the stoi- chiometric point of the titration.
the indicator changes colour in neighbouring values. Thus,
phenolphthalein (which has pKIn  9.4, see Table 8.3) is Care must be taken to use an indicator that
also often used. changes colour at the pH appropriate to the type of
titration. Specifically, we need to match the end
point
well below 1 (Fig. 8.7). For instance, if pH  to the stoichiometric point, and therefore select an
 indicator for which pKIn is close to the pH of the stoi-
pKIn then [In]/[HIn]  10, but if pH  pK  1,
In 1, then chiometric point. Thus, in a weak-acid–strong-base
[In]/[HIn]  101, a decrease of two orders of
titration, the stoichiometric point lies at pH  7,
magnitude.
and we should select an indicator that changes at
that pH (Fig. 8.8). Similarly, in a strong-acid–
test 8.13 weak-base titration, we need to select an indicator
is the ratio of the yellow and blue forms of bromocresol green in solution of pH (a) 3.7, (b) 4.7, and (c) 5.7?
er: (a) 10:1, (b) 1:1, (c) 1:10]
with an end point at pH  7. Qualitatively, we
should choose an
indicator with pKIn  7 for strong-acid–strong-base
titrations, one with pKIn  7 for strong-acid–weak-
base titrations, and one with pKIn  7 for weak-
acid–strong-base titrations.
 SOLUBILITY EQUILIBRIA 187

14 calculations are reliable. Once again, we shall con-

centrate on general trends and properties rather
12
than expecting to obtain numerically precise
results and
10 confine numerical calculations to systems at 298 K.
8 SB
8.8 The solubility constant
pH

6
The heterogeneous equilibrium between a sparingly
4 soluble ionic compound, such as calcium hydroxide,
SP Ca(OH)2, and its ions in aqueous solution is
2
WA Ca(OH)2(s) f Ca2(aq)  2 OH(aq)
0
Volume of titrant added, V aCa2 aOH 
Ks  2
2
 aCa2 aOH 
Fig. 8.8 In a weak acid–strong base titration, an indicator aCa(OH)2
with pKIn  7 (the lower band, like bromothymol blue) 1
would give a false indication of the stoichiometric point; it
is neces- sary to use an indicator that changes colour close The equilibrium constant for an ionic equilibrium
to the pH of the stoichiometric point. If that lies at about such as this, bearing in mind that the solid does
pH  9, then phe- nolphthalein would be appropriate. not appear in the equilibrium expression because
its activity is 1, is called the solubility constant

mount in a sample may be determined by titration with sodium hydroxide solution. Should you use methyl red or phe- nolphthalein as the indicator?

(which is also called the solubility product constant

or simply the solubility product). As usual, for very
dilute solutions, we can replace the activity aJ of a
Solubility equilibria species J by the numerical value of its molar
concentration. Experimental values for solubility
A solid dissolves in a solvent until the solution and constants are given in Table 8.4.
the solid solute are in equilibrium. At this stage, We can interpret the solubility constant in terms
the solution is said to be saturated, and its molar of the numerical value of the molar solubility, S, of
con- centration is the molar solubility of the solid. a sparingly soluble substance. For instance, it
That the two phases—the solid solute and the follows from the stoichiometry of the equilibrium
solution— are in dynamic equilibrium implies that equation written above that the molar
we can use equilibrium concepts to discuss the concentration of Ca2
composition of the saturated solution. You should ions in solution is equal to that of the Ca(OH) 2 dis-
note that a solu- bility equilibrium is an example solved in solution, so S  [Ca2]. Likewise, because
of a heterogeneous equilibrium in which the species the concentration of OH ions is twice that of
are in different phases (the solid solute and the Ca(OH)2 formula units, it follows that S  1[OH].
2
solution). The prop- erties of aqueous solutions of Therefore, provided it is permissible to replace
electrolytes are com- monly treated in terms of activ-
equilibrium constants, and in this section we shall ities by molar concentrations,
confine our attention to them. We shall also limit
Ks  S  (2S)2  4S3
our attention to sparingly soluble compounds,
which are compounds that dissolve only slightly in from which it follows that
water. This restriction is applied because the
S  (14Ks)1/3 (8.16)
effects of ion–ion interactions are a complicating
feature of more concentrated solutions and more This expression is only approximate because ion–
advanced techniques are then needed before the ion interactions have been ignored. However,
because the solid is sparingly soluble, the
concentrations of the ions are low and the
inaccuracy is moder- ately low. Thus, from
Table 8.4, Ks  5.5  106, so S  1  102 and
the molar solubility is 1  102 mol dm3.
Solubility constants (which are determined
by electrochemical measurements of the kind
described in Chapter 9) provide a more
accurate way of meas- uring solubilities of very
sparingly soluble compounds than the direct
measurement of the mass that dissolves.
 188 CHAPTER 8: CHEMICAL EQUILIBRIUM: EQUILIBRIA IN SOLUTION

Because solubility products are equilibrium con-

Table 8.4 stants, they may be calculated from
Solubility constants at 298.15 K thermodynamic data, particularly the standard
Gibbs energies of formation of ions in solution and
Compound Formula Ks the relation ΔrG 
1.0  1033 RT ln K). The direct determination of solubilities
Aluminium hydroxide Al(OH)
Antimony
3 Sb2S3sulfide
BaCO3Barium
BaF2 BaSO
carbonate 1.72Ca(OH)
4 Bi2S3 CaCO3 CaF 10932 CaSO4
is very diAcult for almost insoluble salts. Another
fluoride sulfate CuBr 8.1  109
Bismuth sulfide Calcium
CuCl carbonate
CuI Cu2S Cu(IO3)2 CuC2O4 1.7  10 6 application is to the discussion of qualitative ana-
fluoride hydroxide sulfate
CuS 1.1  1010 lysis, where judicious choice of concentrations guided
Copper(I) bromide chloride
Fe(OH)2 1.0  1097 by the values of Ks can result in the successive pre-
iodide sulfide FeS Fe(OH)3 8.7  109 cipitation of compounds (sulfides, for instance)
Copper(II) iodate oxalate
PbBr2 sulfide 4.0  1011
and the recognition of the heavy elements
Iron(II) hydroxide sulfide
PbCl2 PbF2 Pb(IO3)2 PbI2 PbSO4 5.5  10 6
Iron(III) hydroxide Lead(II)
PbS bromide 2.4  105 (barium, for instance), present in a mixture.
chloride fluoride iodate iodide sulfate sulfide 4.2  10 8
Magnesium ammonium phosphate 1.0  106
carbonate fluoride hydroxide 5.1  1012
8.9 The common-ion effect
Mercury(I) chloride iodide 2.0  10 47 The principle that an equilibrium constant
Mercury(II) sulfide 1.4  107 remains unchanged whereas the individual
2.9  10 8
8.5  10 45
concentrations of species may change is applicable
1.6  1014 to solubility con- stants, and may be used to assess
6.3  1018 the effect of the addition of species to solutions.
2.0  1039 An example of par- ticular importance is the effect
7.9  105 on the solubility of a compound of the presence of
1.6  105
another freely soluble solute that provides an ion
3.7  10 8
2.6  1013 in common with the spar- ingly soluble compound
1.4  10 8 already present. For example, we may consider the
1.6  10 8 effect on the solubility of adding sodium chloride
3.4  1028 to a saturated solution of silver chloride, the
common ion in this case being Cl.
We know what to expect from Le Chatelier’s
prin- ciple: when the concentration of the common
2.5 2 1013
MgNH4PO4 MgCO3 MgF2 Mg(OH)
Hg2Cl2 Hg2I2 1.0  105 ion is increased, we can expect the equilibrium to
6.4  109
HgS black: respond by tending to minimize that increase. As a
 1011
red:
1.1 result, the solubility of the original salt can be
1.3  1018 expected to decrease. To treat the effect
1.2  1028
quantitatively, we note that the molar solubility of
1.6  1052
1.4  1053 silver chloride in pure water is related to sits
solubility constant by S  K1/2. To assess the effect
of the common ion, we suppose that Cl ions are
Nickel(II) hydroxide Ni(OH)2 6.5  1018 added to a concentration C mol dm3, which greatly
Silver bromide AgBr 7.7  1013 exceeds the concentration of the same ion that
carbonate Ag2CO3 6.2  1012 stems from the presence of the silver chlo- ride.
chloride AgCl 1.6  1010 Therefore, we can write
hydroxide AgOH 1.5  10 8 K  a  a   [Ag]C
iodide AgI 1.5  1016 s Ag Cl
sulfide Ag2S 6.3  1051 It is very dangerous to neglect deviations from
Zinc hydroxide Zn(OH)2 2.0  1017
ideal behaviour in ionic solutions, so from now on
sulfide ZnS 1.6  1024
the calculation will only be indicative of the kinds
of changes that occur when a common ion is
added to a solution of a sparingly soluble salt: the
qualitative trends are reproduced, but the
quantitative
e of which is chalco- cite, Cu2S. What is the approximate solubility of this com- pound in water at 25°C? Usecalcula-
the data fortions
Cu2S inare
Tableunreliable.
8.4. With
these remarks in mind, it follows that the solubility
S of silver chloride in the presence of added
chloride ions is
K
S  s
C
 CHECKLIST OF KEY IDEAS 189

The solubility is greatly reduced by the presence of

energy that results, the sparingly soluble salt has a
the common ion. For example, whereas the solubility
greater tendency to go into solution. That is, the
of silver chloride in water is 1.3  105 mol dm3, in
presence of the added salt raises the solubility of
the presence of 0.10 M NaCl(aq) it is only 2  109
the sparingly soluble salt.
mol dm3, which is nearly ten thousand times To estimate the effect of an added salt MX on
less. The reduction of the solubility of a
a sparingly soluble salt AB, we write the solubility
sparingly soluble salt by the presence of a
constant for AB in terms of activities:
common ion is called the common-ion effect.
Ks  aAaB  A B[A][B]  A BS2
Self-test 8.16 It follows that S  (Ks /A B)1/2 and therefore that
Estimate the molar solubility of calcium fluoride, CaF2, in
(a) water, (b) 0.010 M NaF(aq). log S  12 log(Ks /A B)  21 log Ks  12log A B
[Answer: (a) 2.2  10 4 mol dm3; (b) 4.0  107 mol dm3]
We shall see in Chapter 9 that the logarithm of the
product of activity coeAcients is proportional to
the square root of the concentration, C, of the
8.10 The effect of added salts on solubility added salt; with log A B  2AC1/2 where A is a
constant that depends on the identity of the
Even a salt that has no ion in common with the
solvent and the temperature; for water at 25°C, A 
sparingly soluble salt can affect the latter’s
0.51. It follows that
solubility. At low concentrations of the added salt,
the solubil- ity of the sparingly soluble salt is log S  21 log Ks  AC1/2 (8.17)
increased. The explanation lies in a phenomenon
Note that AC1/2 increases with increasing
that will move to centre stage in Chapter 9, where
concentra- tion of added salt, so log S, and
we shall see that in aqueous solution, cations tend
therefore S itself, also increases, as we anticipated.
to be found near anions and anions tend to be
The linear dependence of log S on C1/2 is observed,
found near cations. That is, each ion is in an
but only for low concen- trations of added salt.
environment, called an ‘ionic atmosphere’, of
opposite charge. The charge imbal- ance is not
A brief illustration The solubility of AgCl in water at
great, because the ions are ceaselessly churned 25°C is S  K 1/2
; because K s 1.6  1010, it follows that3
5 s 3
around by thermal motion, but it is enough to
lower the energy of the central ion slightly. S  1.3  10 mol dm . In the presence of 0.10 mol dm
When a soluble salt is added to the solution of a KNO3(aq) its solubility increases to
sparingly soluble salt, the abundant ions of the
log S  12  log(1.6  1010)  0.51  (0.10)1/2  4.74
latter form ionic atmospheres around the ions of
the spar- ingly soluble salt. As a result of the corresponding to S  1.8  105 mol dm3.
lowering of

Checklist of key ideas

You should now be familiar with the following

… 4 The pH of a buffer solution containing equal con-
concepts.
centrations of a weak acid and its conjugate
… 1 The strength of an acid HA is reported in terms base is pH  pKa.
of its acidity constant and that of a base B in
… 5 The end-point of the colour change of an
terms of its basicity constant.
indicator occurs at pH  pKIn; in a titration,
… 2 The acid form of a species is dominant if pH  choose an indica- tor with an end-point that
pKa and the base form is dominant if pH  pKa. coincides with the stoi- chiometric point.

… 3 The pH of a mixed solution of a weak acid and … 6 The common-ion effect is the reduction in
its conjugate base is given by the Henderson– solubil- ity of a sparingly soluble salt by the
Hasselbalch equation. presence of a common ion.
190 CHAPTER 8: CHEMICAL EQUILIBRIUM: EQUILIBRIA IN SOLUTION

Table of key equations

The following table summarizes the equations developed in this chapter.

Property
Equation Comment

Acidity constant
Ka  aH3OaA /aHA Definition
Basicity constant
Kb  aBHaOH /aB Definition
Autoprotolysis constant of water
K w  aH3OaOH Definition
Relation between pH and pOH
pH  pOH  pK
Conjugate relation w

pH of the solution of an K aK b  K w and pK a  pK b 

amphiprotic salt of concentration F  K w /K a2 and F  K a1
pK w
A
pH  12(pK a1  pK a2)
Henderson–Hasselbalch equation Weak acid and base

Solubility constant pH  pKa  log([acid]/[base]) Sparingly soluble salt MA

Ks  aMaA

Questions and exercises

Discussion questions biochemically important acids in aqueous solution:

(a) lactic acid (CH3CHOHCOOH), (b) glutamic acid
8.1 Describe the changes in pH that take place during the
titration of: (a) a weak acid with a strong base, (b) a weak
base with a strong acid.

8.2 Describe the basis of buffer action and indicator

detection.

8.3 Explain the difference between ‘stoichiometric (equi-

valence) point’ and ‘end-point’ in the context of a
titration.

8.4 Outline the change in composition of a solution of the

salt of a triprotic acid as the pH is changed from 1 to 14.

8.5 State the limits to the generality of the expression for

estimating the pH of an amphiprotic salt solution. Suggest
reasons for why these limitations exist.

8.6 Describe and justify the approximations used in the

derivation of the Henderson–Hasselbalch equation.

8.7 Explain the common-ion effect.

Exercises
8.1 Write the proton-transfer equilibria for the following
acids in aqueous solution and identify the conjugate acid–
base pairs in each one: (a) H 2SO4, (b) HF (hydrofluoric
acid), 3(c) C6H5NH (anilinium 4 ion), (d) H 2PO 
(dihydrogenphosphate ion), (e) HCOOH3 (formic acid), (f)
NH2NH (hydrazinium ion).

8.2 Numerous acidic species are found in living systems.

Write the proton-transfer equilibria for the following
(HOOCCH2CH2CH(NH2)COOH), (c) glycine (NH2CH2COOH),
(d) oxalic acid (HOOCCOOH).

8.3 For biological and medical applications we often

need to consider proton transfer equilibria at body
temperature (37°C). The value of Kw for water at body
temperature is 2.5  1014.
(a) What is the value of [H3O] and the pH of neutral water at
37°C? (b) What is the molar concentration of OH  ions
and the pOH of neutral water at 37°C?
8.4 Suppose that something had gone wrong in the Big
Bang, and instead of ordinary hydrogen there was an
abund- ance of deuterium in the universe. There would
be many subtle changes in equilibria, particularly the
deuteron transfer equilibria of heavy atoms and bases.
The Kw for D2O, heavy water, at 25°C is 1.35  1015. (a)
Write the chemical equation for the autoprotolysis
(more precisely, autodeuterolysis) of D 2O. (b) Evaluate
pKw for D2O at 25°C. (c) Calculate the molar
concentrations of D3O and OD in neutral heavy water at
25°C.
(d)Evaluate the pD and pOD of neutral heavy water at 25°C.
(e)Formulate the relation between pD, pOD, and pKw(D2O).
8.5 Estimate the pH of a solution of 0.50 M HCl(aq). The
mean activity coefficient at this concentration is 0.769.
What is a more reliable value of the pH?
8.6 Use the van ’t Hoff equation (eqn 7.15) to derive an
expression for the slope of a plot of pKa against
temperature.
8.7 The pKw of water varies with temperature as follows:
q/°C 10 15 20 25 30 35
pKw 14.5346 14.3463 14.1669 13.9965 13.8330 13.6801
Determine the standard enthalpy of deprotonation of water.
 QUESTIONS AND EXERCISES 191

8.8 The pK b of ammonia in water varies with temperature

8.20 Show how the composition of an aqueous solution
as follows:
that contains 20 mmol dm3 glycine varies with pH.
q/°C 10 15 20 25 30 35
8.21 Show how the composition of an aqueous solution
pK b 4.804 4.782 4.767 4.751 4.740 4.733
that contains 30 mmol dm3 tyrosine varies with pH.
Deduce as much information as you can from these values.
8.22 Estimate the pH of an aqueous solution of sodium
8.9 The pKb of the organic base nicotine (denoted Nic) is hydrogenoxalate. Under what conditions is this estimate
5.98. Write the corresponding protonation reaction, the reas- onably reliable?
deprotonation reaction of the conjugate acid, and the
value of pK a for nicotine. 8.23 Calculate the pH of the following acid solutions at

25°C; ignore second deprotonations only when that
8.10 The molar concentration of H3O ions in the follow- approximation is justified. (a) 1.0  104 M H3BO3(aq) (boric
ing solutions was measured at 25°C. Calculate the pH and acid acts as a monoprotic acid), (b) 0.015 M H3PO4(aq), (c)
pOH of the solution: (a) 1.5  105 mol dm3 (a sample
0.10 M H2SO3(aq).
of rain water), (b) 1.5 mmol dm3, (c) 5.1  1014 mol dm3,
(d) 5.01  105 mol dm3. 8.24 The weak base colloquially known as Tris, and more
 precisely as tris(hydroxymethyl)aminomethane (3), has pKa
8.11 Calculate the molar concentration of H3O ions and
the pH of the following solutions: (a) 25.0 cm3 of 0.144 M 
8.3 at 20°C and is commonly used to produce a buffer for bio-
HCl(aq) was added to 25.0 cm3 of 0.125 M NaOH(aq), (b)
chemical applications. At what pH would you expect Tris
25.0 cm3 of 0.15 M HCl(aq) was added to 35.0 cm3 of 0.15 M
to act as a buffer in a solution that has equal molar
KOH(aq),
concentra- tions of Tris and its conjugate acid?
(c) 21.2 cm3 of 0.22 M HNO3(aq) was added to 10.0 cm3 of
0.30 M NaOH(aq).
HO
8.12 Determine whether aqueous solutions of the OH
following salts have a pH equal to, greater than, or less H2N
than 7; if pH  7 or pH  7, write a chemical equation to
justify your answer. HO
(a)NH4Br, (b) Na2CO3, (c) KF, (d) KBr, (e) AlCl3, (f ) 3 tris(hydroxymethyl)aminomethane
Co(NO3)2.
8.13 Sodium acetate, NaCH3CO2, of mass 7.4 g is used to 8.25 The amino acid tyrosine has pKa  2.20 for deprotona-
prepare 250 cm3 of aqueous solution. What is the pH of the tion of its carboxylic acid group. What are the relative
solution? con- centrations of tyrosine and its conjugate base at a pH
of (a) 7, (b) 2.2, (c) 1.5?
8.14 What is the pH of a solution when 2.75 g of
ammonium chloride, NH4Cl, is used to make 100 cm3 of 8.26 (a) Calculate the molar concentrations of (COOH) 2,
aqueous solution?solution of volume 1.0 dm3 contains 10.0 HOOCCO, (CO )2, H O, and OH in 0.15 M (COOH) (aq).
8.15 An aqueous
g 2 22 3  2
2 


of potassium bromide. What is the percentage of Br ions (b)Calculate the molar concentrations of H2S, , H 3O ,
that are protonated? HS , S and OH in 0.065 M H2S(aq).
8.16 There are many organic acids and bases in our cells, 8.27 A sample of 0.10 M CH3COOH(aq) of volume 25.0 cm3
and their presence modifies the pH of the fluids inside is titrated with 0.10 M NaOH(aq). The K a for CH3COOH is 1.8
them. It is useful to be able to assess the pH of solutions  105. (a) What is the pH of 0.10 M CH3COOH(aq)? (b) What
of acids and bases and to make inferences from measured is the pH after the addition of 10.0 cm3 of 0.10 M
values of the pH. A solution of equal concentrations of NaOH(aq)?
(c)What volume of 0.10 M NaOH(aq) is required to reach
lactic acid and sodium lactate was found to have pH 
half- way to the stoichiometric point? (d) Calculate the pH
3.08. (a) What are the values of pKa and Ka of lactic acid?
at that half-way point. (e) What volume of 0.10 M
(b) What would the pH be if the acid had twice the
NaOH(aq) is required to reach the stoichiometric point? (f)
concentration of the salt?
Calculate the pH at the stoichiometric point.
8.17 Sketch reasonably accurately the pH curve for the
8.28 A buffer solution of volume 100 cm3 consists of 0.10 M
titra- tion of 25.0 cm3 of 0.15 M Ba(OH)2(aq) with 0.22 M CH COOH(aq) and 0.10 Na(CH CO )(aq). (a) What is its pH?
HCl(aq). 3
Mark on the curve (a) the initial pH, (b) the pH at the stoichio- M 3 2

metric point. (a)0.150 M CH3CH(OH)COOH(aq) (lactic acid), (b) 2.4  104 M

CH3CH(OH)COOH(aq), (c) 0.25 M C6H5SO3H(aq) (benzenesul- fonic
8.18 Determine the fraction of solute deprotonated or
acid).
proto- nated in (a) 0.25 M C6H5COOH(aq), (b) 0.150 M
NH2NH2(aq) (hydrazine), (c) 0.112 M (CH3)3N(aq)
(trimethylamine).
8.19 Calculate the pH, pOH, and fraction of solute proto-
nated or deprotonated in the following aqueous solutions:
(b)What is the pH after the addition of 3.3 mmol NaOH to the
buffer solution? (c) What is the pH after the addition
of 6.0 mmol HNO3 to the initial buffer solution?
8.29 Predict the pH region in which each of the
following buffers will be effective, assuming equal
molar concentrations of the acid and its conjugate
base: (a) sodium lactate and lactic acid, (b) sodium
benzoate and benzoic acid, (c) potassium
hydrogenphosphate and potassium phosphate, (d)
potassium hydrogenphosphate and potassium
dihydrogenphosphate,
(e) hydroxylamine and hydroxylammonium chloride.
192 CHAPTER 8: CHEMICAL EQUILIBRIUM: EQUILIBRIA IN SOLUTION

8.30 At the half-way point in the titration of a weak acid

Projects
with a strong base the pH was measured as 5.16. What is
the acidity constant and the pKa of the acid? What is the 8.41 Deduce expressions for the fractions of each type of
pH of the solution that is 0.025 M in the acid? species present in an aqueous solution of lysine (4) as a
function of pH and plot the appropriate speciation
8.31 Calculate the pH of (a) 0.10 M NH4Cl(aq), (b) 0.25 M
diagram. Use the following values of the acidity constants:
NaCH3CO2(aq), (c) 0.200 M CH3COOH(aq).
pKa(H3Lys2)
8.32 Calculate the pH at the stoichiometric point of the  2.18, pKa(H2Lys)  8.95, pKa(HLys)  10.53. Hint: Although
titration of 25.00 cm3 of 0.150 M lactic acid with 0.188 M it is instructive to rework Example 8.4 for a triprotic
NaOH(aq). species, the expressions for the fraction can easily be
written down by analogy with those in the example.
8.33 Sketch the pH curve of a solution containing 0.10 M

NaCH3CO2(aq) and a variable amount of acetic acid.

8.34 From the information in Tables 8.1 and 8.2, select

HO
suitable buffers for (a) pH  2.2 and (b) pH  7.0.

8.35 Write the expression for the solubility constants of O NH2 NH2
the following compounds: (a) AgI, (b) Hg2S, (c) Fe(OH)3,
4 Lysine (Lys)
(d) Ag2CrO4.

8.36 Use the data in Table 8.4 to estimate the molar solu-
bilities of (a) BaSO4, (b) Ag2CO3, (c) Fe(OH)3, (d) Hg2Cl2 in
water. 8.42 Using the insights gained through your work on Exer-
cise 8.41, and without doing a calculation, sketch the
8.37 Use the data in Table 8.4 to estimate the solubility in speci- ation diagram for histidine (5) in water and label
water of each sparingly soluble substance in its respective the axes with the significant values of pH. Use pKa(H3His2)
solution: (a) silver bromide in 1.4  103 M NaBr(aq), (b)  1.77, pKa(H2His)  6.10, pKa(HHis)  9.18.
mag- nesium carbonate in 1.1  105 M Na2CO3(aq), (c)
lead(II) sulfate in a 0.10 M CaSO4(aq), (d) nickel(II)
hydroxide in 2.7  105 M NiSO4(aq).
O
8.38 The solubility of mercury(I) iodide is 5.5 fmol dm 3
N
(1 fmol  1015 mol) in water at 25°C. What is the standard OH
Gibbs energy of dissolution of the salt? HN NH2
8.39 Thermodynamic data can be used to predict the 5 Histidine (His)
solubil- ities of compounds that would be very difficult to
measure directly. Calculate the solubility of mercury(II)
chloride in water at 25°C from standard Gibbs energies of 8.43 Here we explore buffer action in blood more
formation. quantita- tively. (a) What are the values of 3 the
2 ratio
3
[HCO]/[H CO ] at the onset of acidosis and alkalosis? (b)
8.40 (a) Derive an expression for the ratio of solubilities
The Bohr effect may be understood in terms of a
of AgCl at two different temperatures; assume that the
dependence on pH of the degree of cooperativity in the
standard enthalpy of solution of AgCl is independent of
binding of O2 by haemoglobin. Based on the description of
temperature in the range of interest. (b) Do you expect
the Bohr effect given here and the in- formation provided
the solubility of AgCl to increase or decrease as the
temperature is raised? in Exercise 7.44, does the Hill coefficient of haemoglobin
increase or decrease with pH?