CHAPTER 10

ACIDS AND BASES

10.2 (a) (b) H
3
H O
+
2
O (c)
6 5 3
C H NH
+
(d) HS

(e)
3
4
PO

(f)
4
ClO



10.4 (a) H
2
O(l) + CN

(aq) HCN(l) + OH

(aq)

conjugate

acid
1
base
2
acid
2
base
1

conjugate


(b)

conjugate
H
2
O(l) + NH
2
NH
2
(aq) NH
2
NH
3
+
(aq) + OH

(aq)
acid
1
base
2
acid
2
base
1

conjugate

conjugate

(c) H
2
O(l) + CO
3
2
(aq) HCO
3

(aq) + OH

(aq)
acid
1
base
2
acid
2
base
1

conjugate

conjugate

(d) H
2
O(l) + HPO
4
2
(aq) H
2
PO
4

(aq) + OH

(aq)
acid
1
base
2
acid
2
base
1

conjugate

conjugate

(e) H
2
O(l) + NH
2
CONH
2
(aq) NH
2
CONH
3
+
(aq) + OH

(aq)
acid
1
base
2
acid
2
base
1

conjugate

291
10.6 (a) Brnsted acid: NH
4
+
Brnsted base:
3
HSO


(b) Conjugate base to NH
4
+
: NH
3
Conjugate acid to
3
HSO

: H
2
SO
3

10.8 (a) as an acid: H
2
PO
4

(aq) + H
2
O(l) H
3
O
+
(aq) + HPO
4
2
(aq)
Conjugate acid/base pairs: H
2
PO
4

(aq) / HPO
4
2
(aq)
H
3
O
+
(aq) / H
2
O(l)
as a base: H
2
PO
4

(aq) + H
2
O(l) OH

(aq) + H
3
PO
4
(aq)
Conjugate acid/base pairs: H
3
PO
4
(aq) / H
2
PO
4

(aq)
H
2
O(l) / OH

(aq)
(c) as an acid: HC
2
O
4

(aq) + H
2
O(l) H
3
O
+
(aq) + C
2
O
4
2
(aq)
Conjugate acid/base pairs: HC
2
O
4

(aq) / C
2
O
4
2
(aq)
H
3
O
+
(aq) / H
2
O(l)
as a base: HC
2
O
4

(aq) + H
2
O(l) OH

(aq) + H
2
C
2
O
4
(aq)
Conjugate acid/base pairs: H
2
C
2
O
4
(aq) / HC
2
O
4

(aq)
H
2
O(l) / OH

(aq)

10.10 (a) acidic; (b) basic; (c) acidic; (d) amphoteric

10.12 (a) 2 OH

(aq) + SiO
2
(s) SiO
3
2
(aq) + H
2
O(l)
(b)
O
Si
O O
Si
O
O O
Si
O
O O

(c) Lewis Acid: SiO
2
(s), Lewis Base: OH

(aq)

10.14 In each case use then
14
w 3
[H O ][OH ] 1.0 10 ,
+
= = K
292
14
w
3
1.0 10
[H O ]
[OH ] [OH ]

= =
K

(a)
14
13
3
1.0 10
[H O ] 8.3 10
0.012

= =
(b)
14
10
3
5
1.0 10
[H O ] 1.6 10
6.2 10

= =

(c)
14
12
3
3
1.0 10
[H O ] 4.3 10
2.3 10

= =

10.16 (a)
8 1
3
[H O ] [OH ] 3.9 10 mol L
+
= =

8 2 15
w 3
15
w w
[H O ][OH ] (3.9 10 ) 1.5 10
p log log(1.5 10 ) 14.82
+

= = =
= = =
K
K K

(b)
8
pH log(3.9 10 ) 7.41 pOH

= = =

10.18 [KNH
2
]
0
= nominal concentration of KNH
2
[KNH
2
]
0
=
1 2 2
2
0.5 g KNH 1mol KNH
0.036 mol L
0.250 L 55.13 g KNH


=



Because KNH
2
is a soluble salt, [KNH
2
]
0
= [K
+
] = (where
is the nominal concentration of
2 0
[NH ]

2 0
[NH ]

2
NH

); thus [K
+
] and =
0.036 .
2
[NH ]

1
mol L

2
NH

reacts with water:
2 2 3
NH (aq) H O(l) NH (aq) OH (aq)

+ +
Because is a strong base, this reaction goes essentially to
completion; therefore
2
NH

1
2 0
[NH ] [OH ] 0.036 mol L

= =


14
13 1 w
3
1.0 10
[H O ] 2.8 10 mol L
[OH ] 0.036
K

+

= = =



293
10.20
pH 1
3
[H O ] 10 mol L (antilog pH, mol L )
+
=
1

(a)
5 1
3
[H O ] antilog( 5) 1 10 mol L
+
= =
(b)
2.3 1 3 1
3
[H O ] 10 mol L ; antilog ( 2.3) 5 10 mol L
+
= =
(c)
7.4 1 8 1
3
[H O ] 10 mol L ; antilog ( 7.4) 4 10 mol L
+
= =
(d)
10.5 1 11 1
3
[H O ] 10 mol L ; antilog ( 10.5) 3 10 mol L
+
= =
Acidity increases as pH decreases. The order is thus:
milk of magnesia < blood < urine < lemon juice

10.22 (a) pH log(0.0356) 1.448
pOH 14.00 1.448 12.55
= =
= =
(b) pH log(0.0725) 1.12
pOH 14.00 1.12 12.86
= =
= =

(c)
2
2
Ba(OH) Ba 2 OH
+
+

3 1 3 1
3
[OH ] 2 3.46 10 mol L 6.92 10 mol L
pOH log(6.92 10 ) 2.160
pH 14.00 2.160 11.84

= =
= =
= =

(d)
3
4
1
4
2 1
2
10.9 10 g
1.94 10 mol KOH
56.11 g mol
1.94 10 mol
[OH ] 1.94 10 mol L
0.0100 L
pOH log(1.94 10 ) 1.712
pH 14.00 1.712 12.29

= =
= =
= =

(e)
1 1
10.0 mL
[OH ] (5.00 mol L ) 0.0200 mol L
2500 mL
pOH log(0.200) 1.70
pH 14.00 0.699 12.30


= =


= =
= =

(f)
4 1 5
3
5
5.0 mL
[H O ] (3.5 10 mol L ) 7.0 10 mol L
25.0 mL
pH log(7.0 10 ) 4.15
pOH 14.00 4.15 9.85
+

= =


= =
= =
1

294
10.24 Base K
b
pK
b
(a) NH
3

5
1.8 10

4.74
(b) ND
3

5
1.1 10

4.96
(c) NH
2
NH
2

6
1.7 10

5.77
(d) NH
2
OH
8
1.1 10

7.96
(e) NH
2
OH < NH
2
NH
2
< ND
3
< NH
3

10.26 (a)
3 2 2 3 2 2
3 2 2
b
3 2
(CH ) NH(aq) H O(l) (CH ) NH (aq) OH (aq)
[(CH ) NH ][OH ]

[(CH ) NH]
K
+
+
+ +
=

3 2 2 2 3 3 2
3 3 2
a
3 2 2
(CH ) NH (aq) H O(l) H O (aq) (CH ) NH(aq)
[H O ][(CH ) NH]

[(CH ) NH ]
K
+ +
+
+
+ +
=

(b)
14 10 2 2 14 10 2
14 10 2
b
14 10 2
C H N (aq) H O(l) C H N H (aq) OH (aq)
[C H N H ][OH ]

[C H N ]
K
+
+
+ +
=

14 10 2 2 3 14 10 2
3 14 10 2
a
14 10 2
C H N H (aq) H O(l) H O (aq) C H N (aq)
[H O ][C H N ]

[C H N H ]
K
+ +
+
+
+ +
=

(c)
6 5 2 2 6 5 3
6 5 3
b
6 5 2
C H NH (aq) H O(l) C H NH (aq) OH (aq)
[C H NH ][OH ]

[C H NH ]
K
+
+
+ +
=

6 5 3 2 3 6 5 2
3 6 5 2
a
6 5 3
C H NH (aq) H O(l) H O (aq) C H NH (aq)
[H O ][C H NH ]

[C H NH ]
K
+ +
+
+
+ +
=

10.28 Decreasing pK
a
will correspond to increasing acid strength because pK
a

= The pK
a
log . K
a
values (given in parentheses) determine the following
ordering:

295
3 3 2 5
(CH ) NH (14.00 4.19 9.71) N H (14.00 5.77 8.23)
+ +
= < =
< HCOOH (3.75) < HF (3.45)
Remember that the pK
a
for the conjugate acid of a weak base will be given
by
pK
a
+ pK
b
= 14.

10.30 Decreasing pK
b
will correspond to increasing base strength because pK
b

=
b
log K . The pK
b
values (given in parentheses) determine the following
ordering:

2 4
2 5 3
N H (5.77) BrO (14.00 8.69 5.31) CN (14.00 9.31 4.69)
(C H ) N(2.99)

< = < =
<
Remember that the pK
b
for the conjugate base of a weak acid will be given
by
pK
a
+ pK
b
= 14.

10.32 Any base whose conjugate acid lies below water in Table 10.3 will be a
strong base, that is, the conjugate acid of the base will be a weaker acid
than water, and so water will preferentially protonate the base. Based upon
this information, we obtain the following analysis: (a) , strong;
2
O

(b) , weak; (c) Br

4
HSO

, weak; (d)
3
HCO

, weak; (e) CH
3
NH
2
,
weak; (f) H , strong; (g)

3
CH

, strong.

10.34 In oxoacids with the same number of oxygen atoms attached to the central
atom, the greater the electronegativity of the central atom, the more the
electrons of the OH bond are withdrawn, making the bond more polar.
This allows the hydrogen of the OH group to be more readily donated as a
proton to H
2
O, due to the stronger hydrogen bonds that it forms with the
oxygen of water. Therefore, HClO is the stronger acid, with the lower pK
a
.

10.36 (a) H
3
PO
4
is stronger; it has the more electronegative central atom.
296
(b) HBrO
3
is stronger; there are more O atoms attached to the central
atom in HBrO
3
, making the HO bond in HBrO
3
more polar than in
HBrO.
(c) We would predict H
3
PO
4
to be a stronger acid due to more oxygens on
the central atom.
(d) H
2
Te is the stronger acid, because the HTe bond is weaker than the
HSe bond.
(e) HCl is the stronger acid. Within a period, the acidities of the binary
acids are controlled by the bond polarity rather than the bond strength, and
HCl has the greater bond polarity, due to the greater electronegativity of
Cl relative to S.
(f) HClO is stronger because Cl has a greater electronegativity than I.

10.38 (a) Methylamine is CH
3
NH
2
, ammonia is NH
3
. Methylamine can be
thought of as being formed from NH
3
by replacing one H atom with CH
3
.
Because CH
3
is less electron withdrawing than H, CH
3
NH
2
is a weaker
acid and therefore a stronger base.
(b) Hydroxylamine is HONH
2
, hydrazine is H
2
NNH
2
. The former can
be thought of as being derived from NH
3
by replacement of one H atom
with OH; the latter by replacement of one H atom with NH
2
. Because the
hydroxyl group is more electron withdrawing than the amino group, NH
2
,
hydroxylamine is the stronger acid and therefore a weaker base.

10.40 The solution of 0.10 M H
2
SO
4
would have the higher pH (would be the
weaker acid) because the conjugate base, HSO
4
,
is less electronegative
than the conjugate base of hydrobromic acid, namely Br

.

10.42 The smaller the value of pK
b
, the stronger the base; hence, aniline is the
stronger base. 4-Chloroaniline is the stronger acid due to the presence of
the electron-withdrawing Cl atom, making it the weaker base; and again
we see that aniline is the stronger base.
297
10.44 The higher the pK
a
of an acid, the stronger the corresponding conjugate
base; therefore, the order is
3-hydroxyaniline < aniline < 2-hydroxyaniline < 4-hydroxyaniline
No simple pattern exists, but the position of the OH group does affect
the basicity.

10.46 (a)
2 2
4 3 3 2
a
3
[H O ][CH CH(OH)CO ]
8.4 10
[CH CH(OH)COOH] 0.12 0.12
+

= = =

x x
K
x

Here we have assumed that x is small enough to neglect it relative to 0.12
. This is a borderline case. We will also solve this exercise
without making this approximation and compare the results below.
1
mol L

1
3
[H O ] 0.010 mol L
pH log(0.010) 2.00
pOH 14.00 2.00 12.00
+
= =
= =
= =
x

Without the approximation, the quadratic equation that must be solved is
2
4
2 4 4
4 4 2
3
8.4 10
0.12
or 8.4 10 1.01 10 0
8.4 10 (8.4 10 ) 4( 1.01 10 )
2
0.0096, 0.018.
[H O ] 0.0096

+
=

+ =

=
=
= =
x
x
x x
x
x
x
4

pH log(0.0096) 2.02 = =
(b)
2
4
a
3
8.4 10
1.2 10

= =

x
K
x

or
2 4
3 3
8.4 10 1.0 10 0
1.5 10 , 1.1 10


+ =
=
x x
x
6
The negative root can be eliminated:
3
3
3
[H O ] 1.1 10
pH log(1.1 10 ) 2.96
pOH 14.00 2.96 11.04
+

= =
= =
= =
x

298
(c)
2
4
5
8.4 10
1.2 10

=

x
x

or
2 4
5 4
8.4 10 1.0 10 0
1.2 10 , 8.5 10


+ =
=
x x
x
8
The negative root can be eliminated.
5
3
5
[H O ] 1.2 10
pH log(1.2 10 )
pH 4.92
pOH 14.00 4.92 9.08
+

=
=
=
= =


10.48 (a)
9
b
(pyridine) 1.8 10

= K
6 5 2 6 5
C H N H O C H NH OH
+
+ +
Concentration C
1
(mol L )

6
H
5
N + H
2
O C
6
H
5
NH
+
+ OH

initial 0.075 0 0
change x +x +x
final 0.075 x +x +x
2 2
9
b
5 1
5
1.8 10
0.075 0.075
[OH ] 1.2 10 mol L
pOH log(1.2 10 ) 4.92
pH 14.00 4.92 9.00

= =

= =
= =
= =
x x
K
x
x
Percentage ionized =
5
2
1.2 10
100% 1.6 10 %
0.075

=
(b) The setup is similar to that in (a).
2 2
6
b
1.0 10 [OH ]
0.0112 0.0112

= = =

x x
K x
x

299
4 1
4
4
1.1 10 mol L
pOH log(1.1 10 ) 3.97
pH 14.00 3.97 10.03
3.2 10
Percentage protonation 100% 2.6%
0.0122

=
= =
= =

= =
x

(c)
b
p 14.00 8.52 5.48 = = K
6
b
3.3 10

= K
2
quinine H O quinineH OH
+
+ +
2 2
6
b
3.3 10
0.021 0.021

= =

x x
K
x

4 1
4
4
[OH ] 2.6 10 mol L
pOH log(2.6 10 ) 3.58
pH 14.00 3.58 10.42
2.6 10
Percentage protonation 100% 1.2%
0.021

= =
= =
= =

= =
x

(d)
2
strychnine H O strychnineH OH
+
+ +

14
6 w
b
9
a
2 2
6
b
4 1
4
4
[OH ]
1.00 10
1.82 10
5.49 10
1.82 10
0.059 0.059
[OH ] 3.3 10 mol L
pOH log(3.3 10 ) 3.48
pH 14.00 3.48 10.52
3.3 10
Percentage protonation 100% 0.56%
0.059

= = =

= =

= =
= =
= =

= =
x
K
K
K
x x
K
x
x





300
10.50 (a) HN
2 2 3 2
O H O H O NO
+
+ +

2.63 3 1
3 2
3 2
4
a
3
4
a
[H O ] [NO ] 10 antilog ( 2.63) 2.3 10 mol L
(2.3 10 )
4.2 10
0.015 2.3 10
p log(4.3 10 ) 3.38
+

= = = =

= =

= =
K
K

(b)
4 9 2 2 4 9 3
C H NH H O C H NH OH
+
+ +
1.96 1
4 9 3
pOH 14.00 12.04 1.96
[C H NH ] [OH ] 10 antilog ( 1.96) 0.011 mol L
+
= =
= = = =


2
3 4 9 3
b
4 9 2
3
b
[C H NH ][OH ] (0.011)
1.4 10
[C H NH ] 0.10 0.011
p log(1.4 10 ) 2.85
+

= = =

= =
K
K

10.52 (a)
10
a
(HCN) 4.9 10

= K
pH 5.3 6
3
[H O ] 10 10 antilog ( 5.3) 5 10 mol L
+ 1
= = = =
Let x = nominal concentration of HCN, then
Concentration HCN + H
1
(mol L )

2
O H
3
O
+
+ CN

nominal x 0 0
equilibrium
6
5 10

x
6
5 10

6
5 10

6 2
10
6
2 1 1
(5 10 )
4.9 10
5 10
Solve for : 5 10 mol L 0.05 mol L

=

= =
x
x x

(b)
9
b
(pyridine) 1.8 10

= K
pOH 5.2 6 1
pOH 14.00 8.8 5.2
[OH ] 10 10 antilog ( 5.2) 6 10 mol L

= =
= = = =


Let x = nominal concentration of C
5
H
5
N, then
Concentration C
1
(mol L )

5
H
5
N + H
2
O C
5
H
6
N
+
+ OH

nominal x
equilibrium
6
6 10

x
6
6 10

6
6 10

301
6 2
9
6
2 1
(6 10 )
1.8 10
6 10
Solve for : 2 10 mol L 0.02 mol L

=

= =
x
x x


10.54 veronal + H
2
O H
3
O
+
+ veronalate ion
The equilibrium concentrations are
1
5 1
3
5
5 2
8 3
a
[veronal] 0.020 0.0014 0.020 0.020 mol L
[H O ] [veronalate ion] 0.0014 0.020 2.8 10 mol L
pH log(2.8 10 ) 4.55
[H O ][veronalate ion] (2.8 10 )
3.9 10
[veronal] 0.020

= =
= = =
= =

= = = K


10.56 cacodylic acid + H
2
O H
3
O
+
+ cacodylate ion
The equilibrium concentrations are
1
5 1
3
5
5 2
3
a
[cacodylic acid] 0.0110 (0.0077 0.0110) 0.0110 0.000 08 0.109 mol L
[H O ] [cacodylate ion] 0.0077 0.0110 8.5 10 mol L
pH log(8.5 10 ) 4.07
[H O ][cacodylate ion] (8.5 10 )
[cacodylic acid] 0.010

+
= = =
= = =
= =

= = K
7
6.6 10
9

=


C N
H
H
H
H
H
C N
+
H
H
H
H
H
H
methylamine conjugate acid
10.58 (a)



(b) First determine the concentration of methylamine following dilution.
Moles of methylamine are found by:

302
( ) ( )
( ) ( )
( )
( )
1
1
50 mL 0.85 g mL 42.5 g of solution
42.5 g 0.35 14.9 g of methylamine
14.9 g
0.479 mol of methylamine
31.06 g mol
diluted to 1.000 L, the resulting solution is 0.479 M in methylamine

=
=
=

Concentration CH
1
(mol L )

3
NH
2
+ H
2
O CH
3
NH
3
+
+ OH

initial 0.479 0 0
equilibrium 0.479 x x x
[ ]
2
3 3
4
b
3 2
2
2
CH NH OH
3.6 10
CH NH 0.479
solving for x we find:
1.3 10 M OH
pOH log(1.3 10 ) 1.9
pH 14.0 1.9 12.1
+

= = =

= =

= =
= =
x
K
x
x

10.60 (a)
2
2 2 4 2 4
pH 7, basic: H O(l) C O (aq) HC O (aq) OH (aq)

> + +

O (aq) Fe(H O) OH (aq)

+ +
+
(b)
2
3
pH 7, neutral: Ca is not an acid and NO is not a base
+
=
(c)
3 3 2 3 3 2
pH 7, acidic: CH NH (aq) H O(l) H O (aq) CH NH (aq)
+ +
< + +
(d)
3 2
2 4 4
pH 7, basic: H O(l) PO (aq) HPO (aq) OH (aq)

> + +
(e)
3
2 6 2
pH 7, acidic: Fe(H O) (aq) H O(l)
+
< +
H
2
3 2 5
(f)
5 5 2 3 5 5
pH 7, acidic: C H NH (aq) H O(l) H O (aq) C H N(aq)
+ +
< + +

10.62 (a) Concentration
CH
1
(mol L )

3
NH
3
+
+ H
2
O(l) CH
3
NH
2
+ H
3
O
+
initial 0.25 0 0
change x +x +x
equilibrium 0.25 x x x
303
(See Table 10.2 for K
b
of CH
3
NH
2
, the conjugate base of CH
3
NH
3
+
.)
14
11 w 3 2
a
4
b 3 3
2 2
11
6 1 6
3
[CH NH ][H O ] 1.00 10
2.8 10
3.6 10 [CH NH ]
2.8 10
0.25 0.25
2.6 10 mol L [H O ] and pH log(2.6 10 ) 5.58
+

= = = =

= = = =
K
K
K
x x
x
x
3

(b) Concentration
SO
1
(mol L )

2
3

+ H
2
O(l)
3
HSO

+ OH

initial 0.13 0 0
change +x +x x
equilibrium 0.13 x x x
[See Table 10.9 for
a 3 a2 2 3
(HSO ) (H SO ).]

= K K
14 2 2
8 w 3
b 7 2
a2 3
2
8
[HSO ][OH ] 1.00 10
8.3 10
1.2 10 [SO ] 0.13 0.13
8.3 10
0.13
K x x
K
K x
x

= = = = =

=
4 1
4
1.0 10 mol L [OH ]
pOH log(1.0 10 ) 4.00
pH 14.00 pOH 10.00

= =
= =
= =
x


(c) Concentration
Fe(H
1
(mol L )

2
O)
6
3+
(aq) + H
2
O(l) H
3
O
+
(aq) + Fe(H
2
O)
5
OH
+
(aq)
initial 0.071 0 0
change +x +x x
equilibrium 0.071 x x x
2
3 3 2 5
a
3
2 6
[H O ][Fe(H O) OH (aq)]
3.5 10
0.071 [Fe(H O) ]
+ +

+
= = =

x
K
x

2 3
3.5 10

+ x x
4
2.5 10 0

=
x = 0.014, 0.018
The negative root can be discarded
3
[H O ] 0.014, pH log 0.014 .85
+
= = =
304

10.64 (a) Initial concentration of C
6
H
5
NH
3
+
is:

( )
1
1
7.8 g
94.133 g mol
0.24 M
0.350 L

=
Given this initial concentration and the Ka for this acid found in Table
10.7, the percent deprotonation is found as follows:
Concentration
C
1
(mol L )

6
H
5
NH
3
+
+ H
2
O(l) C
6
H
5
NH
2
2+
+ H
3
O
+
initial 0.24 0 0
change +x +x x
equilibrium 0.24 x x x
2+
5 6 5 2 3
a
+
6 5 3
2 2
5
3 1
3
3 1
1
[C H NH ][H O ]
2.3 10
[C H NH ]
2.3 10
0.24 0.24
2.3 10 mol L [H O ]
2.3 10 mol L
percent dissociation 100% 1.0%
0.23 mol L
+

= =
=

= =

= =

K
x x
x
x


10.66 (a) can act as both an acid and a base. Both actions need to be
considered simultaneously:
3
HSO

2
3 2 3 3
3 2 2 3
HSO H O H O SO
HSO H O H SO OH
+

+ +
+ +

3


Summing,
2
3 3 2 3
HSO HSO H SO SO

+ +
The simplest approach is to recognize that there are two conjugate acid-
base pairs and to use the Henderson-Hasselbalch equation twice, once for
each pair.
305
3
a1
2 3
2
3
a2
3
[HSO ]
pH p log
[H SO ]
[SO ]
pH p log
[HSO ]

= +



= +


K
K

Summing,
2
3 3
a1 a2
2 3 3
[HSO ] [SO ]
2pH p p log
[H SO ] [HSO ]

= + +


K K
Because [
2
2 3 3 a1 a2
H SO ] [SO ], 2pH p p

= = + K K
Therefore,
1 1
a1 a2 2 2
pH (p p ) (1.81 6.91) 4.36 = + = + = K K
Note that it is not necessary to know the concentration of because
it cancels out of the equation. At extremely low concentrations of
however, the approximations upon which the use of this equation are
based are no longer valid.
3
HSO ,

3
HSO ,

(b) Neither silver ion nor nitrate ion is acidic or basic in aqueous solution.
Therefore, the pH is that of neutral water, 7.00.

10.68 (a)
1
1
0
0.250 mol L KCN 0.0350 L
0.0875 mol L KCN [CN ]
0.1000 L

= =
Concentration
H
1
(mol L )

2
O(l) + HCN(aq) + CN (aq)

OH (aq)

initial 0.0875 0 0
change x +x +x
equilibrium 0.0875 x x x

14
5 w
b
10
a
2 2
5
3 1
1.00 10 [HCN][OH ]
2.0 10
4.9 10 [CN ]
2.0 10
0.0875 0.0875
1.3 10 mol L [HCN]

= = = =

= =
K
K
K
x x
x
x

306
(b)
3
3 3
2 1
3
1.59 g NaHCO 1
84.01 g NaHCO /mol NaHCO 0.200 L
9.46 10 mol L NaHCO

=

Concentration
H
1
(mol L )

2
O(l) + H
3
HCO (aq)

2
CO
3
(aq) + OH (aq)

initial
2
9.46 10

0 0
change x +x +x
equilibrium
2
9.46 10

x x x

14
8 2 3 w
b1
7
a1 3
2 2
8 5 1
2 2
5
[H CO ][OH ] 1.00 10
2.3 10
[HCO ] 4.3 10
2.3 10 , 4.7 10 mol L
9.46 10 9.46 10
[OH ]
pOH log(4.7 10 ) 4.33, pH 14.00 4.33 9.67

= = = =

= =

=
= = = =
K
K
K
x x
x
x



10.70 The reaction of interest is:
C
6
H
5
CH
2
(CH
3
)NH
3
+
(aq) + H
2
O(l) C
6
H
5
CH
2
(CH
3
)NH
2
(aq) +
H
3
O
+
(aq)
K
a
for this reaction is:
14
11
a
4
1 10
1.3 10
7.8 10

= =

K
The initial concentration of C
6
H
5
CH
2
(CH
3
)NH
3
+
(aq) is:

( ) ( )
-1
-1
6.48 g 216.12 g mol
0.150 mol L
0.200 L

=
Concentration
H
1
(mol L )

2
O(l) + C
6
H
5
CH
2
(CH
3
)NH
3
+
(aq) C
6
H
5
CH
2
(CH
3
)NH
2
(aq) + H
3
O
+
(aq)
initial 9.46
2
10

0 0
change x +x +x
equilibrium 9.46
2
10

x x x
307

2 2
11 6 1
+
3
6
1.3 10 , 1.4 10 mol L
0.145 0.145
[H O ]
pH log(1.4 10 ) 5.9
x x
x
x

= =

=
= =

O (aq) H O(l) H O (aq) H PO (aq)

+
+ +

10.72 (a) H P
3 4 2 3 2 4

2
2 4 2 3 4
2 3
4 2 3 4
H PO (aq) H O(l) H O (aq) HPO (aq)
HPO (aq) H O(l) H O (aq) PO (aq)
+
+
+ +
+ +

(b)

2 4 2 2 3 2 4 2
2
2 4 2 2 3 2 4 2 2
(CH ) (COOH) (aq) H O(l) H O (aq) (CH ) (COOH)CO (aq)
(CH ) (COOH)CO (aq) H O(l) H O (aq) (CH ) (CO ) (aq)
+
+
+ +
+ +

(c)

2 2 2 2 3 2 2 2
2
2 2 2 2 3 2 2 2 2
(CH ) (COOH) (aq) H O(l) H O (aq) (CH ) (COOH)CO (aq)
(CH ) (COOH)CO (aq) H O(l) H O (aq) (CH ) (CO ) (aq)
+
+
+ +
+ +

10.74 The reaction is (after the first, essentially complete ionization)
2
4 2 3 4
HSeO H O H O SeO
+
+ +
The initial concentrations of
1
4 3
HSeO and H O are both 0.010 mol L
+

due to the complete ionization of H
2
SeO
4
in the first step. The second
ionization is incomplete.


1
(mol L )

4
HSeO

+ H
2
O H
3
O
+
+ Se
2
4
Concentration
O

initial 0.010 0.010 0
change x +x +x
equilibrium 0.010 x 0.010 + x x
308
2
2 3 4
a2
4
2 4
2 4
3
3 1 2
3
2
[H O ][SeO ] (0.010 )( )
1.2 10
0.010 [HSeO ]
0.022 1.2 10 0
0.022 (0.022) (4)( 1.2 10 )
4.5 10
2
[H O ] 0.010 (0.010 4.5 10 ) mol L 1.5 10 mol L
pH log(1.5 10 ) 1.82
+

+
= = =

+ =
+
= =
1
= + = + =
= =
x x
K
x
x x
x
x


10.76 (a) Second ionization is ignored because
a2 a1
<< K K
+
2 2 3
H S H O H O HS

+ +
2 2
7 3
a1
2
4 1
3
4
[H O ][HS ]
1.3 10
[H S] 0.10 0.10
[H O ] 1.1 10 mol L
pH log(1.1 10 ) 3.96
+

= = =

= =
= =
x x
K
x
x
(b) This is a situation where it may not be justified to ignore the second
ionization. . This is a
marginal case; we can work it both ways, first without ignoring the second
ionization. Adopt the following notation:
4 5
a1 a2 a2 a1
6.0 10 , 1.5 10 , and / 40

= = = K K K K
H
+
= H
3
O
+
[H
+
] = [H
3
O
+
] = equilibrium concentration of H
3
O
+
H
2
A = tartaric acid
1
0
c solute molarity 0.15 mol L

= =

=

2
0 2
c [H A] [HA ] [A ]

= + + (1)
2 0
H total H present [H ] 2[H A] [HA ] 2c
+
= = + + (2)
The following equilibria occur:
2
H A H HA
+
+
a1
2
[H ][HA ]
[H A]
+
= K (3)
2
HA H A
+
+


2
a2
[H ][A ]
[HA ]
+

= K (4)
309
Examination of Eqs. 1 to 4 shows that there are four unknowns,
, to be determined. However, these four
simultaneous equations allow for their determination.
2
2
[H ], [H A], [HA ], and [A ]
+
The unknowns
2
2
[H A], [HA ], and [A ]

may all be expressed in terms of
one unknown, [H
+
].
2
0 2
According to Eq. 1, c [H A] [HA ] [A ]

= + +
2
a1
2
a2
2 2
2
a1 a 2
[H ][HA ]
From Eq. 3, [H A]
[H ][A ]
From Eq. 4, [HA ]
[H ] [A ]
Substituting, [H A]
+
+

+
=
=
=
K
K
K K

2
2
0
a2 a1 a2
[H ] [H ]
Then Eq. 1 becomes c [A ] 1
+ +

= + +


K K K
(5)
Now, subtract 2 Eq. 1 from Eq. 2 :
0 2
2c [H ] 2[H A] [HA ]
+
= + + Eq. 2
2
0 2
2
2c 2[H A] 2[HA ] 2[A ]
[H ] [HA ] 2[A ] 0

+
= + +
=
2 Eq. 1
2 2
a2
[H ]
[A ], [A ]
[H ]
2
+

+
=
+
K

Substitute this into Eq. 5 to give
2 3
0
a2 a2 a1 a2
[H ] [H ] [H ]
c 2 [H ]
+ +
+

+ = + +


K K K
+
K

Rearranging into standard cubic form gives
3 2
0
0
a1 a2 a2 a2
c [H ] [H ]
[H ] 1 2c 0
+ +
+

+ +


K K K K
=
=

Now, put in the numerical values for c
0
, K
a1
, and K
a2
:
8 3 4 2 4
1.1 10 [H ] 6.7 10 [H ] 1.0 10 [H ] 0.30 0
+ + +
+
Solution of this cubic by standard methods gives
310
3 1
3
3
[H ] [H O ] 9.2 10 mol L
pH log(9.2 10 ) 2.04
+ +

= =
= =

It is left as an exercise for the reader to show that, if the second ionization
is ignored,
3 1
[H ] 9.5 10 mol L and pH 2.02
+
= =
The difference is small but, perhaps, not within experimental error.
(c) The second ionization can be ignored because K
a2
<< K
a1
.
2 4 2 3 4
2 2
8 3 4
a1
3 3
2 4
6 1
3
6
H TeO H O H O HTeO
[H O ][HTeO ]
2.1 10
[H TeO ] 1.1 10 1.1 10
[H O ] 4.8 10 mol L
pH log(4.8 10 ) 5.32
+
+

+ +
= = =

= =
= =

x x
K
x
x

10.78 (a) The pH is given by pH =
1
a1 a2 2
(p p ) + K K . From Table 10.9, we find
7
a1
4.3 10

= K
a1
p 6.37 = K
11
a2
5.6 10

= K
a2
p 10.25 = K
1
2
pH (6.37 10.25) 8.31 = + =
(b) The nature of the spectator counter ion does not affect the equilibrium
and the pH of a salt solution of a polyprotic acid is independent of the
concentration of the salt, therefore pH = 8.31.

10.80 The pH is given by pH =
1
a1 a2 2
(p p ) + K K .
1
2
pH (2.46 7.31) 4.89 = + =

10.82 The equilibrium reactions of interest are
2 3 2 3 3
H SO (aq) H O(l) H O (aq) HSO (aq)
+
+ +
2
a1
1.5 10

= K
2
3 2 3 3
HSO (aq) H O(l) H O (aq) SO (aq)
+
+ +
7
a2
1.2 10

= K
Because the second ionization constant is much smaller than the first, we
can assume that the first step dominates:
311

Concentration
1
(mol L )

H
2
SO
3
(aq) + H
2
O(l) H
3
O
+
(aq) +
3
HSO (aq)

initial 0.125 0 0
change +x +x x
final 0.125 x +x +x
3 3
a1
2 3
2
2
[H O ][HSO ]
[H SO ]
( )( )
1.5 10
0.125 0.125
+

=
= =

K
x x x
x x

Assume that x << 0.125, then
2 2
(1.5 10 )(0.125)
0.043

=
=
x
x

Because x > 5% of 0.0456, the assumption was not valid, and the full
expression must be evaluated using the quadratic:
2 2 2
1.5 10 (1.5 10 )(0.125) 0

+ = x x
Solving with the quadratic equation gives
1
0.036 mol L

= x .
1
3 3
1 1 1
2 3
[H O ] [HSO ] 0.036 mol L
[H SO ] 0.125 mol L 0.036 mol L 0.089 mol L
+

= = =
= =
x

We can then use the other equilibria to determine the remaining
concentrations:
2
3 3
a2
3
2
7 3
2 7
3
[H O ][SO ]
[HSO ]
(0.036)[SO ]
1.2 10
(0.036)
[SO ] 1.2 10 mol L
+

=
=
1
=
K

Because 1.2 , the initial assumption that the first
dissociation would dominate is valid. To calculate [
7
10 0.036

<<
OH ]

, we use the K
w
relationship:
312
w 3
14
13 1 w
3
[H O ][OH ]
1.00 10
[OH ] 2.8 10 mol L
0.036 [H O ]
+

+
=

= = =
K
K

2

In summary,
1 1
2 3 3 3 3
[H SO ] 0.089 mol L , [H O ] [HSO ] 0.036 mol L , [SO ]
+
= = =

1


7 1 13
1.2 10 mol L , [OH ] 2.8 10 mol L

= =

10.84 The equilibrium reactions of interest are now the base forms of the
carbonic acid equilibria, so K
b
values should be calculated for the
following changes:
2
3 2 3
14
8 w
b1
7
a2
3 2 2 3
14
13 w
b2
2
a2
SO (aq) H O(l) HSO (aq) OH (aq)
1.00 10
8.3 10
1.2 10
HSO (aq) H O(l) H SO (aq) OH (aq)
1.00 10
6.7 10
1.5 10

+ +

= = =

+ +

= = =

K
K
K
K
K
K

Because the second hydrolysis constant is much smaller than the first, we
can assume that the first step dominates:
Concentration
1
(mol L )

+ H
2
3
SO (aq)

2
O(l) +
3
HSO (aq)

OH (aq)

initial 0.125 0 0
change +x +x x
final 0.125 x +x +x
3
b1
2
3
2
8
[HSO ][OH ]
[SO ]
( )( )
8.3 10
0.125 0.125

=
= =

K
x x x
x x

Assume that x << 0.125, then
2 8
4
(8.3 10 )(0.125)
1.0 10

=
=
x
x

313
Because x < 1% of 0.125, the assumption was valid.
4 1
3
2 1 4 1
3
[HSO ] [OH ] 1.0 10 mol L
Therefore, [SO ] 0.125 mol L 1.0 10 mol L 0.125 mol L


= = =
=
x
1

We can then use the other equilibria to determine the remaining
concentrations:
2 3
b2
3
4
13 2 3
4
13 1
2 3
[H SO ][OH ]
[HCO ]
[H SO ](1.0 10 )
6.7 10
(1.0 10 )
[H SO ] 6.7 10 mol L

=
K

Because , the initial assumption that the first
hydrolysis would dominate is valid.
13 4
6.7 10 1.0 10

<<

To calculate [H
3
O
+
], we use the K
w
relationship:
w 3
14
10 1 w
3
14
[H O ][OH ]
1.00 10
[H O ] 1.0 10 mol L
[OH ] 1.0 10
+

+

=

= = =

K
K

1

13 1
2 3
4 1 2
3 3
1 10
3
In summary, [H SO ] 6.7 10 mol L , [OH ]
[HSO ] 1.0 10 mol L , [SO ]
0.125 mol L , [H O ] 1.0 10 mol L


+
=
= =
= =


10.86 (a) tartaric acid: The two pK
a
values are 3.22 and 4.82. Because pH = 5.0
lies above both of these values, the major form present will be the doubly
deprotonated ion . (b) hydrosulfuric acid: The two pK
2
A

a
values are
6.89 and 14.15. Because the pH of the solution lies below both of these
values, the dominant form will be the doubly protonated H
2
A. (c)
phosphoric acid: The three pK
a
values are 2.12, 7.21, and 12.68. The pH of
the solution lies between the first and second ionization, so the
predominant species should be the singly deprotonated ion
2 4
H PO .

314
10.88 The equilibria present in the solution are:
2 2 3
2
2 3
H (aq) H O(l) H O (aq) HS (aq)
HS (aq) H O(l) H O (aq) S (aq)
+
+
+ +
+ +

7
a1
15
a2
1.3 10
7.1 10

=
=
K
K

The calculation of the desired concentrations follows exactly after the
method derived in Eq. 25, substituting H
2
S for H
2
CO
3
, HS

for ,
and for . First, calculate the quantity
:
3
HCO

2
S
2
3
CO

9.35 10 1
3
(at pH 9.35 [H O ] 10 4.5 10 mol L )
+
= = = f

2
3 3 a1 a1 a2
10 2 10 7 7 15
17
[H O ] [H O ]
(4.5 10 ) (4.5 10 )(1.3 10 ) (1.3 10 )(7.1 10 )
5.9 10
+ +

= + +
= + +
=
f K K K

The fractions of the species present are then given by
10 2
3 3
2
17
[H O ] (4.5 10 )
(H S) 3.4 10
5.9 10

= = =
f

10 7
3 a1
17
[H O ] (4.5 10 )(1.3 10 )
(HS ) 0.99
5.9 10

= = =

K
f

17 15
2 15 a1 a2
17
(1.3 10 )(7.1 10 )
(S ) 1.6 10
5.9 10

= = =

K K
f

Thus, in a solution at pH 9.35, the dominant species will be with a
concentration of
HS

1 1
(0.250 mol L )(0.99) 0.25 mol L

. The
concentration of H
2
S will be
, and the concentration of
will be
3 1 4
(3.4 10 )(0.250 mol L ) 8.5 10 mol L

=
1

2
S
5 1 6
(1.6 10 )(0.250 mol L ) 4.0 10 mol L .

=

10.90 For the first ionization of (COOH)
2
or H
2
C
2
O
4
we write
2
2 2 4 2 3 2 4 a1
H C O H O H O HC O , 5.9 10
+
+ + = K




315
Concentration
1
(mol L )

H
2
C
2
O
4
+ H
2
O H
3
O
+
+
2 4
HC O

initial 0.10

0 0
change +x +x x
equilibrium 0.10 x

x x
2 5
a1 a2
5.9 10 , 6.5 10

= = K K
Because K
a2
<< K
a1
, the second ionization can safely be ignored in the
calculation of [H
3
O
+
].
2
2
a1
2
2
1
3
14
13 1
1
2 2 4
5.9 10
0.10
0.059 0.0059 0
0.059 (0.059) (4)(1)(0.0059)
0.053 mol L [H O ]
2
1.0 10
[OH ] 1.9 10 mol L
0.053
[H C O ] 0.10 0.053 0.05 mol L

= =

+ =
+ +
= =

= =
= =
x
K
x
x x
x =
1
Concentration (mol L )

2 4
HC O


+H
2
O H
3
O
+
+ C O
2
2 4

initial 0.053 0.053 0
change x +x +x
equilibrium 0.053 x

0.053 + x x
5
a2
2 5 1
2 4
1
2 4
(0.053 )( )
6.5 10 (because is small)
0.053
or [C O ] 6.5 10 mol L , and
[HC O ] 0.053 0.053 0.000 065 0.053 mol L

+
= =

= =
= = =
x x
K x
x
x
x
x


10.92 The equilibria involved are:
H
2
CO
3
(aq) + H
2
O(l) HCO
3

(aq) + H
3
O
+
K
a1
= 4.3 10
7

HCO
3

(aq) + H
2
O(l) CO
3
2
(aq) + H
3
O
+
K
a2
= 5.6 10
11
Given these two equilibria, two equations can be written:
316

[ ]
[ ]
+
3 3
a1
2 3
2 +
3 3
a2
3
2 3
2 3 3 3
+ 4.8 5
3
HCO H O
H CO
CO H O
HCO
also, enough information is provided to construct two other equations:
H CO HCO CO 4.5 10
H O 10 1.6 10

=


=


+ + =

= =

K
K

Solving this set of simultaneous equations for the three unknown
concentrations, one finds:

[ ]
3
2 3
4
3
2 1
3
H CO 4.38 10
HCO 1.19 10
CO 4.23 10

=
=

=

0
4
=
4


10.94 We can use the relationship derived in the text:

2
3 initial 3 w
2 8 1
3 3
[H O ] [HA] [H O ] 0
[H O ] (7.49 10 )[H O ] (1.00 10 ) 0
+ +
+ +
=
=
K
Solving using the quadratic equation gives

7
3
[H O ] 1.44 10 ; pH 6.842
+
= =
This value is lower than the value calculated, based on the acid
concentration alone
8
(pH log(7.49 10 ) 7.126).

= =

10.96 We can use the relationship derived in the text:
in which B is any strong base.
2
3 initial 3 w
[H O ] [B] [H O ] 0,
+ +
+ K

2 7 1
3 3
[H O ] (8.23 10 )[H O ] (1.00 10 ) 0
+ +
+ =
Solving using the quadratic equation gives

8
3
[H O ] 1.20 10 , pH 7.922
+
= =
This value is slightly higher than the value calculated, based on the base
concentration alone

7
(pOH log(8.23 10 ) 6.084, pH 14.00 6.084 7.916).

= = = =
317
10.98 (a) In the absence of a significant effect due to the autoprotolysis of
water, the pH values of the
4
2.50 10

M and
6
2.50 10

M C
6
H
5
OH
solutions can be calculated as described earlier.
For
4 1
2.50 10 mol L :


Concentration
C
1
(mol L )

6
H
5
OH(aq) + H
2
O(l) +
3
H O (aq)
+
6 5
C H O (aq)

initial
4
2.50 10

0 0
change x +x +x
final
4
2.50 10

x +x +x

3 6 5
a
6 5
2
10
4 4
[H O ][C H O ]
[C H OH]
( )( )
1.3 10
2.50 10 2.50 10
+

=
= =

K
x x x
x x

Assume x <<
4
2.50 10

2 10
7
(1.3 10 )(2.50 10 )
1.8 10

=
=
x
x
4
10 , Because x < 1% of 2.50
4

10 mol L :

the assumption was valid. Given this
value, the pH is then calculated to be
8
log(1.8 10 ) 6.74.

=
For 2.50
6 1

O (aq)

Concentration
C
1
(mol L )

6
H
5
OH(aq) + H
2
O(l) + C H
initial
3
H O (aq)
+
6 5
6
2.50 10

0 0
change x +x +x
final
6
2.50 10

x +x +x

3 6 5
a
6 5
2
10
6 6
[H O ][C H O ]
[C H OH]
( )( )
1.3 10
2.50 10 2.50 10
+

=
= =

K
x x x
x x

318
Assume x <<
6
2.50 10

2 10
8
(1.3 10 )(2.50 10 )
1.8 10

=
=
x
x
6
Because x < 1% of
6
2.50 10 ,

the assumption is valid and the pH should

be 7.74. However, this number does not make sense because an acid was
added to the water.
(b) To calculate the value, taking into account the autoprotolysis of water,
we can use Eq. 22:
where x = [H
3 2
a w a initial w a
( [HA] ) + + = x K x K K x K K 0,
3
O
+
].
To solve the expression, you substitute the values of
the initial concentration of acid, and
14
w
1.00 10 ,

= K
10
a
1.3 10

= K into this equation

and then solve the expression either by trial and error or, preferably, using
a graphing calculator. Alternatively, you can use a computer program
designed to solve simultaneous equations. Because the unknowns include
[H
3
O
+
], [ [HClO], and [ you will need four equation. As
seen in the text, the pertinent equations are
OH ],

ClO ],

3 6 5
a
6 5
w 3
3 6 5
6 5 initial 6 5 6 5
[H O ][C H O ]
[C H OH]
[H O ][OH ]
[H O ] [OH ] [C H O ]
[C H OH] [C H OH] [C H O ]
+
+
+

=
=
= +
= +
K
K
Using either method should produce the same result.
The values obtained for
4 1
2.50 10 mol L

are
(compare to 6.74 obtained in (a))
7 1
3
[H O ] 2.1 10 mol L , pH 6.68
+
= =

7 1
6 5
4 1
6 5
8 1
[C H O ] 1.6 10 mol L
[C H OH] 2.5 10 mol L
[OH ] 4.8 10 mol L



=

=

Similarly, for
6
6 5 initial
[C H OH] 2.50 10 :

=
(compare to 7.74 obtained in (a))
7 1
3
[H O ] 1.0 10 mol L , pH 7.00
+
= =
319

9 1
6 5
6 1
6 5
8 1
[C H O ] 3.2 10 mol L
[C H OH] 2.5 10 mol L
[OH ] 9.8 10 mol L



=

=

Note that for the more concentrated solution, the effect of the
autoprotolysis of water is very small. Notice also that the less concentrated
solution is more acidic, due to the autoprotolysis of water, than would be
predicted if this effect were not operating.

10.100 (a) In the absence of a significant effect due to the autoprotolysis of
water, the pH values of the
5
1.89 10

M and
7
9.64 10

M HClO
solutions can be calculated as described earlier.
For :
5 1
1.89 10 mol L


Concentration
HClO(aq) + H
1
(mol L )

2
O(l) H
3
O
+
(aq) + Cl O (aq)

initial
5
1.89 10

0 0
change +x +x x
final
5
1.89 10

x +x +x

3
a
2
8
5 5
[H O ][ClO ]
[HClO]
( )( )
3.0 10
1.89 10 1.89 10
+

=
= =

K
x x x
x x

Assume
5
1.89 10

<< x

2 8
7
(3.0 10 )(1.89 10 )
7.5 10

=
=
x
x
5
10 Because x < 5% of 1.89
5

10 mol L

, the assumption was valid. Given this
value, the pH is then calculated to be
7
log(7.5 10 ) 6.12.

=
For 9.64
7 1
:


320
Concentration
HClO(aq) + H
1
(mol L )

2
O(l) H
3
O
+
(aq) + Cl O (aq)

initial
7
9.64 10

0 0
change +x +x x
final
7
9.64 10

x +x +x

3
a
2
8
7 7
[H O ][ClO ]
[HClO]
( )( )
3.0 10
9.64 10 9.64 10
+

=
= =

K
x x x
x x

Assume
7
9.64 10

<< x x

2 8 7
7
(3.0 10 )(9.64 10 )
1.7 10

=
=
x x
x

x is approximately 10% of
7
9.64 10

; the assumption is not reasonable,

and so you must calculate the value explicitly for the following
expression, using the quadratic equation.

2 8 8 7
3.0 10 (3.0 10 )(9.64 10 ) 0

+ = x x
Upon solving the quadratic equation, a value of is obtained,
yielding pH = 6.80.
7
1.6 10

= x
(b) To calculate the value, taking into account the autoprotolysis of water,
we can use Eq. 21:
.
3 2
a w a initial w a 3
( [HA] ) 0, where [H O ]
+
+ + = = x K x K K x K K x
To solve the expression, you substitute the values of ,
the initial concentration of acid, and
14
w
1.00 10

= K
8
a
3.0 10

= K into this equation and

then solve the expression either by trial and error or, preferably, using a
graphing calculator. Alternatively, you can use a computer program
designed to solve simultaneous equations. Because the unknowns include
[H
3
O
+
], [ , [HClO], and [ OH ]

ClO ]

, you will need four equations. As

seen in the text, the pertinent equations are
321

3
a
[H O ][ClO ]
[HClO]
+
= K

w 3
[H O ][OH ]
+
= K

3
[H O ] [OH ] [ClO ]
+
= +


initial
[HClO] [HClO] [ClO ]

= +
Using either method should produce the same result.
The values obtained for
5 1
1.89 10 mol L

are

7 1
3
[H O ] 7.4 10 mol L , pH 6.13 (compare to 6.12 obtained in (a))
+
= =

7 1
[ClO ] 7.3 10 mol L

=

5 1
[HClO] 1.8 10 mol L



8 1
[OH ] 1.3 10 mol L

=

7
initial
Similarly, for [HClO] 9.64 10 :

=

7 1
3
[H O ] 1.9 10 mol L , pH 6.72 (compare to 6.80 obtained in (a))
+
= =

7 1
[ClO ] 1.3 10 mol L

=

7 1
[HClO] 8.3 10 mol L



8 1
[OH ] 5.3 10 mol L

=
Note than for the more concentrated solution, the effect of the
autoprotolysis of water is very small. Notice also that the less concentrated
solution is more acidic, due to the autoprotolysis of water, than would be
predicted if this effect were not operating.

10.102 Because the process is only 90% efficient, to remove 50.0 kg of SO
2
one
must supply enough CaCO
3
to remove 55.6 kg of SO
2
(50.0 kg is 90% of
55.6 kg). The moles of to be removed is given by:
2
SO

2
1
55600 g
867 mol SO
65.06 g mol

=

( )( )
2 3
1
3
1 mole of SO is consummed by 1 mole of CaCO . Therefore,
867 mol CaCO 100.09 g mol 86.8 kg

=
322

10.104 (1)
2 3
2 H O(l) H O (aq) OH (aq)
+
+
14
w
1.00 10

= K
(2)
3 2 4
NH (aq) H O(l) NH (aq) OH (aq)
+
+ +
5
b 3
(NH ) 1.8 10

= K
or
(3)
4 2 3 3
10
a 4 w b 3
NH (aq) H O(l) NH (aq) H O (l)
(NH ) / (NH ) 5.56 10
+ +
+
+ +
= =

K K K

(4)
3 2 3 3
5
a 3
CH COOH(aq) H O(l) H O (l) CH COO (aq)
(CH COOH) 1.8 10
+

+ +
=

K
or
(5)

3 2 3
b 3 w a 3
10
CH COO (aq) H O(l) CH COOH(aq) OH (aq)
(CH COO) / (CH COOH)
5.56 10

+ +
=
=

K K K
(6)
4 3 3 3
3 3
4 3
4 3
NH (aq) CH COO (aq) NH (aq) CH COOH(aq)
[NH ][CH COOH]
(NH CH COO)
[NH ][CH COO ]
+
+
+ +
=

K

This equation is obtained by adding Equations (3) and (5) and subtracting
Equation (1):
4 2 3 3
[NH (aq) H O(l) NH (aq) H O (l)]
+ +
+ + +

w b 3
/ (NH K K )
)
3 2 3
[CH COO (aq) H O(l) CH COOH(aq) OH(aq)]

+ + +

w a 3
/ (CH COOH K K
2 3
[2 H O(l) H O (aq) OH (aq)]
+
+
w
K
Because we are starting with pure ammonium acetate, we will use the last
relationship to calculate the concentrations of

4 3 3 3
NH , CH COO , NH , and CH COOH in solution.
+

323
Concentration
1
(mol L )

4
NH (aq)
+
+ + CH
3
CH COO (aq) NH (aq)

3
3
COOH(aq)
initial 0.100 0.100 0 0
change x x +x +x
equilibrium 0.100 x 0.100 x +x +x
For the initial calculation, we will assume that the subsequent
deprotonation of acetic acid by water or the protonation of ammonia by
water will be small compared to the reaction of the ammonium ion with
the acetate ion.
5 3 3
4 3
[NH ][CH COOH]
3.09 10
[NH ][CH COO ]

+
=
2
5
2
5
5
5 5
4
3.09 10
(0.100 )
3.09 10
0.100
(0.100 ) 3.09 10
(1 3.09 10 ) (0.100) 3.09 10
5.52 10

=
+ =
=
x
x
x
x
x x
x
x

By using this as the value of the concentrations of NH
3
and CH
3
COOH,
we can calculate the concentrations of NH
4
+
,
3
CH COO ,

H
3
O
+
, and OH

in solution using the above equilibrium relationship. The values calculated
are
[NH
4
+
] = [CH
3
COOH] = 0.099
7
3
[H O ] [OH ] 1.00 10
+
= =


If we substitute these numbers back into each of the equilibrium constants
expressions, we get very good agreement. This justifies the assumption
that the subsequent hydrolysis reactions of the NH
3
and CH
3
COOH were
small compared to the main reaction.
Alternatively (had this not been the case), we could have solved the
system of equations using a graphing calculator or suitable computer
324
software package by setting up a system of simultaneous equations. The
answer is the same in any case. This problem is simplified by the fact that
the tendency for subsequent hydrolysis of NH
3
and CH
3
COOH have the
same magnitude.

10.106 According to Table 10.3, the amide ion that is formed from the
autoionization of ammonia, 2
3 4
NH NH NH ,
2
+
+ is a stronger base
than . Therefore, carbonic acid (and other weak acids) is expected to
be stronger in liquid ammonia than in water. Furthermore, carbonic acid is
a stronger acid than NH
OH

4
+
; therefore, it will donate a proton to NH
3
to
form NH
4
+
. It can then be concluded that carbonic acid will be leveled in
liquid NH
3
and will behave as a strong acid.

10.108 (a) The pH is given by pH = ( )
1
a1 a2 2
p p + K K . The first and second
dissociations of H
3
AsO
4
are the pertinent values for NaH
2
AsO
4
:
( )
1
2
pH 2.25 6.77 4.51 = + =
(b) For Na
2
HAsO
4
the second and third acid dissociation constants must
be used:
( )
1
2
pH 6.77 11.60 9.19 = + =

10.110 (a)
3 3 4
NH NH NH NH
2
+
+ +
(b) acid =
4 2
NH , base NH
+
=
(c)
33
am am
p log log(1 10 ) 33.0

= = = K K
(d)
2
am 4 2 4 2
33 17 1
4
p [NH ][NH ] ( [NH ] [NH ])
[NH ] 1 10 3 10 mol L
+ +
+
= = = =
= =
K x x
(e)
17
4 2
pNH pNH log(3.2 10 ) 17
+
= = =
(f)
4 2 am
pNH pNH p 33.0
+
= = K

325
10.112 The osmotic pressure of 0.10 H
2
SO
4
will be slightly higher than that of
0.10 M HCl. When H
2
SO
4
is added to solution it completely deprotonates
into HSO
4
,
a small fraction of which deprotonates further to SO
4
2-
.
Therefore, each mole of H
2
SO
4
gives rise to slightly more than 2 moles of
dissolved ions. HCl, on the other hand, is a strong monoprotic acid giving
exactly two moles of dissolved ions per mole of HCl molecules.
To calculate the moles of dissolved ions in a 0.10 M solution of H
2
SO
4

one assumes that H
2
SO
4
is completely deprotonated, and solves the
equilibrium problem:
Concentration
HSO
1
(mol L )

4
(aq) + H
2
O(l) H
3
O
+
(aq) + SO
4
2
(aq)
initial 0.10 0.10 0
change +x +x x
final 0.10 x 0.10 + x +x

2
3 4
a
4
2
[H O ][SO ]
[HSO ]
(0.10 )( )
1.2 10
0.10

=
+
=

K
x x
x

Using the quadratic equation one finds that x = 9.8 10
3
and, therefore:
[HSO
4
-
] = 0.0902 M, [H
3
O
+
] = 0.1098 M, and [SO
4
2
] = 0.0098 M giving
a total dissolved ion concentration of 0.210 M (compared to a total
dissolved ion concentration of 0.20 for the 0.10 M HCl solution).
Assuming a temperature of 298 K, the osmotic pressure of the 0.10 M
H
2
SO
4
solution is:

( )( )( )
1 1
0.082057 L atm K mol 298 K 0.210 mol L
5.13 atm

= =
=
RTc
1

While that of the HCl solution is:

( )( )( )
1 1
0.082057 L atm K mol 298 K 0.200 mol L
4.89 atm

= =
=
RTc
1


326
10.114 (where 1 mol refers to the reaction as written)
1
57 kJ mol

= + H
1
2 1 2
1
2 1
1
2 1
1 2
1 2
1 1
ln
1 1
2.303 log
1 1
2.303 log
1 1
p p
2.303

=



=



=



=


K H
K R T T
K H
K R T T
K H
K R T T
H
K K
R T T
2
2

4 :

Let condition 2 be where 25 C,
w
p 1 = K
1
1 1
1
1
1 1
1
57 000 J 1 1
p 14
298 K 2.303 8.314 J K mol
57 000 J 1 1
p 14
298 K 2.303 8.314 J K mol



=




= +



K
T
K
T

We will not define K
1
as the K
w
value at some unknown temperature T:
1
w
1 1
3
w
57 000 J mol 1 1
p 14
298 K 2.303 8.314 J K mol
3.0 10 K
p 4.00
T

= +

= +
K
T
K

Substituting the value of T = 373 K gives pK
w
= 12.04. If the solution is
neutral, the pH = pOH = 6.02.

10.116 (a) The structures of alanine, glycine, phenylalanine, and cysteine are


C C
C
O O
N
H
H
H H
H
H
H
H C
C
O O
N
H
H
H
H
alanine
glycine






327

C C
C
O O
N
H
H
H H
H
H
H
H C
C
O O
N
H
H
H
H
alanine
glycine






All the amino acids have an amine NH
2
function as well as a carboxylic
acid COOH group.
(b) The pK
a
value of the COOH group of alanine is 2.34 and the pK
b
of
the NH
2
group is 4.31. Often, we find instead of the pK
b
value, the pK
a

value of the conjugate acid of the NH
2
group. The relationship
is used to convert to the pK
a b
p p p = K K K
w
b
value.
(c) To find the equilibrium constant of the reaction of the acid function,
with the base function in the amino acid, we first write the known
equilibrium reactions and corresponding K values:

2 3
R COOH(aq) H O(l) H O (aq) R COO (aq)
+
+ +

pK
a
= 2.34

3
a
4.6 10

= K

2 2 3
R NH (aq) H O(l) RNH (aq) OH (aq)
+
+ + pK
b
= 4.31

5
b
4.9 10

= K
If we sum these reactions, we obtain

2 2 3
7
3 a b
R COOH(aq) R NH (aq) 2 H O(l) H O (aq) OH (aq)
R COO (aq) RNH (aq) 2.3 10
+
+
+ + +
+ + =

K K

The presence of the H
2
O, H
3
O
+
, and OH

can be eliminated by
subtracting the autoprotolysis reaction of water to give the desired final
equation:

328

2 3
2 H O(l) H O (aq) OH (aq)
+
+
14
w
1.00 10

= K

2 3
1
a b w
7
R COOH(aq) R NH (aq) R COO (aq) RNH (aq)
2.3 10
+

+ = +
=
=
K K K K
K

(d) A zwitterion is a compound that contains both a positive ion and a
negative ion in the same molecule. Overall, the molecule is neutral, but it
is ionic in that it possesses both positive and negative ions within itself.
This is a common occurrence for the amino acids in which the acid
function reacts to protonate the base site. Given the large value of the
equilibrium constant found in (c), it is more appropriate to write an amino
acid as then as R(NH
3
R(NH )(COO )
+
2
)(COOH).


10.118 (a)

1.0


0.5


0
14 7 0

pH
(b) The major species at pH 7.5 is the doubly deprotonated form.
(c) pH = 5.97
(d) at pH values greater than about 11.4
(e) from approximately pH = 7.0 to 8.4

329