CHAPTER 10

ACIDS AND BASES

10.1 (a) (b)
3 3
CH NH
+
2 3
NH NH
+
(c) (d)
2
H CO
3
2
3
CO

(e) (f)
6 5
C H O

3 2
CH CO



10.3 For all parts (a) (e), H
2
O and H
3
O
+
form a conjugate acid-base pair in
which H
2
O is the base and H
3
O is the acid
(a)
+
2 4 2 3 4
H SO (aq) H O(l) H O (aq) HSO (aq)

+ +
2 4 4
H SO and HSO (aq)

form a conjugate acid-base pair in which

2 4 4
H SO is the acid and HSO (aq) is the base.

(b)
6 5 3 2 3 6 5 2
C H NH (aq) H O(l) H O (aq) C H NH (aq)
+ +
+ +
6 5 3 6 5 2
C H NH and C H NH (aq)
+
form a conjugate acid-base pair in which

6 5 3 6 5 2
C H NH is the acid and C H NH (aq) is the base.
+
(c)
2
2 4 2 3 4
H PO (aq) H O(l) H O (aq) HPO (aq)
+
+ +

2
2 4 4
H PO (aq) and HPO (aq)

form a conjugate acid-base pair in which

2
2 4 4
H PO (aq) is the acid and HPO (aq) is the base.

(d)
2 3 2
HCOOH(aq) H O(l) H O (aq) HCO (aq)
+
+ +
2
HCOOH(aq) and HCO (aq)

form a conjugate acid-base pair in which

2
HCOOH(aq) is the acid and HCO (aq) is the base.

(e)
2 3 2 3 2 2
NH NH (aq) H O(l) H O (aq) NH NH (aq)
+ +
+ +
2 3 2 2
NH NH (aq) and NH NH (aq)
+
form a conjugate acid-base pair in
which
2 3 2 2
NH NH (aq) is the acid and NH NH (aq) is the base.
+

SM-274
10.5 (a) Brnsted acid:
3
HNO
Brnsted base:
2
4
HPO


(b) conjugate base to
3 3
HNO :NO


conjugate acid to
2
4 2 4
HPO :H PO



10.7 (a) as an acid:
HCO
3
HCO ,
2
3 2 3 3
HCO (aq) H O(l) H O (aq) CO (aq)
+
+ +

.

4

3
-
and CO
3
2-
form a conjugate acid-base pair in which HCO
3
-
is the
acid and CO
3
2-
is the base.
3
HCO ,

as a base: .
CHO
2 3 2 3
H O(l) HCO (aq) H CO (aq) OH (aq)

+ +
3
-
and H
2
CO
3
form a conjugate acid-base pair in which HCO
3
-
is the
base and H
2
CO
3
is the acid. H
2
O and OH
-
form a conjugate acid-base pair
in which H
2
O is the acid and OH
-
is the base.
(b) , as an acid:
.
form a conjugate acid-base pair in which
H
2
4
HPO

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

2 3
4 4
HPO (aq) is the acid and PO (aq) is the base.

2
O and H
3
O
+
form a
conjugate acid-base pair in which H
2
O is the base and H
3
O
+
is the acid.
2
4
HPO ,

as a base: .
form a conjugate acid-base pair in which HPO
2
4 2 2 4
HPO (aq) H O(l) H PO (aq) OH (aq)

+ +
2
4 2
HPO and H PO

4
2-
is
the base and H
2
PO
4
-
is the acid. H
2
O and OH
-
form a conjugate acid-base
pair in which H
2
O is the acid and OH
-
is the base.

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

10.11 (a) ;
3 2 4 2 2 7
SO (g) H SO H S O (l) +
H
S
+
O
O
O
O
S
+
O
O
O
H
(b)


SM-275

(c) sulfuric acid acts as the Lewis base while SO
3
acts as a Lewis acid.

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

+ +

= =
(a)
14
13 1
1.0 10
[OH ] 5.0 10 mol L
0.02

= =


(b)
14
9 1
5
1.0 10
[OH ] 1.0 10 mol L
1.0 10

= =

(c)
14
12 1
3
1.0 10
[OH ] 3.2 10 mol L
3.1 10

= =

10.15 (a)
14 2
w 3 3
2.1 10 [H O ][OH ] , where [H O ] [OH ] K x x
+ +
= = = = =
14 7 1
3
2.1 10 1.4 10 mol L
pH log[H O ] 6.80
x

+
= =
= =

=

(b)
7 1
3
[OH ] [H O ] 1.4 10 mol L
pOH log[OH ] 6.80
+

= =
= =

10.17 Because is a strong base,

2
Ba(OH)
2
2
Ba(OH) (aq) Ba (aq) 2 OH (aq), 100%.
+
+
Then

2
2 0 2 0 2 0
[Ba(OH) ] [Ba ], [OH ] 2 [Ba(OH) ] , where [Ba(OH) ]
+
= =
nominal concentration of
2
Ba(OH) .
moles of
3
2
1
0.25 g
Ba(OH) 1.5 10 mol
171.36 g mol

= =

3
2 1
2 0
1.5 10 mol
[Ba(OH) ] 1.5 10 mol L [Ba ]
0.100 L

2 +

= = =
2 1 2 1
2 0
[OH ] 2 [Ba(OH) ] 2 1.5 10 mol L 2.9 10 mol L

= = =


SM-276
14
13 1 w
3
2
1.0 10
[H O ] 3.4 10 mol L
[OH ] 2.9 10
K

+

= = =

10.19 Because if Taking the antilogs
of both sides gives
3 3
pH log[H O ], log[H O ] pH.
+ +
= =
pH 1
3
[H O ] 10 mol L
+
=
(a)
3.3 4 1
3
[H O ] 10 5 10 mol L
+
= =

(b)
6.7 1 7 1
3
[H O ] 10 mol L 2 10 mol L
+
= =
(c)
4.4 1 5 1
3
[H O ] 10 mol L 4 10 mol L
+
= =
(d)
5.3 1 6 1
3
[H O ] 10 mol L 5 10 mol L
+
= =

10.21 (a)
1
3 3
[HNO ] [H O ] 0.0146 mol L
+
= =
pH log(0.0146) 1.84, pOH 14.00 ( 1.84) 12.16 = = = =
(b)
1
3
[HCl] [H O ] 0.11 mol L
+
= =
pH log(0.11) 0.96, pOH 14.00 0.96 13.04 = = = =
(c) M
2
[OH ] 2 [Ba(OH) ] 2 0.0092

= =
1
0.018 mol L

=
pOH log(0.018) 1.74, pH 14.00 1.74 12.26 = = = =
(d)
0
[KOH] [OH ]

=
1 4
2.00 mL
[OH ] (0.175 mol L ) 7.0 10 mol L
500 mL


= =


1

4
pOH log(7.0 10 ) 3.15, pH 14.00 3.15 10.85

= = = =
(e)
0
[NaOH] [OH ]

=
4
1
0.0136 g
number of moles of NaOH 3.40 10 mol
40.00 g mol

= =

4
4 1
0
3.40 10 mol
[NaOH] 9.71 10 mol L [OH ]
0.350 L

= = =
4
pOH log(9.71 10 ) 3.01, pH 14.00 3.01 10.99

= = = =
(f)
0 3
[HBr] [H O ]
+
=
SM-277
4 1 5
3
75.0 mL
[H O ] (3.5 10 mol L ) 5.3 10 mol L
500 mL
+

1
= =



5
pH log(5.3 10 ) 4.28, pOH 14.00 4.28 9.72

= = = =

10.23 therefore, after taking antilogs,
a1 a1
p log ; K = K
a1
p
a1
10
K
K

=
Acid
a1
pK
a1
K
(a) 2.12
3
H PO
4
3
7.6 10

(b) 2.00
3
H PO
3
2
1.0 10

(c) 2.46
2
H SeO
3
3
3.5 10

(d) 1.92
4
HSeO
2
1.2 10

(e) The larger , the stronger the acid; therefore
a1
K
2 3 3 4 3 3 4
H SeO H PO H PO HSeO

< < <

10.25 (a)

2 2 3 2
HClO (aq) H O(l) H O (aq) ClO (aq)
+
+ +
3 2
a
2
[H O ][ClO ]
[HClO ]
K
+
=


2 2 2
ClO (aq) H O(l) HClO (aq) OH (aq)

+ +
2
b
2
[HClO ][OH ]
[ClO ]
K

=
(b)

2 3
HCN(aq) H O(l) H O (aq) CN (aq)
+
+ +
3
a
[H O ][CN ]
[HCN]
K
+
=


2
CN (aq) H O(l) HCN(aq) OH (aq)

+ +
b
[HCN][OH ]
[CN ]
K

=
SM-278
(c)

6 5 2 3 6 5
C H OH(aq) H O(l) H O (aq) C H O (aq)
+
+ +
3 6 5
a
6 5
[H O ][C H O ]
[C H OH]
K
+
=


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

+ +
6 5
b
6 5
[C H OH][OH ]
[C H O ]
K

=

10.27 Decreasing will correspond to increasing acid strength because
. The values (given in parentheses) determine the
following ordering:
a
pK
a a
p log K K =
a
pK

3 2 2 3
(CH ) NH (14.00 3.27 10.73) NH OH (14.00 7.97 6.03)
+ +
= < =

2 2
HNO (3.37) HClO (2.00). < <
Remember that the for the conjugate acid of a weak base will be
given by
a
pK
a b
p p 1 K K + = 4.

10.29 Decreasing
b
pK will correspond to increasing base strength because
b b
p log . K K = The
b
pK values (given in parentheses) determine the
following ordering:
3
5 5 3
(14.00 3.45 10.55) CH COO (14.00 4.75 9.25)
C H N (8.75) NH (4.75).
F

= < =
< <<

Remember that the
b
pK for the conjugate base of a weak acid will be
given by
a b
p p 1 K K + = 4.

10.31 Any acid whose conjugate base lies above water in Table 10.3 will be a
strong acid; that is, the conjugate base of the acid will be a weaker base
than water, and so water will accept the H
+
preferentially. Based upon
this information, we obtain the following analysis: (a) , strong;
(b) weak; (c)
3
HClO
2
H S,
4
HSO

, weak (Note: even though is a
2
H SO
4
SM-279
strong acid, is a weak acid. Its conjugate base is ); (d)
weak acid; (e)
4
HSO
2
4
SO

3 3
CH NH ,
+
3
HCO ,

weak; (f) strong; (g)

weak.
3
HNO ,
4
CH ,

10.33 For oxoacids, the greater the number of highly electronegative O atoms
attached to the central atom, the stronger the acid. This effect is related to
the increased oxidation number of the central atom as the number of O
atoms increases. Therefore, is the stronger acid, with the lower
3
HIO
a
p . K

10.35 (a) HCl is the stronger acid, because its bond strength is much weaker
than the bond in HF, and bond strength is the dominant factor in
determining the strength of binary acids.
(b) is stronger; there is one more O atom attached to the Cl atom
in than in HClO. The additional O in helps to pull the
electron of the H atom out of the HO bond. The oxidation state of Cl is
higher in than in HClO.
2
HClO
2
HClO
2
HClO
2
HClO
(c) is stronger; Cl has a greater electronegativity than Br, making
the HO bond more polar than in
2
HClO
2
HClO
2
HBrO .
(d) is stronger; Cl has a greater electronegativity than P.
4
HClO
(e) is stronger. The explanation is the same as that for part (b).
has one more O atom.
3
HNO
3
HNO
(f) is stronger; C has greater electronegativity than Ge. See part
(c).
2
H CO
3

10.37 (a) The group that is bonded to the carboxyl group, COOH, in
trichloroacetic acid, is more electron withdrawing than the group
in acetic acid. Thus, trichloroacetic acid is the stronger acid.
3
CCl
3
CH
SM-280
(b) The group in acetic acid has electron-donating properties,
which means that it is less electron withdrawing than the H attached to
the carboxyl group in formic acid, HCOOH. Thus, formic acid is a slightly
stronger acid than acetic acid. However, it is not nearly as strong as
trichloroacetic acid. The order is
3
CH
3 3
CCl COOH HCOOH CH COOH. >> >

10.39 (a) Nitrous acid is a stronger acid than acetic acid and, therefore, the
acetate ion is a stronger base than the nitrite ion. Since the definition of a
strong acid is one that favors products in the deprotonation reaction, the
presence of acetate ions will shift the nitrous acid deprotonation reaction
toward products by consuming protons making nitrous acid behave like a
strong acid. Carbonic acid is a weaker acid and, therefore, will not behave
like a strong acid in the presence of acetic acid.
(b) Ammonia will act like a strong base because its conjugate acid, the
ammonium ion, is a weaker acid than acetic acid. The presence of acetic
acid will shift the reaction:
3 2 4
NH H O NH OH
+
+ + toward products.

10.41 The larger the the stronger the corresponding acid. 2,4,6-
Trichlorophenol is the stronger acid because the chlorine atoms have a
greater electron-withdrawing power than the hydrogen atoms present in
the unsubstituted phenol.
a
, K

10.43 The larger the of an acid, the stronger the corresponding conjugate
base; hence, the order is aniline < ammonia < methylamine < ethylamine.
Although we should not draw conclusions from such a small data set, we
might suggest the possibility that
a
pK
(1) arylamines < ammonia < alkylamines
(2) methyl < ethyl < etc.
(Arylamines are amines in which the nitrogen of the amine is attached to a
benzene ring.)
SM-281

10.45 (a) Concentration

1
3 2 3
(mol L ) CH COOH H O H O CH CO

+ +
3 2
initial 0 0 0.29
change x x + x +
equilibrium 0.29 x x x
2 2
5 3 3 2
a
3
3 1
3
3
[H O ][CH CO ]
1.8 10
[CH COOH] 0.29 0.29
[H O ] 2.3 10 mol L
pH log(1.6 10 ) 2.64, pOH 14.00 2.64 11.36
x x
K
x
x
+

= = =

= =
= = = =

(b) The equilibrium table for (b) is similar to that for (a).
2
1 3 3 2
a
3
2 1
1 1 2
[H O ][CCl CO ]
3.0 10
[CCl COOH] 0.29
or 3.0 10 0.087 0
3.0 10 (3.0 10 ) (4) ( 0.087)
0.18, 0.48
2
x
K
x
x x
x
+

= = =

+ =

= =
2

The negative root is not possible and can be eliminated.
1
3
[H O ] 0.18 mol L
pH log(0.18) 0.74, pOH 14.00 0.74 13.26
x
+
= =
= = = =

(c) Concentration
1
2 3
(mol L ) HCOOH H O H O HCO
+
+ +
initial 0 0.29 0
change x x + x +
equilibrium 0.29 x x x
2
4 3 2
a
4 3 1
3
3
[H O ][HCO ]
1.8 10
[HCOOH] 0.29 0.29
[H O ] 0.29 1.8 10 7.2 10 mol L
pH log(7.2 10 ) 2.14, pOH 14.00 2.14 11.86
x x x
K
x
x
+

= = =

= = =
= = = =

SM-282
10.47 (a) Concentration

1
2 3 4
(mol L ) H O NH NH OH
+
+ +

initial 0.057 0 0
change x x + x +
equilibrium 0.057 x x x
2
5 4
b
3
5 3 1
3
3
[NH ][OH ]
1.8 10
[NH ] 0.057 0.057
[OH ] 0.057 1.8 10 1.0 10 mol L
pOH log(1.0 10 ) 3.00, pH 14.00 3.00 11.00
1.0 10
percentage protonation 100% 1.8%
0.057
x x x
K
x
x
+

= = =

= = =
= = = =

= =

+

(b) Concentration

1
2 2 3
(mol L ) NH OH H O NH OH OH
+
+
initial 0.162 0 0
change x x + x +
equilibrium 0.162 x x x
2 2
8
b
5 1
5
5
1.1 10
0.162 0.162
[OH ] 4.2 10 mol L
pOH log(4.2 10 ) 4.38, pH 14.00 4.38 9.62
4.2 10
percentage protonation 100% 0.026%
0.162
x x
K
x
x

= =

= =
= = = =

= =

(c) Concentration

1
3 3 2 3 3
(mol L ) (CH ) N H O (CH ) NH OH
+
+ +
initial 0.35 0 0
change x x + x +
equilibrium 0.35 x x + x +
SM-283
2
5
3 1
3 1
3
3
6.5 10
0.35
Assume 0.35
Then 4.8 10 mol L
[OH ] 4.8 10 mol L
pOH log(4.8 10 ) 2.32, pH 14.00 2.32 11.68
4.8 10
percentage protonation 100% 1.4%
0.35
x
x
x
x

<<
=
=
= = = =

= =

(d)
6
b a b
p 14.00 p 14.00 8.21 5.79, 1.6 10 K K K

= = = =
2
2 2
6
b
4 1
4
4
codeine H O codeineH OH
1.6 10
0.073 0.073
[OH ] 1.1 10 mol L
pOH log(1.1 10 ) 3.96, pH 14.00 3.96 10.04
1.1 10
percentage protonation 100% 2.5%
0.0073
x x
K
x
x
+

+ +
= =

= =
= = = =

= =
L


10.49 (a)
2 2 3 2
HClO H O H O ClO
+
+ +
pH 1.2
3 2
2
3 2
a
2
a
[H O ] [ClO ] 10 10 0.06 mol L
[H O ][ClO ] (0.06)
0.09 (1sf )
[HClO ] 0.10 0.06
p log(0.09) 1.0
K
K
+
+
1
= = = =
= = =

= =

(b)
+
3 7 2 2 3 7 3
C H NH H O C H NH +OH

+ L
2.14 3 1
3 7 3
3 2
4 3 7 3
b
3
3 7 2
4
b
pOH 14.00 11.86 2.14
[C H NH ] [OH ] 10 7.2 10 mol L
[C H NH ][OH ] (7.2 10 )
5.6 10
[C H NH ] 0.10 7.2 10
p log(5.6 10 ) 3.25
K
K
+
+

= =
= = =

= = =

= =

10.51 (a)
pH 4.60 5
3
pH 4.60, [H O ] 10 10 2.5 10 mol L
1 +
= = = =


Let nominal concentration of HClO, then x =
SM-284
Concentration
+
1
(mol L )

HClO
2 3
H O H O ClO
+
+
nominal x 0 0
equilibrium
5
2.5 10 x


5
2.5 10

5
2.5 10

5 2
8
a
5
(2.5 10 )
3.0 10
2.5 10
K
x

= =


5 2 5 8
8
2 1 1
(2.5 10 ) (2.5 10 ) (3.0 10 )
Solve for ;
3.0 10
2.1 10 mol L 0.021 mol L
x x

+
=

= =

(b) pOH 14.00 pH 14.00 10.20 3.80 = = =
pOH 3.80 4
2 2
[OH ] 10 10 1.6 10
Let nominal concentration of NH NH , then x

= = =
=

Concentration

1
(mol L )

2 2 2 2 3
NH NH H O NH NH OH
+
+ +
nominal 0 0 x
equilibrium
4
1.6 10 x


4
1.6 10

4
1.6 10

4 2
6
b
4
2 1
(1.6 10 )
1.7 10
1.6 10
Solve for ; 1.5 10 mol L
K
x
x x

= =

=


10.53 Concentration
1
6 5 2 3 6 5 2
(mol L ) C H COOH H O H O C H CO
+
+ +


initial 0. 0 110 0
change x x + x +
equilibrium 0.110 x

x x
2
H O octylamine octylamineH OH
+
+ +
SM-285
1
3 6 5 2
2
5 3 6 5
a
6 5
3
0.024 0.110 mol L [H O ] [C H CO ]
[H O ][C H COO ] (0.024 0.110)
6.3 10
[C H COOH] (1 0.024) 0.110
pH log(2.6 10 ) 2.58
x
K
+
+

= = =

= = =

= =


10.55 The change in the concentration of octylamine is

1
0.067 0.10 0.0067 mol L . x

= = Thus the equilibrium table is
Concentration
1
(mol L )

2
H O octylamine octylamineH OH
+
+ +
initial 0.100 0 0
change 0.0067 0.0067 + 0.0067 +
equilibrium 0.100 0.0067 0.0067 0.0067
The equilibrium concentrations are
[octylamine]
1
0.100 0.067 0.10 0.093 mol L

= =
1
3 2
4
b
[OH ] [octylamineH ] 0.0067 mol L
pOH log(0.0067) 2.17, pH 14.00 2.17 11.83
[octylamineH ][OH ] (6.7 10 )
4.8 10
[octylamine] 0.093
K
+
+

= =
= = = =

= = =


10.57
- +
3 2 2 3 2 3
CH CH COOH(aq) H O(1) CH CH COO (aq) H O (aq) + +
Concentration
1
(mol L )

initial 0.0147 0 0
change x x + x +
equilibrium0.0147 x x x
+ 2 2
5 3 2 3
a
3 2
[CH CH COO ][H O ]
1.3 10
[CH CH COOH] 0.0147 0.0147
x x
K
x

= = =

4
4
4.4 10
4.4 10 , Percent deprotonated 100% 3.0%
0.0147
x

= = =

SM-286
10.59 (a)
4 2 3 3
less than 7, NH (aq) H O(l) H O (aq) NH (aq)
+ +
+ +
(b)
2
2 3 3
greater than 7, H O(l) CO (aq) HCO (aq) OH (aq)

+ +

+
+
(c)
2
greater than 7, H O(l) F (aq) HF(aq) OH (aq)

+ +
(d) neutral
(e) less than 7,
3 2
2 6 2 3 2 5
Al(H O) (aq) H O(l) H O (aq) Al(H O) OH (aq)
+ +
+ +
(f) less than 7,
2
2 6 2 3 2 5
Cu(H O) (aq) H O(l) H O (aq) Cu(H O) OH (aq)
+ +
+ +

10.61 (a)
14
10 w
b
5
a
1.00 10
5.6 10
1.8 10
K
K
K

= = =

Concentration

1
3 2 2 3 2
(mol L ) CH CO (aq) H O(1) HCH CO (aq) OH (aq)

+ +
initial 0.63 0 0
change x x + x +
equilibrium 0.63 x x x

2 2
10 3 2
b
3 2
[HCH CO ][OH ]
5.6 10
0.63 0.63 [CH CO ]
x x
K
x

= = =

5 5
1.9 10 [OH ], pOH log(1.9 10 ) 4.72 x

= = = =
pH 14.00 pOH 14.00 4.72 9.28 = = =
(b)
14
10 w
a
15
b
1.00 10
5.6 10
1.8 10
K
K
K

= = =

1
4 2 3
Concentration (mol L ) NH (aq) H O(l) H O (aq) NH (aq)
+ +
+ +
3
initial 0.19 0 0
change x x + x +
equilibrium 0.19 x x x
2 2
10 3 3
a
4
[H O ][NH ]
5.6 10
[NH Cl] 0.19 0.19
x x
K
x
+

= = =

SM-287
5 1
3
1.0 10 mol L [H O ] x

= =
+
+

5
pH log(1.0 10 ) 5.00

= =
(c) Concentration
1 3 2
2 6 2 3 2 5
(mol L ) Al(H O) (aq) H O(l) H O (aq) Al(H O) OH (aq)
+ +
+ +
initial 0.055 0 0
change x x + x +
equilibrium 0.055 x x x
2 2 2
5 3 2 5
a
3
2 6
[H O ][Al(H O) OH ]
1.4 10
0.055 0.055 [Al(H O) ]
x x
K
x
+ +

+
= = =

4 1
3
8.8 10 mol L [H O ] x

= =
4
pH log(8.8 10 ) 3.06

= =
(d) Concentration

1
2
(mol L ) H O(l) CN (aq) HCN(aq) OH (aq)

+ +
initial 0.065 0 0
change x x + x +
equilibrium 0.065 x x x
14 2 2
5 w
b
10
a
1.00 10 [HCN][OH ]
2.0 10
0.065 0.065 4.9 10 [CN ]
K x x
K
K x

= = = = =


3 1
[OH ] 1.1 10 mol L x

= =


3
pOH log(1.1 10 ) 2.96, pH 11.04

= = =

10.63 Concentration
1
3 3 2 3 3 2
(mol L ) CH NH (aq) H O(l) H O (aq) CH NH (aq)
+ +
+ +
initial 0.510 0 0
change x x + x +
equilibrium 0.510 x x x
SM-288
2 2
11 3 3 2
a
3 3
[H O ][CH NH ]
2.8 10
0.510 0.510 [CH NH ]
x x
K
x
+

+
= = =

+

6 1
3
3.8 10 mol L [H O ] x

= =
6
pH log(3.8 10 ) 5.4

= =

10.65 (a) 250 mL of solution contains , molar
mass=
2 3 2
5.34 g KC H O
1
98.14 g mol

2 3 2
2 3 2 2 3 2
2 3 2
1 mol KC H O 1
(5.34 g KC H O ) 0218 KC H O
98.14 g KC H O 0.250 L
M

=



Concentration
1
2 2 3 2 2 3 2
(mol L ) H O(l) C H O (aq) HC H O (aq) OH (aq)

+ +


initial 0.218 0 0
change x x + x +
equilibrium 0.218 x x x
14 2 2
5
1.0 10
0.218 0.218 1.8 10
x x
x

=


5 1
[OH ] 1.1 10 mol L

=

10 1
3
[H O ] 9.1 10 mol L
+
=
10
pH log(9.1 10 ) 9.04

= =
(b) 100 mL of solution contains molar mass =

4
5.75 g NH Br,
1
97.95 g mol

4
4 4
4
M
1 mol NH Br 1
(5.75 g NH Br) 0.587 NH Br
97.95 g NH Br 0.100 L

=



Concentration
1
4 2 3 3
(mol L ) NH (aq) H O(l) NH (aq) H O (aq)
+ +
+ +
initial 0.587 0 0
change x x + x +
SM-289
equilibrium 0.587 x x x
14 2 2
5
1.0 10
0.587 0.587 1.8 10
x x
x

=


5 1
3
[H O ] 1.8 10 mol L
+
=
5
pH log(1.8 10 ) 4.74

= =

10.67 (a)
1
1 3 2
0.020 mol L NaCH CO 0.150 L
0.0400 mol L
0.500 L

=
Concentration
1
(mol L )

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

+ +
initial 0.0400 0 0
change x x + x +
equilibrium 0.0400 x x x
14
10 w 3
b
5
a 3 2
[CH COOH][OH ] 1.00 10
5.6 10
1.8 10 [CH CO ]
K
K
K

= = = =

2 2
10
5.6 10
0.0400 0.0400
x x
x

6 1
3
4.7 10 mol L [CH COOH] x

= =
(b)
4 4
3
4
2.16 g NH Br 1 mol NH Br 1 mL
400 mL 97.95 g NH Br 10 L

1
4
0.0551 (mol NH Br) L

=
Concentration

1
(mol L )

4 2 3 3
NH (aq) H O(l) H O (aq) NH (aq)
+ +
+ +
initial 0.0551 0 0
change x x + x +
equilibrium 0.0551 x x x
14
10 w 3
a
5
b 4
[NH ][H O ] 1.00 10
5.6 10
1.8 10 [NH ]
K
K
K
3
+

= = = =

SM-290
2 2
10
5.6 10
0.0551 0.0551
x x
x

6 1
3
5.5 10 mol L [H O ] x

= =
+
and
6
pH log(5.5 10 ) 5.26

= =

10.69 (a)
C C C
H
H
H
N
H
H
O
O
Na
+


(b)
1 2
1 1
2 2
pH = + (p p ) (2.34 9.89) 6.1
a a
K K = + =

10.71 (a)
2 4 2 3 4
H SO (aq) H O(l) H O (aq) HSO (aq)
+
+ +
2
4 2 3 4
HSO (aq) H O(l) H O (aq) SO (aq)
+
+ +
(b)
3 4 2 3 2 4
H AsO (aq) H O(l) H O (aq) H AsO (aq)
+
+ +
2
2 4 2 3 4
2 3
4 2 3 4
H AsO (aq) H O(l) H O (aq) HAsO (aq)
HAsO (aq) H O(l) H O (aq) AsO (aq)
+
+
+ +
+ +

(c)

6 4 2 2 3 6 4 2
C H (COOH) (aq) H O(l) H O (aq) C H (COOH)CO (aq)
+
+ +
2
6 4 2 2 3 6 4 2 2
C H (COOH)CO (aq) H O(l) H O (aq) C H (CO ) (aq)
+
+ +

10.73 The initial concentrations of
1
4 3
HSO and H O are both 0.15 mol L
+
as a
result of the complete ionization of in the first step. The second
ionization is incomplete.
2
H SO
4
4

Concentration
1 2
4 2 3
(mol L ) HSO H O H O SO
+
+ +
initial 0.15 0.15 0
change x x + x +
equilibrium 0.15 x 0.15 x + x
SM-291
2
2 3 4
a2
4
2 3
2 3
1
1 1
3
[H O ][SO ] (0.15 ) ( )
1.2 10
0.15 [HSO ]
0.162 1.8 10 0
0.162 (0.162) (4) (1.8 10 )
0.0104 mol L
2
[H O ] 0.15 (0.15 0.0104) mol L 0.16 mol L
pH log(0.16) 0.80
x x
K
x
x x
x
x
+

+
+
= = =

+ =
+ +
= =

= + = + =
= =


10.75 (a) Because the second ionization can be ignored.
a2 a1
, K K <<
Concentration
1
2 3 2 3 3
(mol L ) H CO H O H O HCO
+
+ +


initial 0 0.010 0
change x x + x +
equilibrium 0.010 x x x
2 2
7 3 3
a1
2 3
5 1
3
5
[H O ][HCO ]
4.3 10
[H CO ] 0.010 0.010
[H O ] 6.6 10 mol L
pH log(6.6 10 ) 4.18
x x
K
x
x
+

= = =

= =
= =

(b) Because the second ionization can be ignored.
a2 a1
, K K <<
Concentration

1
2 2 3
(mol L ) (COOH) H O H O (COOH)CO
+
+ +
initial 0.10 0 0
change x x + x +
equilibrium 0.10 x x x
2
2 3 2
a1
2
2 2 3
2 2 2 3
1
[H O ][(COOH)CO ]
5.9 10
[(COOH) ] 0.10
5.9 10 5.9 10 0
5.9 10 (5.9 10 ) (4)(5.9 10 )
0.053 mol L
2
pH log(0.053) 1.28
x
K
x
x x
x
+

= = =

+ =
+ +
= =
= =

SM-292
(c) Because the second ionization can be ignored.
a2 a1
, K K <<
Concentration
1
2 2 3
(mol L ) H S H O H O HS
+
+ +
equilibrium 0.20 x x x
2 2
7 3
a1
2
4 1
3
4
[H O ][HS ]
1.3 10
[H S] 0.20 0.20
[H O ] 1.6 10 mol L
pH log(1.6 10 ) 3.80
x x
K
x
x
+

= = =

= =
= =


10.77 (a) The pH is given by
1
a1 a2 2
pH (p p ). K K = + From Table 10.9, we find
2
a1 a1
7
a2 a2
1
2
1.5 10 p 1.82
1.2 10 p 6.92
pH (1.82 6.92) 4.37
K K
K K

= =
= =
= + =

(b) The pH of a salt solution of a polyprotic acid is independent of the
concentration of the salt, therefore pH 4.37. =

10.79 (a) The pH is given by
1
a1 a2 2
pH (p p ). K K = + For the monosodium salt,
the pertinent values are
a1 a2
p and p K K :
1
2
pH (3.14 5.95) 4.55 = + =
(b) For the disodium salt, the pertinent values are
a2 a3
p and p K K :
1
2
pH (5.95 6.39) 6.17 = + =

10.81 The equilibrium reactions of interest are
7
2 3 2 3 3 a1
2 1
3 2 3 3 a2
H CO (aq) H O(l) H O (aq) HCO (aq) 4.3 10
HCO (aq) H O(l) H O (aq) CO (aq) 5.6 10
K
K
1
+
+
+ + =
+ + =

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


SM-293
Concentration

1
2 3 2 3 3
(mol L ) H CO (aq) H O(l) H O (aq) HCO (aq)
+
+ +

initial 0.0456 0 0
change x x + x +
final 0.0456 x x + x +
3 3
a1
2 3
2
7
2 7
4
4 1
3 3
[H O ][HCO ]
[H CO ]
( ) ( )
4.3 10
0.0456 0.0456
Assume that 0.0456
Then (4.3 10 ) (0.0456)
1.4 10
Because 1%of 0.0456, the assumption was valid.
[H O ] [HCO ] 1.4 10 mol L
K
x x x
x x
x
x
x
x
x
+

+
=
= =

<<
=
=
<
= = =

This means that the concentration of
1
2 3
H CO is 0.0456 mol L

1
0.00014 mol L 0.0455 mol L .

=
1
We can then use the other equilibria
to determine the remaining concentrations:
2
3 3
a2
3
4 2
11 3
4
2 11
3
[H O ][CO ]
[HCO ]
(1.4 10 )[CO ]
5.6 10
(1.4 10 )
[CO ] 5.6 10 mol L
K
+

Because the initial assumption that the first
ionization would dominate is valid.
11 4
5.6 10 1.4 10 ,

<<
To calculate [ we use the relationship: OH ],

w
K
w 3
14
11 1 w
4
3
1
2 3 3 3
4 1
2 11 1 11
3
[H O ][OH ]
1.00 10
[OH ] 7.1 10 mol L
[H O ] 1.4 10
In summary, [H CO ] 0.0455 mol L , [H O ] [HCO ]
1.4 10 mol L ,
[CO ] 5.6 10 mol L , [OH ] 7.1 10 mol L .
K
K
+

+
1

+


=

= = =

= =
=
= =


SM-294
10.83 The equilibrium reactions of interest are now the base forms of the
carbonic acid equilibria, so
b
K values should be calculated for the
following changes:
2
3 2 3
14
4 w
b1
11
a2
CO (aq) H O(l) HCO (aq) OH (aq)
1.00 10
1.8 10
5.6 10
K
K
K

+ +

= = =

3 2 2 3
14
8 w
b2
7
a1
HCO (aq) H O(l) H CO (aq) OH (aq)
1.00 10
2.3 10
4.3 10
K
K
K

+ +

= = =

L

Because the second hydrolysis constant is much smaller than the first, we
can assume that the first step dominates:
Concentration
1 2
3 2 3
(mol L ) CO (aq) H O(l) HCO (aq) OH (aq)

+ +
initial 0.0456 0 0
change x x + x +
final 0.0456 x x + x +
3
b1
2
3
[HCO ][OH ]
[CO ]
K

=
2
4
( ) ( )
1.8 10
0.0456 [0.0456 ]
x x x
x x

= =


Assume that 0.0456 x <<
Then
2 4
(1.8 10 ) (0.0456) x

=
3
2.9 10 x

=
Because of 0.0456, the assumption was not valid and the full
expression should be solved using the quadratic equation:
5% x >
2 4 4
1.8 10 (1.8 10 ) (0.0456) 0 x x

+ =
Solving using the quadratic equation gives
1
0.0028 mol L . x

=
1
3
[HCO ] [OH ] 0.0028 mol L x

= = =

1

Therefore,
2 1 1
3
[CO ] 0.0456 mol L 0.0028 mol L 0.0428 mol L

= =
SM-295
We can then use the other equilibria to determine the remaining
concentrations:
2 3
b2
3
[H CO ][OH ]
[HCO ]
K

=
8 2 3
[H CO ](0.0028)
2.3 10
(0.0028)

=
8 1
2 3
[H CO ] 2.3 10 mol L

=
Because , the initial assumption that the first
hydrolysis would dominate is valid. To calculate
8
2.3 10 0.0028

<<
3
[H O ]
+
, we use the
relationship:
w
K
w 3
[H O ][OH ] K
+
=
14
12 1 w
3
1.00 10
[H O ] 3.6 10 mol L
0.0028 [OH ]
K

+

= = =
In summary,
8 1
2 3 3
[H CO ] 2.3 10 mol L , [OH ] [HCO ]

= = =
1

,

1 2 1 12
3 3
0.0028 mol L , [CO ] 0.0428 mol L , [H O ] 3.6 10 mol L
+
= =

10.85 (a) phosphorous acid: The two values are 2.00 and 6.59. Because
lies between the dominant form will be the
singly deprotonated HA
a
pK
pH 6.30 =
a1 a2
p and p K K

ion.
(b) oxalic acid: The two values are 1.23 and 4.19. Because
lies above the species present in largest concentration
will be the doubly deprotonated
a
pK
pH 6.30 =
a 2
pK ,
2
A

ion.
(c) hydrosulfuric acid: The two values are 6.89 and 14.15. Because
lies below both values, the species present in highest
concentrations will be the fully protonated form.
a
pK
pH 6.30 =
a
pK
2
H A

10.87 The equilibria present in solution are
SM-296
2
2 3 2 3 3 a1
2 7
3 2 3 3 a2
H SO (aq) H O(l) H O (aq) HSO (aq) 1.5 10
HSO (aq) H O(l) H O (aq) SO (aq) 1.2 10
K
K
+
+
+ + =
+ + =

3
2

The calculation of the desired concentrations follows exactly after the
method derived in Eq. 25, substituting for
First, calculate the
quantity
2
H SO
2
2 3 3 3 3 3
H CO , HSO for HCO , and SO for CO .

5.5 6 1
3
(at pH 5.50 [H O ] 10 3.2 10 mol L ) : f
+
= = =
2
3 3 a1 a1 a2
6 2 6 2 2 7
8
[H O ] [H O ]
(3.2 10 ) (3.2 10 ) (1.5 10 ) (1.5 10 ) (1.2 10 )
5.0 10
f K K K
+ +

= + +
= + +
=

The fractions of the species present are then given by
6 2
4 3
2 3
8
6 2
3 a1
3
8
2 7
2 a1 a2
3
8
[H O ] (3.2 10 )
(H SO ) 2.1 10
5.0 10
[H O ] (3.2 10 ) (1.5 10 )
(HSO ) 0.96
5.0 10
(1.5 10 ) (1.2 10 )
(SO ) 0.036
5.0 10
f
K
f
K K
f

= = =

= = =

= = =

Thus, in a
1
0.150 mol L

solution at the dominant species will

be with a concentration of
pH 5.50,
3
HSO
1 1
(0.150 mol L ) (0.96) 0.14 mol L .

=
The concentration of
4 1 5
2 3
H SO will be (2.1 10 ) (0.150 mol L ) 3.2 10 mol L
1
=

and the
concentration of
2
3
SO

will be
1 1
(0.036) (0.150 mol L ) 0.0054 mol L .

=

10.89 (a) Concentration

1
3 2 3
(mol L ) B(OH) 2 H O H O B(OH)
+
+ +
4

initial
4
1.0 10

0 0
change x x + x +
equilibrium
4
1.0 10 x

x x
SM-297
2 2
10 3 4
a
4 4
3
7 1
3
7
[H O ][B(OH) ]
7.2 10
[B(OH) ] 1.0 10 1.0 10
[H O ] 2.7 10 mol L
pH log(2.7 10 ) 6.57
x x
K
x
x
+

= = =

= =
= =

Note: this value of
3
[H O ]
+
is not much different from the value for pure
water, therefore, it is at the lower limit of safely
ignoring the contribution to
7
1.0 10 mol L ;

1
3
[H O ]
+
from the autoprotolysis of water. The
exercise should be solved by simultaneously considering both equilibria.
Concentration
1
3 2 3
(mol L ) B(OH) 2 H O H O B(OH)
+
+ +
4


equilibrium
4
1.0 10 x

x y
Concentration
1
2 3
(mol L ) 2 H O H O OH
+
+
equilibrium x z
Because there are now two contributions to
3 3
[H O ], [H O ]
+ +
is no longer
equal to nor is it equal to [ as in pure water. To avoid a
cubic equation, will again be ignored relative to
4
[B(OH) ],

OH ],

x
4 1
1.0 10 mol L .


This approximation is justified by the approximate calculation above, and
because is very small relative to
concentration of then
a
K
4
1.0 10 . Let initial a

=
3
B(OH) ,
10 a
a
14
w
7.2 10 or
1.0 10
aK xy xy
K y
a x a x
K xz

= = =

= =

Electroneutrality requires
w
or ; hence, ( ). x y z z x y K xz x x y = + = = =
Substituting for from above: y
SM-298
a
w
2
a w
2
w a
14 4 10
w a
7 1
3
7
1 0 10 1 0 10 7 2 10
2 9 10 mol L [H O ]
pH log(2.9 10 ) 6.54
aK
x x K
x
x aK K
x K aK
x K aK . . .
x .

+

=


=
= +
= + = +
= =
= =

This value is slightly, but measurably, different from the value 6.57
obtained by ignoring the contribution to
3
[H O ]
+
from water.
(b) In this case, the second ionization can safely be ignored;
a2 a1
. K K <<
Concentration
1
(mol L )

3 4 2 3 2 4
H PO H O H O H PO
+
+ +
initial 0.015 0 0
change x x + x +
equilibrium 0.015 x x x
2
3
a1
2 3 4
3 3 2
3
3 1
3
7.6 10
0.015
7.6 10 1.14 10 0
7.6 10 (7.6 10 ) 4.56 10
[H O ]
2
7.5 10 mol L
pH log(7.5 10 ) 2.12
x
K
x
x x
x

4
+

= =

+ =
+ +
= =
=
= =

(c) In this case, the second ionization can safely be ignored;
a2 a1
. K K <<
Concentration

1
2 3 2 3 3
(mol L ) H SO H O H O HSO
+
+ +

initial 0.1 0 0
change x x + x +
equilibrium 0.1 x x x
SM-299
2
2
a1
2 2 3
2 2 2 3
1
3
1.5 10
0.10
1.5 10 1.5 10 0
1.5 10 (1.5 10 ) 6.0 10
[H O ] 0.032 mol L
2
pH log(0.032) 1.49
x
K
x
x x
x

+
= =

+ =
+ +
= = =
= =


10.91 The three equilibria involved are:
1
2
3
+ -
- + 3 3 2
3 4 2 4 3
3 4
+ 2
- 2- + 8 3 4
2 4 4 3
-
2 4
+
2- 3- + 13 3
4 4 3
[H O ][H PO ]
H PO (aq) H PO (aq) H O (aq), 7.6 10
[H PO ]
[H O ][HPO ]
H PO (aq) HPO (aq) H O (aq), 6.2 10
[H PO ]
[H O ][P
HPO (aq) PO (aq) H O (aq), 2.1 10
a
a
a
K
K
K

+ = =
+ = =
+ = =

4
-
3-
4
2-
4
O ]
[HPO ]
We also know that the combined concentration of all the phosphate
species is:
[ ]
- 2- 3-
3 4 2 4 4 4
-pH 2.25 3 -1
H PO +[H PO ] [HPO ] [PO ] 1.5 10
and the hydronium ion concentration is:
[H] 10 10 5.62 10 mol L
2

+ + =
= = =

At this point it is a matter of solving this set of simultaneous equations to
obtain the concentrations of the phosphate containing species. We start by
dividing both sides of the equilibrium constant expressions above by the
given hydronium ion concentration to obtain three ratios:
- 2-
5 1 2 4 4 4
- 2
3 4 2 4 4
[H PO ] [HPO ] [PO ]
1.35 , 1.10 10 , and 3.74 10
[H PO ] [H PO ] [HPO ]

= = =
3-
1
-
4
3 4

Through rearrangement and substitution of these three ratios, we can
obtain the following expressions:
-
2 4 3 4
2- -5 - -5
4 2 4 3
-5
3 4
3- 11 2- 11 -5
4 4
-16
3 4
[H PO ] 1.35 [H PO ],
[HPO ] 1.1010 [H PO ] 1.1010 1.35 [H PO ]
1.4810 [H PO ], and
[PO ] 3.74 10 [HPO ] 3.74 10 1.4810 [H PO ]
5.5410 [H PO ].

=
= =
=
= =
=

SM-300
Substituting these expressions back into the sum:
[ ]
[ ] ( ) ( ) (
[ ]
- 2- 3-
3 4 2 4 4 4
-5 -16
3 4 3 4 3 4 3 4
2
-3
3 4
- -3
2 4 3 4
2- -5 -8
4 3 4
3-
4
H PO +[H PO ] [HPO ] [PO ]
H PO + 1.35 [H PO ] 1.4810 [H PO ] 5.5410 [H PO ]
1.5 10
we find:
H PO 6.410 ,
[H PO ] 1.35 [H PO ] 8.610 ,
[HPO ] 1.4810 [H PO ] 9.410 , and
[PO ]

+ + =
= + +
=
=
= =
= =
=
-16 -18
3 4
5.5410 [H PO ] 3.510 . =
)
=
4
=
4

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

2 7 1
3 3
[H O ] (6.55 10 )[H O ] (1.00 10 ) 0
+ +
=
Solving using the quadratic equation gives

7
3
[H O ] 6.70 10 , pH 6.174.
+
= =
This value is slightly lower than the value calculated, based on the acid
concentration alone
7
(pH log(6.55 10 ) 6.184).

= =

10.95 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 8 1
3 3
[H O ] (9.78 10 )[H O ] (1.00 10 ) 0
+ +
+ =
Solving using the quadratic equation gives

8
3
[H O ] 6.24 10 , pH 7.205.
+
= =
This value is higher than the value calculated, based on the base
concentration alone
8
(pOH log(9.78 10 ) 7.009).

= =

10.97 (a) In the absence of a significant effect due to the autoprotolysis of
water, the pH values of the
4
1.00 10

M and
6
1.00 10

M HBrO
solutions can be calculated as described earlier.
SM-301
For
4 1
1.00 10 mol L :


Concentration

1
(mol L )

2 3
HBrO(aq) H O(l) H O (aq) BrO (aq)
+
+ +
initial 0 0
4
1.00 10

change x x + x +
final
4
1.00 10 x

x + x +
3
a
[H O ][BrO ]
[HBrO]
K
+
=
2
9
4 4
( )( )
2.0 10
1.00 10 [1.00 10 ]
x x x
x x

= =


Assume
4
1.00 10 x

<<
2 9
(2.0 10 ) (1.00 10 ) x

=
4

7
4.5 10 x

=
Because
4
1%of 1.00 10 x

< , the assumption was valid. Given this
value, the pH is then calculated to be
7
log(4.5 10 ) 6.35.

=
For
6 1
1.00 10 mol L :


Concentration
1
(mol L )

HBrO(aq) +
2 3
H O(l) H O (aq) BrO (aq)
+
+
initial
6
1.00 10

0 0
change x x + x +
final
6
1.00 10 x

x + x +
3
a
[H O ][BrO ]
[HBrO]
K
+
=
2
9
6 6
( )( )
2.0 10
1.00 10 [1.00 10 ]
x x x
x x

= =


Assume
6
1.00 10 x

<<
2 9
8
(2.0 10 ) (1.00 10 )
4.5 10
x
x

=
=
6

SM-302
6
is 4.5%of 1.00 10 , x

so the assumption is less acceptable. The pH is
calculated to be Because this predicts a basic
solution, it is not reasonable.
8
log(4.5 10 ) 7.35.

=
(b) To calculate the value taking into account the autoprotolysis of water,
we can use equation (22):
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

=
9
a
2.0 10 K

= into this equation and
then solve the expression either by trial and error or, preferably, using a
graphing calculator such as the one found on the CD accompanying this
text.
Alternatively, you can use a computer program designed to solve
simultaneous equations. Because the unknowns include
you will need four equations. As
seen in the text, pertinent equations are
3
[H O ], [OH ], [HBrO], and [BrO ],
+
3
a
w 3
3
initial
[H O ][BrO ]
[HBrO]
[H O ][OH ]
[H O ] [OH ] [BrO ]
[HBrO] [HBrO] [BrO ]
K
K
+
+
+

=
=
= +
= +

Both methods should produce the same result.
The values obtained are
7 1
3
7 1
5 1
8 1
[H O ] 4.6 10 mol L , pH 6.34 (compare to 6.35 obtained in (a))
[BrO ] 4.4 10 mol L
[HBrO] 1.0 10 mol L
[OH ] 2.2 10 mol L
+



= =
=

=

Similarly, for
6
initial
[HBrO] 1.00 10 :

=
SM-303
7 1
3
8 1
7 1
8 1
[H O ] 1.1 10 mol L , pH 6.96 (compare to 7.32 obtained in (a))
[BrO ] 1.8 10 mol L
[HBrO] 9.8 10 mol L
[OH ] 9.1 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.

10.99 (a) In the absence of a significant effect due to the autoprotolysis of
water, the pH values of the
solutions can be calculated as described earlier.
5 6
M M 8.50 10 and 7.37 10 HCN


For
5 1
8.50 10 mol L :


Concentration
1
2 3
(mol L ) HCN(aq) H O(l) H O (aq) CN (aq)
+
+ +


initial
5
8.50 10

0 0
change x x + x +
final
5
8.50 10 x

x + x +
[ ]
3
a
2
10
5 5
5
2 10 5
7
[H O ][CN ]
HCN
( ) ( )
4.9 10
8.5 10 [8.5 10 ]
Assume 8.5 10
(4.9 10 ) (8.5 10 )
2.0 10
K
x x x
x x
x
x
x
+

=
= =

<<
=
=

5
Because 1%of 8.50 10 , x

< the assumption was valid. Given this
value, the pH is then calculated to be
7
log(2.0 10 ) 6.69.

=
6 1
For 7.37 10 mol L :




SM-304
Concentration
2 3
(mol L ) HCN(aq) H O(l) H O (aq) CN (aq)
+
+ +


initial
6
7.37 10

0 0
change x x + x +
final
6
7.37 10 x

x + x +
3
a
2
10
6 6
6
2 10 6
8
6
[H O ][CN ]
[HCN]
( ) ( )
4.9 10
7.37 10 [7.37 10 ]
Assume 7.37 10
(4.9 10 ) (7.37 10 )
6.0 10
is 1%of 7.37 10 , so the assumption is still reasonable. The pH
is then calculated to be log(6.0
K
x x x
x x
x
x
x
x
+

=
= =

<<
=
=
<

8
10 ) 7.22. This answer is
not reasonable because we know HCN is an acid.

=

(b) To calculate the value, taking into account the autoprotolysis of water,
we can use equation (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
1.00 10 ,
w
K

=
10
a
4.9 10 K

= into this equation
and then solve the expression either by trial and error or, preferably, using
a graphing calculator such as the one found on the CD accompanying this
text.
Alternatively, you can use a computer program designed to solve
simultaneous equations. Because the unknowns include
you will need four equations. As
seen in the text, the pertinent equations are
3
[H O ], [OH ], [HBrO], and [BrO ],
+
SM-305
[ ]
3
a
w 3
3
initial
[H O ][CN ]
HCN
[H O ][OH ]
[H O ] [OH ] [CN ]
[HCN] [HCN] [CN ]
K
K
+
+
+

=
=
= +
= +

Both methods should produce the same result.
For
5
[HCN] 8.5 10 mol L ,
1
= the values obtained are
7 1
3
[H O ] 2.3 10 mol L , pH 6.64 (compare to 6.69 obtained in (a))
+
= =
7 1
5 1
8 1
6
initial
7 1
3
8 1
6 1
[CN ] 1.8 10 mol L
[HCN] 8.5 10 mol L
[OH ] 4.4 10 mol L
Similarly, for [HCN] 7.37 10 :
[H O ] 1.2 10 mol L , pH 6.92 (compare to 7.22 obtained in (a))
[CN ] 3.1 10 mol L
[HCN] 7.3 10 mol L
[

+


=

=
=
= =
=

8 1
OH ] 8.6 10 mol L

=

Note that for the more concentrated solution, the effect of the
autoprotolysis of water is smaller. 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.

10.101 (a) Assuming all sulfur is converted to SO
2
, the amount of SO
2
produced
is:
( )( )( )
( )( )
3 -1
-1
-1
2
1.00 10 kg 0.025 1000 g kg
780 mol of S
32.07 g mol
Therefore, 780 mol 64.07 g mol 50, 000 g or 50 kg of SO is produced

=

=
(b) To determine the pH we first must calculate the volume of water in
which this 50 kg of SO2 is dissolved:
( )( )
2 2
7
3
1000 m 100 cm 1 L
2 cm 2.6 Km 5.2 10 L
1 Km 1 m 1000 cm
V

= =



SM-306
The concentration of SO
2
(aq) is then:
( ) ( )
7
780 mol 5.2 10 L 1.5 10 M

=
5

. We can assume that upon

solution the SO
2
(aq) is converted to sulfurous acid and the pH is
calculated as described earlier:
Concentration

1
2 3 2 3 3
(mol L ) H SO (aq) H O(l) H O (aq) HSO (aq)
+
+ +
initial
5
1.50 10

0 0
change x x + x +
final
5
1.50 10 x

x + x +
[ ]
3 3
a
2 3
2
5
5
3
5
[H O ][HSO ]
H SO
( ) ( )
1.55 10
1.5 10
Employing the quadratic formula we find
[H O ] 1.5 10 , giving a pH of
pH log(1.5 10 ) 4.8
K
x x
x
x
+

=
=

= =
= =

(c) When dissolved in water, SO
3
will form sulfuric acid:
3 2 3 4
SO (aq) 2 H O(l) H O (aq) HSO (aq)
+
+ +
The fist deprotonation of sulfuric acid is complete, the concentration of
hydronium ion due to the second deprotonation of sulfuric acid may be
found as described earlier:
Concentration

4 4
1 - 2-
2 3
(mol L ) HSO (aq) H O(l) H O (aq) SO (aq)
+
+ +
initial
5
1.50 10

5
1.50 10

0
change x x + x +
final
5
1.50 10 x

5
1.50 10 x

x +
SM-307
2
3 4
a
4
5
2
5
5
3
5 5 5
[H O ][SO ]
HSO
(1.5 10 ) ( )
1.2 10
1.5 10
Employing the quadratic formula we find
[H O ] 1.495 10 ,
and the total hydronium ion concentration to be
1.495 10 1.5 10 3.0 10 .
Theref
K
x x
x
x
+

+

=


+
=

= =
+ =
5
ore, pH = log(3.0 10 ) 4.5

=


10.103 (a)
2 7
w 3
[H O ][OH ] 3.8 10 K x
+
= = =
7 1
3
3
[H O ] 1.9 10 mol L
pH log[H O ] 6.72
x
+
+
= =
= =

(b) There are three data points available:


14
w w
25 C ( 1.0 10 ), 40 C ( K K

= =
14 14
w
3.8 10 ), and 37 C (K 2.1 10 )

=
ln T
1
1/ (K )

T
w
K
0.003356 25 C 32.2362
0.003226 37 C 31.4943
0.003195 40 C 31.1376
The slope is equal to / H R and the intercept equals / . S R
1 1
1 1 1
( 6502 K) (8.314 J K mol ) 54 kJ mol
( 10.43)(8.314 J K mol ) 87 J K mol
H
S
1
1


= =
= =


(c) The equation determined from the graph is for ln In order to write
an equation for the pH dependence of pure water, we must rearrange the
equation.
w
. K
First we note the relationship between and the pH of pure water.
w
K
SM-308
1/2
3 w
3 w
w
w
w
[H O ]
1
pH log[H O ] log
2
6501
ln 10.43
6501
2.303 log 10.43
2823
log 4.529
K
K
K
T
K
T
K
T
+
+
=
= =
=
=
=

w
1
pH log
2
1411
pH 2.264
K
T
=
= +


10.105 (a) We begin by finding the empirical formula of the compound:

2
2
-1
-1
2
2
-1
0.942 g CO
C: 0.0214 mol CO 0.214 mol C
44.011 g mol
(0.214 mol C)(12.011 g mol ) 0.257 g C
0.0964 g H O
H: 0.00535 mol H O 0.0107 mol H
18.0158 g mol
(0.0107 mol H)(1.008
=

=
=

-1
2
-1
-1
g mol ) 0.0108 g H
0.246 g H O
Na: 0.0107 mol Na
22.99 g mol
(0.0107 mol Na)(22.99 g mol ) 0.0246 g Na
O: mass of O 1.200 g 0.257 g 0.0108 g 0.0246 g 0.686 g of O
0.686 g O

16.00
=
=

=
= =
-1
0.0429 mol O
g mol
=

Dividing through by 0.0107 moles, we find the empirical formula to be:
C
2
HNaO
4
.
A molar mass of 112.02 gmol
-1
indicates that this is also the molecular
formula.
(b)
C C
O
O
O
O
H
-


SM-309
(c) The dissolved substance is sodium oxalate, it is capable of gaining or
loosing a proton and, therefore, amphiprotic.
( )
1
1
2 2
pH p p 2.7
a a
K K = + =

10.107 We wish to calculate for the reaction
a
K
2 3
HF(aq) H O(l) H O (aq) F (aq)
+
+ +
This equation is equivalent to
HF(aq) H (aq) F (aq)
+
+
This latter writing of the expression is simpler for the purpose of the
thermodynamic calculations.
The value for this reaction is easily calculated from the free energies
given in the appendix:
G
1 1 1
1 1
/
(18030 J mol ) / [8.314 J K mol ) (298 K)] 4
( 278.79 kJ mol ) ( 296.82 kJ mol ) 18.03 kJ mol
ln
6.9 10
G RT
RT K
K e
K e

1


= =

=
= =


10.109 (a)
2 2 3
D O D O D O OD
+
+ +
(b)
2 2 2
15
D 0 3 D 0 D 0
[D O ][OD ] 1.35 10 , p log 14.870 K K
+
= = = = K
(c)
15 8 1
3
[D O ] [OD ] 1.35 10 3.67 10 mol L
+
= = =


(d)
8
pD log(3.67 10 ) 7.435 pOD

= = =
(e)
2
D 0 2
pD pOD p (D O) 14.870 K + = =

10.111
Concentration
+
3 2 3 3
CH CH(OH)COOH(aq) + H O(l) H O (aq) + CH CH(OH)COO (aq)

1
(mol L )

initial 1.00 0 0
change x x + x +
equilibrium 1.00 x x x
SM-310
+ 2
4 3 3
a
3
[H O ][CH CH(OH)COO ]
8.4 10
[CH CH(OH)COOH] 1.00-
0.029
0.029
Percent deprotonation (100%) 2.9% deprotonated
1.00
x
K
x
x

= = =
=
= =

To calculate T
f
for this solution we need the concentration in moles of
solute per kilogram of solvent. Assuming a density of 1 gcm-1, 1.00 L of
solution will weigh 1000 g. One liter of solution will contain 1 mole
(90.08 g) of lactic acid. Therefore, one liter of solution will contain 1000 g
90.08 g = 910 g or 0.910 kg of solvent.
The molarity of the solution is:
1.029 mol solute
1.13
0.910 kg solvent
m = .
( )( )
-1 -1
1.86 K Kg mol 1.13 mol Kg 2.1 K
The temperature at which the solution will freeze is 271 K
f
T = =


10.113 30 C 303 K, 20 C 293 K T T = = = =
a
a
1 1
ln
K H H T T
K R T T R TT

= =

This is the vant Hoff equation.
4
4 1 1
1.768 10 303 K 293 K
ln 0.0017
293 K 303 K 1.765 10 8.314 J K mol
H

= =





10.115 (a) The equilibrium constant for the autoprotolysis of pure deuterium
oxide is given by:

( )( )
-1
-1 -1
15
84800 J mol
8.3145J K mol 298 K
1.37 10
G
R T
K e e

= = =
The concentration of D
3
O
+
(aq) at equilibrium is found in the familiar way:
Concentration
1
(mol L )

2 3
2 D O D O (aq) + OD (aq)
+

initial 0 0
change x + x +
SM-311
equilibrium x + x +
15
3
8
3
8
[D O ][OD ] 1.37 10
[D O ] 3.7 10
pD log(3.7 10 ) 7.4
K
+
+

= =
=
= =

O and H PO

(b) Given the expression for K in part (b) above, it is apparent that as T
increases K will increase resulting in an increase in [D
3
O
+
(aq)] and a
decrease in pD.

10.117 (a) and (b) Buffer regions are marked A, B, and C.

1.0


A B C
0.5


0
14 7 0

pH
(c) Region A: H P
3 4 2 4


Region B: H P
2
2 4 4
O and HPO

and PO

4
Region C: HPO
2 3
4 4
(d)




(e) The major species present are similar for both and
and
3
H PO
3 4 2 4
H AsO : H EO
2
4
HEO

where E P = or As. For As, there is more
than
2
4
HAsO

2 4
H AsO ,

with a ratio of approximately 0.63 to 0.37, or

1.7 : 1. For P, the situation is reversed, with more
2 4
H PO

than HP
in a ratio of about 0.61 to 0.39, or 2.2 : 1.
2
4
1.0
A C B
0.5
0
14 7 0
pH
O


SM-312
10.119 Given that CO
2
will react with water to form carbonic acid, H
2
CO
3
, it only
remains to determine the concentration of H
3
O
+
due to the deprotonation
of H
2
CO
3
.
( )( )
2 -1 -1 4 6
2
[CO ] 2.3 10 mol L atm 3.04 10 atm 7.0 10 mol L

= =
-1

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

initial 7.0 10
6
0 0
change x x + x +
equilibrium
-6
7.0 10 x x x

2
a 6.37 7
6
6
3
6
a 10 10 4.27 10
7.0 10
[H O ] 1.73 10
pH log(1.73 10 ) 5.75
pK
x
K
x

= = = =

= =
= =

SM-313