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Resolução Cap 10 Atkins
Resolução Cap 10 Atkins
(e) C6 H 5 O − (f) CH 3 CO 2 −
10.3 For all parts (a) – (e), H2O and H3O+ form a conjugate acid-base pair in
which H2O is the base and H3O is the acid
(a) H 2 SO 4 (aq) + H 2 O(l) U H 3 O + (aq) + HSO 4 − (aq)
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10.5 (a) Brønsted acid: HNO3
10.7 (a) HCO 3− , as an acid: HCO 3− (aq) + H 2 O(l) U H 3 O + (aq) + CO32− (aq) .
HCO3- and CO32- form a conjugate acid-base pair in which HCO3- is the
acid and CO32- is the base.
HCO 3 − , as a base: H 2 O(l) + HCO3 − (aq) U H 2 CO3 (aq) + OH − (aq) .
CHO3- and H2CO3 form a conjugate acid-base pair in which HCO3- is the
base and H2CO3 is the acid. H2O and OH- form a conjugate acid-base pair
in which H2O is the acid and OH- is the base.
(b) HPO 4 2− , as an acid:
HPO 4 2 − (aq) is the acid and PO 4 3− (aq) is the base. H2O and H3O+ form a
conjugate acid-base pair in which H2O is the base and H3O+ is the acid.
HPO 4 2 − , as a base: HPO 4 2− (aq) + H 2 O(l) U H 2 PO 4 − (aq) + OH − (aq) .
the base and H2PO4- is the acid. H2O and OH- form a conjugate acid-base
pair in which H2O is the acid and OH- is the base.
(b) H
O O
+ +
O S O S O
O O
H
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(c) sulfuric acid acts as the Lewis base while SO3 acts as a Lewis acid.
− Kw 1.0 × 10−14
[OH ] = =
[H 3 O + ] [H 3 O + ]
1.0 × 10−14
(a) [OH − ] = = 5.0 × 10−13 mol ⋅ L−1
0.02
1.0 × 10−14
(b) [OH − ] = −5
= 1.0 × 10−9 mol ⋅ L−1
1.0 × 10
1.0 × 10−14
(c) [OH − ] = = 3.2 × 10−12 mol ⋅ L−1
3.1 × 10−3
Then
[Ba(OH) 2 ]0 = [Ba 2 + ], [OH − ] = 2 × [Ba(OH) 2 ]0 , where [Ba(OH) 2 ]0 =
0.25 g
moles of Ba(OH) 2 = = 1.5 × 10−3 mol
171.36 g ⋅ mol−1
[OH − ] = 2 × [Ba(OH) 2 ]0 = 2 × 1.5 × 10−2 mol ⋅ L−1 = 2.9 × 10−2 mol ⋅ L−1
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+ Kw 1.0 × 10−14
[H 3 O ] = −
= −2
= 3.4 × 10−13 mol ⋅ L−1
[OH ] 2.9 × 10
⎛ 2.00 mL ⎞
[OH − ] = ⎜ −1 −4
⎟ × (0.175 mol ⋅ L ) = 7.0 × 10 mol ⋅ L
−1
⎝ 500 mL ⎠
pOH = −log(7.0 × 10−4 ) = 3.15, pH = 14.00 − 3.15 = 10.85
0.0136 g
number of moles of NaOH = −1
= 3.40 × 10−4 mol
40.00 g ⋅ mol
(f) [HBr]0 = [H 3 O + ]
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⎛ 75.0 mL ⎞
[H3 O + ] = ⎜ −4 −1 −5
⎟ × (3.5 × 10 mol ⋅ L ) = 5.3 × 10 mol ⋅ L
−1
⎝ 500 mL ⎠
pH = −log(5.3 × 10−5 ) = 4.28, pOH = 14.00 − 4.28 = 9.72
Acid pK a1 K a1
[H 3 O + ][ClO 2 − ]
Ka =
[HClO 2 ]
[HClO 2 ][OH − ]
Kb =
[ClO 2 − ]
[H3 O+ ][CN − ]
Ka =
[HCN]
[HCN][OH − ]
Kb =
[CN − ]
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(c) C6 H 5 OH(aq) + H 2 O(l) U H 3 O + (aq) + C6 H 5 O − (aq)
[H 3 O + ][C6 H 5 O − ]
Ka =
[C6 H 5 OH]
[C6 H5 OH][OH − ]
Kb =
[C6 H 5 O − ]
Remember that the pK a for the conjugate acid of a weak base will be
given by pK a + pK b = 14.
following ordering:
F − (14.00 − 3.45 = 10.55) < CH 3 COO− (14.00 − 4.75 = 9.25)
< C5 H5 N (8.75) << NH3 (4.75).
Remember that the pK b for the conjugate base of a weak acid will be
given by pK a + pK b = 14.
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) HClO3 , strong;
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strong acid, HSO 4 − is a weak acid. Its conjugate base is SO 4 2 − ); (d)
CH 4 , weak.
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, HIO3 is the stronger acid, with the lower pK a .
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) HClO 2 is stronger; there is one more O atom attached to the Cl atom
electron of the H atom out of the H—O bond. The oxidation state of Cl is
higher in HClO 2 than in HClO.
(e) HNO3 is stronger. The explanation is the same as that for part (b).
(f) H 2 CO3 is stronger; C has greater electronegativity than Ge. See part
(c).
10.37 (a) The — CCl3 group that is bonded to the carboxyl group, —COOH, in
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(b) The — CH 3 group in acetic acid has electron-donating properties,
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 it’s conjugate acid, the
ammonium ion, is a weaker acid than acetic acid. The presence of acetic
acid will shift the reaction: NH 3 + H 2 O U NH +4 + OH − toward products.
10.41 The larger the K a , the stronger the corresponding acid. 2,4,6-
10.43 The larger the pK a 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
(1) arylamines < ammonia < alkylamines
(2) methyl < ethyl < etc.
(Arylamines are amines in which the nitrogen of the amine is attached to a
benzene ring.)
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10.45 (a) Concentration
(mol ⋅ L−1 ) CH 3 COOH + H 2 O U H 3 O − + CH 3 CO 2
initial 0.29 — 0 0
change −x — +x +x
equilibrium 0.29 − x — x x
[H 3 O + ][CH 3 CO 2 − ] x2 x2
K a = 1.8 × 10−5 = = ≈
[CH 3 COOH] 0.29 − x 0.29
x = [H 3 O + ] = 2.3 × 10−3 mol ⋅ L−1
pH = −log(1.6 × 10−3 ) = 2.64, pOH = 14.00 − 2.64 = 11.36
(b) The equilibrium table for (b) is similar to that for (a).
[H 3 O + ][CCl3 CO 2 − ] x2
K a = 3.0 × 10−1 = =
[CCl3 COOH] 0.29 − x
or x 2 + 3.0 × 10−1 x − 0.087 = 0
−3.0 × 10−1 ± (3.0 × 10−1 ) 2 − (4) (−0.087)
x= = 0.18, −0.48
2
The negative root is not possible and can be eliminated.
x = [H 3 O + ] = 0.18 mol ⋅ L−1
pH = −log(0.18) = 0.74, pOH = 14.00 − 0.74 = 13.26
initial 0.29 — 0 0
change −x — +x +x
equilibrium 0.29 − x — x x
[H 3 O + ][HCO 2 − ] x⋅x x2
Ka = = ≈ = 1.8 × 10−4
[HCOOH] 0.29 − x 0.29
x = [H 3 O + ] = 0.29 × 1.8 × 10−4 = 7.2 × 10−3 mol ⋅ L−1
pH = −log(7.2 × 10−3 ) = 2.14, pOH = 14.00 − 2.14 = 11.86
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10.47 (a) Concentration
(mol ⋅ L−1 ) H2O + NH 3 U NH 4 + + OH −
initial — 0.057 0 0
change — −x +x +x
equilibrium — 0.057 − x x x
initial 0.162 — 0 0
change −x — +x +x
equilibrium 0.162 − x — x x
x2 x2
K b = 1.1 × 10−8 = ≈
0.162 − x 0.162
x = [OH − ] = 4.2 × 10−5 mol ⋅ L−1
pOH = −log(4.2 × 10−5 ) = 4.38, pH = 14.00 − 4.38 = 9.62
4.2 × 10−5
percentage protonation = × 100% = 0.026%
0.162
(c) Concentration
(mol ⋅ L−1 ) (CH 3 )3 N + H 2 O U (CH 3 )3 NH + + OH −
initial 0.35 — 0 0
change −x — +x +x
equilibrium 0.35 − x — +x +x
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−5 x2
6.5 × 10 =
0.35 − x
Assume x << 0.35
Then x = 4.8 × 10−3 mol ⋅ L−1
[OH − ] = 4.8 × 10−3 mol ⋅ L−1
pOH = −log(4.8 × 10−3 ) = 2.32, pH = 14.00 − 2.32 = 11.68
4.8 × 10−3
percentage protonation = × 100% = 1.4%
0.35
(d) pK b = 14.00 − pK a = 14.00 − 8.21 = 5.79, K b = 1.6 × 10−6
codeine + H 2 O L codeineH + + OH −
x2 x2
K b = 1.6 × 10−6 = ≈
0.073 − x 0.073
x = [OH − ] = 1.1 × 10−4 mol ⋅ L−1
pOH = −log(1.1 × 10−4 ) = 3.96, pH = 14.00 − 3.96 = 10.04
1.1 × 10−4
percentage protonation = × 100% = 2.5%
0.0073
(b) C3 H 7 NH 2 + H 2 O L C3 H 7 NH 3+ +OH −
pOH = 14.00 − 11.86 = 2.14
[C3 H 7 NH 3 + ] = [OH − ] = 10−2.14 = 7.2 × 10−3 mol ⋅ L−1
[C3 H 7 NH3 + ][OH − ] (7.2 × 10−3 ) 2
Kb = = −3
= 5.6 × 10−4
[C3 H 7 NH 2 ] 0.10 − 7.2 × 10
pK b = −log(5.6 × 10−4 ) = 3.25
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Concentration
(mol ⋅ L−1 ) HClO + H2O U H3O+ + ClO −
nominal x — 0 0
equilibrium x − 2.5 × 10−5 — 2.5 × 10−5 2.5 × 10−5
(2.5 × 10−5 ) 2
K a = 3.0 × 10−8 =
x − 2.5 × 10−5
nominal x — 0 0
equilibrium x − 1.6 × 10−4 — 1.6 × 10−4 1.6 × 10−4
(1.6 × 10−4 ) 2
K b = 1.7 × 10−6 =
x − 1.6 × 10−4
Solve for x; x = 1.5 × 10−2 mol ⋅ L−1
10.53 Concentration
(mol ⋅ L−1 ) C6 H 5 COOH + H 2 O U H 3 O + + C 6 H 5 CO 2 −
initial 0.110 — 0 0
change −x — +x +x
equilibrium 0.110 − x — x x
H 2 O + octylamine U octylamineH + + OH −
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x = 0.024 × 0.110 mol ⋅ L−1 = [H 3 O + ] = [C6 H 5 CO 2 − ]
[H 3 O + ][C6 H 5 COO − ] (0.024 × 0.110) 2
Ka = = = 6.3 × 10−5
[C6 H 5 COOH] (1 − 0.024) × 0.110
pH = −log(2.6 × 10−3 ) = 2.58
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] = 0.100 − 0.067 × 0.10 = 0.093 mol ⋅ L−1
4.4 × 10−4
x = 4.4 × 10−4 , Percent deprotonated = × 100% = 3.0%
0.0147
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10.59 (a) less than 7, NH 4 + (aq) + H 2 O(l) U H 3 O + (aq) + NH 3 (aq)
K w 1.00 × 10−14
10.61 (a) K b = = −5
= 5.6 × 10−10
Ka 1.8 × 10
Concentration
(mol ⋅ L−1 ) CH 3 CO 2 − (aq) + H 2 O(1) U HCH 3 CO 2 (aq) + OH − (aq)
initial 0.63 — 0 0
change −x — +x +x
equilibrium 0.63 − x — x x
K w 1.00 × 10−14
(b) K a = = −15
= 5.6 × 10−10
Kb 1.8 × 10
[H3 O + ][NH 3 ] x2 x2
Ka = = 5.6 × 10−10 = ≈
[NH 4 Cl] 0.19 − x 0.19
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x = 1.0 × 10−5 mol ⋅ L−1 = [H 3 O + ]
initial 0.055 — 0 0
change −x — +x +x
equilibrium 0.055 − x — x x
[H 3 O + ][Al(H 2 O)5 OH 2+ ] −5 x2 x2
Ka = = 1.4 × 10 = ≈
[Al(H 2 O)63+ ] 0.055 − x 0.055
initial — 0.065 0 0
change — −x +x +x
equilibrium — 0.065 − x x x
10.63 Concentration
(mol ⋅ L−1 ) CH 3 NH 3+ (aq) + H 2 O(l) U H 3 O + (aq) + CH 3 NH 2 (aq)
initial 0.510 — 0 0
change −x — +x +x
equilibrium 0.510 − x — x x
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[H 3 O + ][CH 3 NH 2 ] −11 x2 x2
Ka = = 2.8 × 10 = ≈
[CH 3 NH 3+ ] 0.510 − x 0.510
⎛ 1 mol KC2 H3 O 2 ⎞ ⎛ 1 ⎞
(5.34 g KC 2 H 3 O 2 ) ⎜ ⎟⎜ ⎟ = 0218 M KC2 H 3 O 2
⎝ 98.14 g KC2 H 3 O 2 ⎠ ⎝ 0.250 L ⎠
Concentration
(mol ⋅ L−1 ) H 2 O(l) + C 2 H 3 O 2 − (aq) U HC 2 H 3 O 2 (aq) + OH − (aq)
initial — 0.218 0 0
change — −x +x +x
equilibrium — 0.218 − x x x
1.0 × 10−14 x2 x2
= ≈
1.8 × 10−5 0.218 − x 0.218
97.95 g ⋅ mol−1
⎛ 1 mol NH 4 Br ⎞ ⎛ 1 ⎞
(5.75 g NH 4 Br) ⎜ ⎟⎜ ⎟ = 0.587 M NH 4 Br
⎝ 97.95 g NH 4 Br ⎠ ⎝ 0.100 L ⎠
Concentration
(mol ⋅ L−1 ) NH 4 + (aq) + H 2 O(l) U NH 3 (aq) + H 3 O + (aq)
initial 0.587 — 0 0
change −x — +x +x
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equilibrium 0.587 − x — x x
1.0 × 10−14 x2 x2
= ≈
1.8 × 10−5 0.587 − x 0.587
x2 x2
5.6 × 10−10 = ≈
0.0400 − x 0.0400
⎛ 2.16 g NH 4 Br ⎞ ⎛ 1 mL ⎞ ⎛ 1 mol NH 4 Br ⎞
(b) ⎜ ⎟ ⎜ −3 ⎟ ⎜ ⎟
⎝ 400 mL ⎠ ⎝ 10 L ⎠ ⎝ 97.95 g NH 4 Br ⎠
= 0.0551 (mol NH 4 Br) ⋅ L−1
Concentration
(mol ⋅ L−1 ) NH 4 + (aq) + H 2 O(l) U H 3 O + (aq) + NH 3 (aq)
initial 0.0551 — 0 0
change −x — +x +x
equilibrium 0.0551 − x — x x
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−10 x2 x2
5.6 × 10 = ≈
0.0551 − x 0.0551
10.69 (a) H
H N H
H C C C O Na+
H O
10.73 The initial concentrations of HSO 4 − and H 3 O + are both 0.15 mol ⋅ L−1 as a
SM-291
−2 [H 3 O + ][SO 4 2− ] (0.15 + x) ( x)
K a2 = 1.2 × 10 = =
[HSO 4 − ] 0.15 − x
x 2 + 0.162 x − 1.8 × 10−3 = 0
−0.162 + (0.162) 2 + (4) (1.8 × 10−3 )
x= = 0.0104 mol ⋅ L−1
2
[H 3 O ] = 0.15 + x = (0.15 + 0.0104) mol ⋅ L−1 = 0.16 mol ⋅ L−1
+
pH = − log(0.16) = 0.80
initial 0.010 — 0 0
change −x — +x +x
equilibrium 0.010 − x — x x
[H 3 O + ][HCO3− ] x2 x2
K a1 = = ≈ = 4.3 × 10−7
[H 2 CO3 ] 0.010 − x 0.010
x = [H 3 O + ] = 6.6 × 10−5 mol ⋅ L−1
pH = − log(6.6 × 10−5 ) = 4.18
initial 0.10 — 0 0
change −x — +x +x
equilibrium 0.10 − x — x x
[H 3 O + ][(COOH)CO 2 − ] x2
K a1 = 5.9 × 10−2 = =
[(COOH) 2 ] 0.10 − x
x 2 + 5.9 × 10−2 x − 5.9 × 10−3 = 0
−5.9 × 10−2 + (5.9 × 10−2 ) 2 + (4)(5.9 × 10−3 )
x= = 0.053 mol ⋅ L−1
2
pH = − log(0.053) = 1.28
SM-292
(c) Because K a2 << K a1 , the second ionization can be ignored.
equilibrium 0.20 − x — x x
[H 3 O + ][HS− ] x2 x2
K a1 = 1.3 × 10−7 = = ≈
[H 2 S] 0.20 − x 0.20
x = [H 3 O + ] = 1.6 × 10−4 mol ⋅ L−1
pH = − log(1.6 × 10−4 ) = 3.80
(b) For the disodium salt, the pertinent values are pK a2 and pK a3 :
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Concentration
(mol ⋅ L−1 ) H 2 CO3 (aq) + H 2 O(l) U H 3 O + (aq) + HCO3 − (aq)
initial 0.0456 — 0 0
change −x — +x +x
final 0.0456 − x — +x +x
[H3 O + ][HCO3− ]
K a1 =
[H 2 CO3 ]
( x) ( x) x2
4.3 × 10−7 = =
0.0456 − x 0.0456 − x
Assume that x << 0.0456
Then x 2 = (4.3 × 10−7 ) (0.0456)
x = 1.4 × 10−4
Because x < 1% of 0.0456, the assumption was valid.
x = [H 3 O + ] = [HCO3− ] = 1.4 × 10−4 mol ⋅ L−1
0.00014 mol ⋅ L−1 = 0.0455 mol ⋅ L−1 . We can then use the other equilibria
to determine the remaining concentrations:
[H 3 O + ][CO3 2− ]
K a2 =
[HCO3 − ]
(1.4 × 10−4 )[CO32− ]
5.6 × 10−11 =
(1.4 × 10−4 )
[CO3 2− ] = 5.6 × 10−11 mol ⋅ L−1
Because 5.6 × 10−11 << 1.4 × 10−4 , the initial assumption that the first
ionization would dominate is valid.
To calculate [OH − ], we use the K w relationship:
K w = [H 3 O + ][OH − ]
Kw 1.00 × 10−14
[OH − ] = +
= −4
= 7.1 × 10−11 mol ⋅ L−1
[H 3 O ] 1.4 × 10
In summary, [H 2 CO3 ] = 0.0455 mol ⋅ L−1 , [H 3 O + ] = [HCO3 − ]
= 1.4 × 10−4 mol ⋅ L−1 ,
[CO3 2− ] = 5.6 × 10−11 mol ⋅ L−1 , [OH − ] = 7.1 × 10−11 mol ⋅ L−1 .
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10.83 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:
CO3 2− (aq) + H 2 O(l) U HCO3− (aq) + OH − (aq)
K w 1.00 × 10−14
K b1 = = −11
= 1.8 × 10−4
K a2 5.6 × 10
initial 0.0456 — 0 0
change −x — +x +x
final 0.0456 − x — +x +x
[HCO3 − ][OH − ]
K b1 =
[CO3 2− ]
( x) ( x) x2
1.8 × 10−4 = =
0.0456 − x [0.0456 − x]
Assume that x << 0.0456
x = 2.9 × 10−3
Because x > 5% of 0.0456, the assumption was not valid and the full
expression should be solved using the quadratic equation:
x 2 + 1.8 × 10−4 x − (1.8 × 10−4 ) (0.0456) = 0
Therefore, [CO3 2 − ] = 0.0456 mol ⋅ L−1 − 0.0028 mol ⋅ L−1 = 0.0428 mol ⋅ L−1
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We can then use the other equilibria to determine the remaining
concentrations:
[H 2 CO3 ][OH − ]
K b2 =
[HCO3 − ]
[H 2 CO 3 ](0.0028)
2.3 × 10−8 =
(0.0028)
Because 2.3 × 10−8 << 0.0028 , the initial assumption that the first
+ Kw 1.00 × 10−14
[H3 O ] = −
= = 3.6 × 10−12 mol ⋅ L−1
[OH ] 0.0028
0.0028 mol ⋅ L−1 , [CO3 2 − ] = 0.0428 mol ⋅ L−1 , [H 3 O + ] = 3.6 × 10−12 mol ⋅ L−1
10.85 (a) phosphorous acid: The two pK a values are 2.00 and 6.59. Because
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H 2SO3 (aq) + H 2 O(l) U H3 O + (aq) + HSO3 − (aq) K a1 = 1.5 × 10−2
HSO3 − (aq) + H 2 O(l) U H3 O+ (aq) + SO3 2− (aq) K a2 = 1.2 × 10−7
The calculation of the desired concentrations follows exactly after the
method derived in Eq. 25, substituting H 2 SO3 for
H 2 CO3 , HSO3− for HCO3− , and SO32− for CO32− . First, calculate the
f = [H 3 O + ]2 + [H 3 O + ] K a1 + K a1 K a 2
= (3.2 × 10−6 ) 2 + (3.2 × 10−6 ) (1.5 × 10−2 ) + (1.5 × 10−2 ) (1.2 × 10−7 )
= 5.0 × 10−8
The fractions of the species present are then given by
[H 3 O + ] (3.2 × 10−6 ) 2
α (H 2 SO3 ) = = −8
= 2.1 × 10−4
f 5.0 × 10
[H 3 O + ]K a1 (3.2 × 10−6 ) (1.5 × 10−2 )
α (HSO3 − ) = = = 0.96
f 5.0 × 10−8
K a1 K a2 (1.5 × 10−2 ) (1.2 × 10−7 )
α (SO3 2− ) = = = 0.036
f 5.0 × 10−8
Thus, in a 0.150 mol ⋅ L−1 solution at pH 5.50, the dominant species will
be HSO 3 − with a concentration of (0.150 mol ⋅ L−1 ) (0.96) = 0.14 mol ⋅ L−1 .
The concentration of
H 2 SO3 will be (2.1 × 10 −4 ) (0.150 mol ⋅ L−1 ) = 3.2 × 10−5 mol ⋅ L−1 and the
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−10 [H 3 O + ][B(OH) 4 − ] x2 x2
K a = 7.2 × 10 = = ≈
[B(OH)3 ] 1.0 × 10−4 − x 1.0 × 10−4
x = [H3 O + ] = 2.7 × 10−7 mol ⋅ L−1
pH = −log(2.7 × 10−7 ) = 6.57
Note: this value of [H 3 O + ] is not much different from the value for pure
water, 1.0 × 10−7 mol ⋅ L−1 ; therefore, it is at the lower limit of safely
equilibrium — x z
Because there are now two contributions to [H 3 O + ], [H 3 O + ] is no longer
cubic equation, x will again be ignored relative to 1.0 × 10−4 mol ⋅ L−1 .
This approximation is justified by the approximate calculation above, and
because K a is very small relative to 1.0 × 10−4. Let a = initial
xy xy aK a
K a = 7.2 × 10−10 = ≈ or y =
a−x a x
K w = 1.0 × 10−14 = xz
Electroneutrality requires
x = y + z or z = x − y; hence, K w = xz = x( x − y ).
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⎛ aK a ⎞
x×⎜x − = Kw
⎝ x ⎟⎠
x 2 − aK a = K w
x 2 = K w + aK a
x = K w + aK a = 1.0 × 10−14 + 1.0 × 10−4 × 7.2 × 10−10
x = 2.9 × 10−7 mol ⋅ L−1 = [H 3 O + ]
pH = −log(2.9 × 10−7 ) = 6.54
This value is slightly, but measurably, different from the value 6.57
obtained by ignoring the contribution to [H 3 O + ] from water.
(b) In this case, the second ionization can safely be ignored; K a 2 << K a1 .
Concentration
(mol ⋅ L−1 ) H 3 PO 4 + H2O U H3O+ + H 2 PO 4 −
initial 0.015 — 0 0
change −x — +x +x
equilibrium 0.015 – x — x x
x2
K a1 = 7.6 × 10−3 =
0.015 − x
x 2 + 7.6 × 10−3 x − 1.14 × 10−4 = 0
(c) In this case, the second ionization can safely be ignored; K a2 << K a1 .
Concentration
(mol ⋅ L−1 ) H 2 SO3 + H2O U H3 O+ + HSO3 −
initial 0.1 — 0 0
change −x — +x +x
equilibrium 0.1 − x — x x
SM-299
−2 x2
K a1 = 1.5 × 10 =
0.10 − x
x 2 + 1.5 × 10−2 x − 1.5 × 10−3 = 0
SM-300
Substituting these expressions back into the sum:
[ H3 PO4 ] +[H 2 PO-4 ] + [HPO 2-4 ] + [PO3-4 ] =
= [ H 3 PO 4 ] + (1.35 ⋅ [H 3 PO 4 ]) + (1.48×10-5 ⋅ [H 3 PO 4 ]) + ( 5.54×10-16 ⋅ [H 3 PO 4 ])
= 1.5 × 10−2
we find:
[ H3 PO4 ] = 6.4×10-3 ,
[H 2 PO-4 ] = 1.35 ⋅ [H 3 PO 4 ] = 8.6×10-3 ,
[HPO 2-4 ] = 1.48×10-5 ⋅ [H 3 PO 4 ] = 9.4×10-8 , and
[PO3-4 ] = 5.54×10-16 ⋅ [H 3 PO 4 ] = 3.5×10-18 .
This value is slightly lower than the value calculated, based on the acid
concentration alone (pH = − log(6.55 × 10−7 ) = 6.184).
This value is higher than the value calculated, based on the base
concentration alone (pOH = − log(9.78 × 10−8 ) = 7.009).
SM-301
For 1.00 × 10−4 mol ⋅ L−1 :
Concentration
(mol ⋅ L−1 ) HBrO(aq) + H 2 O(l) U H 3 O + (aq) + BrO − (aq)
[H3 O+ ][BrO − ]
Ka =
[HBrO]
( x)( x) x2
2.0 × 10−9 = =
1.00 × 10−4 − x [1.00 × 10−4 − x]
x = 4.5 × 10−7
Because x < 1% of 1.00 × 10−4 , the assumption was valid. Given this
[H3 O+ ][BrO − ]
Ka =
[HBrO]
( x)( x) x2
2.0 × 10−9 = =
1.00 × 10−6 − x [1.00 × 10−6 − x]
SM-302
x is 4.5% of 1.00 × 10−6 , so the assumption is less acceptable. The pH is
the initial concentration of acid, and K a = 2.0 × 10−9 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
[H 3 O + ], [OH − ], [HBrO], and [BrO − ], you will need four equations. As
SM-303
[H 3 O + ] = 1.1 × 10−7 mol ⋅ L−1 , pH = 6.96 (compare to 7.32 obtained in (a))
[BrO − ] = 1.8 × 10−8 mol ⋅ L−1
[HBrO] ≅ 9.8 × 10−7 mol ⋅ L−1
[OH − ] = 9.1 × 10−8 mol ⋅ L−1
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.
[H 3 O + ][CN − ]
Ka =
[ HCN ]
(x) (x) x2
4.9 × 10−10 = =
8.5 × 10−5 − x [8.5 × 10−5 − x]
Assume x << 8.5 × 10−5
x 2 = (4.9 × 10−10 ) (8.5 × 10−5 )
x = 2.0 × 10−7
Because x < 1% of 8.50 × 10−5 , the assumption was valid. Given this
SM-304
Concentration
(mol ⋅ L− ) HCN(aq) + H 2 O(l) U H 3 O + (aq) + CN − (aq)
[H 3 O + ][CN − ]
Ka =
[HCN]
−10 (x) (x) x2
4.9 × 10 = =
7.37 × 10−6 − x [7.37 × 10−6 − x]
Assume x << 7.37 × 10−6
x 2 = (4.9 × 10−10 ) (7.37 × 10−6 )
x = 6.0 × 10−8
x is < 1% of 7.37 × 10−6 , so the assumption is still reasonable. The pH
is then calculated to be − log(6.0 × 10−8 ) = 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):
x 3 + K a x 2 − ( K w + K a ⋅ [HA]initial ) x − K w ⋅ K a = 0, where x = [H 3 O + ].
the initial concentration of acid, and K a = 4.9 × 10−10 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
[H 3 O + ], [OH − ], [HBrO], and [BrO − ], you will need four equations. As
SM-305
[H3 O + ][CN − ]
Ka =
[ HCN ]
K w = [H 3 O + ][OH − ]
[H 3 O + ] = [OH − ] + [CN − ]
[HCN]initial = [HCN] + [CN − ]
Both methods should produce the same result.
For [HCN] = 8.5 × 10−5 mol ⋅ L−1 , the values obtained are
10.101 (a) Assuming all sulfur is converted to SO2, the amount of SO2 produced
is:
(1.00 × 10 3
kg ) ( 0.025 ) (1000 g ⋅ kg -1 )
= 780 mol of S
32.07 g ⋅ mol-1
Therefore, ( 780 mol ) ( 64.07 g ⋅ mol-1 ) = 50, 000 g or 50 kg of SO 2 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
⎛ 1000 m ⎞ ⎛ 100 cm ⎞ ⎛ 1 L ⎞
V = ( 2 cm )( 2.6 Km ) ⎜ ⎟ ⎜ ⎟ ⎜ 3 ⎟
= 5.2 × 107 L
⎝ 1 Km ⎠ ⎝ 1 m ⎠ ⎝ 1000 cm ⎠
SM-306
The concentration of SO2(aq) is then:
[H 3 O + ][HSO3− ]
Ka =
[ H 2SO3 ]
(x) (x)
1.55 × 10−2 =
1.5 × 10−5 − x
Employing the quadratic formula we find
x = [H 3 O + ] = 1.5 × 10−5 , giving a pH of
pH = log(1.5 × 10−5 ) = 4.8
(c) When dissolved in water, SO3 will form sulfuric acid:
SO3 (aq) + 2 H 2 O(l) → H 3 O + (aq) + HSO −4 (aq)
SM-307
[H 3 O + ][SO 4 2− ]
Ka =
⎡⎣ HSO 4 − ⎤⎦
(1.5 × 10−5 + x) (x)
1.2 × 10−2 =
1.5 × 10−5 − x
Employing the quadratic formula we find
x = [H 3 O + ] = 1.495 × 10−5 ,
and the total hydronium ion concentration to be
1.495 × 10−5 + 1.5 × 10−5 = 3.0 × 10−5.
Therefore, pH = − log(3.0 × 10−5 ) = 4.5
T 1/T (K −1 ) ln K w
(c) The equation determined from the graph is for ln K w . In order to write
an equation for the pH dependence of pure water, we must rearrange the
equation.
First we note the relationship between K w and the pH of pure water.
SM-308
[H3 O+ ] = K w1/2
1
pH = −log[H3 O + ] = − log K w
2
6501
ln K w = − − 10.43
T
6501
2.303 log K w = − − 10.43
T
2823
log K w = − − 4.529
T
1
pH = − log K w
2
1411
pH = + 2.264
T
SM-309
(c) The dissolved substance is sodium oxalate, it is capable of gaining or
loosing a proton and, therefore, amphiprotic. pH = 1
2 ( pK a1 )
+ pK a 2 = 2.7
10.109 (a) D 2 O + D 2 O U D3 O + + OD −
10.111
CH 3 CH(OH)COOH(aq) + H 2 O(l) U H 3 O + (aq) + CH 3 CH(OH)COO − (aq)
Concentration (mol ⋅ L−1 )
initial 1.00 — 0 0
change −x — +x +x
equilibrium 1.00 − x — x x
SM-310
[H 3 O + ][CH 3 CH(OH)COO− ] x2
Ka = = = 8.4 × 10−4
[CH3 CH(OH)COOH] 1.00-x
x = 0.029
0.029
Percent deprotonation = (100%) = 2.9% deprotonated
1.00
To calculate Tf for this solution we need the concentration in moles of
solute per kilogram of solvent. Assuming a density of 1 g⋅cm-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.
1.029 mol solute
The molarity of the solution is: = 1.13 m .
0.910 kg solvent
⎛ K ′ ⎞ ∆H ° ⎛ 1 1 ⎞ ∆H ° ⎛ T⬘ − T ⎞
ln ⎜ a ⎟ = ⎜ − ⎟= ⎜ ⎟
⎝ Ka ⎠ R ⎝T T′⎠ R ⎝ TT ⬘ ⎠
10.115 (a) The equilibrium constant for the autoprotolysis of pure deuterium
oxide is given by:
−84800 J ⋅mol-1
− ∆G (8.3145J⋅K -1
)
⋅mol-1 ( 298 K ) −15
K =e R ⋅T
=e = 1.37 × 10
The concentration of D3O+(aq) at equilibrium is found in the familiar way:
Concentration
(mol ⋅ L−1 ) 2 D2 O U D3 O + (aq) + OD − (aq)
initial — 0 0
change — +x +x
SM-311
equilibrium — +x +x
1.0
A B C
0.5
0
0 7 14
pH
A B C
0.5
0
0 7 14
(e) The major speciespHpresent are similar for both H3 PO4 and
SM-312
10.119 Given that CO2 will react with water to form carbonic acid, H2CO3, it only
remains to determine the concentration of H3O+ due to the deprotonation
of H2CO3.
[CO 2 ] = ( 2.3 × 10 −2 mol ⋅ L-1 ⋅ atm -1 )( 3.04 × 10 −4 atm ) = 7.0 × 10 −6 mol ⋅ L-1
⎛ x2 ⎞
Ka = 10− pKa = 10−6.37 = 4.27 × 10−7 = ⎜ −6 ⎟
⎝ 7.0 × 10 ⎠
x = [H 3 O + ] = 1.73 × 10−6
pH = − log(1.73 × 10−6 ) = 5.75
SM-313