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Skoog - Solucionário Capítulo 9
Skoog - Solucionário Capítulo 9
Skoog - Solucionário Capítulo 9
Chapter 9
Chapter 9
9-1 (a) A weak electrolyte only partially ionizes when dissolved in water. NaHCO3 is an
(b) A Brønsted-Lowry acid is a molecule that donates a proton when it encounters a base
(c) The conjugate acid of a Brønsted-Lowry base is the species formed when a Brønsted-
Lowry base accepts a proton. For example, the NH4+ is the conjugate acid of NH3.
involving an acid and its conjugate base is combined with a second reaction involving a
+
NH 3 + H 2 O →
←
NH 4 + OH −
In the example above, NH3 acts as a base with NH4+ as its conjugate acid. H2O acts as an
(e) An amphiprotic solvent can act either as an acid or a base depending on the solute.
(f) A zwitterion is a chemical species that bears both positive and negative charges. Free
(h) A strong acid dissociates completely such that no undissociated molecules are left in
(i) The Le Châtelier principle states that the position of an equilibrium always shifts in
(j) The common-ion effect is responsible for the reduced solubility of an ionic precipitate
when one of the soluble components reacting to form the precipitate is added to the
9-2 (a) An amphiprotic solute is a chemical species that possesses both acidic and basic
solute.
anhydrous acetic acid is a differentiating solvent because perchloric acid dissociates 5000
(c) A leveling solvent is one in which a series of acids (or bases) all dissociate completely.
Water is an example, since strong acids like HCl and HClO4 ionize completely.
(d) A mass-action effect arises when a shift in the chemical equilibrium occurs due to the
introduction of one of the participating chemical species (i.e., addition of one of the
reactants or products.
9-3 For an aqueous equilibrium in which water is a participant, the concentration of water is
normally so much larger than the concentrations of the other reactants or products that it
can be assumed to be constant and independent of the equilibrium position. Thus, its
concentration is included within the equilibrium constant. For a pure solid, the
concentration of the chemical species in the solid phase is constant. As long as some
solid exists as a second phase, its effect on the equilibrium is constant and is included
9-4
9-6 (a) 2 H 2 O →
←
H 3O + + OH −
+
(b) 2CH 3COOH →
←
CH 3COOH 2 + CH 3COO −
+
(c) 2CH 3 NH 2 →
←
CH 3 NH 3 + CH 3 NH −
+
(d) 2CH 3OH ←→ CH 3OH 2 + CH 3O −
+
9-7 (a) C 2 H 5 NH 2 + H 2 O →
←
C 2 H 5 NH 2 + OH −
+
K w 1.00 × 10 −14 [C 2 H 5 NH 2 ][OH − ]
Kb = = −11
= = 4.33 × 10 −4
K a 2.31 × 10 [C 2 H 5 NH 2 ]
(b) HCN + H 2O →
←
CN − + H 3O +
Fundamentals of Analytical Chemistry: 8th ed. Chapter 9
K w [CN − ][H 3O + ]
Ka = = = 6.2 × 10 −10
Kb [HCN]
(c) C 5 H 5 NH + + H 2 O →
←
C 5 H 5 N + H 3O +
K w [C 5 H 5 N][H 3O + ]
Ka = = +
= 5.90 × 10 −6
Kb [C 5 H 5 NH ]
(d) CN − + H 2 O →
←
HCN + OH −
−14
K 1.00 × 10 [HCN][OH − ]
Kb = w = = = 1.6 × 10 −5
K a 6.2 × 10 −10 −
[CN ]
(e)
−
H 3 AsO 4 + H 2 O →
←
H 2 AsO 4 + H 3O +
− 2−
H 2 AsO 4 + H 2 O →
←
HAsO 4 + H 3O +
2− 3−
HAsO 4 + H 2O →
←
AsO 4 + H 3O +
3−
H 3 AsO 4 + 3H 2 O →
←
AsO 4 + 3H 3O +
− 2− 3−
[H 2 AsO 4 ][H 3O + ] [HAsO 4 ][H 3O + ] [AsO 4 ][H 3O + ]
K a1 = Ka2 = −
Ka3 = 2−
[H 3 AsO 4 ] [H 2 AsO 4 ] [HAsO 4 ]
3− 2− −
[AsO 4 ][H 3O + ]3 K a 3 [HAsO 4 ][H 3O + ]2 K a 3 K a 2 [H 2 AsO 4 ][H 3O + ]
β3 = = = = K a 3 K a 2 K a1
[H 3 AsO 4 ] [ H 3 AsO 4 ] [H 3 AsO 4 ]
β 3 = (3.2 × 10 −12 ) × (1.1 × 10 −7 ) × (5.8 × 10 −3 ) = 2.0 × 10 −21
(f)
2− −
CO 3 + H 2O →
←
HCO 3 + OH −
−
HCO 3 + H 2 O ←→ H 2 CO 3 + OH −
2−
CO 3 + 2H 2O ←
→
H 2 CO 3 + 2OH −
Fundamentals of Analytical Chemistry: 8th ed. Chapter 9
− −
[HCO 3 ][OH − ] [ HCO 3 ]K w K
K b1 = 2−
= + 2−
= w
[CO 3 ] [ H 3O ][CO 3 ] K a 2
[H 2 CO 3 ][OH − ] [ H 2 CO 3 ]K w K
K b2 = −
= + −
= w
[HCO 3 ] [ H 3O ][HCO 3 ] K a1
− 2
[H 2 CO 3 ][OH − ]2 K b 2 [ HCO 3 ][OH − ] Kw
β2 = 2−
= 2−
= K b 2 K b1 =
[CO 3 ] [CO 3 ] K a1 K a 2
(1.0 × 10 −14 ) 2
β2 = −4 −11
= 1.4 × 10 −14
(1.5 × 10 ) × ( 4.69 × 10 )
(c) PbI 2 ( s ) →
←
Pb 2+ + 2I − K sp = [Pb 2+ ][I − ]2
(d) BiI 3 ( s ) →
←
Bi 3+ + 3I − K sp = [Bi 3+ ][I − ]3
+ 3− + 3−
(e) MgNH 4 PO 4 ( s ) →
←
Mg 2+ + NH 4 + PO 4 K sp = [ Mg 2+ ][NH 4 ][PO 4 ]
9-10 (a)
= 2.02 × 10 −8
(b)
(d)
9-11 (a)
2.0 × 10 −8
S = [SeO32-] = = 4.0 × 10 −7 M
0.050
(b)
(c)
(d)
9-12 (a)
2−
K sp = 2.02 × 10 −8 = [Cu 2+ ][SeO 3 ] = [Cu 2+ ](0.050M )
2.02 × 10 −8
S = [Cu 2+ ] = = 4.0 × 10 −7 M
0.050
(b)
−
K sp = 3.2 × 10 −13 = [ Pb 2+ ][IO 3 ]2 = [ Pb 2+ ](0.050M ) 2
3.2 × 10 −13
S = [ Pb 2+ ] = = 1.3 × 10 −10 M
(0.050) 2
(c)
2.5 × 10 −9
S = [Sr2+] = = 1.0 × 10 −6 M
(0.050) 2
Fundamentals of Analytical Chemistry: 8th ed. Chapter 9
(d)
1.0 × 10 −15
S = [Th4+] = = 1.6 × 10 −10 M
(0.050) 4
2− 2−
9-13 Ag 2CrO 4 ( s ) →
←
2Ag + + CrO4 Ksp = 1.2 × 10−12 = [ Ag + ]2 [CrO 4 ]
2− 1.2 × 10 −12
(a) [CrO 4 ] = = 1.0 × 10 −9 M
(3.41 × 10 −2 ) 2
2− 1.2 × 10 −12
(b) [CrO 4 ] = = 0.30 M
( 2.00 × 10 −6 ) 2
9-14 Al(OH)3 ( s ) →
←
Al 3+ + 3OH − K sp = 3.0 × 10− 34 = [Al 3+ ][OH − ]3
1
Molar solubility of Al(OH) 3 = [OH − ]
3
1
[Al 3+ ] = 5.0 × 10− 2 M + [OH − ]
3
⎛ 1 ⎞
K sp = ⎜ 5.0 × 10− 2 M + [OH − ] ⎟[OH − ]3 = 3.0 × 10− 34
⎝ 3 ⎠
(a) Because the Ksp is so small, we can assume the solubility of Al(OH)3 is not large.
Therefore, it is reasonable that the [Al3+] ≈ 5.0 X 10-2 M. The Ksp equation then
simplifies to
1
⎛ 3.0 × 10 −34 ⎞ 3
[OH-] = ⎜⎜ −2
⎟⎟ = 2.0 × 10 −11 M
⎝ 5 .0 × 10 M ⎠
Fundamentals of Analytical Chemistry: 8th ed. Chapter 9
− ⎛ 3.0 × 10 −34 ⎞ 3
[OH ] = ⎜⎜ −7
⎟⎟ = 1.1 × 10 −9 M
⎝ 2.00 × 10 M ⎠
−
9-15 K sp = [Ce3+ ][IO3 ]3 = S(3S)3 = 3.2 × 10−10
(a)
mole L
0.0250 M Ce 3+ ≡ 2.5 × 10 −2 × × 50.0 mL = 1.25 × 10 −3 mole
L 1000 mL
1.25 × 10 −3 mole 1000 mL
× = 0.0125 M
(50.0 mL + 50.0 mL) L
− mole L
(b) 0.040 M IO 3 ≡ 4.0 × 10 −2 × × 50.0 mL = 2.0 × 10 −3 mole
L 1000 mL
K sp = (5.833 × 10 −3 + S) (3S) 3
We start by solving for S assuming no contribution to [Ce3+] other than from the
dissociation of Ce(IO3)3. In this case, S equals 1.855 × 10-3. Now, we substitute 1.855 ×
10-3 back into the Ksp equation above and solve for Kiterative. Kiterative equals 1.3259 × 10-9.
S is too large; we choose a smaller S (i.e., 1 × 10-3) and recalculate Kiterative. Iteration
continues until Kiterative ≈ Ksp. The results of this approach are shown in the Table below.
Fundamentals of Analytical Chemistry: 8th ed. Chapter 9
Iteration S Kiterative
1 1.855×10-3 1.3259×10-9
2 1×10-3 1.8449×10-10
3 1.2×10-3 3.2813×10-10
4 1.19×10-3 3.1954×10-10
(c)
− mole L
0.250 M IO 3 ≡ 2.5 × 10 −1 × × 50.0 mL = 0.0125 mole
L 1000 mL
−
moles IO 3 unreacted = 0.0125 mole − 3(1.25 × 10 −3 mole) = 8.75 × 10 −3 mole
− ⎛ 8.75 × 10 −3 mole 1000 mL ⎞
[ IO 3 ] = ⎜⎜ × ⎟⎟ + 3S = 0.0875 M + 3S
⎝ 100.0 mL L ⎠
−10
K sp = S(0.0875 M + 3S) = 3.2 × 10
3
(d)
− mole L
0.150 M IO 3 ≡ 1.5 × 10 −1 × × 50.0 mL = 7.5 × 10 −3 mole
L 1000 mL
Fundamentals of Analytical Chemistry: 8th ed. Chapter 9
−
moles IO 3 unreacted = 7.5 × 10 −3 mole − 3(1.25 × 10 −3 mole) = 3.75 × 10 −3 mole
− ⎛ 3.75 × 10 −3 mole 1000 mL ⎞
[ IO 3 ] = ⎜⎜ × ⎟⎟ + 3S = 0.0375 M + 3S
⎝ 100.0 mL L ⎠
−10
K sp = S(0.0375 M + 3S) = 3.2 × 10
3
2−
9-16 K sp = [ K + ]2 [PdCl 6 ] = ( 2S) 2 (S) = 6.0 × 10 −6
mole L
0.200 M K + ≡ 2.0 × 10 −1 × × 50.0 mL = 0.0100 mole
L 1000 mL
1.00 × 10 −2 mole 1000 mL
× = 0.100 M
(50.0 mL + 50.0 mL) L
2− mole L
(a) 0.0500 M PdCl 6 ≡ 5.0 × 10 −2 × × 50.0 mL = 2.5 × 10 −3 mole
L 1000 mL
The [K+] is 0.05 M plus the contribution from the dissociation of the precipitate, x, or
[K+] = 0.05 M + 2x
2−
K sp = [ K + ]2 [ PdCl 6 ] = (0.05 + 2 x ) 2 x
4 x 3 + 0.20 x 2 + ( 2.5 × 10 −3 ) x = 6.0 × 10 −6
We use an iterative approach to solve for x. We begin by ignoring the contribution to [K+]
6.0 × 10 −6
x= 3 = 0.011447
4
Substituting this value back into the Ksp equation above, we obtain Kiterative equal to
6.0824 × 10-5, which is too large. We now proceed by choosing a smaller value of x equal
1 × 10-3 and obtain Kiterative equals to 2.7040× 10-6. We continue the iterative approach
Iteration x Kiterative
(b)
2− mole L
0.100 M PdCl 6 ≡ 1.0 × 10 −1 × × 50.0 mL = 5.00 × 10 −3 mole
L 1000 mL
2−
[ K + ] = 2S [ PdCl 6 ] = S
K sp = ( 2S) 2 S = 4S3 = 6.0 × 10 −6
1
⎛ 6.0 × 10 −6 ⎞ 3
S = ⎜⎜ ⎟⎟ = 0.011
⎝ 4 ⎠
+
[ K ] = 2S = 2(0.011 M ) = 0.022 M
Fundamentals of Analytical Chemistry: 8th ed. Chapter 9
(c)
2− mole L
0.200 M PdCl 6 ≡ 2.0 × 10 −1 × × 50.0 mL = 0.010 mole
L 1000 mL
2− 1
moles PdCl 6 unreacted = 1.0 × 10 −2 mole − (1.00 × 10 −2 mole) = 5.0 × 10 -3 mole
2
2− ⎛ 5.0 × 10 −3 mole 1000 mL ⎞
[PdCl 6 ] = ⎜⎜ × ⎟⎟ + S = 0.05 M + S
⎝ 100.0 mL L ⎠
Assume that S << 0.05 M
2−
[ PdCl 6 ] = 0.05 M
K sp = 4S 2 (0.05 M ) = 6.0 × 10 −6
1
⎛ 6.0 × 10 ⎞−6 2
S = ⎜⎜ ⎟⎟ = 5.477 × 10 −3 M
⎝ 4(0.05) ⎠
[ K ] = 2S = 2(5.477 × 10 −3 M ) = 0.011 M
+
(a)
(b)
1 × 10 −12
SCuI = = 1 × 10 −11
0.10 M
8.3 × 10 −17
S AgI = = 8.3 × 10 −16
0.10 M
7.1 × 10 −9
S PbI 2 = 2
= 7.1 × 10 −7
(0.10 M )
8.1 × 10 −19
S BiI3 = = 8.1 × 10 −16
(0.10 M ) 3
PbI 2 > CuI > AgI > BiI 3 in 0.10 M NaI
(c)
1 × 10 −12
S CuI = = 1 × 10 −10
0.010 M
8.3 × 10 −17
S AgI = = 8.3 × 10 −15
0.010 M
1 7.1 × 10 −9
S PbI 2 = = 4.2 × 10 − 4
2 0.010 M
1 8.1 × 10 −19
S BiI3 = 3 = 1.4 × 10 −6
3 0.010 M
PbI 2 > BiI 3 > CuI > AgI in a 0.010 M solution of the solute cation
(a)
2+ 1 − 7.0 × 10 −22
S Be ( OH )2 = [ Be ] = [OH ] S = 3 = 5.6 × 10 −8
2 4
3+1 − 3.0 × 10 −24
STm ( OH )3 = [Tm ] = [OH ] S = 4 = 5.8 × 10 −7
3 27
4+1 − 4.0 × 10 −26
S Hf ( OH )4 = [ Hf ] = [OH ] S = 5 = 2.7 × 10 −6
4 256
Be(OH) 2 has the lowest solubility in water.
(b)
4.0 × 10 −10
S BiOOH = = 4.0 × 10 −9
0.10 M
7.0 × 10 −22
S Be ( OH )2 = = 7.0 × 10 −20
(0.10 M ) 2
3.0 × 10 −24
S Tm ( OH )3 = 3
= 3.0 × 10 −21
(0.10 M )
4.0 × 10 −26
S Hf ( OH )4 = 4
= 4.0 × 10 −22
(0.10 M )
Hf(OH) 4 has the lowest solubility in 0.10 M NaOH.
9-19 At 0ºC,
At 100ºC,
9-20 (a)
[OCl − ][H 3O + ]
HOCl + H 2 O →
←
OCl − + H 3O + Ka = = 3.0 × 10 −8
[HOCl]
[ H 3O + ] = [OCl − ] [HOCl] = 0.0300 M − [H 3O + ]
[H 3O + ]2
+
= 3.0 × 10 −8 [H 3O + ]2 = 3.0 × 10 −8 (0.0300 M − [H 3O + ])
(0.0300 M − [H 3O ])
[H 3O + ]2 + 3.0 × 10 −8 [H 3O + ] − 9.0 × 10 −10 = 0
3.0 × 10 −8 + (3.0 × 10 −8 ) 2 + 4(9.0 × 10 −10 )
[H 3O + ] = − = 3.0 × 10 −5 M
2
−14
1.0 × 10
[OH − ] = = 3.3 × 10 −10 M
3.0 × 10 −5 M
(b)
CH 3CH 2 CH 2 COOH + H 2 O →
←
CH 3CH 2 CH 2 COO − + H 3O +
(c)
+
C 2 H 5 NH 2 + H 2 O →
←
C 2 H 5 NH 3 + OH −
+
[C H NH 3 ][OH − ] K w 1.0 × 10 −14
Kb = 2 5 = = −11
= 4.33 × 10 −4
[C 2 H 5 NH 2 ] K a 2.31 × 10
+
[OH − ] = [C 2 H 5 NH 3 ] [C 2 H 5 NH 2 ] = 0.100 M − [OH − ]
[OH − ]2
−
= 4.33 × 10 −4 [OH − ]2 = 4.33 × 10 −4 (0.100 M − [OH − ])
(0.100 M − [OH ])
[OH − ]2 + 4.33 × 10 −4 [OH − ] − 4.33 × 10 −5 = 0
4.33 × 10 −4 + (4.33 × 10 −4 ) 2 + 4(4.33 × 10 −5 )
[OH − ] = − = 6.4 × 10 −3 M
2
1.0 × 10 −14
[H 3O + ] = = 1.6 × 10 −12 M
6.37 × 10 −3 M
(d)
(CH 3 ) 3 N + H 2 O →
←
(CH 3 ) 3 NH + + OH −
(e)
(f)
C 2 H 5COO − + H 2 O →
←
C 2 H 5COOH + OH −
(g)
+ [HONH 2 ][H 3O + ]
HONH 3 + H 2 O →
←
HONH 2 + H 3O + Ka = +
= 1.10 × 10 −6
[HONH 3 ]
+
[H 3O + ] = [HONH 2 ] [HONH 3 ] = 0.250 M − [H 3O + ]
[H 3O + ]2
= 1.10 × 10 −6 [H 3O + ]2 = 1.10 × 10 −6 (0.250 M − [H 3O + ])
(0.250 M − [H 3O + ])
[H 3O + ]2 + 1.10 × 10 −6 [H 3O + ] − 2.75 × 10 −7 = 0
1.10 × 10 −6 + (1.10 × 10 −6 ) 2 + 4(2.75 × 10 −7 )
[H 3O + ] = − = 5.24 × 10 −4 M
2
−14
1.0 × 10
[OH − ] = −4
= 1.91 × 10 −11 M
5.24 × 10 M
(h)
+ + [OHC 2 H 4 NH 2 ][H 3O + ]
HOC 2 H 4 NH 3 + H 2 O →
←
HOC 2 H 4 NH 2 + H 3O Ka = +
= 3.18 × 10 −10
[HOC 2 H 4 NH 3 ]
+
[H 3O + ] = [HOC 2 H 4 NH 2 ] [HOC 2 H 4 NH 3 ] = 0.0250 M − [H 3O + ]
[H 3O + ]2
+
= 3.18 × 10 −10 [H 3O + ]2 = 3.18 × 10 −10 (0.0250 M − [H 3O + ])
(0.0250 M − [H 3O ])
[H 3O + ]2 + 3.18 × 10 −10 [H 3O + ] − 7.95 × 10 −12 = 0
3.18 × 10 −10 + (3.18 × 10 −10 ) 2 + 4(7.95 × 10 −12 )
[H 3O + ] = − = 2.82 × 10 −6 M
2
1.0 × 10 −14
[OH − ] = −6
= 3.55 × 10 −9 M
2.82 × 10 M
Fundamentals of Analytical Chemistry: 8th ed. Chapter 9
9-21 (a)
(b)
ClCH 2 COO − + H 2 O →
←
ClCH 2 COOH + OH −
(c)
+
CH 3 NH 2 + H 2 O →
←
CH 3 NH 3 + OH −
+
[CH 3 NH 3 ][OH − ] K w 1.0 × 10 −14
Kb = = = −11
= 4.35 × 10 −4
[CH 3 NH 2 ] K a 2.3 × 10
+
[OH − ] = [CH 3 NH 3 ] [CH 3 NH 2 ] = 0.0100 M − [OH − ]
[OH − ]2
−
= 4.35 × 10 −4 [OH − ]2 = 4.35 × 10 −4 (0.0100 M − [OH − ])
(0.0100 M − [OH ])
[OH − ]2 + 4.35 × 10 −4 [OH − ] − 4.35 × 10 −6 = 0
4.35 × 10 −4 + (4.35 × 10 −4 ) 2 + 4(4.35 × 10 −6 )
[OH − ] = − = 1.88 × 10 −3 M
2
1.0 × 10 −14
[H 3O + ] = = 5.32 × 10 −12 M
1.88 × 10 −3 M
(d)
+ [CH 3 NH 2 ][H 3O + ]
CH 3 NH 3 + H 2 O →
←
CH 3 NH 2 + H 3O + Ka = +
= 2.3 × 10 −11
[CH 3 NH 3 ]
+
[H 3O + ] = [CH 3 NH 2 ] [CH 3 NH 3 ] = 0.0100 M − [H 3O + ]
[H 3O + ]2
= 2.3 × 10 −11 [H 3O + ]2 = 2.3 × 10 −11 (0.0100 M − [H 3O + ])
(0.0100 M − [H 3O + ])
[H 3O + ]2 + 2.3 × 10 −11 [H 3O + ] − 2.3 × 10 −13 = 0
(e)
+ + [C 6 H 5 NH 2 ][H 3O + ]
C 6 H 5 NH 3 + H 2 O →
←
C 6 H 5 NH 2 + H 3O Ka = +
= 2.51 × 10 −5
[C 6 H 5 NH 3 ]
+
[H 3O + ] = [C 6 H 5 NH 2 ] [C 6 H 5 NH 3 ] = 0.0010 M − [H 3O + ]
[H 3O + ]2
+
= 2.51 × 10 −5 [H 3O + ]2 = 2.51 × 10 −5 (0.0010 M − [H 3O + ])
(0.0010 M − [H 3O ])
[H 3O + ]2 + 2.51 × 10 −5 [H 3O + ] − 2.51 × 10 −8 = 0
2.51 × 10 −5 + (2.51 × 10 −5 ) 2 + 4(2.51 × 10 -8 )
[H 3O + ] = − = 1.46 × 10 −4 M
2
Fundamentals of Analytical Chemistry: 8th ed. Chapter 9
(f)
−
− [IO 3 ][H 3O + ]
HIO 3 + H 2 O →
←
IO 3 + H 3O + Ka = = 1.7 × 10 −1
[HIO 3 ]
−
[ H 3O + ] = [IO 3 ] [HIO 3 ] = 0.200 M − [H 3O + ]
[H 3O + ]2
= 1.7 × 10 −1 [H 3O + ]2 = 1.7 × 10 −1 (0.200 M − [H 3O + ])
(0.200 M − [H 3O + ])
[H 3O + ]2 + 1.7 × 10 −1 [H 3O + ] − 0.034 = 0
1.7 × 10 −1 + (1.7 × 10 −1 ) 2 + 4(0.034)
[H 3O + ] = − = 0.12M
2
9-22 A buffer solution resists changes in pH with dilution or with addition of acids or bases. A
9-23 Buffer capacity of a solution is defined as the number of moles of a strong acid (or a
strong base) that causes 1.00 L of a buffer to undergo a 1.00-unit change in pH.
[NH 3 ] (0.100M)
9-24 (a) pH = pK a + log +
= − log(5.7 × 10 −10 ) + log = 8.943
[NH 4 ] (0.200M)
[NH 3 ] (0.050M)
(b) pH = pK a + log +
= − log(5.7 × 10 −10 ) + log = 8.943
[NH 4 ] (0.100M)
The solutions have identical pH values, but the solution in part (a) has the greater buffer
capacity because it has the higher concentration of weak acid and conjugate base.
Fundamentals of Analytical Chemistry: 8th ed. Chapter 9
9-25 (a)
HOAc + H 2 O →
←
H 3O + + OAc −
OAc − + H 2 O →
←
HOAc + OH −
0.100 mole L
0.100 M HOAc ≡ × × 200 mL = 0.020 mole
L 1000 mL
0.008
pH = − log(1.75 × 10 −5 ) + log = 4.359
0.020
(b)
0.175 mole L
0.175 M HOAc ≡ × × 100 mL = 0.0175 mole
L 1000 mL
0.0500 mole L
0.0500 M NaOH ≡ × × 100 mL = 0.005 mole
L 1000 mL
(0.0175 − 0.0050)mole 1000 mL
[HOAc] = × = 6.25 × 10 −2 M
200 mL L
0.0050 mole 1000 mL
[OAc − ] = × = 2.50 × 10 −2 M
200 mL L
2.50 × 10 −2
pH = −log(1.75 × 10 −5 ) + log = 4.359
6.25 × 10 −2
(c)
0.042 mole L
0.0420 M OAc − ≡ × × 160 mL = 0.00672 mole
L 1000 mL
0.1200 mole L
0.1200 M HCl ≡ × × 40.0 mL = 0.0048 mole
L 1000 mL
(0.00672 − 0.0048)mole 1000 mL
[OAc − ] = × = 9.6 × 10 −3 M
200 mL L
0.0048 mole 1000 mL
[HOAc] = × = 2.4 × 10 −2 M
200 mL L
9.6 × 10 −3
pH = −log(1.75 × 10 −5 ) + log = 4.359
2.4 × 10 −2
Fundamentals of Analytical Chemistry: 8th ed. Chapter 9
Since the ratios of the amounts of weak acid to conjugate base are identical the three
solutions will have the same pH. They will differ in buffer capacity, however, with (a)
9-27
9-28
[HOCH 2 COO − ]
pH = 4.00 = pK a + log
[HOCH 2 COOH]
[HOCH 2 COO − ] [HOCH 2 COO − ]
= − log(1.47 × 10 −4 ) + log = 3.83 + log
[HOCH 2 COOH] [HOCH 2 COOH]
[HOCH 2 COO − ] [HOCH 2 COO − ]
log = 0.167 = 10 0.167 = 1.47
[HOCH 2 COOH] [HOCH 2 COOH]
mole HOCH 2 COO −
= 1.47
mole HOCH 2 COOH
1.00 mole L
1.00 M HOCH 2 COOH ≡ × × 300.0 mL = 0.300 mole HOCH 2 COOH
L 1000 mL
mole HOCH 2 COO − = (1.47) × (0.300 mole HOCH 2 COOH) = 0.441 mole
1 mole HOCH 2 COONa 98.01g
weight HOCH 2 COONa = 0.441 mole HCOO − × × = 43.2 g
1 mole HOCH 2 COO − 1 mole
Fundamentals of Analytical Chemistry: 8th ed. Chapter 9
9-29
0.300 mole L
0.300 M C 6 H 5CHOHCOONa ≡ × × 250.0 mL
L 1000 mL
= 0.0750 mole C 6 H 5CHOHCOONa
[C 6 H 5CHOHCOO − ]
pH = 3.37 = pK a + log
[C 6 H 5CHOHCOOH]
[C 6 H 5CHOHCOO − ] [C H CHOHCOO − ]
= − log(4.0 × 10 −4 ) + log = 3.40 + log 6 5
[C 6 H 5CHOHCOOH] [C 6 H 5CHOHCOOH]
[C 6 H 5CHOHCOO − ] [C 6 H 5CHOHCOO − ]
log = −0.03 = 10 −0.03 = 0.933
[C 6 H 5CHOHCOOH] [C 6 H 5CHOHCOOH]
mole C 6 H 5CHOHCOO −
= 0.933
mole C 6 H 5CHOHCOOH
(mole C 6 H 5CHOHCOO − − x mole HCl)
= 0.933
x mole HCl
mole C 6 H 5CHOHCOO − − x mole HCl = 0.933 ( x mole HCl)
mole C 6 H 5CHOHCOO − 0.075 mole
x mole HCl = = = 0.0388
1.933 1.933
L 1000 mL
volume HCl = 0.0388 mole × × = 194 mL HCl
0.200 mole L
Fundamentals of Analytical Chemistry: 8th ed. Chapter 9
9-30
1.00 mole L
1.00 M HOCH 2 COOH ≡ × × 300.0 mL = 0.300 mole HOCH 2 COOH
L 1000 mL
[ HOCH 2 COO − ]
pH = 4.00 = pK a + log
[ HOCH 2 COOH ]
− −
= − log(1.47 × 10 ) + log
−4 [ HOCH COO ] [ HOCH COO ]
= 3.83 + log
2 2
[ HOCH COOH ] 2 [ HOCH COOH ] 2
− −
[ HOCH 2 COO ] [ HOCH 2 COO ] −1
log = 0.167 = 101.67×10 = 1.47
[ HOCH 2 COOH ] [ HOCH 2 COOH ]
mole HOCH 2 COO −
= 1.47
mole HOCH 2 COOH
x mole NaOH
= 1.47
( mole HOCH 2 COOH − x mole NaOH )
x mole NaOH = 1.47 × ( mole HOCH 2 COOH − x mole NaOH )
1.47 × ( mole HOCH 2 COO − ) 1.47 × (0.300 mole)
x mole NaOH = = = 0.179 mole
2.47 2.47
L 1000 mL
volume NaOH = 0.179 mole × × = 89.3 mL NaOH
2.00 mole L
9-31 The statement “A buffer maintains the pH of a solution constant” is false. The change in
pH of a buffered solution is relatively small with the addition of a small volume of acid
[ NaA ]
pH = pK a + log
[ HA ]
[ NaA ]
mL of 0.050M NaOH ∆pH
[ HA ]
1.48 0.170
100 1.59 0.200
200 1.70 0.230
300 1.83 0.262