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Chapter 17

Acids, Bases and


Buffers
Overview
strong acid : strong base
strong acid : weak base
weak acid : strong base
weak acid : weak base
common ion effect
buffers
Henderson-Hasselbalch Equation
titration curves
strong acid : strong base
at the equivalence point (OH
-
= H
+
) the pH = 7
strong acid : weak base
at the equivalence point, pH < 7
weak acid : strong base
at the equivalence point, pH > 7
weak acid : weak base
at the equivalence point, pH depends on the
relative value of the K
a
and the K
b
of the acid
and base
example: weak acid : strong base solution
H
2
O + HCN H
3
O
+
+ CN
-
K
a

H
3
O
+
+ OH
-
2H
2
O 1/K
w

HCN + OH
-
H
2
O + CN
-

K
a
/K
w

K
a
/K
w
is large so rxn. will be, essentially, complete
WA SB
example: strong acid : weak base solution
H
2
O + CN
-
HCN + OH
-
K
b

H
3
O
+
+ OH
-
2H
2
O 1/K
w
CN
-
+ H
3
O
+
H
2
O + HCN

K
b
/K
w
K
b
/K
w
is large so rxn. will be, essentially, complete
SA WB
example: weak acid : weak base solution
H
2
O + HCN H
3
O
+
+ CN
-
K
a

H
2
O + NH
3
OH
-
+ NH
4
+
K
b
pH depends upon relative magnitude of K
a
and K
b

Common Ion Effect:
HCN + H
2
O H
3
O
+
+ CN
-

Initial addition of CN
-
(as NaCN) shifts equilibrium,
decreasing H
3
O
+
thereby increasing the pH
How does this affect the pH quantitatively?
HCN + H
2
O H
3
O
+
+ CN
-

0.20 M 0 0.10 M initail
-x + x + x change
0.20 - x x 0.10 + x equil.
4.9 x 10
-10
= (x)(0.10 + x)
0.20 - x
x = 9.8 x 10
-10
M = [H
3
O
+
] = pH = 9.0
(vs. 9.9 x 10
- 6
M = pH = 5.0 with no added NaCN)
Buffers:
Resist change in pH on addition of
small amounts of strong acid or base
Composed of :
A weak acid and the salt of its conj. base
or
A weak base and the salt of its conj. acid
Most effective when pH is 1 of the pK
a

HX H
+
+ X
-

[H
+
] = K
a
[HX]
[X
-
]
adding OH
-
causes inc. in X
-
dec. in HX
OH
-
+ HX H
2
O + X
-


adding H
+
causes dec. in X
-
inc. in HX
H
+
+ X
-
HX

as long as amt. of OH
-
or H
+
is small compared
to HX & X
-
, ratio changes little
[H
+
] = K
a
[HX]
[X
-
]
-log [H
+
] = - log K
a
-log [HX]
[X
-
]
pH = pK
a
- log [HX]
[X
-
]
pH = pK
a
+ log [X
-
]
[HX]
Henderson-Hasselbalch Equation
Henderson-Hasselbalch Equation:
Calculates pH of buffer solutions
Can be used only for buffer solutions
Can be used only when the equilibrium
approximation can be used
pH = pK
a
+ log ([X
-
] / [HX]) where HX is
the weak acid and X
-
is its conjugate base
Titration Curves:
strong acid : strong base
Calculation of pH after addition of aliquots of base
HCl + NaOH H
2
O + NaCl pH
50 mL 0.10 0 mL 0.10 M 1.0
10 mL 1.2
20 mL 1.4
49 mL 3.0
50 mL 7.0
55 mL 11.7
80 mL 12.4
100 mL 12.5
Note: large increase in pH near equivalence pt.

12

10

8

6

4

2

50
Volume of Base, mL
pH
Equivalence Pt.
50 mL 0.10 M HCl titrated with 0.10 M NaOH
Titration Curves:
Weak acid : strong base
Calculation of pH after addition of aliquots of base
HC
2
H
3
O
2
+ NaOH H
2
O + NaC
2
H
3
O
2
pH
50 mL 0.10 0 mL 0.10 M 2.9
10 mL 4.1
20 mL 4.6
25 mL half equivalence point [ pH = pK
a
] 4.7
49 mL 6.4
50 mL equivalence point 8.7
55 mL 11.7
80 mL 12.4
100 mL 12.5
Note: large increase in pH near equivalence pt.

12

10

8

6

4

2

50
Volume of Strong Base, mL
pH
Equivalence Pt.
50 mL 0.10 M HC
2
H
3
O
2
titrated with 0.10 M NaOH
half equivalence point = pK
a

25
Strong Base Titrated with Strong Acid
12

10

8

6

4

2

50
Volume of Strong Acid, mL
pH
Equivalence Pt.
50 mL 0.10 M NH
3
titrated with 0.10 M HCl
half equivalence point = pK
b

25
12

10

8

6

4

2

200
Volume of Base, mL
pH
second equivalence pt.
Diprotic acid, H
2
C
2
O
4
, titrated with 0.10 M NaOH
first equivalence point = pK
a

100
Indicators:
Indicators are generally weak acids
HInd + H
2
O H
3
O
+
+ Ind
-

K
a

Ind
= [H
3
O
+
][Ind
-
]
[HInd]
[H
3
O
+
] = [HInd] this ratio controls color
K
a
[Ind
-
]
Solubility Equilibria
Solubility and Solubility Product
Precipitation of Insoluble Salts K
sp
and Q
Common Ion Effect and Solubility
Simultaneous Equilibria
Solubility and pH
Solubility and Complex Ions
Separations and Qualitative Analysis
Solubility Product Constant:
The equilibrium constant expression for
the solution of a solid
AgCl
(s)
Ag
+
(aq)
+ Cl
-
(aq)


K
sp
= [Ag
+
][Cl
-
]
All rules for equilibrium constants and expressions apply
Solubility Product
Examples:
CaF
2(s)
Ca
2+
(aq)
+ 2F
-
(aq)

K
sp
= [Ca
2+
][F
-
]
2

Ag
3
PO
4(s)
3Ag
+
(aq)
+ PO
4
3-
(aq)


K
sp
= [Ag
+
]
3
[PO
4
3-
]
Ca
2+

F
-

F
-

F
-

F
-

Ca
2+

solid CaF
2(s)

dissolved Ca
2+
(aq)
& F
-
(aq)
ions
CaF
2(s)
Ca
2+
(aq)
+ 2F
-
(aq)

The quantity of CaF
2(s)

dissolved is reflected by
the quantity of Ca
2+
(aq)

ions in solution
The Molar Solubility of
CaF
2(s)
is equal to the
[Ca
2+
] at the eq. point = a
saturated solution
Calculate the K
sp
from experimental data:
Prob: [Ba
2+
] = 7.5 x 10
-3
M in saturated BaF
2
. Calculate K
sp
.
BaF
2(s)
Ba
2+
(aq)
+ 2F
-
(aq)

x 2x
7.5 x 10
-3
2(7.5 x 10
-3
)
K
sp
= (7.5 x 10
-3
)(15.0 x 10
-3
)
2
= 1.6 x 10
-6
Estimating Solubility:
Much like doing equilibrium problems:
Determine the molar solubility of CaCO
3
if the K
sp
is
3.8 x 10
-9
at 25 C
CaCO
3(s)
Ca
2+
(aq)
+ CO
3
2-
(aq)

initial 0 0
change +x +x
equil. x x
x
2
= 3.8 x 10
-9
x = 6.2 x 10
-5
M = [Ca
2+
] = [CO
3
2-
]
Prob: Calculate the molar solubility of Mg(OH)
2
if
the K
sp
is 1.5 x 10
-11

Mg(OH)
2(s)
Mg
2+
(aq)
+ 2OH
-
(aq)

initial 0 0
change +x +2x
equil. x 2x
(x)(2x)
2
= 4x
3
= 1.5 x 10
-11
x = 1.6 x 10
-4
M
[Mg
2+
] = 1.6 x 10
-4
M [OH
-
] = 3.2 x 10
-4
M
K
sp
= [Mg
2+
][OH
-
]
2


(x) (2x)
Which is more soluble in water?
AgCl or Ag
2
CrO
4

AgCl
(s)
Ag
+
(aq)
+ Cl
-
(aq)
K
sp
= 1.8 x 10
-10

Ag
2
CrO
4(s)
2Ag
+
(aq)
+ CrO
4

2-

(aq)
K
sp
= 9.0 x 10
-12

molar solubility = 1.3 x 10
-5
M

molar solubility = 1.3 x 10
-4
M

Direct comparisons of K
sp
s can only be used if the ion ratios
are the same
Which is more soluble in water?
AgCl K
sp
= 1.8 x 10
-10

or
AgCN K
sp
= 1.2 x 10
-16



Mg(OH)
2
K
sp
= 1.5 x 10
-11

or
Ca(OH)
2
K
sp
= 7.9 x 10
-9

Q, Reaction Quotient
Q = K
sp
system is at equilibrium
Q > K
sp
system not at equilibrium
solid forms (rxn. shifts
)
Q < K
sp
system not at equilibrium
solid dissolves (rxn. shifts )
Prob: PbI
2(s)
(K
sp
= 8.7 x 10
-9
) placed in solution where [Pb
2+
] =
1.1 x 10
-3
M. Is the solution saturated?
PbI
2(s)
Pb
2+
(aq)
+ 2I
-
(aq)

Q = 5.3 x 10
-9
< K
sp

No, more will
dissolve
Concentrations required for precipitation:
Prob: What is the minimum conc. of I
-
that can
cause precipitation of PbI
2
from a 0.050 M solution
of Pb(NO
3
)
2
? K
sp
(PbI
2
) = 8.7 x 10
-9
.
K
sp
= [Pb
2+
][I
-
]
2

8.7 x 10
-9
= [I
-
]
2

0.050
[I
-
] = 4.2 x 10
-4
M

How much Pb
2+
remains when [I
-
] = 0.0015 M
[Pb
2+
] = 8.7 x 10
-9
= 3.9 x 10
-3
M
(0.0015)
2
K
sp
and Precipitation:
Prob: You have 100.0 mL of 0.0010 M AgNO
3
. Does
AgCl precipitate if you add 5.0 mL of 0.025 HCl?
AgCl
(s)
Ag
+
(aq)
+ Cl
-
(aq)

AgNO
3(aq)
Ag
+
(aq)
+ NO
3
-
(aq)

HCl
(aq)
+ H
2
O H
3
O
+
(aq)
+ Cl
-
(aq)

1.0 x 10
-4
mol 1.25 x 10
-4
mol
0.105 L 0.105 L
9.5 x 10
-4
M 1.2 x 10
-3
M
Q = (9.5 x 10
-4
)(1.2 x 10
-3
)
Q = 1.1 x 10
-6
> K
sp

will precipitate
Solubility and Common Ion Effect:
CaF
2(s)
Ca
2+
(aq)
+ 2F
-
(aq)

Adding extra Ca
2+
or F
-
shifts equilibrium
causing a decrease in solubility of CaF
2(s)

shift toward solid CaF
2

Molar Solubility of CaF
2
(no added F
-
):
CaF
2(s)
Ca
2+
(aq)
+ 2F
-
(aq)
initial 0 0
change +x +2x
equil. x 2x
x = 2.1 x 10
-4
M = [Ca
2+
]
K
sp
= 3.9 x 10
-11
= (x)(2x)
2
molar solubility is 2.1 x 10
-4
moles CaF
2
/ L
Molar Solubility of CaF
2
(with 0.010 M NaF):
CaF
2(s)
Ca
2+
(aq)
+ 2F
-
(aq)
initial 0 0.010
change +x +2x
equil. x 0.010 + 2x
K
sp
= 3.9 x 10
-11
= (x)(0.010 + 2x)
2

x = 3.9 x 10
-7
M = [Ca
2+
]
molar solubility is 3.9 x 10
-7
moles CaF
2
/ L
with added NaF which suppresses solubility
What happens if acid is added to CaF
2
?
CaF
2(s)
Ca
2+
(aq)
+ 2F
-
(aq)
H
3
O
+
+ F
-
HF + H
2
O
SA WB
The second rxn. has the effect of removing F
-
from
the first equilibrium, affecting the solubility of CaF
2

H
+
addition shifts rxn, increasing solubility
complete reaction
Which of the following would be more soluble in
acid solution?
PbCl
2
CaCO
3
Mg(OH)
2

the stronger the conj. base the more soluble
if the anion is a hydrolyzing conjugate base, the stronger
base it is, the more soluble the salt is in acid solution
Cl
-
+ H
2
O HCl + OH
-
K very small
CO
3
2-
+ H
2
O HCO
3
-
+ OH
-
K
b
2.1 x 10
-4

OH
-
+ H
2
O H
2
O + OH
-
K very large
For example:
CaCO
3(s)
Ca
2+
(aq)
+ CO
3
2-
(aq)
K
sp
3.8 x 10
-9

CO
3
2-
(aq)
+ H
2
O HCO
3
-
+ OH
-
K
b
2.1 x 10
-4

OH
-
+ H
3
O
+
2H
2
O K
w
-1
1.0 x 10
14

CaCO
3(s)
+ H
3
O
+
Ca
2+
+ HCO
3
-
+ H
2
O
K = 79.8
Which of the following would be more
soluble in acid solution?
Ca
10
(PO
4
)
6
(OH)
2

Ca
10
(PO
4
)
6
F
2

hydroxy apatite - tooth enamel
fluoro apatite - fluoridated tooth
enamel
Formation of Complex Ions:
Complex ions are large, polyatomic ions
Most complex ions have large K values
Formation of complex ions can affect solubility
of some salts
K
f
is the formation constant
Most transition metals form stable complex ions-
the transition metal is a Lewis Acid
Ag
+
+ 2NH
3(aq)
Ag(NH
3
)
2
+
K
f
1.7 x 10
7

x M 0.20 M (0.010 - x) M
K = 1.7 x 10
7
= [Ag(NH
3
)
2
+
] = 0.010
[Ag
+
][NH
3
]
2
(x)(0.20)
2

For example: Ex. 17.14 Calc. [Ag
+
] present at eq.
when conc. NH
3
added to 0.010 M AgNO
3
to give eq.
[NH
3
] = 0.20 M. Neglect vol. change.
x = 1.5 x 10
-8
M = [Ag
+
]
Selective Precipitation:
Prob: 0.050 M Mg
2+
& 0.020 M Cu
2+
. Which will ppt
first as OH
-
is added?
Mg(OH)
2
Mg
2+
+ 2OH
-
K
sp
= 1.8 x 10
-11

Cu(OH)
2
Cu
2+
+ 2OH
-
K
sp
= 2.2 x 10
-20

[OH
-
] = (K
sp
/ [M
2+
])
1/2

Cu(OH)
2

What concentration of OH
-
is necessary?
[OH
-
] = (K
sp
/ [Cu
2+
])
1/2


= (2.2 x 10
-20
/ 0.020)
1/2


= 1.0 x 10
-9
M
[OH
-
] = (K
sp
/ [Mg
2+
])
1/2


= (1.8 x 10
-11
/ 0.050)
1/2


= 1.9 x 10
-5
M
takes less OH
-

AgCl
(s)
Ag
+
(aq)
+ Cl
-
(aq)
K
sp
1.8 x 10
-10

Ag
+
+ 2NH
3(aq)
Ag(NH
3
)
2
+
K
f
1.7 x 10
7

AgCl
(s)
+ 2NH
3(aq)
Ag(NH
3
)
2
+
+ Cl
-

K = 3.1 x 10
-3
= [Ag(NH
3
)
2
+
][Cl
-
]
[NH
3
]
2

formation
For example:
Prob: Does 100 mL of 4.0 M aqueous ammonia
completely dissolve 0.010 mol of AgCl suspended in
1.0 L of solution?
AgCl
(s)
+ 2NH
3(aq)
Ag(NH
3
)
2
+
+ Cl
-

[NH
3
]
2
= (1.0 x 10
-2
)(1.0 x 10
-2
) = (0.032)
1/ 2
= 0.18 M
(3.1 x 10
-3
)

we have 0.4 moles of NH
3
available which is plenty to provide
the 0.020 mol necessary to form the complex plus 0.16 mol to
achieve an equilibrium concentration of 0.18 M [NH
3
]
K = 3.1 x 10
-3
= [Ag(NH
3
)
2
+
] [Cl
-
]
[NH
3
]
2
0.010 moles 0.020 moles 0.010 moles 0.010 moles

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