Aqueous

Ionic
Equilibrium
 Buffers
• buffers are solutions that resist changes in pH
when an acid or base is added
• they act by neutralizing the added acid or base
• but just like everything else, there is a limit to
what they can do, eventually the pH changes
• many buffers are made by mixing a solution of
a weak acid with a solution of soluble salt
containing its conjugate base anion
 Buffers (continued)
When an acid or base
is added
• to water, the pH
changes drastically
• to a buffer solution,
the pH does not
change very much;
pH is maintained

33
 Components of a Buffer
The components of a buffer solution
• are acid–base conjugate pairs
• can be a weak acid and a salt of its
conjugate base
• typically have equal concentrations of
the weak acid and its salt
• can also be a weak base and a salt of its
conjugate acid
44
Making an Acid Buffer
 Learning Check
Does each of the following combinations
produce a buffer solution or not? Explain.
A. HCl and KCl
B. H2CO3 and NaHCO3
C. H3PO4 and NaCl
D. HC2H3O2 and KC2H3O2

66
 Solution

Does each of the following combinations produce a buffer

solution or not? Explain.
A. HCl + KCl No; HCl is a strong acid.
B. H2CO3 + NaHCO3 Yes; this is a weak acid and
its salt
C. H3PO4 + NaCl No; NaCl does not contain a
conjugate base of H3PO4.
D. HC2H3O2 and KC2H3O2 Yes; this is a weak acid and
its salt

7
 How Acid Buffers Work
HA(aq) + H2O(l)  A−(aq) + H3O+(aq)
• buffers work by applying Le Châtelier’s Principle to
weak acid equilibrium
• buffer solutions contain significant amounts of the
weak acid molecules, HA – these molecules react with
added base to neutralize it
 you can also think of the H3O+ combining with the OH− to
make H2O; the H3O+ is then replaced by the shifting
equilibrium
• the buffer solutions also contain significant amounts of
the conjugate base anion, A− - these ions combine with
added acid to make more HA and keep the H3O+
constant
8
 Buffer Action

An acetic acid/acetate buffer contains the weak acid

acetic acid (HC2H3O2) and the salt of its conjugate base
sodium acetate (NaC2H3O2).
• Acid dissociation occurs:
HC2H3O2(aq) + H2O(l) C2H3O2(aq) + H3O+(aq)
• The salt provides a higher concentration of the conjugate
base C2H3O2 than provided by the dissociation of the weak
acid by itself.
NaC2H3O2(aq) Na+(aq) + C2H3O2(aq)

99
 Function of the Weak Acid in a Buffer
• The function of the weak acid in a buffer is to neutralize
added base.
• The acetate ion produced by the neutralization
becomes part of the available acetate.
HC2H3O2(aq) + OH−(aq) C2H3O2(aq) + H2O(l)
acetic acid base acetate ion water

10
10
 Function of the Conjugate Base
• The function of the acetate ion C2H3O2 is to neutralize
added H3O+.
• The acetic acid produced by the neutralization contributes to
the available weak acid.
C2H3O2(aq) + H3O+(aq) HC2H3O2(aq) + H2O(l)
acetate ion acid acetic acid water

11
11
 How Buffers Work
H2O
new
HA

HA
HA  A −
− + H3O+

Added
H3O+
 How Buffers Work
new H2O
A−

HA
HA  A −
− + H3O+

Added
HO−
 Common Ion Effect
HA(aq) + H2O(l)  A−(aq) + H3O+(aq)

• adding a salt containing the anion, NaA, that is

the conjugate base of the acid (the common ion)
shifts the position of equilibrium to the left
• this causes the pH to be higher than the pH of
the acid solution
lowering the H3O+ ion concentration
 Ex 16.1 - What is the pH of a buffer that is
0.100 M HC2H3O2 and 0.100 M NaC2H3O2?
Write the reaction HC2H3O2 + H2O  C2H3O2 + H3O+
for the acid with
water
[HA] [A-] [H3O+]
Construct an ICE
table for the reaction initial 0.100 0.100 ≈0
Enter the initial change
concentrations – equilibrium
assuming the [H3O+]
from water is ≈ 0
 Ex 16.1 - What is the pH of a buffer that is
0.100 M HC2H3O2 and 0.100 M NaC2H3O2?
HC2H3O2 + H2O  C2H3O2 + H3O+
represent the change
in the concentrations [HA] [A-] [H3O+]
in terms of x initial 0.100 0.100 0
change x +x +x
sum the columns to
find the equilibrium equilibrium 0.100 x 0.100 + x x
concentrations in
terms of x [C2 H3O-2 ][H3O ]  0.100  x  x 
Ka  
substitute into the
equilibrium constant
 HC2H3O2   0.100  x 
expression
Ka for HC2H3O2 = 1.8 x 10-5
 Ex 16.1 - What is the pH of a buffer that is
0.100 M HC2H3O2 and 0.100 M NaC2H3O2?
Ka for HC2H3O2 = 1.8 x 10-5
determine the value of Ka [HA] [A-] [H3O+]
since Ka is very small, initial 0.100 0.100 ≈0
approximate the
[HA]eq = [HA]init and [A−]eq change -x +x +x
= [A−]init solve for x 0.100x 0.100
equilibrium 0.100 0.100+x x
[C2 H3O-2 ][H3O  ]  0.100  x  x 
Ka  
 HC2H3O2   0.100  x 
[C2 H3O-2 ][H3O  ]  0.100  x 
Ka  
 HC2H3O2   0.100
1.8  105  x
 Ex 16.1 - What is the pH of a buffer that is
0.100 M HC2H3O2 and 0.100 M NaC2H3O2?
Ka for HC2H3O2 = 1.8 x 10-5
check if the [HA] [A-] [H3O+]
approximation is
valid by seeing if initial 0.100 0.100 ≈0
x < 5% of change -x +x +x
[HC2H3O2]init
equilibrium 0.100 0.100 x
x = 1.8 x 10-5
5
1.8  10
1
 100%  0. 018%  5%
1.00  10
the approximation is valid
 Ex 16.1 - What is the pH of a buffer that is
0.100 M HC2H3O2 and 0.100 M NaC2H3O2?

[HA] [A-] [H3O+]

substitute x into the
equilibrium initial 0.100 0.100 ≈0
concentration
change -x +x +x
definitions and solve
0.100x 0.100
equilibrium 0.100 + x 1.8E-5
0.100 x
x = 1.8 x 10-5
 HC2H3O2   0.100  x  0.100  1.8  105   0.100 M
[C2H3O 2 
]  0.100  x  0.100  1.8  10   0.100 M
5

[H3O  ]  x  1.8  105 M

 Ex 16.1 - What is the pH of a buffer that is
0.100 M HC2H3O2 and 0.100 M NaC2H3O2?

[HA] [A-] [H3O+]

substitute [H3O+] into
the formula for pH initial 0.100 0.100 ≈0
and solve change -x +x +x
equilibrium 0.100 0.100 1.8E-5

pH  -log H3O  


  log 1.8  10 5
  4.74
 Ex 16.1 - What is the pH of a buffer that is
0.100 M HC2H3O2 and 0.100 M NaC2H3O2?
Ka for HC2H3O2 = 1.8 x 10-5
check by substituting [HA] [A-] [H3O+]
the equilibrium
concentrations back into initial 0.100 0.100 ≈0
the equilibrium constant change -x +x +x
expression and
comparing the calculated
equilibrium 0.100 0.100 1.8E-5
Ka to the given Ka - 
[C H O ][H O ]
2 3 2 3
Ka 
 HC2H3O2 
the values match  0.100  1.8  105 
  1.8  105
 0.100
Practice - What is the pH of a buffer that is
0.14 M HF (pKa = 3.15) and 0.071 M KF?
 Practice - What is the pH of a buffer that is
0.14 M HF (pKa = 3.15) and 0.071 M KF?
Write the reaction HF + H2O  F + H3O+
for the acid with
water
[HA] [A-] [H3O+]
Construct an ICE
table for the reaction initial 0.14 0.071 ≈0
Enter the initial change
concentrations – equilibrium
assuming the [H3O+]
from water is ≈ 0
 Practice - What is the pH of a buffer that is
0.14 M HF (pKa = 3.15) and 0.071 M KF?
HF + H2O  F + H3O+
represent the change
in the concentrations [HA] [A-] [H3O+]
in terms of x initial 0.14 0.071 0
change x +x +x
sum the columns to
find the equilibrium equilibrium 0.14 x 0.071 + x x
concentrations in
terms of x [F- ][H3O  ]  0.071  x  x 
Ka  
substitute into the
equilibrium constant
 HF  0.14  x 
expression
 Practice - What is the pH of a buffer that is
0.14 M HF (pKa = 3.15) and 0.071 M KF?
Ka for HF = 7.0 x 10-4
determine the value of Ka [HA] [A-] [H3O+]
since Ka is very small, initial 0.14 0.071 ≈0
approximate the
[HA]eq = [HA]init and [A−]eq change -x +x +x
= [A−]init solve for x equilibrium 0.14 x 0.071
0.012 0.100+x x
[F- ][H3O  ]  0.071  x  x 
K a  10 pK a  103.15 Ka 
 HF

 0.14  x 
K a  7.0  10 4  0.071 x 
K a  7.0  10 4 
 0.14
1.4  103  x
 Practice - What is the pH of a buffer that is
0.14 M HF (pKa = 3.15) and 0.071 M KF?
Ka for HF = 7.0 x 10-4
check if the [HA] [A2-] [H3O+]
approximation is
valid by seeing if initial 0.14 0.071 ≈0
x < 5% of change -x +x +x
[HC2H3O2]init
equilibrium 0.14 0.071 x
x = 1.4 x 10-3
3
1.4  10
1
 100%  1%  5%
1.4  10
the approximation is valid
 Practice - What is the pH of a buffer that is
0.14 M HF (pKa = 3.15) and 0.071 M KF?

[HA] [A2-] [H3O+]

substitute x into the
equilibrium initial 0.14 0.071 ≈0
concentration
change -x +x +x
definitions and solve
0.14x 0.071
equilibrium 0.14 0.072+ x 1.4E-3
x
x = 1.4 x 10-3
 HF  0.14  x  0.14  1.4  103   0.14 M
[C2H3O2 
]  0.071  x  0.071  1.4  10   0.072 M
3

[H3O  ]  x  1.4  103 M

 Practice - What is the pH of a buffer that is
0.14 M HF (pKa = 3.15) and 0.071 M KF?

[HA] [A-] [H3O+]

substitute [H3O+] into
the formula for pH initial 0.14 0.071 ≈0
and solve change -x +x +x
equilibrium 0.14 0.072 1.4E-3

pH  -log H3O  


  log 1.4  10 3
  2.85
 Practice - What is the pH of a buffer that is
0.14 M HF (pKa = 3.15) and 0.071 M KF?
Ka for HF = 7.0 x 10-4
check by substituting [HA] [A-] [H3O+]
the equilibrium
concentrations back into initial 0.14 0.071 ≈0
the equilibrium constant change -x +x +x
expression and
comparing the calculated
equilibrium 0.14 0.072 1.4E-3
Ka to the given Ka - 
[F ][H3O ]
Ka 
the values are  HF
close enough

 
0.072 1.4  103 7.2  10 4
 0.14
 Henderson-Hasselbalch Equation
• calculating the pH of a buffer solution can be
simplified by using an equation derived from
the Ka expression called the Henderson-
Hasselbalch Equation
• the equation calculates the pH of a buffer from
the Ka and initial concentrations of the weak
acid and salt of the conjugate base
as long as the “x is small” approximation is valid
[conjugate base anion]initial
pH  pK a  log
[weak acid]initial
Deriving the Henderson-Hasselbalch Equation

[A- ][H3O  ]
Ka 
 HA
  [HA] 
[H3O ]  K a  - 
 [A ] 
 [A [HA]
]  [HA]
-
[HA]  
H3OpH
 log[pH 
pK
p]Ka logKKa
a 
log 
 [HA]
a
 log    
log
[A- ][A
- ][A
 - ]  
          
pH  - log[H3O ] pK a  -[HA] log K a [A ]
 log 
 log
[A ] [HA]
 Ex 16.2 - What is the pH of a buffer that is
0.050 M HC7H5O2 and 0.150 M NaC7H5O2?
Assume the [HA] and HC7H5O2 + H2O  C7H5O2 + H3O+
[A-] equilibrium
concentrations are the Ka for HC7H5O2 = 6.5 x 10-5
same as the initial pK a   log K a 
Substitute into the
Henderson-Hasselbalch
 
  log 6.5  105  4.187
Equation
p.K18a 7log
pH  4 
log 

 [A ]  
- 
0.150
 
Check the “x is small”  [HA ] 
0.050
approximation pH  4.66
5 -pH
[ H O
2.2 310 ]  10
  100- 4.66
%  0.044% 55%
3O ]  10
[0H.050  2.2  10
Practice - What is the pH of a buffer that is
0.14 M HF (pKa = 3.15) and 0.071 M KF?
 Practice - What is the pH of a buffer that is
0.14 M HF (pKa = 3.15) and 0.071 M KF?
find the pKa from the HF + H2O  F + H3O+
given Ka  [A - ] 
Assume the [HA] and pH  pK a  log 

 [HA ] 
[A-] equilibrium
concentrations are the   0.071 
same as the initial pH  3.15  log   2.86
 0.14 
Substitute into the
Henderson-Hasselbalch [H 3O  ]  10-pH
Equation
[H 3O  ]  10-2.86  1.4  103
Check the “x is small” 1.4  103
approximation  100%  1%  5%
0.14
Do I Use the Full Equilibrium Analysis or
the Henderson-Hasselbalch Equation?
• the Henderson-Hasselbalch equation is generally
good enough when the “x is small” approximation is
applicable
• generally, the “x is small” approximation will work
when both of the following are true:
a) the initial concentrations of acid and salt are not very
dilute
b) the Ka is fairly small
• for most problems, this means that the initial acid and
salt concentrations should be over 1000x larger than
the value of Ka
 How Much Does the pH of a Buffer
Change When an Acid or Base Is Added?
• though buffers do resist change in pH when acid or
base are added to them, their pH does change
• calculating the new pH after adding acid or base
requires breaking the problem into 2 parts
1. a stoichiometry calculation for the reaction of the
added chemical with one of the ingredients of the
buffer to reduce its initial concentration and increase
the concentration of the other
 added acid reacts with the A− to make more HA
 added base reacts with the HA to make more A−
2. an equilibrium calculation of [H3O+] using the new
initial values of [HA] and [A−]
 Ex 16.3 - What is the pH of a buffer that has 0.100 mol
HC2H3O2 and 0.100 mol NaC2H3O2 in 1.00 L that has
0.010 mol NaOH added to it?
If the added chemical is HC2H3O2 + OH−  C2H3O2 + H2O
a base, write a reaction
for OH− with HA. If the
added chemical is an HA A- OH−
acid, write a reaction mols Before 0.100 0.100 0
for it with A−.
mols added - - 0.010
Construct a
stoichiometry table for mols After
the reaction
 Ex 16.3 - What is the pH of a buffer that has 0.100 mol
HC2H3O2 and 0.100 mol NaC2H3O2 in 1.00 L that has
0.010 mol NaOH added to it?
HC2H3O2 + OH−  C2H3O2 + H2O
Fill in the table –
tracking the changes in
the number of moles HA A- OH−
for each component mols Before 0.100 0.100 ≈ 0
mols added - - 0.010
mols After 0.090 0.11 ≈0
 Ex 16.3 - What is the pH of a buffer that has 0.100 mol
HC2H3O2 and 0.100 mol NaC2H3O2 in 1.00 L that has
0.010 mol NaOH added to it?
Write the reaction HC2H3O2 + H2O  C2H3O2 + H3O+
for the acid with
water
[HA] [A-] [H3O+]
Construct an ICE
table for the reaction initial 0.090 0.11 ≈0
Enter the initial change
concentrations – equilibrium
assuming the [H3O+]
from water is ≈ 0,
and using the new
molarities of the
[HA] and [A−]
 Ex 16.3 - What is the pH of a buffer that has 0.100 mol
HC2H3O2 and 0.100 mol NaC2H3O2 in 1.00 L that has
0.010 mol NaOH added to it?
HC2H3O2 + H2O  C2H3O2 + H3O+
represent the change
in the concentrations [HA] [A-] [H3O+]
in terms of x initial 0.090 0.11 0
change x +x +x
sum the columns to
find the equilibrium equilibrium 0.090 x 0.11 + x x
concentrations in
terms of x [C 2 H 3O -2 ][H 3O  ]  0.110  x  x 
Ka  
substitute into the  HC 2 H 3O 2   0.090  x 
equilibrium constant
expression
 Ex 16.3 - What is the pH of a buffer that has 0.100 mol
HC2H3O2 and 0.100 mol NaC2H3O2 in 1.00 L that has
0.010 mol NaOH added to it?
Ka for HC2H3O2 = 1.8 x 10-5
determine the value of Ka [HA] [A-] [H3O+]
since Ka is very small, initial 0.100 0.100 ≈0
approximate the
[HA]eq = [HA]init and [A−]eq change -x +x +x
= [A−]init solve for x equilibrium 0.090
0.090 0.110
0.110+x x
[C 2 H 3O -2 ][H 3O  ]  0.110x  x  x 
Ka  
 HC 2 H 3O 2   0.090  x 
[C2 H 3O -2 ][
K a  1.8  10 
H
5 3 
O 0
] 0x.110
.110

  x
 HC2 H 3O 2   0.0900.090
1.47  10 5  x
 Ex 16.3 - What is the pH of a buffer that has 0.100 mol
HC2H3O2 and 0.100 mol NaC2H3O2 in 1.00 L that has
0.010 mol NaOH added to it?
Ka for HC2H3O2 = 1.8 x 10-5
check if the [HA] [A-] [H3O+]
approximation is
valid by seeing if initial 0.090 0.110 ≈0
x < 5% of change -x +x +x
[HC2H3O2]init
equilibrium 0.090 0.110 x
x = 1.47 x 10-5
5
1.47  10
2
 100%  0.016%  5%
9.0  10
the approximation is valid
 Ex 16.3 - What is the pH of a buffer that has 0.100 mol
HC2H3O2 and 0.100 mol NaC2H3O2 in 1.00 L that has
0.010 mol NaOH added to it?
[HA] [A-] [H3O+]
substitute x into the
equilibrium initial 0.090 0.110 ≈0
concentration
change -x +x +x
definitions and solve
0.090x 0.110
equilibrium 0.090 x
+ x 1.5E-5
0.110
x = 1.47 x 10-5
 HC 2 H 3O 2   0.090  x  0.090  1.47  105   0.090 M


[C 2 H 3O 2 ]  0.110  x  0.110  1.47  10 5
  0.110 M
[H 3O  ]  x  1.47  105 M
 Ex 16.3 - What is the pH of a buffer that has 0.100 mol
HC2H3O2 and 0.100 mol NaC2H3O2 in 1.00 L that has
0.010 mol NaOH added to it?
[HA] [A-] [H3O+]
substitute [H3O+] into
the formula for pH initial 0.090 0.110 ≈0
and solve change -x +x +x
equilibrium 0.090 0.110 1.5E-5

pH  -log H 3O  


  log 1.47  10 5
  4.83
 Ex 16.3 - What is the pH of a buffer that has 0.100 mol
HC2H3O2 and 0.100 mol NaC2H3O2 in 1.00 L that has
0.010 mol NaOH added to it?
Ka for HC2H3O2 = 1.8 x 10-5
check by substituting [HA] [A-] [H3O+]
the equilibrium
concentrations back into initial 0.090 0.110 ≈0
the equilibrium constant change -x +x +x
expression and
comparing the calculated
equilibrium 0.090 0.110 1.5E-5
Ka to the given Ka
[C 2 H 3O -2 ][H 3O  ]
Ka 
 HC 2 H 3O 2 
the values match  0.110  1.47  10 5 
  1.8  10 5
 0.090
 Ex 16.3 - What is the pH of a buffer that has 0.100
mol HC2H3O2 and 0.100 mol NaC2H3O2 in 1.00 L that
has 0.010 mol NaOH added to it?
find the pKa from the
given Ka HC2H3O2 + H2O  C2H3O2 + H3O+
Assume the [HA] and
[A-] equilibrium Ka for HC2H3O2 = 1.8 x 10-5
concentrations are the
same as the initial
pK a   log K a
[HA] [A ]
- [H3O ]+   log1.8  10  5

initial 0.090 0.110 ≈0  4.7 45

change -x +x +x
equilibrium 0.090 0.110 x
 Ex 16.3 - What is the pH of a buffer that has
0.100 mol HC2H3O2 and 0.100 mol NaC2H3O2
in 1.00 L that has 0.010 mol NaOH added to it?
Substitute into the HC2H3O2 + H2O  C2H3O2 + H3O+
Henderson-Hasselbalch
Equation pKa for HC2H3O2 = 4.745
Check the “x is small”  [A - ] 
pH  pK a  log 

approximation [HA ]
 
[H 3O  ]  10-pH   0.110  
pH  4.7 45  log   4.83
[H 3O  ]  10-4.83  1.47  10 5  0.090 

1.47  10 5
 100%  0.016%  5%
0.090
 Ex 16.3 – Compare the effect on pH of adding 0.010 mol
NaOH to a buffer that has 0.100 mol HC2H3O2 and 0.100
mol NaC2H3O2 in 1.00 L to adding 0.010 mol NaOH to
1.00 L of pure water?
HC2H3O2 + H2O  C2H3O2 + H3O+  0.010 mol
[OH ]   0.010 M
1.00 L
pKa for HC2H3O2 = 4.745 pOH   log[OH  ]
 [A - ] 
pH  pK a  log 
 
  log 1.0  10  2  2.00
[HA ]  pH  pOH  14.00
 
pH  14.00 - pOH
  0.110  
pH  4.7 45  log   14.00 - 2.00
 0.090 
 4.83  12.00
 Basic Buffers
B:(aq) + H2O(l)  H:B+(aq) + OH−(aq)
• buffers can also be made by mixing a weak
base, (B:), with a soluble salt of its conjugate
acid, H:B+Cl−
H2O(l) + NH3 (aq)  NH4+(aq) + OH−(aq)
 Ex 16.4 - What is the pH of a buffer that is
0.50 M NH3 (pKb = 4.75) and 0.20 M NH4Cl?
find the pKa of the NH3 + H2O  NH4+ + OH−
conjugate acid (NH4+) pK a  pK b  14
from the given Kb pK a  14 - pK b  14 - 4.75  9.25
Assume the [B] and  [B] 
[HB+] equilibrium pH  pK a  log 
 
concentrations are the  [HB ] 
same as the initial   0.50 
pH  9.25  log   9.65
Substitute into the   0.20  
Henderson-Hasselbalch
Equation [H 3O  ]  10-pH
Check the “x is small” [H 3O  ]  10-9.65  2.23  10 10
approximation 2.23  10 10
 100%  5%
0.20
 Buffering Effectiveness
• a good buffer should be able to neutralize moderate
amounts of added acid or base
• however, there is a limit to how much can be added
before the pH changes significantly
• the buffering capacity is the amount of acid or base a
buffer can neutralize
• the buffering range is the pH range the buffer can be
effective
• the effectiveness of a buffer depends on two factors (1)
the relative amounts of acid and base, and (2) the
absolute concentrations of acid and base
 Effect of Relative Amounts of Acid and
Conjugate Base
a buffer is most effective with equal
concentrations of acid and base
Buffer 1 Buffer 12
0.100 mol HA & 0.100 mol A- 0.18 mol HA & 0.020 mol A-
Initial pH = 5.00 pKa (HA) = 5.00 Initial pH = 4.05
 [A - ] 
pH  pK a  log 

 [HA] 
HA + OH−  A + H2O
% Change % Change
after adding 0.010 mol NaOH after adding 0.010 mol NaOH −

 5.09 -pH
5.00=
HA 5.09
100%
A -
OH −

 HA=-4.25
4.25
pH 4.05A-
OH
100%
mols Before5.00 0.100 0.100 0 mols Before 0.18 4.05 0.020 0
  0.030     0.110  
 added
pH
mols 1.85%
.00  log- -   4.0.010
25 mols  5.005log
pHadded -  0.090-   50.010
.0% .09
 0.17   
mols After 0.090 0.110 ≈ 0 mols After 0.17 0.030 ≈ 0
 Effect of Absolute Concentrations of
Acid and Conjugate Base
a buffer is most effective when the
concentrations of acid and base are largest
Buffer 1 Buffer 12
0.50 mol HA & 0.50 mol A- 0.050 mol HA & 0.050 mol A-
Initial pH = 5.00 pKa (HA) = 5.00 Initial pH = 5.00
 [A - ] 
pH  pK a  log 

 [HA] 
HA + OH−  A + H2O
% Change % Change
after adding 0.010 molANaOH after adding
 0.010 mol NaOH

 5.02 - 5.00
pH 
HA
= 5.02
100%
-
OH − HA
5.18 - 5.00
 pH = 5.18100%
A -
OH −

mols Before 5.00 0.50 0.500 0 mols Before 0.050 5.00 0.050 0
  0.060     0.51 
.45%
 0added
pH
mols .00  log- - 18 molspH
  5.0.010 added  3.log
 5.00 -  0.49 -  5.0.010
6% 02
 0.040   
mols After 0.49 0.51 ≈ 0 mols After 0.040 0.060 ≈ 0
 Effectiveness of Buffers
• a buffer will be most effective when the [base]:
[acid] = 1
equal concentrations of acid and base
• effective when 0.1 < [base]:[acid] < 10
• a buffer will be most effective when the [acid]
and the [base] are large
 Buffering Range
• we have said that a buffer will be effective when
0.1 < [base]:[acid] < 10
• substituting into the Henderson-Hasselbalch we can
calculate the maximum and minimum pH at which
the buffer will be effective
 [A - ] 
pH  pK a  log 

 [HA ]  Highest pH
Lowest pH
pH  pK a  log 0.10 pH  pK a  log10
pH  pK a  1 pH  pK a  1
therefore, the effective pH range of a buffer is pKa ± 1
when choosing an acid to make a buffer, choose
one whose is pKa is closest to the pH of the buffer
 Ex. 16.5a – Which of the following acids
would be the best choice to combine with its
sodium salt to make a buffer with pH 4.25?
Chlorous Acid, HClO2 pKa = 1.95
Nitrous Acid, HNO2 pKa = 3.34
Formic Acid, HCHO2 pKa = 3.74
Hypochlorous Acid, HClO pKa = 7.54
 Ex. 16.5a – Which of the following acids
would be the best choice to combine with its
sodium salt to make a buffer with pH 4.25?
Chlorous Acid, HClO2 pKa = 1.95
Nitrous Acid, HNO2 pKa = 3.34
Formic Acid, HCHO2 pKa = 3.74
Hypochlorous Acid, HClO pKa = 7.54
The pKa of HCHO2 is closest to the desired pH of
the buffer, so it would give the most effective
buffering range.
 Ex. 16.5b – What ratio of NaCHO2 : HCHO2
would be required to make a buffer with pH 4.25?
Formic Acid, HCHO2, pKa = 3.74
 [CHO 2  ] 
 [A - ]  log 
 [HCHO 2 ] 

pH  pK a  log  10  
 10 0.51

 [HA]  
 [CHO 2  ]  [CHO 2 ]
4.25  3.74  log   3.24
[HCHO ]  [HCHO 2 ]
 2 

 [CHO 2  ]  to make the buffer with pH

0.51  log 
 4.25, you would use 3.24 times
 [HCHO ]
2  as much NaCHO2 as HCHO2
 Buffering Capacity
• buffering capacity is the amount of acid or base that
can be added to a buffer without destroying its
effectiveness
• the buffering capacity increases with increasing
absolute concentration of the buffer components
• as the [base]:[acid] ratio approaches 1, the ability of the
buffer to neutralize both added acid and base improves
• buffers that need to work mainly with added acid
generally have [base] > [acid]
• buffers that need to work mainly with added base
generally have [acid] > [base]
 Titration
• in an acid-base titration, a solution of unknown
concentration (titrant) is slowly added to a solution of
known concentration from a burette until the reaction
is complete
 when the reaction is complete we have reached the endpoint
of the titration
• an indicator may be added to determine the endpoint
 an indicator is a chemical that changes color when the pH
changes
• when the moles of H3O+ = moles of OH−, the titration
has reached its equivalence point
Titration
 Indicators
• many dyes change color depending on the pH of the solution
• these dyes are weak acids, establishing an equilibrium with the
H2O and H3O+ in the solution
HInd(aq) + H2O(l)  Ind(aq) + H3O+(aq)
• the color of the solution depends on the relative concentrations
of Ind:HInd
 when Ind:HInd ≈ 1, the color will be mix of the colors of Ind
and HInd
 when Ind:HInd > 10, the color will be mix of the colors of Ind
 when Ind:HInd < 0.1, the color will be mix of the colors of HInd

65
Phenolphthalein

66
 Methyl Red
H H H H
C C C C

(CH3)2N C C N N N C CH
H
C C C C
H H H
NaOOC
H3O+ OH-

H H H H
C C C C

(CH3)2N C C N N N C CH

C C C C
H H H
NaOOC

67
 Monitoring a Titration with
an Indicator
• for most titrations, the titration curve shows a
very large change in pH for very small additions
of base near the equivalence point
• an indicator can therefore be used to determine
the endpoint of the titration if it changes color
within the same range as the rapid change in pH
pKa of HInd ≈ pH at equivalence point

68
Acid-Base Indicators

69
70
 Titration Curve
• a plot of pH vs. amount of added titrant
• the inflection point of the curve is the equivalence
point of the titration
• prior to the equivalence point, the known solution in
the flask is in excess, so the pH is closest to its pH
• the pH of the equivalence point depends on the pH of
the salt solution
 equivalence point of neutral salt, pH = 7
 equivalence point of acidic salt, pH < 7
 equivalence point of basic salt, pH > 7
• beyond the equivalence point, the unknown solution in
the burette is in excess, so the pH approaches its pH
 Monitoring pH During a Titration
• the general method for monitoring the pH during the
course of a titration is to measure the conductivity of
the solution due to the [H3O+]
 using a probe that specifically measures just H3O+
• the endpoint of the titration is reached at the
equivalence point in the titration – at the inflection
point of the titration curve
• if you just need to know the amount of titrant added to
reach the endpoint, we often monitor the titration with
an indicator
72
Monitoring pH During a Titration

73
 Titration Curve:
Unknown Strong Base Added to
Strong Acid
 Titration of 25 mL of 0.100 M HCl with
0.100 M NaOH
• HCl(aq) + NaOH(aq)  NaCl(aq) + H2O(aq)
• initial pH = -log(0.100) = 1.00
• initial mol of HCl = 0.0250 L x 0.100 mol/L = 2.50 x 10-3
• before equivalence point added 5.0 mL NaOH
mol HCl excess1 mol HCl
0.100 mol NaOH  42.00
5.0 x 
10 -4 -3
10 
0.100
-3mol
mol 1mol
mol NaOH
HCl
NaOH HCl
L ofmole NaOH 
added NaOH  5 .0 
0.0050 10 2.00L NaOH
mol x 10
NaOH 
mol HCl
L HCl  L NaOH 1L
1 mol NaOH 0.0250 L4HCl  0.0050 1 LNaOH
1 mol
L NaOH
 moles added
moles HClNaOH
used
M HCl  [H3O ]    5 5
.0.0 
1010 4
molHCl
mol NaOH used 

-3
0.0667 M HCl  [H
-4 3
O ]
initial mol HCl - mol HCl used 2.50  10 mol HCl - 5.0  10 mol HCl used
pHHCl
 mol  -log[H
excess 3O ]

 2.00  10pH -3
molHCl 
-logexcess 
0.0667  1.18
 Titration of 25 mL of 0.100 M HCl with
0.100 M NaOH
• HCl(aq) + NaOH(aq)  NaCl(aq) + H2O(aq)
• at equivalence, 0.00 mol HCl and 0.00 mol NaOH
• pH at equivalence = 7.00
• after equivalence point added 30.0 mL NaOH
0.0300 L NaOH mol NaOH xs
5.0 x 10
0.100 mol NaOH -4 0.100 mol NaOH
L of added NaOH 
mol NaOH added - initial mol
1 HCl
L  K-4w 1L
mol NaOH excess
 -3
3.00  10 mol [ H O 5 .0
] 
 10 mol -3 NaOH
mol
[H3NaOH
O added
][OH ]  Kw  3NaOH
.00  10-2.50mol10
] mol NaOH used
3 3
moles excess
NaOH [OH NaOH
L HCl  L NaOH  5.0  10-4 0.0250
mol NaOH
HCl  0.0300 L NaOH
Lexcess
14
1  10 M NaOH  [OH 12  ]
 M NaOH  [OH  ] 0.00909  1.10  10
9.09  103
pH  - log[H3O  ]  
pH  - log 1.10  10-9  11 .96
Adding NaOH to HCl

added
25.0 mL
added 30.0
35.0
10.0
25.0
5.00.100
mL
mL
mLNaOH
NaOH
M
NaOH
HCl
0.00050
0.00100
0.00250mol
0.00200
0.00150
equivalence
molpoint
NaOH
HCl
pH
pH==12.22
11.96
1.00
1.37
7.00
1.18
added 40.0
15.0 mL NaOH
0.00100 mol NaOH
0.00150 HCl
pH = 12.36
1.60
added 50.0
20.0 mL NaOH
0.00050 mol NaOH
0.00250 HCl
pH = 12.52
1.95
 Titration of 25 mL of 0.100 M HCHO2
with 0.100 M NaOH
• HCHO2(aq) + NaOH(aq)  NaCHO2(aq) + H2O(aq)
• Initial pH: K = 1.8 x 10 -4
a
[HCHO2] [CHO2-] [H3O+]
[CHO2  ][H3O  ]
initial 0.100 0.000 ≈0
Ka 
[HCHO 2 ]
change -x +x +x
1.8  10 4 
 x  x  
x 2

equilibrium 0.100 - x x x  0.100  x  0.100

x  [H3O  ]  4.24  103 M
pH  - log[H3O  ]

 -log 4.24  10 -3
  2.37 4.2  103
 100%  4.2%  5%
0.100
 Titration of 25 mL of 0.100 M HCHO2
with 0.100 M NaOH
• HCHO2(aq) + NaOH(aq)  NaCHO2 (aq) + H2O(aq)
• initial mol of HCHO2 = 0.0250 L x 0.100 mol/L = 2.50 x 10-3
• before equivalence
added 5.0 mL NaOH
HA A- OH−  0.100  
mol CHO
mol NaOH
mols Before 2.50E-3 0 0 pH  pL
0.0050  log
K aNaOH 2 
 mol HCHO
1L 2 
4  
mols added - - 5.0E-4  5.0  10 mol NaOH
 5.0  10- 4 
mols After 2.00E-3 5.0E-4 ≈0 pH  3.74  log 
-5 
 2.00  10 
pK a  - logK a pH  3.14
 
 -log 1.8  10- 4  3.74
 Titration of 25 mL of 0.100 M HCHO2
with 0.100 M NaOH
• HCHO2(aq) + NaOH(aq)  NaCHO2 (aq) + H2O(aq)
• initial mol of HCHO2 = 0.0250 L x 0.100 mol/L = 2.50 x 10-3
• at equivalence CHO2−(aq) + H2O(l)  HCHO2(aq) + OH−(aq)
added 25.0 mL-11NaOH
[HCHOHA
2] [CHO2 ]A[OH
-
- −
] OH− Kb = 5.6 x 10 
mol CHO 0.100 mol NaOH
= 1.7x] 10-6 M1 L
0.0250 2
initial [OHL-]NaOH
[HCHO ][OH
mols Before 02.50E-3 2  L NaOH
0.0500 0 ≈ 00K  L HCHO 2
b  3 K
 2.50
[ CHO
  10
 mol
] w NaOH
mols added +x - -x - +x 2.50E-3
change [ H 3M
O CHO
] 
2 2 
[OH -3 ]
mols After x 05.00E-2-x
equilibrium 2.50E-3
x ≈ 50.6  10 11 2.50
1  10

14x 
10 x 
mol CHO
10
 2
2 x
2.50 10- 2 0
L .HCHO
0500  25 
. 9
x 

2.50
10 0
9 - 2 L NaOH
.0500
6
Kw  5.00 1.7  10
- 2 
Kb, CHO     10 M CHO  26
2 K x  [OH ]  1 . 7 
pH  - log[H O M] 10
a 3


1  1014
 5 .6  10 11  
 -log 5.9  10-9  8.23
1.8  10 4
 Titration of 25 mL of 0.100 M HCl with
0.100 M NaOH
• HCHO2(aq) + NaOH(aq)  NaCHO2 (aq) + H2O(aq)
• after equivalence point
added 30.0 mL NaOH
0.100 mol NaOH 0.100 mol NaOH
L of added NaOH  5.0
0.0300 x 10-4 mol NaOH xs
L NaOH
1L 1L
 moles
mol added
NaOH NaOH
excess  3   3 K-4
.0  mol
mol NaOH added - initial mol HCHO
2 [H3O ]  10 wNaOH
.00 10
5 mol NaOH
 mol   excess

[HL3NaOH
HCl L NaOH 3.00  10-3 mol0.0250 [OH -3
O ][OH ]  Kw NaOH L - 2.50
HCl 0] .0300
10 mol NaOH used
L NaOH
14
 M NaOH  [OH ] 1  10excess
 5.0  10- 4 molNaOH
0.0091 M NaOH  [OH 
12 ]
 3
 1.10  10
9.1  10

pH  - log[H3O  ]  
pH  - log 1.10  10-9  11 .96
Adding NaOH to HCHO2
added
initial
added HCHO30.0
35.0
10.0
5.0
25.0mL mL
mL
2 NaOH
solution
NaOH
NaOH
0.00050
0.00100
0.00150
0.00200
equivalence
0.00250 mol point
NaOH 22xs
HCHO
pH
0.00250
= 11.96
12.22
3.56
3.14
pH = 2.37 mol CHO 2
−

added
[CHO 12.5
−
added 240.0]init =mL NaOH
0.0500
mL NaOH M
0.00125
[OH −
0.00150 ] mol
= 1.7 HCHO
x 10
eq mol NaOH 2xs
-6

pH
pH =
pH == 3.74
8.23 = pKa
12.36
half-neutralization
added 50.015.0 mL NaOH
0.00100 mol NaOH
0.00250 HCHO2xs
pH = 12.52
3.92
added 20.0 mL NaOH
0.00050 mol HCHO2
pH = 4.34
Titrating Weak Acid with a Strong Base
• the initial pH is that of the weak acid solution
calculate like a weak acid equilibrium problem
e.g., 15.5 and 15.6
• before the equivalence point, the solution
becomes a buffer
calculate mol HAinit and mol A−init using reaction
stoichiometry
calculate pH with Henderson-Hasselbalch using mol
HAinit and mol A−init
• half-neutralization pH = pKa
Titrating Weak Acid with a Strong Base
• at the equivalence point, the mole HA = mol Base, so
the resulting solution has only the conjugate base anion
in it before equilibrium is established
mol A− = original mole HA
calculate the volume of added base like Ex 4.8
[A−]init = mol A−/total liters
calculate like a weak base equilibrium problem
e.g., 15.14
• beyond equivalence point, the OH is in excess
[OH−] = mol MOH xs/total liters
[H3O+][OH−]=1 x 10-14
 Ex 16.7a – A 40.0 mL sample of 0.100 M HNO2 is
titrated with 0.200 M KOH. Calculate the volume of
KOH at the equivalence point
Write an equation for
the reaction for B with HNO2 + KOH  NO2 + H2O
HA.
Use Stoichiometry to 0.001 L
determine the volume 40.0 mL   0.0400 L
1 mL
of added B

0.100 mol NO 2 1 mol KOH 1 L KOH

0.0400 L NO 2   
1 L NO 2 1 mol NO 2 0.200 mol KOH
 0.0200 L KOH
1 mL
0.0200 L   20.0 mL
0.001 L
 Ex 16.7b – A 40.0 mL sample of 0.100 M HNO2 is
titrated with 0.200 M KOH. Calculate the pH after
adding 5.00 mL KOH
Write an equation
for the reaction for HNO2 + KOH  NO2 + H2O
B with HA. 0.001 L 0.100 mol HNO2
40.0 mL    0.00400 mol HNO 2
Determine the 1 mL 1L
moles of HAbefore & 0.001 L 0.200 mol KOH
moles of added B 5.00 mL    0.00100 mol KOH
1 mL 1L
Make a
stoichiometry table HNO2 NO2- OH−
and determine the
moles of HA in
mols Before 0.00400 0 ≈0
excess and moles mols added - - 0.00100
A made
mols After 0.00300 0.00100 ≈ 0
 Ex 16.7b – A 40.0 mL sample of 0.100 M HNO2 is
titrated with 0.200 M KOH. Calculate the pH after
adding 5.00 mL KOH.
Write an equation for HNO2 + H2O  NO2 + H3O+
the reaction of HA
with H2O Table 15.5 Ka = 4.6 x 10-4
Determine Ka and pKa  
pK a   log K a   log 4.6  10 4  3.15
for HA  NO 2  
pH  pK a  log 
Use the Henderson-  HNO 2 
 
Hasselbalch Equation
to determine the pH HNO NO2-
 02.00100 OH−
pH  3.15  log   2.67
 0.00300
mols Before 0.00400 0 ≈0
mols added - - 0.00100
mols After 0.00300 0.00100 ≈ 0
 Ex 16.7b – A 40.0 mL sample of 0.100 M HNO2 is
titrated with 0.200 M KOH. Calculate the pH at
the half-equivalence point
Write an equation
for the reaction for HNO2 + KOH  NO2 + H2O
B with HA. 0.001 L 0.100 mol HNO2
40.0 mL    0.00400 mol HNO 2
Determine the 1 mL 1L
moles of HAbefore &
moles of added B at half-equivalence, moles KOH = ½ mole HNO2
Make a
stoichiometry table HNO2 NO2- OH−
and determine the
moles of HA in
mols Before 0.00400 0 ≈0
excess and moles mols added - - 0.00200
A made
mols After 0.00200 0.00200 ≈ 0
 Ex 16.7b – A 40.0 mL sample of 0.100 M HNO2 is
titrated with 0.200 M KOH. Calculate the pH at
the half-equivalence point.
Write an equation for HNO2 + H2O  NO2 + H3O+
the reaction of HA
with H2O Table 15.5 Ka = 4.6 x 10-4
Determine Ka and pKa  
pK a   log K a   log 4.6  10 4  3.15
for HA  NO 2  
pH  pK a  log 
Use the Henderson-  HNO 2 
 
Hasselbalch Equation
to determine the pH HNO NO2-
 02.00200 OH−
pH  3.15  log   3.15
 0.00200
mols Before 0.00400 0 ≈0
mols added - - 0.00200
mols After 0.00200 0.00200 ≈ 0
Titration Curve of a Weak Base with
a Strong Acid
 Titration of a Polyprotic Acid
• if Ka1 >> Ka2, there will be two equivalence
points in the titration
the closer the Ka’s are to each other, the less
distinguishable the equivalence points are

titration of 25.0 mL of 0.100 M H2SO3

with 0.100 M NaOH
 Solubility Equilibria
• all ionic compounds dissolve in water to some
degree
however, many compounds have such low solubility
in water that we classify them as insoluble
• we can apply the concepts of equilibrium to
salts dissolving, and use the equilibrium
constant for the process to measure relative
solubilities in water
 Molecular, Ionic and Net Ionic
Equations
1. Sodium chloride and silver nitrate

→ sodium nitrate and silver chloride

NaCl + AgNO3 → NaNO3 + AgCl(s)

The AgCl is labeled with (s) because it is insoluble

and forms a precipitate.
99
 Ionic Equation
Na+ + Cl- + Ag+ + NO3-
→ Na+ + NO3- + AgCl(s)

All substance are ionised except for the insoluble

AgCl(s)

100
 Net Ionic Equation
The ions not involved in forming the precipitate (Na+ and
NO3-) are called "Spectator Ions" and are eliminated to
form the net ionic equation.

Ag+ + Cl- → AgCl(s)

Any source of silver ions and chloride ions would result in

the same net ionic equation. Sodium chloride substitutes
contain potassium chloride.
101
2. Copper(II) chloride + sodium sulfide
→ copper(II)sulfide and sodium chloride

CuCl2 + Na2S → CuS + NaCl

CuCl2 + Na2S → CuS(s) + 2NaCl

Cu2+ + 2Cl- + 2Na+ + S2-

→ CuS(s) + 2Na+ + 2Cl-

The spectator ions are Na+ and Cl-

Cu2+ + S2- → CuS(s)

102
3. Calcium chloride + sodium carbonate
calcium carbonate and sodium chloride

CaCl2 + Na2CO3 → CaCO3(s) + 2NaCl

Ca2+ + 2Cl- + 2Na+ + CO32-

→ CaCO3(s) + 2Na+ + 2Cl-

The spectator ions are Na+ and Cl-

Ca2+ + CO32- → CaCO3(s)

103
4. Barium nitrate + sodium phosphate
→ barium phosphate and sodium nitrate

Ba(NO3)2 + Na3PO4 → Ba3(PO4)2(s) + NaNO3

3Ba(NO3)2 + 2Na3PO4 → Ba3(PO4)2(s) + 6NaNO3

3Ba2+ + 6NO3- + 6Na+ + 2PO43-

→ Ba3(PO4)2(s) + 6Na+ + 6NO3-

The spectator ions are Na+ and NO3-

3Ba2+ + 2PO43- → Ba3(PO4)2(s)
104
5. Chromium(III) chloride + silver nitrate
→ chromium(III) nitrate and silver chloride

CrCl3 + 3AgNO3 → Cr(NO3)3 + 3AgCl(s)

Cr3+ + 3Cl- + 3Ag+ + 3NO3-

→ Cr3+ + 3NO3- + 3AgCl(s)

3Ag+ + 3Cl- → 3AgCl(s)

Ag+ + Cl- → AgCl(s)
105
 Solubility Product
• the equilibrium constant for the dissociation of a solid
salt into its aqueous ions is called the solubility
product, Ksp
• for an ionic solid MnXm, the dissociation reaction is:
MnXm(s)  nMm+(aq) + mXn−(aq)
• the solubility product would be
Ksp = [Mm+]n[Xn−]m
• for example, the dissociation reaction for PbCl2 is
PbCl2(s)  Pb2+(aq) + 2 Cl−(aq)
• and its equilibrium constant is
Ksp = [Pb2+][Cl−]2
 Molar Solubility
• solubility is the amount of solute that will dissolve in a
given amount of solution
 at a particular temperature
• the molar solubility is the number of moles of solute that
will dissolve in a liter of solution
 the molarity of the dissolved solute in a saturated solution
• for the general reaction MnXm(s)  nMm+(aq) + mXn−(aq)
K sp
molar solubility   n  m  n m
n m
 Ex 16.8 – Calculate the molar solubility of PbCl 2
in pure water at 25C
Write the
dissociation
PbCl2(s)  Pb2+(aq) + 2 Cl−(aq)
reaction and Ksp
expression Ksp = [Pb2+][Cl−]2
Create an ICE [Pb2+] [Cl−]
table defining the
change in terms Initial 0 0
of the solubility Change +S +2S
of the solid
Equilibrium S 2S
 Ex 16.8 – Calculate the molar solubility of PbCl 2
in pure water at 25C
Substitute into the
Ksp expression Ksp = [Pb2+][Cl−]2
Ksp = (S)(2S)2

Find the value of 3

sp ]4 S
K[Pb [Cl−]
2+
Ksp from Table
Initial K sp 0 0 5
16.2, plug into the 1.17  10
equation and Change
3  S 
+S
3

solve for S
4 4 +2S
EquilibriumS  1.43S 10 2 M 2S
Practice – Determine the Ksp of PbBr2 if its molar
solubility in water at 25C is 1.05 x 10-2 M
 Practice – Determine the Ksp of PbBr2 if its molar
solubility in water at 25C is 1.05 x 10-2 M
Write the
dissociation
PbBr2(s)  Pb2+(aq) + 2 Br−(aq)
reaction and Ksp
expression Ksp = [Pb2+][Br−]2
Create an ICE [Pb2+] [Br−]
table defining the
change in terms Initial 0 0
of the solubility Change +(1.05 x 10-2) +2(1.05 x 10-2)
of the solid
Equilibrium (1.05 x 10-2) (2.10 x 10-2)
 Practice – Determine the Ksp of PbBr2 if its molar
solubility in water at 25C is 1.05 x 10-2 M
Substitute into the
Ksp expression Ksp = [Pb2+][Br−]2
Ksp = (1.05 x 10-2)(2.10 x 10-2)2
plug into the
equation and
solve
K sp
Initial

 1.05  10 0

[Pb2+]
2
2. 10  10
[Br−2]
2
0

6
K
Change
sp  4. 63  10
+(1.05 x 10-2) +2(1.05 x 10-2)
Equilibrium (1.05 x 10-2) (2.10 x 10-2)
 Ksp and Relative Solubility
• molar solubility is related to Ksp
• but you cannot always compare solubilities of
compounds by comparing their Ksps
• in order to compare Ksps, the compounds must
have the same dissociation stoichiometry
The Effect of Common Ion on Solubility

• addition of a soluble salt that contains one of the

ions of the “insoluble” salt, decreases the
solubility of the “insoluble” salt
• for example, addition of NaCl to the solubility
equilibrium of solid PbCl2 decreases the
solubility of PbCl2
PbCl2(s)  Pb2+(aq) + 2 Cl−(aq)
addition of Cl− shifts the equilibrium to the left
 Ex 16.10 – Calculate the molar solubility of CaF 2
in 0.100 M NaF at 25C
Write the
dissociation
CaF2(s)  Ca2+(aq) + 2 F−(aq)
reaction and Ksp
expression Ksp = [Ca2+][F−]2
Create an ICE [Ca2+] [F−]
table defining the
change in terms Initial 0 0.100
of the solubility Change +S +2S
of the solid
Equilibrium S 0.100 + 2S
 Ex 16.10 – Calculate the molar solubility of CaF 2
in 0.100 M NaF at 25C
Substitute into the
Ksp expression Ksp = [Ca2+][F−]2
assume S is small Ksp = (S)(0.100 + 2S)2
Ksp = (S)(0.100)2
Find the value of
K sp  S  [Ca ] 2 [F−]
2+
Ksp from Table 0.100
Initial 0 0.100
16.2, plug into the 1.46  1010
equation and ChangeS  +S 2 +2S
solve for S  0.100
Equilibrium S 8 0.100 + 2S
S  1.46  10 M
 The Effect of pH on Solubility
• for insoluble ionic hydroxides, the higher the pH, the
lower the solubility of the ionic hydroxide
 and the lower the pH, the higher the solubility
 higher pH = increased [OH−]
M(OH)n(s)  Mn+(aq) + nOH−(aq)
• for insoluble ionic compounds that contain anions of
weak acids, the lower the pH, the higher the solubility
M2(CO3)n(s)  2 Mn+(aq) + nCO32−(aq)
H3O+(aq) + CO32− (aq)  HCO3− (aq) + H2O(l)
 Precipitation
• precipitation will occur when the concentrations of the
ions exceed the solubility of the ionic compound
• if we compare the reaction quotient, Q, for the current
solution concentrations to the value of Ksp, we can
determine if precipitation will occur
 Q = Ksp, the solution is saturated, no precipitation
 Q < Ksp, the solution is unsaturated, no precipitation
 Q > Ksp, the solution would be above saturation, the salt
above saturation will precipitate
• some solutions with Q > Ksp will not precipitate unless
disturbed – these are called supersaturated solutions
 a supersaturated solution will
precipitation occurs precipitate if a seed crystal is added
if Q > Ksp
 Selective Precipitation
• a solution containing several different cations
can often be separated by addition of a reagent
that will form an insoluble salt with one of the
ions, but not the others
• a successful reagent can precipitate with more
than one of the cations, as long as their Ksp
values are significantly different
Ex 16.13 What is the minimum [OH−] necessary to just
begin to precipitate Mg2+ (with [0.059]) from seawater?

precipitating may just occur when Q = Ksp

Q  [Mg 2  ][OH  ]2
Q  K sp
[ 0.059 ][OH ]  2.06  10
 2 13


[OH ] 
2.06 10   1.9 10
13
6
 0.059
 Ex 16.14 What is the [Mg2+] when Ca2+ (with
[0.011]) just begins to precipitate from seawater?
precipitating Mg2+ begins when [OH−] = 1.9 x 10-6 M
Q  [Ca 2  ][OH  ]2
Q  K sp
[ 0.011 ][OH ]  4.68  10
 2 6


[OH ] 
4.68 10   2.06 10
6
2
 0.011
 Ex 16.14 What is the [Mg2+] when Ca2+ (with
[0.011]) just begins to precipitate from seawater?
precipitating Mg2+ begins when [OH−] = 1.9 x 10-6 M
precipitating Ca2+ begins when [OH−] = 2.06 x 10-2 M
2  2
Q  [Mg ][OH ] when Ca2+ just
when Q  K sp begins to

 
[Mg 2  ][ 2.06  10 2 ]2  2.06  1013
precipitate out, the
[Mg2+] has dropped

[Mg 2  ] 

2 . 06  10 13


4 . 8  10 10
M
from 0.059 M to

 
2 4.8 x 10-10 M
2.06  10 2
 Qualitative Analysis
• an analytical scheme that utilizes selective
precipitation to identify the ions present in a
solution is called a qualitative analysis scheme
wet chemistry
• a sample containing several ions is subjected to
the addition of several precipitating agents
• addition of each reagent causes one of the ions
present to precipitate out
Qualitative Analysis
 Group 1
• group one cations are Ag+, Pb2+, and Hg22+
• all these cations form compounds with Cl− that
are insoluble in water
as long as the concentration is large enough
PbCl2 may be borderline
molar solubility of PbCl2 = 1.43 x 10-2 M
• precipitated by the addition of HCl
 Group 2
• group two cations are Cd2+, Cu2+, Bi3+, Sn4+,
As3+, Pb2+, Sb3+, and Hg2+
• all these cations form compounds with HS− and
S2− that are insoluble in water at low pH
• precipitated by the addition of H2S in HCl
 Group 3
• group three cations are Fe2+, Co2+, Zn2+, Mn2+,
Ni2+ precipitated as sulfides; as well as Cr3+,
Fe3+, and Al3+ precipitated as hydroxides
• all these cations form compounds with S2− that
are insoluble in water at high pH
• precipitated by the addition of H2S in NaOH
 Group 4
• group four cations are Mg2+, Ca2+, Ba2+
• all these cations form compounds with PO43−
that are insoluble in water at high pH
• precipitated by the addition of (NH 4)2HPO4