A Molecular Approach ch16

Chemistry: A Molecular Approach, 2nd Ed.
Nivaldo Tro
Chapter 16
Aqueous Ionic
Equilibrium
Roy Kennedy
Massachusetts Bay Community College
Wellesley Hills, MA
Copyright  2011 Pearson Education, Inc.
The Danger of Antifreeze
• Each year, thousands of pets and wildlife
species die from consuming antifreeze
• Most brands of antifreeze contain ethylene
glycol
sweet taste
initial effect drunkenness
• Metabolized in the liver to glycolic acid
HOCH2COOH
ethylene glycol glycolic acid

(aka 1,2–ethandiol) (aka a-hydroxyethanoic acid)
Tro: Chemistry: A Molecular Approach, 2/e 2 Copyright  2011 Pearson Education, Inc.
Why Is Glycolic Acid Toxic?
• If present in high enough concentration in the
bloodstream, glycolic acid overwhelms the
buffering ability of the HCO3− in the blood,
causing the blood pH to drop
• When the blood pH is low, its ability to carry O2
is compromised
acidosis
HbH+(aq) + O2(g)  HbO2(aq) + H+(aq)
• One treatment is to give the patient ethyl
alcohol, which has a higher affinity for the
enzyme that catalyzes the metabolism of
ethylene glycol
Buffers
• Buffers are solutions that resist changes in pH
when an acid or base is added
• They act by neutralizing acid or base that is
added to the buffered solution
• But just like everything else, there is a limit to
what they can do, and 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
blood has a mixture of H2CO3 and HCO3−
Making an Acid Buffer
How Acid Buffers Work:
Addition of Base
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
HA(aq) + OH−(aq) → A−(aq) + H2O(l)
 you can also think of the H3O+ combining with the OH−
to make H2O; the H3O+ is then replaced by the shifting
equilibrium
How Buffers Work
new H2O
A−
HA
HA  A−− + H3O+
Added
HO−
How Acid Buffers Work:
Addition of Acid
• The buffer solution also contains significant
amounts of the conjugate base anion, A−
• These ions combine with added acid to make
more HA
H+(aq) + A−(aq) → HA(aq)
• After the equilibrium shifts, the concentration
of H3O+ is kept constant
How Buffers Work
H2O
new
HA
HA  A−− + H3O+
Added
H3O+
Common Ion Effect
• Adding a salt containing the anion NaA, which

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
Common Ion Effect
Example 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 initial 0.100 0.100 ≈0
table for the
reaction change
enter the initial equilibrium
concentrations –
assuming the
[H3O+] from
water is ≈ 0
represent the HC2H3O2 + H2O  C2H3O2 + H3O+
change in the
concentrations in [HA] [A−] [H3O+]
terms of x initial 0.100 0.100 0
sum the columns change x +x +x
to find the
equilibrium equilibrium 0.100 x 0.100 + x x
concentrations in
terms of x
substitute into the
equilibrium
constant
expression
Ka for HC2H3O2 = 1.8 x 10−5
determine the [HA] [A−] [H3O+]
value of Ka
initial 0.100 0.100 ≈0
because Ka is very
small, approximate change −x +x +x
the [HA]eq = [HA]init equilibrium 0.100x 0.100
0.100 0.100+x x
and [A−]eq = [A−]init ,
then solve for x
Ka for HC2H3O2 = 1.8 x 10−5
check if the [HA] [A−] [H3O+]
approximation
initial 0.100 0.100 ≈0
is valid by
seeing if x < change −x +x +x
5% of equilibrium 0.100 0.100 x
[HC2H3O2]init
x = 1.8 x 10−5
the approximation is valid

substitute x [HA] [A−] [H3O+]
into the
initial 0.100 0.100 ≈0
equilibrium
concentration change −x +x +x
definitions equilibrium 0.100x 0.100
0.100 0.100
+ x 1.8E-5
x
and solve
x = 1.8 x 10−5
[HA] [A−] [H3O+]
substitute [H3O+]
into the formula initial 0.100 0.100 ≈0
for pH and solve change −x +x +x
equilibrium 0.100 0.100 1.8E−5
check by Ka for HC2H3O2 = 1.8 x 10−5
substituting the [HA] [A−] [H3O+]
equilibrium
initial 0.100 0.100 ≈0
concentrations
back into the change −x +x +x
equilibrium equilibrium 0.100 0.100 1.8E−5
constant
expression and
comparing the
calculated Ka to the the values
given Ka match
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 HF + H2O  F + H3O+
reaction for the
acid with water
[HA] [A−] [H3O+]
construct an
ICE table for initial 0.14 0.071 ≈ 0
the reaction change
enter the initial equilibrium
concentrations
– 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?
represent the HF + H2O  F + H3O+
change in the
terms of x initial 0.14 0.071 0
to find the
concentrations in
terms of x
substitute into
the equilibrium
constant
expression
0.14 M and 0.071 M KF?
Ka pK
fora HF
for =
HF7.0 x 10−4
= 3.15
determine the [HA] [A−] [H3O+]
value of Ka
initial 0.14 0.071 ≈0
because Ka is
very small, change −x +x +x
approximate the equilibrium 0.012
0.14 x 0.071
0.100+x x
[HA]eq = [HA]init
and [A−]eq = [A−]init
solve for x
0.14 M HF (pKa = 3.15) and 0.071 M KF?
Ka for HF = 7.0 x 10−4
check if the [HA] [A−] [H3O+]
approximation
initial 0.14 0.071 ≈0
is valid by
seeing if change −x +x +x
x < 5% of equilibrium 0.14 0.071 x
[HC2H3O2]init
x = 1.4 x 10−3

0.14 M HF (pKa = 3.15) and 0.071 M KF?
substitute x into [HA] [A−] [H3O+]
the equilibrium
initial 0.14 0.071 ≈0
concentration
definitions and change −x +x +x
solve 0.14x 0.071
equilibrium 0.14 0.072
+ x 1.4E-3
x
x = 1.4 x 10−3
0.14 M HF (pKa = 3.15) and 0.071 M KF?
substitute [HA] [A−] [H3O+]
[H3O+] into the
initial 0.14 0.071 ≈0
formula for pH
and solve change −x +x +x
equilibrium 0.14 0.072 1.4E−3
0.14 M HF (pKa = 3.15) and 0.071 M KF?
Ka for HF = 7.0 x 10−4
check by
equilibrium initial 0.14 0.071 ≈0
concentrations
constant
expression and
comparing the the values are
calculated Ka to close enough
the given Ka
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 pKa and initial concentrations of the
weak acid and salt of the conjugate base
as long as the “x is small” approximation is valid
Deriving the Henderson-Hasselbalch
Equation
assume the [HA] and HC7H5O2 + H2O  C7H5O2 + H3O+
[A−] equilibrium Ka for HC7H5O2 = 6.5 x 10−5
concentrations are
the same as the
initial
substitute into the
Henderson-
Hasselbalch
Equation
check the “x is small”
approximation
0.14 M HF (pKa = 3.15) and 0.071 M KF?
0.14 M HF (pKa = 3.15) and 0.071 M KF?
find the pKa from the
given Ka HF + H2O  F + H3O+
assume the [HA]
and [A−] equilibrium
concentrations are
the same as the
initial
substitute into the
Henderson-
Hasselbalch
equation
check the “x is
small”
approximation
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 100
to 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 is added to them, their pH does change
• Calculating the new pH after adding acid or base
requires breaking the problem into two 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−]
Example 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 HC2H3O2 + OH−  C2H3O2 + H2O
chemical is a
base, write a
reaction for OH− HA A− OH−
with HA. If the mols before 0.100 0.100 0
added chemical
is an acid, write a mols added ─ ─ 0.010
reaction for H3O+ mols after
with A−.
construct a
stoichiometry
table for the
reaction
fill in the table HC2H3O2 + OH−  C2H3O2 + H2O

– tracking the
changes in the HA A− OH−
number of mols before 0.100 0.100 ≈0
moles for each
component mols added ─ ─ 0.010
mols after 0.090 0.110 ≈0
If the added
chemical is a base, HC2H3O2 + OH  C2H3O2 + H2O
− 
write a reaction for

OH− with HA. If the HA A– OH−
added chemical is mols before 0.100 0.100 0.010
an acid, write a
reaction for it with A−. mols change
construct a mols end
stoichiometry table new molarity
for the reaction
enter the initial
number of moles for
each
using the added HC2H3O2 + OH−  C2H3O2 + H2O
chemical as the
limiting reactant, HA A− OH−
determine how the
mols before 0.100 0.100 0.010
moles of the other
chemicals change mols change −0.010 +0.010 −0.010
add the change to mols end 0.090 0.110 0
the initial number of
new molarity 0.090 0.110 0
moles to find the
moles after reaction
divide by the liters
of solution to find
the new molarities
write the reaction
for the acid with HC2H3O2 + H2O  C2H3O2 + H3O+
water
construct an ICE [HA] [A−] [H3O+]
table for the
initial 0.090 0.110 ≈0
reaction
enter the initial change
concentrations – equilibrium
assuming the
[H3O+] from water
is ≈ 0, and using
the new
molarities of the
[HA] and [A−]
represent the HC2H3O2 + H2O  C2H3O2 + H3O+
change in the
terms of x initial 0.090 0.110 ≈0
to find the
concentrations in
terms of x
substitute into
the equilibrium
constant
expression
K for HC H O = 1.8 x 10 −5
determine the a 2 3 2
value of Ka [HA] [A−] [H3O+]
because Ka is very initial 0.100 0.100 ≈0
small, approximate
the [HA]eq = [HA]init change −x +x +x
and [A−]eq = [A−]init 0.090x 0.110
equilibrium 0.090 0.110+x x
solve for x
Ka for HC2H3O2 = 1.8 x 10−5
check if the
approximation
[HA] [A−] [H3O+]
is valid by initial 0.090 0.110 ≈0
seeing if
change −x +x +x
x < 5% of
[HC2H3O2]init equilibrium 0.090 0.110 x
x = 1.47 x 10−5

substitute x [HA] [A-] [H3O+]
into the
initial 0.090 0.110 ≈0
equilibrium
concentration change −x +x +x
definitions equilibrium 0.090x 0.110
0.090 0.110+ x 1.5E-5
x
and solve
x = 1.47 x 10−5
substitute [HA] [A−] [H3O+]
[H3O+] into
initial 0.090 0.110 ≈0
the formula
for pH and change −x +x +x
solve equilibrium 0.090 0.110 1.5E−5
Ka for HC2H3O2 = 1.8 x 10−5
check by
equilibrium
initial 0.090 0.110 ≈0
concentrations
constant
expression and
comparing the the values
calculated Ka to match
the given Ka
or, by using the
Henderson-Hasselbalch
Equation

write the reaction for
the acid with water HC2H3O2 + H2O  C2H3O2 + H3O+
construct an ICE
table for the reaction [HA] [A−] [H3O+]
enter the initial
concentrations – initial 0.090 0.110 ≈0
assuming the [H3O+]
change x +x +x
from water is ≈ 0,
and using the new equilibrium 0.090 x 0.110 + x x
molarities of the [HA]
and [A−]
fll in the ICE table
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
[HA] [A−] [H3O+]

initial 0.090 0.110 ≈0
change −x +x +x
equilibrium 0.090 0.110 x
substitute into the HC2H3O2 + H2O  C2H3O2 + H3O+
Henderson-
Hasselbalch pKa for HC2H3O2 = 4.745
equation
check the “x is
small”
approximation
Example 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+
pKa for HC2H3O2 = 4.745
Practice – What is the pH of a buffer that has
0.140 moles HF (pKa = 3.15) and 0.071 moles
KF in 1.00 L of solution when 0.020 moles of
HCl is added?
(The “x is small” approximation is valid)
0.140 moles HF and 0.071 moles KF in 1.00 L of
solution when 0.020 moles of HCl is added?
If the added F− + H3O+  HF + H2O
chemical is a
base, write a
reaction for OH− F− H3O+ HF
with HA. If the mols before 0.071 0 0.140
added chemical
is an acid, write a mols added – 0.020 –
reaction for H3O+ mols after
with A−.
construct a
stoichiometry
table for the
reaction
fill in the table F− + H3O+  HF + H2O

– tracking the
changes in the
F− H3O+ HF
number of
moles for each mols before 0.071 0 0.140
component mols added – 0.020 –
mols after 0.051 0 0.160
If the added chemical
is a base, write a F− + H3O+  HF + H2O
reaction for OH− with
HA. If the added F− H3O+ HF
chemical is an acid,
mols before 0.071 0.020 0.140
write a reaction for
H3O+ with A−. mols change
construct a mols after
stoichiometry table
new molarity
for the reaction
enter the initial
number of moles for
each
using the added
chemical as the
F− + H3O+  HF + H2O
limiting reactant,
determine how the F− H3O+ HF
moles of the other mols before 0.071 0.020 0.140
chemicals change
mols change −0.020 −0.020 +0.020
add the change to
the initial number of mols after 0.051 0 0.160
moles to find the new molarity 0.051 0 0.160
moles after reaction
divide by the liters
of solution to find
the new molarities
write the reaction for HF + H2O  F + H3O+
the acid with water
[HF] [F−] [H3O+]
construct an ICE
table. initial 0.160 0.051 ≈0
assume the [HA] and change −x +x +x
[A−] equilibrium
concentrations are equilibrium 0.160 0.051 x
the same as the
initial
substitute into the
Henderson-
Hasselbalch
equation
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)
Henderson-Hasselbalch Equation for
Basic Buffers
• The Henderson-Hasselbalch equation is written for a
chemical reaction with a weak acid reactant and its
conjugate base as a product
• The chemical equation of a basic buffer is written with a
weak base as a reactant and its conjugate acid as a
product
B: + H2O  H:B+ + OH−
• To apply the Henderson-Hasselbalch equation, the
chemical equation of the basic buffer must be looked at like
an acid reaction
H:B+ + H2O  B: + H3O+
 this does not affect the concentrations, just the way we are looking
at the reaction
Relationship between pKa and pKb
• Just as there is a relationship between the Ka
of a weak acid and Kb of its conjugate base,
there is also a relationship between the pKa of
a weak acid and the pKb of its conjugate base
Ka  Kb = Kw = 1.0 x 10−14
−log(Ka  Kb) = −log(Kw) = 14
−log(Ka) + −log(Kb) = 14
pKa + pKb = 14
Example 16.4: What is the pH of a buffer that is
0.50 M NH3 (pKb = 4.75) and 0.20 M NH4Cl?
NH3 + H2O  NH4+ + OH−
find the pKa of the
conjugate acid (NH4+)
from the given Kb
assume the [B] and
[HB+] equilibrium
concentrations are the
same as the initial
substitute into the
Henderson-
Hasselbalch equation
approximation
Henderson-Hasselbalch Equation for
Basic Buffers
• The Henderson-Hasselbalch equation is written for a
chemical reaction with a weak acid reactant and its
conjugate base as a product
• The chemical equation of a basic buffer is written
with a weak base as a reactant and its conjugate
acid as a product
B: + H2O  H:B+ + OH−
• We can rewrite the Henderson-Hasselbalch equation
for the chemical equation of the basic buffer in terms
of pOH
Example 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 pKb if given Kb
NH3 + H2O  NH4+ + OH−
assume the [B] and

[HB+] equilibrium
concentrations are the
same as the initial
substitute into the
Henderson-Hasselbalch
equation base form,
find pOH
approximation
calculate pH from pOH
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 2
0.100 mol HA & 0.100 mol A− 0.18 mol HA & 0.020 mol A−
Initial pH = 5.00 pK (HA) = 5.00 Initial pH = 4.05
a
HA + OH−  A + H2O
after adding 0.010 mol−NaOH − after adding 0.010 mol NaOH
HA A OH HA A− OH−
pH = 5.09 pH = 4.25
mols before 0.100 0.100 0 mols before 0.18 0.020 0
mols added ─ ─ 0.010 mols added ─ ─ 0.010
mols after 0.090 0.110 ≈ 0 mols afterCopyright0.17 0.030 ≈ 0
 2011 Pearson Education, Inc.
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 2
0.50 mol HA & 0.50 mol A− 0.050 mol HA & 0.050 mol A−
Initial pH = 5.00 pK (HA) = 5.00 Initial pH = 5.00
a
HA + OH−  A + H2O
after adding 0.010
HA molA−NaOH
OH− after addingHA
0.010 mol
A− NaOH
OH−
pH = 5.02 pH = 5.18
mols before 0.50 0.500 0 mols before 0.050 0.050 0
mols added ─ ─ 0.010 mols added ─ ─ 0.010
mols after 0.49 0.51 ≈ 0 mols afterCopyright0.040 0.060 ≈ 0
 2011 Pearson Education, Inc.
Buffering Capacity
a concentrated
buffer can
neutralize
more added
acid or base
than a dilute
buffer
Effectiveness of Buffers
• A buffer will be most effective when the

[base]:[acid] = 1
equal concentrations of acid and base
• A buffer will be 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
equation we can calculate the maximum and
minimum pH at which the buffer will be effective
Lowest pH Highest pH
Therefore, the effective pH range of a buffer is pKa ± 1

When choosing an acid to make a buffer, choose
one whose is pKa closest to the pH of the buffer
Example 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, HClOpKa = 7.54
The pKa of HCHO2 is closest to the desired
pH of the buffer, so it would give the most
effective buffering range
Example 16.5b: What ratio of NaCHO2 : HCHO2
would be required to make a buffer with pH 4.25?
Formic acid, HCHO2, pKa = 3.74
To make a buffer with

pH 4.25, you would use
3.24 times as much
NaCHO2 as HCHO2
Practice – What ratio of NaC7H5O2 : HC7H5O2
Benzoic acid, HC7H5O2, pKa = 4.19
Practice – What ratio of NaC7H5O2 : HC7H5O2
Benzoic acid, HC7H5O2, pKa = 4.19
to make a buffer with

pH 3.75, you would use
0.363 times as much
NaC7H5O2 as HC7H5O2
Buffering Capacity
• Buffering capacity is the amount of acid or base
that can be added to a buffer without causing a
large change in pH
• 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
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
Titration Curve:
Unknown Strong Base Added
to Strong Acid
Titration of 25 mL of 0.100 M HCl with 0.100 M NaOH
Because the
solutions are equal After Equivalence
concentration, and (excess base)
1:1 stoichiometry, the
equivalence point is Equivalence Point
at equal volumes  equal moles of
HCl and NaOH
pH = 7.00
Before Equivalence
(excess acid)
• HCl(aq) + NaOH(aq)  NaCl(aq) + H2O(l)
• 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
5.0 x 10−4 mole NaOH added
HCl NaCl NaOH
mols before 2.50E-3 0 5.0E-4
mols change −5.0E-4 +5.0E-4 −5.0E-4
mols end 2.00E-3 5.0E-4 0
molarity, new 0.0667 0.017 0
Titration of 25 mL of 0.100 M HCl with
0.100 M NaOH
• HCl(aq) + NaOH(aq)  NaCl(aq) + H2O(aq)
• To reach equivalence, the added moles NaOH =
initial moles of HCl = 2.50 x 10−3 moles
• At equivalence, we have 0.00 mol HCl and 0.00
mol NaOH left over
• Because the NaCl is a neutral salt, the pH at
equivalence = 7.00
• Initial pH = −log(0.100) = 1.00
• At equivalence point added 25.0 mL NaOH
HCl NaCl NaOH
mols change −2.5E-3 +2.5E-3 −2.5E-3
mols end 0 2.5E-3 0
molarity, new 0 0.050 0
• Initial pH = −log(0.100) = 1.00
• After equivalence point added 30.0 mL NaOH
0.100 mol NaOH 3.0 x 10−3 mole NaOH added
L of added NaOH 
1L HCl NaCl NaOH
 moles added NaOH
mols change −2.5E-3 +2.5E-3 −2.5E-3
mols end 0 2.5E-3 5.0E-4
molarity, new 0 0.045 0.0091

Adding 0.100 M NaOH to 0.100 M HCl
added 30.0
35.0
5.0
10.0
25.0 mL25.0
mLmLNaOH
0.100 MNaOH
HCl
0.00050
0.00100
0.00200
0.00150
equivalence
0.00250 mol point
NaOH
HCl
pH = 12.22
11.96
1.18
1.37
7.00
1.00
added 15.0
40.0 mL NaOH
0.00150 mol HCl
0.00100 NaOH
pH = 1.60
12.36
added 20.0
50.0 mL NaOH
0.00250 mol HCl
0.00050 NaOH
pH = 1.95
12.52
Practice – Calculate the pH of the solution that
results when 10.0 mL of 0.15 M NaOH is added to
50.0 mL of 0.25 M HNO3
50.0 mL of 0.25 M HNO3
• HNO3(aq) + NaOH(aq)  NaNO3(aq) + H2O(l)
• Initial pH = −log(0.250) = 0.60
• Initial mol of HNO3= 0.0500 L x 0.25 mol/L=1.25 x 10−2
• Before equivalence point added 10.0 mL NaOH
HNO3 NaNO3 NaOH
mols change −1.5E-3 +1.5E-3 −1.5E-3
mols end 1.1E-3 1.5E-3 0
molarity, new 0.018 0.025 0
Practice – Calculate the amount of 0.15 M NaOH
solution that must be added to 50.0 mL of 0.25 M
HNO3 to reach equivalence
Practice – Calculate the amount of 0.15 M NaOH
solution that must be added to 50.0 mL of 0.25 M
HNO3 to reach equivalence
• Initial pH = −log(0.250) = 0.60
• At equivalence point: moles of NaOH = 1.25 x 10−2
50.0 mL of 0.25 M HNO3
50.0 mL of 0.25 M HNO3
• Initial pH = −log(0.250) = 0.60
HNO3 NaNO3 NaOH
mols change −1.25E-2 +1.25E-2 −1.25E-2
mols end 0 1.25E-2 0.0025
molarity, new 0 0.0833 0.017

50.0 mL of 0.25 M HNO3
• Initial pH = −log(0.250) = 0.60
• initial mol of HNO3= 0.0500 L x 0.25 mol/L=1.25 x 10−2
HNO3 NaNO3 NaOH
mols change −1.25E-2 +1.25E-2 −1.25E-2
mols end 0 1.25E-2 0.0025
molarity, new 0 0.0833 0.017
Titration of a Strong Base with a Strong Acid
• If the titration is run
so that the acid is in
the burette and the
base is in the flask,
the titration curve
will be the reflection
of the one just
shown
Titration of a Weak Acid with a Strong Base
• Titrating a weak acid with a strong base results in
differences in the titration curve at the equivalence
point and excess acid region
• The initial pH is determined using the Ka of the
weak acid
• The pH in the excess acid region is determined as
you would determine the pH of a buffer
• The pH at the equivalence point is determined
using the Kb of the conjugate base of the weak acid
• The pH after equivalence is dominated by the
excess strong base
 the basicity from the conjugate base anion is negligible
Titration of 25 mL of 0.100 M HCHO2 with
0.100 M NaOH
• HCHO2(aq) + NaOH(aq)  NaCHO2(aq) + H2O(aq)
• Initial pH
[HCHO2] [CHO2 [H3 −] O+ ]
Ka = 1.8 x 10−4
initial 0.100 0.000 ≈0
change −x +x +x
equilibrium 0.100 − x x x
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−
mols before 2.50E-3 0 0
mols added – – 5.0E-4
mols after 2.00E-3 5.0E-4 ≈0
0.100 M NaOH
• HCHO2(aq) + NaOH(aq)  NaCHO2 (aq) + H2O(aq)
• At equivalence
CHO2−(aq) + H2O(l)  HCHO2(aq) + OH−(aq)
[HCHO2] [CHO2−] [OH−] added 25.0 mL NaOH
HA A− OH− Kb = 5.6 x 10−11
initial 0 0.0500 ≈0 [OH−] = 1.7 x 10−6 M
mols before 2.50E-3 0 0
change
mols added +x – −x – +x
2.50E-3
equilibrium x 0 5.00E-2-x
mols after 2.50E-3 x ≈ 0

0.100 M NaOH
• HCHO2(aq) + NaOH(aq)  NaCHO2(aq) + H2O(aq)
• After equivalence
added 30.0 mL NaOH
HA A− NaOH
mols change −2.5E-3 +2.5E-3 −2.5E-3
mols end 0 2.5E-3 5.0E-4
molarity, new 0 0.045 0.0091
95 Copyright  2011 Pearson Education, Inc.

Adding NaOH to HCHO2
added 25.05.0 mL
30.0
10.0 mLNaOH
NaOH
initial HCHO2 solution
equivalence
0.00200
0.00050
0.00150
added molmL
35.0 point
NaOH
HCHO
NaOH 2xs
0.00250 mol HCHO − 2
0.00250
pH =
0.001003.14
11.96
3.56 mol CHO
mol NaOH xs2
pH = 2.37
−
[CHO 2 ]init = 0.0500 M
pH =− 12.22
[OH ]eq = 1.7 x 10−6
added
pH 12.5 mL NaOH
= 8.23
added 40.0 mL NaOH
0.00125 mol HCHO2
0.00150 mol NaOH xs
pH = 3.74 = pKa
pH = 12.36
half-neutralization
added 50.0
15.0 mL NaOH
0.00100 mol HCHO
0.00250 NaOH 2xs
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 as you did in
Example 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
Example 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 HNO2 + KOH  NO2 + H2O
with HA
use stoichiometry to
determine the volume
of added B
Example 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 HNO2 + KOH  NO2 + H2O
reaction for B
with HA
determine the
moles of HAbefore
& moles of
added B
HNO2 NO2− OH−
make a
stoichiometry mols before 0.00400 0 ≈0
table and
determine the
mols added – – 0.00100
moles of HA in mols after 0.00300 0.00100 ≈0
excess and
moles A made
is titrated with 0.200 M KOH. Calculate the pH after
adding 5.00 mL KOH.
write an
HNO 2 + H 2 O  NO2
 + H O+
3
equation for the Table 15.5 Ka = 4.6 x 10−4
reaction of HA
with H2O
determine Ka
and pKa for HA
use the
Henderson-
Hasselbalch HNO2 NO2− OH−
equation to mols before 0.00400 0 ≈0
determine the
pH mols added – – 0.00100
mols after 0.00300 0.00100 ≈0
is titrated with 0.200 M KOH. Calculate the pH at
the half-equivalence point.
write an
equation for the HNO2 + KOH  NO2 + H2O
reaction for B
with HA
determine the
moles of HAbefore at half-equivalence, moles KOH = ½ mole HNO2
& moles of added
B
HNO2 NO2− OH−
make a
stoichiometry mols before 0.00400 0 ≈0
table and mols added – – 0.00200
determine the
moles of HA in mols after 0.00200 0.00200 ≈0
excess and
moles A made
is titrated with 0.200 M KOH. Calculate the pH at
the half-equivalence point.
write an equation
HNO2 + H2O  NO2 + H3O+
for the reaction of Table 15.5 Ka = 4.6 x 10-4
HA with H2O
determine Ka and
pKa for HA
use the
Henderson-
Hasselbalch HNO2 NO2− OH−
equation to
mols before 0.00400 0 ≈0
determine the pH
mols added – – 0.00200
mols after 0.00200 0.00200 ≈0
Titration Curve of a Weak Base with a
Strong Acid
Practice – Titration of 25.0 mL of 0.10 M NH3 (pKb =
4.75) with 0.10 M HCl. Calculate the initial pH of the
NH3 solution.
Practice – Titration of 25.0 mL of 0.10 M NH3 with
0.10 M HCl. Calculate the initial pH of the NH3(aq)
pKb = 4.75
• NH3(aq) + HCl(aq)  NH4Cl(aq) Kb = 10−4.75 = 1.8 x 10−5
• Initial: NH3(aq) + H2O(l)  NH4+(aq) + OH−(aq)

[HCl] [NH4+] [NH3]
initial 0 0 0.10
change +x +x −x
equilibrium x x 0.10−x
Practice – Titration of 25.0 mL of 0.10 M NH3 with
0.10 M HCl. Calculate the initial pH of the NH3(aq)
pKb = 4.75
• NH3(aq) + HCl(aq)  NH4Cl(aq) Kb = 10−4.75 = 1.8 x 10−5
• Initial: NH3(aq) + H2O(l)  NH4+(aq) + OH−(aq)

[HCl] [NH4+] [NH3]
initial 0 0 0.10
change +x +x −x
equilibrium x x 0.10−x
4.75) with 0.10 M HCl. Calculate the pH of the solution
after adding 5.0 mL of HCl.
4.75) with 0.10 M HCl. Calculate the pH of the
solution after adding 5.0 mL of HCl.
• NH3(aq) + HCl(aq)  NH4Cl(aq)
• Initial mol of NH3 = 0.0250 L x 0.100 mol/L = 2.50 x 10−3
• Before equivalence: after adding 5.0 mL of HCl
NH4+(aq) + H2O(l)  NH4+(aq) + H2O(l) pKb = 4.75
pKa = 14.00 − 4.75 = 9.25
NH3 NH4Cl HCl
mols change −5.0E-4 −5.0E-4 −5.0E-4
mols end 2.00E-3 5.0E-4 0
molarity, new 0.0667 0.017 0
4.75) with 0.10 M HCl. Calculate the pH of the solution
after adding 5.0 mL of HCl.
• Before equivalence: after adding 5.0 mL of HCl
NH3 NH4Cl HCl

mols change −5.0E-4 −5.0E-4 −5.0E-4
mols end 2.00E-3 5.0E-4 0
molarity, new 0.0667 0.017 0
solution at equivalence.
• At equivalence mol NH3 = mol HCl = 2.50 x 10−3
NH3 NH4Cl HCl
added 25.0 mL HCl
mols change −2.5E-3 +2.5E-3 −2.5E-3
mols end 0 2.5E-3 0
molarity, new 0 0.050 0
NH3(aq) + HCl(aq)  NH4Cl(aq)
at equivalence [NH4Cl] = 0.050 M
NH4+(aq) + H2O(l)  NH3(aq) + H3O+(aq)
[NH3] [NH4+] [H3O+]

initial 0 0.050 ≈0
change +x −x +x
equilibrium x 0.050−x x
• After equivalence: after adding 30.0 mL HCl
NH3 NH4Cl HCl
mols change −2.5E-3 +2.5E-3 −2.5E-3
mols end 0 2.5E-3 5.0E-4
molarity, new 0 0.045 0.0091
when you mix a strong acid, HCl,

with a weak acid, NH4+, you only
need to consider the 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
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
Monitoring pH During a 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
Phenolphthalein
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
Monitoring a Titration with an
Indicator
• For most titrations, the titration curve shows a
very large change in pH for very small
additions of titrant 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
Acid-Base Indicators
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
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)
Example 16.8: Calculate the molar solubility of
PbCl2 in pure water at 25 C
write the
dissociation
reaction and Ksp
expression
Ksp = [Pb2+][Cl−]2
create an ICE [Pb2+] [Cl−]
table defining
the change in Initial 0 0
terms of the Change +S +2S
solubility of the
Equilibrium S 2S
solid
Example 16.8: Calculate the molar solubility of
PbCl2 in pure water at 25 C
substitute into
the Ksp Ksp = [Pb2+][Cl−]2
expression Ksp = (S)(2S)2
find the value of [Pb2+] [Cl−]

Ksp from Table
16.2, plug into Initial 0 0
the equation, Change +S +2S
and solve for S
Equilibrium S 2S
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 initial 0 0
terms of the change +(1.05 x 10−2) +2(1.05 x 10−2)
solubility of the
equilibrium (1.05 x 10−2) (2.10 x 10−2)
solid
substitute into
the Ksp
Ksp = [Pb2+][Br−]2
expression Ksp = (1.05 x 10−2)(2.10 x 10−2)2
plug into the [Pb2+] [Br−]

equation and
solve initial 0 0
change +(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
• 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
addition of Cl− shifts the
equilibrium to the left
Example 16.10: Calculate the molar solubility
of CaF2 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 initial 0 0.100
terms of the change +S +2S
solubility of the
solid equilibrium S 0.100 + 2S
Example 16.10: Calculate the molar solubility
of CaF2 in 0.100 M NaF at 25 C
substitute into
Ksp = [Ca2+][F−]2
the Ksp
expression, Ksp = (S)(0.100 + 2S)2
assume S is
small Ksp = (S)(0.100)2
find the value of
Ksp from Table [Ca2+] [F−]
16.2, plug into initial 0 0.100
the equation, change +S +2S
and solve for S
equilibrium S 0.100 + 2S
Practice – Determine the concentration of Ag+
ions in seawater that has a [Cl−] of 0.55 M
Ksp of AgCl = 1.77 x 10−10
write the
dissociation
AgCl(s)  Ag+(aq) + Cl−(aq)
reaction and Ksp
expression
Ksp = [Ag+][Cl−]
create an ICE [Ag+] [Cl−]
table defining
the change in initial 0 0.55
terms of the change +S +S
solubility of the
solid equilibrium S 0.55 + S
substitute into
the Ksp
Ksp = [Ag+][Cl−]
expression, Ksp = (S)(0.55 + S)
assume S is
small Ksp = (S)(0.55)
find the value of
[Ag+] [Cl−]
Ksp from Table
16.2, plug into Initial 0 0.55
the equation, Change +S +S
and solve for S
Equilibrium S 0.55 + S
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 precipitate if a seed crystal is
occurs if Q > Ksp added
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
Example 16.12: Will a precipitate form when we mix
Pb(NO3)2(aq) with NaBr(aq) if the concentrations after
mixing are 0.0150 M and 0.0350 M respectively?
write the equation for
the reaction Pb(NO3)2(aq) + 2 NaBr(aq) → PbBr2(s) + 2 NaNO3(aq)
determine the ion Pb(NO3)2 = 0.0150 M NaBr = 0.0350 M
concentrations of the Pb2+ = 0.0150 M, Na+ = 0.0350 M,
original salts
NO3− = 2(0.0150 M) Br− = 0.0350 M
determine the Ksp for
any “insoluble” Ksp of PbBr2 = 4.67 x 10–6
product
PbBr2(s)  Pb2+(aq) + 2 Br−(aq)
write the dissociation
reaction for the
insoluble product
calculate Q, using the
ion concentrations
compare Q to Ksp. If
Q > Ksp, precipitation Q < Ksp, so no precipitation
Practice – Will a precipitate form when we mix
Ca(NO3)2(aq) with NaOH(aq) if the concentrations after
mixing are both 0.0175 M?
Ksp of Ca(OH)2 = 4.68 x 10−6
Practice – Will a precipitate form when we mix
Ca(NO3)2(aq) with NaOH(aq) if the concentrations after
mixing are both 0.0175 M?
write the equation for
the reaction Ca(NO3)2(aq) + 2 NaOH(aq) → Ca(OH)2(s) + 2 NaNO3(aq)
determine the ion Ca(NO3)2 = 0.0175 M NaOH = 0.0175 M
concentrations of the Ca2+ = 0.0175 M, Na+ = 0.0175 M,
original salts
NO3− = 2(0.0175 M) OH− = 0.0175 M
determine the Ksp for
any “insoluble” Ksp of Ca(OH)2 = 4.68 x 10–6
product
Ca(OH)2(s)  Ca2+(aq) + 2 OH−(aq)
write the dissociation
reaction for the
insoluble product
calculate Q, using the
ion concentrations
compare Q to Ksp. If Q > Ksp, so precipitation
Q > Ksp, precipitation
Example 16.13: What is the minimum [OH−]
necessary to just begin to precipitate Mg2+ (with
[0.059]) from seawater?
Mg(OH)2(s)  Mg2+(aq) + 2 OH−(aq)

precipitating may just occur when Q = Ksp
Practice – What is the minimum concentration of
Ca(NO3)2(aq) that will precipitate Ca(OH)2 from
0.0175 M NaOH(aq)?
Ksp of Ca(OH)2 = 4.68 x 10−6
Practice – What is the minimum concentration of
Ca(NO3)2(aq) that will precipitate Ca(OH)2 from
0.0175 M NaOH(aq)?
Ca(NO3)2(aq) + 2 NaOH(aq) → Ca(OH)2(s) + 2 NaNO3(aq)
Ca(OH)2(s)  Ca2+(aq) + 2 OH−(aq)
[Ca(NO3)2] = [Ca2+] = 0.0153 M

Example 16.14: What is the [Mg2+] when Ca2+
(with [0.011]) just begins to precipitate from
seawater?
Ca(OH)2(s)  Ca2+(aq) + 2 OH−(aq)
Example 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
Mg(OH)2(s)  Mg2+(aq) + 2 OH−(aq)
when Ca2+ just
begins to
precipitate out, the
[Mg2+] has dropped
from 0.059 M to
4.8 x 10−10 M
Practice – A solution is made by mixing Pb(NO3)2(aq) with
AgNO3(aq) so both compounds have a concentration of
0.0010 M. NaCl(s) is added to precipitate out both AgCl(s)
and PbCl2(aq). What is the [Ag+] concentration when the
Pb2+ just begins to precipitate?
Practice – What is the [Ag+] concentration when
the Pb2+(0.0010 M) just begins to precipitate?
AgNO3(aq) + NaCl(aq) → AgCl(s) + NaNO3(aq)
the Pb2+(0.0010 M) just begins to precipitate?
Pb(NO3)2(aq) + 2 NaCl(aq) → PbCl2(s) + 2 NaNO3(aq)

the Pb2+(0.0010 M) just begins to precipitate
precipitating Ag+ begins when [Cl−] = 1.77 x 10−7 M
precipitating Pb2+ begins when [Cl−] = 1.08 x 10−1 M
when Pb2+ just
begins to
precipitate out, the
[Ag+] has dropped
from 0.0010 M to
1.6 x 10−9 M
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 (NH4)2HPO4
Group 5
• Group five cations are Na+, K+, NH4+
• All these cations form compounds that are
soluble in water – they do not precipitate
• Identified by the color of their flame
Complex Ion Formation
• Transition metals tend to be good Lewis acids
• They often bond to one or more H2O molecules to
form a hydrated ion
 H2O is the Lewis base, donating electron pairs to form
coordinate covalent bonds
Ag+(aq) + 2 H2O(l)  Ag(H2O)2+(aq)
• Ions that form by combining a cation with several
anions or neutral molecules are called complex
ions
 e.g., Ag(H2O)2+
• The attached ions or molecules are called
ligands
 e.g., H2O
Complex Ion Equilibria
• If a ligand is added to a solution that forms a
stronger bond than the current ligand, it will
replace the current ligand
Ag(H2O)2+(aq) + 2 NH3(aq)  Ag(NH3)2+(aq) + 2 H2O(l)
generally H2O is not included, because its complex
ion is always present in aqueous solution
Ag+(aq) + 2 NH3(aq)  Ag(NH3)2+(aq)
Formation Constant
• The reaction between an ion and ligands to form
a complex ion is called a complex ion
formation reaction
Ag+(aq) + 2 NH3(aq)  Ag(NH3)2+(aq)
• The equilibrium constant for the formation
reaction is called the formation constant, Kf
Formation Constants
Example 16.15: 200.0 mL of 1.5 x 10−3 M
Cu(NO3)2 is mixed with 250.0 mL of 0.20 M NH3.
What is the [Cu2+] at equilibrium?
Write the Cu2+(aq) + 4 NH3(aq)  Cu(NH3)22+(aq)
formation
reaction and Kf
expression.
Look up Kf value
determine the
concentration of
ions in the
diluted solutions
Example 16.15: 200.0 mL of 1.5 x 10−3 M
Cu(NO3)2 is mixed with 250.0 mL of 0.20 M
NH3. What is the [Cu2+] at equilibrium?
Cu2+(aq) + 4 NH3(aq)  Cu(NH3)22+(aq)
Create an ICE
table. Because [Cu2+] [NH3] [Cu(NH3)22+]
Kf is large,
initial 6.7E-4 0.11 0
assume all the
Cu2+ is change ≈−6.7E-4 ≈−4(6.7E-4) ≈+6.7E-4
converted into
complex ion, equilibrium x 0.11 6.7E-4
then the system
returns to
equilibrium.
Example 16.15: 200.0 mL of 1.5 x 10-3 M
Cu(NO3)2 is mixed with 250.0 mL of 0.20 M
NH3. What is the [Cu2+] at equilibrium?
substitute in Cu2+(aq) + 4 NH3(aq)  Cu(NH3)22+(aq)
and solve
for x
confirm the
“x is small”
approxima- [Cu2+] [NH3] [Cu(NH3)22+]
tion initial 6.7E-4 0.11 0
change ≈−6.7E-4 ≈−4(6.7E-4) ≈+6.7E-4
equilibrium x 0.11 6.7E-4
2.7 x 10−13 << 6.7 x 10−4, so the approximation is valid
Practice – What is [HgI42−] when 125 mL of 0.0010 M
KI is reacted with 75 mL of 0.0010 M HgCl2?
4 KI(aq) + HgCl2(aq)  2 KCl(aq) + K2HgI4(aq)
Write the Hg2+(aq) + 4 I−(aq)  HgI42−(aq)
formation
reaction and Kf
expression.
Look up Kf value
determine the
concentration of
ions in the
diluted solutions
Hg2+(aq) + 4 I−(aq)  HgI42−(aq)
Create an ICE
table. Because I− is the limiting reagent
Kf is large,
assume all the [Hg2+] [I−] [HgI42−]
lim. rgt. is
initial 3.75E-4 6.25E-4 0
converted into
complex ion, change ≈¼(−6.25E-4) ≈−(6.25E-4) ≈¼(+6.25E-4)
then the system
equilibrium 2.19E-4 x 1.56E-4
returns to
equilibrium.
substitute in Hg2+(aq) + 4 I−(aq)  HgI42−(aq)

and solve for
x
confirm the
“x is small” [Hg2+] [I−] [HgI42−]
approximation
initial 3.75E-4 6.25E-4 0
change ≈¼(−6.25E-4) ≈−(6.25E-4) ≈¼(+6.25E-4)
equilibrium 2.19E-4 x 1.56E-4
2 x 10−8 << 1.6 x 10−4, so the approximation is valid

[HgI42−] = 1.6 x 10−4
The Effect of Complex Ion Formation
on Solubility
• The solubility of an ionic compound that
contains a metal cation that forms a complex
ion increases in the presence of aqueous
ligands
AgCl(s)  Ag+(aq) + Cl−(aq) Ksp = 1.77 x 10−10
Ag+(aq) + 2 NH3(aq)  Ag(NH3)2+(aq) Kf = 1.7 x 107
• Adding NH3 to a solution in equilibrium with
AgCl(s) increases the solubility of Ag+
Solubility of Amphoteric
Metal Hydroxides
• Many metal hydroxides are insoluble
• All metal hydroxides become more soluble in acidic
solution
 shifting the equilibrium to the right by removing OH−
• Some metal hydroxides also become more soluble
in basic solution
 acting as a Lewis base forming a complex ion
• Substances that behave as both an acid and base
are said to be amphoteric
• Some cations that form amphoteric hydroxides
include Al3+, Cr3+, Zn2+, Pb2+, and Sb2+
Al3+
• Al3+ is hydrated in water to form an acidic

solution
Al(H2O)63+(aq) + H2O(l)  Al(H2O)5(OH)2+(aq) + H3O+(aq)
• Addition of OH− drives the equilibrium to the right
and continues to remove H from the molecules
Al(H2O)5(OH)2+(aq) + OH−(aq)  Al(H2O)4(OH)2+(aq) + H2O (l)
Al(H2O)4(OH)2+(aq) + OH−(aq)  Al(H2O)3(OH)3(s) + H2O (l)

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Chemistry: A Molecular Approach, 2nd Ed.

ethylene glycol glycolic acid

• Adding a salt containing the anion NaA, which

the approximation is valid

the approximation is valid

fill in the table HC2H3O2 + OH−  C2H3O2 + H2O

write a reaction for

the approximation is valid

Copyright  2011 Pearson Education, Inc.

[HA] [A−] [H3O+]

pKa for HC2H3O2 = 4.745

fill in the table F− + H3O+  HF + H2O

H2O(l) + NH3 (aq)  NH4+(aq) + OH−(aq)

assume the [B] and

• A buffer will be most effective when the

Therefore, the effective pH range of a buffer is pKa ± 1

To make a buffer with

to make a buffer with

Copyright  2011 Pearson Education, Inc.

Copyright  2011 Pearson Education, Inc.

Copyright  2011 Pearson Education, Inc.

95 Copyright  2011 Pearson Education, Inc.

• Initial: NH3(aq) + H2O(l)  NH4+(aq) + OH−(aq)

• Initial: NH3(aq) + H2O(l)  NH4+(aq) + OH−(aq)

NH3 NH4Cl HCl

[NH3] [NH4+] [H3O+]

when you mix a strong acid, HCl,

titration of 25.0 mL of 0.100 M

• All ionic compounds dissolve in water to some

find the value of [Pb2+] [Cl−]

plug into the [Pb2+] [Br−]

• A solution containing several different cations

Mg(OH)2(s)  Mg2+(aq) + 2 OH−(aq)

[Ca(NO3)2] = [Ca2+] = 0.0153 M

precipitating may just occur when Q = Ksp

PbCl2(s)  Pb2+(aq) + 2 Cl−(aq)

• Group one cations are Ag+, Pb2+ and Hg22+

substitute in Hg2+(aq) + 4 I−(aq)  HgI42−(aq)

equilibrium 2.19E-4 x 1.56E-4

2 x 10−8 << 1.6 x 10−4, so the approximation is valid

• Al3+ is hydrated in water to form an acidic

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