Titrations

Titration
A known
concentration of
base (or acid) is
slowly added to a
solution of acid (or
base).

Aqueous
Equilibria
Titration
A pH meter or
indicators are used
to determine when
the solution has
reached the
equivalence point,
at which the
stoichiometric
amount of acid
equals that of base.
Aqueous
Equilibria
Titration of a Strong Acid with a
Strong Base

Acid solution
& indicator in
the flask Aqueous
Equilibria
Titration of a Strong Acid with a
Strong Base

Base
solution in
the buret

Acid solution
& indicator in
the flask Aqueous
Equilibria
Titration of a Strong Acid with a
Strong Base—initial sample

Cl-

H+

H+ & A- = Dominant species before titration begins

(water molecules omitted for clarity) Aqueous
Equilibria
Titration of a Strong Acid with a
Strong Base
From the start of
the titration to
near the
equivalence point,
the pH goes up
slowly.

Aqueous
Equilibria
Titration of a Strong Acid with a
Strong Base—adding some base

Slow
increase
in pH

Aqueous
Equilibria
Titration of a Strong Acid with a
Strong Base

Cl-
H+

H2O

Na+

As hydroxide is added, some of the H+ ions are consumed

Aqueous
Equilibria
Titration of a Strong Acid with a
Strong Base
Just before and
after the
equivalence point,
the pH increases
rapidly.

Aqueous
Equilibria
Titration of a Strong Acid with a
Strong Base: Equivalence Point
 moles acid initially
present = moles
base added
 solution contains

only water and the

salt from the cation
of the base and the
anion of the acid.

Aqueous
Equilibria
SA:SB titration: equivalence point

Cl-

H+

H2O
Na+

At the equivalence point, all the H+ ions have been Aqueous

consumed by an equal number of OH- ions Equilibria
SA:SB titration @ equivalence point

Cl-
H+

H2O
Na+

Major species at equivalence point: water, sodium ions

(cation from base), chloride ions (anion from acid)
Aqueous
Equilibria
Titration of a Strong Acid with a
Strong Base

Cl-
H+
Note that pH H2O
is 7 at
equivalence
Na+
point

Aqueous
Equilibria
Titration of a Strong Acid with a
Strong Base

Cl-
H+
H2O

Na+

Endpoint:
indicator
turns color Aqueous
Equilibria
Titration of a Strong Acid with a
Strong Base
As more base is
added, the
increase in pH
again levels off.

Aqueous
Equilibria
Titration of a Strong Acid with a
Strong Base

Excess
hydroxide
ions

Aqueous
Equilibria
SA:SB titration…beyond the
equivalence point Excess hydroxide ions (and
sodium ions, too), and
leftover chloride ions

Water molecules omitted for clarity

Aqueous
Equilibria
 Titrating a weak acid with a strong
base
 Unlike in the previous
case, the conjugate
base of the acid affects
the pH when it is
formed.

Aqueous
Equilibria
Titrating a weak acid with a strong
base

Initial pH is
low (but not
as low as an
equimolar
strong acid Aqueous
solution) Equilibria
 Titrating a weak acid with a strong
base—initial acid sample
HA
A-
H+

 Dominant species at
beginning: HA molecules
(5% dissociation not
shown) Aqueous
 Water molecules and indicator omitted Equilibria
for clarity
As some NaOH is added
Na+ + OH- + HA → H2O + A- + Na+

Aqueous
Equilibria
 As some NaOH is added
HA
A-
H+
Na+
H2O

 Both HA and A- are

present
 A buffer!
◦ HA:A- ratio is changing Aqueous
Equilibria
As some NaOH is added

pH increases
slowly in the
buffer region

Aqueous
Equilibria
Halfway to the equivalence point

[HA]=[A-]

Aqueous
Equilibria
Halfway to the equivalence point

pH = pKa at the
half-equivalence
point

Aqueous
Equilibria
At the equivalence point
Na+ + OH- + HA → H2O + A- + Na+

Initial moles of HA = moles of OH- added

All of the moles of HA and OH- are consumed

Aqueous
Equilibria
At the equivalence point
HA
A-
H+
Na+
H2O

Major species: A-,

Also Na+ (cation from base), water
Aqueous
Equilibria
At the equivalence point

pH >7 at
equivalence
point

Aqueous
Equilibria
At the equivalence point

Dominant
species is A-…
the conjugate
base of the
original weak
acid

Aqueous
Equilibria
Titration of a Weak Acid with a
Strong Base
With weaker acids,
the initial pH is
higher and pH
changes near the
equivalence point
are more subtle.

Aqueous
Equilibria
Titrations of Polyprotic Acids
In these cases
there is an
equivalence
point for each
dissociation.

Aqueous
Equilibria
Titration of a weak base with a
strong acid

Weak
base &
indicator
in flask

Aqueous
Equilibria
Titration of a weak base with a
strong acid B

Dominant species in flask: Aqueous

B molecules Equilibria
Water molecules not shown
Titration of a weak base with a
strong acid

Strong
acid
solution
in buret

Aqueous
Equilibria
Titration of a weak base with a
strong acid

Initial
pH in
flask is
high

Aqueous
Equilibria
Titration of a weak base with a
strong acid—half titration point
[B] = [HB+]

Aqueous
Equilibria
Titration of a weak base with a
strong acid

At half equivalence point,

pOH = pKb
pH = pKa of HB+

Aqueous
Equilibria
Titration of a weak base with a
strong acid Dominant species: HB +

It will react with water…

ICE problem to calculate pH

Aqueous
Equilibria
 Titration of a weak base with a
strong acid

pH < 7 at
equivalence
point

Aqueous
Equilibria
 Titration of a weak base with a
strong acid

Choose an
indicator
that
changes
color at the
correct pH

Aqueous
Equilibria
Titration of a Weak Base with a
Strong Acid
 The pH at the
equivalence point
in these titrations
is < 7.
 Methyl red is the

indicator of choice.
◦ Choose indicator so
that its pKa ~ pH at
equivalence point
Aqueous
Equilibria