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Titration Curves

A titration curve provides us with a visual picture of how a property of the


titration reaction changes as we add the titrant to the titrand. The titration curve
in Figure 9.1, for example, was obtained by suspending a pH electrode in a
solution of 0.100 M HCl (the titrand) and monitoring the pH while adding 0.100
M NaOH (the titrant).

The titration of strong acids with bases is described on page 418 in the text. The pH or pOH is
determined from the amount of excess strong acid or strong base in the system. We assume that
strong acids and bases completely dissociate.

Region

Point C
Region
B
Point A

Titration Curves: Weak Acid with Strong Base


HA + OH- A- + H2O

Titration Curves: Weak base with Strong acid


B + H+ HB+ + H2O

For the Weak Acid, HA, titrated with a strong base,


OH-, the stoichiometry dictates that the number of
moles of the conjugate base, A-, is the same as the
number of moles of base introduced into the titration
flask. The number of moles of acid left at any point
in the titration, HA, is the original number of moles
of acid minus the number moles of base added.

For the Weak base, B, titrated with a strong acid, H+,


the stoichiometry dictates that the number of moles
of the conjugate acid, HB+, is the same as the number
of moles of acid introduced into the titration flask.
The number of moles of base left at any point in the
titration, B, is the original number of moles of acid
minus the number moles of base added.

Point A Start of the titration


Simple acid dissociation problem

Point A Start of the titration


Simple basic dissociation problem

Ka = [H+][A-]/[HA] = x2/[HA]o x

Kb = [HB+][OH-]/[B] = x2/[B]o x

From ICE table, [HA]o is the original concentration


of the weak acid.
When Ka is small, less than 10-5
Ka = x2/[HA]o
X = (Ka[HA]o) = [H+]
pH = -log[H+]

From ICE table, [B]o is the original concentration of


the weak base.
When Kb is small, less than 10-5
Kb = x2/[B]o
X = (Kb[B]o) = [OH-]
pOH = -log[OH-], pH = 14 -pOH

Region B Buffer
In this region there is a mixture of the acid and the
conjugate base. The system is a buffer and the pH is
calculated from the Henderson Hasselbach equation :
pH = pKa + log [A-]/[HA]

Region B Buffer
In this region there is a mixture of the base and the
conjugate acid. The system is a buffer and the pOH
is calculated from the Henderson Hasselbach
equation : pOH = pKb + log [HB+]/[B]

pH = pKa + log((MbVb)/(MHAoVHA - MbVb)


where Mb is the concentration of the base, Vb is the
volume of the base, MHAo is the original concentration
of the weak acid, VHA is the volume of the weak acid
sample that is being titrated.
Special case: at the half way point in the titration,
pH = pKa.

pOH = pKb + log((MaVa)/(MBoVB MaVa)


where Ma is the concentration of the acid, Vais the
volume of the base, MBo is the original concentration
of the weak base, VB is the volume of the weak base
sample that is being titrated.
Special case: at the half way point in the titration,
pOH = pKb, pH = 14 - pOH.

Point C Hydrolysis of a Salt


A- + H2O HA + OHKb = [HA][OH-]/[A-] = x2/[A-] x
Where kb = Kw/Ka
x = ([A-]Kb) = [OH-]
pOH = -log [OH-]
pH = 14-pOH
where [A-] = MbVb/(VHA + Vb)

Point C Hydrolysis of a Salt


HB+ + H2O B + H+
Ka = [B][H+]/[HB+] = x2/[HB+] x
Where ka = Kw/Kb
x = ([HB+]Ka) = [H+]
pH = -log [H+]
where [HB+] = MaVa/(VB + Va)

Region D Past the equivalence point


The amount of excess base, [OH-]inxs is
[OH-]inxs = (MbVb MHAVHA)/(VHA + Vb)
pOH = -log[OH-]inxs, pH = 14 pOH

Region D Past the equivalence point


The amount of excess acid, [H+]inxs is
[H+]inxs = (MaVa MBVB)/(VB + Va)
pH = -log[H+-]inxs,

Impact of acid concentration and strength on the shape of the titration curve

As the concentration of the weak acid decreases, the break in the sigmoid titration curve becomes less
pronounced and the endpoint is harder to detect. The same is true of the weak acid strength. As the
strength of the weak acid decreases (pKa increases) the break in the curve becomes less pronounced.