Precipitation Reactions and

Gravimetric Analysis
Titrations where the titrant forms a precipitate with the
analyte.
Not always so straightforward a number of
requirements need to be met.
Precipitation reactions are often slow and have the
tendency to absorb and co-precipitation other species.
Major applications: determination of halides by the
precipitation silver salts.
the determination of sulphate by
precipitation as barium sulphate.

Precipitation Equilibria: The solubility

product
What do we mean by the term insoluble?
AgCl Ag+ + ClWe can write the equilibrium constant or the solubility
product:
Ksp = [Ag+][Cl-]
Precipitation will not take place unless the product of
[Ag+] and [Cl-] exceeds the Ksp
E.g. AgCl = 1.82 x 10-10

Solubility product constants of selected slightly

soluble salts.

Factors affecting Ksp

1. The common ion effect
If there is an excess of one ion over the other, the
solubility of the precipitate will decrease - Le Chateliers
principle.
2. The effect of complex-ion formation
The presence of complexing agents that are able to
combine with either the cation or anion of a slightly
soluble compound - will result in an increase in its
solubility.
AgCl
Ag+ + NH3
AgNH3+ + NH3

Ag+ + ClAgNH3+
Ag(NH3)2+

Precipitation titrations
Calculate pCl for the titration of 100.0 ml of 0.100 M Cl- with 0.100 M
AgNO3 after the addition of 0.00, 20.00, 100.0 and 110.0 ml of AgNO3.

At 100.0 ml:
All Cl- has reacted with Ag+
[Cl-]
=
K sp = 1.0x10 10
pCl

=
=

1.0 x 10-5 M
-log(1.0 x 10-5)

5.00

At 110.0 ml:
mmol Ag+
Ag+ left
[Ag+]
[Cl-]
pCl

=
=
=
=
=

110.0 ml x 0.100 M
11.00 10.00
1.00 mmol/210 ml
Ksp/[Ag+]
-log(2.1 x 10-8)

=
=
=
=
=

11.00 mmol
1.00 mmol
4.76 x 10-3 M
2.1 x 10-8 M
7.67

A titration curve can be obtained by plotting pAg (-log[Ag+]) or pCl

against the volume of AgNO3, in a similar manner as you did for
acid-base titrations.

The smaller the Ksp, the sharper the end point.

16

AgI Ksp = 8.3 x10-17

14

12

AgBr Ksp = 5.0 x10-13

pAg

10

AgCl Ksp = 1.82 x10-10

8

0
0.0

10.0

20.0

30.0

40.0

vol Ag (ml)

50.0

60.0

70.0

The more concentrated the reagents, the bigger the end

point break.
18

0.1 M NaI
0.5 M NaI

16

14

12

pAg

10

0.0

10.0

20.0

30.0
vol Ag (ml)

40.0

50.0

60.0

If we look at the Ksp value for AgI

(8.3 10-17) we see that the
calculated solubility at equivalence
point is

What about solutions that contain a

mixture of anions?
The compound that is least soluble
precipitates first.

[Ag+ ] = [I - ] = Ksp

(AgI)

= 9.1 10 -9

16

Will the chloride start to

precipitate?

14

AgI
12

If we started with 25 ml of 0.1 M

chloride, at the first equivalence
point it will be

8.3 x 10-17
pAg

10

25 mL 0.1 M
= 0.0333 M
25 mL + 50 mL

AgCl

1.82 x 10-10

Ksp = [9.1 x 10-9][0.03] = 3 10-10.

which is greater than Ksp(AgCl)

0
0

10

20

30

40

50

60
vol Ag (mL)

70

80

90

100

110

120

AgCl starts to precipitate just

before the equivalence point of
AgI.

Detection of the end point: Indicators

1.
2.

Indicators reacting with the titrant

Adsorption indicators

1. Indicators reacting with the titrant

Mohr method
Chloride is titrated with standard silver nitrate solution
using a soluble chromate salt indicator.
CrO4-2 + 2Ag+ Ag2CrO4
(yellow)
(red)
The concentration of the indicator is important. The
Ag2CrO4 should just start precipitating at the
equivalence point.

 From Ksp, the concentration of Ag+ at the equivalence

point is 1 x 10-5 M, meaning that Ag2CrO4 should
precipitate just when [Ag+] = 1 x 10-5 M. If the solubility
product of Ag2CrO4 is 1.1 x 10-12, we can calculate what
the concentration of CrO4-2 should be:
Ksp
[CrO4-2]

=
=

[Ag+]2[CrO4-2]
1.1 x 10-2 M

If greater: Ag2CrO4 will begin to precipitate before the

equivalence point.
If less: Ag2CrO4 will only begin to precipitate after the
equivalence point has been reached.

Volhard titration
Indirect titration for determining anions that precipitate
with silver (Cl-, Br-, SCN-).
A measured excess of AgNO3 is added in acidic solution
to precipitate the anion.
X- + Ag+

AgX + excess Ag+

Excess Ag+ is then back-titrated with standard potassium

thiocyanate solution.
Excess Ag+ + SCN-

AgSCN

The endpoint is detected by using Fe3+, which forms a

soluble red complex with the first excess of titrant (SCN-):
Fe3+ + SCN- Fe(SCN)2+

2. Adsorption indicators (Fajan's method)

These are dyes that adsorb to the surface of a
precipitate near the equivalence point.
The bestknown example is fluorescein, which is used
to indicate the equivalence point in the titration of Cl
with Ag+.

Fluorescein

Fluoresceinate anion (yellow green)

Consider the titration of Cl with Ag+ in the presence of

fluorescein.
Before equivalence point: Cl- is in excess and is the
primary adsorbed layer around the AgCl particles.
This repels the negatively charged fluoresceinate anions.
AgCl : Cl When Ag+ is added in excess, the surface of the
precipitate become positively charge.
The fluoresceinate anions become adsorbed in the
counterion layer of the AgCl colloids.
AgCl : Ag+ :: InThis gives these particles a red colour, thus indicating end
point.

 If an indicator is adsorbed more strongly than the analyte

ion, it cannot be used.
Dichlorofluorescein/ fluorescein is adsorbed less strongly
than Cl, Br, I or SCN and can be used in the titration
of any of these ions.

 We want the maximum surface area for adsorption (i.e. a

colloidal precipitate).
The indicator ion must form a precipitate with the ions
adsorbed in the primary adsorption layer.
The photocomposition of AgX can be a major source of
error in titrations involving silver - proper standardisation
is important.

Gravimetric Analysis
The analyte is selectively converted to an insoluble form,
which can then be dried and accurately weighed.
Can be one of the most accurate and precise methods of
quantitative analysis.
However, gravimetric methods have certain limitations!
The ideal product of a gravimetric analysis should be
insoluble, easily filterable, very pure, and should have a
known composition.

Steps in gravimetric analysis:

1.
2.
3.
4.
5.
6.
7.
8.

Preparation of the solution

Precipitation
Digestion
Filtration
Washing
Drying or igniting
Weighing
Calculation

Supersaturation and Nucleation

Crystallisation occurs in two phases: nucleation and
particle growth.
Nucleation - molecules in solution come together and
form small aggregates.
The addition of further molecules to these nuclei results
in the formation of crystals.
Supersaturated sugar water is used make rock candy,
with the sugar crystals nucleating and growing into
crystals.

Particle size
The particle size of solids formed by precipitation varies.
Colloidal suspensions have tiny particles (10-7 to 10-4 cm
in diameter) cannot be easily filtered.

Crystalline suspensions - particles settle quickly and are

readily filtered.

Large particles are also less prone to surface adsorption

and are more easily washed free from impurities.

Rate of precipitation
Supersaturated solutions contain more solute than
should be present at equilibrium.
Relative supersaturation = Q S
S

where Q is the actual concentration of solute and S is

the concentration at equilibrium.
Highly supersaturated solutions fast nucleation,
resulting in a suspension of many small particles.
Less supersaturated solutions produce fewer, larger
crystals.

Precipitation conditions
We want to keep Q low and S high during precipitation.
1. Precipitate from dilute solutions - keeps Q low.
2. Add dilute precipitating reagents slowly while stirring keeps Q low and promotes the formation of large
crystals.
3. Precipitate from hot solutions - increases S.
4. Precipitate at a low pH. Many precipitates are more
soluble in acid medium and this slows the rate of
precipitation.

Digestion
Precipitate is allowed to stand in solution.
Done at elevated temperatures.
Large crystals grow at the expense of the small ones
decreases surface area.

Impurities in precipitates

Precipitates may contain varying amounts of

impurities.

Contamination of the precipitate occurs through coprecipitation.

Two main mechanisms:
1. occlusion or inclusion
2. adsorption on the surface

Occlusion and Inclusion

Inclusions - impurity ions that occupy site in the crystal
lattice.
Generally occurs when the impurity ion has a similar size
and charge.
Occlusions - pockets of impurity that become trapped
within a crystal.
Occluded or included impurities are difficult to remove digestion or reprecipitating may be helpful.

Surface Adsorption
Adsorbed impurities - those bound to the surface of a
crystal.
The most common form of contamination.
Can often be removed by washing or digestion.
Some impurities can be treated with a masking agent to
prevent them from reacting with the precipitant.

Washing the precipitate

Some impurities can be removed by washing the
precipitate after filtering.
Cannot always wash with pure water!
This causes peptization (formation of colloids).
Prevented by adding an electrolyte to the washing
solution.
Example: nitric acid is used as a wash solution for AgCl.

Drying or igniting the precipitate

Precipitates must generally be heated to remove water
and adsorbed electrolytes.
Usually be done by heating at 110 oC for 1 to 2 hours.
Ignition - required if a precipitate must be converted to a
more suitable form for weighing.
Many metals that are precipitated using organic reagents
can be ignited to their oxides.

Gravimetric calculations
The precipitate we weigh is usually in a different to the
anayte whose weight we wish to report.
A gravimetric factor (GF) is used to help us with this
conversion.
formula wt. analyte
a
GF =
x
formula wt. precipitat e
b

Example: If we wish to calculate the quantity of

phosphorus in a Ag3PO4 precipitate, the GF would be
calculated as follows:
GF =

at wt. P
1
x
formula wt. Ag3PO4
1

GF = 0.07399

GF =

30.97
1
x
1
418.58

An ore is analysed for the manganese content by

converting the manganese to Mn3O4 and weighing it.
If a 1.52 g sample yields Mn3O4 weighing 0.126 g,
what would be the percent Mn2O3 in the sample? What
about the percent Mn?
We need to convert from Mn3O4 to Mn2O3

formula wt. analyte

a
GF =
x
formula wt. precipitate
b
GF =

157.9
3
x
= 1.035
228.8
2

0.126 g x GF
%Mn2O3 =
x 100
1.52

= 8.58%

GF =

Mn
3
x
Mn3O4
1

= 5.97%