Gravimetric method

Sharifah Zati Hanani Syed

Zuber

Gravimetry
Includes all analytical methods in
which
analytical
signal
is
a
measurement of mass or change
in mass.

Types of gravimetric method

Precipitation gravimetry
Electrogravimetry
Volatilization gravimetry
Gravimetric titrimetry

Types of gravimetric method

Precipitation gravimetry analyte is
separated from solution of sample as
precipitate and is converted to a
compound of known composition that
can be weighed
Volatilization gravimetry analyte is
separated from sample by converting
it to gas of known composition and
weighed.

Types of gravimetric method

Gravimetric titrimetry
-analyte concentration is determined
by titrating analyte with the known
concentration of certain reagent.
Electrogravimetry
- Deposits the analyte as a solid film
on the electrode in an electrochemical
cell.

Precipitation Gravimetry
Steps in precipitation gravimetry:
1. Analyte is converted to a sparingly
soluble precipitate
2. This precipitate is then filtered,
washed free of impurities
3. This precipitate converted to a
product of known composition by
suitable heat treatment
4. Sample weighed

Example of Precipitation Gravimetry

Precipitation method for determining
calcium in water
-In technique, an excess of oxalic acid,
H2C2O4, is added to an aqueous solution
of sample.
-Ammonia is then added, which
neutralize the acid and causes all the
calcium in sample to precipitate as
calcium oxalate.
-The reaction are:

Example of Precipitation Gravimetry

cont.
Calcium oxalate is then filtered , dried
and ignited.
Calcium oxalate converted to calcium
oxide.
The reaction is:

The mass of calcium oxide is then

weighed.

Gravimetric calculation
Is based on fundamental
stoichiometric calculation.
The basic form of calculation is:
% analyte = (weight precipitate)(gravimetric
factor)(100)
weight
sample

Gravimetric factor
Combinations of the mole ratios and
the formula weights used in
stoichiometric calculation
Gravimetric factor (GF) = substance
sought
substance known

Gravimetric factor
For example: SO3 is the substance
sought but the substance known is
BaSO4.
Gravimetric factor = SO3 = 80.064
= 0.343
BaSO4 233.391
Hint: To calculate GF, simply balance
the common ion (Oxygen is NOT

Gravimetric factor
Example 2:
Ag2O is the substance sought but AgCl is
the substance known.

Gravimetric factor
Example 2:
Ag2O is the substance sought but AgCl is
the substance known.
-

Gravimetric Calculation
Example 3:

Hint: Calculate the GF first

Example 3 solution

Gravimetric Calculation
Example 4:

Hint: Calculate the GF first

Example 4 solution
% analyte = (weight precipitate)(gravimetric
factor)(100)

weight
sample
(a)

= 0.5394 x 0.6695 x 100

1.1324
%Fe = 33.32 %

Example 4 solution

Precipitation (Insoluble
Salts)
Many metal ions form compounds that are
insoluble in water.
We call them insoluble or slightly soluble
salts or precipitates.
Common precipitates are carbonates,
hydroxides, sulfates, and sulfides.

Precipitation (Insoluble
Salts)
An insoluble salt in contact with water
maintains an equilibrium with the ions. In
simple cases where there are no common
ions or competing equilibria, the ion
concentrations depend only on the
equilibrium constant for the particular
precipitate.
When we talk about solubility equilibria
we always write the equilibrium with the
solid on the left. For example:
Ba(IO3)2 (s)
Ba2+(aq) +
2 IO3-(aq)

Solubility product, Ksp

The equilibrium constant
expression for an insoluble salt
is written following the same
rules as for any other
equilibrium.
The equilibrium constant is
called the solubility product, Ksp.
The Ksp expression for the below
equilibrium is:
Ksp = [Ba2+][IO3-]2

Ksp Values for Some Precipitates

Formula

Name

Ksp

AgCl

silver chloride

1.8x10-10

Al(OH)3

aluminum hydroxide

2x10-32

BaCO3

barium carbonate

5x10-9

Ba(IO3)2

barium iodate

1.6x10-9

BaSO4

barium sulfate

1.3x10-10

Fe(OH)2

iron(II) hydroxide

8x10-16

Fe(OH)3

iron(III) hydroxide

4x10-38

FeS

iron sulfide

6x10-18

PbCrO4

lead chromate

1.8x10-14

Pb(OH)2

lead hydroxide

2.5x10-16

PbS

lead sulfide

7x10-28

PbSO4

lead sulfate

1.6x10-8

Solubility (Precipitation
Equilibria)
Solubility is defined as moles/L, g/L, or mg/L
of the dissolving species in solution.
Example :
How is the solubility of lead chloride, PbCl 2,
related to the solution concentrations of
Pb2+ and Cl-?
Each formula unit of PbCl2 that dissolves
produces one lead ion, Pb2+, and two
chloride ions, Cl-.
The molar solubility of PbCl2 is equivalent to
the concentration of Pb2+, SPbCl2 = [Pb2+].
Since two Cl-s are produced per PbCl2
formula unit that dissolves, the molar
solubility of PbCl2 equals one-half the
solution concentration of Cl-,

Example of Precipitation
Equilibria
How is the solubility of lead chloride, PbCl ,
2

related to the solution concentrations of Pb 2+

and Cl-?

Each formula unit of PbCl2 that dissolves

produces 1 Pb2+, and 2 Cl-.
The molar solubility of PbCl2 is equivalent to the
concentration of Pb2+, SPbCl2 = [Pb2+].
Since 2 Cl-s are produced per PbCl2 formula unit
that dissolves, the molar solubility of PbCl 2
equals one-half the solution concentration of Cl -,
SPbCl2 = 0.5*[Cl-].
SPbCl2 = [Pb2+] = 0.5*[Cl-].

Example 5
What is the solubility of barium iodate, Ba(IO 3)2, in pure water at 25
oC?
The solubility equilibrium is:
Ba(IO3)2 (s)

Ba2+(aq) + 2 IO3-(aq)
x
2x

Ksp = [Ba2+][IO3-]2 = 1.5x10-9

[Ba2+] = x

[IO3-] = 2x

Ksp = (x) (2x)2 = 1.5x10-9

4[x]3 = 1.5x10-9
x3

[x]3 = [Ba2+]3

[Ba2+]3 = 3.75x10-10 M

X = S (solubility) = [Ba2+] = 7.2x10-4 M

Or in mass terms: S = (7.2x10-4 M)(487 g/mol) = 0.35 g/L

Common ion effect

This concept involves how the
solubility of a salt changes when some
ion that is common to both added
substance and the salt in question.

Example of common ion

effect
Consider the equilibrium reaction involving
the saturated solution of silver chloride that
is described below.
AgCl(s)

Ag+ (aq) + Cl- (aq)

Let us add some amount of silver nitrate

(AgNO3) to the above equilibrium system and
see what happens to the solubility of silver
chloride.

Example of common ion

effect

Silver nitrate dissociates and produces silver

ion (Ag+ ) and nitrate ion (NO3 - ) according to:
Ag(NO3(s)
Ag+(aq) + NO3 -(aq)
where Ag+ is a common ion to both AgNO3 and
AgCl
According to Le Chateliers principle, it is a
shift in equilibrium from right to left by
forming more solid AgCl. The net result is the
decrease in the solubility of AgCl because Ag+
ion and Clion are removed from the solution in
the form of solid AgCl.

Example of common ion

effect

The net result is the decrease in the

solubility of AgCl because Ag+ ion and
Cl- ion are removed from the solution in
the form of solid AgCl.
Therefore, the effect of common ion is
to decrease the solubility of the salt.
Q: Will adding NaCl will have an effect
on the solubility of AgCl? How about
NaNO3?

Example 6

What is the solubility of barium iodate,

Ba(IO3)2, at 25 oC in a solution of 0.10
M barium nitrate, Ba(NO3)2?
The problem is set up the same as
before:
Ba2+(aq) + 2 IO3-(aq)
Ba(IO3)2 (s)
Initial

After addition

2x

0.1 + x

2x

Ksp = [Ba2+][IO3-]2 = 1.5x10-9

The difference is that there are two

Example 6

Ksp = [Ba2+][IO3-]2 = 1.5x10-9

Ksp = (0.10 M +x)[2x-]2 = 1.5x10-9
We could solve a cubic equation or we
could try neglecting the [Ba2+] that
comes from dissolution of Ba(IO3)2
compared to 0.10 M barium nitrate.
Since 0.1>>> x
0.1
2

then 0.1 + x