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PRINCIPLE OF

GRAVIMETRIC
ANALYSIS
GROUP 1 :MIC 3A1

GRAVIMETRIC
ANALYSIS
Gravimetric

analysis is one of the


most accurate and precise method of
macroquantitative (large quantity)
analysis.
In this process the analyte is
selectively converted into insoluble
form

STEPS IN A GRAVIMETRIC ANALYSIS


PREPARARION OF THE SOLUTION
PRECIPITATION
DIGESTION
FILTERATION
WASHING
DRYING AND IGNITING
CALCULATION

PREPARING OF THE SOLUTION


Factor that must considered during prepararion of
solution :
1.

2.
3.
4.

5.

Volume of the solution during precipitation


The concentration range of the test substance
The presence and concentration of other constituents
Temperature
pH

Some form of preliminary separation may be necessary


to eliminate interfering material.
Adjust the solution condition to maintain low solubility of
the precipitate and to obtain it in a form suitable for
filtration.
Proper adjustment of the solution conditions prior to
precipitation may also mask potential interferences.
pH is important because it often influences both the
solubility of the analytical precipitate and the possibility of
interferences from other substances.

PRECIPITATION

Important conditions of substance that must be


taken into account before conducting precipitation:
The precipitate should first be sufficiently insoluble that
the amount lost due to solubility will be negligible.
It should consist of consist of large crystals that can be
easily filtered.
All precipitates tend to carry some of other constituents
of the solution with them.
This contamination should be negligible. Keeping the
crystals large can minimize this contamination.

PRECIPITATION PROCESS:

After adding precipating agent such as AgNO3


,precipitation occur but in series(step by step)
1.
2.

SUPERSATURATION-The solution phase contain


more of the dissolved salt than occurs at equilibrium.
NUCLEATION

A minimum number of partical must come


together to produce microscopic nuclei of the
solid phase.
The higher the degree of supersaturation the
greater the rate of nucleation.

Von Weimarn ratio:

Relative supersaturation

Q -S
S

Q - degree of supersaturation(the concentration of


the mixed reagent before precipitation occur)

S - solubility of the precipitate at equilibrium

High relative supersaturation- many small crystal (high


surface area)
Low relative supersaturation- fewer, larger crystal (low
surface area)

STEPS TO MAINTAIN FAVOURABLE CONDITIONS


FOR PRECIPITATIONS
1.
2.

3.

4.

Precipitate from dilute solution. This keeps Q low.


Add dilute precipitating reagents slowly, with effective
stirring. This also keeps Q low. Stirring prevents local
excesses of the reagent.
Precipitate from hot solution. This increase S. the solubility
should not be too great or the precipitation will not be
quantitative (with less than 1 part per thousand remaining).
The bulk of the precipitation maybe performed in the hot
solution, and then the solution may be cooled to make the
precipitation quantitative.
Precipitate at as low a pH as is possible to maintain
quantitative precipitation. As we have seen, many
precipitates are more soluble in acid medium, and this slows
the rate of precipitation. They are more soluble because the
anion of the precipitate combines with protons in the
solution.

DIGESTION
To make precipitate become larger and more pure
crystals.
Also known as Ostwald ripening (digestion).
Ostwald ripening improves the purity and
crystallinity of the precipitate.
In digestion, colloidal particles formed counter
layer(secondary layer) , primary absorptive layer
and colloidal(large number of small particle) AgCl.
There are 2 types of colloidal particles which is
hydrophilic and hydrophobic.

FILTRATION(IMPURITIES IN PRECIPITATE)

Precipitates tend to carry down from the solution other


constituents, causing the precipitate to become
contaminated. This process of contamination is called
coprecipitation. Ways in which a foreign material may be
coprecipitate.
OCCLUSION AND INCLUSION.

1.
o

In the process of occlusion, material that is not part of


the crystal structure is trapped within a crystal.
For example, water may be trapped in pockets when
AgNO3 crystals are formed, and this can be driven off by
melting.
Inclusion occurs when ions, generally of similar size and
charge, are trapped within the crystal lattice
(isomorphous inclusion, as with K+ in NH4MgPO4
precipitation).

2. SURFACE ADSORPTION
The surface of the precipitate will have a primary adsorbed
layer of the lattice ions in excess.
For example, after the barium sulfate is completely
precipitated, the lattice ion in excess will be barium, and this
will form the primary layer.
Digestion reduces the surface area and the amount of
adsorption.
Surface adsorption of impurities is the most common source of
error in gravimetry. It is reduced by proper precipitation
technique, digestion, and washing.

3. ISOMORPHOUS REPLACEMENT
Two compound are said to be isomorphous if they have same
type of formula and crystallize in similar geometric forms.
When the lattice dimensions are about the same, one ions can
replace another in the crystal, resulting in a mixed crystal.
For example, in the precipitation of Mg2+ as magnesium
ammonium phosphate, K+ has nearly the same ionic size as
NH4+ and can replace it to form magnesium potassium
phosphate.
It is very serios and little can be done about it,so precipitates in
which it occurs are seldom used analytically.

4. POSTPRECIPITATION.
When the precipitate is allowed to stand in contact with the
mother liquor(the solution from it was precipitate), a second
substance will slowly form a precipitate with the precipitating
regent.
For example, when calcium oxalate is precipitated in the
presence of magnesium ions, magnesium oxalate does not
immediately precipitate because it tends to form
supersaturated solutions.
It will come down if the solution is allowed to stand too long
before being filtered.

WASHING

Coprecipitated impurities, especially those on the surface, can


be removed by washing the precipitate after filtering.
The precipitate will be wet with the mother liquor, which is also
removed by washing.
Many precipitates cannot be washed with pure water, because
peptization(washing particles with water increases the extend
of solvent/water moleculer between the layers, causing the
secondary layer to be loosely bound,the particles revert to
colloidal state) occurs.
This is the reverse of coagulation
Coagulated particles have a neutral layer of adsorbed primary
and counterions.

presence of another electrolyte will cause the


counterions(an ion having a charge opposite to that of
the substance with which is associated).
These foreign ions are carried along in the coagulation.
Washing with water will dilute and remove foreign ions,
and the counterion will occupy a larger volume, with more
solvent molecules between it and the primary layer.
The repulsive forces between particles between particles
become strong again, and the particles partially revert to
the colloidal state and pass through the filter.
This can be prevented by adding an electrolyte to the
wash liquid. Eg: HNO3 or NH4NO3 for AgCl precipitate.

DRYING OR IGNITING
This process is to removes the solvent and wash
electrolytes.
If the collected precipitate is in a form suitable for
weighing, it must be heated to remove the water
and the absorbed electrolyte from the wash liquid.
The preferable temperature use for drying is by
drying it at 110C to 120C for 1 or 2 hours.
Ignition at a higher temperature are required if a
precipitate must be converted to a more suitable
form for weighing.

CALCULATION

Gravimetric factor(GF)-the weight of analyte per


unit weight of precipitate

f wt analyte (g/mol)
a
GF
(mol analyte/mol precipitate)
f wt precipitate (g /mol) b
g analyte/g precipitate

So, if Cl2 in a sample is converted to chloride and


precipitated as AgCl, the weight of Cl2 that gives 1 g of
AgCl is

f wt Cl2 (g Cl2/mol Cl2)


1
g Cl2 g AgCl
(mol Cl2/mol AgCl)
f wt AgCl (g AgCl/mol AgCl ) 2
g AgCl GF (g Cl2/g AgCl)
g AgCl 0.24737 (g Cl2/g AgCl)

EXAMPLE 1
CALCULATE THE GRAMS OF ANALYTE PER GRAM OF
PRECIPITATE FOR THE FOLLOWING CONVERSION:
Analyte

Precipitate

Ag3PO4

K2HPO4

Ag3PO4

Bi2s3

3BaSO4

Solution

at wt P (g/mol)
1
( mol P/mol Ag3PO4)
g wt Ag3PO4 (g/mol) 1
30.97 (g P/mol )
1

418.58( g Ag3PO4/mol) 1
0.07399g P/g Ag3PO4 GF

g P/g Ag3PO4

f wt K2HPO4 (g/mol) 1
(mol K2HPO4/mol Ag3PO4)
f wt Ag3PO4 (g/mol) 1
174.18(g K2HPO4(g/mol ) 1

418.58( g Ag3PO4/mol) 1
0.41612g K2HPO4/g Ag3PO4 GF

g K2HPO4/g Ag3PO4

f wt Bi 2S3 (g/mol) 1
g Bi 2S3/g BaSO 4
(mol Bi 2S3/mol BaSO 4)
f wt BaSO 4 (g/mol) 3
514.15 (g Bi 2S3/mol) 1

233.40 (g BaSO 4)
3
0.73429g Bi 2S3/g BaSO 4 GF

In order to calculate the percent composition by weight of analyte in the


sample, the weight of substance sought was divided with the weight of
sample and times with 100%.
The weight of sample sought can be obtain from the weight of
precipitate and the corresponding weight/mole relationship, as in
equation below:
weight of substance sought (g) weight of precipitate(g)
f wt substance sought (g/mol)
f wt precipitate (g/mol)
a
( mol substance sought/mol precipitate)
b
weight of precipitate (g) GF (g sought/g precippitate)

Thus, the general formula would be:

weight of precipitate (g) GF (g sought/g precipitate)


% sought
100%
weight of sample (g)

EXAMPLE 2
An ore is analyzed for the manganese content by converting the
manganese
to Mn3O4 and weighing it. If a 1.52g sample yeilds Mn3O4 weighing
0.126g,what would be the percent Mn2O3 in the sample? The percent
Mn?
Solution
3Mn2O3
(g Mn2O3 / g Mn3O4)
2Mn3O4
% Mn2O3
100%
1.52g sample
0.126 g 3(157.9)/2(228.8)

100% 8.58%
1.52 g
0.126 g Mn3O4

3Mn
( g Mn/ g Mn3O4)
Mn3O4
% Mn
100%
1.52 g sample
0.126 g 3(54.94)/228.8

100% 5.97%
1.52 g
0.126 g Mn3O4

EXAMPLE 3:
What weight of pyrite ore (impure FeS2 ) must be taken for analysis so
that
the BaSO 4 precipitate weight obtained will be equal to one-half that of
the
percent S in the sample?

Solution:
gA
100%
g sample
1
S
A(g BaSO 4)
(g S/g BaSO 4)
BaSO 4
A %S 2
100%
g sample
1 32.064

2
233.40 100%
1% S
g sample
g sample 6.869g
%A

THE END.