Objectives

 Mention the main steps of gravimetric

analysis.
 Define supersaturation.
 Identify types of impurities in precipitates.
 Define peptization.
 Define gravimetric factor.
 Apply gravimetric analysis to different
samples.

1
 Gravimetric analysis
 Gravimetric analysis is one of the most accurate
and precise methods of macro-quantitative
analysis.

 In this process, the analyte is selectively

1. converted to an insoluble form. The separated
precipitate is 2. dried or ignited, possibly to
another form and is 3. accurately weighed.

 From the weight of the precipitate and knowledge of

its chemical composition, we can calculate the
weight of the analyte in the desired form.
2
 Steps of Gravimetric analysis
 1. Precipitation.
 2. Digestion.
 3. Filtration.
 4. Washing.
 5. Drying or ignition.
 6. Weighing.
 7. Calculations

3
 1. Mechanism of precipitation
 When a solution of precipitating agent is added
to a test solution to form a precipitate, such as
in the addition of AgNO3 to a chloride solution to
precipitate AgCl,
 The actual precipitation occurs in a series of
steps:
 1. Super saturation, (The ionic product of
concentrations should be  the solubility
product).
 2. Nucleation, where a minimum number of
particles come together to produce
microscopic nuclei of the solid phase.
 3. Particle growth, where nuclei join together
to form a crystal of a certain geometric shape.
4
Mechanism of precipitation (cont.)

5
Mechanism of precipitation (cont.)

6
 Notice that:
 Although nucleation should occur theoretically
spontaneously, but induced nucleation can occur
on dust particles, scratches on the vessel
surface.

 The higher the degree of supersaturation, the

greater the rate of nucleation.

 This means the formation of great number of

nuclei per unit time, increasing also the rate of
particle growth.
 This increases the total surface area of the
precipitate thus more possibility of entrapment
of impurities. 7
 Degree of supersaturation
 Von Weimarn discovered that the particles size
of precipitates is inversely proportional to
the relative supersaturation of the solution
during the precipitation process:
QS
 Relative supersaturation (RSS) = S

 Where Q is the concentration of the mixed

reagents before precipitation occurs and is referred
to as the degree of supersaturation and S is
the solubility of the precipitate at equilibrium.
 This ratio is called the Von Weimarn Ratio.
8
 Degree of supersaturation (cont.)
 When a solution is supersaturated, it is in a
state of metastable equilibrium and this favours
rapid nucleation to form a large number of
small particles, that is
 High RSS Many small crystals
(high Surface area)
 Low RSS Fewer, larger crystals
(low surface area)

 Thus, we want Q low and S high during

precipitation.
9
 Favourable conditions for precipitation
 1. Precipitate from dilute solutions.
(This keeps Q low)
 2. Add dilute precipitating agents
slowly with constant stirring.
(This Keeps Q low)
 3. Precipitate from hot solution.
(This increases solubility)
 4. Precipitate at as low pH as possible.
(This increases the solubility of the precipitate)
10
 *

 The best conditions can be

obtained by using concentrations
at the point of interaction of the
above two curves (*). 11
 2. Digestion
 We have two types of precipitates, according
to the size of the formed particles, colloidal (1-
100 m) or amorphous, crystalline (> 100
m) precipitates.

 Digestion of 1. Crystalline precipitates can be

obtained by allowing the precipitate to stand with
the mother liquor for a long time.

 2. Colloidal precipitate is digested by standing

with the mother liquor (the solution from which it
was precipitated) at high temperature. 12
 Digestion (cont.)
 During digestion,
 (i) the small particles tend to dissolve and re-
precipitate on the surfaces of large crystal.
 In addition,

(ii) individual particles agglomerate to together

around a counter ion until they finally cement
together by forming connecting bridges.
 Also,

(iii) imperfections of the crystals tend to

disappear and adsorbed or trapped impurities
tend to go into solution. 13
 Notice that:
 For colloidal precipitates, e.g.
AgCl the ions are arranged in a
fixed pattern.
 The surface of the precipitate tend
to absorb the ion of the
precipitated particle that is in
excess in the solution,
(Ag+ or Cl-)
 This primary adsorbed layer
attracts oppositely charged ion in a
secondary layer, so the particle will
have an overall neutral charge.
 These secondary layers come
closer to form coagulated
precipitate.
14
 Impurities in precipitates
 1. Occlusion
 This occurs when materials
that are not part of the
crystal structure are trapped
within the crystal.

 For example, water or any

counter ion can be occluded in
any precipitate (AgCl). This
causes deformation in the
crystal.

 This type is hard to be removed,

digestion can decrease it to a
certain extent. 15
 Impurities in precipitates (cont.)
 2. Inclusion (isomorphous replacement)
 This occurs when a compound that is
isomorphous to the precipitate is entrapped
within the crystal.
 Isomorphous means they have the same type
of formula and crystals in similar geometric
form.

 Example, K+ has nearly the same size of NH4+ so it

can replace it in Magnesium ammonium phosphate.
 Digestion cannot handle this type and mixed
crystals will be formed. 16
 Impurities in precipitates (cont.)
 3. Surface adsorption
 Surface adsorption is very common especially in
colloidal precipitates.
 Example, AgCl, BaSO4, where each of them will
have a primary adsorption layer of the lattice ion
present in excess followed by a secondary layer of
the counter ion of opposite charge so as to have a
neutral net charge.

 These adsorbed layers can often be removed by

washing where they can be replaced by ions
than can be easily volatilized.
17
 Impurities in precipitates (cont.)
 4. Post precipitation
 When the precipitate is allowed to stand in contact
with the mother liquor, a second substance will
slowly form a precipitate on the surface of the
original one.
 Examples, When calcium oxalate is precipitated in
the presence of magnesium ions, magnesium
oxalate may be if the solution is left without
filtration for a long time.

 Digestion will increase the extent of such

type, dissolution and reprecipitation will
decrease the extent of post precipitation. 18
 Washing and filtering the precipitates
 Coprecipitated impurities especially
occluded or surface adsorbed ions can be
removed by washing of the precipitate
after filtration.
 The precipitate will also be wet with the
mother liquor which is also removed by
washing.

 Colloidal precipitates can not be washed with

pure water, because peptization occurs.
This is the reverse of coagulation.
19
 Peptization
 As we said before that coagulated particles have
neutral layer of adsorbed primary and counter ions.
 The presence of another electrolyte will cause
the counter ions to be forced into closer
contact with primary layer, thus promoting
coagulation.

 Washing with water will dilute and remove

foreign ions and the counter ion will occupy a
larger volume, with more solvent molecules
between it and the primary layer.
20
 Peptization (cont.)
 The results is that the repulsive forces increases
and the particles reverts to the colloidal state
pass through the filter (peptization occurs).

 This can be prevented by adding an electrolyte to

the washing liquid. e.g. HNO3 is used to wash
AgCl.

 N.B. This electrolyte should be volatile at the

temperature of drying or ignition and must not
dissolve the precipitate.
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22
 Drying or ignition
 If the collected precipitate is in a form suitable
for weighing, it must be heated to remove water
and to remove adsorbed electrolyte from the wash
liquid.
 This drying can be done by heating at 110 to
120°C for 1-2H.

 Ignition at much higher temperature is

usually required if a precipitate must be
converted to a more suitable form for
weighing.

 In this case, the weighed form of the precipitate

might be different from the precipitated form.
Examples are given in the table 23
Example of Gravimetric Analysis
TABLE FOR COMMON
GRAVIMETRIC ANALYSIS

24
Drying or ignition ( cont.)

25
 Calculations in Gravimetric analysis
 If we start with 10 ml of the analyte A which is precipitated in
the form of P by the following equation
 nA + B mP + S
nMwt mMwt
W2 W1
  W2 = W1 (nMwtanalyte/mMwtppt)

 Where W2 is the weight of the analyte ion (only)

present in 10 ml of solution and W1 is the weight of
precipitate (ppt).

 (nMwtanalyte/mMwtppt) is called the gravimetric or

conversion factor.

 It can be calculated from the ratio of the molecular weight of

the substance sought (analyzed) to that of substance
weighed. 26
 Example 1
 Calculate the gravimetric factor for each of
the following:
P Ag3PO4, K2HPO4 AgPO4, Bi2S3 BaSO4
As2O3Ag3AsO4, K2OKB(C6H5)4
 P/Ag3PO4 = atwt P/ Mwt Ag3PO4

 K2HPO4/Ag3PO4= Mwt K2HPO4/MwtAg3PO4

 Bi2S3/BaSO4 = MWt Bi2S3/3MWt BaSO4

 As2O3/Ag3AsO4 = Mwt As2O3/2MWt Ag3AsO4

 K2O/KB(C6H5)4 = Mwt K2O/ 2MWt KB(C6H5)4

27
 Example 2
 Orthophosphate (PO43-) is determined by weighing as ammonium
phosphomolybdate, (NH4)PO4.12MoO3. Calculate the percent P in
the sample and the percent P2O5 if 1.1682g precipitate were
obtained from a 0.2711 g sample.
 Remember: Wt of analyte = Wt of ppt x Gravimetric Factor
At. wt P
 Wt of P = 1.1682 X 
Mwt (NH ) PO .12MoO
4 3 4 3

30.97
 1.1682 x  0.0193 g
1876.5

% P = (0.0193/0.2711) x 100 = 7.11%

28
 Example 2 (cont.)
In general,
Wt ppt X gravimetric factor
%ppt  x100
Wt of sample

Mwt P2O5
1.1682 x
2 Mwt (NH4 )3 PO 4 .12MoO 3
 %P2O5  X 100
0.2711
141.95
1.1682 x
 2x1876.5 x100  16.30%
0.2711

29
 Example 3
 An ore is analyzed for the manganese content by converting the
manganese to Mn3O4 and weighing it. If a 1.52 g sample yields
Mn3O4 weighing 0.126g, what would be the percent Mn and Mn2O3
in the sample?

3 Mwt Mn2O3
0.126 x
2 Mwt Mn3O 4
%Mn2O3  X 100
1.52
3 (157.9)
0.126 x
2 (228.8)
 X 100  8.58%
1.52

30
 Example 3 (cont.)
3 At.wt Mn
0.126 x
Mwt Mn3O 4
% Mn  X 100
1.52
3 (54.94)
0.126 X
 228.8 X 100  5.97%
1.52

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