Gravimetric Analysis

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 Gravimetric Analysis
In this technique, the analyte is converted to an
insoluble form which can then be washed, dried,
and weighed in order to determine the
concentration of the analyte in the original solution.
Gravimetry is applied to samples where a good
precipitating agent is available. The precipitate
should be quantitative, easily washed and filtered
and of a suitable quantity for accurate weighing.

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Therefore, gravimetry is regarded as a macro
analytical technique. However, it is
considered, when appropriately done, one of
the most accurate analytical techniques.
Also, Gravimetry is one of a few analytical
methods that do not require standard
solutions as the weight of precipitate is the
only important parameter in analyte
determination.

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 Properties of Precipitates
1. Low solubility
No significant loss of the analyte occurs during
filtration and washing
2. High purity
3. Known composition
After drying and ignition, known chemical
composition
4. Easy to separate from reaction mixture
5. Stable under atmospheric conditions

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 Steps in a Gravimetric Analysis
After appropriate dissolution of the sample, the
following steps should be followed for a successful
gravimetric procedure:

1. Preparation of the Solution: This may involve

several steps including adjustment of the pH of the
solution in order for the precipitate to occur
quantitatively and get a precipitate of desired
properties, removing interferences, adjusting the
volume of the sample to suit the amount of
precipitating agent to be added.

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2. Precipitation: This requires addition of a precipitating agent
solution to the sample solution. Upon addition of the first
drops of the precipitating agent, supersaturation occurs,
and then nucleation starts to occur where every few
molecules of precipitate aggregate together forming a
nucleous. At this point, addition of extra precipitating
agent will either form new nuclei or will build up on
existing nuclei to give a precipitate. This can be predicted
by Von Weimarn ratio where, according to this relation
the particle size is inversely proportional to a quantity
called the relative supersaturation where:

Relative Supersaturation = (Q – S)/S

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The Q is the concentration of reactants before
precipitation, S is the solubility of precipitate in the
medium from which it is being precipitated.
Therefore, in order to get particle growth instead of
further nucleation we need to make the relative
supersaturation ratio as small as possible.

The optimum conditions for precipitation which make the

supersaturation low are:

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1. Precipitation using dilute solutions to decrease Q
2. Slow addition of precipitating agent to keep Q as low as
possible
3. Stirring the solution during addition of precipitating agent
to avoid concentration sites and keep Q low
4. Increase solubility by precipitation from hot solution
5. Adjust the pH in order to increase S but not a too much
increase as we do not want to lose precipitate by
dissolution
6. Usually add a little excess of the precipitating agent for
quantitative precipitation and check for completeness of
the precipitation

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 7. Precipitation from Homogeneous Solution
In order to make Q minimum we can, in some
situations, generate the precipitating agent in the
precipitation medium rather then adding it. For
example, in order to precipitate iron as the
hydroxide, we dissolve urea in the sample.
Heating of the solution generates hydroxide ions
from the hydrolysis of urea. Hydroxide ions are
generated at all points in solution and thus there
are no sites of concentration. We can also adjust
the rate of urea hydrolysis and thus control the
hydroxide generation rate. This type of procedure
can be very advantageous in case of colloidal
precipitates.

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3. Digestion of the Precipitate: The precipitate is left
hot (below boiling) for 30 min to 1 hour in order
for the particles to be digested. Digestion involves
dissolution of small particles and reprecipitation
on larger ones resulting in particle growth and
better precipitate characteristics. This process is
called Ostwald ripening. An important advantage
of digestion is observed for colloidal precipitates
where large amounts of adsorbed ions cover the
huge area of the precipitate. Digestion forces the
small colloidal particles to agglomerate which
decreases their surface area and thus adsorption.

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During digestion at elevated temperature:
1. Small particles tend to dissolve and reprecipitate on larger ones.
2. Individual particles agglomerate.
3. Adsorbed impurities tend to go into solution.

Ostwald ripening
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4. Filtering and Washing the Precipitate: It is crucial to
wash the precipitate very well in order to remove
all adsorbed species which will add to weight of
precipitate. One should be careful not to use too
much water since part of the precipitate may be
lost. Also, in case of colloidal precipitates we
should not use water as a washing solution since
peptization would occur. In such situations dilute
nitric acid, ammonium nitrate, or dilute acetic
acid may be used. Usually, coagulated particles
return to the colloidal state if washed with water,
a process called peptization.

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Washing of Precipitates

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 Adsorption and Particle size
You should know that adsorption is a major problem
in gravimetry in case of colloidal precipitate since a
precipitate tends to adsorb its own ions present in
excess, forming what is called a primary ion layer
which attracts ions from solution forming a
secondary or a counter ion layer. Individual particles
repel each other keeping the colloidal properties of
the precipitate. Particle coagulation can be forced
by either digestion or addition of a high
concentration of a diverse ions strong electrolytic
solution in order to shield the charges on colloidal
particles and force agglomeration.

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Representation of silver chloride colloidal particle
and adsorptive layers when Cl- is in excess.

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Cl- or Ag+ adsorbs on the particles when in
excess (primary ion layer).
A counter layer of cations forms. Washing with
water will dilute the counter ion layer and
the primary layer charge causes the particles
to revert to the colloidal state (peptization).
So we wash with an electrolyte that can be
volatilized on heating (HNO3).

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5. Drying and Ignition: The purpose of drying
(heating at about 120-150 oC in an oven) or
ignition in a muffle furnace at temperatures
ranging from 600-1200 oC is to get a material
with exactly known chemical structure so
that the amount of analyte can be accurately
determined.

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6. Calculations:

The last step in the gravimetric procedure is

performing the analytical calculations, as will
be seen shortly.

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 Impurities in Precipitates
1. Occlusion: Some constituents of the precipitation
medium may be trapped in the crystal structure
resulting in positive or negative errors. The trapped
materials can be water, analyte ions, precipitating
agent ions, or other constituents in the medium.
Slow addition of precipitating agent and stirring
may avoid occlusion but if it does occur, dissolution
of precipitate and reprecipitation may have to be
done.

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2. Inclusion: If the precipitation medium contains ions of the
same charge and size as one forming the crystal structure of
the precipitate, this extraneous ion can replace an ion from
the precipitate in the crystal structure. For example, in the
precipitation of NH4MgPO4 in presence of K+, ammonium
leaves the crystal magnesium ammonium phosphate and is
replaced by K+ since both have the same charge and size.
However, the FW fro NH4+ is 18 while that of K+ is 39. In this
case a positive error occurs as the weight of precipitate will
be larger when K+ replaces NH4+. In other situations we may
get a negative error when the FW of the included species is
less than the original replaced species

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3. Surface Adsorption: This always results in positive errors in
gravimetric procedures. See previous discussion on
colloidal precipitates.

4. Postprecipitation: In cases where there are ions other than

analyte ions which form precipitates with the precipitating
agent but at much slower rate then analyte, and if the
precipitate of the analyte is left for a long time without
filtration then the other ions start forming a precipitate
over the original precipitate leading to positive error.
Examples include precipitation of copper as the sulfide in
presence of zinc. Copper sulfide is formed first but if not
directly filtered, zinc sulfide starts to precipitate on the top
of it. The same is observed in the precipitation of calcium
as the oxalate in presence of magnesium.

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 Gravimetric Calculations
The point here is to find the weight of analyte from the weight
of precipitate. We can use the concepts discussed previously
in stoichiometric calculations but let us learn something
else. Assume Cl2 is to be precipitated as AgCl, then we can
write a stoichiometric factor reading as follows: one mole of
Cl2 gives 2 moles of AgCl. We can define a quantity called the
gravimetric factor (GF) where:
GF(analyte) = (a/b)*(FW analyte/FW ppt)
a,b are stoichiometric coefficients
GF for Cl2 = (1 mol Cl2/2 mol AgCl) * (FW Cl2/FW AgCl)

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Weight of substance sought = weight of precipitate x GF

One can also consider the problem by looking at the

number of mmoles of analyte in terms of the
mmoles of the precipitate where for the precipitation
of Cl2 as AgCl, we can write

Cl2 D 2 AgCl
mmol Cl2 = 1/2 mmol AgCl
(mg Cl2/FW Cl2) = 1/2 (mg AgCl/FW AgCl)

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Example

Calculate the mg analyte to mg precipitate for the following: P

(at wt =30.97) in Ag3PO4 (FW = 711.22), Bi2S3 (FW 514.15) in
BaSO4 (FW = 233.40)

Solution

P D Ag3PO4
mmol P = mmol Ag3PO4
Mg P/30.97 = mg Ag3PO4/711.22
Mg P/mg Ag3PO4 = 30.97/711.22 = 0.04354

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 Bi2S3 D 3 BaSO4
mmol Bi2S3 = 1/3 mmol BaSO4

mg Bi2S3/FW Bi2S3 = 1/3 mg BaSO4/FW BaSO4

mg Bi2S3/514.15 = 1/3 mg BaSO4/233.40

mg Bi2S3/ BaSO4 = 1/3 (514.15/ 233.40) = 0.73429

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Phosphate in a 0.2711 g sample was precipitated giving 1.1682 g of
(NH4)2PO4.12 MoO3 (FW = 1876.5). Find percentage P (at wt = 30.97) and
percentage P2O5 (FW = 141.95) in the sample.

Solution

First we set the mol relationship between analyte and precipitate

P D (NH4)2PO4.12 MoO3

mmol P = mmol (NH4)2PO4.12 MoO3

mg P/at wt P = mg (NH4)2PO4.12 MoO3/ FW (NH4)2PO4.12 MoO3

mg P = at wt P x (mg (NH4)2PO4.12 MoO3/ FW (NH4)2PO4.12 MoO3)

mg P = 30.97 (1.1682x103 / 1876.5) = 19.280 mg

% P = (19.280/271.1) x 100 = 7.111%

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The same procedure is applied for finding the percentage of
P2O5

P2O5 D 2 (NH4)2PO4.12 MoO3

mmol P2O5 = 1/2 (NH4)2PO4.12 MoO3
mg P2O5/FW P2O5 = 1/2 (mg (NH4)2PO4.12 MoO3/ FW
(NH4)2PO4.12 MoO3)
mg P2O5 = 1/2 x FW P2O5 x (mg (NH4)2PO4.12 MoO3/ FW
(NH4)2PO4.12 MoO3)
mg P2O5 = 1/2 x 141.95 (1.1682x103/1876.5) = 44.185 mg
% P2O5 = (44.185/271.1) x 100 = 16.30%

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Manganese in a 1.52 g sample was precipitated as Mn3O4 (FW =
228.8) weighing 0.126 g. Find percentage Mn2O3 (FW =
157.9) and Mn (at wt = 54.94) in the sample.

Solution

3 Mn2O3 D 2 Mn3O4
mmol Mn2O3 = 3/2 mmol Mn3O4
mg Mn2O3 / FW Mn2O3 = 3/2 (mg Mn3O4/FW Mn3O4)
mg Mn2O3 = 3/2 FW Mn2O3 (mg Mn3O4/FW Mn3O4)
mg Mn2O3 = 3/2 x 157.9 ( 126/228.8) = 130 mg

% Mn2O3 = (130/1520) x 100 = 8.58%

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The same idea is applied for the determination of Mn in the
sample
3 Mn D Mn3O4
mmol Mn = 3 mmol Mn3O4
mg Mn / at wt Mn = 3 (mg Mn3O4/FW Mn3O4)
mg Mn = 3 at wt Mn (mg Mn3O4/FW Mn3O4)
mg Mn = 3 x 54.94 ( 126/228.8) = 90.8 mg

% Mn = (90.8/1520) x 100 = 5.97%

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What weight of sulfur (FW = 32.064) ore which should be taken so that the
weight of BaSO4 (FW = 233.40) precipitate will be equal to half of the
percentage sulfur in the sample.

Solution

S D BaSO4
mmol S = mmol BaSO4
mg S/at wt S = mg BaSO4/FW BaSO4
mg S = at wt S x ( mg BaSO4 / FW BaSO4)
mg S = 32.064 x (1/2 %S/233.40)
mg S = 0.068689 %S

%S = (mg S/mg sample) x 100

%S = 0.068689 %S/mg sample) x 100
mg sample = 0.068689 %S x 100 /%S = 6.869 mg

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A mixture containing only FeCl3 (FW = 162.2)
and AlCl3 (FW = 133.34) weighs 5.95 g. The
chlorides are converted to hydroxides and
ignited to Fe2O3 (FW = 159.7) and Al2O3 (FW =
101.96). The oxide mixture weighs 2.62 g.
Calculate the percentage Fe (at wt = 55.85)
and Al (at wt = 26.98) in the sample.
Solution
g FeCl3 + g AlCl3 = 5.95
g Fe2O3 + g Al2O3 = 2.62

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 Fe D FeCl3
1 mol Fe = 1 mol FeCl3
g Fe/at wt Fe = g FeCl3/ FW FeCl3
Rearrangement gives
g FeCl3 = g Fe (FW FeCl3/at wt Fe)
In the same manner
g AlCl3 = g Al ( FW AlCl3/at wt Al)

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g FeCl3 + g AlCl3 = 5.95
g Fe (FW FeCl3/at wt Fe) + g Al ( FW AlCl3/at wt
Al) = 5.95
assume g Fe = x, g Al = y then:
x (FW FeCl3/at wt Fe) + y ( FW AlCl3/at wt Al) =
5.95
x (162.2/55.85) + y (133.34/26.98) = 5.95
2.90 x + 4.94 y = 5.95 (1)

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The same treatment with the oxides gives
2 Fe D Fe2O3
mol Fe = 2 mol Fe2O3
g Fe/at wt Fe = 2 (g Fe2O3/FW Fe2O3)
g Fe2O3 = 1/2 g Fe (FW Fe2O3/at wt Fe)
In the same manner
g Al2O3 = 1/2 g Al (FW Al2O3/at wt Al)
g Fe2O3 + g Al2O3 = 2.62
1/2 g Fe (FW Fe2O3/at wt Fe) + 1/2 g Al (FW Al2O3/at wt Al) =
2.62
1/2 x (159.7/55.85) + 1/2 y (101.96/26.98) = 2.62
1.43 x + 1.89 y = 2.62 (2)

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2.90 x + 4.94 y = 5.95 (1)
1.43 x + 1.89 y = 2.62 (2)
from (1) and (2) we get
x = 1.07
y = 0.58
% Fe = (1.07/5.95) x 100 = 18.0%
% Al = (0.58/5.95) x 100 = 9.8%
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