Gravimetric

analysis
 Definition
A Gravimetric analysis is based upon the
measurement of the weight of a substance that
has a KNOWN composition & is
CHEMICALLY RELATED TO THE
ANALYTE.

• GA is a macroscopic method
• Large samples required for analysis
 Advantages of GA
Accurate and precise.

Possible sources of errors can be checked.

It is an ABSOLUTE method.

Relatively inexpensive
 Types of gravimetric method

Precipitation methods.

Volatilisation methods.

Electrogravimetry.

Thermogravimetry.
 Steps involved in gravimetric
analysis (Unit operation in GA)

1. Preparation of the solution: Dissolve

sample

2. Precipitation: Add precipitating

reagent in excess

3. Digestion: Coagulate precipitate usually

by heating
4. Filtration: Filtration-separate ppt from
mother liquor

5. Washing: Wash precipitate

6. Drying or igniting: Dry

7. Weighing: weigh to constant weight

8. Calculation
 Preparation of the solution
• First step in preparation of solution is to
eliminate interfering material by
preliminary separation.

• Then adjust the solution conditions to

maintain low solubility of the precipitate
and to obtain it in a form suitable for
filtration.
Factors that must be considered include:

The volume of the solution during precipitation

The concentration range of the test substance

The Presence & concentrations of other constituents

The temperature

The pH
• The pH is important because it often
influences both the solubility of the
analytical precipitate and the possibility of
interferences from other substances.

• E.g. calcium oxalate is insoluble in basic

medium, but at low pH the oxalate ion
combines with the hydrogen ions to form a
weak acid.
• 8-hydroxiquinoline(oxine) can be used to
precipitate a large number of elements,
but by controlling pH, we can precipitate
elements selectively.

• Aluminum ion can be precipitated at pH 4,

but the concentration of the anion form of
oxine is too low at this pH to precipitate
magnesium ion.
• A higher pH is required to shift the
ionization step to the right in order to
precipitate magnesium.

• If the pH is too high, however magnesium

hydroxide will precipitate, causing
interference.
 Precipitation
Ideal properties of precipitate:

The precipitate should be sufficiently insoluble that

the amount lost due to solubility will be negligible.

It should consist of large crystals that can be easily

filtered.

The contamination should be negligible. keeping

the crystal large can minimize this contamination.
Precipitation process:
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.
• The precipitation process involves
heterogeneous equilibria, & as is not
instantaneous.

• First step in precipitation process is

supersaturation.

• In this step the solution phase contains

more of the dissolved salt than occurs at
equilibrium.
• This is the metastable condition for the
solution & the driving force will be for the
system to approach equilibrium
(saturation). This is started by nucleation.

• In nucleation stage a minimum number of

particles come together to produce
microscopic nuclei of the solid phase.

• The higher the degree of supersaturation,

the greater the rate of nucleation.
• The formation of a greater number of
nuclei per unit time produce more total
crystals of smaller size.

• The increased growth rate of crystals

increases the chances of imperfections in
the crystal and trapping of impurities.
• The particle size of precipitates is
inversely proportional to the relative
supersaturation of the solution during the
precipitation process.
• According to Von-Weimarn, relative
supersaturation plays an important part in
determination of particle size of
precipitate.

Q-S
(Von Weimarn ratio) Relative supersaturation =
S

• Where
Q = concentration of the mixed reagents
before precipitation occur
S = solubility of the ppts at equilibrium
• High relative supersaturation many
small crystals

• Low relative supersaturation fewer,

larger crystals

• So for better precipitation Q should be low

and S high
 For better precipitation following
modification is done
1. Precipitate from dilute solution. This keeps
Q low
2. Add dilute precipitating reagents slowly,
with effective stirring
3. Precipitation done in hot solution which
increases S
4. Precipitate at as low a pH as is possible to
maintain quantitative precipitation
• Very insoluble precipitates are best
candidates for gravimetric analysis.

• When precipitation is performed, a slight

excess of precipitating reagent is added to
decrease the solubility by mass action & to
assure complete precipitation.

• Addition of too much excess precipitating

agent increasing the chance of absorption
on the surface.
• Completeness of precipitation is checked by
waiting until the precipitate has settled & then
adding a few drops of precipitating reagent to
the clear solution above it.

• If no new precipitate forms, precipitation is

complete.
 Digestion
• When a precipitate is allowed to stand in the
presence of the mother liquor the large
crystals grow at the expense of the small
ones. This process is called digestion or
Ostwald ripening.

• The smaller particles tend to dissolve &

reprecipitate on the surfaces of the large
crystals.
• Individual particles agglomerate & finally
cement together by forming connecting
bridges.

• Digestion is usually done at elevated

temperatures to speed the process but in
some cases it is done at room temperature
also.

• Digestion improves the purity, filterability &

crystallinity of the precipitate.
• Initially the precipitates are colloidal small
particles & have a very large surface-to-mass
ratio, which promotes surface adsorption.

• The adsorption creates a primary layer that is

strongly adsorbed & is an integral part of the
crystal.

• It will attract ions of the opposite charge in a

counter layer or secondary layer so the
particle will have an overall neutral charge.
• The counter layer completely neutralizes the
primary layer & is close to it, so the particles
will collect together to form larger-sized
particles which will coagulate.

• Washing the particles with water increases

the extent of solvent molecules between the
layers, causing the secondary layer to be
loosely bound, & the particles revert to the
colloidal state. This process is called
Peptization.
• There are two types of colloids. Hydrophilic &
hydrophobic.

• Hydrophilic colloids have a strong affinity for

water. So the solution is viscous.

• A solution of hydrophobic colloids have a less

affinity for water & the solution is called a Sol.
 Impurities in precipitates

Precipitates tend to carry down from the

solution, other constituents that are normally
soluble, causing the precipitate to become
contaminated. This process is called
Coprecipitation.
• There are number of ways in which a foreign
material may be coprecipitated.

1.Occlusion & Inclusion:

In occlusion the material i.e. not part of
the crystal structure is trapped within a
crystal.
e.g. water trapped in AgNO3 crystals are
formed, & this can be driven off by
melting.
• Inclusion occurs when ions, generally of similar
size & charge, are trapped within the crystal lattice.

• Occluded or included impurities are difficult to

remove.

• Digestion may help some but is not completely

effective.

• Purification by dissolving & reprecipitating may be

helpful.
2. Surface adsorption:
This is the most common form of contamination.

e.g. in case of precipitation of BaSO4 barium will

be present in excess form primary layer the
counter ion will be a foreign anion say a nitrate
anion so the net effect then is an adsorbed layer of
barium nitrate.

these adsorbed layers can be removed by washing

or they can be replaced by ions that are readily
volatilized.
3. Isomorphous Replacement:
The two compounds are said to be
isomorphous if they have the same type of
formula and crystallize in similar geometric
forms.

when lattice dimensions of two compounds

are same, one ion can replace another in a
crystal, resulting in a mixed crystal. This
process is called isomorphous
replacement.
• E.g. in precipitation of Mg2+ as magnesium
ammonium phosphate, K+ has nearly the
same ionic size as NH4+ & can replace it to
form magnesium potassium phosphate.

• This type of impurities is difficult to remove.

4. Postprecipitation:

When the precipitate is allowed to stand in

contact with the mother liquor, a second
substance will slowly form a precipitate
with the precipitating reagent. This is
called postprecipitation.

it is a slow equilibrium process.

5. Washing & filtering the Precipitates

Coprecipitated impurities, especially those on the

surface can be removed by washing the
precipitate after filtering.

The precipitates will be wet with the mother

liquor, which is also removed by washing.
Many precipitates cannot be washed with pure
water, because peptization occurs.

This can be prevented by adding an electrolyte to the

wash liquid, e.g. HNO3 or NH4NO3 for AgCl
precipitate.

The electrolyte must be one that is volatile at the

temperature to be used for drying or ignition & it
must not dissolve the precipitate.
 Drying or Igniting the precipitate

If the collected precipitate is in a form suitable for

weighting, it must be heated to remove water & to
remove the adsorbed electrolyte from the wash
liquid.

This drying can usually be done by heating at 110

to 120 °C for 1 to 2 hr.
Ignition at a much higher temperature is usually
required if a precipitate must be converted to a more
suitable form for weighing.

e.g. Magnesium ammonium phosphate is

decomposed to the pyrophosphate by heating at 900
°C.

Hydrous ferric oxide is ignited to the anhydrous

ferric oxide.

Many metals that are precipitated by organic

reagents or by sulfide can be ignited to their oxides.
 Gravimetric Calculations

The precipitate we weight is usually in a different

form than the analyte whose weight we wish to
report.

So for that gravimetric factor (GF) is used which

represents the weight of analyte per unit weight of
precipitate.

It is obtained from the ratio of the formula weight

of the analyte to that of the precipitate, multiplied
by the moles of analyte per mole of precipitate
obtained from each mole of analyte, i.e.
 f wt analyte (g/mol)
GF = X a/b (mol analyte/mol precipitate)
f wt precipitate (g/mol)

= g analyte/ g precipitate
In gravimetric analysis, we are generally interested
in the percent composition by weight of the analyte
in the sample, i.e.
wt of analyte(g)
% Analyte = X 100 %
wt of sample (g)

Wt of Analyte = wt. of precipitate (g) X GF (g sought/g precipitate)

Factors affecting Gravimetric analysis

Solubility:

The precipitate must be so insoluble that no appreciable loss

occurs when it is collected by filtration.

Physical Nature:

The physical nature of the precipitate must be such that it

can be readily separated from the solution by filtration and
can be washed free of soluble impurities.
Chemical Composition:

The precipitate must be convertible into a pure

substance of definite chemical composition.

Temperature:

Precipitates are more readily coagulated and

hence more easily filtered if the solution is hot
and dilute.
Time:

Time is very important for the following two

reasons—

A suitable length of time elapses between the

addition of the precipitant and the removal of
the precipitant.

A time lapse also allows the precipitate to

assume a form suitable for easy filtration.
pH:
There are three main reasons for adjusting the pH
of a solution prior to a gravimetric analysis:

To ensure maximum precipitation.

To prevent precipitation of undesirable

compounds.

To influence the physical state of the

precipitate and to render it more amenable to
filtration.
 Purity, Composition, and Stability of the
Precipitation:

• Coprecipitation should be avoided.

– Causes
– General procedures to minimize coprecipitation.

• Final residue must be of known composition.

• Should be sufficiently stable.

• Hygroscopic or thermolabile residues are undesirable.

• Inorganic & organic precipitates:

The vast majority of gravimetric precipitations are carried

out using a range of organic reagents.

Although some very well-established determinations, such

as barium (as sulphate) & lead (as chromate) do involve the
use of inorganic reagents.

However, organic reagents not only have the expected

advantage of producing compounds which are sparingly
soluble & usually colored, but also have high relative
molecular masses which will yield a corresponding large
amount of precipitate from a small amount of available ions
being measured.
• The ideal organic precipitant should be specific in
character, i.e. it should give a precipitate with only
one particular ion.

• But rarely has this ideal been attained it is more

usual to find that the organic reagent will react with
a group of ions, but frequently by a rigorous control
of the experimental conditions it is possible to
precipitate only one of the ions of the group.
• Sometimes the precipitated compound may be
weighed after drying at a suitable temperature in
other cases the composition is not quite definite &
the substance is converted by ignition to the oxide
of the metal.

• In a few instances, a titrimetric method is employed

which utilizes the quantitatively precipitated
organic complex.
• Organic precipitating agents have the advantages of
giving precipitates with very low solubility in water
& a favourable gravimetric factor.

• Most of them are chelating agents that form slightly

soluble, uncharged chelates with the metal ions.

• A chelating agent is a type of complexing agent

that has two or more groups capable of complexing
with a metal ion.
• The complex formed is called a chelate.
Applications
Assay of Nickel by Dimethylglyoximate (DMG)

Equation: Ni2+ + 2H2DMG = Ni(HDMG)2 + 2H+

Characteristic bright red ppt

1. DMG insoluble in water so added as 1% solution
in 90% ethanol.
2. Take analyte (nickel) and make acidic solution.
3. Reagent of DMG added to hot acidic solution of
nickel salt
4. Only slight excess of reagent should be used
5. PPT washed with cold water, dried at 110-120 0C
 Assay of Aluminium by Oxine (8-hydroxyquinoline)

• Separates Al from beryllium & other earth

metals
• 2 or 5 % solution of Oxime in 2M Ethanoic
acid
• 1 ml sol can ppt 3 mg of aluminium
Procedure
1. Dissolve 0.4 g of Al ammonium sulphate in 100
ml of water
2. Heat to 70 – 80 0C
3. Add appropriate volume of oxine reagent
4. Keep adding reagent to ensure complete ppt
5. Allow to cool, collect Al-oxinate
6. Wash with water, dry to constant weight at 110
0C
Assay of Barium as Barium sulphate