Chapter 5

Gravimetric Methods of
Analysis
 Principle
Solution reaction between analytes and reagents to
give sparingly soluble products; filtration, drying or
ignition of precipitates; electrolytic deposition of
metals; weighing
 Types of Gravimetric Methods

 Precipitation gravimetry - A gravimetric method in

which the signal is the mass of a precipitate
 Electrogravimetry - A gravimetric method in which
the signal is the mass of an electrodeposit on the
cathode or anode in an electrochemical cell
 Volatilization gravimetry (indirect method) – A
gravimetric method in which the loss of a volatile
species gives rise to the signal
 Particulate gravimetry (direct method) – A
gravimetric method in which the mass of a
particulate analyte is determined following its
separation from its matrix.
 Precipitation Gravimetry
 Gravimetry is among the most accurate and precise
methods of macroquantitative analysis.
 The analyte is selectively converted to an insoluble
form.
 The separated precipitate is dried or ignited,
possibly to another form, and is accurately
weighed.
 The weight of analyte in the desired form is
calculated from the weight of the precipitate and a
knowledge of its chemical composition
(stoichiometric mole relationships)
 Precipitation Gravimetry
 sample pretreatment;
 precipitation;
 filtration;
 drying and ignition;
 weighing
 Example

An ore containing magnetite, Fe3O4, was analyzed by

dissolving a 1.5419-g sample in concentrated HCl, giving
a mixture of Fe2+ and Fe3+. After adding HNO3 to oxidize
any Fe2+ to Fe3+, the resulting solution was diluted with
water and the Fe3+ precipitated as Fe(OH)3 by adding
NH3. After filtering and rinsing, the residue was ignited,
giving 0.8525 g of pure Fe2O3. Calculate the %w/w Fe3O4
in the sample.
 Practical gravimetric procedures
Stage Practical manipulations
sample pre- dissolution of sample, separation or
treatment masking of interfering ions
precipitation from hot dilute solution, careful
addition or homogeneous
generation of precipitating agent in
small excess, with stirring: digestion
filtration cooled solution filtered, precipitate
washed with dilute electrolyte
solution
drying and careful drying at 110–140°C access
ignition of air during ignition
weighing weighings carried out to nearest 0.1
mg reheating and reweighing until
constant weight is obtained;
samples stored in a desiccator
Remarks
prevents simultaneous
precipitation and reduces
inclusion of impurities
promotes particle growth
and reduces occlusion.
N.B. digestion can increase
post-precipitation
decreases solubility,
reduces adsorbed
impurities and prevents
peptization
prevents sputtering losses,
ensures complete oxidation
to a stoichiometric product
special care required for
hygroscopic solids
Precipitation Gravimetry
 Gravimetric Analysis

 Types of precipitates
• crystalline precipitate (0.2 – 0.6 g)
• colloidal precipitates (peptization, gelatinous) (0.05 –
0.3 g)
 The precipitation process (supersaturation)
 Impurities in precipitates
• isomorphic and non-isomorphic inclusion
• Occlusion
• Surface Adsorption
 Check for the completeness of precipitation
 The precipitation process
(supersaturation)
 Relative supersaturation Rs
Rs = (Q-S)/S
where Q is the actual concentration of the solute and S
is the equilibrium concentration
 Nucleation
 Particle growth: crystalline precipitate/colloidal
precipitate
(Q–S) should be controlled and kept to a minimum
 Peptization
 Digestion - The process by which a precipitate is
given time to form larger, purer particles.
 Purity of Precipitates
The major types of coprecipitation and their relation
to the precipitate type
Type of Mode of contamination Precipitate
coprecipitation type most
affected
isomorphic substitution of the precipitate crystalline
inclusion lattice with impurity ions of similar
crystallinity
non-isomorphic solid solution of the impurity crystalline
inclusion within the precipitate
occlusion physical trapping of impurities crystalline
within precipitate particles and colloidal
surface chemisorption of impurities from colloidal
adsorption the solution onto the precipitate
surface
Filtration

 Isolate precipitate
 Remove impurity
 Filtration - Filter paper
 The most common filtering medium is cellulose-based
filter paper
 Filter classified according to its filtering speed, its size,
and its ash content on ignition.
 For quantitative analytical procedures a lowash filter
paper must be used. This grade of filter paper is
pretreated by washing with a mixture of HCl and HF to
remove inorganic materials.
 Filter paper classed as quantitative has an ash content
of less than 0.010% w/w.
 Qualitative filter paper typically has a maximum ash
content of 0.06% w/w.
Calculation of result
Calculation of result
 CÁC GIAI ĐOẠN CỦA PP KẾT TỦA
TÍNH KẾT QUẢ
 MẪU Ở DẠNG RẮN
 Ví dụ 1. Định hàm lượng Si trong mẫu đất ở ví dụ trên,
với dạng cân là SiO2 = 0,1200 g:
M Si 100
%%Si
SiO 2  0,1200    17,53%
M SiO 2 0,3200
 Ví dụ 2 . Dạng cân Mg2P2O7, dạng tính Mg, MgO, MgCO3 :
2 M Mg 2 M MgO 2 M MgCO3
FMg = ; FMgO = ; FMgCO3 =
M Mg 2 P2O7 M Mg P O M Mg P O
2 2 7 2 2 7

 Ví dụ 3 . Dạng cân là Fe2O3, dạng tính là Fe, Fe3O4 :
2 M Fe 2 M Fe 3O4
FFe = ; FFe3O4 =
M Fe2O3 3 M Fe 2O3
Calculation of result
 Applications of Gravimetry
 a wide utility in chemical analysis
 best suited to the determination of major constituents in
samples because of the practical limitations in accurately
weighing quantities of less than 0.1 g.
 The analysis of rocks, ores, soils, metallurgical and other
inorganic samples for their major components has
depended very much on gravimetric methods.
 time consuming and demanding, with the result that there
is a steady trend towards the use of quicker,
instrumentally based methods (X-ray fluorescence
analysis).
 Nevertheless gravimetric methods are still very much
needed to calibrate these newer procedures.