Analytical Chemistry

Chapter 6. Gravimetric Methods of Analysis

Module Name: Analytical Chemistry

Module No.: 02
Module Code: M02
Course Code: Iche2023

1
6 Principle and Types of gravimetric analysis
 Gravimetric method of analysis involves the measurement of the mass of
the analyte or some compound chemically related to it.
 The signal is mass or change in mass.
 Three types of gravimetric analysis may be distinguished:
a) Precipitation gravimetry: the substance to be determined is isolated
from the other constituents in the sample by the formation of an
insoluble precipitate.
b) Volatilization gravimetry: the substance to be determined is isolated
by distillation by taking advantages of the property of volatility.
 The product may either be collected and weighed, or the weight
loss in the sample as a result of the distillation may be measured.
a) Electrogravimetry: In this type of gravimetric method of analysis, the
analyte to be determined is deposited as a solid film on one electrode in
an electrochemical cell.
 The weight gain in the electrode as a result of the deposition is
measured. 2
Precipitation Gravimetry
 Precipitation gravimetry is the most common method for effecting
separation
 The substance to be determined is isolated from the other constituents
in the sample by the formation of an insoluble precipitate.
 There are two distinct processes involved in precipitate formation:
Nucleation and crystal growth.
 Nucleation: only when the particle has reached a certain critical size,
increasing in the size of a particle (crystal growth) become
spontaneous. This critical particle is the nucleus, and the process
leading to its formation is termed nucleation.
 Crystal growth: the process in which very small aggregates of a
precipitating solid is converted into a particle of appropriate size is
called crystal growth.
 After the desired size of a particle has been formed through crystal growth,
it is then filtered, washed free of impurities, converted to a product of
known composition, and finally weighed.
3
6.1 Steps in precipitation gravimetric analysis
 In precipitation gravimetry, first, the analyte is converted to a sparingly
soluble precipitate using precipitating agent, it is then filtered, washed
free of impurities, converted to a product of known composition by
suitable heat treatment, and weighed.

 Precipitating the analyte using a precipitating agent

 Avoiding Impurities - digesting the precipitate

 Filtering and washing the precipitate

 Drying and igniting the precipitate

 Weighing the precipitate and gravimetric calculation.

4
6.2.1 Precipitating the analyte using appropriate precipitating agent
 The desired properties of a precipitate:
 It should be of high purity (the isolated precipitate must account for
at least 99.9% of the analyte).
 It should be easily filtered and washed free of contaminants.
 It should be of sufficiently low solubility that no significant loss of the
analyte occurs during filtration and washing.
 It should be unreactive with constituents of the atmosphere.
 It should be of known chemical composition after it is dried (ignited).
 The desired properties of precipitating reagent:
 Ideally, it should react specifically or at least selectively with the
analyte.
 Specific reagents react only with a single chemical species.
 Selective reagents react with a limited number of species.
 It should produce a product that possesses all the desirable properties
of a precipitate. 5
 Some homogeneous precipitation processes
Reagent Generation Reaction Precipitati Elements
ng Agent Precipitated
Urea (NH2)2CO + 3H2O → CO2 + 2NH+ + 2OH- OH– Al. Ga, Th. Bi.
Fe, Sn
Trimethyl (CH3)3PO4 + 3H2O →3CH3OH + H3PO4 PO43– Zr. Hf
phosphate
Ethyl oxalate (C2H5)2C2O4 + 2H2O→ 2C2H5OH + H2C2O4 C2O42– Mg. Zn. Ca
Dimethyl sulfate (CH3)2SO2 + 4H2O→ 2CH3OH + SO42- + 2H3O+ SO42– Ba. Ca. Sr, Pb
Trichloroacetic Cl3CCOOH + 2OH- → CHCI3 + CO32- + H2O CO32– La. Ba. Ra
acid
Thioacetamide CH3CSNH2 + H2O → CH3CONH2 + H2S H2S Sb, Mo. Cu, Cd
Biacetyl + CH3COCOCH3 + 2H2NOH → DMG +2H2O DMG Ni
hydroxylamine
8- CH3COOQ + H2O →CH3COOH + HOQ HOQ AI, U. Mg. Zn
Acetoxyquinoline

Thioacetamide 8-Acetoxyquinoline
DMG = Dimethylglyoxime HOQ = 8-Hydroxyquinoline
6
6.2.2 Avoiding Impurities
 Since precipitation typically occurs in a solution rich in dissolved solids,
the initial precipitate is often impure.
 Any impurities present in the precipitate’s matrix must be removed
before obtaining its weight.
 The greatest source of impurities results from chemical and physical
interactions occurring at the precipitate’s surface.
 Incorporation of impurities into the precipitate may occur by
 Coprecipitation
 post-precipitation.
 The former arises during the formation of the precipitate, and the latter
after it has been formed.
 The various modes of coprecipitation include:
 Inclusions
 Occlusions
 Surface adsorbates
7
Inclusion
 Potential interfering ions whose size and charge are similar to a lattice
ion may substitute into the lattice structure by chemical adsorption:
 The only way to remove included material is through reprecipitation.
 Reprecipitation – after isolating the precipitate from the supernatant
solution, it is dissolved in a small portion of a suitable solvent at an
elevated temperature. The solution is then cooled to re-form the precipitate.
Occlusions
 Occur when physically adsorbed interfering ions become trapped
within the growing precipitate.
 Occlusions are minimized by digestion.
 Digestion - maintaining the precipitate in equilibrium with its
supernatant solution for an extended time at room or at an elevated
temperature usually at a temperature near the boiling point of the liquid.

8
Surface adsorbates
 After precipitation is complete the surface continues to attract ions
from solution which may be chemically or physically adsorbed.
 Surface adsorption is minimized by decreasing the precipitate’s
available surface area through digestion.
 During digestion larger particles of precipitate increase in size at the
expense of smaller particles. One consequence of forming fewer particles
of larger size is an overall decrease in the precipitate’s surface area.
 Surface adsorbates also may be removed by washing the precipitate.
 Another source of impurities occurs when other species in solution
precipitate under the conditions of the analysis.
 Solution conditions necessary to minimize the solubility of a desired
precipitate may lead to the formation of an additional precipitate that
interferes in the analysis.

9
6.2.3 Filtering and washing the precipitate
 After precipitation and digestion are complete, the precipitate is
separated from solution by filtration using either filter paper or a
filtering crucible.
 The most common filtering medium is cellulose-based filter paper,
which is classified according to its filtering speed, its size, and its ash
content on ignition.

Transferring the supernatant Filtering a precipitate through a

to the filter paper filtering crucible. 10
6.2.4 Drying and igniting the precipitate
 After separating the precipitate from its supernatant solution the
precipitate is dried to remove any residual traces of rinse solution and
any volatile impurities.
 A temperature of 110 °C is usually sufficient when removing water
and other easily volatilized impurities.
 Higher temperatures require the use of a muffle furnace, or a Bunsen
or Meker burner, and are necessary when the precipitate must be
thermally decomposed before weighing or when using filter paper.

Example of a muffle furnace. Example of a desiccator.

11
6.2.5 Weighing and gravimetric calculations
 Weighings carried out to nearest 0.1 mg reheating and reweighing until
constant weight is obtained; samples stored in a desiccator.
 The results of a gravimetric analysis are generally computed from two
experimental measurements:
 the mass of sample, and
 the mass of a product of known composition.
 In the second case, the relationship between mass of the precipitate and the
mass of analyte is established through gravimetric factor.
 Gravimetric factor is numerical factor that is obtained from stoichiometric
relationship between the precipitate and the analyte
 It used to convert the weight of the precipitate to the corresponding weight
of the analyte.
a(precipitate) ⇌ b(analyte)
𝑏 𝐹𝑊𝑡 𝑜𝑓 𝑎𝑛𝑎𝑙𝑦𝑡𝑒
𝐺𝑟𝑎𝑣𝑖𝑚𝑒𝑡𝑟𝑖𝑐 𝑟𝑎𝑡𝑖𝑜(𝐺𝐹) = 
𝑎 𝐹𝑊𝑡 𝑜𝑓 𝑝𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑒
where a is coefficient of the precipitate and b is coefficient of the analyte
12
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑡𝑕𝑒 𝑎𝑛𝑎𝑙𝑦𝑡𝑒 = (𝐺)(𝑚𝑎𝑠𝑠 𝑜𝑓 𝑡𝑕𝑒 𝑝𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑒
 Example 1. What is the weight of Fe2O3 (FW = 159.69 g/mol) that is obtained from
1.63 g of Fe3O4 (F.Wt. = 231.22 g/mol) gravimetrically according to the following
reaction?
2Fe3O4(aq.) + ½ O2(g) ⇋ 3Fe2O3(s)
3 𝐹𝑊𝑡 𝑜𝑓 𝐹𝑒2𝑂3
𝐺𝐹 = 
2 𝐹𝑊𝑡 𝑜𝑓 𝐹𝑒3𝑂4
3 159.70 𝑔/𝑚𝑜𝑙
𝐺𝐹 =  = 1.03
2 231.55 𝑔/𝑚𝑜𝑙
𝑚𝑎𝑠𝑠 𝑜𝑓 𝐹𝑒2𝑂3 = 𝐺𝐹 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑝𝑝𝑡 = 1.03 1.63 𝑔 = 1.68 𝑔
 Example 2. Establish chemical equivalence and determine the gravimetric factor in
an indirect analysis for the iron in a sample of iron(III) sulfate that involves
precipitation and weighing of barium sulfate.
Fe2(SO4)3(aq.) ⇋ 2Fe3+(aq.) + 3SO42–(aq.)
3Ba2+(aq.) + 3SO42– aq.) ⇋ 3BaSO4(s)
2Fe ≡ Fe2(SO4)3 ≡ 3SO42– ≡ 3BaSO4
2 𝐹𝑊𝑡 𝑜𝑓 𝐹𝑒
𝐺𝐹 = 
3 𝐹𝑊𝑡 𝑜𝑓 𝐵𝑎𝑆𝑂4
2 55.85 𝑔/𝑚𝑜𝑙
𝐺𝐹 =  = 0.16
3 233.39 𝑔/𝑚𝑜𝑙 13
 Example 3. The calcium in a 100.0 mL sample of natural water was
determined by precipitating the cation as calcium oxalate (CaC2O4). The
precipitate was filtered and washed, and finally ignited to form calcium
oxide (CaO) which is pure and easily weighable. The mass of empty crucible
was found to be 26.6002 g. The mass of the crucible plus CaO (FW = 56.077
g/mol) was 26.7134 g. Calculate the concentration of Ca (AW = 40.078
g/mol) in the water in units of grams per liter (g/L).
Solution:
The mass of CaO is 26.7134 g – 26.6002 g = 0.1132 g
The number of moles Ca in the sample is equal to the number of moles CaO.
1 𝑚𝑜𝑙 𝐶𝑎𝑂 1 𝑚𝑜𝑙 𝐶𝑎
𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝐶𝑎 = 0.1132 𝑔 𝑥 
56.077 𝑔 𝐶𝑎𝑂 1 𝑚𝑜𝑙 𝐶𝑎𝑂
𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝐶𝑎 = 2.018 𝑥 10−3 𝑚𝑜𝑙 𝐶𝑎
2.018  10−3 𝑚𝑜𝑙 𝐶𝑎 40.078 𝑔 𝑚𝑜𝑙 𝐶𝑎
𝐶𝑜𝑛𝑐. 𝑜𝑓 𝐶𝑎 𝑔 𝐿 =
0.1 𝐿
𝐶𝑜𝑛𝑐. 𝑜𝑓 𝐶𝑎 𝑔 𝐿 = 0.81 𝑔/𝐿
14
THE END OF THE COURSE

Good Luck!!

15