THEORY OF GRAVIMETRIC ANALYSIS OF INORGANIC MIXTURES

Dr. Fabian Ifeanyi Eze, Department of Pharmaceutical and Medicinal Chemistry,

Faculty of Pharmacy, University of calabar
Course: PCH 202, Second Semester, 2022/2023

Introduction
Gravimetric analysis is the analytical method for the quantitative determination of analyte based on the
determination of the amount of solid left or the volume of gas evolved during chemical reaction. In other
words, it is a precipitation or volatilization method based on the determination of weight of a substance of
known composition that is chemically related to the analyte. The test substance is first converted into a
definite chemical compound by precipitation, ignition, solvent extraction or volatilization. Gravimetric
analysis is experimentally simple and elegant, and often gives accurate and precise results. It is, however,
a macroscopic technique and requires at least 10 mg precipitate to collect and weigh properly. It is also
time-consuming and may take many hours to accomplish.

Types of gravimetry
Gravimetry can be grouped into three types based on the kind of chemical reaction involved:
(i) Precipitation gravimetry: The analyte is separated from a solution of the sample as a precipitate and is
converted to a compound of known composition that can be weighed. It is a necessary requirement that
the ions be completely precipitated out of the solution. The calcium content of water is usually determined
by precipitating the calcium ions with oxalic acid.
(ii) Volatilization gravimetry: The analyte is separated from other constituents of a sample by converting
it to a gas of known chemical composition that can be weighed or whose volume can be measured.
Sulphides and sulphites can be determined by volatilization where the hydrogen sulphide or sulphur (IV)
oxide evolved from the sample, after treatment with an acid, is collected in a suitable absorbent. It is also
the classical method for the determination of carbon and hydrogen in organic compounds. In this case, the
combustion products (H2O and CO2) are collected selectively on weighed absorbents.
(iii) Electrogravimetry: The analyte is separated by deposition on an electrode by an electrical current.

Qualities of a good gravimetric precipitate and precipitating reagent

(i) The precipitate must have enough particle size for retaining on filter papers.
(ii) The precipitate must be stable or be converted to a stable substance.
(iii) It must be of very high purity (free of contaminants).
(iv) It must be of very low solubility such that no significant loss of the analyte occurs during filtration
and washing
(v) The stoichiometry of the reaction or the stoichimetric composition of the precipitates must be known.
(v) A gravimetric precipitating agent should react specifically or at least selectively with the analyte.
Gravimetric factor: A gravimetric factor is an algebraic expression that converts the weight of a sample
or precipitate into the weight of a single element. It is the ratio of the formula weight (FW) of the
substance being sought (analyte) to that of the substance weighed.

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Sources of weighing error
(i) Coprecipitation: a process in which normally soluble compounds are carried out of solution by a
precipitate resulting in impurities within the desired precipitates. There are four types of coprecipitation:
surface adsorption, mixed-crystal formation, occlusion, and mechanical entrapment. Adsorption is the
major source of contamination in coagulated colloids but of not significance in crystalline precipitates.
The impurity is chemically or physically adsorbed onto the surface of precipitates.
Adsorbed impurities can be minimized on colloids by (i) washing the coagulated colloid with a solution
containing a volatile electrolyte (ii) digestion, a process during which water is expelled from the solid to
give a denser mass that has a smaller specific surface area for adsorption (iii) re-precipitation, a process
during which the filtered solid is re-dissolved and re-precipitated.

(ii) Post-precipitation a process in which a precipitate standing in contact with the mother liquor becomes
contaminated by the precipitation of an impurity on top of the desired precipitate. To reduce
postprecipitation, filtration is done as soon as the precipitation is complete.

Some numerical problems

Example 1: To determine the amount of calcium in a sample of table water, an excess oxalic acid was
added to 400 ml of the water sample followed by ammonia solution. The precipitate formed was
recovered, dried and heated to a constant mass and 0.14 g of solid was left. What is the concentration of
calcium in the water sample in ppm? (Ca = 40, C=12, O = 16)

Solution

Ca2+ (aq) + H2C2O4 (aq) → CaC2O4 (s) + 2H+

CaC2O4 (s) → CaO (s) + CO (g) + CO2 (g)

From the stoichiometry, 1 mole of calcium yields 1 mole of CaC2O4, which in turn decomposes upon
heating to yield 1 mole of CaO,
I.e. 1 mole × (40 g/mol) of Ca2+ yields 1 mole × [(40 + 16) g/mole] of CaO,
If 40 g of Ca2+ yields 56 g of CaO
x g of Ca2+ yields 0.14 g of CaO.
40 ×0.14
x= = 0.1 g of Ca2+
56
If 0.1 g (100 mg) of Ca2+ is contained in 400 ml (0.4 L) of the water, then, the concentration of the Ca2+ in
ppm = 100 mg/0.4L = 250 ppm. (Note that 1 ppm = 1 mg/L or 1 mg/Kg or 1 µg/ml or 1 µg/g ).

Example 2: A sample of 1.24 g of a drug containing manganese (III) salt was heated in a solution of nitric
acid, the resulting solution made alkaline with NH4OH and then excess H2S bubbled through it. Given
that 0.29 g of manganese sulphide precipitate was obtained, calculate the percentage of manganese in the
original drug sample. (Mn =55; S = 32, H=1)

Solution

2Mn3+ (aq) + 3H2S (g) → Mn2S3 (s) + 6H+ (aq)

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From the stoichiometry, 2 moles of Mn3+ yield 1 mole of the sulphide
2 moles × (55 g/mol) of Mn3+ yields 1 mole × [(55× 2) + 32 × 3 𝑔/𝑚𝑜𝑙] of Mn2S3
I.e. 110 g of Mn3+ yields 206 g of Mn2S3
0.29 × 110
0.29 g of Mn2S3 would be yielded by = 0.155 g of Mn3+
206
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑀𝑛 3+ 0.155
Percentage of manganese = 𝑀𝑎𝑠𝑠 𝑜𝑓 𝑡𝑕𝑒 𝑑𝑟𝑢𝑔 × 100% = × 100% = 12.48 %
𝑠𝑎𝑚𝑝𝑙𝑒 1.24

Example 3: In an experiment to remove barium contaminant in a food sample, 0.5 g of the sample,
contaminated with barium chloride dihydrate, was dissolved in 200 ml of water and an excess sulphuric
acid added. The mixture was then heated, held at boiling for 45 minutes, and 0.2533 g of precipitate was
obtained. Calculate the
(a) percentage of the BaCl2. 2H2O in the food sample.
(b) percentage of barium in the food sample.
(c) concentration of barium in the food sample in ppm.
(H=1, O =16, S=32, Cl = 35.5, Ba =137)
Solution

BaCl2. 2H2O (aq) + H2SO4 (aq) → BaSO4 (s) + 2HCl (aq) + 2H2O (l)

(a) From the stoichiometry, 1 mole of barium chloride dihydrate precipitates 1 mole of barium suphate,
Mass of 1 mole of BaCl2. 2H2O =137 + (35.5 × 2) + 2(18) = 244 g
Mass of 1 mole of BaSO4 = 137 + 32 + (16× 4) = 233 g
Therefore, 244 g of BaCl2. 2H2O precipitates 233 g of BaSO4,
02533 ×244
0.2533g of BaSO4 would be precipitated by = 0.265 g of BaCl2. 2H2O
233
𝑊𝑒𝑖𝑔 𝑕𝑡 𝑜𝑓 𝑝𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑒 ×𝐺𝐹 𝑜𝑓 𝐵𝑎𝑟𝑖𝑢𝑚 ×100 %
(b) Percentage of barium in the sample = 𝑊𝑒𝑖𝑔 𝑕𝑡 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒
Gravimetric factor (GF) of an analyte = formula weight (FW) of the analyte/formula weight of precipitate.
GF of barium = FW of barium/ FW of BaSO4 = 137/244 = 0.56
0.265×0.56× 100 %
Percentage of barium = = 28.672 %
0.5
(c) Concentration of barium in ppm = wt. of Ba (in mg) / wt. of sample (in Kg)
28.672 ×1000 𝑚𝑔
= 100 = 286720 ppm
𝐾𝑔
1000
(Note that 28.672 % means 28.672 g of Ba per 100 g of sample. To convert % to ppm, simply multiply by 10,000)

Example 4: A 7.5 g sample of gastric antacid residue, composed of a mixture of sodium carbonate and
sodium bicarbonate, was heated to a constant mass and 0.56 dm3 of carbon dioxide, measured at s.t.p, was
liberated. Determine the percentage of sodium carbonate in the mixture. (Na=23, H=1, C=12, O=16,
Molar volume of gases at s.t.p =224dm3)

Solution
Note that Na2CO3 is stable to heat and only NaHCO3 decomposes to liberate carbondioxide.

2NaHCO3 → Na2CO3 + H2O + CO2

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From the stoichiometry, 2 moles of NaHCO3 liberate 1 mole of CO2.
Mass of 2 moles of NaHCO3 = 2[23+1+12+ (16×3)] =168 g; Volume of 1 mole of CO2 = 22.4dm3.
168 g of NaHCO3 liberates 22.4dm3 of CO2
0.56×168
0.56 dm3 of CO2 would be liberated by = 4.2 g of NaHCO3
22.4
But total mass of mixture (Na2CO3 + NaHCO3) =7.5 g,
Mass of Na2CO3 = (7.5 – 4.2) g = 3.3 g,
3.3×100
Percentage of Na2CO3 = =
7.5

Revision Exercises
1. What volume of 0.2 M solution of silver nitrate solution must be added to 10 ml of 0.1 M solution of a
sulphide to completely precipitate the suphide ion in form of silver sulphide? (Hint: No of mmoles =
molarity × volume; Note that for complete precipitation, at least 50 % excess precipitating reagent is
added) 2AgNO3 (aq) + S2-(aq) ↔ Ag2S (s) + 2NO3- (aq)
(A) 5 ml (B) 15 ml (C) 25 ml (D) 20 ml
2. The aluminum content of a 5 g sample of an antacid residue was determined gravimetrically by
precipitating the aluminum as Al2S3. If the weight of the precipitate formed was 0.5g , calculate the
percentage of aluminum in the antacid sample. (Al = 27, S=32). 2 Al 3+ (aq) + 3S2- (aq) ↔ Al2S3 (s)
(A) 1.8 % (B) 18 % (C) 3.6% (D) 36 %

3. In an experiment to determine the percentage purity of potassium chloride reagent, 0.4 g of an impure
KCl was dissolved in water and an excess of AgNO3 solution added producing 0.7332 g of AgCl
precipitate. What is the percentage purity of the KCl reagent? (K = 39, Ag = 108, Cl = 35.5)
(A) 65.6 % (B) 96.0 % (C) 4.8 % (D) 95.2 %

4. To establish the amount of calcium in a sample of water, excess oxalic acid was added to 500 mL of the
water sample followed by ammonia solution. The precipitate was dried and heated to a constant mass and
1.12 g of residue was left. What is the concentration of calcium in the table water? (Ca=40, C=12, O=16)
Ca2+ (aq) + C2O42- (aq) CaC2O4(s); CaC2O4 (s) CaO(s) +CO (g) +CO2(g)
(A) 0.8 g/L (B) 1.6 g/L (C) 3.2 g/L (D) 1.12 g/L

5. What mass of precipitate will be obtained when 13.4 g of aluminum chloride reacts with 11.8 g of
ammonium hydroxide? (Al=27, Cl=35.5, N=14, O=16, H=1)
AlCl3 (aq) + 3NH4OH (aq) → Al(OH)3 (s) + 3NH4Cl (aq)
(A) 8.77 g (B) 16.23 g (C) 18.04 g (D) 7.83 g

(6) A 500 ml antacid suspension was found to contain 0.25 g of magnesium. The concentration of
magnesium, in ppm, in the syrup is
(A) 0.005 ppm (B) 5000 ppm (C) 50 ppm (D) 500 ppm

(7) Which of the following units does not represent ppm?

(A) mg/dm3 (B) µg/ml (C) g/dL (D) mg/L