Principles of Gravimetric Analysis

Asst. Prof. Jonyl L. Garcia, M.Sc., RCh.

Chemistry Department
Adamson University
Ermita, Manila

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 Gravimetric Method of Analysis
• Quantitative method in which he mass of a
pure compound (product) is used to
determine the quantity of the analyte from
the original sample.
• The oldest analytical technique, one of the
most accurate and precise macroanalytical
technique.

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 Types of Gravimetric Methods
• 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
• Example: Analysis of KCl sample by
precipitation to AgCl

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 Types of Gravimetric Methods
• Volatilization Gravimetry
– The analyte is separated from other constituents
of a sample by conversion to a gas of known
composition. The weight of the gas serves as a
measure of analyte concentration.
• Example: Determination of NaHCO3 by
decomposing the sample with strong acid to
convert the analyte into CO2(g) and water. The
gas is then weighed.
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 Types of Gravimetric Methods
• Electrogravimetry
– The analyte is separated by deposition on an
electrode by an electrical current. The mass of the
product then provides a measure of the analyte
concentration.
• Example: Analysis of Cu by electrodeposition
method

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 Types of Gravimetric Methods
• Particulate Gravimetry
– Involves the determination of a particulate
analyte’s mass following its separation from the
sample matrix

• Example: Determination of total suspended

solids by filtering a liquid sample through a
pre-weighed filtering material.

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 PRECIPITATION METHODS

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 Precipitation Gravimetry
• Analyte is converted to a sparingly soluble
precipitate by addition of a precipitating
agent.
• The precipitate is then filtered, washed free
from impurities, converted to a product of
known composition by suitable heat
treatment, and weighed.

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 General Steps in Precipitation Gravimetry

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 Properties of Precipitates and Precipitating
Agents
• Precipitating agent should react specifically or
at least selectively with the analyte
• The precipitate formed should be:
– Easily filtered and washed free from contaminants
– Of sufficiently low solubility that no significant loss
of the analyte occurs during filtration and washing
– Unreactive with constituents of the atmosphere
– Of known composition after it is dried or, if
necessary, ignited.
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 Types of Precipitates
• Curdy precipitate / Coagulated
Suspensoids
– Made up of fine particles that have
not grown together to form an
extensive lattice structure
• Gelatinous precipitate /
Coagulated Emulsoids
– Much larger in number and much
smaller dimension than those of
crystalline precipitate where a
large quantity of water is adsorbed
• Crystalline precipitates
– Regularly shaped discrete particles

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 Types of Precipitates
• Curdy precipitate / Coagulated
Suspensoids
– Made up of fine particles that have
not grown together to form an
extensive lattice structure
• Gelatinous precipitate /
Coagulated Emulsoids
– Much larger in number and much
smaller dimension than those of
crystalline precipitate where a
large quantity of water is adsorbed
• Crystalline precipitates
– Regularly shaped discrete particles

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 Types of Precipitates
• Curdy precipitate / Coagulated
Suspensoids
– Made up of fine particles that have
not grown together to form an
extensive lattice structure
• Gelatinous precipitate /
Coagulated Emulsoids
– Much larger in number and much
smaller dimension than those of
crystalline precipitate where a
large quantity of water is adsorbed
• Crystalline precipitates
– Regularly shaped discrete particles

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 Particle Size and Filterability of Precipitates

• Large particles as precipitates

– Generally desirable
– Easy to filter and wash free of impurities
– Purer than particles of finer size

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 Particle Size and Filterability of Precipitates

• Crystalline suspension
– Particles with sizes of at least 10-4 cm
– Tends to settle spontaneously and are easily
filtered
• Colloidal suspension
– Less than 10-4 cm particle size (10-4 to 10-7 cm)
– No tendency to settle
– Due to electric double-layer effect

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 Mechanism of Precipitate Formation
• Nucleation
– A process in which a minimum number of atoms, ions,
or molecules join together to give a stable solid
• Particle Growth
• Competition between nucleation and particle
growth
– If nucleation predominates  large number of fine
particles
– If particle growth predominates  smaller number of
larger particles predominate
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 Particle Size
• If rate of nucleation < rate of particle growth
= then fewer particles are finally produced
which are relatively larger and purer
• If rate of nucleation > rate of particle growth
= then many fine particles are produced

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 Factors that affect particle size
• Precipitate solubility R.S.  colloidal
• Temperature
• Reactant concentrations R.S.  crystalline
• Rate of mixing
• Reaction pH

Von Weimarn Equation

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 Experimental Control of Particle Size

• Aims to lower the relative supersaturation

– Elevated temperature (increases S)
– Precipitation from dilute solutions (minimize Q)
– Slow addition of precipitating agent with good
stirring (minimizes Q at any given instant)
– Control of pH

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Precipitation from Homogeneous Solution

• A process in which a precipitate is formed by

slow generation of precipitating agent
homogeneously throughout the solution
• Decreases Q

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 Colloidal Precipitates
• Too small to be retained by ordinary filters
• Brownian motion prevents from settling down
• Can be coagulated or agglomerated to give a
filterable mass
• Can be coagulated by heating, stirring, and
adding an excess electrolyte

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 Stability of Colloids: The Electric Double layer

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 Colloidal Precipitates
• Peptization
– Is a process by which a coagulated colloid returns to
its dispersed state
• Digestion
– Is a process in which a precipitate is heated for an
hour or more in the solution from which it was
formed  mother liquor
– Results in the removal of weakly bound water
molecules from the precipitate; improves filterability

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 Colloidal Precipitates
• Aging
– Allow impurities to be removed (equilibrium
process)
– Allow precipitate to come into contact with
supernatant liquid for some time

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 Sources of Contamination
• Coprecipitation – is a process in which
normally soluble compounds are carried out
of a solution by a precipitate

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 Types of Coprecipitation
• Surface Adsorption
– Major source of contamination for coagulated
colloids
– Significant contamination of precipitates with
large surface areas
– Carries down an otherwise soluble compound as a
surface contaminant

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 Types of Coprecipitation
• Mixed-crystal formation / Inclusion
– Contaminant ion replaces an ion in the lattice of a
crystal

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 Types of Coprecipitation
• Occlusion
– A compound is trapped within a pocket formed
during rapid crystal growth

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 Types of Coprecipitation
• Mechanical Entrapment
– Occurs when crystals lie close together during
growth. Several crystals grow together and in so
doing trap a portion of the solution in a tiny
pocket.

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 Postprecipitation

• Precipitation of sparingly soluble substances

after the initial precipitate has been formed,
normally occurs on the surface of the analyte
precipitate
– E.g. Mg2C2O4 postprecipitating on CaC2O4.

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 Washing and Filtration
• Washing of Precipitates
– Removal of impurities from
the precipitate
– Water is not always used
since this may lead to
peptization.
• Filtration
– Choose proper filtration
media depending on the type
of precipitate
– If paper is used  must be
ashless  will be removed
afterwards via ignition

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 Washing and Filtration
• Washing of Precipitates
– Removal of impurities from
the precipitate
– Water is not always used
since this may lead to
peptization.
• Filtration
– Choose proper filtration
media depending on the type
of precipitate
– If paper is used  must be
ashless  will be removed
afterwards via ignition

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 Drying and Ignition
• Drying
– Removes solvent and any
volatile species carried
down by the precipitate
• Ignition
– Decomposition of the
precipitate by high
temperature treatment
that causes conversion to
a more stable, weighable
form

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 VOLATILIZATION METHODS

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 Volatilization Gravimetry
• Thermal or chemical decomposition of solid
analyte
• Volatile decomposition products are collected
and weighed
• Alternate procedure  mass of residue
measured

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 Determination of Water Content
• Non-essential water
– Physically-retained water
• Adsorbed water: solids
• Sorbed water: colloidal solids
• Occluded water: liquid water entrapped in microscopic
pockets spaced irregularly throughout solid crystal

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 Determination of Water Content
• Essential water
– Water of Crystallization
• Water that is integral part of the molecular or
crystalline structure of a compound in its solid state
(e.g. BaCl2 · 2 H2O)
– Water of Constitution
• Water that is formed when a pure solid is decomposed
by heat or other chemical treatment (eg. Ca(OH)2 
CaO + H2O)

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 Determination of Other Samples

Ex. NaHCO3(aq) + H2SO4(aq) = CO2(g) + H2O(l) + NaHSO4(aq)

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 Applications of Gravimetric Analysis
• Sensitivity
– Samples having analyte concentration greater than about 1%
• Accuracy
– Relative error as low as 0.1 % - 0.2 %
• Precision
– 1-2 pptRSD
• Selectivity
– Depends on the nature of the precipitant and analyte
• Ease of Operation
– Time consuming
• Time
– 3 to 6 h
• Cost
– Small reagent and equipment cost
– High personnel cost

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 CALCULATIONS INVOLVING
GRAVIMETRIC DATA

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 Gravimetric Calculations

Mass A Moles A Moles B Mass B

Divide by Multiply by Divide by
MW A Stoichiometric MW B
ratio

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 Gravimetric Factors

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 Some Gravimetric Factors
Substance Substance GF
Weighed Sought
AgCl Cl

BaSO4 SO3

Fe2O3 Fe3O4

PbCrO4 Cr2O3

Mg2P2O7 MgO

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 Worked Problems - 1
• What mass of AgNO3 (169.99 g/mol) is
needed to convert 2.33 g of Na2CO3 (106.0
g/mol) to Ag2CO3?
• What mass of Ag2CO3 will be formed?

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 Worked Problems - 1
• What mass of AgNO3 (169.99 g/mol) is
needed to convert 2.33 g of Na2CO3 (106.0
g/mol) to Ag2CO3?
• What mass of Ag2CO3 will be formed?

7.47 g AgNO3
6.06 g Ag2CO3

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 Worked Problems - 2
• The calcium sample of a 200-mL natural water
was determined by precipitating the cation as
CaC2O4. The precipitate was filtered, washed,
and ignited in a crucible with an empty mass
of 26.6002 g. The mass f the crucible plus CaO
(56.077 g/mol) was 26.7134 g. Calculate the
concentration of Ca (40.078 g.mol) in water in
units of g per 100 mL of the water sample

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 Worked Problems - 2
• The calcium sample of a 200-mL natural water
was determined by precipitating the cation as
CaC2O4. The precipitate was filtered, washed,
and ignited in a crucible with an empty mass
of 26.6002 g. The mass f the crucible plus CaO
(56.077 g/mol) was 26.7134 g. Calculate the
concentration of Ca (40.078 g.mol) in water in
units of g per 100 mL of the water sample
0.04045 g/100 mL
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 Worked Problems - 3
• An iron ore was analyzed by dissolving a 1.1324-g
sample in concentrated HCl. The resulting solution
was diluted with water, and the iron (III) was
precipitated as the hydrous oxide Fe2O3 · xH2O by the
addition of ammonia. After filtration and washing,
the residue was ignited at high temperature to give
0.5394 g of pure Fe2O3 (159.69 g.mol). Calculate (a)
%Fe (55.547 g/mol) and (b) %%Fe3O4 (231.54 g/mol)
in the sample

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 Worked Problems - 3
• An iron ore was analyzed by dissolving a 1.1324-g
sample in concentrated HCl. The resulting solution
was diluted with water, and the iron (III) was
precipitated as the hydrous oxide Fe2O3 · xH2O by the
addition of ammonia. After filtration and washing,
the residue was ignited at high temperature to give
0.5394 g of pure Fe2O3 (159.69 g.mol). Calculate (a)
%Fe (55.547 g/mol) and (b) %%Fe3O4 (231.54 g/mol)
in the sample
33.32% Fe
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46.04% Fe3O4 64
 Worked Problems - 4
• A 0.2356 g sample containing ONLY NaCl
(58.44 g/mol) and BaCl2 (208.23 g/mol)
yielded 0.4637 g of dried AgCl (143.32 g/mol).
Calculate the % of each halogen compound in
the sample

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 Worked Problems - 4
• A 0.2356 g sample containing ONLY NaCl
(58.44 g/mol) and BaCl2 (208.23 g/mol)
yielded 0.4637 g of dried AgCl (143.32 g/mol).
Calculate the % of each halogen compound in
the sample
55.01 %NaCl
44.99 %BaCl2

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 Worked Problems - 5
• A sample containing NaCl, NaBr, & inert material
weighs 1.000 g and with excess AgNO3 gives a white
precipitate consisting of AgCl and AgBr which weighs
0.5260 g. By heating the precipitate in a current of
Cl2 gas, the AgBr (187.78 g/mol) is converted to AgCl
(143.32 g/mol) and the precipitate weighs 0.4260 g.
Find the %NaCl (58.44 g.mol) and % NaBr (102.909
g/mol) in the sample.

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 Worked Problems - 5
• A sample containing NaCl, NaBr, & inert material
weighs 1.000 g and with excess AgNO3 gives a white
precipitate consisting of AgCl and AgBr which weighs
0.5260 g. By heating the precipitate in a current of
Cl2 gas, the AgBr (187.78 g/mol) is converted to AgCl
(143.32 g/mol) and the precipitate weighs 0.4260 g.
Find the %NaCl (58.44 g.mol) and % NaBr (102.909
g/mol) in the sample.
4.219 %NaCl; 23.15 %NaBr

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 Worked Problems - 6
• 1.000 g of soil, as-received, gave a moisture
content of 14.00%. The oven-dried sample,
completely moisture-free, showed 18.00% K.
Find the percentage of K in the sample as
received.

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 Worked Problems - 6
• 1.000 g of soil, as-received, gave a moisture
content of 14.00%. The oven-dried sample,
completely moisture-free, showed 18.00% K.
Find the percentage of K in the sample as
received.

15.48%

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 Worked Problems - 8

 
A 101.3-mg sample of an organic compound known to contain Cl is
burned in pure O2 and the combustion gases collected in absorbent
tubes. The tube used to trap CO2 increases in mass by 167.6 mg, and
the tube for trapping H2O shows a 13.7-mg increase. A second
sample of 121.8 mg is treated with concentrated HNO3 producing
Cl2, which subsequently reacts with Ag+, forming 262.7 mg of AgCl.
Determine the compound’s composition, as well as its empirical
formula.
  C5H2Cl2
 
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 References
• Harris, Quantitative Chemical Analysis, 8th ed.,
2010 W.H. Freeman & Co.
• Christian, Analytical Chemistry, 6th ed., 2004
John Wiley and Sons, Inc.
• Harvey, Modern Analytical Chemistry, 2000
McGraw-Hill Inc.
• Skoog, West, Holler, & Crouch, Fundamentals of
Analytical Chemsitry, 9th ed., 2014 Brooks/Cole.

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 END

More Problem Sets to Come 

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