Gravimetric methods of analysis (15 – 19

Jul 2022)
At the completion of this chapter a student should be able to
know:
❖ The concept of using precipitation reactions for gravimetric
analysis.
❖ What do the terms: surface potential charge, primary
adsorption layer, counter-ion layer, and zeta potential?
❖ How to collect and dry samples?
❖ How to use dimethyglyoxime (DMG) gravimetric approach to
calculate nickel content of an aqueous sample?
❖ What is meant by solubility product and how this can be used
to predict the formation of a precipitate?
❖ What is meant by the relative super saturation of a solution
and how to calculate it?
❖ What is meant by a chelating agent and how these are used
in gravimetric analysis to form co-ordination compounds?
 Gravimetric analysis

Gravimetric analysis is the quantitative determination of

analyte concentration through a process of precipitation of the
analyte, isolation of the precipitate, and weighing the isolated
product.
Uses of gravimetric analysis…
➢ Chemical analysis of ores
and industrial materials

➢ Elemental analysis of
inorganic compounds
 Gravimetric analysis

Gravimetric methods of analysis are based on determining the

mass of a pure compound to which the analyte is chemically
related.
Types of gravimetric methods:
➢ Precipitation methods
➢ Volatilization methods
➢ Electroanalytical
➢ Miscellaneous
 Gravimetric analysis

Gravimetric analysis used for:

➢ To determine the percentage of an amount of an element
➢ To determine the concentration of elements (e.g. Cl in
H2O).
Advantages:
➢ If followed carefully can give precise measurements
➢ Used to determine the atomic masses of many elements
➢ Does not require a series of standards
 Gravimetric analysis

Disadvantages:
➢ Provides analysis of single element/limited group of
elements
➢ Compared to current or new methods, method is very slow
➢ New Methods allow for simultaneous determination of
elements e.g., Chromatography, spectroscopic techniques
 Gravimetric analysis

Precipitation method:
Analyte is converted into sparingly soluble precipitate.
Precipitate is then filtered, washed free of impurities, and
converted to a product of known composition by suitable heat
treatment, and the product is weighed.
Precipitation: creation of a solid from a solution
 Gravimetric analysis

• When reaction occurs in a solution, the solid formed is a

“precipitate”
• The chemical that causes the solid to form is a “precipitant”

• Formation of a precipitate can also indicate the occurance of

a chemical reaction
Gravimetric analysis

Volatilization methods
The analyte or its decomposition products are volatilized at a
suitable temperature. The volatile product (or gas) is then
collected and weighed.
 Gravimetric analysis

Steps:
1. A weighed sample is dissolved.
2. An excess of a precipitating agent is added to this solution.
3. The resulting precipitate is filtered, dried (or ignited) and
weighed.
4. From the mass and known composition of the precipitate,
the amount of the original ion can be determined.
Gravimetric analysis

Precipitation
dissolved
components
Dissolve sample
sample
Add ppt’ing reagent
Filter
Dry precipitating agent

Weigh
 Gravimetric analysis

Properties of precipitates and precipitating agents

Ideally, a gravimetric precipitating agent should react
specifically or at least selectively with the analyte.

Specific reagents: are rare and react only with a single

chemical species.
Dimethylglyoxime is a specific reagent that precipitates only Ni2+
from alkaline solutions.

Selective reagents: are more common and react with a limited

number of species. AgNO3 is a selective reagent that precipitates
Cl-, Br-, I-, and SCN- from acidic solutions.
 Gravimetric analysis

In addition to specificity and selectivity, the ideal precipitating

reagent would react with the analyte to give a product that is:

➢ easily filtered and washed free of contaminants;

➢ of sufficiently low solubility so that no significant loss of the
analyte occurs during filtration and washing;
➢ unreactive with constituents in the atmosphere;
➢ of known chemical composition after it is dried or ignited.
 Gravimetric analysis

Mechanism of precipitate formation

Two ways in which precipitates form: Nucleation and particle

growth
➢ Nucleation: a process in which a minimum number of atoms, ions, or
molecules join together to form a stable solid.
➢ Often, these nuclei form on the surface of suspended solid
contaminants, such as dust particles.

➢ Particle growth: The particle grows with the addition of ions of the
precipitate until the system comes to equilibrium.
➢ Additional precipitation involves a competition between additional
nucleation and growth on existing nuclei.
 Gravimetric analysis
Mechanism of precipitation continued

➢If nucleation predominates, a precipitate containing a larger

number of very fine particles results.
➢ If particle growth predominates, a smaller number of larger
particles is produced.

Induction period
The time before nucleation occurs after the addition of the
precipitating agent to the solution (milliseconds to several
minutes).
 Gravimetric analysis

Particle size and filterability of precipitates

❖ Precipitates consisting of large particles are generally

desirable for gravimetric work because these particles are easy
to filter and wash free of impurities.

❖ Precipitates of this type are usually purer than precipitates

that are made up of fine particles.
 Mechanism of precipitation

Adsorption is a process in which a substance (gas, liquid, or

solid) is held on the surface of a solid.

Absorption involves retention of a substance within the

pores of a solid.

➢ The adsorption of ions on an ionic solid originates from the

normal bonding forces that are responsible for crystal growth.
 Mechanism of precipitation

For example: Silver nitrate (AgNO3) is added very slowly to

an acidic solution containing chloride (Cl−). Silver chloride
nuclei form with a surface layer of ions.

➢ The charge on a colloidal particle formed in a

gravimetric analysis is determined by the charge of the
lattice ion that is in excess when the precipitation is
complete.
Adsorption and Particle size

You should know that adsorption is a major problem in

gravimetry in case of colloidal precipitate since a
precipitate tends to adsorb its own ions present in
excess, forming what is called a primary ion layer which
attracts ions from solution forming a secondary or a
counter ion layer. Individual particles repel each other
keeping the colloidal properties of the precipitate.
Particle coagulation can be forced by either digestion or
addition of a high concentration of a diverse ions strong
electrolytic solution in order to shield the charges on
colloidal particles and force agglomeration.
Representation of silver chloride colloidal particle
and adsorptive layers when Cl- is in excess.
Mechanism of precipitation
Ideal Analytical Precipitation

➢ In an ideal world, an analytical precipitate for gravimetric

analysis should consist of perfect crystals large enough to be
easily washed and filtered.
➢ The perfect crystal would be free from impurities and be
large enough so that it presented a minimum surface area onto
which foreign ions could be adsorbed.
➢The precipitate should also be "insoluble" (i.e., low solubility
such that loses from dissolution would be minimal).
Particle size and filterability of precipitates

➢ Precipitates consisting of large particles are generally

desirable for gravimetric work because these particles are easy
to filter and wash free of impurities.

➢ Precipitates of this type are usually purer than precipitates that

are made up of fine particles.

Factors that determine the particle size of precipitates

The particle size of solids formed by precipitation varies
enormously.
Colloidal suspensions Crystalline suspension
(tiny particles) (large particles)
 Particle size and filterability of precipitates

Particle size of precipitates is influenced by

o Precipitate solubility
o Temperature
o Reactant concentrations
o Rate at which reactants are mixed

The net effect of these experimental variables can be accounted for, at

least qualitatively, by assuming that the particle size is related to a single
property of the system called the relative supersaturation.
A supersaturated solution is an unstable solution that contains a higher
solute concentration than a saturated solution. Supersaturation is relieved
by precipitation of the excess solute with time.
 Conditions for analytical precipitation

Von Weimarn: Particle size of precipitates is inversely

proportional to the relative supersaturation of the solution
during precipitation.
Q−S
Relative supersaturation = S

Q is the concentration of the solute at any instant and S is its

equilibrium solubility.
Conditions for analytical precipitation

When Q − S is large, the precipitate tends to be colloidal.

S

When Q − S is small, a crystalline solid is more likely.

S

To increase the particle size of precipitates, Q should be low

and S should be relatively large.
 Conditions that improve particle size of precipitates

Experimental variable that minimize super saturation and thus

produce crystalline precipitates include:
➢ Precipitation from hot solution
The solubility (S) increases with an increase in temperature.

An increase in S decreases the supersaturation and increases

the size of the particle. (Most substances are more soluble in
warm solution than in cold solution.)
➢ Precipitation from dilute solution

This keeps the concentration of the mixed reagents (Q) low.

 Conditions that improve particle size of precipitates

➢ Slow addition of precipitating reagent with vigorous stirring

keeps Q low. Uniform stirring prevents high local concentrations
of the precipitating agent.

➢ Controlling the pH of solution

Precipitation at a pH near the acidic end of the pH range in

which the precipitate is quantitative.

Many precipitates are more soluble at the lower (more acidic) pH

values.
Precipitation from an acidic solution (Initially, S is kept large.
When Q is very small at the end of the precipitation, S is reduced
by neutralizing the solution.)
Conditions that improve particle size of precipitates

The rate of nucleation increases enormously with

increasing relative super saturation .

Particle growth tends to predominate at low relative

super saturation.
 Colloids/Colloidal precipitates or suspensions

❖ A colloid consists of tiny solid particles that are invisible to

the naked eye (10−7 to 10−4 cm in diameter).
❖ Individual colloidal particles are so small that they are not
retained by ordinary filters and Brownian motion prevents
their settling out of solution under the influence of gravity.

Properties of colloids
o They show no tendency to settle from solution.
o They are not easily filtered.
 Coagulation of Colloids

➢ Colloids could be converted to filterable solids by

coagulation or agglomeration.

➢ Coagulations is the process whereby particles with colloidal

dimensions are caused to form larger aggregates.
➢ Coagulation can be hastened by heating, stirring, and
adding an electrolyte to the medium.
Peptization

Peptization: a process by which a coagulated colloid returns to

its original dispersed state.

When a coagulated colloid is washed, part of the precipitate

reverts to the colloidal form because some of the electrolyte
responsible for its coagulation is leached from the internal liquid
in contact with the solid particles.

Cooling the system with an ice-water bath minimizes loss of

precipitate due to dissolution.
Peptization

Peptization is caused by washing the precipitate with pure

water that results in the removal of electrolyte responsible for its
coagulation.

Peptization is prevented by washing the precipitate with a

solution containing an electrolyte that volatilizes when the
precipitate is dried or ignited.

Washing is needed to remove impurities or minimize

contamination .
Practical Treatment of Colloidal Precipitates

Colloids are best precipitated from hot, stirred solutions

containing sufficient electrolyte to ensure coagulation.
➢ The filterability of a coagulated colloid improves if it is
allowed to stand for an hour or more in contact with the hot
solution from which it was formed.
➢ During this digestion process, weakly bound water appears
to be lost from the precipitate, which results in a denser mass
that is easier to filter.
Digestion of the precipitate

Heating the precipitate within the mother liquor for a certain

period of time to encourage densification of nuclei.
Mother liquor is the solution from which a precipitate was formed.
During digestion, small particles dissolve and larger ones grow
(Ostwald ripening). This process helps to produce larger crystals
that are more easily filtered from solution.

DT
Digestion of the precipitate

➢ The digestion period can lead to improvements in the

organization of atoms within the crystalline nuclei, such as
expulsion of foreign atoms (or other impurities).

➢ Digestion improves the purity and filterability of both colloidal

and crystalline precipitates.

➢ The improvement in filterability undoubtedly results from the

dissolution and recrystallization that occur continuously and at
enhanced rate at elevated temperatures.
Crystalline suspensions or precipitates

They are particles with dimensions on the order of tenths

of a millimeter or greater.

They tend to settle spontaneously.

They are easily filtered.

The size of individual crystalline particles and their

filterability can be controlled to a degree.
Impurities in Precipitates

Coprecipitation

❖ It is the precipitation of an unwanted species along with your

analyte of interest.
❖ Normally soluble compounds are carried out of solution by a
precipitate.
It cannot be avoided but can be minimized by careful
precipitation and a thorough washing of the precipitate.
Impurities in Precipitates

Four types of coprecipitation:

o Surface adsorption
o Mixed-crystal formation
o Occlusion
o Mechanical entrapment
Impurities in Precipitates

Surface adsorption: Unwanted material is adsorbed onto

the surface of the precipitate .

Adsorption is often the major source of contamination of

precipitates with large specific surface areas (coagulated
colloids).

The effect of adsorption on crystalline solids are usually

undetectable because of the relatively small specific surface
area of these solids.
Impurities in Precipitates

Minimizing Adsorbed Impurities on Colloids

Digestion of a precipitate reduces the relative surface area and, therefore,

the area available for adsorption of impurities. Thus, the purity of many
coagulated colloids is improved by digestion.

During digestion process, water is expelled from the solid to give a denser
mass that has a smaller specific surface area for adsorbtion.

Washing a coagulated colloid with a solution containing a volatile electrolyte

may remove impurities bound to the surface because any nonvolatile
electrolyte added earlier to cause coagulation is displaced by the volatile
species.

Reprecipitation: the filtered solid is redissolved and reprecipitated.

It is a time consuming process but effective way to minimize the effects of

adsorption.
 Impurities in Precipitates

Mixed-Crystal Formation:
A type of coprecipitation in which a contaminant
ion replaces an ion in the lattice of a crystal.

Occlusion
A type of coprecipitation in which impurities
are trapped within the growing crystal.

Mechanical Entrapment
It is coprecipitation in which a portion
of solution (impurities) is trapped in
a tiny pocket of crystals. It occurs when
crystals lie close together during growth
Impurities in Precipitates

Increasing Purity
Re-precipitation
It reduces the amount of contaminants and less adsorption
occurs.

Drying the solid

Generally, the solids are dried at ~120oC, but conditions
for drying can vary considerably.
 Impurities in Precipitates

Increasing Purity

Precipitation in the presence of electrolyte

Coulombic repulsion is diminished in the presence of electrolyte
because of a compression of the volume of the ionic atmosphere.

Digestion
Raising the temperature will increase the collision energy for
colloidal particles and overcome Coulombic repulsion, leading
to formation of larger particles (coalescence)
 Homogeneous precipitation

Homogeneous precipitation is a process in which a precipitate is formed by

slow generation of a precipitating reagent homogeneously throughout a
solution.
The relative supersaturation is kept low during the entire precipitation.
Solids formed by homogeneous precipitation are generally purer and more
easily filtered than precipitates generated by direct addition of a reagent to the
analyte solution.
Urea is used for the generation of OH− to precipitate hydrous oxides of Al & Fe
(H2N)2CO + 3H2O → CO2 + 2NH4++ 2OH-
Drying and ignition of precipitates

After filtration, a gravimetric precipitate is heated until its mass

is constant.
Heating removes the solvent and any volatile species
carried with the precipitate.

Some precipitates are ignited to decompose the solid and form

a compound of known composition (weighing form).
Gravimetric analysis

How to perform a successful gravimetric analysis

What steps are needed?

1. Samples dried, triplicate portions weighed

2. Preparation of the solution
3. Digestion
4. Precipitation
5. Filtration
6. Washing
7. Drying or igniting
8. Weighing
9. Calculation
Gravimetric analysis

Gravimetric Calculations

Need to know:
1. Weight of the sample
2. Composition of substance weighed
3. Weight of substance weighed
4. Relationship between moles of substance sought
(analyte) and moles of substance weighed
(precipitate) through balanced chemical equation(s)
Gravimetric analysis
Gravimetric Calculations
wt analyte
% Analyte = 100
wt sample
wt ppt
% Analyte =  GF 100
wt sample

fw analyte a mol analyte

GF = 
fw ppt b mol ppt

GF = Gravimetric factor
Gravimetric analysis
Example 1 (volatilization precipitation method)
The Fe in a 1.1324 g sample of iron ore is precipitated as Fe2O3 • x H2O by
the addition of aqueous NH3. The residue is ignited at high temperature to
give 0.5394 g of pure Fe2O3 (fw= 159.69 g/mol). Calculate the % Fe (fw =
55.847 g/mol) in the iron ore.
2 mol Fe = 1 mol Fe2O3 mole fraction=2 mol Fe/1 mol Fe2O3

mass Fe2O3 0.5394 g −3

mol Fe2O3 = = −1
= 3 . 378  10 mol
fw 159.69 g mol
−3 2 mol Fe
mol Fe = 3.378 10 mol Fe2O3  = 6.756 10 −3 mol Fe
1 mol Fe2O3
mass Fe = 6.756 10 −3 mol Fe  55.847 g mol −1 = 0.3773 g Fe
wt Fe 0.3773 g
% Fe =  100 = 100 = 33.32%
wt Sample 1.1324 g
Gravimetric analysis

Application of Gravimetric factor

2 mol Fe = 1 mol Fe2O3

fw Fe 2 mol Fe 55.847 2
GF =  =  = 0.6994
fw Fe2O3 1 mol Fe2O3 159 .69 1
wt Fe2O3 0.5394 g
% Fe =  GF 100 =  0.6994 100 = 33.32
wt sample 1.1324 g
Gravimetric analysis

Based on information given in the previous example,

determine the % Fe3O4 (fw = 231.53 g/mol).

3 Fe2O3 2Fe3O4 + ½ O2
3 mol Fe2O3 = 2 mol Fe3O4

wt Fe2O3
% Fe3O4 =  GF 100
wt sample
wt Fe2O3 fw Fe3O4 2 mol Fe3O4
% Fe3O4 =   100
wt sample fw Fe2O3 3 mol Fe2O3
0.5394 g 231 .53 2
% Fe3O4 =   100 = 46.04%
1.1324 g 159 .69 3
 Gravimetric analysis
Example 2: An organic compound weighing 5.714 mg produced 14.414 mg of
CO2 and 2.529 mg of H2O upon combustion. Find the weight percent of C and
H in the sample.
 Gravimetric analysis
Example 2: An organic compound weighing 5.714 mg produced 14.414 mg of
CO2 and 2.529 mg of H2O upon combustion. Find the weight percent of C and
H in the sample.

moles of C in sample = moles of CO2 produced

= 14.414 x 10-3 g CO2 = 3.275 x 10-4 mol
44.010 g/mol CO2
mass of C in sample = (3.275 x 10-4 mol C) (12.011 g/mol C) = 3.934 mg

weight percent of C = 3.934 mg C x 100 = 68.84%

5.714 mg sample
 Gravimetric analysis
Example 2: An organic compound weighing 5.714 mg produced 14.414 mg of
CO2 and 2.529 mg of H2O upon combustion. Find the weight percent of C and
H in the sample.

moles of H in sample = x moles of H2O produced

= 2 x 2.529 x10-3 g H2O = 2.808 x 10-4 mol
18.0152 g/mol H2O
mass of H in sample = 2.808 x 10-4 mol H x 1.0079 g/mol H = 2.830 x 10-4 g

weight percent of H = 0.2830 mg H x 100 = 4.952%

5.714 mg sample
 Gravimetric analysis
Example 2: An organic compound weighing 5.714 mg produced 14.414 mg of
CO2 and 2.529 mg of H2O upon combustion. Find the weight percent of C and
H in the sample.

moles of C in sample = moles of CO2 produced

= 14.414 x 10-3 g CO2 = 3.275 x 10-4 mol
44.010 g/mol CO2
mass of C in sample = (3.275 x 10-4 mol C) (12.011 g/mol C) = 3.934 mg

weight percent of C = 3.934 mg C x 100 = 68.84%

5.714 mg sample
moles of H in sample = 2 x moles of H2O produced
= 2 x 2.529 x10-3 g H2O = 2.808 x 10-4 mol
18.0152 g/mol H2O
mass of H in sample = 2.808 x 10-4 mol H x 1.0079 g/mol H = 2.830 x 10-4 g

weight percent of H = 0.2830 mg H x 100 = 4.952%

5.714 mg sample
 Gravimetric analysis
Example 3: 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 percent of each halogen
compound in the sample.
 Gravimetric analysis
Example 3: 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 percent of each halogen
compound in the sample.

xg 1 mol AgCl
mol AgCl from NaCl = = 0.017111 x mol NaCl 
58.44 g mol −1 1 mol NaCl

mass AgCl from NaCl = 0.017111 x mol AgCl 143.32 g mol −1 = 2.4524 xg AgCl
 Gravimetric analysis
Example 3: 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 percent of each halogen
compound in the sample.

mol AgCl from BaCl2 = y g BaCl2 x 1mol BaCl2 x 2 mol AgCl

208.23 g BaCl2 1 mol BaCl2
= 9.605 x 10-3 y mol AgCl

Mass of AgCl from BaCl2 = 9.605 x 10-3 y mol AgCl x 143.32 g AgCl

= 1.3766y g AgCl
2.4524 x + 1.3766 y = 0.4637 (1)
y = 0.2356 − x ( 2)
Therefore,
2.4524 x + 1.3766 (0.2356 − x ) = 0.4637
1.0758 x = 0.13942
x = mass NaCl = 0.12960 g NaCl
0.12956 g NaCl
% NaCl =  100 = 55.01%
0.2356 g sample
% BaCl2 = 100 − 55.01 = 44.99%
Example 4: A certain barium halide exists as the hydrated salt
BaX2.2H2O, where X is the halogen. The barium content of the salt
can be determined by gravimetric methods. A sample of the halide
(0.2650 g) was dissolved in water (200 cm3) and excess sulphuric
acid added. The mixture was then heated and held at boiling for
45 minutes. The precipitate (barium sulphate, fw= 233.40) was
filtered off, washed and dried and its final mass was 0.2533 g.

Determine the identity of X.

0.2533 g −3
mol BaSO4 = −1
= 1 . 09  10 mol
233 .40 g mol
1 mol BaX 2 .2 H 2O = 1 mol BaSO4
m
mol BaX 2 .2 H 2O =
M
 mass 0.2650 g −1
fw = = = 244 .18 g mol
mol BaX 2 .2H 2 O 1.09 10 −3 mol
fw 2X = fw BaX 2 .2H 2 O − fw Ba − 2  fw H 2 O
2X = 244 .18 − 137 .34 − 2 18.02 = 70.81
−1
X = 35.41 g mol

The halide with the fw of 35.41 is chlorine, Cl

Final formula is BaCl2.2H2O