Fundamenta

ls of
Analytical
Chemistry
Gravimetric Analysis
 Gravimetric Analysis:
Definition

– Quantitative methods that are

based on determining the mass
of a pure compound to which the
analyte is chemically related.
 Gravimetric Analysis
Steps Commonly Observed in the Gravimetric
Analysis:

1. Preparation of a solution with the use of an acknowledged

weight of the sample analyte.

2. Separation of the preferred ion/element/radical in pure

forms by using diverse separation methods

3. After the ion has been separated, the amount of the

natural insoluble compound is formed.

4. Calculating the value of the component of interest,

primarily based on the weight of the compound observed.
 Types of Gravimetric Analysis

A. Precipitation Gravimetry
B. Volatilization Gravimetry
C. Electrogravimetry
D. Thermogravimetry
E. Gravimetric Titrimetry
F. Atomic mass spectrometry
 Types of Gravimetric Analysis

A. Precipitation Gravimetry
 Determining analyte concentration by
measuring the mass of a solid precipitate
formed during a chemical reaction.

 Example: Measuring chloride ions in water

by precipitating silver chloride (AgCl) and
weighing the resulting solid.
 Types of Gravimetric Analysis

B. Volatilization Gravimetry
 Analyzing volatile substances by
measuring mass changes when they are
converted to gases upon heating.

 Example: Determining sulfur content in a

sample by heating it to convert sulfur to
sulfur dioxide (SO2) gas and measuring
mass loss.
 Types of Gravimetric Analysis

C. Electrogravimetry
 Quantifying analyte concentration by
depositing or dissolving it on an electrode
using an electric current.

 Example: Measuring copper ion

concentration by depositing copper metal
on an electrode and measuring the mass
gain.
 Types of Gravimetric Analysis

D. Thermogravimetry
Studying a sample's composition and
thermal properties by monitoring mass
changes during controlled heating.

Example: Analyzing polymer

decomposition by heating it while
measuring mass changes.
 Types of Gravimetric Analysis

E. Gravimetric titrimetry
Determining analyte concentration
through the mass of a precipitate formed
during a titration.

Example: Measuring sulfate ion

concentration by titrating with barium
chloride to form barium sulfate precipitate
 Types of Gravimetric Analysis

F. Atomic mass spectrometry

Identifying elements and isotopes by
measuring mass-to-charge ratios of ions.

Example: Analyzing carbon isotopes to

date archaeological materials using
radiocarbon dating.
Common Procedure Involved in Gravimetric
Analysis
1. Preparation of the sample 5. Washing
2. Precipitation 6. Drying of Igniting
3. Digestion 7. Weighing
4. Filtration 8. Calculation
Advantages/Disadvantages of Gravimetric
Analysis
Advantages:
• Experimentally simple and elegant
• Accurate
• Precise (0.1 - 0.3%)

Disadvantages:
• Macroscopic technique-requires at least 10 mg pp to
collect and weigh properly
• Time-consuming
 Precipitation Gravimetry
– analyte is converted to a sparingly soluble precipitate
– precipitate is filtered, washed free of impurities, converted to
a product of known composition (by suitable heat treatment),
and weighed

Example:
Determination of calcium in water
 Precipitation Gravimetry
Properties of Precipitates and Precipitating
Reagents

Gravimetric precipitating agents should:

– react specifically or at least selectively with the analyte

SPECIFIC REAGENTS
‒ react only with a single chemical species
‒ rare
‒ E.g. Dimethylglyoxime for Nickel test in alkaline solutions

SELECTIVE REAGENTS
‒ react with a limited number of species
‒ Common
‒ E.g. AgNO3 to test halogens (Cl, Br, I)
 Precipitation Gravimetry
Properties of Precipitates and Precipitating
Reagents
Gravimetric precipitating agents should react with
analyte to give a product that is:

1. easily filtered and washed free of contaminants;

2. of sufficiently low solubility that no significant loss of
the analyte occurs during filtration and washing;
3. unreactive with constituents of the atmosphere;
4. of known chemical composition after it is dried or, if
necessary, ignited
 Precipitation Gravimetry

Particle Size and Filterability of Precipitates

‒ Precipitates with large particles are generally desirable

Factors That Determine the Particle Size of

Precipitates
 precipitate solubility
 Temperature
 reactant concentrations
 rate at which reactants are mixed
 Precipitation Gravimetry
Particle Size and Filterability of Precipitates
• This equation is known as the Von Weimarn equation in
recognition of the scientist who proposed it in 1925.
• In this equation, Q is the concentration of the solute at any
instant, and S is its equilibrium solubility.

If Q < S then solution is unsaturated

If Q = S then solution is saturated
If Q > S then solution is supersaturated
 Precipitation Gravimetry
Particle Size and Filterability of Precipitates
Mechanism of Precipitate Formation
Effect of relative supersaturation on particle size can be
explained in two ways:
Nucleation
‒ a process in which a minimum number of atoms, ions, or
molecules join together to give a stable solid
‒ predominates at high relative supersaturation
‒ Produces large number of very fine particles

Particle growth
‒ growth of existing nuclei
‒ Predominates at low relative supersaturations
‒ produces crystalline suspensions (DESIRED OUTCOME)
 Precipitation Gravimetry
Particle Size and Filterability of Precipitates
Experimental Control of Particle Size

Goal: minimize supersaturation to produce crystalline

precipitates

 Increase S (solubility of the precipitate):

‒ elevate temperatures
‒ control pH (depends on type of precipitate)

 minimize Q (concentration of the solute):

- Use dilute solutions
‒ slow addition of the precipitating agent with good stirring
 Precipitation Gravimetry
Colloidal Precipitates
‒ very small and hard to filter
‒ do not settle (Brownian motion)
‒ Can be coagulated or agglomerated to be filterable
Coagulation of Colloids
Coagulation
‒ a process of aggregation or accumulation of colloidal
particles to settle down as a precipitate
‒ increased by heating, stirring, and adding an electrolyte
 Precipitation Gravimetry
Colloidal Precipitates

Peptization of Colloids
‒ the process by which a coagulated colloid reverts to its
original dispersed state

Practical Treatment of Colloidal Precipitates

‒ colloids are best precipitated from hot, stirred solutions

containing sufficient electrolyte to ensure coagulation

 Digestion
‒ a process in which a precipitate is heated in the solution from
which it was formed (the mother liquor) and allowed to stand
in contact with the solution
 Precipitation Gravimetry
Crystalline Precipitates
Methods of Improving Particle Size and Filterability
– Can be done by digestion (without stirring)

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

Four Types of Coprecipitation

1. surface adsorption
2. mixed-crystal formation
3. Occlusion
4. mechanical entrapment
 Precipitation Gravimetry
Coprecipitation
Surface Adsorption
– common source of coprecipitation
– major source of contamination in coagulated colloids

Minimizing Adsorbed Impurities on Colloids

– by digestion and washing with a solution of volatile electrolyte

Reprecipitation
– drastic but effective way to minimize the effects of adsorption
– filtered solid is redissolved and reprecipitated
– solution containing the redissolved precipitate has a
significantly lower contaminant concentration than the
original
 Precipitation Gravimetry
Coprecipitation
Mixed-Crystal Formation
– a type of coprecipitation in which a contaminant ion replaces
an ion in the lattice of a crystal
– troublesome type of coprecipitation because little can be
done about it when certain combinations of ions are present
in a sample matrix
– occurs with both colloidal suspensions and crystalline
precipitates
Occlusion and Mechanical Entrapment
– a compound is trapped within a pocket formed during rapid
crystal growth
– confined to crystalline precipitates
Applications of Gravimetric Methods
Inorganic Precipitating Agents
Applications of Gravimetric Methods
Inorganic Precipitating Agents
Applications of Gravimetric Methods
Reducing Agents Organic Precipitating
Agents
Applications of Gravimetric Methods
Organic Precipitating Agents
8-Hydroxyquinoline (Oxine)

Magnesium complex with

8-hydroxyquinoline
Applications of Gravimetric Methods
Organic Precipitating Agents
Dimethylglyoxime
Applications of Gravimetric Methods
Organic Precipitating Agents
Sodium Tetraphenylborate
Applications of Gravimetric Methods
Organic Functional Group Analysis
Volatilization Gravimetry
 Calculation of Results from
Gravimetric Data
Problem 1

The calcium in a 200.0-mL sample of a 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 of 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 grams per 100 mL of the water.
Calculation of Results from Gravimetric Data
Problem 1: Solution
Calculation of Results from Gravimetric Data

Problem 2

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 NH3. After filtration and
washing, the residue was ignited at a high temperature to give
0.5394 g of pure Fe2O3 (159.69 g/mol). Calculate

a) the % Fe (55.847 g/mol); and

b) (b) the % Fe3O4 (231.54 g/mol) in the sample.
Calculation of Results from Gravimetric Data
Problem 2: Solution
Calculation of Results from Gravimetric Data
Problem 2: Solution Cont…
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Problem 2: Solution Cont…
Calculation of Results from Gravimetric Data
Problem 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.

Solution
Calculation of Results from Gravimetric Data
Problem 3: Solution Cont…
Calculation of Results from Gravimetric Data
Problem 3: Solution Cont…
Calculation of Results from Gravimetric Data
Problem 3: Solution Cont…
Calculation of Results from Gravimetric Data
Problem 3: Solution Cont…