Debre Berhan University

Asrat Woldeyes Health Science

Campus
Department of Pharmacy
Pharmaceutical Analysis
Group Assignment
Group-3

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 Gravimetric Analysis

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Group Members
NO NAME ID
1 Sisay Temesgen 1402385
2 Afomiya Aschalew 1402863
3 Mihret Abebe 1401807
4 Dereje Mulatie 1402614
5 Endegena Mekash 1402666
6 Muluken Kasaye 1402003
7 Tinsae Wubshet 1402545
8 Amare Tsige 1404847
9 Habtamu Addis 1401335

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Objective
Define gravimetric analysis
Understand the underlying principles of gravimetric analysis
Identify different types of gravimetric analysis
Follow and understand the basic steps in gravimetric analysis
Know the advantages and disadvantages of gravimetric analysis
Comprehend the applications of gravimetric analysis

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Outline
Introduction
Types of gravimetric analysis
Steps in gravimetric analysis
Advantages and disadvantages of gravimetric analysis
Applications of gravimetric analysis
Summary

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Introduction

• Gravimetric analysis is a method used in analytical chemistry to

determine the quantity of analyte based on its mass.
• It involves converting the analyte into a pure, stable compound of
known composition, isolating it, and measuring its mass accurately.
• The three major types of gravimetric analysis are; precipitation,
volatilization, and electro gravimetry.

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Introduction...

Principle
• The principle behind the gravimetric analysis is that the mass of an
ion in a pure compound can be determined.
• Later it can be used to find the mass percent of the same ion in a
known quantity of an impure compound.

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Introduction...

Principle.....
• The analyte is converted into a pure stable compound of known
composition.
• This compound is then isolated, usually by pricipitation, filtration,
and drying.
• The mass of the isolated compound is measured accurately.

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Introduction...

Principle.....
• From this mass, the amount of original analyte is calculated using
stoichiometric relashionships.
Not all insoluble precipitates are well suited for gravimetric
analysis.

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Types of Gravimetric Analysis

There are three fundamental types of gravimetric analysis:

Precipitation Gravimetry
Volatilization Gravimetry
Electro Gravimetry

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Types of Gravimetric Analysis

Precipitation Gravimetry
• The analyte is separated from a solution of the sample as a
priciptate and is converted to a compound of known composition
that can be weighed.
• For example, a precipitation mathod for determining calcium in
natural waters involves the addition of C2O42- as a precipitating
agent.
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Types of Gravimetric Analysis

Ca2+ (aq) + C2O42- (aq) CaC2O4 (s)

• The precipitate CaC2O4 (s) is filtered, then dried and ignited to convert
it entirely to calcium oxide.
CaC2O4 (s) CaO (s) + CO (g) + CO2 (g)

• After cooling, the precipitate is weighed, and calcium content of the

sample is computed.

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Types of Gravimetric Analysis

Volatilization Gravimetry
• The analyte is separated from the other constituents of a sample by
converting it to a gas.
• The weight of this gas then serves as a measure of the analyte
concentration.

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Types of Gravimetric Analysis

• Example, Water can be separated from most inorganic compounds by

ignition.
• The evolved water can then be absorbed on any one of several solid
desiccants.
• The weight of water evolved may be calculated from the gain in
weight of the absorbent.

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Types of Gravimetric Analysis

Electro Gravimetry
• The analyte is separated by deposition on an electrode by an
electrical current.
• The mass of this product then provides a measure of the analyte
concentration.
• Example, Determination of Pb2+ by oxidizing to PbO2 and
deposited on Pt anode (chemical converting).
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Steps in Gravimetric Analysis
Preparation of the solution
Precipitation
Digestion
Filtration
Washing
Drying or igniting
Weighing and,
Finally calculation.
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Preparation of the solution

• This may involve several steps including:

• Adjustment of the pH of the solution in order for the precipitate to
occur quantitatively and get a precipitate of desired properties.
• Adjusting the volume of the sample to suit the amount of
precipitating agent to be added.
• Removing interferences …etc.

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Precipitation

• This requires addition of a precipitating agent solution to the

sample solution.
• Upon addition of the first drops of the precipitating agent,
supersaturation occurs, then nucleation starts to occur where every
few molecules of precipitate aggregate together forming a nucleus.

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Precipitation...

• At this point, addition of extra precipitating agent will either form

new nuclei ( precipitate with small particles ) or will build up on
existing nuclei to give a precipitate with large particles.
• This can be predicted by Von Weimarn ratio where, according to
this relation the particle size is inversely proportional to a quantity
called the relative supersaturation.

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Precipitation...
Relative Supersaturation = (Q – S) / S

• Where,
• The Q is the concentration of reactants before precipitation at any point ,
• S is the solubility of precipitate in the medium from which it is being
precipitated.

• Therefore, in order to get particle growth instead of further nucleation (

i.e granular precipitate and then low surface area) we need to make the
relative supersaturation ratio as small as possible.
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Precipitation...

• In other words conditions need to be adjusted such that Q will be as low as

possible and S will be relatively large.
• The optimum conditions for precipitation which make the supersaturation
low are:
Precipitation using dilute solutions to decrease Q
Slow addition of precipitating agent to keep Q as low as possible
Stirring the solution during addition of precipitating agent to avoid concentration sites
and keep Q low
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Precipitation...

Increase solubility S by precipitation from hot solution.

Adjust the pH in order to increase S but not too much increase as we do not

want to loose precipitate by dissolution .

Precipitation from Homogeneous Solution: In order to make Q minimum we

can, in some situations, generate the precipitating agent in the precipitation

medium rather than adding it.

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Digestion of the Precipitate

• The precipitate is left hot (below boiling) for 30 min to 1 hour in

order for the particles to be digested.
• Digestion involves dissolution of small particles and reprecipitation
on larger ones resulting in particle growth and better precipitate
characteristics.
• This process is called Ostwald ripening.

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Digestion of the Precipitate...

• An important advantage of digestion is observed for colloidal

precipitates where large amounts of adsorbed ions cover the huge
area of the precipitate.
• Digestion forces the small colloidal particles to agglomerate which
decreases their surface area and thus adsorption.

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Washing and Filtering

• Problems with surface adsorption may be reduced by careful

washing of the precipitate.
• With some precipitates, peptization occurs during washing.
• Each particle of the precipitate has two layers , in primary layer
certain ions are adsorbed and in the outer layer other ions of
opposite charge are adsorbed.

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Washing and Filtering...

• This situation makes the precipitate settle down.

• If the outer layer ions are removed then all the particles will have
the same charge so the particles will be dissonant. This is called
peptization.
• This results in the loss of part of the precipitate because the
colloidal form may pass through on filtration.

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Washing and Filtering...

• In case of colloidal precipitates we should not use water as a

washing solution since peptization would occur.
• In such situations dilute volatile electrolyte such as nitric acid,
ammonium nitrate, or dilute acetic acid may be used

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Washing and Filtering...

• Usually, it is a good practice to check for the presence of

precipitating agent in the filtrate of the final washing solution.
• The presence of precipitating agent means that extra washing is
required.
• Filtration should be done in appropriate sized Goosh or ignition
ashless filter paper.

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Washing and Filtering...

• After the solution has been filtered, it should be tested to make sure
that the analyte has been completely precipitated.
• This is easily done by adding a few drops of the precipitating
reagent to the filtrate ; if a precipitate is observed, the precipitation
is incomplete.

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Drying or igniting

• The purpose of drying (heating at about 120-150 oC in an oven) is

to remove the remaining moisture.
• While the purpose of ignition in a muffle furnace at temperatures
ranging from 600-1200 oC is to get a material with exactly known
chemical structure so that the amount of analyte can be accurately
determined.

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Drying or igniting...

• The precipitate is converted to a more chemically stable form.

• For instance, calcium ion might be precipitated using oxalate ion,
to produce calcium oxalate (CaC2O4) which is hydrophil , therefore
it is better to be heated to convert it into CaCO 3 or CaO.
• The CaCO3 formula is preferred to reduce weighing errors as
mentioned in previous lectures .

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Weighing the precipitate

• The precipitate can not be weighed with the necessary accuracy in

place on the filter paper; nor can the precipitate be completely
removed from the filter paper in order to weigh it.
• The precipitate can be carefully heated in a crucible until the filter
paper has burned away; this leaves only the precipitate.
• As the name suggests, "ashless" paper is used so that the precipitate
is not contaminated with ash.

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Weighing the precipitate...
Impurities in Precipitates
• There are two types of impurities:
1) Coprecipitation: This is anything unwanted which precipitates with the
analyte during precipitation.
2) Postprecipitation: Sometimes 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 filter as soon as the
precipitation is complete and avoid digestion.

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Calculations in Gravimetric Analysis
• The results of a gravimetric analysis are generally computed from two
experimental measurements:
1) The weight of sample and
2) The weight of a known composition precipitate
• The precipitate we weigh is usually in a different form than the analyte
whose weight we wish to find.
• The principles of converting the weight of one substance to that of another
depend on using the stoichiometric mole relationships.
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Calculations ...

• The gravimetric factor(GF), which represents the weight of analyte per

unit weight of precipitate, should be introduced.
• It is obtained from the ratio of the formula weight of the analyte to that
of the precipitate, multiplied by the moles of analyte per mole of
precipitate obtained from each mole of analyte, that is,

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Calculations ...
• Example: Calculate GF for the conversions in the table.
Solution

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Calculations ...

• In gravimetric analysis, we are generally interested in the percent

composition by weight of the analyte in the sample, that is,

• We obtain the weight of analyte from the weight of the precipitate and
the corresponding weight/mole relationship
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Calculations ...

• We can write a general formula for calculating the percentage

composition of the analyte:

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 Advantages and Disadvantages of
Gravimetric Analysis
Advantages
1) Precision: When carefully followed, gravimetric analysis provides
exceedingly precise results.
2) Atomic Mass Determination: It has been used to determine the atomic
masses of many elements with high accuracy (up to six decimal place).
3) Minimal Instrumental Error: Unlike some other methods, it does not rely
on a series of standards for calculating unkown quantities.

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 Advantages and Disadvantages of
Gravimetric Analysis
Disadvantages
a) Single Element Analysis: Typically gravimetric analysis focuses on a single
element or a limited group of elements at a time.
b) Time consuming: The process can be slow due to the need for precise
measurments and through separation steps.
c) Costly: It may require specialized equipment and skilled personnel, making
it relatively expensive.

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Applications of Gravimetric Analysis

• It can be used to calibrate other instruments since it can easily provide

accurate and highly correct data.

• It helps to limit the number of instrumental errors when measuring the

mass of substances.

• It is used to measure the volume of plasma.

• The method is helpful in chloride determination in a particular mixture.

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Applications of Gravimetric Analysis...

• Quantification of Organic and Inorganic Analytes

• Determination of Total Suspended Solids in Treated Wastewater
• Determination of crude total fat in chocolate
• Determination of organic ash content of polymers
• Moisture Determination.
• Loss on Drying Test for Drug Substances

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Summary
• Gravimetric analysis is a quantitative chemical method used to determine the
amount of specific substance in a sample based on the mass of a solid compound
formed.
• The three major types of gravimetric analysis are: precipitation, volatilization, and
electro gravimetry.
• The steps required in gravimetric analysis, after the sample has been dissolved,
can be summarized as follows: preparation of the solution, precipitation,
digestion, filtration, washing, drying or igniting, weighing and finally calculation.

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References

• David G. Watson. (2016). Pharmaceutical Analysis: Text Book for

Pharmacy Students and Pharmaceutical Chemists. Elsevier.
• Ashutosh Kar. (2005). Pharmaciutical Drug Analysis. New Age
International (P) Limited.
• James W. Munson and James W. Heineman. (1984). Pharmaceutical
Analysis: Principles and Techniques. Marcel Dekker.

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