9/13/2021

Analytical Chemistry- Drug Quality control

Gravimetric Methods
of Analysis

Assoc. Prof. Hà Diệu Ly

Gravimetric analysis:

Gravimetry: Any method in which the signal is a mass

or change in mass.

a quantitative method for accurately determining the

amount of substance by selective precipitation of the
substance from an aqueous solution

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Types of Gravimetric Methods

- Precipitation gravimetry: A gravimetric method in which
the signal is the mass of a precipitate.

Types of Gravimetric Methods

-Volatilization gravimetry: A gravimetric method in

which the loss of a volatile species gives rise to the signal.

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Types of Gravimetric Methods

- Particulate gravimetry: removal from the sample

matrix by filtration or extraction.

- Electrogravimetry: deposit the analyte as a solid film

an electrode in an electrochemical cell.

Precipitation Gravimetry
 The precipitate must be of low solubility, high purity,
and of known composition.
 The precipitate must be in a form that is easy to
separate from the reaction mixture
BaCl2 + Na2SO4 = BaSO4 ↓ + 2NaCl

Precipitate formed : BaSO4, precipitate is also

isolated and heated, weighed,

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Precipitation Gravimetry
 Solubility consideration
 Controlling particle size: Larger particles are
easier to filter
 Filtering the precipitate
- The precipitate must have a low solubility
- The precipitate must be of high purity
- The precipitate requires large crystals
- The precipitate converte to a precipitat weighed

Precipitation Gravimetry

Filter paper is rated as fast (retains particles

larger than 20–25 mm), medium–fast (retains particles
larger than 16 mm), medium (retains particles larger
than 8 mm), and slow (retains particles larger than 2–3
mm)
- Avoiding impurities: by heating in a small portion of
a suitable solvent to dissolve

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Precipitation Gravimetry

Precipitate weighted
- Must be stable in the
environment
- do not absorb moisture or
decompose
- F corresponds to the balance
form as small as possible
Rinsing the precipitate

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Precipitation Gravimetry

Rinsing the precipitate

Precipitation Gravimetry

Drying the precipitate

- Placing the precipitate in a laboratory oven and heating to
a temperature of 110 oC is sufficient when removing water
and other easily volatilized impurities.
- Fritted-glass crucibles can not withstand high
temperatures and must be dried in an oven at temperatures
below 200 oC.
- The glass fiber mats used in Gooch crucibles can be
heated to a maximum temperature of approximately 500 oC

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Precipitation Gravimetry

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P.F
C (%)w / v  .100
V

Precipitation Gravimetry

Example . 0.825 g of FeCl3 solution was diluted with

water and the precipitated as Fe(OH)3 by NaOH solution.
After filtering and rinsing, the residue was ignited, giving
0.8525 g of pure Fe2O3. Calculate the %w/w Fe in the
sample.

3NaOH + FeCl3 = Fe(OH)3 ↓ + 3NaCl

2Fe(OH)3  Fe2O3 ↓ + 3H2O

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Precipitation Gravimetry


Precipitation Gravimetry

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Precipitation Gravimetry

Precipitation Gravimetry

Calculate g amount of Fe(NO3)3. H2O in sample

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Precipitation Gravimetry

Example
Cr 3+ (Cr=52) Cr2O3
BaCrO4
Compare to 2 precipitate formed and select the precipitant ?

Precipitation Gravimetry

Solution

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Precipitation Gravimetry

Volatilization Gravimetry

Thermogravimetry: A form of volatilization gravimetry

in which the change in a sample’s mass is monitored while
it is heated.

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Volatilization Gravimetry

Example
The thermogram in Figure shows the change in mass for a
sample of calcium oxalate monohydrate, CaC2O4 ⋅ H2O.
The original sample weighed 24.60 mg and was heated
from room temperature to 1000 °C at a rate of 5 °C min.
The following changes in mass and corresponding
temperature ranges were observed:
Loss of 3.03 mg from 100–250 °C
Loss of 4.72 mg from 400–500 °C
Loss of 7.41 mg from 700–850 °C
Determine the identities of the volatilization products and the
solid residue at each step of the thermal decompotion

Volatilization Gravimetry

Example

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Volatilization Gravimetry

Solution
 The loss of 3.03 mg from 100–250 °C corresponds to a
12.32% decrease in the original sample’s mass.

In terms of CaC2O4⋅ H2O, this corresponds to a loss of 18.00

g/mol

Volatilization Gravimetry
Solution
The loss of 4.72 mg from 400–500 °C represents a
19.19% decrease in the original mass of 24.60 g, or a loss
of

This loss is consistent with CO as the volatile product,

leaving a residue of CaCO3. Finally, the loss of 7.41 mg
from 700–850 °C is a 30.12% decrease in the original
mass of 24.60 g. This is equivalent to a loss of

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Volatilization Gravimetry

Equipment
- A laboratory oven or a muffle furnace,
- The weight of the sample and the solid residue are
determined using an analytical balance.
Quantitative Applications
The most frequently encountered example of a direct
volatilization gravimetric analysis is the determination
of a compound’s elemental composition.

Volatilization Gravimetry

Example

A sample of slag from a blast furnace is analyzed for

SiO2 by decomposing a 0.5003 g sample with HCl,
leaving a residue with a mass of 0.1414 g. After treating
with HF and H2SO4 and evaporating the volatile SiF4, a
residue with a mass of 0.0183 g remains. Determine the
%w/w SiO2 in the sample.

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Volatilization Gravimetry

Solution
In this procedure the difference in the residue’s mass
before and after volatilizing SiF4 gives the mass of SiO2 in
the sample. Thus the sample contained

The %w/w SiO2, therefore, is

Volatilization Gravimetry

Example: A 26.23 mg sample of MgC2O4 • H2O and

inert materials is heated to constant weight at 1200 °C,
leaving a residue weighing 20.98 mg. A sample of pure
MgC2O4 • H2O, when treated in the same fashion,
undergoes a 69.08% change in its mass. Determine the
%w/w MgC2O4 • H2O in the sample.

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Volatilization Gravimetry

SOLUTION
The change in mass when analyzing the mixture is 5.25
mg, thus the grams of MgC2O4 • H2O in the sample is

The %w/w MgC2O4 • H2O, therefore, is

Volatilization Gravimetry

Evaluating Volatilization Gravimetry

Indirect analysis:
- Sensitivity can be improved by carefully choosing the
conditions for combustion or volatilization so that the
change in mass is as large as possible
- Direct volatilization gravimetric methods: the analyte is
a gaseous product retained in an absorbent trap

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Particulate Gravimetry

- Filtration: solid particulates are separated from their

gas, liquid, or solid matrix
- Filters are constructed from a variety of materials,
including cellulose fibers pore size from 30 µm to 2–3
µm
- Glass fibers: pore size from 2.5 µm to 0.3 µm
- Membrane filters : cellulose nitrate, and
polytetrafluoroethylene (PTFE) with pore sizes from 5.0
µm to 0.1 µm.

Particulate Gravimetry

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Particulate Gravimetry

Particulate Gravimetry
- Liquid-phase or solid-phase extraction:
Poorly filterable solids if the analyte can be extracted
from its matrix with a suitable solvent

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After extraction, the solvent can be evaporated and the mass

of the extracted analyte determined

Particulate Gravimetry

Quantitative Applications
After filtering and drying the filter to constant weight at
103–105 °C.
The result of a quantitative analysis by particulate
gravimetry is just the ratio, using appropriate units, of
the amount of analyte to the amount of samp

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Particulate Gravimetry

Example

A 200.0 mL sample of water was filtered through a

preweighed glass fiber filter. After drying to constant
weight at 105 °C, the filter was found to have increased
in mass by 48.2 mg. Determine the total suspended
solids for the sample in parts per million.

Particulate Gravimetry

SOLUTION

Parts per million is the same as milligrams of analyte

per liter of solution; thus, the total suspended solids for
the sample is

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Particulate Gravimetry

Evaluating Particulate Gravimetry

Particulate gravimetric methods based on filtration are

generally less time-,labor-, and capital-intensive than
other gravimetric methods since they require only a
filtration step.

Electrogravimetry

The deposition as PbO2 at a Pt anode is one example of

electrogravimetry. The reduction of Cu 2+ to Cu at a Pt
cathode is another example of electrogravimetry.

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Summary

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The Language of Analytical Chemistry

Technique: A chemical or physical principle that can

be used to analyze a sample.
Method: A means for analyzing a sample for a
specific analyte in a specific matrix.
Procedure: Written directions outlining how to analyze a
sample
Protocol: A set of written guidelines for analyzing a
sample specified by an agency
Signal: An experimental measurement that is
proportional to the amount of analyte (S).

The Language of Analytical Chemistry

Calibration The process of ensuring that the signal

measured by a piece of equipment or an instrument
is correct

Standardization The process of establishing the

relationship between the amount of analtye and a
method’s signal.

Validation The process of verifying that a procedure

yields acceptable results.

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The Language of Analytical Chemistry

Selecting an Analytical Method

Accuracy is a measure of how closely the result of an

experiment agrees with the expected result.

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Selecting an Analytical Method

Precision An indication of the reproducibility of a

measurement or result.

Sensitivity A measure of a method’s ability to

distinguish between two samples; reported as the change in
signal per unit change in the amount of analyte (k).

Detection limit A statistical statement about the smallest

amount of analyte that can be determined with confidence
Selectivity A measure of a method’s freedom from
interferences as defined by the method

Selecting an Analytical Method

Robust: A method that can be applied to analytes

in a wide variety of matrices is considered robust.

Rugged : A method that is insensitive to changes

in experimental conditions is considered rugged.

Method blank: A sample that contains all components

of the matrix except the analyte.

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The
Importance
of Analytical
Methodology

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