15.

Gravimetric Analysis
Dr. apt. Dhania Novitasari
Department of Pharmaceutical Analysis and Medicinal Chemistry

Course: Basic Pharmaceutical Chemistry

(Kimia Farmasi Dasar)
academic year 2024/2025
 Principle of Gravimetric Analysis

➢ Gravimetric analysis is one of the most accurate and precise methods of macro-quantitative analysis.
➢ In this process the analyte is selectively converted to an insoluble form.
➢ The separated precipitate is dried or ignited, possibly to another form, and is accurately weighed. From the
weight of the precipitate and a knowledge of its chemical composition, we can calculate the weight of analyte
in the desired form.
➢ Gravimetry does not require a series of standards for calculation of an unknown since calculations are based only
on atomic or molecular weights. Only a precise analytical balance is needed for measurements.
➢ Gravimetric analysis, due to its high degree of accuracy, can also be used to calibrate other instruments in lieu of
reference standards.
 Steps in Gravimetric Analysis

➢ A successful gravimetric analysis consists of a number of important operations designed to obtain a pure and
filterable precipitate suitable for weighing.
➢ One thing to note, the sample needs to be dissolved before can be proceeded into the next step as follows:
Steps in Gravimetric Analysis: 1. Preparation of the solution
❖ The first step in performing gravimetric analysis is to prepare
the solution. Some form of preliminary separation may be
necessary to eliminate interfering materials. Also, we must adjust
the solution conditions to maintain low solubility of the
precipitate and to obtain it in a form suitable for filtration.
Factors that must be considered include the volume of the
solution during precipitation, the concentration range of the
test substance, the presence and concentrations of other
constituents, the temperature, and the pH.

❖ Although preliminary separations may be required, in other

instances the precipitation step in gravimetric analysis is
sufficiently selective that other separations are not required.
❖ The pH is important because it often influences both the solubility
of the analytical precipitate and the possibility of interferences
from other substances. For example, calcium oxalate is insoluble in
basic medium, but at low pH the oxalate ion combines with the
hydrogen ions to form a weak acid and begins to dissolve.
 Steps in Gravimetric Analysis: 2. Precipitation
❖ The precipitate should first be sufficiently insoluble that the amount lost
due to solubility will be negligible. It should consist of large crystals that
can be easily filtered.
❖ All precipitates tend to carry some of the other constituents of the
solution with them. This contamination should be negligible. Keeping
the crystals large can minimize this contamination.
❖ The precipitation process involves heterogeneous equilibria and is not
instantaneous. First, supersaturation occurs, that is, the solution
phase contains more of the dissolved salt than it can carry at equilibrium.
This is a metastable condition, and the driving force will be for the
system to approach equilibrium (saturation). This is started by
nucleation. For nucleation to occur, a minimum number of particles
must come together to produce microscopic nuclei of the solid phase.
❖ Following nucleation, the initial nucleus will grow by depositing other
precipitate particles to form a crystal of a certain geometric shape. The
greater the supersaturation, the more rapid the crystal growth rate. An
increased growth rate increases the chances of imperfections in the
crystal and trapping of impurities.
Steps in Gravimetric Analysis: 2. Precipitation (cont.)

How to minimize saturation and form larger crystals:

The precipitate formation

Steps in Gravimetric Analysis: 2. Precipitation (cont.)
Steps in Gravimetric Analysis: 2. Precipitation (cont.)
 Steps in Gravimetric Analysis: 3. Digestion
❖The very small crystals with a large specific surface area have a
higher surface energy and a higher apparent solubility than large
crystals.
❖When a precipitate is allowed to stand in the presence of the mother
liquor (the solution from which it was precipitated), the large
crystals grow at the expense of the small ones. This process is called
digestion, or Ostwald ripening.
❖Small particles have greater surface energy associated with a greater
surface area and display somewhat greater solubility than larger
particles. The small particles tend to dissolve and reprecipitate on
the surfaces of the larger crystals.
❖In addition, individual particles agglomerate to effectively share a
common counterion layer, and the agglomerated particles finally
cement together by forming connecting bridges. This noticeably
decreases surface area.
❖Also, imperfections of the crystals tend to disappear, and adsorbed
or trapped impurities tend to go into solution. Digestion is usually
done at elevated temperatures to speed the process, although in
some cases it is done at room temperature. It improves both the
filterability of the precipitate and its purity.
Steps in Gravimetric Analysis: 4. Washing and 5. Filtering

➢ Coprecipitated impurities, especially those on the surface, can be removed by

washing the precipitate after filtering. The precipitate will be wet with the mother
liquor, which is also removed by washing.
➢ Many precipitates cannot be washed with pure water, because peptization (the
precipitate reverts to a colloidal state and is lost) is occurred.
➢ When you wash a precipitate, you should conduct a test to determine when the
washing is complete. This is usually done by testing the filtrate for the presence of
an ion of the precipitating reagent.
➢ After several washings with small volumes of the wash liquid, a few drops of the
filtrate are collected in a test tube for the testing. For example, if chloride ion is
determined by precipitating with silver nitrate reagent, the filtrate is tested for
silver ion by adding sodium chloride or dilute HCl.
Steps in Gravimetric Analysis: 4. Washing and 5. Filtering

The principle during washing the precipitate:

• Able to dissolve the contaminant but not the precipitate

• Able to minimize the peptization during washing.

• able to induce electrolyte changes to the wash liquid, then able to

evaporate during ignition. For example, HNO 3 or NH4NO3 for AgCl
precipitate.

• The resulting precipitate can be filtered with ash-free filter paper, or a

glass filter.
Steps in Gravimetric Analysis: 6. Drying or Igniting

❖ If the collected precipitate is in a form suitable for weighing, it must

be heated to remove water and to remove the adsorbed electrolyte
from the wash liquid.
❖ This drying can usually be done by heating at 110 to 120◦C for 1 to 2
h. Ignition at a much higher temperature is usually required if a
precipitate must be converted to a more suitable form for weighing.
❖ For example, magnesium ammonium phosphate, MgNH 4PO4 , is
decomposed to the pyrophosphate, Mg2P2O7 , by heating at 900◦C.
Many metals that are precipitated by organic reagents (e.g., 8-
hydroxyquinoline) or by sulfide can be ignited to their oxides.
Gravimetric Analysis Calculation
Gravimetric Analysis Calculation
Gravimetric Analysis Calculation
Gravimetric Analysis Calculation
Example
Thank you!