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Gravimetry/gravimetric.html

Gravimetric Analysis
General Principles
In gravimetric analysis measures the mass of a material formed in the reaction of the
analyte with the reagent. A chemical reaction for gravimetric analysis is

where a moles of analyte A contained in the sample reacts with r moles of the reagent
R to form the precipitate AaRr, noted as solid phase (s) in the reaction. Since one
does not know the concentration of the analyte before hand, an excess of reagent is
used. In electrogravimtery, the reagent is the electron, which is added to the solution
bay passage of electrical current at a potential appropriate for oxidation or reduction
of the analyte.
There are several factors to keep in mind when designing the chemistry:
1. There must be a phase change so that the product can be separated from the
reaction solution. This is satisfied when the product is a solid precipitated from
solution.
2. The reaction must be significantly complete. This is satisfied when the Ksp of
the product is small. It also means that there are no competing equilibria that
might re-dissolve the product.
3. The final product must be pure and must be of a definite chemical composition.
4. The rate of reaction must be fast enough to be practical.
The reaction is generally carried out in a flask containing (liquid-phase) dissolved
sample. The reagent solution is added to the reaction flask until the reaction
apparently stops. This is detected by noting that there is no longer any precipitate
formed upon adding reagent.

Separation
When the reaction is complete, we are left with precipitate containing all, or most of
the analyte that was initially in our solution. This precipitate product is subsequently
from the reaction solution using filtration. This is done using one of the several
techniques discussed in class. Repetitive rinsing of the reaction flask with an
electrolyte solution insures quantitative transfer of the precipitate to the filter paper or
crucible. The filtrate must also be pure. To insure purity, the filtrate is rinsed with an
appropriate electrolyte solution.
An electrolyte solution is used to avoid breaking up the colloids that may be glued
together with counter ions (peptization). The electrolyte ions replace ions from the
reagent or that might have been present in the analyte solution. The electrolyte should
be volatile and the ions of the electrolyte should not be part of the product complex.
For example, use of ammonium nitrate (NH4NO3) or ammonium hydroxide
(NH4OH) in distilled water results in the volatile species; NH3, HNO3, and H2O.

Digestion
The precipitate often contains ions that where trapped when the precipitate was
formed. This is mostly a problem for crystalline precipitates. If the trapped ions are
not volatile, then their presence will corrupt the weighing step. Concentration of
interfering species may be reduced by digestion.
Digestion is a process where the precipitate is re-dissolved and precipitated out of a
cleaner environment (solution). The precipitate obtained in the separation step is
placed into a volatile electrolyte solution and heated. Large particles are broken up to
speed up digestion. This "solution" is often heated to increase the kinetic rates of
dissolution and precipitation. Since the solid is in dynamic equilibrium with the
solution, in time, all material will cycle from solid to solution and back. Observation
does not speed up the chemical kinetics, so we take a cola break during digestion.
The solution is cooled after digesting for an hour or more. The precipitate is now
refiltered.

Preparation for Weighing

After separation, the material must be prepared for weighing. This is accomplished
by heating up the precipitate to drive off excess solvent and volatile electrolytes. Low
temperature drying may be used for some lyophobic (solvent phobic) precipitates.
High temperature drying, called ignition, is used for the lyophilic (solvent liking)
precipitates. The thing to remember is that drying or ignition may change the
chemical composition of the precipitate.

Weighing
The dried or ignited is solid cooled prior to weighing. This avoids convection
currents from altering the mass measurement. The hot sample is placed into a
desiccator during the cooling stage to reduce adsorption of water from the air. Since
weighing is performed in a vessel, e.g, a weighing bottle or a crucible, the dry weight
of the vessel must be determined before hand. The solid weight is determined by
difference.

More Rules for a Successful Gravimetric Analysis

A few additional rules of thumb for a successful quantitative precipitation are:
• The precipitate must be large enough to settle out of solution
• The precipitate must be large enough to be filtered
 • The precipitation process must be complete
• The precipitate must be pure
• The precipitate must be stable when dry, or produce a stable product upon
ignition

Example of a Gravimetric Analysis

A 0.5962 g sample of iron ore is dissolved in perchloric acid (HClO4). All iron
present is oxidized to Fe3+. The solution is filtered to remove solid matrix materials
and made basic with addition of ammonium hydroxide. The iron precipitates as the
Fe(OH)3 .xH2O gel. The precipitate is collected in a cistern crucible and ignited to
produce Fe2O3. What is the wt. % of iron in the sample if the analysis produced
0.3210 g Fe2O3?
First, examine the chemistry
The overall reaction is

From this we derive the gravimetric factor relating weight of final material to the
weight of iron analyte

Second, calculate the mass of iron

The mass of iron in the ignited precipitate is

Last, calculate weight %

The weight % of iron in the ore is obtained from the mass of iron and the sample
weight,

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This page was created by Professor Stephen Bialkowski, Utah State University.
Last Updated Tuesday, August 03, 2004