Gravimetric Methods of
Analysis
Gravimetric Methods
Gravimetric methods: The quantitative methods that are based on
determining the mass of a pure compound to which the analyte is chemically
related.
Gravimetric analysis describes a set of methods used in
analytical chemistry for the quantitative determination of an analyte (the ion
being analyzed) based on its mass.
The principle of this type of analysis is that once an ion's mass has been
determined as a unique compound, that known measurement can then be
used to determine the same analyte's mass in a mixture, as long as the
relative quantities of the other constituents are known.
The four main types of this method of analysis
are precipitation, volatilization, electro-analytical method.
Precipitationgravimetry: The analyte is separated
from a solution of the sample as a precipitate and is
converted to a compound of known composition that
can be weighed.
The precipitation method is the one used for the determination of the
amount of calcium in water. Using this method, an excess of oxalic acid,
H2C2O4, is added to a measured, known volume of water. By adding a
reagent, here ammonium oxalate, the calcium will precipitate as calcium
oxalate. The proper reagent, when added to aqueous solution, will produce
highly insoluble precipitates from the positive and negative ions that would
otherwise be soluble with their counterparts
The reaction is:
Formation of calcium oxalate:
Ca2+(aq) + C2O42- → CaC2O4
The precipitate is collected, dried and ignited to high (red) heat which
converts it entirely to calcium oxide.
The reaction is pure calcium oxide formed
CaC2O4 → CaO(s) + CO(g)+ CO2(g)
The pure precipitate is cooled, then measured by weighing, and the
difference in weights before and after reveals the mass of analyte lost, in
this case calcium oxide. That number can then be used to calculate the
amount, or the percent concentration, of it in the original mix.
Volatilization gravimetry: The analyte is separated from
other constituents of a sample by converting it to a gas of
known chemical composition that can be weighed.
Volatilization gravimetry involves separating components of
our mixture by heating or chemically decomposing the
sample. The heating or chemical decomposition separates
out any volatile compounds, which results in a change in
mass that we can measure.
Electrogravimetry: The analyte is separated by deposition on an electrode
by an electrical current.
Electrogravimetry is a method used to separate and quantify ions of a
substance, usually a metal. In this process, the analyte solution is
electrolyzed.
Electrochemical reduction causes the analyte to be deposited on the
cathode.
The mass of the cathode is determined before and after the experiment,
and the difference is used to calculate the mass of analyte in the original
solution. Controlling the potential of the electrode is important to ensure
that only the metal being analyzed will be deposited on the electrode.
The process is similar to electroplating.
Calculation of Results from Gravimetric
Data
I. Given:
= 26.7134 g
= 200.0 mL
II. Unknown: Concentration of Ca = ?
III. Solution:
* mass of CaO = ?
mass of CaO = -
= 26.7134 g -
mass of CaO = 0.1132 g CaO
* amount of Ca = ?
amount of Ca = 0.1132 g CaO x x
= mol Ca or 0.0020186
* concentration of Ca = ?
concentration of Ca = mol Ca x = g Ca
= x
= /
=
Calculation of the percent by mass of analyte
in a sample
General calculation of the percent by mass of analyte in a sample:
Write the balanced chemical equation for the precipitation reaction
Calculate the moles of precipitate: moles = mass ÷ molar mass
Calculate moles of analyte from the balanced chemical equation using the mole ratio of
analyte : precipitate
(also known as the stoichiometric ratio of analyte to precipitate)
Calculate mass of analyte: mass = moles × molar mass
Calculate percent by mass of analyte in sample: (mass analyte ÷ mass sample) × 100
Sample Problem:
A 2.00 g sample of limestone was dissolved in hydrochloric acid and all the
calcium present in the sample was converted to Ca2+(aq).Excess ammonium
oxalate solution, (NH4)2C2O4(aq), was added to the solution to precipitate the
calcium ions as calcium oxalate, CaC2O4(s).
The precipitate was filtered, dried and weighed to a constant mass of 2.43 g.
Determine the percentage by mass of calcium in the limestone sample.
Answer:
1.Wite the balanced chemical equation for the precipitation reaction:
Ca2+(aq) + C2O42-(aq) → CaC2O4(s)
2.Calculate the moles of calcium oxalate precipitated.
moles(CaC2O4(s)) = mass ÷ molar mass
moles(CaC2O4(s)) = 2.43 g ÷ (40.08 + 2 x 12.01 + 4 x 16.00) g/mol
moles(CaC2O4(s)) = 2.43 g÷ 128.10 g/mol
moles(CaC2O4(s)) = 0.019 mol
3.Find the moles of Ca2+(aq).
From the balanced chemical equation, the mole ratio of Ca2+ : CaC2O4(s) is 1 : 1
So, moles(Ca2+(aq)) = moles(CaC2O4(s)) = 0.019 mol 0.019 mol CaC O x = 0.019 mol
2 4
4.Calculate the mass of calcium in grams
mass (Ca) = moles × molar mass
mass (Ca) = 0.019 mol × 40.08 g/mol= 0.76 g
5.Calculate the percentage by mass of calcium in the original sample:
%Ca = (mass Ca ÷ mass sample) × 100
%Ca = (0.76 g ÷ 2.00 g) x 100 = 38%
References:
https://en.wikipedia.org/wiki/Electrogravimetry#:~:text=Electrogravimetry%20is%20
a%20method%20used,the%20analyte%20solution%20is%20electrolyzed.&
text=Controlling%20the%20potential%20of%20the,be%20deposited%20on%20the%
20electrode
https://www.sciencedirect.com/topics/chemistry/electrogravimetry
https://www.ausetute.com.au/gravimetric.html
