REPORT: ELECTROGRAVIMETRY

Apoorva Pathania(22MSC10008) section 1, Group A

Chemistry Department, UIS, Chandigarh University, Mohali, Punjab
Email – apoorvapathania@gmail.com
ABSTRACT
This report provides a comprehensive overview of electrogravimetry, a precise analytical
technique widely employed for the quantitative determination of substances in various
applications. The report begins with an in-depth exploration of the theoretical underpinnings,
elucidating the fundamental principles rooted in Faraday's laws of electrolysis. The procedure
for conducting electro gravimetric analyses is meticulously outlined, covering the preparation
of electrolytes, electrode setup, electrolysis, and subsequent handling of deposited substances.
Highlight
• Historical Perspective: Provide an overview of the historical development of
electrogravimetry, starting with 1833, Michael Faraday conducted experiments
that demonstrated the fundamental principles of electrochemistry, including the
deposition of metal ions onto an electrode.
• Basic Components: Explain the fundamental components of an
electrogravimetry and the principle on which it works.
• Types of Electrogravimetry: Discuss the types of electrogravimetry, such as
constant current electrogravimetry and constant current electrogravimetry.
• Applications: Detail the wide range of practical applications of
electrogravimetry, from metal analysis to pharmaceutical uses.
Introduction
Gravimetric analysis is the quantitative estimate of a particular species by measurement of its
weight. This is usually achieved by converting the analyte into an almost insoluble compound
(precipitate reaction), which can then be weighed directly or can be convert ted into a stable
form and then weighed. Other gravimetric procedures include measurements based on loss in
weight of a sample (e.g., determination of moisture content) or gain in weight (e.g., increase in
weight due to absorption of gases). Two other types of gravimetric analyses that deserve
mention are electrogravimetry and thermogravimetry. Electro gravimetric analysis deals with
the deposition of an element electrolytically on a suitable electrode. So, we are practically
avoiding most of the filtration and co deposition. In normal gravimetry, there is always certain
amount of mechanical drudgery involved. Because, you have to precipitate, you have to make
sure that everything is settled then first you remove their clear solution, filter it, collected that
on the filter paper, burn the filter paper, make it almost ash less and you take the difference
between the weights. It is a sort of mechanical drudgery. It does not happen easily. But it has
got its own utility also. For example, if you want to determine how much of a metal is there in
an ore. There is no other reliable method unless you specifically separate the metal ion of
interest from the ores that is containing all other elements. So, it has got its own use.
But in electrogravimetry, we are avoiding the filtration. Because, we are going to deposit it on
the cathode. Electrode cannot be a general electrode; it has to be a suitable electrode. That
means, the metal ion should be capable of getting deposited and stored safely until you are
ready to weigh. In normal gravimetry there will be always certain amount of co deposition,
coagulation, co-precipitation and other metal elements deposition occurs. Like that several
other complications are essential evils associated with gravimetry. So, one has to learn a lot of
chemistry to do the gravimetric analysis. Here we are avoiding filtration, we are avoiding co-
deposition. Codeposition is the deposition of other elements under the given conditions. When
one element is being deposited at a particular voltage or current, at that same voltage any other
element can deposit only can precipitate. Such conditions are very rare in the electrogravimetry.
Therefore, essentially what we are going to do is, almost specific determination of the metals.
This is one of the greatest advantages of electrogravimetry. An electro gravimetric technique
gives you the specificity. That is very important because no other metal ion will be precipitating
under the given conditions with the same amount of voltage. For every element deposition
voltage and current are different. This is a characteristic of the element that we want to
determine.
Principle
The electro gravimetric analysis is based upon Ohm’s law and Faradays laws of electrolysis.
Ohm’s law states that, the current ‘I’ is directly proportional to the electromotive force and
inversely proportional to the resistance. So, I can write
I α E /R or
I = E/R.
A is a unit of current in amperes which will cause deposition of 1.11800 milligrams of silver
or 0.32925 milligram of copper from respective solutions of their salts in one second. That is
the definition of ampere.
Ώ is the unit of electrical resistance which is defined as the resistance caused by 14.4521 gram
of mercury contained in 106.300-centimeter-long column of 1 square centimetre’s cross-
sectional area at 0° centigrade.
V is the volt. That is the unit of electromotive force(emf). The volt is also very useful quantity.
It is the difference electrical potential required to maintain a current of 1 ampere through a
system having resistance of 1 ohm. These are only the units and we cannot see them. They are
all electromagnetic forces. So, we have to depend upon the definitions and some other alternate
measuring techniques to determine all these numbers.
The job of the current is to reduce the metal. If I can calculate how many Coulombs of currents,
I am passing through then we can know weight of the element liberated by 1 Coulomb of
electricity. That is called electrochemical equivalent of the element. That is 107.880 gram of
silver. This is a choice made by the scientists. To liberate 107.880 gram of silver, I have to pass
96493 Coulomb’s of current. It is a very simple straightforward law. That is definition of
Coulomb.
Faraday’s law of electrolysis
There are two laws. First one states that, the amount of substance liberated at the electrodes
of a cell are directly proportional to the quantity of electricity which passes through the
solution.
This is a sort of one’s observation and intuition. If I pass more current, more quantity of the
substance will be liberated. If I pass less current, less quantity of the substance will be liberated
at the cathode and the cathode weight will increase. So, it is a general observation. But, verified
scientifically since last 200 years that, this is exactly what is happening in an electrochemical
system. The amount of substance that is liberated at the electrodes of a cell is directly
proportional to the quantity of electricity. Suppose, you pass 96493 Coulomb’s, 1 gram
equivalent will be deposited. Suppose, you pass half of that, that is approximately 48246
Coulomb’s then you will be getting approximately 53.44 gram (107.880÷2) of silver. Suppose,
if you still reduce the current then you will get still less silver deposited. That is first law.
Second law states that, the amount of different substances deposited by the same quantity of
electricity are proportional to their electrochemical equivalence. That means, you do not have
to pass all the time 96493 Coulomb’s to find out how much of material is deposited. You can
calculate. But only thing is you should know the atomic weight of the substance. Because, 1
gram equivalent of the substance is nothing but the atomic weight of any element. There are
certain technical terms used in electrochemical cells. First is cell. A cell is nothing but a glass
beaker containing two electrodes dipped in a solution. These two electrodes are connected
through a battery and a resistor. I pass current from battery to the anode electrode and cathode
electrode. This arrangement is called as a cell. I can have one electrode in one beaker and
another electrode in another beaker connected to each other from outside.
Historical prospective
Electrogravimetry has a rich history in the field of analytical chemistry. Here's a brief historical
perspective of electrogravimetry:
Early Developments (19th Century):
• The roots of electrogravimetry can be traced back to the early 19th century when
scientists began exploring the relationship between electricity and chemical
reactions.
• In 1833, Michael Faraday conducted experiments that demonstrated the
fundamental principles of electrochemistry, including the deposition of metal
ions onto an electrode.
Faraday's Laws (1834):
• Michael Faraday formulated the laws of electrolysis, which established a
quantitative relationship between the amount of substance deposited on an
electrode and the amount of electric charge passed through the electrolyte.
These laws are fundamental to electrogravimetry.
Becquerel and Electroplating (1867):
• Henri Becquerel made significant contributions to the understanding of
electroplating processes, which are closely related to electrogravimetry. His
work helped refine the techniques used in electrochemical depositions.
Bunsen and Gustav Kirchhoff (1860s):
• Robert Bunsen and Gustav Kirchhoff developed the spectroscope, which
enabled the identification and quantification of elements based on their emission
spectra. This laid the groundwork for later advancements in analytical
chemistry, including electrogravimetry.
Analytical Applications (Late 19th Century):
 • By the late 19th century, electrogravimetry had become an established analytical
technique for quantifying metals in solution. It was particularly valuable for
metals that formed insoluble compounds.
Incorporation of Electrogravimetry into Standard Methods (Early 20th Century):
• Electrogravimetry became an integral part of standard analytical methods, with
established procedures and protocols. It was widely used for metal analysis,
including in industries like metallurgy and electroplating.
Advancements in Instrumentation (Mid-20th Century):
• The mid-20th century saw significant advancements in instrumentation and
automation, which enhanced the precision and accuracy of electro gravimetric
measurements.
Competition from Modern Techniques (Late 20th Century):
• In the latter half of the 20th century, electrogravimetry faced competition from
newer and more sophisticated techniques like atomic absorption spectroscopy,
inductively coupled plasma mass spectrometry, and voltammetry. These
techniques often offered higher sensitivity, faster analysis times, and the ability
to handle a wider range of sample types.
Current Status (21st Century):
• Electrogravimetry remains a valuable technique in certain applications,
particularly when dealing with specific types of samples or when high precision
is required. However, it may not always be the first choice due to the availability
of more versatile and sensitive methods.
Overall, electrogravimetry has played a crucial role in the development of analytical chemistry
and has been instrumental in various industries and research fields. While its prominence may
have diminished in some areas, its historical significance and continued relevance in specific
applications are testament to its enduring importance in the field of analytical chemistry.

Discussion
In the discussion part we will discuss about the different types of electro-gravimetric
techniques. Electro- gravimetric are of two main types, as discussed below:
• Constant current electrogravimetry
• Constant potential electrogravimetry
Constant current electrogravimetry
Here in electrodeposition is carried out by keeping the current constant. Here periodic increase
in the applied potential is required (adjust the potential of the cell) as the electrolysis proceeds.
The apparatus for constant current electrolysis consists of a suitable cell and a direct current
source. A 6V storage battery can be used for DC power source. An ammeter and voltameter are
used to indicate the current and applied voltage respectively. The voltage applied to the cell is
controlled by a resistor. The cathode is usually a cylindrical platinum gauze.
Figure 1: diagrammatical representation of constant current electrogravimetry

Constant potential electrogravimetry

By controlled potential electrolysis, it is possible to separate two elements whose deposition
potentials differ sufficiently (by a few tenths of a volt). The potential of the cathode is
controlled so that it never becomes sufficiently negative to allow the deposition of the next. As
can be seen from the potential of the cathode becomes negative (due to concentration
polarisation) and that co-deposition of the other species begins before the analyte is completely
deposited.
Figure 2: working of constant voltage electrogravimetry

Applications of Electrogravimetry
Electrogravimetry is a technique used in analytical chemistry to quantify the amount of a
substance in a sample through the measurement of the mass of a solid deposited on an electrode
as a result of a redox reaction. This method finds applications in various industries and research
fields. Here are some of the key applications of electrogravimetry:
1. Metal Analysis: Electrogravimetry is widely used for the determination of metal ions in
solution. It is particularly useful for the analysis of metals that form insoluble
compounds, such as silver, copper, and mercury.
2. Corrosion Studies: Electrogravimetry can be used to study the corrosion of metals by
measuring the rate at which metal ions are deposited onto a cathode during the corrosion
 process. This information is crucial for industries like automotive, aerospace, and
construction.
3. Electroplating and Electrorefining: Electrogravimetry is employed in electroplating
processes to ensure that the desired amount of metal is deposited on a substrate. It is
also used in the purification of metals through electrorefining.
4. Determination of Trace Elements: Electrogravimetry can be sensitive enough to detect
and quantify trace elements in a sample. This is important in environmental monitoring,
where even small amounts of certain elements can be significant.
5. Environmental Analysis: It can be used to analyze environmental samples like water,
soil, and air for the presence of pollutants or contaminants. This is essential for
regulatory compliance and pollution control efforts.
6. Pharmaceutical Analysis: Electrogravimetry is used in pharmaceutical industries for
quality control and to determine the concentration of active ingredients in drug
formulations.
7. Research in Material Science: Electrogravimetry is used to study the deposition and
properties of thin films and coatings, which are critical in the development of advanced
materials and electronic devices.
8. Analysis of Alloys: It is used to determine the composition of alloys, which is crucial
for ensuring that materials have the desired properties in industries like aerospace,
automotive, and construction.
9. Analysis of Complex Matrices: Electrogravimetry can be employed in situations where
other analytical techniques may be less suitable, especially when dealing with complex
mixtures or matrices.
10. Nuclear Chemistry: It has applications in nuclear chemistry for the determination of
radionuclides, which is important for both research and nuclear industry purposes.
11. Forensic Analysis: Electrogravimetry can be used in forensic science for the analysis of
trace elements or metals in samples related to criminal investigations.
12. Quality Control in Plating Industries: Industries involved in metal finishing and plating
use electrogravimetry to ensure that products meet specific quality standards.
13. Waste Water Treatment: It can be used to monitor the removal of heavy metals from
wastewater during treatment processes.
14. Education and Research: Electrogravimetry is a valuable technique for teaching and
research purposes in analytical chemistry, physical chemistry, and related fields.
Conclusion
Electrogravimetry, a fundamental technique in analytical chemistry, quantifies substances by
measuring the mass of a solid deposit resulting from a redox reaction on an electrode. Its
applications are diverse and crucial across industries. It enables precise metal analysis, aids
corrosion studies for industries like aerospace and automotive, and ensures controlled
electroplating. Electrogravimetry's sensitivity extends to trace element detection in
environmental samples, vital for regulatory compliance. It's utilized in pharmaceutical quality
control and material science research, notably in thin film deposition. Its role in alloy
composition determination is pivotal for materials with specific properties. In complex
matrices, it offers a specialized analysis. In nuclear chemistry, it determines radionuclides, vital
for research and nuclear industries. Forensic applications involve trace element analysis, and
it's pivotal in quality control for plating industries. In wastewater treatment, it monitors heavy
metal removal. Finally, electrogravimetry is an invaluable tool for teaching and research in
chemistry-related fields.
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