Review of

Electroanalytical Techniques:
Electrogravimetry
CHM4112L
Week 10

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Electrogravimetry
• Based on the electrolytic oxidation or reduction of an analyte for an amount of time to ensure
complete conversion to a new oxidation state
• Material is deposited on an electrode by application of a potential
• The product of electrolysis is weighed as a deposit on one of the electrodes
Wproduct = Wafter deposition – Wbefore deposition
• Follows Faraday’s Law of Electrolysis
• Moderate selectivity, sensitivity, and speed
• High accuracy and precision
• Does not require calibration standards

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Faraday’s Laws of Electrolysis
• First Law: the mass of a substance liberated at the electrodes during electrolysis is directly
proportional to the quantity of electrical charge (Q) that passed through the electrolyte
• the amount of substance produced at each electrode is directly proportional to the quantity of
charge flowing through the cell
Faraday’s Equation:
𝑄𝐹𝑊 𝐼𝑡𝐹𝑊
𝑤= =
𝐹𝑛 𝐹𝑛
Q = charge in coulombs (C) = I x t
I = current in amperes (C/s) = V/R = volt / ohm
t = time (s)
F = Faraday’s Constant = 96,500 C/mol e-
FW = formula weight or molar mass of substance deposited (g/mol)
w = weight of substance deposited

• Second Law: mass of different substances evolved/deposited by the passage of same quantity of
electricity are proportional to their chemical equivalence (eq. wt. = FW/n)

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 Overpotential
• Driving force of for the electrolysis reaction
• Actual potential needed to drive the reaction
• Must overcome theoretical potential and kinetic barriers
• May be broken into:
• Mass transfer overpotential (movement of reactants)
• Charge transfer overpotential (movement of ions)
• Reaction (Chemical) over potential (reduction / oxidation)
• Adsorption / Desorption overpotential (adherence to electrode)
https://www.thinglink.com/scene/555588009567715329
• Cell overpotential – the sum of overpotentials at the two electrodes
and the ohmic drop due to the current through the electrolyte

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Overpotential

https://www.upsbatterycenter.com/blog/overpotential-battery/
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 Electrogravimetry Set-up

http://akcbodhegaon.com/wp-content/uploads/2016/04/Electrogravimetry-and-coulometry-ppt-1.pdf

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Electrogravimetry Simulation
Electrogravimetric Estimation of
Metals (VALUE@Amrita)
http://vlab.amrita.edu/?sub=2&brch=294&
sim=367&cnt=2

Objectives:
To determine the mass of a metal
deposited at an electrode using
electrogravimetry and Faraday’s law

Instructions:
• Perform three trials for three metal
salts
• Calculate the amount of metal
deposited on the electrode using the
electrogravimetry parameters
• Calculate the value based on the
weight deposited in the simulation.
• Compare the average of both

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