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Coulometry

Coulometry is a quantitative electroanalytical technique that measures the quantity of electricity (coulombs) required to oxidize or reduce an analyte during an electrolysis reaction. The amount of electricity passed is directly proportional to the amount of analyte, according to Faraday's laws of electrolysis. There are two main types of coulometric methods - constant current (amperometric) coulometry and constant potential (potentiometric) coulometry. Coulometry provides a highly sensitive and accurate means for determining inorganic and organic analytes, and is widely used for applications like inorganic analysis, analysis of radioactive materials, and microanalysis.

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1K views19 pages

Coulometry

Coulometry is a quantitative electroanalytical technique that measures the quantity of electricity (coulombs) required to oxidize or reduce an analyte during an electrolysis reaction. The amount of electricity passed is directly proportional to the amount of analyte, according to Faraday's laws of electrolysis. There are two main types of coulometric methods - constant current (amperometric) coulometry and constant potential (potentiometric) coulometry. Coulometry provides a highly sensitive and accurate means for determining inorganic and organic analytes, and is widely used for applications like inorganic analysis, analysis of radioactive materials, and microanalysis.

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kusum
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© © All Rights Reserved
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COULOMETRY

-SAKSHI SOAM
-ROLL NO: 10
INTRODUCTION
• Coulometry involves measurement of coulombs i.e. the measurement
of quantity of charge/ electricity passed through the solution of an
analyte when it is electrolyzed.

• The quantity of electricity measured is for a specific reaction at an


electrode in electrolysis.

• The quantity measured can be related to the weight of the


component through Faraday's laws of electrolysis.
PRINCIPLE
• During the electrolysis process , the total charge , Q ( coulombs ) ,
passing through the electrolytic cell is proportional to the absolute
amount of analyte as per FARADAY’S LAW.
• Q(A.Sec)= n.F.NA…….. (1)

• n=the number of electrons per mole of analyte


• F=Faraday’s constant ( 96487 C mol-1)
• NA=moles of analyte
• Q=ite…….(2)
• Te= time of electrolysis
• i= constant current

• COULOMETRIC ANALYSIS REQUIRES 100% CURRENT EFFICIENCY


GRAVIMETRIC COULOMETER
TYPES OF COULOMETRIC
METHODS

CONSTANT CURRENT ( AMPEROSTATIC)

CONSTANT POTENTIAL ( POTENTIOSTATIC )


CONSTANT CURRENT COULOMETRY
• Amperostatic coulometry

• Coulometric titrimetry ( electrons serve as the titrant)

• Constant current is maintained until the indicator indicates the


completion of the electrolytic reaction

• At the end point potential of the working electrode shifts dramatically


POTENTIOSTATIC COULOMETRY
• The potential of the working electrode is held constant so that only
the reaction of interest occurs and no other reaction.

• With time the concentration of analyte decreases and as a result


current also decreases.

• Integrating the area in the curve from t=0 to t=te is the total charge
Experimental setup
• The three electrode potentiostat is used in controlled potential
coulometry.

• The working electrodes ( electrochemical generation of titrant) is


usually one of two types: a cylindrical Pt electrode or a Hg pool
electrode
• The auxillary electrode or counter electrode ( Pt wire)

• The electrode is separated by a salt bridge

• A saturated calomel electrode or Ag/Agcl electrode serves as the


reference electrode .
INSTRUMENTATION
APPLICATIONS
• Inorganic analysis
Determination of several metal ions eg. Iron, calcium.
 To determine the purity and impurity of Inorganic compound

• Analysis of radioactive material


Widely adopted for the determination of uranium and pluotinum and
their extensive use in the nuclear energy field
• Micro analysis
Especially used for the determination of small amount of analyte
(0.01-1mg) with an accuracy of (0.5%)

• Electrolytic determination of organic compounds


 Controlled potential coulometry offers a new step for the electrolytic
determination of organic compounds
ADVANTAGES
• Highly sensitive

• Both time and current can be measured with high degree of precision
and accuracy

• No indicator electrode system is necessary( in potentiostatic) , since


the magnitude of the final current is sufficient indication of the
degree of completion of the reaction.
REFERENCES
• 11.3: Coulometric Methods - Chemistry LibreTexts. (n.d.). Retrieved June 25, 2021, from
https://chem.libretexts.org/Courses/Northeastern_University/11%3A_Electrochemical_Methods
/11.3%3A_Coulometric_Methods
• Principles of Instrumental Analysis - Google Books. (n.d.). Retrieved June 25, 2021, from
https://www.google.co.in/books/edition/Principles_of_Instrumental_Analysis/D13EDQAAQBAJ?
hl=en&gbpv=1&dq=SKOOG&printsec=frontcover
• Vogel’s Textbook of Practical Organic Chemistry - Arthur Israel Vogel, B. S. Furniss, A. J.
Hannaford, A. R. Tatchell, P. W. G. Smith - Google Books. (n.d.). Retrieved June 25, 2021, from
https://books.google.co.in/books/about/Vogel_s_textbook_of_practical_organic_ch.html?
id=2eQPAQAAMAAJ
THANKYOU

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