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Electro Chem Lecture 8

Chronoamperometry involves applying a constant potential to a stationary working electrode and measuring the resulting current over time. The current follows the Cottrell equation and provides information about diffusion processes and coupled chemical reactions. Chronopotentiometry applies a constant current and measures the changing potential over time, allowing analysis of concentration changes at the electrode surface. Coulometry techniques integrate current over time to quantify the amount of material oxidized or reduced based on Faraday's law. Voltammetry varies the potential linearly and measures current, providing both qualitative reaction information and quantitative diffusion and concentration data.

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Abeera Hassan Chohan
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75 views17 pages

Electro Chem Lecture 8

Chronoamperometry involves applying a constant potential to a stationary working electrode and measuring the resulting current over time. The current follows the Cottrell equation and provides information about diffusion processes and coupled chemical reactions. Chronopotentiometry applies a constant current and measures the changing potential over time, allowing analysis of concentration changes at the electrode surface. Coulometry techniques integrate current over time to quantify the amount of material oxidized or reduced based on Faraday's law. Voltammetry varies the potential linearly and measures current, providing both qualitative reaction information and quantitative diffusion and concentration data.

Uploaded by

Abeera Hassan Chohan
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Chronoamperometry

• Stationary electrode
• Unstirred = mass transport by diffusion
• Constant potential
• Measure current vs time
Theory
assume Ox + n e-  Red
- both Ox and Red are soluble
- reversible reaction (electrochemically)
- potential set so reduction goes to
completion at the electrode surface
Components of output signal
in Chronoamperometry
IFar decreases because Ox used up at electrode surface
and Ox is only replenished by diffusion

Faradaic current (IFar)


follows Cottrell equation

I Capacitive current (Icap)


(current) decays exponentially for a
constant applied potential

t (time)

Icap is high as electrode capacitive layer charges up, then drops off
Processes perturbing system can cause
data to differ from Cottrell Equation
1) Capacitive Current – charging current is
exponential as shown
Icap = e-kt
Note: Capacitive current decreases more
rapidly than Faradaic current so at longer
times the ratio IFar/Icap is larger
2) Occurrence of coupled chemical
reactions e.g. Ox + n e-  Red
2 Red  A
A + n e-  B
Affects the shape of the current-time curve
Chronoamperometry Applications
• Can measure concentration by measuring
I vs conc. at any fixed time
• Can analyze the shape of the current-time
curve in order to study coupled chemical
reactions
• There are better ways to do both of these
with more modern techniques
• Chronoamperometry is important because
it is a fundamental method on which other
techniques are based
Chronopotentiometry
• Stationary electrode
• Unstirred = mass transport by diffusion
• Constant current applied between electrodes
• Measure potential vs time
Theory Galvanostat
assume Ox + n e-  Red
- both Ox and Red are soluble
- reversible reaction (electrochemically)
- apply current and use up Ox at electrode
surface producing Red
[Ox]

Ox + n e-  Red

Apply current & use up


Ox at electrode surface
while producing Red

[Red]
Theory of Chronopotentiometry

0.059 [Red]
E = Eo - ----------- log -----------
n [Ox]

A gradual change in E occurs as [Red] goes


up and [Ox] goes down (transition region)
Ultimately the surface concentration of Ox
goes to zero & to sustain the constant
current applied, electrode potential makes
a rapid change to the value required to
make a new process go
Chronopotentiometry Output Wave

Transition
Time (τ)

Point at which Ox
E is used up

At start no Red is present so E is not defined

time
½½2[
τ½ 


  
Summary of Chronopotentiometry
• In principle quantitative analysis can be
τ
done by relating ½ R[
•     
•     
     
•    
       
Coulometry
Methods based on counting coulombs (C), the
basic unit of electrical charge (Q)

Q M
Faraday’s Law W = ------------
n F

Where: M = molecular weight (g/mole)


W = weight (g)
n = number of electrons (unitless)
F = Faraday’s constant (96,500 C/mol)
Fundamental assumption is that reaction is
100 % current efficient i.e, all coulombs go
to oxidizing or reducing species of interest

Kinds of coulometry
1) Controlled Potential Coulometry
t Nothing more than integrating area


under the curve in chronoamperometry
Q= i dt
Can be referred to as chronocoulometry
0
2) Constant Current Coulometry
Care must be taken so that there is enough
Q = it stuff to carry the current at electrode surface
Rarely used anymore
Major application is coulometric titrations
where titrant is prepared electrochemically
and standardized by counting coulombs
e.g. bromine Br2 as titrant
2 Br-  Br2 + 2 e-

1) Useful for titrants that can’t be stored as


stable solutions
2) Small currents can be measured
accurately so even very dilute titrants can
be used
3) In theory can count coulombs for any
method where current is measured by
integrating
Coulometric cell

2 Br-  Br2 + 2 e-

Br2 + C6H10  C6H10Br2


Voltammetry
• Stationary electrode
• Stirred = mass transport by convection
• Vary potential linearly with time
• Measure current vs time
Theory
assume Ox + n e-  Red
- both Ox and Red are soluble
- reversible reaction (electrochemically)
- potential varies
Define - Limiting Current as steady state
current when [Ox] = 0 at electrode surface
i.e., applied potential is sufficiently cathodic
such that all Ox is reduced at electrode

nFADCbulk
transport-limited current I = -----------------
δ
I limiting current

Gives quantitative
E information

Nernst controlled current

RT [Red]
E = Eo - ----- ln --------
nF [Ox]
quantitative
information

qualitative
information

for stirred solution

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