Amperometry

apply a constant potential to the working electrode and measure current

as a function of time.

---- do not vary the potential ------ does not result in a voltammogram

application of amperometry
----- in the construction of chemical sensors

1) One of the first amperometric sensors was developed in 1956 by

L. C. Clark to measure dissolved O2 in blood.

Clark amperometric sensor for determining dissolved O2. The diagram on

the right is a cross-section through the electrode, showing the Ag ring
electrode and the Pt disk electrode.

----A thin, gas-permeable membrane is stretched across the end of the

sensor and is separated from the working electrode and the counter
electrode by a thin solution of KCl.

------working electrode is a Pt disk cathode, and a Ag ring anode serves

as the counter electrode.

---- Although several gases can diffuse across the membrane, including
O2, N2, and CO2, only oxygen undergoes reduction at the cathode
with its concentration at the electrode’s surface quickly reaching zero.

----- concentration of O2 at the membrane’s inner surface is fixed by its

diffusion through the membrane, creating a diffusion profile similar to
that given below [Analyte]

---- The result is a steady-state current proportional to the concentration

of dissolved oxygen.

------ Because the electrode consumes oxygen, the sample must be stirred
to prevent the depletion of O2 at the membrane’s outer surface.
 2) glucose sensor

Glucose oxidase (GOD)

oxidation reaction is performed by the FAD cofactors bound deep inside

the enzyme, shown in red.
Glucose oxidase (GOD)
----- dimeric protein that catalyzes the oxidation of β-d-
glucose to d-glucono-1,5-lactone, which subsequently hydrolyzes
non-enzymatically to gluconic acid.

Two flavin adenine dinucleotide (FAD) cofactors are tightly bound

to and deeply buried in the protein

GOD catalyzed glucose oxidation

FAD serves as the initial electron acceptor and is reduced to FADH2.

FADH2 is oxidized by the final electron acceptor, molecular oxygen (O2)

----- O2 is reduced to hydrogen peroxide.

GOD-based glucose sensing can be accomplished by directly measuring

the electrons released by GOD

----- three membrane

the reactions by which an amperometric biosensor responds to glucose.

------ outermost membrane is of polycarbonate, which is permeable

to glucose and O2.
---- second membrane contains an immobilized preparation of
glucose oxidase that catalyzes the oxidation of glucose to
gluconolactone and hydrogen peroxide.

------ hydrogen peroxide diffuses through the innermost membrane of

cellulose acetate where it undergoes oxidation at a Pt anode.

FAD is the oxidized form of flavin adenine nucleotide—the active site of

the enzyme glucose oxidase—and FADH2 is the active site’s reduced
form ------ O2 serves a mediator, carrying electrons to the electrode.
Coulometry

Coulometry is based on an exhaustive electrolysis of the analyte

---- analyte is completely oxidized or reduced at the working
electrode

Or

------ analyte reacts completely with a reagent generated at the

working electrode.

Two forms of coulometry:

(a) controlled-potential coulometry ----- apply a constant potential
to the electrochemical cell
(b) controlled-current coulometry ---- pass a constant current
through the electrochemical cell.

During an electrolysis, the total charge, Q (in coulombs), passing through

the electrochemical cell is proportional to the absolute amount of analyte
by Faraday’s law

n = number of electrons per mole of analyte

F = Faraday’s constant (96487 C mol–1)
NA = moles of analyte

A coulomb is equivalent to an [Link]

when passing a constant current, i, the total charge

te = electrolysis time

If the current varies with time --- controlled-potential coulometry ---- then
the total charge is

In coulometry current is monitored as a function of time and Q is

calculated

Knowing the total charge, the moles of analyte can be determined

To obtain an accurate value for NA, all the current must be used to oxidize
or reduce the analyte. ------------ coulometry requires 100% current
efficiency (or an accurately measured current efficiency established using
a standard)

Current efficiency is the percentage of current that actually leads to the

analyte’s oxidation or reduction.
Controlled-Potential Coulometry

The easiest way to ensure 100% current efficiency is to hold the working
electrode at a constant potential, chosen so that the analyte reacts com-
pletely without simultaneously oxidizing or reducing an interfering
species.

As electrolysis progresses the analyte’s concentration decreases, as does

the current.
current

Current versus time for a controlled-potential coulometric analysis

--measured current is shown by the red curve

---- integrated area under the curve, shown in blue, is the total charge.

Integrating the area under the curve from t = 0 to t = te gives the total
charge.
Selecting a Constant Potential
Selection of appropriate potential for the working electrode

Example

constant-potential coulometric method for Cu2+ based on its reduction to

copper metal at a Pt working electrode.

----Cu2+ to Cu reduction is favored when the working electrode’s potential

is more negative than +0.342 V versus the standard hydrogen electrode

------ to ensure a 100% current efficiency, the potential must be

sufficiently more positive than +0.0 V so that the reduction of H3O+ to H2
does not contribute significantly to the total current flowing through the
electrochemical cell

Minimizing ElectrolysisTime

In controlled-potential coulometry, the current decreases over time.

As a result, the rate of electrolysis becomes slower and an exhaustive

electrolysis of the analyte may require a long time.
time is an important consideration when choosing and designing
analytical methods

approximate the change in current as a function of time by an exponential

decay;

the current at time t

i0 = current at t = 0

k = rate constant that is directly proportional to the area of the working

electrode and the rate of stirring, and that is inversely proportional to the
volume of solution

----- usually carry out a controlled-potential coulometric analysis in a

small volume electrochemical cell, using an electrode with a large surface
area, and with a high stirring rate

----- A quantitative electrolysis typically requires approximately 30–60

min

Instrumentation
three-electrode potentiostat ----- to set the potential in controlled-potential
coulometry.
working electrode
cylindrical Pt electrode manufactured from platinum-gauze

Electrogravimetry
If the product of controlled-potential coulometry forms a deposit on the
working electrode ------ use the change in the electrode’s mass as the
analytical signal.

Controlled-Current Coulometry

------- use a constant current in place of a constant potential

------ produces the current-versus-time

Current versus time for a controlled-current coulometric analysis

------ measured current is shown by the red curve
------ integrated area under the curve, shown in blue, is the total charge.
--------- Controlled-current coulometry has two advantages over
controlled-potential coulometry

(i) analysis time is shorter because the current does not decrease
over time. A typical analysis time for controlled-current
coulometry is less than 10 min, compared to approximately
30–60 min for controlled-potential coulometry.

(ii) the total charge is the product of current and time ------ there
is no need to integrate the current-time curve

Using a constant current presents two important experimental problems.

(a) during electrolysis the analyte’s concentration — and, therefore,
the current due to the its oxidation or reduction—continuously
decreases. To maintain a constant current we must allow the
potential to change until another oxidation reaction or reduction
reaction occurs at the working electrode. Unless we design the
system carefully, this secondary reaction decreases the current
efficiency to less than 100%.

(b) we need a method for determining when the analyte's electrolysis

is complete.

---------- in a controlled-potential coulometric analysis

we know that electrolysis is complete when the current reaches
zero, or when it reaches a constant background or residual
current.
 ------- In a controlled-current coulometric analysis, current
continues to flow even when the analyte’s electrolysis is
complete. A suitable method for determining the reaction’s
endpoint, te, is needed.

Maintaining Current Efficiency

why a change in the working electrode’s potential may result in a current

efficiency <100% ?

the coulometric analysis for Fe2+ based on its oxidation to Fe3+ at a Pt

working electrode in 1 M H2SO4.

Ladder diagram for the constant-current coulometric analysis of Fe2+

red arrow ---- potential drifts to more positive values ---- decreasing the
current efficiency.

----- At the beginning, the potential of the working electrode remains

nearly constant at a level near its initial value

------ As the concentration of Fe2+ decreases, the working electrode’s

potential shifts toward more positive values until the oxidation of H2O
begins.

----- a portion of the total current comes from the oxidation of H2O, the
current efficiency for the analysis is less than 100% and we cannot use
following equation to determine the amount of Fe2+ in the sample

----------- can maintain a 100% current efficiency if the product of that

oxidation reacts both rapidly and quantitatively with the remaining Fe2+

----------- add an excess of Ce3+ to the analytical solution.

Ladder diagram for the constant-current coulometric analysis of Fe2+ in the presence
of a Ce3+ mediator

----------- As the potential drifts to more positive values ----------- reach a

potential where Ce3+ undergoes oxidation

------ Ce4+, the product of the oxidation of Ce3+, reacts with Fe2+ -----------
maintain current efficiency

----------- when the potential of the working electrode shifts to a more

positive potential Ce3+ begins to oxidize.

---- Ce4+ that forms at the working electrode rapidly mixes with the
solution where it reacts with any available Fe2+.

Combining reaction above two equations ---- the net reaction is the
oxidation of Fe2+ to Fe3+

maintaining a current efficiency of 100%.

 ---------- A species, such as Ce3+, which is used to maintain 100% current
efficiency, is called a mediator.

Endpoint Determination

------ Adding a mediator solves the problem of maintaining 100% current

efficiency

------ but when the analyte's electrolysis is complete?

--------- when the oxidation of Fe2+ is complete current continues to flow

from the oxidation of Ce3+, and, eventually, the oxidation of H2O

---------- need a signal that tells us when there is no more Fe2+ in solution

--------- convenient to treat a controlled-current coulometric analysis as a

reaction between the analyte, Fe2+, and the mediator, Ce3+

-------- reaction is identical to a redox titration

---------- visual indicators

Example
ferroin ------- for the Ce3+ mediated coulometric analysis for Fe2+,
changing color from red to blue when the electrolysis of Fe2+ is complete.

Ferroin: A blood-red complex of Fe2+ ion with 1,10-

phenanthroline, used as a redox indicator. Ferroin changes from
red to pale blue when oxidized.
Analytical Chemistry 2.0 by David Harvey