CM4011 – Advanced Analytical Chemistry

Topic 4 – Voltammetric Analysis

Question 1

The diagram below shows a linear sweep hydrodynamic voltammogram for the reduction reaction:

A + ne– ⇌ P

Draw concentration profiles showing how the amount of A and P vary within the diffusion layer as
a potential is applied at positions x, y and z.

Answer:

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Question 2

(a) The picture below shows a pulse sequence for differential pulse voltammetry. Briefly describe
the main features of differential pulse voltammetry and how the pulse sequence is performed.

In differential pulse voltammetry, the potential steps are increased linearly at set intervals (usually
around 2 mV).

On top of the 2 mV potential steps, large pulses are applied (usually 50 mV) for short periods of
time (around 50 ms).

The current is then sampled at two different points; S1 is before the pulse is applied and S2 is at the
end of the pulse.

The difference between S1 and S2 is then plotted as a function of the applied potential steps.

(b) What are the main advantages of pulse voltammetric methods as an analytical technique
compared to linear sweep methods?

Because the current is sampled in a differential way, the resulting current voltage curve appears as a
symmetrical peak shape. There are two main advantages of pulse techniques.

(1) The peak shape is easier to detect against the background current.

(2) The peaks enable processes that are very close together to be differentiated (0.04 V).

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(c) Describe (with diagrams) anodic stripping voltammetry (ASV) and state its main use.

(See lecture notes for diagram)

A constant negative potential is applied to the electrode for a fixed period of time. This causes metal
ions that are in solution to be deposited on the electrode in their metallic forms (e.g. Cu 2+(aq) is
reduced to Cu(s)).

The electrode is then swept in the positive potential direction, which causes the metal elements to
be oxidised (stripped) off the electrode surface, and a peak is obtained at the oxidation potential of
the metal.

ASV is mainly used to improve the sensitivity of the measurement for trace analysis. By applying a
reducing potential for a long period of time, the amount of metal undergoing deposition can be
increased to improve the peak current on the stripping scan.

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Question 3

(a) The reduction of dopamine o-quinone (DAQ) to dopamine (DA) has an E0 = +0.6 V vs.
Ag/AgCl at 25 oC.

O NH2 Er1/2 HO NH2

_ +
+ 2e + 2H
O HO
Dopamine o-quinone (DAQ) Dopamine (DA)

Calculate the reversible half-wave potential (Er1/2) (vs. Ag/AgCl) for the reaction at pH 1 and at pH
7 (Hint: Use the Nernst equation).

Er1/2 = E0 – (2.303RT/nF) × log([red]/[ox])

Er1/2 = E0 – (0.0296) × log([DA]/[DAQ][H+]2)

At the Er1/2; [DAQ] = [DA], (E0 = +0.6 V vs. Ag/AgCl)

At pH 1 Er1/2 = 0.6 – (0.0296) × log(1/[0.1]2) = 0.5408

At pH 7 Er1/2 = 0.6 – (0.0296) × log(1/[1e–7]2) = 0.1856

(b) What are the advantages of pulsed voltammetric techniques, such as differential pulse
voltammetry (DPV) and square wave voltammetry (SWV), compared to linear sweep methods?

(i) They enable better resolution of voltammetric processes (multiple redox processes are more
easily detected).

(ii) The enable better sensitivity (lower analyte concentrations can be detected).

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Question 4

(a) (i) The diagram below shows a linear sweep voltammogram (LSV) obtained for the two-
electron reduction of dopamine quinone at pH 1. Calculate the new Er1/2-value and draw on
the diagram the new position of the LSV if the reduction was carried out at pH 7 and 25 oC.
Assume that the formal electrode potential = + 0.600 V vs. Ag/AgCl.

O NH2 Er1/2 HO NH2

+ 2e_ + 2H+
O HO
Dopamine o-quinone (DAQ) Dopamine (DA)

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0 r
E 1/2 = +0.186 V

-20
i / A

r
-40 E 1/2 = +0.54 V

-60
pH = 7 pH = 1
-80
-0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0
Eapplied / V vs. Ag/AgCl

Eapplied = Eo – RT/nF x ln ([DA]/[DAQ][H+]2)

At the Er1/2, [DA] = [DAQ]

Therefore, Er1/2 = Eo – RT/nF x ln (1/[H+]2)

Er1/2 = 0.600 – RT/nF x ln (1/[1 x 10–7]2) = +0.186 V vs. Ag/AgCl

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 (ii) Draw on the diagram below the appearance and position of a differential pulse
reductive voltammogram of dopamine quinone at pH 1 when the pulse amplitude (E) is
–50 mV.

20

-20
i / A

-40

-60
0.565 V
-80
0.20 0.30 0.40 0.50 0.60 0.70 0.80
Eapplied / V vs. Ag/AgCl

Er1/2 = Ep + [E/2]
Ep = Er1/2 – [E/2]
= 0.54 – [(–0.05)/2]
= 0.565

(b) Briefly describe anodic stripping voltammetry and its main advantages as an analytical
technique compared to other voltammetric methods.

Anodic stripping voltammetry (ASV) functions by first applying a negative potential to an electrode
surface for a fixed period of time.

Any species that are present in solution that undergo adsorption when they are reduced (such as
metal ions), will be reduced and coat the surface of the electrode. The longer the potential is applied
and the more the solution is stirred, the greater will be the amount of material adsorbed.

After a certain time, the potential is scanned in the positive potential and the species that were
adsorbed onto the electrode get oxidized off the electrode at a potential corresponding to their
(formal oxidation potential), resulting in an increase in positive current. The current is proportional
to the amount of material adsorbed onto the electrode; therefore, the technique is quantitative
provided a suitable calibration curve is prepared.

ASV is particularly sensitive because the deposition step is essentially a pre-concentration step,
which means that the longer the reducing potential is applied (and the more the stirring), the greater
will be the stripping peak. Therefore, in very low concentration solutions it is possible to hold the
deposition potential for a long time to improve the sensitivity.

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Question 5

The glucose electrode is an example of a voltammetric chemical sensor used to determine glucose
levels. The principal reaction involves the oxidation of glucose to gluconic acid.

Describe the operation of the glucose electrode used to determine glucose in blood. Include in your
description: (i) the overall reactions that occur, (ii) the importance of the ferrocene derivative and
the applied potential, and, (iii) how the current response relates to the concentration of glucose.
(10 marks)

(i) glucose + GODoxidized ⇌ gluconic acid + GODreduced

GODreduced + 2[Fe(cp)2Me2]+ ⇌ GODoxidized + 2[Fe(cp)2Me2] + 2H+

(ii) The ferrocene derivative, [Fe(cp)2Me2], is used as the electron acceptor. It is located at the
anode and undergoes oxidation to the cation, [Fe(cp)2Me2]+. The cation reacts with the reduced
from of glucose oxidase (GODreduced) and oxidizes it to GODoxidized. The ferrocene derivative is used
instead of molecular oxygen because the applied potential (+0.160 V) is lower and reduces the risk
of other metabolites being oxidized.

+
CH3 Eappl = +0.160 V CH3
Fe2+ Fe2+ + e-
CH3 CH3

(iii) The [Fe(cp)2Me2]+ that is produced anodically reacts immediately with any GODreduced that has
been produced by the reaction of glucose with GODoxidized. The [Fe(cp)2Me2]+ will continue to be
regenerated and react with any GODreduced until all the glucose has reacted with GODoxidized.
Therefore, the current is directly proportional to the amount of glucose.

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Question 6

(a) Match the following molecules (1 – 3) with their most likely shaped cyclic voltammogram (x, y,
z) from the list below.

MeO OMe

N N 1

MeO OMe

MeO OMe

N N 2

MeO OMe

MeO OMe

N N 3

MeO OMe

Compound Voltammogram
1 z
2 y
3 x

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(b) Explain your answer to part (a) above.

The molecules are symmetrical and contain two redox active centers. The further apart the centers
are, the more likely that the electron transfer steps will appear independently of one another (i.e. the
two halves of the molecule are non-communicating). Therefore, the voltammogram will appear as
one process corresponding to two-electrons per molecule (hence the peak current is bigger).

As the two halves of the molecule come closer together, they are more likely to electronically
interact with each other. Therefore, when the first electron is removed, the resulting unpaired
electron will be shared over the structure and it will take more energy to remove the second electron
and the voltammogram will appear as two widely spaced one-electron processes.

(c) The figure below shows cyclic voltammograms for the reduction and oxidation of C60.

(i) How many oxidation and how many reduction processes are there?

Four reduction and one oxidation.

(ii) How do you know that each process occurs by the same number of electrons?

The peak heights are approximately equal.

(ii) If you applied a constant potential of –2.2. V under electrolysis conditions, would you
obtain C603– in the bulk solution? Explain your answer.

Eventually, but only after all the C60 has been converted to C602–. C603– cannot exist in the
bulk solution with C60 (it will immediately react according to comproportionation reactions).

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Question 7

(a) Figure (i) shows a cyclic voltammogram for p-chlorobenzonitrile [p-Cl(C6H4)CN] dissolved in
deoxygenated N,N-dimethylformamide solvent, measured at a 1 mm diameter planar Pt electrode at
a scan rate of 0.1 V s−1 at 25 oC. Figure (ii) shows the corresponding measurement under identical
conditions for benzonitrile [(C6H5)CN]. Negative current signifies reduction.

Write a chemical mechanism to account for the voltammetric behaviour in Figure (i) and justify
your mechanism.

The cyclic voltammograms indicate that [p-Cl(C6H4)CN] is being reduced by two electrons to form
[(C6H5)CN], which can then be reduced by one-electron.

[p-Cl(C6H4)CN] + e− ⇌ [p-Cl(C6H4)CN]−•

[p-Cl(C6H4)CN]−• ⇌ [(C6H4)CN]• + Cl−

[(C6H4)CN]• + e− ⇌ [(C6H4)CN]−

[(C6H4)CN]− + "H+" ⇌ [(C6H5)CN] where "H+" is derived from the solvent.

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(b) The cyclic voltammogram of p-bromonitrobenzene [p-Br(C6H4)NO2] in deoxygenated
acetonitrile at a scan rate of 0.1 V s−1 at a 1 mm diameter Pt electrode at 25 oC is shown below.
Negative current signifies reduction.

The electroreduction of [p-Br(C6H4)NO2] is thought to proceed as follows:

[p-Br(C6H4)NO2] + e− ⇌ [p-Br(C6H4)NO2]−•

[p-Br(C6H4)NO2]−• ⇌ [(C6H4)NO2]• + Br−

[(C6H4)NO2]• + e− ⇌ [(C6H4)NO2]−

[(C6H4)NO2]− + "H+" ⇌ [(C6H5)NO2] where "H+" is derived from the solvent.

How would you use cyclic voltammetry measurements at different scan rates to demonstrate such a
mechanism? What other electrochemical methods could you use to gain information about the
mechanism?

The mechanism can be verified by fast scan cyclic voltammetry. At faster scan rates it is possible
that the second electron transfer will be outrun, hence a chemically reversible one-electron process
will be detected.

[p-Br(C6H4)NO2] + e− ⇌ [p-Br(C6H4)NO2]−•

It should be possible to voltammetrically detect the product of the reduction [(C6H5)NO2].

Performing coulometry measurements will allow the number of electrons transferred to be

calculated.

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(c) Figure (i) shows a cyclic voltammogram of compound A recorded in deoxygenated
dichloromethane at a scan rate of 0.1 V s−1 at a 1 mm diameter Pt electrode at 25 oC. Figure (ii)
shows the cyclic voltammogram obtained of the same compound under identical conditions except
at a scan rate of 100 V s−1. The solid lines represent the first scan cycle, whilst the dashed lines are
the second scan cycle. Negative current signifies reduction. The initial potential is 0 V vs.
ferrocene0/+.

It was found that the voltammetric behaviour observed in the Figures above could be accounted for
by the following square scheme mechanism:

(i) Trace or redraw Figure (i) in your answer booklet and label each voltammetric peak with the
correct electrochemical reaction associated with compounds A, B, C and D.

Answer

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(ii) Why does an additional electrochemical process appear at −0.5 V in Figure (i) during the second
scan?

The additional peak that is observed at −0.5 V is due to the reduction of D to C. It occurs because of
the equilibrium transformation of B to C in the square scheme. It is not detected in the first scan,
because only A is initially present.

(iii) Why does the appearance of the voltammograms change as the scan rate is changed?

As the scan rate is increased, the homogeneous reaction of B going to C is outrun, therefore, the CV
appears as a chemically reversible one electron transfer.

(iv) Why might the voltammogram in Figure (i) change in appearance as the temperature is
lowered?

The equilibrium constant for the homogeneous reaction should change as the temperature is
changed. Therefore, the CVs will change in appearance. Usually, the rate constants for the
transformations also change.

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Question 8

Two organometallic compounds (A and B) containing osmium were isolated from a reaction
mixture. Compound A was obtained as a 1:1 salt with PF6–, while compound B was a neutral
compound. The molar mass of compound A (without PF6–) and compound B were found to be
identical. The cyclic voltammograms of compounds A and B in acetonitrile at two different scan
rates (0.1 V s–1 and 10 V s–1) are given in Figure 1. Coulometry measurements made during the
constant potential electrolysis of 0.0001 mols of A at –1.0 V vs. ferrocene0/+ led to the transfer of -
9.6 coulombs (C).

Figure 1. Cyclic voltammograms of 1 mM solutions of compounds A and B in acetonitrile at 25 oC.

The starting/finishing potentials for solutions containing compound A are –0.2 V and for compound
B are –1.2 V.

Based on the information given above, write a chemical mechanism to account for the
voltammograms given in Figure 1. Justify your mechanism and label on Figure 1 the
electrochemical reaction that each voltammetric process corresponds to.

Compound A undergoes reduction and compound B can be oxidised.

The coulometry experiments indicate the transfer of –9.6 coulombs for 0.0001 mols of A.

nA = Q/nF
n = Q/FnA = –9.6/(96485 x 0.0001) = –1 electrons

Therefore, compound A is reduced by one-electron. The peak current for compound is very similar
to compound B. This indicates that B is also oxidised by one-electron.

A is a cation therefore, can be reduced. However, A is not directly reduced into B. The
voltammetric data shows that A is reduced by one-electron to form A1, and then undergoes a
reaction to form B. Similarly, B is oxidised by one-electron to form B1, and then undergoes a
reaction to form A. An isomerisation reaction is quite likely. This can be determined from the
voltammograms by the position of the peaks.

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A + e– ⇌ A1 E = –0.85 V vs. ferrocene0/+
B – e– ⇌ B1 E = –0.65 V vs. ferrocene0/+

The best mechanism is therefore the square-scheme reaction.

Er1/2 = -0.85 V
+ e_
A - e_ A1

+ e_
B1 - e_ B
Er1/2 = -0.65 V

The variable scan rate experiments indicate that the isomerisation reaction can be outrun at faster
scan rates (10 V s–1), so the homogeneous chemical steps do not occur.

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Question 9

The diagrams below show cyclic voltammograms for the oxidation of vitamin E in (a) basic, (b)
neutral, and (c) acidic conditions. Write reaction schemes showing what each voltammetric process
correspond to.

OH

O
R
Vitamin E

(a) 4
i / A

-1.0 0.0 1.0

+
E / V vs. Fc/Fc

(b) 4
i / A

-1.0 0.0 1.0

+
E / V vs. Fc/Fc

(c) 4
i / A

-1.0 0.0 1.0

+
E / V vs. Fc/Fc

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 O O
(a) - 1e-

+ 1e-
O O
R R
O O

+
Dimer

O O
R R

OH OH O O
(b)
- 1e- - H+ - 1e-

+ 1e- + H+ + 1e-
O O O O
R R R R

OH OH OH 2+
(c)
- 1e- - 1e-

+ 1e- + 1e-
O O O
R R R

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Question 10

The figure below shows cyclic voltammograms of the neutral compound A dissolved in
deoxygenated acetonitrile (CH3CN) solvent, measured at a 1 mm diameter planar Pt electrode at a
range of scan rates (). The potential and current follow the IUPAC convention. The starting and
finishing potential of the scans is –0.5 V vs. Ag/AgCl. The current axis has been scaled by
multiplying the current by –0.5.

The oxidation of A is known to occur via a reversible dimerisation mechanism where A is oxidized
by one electron to form a cation radical (A+•), which then dimerises to form a dimer dication (A22+).

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(a) Draw or trace the voltammogram recorded at 100 V s–1 into your answer booklet and label what
reactions the peaks correspond to.

A - e- A

 = 0.1 V s-1

A + e- A

 = 1.0 V s-1

 =10 V s-1
Current

 =100 V s-1

A22+ + e- B

 =1,000 V s-1

 =10,000 V s-1

-0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0

E / V vs. Ag/AgCl (3 M KCl)

(b) With reference to the dimerization mechanism, clearly explain why the voltammograms change
in appearance as the scan rate is increased progressively from 0.1 V s–1 to 10,000 V s–1. Why do the
voltammograms at the slowest and fastest scan rate appear similar?

The dimerisation mechanism can be written:

A – e– A+• (1) E0 = +0.59 V

A+• + A+• A22+ (2) Keq >> 1, kf > kb
–
2+
A2 + e B (3) E0 = +0.26 V

The key to the appearance of the cyclic voltammograms is the dimerisation step (2) and the
corresponding rate constants for the forward dimerisation (kf) and back monomerisation (kb)
reactions.

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At slow scan rates, kf and kb are faster than the scan rate, therefore, the dication (A22+) has sufficient
time to be converted back to the monocation radical (A+•) on the time-scale of the experiment and
the voltammogram appears as a simple one-electron transfer.

At the fastest scan rate (10,000 V s–1), the scan rate is faster than the kf value and the cation radical
(A+•) is reversibly reduced back to the starting material (A) before the dimerization reaction (kf) has
time to occur.

At intermediate scan rates, the scan rate is faster than the back reaction (kb), but slower than the
forward reaction (kf), so the peak for the reduction of the dimer (A22+) becomes larger while the
peak for the reduction of the cation radical (A+•) gets smaller.

(c) With reference to the dimerization mechanism, explain why voltammograms that are recorded
at a fixed scan rate might change in appearance as the temperature is changed.

The equilibrium constant (Keq) and rate constants (kf and kb) in step 2 are affected by changes in
temperature, therefore, it would be expected that the voltammograms should change in appearance
as the temperature is changed.

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