Electroanalysis 201 Tutorial Solutions (total marks = 41)
A. Briefly describe five components of the potentiometric cell and their function. (10)
Components of the Potentiometric cell
a) Reference electrode A half-cell with an accurately known electrode potential, Eref, that is independent of
the concentration of the analyte or any other ions in the solution.
b) Salt bridge (Ej) preventing components of the analyte solution from mixing with those of the reference
electrode.
c) Analyte solution a solution to be measured and monitor the change in the pH as a result of the
concentration.
d) Indicator electrode an electrode which is immersed in a solution of the analyte, develops a potential,
Eind, that depends on the activity of the analyte. It is selective in their response. (contains [analytes]
information)
e) Voltmeter/digital meter - shows the measured potential between the analyte after the reference and the
ohmic resistance is subtracted.
B. For the short hand notation (below).
SCE || [H3O+] = a1 | Glass membrane | [H3O+] = a2, [Cl-] = 1.0 M, AgCl(sat’d) | Ag
Draw a rough sketch of the electrochemical cell and label its components. (8)
C. (i) What are the three reference electrodes that were covered in the module? (3)
a) Silver silver chloride
b) Saturated calomel electrode
c) Standard hydrogen electrode
(ii) What are the characteristics of the reference electrodes? (4)
a) Must have a known potential window.
b) Response to concentration must be constant.
c) Must be stable and insensitive to the composition of analyte.
d) Must be easy to assemble.
(iii) What are the equations involved and that are the origins of potentials? (6)
a) Saturated calomel reference electrode (SCE)
Hg2Cl2 (s) + 2 e- ↔ 2Hg (l) + 2 Cl (aq) Eref = 0.2444 V (at 25⁰C)
b) Silver silver chloride (Ag|AgCl)
AgCl(s) + 2 ↔ Ag(s) + Cl(aq) Eref = 0.199 V (at 25°C)
c) Standard hydrogen reference electrode (SHE)
2H+ (aq) + 2e ↔ H2(g) Eref = 0.000 (at 25ºC)
D. Compare and contrast the three stripping methods. Give examples of analytes that each
method is selective towards. (10)
Stripping methods involves two steps (pre-concentration/deposition step) and
This then is followed by stripping step.
Eg. Deposition at -0.9 V and tripping scanned from -0.9V to 0V.
The figure below shows the excitation signal and the voltammogram for the detection of cadmium
and copper.
Anodic stripping
The electrode behaves as a cathode during the
deposition/pre-concentration step, and
The electrode behaves as an anode (i.e. a pre-
concentrated metal phase is oxidized) during the
stripping step.
Eg. Deposition step - the metal phase is
concentrated onto the electrode surface or Hg: Zn2+
+ 2e- + Hg = Zn(Hg);
Stripping step metal is re-dissolved into solution:
Zn(Hg) = Zn2+ + 2e- + Hg.
The advantage of the stripping voltammetry leads
to low detection limits.
The applications of anodic stripping voltammetry
are in the analysis of metal ions or trace metal
determination.
Very good detection limits down to 0.1 nM – 1
pM.
Peak currents (Ip) is linearly dependant on the
analyte concentration.
ASV is useful in multi-element analysis as the
stripping or reduction potentials differ for
difference metal ions. Eg. Cu2+, Cd2+ and Zn2+.
The cathodic stripping (CSV) is the opposite of the anodic stripping voltammetry
The electrode behaves as an anode during the deposition step first: X- = X + e-
The electrode behaves as a cathode during the stripping step: X + e- = X-
The cathodic stripping voltammetry is useful in the analysis of anions, i.e. CN-, SO42-, etc.
The method can be used to determine substances that form insoluble salts with the mercurous ion.
Adsorptive stripping voltammetry (ASV) is similar to ASV and CSV.
The working electrodes are solids of Pt, Au, etc.
AdSV is used for the analysis of organic molecules and pharmaceuticals.
The condition is that the ligands should adsorb to the electrode.
Several steps are involved :
(i) complex formation in solution (Mn+ + L = Mn+L(aq)),
(ii) adsorption of the complex onto electrode (Mn+L(aq) = Mn+(aq)),
(iii) cathodic stripping: at the metal: Mn+L(ads) + e- = Mn-1+ L(ads),
(iv) at the ligand: Mn+L(ads) + e- = Mn+L-1 (ads).
AdSV is also used for metals which have very close potentials hence cannot be analysed ASV.
A ligand which is selective for a certain metal may be employed to analyze it in the presence of others.