Voltammetry

Voltammetry
• In voltammetry current (I) is measured as a function of potential (E) as potential is
applied, electrolysis of the analyte starts and the current rises until it reaches a
limiting current
Cd2+ + 2e Cd
The magnitude of this current is directly proportional to the activity or
concentration of analyte I=kC
C= concentration of analyte, k=constant, I=current
• E1/2=half wave potential
 Voltammetric cell

Electrolytic cell with 3 electrodes

1. Micro indicator electrodes like Pt, Ag,Au, C,
Hg, and others
2. Reference electrode like Ag/AgCl or SCE
3. Auxiliary counter electrodes like Pt wire
Voltammogram
Voltammetric cell
 Voltammetric cell

• Change in potential (E) is applied on the indicator electrode (working electrode)

to drive a nonspontaneous redox reaction
• The counter electrode serves to conduct electricity between the two electrodes
• Reference electrode has a constant potential throughout
• A supporting electrolyte is a salt added in excess to the analyte solution
• Mostly in alkali metal salt that does not react at the working electrode as the
potential is being used, the salt reduces the effects of immigration and lowers the
resistance of the solution
• Influence of applied potential on the faradaic
current
• When the potential applied to the WE reaches the
reduction potential of the electroactive species, a
reduction will take place at the electrode surface
• Hence, electroactive species diffuse from the bulk
solution to the electrode surface and the
reduction products diffuse from the electrode
surface towards the bulk solution, this creates a
faradaic current
 Current in voltammetry
• When an analyte is oxides at the working electrode, a current passes electrons through the
external electric circuitry to the auxiliary electrode
• This current flows from the auxiliary to the WE, where the reduction of the solvent or other
components of the solution matrix occurs
• The current resulting from redox reactions at the working and axillary electrodes is called the
faradaic current
• Sign conventions: A current due to the analyte’s reduction is called a cathodic current and by
convention is considered positive, anodic currents are due to oxidation reactions and carry a
negative value
• The magnitude of the faradaic current is determined by the rate of the resulting oxidation or
reduction reaction at the electrode surface
• Two factors contribute to the rate of the electrochemical reaction: (i) the rate at which the
reactants and products are transported to and from the surface of the electrode (mass transfer)
• (ii) the rate at which electrons pass between the electrode and the reactants and products in
the solution (kinetics of electron transfer at the electrode surface)
 Influence of mass transport on the Faradaic current
• Diffusion from a region of high concentration to a region of low concentration occurs whenever the concentration
of an ion or molecule at the surface of the electrode is different from that in bulk solution
• Convection occurs when a mechanical means is used to carry reactants toward the electrode and to remove
products from the electrode. The most common means of convection is to stir the solution using a stir bar. Other
methods include rotating the electrode and incorporating the electrode into a flow cell
• Migration occurs when charged particles in solution are attracted or repelled from an electrode that has a positive
or negative surface charge. unlike diffusion and convection, migration only affects the mass transport of charged
particles
• Diffusion is the only significant means for the mass transport of the reactants and products, the current in a
voltammetric cell is given by i=nFAD(Cbulk-Cx=0)/δ
• N=number of electrons transferred in the redox reaction, F=Faraday’s constant, A=area of the electrode, D= the
diffusion coefficient for the reactant or product, Cbulk and Cx=0 are the concentration of the analyte in the bulk
solution and at the electrode surface, δ is the thickness of the diffusion layer
• Diffusion current: Id is directly proportional to the concentration of the analyte
• Id= limiting current- residual current IIkovic equation
 Types of voltammetry

• Polarography
• Linear sweep and cyclic voltammetry
• Hydrodynamic voltammetry
• Pulsed method
• Stripping voltammetry
• AC voltammetry
• Polarography: in polarography, the WE is a dropping mercury electrode (DME) or
a mercury droplet suspended from a bottom of a glass capillary tube
• The analyte is either reduced or oxidized at the surface of the mercury drop
• The current-carrier auxiliary electrode is a platinum wire
• SCE or Ag/AgCl reference electrode is used
• The potential of the mercury drop is measured with respect to the reference
electrode
 Advantages of dropping mercury electrode

• Mercury form amalgam with most metals

• Mercury has a high hydrogen overvoltage
• It provides a smooth, fresh surface for the reaction
• Each drop remains unaffected and does not become contaminated by the
deposited metal
• Diffusion equilibrium is readily established at mercury-solution interface
 Disadvantages

• It is poisonous so care should be taken in its handling

• Surface area of a drop of mercury is never constant
• Applied voltage produces changes in surface tension and hence change in drop
size
• Mercury has limited applications in analysis of more positive potential range
The following care must be taken while using
dropping mercury electrode:
• Pure and triple distilled mercury should be used in DME
• Tip of DME should be always immersed in water when not in use
• Tip of DME should be cleaned by dipping in nitric acid
• The DME assembly should be mounted vertically on a heavy stand to be free from
vibrations
• It is essential to use clean and dust-free tubing while setting the DME
• There should be sufficient mercury in the reservoir so that the pressure changes
are negligible
• Another disadvantage of the dropping mercury electrode is the nonfaradaic
residual or charging current, which limits the sensitivity of the classical method to
concentrations of about 10-5M
• At lower concentrations, the residual current is likely to be greater that the
diffusion current, a situation that prohibits accurate measurement of the latter
• Finally, the dropping mercury electrode is cumbersome to use and tends to
malfunction as a result of clogging
 There are four important pulse methods

• Normal pulse voltammetry/polarography

• Differential pulse voltammetry/polarography

• Square wave voltammetry

• Cyclic voltammetry
 Cyclic Voltammetry (CV)

• CV is an attractive method for the teaching of a number of concepts in

electrochemistry.
• In brief, it is perhaps the most versatile electrochemical technique for the study
of electroactive species.
• The effectiveness of CV results from its capability for rapidly observing the redox
behavior over a wide range of potential.
• The resulting voltammogram is similar to a conventional spectrum in that it
conveys information as a function of an energy scan.
• In spite of its wide applications, this technique is not generally well understood as
compared to other instrumental techniques such as spectroscopy and
chromatography.
 Fundamentals of Cyclic Voltammetry
• It consists of cycling the potential of an electrode that is immersed in an unstirred
solution of the electroactive species and then measuring the resulting current.
• The potential of this working electrode is controlled versus a reference electrode such as
a saturated calomel electrode (SCE) or a silver/silver chloride electrode (Ag/AgCl).
• The controlling potential which is applied across these two electrodes can be considered
as excitation signal.
• The excitation signal for CV is a linear potential scan with a triangular waveform
• This triangular potential excitation signal sweeps the potential of the electrode between
two values, sometimes called the switching potentials.
• The excitation signal causes the potential first to scan negatively from +0.80 (initial
potential) to – 0.20 V (EF final potential) versus SCE at which point the scan direction is
reversed, resulting a positive scan back to the original potential of +0.80 V (Ei).
 STRIPPING METHODS

• Stripping voltammetry is the most sensitive electrochemical

technique for the quantitative analysis of micro quantitative
electroactive analytes which oxidize or reduce reversibly at solid
electrodes or form insoluble species at the electrode surface that can
be subsequently removed electrochemically and analyzed
 Basically, two steps are involved in this technique

1. The analyte of interest is electrolytically deposited on the working

electrode by controlled potential electrolysis.
2. A reverse potential seal or stripping step is applied in which the deposited
analyte is removed from the electrode.
• The first step is basically preconcentration or electrodeposition while the
second one is the stripping step.
This technique has three different types:
• Anodic stripping voltammetry (ASV)
• Cathodic stripping voltammetry (CSV)
• Adsorptive stripping voltammetry
 Anodic Stripping Voltammetry

• This technique is used to determine trace amounts of metal ions that can be
preconcentrated at an electrode by reduction to the metallic state.
• The microelectrode behaves as a cathode during the deposition step and as an anode
during the stripping step with the analyte being oxidized to the original form:
• This may be explained in detail by taking the example of Cu2+, the deposition reaction at
HMDE (Hanging Mercury Drop Electrode) held at a cathodic potential sufficient to
deposit the metal ion on the electrode where Cu(Hg) is copper amalgamated with mercury.

Cu2+ (aq) 2e Cu(Hg)

 ASV

• This step is basically a pre-concentration step where the metal ion from a large
volume of the solution is concentrated on a small volume of the electrode.
• The solution is stirred during the electrolysis to increase the rate of deposition.
Near the end of the deposition time stirring is stopped and usually 1-30 mins are
used for deposition.
• In the second step, the potential is scanned anodically toward a more positive
potential.
• When the potential becomes positive, the analyte is stripped from the electrode
returning to its oxidized form
• Cu (Hg) = Cu2+ (aq) + 2 e
 ASV
• And the current during this step is monitored as a function of potential giving rise to
the voltammogram, the peak current of which is proportional to the analyte
concentration in the solution.
• This technique is sensitive to experimental conditions like the area of the mercury film
electrode or size of the Hg drop, deposition time, rest time, rate of stirring, and scan rate
during the stripping step.
• If properly controlled this method will be quite sensitive and accurate and is best used for
metals that form amalgams.
• Peak currents in this technique are a linear function of concentration and hence this
technique can be used for the determination of many metal ions in trace quantities in
environmental samples
Table 1: Metals that can be determined by ASV
Antimony Gold
Arsenic Gallium
Bismuth Lead
Cadmium Mercury
copper silver
thallium zinc
Indium Tin

Table 2: Species that can be determined by cathodic stripping voltammetry

Arsenic Iodide
Chloride Selenium
Sulfide Thiocyanate (SCN)
bromide Thio compounds
 Cathodic Stripping Voltammetry

• It is used for the determination of anions that form insoluble mercury (I)
salts at the mercury surface or insoluble silver salts on a silver electrode.
• The experimental design is similar to that for A.S.V. with two modifications.
• The decomposition step involves the oxidation of the Hg electrode to Hg2+
which then reacts with the analyte to form an insoluble film at the surface.
• The decomposition step with Cl– is 2Hg(l) +2Cl- (aq)=Hg Cl (s)+2e
• The second step, i.e. stripping, is followed by scanning cathodically towards
a more negative potential reducing Hg2+ back to Hg and returning the
analyte to the solution.
Hg2Cl2 (s) 2e 2Hg(l) 2Cl (aq)
 Adsorptive Stripping Voltammetry

• In this technique analyte is adsorbed on the electrode surface and there is

no
electrolysis step and after complete deposition the potential is scanned in
anodic or cathodic direction depending on whether the analyte is to be
oxidized or reduced.
• The deposition step in this method amounts to an electrochemical pre-
concentration of the analyte,
i.e. the concentration of the analyte on the surface of the microelectrode is
greater than the bulk of solution and hence these methods are extremely
sensitive and the detection limit can be improved by factors of 106 for
selected species.
• Some analytes analyzed by this method are cocaine and testosterone.
• Features of the polarogram
• Residual current- the small current before the potential at which the analyte
reacts, caused by reactive species in the matrix and by the mercury drop behaving
like a capacitor
• Limiting current- the maximum current reached
• Diffusion current- the difference between the limiting and residual, and
proportional to the concentration of analyte
• Half-wave potential- the potential halfway up the polarographic wave, which is
similar to the oxidation/reduction potential
• Current oscillations- caused by mercury drop which repeatedly falls off and is
replenished from the capillary
llkovic equation
• The magnitude of the diffusion current is given by the llkovic equation : Id= (7.08 X104)nCD1/2
m2/3t1/6
Where Id= diffusion current measured at the top of the oscillations with the units µA
N= number of electrons per molecule involved in the reduction or oxidation of the electroactive
species
C=concentration of electroactive species, mmol/L; D=diffusion coefficient of electroactive species,
M2/s
M=rate of flow of Hg, mg/s; T=drop interval in s, the number 7.08 X104 is a combination of several
constants whose dimensions are such that Id will be id=given in µA
• Hence, id is proportional to the concentration of a certain species under specific conditions and
the above equation may be expressed as id=kc
Where k I constant under specific conditions
• If k is constant for a series of standard solutions of various concentrations and an unknown, a
calibration plot can be constructed and the unknown concentration can be determined
Questions

1.In a coulometric titration of U4+ in the presence of excess Ce3+, it was found to
require 652 seconds to reach the equivalence point using a constant current of
100.0 mA. How many moles of U4+ were present in the solution?

2. Calculate the limiting current that would be expected from the reduction of 2
X10-4mmol/L Pb2+, using the DME characteristic m=2.0 mg.s-1 and t=4s. The
diffusion coefficient of Pb2+ is 1.01X10-5 cm2s-1.
 Quantitative analysis

• The principal use of polarography is in quantitative analysis.

• Since the magnitude of the diffusion current is proportional to the
concentration of the analyte, the height of a polarographic wave tells
how much analyte is present
• One standard method: it is assumed that a linear relationship holds
for the concentration and the wave height
• Assuming that the wave heights for the standard and the analyte
were h1 and h2 and the concentrations were Xstandard and Xanalyte then
Hstandard/hanalyte= Xstandard/Xanalyte
 Standard curves
• The most reliable yet tedious method of quantitative analysis is to prepare
a series of known concentrations of analyte in otherwise identical
solutions.
• A polarogram of each solution is recorded and a graph of the diffusion
current vs analyte concentration is prepared.
• Finally, a polarogram of the unknown is recorded, using the same
conditions.
• From the measured diffusion current and the standard curve, the
concentration of the analyte can be determined.
• The figure shows an example of the linear relationship between diffusion
current and concentration
 Question
Suppose that 5.00mL of an unknown sample of Al(III) was placed in a
100 mL volumetric flask containing 25.00 mL of 0.8M sodium acetate
(pH 4.7) and 2.4 mM pontachrome violet SW (a maximum suppressor).
After dilution to 100 mL, an aliquot of the solution was analyzed by
polarography. The height of the polarographic wave was 1.53µA, and
the residual current measured at the same potential with a similar
solution containing no A(III) was 0.12µA. find the concentration of
Al(III) in the unknown.
Standard addition method

• The standard addition method is most useful when the sample matrix
is unknown or difficult to duplicate in synthetic standard solutions.
• This method is faster but usually less reliable than the standard curve
method.
• First, a polarogram of the unknown is recorded.
• Then, a small volume of concentrated solution containing a known
quantity of the analyte is added to the sample.
• With the assumption that the response is linear, the increase in
diffusion current of this new solution can be used to estimate the
amount of unknown in the original solution.
• For the greatest accuracy, several standard additions are made
• The diffusion current of the unknown will be proportional to the
concentration of the unknown, Cx: id(unknown)=kCx
• Where k is a constant of proportionality. Let the concentration of
standard solution be Cs.
• When Vs mL of standard solution is added to Vx mL of unknown. The
diffusion current is the sum of diffusion currents due to the unknown
𝑉𝑥 𝑉𝑠
and the standard 𝐼𝑑(𝑢𝑛𝑘𝑛𝑜𝑤𝑛+𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑) = 𝑘𝐶𝑥 + 𝑘𝐶𝑠
𝑉𝑥 +𝑉𝑠 𝑉𝑥 + 𝑉𝑠
𝐶𝑠 𝑉𝑠
rearrange and solve for Cx 𝐶𝑥 =
𝑅 𝑉𝑥 + 𝑉𝑠 −𝑉𝑠
A 25.0 mL sample of Ni2+ gave a wave height of 2.36µA (corrected for
residual current) in a polarographic analysis.
When 0.500 mL of solution containing 28.7mM Ni2+ was added, the
wave height increased to 3.79µA.
Find the concentration of Ni2+ in the unknown.
Type equation here.