Analytical Chemistry: CHE3704 Module

Dr RC Chokwe
Voltammetry and
Florida Science Campus
Eureka building
polarography
Chemistry Department
K-F-080
[email protected]
+27 11-670-9393
 2022 Discussion classes

• Electrochemical methods & Spectroscopy: 10 September

2022 (09:00 – 12:00)

• Spectroscopy: 17 September 2022 (09:00 – 12:00)

• Sample preparation and Chromatography: 24 September

(09:00 – 12:00)
 Examination
• Year mark (20%)

• Exam mark (80%)

• Preliminary exam date (21st October 2022).

• Exam scope (study all the chapters)

 Examination question paper structure
• SECTION A: Compulsory (40 marks).

• SECTION B: Only answer 3 out of 4 question (60 marks).

• Exam duration time: 3 hours.

• Study material: tutorial letters (101, 201, 202 & 203), study guide,
prescribed text book and old exam question papers.
 Voltammetry
• It is an electro-analytical technique which gives information about the
analyte
• A time-dependent potential is applied to an electrode, and the
current flowing through the cell is measured as a function of that
potential
• A plot of current as a function of applied potential is called a
voltammogram, it provides quantitative and qualitative information
about the species involved in the oxidation and reduction reaction
 Electrochemical cell
• Working electrode: ranges from small
mercury drop to flat platinum disc, gold,
platinum and glassy carbon
• Auxilliary electrode
• Reference electrode
• A time-dependent potential excitation signal
is applied to the WE, changing its potential
relative to the fixed potential of the RE
• The resulting current between the working
and auxiliary electrodes is measured

https://chem.libretexts.org/Bookshelves/Analytical_Chemistry/
Analytical_Chemistry_2.1_(Harvey)/11_Electrochemical_Methods/
 Working electrode
• The type of voltammetry is decided
• Dropping Mercury Electrode is used in Polarography
• Platinum electrode is used in Cyclic voltammetry
• Glassy Carbon is used in Linear Sweep Voltammetry
• The reaction takes place on this electrode
• It is called cathodic or anodic if the reaction is reduction or oxidation
respectively.
 Reference Electrode
• A standard electrode is used as a Reference electrode
• Its potential is constant
• It provides potential to the working electrode
• Calomel electrode and Ag/AgCl electrode are used
 Auxiliary/ counter Electrode
• Usually a thin platinum wire
• Carries the current flowing through the cell
• Redox reaction occur simultaneously at the auxiliary electrode
 Types of voltametric Techniques
• Normal Voltammetry
• Pulse Voltammetry
• Normal-Pulse Voltammetry
• Differential-Pulse Voltammetry
• Staircase Voltammetry
• Square-Wave Voltammetry
https://www.youtube.com/watch?v=Rg0uGBawW-Q

https://www.youtube.com/watch?v=cxZRlvfRTX8
Normal/ Linear voltammetry
Normal/ Linear voltammetry
• The potential is linearly scanned, producing voltammograms
• When the potential is slightly negative with respect to the calomel electrode,
no reduction of Cd2+ occurs.
• At a sufficient negative potential, reduction of Cd2+ commences and the current
increases
• The reduced Cd dissolves in Hg to form an amalgam
• After a steep increase in current, concentration polarization sets in
• The rate of electron transfer becomes limited by the rate at which Cd 2+ can
diffuse from bulk solution to the surface of the electrode
• The magnitude of this diffusion current Id is proportional to Cd 2+ concentration
and is used for quantitative analysis
 Pulse voltammetry
• Makes use of potential pulse
• A sequence of potential steps, each with a duration of about 50 ms, is
applied to the working electrode
• After each potential step
• Charging current decays rapidly and exponentially to a negligible value
• Faradaic current decays slowly
• Hence the observed current late in the pulse life excludes charging
current
• Have better sensitivity and low detection limits (10-8 M levels)
Pulse voltametric Techniques
• (a) Normal pulse polarography
• (b) Differential pulse
polarography
• (c) Staircase polarography
• (d) Square-wave polarography
 Normal-pulse voltammetry
• One potential pulse is applied for each drop mercury when the DME is
used
• Consists of a series of pulses of increasing amplitude applied to
successive drops at a preselected time near the end of each drop
lifetime
• Electrode is kept at a base potential between pulses at which no
reaction occurs
• Base potential is kept constant
 Normal-pulse voltammetry
• Pulse amplitude increases linearly with each drop
• Current is measured about 40 ms after each pulse is applied (at which
time charging current is negligible)
• Diffusion layer is thinner than that of DC polarography due to short
pulse duration
• Higher faradaic current than DC polarography
 Differential-pulse voltammetry
• One potential pulse is applied for each drop of mercury when the DME is used
• Small pulses of constant amplitude are superimposed on a linear potential ramp applied
to the working electrode
• Potentials are applied just before the end of each drop
• Useful for measuring trace levels of organic and Inorganic species
• The drop is the mechanically dislodged
• The current is measured once before the pulse and again for the last 17 ms of the pulse
• The polarograph substracts the first current from the second and plots this difference
versus the applied potential
• The resulting differential pulse polarogram is nearly the derivative of a direct current
polarogram
 Differential-pulse voltammetry
• Current is sampled twice, just before the pulse application and late in
the pulse life when the charging current has decayed
• On the voltammogram, the height of peaks is directly proportional to
the concentration of the analyte
• The peak potential occurs near the polarographic half-wave potential
and can be used to identify the species
• It is useful for analysis of mixtures
 Staircase Voltammetry
• Useful for rejecting background charging current
• Potential-time waveform involves successive potential steps of ̴10 Mv
in height and ̴50 ms duration
• Current is measured at the end of each step where the charging
current is negligible (has decayed)
• Peak-shaped current response is similar to that of linear scan
experiments
 Square-wave voltammetry
• Large amplitude differentia technique
• The wave form applied to the working electrode is a symmetric
square wave superimposed on a base staircase potential
• Current is sampled twice during each square-wave cycle
• One at the end of the forward pulse(i1) and one at the end of the
reverse pulse (i2)
• Resulting in square-wave modulation
 Hydrodynamic Voltammetry
• The so/n is stirred by rotating the electrode. Current is measured as a
function of the potential applied to a solid WE
• The same potential profiles used for the polarography, such a linear
scan or differential pulse, are used in hydrodynamic voltammetry
• The resulting voltammograms are identical to those for polarography,
except for the lack of current oscillations resulting from the growth of
the Hg drops
• Because hydrodynamic voltammetry is not limited to Hg electrodes, it
is useful for the analysis of analytes that are reduced or oxidized at
more positive potentials
 Triangular wave/ cyclic voltammetry
• The potential is ramped from an initial potential (Ei) but at the end of
its linear sweep, the direction of the potential scan is reversed,
usually stopping at the initial potential (Ei).
• The potential at which the reverse occurs is known as switch potential
(Eλ)
• The scan rate between (Ei) and (Eλ) is the same as that between (Eλ)
and (Ei)
• Values of the scan rates Vforward and Vbackward are always written as
positive numbers.
 AC Voltammetry
• An alternating potential is added to the DC potential ramp used for
linear sweep voltammetry.
• Only the AC portion of the total current is measured and plotted as a
function of the DC potential portion of the potential ramp
• Because flow of an alternating current requires the electrochemical
reaction to occur in the forward and reverse directions, Ac
voltammetry is useful for studying the extent to which
electrochemical reactions are reversible
 Differential pulse voltammetry
• Adds a periodically applied potential pulse (temporarily increased in
potential) to the voltage ramp used for linear sweep voltammetry
• The current is measured prior to application of the pulse and at the
applied pulse
• The difference between the two current is plotted as a function of the
linear sweep voltammetry ramp applied
• Pulse voltammetry utilizes a regularly increasing pulse height that is
applied at periodic intervals
• In differential pulse and pulse voltammetry, voltammogram is a plot
of the measured current and potential
 Polarography
• The current flowing through the cell is measured as a function of the WE
• This current is usually proportional to the concentration of the analyte
• The WE is a dropping Hg electrode or a Hg droplet suspended from a bottom of a
glass capillary tube
• Analyte is either reduced or oxidized at the surface of the mercury drop
• The current carrier auxiliary electrode is platinum wire
• SCE or Ag/AgCl reference electrode is used
• The potential of the Hg drop is measured with respect to the RE
• In the hanging mercury drop electrode (HMDE) a drop of the desired size is formed
by the action of a micrometer screw that pushes the mercury through a narrow
capillary tube
 Polarography
• In the dropping mercury electrode (DM,mercury drops form at the end of the capillary tube as a
result of gravity
• Unlike the HMDE, the mercury drop of a DME grows continuously and has a finite lifetime of
several seconds
• At the end of its lifetime the Hg drop is dislodged, either manually or by gravity, and replaced by a
new drop
• The static mercury drop electrode (SMDE) uses a solenoid-driven plunger to control the flow of
mercury
• A single activation of the solenoid momentarily lifts the plunger, allowing enough Hg to flow
through the capillary to form a single drop. To obtain a DME the solenoid is activated repeatedly
• A Hg film electrode consists of a thin layer of mercury deposited on the surface of a solid carbon,
platinum, or gold electrode
• The solid electrode is placed in a so/n of Hg 2+ and held at a potential at which the redn of Hg2+ , to
Hg is favourable, forming a thin Hg film
 Why dropping mercury electrode
Advantages
• Hg yields reproducible current potential data
• This reproducibility can be attributed to the continuous exposure of fresh surface on the growing
mercury drop
• With any other electrode such as Pt in various forms the potential depends on its surface condition and
therefore on its previous treatment
• The vast majority of reactions studied with the Hg electrode are red ns
• At a Pt surface, reduction of the solvent is expected to compete with reduction of many analyte
species, especially in acidic solutions
• The high over potential for H+ redn at the Hg surface, H+ redn does not interfere with many reductions
• A species such as Zn2+, which is difficult to reduce at other electrode without simultaneously reducing
H3O+, is easily reduced at a mercury WE
• Other advantages include the ability of metals to dissolve in the Hg resulting in the form n of an
amalgam and the ability to easily renew the surface of the electrode by extruding a new drop
 Problems with mercury electrode
• Hg electrode is not very useful for performing oxidns because Hg is easily oxidized. For
most oxidns some other WE must be employed
• In a noncomplexing medium Hg is oxidised near +0.25V Vs SCE
• Pt electrode Vs SCE works for a range of +1.2 to -0.2 in acidic so/n +0.7 to -1 in basic so/n
• Solid electrodes constructed using Pt, Au, Ag, or C may be used over a range of potentials
including potentials that are –ve and +ve with respect to the SCE at which Hg electrodes
cannot be used
• Hg is toxic and slightly volatile and spills are almost inevitable, a good vacuum cleaner
• To remove residual mercury, sprinkle elemental zinc powder on the surface and dampen
the powder with 5% aqueous H2SO4
• Hg dissolves in the Zn after working the paste into contaminated areas with a sponge or
brush allow the paste to dry and then sweep it up
• The limiting current (il) is

directly proportion to the

concentration of the analyte,
hence used for quantitative
analysis.

• The half-wave potential (E1/2)

is related to the standard

potential of the half-reaction,
hence used for qualitative
identification.
IIKOVIC EQUATION
id=AnCD1/2m2/3t1/6
Where:

• id: maximum diffusion current(μA)

• n: number of Farads
• C: concentration in the bulk (mM)
• D: diffusion coefficient (cm2.sec-1)
• t: drop time (sec)
• m: mercury flow rate (mg.sec-1)
• A: constant (708)
Standard calibration curve
Standard addition calibration curve
 Standard addition method
• The diffusion current of the unknown will be proportional to the concentration of
unknown, Cx:
• ld(unknown) = kCx

• where k is a constant of proportionality.

• Let the concentration of standard solution be C S. 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 and the
standard.

R=
 Typical exam question
• A 25.0‑mL sample of Ni2+ gave a wave height of 2.36 µA
(corrected for residual current) in a polarographic
analysis.
• When 0.500 mL of solution containing 28.7 mM Ni2+ was
added, the wave height increased to 3.79 µA. Find the
concentration of Ni2+ in the unknown.
Answer
 Question 2
• It has been suggested that many polarograms can be obtained
on a solution without depleting the electroactive analyte.
Suppose that in a polarographic experiment we monitor the
limiting current for 45 minutes in 30 mL of 0.08 M Cu 2+. If the
average current during the time of the experiment is 6.0 µA,
what fraction of the copper is removed from the solution?
 Spectroscopy
• Spectroscopy is the study of the interaction between electromagnetic
radiation and matter as a function of the wavelength/frequency of the
radiation.
Electromagnetic radiation relationships
 Electromagnetic radiation
Energy in a single particle depends on the frequency and can be
given by:

E = hv

where v is the frequency of the wave and h is a constant called

Planck's constant.

h = Planck’s constant = 6.6262 ×10−34 J·s

 Spectroscopic techniques
• Molecular absorption spectroscopy (UV-Vis & IR).

• Atomic absorption spectroscopy (AASs).

• Atomic emission spectroscopy (ICP-OES).

Molecular absorption (UV-VIS)
• Why CuSO4 appears blue?

• Because it absorbs all red light and very little blue light and
therefore it appears blue.

• So…if we direct red light at CuSO4, we get maximum light absorption

and therefore maximum excitation.

• How then do we isolate red light from the rest of the UV-visible
radiation?
 Spectroscopic measurements
Beer-Lamberd Law

A = absorbance, l = path length, Ԑ = molar absorptivity, c= concentration

• There is a linear relation between (A) and (c) for a

given path length and compound.

• knowing the absorbance (A) one can determine

concentration (c).
 Spectroscopic measurements

• Because each colour has a specific λ, each coloured molecule has an optimum λ where it
will absorb the greatest amount of light, λ maximum.

• As much as colour is an indicator that light has been absorbed so can intensity indicate
the amount of light absorbed.
 Practice questions
• In a beam of monochromatic light, 65% of the incident light is
absorbed in its passage through a coloured solution. What is the
absorbance of the solution?

• What process is expected when matter is irradiated with energy?

• Use a diagram to show the process.

• What instrument can be used to determine quantity of light

absorbed by sample?

• What can we do with the light absorbed by the analyte?

 Practice question

The molar extinction coefficient (ε) of compound

riboflavin is 3x103 L.cm-1 Mole. If the absorbance
reading (A) at 350 nm is 0.9 using a cell of 1 cm,
what is the concentration of compound riboflavin in
sample?
 Practice question
Multicomponent Determination
What does Beer’s Law say about multicomponent determination?

A Total = A1+ A2+ A3+ ………………..+ An

= Ɛ1bC1+ Ɛ2bC2+ Ɛ3bC3…………. + ƐnbCn

PRACTISE QUESTION
In the simultaneous determination of nickel and cobalt, the molar
absorptivities of nickel and cobalt with 8-quinolinol are Ԑco=4729 and
ԐNi=4235 at 365nm, and Ԑco=628.9 and ԐNi=80 at 700nm. Calculate
concentration of nickel and cobalt in a solution that gave A=0.715 at
365nm and A=0.0635 at 700nm.
Infrared Spectroscopy
 Infrared spectroscopy
• When energy in the form of Infrared radiation is applied then it
causes the vibration between the atoms of the molecules
• When the applied infrared frequency is equal to the natural frequency
of vibration, then absorption of IR radiation takes place and a peak is
observed
• Different functional groups absorb characteristic frequencies of the IR
radiation. Hence, they give the characteristic peak value
• Therefore, the IR spectrum of a chemical substance is a finger print of
a molecule for its identification
Vibrational modes observed in IR
spectroscopy
 Infrared Spectroscopy

• Infrared spectroscopy is a powerful tool for identification of organic

and inorganic molecules.
• All molecules absorb infrared radiation at unique infrared absorption
spectrum.
• Dispersed and Fourier Infrared spectroscopies are mostly used for
qualitative analysis.
 Take-away
• Review block diagrams of each instrument.

• Make sure you understand the function of major components.

• Advantages and limitations of each instrument.

• Principle behind each instrument.

• Application.
Thank-you for
your time