Electroanalytical chemistry

Lab manual CHEM 352 & 334

Syllabus
Order Contents
1 Introduction to electroanalytical
methods
2 pH Titration of unknown soda
ash using potentiometric
measurements.
3 Potentiometric titration of
chloride-iodide mixture
4 Determination of fluoride
content of toothpaste using
fluoride ion- selective electrode.
5 Electrogravimetric
determination of copper and
nickel in a mixture
6 Determination of arsenic in a
sample by coulometric titration
7 Conductometric titrations of
some acids and bases
8 Polarographic determination of
a trace metal
9 Study of electrode mechanism
by cyclic voltammetry
10 Analysis of trace lead in water
by anodic stripping voltammetry
 EXPERIMENT- 1
Introduction to electroanalytical methods

1- Galvanic and Electrolytic Cells

2- Cell description conventions

Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s)

3- Reference Electrodes
1- Ag | AgCl(s) | Cl–(aq) || ... Ag(s) + Cl–(aq) →AgCl(s) + e–

2- Hg | Hg2+(aq) | KCl || ... Hg(l) + Cl– → ½ HgCl2(s) + e–

‫كل الشرح من المذكرة لهذه المحاضرة‬

 EXPERIMENT- 2
pH Titration of unknown soda ash using potentiometric measurements.
1- POTENTIOMETRIC TITRATION

volume of base pH

0.0000 2.1300
1.0000 2.1600
2.0000 2.2000
3.0000 2.2500
4.0000 2.3000
5.0000 2.3500
6.0000 2.4000
7.0000 2.5200
8.0000 2.6200
9.0000 2.7700
10.0000 3.0000
11.0000 3.6200
11.1000 3.8400
11.2000 4.3900
11.3000 5.6500
11.4000 6.2500
11.5000 6.8400
11.6000 9.0500
11.7000 9.8700
11.8000 10.2200
11.9000 10.4700
12.0000 10.6700
16.0000 11.9000
20.0000 12.1000
 POTENTIOMETRIC TITRATION

14
13
MV (NaOH) = MV(HCl)
0.1* 11.5 =M*10
12
M(HCl)= 0.12 M
11
pH of unknown acid

10
9
8
7
6
5
4
3
2
1
0 1 2 3 4 5 6 7 8 9 101112131415161718192021
Volume of 0.1M NaOH (ml)
 EXPERIMENT-5
ANALYSIS OF COPPER IN A MIXTURE BY ELECTROGRAVIMETRY

Introduction
In this experiment, copper in a copper-nickel mixture is analyzed by
electrodepositing only copper onto a previously weighed inert platinum mesh
electrode.
The increase in weight of the electrode is then related to the amount of metal
present in the unknown. Cu(II) is easier to reduce than Ni(II) at a platinum
cathode, and so when a negative voltage is placed on the electrode, the copper will
selectively plate out. After most of the copper has been removed from the solution
by this process, Ni(II) would then ordinarily begin to deposit (which would prevent
an accurate determination of copper).
This can be avoided by performing the electrolysis in a sulfuric acid-nitric acid
solution.
Both hydrogen ion and nitrate are less easily reduced than Cu(II) but more easily
reduced than Ni(II). When most of the copper has deposited, the following reaction
begins to carry the current, and no Ni(II) is able to deposit.
NO3- + 10H+ + 8e- = NH4+ + 3H2O
It is desirable to have a secondary reaction occur which does not cause gas bubbles
to form at the cathode (e.g., the reduction of hydrogen ion). Gas bubble formation
generally results in a metal deposit with very poor qualities. The reduction of
nitrate avoids this difficulty.
A platinum mesh electrode is used for deposition of the metal because its large
surface area yields low current density (amperes/cm2) and a more adherent deposit
results. A platinum wire anode is centered inside the cylindrical cathode. It is
positioned carefully to produce a uniform deposit on all parts of the cathode.
Fig.1Electrogravimetric Analysis setup
 HOMEWORK(2)

1- Calculate the quantity of the electricity, Q, obtained when a current of 25 amps run for 4

minute.

Q = it

Q = 25  4  60 = 6000Coulombs

2- Calculate the current needed to provide 40000 coulombs of electricity in 6 minutes.

Q = it

Q
i=
t

40000
i= = 111.1ampers
6  60

3- what mass of copper could be deposited from a copper (II) Sulphate solution using a current

of 0.460 A over 13 seconds.

1F → eq.wt (Cu +2 )
i  t → massofCu

63.5
eq.wt (Cu + 2 ) = = 31.75
2

0.460  13  31.75
mass = = 1.967  10 −3 g
96500
 HOMEWORK(2)

4- Calculate the time required to produce 12000 C of electricity using a current of 18 amps.

Q
t=
i

12000
t= = 666.6 sec onds
18

5- calculate the time required to deposit 56 g of silver from a silver nitrate solution using a

current of 4.5 A (Atomic weight of Ag=107.9 g)

1F → eq.wt ( Ag +1 )
i  t → massofAg

107.9
eq.wt ( Ag +1 ) = = 107.9
1

96500  56
t= = 11129.6 sec onds,185.49 min utes
4.5  107.9
 EXPERIMENT-6
Determination of arsenic in a sample by coulometric titration

I. Introduction
Redox reactions may be separated into half reactions involving either the gain or
loss of electrons at electrodes. In this titration to determine the concentration of a
As2O3(aq) solution, I2 is formed from I- by an oxidation half reaction. The I2 then
reacts with the As2O3(aq). The moles of I2 formed is readily determined by
measuring the current and the time and recalling that one mole of electrons equals
96485 coulombs (amp seconds).
One particular advantage of this method is that I2 is formed only as needed and
hence all the disadvantages of trying to store a I2 solution are circumvented. The
purpose of this experiment is to determine the concentration of an unknown
solution of As2O3(aq).
The unbalanced reactions are:

Apparatus
 HOMEWORK(2)

2- In coulometric titration of iodine with 20 cm-3 of thiosulphate, 25 minutes were required to

oxidise thiosulphate and 200 mA of current were used . Calculate the molarity of thiosulphate

solution

Q = it

200
Q = 25  60  = 300Coulombs
1000

Q = n F  N

where n= number of electron n=1

N= number of mole

F = 96500C / mol

2S 2 O 32- (aq) + 3I 3- (aq) → S 4 O 62- (aq) + 3I - (aq)

Q 300
N=  = 3.1  10 −3 molofS 2 O3− 2
F n 96500  1

N 3.1  10 −3
M =  = 1.5  10 −2 M
Vlitre 0.20 L
 HOMEWORK(2)

2- In coulometric titration of iodine with 10 ml of As2 O3 , 299.7 seconds were required to

oxidise As2 O3 and 0.01131 A of current were used . Calculate the molarity of As2 O3 solution

As 2 O 3 (aq) + H 2 O → 2H 3 As 2 O 3 (dissolutio n)

Iodide is generated at the anode:

2I − → I 2 + 2e −

The overall reaction is:

I 2 + H 3 As 2 O 3 + H 2 O → 3I − + H 2 AsO -4 + 3H +

Two electrons for each mole of H 3 As2 O3 gives us four electrons for one mole of As2 O3

Q = it

Q = 0.01131 A  299.7 = 3.389Coulombs

Q = n F  N

where n= number of electron n=4

N= number of mole

F = 96500C / mol

Q 3.389
N=  = 8.7  10 −6 mol
F n 96500  4

N 8.7  10 −6
M=  = 8.7  10 −4 M
Vlitre 0.01L
 EXPERIMENT-7
Conductometric titrations of some acids and bases
Conductometric Titration: Determination of the strength of a solution of
hydrochloric acid by a standard solution of sodium hydroxide.

Introduction:
Electrolytic conductivity is a measure of the ability of a solution to carry electric
current.
Electric solutions conduct electric current by the migration of ions under the
influence of electric field. According to Ohm’s Law, the current strength flowing
through a conductor is directly proportional to the potential difference (E) and
inversely proportional to the resistance (ρ) of the conductor
. i.e. I = E/R or, R = E/I
Where the resistance (R) is the hindrance provided by the solution.
The resistance of any conductor varies directly with the length and inversely with
its area of cross-section.
R = ρ x (l/a)
Where, ρ is the specific resistance and it is the resistance of a unit length of
conductor of unit cross-section.
l/a is called cell constant.
The reciprocal of specific resistance is called specific conductance or
conductivity. Specific conductance (k) = 1/ ρ = (l/a) x (1/R)
Conductance of electrolyte depends upon:
1- number of free ions,
2- changes on the free ions and

mobility of the ions on the substitution of one ion by another of different mobility
(speed of ions).
So, Conductometric method can be used to determine the end point of ionic
titrations like
1) acidimetric titration,
2) precipitation titration,
3) titration involving the formation of complex ion.
When hydrochloric acid solution (HCl) is titrated with sodium hydroxide solution
(NaOH), the highly mobile hydrogen ions (λ° H + = 350 ohm–1 cm–1) are
progressively replaced by slower moving sodium ions (λ° Na + = 50 ohm–1 cm –1) and
the conductance of the solution decreases.
After the end point, the conductance of the solution rises sharply due to the
presence of excess, highly mobile hydroxide ion (λ° OH – = 198 ohm–1 cm–1 ).
Thus the neutralization of a strong acid by addition of a strong base leads to a
minimum conductance at the end points. This is due to the disappearance of H +
ions and their replacement by slower moving Na+ ions of the base followed by the
presence of highly mobile OH– ions after the end point. Therefore the nature of the
plot (conductance of the solution versus volume of base added) will be as given
below:
CONDUCTOMETRIC TITRATION

volume of base Conductance

0.0000 28.2000
5.0000 28.0000
10.0000 27.7000
CONDUCTOMETRIC TITRATION
15.0000 27.2000
30
20.0000 26.6000 MV (NaOH) = MV(HCl)
0.1* 130.5 = M*100
25.0000 21.8000 25
M(HCl)= 0.13 M

30.0000 20.6000
cnductance ( s)

20

35.0000 19.7000
15
40.0000 18.9000
10
45.0000 17.6000
55.0000 16.6000 5

65.0000 13.6000
0
0 50 100 150 200
75.0000 12.0000
Volume of 0.1M NaOH (ml)
85.0000 10.6000
95.0000 9.0000
105.0000 7.8000
110.0000 7.2000
115.0000 6.6000
120.0000 6.0000
130.0000 5.0000
 EXPERIMENT: 8

Polarographic determination of a trace metal

Determination of unknown concentration of Cadmium

 Voltammetry

Measure current (between W.E & C.E) as a function of applied potential (between W.E & R.E)
under conditions that promote polarization of a working electrode

Three transport mechanisms

Convection :motion of the Migration: movement of ions through Diffusion : from a region of high concentration to a
solution as a result of stirring or solution by electrostatic attraction to charged region of low concentration occurs whenever the
flow electrode concentration of an ion or molecule at the surface of
the electrode is different from that in bulk solution.

In Polarography In Polarography In Polarography

Unstirred A supporting electrolyte concentration 50-100 The rate of reduction is controlled by the rate
times greater than the analyte concentration will of diffusion of analyte to the electrode only.
reduce electrostatic transport of the analyte to a
negligible level.

Polarography: Differs from voltammetry in that it employs a Dropping Mercury In Polarography

Electrode (DME) as W.E
Faradaic current is the current resulting
from redox reactions at the working and
auxiliary electrodes.
Working (indicator) Electrode (W.E): Dropping
Mercury Electrode (DME) Counter (auxiliary) Electrode (C.E): Hg or
Pt that completes circuit
Used in the ppm range

Reference (standard) Electrode (R.E): potential remains constant

(Ag/AgCl electrode or calomel Hg/HgCl )
 2+
0.001 M Cd in 0.1 M2+KNO
− 3
supporting electrolyte
Cd + 2e → Cd

Limiting current = diffusion current  concentration [C]o

Ilkovic equation:

ld = (7.08 x 104)nCD1/2 m 2/3 t 1/6

Half wave potential(E½ at ½ i)

It is the potential corresponding to one half the
limiting current i.e. id/2

Residual current
Due to electrolytes
 Taibah University

Electroanalytical chemistry
Lab manual CHEM 352 & 334

First Edition

By

Analytical chemistry Division Members

1437 H

Taibah University Press

 Syllabus
Order Contents

1 Introduction to electroanalytical methods

pH Titration of unknown soda ash using potentiometric

2
measurements.

3 Potentiometric titration of chloride-iodide mixture

Determination of fluoride content of toothpaste using

4
fluoride ion- selective electrode.

Electrogravimetric determination of copper and nickel in a

5
mixture

Determination of arsenic in a sample by coulometric

6
titration

7 Conductometric titrations of some acids and bases

8 Polarographic determination of a trace metal

9 Study of electrode mechanism by cyclic voltammetry

Analysis of trace lead in water by anodic stripping

10
voltammetry

2
 EXPERIMENT- 1
Introduction to Electroanalytical Methods

The laboratory in electroanalytical chemistry is one of the most popular chemistry

laboratories. The experiments have been selected to demonstrate the basic principles
of the instrumental methods and to give the students a sound grasp of the general
applicability of methods to different types of chemical problems.

Galvanic and Electrolytic Cells

It is physically impossible to measure the potential difference between a piece of metal
and the solution in which it is immersed. We can, however, measure
the difference between the potentials of two electrodes that dip into the same solution,
or more usefully, are in two different solutions. In the latter case, each electrode-
solution pair constitutes an oxidation-reduction half cell, and we are measuring the sum
of the two half-cell potentials.

This arrangement is called a galvanic cell. A

typical cell might consist of two pieces of metal,
one zinc and the other copper, each immersed each
in a solution containing a dissolved salt of the
corresponding metal. The two solutions are
separated by a porous barrier that prevents them
from rapidly mixing but allows ions to diffuse
through.

If we connect the zinc and copper by means of a

metallic conductor, the excess electrons that
2+
remain when Zn ions emerge from the zinc in the left cell would be able to flow
through the external circuit and into the right electrode, where they could be delivered
to the Cu2+ ions which become "discharged", that is, converted into Cu atoms at the
surface of the copper electrode. The net reaction is the oxidation of zinc by copper(II)
ions:

Zn(s)+Cu2+→Zn2++Cu(s)
but this time, the oxidation and reduction steps (half reactions) take place in separate
locations:

left electrode: Zn(s) → Zn2+ + 2e– oxidation

right electrode: Cu2+ + 2e–→ Cu(s) reduction

3
Electrochemical cells allow measurement and control of a redox reaction
The reaction can be started and stopped by connecting or disconnecting the two
electrodes. If we place a variable resistance in the circuit, we can even control the rate
of the net cell reaction by simply turning a knob. By connecting a battery or other
source of current to the two electrodes, we can force the reaction to proceed in its non-
spontaneous, or reverse direction. By placing an ammeter in the external circuit, we
can measure the amount of electric charge that passes through the electrodes, and thus
the number of moles of reactants that get transformed into products in the cell reaction.

Electric charge q is measured in coulombs. The amount of charge carried by one mole
of electrons is known as the Faraday, which we denote by F. Careful experiments have
determined that 1 F = 96467 C. For most purposes, you can simply use 96,500
Coulombs as the value of the faraday. When we measure electric current, we are
measuring the rate at which electric charge is transported through the circuit. A current
of one ampere corresponds to the flow of one coulomb per second.

Charge Transport within the Cell

For the cell to operate, not only must there be an
external electrical circuit between the two
electrodes, but the two electrolytes (the solutions)
must be in contact. The need for this can be
understood by considering what would happen if the
two solutions were physically separated. Positive
charge (in the form of Zn2+) is added to the
electrolyte in the left compartment, and removed (as
Cu2+) from the right side, causing the solution in
contact with the zinc to acquire a net positive charge,
while a net negative charge would build up in the
solution on the copper side of the cell. These violations of electron eutrality would
make it more difficult (require more work) to introduce additional Zn2+ ions into the
positively-charged electrolyte or for electrons to flow into right compartment where
they are needed to reduce the Cu2+ ions, thus effectively stopping the reaction after
only a chemically insignificant amount has taken place.

In order to sustain the cell reaction, the charge carried by the electrons through the
external circuit must be accompanied by a compensating transport of ions between the
two cells. This means that we must provide a path for ions to move directly from one
cell to the other. This ionic transport involves not only the electro active species
Cu2+ and Zn2+, but also the counter ions, which in this example are nitrate, NO3-. Thus
an excess of Cu2+ in the left compartment could be alleviated by the drift of these ions
into the right side, or equally well by diffusion of nitrate ions to the left. More detailed
studies reveal that both processes occur, and that the relative amounts of charge carried
through the solution by positive and negative ions depends on their relative mobilities,
4
 which express the velocity with which the ions are able to make their way through the
solution. Since negative ions tend to be larger than positive ions, the latter tend to have
higher mobilities and carry the larger fraction of charge.

In the simplest cells, the barrier between the two solutions can be a porous membrane,
but for precise measurements, a more complicated arrangement, known as a salt bridge,
is used. The salt bridge consists of an intermediate compartment filled with a
concentrated solution of KCl and fitted with porous barriers at each end. The purpose
of the salt bridge is to minimize the natural potential difference, known as the junction
potential, that develops (as mentioned in the previous section) when any two phases
(such as the two solutions) are in contact. This potential difference would combine with
the two half-cell potentials so as introduce a degree of uncertainty into any
measurement of the cell potential. With the salt bridge, we have two liquid junction
potentials instead of one, but they tend to cancel each other out.

Cell description conventions

In order to make it easier to describe a given electrochemical cell, a special symbolic
notation has been adopted. In this notation the cell we described above would be

Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s)

There are several other conventions relating to cell notation and nomenclature that you
are expected to know:

 The anode is where oxidation occurs, and the cathode is the site of reduction. In an
actual cell, the identity of the electrodes depends on the direction in which the net cell
reaction is occurring.

5
 If electrons flow from the left electrode to the right electrode (as depicted in the above
cell notation) when the cell operates in its spontaneous direction, the potential of the
right electrode will be higher than that of the left, and the cell potential will be positive.
 "Conventional current flow" is from positive to negative, which is opposite to the
direction of the electron flow. This means that if the electrons are flowing from the left
electrode to the right, a galvanometer placed in the external circuit would indicate a
current flow from right to left.
 Electrolytic Cells
 An electrolytic cell has an endothermic chemical reaction. The reaction is not
spontaneous so a power source is required. Energy is stored in an
electrochemical cell. That energy can be released when the cell is allowed to run
in a galvanic mode.

Above right is the galvanic cell that we saw previously. The molecules A and
B+ are produced and energy is released. The electrode on the left side of the cell
is the cathode because A+ is reduced to A at that electrode.

Above left is the same cell in an electrolytic mode. An energy source causes the
reaction to go in the direction opposite to the spontaneous direction. Now,
A+ and B are produced. The electrode on the right is the cathode becuase B + is
reduced to B there.

Electrodes and Electrode Reactions

An electrode reaction refers to the net oxidation or reduction process that takes place
at an electrode. This reaction may take place in a single electron-transfer step, or as a

6
succession of two or more steps. The substances that receive and lose electrons are
called the electroactive species.

Fig. 4: Electron transfer at an anode

This process takes place within the very thin interfacial region at the electrode surface,
and involves quantum-mechanical tunneling of electrons between the electrode and the
electroactive species. The work required to displace the H2O molecules in the hydration
spheres of the ions constitutes part of the activation energy of the process.

In the example of the Zn/Cu cell we have been using, the electrode reaction involves a
metal and its hydrated cation; we call such electrodes metal-metal ion electrodes. There
are a number of other kinds of electrodes which are widely encountered in
electrochemistry and analytical chemistry.

Insoluble–salt Electrodes
A typical electrode of this kind consists of a silver wire covered with a thin coating of
silver chloride, which is insoluble in water. The electrode reaction consists in the
oxidation and reduction of the silver:

AgCl(s) + e– → Ag(s) + Cl–(aq)

The half cell would be represented as

... || Cl– (aq) | AgCl (s) | Ag (s)

Although the usefulness of such an electrode may not be immediately apparent, this
kind of electrode finds very wide application in electrochemical measurements, as we
shall see later.

Reference Electrodes
In most electrochemical experiments our interest is concentrated on only one of the
electrode reactions. Since all measurements must be on a complete cell involving two
electrode systems, it is common practice to employ a reference electrode as the other
7
half of the cell. The major requirements of a reference electrode are that it be easy to
prepare and maintain, and that its potential be stable. The last requirement essentially
means that the concentration of any ionic species involved in the electrode reaction
must be held at a fixed value. The most common way of accomplishing this is to use
an electrode reaction involving a saturated solution of an insoluble salt of the ion. One
such system, the silver-silver chloride electrode has already been mentioned:

Ag | AgCl(s) | Cl–(aq) || ...

Ag(s) + Cl–(aq) →AgCl(s) + e–

This electrode usually takes the form of a piece of silver wire coated with AgCl. The
coating is done by making the silver the anode in an electrolytic cell containing HCl;
the Ag+ ions combine with Cl– ions as fast as they are formed at the silver surface.

The other common reference electrode is the calomel electrode; calomel is the common
name for mercury(I) chloride.

Hg | Hg2+(aq) | KCl || ... Hg(l) + Cl– → ½ HgCl2(s) + e–

The potentials of both of these electrodes have been very accurately determined against
the hydrogen electrode. The latter is seldom used in routine electrochemical
measurements because it is more difficult to prepare; the platinum surface has to be
specially treated by preliminary electrolysis. Also, there is need for a supply of
hydrogen gas which makes it somewhat cumbersome and hazardous.

Summary and additional notes

Make sure you thoroughly understand the following essential ideas which have been
presented above. It is especially important that you know the precise meanings of all
the highlighted terms in the context of this topic.

8
 A galvanic cell (sometimes more appropriately called a voltaic cell) consists of
two half-cells joined by a salt bridge or some other path that allows ions to pass
between the two sides in order to maintain electron eutrality.
 The conventional way of representing an electrochemical cell of any kind is to write
the oxidation half reaction on the left and the reduction on the right. Thus for the
reaction

Zn(s) + Cu2+ → Zn2+ + Cu(s)

We write

Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s)

in which the single vertical bars represent phase boundaries. The double bar denotes
a liquid-liquid boundary which in laboratory cells consists of a salt bridge or in ion-
permeable barrier. If the net cell reaction were written in reverse, the cell notation
would become

Cu(s) | Cu2+(aq) || Zn 2+(aq) | Zn (s)

Remember: the Reduction process is always shown on the Right.

 The transfer of electrons between an electrode and the solution takes place by quantum-
mechanical tunneling at the electrode surface. The energy required to displace water
molecules from the hydration shell of an ion as it approaches the electrode surface
constitutes an activation energy which can slow down the process. Even larger
activation energies (and slower reactions) occur when a molecule such as O2 is formed
or consumed.

9
 EXPERIMENT- 2
pH Titration of unknown soda ash using potentiometric measurements.

INTRODUCTION

The measurement of soda ash in industrial samples is important. In this experiment, an

HCl solution is prepared and standardized with dried sodium carbonate. The
standardized HCl is then used to analyze a dried soda ash sample.
In the following procedures both indicator and pH meter methods (potentiometric
titration) will be used.

Purpose: The goal of this lab is to know how to use pH meter and how to calibrate it
and to determine the concentration of soda ash by means of a potentiometric titration.

PROCEDURE:

Indicator Method (note that the indicators are added only for reference purposes; the
important data are the pH readings) Prepare 500 mL of a 0.1M HCl (conc. HCl stock
is approx. 12.1 M) solution by diluting the appropriate quantity of conc. HCl with
water. Standardize against sodium carbonate as follows.
Weigh accurately two samples of 0.2g pure, dried sodium carbonate (by difference)
into a 250ml Erlenmeyer flask. Add 50mL distilled water and 1-2 drops
phenolphthalein indicator. Titrate slowly (0.5mL/sec) until the pink color disappears.
This is a slight excess for half the volume of acid required for total neutralization. Add
two drops of methyl orange indicator; continue titrating until the color changes from
straw to pale orange to pink.
Now weight accurately two 0.3 to 0.4g samples of the dried unknown soda ash and
titrate with the standardized acid in duplicate with indicators as above.
At the start of the experiment on the unknown, the student should run a quick,
approximate titration using the indicators to establish the approximate location of the
end points and the color changes to be expected. With this information, the student
should be able to determine the HCl required for the particular end-point, and then
carefully add the remaining 10% of the HCl slowly so that an accurate endpoint is
obtained.

pH Meter Titration

Weigh accurately 0.2g pure, dried sodium carbonate (by difference) into a 400mL
beaker provided with a magnetic stirring bar. Add 50mL water, dissolve. (No need to
add indicator in this titration since the pH readings will determine the equivalence point
more accurately than an indicator can). Insert a glass and a calomel electrode into the
solution, avoiding contact with the stirring bar. Add titrant and take readings at 1.0 mL
intervals.
10
Record where you think the end points are but don’t forget that you still have to do a
Gran Plot to ascertain the equivalence points. Exceed the final equivalent volume by
an additional 10ml of titrant. Do this titration rapidly, because the pH will tend to drift
as CO2 escapes from the solution. (Read pH meter 5-10 s after adding titrant)
Now weigh accurately 0.3 to 0.4 g of the dried soda ash unknown. Titrate, following
the above procedure using the pH meter. For each pH meter titration, a mandatory
Gran plot is to be plotted for both the first and second equivalence points. Calculate
your results based on the total volume needed to reach the second equivalence point*
ash unknown were sodium carbonate and contained no sodium bicarbonate. Report the
results as % sodium carbonate (Na2CO3) and as % sodium oxide (Na2O). Note that
Na2O can be thought of as the residue remaining after CO2 was removed from the
sodium bicarbonate.

Possible Sources of Determinate Errors.

If you compare the pH at the first end point with the pH at which you observed the
phenolphthalein end point, you may find that the indicator color changes, not at the end
point, but by as much as 3% to 5% of the volume of titrant after the endpoint. (For
example, the equivalence point may occur at pH 8.4, whereas the red color may
disappear at pH 8.0). This has some interesting consequences. One is that, with
indicator, the ratio of the volumes of acid at the second to the first end point is not
exactly ‘2’ but about 1.9 (check your indicator data in the textbook to see whether the
discrepancy occurs and if it agrees with this discussion). Another major difference
between the two end points is that of precision. Refer to your data obtained from the
pH meter titrations. The main factor influencing precision will be the ratio of changes
in pH to changes in volume of added titrant at the first and second end points.

11
12
 EXPERIMENT- 3
Potentiometric Titration of a Halide Mixture

Introduction: In many titrations, a visual change in the solution signals the endpoint.
But it is possible to determine the endpoint without a visible change. Other types of
physical changes can also be used to determine endpoints, such as the physical effects
arising from relatively large changes in the concentrations that occur near equivalent
points. For example, a pH-meter can be used to determine the endpoint in an acid-base
titration by showing where a rapid change in pH occurs. A pH measurement is an
example of a potentiometric measurement, that is, the measurement of an electric
potential across two electrodes. If the potential at one electrode is a function of
concentration of a given species, the voltage across the electrodes will be function of
the concentration of that species provided that the potential of other electrode is stable.

In this experiment, you will measure the potential across two electrodes. The half-
reactions are:

Ag+ + e-  Ag E= + 0.800 V

Cu  Cu2+ + 2e- E= - 0.340 V

If the solutions have a constant composition, the measured potential

should be constant. This is not the case in a titration however. In this
experiment you will be titrating a mixture of chloride and iodide
ions with a solution of silver nitrate. As the titration progresses, the
silver ion concentration will change by many orders of magnitude.
This will change the potential of the Ag/Ag + half-reaction. There
will be no change in the Cu/Cu 2+ potential, so the change in the
measured potential difference will be entirely due to the changing
silver ion concentration.

Neither silver iodide nor silver chloride is soluble so there are two precipitation
reactions that will take place:

AgCl  Ag+ (aq) + Cl- (aq) Ksp = 1.6  10-10

AgI  Ag+ (aq) + I- (aq) Ksp = 1.5  10-16

13
Since the silver iodide is significantly less soluble, it will precipitate from solution first.
As the titration progresses, the silver iodide will come out of solution until the iodide
is nearly entirely consumed. During the precipitation of the silver iodide, there will be
a large excess of iodide in solution (the silver will be virtually entirely removed upon
its addition). The actual concentration of silver can be calculated using
the Ksp relationship:

Once the iodide is consumed, the silver chloride will begin to precipitate and the
silver concentration will be limited by the Ksp of silver chloride:

Since the Ksp of silver chloride is so much higher than that of silver iodide, the
concentration of silver ion will be several orders of magnitude greater after the
silver iodide endpoint than it was prior to it. This increase in the silver ion
concentration will be reflected by a very sharp change in the measured
potential between the electrodes. When potential is plotted as a function of
volume of silver added, this sharp change in potential signals the first
endpoint; from the volume of silver added, the amount of iodide in the solution
initially can be determined.

The second endpoint is another point at which the silver concentration

increases by several orders of magnitude. This occurs when the chloride is
completely consumed. After this point, any silver added to the solution stays
in solution since there is no longer a suitable ion with which it can form a
precipitate. The volume of silver added between the first and second endpoints
can then be used to determine the amount of chloride that was present in the
unknown.

Purpose: The goal of this lab is to determine the composition of a mixture of potassium
chloride and potassium iodide by means of a potentiometric titration.

Procedure:
1) Pour all of your unknown into a 50 or 100 mL beaker. Dissolve in ~20mL of
deionized water and pour into a 100 mL volumetric flask. Thoroughly rinse
14
the beaker with several small portions of deionized water and transfer the
rinse water into the volumetric flask. Dilute to the mark and mix well.

2) Set-up the electrodes in your titration apparatus as described in lab. Both

electrodes must be in contact with the solution. Use a magnetic stir plate to
keep the solution well mixed as the titration progresses.

3) Pipet 25.00 mL of the unknown solution into a beaker and begin stirring. Begin the
titration by recording the initial volume of AgNO3 (Warning!!!) in your buret. Titrate with
~1 mL aliquots (record to the nearest 0.01 mL); record the potential between the electrodes
after each addition. You do not need to wait more than 15 to 30 seconds for each point.
Identify the approximate endpoints ( 1 mL).

4) After both endpoints are identified, empty the beaker into the silver waste receptacle
and clean the beaker and electrodes thoroughly.

5) Repeat the titration with another 25.00 mL aliquot, this time using approximately 0.1
mL aliquots within  1 mL of the endpoints. Use 1 mL aliquots at other regions of the
titration. Again, you do not need to allow more than 30 seconds between data points.

Data Analysis:

Prepare two graphs of your data:

a) potential vs. volume Ag+ added, and

b) a first derivative plot of the raw data (dE/dV vs Vav)

Use the peak maxima of the first derivative plot to indicate the endpoints. From the
endpoints and the concentration of silver nitrate, calculate the mass percent of potassium
chloride and potassium iodide in your sample.

Prepare a formal written lab report that includes a discussion of the theory of the
experiment (e.g., why potential varies with concentration, what chemical reactions are
taking place, etc.) as well as your graphs and results of the mixture analysis.

15
 EXPERIMENT-4

Determination of fluoride content of toothpaste using fluoride ion-

selective electrode.
Introduction:
The development of ion-selective electrodes (ISE) makes possible the determination
of the concentration of ions of choice using selectively sensitive electrode membranes.
More than 20 ions can be determined by ISE, for example cations such as: Ag + , Na+ ,
K+ , Ca2+, Cu2+ and anions like: F- , Cl- , S2-, CN- . The operation of a fluoride-selective
electrode is based on the potential which develops across a single-crystal lanthanum
fluoride membrane.

This potential is proportional to the activity of F- ions in contact with the membrane.
This potential is measured against a convenient reference electrode and closely follows
the Nernst Equation

: E = E° + (0.059 volts/n) log[ion]

Where n = ionic charge.

The above equation is valid for dilute solutions and for solutions whose ionic strength
is kept constant.

Ionic strength, µ, is defined as

µ = (1/2) ci zi2

Where ci = concentration of the ith ion, zi is the charge of the ith ion.

For example, solutions containing 1:1 electrolyte, like NaCl, µ = [NaCl]. In this
experiment, the fluoride content of (1) an unknown NaF solution, and (2) toothpaste
will be measured by direct current potentiometry with a fluoride ion activity electrode
in a high ionic strength medium.

In practical operation, a high ionic strength medium is necessary so that fluoride ion
concentrations may be deduced from measurement of fluoride ion activities. A concept
called TISAB (Total Ionic Strength Adjustment Buffer) has been introduced precisely
for adjusting the conditions of fluoride analysis. The composition of TISAB is not
critical when the same solution is used for standardization and unknowns. A typical
composition is given in the Table below. TISAB is used to “swamp out” standard and

16
sample differences in ionic strength. TISAB also minimizes the influence of polyvalent
cation fluoride complexes.

Table: Composition of TISAB

Sodium chloride 1.0 M

Acetic acid (pKa=4.75) 0.25 M
Sodium acetate 0.75 M
Sodium citratea 0.001 M
pH 5.0
Ionic strength (approx.) 1.83 M
In this experiment, instead of TISAB, a 0.1M KCl solution will be employed.

Purpose: The goal of this lab is to determine the fluoride content of toothpaste using
fluoride ion- selective electrode.

Procedure:
Prepare the solvent:

Prepare 750 mL of 0.10 M KCl. This will serve the same purpose as the TISAB. Note
that all dilutions will be made using this 0.1M KCl solution and not distilled water.

Prepare the calibration solutions:

Prepare a 100-mL stock solution containing 1000 ppm F- using reagent grade sodium
fluoride dried for 1 hour in the oven. (Show your instructor by a clear calculation that
the grams of NaF required for this solution would be somewhere between 0.2 - 0.3
grams.). Dissolve the weighed NaF in a 100-mL beaker, add 50mL of 0.1M KCl.
Transfer the solution to a 100-mL volumetric flask and fill it to the mark with 0.1M
KCl and mix very well. (Depending on your instructor’s discretion, this stock solution
may be shared by all students doing the fluoride analysis on the same lab session).
From this stock solution, prepare a 20-ppm F- calibrating solution (for example, place
2-mLs of the stock in a 100-mL volumetric flask, add 0.10 M KCl and dilute it to the
mark). From this 20-ppm calibrating solution, prepare 10, 5, 2.5 and 1.25 ppm
calibrating fluoride solutions by serial dilution by taking 50-mL of the prior solution
and diluting it to 100-mL with 0.1 M KCl in a 100-mL volumetric flask.

Obtain and prepare samples for analysis:

(1) Obtain a toothpaste sample from the instructor by submitting a clean, dry and
preweighed 20-mL beaker to which 0.2-0.25 g toothpaste will be added by the
17
instructor. A toothpaste sample is prepared as follows: weigh the beaker plus the
sample of toothpaste to determine the net weight of the toothpaste sample. Transfer the
toothpaste sample to a 250 mL beaker with a microspatula or stirring rod and add 50
mL 0.1 M KCl. Boil the solution gently for 2-3 minutes. Filter the suspension by
gravity filtration using a #1 or #5 filter. After cooling, transfer the solution
quantitatively to a 100 mL volumetric flask and make up to volume with 0.1M KCl.

(2) Obtain an unknown NaF sample from the instructor by submitting a clean 10- mL
graduated cylinder. A 7.00-10.0 mL sample of an unknown solution of F- will be
supplied to you by the instructor. Transfer accurately (with a 5-mL transfer pipet), 5.0
mL of the solution and dilute it to 100-mL in a volumetric flask using the 0.1M KCl.

Measurement of F- : The measuring system consists of the fluoride and reference

electrodes and a pH meter in the mV mode. Note that although the fluoride electrode
is a solid state which employs a rugged, epoxy-body construction, it is important to
exercise proper care. The electrode is stored dry when not in use, with a protective end
cap. Carefully remove the end cap so as to avoid any damage to the electrode.

Transfer approximately 20 mL of each solution into 50 mL beakers. Be sure that the

solution is well stirred and record the observed emf (in mV) 3 minutes after the fluoride
and reference electrodes have been immersed in the solution. Repeat for all the
calibrating solutions as well as the sample solutions. Note: If the emf of the toothpaste
falls outside the emf range of the standards additional calibrating solutions may be
needed.

Analysis:

Plot the observed emf in mV vs logarithm of ppm F- to obtain a calibration curve. A

negative slope of -59±4 mV (between 20°-30°C) indicates normal operation.
Determine the ppm F- in your unknown and in the toothpaste from the calibration
curve. The ppm unknown can be determined using the following equation:

Ppm Funk = ppm F- from graph x (100 mL/5mL) = ppm F- (graph) x 20.

Express the fluoride ion concentration in the toothpaste as %F. The following equation
can be used:

18
19
 EXPERIMENT-5

ANALYSIS OF COPPER IN A MIXTURE BY ELECTROGRAVIMETRY

Introduction
In this experiment, copper in a copper-nickel mixture is analyzed by
electrodepositing only copper onto a previously weighed inert platinum mesh
electrode.
The increase in weight of the electrode is then related to the amount of metal present
in the unknown. Cu(II) is easier to reduce than Ni(II) at a platinum cathode, and so
when a negative voltage is placed on the electrode, the copper will selectively plate
out. After most of the copper has been removed from the solution by this process,
Ni(II) would then ordinarily begin to deposit (which would prevent an accurate
determination of copper).
This can be avoided by performing the electrolysis in a sulfuric acid-nitric acid
solution.
Both hydrogen ion and nitrate are less easily reduced than Cu(II) but more easily
reduced than Ni(II). When most of the copper has deposited, the following reaction
begins to carry the current, and no Ni(II) is able to deposit.

NO3- + 10H+ + 8e- = NH4+ + 3H2O

It is desirable to have a secondary reaction occur which does not cause gas bubbles to
form at the cathode (e.g., the reduction of hydrogen ion). Gas bubble formation
generally results in a metal deposit with very poor qualities. The reduction of nitrate
avoids this difficulty.
A platinum mesh electrode is used for deposition of the metal because its large
surface area yields low current density (amperes/cm2) and a more adherent deposit
results. A platinum wire anode is centered inside the cylindrical cathode. It is
positioned carefully to produce a uniform deposit on all parts of the cathode.

Purpose: The goal of this lab is to determine the Copper in a mixture by

Electrogravimetry.

Procedure

Sign out a Pt mesh electrode (it must be returned intact and clean, at the end of the
experiment). It is important to treat the platinum electrodes with care, for they are
quite expensive and easily deformed. Also, do not touch the electrodes while the
power supply is turned on, in the obvious interests of safety.

20
1. Attend a discussion of the electrodeposition apparatus with your instructor. The
unknown is supplied in a vial. Transfer the contents of the vial quantitatively to a
100 mL volumetric flask, dilute to the mark with water and mix well.

2. Wear finger cots or gloves when handling the platinum mesh electrodes to avoid
depositing grease from your hands, and altering the weight of the electrode.
Clean the platinum mesh electrode by immersing it in warm concentrated HNO3 for
about one minute. If the platinum mesh is left in the HNO3 solution for more than 2
min, some platinum can dissolve, leading to error after step 8. Rinse the electrode
with distilled water and then with a small portion of acetone.

CAUTION! Nitric acid and acetone form a dangerous, potentially explosive mixture
if they come into contact. Follow the procedure as described, and also be sure to rinse
acid and acetone down the sink with plenty of tap water, not allowing them to
accumulate in the sink.
Place the electrode in a clean beaker and dry in the oven at 110 °C for 3-5 minutes.
Remove from the oven, allow the electrode to cool in air for 5 minutes, and then
weigh to the nearest 0.1 mg.

3. Place the Pt mesh electrode in the electrolysis assembly, and adjust its position so
that it does not touch the inner Pt wire anode. (If the electrodes touch, the circuit is
shorted, and the power supply could be damaged.)
4. Pipet a 10 mL aliquot of unknown into a 300 mL tall form beaker. Add 5 mL of 2
M HNO3, 10 mL of 3 M H2SO4 and enough deionized water to make the final volume
about 150 mL. Add a stirring bar to the solution.

5. Position the beaker so that the electrodes are centered in it and the top of the Pt
mesh electrode is about 2 mm above the solution level. Stir the solution at a moderate
rate. Cover the solution with the plastic cover provided.

6. Turn on the power supply and slowly increase the applied voltage to the cell until
the current meter indicates one ampere. Allow the electrolysis to proceed for 30
minutes. Make sure that the current stays at one ampere throughout the experiment.
There should be a stream of gas bubbles coming from the anode at all times. If this is
not the case, the anode and cathode may be touching and Cu will no longer be
depositing. Ensure that the electrodes do not touch each other, especially when
placing the plastic cover on the tall form beaker.

7. After 30 minutes, rinse the plastic cover and sides of the beaker with a stream of
water, until the top of the Pt mesh electrode is immersed. Continue the electrolysis
for another 10 minutes.

8. If no visible copper deposit can be seen on the newly immersed portion of the
electrode, the electrolysis is complete. Without turning off the power supply,
21
remove the plastic cover and stirring motor, and slowly lift the electrodes from the
beaker (wear gloves or finger cots) while washing the Pt mesh electrode with a
stream of water. (If the current were turned off while the electrode was immersed in
the acid solution, copper would quickly redissolve.
Similarly, if any acid is allowed to remain on the electrode, copper metal will
dissolve, producing low results.) Immediately wash the electrode with water, and
then with acetone. Dry the electrode in the oven for 5 minutes in a small, clean
beaker, then allow to cool, and weigh.

9. Repeat steps 2 through 8 twice more.

10. Return the Pt mesh electrode to your Teaching Assistant, after cleaning and
drying.
Report the weight of copper (in grams) in your total sample.

EXPERIMENT-6
22
 Determination of arsenic in a sample by coulometric titration

I. Introduction

Redox reactions may be separated into half reactions involving either the gain or loss
of electrons at electrodes. In this titration to determine the concentration of a
As2O3(aq) solution, I2 is formed from I- by an oxidation half reaction. The I2 then
reacts with the As2O3(aq). The moles of I2 formed is readily determined by measuring
the current and the time and recalling that one mole of electrons equals 96485
coulombs (amp seconds).
One particular advantage of this method is that I2 is formed only as needed and hence
all the disadvantages of trying to store an I 2 solution are circumvented. The purpose
of this experiment is to determine the concentration of an unknown solution of
As2O3(aq).
The unbalanced reactions are:

Apparatus

Note: A resistance of approximately 2 ohms prevents the power supply from

generating a high voltage when the titration switch is off.

23
Purpose: The goal of this lab is to use Coulometric titration to determine the arsenic
concentration in a solution.

Procedure:

Set up the apparatus as shown on the previous page. Using a solution containing
0.8 g KI, 3.0 g NaHCO3, and 15 mL starch indicator diluted to 500 mL, fill a 250 mL
narrow mouth Erlenmeyer flask sufficiently to cover the electrodes when inserted.
Place the flask on a magnetic stirrer and insert a stirring bar.
Turn the stirrer on to insure that it stirs smoothly. (If the magnetic stirrer has a separate
on/off switch, leave the switch on and use the speed control knob for adjustment of
speed. Do not ever start the stirrer at high speed using the on/off switch since the
stirring bar will sometimes jump around rather than spin smoothly.)
Set the multimeter to 20 ma and ma DC. Set the power supply initially on 0-15 ma
upper knob) and 0-30 ma constant current (lower knob). With the titration switch off
adjust the current to about 10 ma. Reposition the upper knob to 0-150 volts. (The
current through the cell will be read by the multimeter.)
Lower the electrodes carefully into the flask. Adjust the stirrer speed. Do not stir
extremely rapid. Turn the titration switch on and examine the blue color appearing at
one of the electrodes. After about 15 seconds stop and let the solution clear. If the
solution is bluer than desired add a few drops of the As 2O3 solution until the solution
clears up and then readjust the color. When satisfied with the color, set the timer on
zero. (If the timer used is a ‘count down’ type, there will possibly be a ‘count up’ set
of numbers.)
Pipette 1 mL (check with instructor to see what is recommended for the sample to be
analyzed) of the unknown As2O3 (aq) solution into the Erlenmeyer flask. Turn the
titration switch on. Record the ma (which should be between 7-10 ma) every 30
seconds. Adjust the power supply as necessary to maintain this current. Every 2
minutes turn the titration switch off and let the iodine diffuse off the electrode. When
the entire solution appears to be turning a permanent light blue, turn the titration switch
off and see if the color persists and matches the initial color. The titration switch is
equivalent to the stopcock of a buret. If the color does not persist or does not match,
turn the switch on until the appropriate persistent color is achieved. Record the total
time.
Calculate the concentration of the As2O3 (aq) solution. Repeat the procedure at least
twice more. There is no need to replace the KI solution although it might be
necessary to discard some of it if the Erlenmeyer fills up.

Write-up for Coulometric Titration Experiment

I. Raw Data Tables
II. Calculations and Discussions
A. Identify the possible redox reactions in the electrolysis at each electrode and
predict the actual reactions. Balance the redox equation.
24
B. Write the balanced equation of As2O3 with water to form arsenious acid.
C. Write the balanced redox reaction of arsenious acid with iodine to form arsenic
acid from the balanced half cell reactions.
D. Make a table of the values for each trial to be used: average current, time, volume
and the errors in each quantity.
For the average current error find the standard deviation of the mean and compare to
the scale error. For time estimate the error taking into consideration the difficulty in
obtaining a consistent blue color.
For volume error use the stated calibration error for the pipettor as the scale error.
E. Calculate the molarity of the As2O3 solution for each trial. Explain the
calculation. It is probably best done as a stoichiometry problem with factor label
conversions.
F. Convert your stoichiometry problem into an equation involving current, time,
volume of sample and other constants. Then determine the propagated error in the
molarity for each trial and the best value for the molarity in each trial.
G. Determine the scatter error for the three determinations.
H. Determine the best value obtained for the molarity taking into account both the
propagated and scatter error.
I. Discuss the general usefulness of the method. Comment on sources of error. What
other methods might be used to determine the concentration

25
 EXPERIMENT-7
Conductometric titrations of some acids and bases
Conductometric Titration: Determination of the strength of a solution of hydrochloric
acid by a standard solution of sodium hydroxide.

Introduction:

Electrolytic conductivity is a measure of the ability of a solution to carry electric

current. Electric solutions conduct electric current by the migration of ions under the
influence of electric field. According to Ohm’s Law, the current strength flowing
through a conductor is directly proportional to the potential difference (E) and
inversely proportional to the resistance () of the conductor
. i.e. I = E/R or, R = E/I
Where the resistance (R) is the hindrance provided by the solution.
The resistance of any conductor varies directly with the length and inversely with its
area of cross-section.
R =  x (l/a)
Where,  is the specific resistance and it is the resistance of a unit length of conductor
of unit cross-section.
l/a is called cell constant.
The reciprocal of specific resistance is called specific conductance or conductivity.
Specific conductance () = 1/ = (l/a) x (1/R) Conductance of electrolyte depends
upon
- number of free ions,
- changes on the free ions and
- mobility of the ions on the substitution of one ion by another of different
mobility (speed of ions).
So, Conductometric method can be used to determine the end point of ionic
titrations like i) acidimetric titration, ii) precipitation titration, iii) titration
involving the formation of complex ion.
When hydrochloric acid solution (HCl) is titrated with sodium hydroxide solution
(NaOH), the highly mobile hydrogen ions ( ° H + = 350 ohm–1 cm–1) are
progressively replaced by slower moving sodium ions ( ° Na + = 50 ohm–1 cm –1)
and the conductance of the solution decreases.
After the end point, the conductance of the solution rises sharply due to the
presence of excess, highly mobile hydroxide ion ( ° OH – = 198 ohm–1 cm–1 ).
Thus the neutralization of a strong acid by addition of a strong base leads to a
minimum conductance at the end points. This is due to the disappearance of H+
ions and their replacement by slower moving Na+ ions of the base followed by the
presence of highly mobile OH– ions after the end point. Therefore the nature of the
plot (conductance of the solution versus volume of base added) will be as given
below:
26
 The conductivity cell used for this titration should permit stirring by shaking and
to which the reagent can be added from burette. A large increase in volume during
titration should be avoided.

Purpose: The goal of this lab is to use conductometric Titration for Determination of
the strength of a solution of hydrochloric acid by a standard solution of sodium
hydroxide.

Apparatus:

Conductometer, conductivity cell, beaker, pipette, burette, conical flask.

Chemicals:
Hydrochloric acid (HCl), sodium hydroxide (NaOH), conductivity water.

Procedure:

1. HCl solution of unknown strength is provided.

2. 0.1 (N) NaOH solution is provided.
3. Calibration of the instrument done at room temperature.
27
 4. Conductometric Titration:
i) Rinse the conductivity cell a number of times with conductivity water or
double distilled water.
ii) Pipette out 20 mL of HCl in a beaker and dip the conductivity cell in it, so that
the cell should dip completely in solution.
iii) Note the temperature of the sample solution and accordingly set the
temperature control or keep the cell in a thermostat at room temperature.
iv) Add small amount of NaOH solution (few drops) from burette, stir it and
measure the conductance after each addition.
v) Take at least five readings beyond the end point.

Observation and Calculation:

Conductometric Titration Volume of HCl taken (V1) (mL) Volume of NaOH

added (V2) (mL) Conductance 20 Plot a graph between conductance and volume
of titrant (NaOH solution).
Two intersecting lines will be obtained (as given in the Figure 1) and the points of
intersection of these lines represent the equivalent point. Let, V2 be the volume of
NaOH at the equivalent point (from graph) and the strength of acid is S1 and
strength of NaOH solution is S2 = 0.1(N).
Then,
20 x S1 = V2S 2
 S1 = (V2S 2/20) (N)

Conclusion: The strength of the acid is ______ (N)

Discussions:
i) Normally, the coloured solution which cannot be titrated with volumetric
method using indicator can be titrated by the conductometric method.
ii) ii) The conductometric titration method can be used in case of weak acid vs.
weak base and also in case of very dilute solutions.
iii) iii) Near the end point, no special case is necessary as it is determined
graphically.

Precautions:
i) Electrical connection should be made carefully.

28
ii) Temperature during the experiment should be kept constant as conductance
depends on temperature.
iii) Stirring should be done after each addition of titrant.
iv) To avoid the dilution effect, the concentration of the titrant should be 5-10
times more than that of the solution to be titrated.

29
 EXPERIMENT-8
Polarographic determination of a trace metal
Determination of unknown concentration of Cadmium

Introduction:

Polarography, is a branch of voltammetry, is the study of the electrolysis of solutions

of electrooxidizable and or electroreducible substances between a dropping mercury
electrode (DME) and some reference electrode (RE) which is saturated calomel
electrode (SCE). This falls into the general category of linear-sweep voltammetry. In
this the electrode potential is usually altered in a linear fashion from the initial potential
to the final potential. The only difference in polarography is, the working electrode
takes the form of a dropping mercury electrode(DME). It consists of about 10 cm of a
fine capillary tubing through which mercury is forced by a mercury head of about
50cm. The diameter of the capillary tube is adjusted in such a way that a new drop will
form and breaks at specific timings; usually 2 to 6s. The drop time can be controlled
by a mechanical knocker that will help to dislodge the drop at a fixed time after the
drop begins to form. The potential between the reference electrode and DME is varied
and the resulting change in the current flow is measured. Since the linear sweep method
is controlled by combined diffusion or connection mass transport method, the resulting
the current versus potential response i-E curve is known as Polarogram and it is
sigmoid in shape(S-Shape). The position of a wave in a polarogram along the potential
axis provides an identity of the substance while the magnitude of the limiting current
provides the concentration variation of this material.

Since there is an increased flow of current at the starting region of the polarographic
wave there is a marked decrease in the concentration of electro-active substance at the
surface of the electrode. With the increase in voltage and current the concentration of
the reactive species reaches to a minimal value near to the electrode surface. The
current is then limited which depends on the diffusion rate of the reacting species from
the solution to the electrode surface. The rapid increase of current at the final stage is
30
due to the supporting electrolyte in the reaction. Since the concentration of the
electrolyte is too large within the applied potential range, it will prevent the reactive
species to reach the electrode by the electrical migration process, and hence the limiting
curent is assured as diffusion controlled.

Polarographic cell Tygon tube with mercury

Reference electrode (Saturated

Auxillary electrode (Platinum electrode)
calomel electrode)

Residual current is the slowly increasing current at the foot of the wave which is non
faradaic in nature. The distance between the limiting diffusion plateau and the residual
current is known as diffusion current (id). The potential at the midpoint of the wave is
represented as half-wave potential E1/2, in this region the current is exactly half its
limiting value. The limiting current is found to be the sum of the diffusion residual
current. The wave height can be calculated by subtracting residual current from the
limiting current.
31
The limiting current (the plateau on the sigmoid), called the diffusion current since
diffusion is the most important contribution to the flux of electroactive material at
that point of the Hg drop life, is linked to analyte concentration by the Ilkovic
equation:

Where,

id = average diffusion current during the life of the drop(µA).

D= Diffusion coefficient of the analyte in the medium (cm2/s).
n = Number of electrons transferred per mole of analyte.
m = mass flow rate of Hg through the capillary (mg/sec).
t = drop lifetime(s).
c = analyte concentration (mol/cm3).

32
 Where,
E= applied voltage.
i= current.

Materials Required:

1. Polarographic Instrument.
2. Beaker.
3. 10 mL Pipette.
4. Wash bottle.
5. 100 mL volumetric flask.

Reagents:

1. 1, 2, 3, 4 and 5 mM Cadmium standards.

2. 2 M KCl solution.
3. 0.2% gelatin solution.
4. Distilled water.

Procedure:

1. Select the concentration from the list.

2. Click “Load Cadmium Sample” button.
3. Select “Scan Analysis”.
4. Click “Plot Graph”.
5. Select the unknown concentration from the concentration list.
6. Repeat the steps 2, 3 and 4.
7. Enter the concentration values on the worksheet.
8. Plot calibration curve by clicking the “plot” button on the worksheet.
9. Calculate the unknown concentration value from the calibration curve.

Observations and Calculations:

33
 Diffusion
Concentration current
No
(mM)
(id)

10.Plot concentration Vs difussion current.

11.id of unknown concentration =............................ .
12.Therefore concentration of the given solution =......................................mM.

Result:

Unknown concentration of the given solution =.......................mM.

34
 EXPERIMENT- 9
Study of Electrode Mechanism by Cyclic Voltammetry

Introduction:

Cyclic voltammetry involves applying a voltage to an electrode immersed in an

electrolyte solution, and seeing how the system responds. In CV, a linear sweeping
voltage is applied to an aqueous solution containing the compound of interest. The
voltage is initially given by Equation 1.2 (see below). After the voltage reaches a
certain maximum value, the potential is reversed and the sign of vt reverses and
Ei becomes the maximum voltage, Eλ. The process can then be repeated in a periodic,
or cyclic manner.

As an important tool for studying mechanisms and rates of oxidation and reduction
processes, CV provides the capability for generating a species during the forward scan
and then probing its fate with the reverse scan or subsequent cycles, all within seconds.
The unique aspect of cyclic voltammetry is the three electrodes used, which consist of
a working electrode, a reference electrode, and a counter electrode. The working
electrode can be seen as a medium whose reductive or oxidative power can be
externally adjusted by the magnitude of the applied potential--as the potential is
increased or decreased linearly versus time, it becomes a stronger oxidant or reductant,
respectively. Therefore, the working electrode, which typically consists of a chemically
inert conductive material such as platinum, acts as a donor or acceptor of electrons
participating in the general electrode reaction,

O+ne− →R

The reference electrode, typically AgCl or calomel, keeps the potential between itself
and the working electrode constant. The potential is measured between the reference
and working electrodes, and the current is measured between the working and counter
electrodes. A counter electrode is employed to allow for accurate measurements to be
made between the working and reference electrodes. The counter electrode's role is
essentially to ensure that current does not run through the reference electrode, since
such a flow would change the reference electrodes potential. A voltage sweep from
Ei to Ef is produced using a signal generator, and the voltage is applied to the working
electrode using a potentiostat. By sweeping the voltage slowly, information may be
extracted from a graph of potential versus current going through the
sample. Polarography utilizes this method of analysis where the limited current arising
from a redox process in the solution during the sweep is used to quantitatively
determine the concentration of species that are electrochemically active in solution.

35
CV differs from polarography in two important ways. Firstly, the working electrode
at which the reactions of interest occur has a constant area, not one which changes
with time as in classical polarography. This electrode may be a solid such as graphite
or platinum with a small surface area, or a stationary or hanging mercury drop. The
latter type of electrode may have its surface renewed periodically. The second
difference is that the potential of the working electrode is scanned rapidly over a wide
potential range and then returned to its initial value using an applied potential signal
which varies linearly with time between the initial value and the final value at the
limit of the forward scan. Normally, this technique is applied so that currents due
to reduction processes are observed during the forward scan, and those due
tooxidation on the reverse scan. A typical potential against time profile applied to the
working electrode and the resulting cyclic voltammogram are shown in Figure 1.1.

Figure 1.1. (a) Potential against time program for cyclic voltammetry and (b) current
against time curve.

This laboratory exercise studies the oxidation mechanism of 4-acetminophenol,

otherwise known as acetaminophen, the active ingredient in Tylenol. It will be
refered to as APAP from this point. The oxidation mechanism of APAP is as follows:

36
This process can be electrochemically “mapped out” by varying the pH of the
supporting electrolyte and the scan rate in cyclic voltammetry. At a pH of 6, APAP is
oxidized in a quick pH dependent step involving the loss of two electrons and two
protons to give N-acetyl-p-quinoneimine (NAPQI) as shown in step 1 of the above
mechanism. At a pH greater than or equal to pH 6.0 NAPQI (II) exists in its stable,
unprotonated form. Under more acidic conditions (ex. pH 2.2), NAPQI is readily
protonated to give species III, which is a less stable, but electrochemically active
species. Species III then rapidly yields a hydrated species (IV), which is
electrochemically inactive in the examined potentials. Finally, under increasingly more
acidic conditions the hydrated species (IV) converts to benzoquinone (V). Only under
extremely acidic conditions will the reduction of benzoquinone observed with cyclic
voltammetry.

Purpose:
Use cyclic voltammetry to determine the concentration of acetaminophen in a
children’s pain relief elixir. 2). Study the mechanism of acetaminophen oxidation,
which involves both pH dependent and coupled chemical reactions.

PRE LAB QUESTIONS:

To make sure that you understand the experiment, please answer following questions
in the prelab. These questions must be completed before lab and handed in to the TA
before beginning any experiments. .

1. Does O2 need to be accounted for in this experiment? Why or why not?

2. Why is cyclic voltammetry an unstirred voltammetry technique?
3. Why is a triangular waveform used as the excitation waveform in cyclic
voltammetry rather than a square waveform?

37
Materials

• Pine AFCB1 Bipotentiostat

• Three electrode Cell
• Glassy carbon electrode
• Platinum auxiliary electrode
• Ag/AgCl reference electrode
• pH 2.2 and pH 6.0 McIlvaine Buffer with 0.5 M ionic strength
• 1.8 M sulfuric acid
• 0.070 M 4-acetamidophenol in perchloric acid (stock solution)
• Children’s Tylenol Elixir

Experimental Procedure Note:

All glassware used for electrochemistry experiments must be as clean as possible.

The solvents and reagents used to prepare solutions should be pure. Additionally,
ultrapure (MilliQ) water is required for all dilutions and final rinsing of glassware.

A. Solution Preparation

The TA will prepare the stock solution of 4-acetamidophenol (APAP), both

McIlvaine buffer solutions, and the sulfuric acid. The children’s Tylenol will also be
provided. The following solutions must be prepared before beginning the cyclic
voltammetry experiments:
1. 10 mL of 3mM APAP in each supporting electrolyte (pH 2.2 and 6.0 buffer
solutions and sulfuric acid)
2. Four additional APAP solutions in pH 2.2 buffer spanning the range of 0.10 to 5.0
mM.

B. Cyclic Voltammograms

Several cyclic voltammograms are obtained with solutions of varying concentrations,

supporting electrolytes.
The five standard solutions in the pH 2.2 buffer will be run with a scan rate of 40
mV/sec.
The 3-3mM solutions with different supporting electrolytes (pH 2.2 buffer, pH 6.0
buffer, and 1.8M sulfuric acid) will each be run at scan rates of 40 mV/sec and 250
mV/sec. General instructions for cyclic voltammetry are as follows:

38
1. Equip a clean electrochemical cell with a Ag/AgCl reference electrode, a platinum
auxiliary electrode, and a glassy carbon reference electrode.

2. Fill the cell with the solution to be analyzed (lowest concentration first), making
sure that all three electrodes are immersed in solution.

3. Before making electrical connections between the cell and the potentiostat, assure
that the instrument is in DUMMY mode. This is accomplished by adjusting the
controls on the INSTRUMENT STATUS panel to match the settings. At this point,
the electric connections between the potentiostat and the cell may be made.

4. Select the Analog Sweep Voltammetry option from the Experiment menu and
adjust the experiment settings . The scan rate should either be set to 40 or 250 mV/sec
as discussed above.)

5. Click the PERFORM button to initiate the experiment. A fairly prominent anodic
wave should appear during the sweep from 0 mV to +1000 mV. On the return sweep,
no cathodic wave should be apparent. Note that as displayed by the software,
positive potentials are plotted to the right and anodic currents are plotted to the top of
the graph, which is the opposite of conventional electrochemical techniques.

6. After acquiring a satisfactory voltammogram, save it under

C/pchem/yourgroupnumber and print. Note that if more than one cyclic
voltammogram of the same solution is required slightly move the working electrode
to agitate the solution and replenish the analyte.

7. Plot the voltammogram as a current versus time graph by choosing the I1 vs. t
option from the Plot menu. Then, use the Peak Height Tool found in the Toolbox
menu to measure the height of the anodic peak. Record peak height.
8. Acquire similar cyclic voltammograms for the remaining standard solutions and
different supporting electrolyte solutions in order of increasing concentration APAP
solutions. Adjust the sweep rate as necessary.

9. Finally acquire a voltammogram of the Elixir Test Solution using the same
experimental parameters as for the standard solutions.

39
C. Data Analysis Using the anodic peak currents

for the series of standard solutions, construct a calibration curve of peak current versus
concentration. Perform a least squares analysis on the data to find the equation of best
straight line which fits the data.

Be sure to include error analysis with the least squares fit. Using the equation of the
calibration curve line, compute the concentration of acetaminophen (APAP) in the
elixir.

Remember to take into account any dilution of the original elixir during solution
preparation process (TA will inform of any dilutions).

Report the acetaminophen concentration in grams per liter using three significant
figures. Convert the acetaminophen concentration listed on the manufacturer’s label to
units of grams per liter using three significant figures.

Compare your calculated value to the label value.

40
 EXPERIMENT- 10
Analysis of Trace Lead in Water by Anodic Stripping Voltammetry

Introduction:

ASV is one of the most sensitive, convenient, and cost effective analytical methods
for detection and determination of metal ion contaminants, such as lead, in water
whether from rivers, lakes, process streams or drinking sources. With ASV, it is
possible to analyze simultaneously very low levels of several metals such as Pb, Cu,
Cd and Zn. ASV can detect levels in the range of part-per-million (ppm) or even part-
per-billion (ppb) (i.e., ~10-10 M). Example linear sweep ASVs of Pb are shown in
Figure1. ASV involves a deposition step (often called pre-concentration) at an
applied negative potential for a specified period of time. The metals, as ions in
solution, are concentrated by plating them onto the electrode in their metallic form.
Then the electrode is scanned linearly toward positive potentials so that the metals,
one at a time, are stripped from the electrode and re-oxidized at a potential
characteristic of each metal. The resulting current-voltage peaks can be compared
with those in a calibration curve done with standard solutions of known quantities of
metal ions. Besides determining which metals are present, the quantity of each metal
can be correlated to the peak height of the current or the integrated charge under the
peak.
ASV was originally developed with a hanging Hg drop electrode where the metals
often form an amalgam. However, to limit the quantity of toxic Hg used, thin Hg
films can be pre-deposited onto an electrode such as glassy carbon or co-deposited
simultaneously with the analyte metal ions. The amount of Hg deposited is very little
and can be readily removed at potentials less negative than those of the analyte
metals, such as Pb, Cd and Cu.

Purpose:

To use Anodic Stripping Voltammetry (ASV) to determine low levels of dissolved Pb

BACKGROUND: Why Lead? Lead contamination of drinking water is a major global
problem. Acute lead poisoning in children can cause anorexia, vomiting, malaise,
convulsions and even, permanent brain damage. Chronic lead poisoning can cause
weight loss, weakness and anemia. Lead can leach into water from either solder used
to join copper pipes or from lead pipes in older buildings. Other sources of lead are
41
paints in older buildings, and dust/soil contaminated with tetraethyl-lead (formerly a
gasoline additive.)

Experiment

Equipment

• Use an analog or computer-controlled potentiostat with appropriate data acquisition

equipment for this experiment (ask your lab instructor for directions on use of
potentiostat)
• Electrochemical cell and electrodes o Small volume cell o 1.0 mm or 3.0 mm flat
tipped glassy carbon electrode o Pt auxiliary electrode o Ag/AgCl reference electrode
Polishing kit
• A magnetic stirrer and a small bar inside the cell
• A timer
• 50 ml and 100 ml volumetric flasks

Chemical Solutions

A. Prepare three separate 100 mL solutions at 100 ppb, 500 ppb and 1,000 ppb of
Pb(NO3)2 containing 0.1 M KNO3, 50 mM HNO3 and 40 ppm Hg(NO3)2. Use
doubly distilled water or other high purity water for dilutions.

B. Prepare a background solution containing 0.1 M KNO3, 50 mM HNO3 and 40

ppm Hg(NO3)2.

C. Dilute a sample of tap water or an unknown sample from your instructor. Prepare
the sample by adding an equal volume of 0.1 M KNO3 containing 50 mM HNO3 and
40 ppm Hg(NO3)2.
Note: It is important that glassware is cleaned thoroughly, rinsed several times with
pure water and then dried prior to use. You should look at the bottle labels of
chemicals to note the amount of heavy metal impurities, if any are present. High
purity reagents, absent of heavy metal impurities, can be purchased.

Discuss this issue with the laboratory instructor. Calibration using the method of
standard addition can correct for impurity if it is the same as the sought for metal.

42
Procedure
1. Connect the cell (3- electrodes) to potentiostat (see instructor for direction or
manual for potentiostat use)

2. Place the cell on top of the magnetic stirrer and put the stirring bar, the auxiliary Pt
and the Ag/AgCl reference electrode in place.

3. Polish the glassy carbon electrode under light pressure with an alumina slurry on a
micro-cloth polishing pad.
Rinse the electrode immediately with pure water and remove any excess water by
touching an edge to a Kimwipe™ or clean adsorbent paper. Fit the electrode into the
cell.

4. Add the 100 ppb Pb sample in the cell and replace the cover with the electrodes.

5. Set the applied potential, Ei, at –900 mV, the final potential, Ef , to = 0.00 mV and
the sensitivity to 1 µA/V.

6. Turn the magnetic stirrer ON, set the timer for 2 minutes and then switch the
potentiostat to the ON position so that –900 mV is applied to the glassy carbon
electrode. Turn the stirrer off/on with an inline switch and leave the speed controller
set to the same setting to maintain the same stirring rate from experiment to
experiment.

7. If the current overload light turns on, decrease the sensitivity.

8. After 90 seconds, turn the stirrer off so that the solution quiets.

9. When the timer goes off after 2 minutes, push the scan button ON so that the
potential is scanned from Ei of –900 mV to 0.00 mV. A scan rate of 500 mV/sec is
recommended. A higher scan rate lessens the possibility of error due to oxygen in the
solution oxidizing the deposited metal, like Pb, on the electrode.

10. Remove the Hg film by stepping the potential to +400 mV for 30 seconds. Do not
re-polish the electrode between runs.

11. Repeat the experiment with the background solution and then with all three
standard Pb solutions, running duplicates for each concentration. Always remove the
Hg film between runs. Next, run duplicates on the unknown water sample.
43
12. Plot the peak heights vs. concentration for the blank and standards and then
determine the amount of Pb in the tap water from the calibration plot (noting where
the peak height of the sample lies on the plot of the standard solutions).

13. Do a linear regression analysis to confirm the ppb lead in the unknown water
sample (run at least duplicates on the standards and the sample if time permits).
Note: If you are using a computer-controlled potentiostat like the CS-1200, the
procedure for the analysis of lead is the same as that described above. With this
instrument, you can and should scan at rates as high as 1 or 2 V/s. The timing and
potentials can be set with the computer menu but please remember to turn the stirrer
off at the preset time of 2 minutes. REPORT ( Data Analysis and Discussion):
Consult with the laboratory supervisor about the content and format of your report for
this experiment.

Suggestions and questions to consider are as follows:

1. Write a short summery of what you did in this experiment, noting any deviations
or substitutions in the procedure.

2. Show example stripping voltammograms for Pb at 2 or more concentrations. Plot

Ip vs. Pb concentration (both the uncorrected and corrected for background) and from
the plot, determine the concentration of the Pb in the unknown sample. [Note: If you
could not detect a peak for Pb in your unknown, the amount of Pb is most likely
below 10 ppb.]

3. Were there other metals present in the water sample as evidenced by other peaks?
If yes, how can you identify the metal or metals?

4. If your unknown is tap water, the amount of Pb may depend on whether the water
was left standing in the pipes for hours or days, or whether you let the water run for a
few minutes before sampling. If time permits, you may wish to see whether there is a
difference in the quantity of Pb depending on the sampling time.
5. If time permits, make a run with 100 ppb without the co-deposition of Hg and
report what you observed in the way of the Pb ASV wave shape and height, and
compare it to the result with the Hg film. Note: It is important to use high purity
water throughout in making solutions and high purity reagents that are designated as
being free of heavy metals. Besides trace amounts of Pb in reagents, copper is usually
the main contaminant.
44