COLLEGE OF NATURAL SCIENCE

DPARTMENT OF CHEMISTRY

Practical Physical Chemistry II Laboratory Manual

By: Abdurohman Eshetu (BSc in chemistry)

Editor: Bantie Yasabu (MSc in chemistry)

Dessie, Ethiopia

2018 G.C

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2|Page
Contents page
Experiment1................................................................................................................................................1
Critical Solution Temperature of Phenol-Water System..........................................................................1
Experiment 2...............................................................................................................................................4
Effect of NaCl on the Critical Solution Temperature of Phenol- Water System......................................4
Experiment 3...............................................................................................................................................8
Verification of Onsager’s Equation and Determination of Equivalent Conductance at Infinite Dilution
of Strong Electrolytes..............................................................................................................................8
Experiment 4.............................................................................................................................................11
Molecular Weight of Polymer from Viscosity Measurement................................................................11
Experiment 5.............................................................................................................................................16
Conductometric titration of a strong acid with a strong base.................................................................16
Experiment 6.............................................................................................................................................19
Study of Ferricyanide by Cyclic Voltammetry Using the CV-50W Voltammetric Analyzer................19
Experiment 7.............................................................................................................................................24
Kinetics of Iodination of Acetone by Spectrophotometry......................................................................24

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Experiment: 1

Critical Solution Temperature of Phenol-Water System

Objective: To determine the critical solution temperature of phenol water system.

Theory
When two liquids which do not react chemically are mixed, there are three possible modes of
behavior for the system.
(1) The liquids may be immiscible (i.e. mutually insoluble), for example, mercury and water,
(2) The liquids may be miscible in all proportions, for example, ethanol and water,
(3) The liquids may be partially miscible, that is, each liquid has a limited solubility in the other,
for example, aniline and water. In the case of a liquid pair that exhibits partial miscibility, a rise
in temperature usually increases the solubility of each liquid in the other. Thus, as the
temperature rises, a point is found where complete miscibility results. This temperature at which
mutual solubility become complete, no matter in what proportions the two liquids are mixed, is
called the critical solution temperature (CST) or consolute [Link] and water are typical of
the class in which mutual solubility’s increase with rise in temperature. The two solubility curves
join at the critical solution temperature; above this temperature all possible mixtures are
miscible.
When two partially miscible liquids are mixed and shaken together, we get two solutions of
different compositions. For example, on shaking phenol and water, we get two layers: the upper
layer is a solution of water in phenol, and the lower layer is a solution of phenol in water. At a
fixed temperature, the composition of each solution is fixed, and both the solutions are in
equilibrium. Two solutions of different compositions existing in equilibrium with one another
are known as conjugate solutions. Above a particular temperature, such solutions are completely
miscible in all proportions. Such a temperature is known as the Critical Solution Temperature
(CST) or Consolute Temperature. As the mutual solubility increases with temperature in this
particular case, it is known as Upper Consolute [Link] CST or Consolute
temperature, the liquid mixture is homogeneous. Below CST or Consolute temperature, the
mixture separates into two layers. CST is markedly affected by pressure and also by the presence
of impurities. Hence, the CST may be taken as a criterion for the purity of a substance.

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The solubility of liquid pairs may increase as the temperature is lowered. In this case the system
will exhibit a lower consolute temperature or lower critical solution temperature. Below which
the two members are soluble in all proportions and above which two separate layers are formed.
Apparatus: Beaker, thermometer, glass rod, measuring cylinder, Bunsen burner, wire gauze,
tripod stand, water bath.
Chemicals: Phenol and Water
Procedure
Measure 6 ml of 80% phenol in measuring cylinder and transfer it in to a clean and dry beaker.
To this add 2 ml of water. Insert a thermometer and a glass rod. Stir the solution with the glass
rod. Place the above beaker over a water bath and gradually heat the mixture with continuous
stirring. Note the temperature at which the two layers become miscible with each other and
record this temperature. This temperature is clearing temperature or a temperature which
corresponds to disappearance of turbidity (disappearing of clouding). Take out the flame and
allow the above reaction mixture to cool with continuous stirring. Note the temperature at which
the layers become immiscible with each other and record this temperature. This temperature is a
clouding temperature (a temperature that corresponds to reappearance of turbidity). The mean
value of these two temperatures gives the miscibility temperature (Critical Solution
Temperature) for that particular composition. Repeat the above procedure for different
composition, each time add 2 ml of water to the previous beaker without discarding the mixture
in it and record the clearing and clouding temperature for each composition in a similar manner.
The total volume of water to be added is 24 ml to 80% phenol solution.
Table and Calculations
S.N Phenol volume Volume of Percentage of Temperature
o (ml) solution water (ml) phenol Cleaning Clouding Mean
(Miscibility T0)
1 6 2 6/8*100=75
%
2 6 4
3 6 6
4 6 8
5 “ “

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6 “ “
7 6 24

Graph
The graph is plotted between mean temperatures and percentage of phenol. The graph defined
will be a parabola. The points are gained to form smooth curve that is the miscibility curve. The
temperature corresponding to the peak of the curve is the Critical Solution Temperature (CST).
The curve extrapolated to get the maximum critical point above with thesystem of any
composition is completely miscible.
Precautions: 1. Continuous stirring with glass rod is necessary to avoid super cooling.
2. To ensure uniform temperature gradient the bath is also continuously stirred.
Result: 1. The Critical Solution Temperature (CST) of the phenol-water system is found to be
____________________.
2. The percentage of phenol at CST is found to be _________________.

Experiment: 2
Effect of NaCl on the Critical Solution Temperature of Phenol- Water System
Objective: To observe the effect of NaCl on the critical solution temperature of phenol-water
system and to determine the unknown concentration of a given solution of NaCl
aqueous.
Theory
Critical Solution Temperatures (CSTs) are very sensitive to impurities or added substances. The
addition of a substance to a binary liquid system produces a tertiary system. The miscibility of
phenol and water is reduced by addition of many common salts such as alkali and alkaline-earth
halides. The origin of the effect is the tendency of water molecules to associate with ions,
hydrating them. In that way, simple ions reduce the tendency of water to solvate phenol.
A) If the added material is soluble in only one of the two components or if the solubility in
the two liquids are markedly different, the solubility of the liquid pair is decreased due to
salting-out. In this case if the original binary mixture has an upper critical solution
temperature, the upper critical solution temperature will be increased after the addition of
the third component. The addition of NaCl decreases the mutual solubility of phenol-

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 water system. The critical solution temperature increases linearly with the concentration
of NaCl is added.
Example: If 0.1M naphthalene is added to a mixture of phenol and water, it dissolves
only in the phenol and raises the CST about 20 0C. If 0.1M KCl is added to a phenol
water mixture, it dissolves only in water and raises the CST approximately 8 0C.
B) If the added material is soluble in both of the liquids to about the same extent, the
solubility of the liquid pair is increased. The increase in solubility of two partially
miscible solvents by an addition of an additive is referred to as blending. In this case an
upper CST is lowered and a lower CST is raised. Example: The addition of succinic acid
or Na oleate to a phenol water system.
Apparatus: Beaker, thermometer, glass rod, measuring cylinder, Bunsen burner, wire gauze,
tripod stand, volumetric flask, water bath.
Chemicals: 80% Phenol, 0.25 M NaCl, 0.2 M NaCl, 0.15 M NaCl, 0.10 M NaCl, 0.05 M NaCl,
unknown concentration of aqueous solution of NaCl.
Procedure:
Take 5 ml of 80% phenol in measuring cylinder and transfer it in to a lean and dry beaker. To
this, add 5 ml of 0.25 M NaCl. Place the above beaker on a tripod stand with a wire gauze is
placed on it. Insert a thermometer and a glass rod in to the beaker and heat it slowly with
continuous stirring. Note the temperature at which the mixture becomes clear /disappearance of
turbidity/ Record that this temperature. This temperature is cleaning temperature. Remove the
flame and allow the beaker that contain the reaction mixture to cool with continuous stirring.
Note the temperature at which the reaction mixture becomes turbid/cloud record this
temperature. This temperature is clouding temperature. Repeat the above procedure for each
different concentration of NaCl and finally with the unknown concentration (Each time 5 ml of
80% phenol and 5 ml of a given concentration of NaCl, a clean and dry beaker is used).
Calculate the mean value of clearing and clouding temperature for each composition.
Table and Calculations:
[Link] Concentration of NaCl Temperature (0C)
Clearing Clouding Mean value

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Volume of 80% phenol taken = 5 ml
Volume of NaCl solution added = 5 ml
Graph:
The graph is drawn between the temperature and concentration of NaCl solution and the result is
a straight line. The concentration corresponding to the mean temperature of the given unknown
solution is the concentration of the given unknown NaCl solution.

Precautions: 1. Continuous stirring with glass rod is necessary to avoid super cooling.
2. To ensure uniform temperature gradient the bath is also continuously stirred.
Result: Concentration of unknown NaCl solution is found to be ___________________.

Experiment 3
Verification of Onsager’s Equation and Determination of Equivalent Conductance
at Infinite Dilution of Strong Electrolytes.
Objective: To verify the Onsager’s equation of electrolytic conductance and to determine the
equivalent conductance at infinite dilution of strong electrolytes.
Theory:

Conduction of electricity through an electrolyte solution involves migration of positively charged

species toward the cathode and negatively charged ion toward the anode. The conductance which
is the measure of the current that results from the application of a unit electrical force depends
directly upon the number of charged particles in the solution. The conductance of a solution is
the reciprocal of the electrical resistance and as the units of ohm-1.

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 1
G= Where R = resistance in ohms.
R

The resistance of a uniform conductor is directly proportional to its length (l) and inversely
proportional to the cross-sectional area (A). Thus,
l l
R∝ Or R=ρ where ρ is the proportionality constant called specific resistance.
A A
In the above equation if l=1 cmand A=1 cm2 , then R=ρ
Thus specific resistance ( ρ ) is defined as the resistance of an electrolyte solution of 1 cm in
length and 1 cm2 cross-section i.e. resistance of one cubic centimeter of the electrolytic solution.
The unit of specific resistance is [Link]. The reciprocal of specific resistance ( ρ ) is
called specific conductance. This may be defined as the conductance of one centimeter cube of a
material and is denoted by K . Thus,
1 l
K= = Its unit is ohm–1 cm–1. In SI units, the units of specific conductance ( K ) are Sm–1,
ρ AR
where S stands for Siemen.
Equivalent conductance is defined as the conductance of an electrolyte solution containing on
gram equivalent of the electrolyte. It is usually denoted by λ. The relation between equivalent
conductance ( λ ) and specific conductance is given as
λ=V × K Where V is the volume of the electrolyte solution in ml containing one gram equivalent

of theelectrolyte. If the concentration of the electrolyte solution is C grams per liter. Then
1 1000 ml
volume containing 1 gram equivalent of the electrolyte will be liter or , thus
C C
1000 × K
λ=V × K= , the unit of equivalent conductance is ohm-1cm2eq-1.
C
For strong electrolyte, equivalent conductance ( λ ) increases with dilution and cause of this
variation is fundamentally different from weak electrolytes. Conductivity of an electrolyte
depends on the speed of ion and concentration of ion. The motion of an ionic species in an
electric field is retarded by the oppositely charges ions due to inter ionic attraction. On dilution,
the concentration of electrolyte decreases and the retarding influence of oppositely charged ions
decreases. Consequently the speed of ion increases and equivalent conductance of electrolyte is
increased. The variation of λ with concentration for strong electrolytes is given by Debye-
Huckel-Onsager conductance equation.
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 λ=λ 0−[ A+ B λ0 ] √ C
Where λ=Equivalent conductance at concentration C ,
λ 0=Equivalent conductance at infinite dilution

[ A+ B λ0 ] √ C=Retarding influence
A∧B include two important properties of solvent i. e .dielectric ∧viscosity .
The equivalent conductance can be calculated from the specific conductance (K) using the
K
equation, λ=1000 × where the concentration, C is expressed in equivalents per dm3.
C
When the λ values are plotted against √ C , a straight line with a negative slope will be obtained,
in accordance with the Onsager’s equation. The Y- intercept of this line would then give the λ 0 ,
the equivalent conductance at infinite dilution for the electrolyte.
Apparatus required: Conductivity cell, Conductivity Bridge, 100 or 50 cm 3, volumetric flasks
and pipettes.
Chemicals Required: 0.5 N NaCl solutions in conductivity water.
Procedure:
Dilute the 0.5 N NaCl stock solutions quantitatively with conductivity water, appropriately to get
solutions of 0.1, 0.05, 0.02, 0.01, 0.0005 and 0.001 N concentration. Using a conductivity cell of
known cell constant, measure the resistance (or conductance) for each one of these solutions.
Wash the cell every time with distilled water. Rinse it with conductivity water and then with the
solution under investigation, before making final measurement.

Treatment of Data
Cell constant = __________________ cm-1
Conc. of NaCl Conductance (G) Resistance (R) Specific Equivalent
conductance (κ) conductance (λ)
0.001 N
0.005 N
0.01 N
0.02 N
0.05 N

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0.10 N

Plot the λ values against the √ C as shown below in the graph. Extrapolate and find the Y-
intercept value. This corresponds to λ 0, the equivalent conductance at infinite dilution.

Result:
Report the value for the equivalent conductance at infinite dilution, λ 0 for NaCl in ohm-1cm2 eq-1
Note: 1. K cell =l/A,
1 l
2. K cell = K spec/G then K spec = K cell ×G and K spec = = , K spec = K cell×1/R
ρ AR
K spec
3. λ=1000×
C

Experiment: 4
Molecular Weight of Polymer from Viscosity Measurement
Objective: To determine the mean molecular weight of a polymer from viscosity measurement.

Theory: Fluids resist a flow gradient. This resistance produces a frictional force known as a
viscous force proportional to the area of contact, A, between the flowing regions and to the
dv
velocity gradient, . The constant of proportionality is called the coefficient of viscosity η, as
dx
given

dv
F=ηA
dx
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The SI unit of the coefficient of viscosity is Pa.s; 1 Pa = N.s.m -2= 1 Kg. m-1. S-1. The old unit was
poise. 1 poise = 1 gm cm-1 s-1= 10-1 Kg m-1 [Link] measured quantity is often called the viscosity,
although the major definition of viscosity is “the property of a fluid that resists the force tending
to cause the fluid to flow.” So long as one is clear, it is perfectly acceptable to use the word
“viscosity” to mean “the coefficient of viscosity.”

Viscosity is a property of fluids, i.e. liquids and gases. For liquids, it is dominated by short-range
attractive intermolecular forces, the effects of which are hard to model. For gases, viscosity
arises from momentum transfer between layers of moving molecules. The kinetic theory of gases
gives the following formula for the viscosity of gases:

η=
√ MRT
π σ4 N A2
3

Where M is the molar mass, R is the gas constant, σ is the molecular diameter, and N A is
Avogadro’s number. Perhaps the most important result of the kinetic theory of derivation is the
prediction that the viscosity of a gas increases with temperature and molar mass.

It is well known that the viscosity of a typical liquid decreases with temperature. Eyring’s model
of dynamics in liquid treats a molecule in motion as passing through an energy barrier caused by
the cage of the molecules surrounding it. Using the definition of the viscous force in first
equation, this gives the theoretical prediction for the viscosity coefficient as:

ԑ/ kT
η=ch e

Where k is Boltzmann’s constant, T is the absolute temperature, and h is Planck’s constant, c is

the concentration in molecules per cubic centimeter, and ԑ is the barrier energy.

It is usual to define the specific viscosity, η sp, of a polymer solution by equation:

η−η 0
η sp=
η0

Where η0 and η are the viscosities of the solvent and the solution respectively.

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The specific viscosity is the fractional increase in the viscosity over that of the pure solvent
ηsp
caused by the addition of the polymer. It is the ratio referred to as the relative increase in
C
viscosity per unit concentration of polymer. Since the ratio varies with the concentration, it is
ηsp
necessary to extrapolate a plot of against concentration to infinite dilution and the value thus
C
obtained is called the intrinsic viscosity, [η], so that;

η sp
[η]=lim
C m →0 Cm

The dependence of intrinsic viscosity on molar mass is given by the empirical Mark-Houwink
equation:

[ η ] =K M α

Where K and αare constants that depend on polymer composition, temperature and solvent. The
quantity calculated with the Mark-Houwink equation is the viscosity-average molecular weight.
If K and αare known for a particular polymer, then the molecular weight can be determined from
viscosity measurements.

Poiseuille derived a formula, which is applicable to the Ostwald procedure, for the volume, ΔV,
of an incompressible fluid of viscosity, η, moved through a length of l and radius, r, in a time, Δt,
subject to a pressure drop, ΔP, the equation:

4
ΔV πr
= ΔP
Δt 8 ηl

From this equation, one sees that a measure of the time it takes a specific volume to move
through a tube under a constant pressure drop is a direct measure of the viscosity. However,
usual procedure is to determine the viscosity relative to a reference substance at a selected
temperature. This is determined as the relative viscosity. Water at 20 0C is usually used as the
reference liquid. To obtain the relative viscosity of a substance at a given temperature, it is
necessary to measure its time of flow at the temperature and the corresponding time of flow for
the same volume of water (or another reference liquid) in the same viscometer at same

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temperature. Since the pressure of a liquid in a viscometer of this type is proportional to its
density, and the terms r, V and l in the Poiseuille equation are the same for both liquids, it
follows the ratio of viscosities is given by the following equation:

η1 ρ 1 t 1
=
η2 ρ 2 t 2

Equipments required: Ostwald viscometer, thermostat, 10 ml pipettes, 25 ml volumetric 5

flasks and stop watch.

Chemicals required: Toluene, polystyrene (or any polymer soluble in toluene)

Procedure:

Make a solution of polystyrene by dissolving 0.5 g of the solute in toluene in 25 ml volumetric

flask. Heat the solution in water bath to facilitate the dissolution process. Thoroughly clean the
viscometer with acetone and dry it before mounting in thermostat at 20 0C. Determine the flow
time in the viscometer of toluene. Dilute the solution with toluene to concentrations of each
solution. In all cases, measure the flow time at least three times and take the mean. Clean and dry
carefully the viscometer between measurements.

Results:

1. Prepare a table containing the mean flow time of a fluid, concentrations of the solutions
ηsp
and .
C
ηsp
2. Construct a plot of against concentration. Extrapolate the graph at C = 0 to determine
C
the intrinsic viscosity, [η].
3. Use the literature values of K and α for polystyrene in toluene at the experimental
condition and determine the mean molecular weight of polystyrene sample.

Discussions: Determine the values of K and α for polystyrene from the experimental data,
compare them with that of literature and discuss discrepancy.

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Experiment 5
Conductometric titration of a strong acid with a strong base
Objective: To investigate neutralization and precipitation titrations by observing the change in
electrical conductivity and determine the concentration of a given HCl solution by
conductometric titration.

Theory:

Conductometry is a measurement of electrolytic conductivity to monitor a progress of chemical

reaction. In chemical reactions, such as titration, a change in electrical conductance frequently
takes place. Conductometric titration is a type of titration in which the electrolytic conductivity
of the reaction mixture is continuously monitored as one reactant is added.

The titration reaction as involves the addition of a reagent to a solution that contains a substance
with unknown molarity. Just before and after the equivalence point, there is a marked difference
in the rate of change of conductance with incremental addition of reagent. It is then possible to
find the amount of reagent equivalent to the solution titrated by measuring the conductance. The
latter is defined as the inverse of the resistance R. The unit of conductance is Ω -1, or officially
denoted as S (Siemens).The use of an excess of the standard reagent establishes the correct
location of the equivalence point. There are some advantages of conductometric titrations;

A. No need of indicator.

B. End point can be identified graphically with minimum error.

C. Can be used with colored liquids for which ordinary indicators cannot work.

D. Can be used for dilute solutions as well as for very weak acids.

Consider first the titration of a strong acid like HCl with a strong base like NaOH. Before the
addition of the base, the acid solution has a high conductance. As alkali is added the hydrogen
ions are removed to form water, and they are replaced by the much slower cations of the base.
Consequently, the conductance of the solution decreases, and keeps on falling with addition of
the base until the equivalence point is reached. Further addition of alkali introduces now an

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 excess of the fast hydroxyl ions, and they causes the conductance to rise again. When this
variation of the conductance of the solution is plotted against the volume of alkali added the
result looks like the curve shown in figure below. At the minimum there is no excess present of
either acid or base, and hence it is the equivalence point. This minimum can be used instead of
an indicator dye to determine the endpoint of titration.

Fig.: Conductometric titration of a strong acid (HCl) vs. a strong base (NaOH)

Equipments Required: Conductivity meter, conductivity cell, burette, stirrer, 10 ml pipettes

and 250 ml beakers.

Chemicals Required: HCl and 0.1M NaOH

Procedure:

Pipette out 20 ml of the given HCl solution in to a clean conductivity cell of known cell
constant. Take the standardized 0.1M solution of NaOH, should be at least five times higher
than that of the acid solution, so that the volume change would be minimal. Add the NaOH
solution taken in a burette carefully; say 0.1 ml each time. After each addition, stir the contents
well and note down the resistance or conductance value. Continue the titration, till two limbs of
curve are clearly traced.

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Treatment of data:

Cell constant = ………….. cm-1 (obtained from the conductivity cell)

Volume of HCl solution = 20 ml
Concentration of NaOH solution = 0.1 M

Volume of NaOH added (ml) Resistance(R) (ohm) Conductance (ohm-1) (1/R)

0.1
0.2
0.3
____
____

Result:

Read the volume of NaOH at equivalent point. Plot the conductance value against the
corresponding volume of NaOH added. A curve with two limbs as shown in the figure above
will be obtained. The point of intersection of these two lines corresponds to the volume of
NaOH (V NaOH ¿ required for exact neutralization of the acid. Find the concentration of HCl
solution.

Discussion:

Sketch the curve for conductometric titration of a strong acid with a weak base. Give
explanation on the shape of the curve.

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Experiment: 6
Study of Ferricyanide by Cyclic Voltammetry Using the CV-50W Voltammetric
Analyzer
3 +¿
Fe
Objective: The 2+¿
¿ couple is used as an example of an electrochemically reversible redox
Fe ¿
system in order to introduce some of the basic concepts of cyclic voltammetry.

Theory:

Cyclic Voltammetry (CV) is often the first experiment performed in an electrochemical study of
a compound, a biological material or an electrode surface. It is effectively used in the fields of
Environmental Electrochemistry, Organic Chemistry, Inorganic Chemistry and Biochemistry.
The effectiveness of CV results from its capability for rapidly observing the redox behavior
over a wide potential range. The resulting voltammogram is analogous to a conventional
spectrum in the sense that it conveys information as a function of an energy scan.

It is the most widely used technique for acquiring qualitative informationabout electrochemical
reactions. The power of cyclic voltammetry results from its abilityto rapidly provide
considerable information on the thermodynamics of redox processes and the kinetics of
heterogeneous electron-transfer reactions, and on coupled chemical reactions or adsorption
processes. In particular, it offers a rapid location of redox potentials of the electroactive species,
and convenient evaluation of the effect of media upon the redox process.

Cyclic voltammetry consists of cycling the potential of an electrode that is immersed in an

unstirred solution of the electroactive species and then measuring the resulting current. The
potential of this working electrode is controlled versus a reference electrode such as a saturated
calomel electrode (SCE) or a silver/silver chloride electrode (Ag/AgCl). The controlling
potential which is applied across these two electrodes can be considered as an excitation signal.
The excitation signal for CV is a linear potential scan with a triangular waveform. This
triangular potential excitation signal sweeps the potential of the electrodebetween two values,
sometimes called the switching potentials, whereby the potential rises from a start value E ito a
final value Efthen returns back to the start potential at a constant potential sweep rate as shown
below in the figure. The cyclic voltammogram is then obtained by measuring the current at the

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 working electrode during the potential scan. The current can be considered the response signal
to the potential excitation signal.

The cyclic voltammogram shows characteristics of an analyte by several important parameters

such as the magnitudes of the anodic peak current (i pa) and Cathodic peak current (ipc) and the
potentials at which peaks occur, anodic peak potential (E pa) and Cathodic peak potential (E pc)
that can be used in the analysis of the cyclic voltammetric response either the reaction is
reversible, irreversible or quasi-reversible (Figure 1.2)

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 Figure 1.2: A typical cyclic voltammetry showing important parameters

The peak current for a reversible couple (at 250C), is given by the Randles-Sevcik equation:

Where n is the number of electrons involved in the reduction/oxidation, A is the electrode area
(in cm2), C is the concentration (in mol/cm 3), D is the diffusion coefficient (in cm 2/s), and ν is
the scan rate (in V/s). Accordingly, the current is directly proportional to concentration and
increases with the square root of the scan rate. The ratio of the anodic to cathodic peak currents,
ipa/ipc, is unity for a simple reversible couple. This peak ratio can be strongly affected by
chemical reactions coupled to the redox process. The current peaks are commonly measured by
extrapolating the preceding baseline current. The position of the peaks on the potential axis (E p)
is related to the formal potential ofthe redox process. The formal potential for a reversible
couple is centered between Epaand Epc:

The separation between the peak potentials (for a reversible couple) is given by:

Thus, the peak separation can be used to determine the number of electrons transferred.
Accordingly, a fast one-electron process exhibits ∆Epof about 59 mV. Both the cathodicand
anodic peak potentials are independent of the scan rate.

Apparatus: BAS CV-50W Voltammetric Analyzer, electrochemical cell, volumetric flask,

glassy carbon working electrode, Ag/AgCl reference electrode and platinum wire auxiliary
electrode.

Chemicals Required: 100 ml stock solution of 10 mM K3Fe(CN)6 in 1 M KNO3

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Procedure: Add the 2 mM solution of K3Fe(CN)6 to the cell and connect the electrodes. Open
the CV-50W software and switch on the potentiostat. Use Select Mode in the Method menu to
select cyclic voltammetry (CV) as the technique and click OK.

Enter the parameters shown below in General Parameters dialog box.

CV General Parameters
Initial E 650 mV
High E 650 mV
Low E 0 mV
Scan rate 20 mV/s
Initial direction Negative  Positive
Number of segment 2
Sensitivity 10 V A/V
Cancel OK Specific
Select Start Run in the Control menu to start the experiment. The cyclic voltammogram (CV)
will appear on screen as it is generated, and it will be rescaled automatically upon conclusion.
Select Results Graph in the Analysis menu to redisplay the voltammogram together with the
baselines used for the measurement of the peak potentials and peak currents. The numerical
value of these peak parameters are displayed in the Main window. Save the experimental data.

Effect of Scan Rate

Select the General Parameters in the Method menu, and change the scan rate from 20 mV/s to
50 mV/s. Run the experiment again and save the data. Repeat this procedure for scan rates of
100, 150 and 200 mV/s. Open the Graph Options dialog box and then select Multi-Graph and
click the filenames of the CVs to be plotted from the File Name list box.

Effect of Concentration

Select Calibration from the Analysis menu. Then enter the Number of samples, the
Concentration Unit (mM), the Base Filename, and the Report Name. Open the Samples
dialog box. For each sample, click Standard and enter the concentration. Enter the peak
potential for the peak on the first (cathodic) scan. Click Escape to exist the Samples dialog box.

18 | P a g e
 Run the experiment for each concentration (including the unknown concentration as well).
Construct a calibration curve from the peak currents of the solutions of known concentration
(using a least-squares fit).

Results

1. Show the scan rate dependence of the peak currents and peak potentials by plots of ipvs.
(Scan rate) 1/2, and ΔEpvs. Scan rate respectively.
2. Calculate the unknown concentration from the ip vs. Concentration plot.

Discussion: Explain the scan rate dependence of the peak currents and peak potentials.

19 | P a g e
Experiment: 7
Kinetics of Iodination of Acetone by Spectrophotometry
Objective: To study the kinetics of iodination of acetone spectrophotometry

Theory

The rate of a chemical reaction is the amount of substance reacted or produced per unit time.

−Δ [Reactant ] Δ [Product ]
Rate= =
Δt Δt

Consider a reaction:aA +bB → cC+ dD ;whereA, B, C andDare the chemical species, and a, b, c
and d are coefficients in the balanced [Link] rate is related to the concentration of the
reactants by the expression of the form:

α β
r =K [ A ] [B ]

Where α and β are partial orders and are usually integrals or half integrals, and K is the rate
constant and is characteristics of the reaction. The overall order of the reaction is the sum of the
components. An experimentally determined equation of this kind is called the rate law of the
reaction.

Solid iodine crystals have a dark red/black color. An aqueous iodine solution is yellow. When an
aqueous iodine solution reacts with acetone, the yellow color slowly fades as the iodine is
consumed. When iodine is mixed with acetone, the following reaction occurs:

C H 3 COC H 3 + I 2 → C H 3 COC H 3 I + HI

The reaction is quite slow in the pH range of 4-7, but it occurs quite rapidly if the pH is below 3
or above 8. This implies an acid or base dependence. The reaction rate increases with the
+¿¿ −¿¿
concentration of H in acidic solution or with the concentration of OH in basic solution.

For the acid catalyzed iodination of acetone, the rate law is assumed to have the form:

x y
rate=[ I ¿ ¿ 2] [acetone] ¿ ¿ ¿ ¿

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In this experiment we will use the method of initial rates to determine the value of the constant
and the order of the reaction. The progress of the iodination of acetone is easily followed by
directly observing the decrease in iodine concentration spectrophotometrically at a wavelength
where none of the other reagents has significant absorption. We will perform at least four runs
using different concentrations of reactants. For each run, you will produce an absorbance vs.
time plot. The slope of each plot can be used to find the initial rate of the reaction for that
particular run. Since the iodine concentration is proportional to absorbance (A), we must also
calculate the constant (b) relating absorbance to iodine concentration for our spectrometer using
the following equation.

A=b[ I ]2

Because we are following the rate of the reaction by measuring the change in absorbance of the
solution, we will need to divide the change in absorbance vs. time by constant b.

− Δ[ I ]2 − ΔA
rate= =
Δt bΔt

In this manner, the absorbance vs. time plot can be used to obtain the initial rate of the reaction
in concentration per unit time. That is, for each set of reaction conditions, the slope of the line
plotted above divided by the constant, b, will give the initial rate of the reaction.

Equipments Required: Spectrophotometer and cuvettes, Erlenmeyer flasks, test tubes, watch
glasses and graduate cylinder.

Chemicals required: 4.0 M acetone, 1.0 M HCl and 0.01 M iodine

Procedure: Prepare the four different reaction mixtures in test tubes as given in the table below.

Reactant Acetone (ml) HCl (ml) Water (ml) Iodine (ml)

Experiment 1 1.0 1.0 2.0 1.0
Experiment 2 2.0 1.0 1.0 1.0
Experiment 3 1.0 2.0 1.0 1.0
Experiment 4 1.0 1.0 1.0 2.0

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Prepare the mixtures of acetone, HCl, and water in four test tubes as indicated in the table above.
Calibrate the spectrometer by filling one cuvette (about ¾ full) with the blank (distilled water).
To the first test tube that contains 1.0 ml of acetone, 1.0 ml of HCl and 2.0 ml of water, add 1.0
ml of iodine solution (always add iodine solution as soon as the measurement will be done). Mix
well, then quickly fill the cuvette about ¾ full and place it in the spectrometer and record the
absorbance at wavelength of 450 nm as a function of time until the absorption value decreases to
25% of its initial value. Do the same for the other experiments.

Results:

Determine the order with respect to each reactant and the overall order for the reaction. Calculate
the value of the rate constant for each of the four runs of the experiment and an average value of
the rate constant.

Experiment [Acetone] [HCl] [Iodine] Initial rate Rate constant

Experiment 1
Experiment 2
Experiment 3
Experiment 4
Average value of rate constant

Rewrite the rate law:

x y
rate=[ I ¿ ¿ 2] [ Acetone] ¿ ¿ ¿ ¿; With substituting in the numerical values you calculated for K
(average), x, y, and z.

Discussions

1. Why the measurement will be done as soon as the iodine solution is added.
2. Compare your rate law with the literature and comment on it.

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