School of ChE-Chm CHM 171L Physical Chemistry Laboratory 2

Discussion of Principles of Experiments 1-4

Experiment No. 1
ELECTROCHEMISTRY: DETERMINATION OF FARADAY’S CONSTANT

Electrochemistry is the branch of chemistry that deals with the generation of electricity from a
spontaneous reactions and use of electricity to drive non-spontaneous reactions. It is concerned with the
properties of solutions of electrolytes and with the processes that occur at electrodes. It involves the flow of
electrons and is described by a oxidation reduction reaction (Redox).

Electrochemical Cell is the experimental apparatus of generating electricity through the use of
spontaneous redox reaction and is composed of an anode at which oxidation occurs and a cathode at
which reduction occurs. There are two types of cell namely Galvanic/Voltaic Cell courtesy of Luigi Galvani
and Alessandro Volta , a type of cell in which a chemical reaction is used to generate electricity and
Electrolytic Cell courtesy of William Nicholson and Anthony Carlisle, a type of cell in which electricity is
used to cause a chemical reaction.

Electrolysis is the process in which electrical energy is used to cause a non-spontaneous chemical
reaction to occur. The products formed at the electrodes are determined qualitatively by the following
guidelines:

At the inert cathode:

 For metals below hydrogen in the activity series, the metal deposits at the cathode
 For metals above hydrogen in the activity series, reduction of water occurs (hydrogen gas is
liberated).
Reaction: 2H2O + 2e-  H2 + 2OH-
 For acids, hydrogen gas is liberated
Reaction: 2H+ + 2e-  H2

At the inert anode:

 For anions containing oxygen such as SO42-, NO3-, etc., oxidation of water occurs (oxygen is
liberated
Reaction: 2H2O  O2 + 4H+ + 4e-
 For anions such as Cl-, Br-, and I- (but not F-), these ions are more readily oxidized than water free
halogen is liberated.
 For bases, formation of O2 and H2O occurs.
Reaction: 4OH-  O2 + 2H2O + 4e-

On the other hand, the quantitative determination is governed by Faraday’s Law of Electrolysis, which
maybe summarized as:

1. The mass of an element produced at an electrode is proportional to the quantity of electricity (Q )

passed through the solution. The quantity of electricity is defined as equal to the current (I)
multiplied by the time (t).

Q=Ixt

2. The mass (m) of an element produced at an electrode is proportional to the equivalent weight of
the element.

m = MW / f

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When a cell operates, there is an electron transfer at the electrodes. The amount of electron transferred (η)
is expressed in moles and defined as

η = m / (MW x f)

It is also defined that the quantity of electricity Q passed the solution is directly proportional to the amount
of electron transferred (η). The proportionality factor is known as the Faraday’s constant (F).

Q=ηxF

where: Q – quantity of electricity in coulomb (C)

I – current in Ampere (A)
t – time in second (s)
m – mass of element produced in gram (g)
MW – molar mass in gram per mole (g/mole)
f – mole of electron lost or gained per mole of element (mole e-/mole)
η – amount of electron transferred in mole (mole e-)
F = 96, 485.3 C/mol e-  96, 500
1 Coulomb = 1 Amp-sec

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Experiment No. 2
CONDUCTIMETRY: DETERMINATION OF THE ELECTRICAL
CONDUCTANCE OF SOLUTIONS

There are properties of solution of electrolytes that are of importance. These are the resistance, the
conductance, and the electrical conductivity.

Resistance (R) of a slab of material, according to Ohm’s Law, is equal to the electrical potential
difference (V) divided by the electric current (I):

R=V/I

The SI unit of potential is volt (v), for current is ampere (A) and that for resistance is ohm (Ω).

Conductance (G) is the measure of the ability of a circuit or circuit element to carry current that is
effective in producing power. It is the reciprocal of the electrical resistance and has a SI unit of siemens (S).
The electrical conductivity is directly proportional to cross sectional area (A) and inversely proportional to
the length (l) of a material.

G=κA/l

where κ is the proportionality constant known as the electrolytic conductivity whose SI unit is S – m-1.

For a more suitable quantity for comparing the conductivities of different solutions, molar
conductivity is introduced. Molar conductivity (Λ) is defined as the electrical conductivity divided by
concentration c.

Λ=κ/c

It is the conductivity of the ions produced in solution by 1 mole of a substance. It diminishes as the
concentration is raised. For weak electrolytes, molar conductivity depends on concentration but to
extremely low concentration, molar conductivity rises similar to that of the strong electrolytes.

Conductivity measurements are used to distinguish weak & strong electrolytes, measure degree of
ionization, and determine solubility of soluble salts.

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School of ChE-Chm CHM 171L Physical Chemistry Laboratory 2
Discussion of Principles of Experiments 1-4

Experiment No. 3
TRANSFERENCE NUMBER

Transport number, also known as transference number or migration number, is the fraction of the
current carried by the each ion present in solution. It is associated with the ionic mobility defined as he
speed with which the ion moves under a unit potential gradient.

I
t 
I
I
t 
I
t  t  1

where: t = transference number

I = total current
I+ = current by cation
I- = current by anion

In accordance with the difference in mobility of ions in an electric field, cations and anions
contribute to the charge transport in electrolytic processes. This ionic mobility can be observes using the
Hittorf Method. Hittorf transference numbers are experimentally accessible via the resulting characteristic
concentration changes occurring at the cathode and the anode. These characterize the proportion of a
single type of ion on the total charge transport through the given electrolytes and enable the calculation of
ionic conductivities.

Hittorf Equation
M (An  Kn )
t 
Z R (Km  Am )

C1V K / A (V1K / A  V10

Kn / A 
V2

where: VK/A = volume cathode or anode region (W tube)

V10, V1K/A = volume NaOH used
C1 = 0.1M concentration of NaOH
ZR = 2 = charge # of reaction
mK/A = changes in mass of copper on anode/cathode
M = 63.54 g/m of Cu
V2 = 5 mL

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Ions with the largest concentrations generally have the largest transference number and can dominate
in determining the liquid junction potential. As a rule, the transference number that is large in dilute
solutions increases with rise in concentration, while those, which is small decrease. However, there’s an
exception to this rule. With an increase in temperature, the transport numbers of the cation & anion tend to
equalize and approach a value of 0.5. Hence, transference numbers greater than 0.5 decreases as the
temperature is raised, while those less than 0.5 increases.

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School of ChE-Chm CHM 171L Physical Chemistry Laboratory 2
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Experiment No. 4
SPECTROPHOTOMETRY

Spectroscopy is the study of molecules by their absorption or emission of light, heat & other
electromagnetic radiation. It deals with light that is resolved into its component wavelengths to produce
spectra, which are plots of some function of radiant intensity vs. wavelength or frequency. Spectroscopy
played a vital role in development of modern atomic theory. It is used for elucidation of structure of
molecular species as well as quantitative and qualitative determination of inorganic and organic
compounds.

Spectrophotometer is an instrument used compare the intensity of the light transmitted through an
absorbing medium to the light intensity when no material is present in the light path. It uses a photoelectric
cell, a detector, & provides a meter for reading the spectral wavelength and amount of absorption.

Absorption is a process in which a chemical species in a transparent medium selectively weakens a

certain frequency of electric radiation. The property that is mesured is called absorbance (A). It is directly
proportional to the light path through the sample and the concentration of the absorbing material but
inversely proportional to the wavelength.

Atomic absorption uses beam of polychromatic UV or visible radiation that passes through a medium of
gaseous atoms. The spectrum consists of a number of very narrow absorption lines.

 Color Complimentary
Region Color
400-435 Violet Yellow-green
435-480 Blue Yellow
480-490 Blue-green Orange
490-500 Green-blue Red
500-560 Green Purple
560-580 Yellow-green Violet
580-595 Yellow Blue
595-650 Orange Blue-green
650-750 Red Green-blue

Emission is a process in which chemical species is subjected to a flame, to an electric discharge or

radiation that excites it in some ways. It usually takes the form of a plot of the relative power of the emitted
radiation as a function of wavelength or frequency.

Spectrophotometry is governed by laws propounded by Johann Heinrich Lambert and Wilhelm

Beer. These laws are concerned with the intensities of light absorbed or transmitted when incident light is
passed through some material. Lambert’s Law states that the proportion of radiation absorbed by a
substance is independent of the intensity of the incident radiation. Beer studied the influence of the
concentration of a substance in solution on the absorbance. Combining the two laws yields a single
equation:

Io
A  log  cl
I

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where: A = absorbance
Io/I = ratio of intensities of incident to transmitted light
Є = absorption coefficient
c = solution concentration
l = length of the light path

According to Beer-Lamberts’ Law, in a monochromatic radiation, the intensity of electromagnetic radiation

transmitted through a sample at a given wave number decreases exponentially with the sample thickness
and the concentration. A linear graph is produced if the absorbance is plot against concentration.

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