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Experiment No. 1
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 SO 42-, 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 + 4eOn the other hand, the quantitative determination is governed by Faradays 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 ()
is expressed in moles and defined as
= m x (MW / f)
It is also defined that the quantity of electricity Q passed the solution is directly proportional to the amount
of electron transferred (). The proportionality factor is known as the Faradays constant (F).
Q=xF
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)
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
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School of ChE-Chm
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
I
I
t
I
t t 1
t
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 )
K/A
n
where:
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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, theres 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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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.
Region
Color
Complimentary
Color
400-435
435-480
480-490
490-500
500-560
560-580
580-595
595-650
650-750
Violet
Blue
Blue-green
Green-blue
Green
Yellow-green
Yellow
Orange
Red
Yellow-green
Yellow
Orange
Red
Purple
Violet
Blue
Blue-green
Green-blue
A log
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Io
cl
I
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Discussion of Principles of Experiments 1-4
where:
A = absorbance
Io/I = ratio of intensities of incident to transmitted light
= absorption coefficient
c = solution concentration
l = length of the light path
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