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Electro Chemistry is the Branch of Chemistry, Which Deals With

Electro Chemistry is the Branch of Chemistry, Which Deals With

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electro chemistry jntu engineering complete materlal
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ELECTRO CHEMISTRY
LECTRO CHEMISTRY
Electro chemistry is the branch of chemistry, which deals with chemical applications of electricity. The passage of electricity through a substance is called electrical conductance. Electricalconductance involves movement of electrons or ions. A substance which allows electric current to pass through it, is called a conductor. Eg: all metals fused salts, acids, alkalis. The electricalconductors are of two types.1.Metallic or Electronic conductors2.Electrolytic conductors
Metallic or Electronic conductors:
Metallic conductors conduct electricity due to the movement of electrons from one end to another end.In a solid, the electrical conduction involves the free movement of electrons in the metallic lattice,without any movement of the lattice atom; this type pf conduction is called metallic conduction. Inmetallic conductors, the electricity is carried by the electrons, the atomic nuclei remaining stationary.These conductors are further sub classified in to three types.A.Good conductor B.Semi- conductor C.Non- conductor or Insulator.
Good conductor:
It is a substance, which conducts electricity fully and freely. Eg: Metals likeCopper, Aluminum, and Iron.
Semi- conductor:
It is a substance, which partially conducts electricity. Eg: Silicon, Germanium.
Non- conductor or Insulators:
It is a substance, which does not conduct electric current i.e., whichdoes not allow the passage of current through it. Eg: Wood, Graphite.
Electrolytic conductor:
It is a substance, which in aqueous solution of in molten state liberates ionsand allows electric current to pass through. Electrolytic conductors are further sub classified in to threetypes, depending upon the extent of dissociation at ordinary dilutions.
Strong electrolytes:
Strong electrolytes are completely dissociated into ions at all concentrations.Eg. NaCl, HCl, NaOH.
Weak Electrolytes
: Weak electrolytes dissociate only to a small extent even at very highdilutions. Eg: CH
3
COOH, NH
4
OH.
Non-Electrolytes:
Non-Electrolytes do not dissociate into ions even at low dilutions. Eg: Glucose,Sugar.
S.NOMetallic conductorsElectrolytic conductors
1.It involves the flow of electrons in aconductor.It involves the movement of ions in asolution.2.It does not involve any transfer of matter.It involves transfer of electrolyte in theforms of ions.3.Generally metallic conduction shows anincrease in resistance as the temperatureis raised.But the resistance of an electrolyticsolution decreases as the temperatureis raised.4.No net chemical change takes placeChemical reactions takes place at thetwo electrodes.
Conductivity of electrolytes:
Electrolytic conduction involves the transfer of electrons through themigration of positive and negative ions towards the electrodes. In an ionic solution, the cations and theanions are free to move and both can transport charge. When a current is passed through the solution,the ions carry a current. The ability of the ions in solution to carry current is conductivity. Theconductivity of a solution depends on the number of anions and cations present in it and also on howreadily these ions can move. Like electronic conductors, electrolytes also obey ohm’s law. _______________________________________________________________________________ I B.Tech Engineering Chemistry (Unit-I) Electrochemistry By… B.SRINIVAS1
 
Ohm’s law:
 
The resistance ® of a conductor is directly proportional to its Length (l) and inversely proportional to its cross sectional area (a)`
α
l
α
a
α
l/aR =
ρ
l/a
ρ
= specific resistanceThus, if length of the conductor is 1 cm and its cross sectional area is 1 cm
2
, soR =
ρ
l/a =
ρ
1/1 =
ρ
R =
ρ
Units: Resistance = R = Ohm
ρ
= specific resistance = Ohm cm
1. Define the following and mention their units? a) Specific conductance b) equivalentconductance c) molar conductance d) Ionic mobility
Conductance and specific conductance:
Resistance and specific resistance are commonly used for metallic conductors, where the atomsare static. In case of electrolytic solutions the electricity is virtually conducted by constantly movingions. So it was thought more meaningful to define another quantity called
conductance.
Theconductance of an electrolytic solution is defined as the reciprocal of its resistance.Conductance (L) = 1/R Ohm
-1
or mho or Ω
-1
or Siemens (S)
Specific Conductance:
 
reciprocal of specific resistance is known as Specific conductance, thistype of conductivity is called specific conductivity.k = 1/
ρ
(R =
ρ
l/a

 
ρ
= Ra/l)k = _1_ = _1_ Ra/l RaSpecific conductivity is defined as the conductance of a one centimeter cube of substance or solution.It is represented by the symbol (k) k = kappa.In CGS system the conductivity is expressed in S cm
-1
or mho cm
-1
Conductivity k =1/
ρ = ___1____
= mho cm
-1
= S cm
-1
Ohm CmIn SI system, meter being the fundamental unit of distance, the conductivity is expressed as S m-1.The conversion factor of both CGS & SI system is,1 S cm
-1
= 100 S m
-1
or 1 S m
-1
= 0.01 S cm
-1
Equivalent Conductivity:
Equivalence conductance is defined as the conductance of all ions present in one gramequivalent of the substance or electrolyte in the solution at the given concentration.
Equivalent conductivity/ equivalent conductance
is represented by Λ (Greek : Capital Lambda).Λ
 
= 1000 X C _______________________________________________________________________________ I B.Tech Engineering Chemistry (Unit-I) Electrochemistry By… B.SRINIVAS2
 
Units of Equivalent conductivity: Ohm
-1
Cm
2
eq
-1
Molar Conductivity:
Molar conductivity is defined as the conductance of all the ions present in mole of theelectrolyte in the solution.µ = 1000k MThe units of molar conductivity:CGS system: Ohm
-1
cm
2
mol
-1
or S cm
2
mol
-1
 
Ionic Conductivity and Ionic Mobilities:
Equivalent conductivity of any electrolyte at any dilution is directly proportional to the chargecarried by the ions and their velocities. The conductivity is thus given by the products of charge andvelocity of individual ions. At infinite dilution the ionization is complete and the solution containingone equivalent of various electrolytes contains equivalent number of ions. Hence at infinite dilutiontotal charge carried by all ions is same in every case. Because the total charge is constant at infinitedilution, the Λ
α
must depend exclusively on ionic velocities.Defining the ionic velocity or mobility
as the speed with which a charged a particle at infinitedilution moves under a potential gradient of one volt per cm, we have,
λ
+
α
u
+
 
λ
α
u
-
 
Or 
λ
+
 
= ku
+
λ
 
= ku
-
Where k is a proportionality constant and u
+
and u
-
represent the ionic velocities at infinitedilution. Since 1 equivalent of an ion under unit potential gradient carries a charge of 1 Faraday per sec., the proportionality constant k = 96500 coulombs.Therefore,u
+
=
λ
+
 
/k and u
-
=
λ
 
/k Ionic conductivity is expressed in S cm
2
, while ionic mobility is expressed in cm s
-1
.Calculated ionic mobilities of few common ions at 25
o
C are given in Table
2. What is Kohlrausch law? Give its applications (Or) what is Kohlrausch law of independentmigrations? Give its application.
Kohlrausch Law :
In a state of infinite dilution all electrolytes ionize or dissociate cent percentage, and the ions can be carried by the ions independent of each other. During our discussion on the variation of equivalentconductivity with square root of concentration we noticed that equivalent conductivity increased withdilution to reach a limiting value characteristic of the electrolyte and named it as equivalentconductivity at infinite dilution.
Λ
0
, In 1875 Kohlrausch made a series of measurements, involvingelectrolytes with common cations, common anions and calculated their differences. He obtain aconstant difference in
Λ
0
values of an ion pair, irrespective of the nature of the common counter ionemployed, as exemplified by following results obtained at 25
0
C.Kohlrausch studied the equivalent conductance of some pairs of having the same anion and cation atinfinite dilution and experimental results are given in the table.  _______________________________________________________________________________ I B.Tech Engineering Chemistry (Unit-I) Electrochemistry By… B.SRINIVAS3

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