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II Semester/Unit 1/Electrochemistry

II Semester/Unit 1/Electrochemistry

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03/18/2014

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Electrochemistry
Electrochemistry
deals with the links between chemical reactions and electricity.This includes the study of chemical changes caused by the passage of an electric currentacross a medium, as well as the production of electric energy by chemical reactions.Electrochemistry also embraces the study of electrolyte solutions and the chemicalequilibria that occur in them.The devices used for the inter-conversion between chemical and electrical formsof energy are called
electrochemical cells
.Electrochemical cells which generate an electric current are called voltaic cells or galvanic cells, and common batteries consist of one or more such cells. In otheelectrochemical cells an externally supplied electric current is used to drive a chemicalreaction which would not occur spontaneously. Such cells are called electrolytic cells.
Electrolytic cell
An
electrolytic cell
decomposes chemical compounds by means of electricalenergy, in a process called electrolysis. The result is that the chemical energy isincreased.An electrolytic cell has three component parts: an electrolyte and two electrodes(a cathode and an anode). The electrolyte is usually a solution of water or other solventsin which ions are dissolved. Molten salts such as sodium chloride are also electrolytes.When driven by an external voltage applied to the electrodes, the electrolyte providesions that flow to and from the electrodes, where charge-transferring or redox, reactionscan take place.The electrolytic cell is the industrial chloralkali cell in which
brine
(an aqueous sodiumchloride solution) is electrolytically converted to chlorine and caustic soda (sodiumhydroxide, NaOH). The external power source supplies electric energy to drive theoverall reaction.1
 
2Cl
+ 2H
2
O → Cl
2
+ H
2
+ 2OH
 Chloride ion is oxidized to chlorine gas at the carbon electrode, and water is reduced tohydrogen gas (H
2
) and hydroxide ion (OH
) at the iron electrode. The electrolytes aremaintained as electrically neutral by a flow of sodium ions through the separator (such asan ion exchange membrane).For the electrolytic cell, the external markings of anode and cathode are opposite thechemical definition. That is, the electrode marked as anode for discharge acts as thecathode while charging and the electrode marked as cathode acts as the anode whilecharging.
Voltaic Cells
When zinc metal is placed in a solution of copper ions as described by the netionic equation shown below.Cu
+2
(aq) + Zn (s) -------> Cu(s) + Zn
+2
(aq)The zinc metal slowly "dissolves" as its oxidation produces zinc ions which enter intosolution. At the same time, the copper ions gain electrons and are converted into copper atoms which coats the zinc metal or sediments to the bottom of the container. The energy produced in this reaction is quickly dissipated as heat, but it can be made to do usefulwork by a device called, a voltaic cell.A voltaic cell is composed to two compartments or 
half-cells
, each composed of an electrode dipped in a solution of electrolyte. These half-cells are designed to containthe oxidation half-reaction and reduction half-reaction separately as shown below.2
 
The half-cell, called the
anode
, is the site at which the
oxidation
of zinc occurs as shown below.Zn (s) ----------> Zn
+2
(aq) + 2e
-
During the oxidation of zinc, the zinc electrode will slowly dissolve to produce zinc ions(Zn
+2
), which enter into the solution containing Zn
+2
(aq) and SO
4-2
(aq) ions.The half-cell, called the
cathode
, is the site at which
reduction
of copper occurs asshown below.Cu
+2
(aq) + 2e
-
-------> Cu (s)When the reduction of copper ions (Cu
+2
) occurs, copper atoms accumulate on the surfaceof the solid copper electrode.The reaction in each half-cell does
not
occur unless the two half cells are connected toeach other.In order for oxidation to occur, there must be a corresponding reduction reaction that islinked or "coupled" with it. Moreover, in an isolated oxidation or reduction half-cell, animbalance of electrical charge would occur, the anode would become more positive aszinc cations are produced, and the cathode would become more negative as copper cations are removed from solution. This problem can be solved by using a
"salt bridge"
3

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