ELECTRICAL DOUBLE LAYER In heterogeneous systems, an electrode can only donate or accept electrons from species that is present

in a layer of solution which is immediately adjacent to the electrode. Thus, this layer may have a composition that differs significantly from that of the bulk of solution. Lets consider the structure of the solution immediately adjacent to an electrode when a positive potential is first applied to that electrode, immediately after impressing the potential, there will be a momentary surge of current, which rapidly decays to zero if no reactive species are present at the surface of the electrode. This current is a charging current that creates an e cess !or a deficiency" of negative charge at the surface of the two electrodes. #s a conse$uence of ionic mobility, however, the layers of solution immediately adjacent to the electrodes ac$uire an opposing charge. The figure below is %lectrical double layer formed at electrode surface as a result of an applied field potential. &'I()*%+ ,a - b are not in this te t This effect is illustrated in figure !,a". The surface of the metal electrode is shown having an e cess of positive charge as a conse$uence of an applied positive potential. The charged solution layer consists of two parts . !," a compact inner layer !do to d," in which the potential decreases linearly with distance from electrode surface and !/" a diffuse layer !d, to d/" in which the decrease is e ponential !fig ,b". The assemblage of charge at the electrode surface and the solution adjacent to the surface is termed an electrical double layer. Faradaic and Non faradaic current Two types of processes can conduct current across an electrode 0 solution interface. 1ne kind involves a direct transfer of electrons via o idation reaction at one electrode and a reduction at the other. 2rocesses of this type are called faradaic processes because they are governed by faradaic laws which state that an amount of chemical reaction at one electrode is proportional to the current i.e. faradaic current. To understand the basic difference between a faradaic and a non3faradaic current, imagine an electron travelling down the e ternal circuit to an electrode surface when the electron reaches the solution interface, it can do one of only two things, it can remain at the electrode surface and increase the charge on the double layer which constitutes a non3faradaic current. #lternatively, it can leave the electrode surface and transfer to a species in the solution, thus becoming a part of a faradaic current. Mass Transfer in Cells with the assa!e of Current # faradaic current re$uires continuous mass transfer of reactive species from the bulk of the solution to the electrode surface. Three mechanism bring about this mass transfer4 5onvection, 6igration and 7iffusion. 5onvection. Involves mechanical motion of the solution as a result of stirring or the flow of the solution past the surface of the electrodes. 6igration. is the movement of ions through the solution brought about by electrostatics attraction between the ions and the charged electrode. 7iffusion. is the motion of species brought about by a concentration gradient. Mechanis" of Mass Trans#ort It is important to investigate the mechanism by which ions or molecules transported from the bulk of the solution to a surface layer !or the reverse" because knowledge of these mechanisms

provides insight into how concentration polarization can be prevented or induced as re$uired. *ecall that three mechanisms of mass transport can be recognised !," 7iffusion, !/" 6igration, !8" 5onvection. 9henever a concentration difference develops between two regions of a solution, as it does when a species is reduced at a cathode surface !or o idized at an anode surface" ions or molecules move from the more concentrated region to the more dilute as a result of diffusion. The rate of diffusion d50dt is given by. d50dt : ;!5 3 5o".................................................................!," 9here 5 is the reactant concentration in bulk of the solution, 5o is its e$uilibrium concentration at the electrode surface, ; is proportionality constant. #s shown earlier, the value of 5o is fi ed by the potential of the electrode and can be calculated from the <ernst e$uation. #s higher potentials are applied to the electrode, 5o becomes smaller and smaller and the diffusion rate becomes greater and greater, ultimately, 5o becomes negligible with respect to 54 the rate then becomes constant, i.e. when 5o =>. d50dt : k5 ...............................................................................!/" )nder this condition, concentration polarization is said to be complete, and the electrode operates as an ideal polarized electrode. The process by which ions move under the influence of an electrostatic field is called 6igration. It is often the primary process by which mass transfer occurs in a bulk of the solution in a cell. The electrostatic attraction !or repulsion" between a particular ionic species and the electrode becomes smaller as the total electrolyte concentration of the solution becomes greater. It may approach zero when the reactive species is but a small fraction, say ,0,>>, of the total concentration of ions with a given charge. *eactants can also be transferred to or from an electrode by mechanical means. Thus forced convection such as stirring or agitation tends to decrease concentration resulting from temperature or density differences also contributes to material transport. $al%anic and Electrol&tic Cells &'I()*% / is not in this te t 'igure !/" refers to a galvanic electrochemical cell with salt bridge. The net cell reaction that occurs in the figure !/" above is the sum of the two half3cell reactions.3 ?n!s" @ ?n/A A /e3................................................!8" #nd 5u/A A /e3 @ 5u.................................................!B" That is ?n!s" A 5u/A @ ?n/A A 5u!s"............................!C" The potential that develops in this cell is a measure of the tendency for this reaction to proceed towards e$uilibrium. Thus, as shown in this figure, when the copper and ?inc ion activities are >.>,6, a potential of ,.,>D develops, which shows that the reaction is far from e$uilibrium. #s the reaction proceeds, the potential becomes smaller and smaller, ultimately reaching >.>>D when the system achieves e$uilibrium. 5ells such as the one shown in this figure that are operated in a way that produces electrical energy. 'or e ample, the cell under discussion could be made electrolytic by connecting the negative terminal of a dc power supply to the ?inc electrode and the positive terminal to the copper electrode. If the output of the supply was made somewhat greater than ,.,>D, the two electrode reactions would be reversed and the net cell reaction would becomes ?n/A A 5u!s" @ ?n!s" A 5u/A # cell in which reversing the direction of the current supply reverses the reaction at the two cell electrodes is termed a chemically reversed cell. Anodes and Cathodes' The cathode of an electrochemical cell is the electrode of which reduction occurs while the

anode is the electrode where o idation takes place in both galvanic and electrolytic cells. 'or galvanic cell in figure /, the copper electrode is the anode. In contrast, where this same cell is operated as an electrolytic cell, the copper electrode would be the anode and the ?inc electrode the cathode. Oh"ic otential( IR Dro#' To develop a current in either a galvanic or an electrolytic cell, a driving force in the form of a potential is re$uired to overcome the resistance of the ions to movement toward the anode and the cathode. Eust as in metallic conduction, this force follows 1hms law and is e$ual to the product of the current in amperes and the resistance of the cell in 1hms. The force is generally referred to as the ohmic potential or the I* drop. The net effect of I* 7rop us to increase the potential re$uired to operate an electrolytic cell and to decrease the measured potential of a galvanic cell. Therefore, the I* drop is always subtracted from the theoretical cell potential. i.e. %cell : %cathode F %anode F I*.......................................!G" olari)ation *ecall the e$uation %cell : %cathode F %anode F I* This e$uation predicts that at constant electrode potentials, a linear relationship should e ist between the cell voltage and the current. In fact, departures from linearity are often encountered, under these circumstances, the cell is said to be polarized. 2olarization may arise at one or bith electrodes. Ideal #olari)ed and Non*#olari)ed Electrodes and Cells The ideal polarized electrode is one in which current remains constant and independent of potential over a considerable range. 'igure !8a" and !8b" &'I()*%+ 8a - b are not in this te t 'igure !8a" is a current3voltage curve for an electrode that behaves ideally in the region between # and H. 'igure !8b" depicts the current3voltage relationship for a depolarized electrode that behaves ideally in the region # and H. Ience the potential is independent of the current. 'igure !B" 5urrent3voltage curve for a cell showing real non3polarized behaviour between a and H !solid line" and polarised behaviour !dashed line". &'I()*%+ B is not in this te t Hecause of the internal resistance of the cell, the current3voltage curve has a definite slope e$ual to *. !e$uation G" rather than, the infinite slope for the ideal non3polarized electrode in fig. B. Heyond point # and H, polarization occurs at one or both electrodes resulting in departures from the ideal straight line. <ote that when polarization arises in an electrolytic cell, a higher potential is re$uired to achieve a given current. +imilarly polarization of a galvanic cell produces a potential that is lower than e pected. Concentration olari)ation' 5oncentration polarization is observed when diffusion, migration and convection are insufficient to transport the reactant to or from an electrode surface at a rate demanded by the theoretical current. 5oncentration polarization causes the potential of a galvanic cell to be smaller than the value predicted on the basis of the thermodynamic potential and the I* drop or ohmic potential !a driven force in galvanic or electrolytic cell that is e$ual to the product of the current in amperes and the resistance of the cell in ohms". +imilarly, in an electrolytic cell, a potential more negative than the theoretical is re$uired to maintain a given current. 5oncentration polarization is important in general elecctroanalytical

methods. In some applications, steps are taken to eliminate it4 in others however, it is essential to the method, and every effort is made to promote it. The degree of concentration polarization is influenced e perimentally by.3 !," the reactant concentration, with polarization becoming more probable at low concentration, !/" the total electrolyte concentration, with polarization becoming more probable at high concentration, !8" mechanical agitation with polarization decreasing in well3stirred solutions and !B" electrode size with polarization effects decreasing as the electrode surface area increases. There e ist three regions of a half3cell where polarization can occur. These regions include the electrode itself, a surface film of solution immediately adjacent to the electrode, and the bulk of the solution. The overall electrode reaction is. 1 A ne3 @ *ed. +everal factors limit the rate at which this overall reaction occurs and thus the magnitude of the current. 1ne of this is mass transfer which involves movement of o idized from the bulk of the solution to the surface film. 9hen this step or the reverse mass transfer of reduced to the bulk limits the rate of the overall reaction and thus the current, concentration polarization is said to e ist. 5oncentration polarization arises when the rate of transport of reactive species to the electrode surface is insufficient to maintain the current determined by the e$uation.3 %cell : %cathode F %anode F I* 'or e ample, consider a cell made up of an ideal non3polarized anode and a polarized cathode consisting of a small 5admium electrode immersed in a solution of 5admium ions. The reduction of 5admium ions is a rapid and reversible process so that when a potential is applied to this electrode the surface layer of the solution comes to e$uilibrium with the electrode essentially. Instantaneously i.e. a brief current is generated that reduces the surface concentration of cadmium ions to the e$uilibrium concentration 5o given by.3 % : %o 5d F !>.>CJ/0/"logK,0 5oL.................................................!M" In summary concentration polarization is observed when diffusion, migration and convection are insufficient to transport the reactant to or from electrode surface at a rate demanded by the theoretical current. 5oncentration polarization causes the potential of a galvanic cell to be smaller than the value predicted on the basis of the thermodynamic potential and the I* drop. +imilarly, in an electrolytic cell, a potential more negative than the theoretical is re$uired to maintain a given current. 5oncentration polarization is important in general elecctroanalytical methods. In some applications, steps are taken to eliminate it4 in others however, it is essential to the method, and every effort is made to promote it. The degree of concentration polarization is influenced e perimentally by.3 !," the reactant concentration, with polarization becoming more probable at low concentration, !/" the total electrolyte concentration, with polarization becoming more probable at high concentration, !8" mechanical agitation with polarization decreasing in well3stirred solutions and !B" electrode size with polarization effects decreasing as the electrode surface area increases. Diffusion Coefficient *ecall that a faradaic current re$uires continuous mass transfer of reactive species from the bulk of the solution to the electrode surface above one of the three mechanisms that bring about this mass transfer is 7iffusion. 7iffusion is one main cause of band spreading. The diffusion coefficient measures the rate at which a substance moves randomly from a region of high concentration to a region of lower concentration, as shown below. &'I()*%+ C is not in this te t

This figure C shows spontaneous diffusion of solute across a plane with a concentration gradient d 0dc. The number of moles crossing each s$uare metre per second called the flu !E", is proportional to the concentration gradient.3 i.e. 7iffusion 5oefficient : 'lu Kmol0m/sL : E : 37Kdc0d L....................................!N" The constant of proportionality !7" is the diffusion coefficient, and the negative sign is necessary because the net flu is from the region of high concentration to the region of low concentration. The above e$uation is called 'icks law of diffusion. The ficks law of diffusion states that the flu of molecules diffusing across a plane of unit area is proportional to the concentration gradient and to the diffusion coefficient. If the concentration is e pressed as mol0m8, the unit of 7 are m/0s i.e. E : 37Kdc0d L.................................................................................................!J" 'icks laws are differential e$uations describing the flu or movement of substance and its concentration under diffusion control as function of time and position. 5onsider a particular location . #t time t, assume that <! " molecules are to the left of this location and that <! A d " molecules are to the right. #fter a time increment, dt, the molecules originally at will have moved an average distance d . Hecause the driving force for the motion of these molecules is a random thermal process the same number goes to the right as to go to the left. The net number of molecules that move between and ! A d " is given by the difference between the number of molecules on the left and the number on the right. The net movement per unit time or flu through an area # is K,0#Ld<0dt : flu 0area : OK<! "0/L FK!<! " A d "0/LP0#dt.................................!,>" 6ultiplying the right hand side of e$uation !,>" by !d "/0!d " converts the number of molecules to the concentration, and noting that the concentration of the species is given by 5 : <0!#d "...................................................................................!,," 1ne obtains 'lu : E : K!d "/0dtLK5! A d " F 5! "L0d ................................!,/" The first term on the right3hand side of e$n !,/" is a function of the average distance the molecules have moved, d , in a given time, dt. It is a constant, characteristic of the particular system of solute and solvent molecules, and is called the diffusion 5oefficient 7. Hy allowing d and dt approach zero, the differential form. 'icks first law is obtained. 'lu per unit area : 3 K,0#Ld<0dt : 3 7!d50d "...............................!,8" 9hich states that the flu is proportional to the concentration gradient dc0d which is decreasing as the electrode surfaces is approached. The net transfer of solute mass per unit time across a plane intersecting a concentration profile is proportional to the steepness of the profile concentration gradient, meaning that they diffuse in the direction in which the sign of dc0d is negative from the molecules frame of reference. Fic+,s -econd Law This law involves the change in the concentration gradient as a function of time. It is derived from the first law by noting that the change in concentration at location / is given by the differences in the flu into and the flu out of an element width d . !dc0dt" / : K7!dc0dt" /3d 3 7!dc0dt" / A d L0d ..........................!,B" 9hen d and dt approach zero, and because 7 is assumed independent of and t, for planar electrodes 'icks second law becomes dc0dt : 7Kd/50!d "/L.............................................................................!,C" Le%ich E.uation This e$uation deals with methods involving convective mass transport of reactants and products.

These involve systems where the electrode is in motion or where there is forced solution flow past a stationary electrode these methods take advantage of enhanced sensitivity resulting from the enhanced mass transfer of electro active substance to the electrode that occurs under hydrodynamic conditions. # steady state is attained rather $uickly and measurements can be made with high precision. #t steady state, double layer charging does not enter into the measurement. In a rotatory disk electrode !which consists of a disk of electrode material embedded in a rod of an insulting material with a platinum wire sealed in a glass tubing with the sealed end ground smooth and perpendicular to the rod a is. The addition of an independent ring surrounding the disk produces a ring disk electrode. In this electrode, the spinning disk drags with it the fluid at its surface. The hydrodynamic flow pattern that results from rapid rotation of the disk moves li$uid horizontally out of and away from the centre of the disk. The fluid at the disk surface is replenished by an upward a ial flow normal to the surface once the velocity profile has been determined, the convective3diffusion relationships can be solved to give the mass transfer3 limited current by Levich e$uation. Ilim : >.G/>n'#7/08Q,0/D3,0G5.........................................................!,G" 9here D is the kinematic viscosity !: viscosity0density" in cm/0sec and w is the angular fre$uency of rotation !/R rotation rate". The rotation rate should be faster than ,>sec3, but slow enough to maintain laminar flow because turbulent flow must be avoided. The rate at which the electrode potential is scanned must be slow with respect to the rotation rate to allow the steady state conditions to be achieved. 'or a totally reversible reaction, the shape of the currentpotential wave is independent of the rotation rate. 7eviation of the plot of i versus w,0/ form a straight line that intersects the origin suggests that some kinetic step is involved in the electrontransfer reaction. 9hen this arises, the plot will be curved and tend towards the kinetically limited current as the s$uare root of the rotation rate approaches infinity. 2lotting ,0i versus ,0Q,0/ yields ,0ik the kinetic current upon e trapolation. 7etermination of the kinetic current at different values of potential then allows determination of the kinetic parameters. Oh"ic otential 9henever current flows, three factors decrease the magnitude of the output voltage of a galvanic cell and increase the magnitude of the applied voltage needed for electrolysis. These factors are. The ohmic potential, concentration polarization and over potential. #ny cell has some electric resistance the voltage needed to force currents !ions" to flow through the cell is called ohmic potential given as 1hmic potential : %ohmic : I*. In a cell with no current flowing, there is no ohmic potential because I : >. If current is drawn from the cell, the output voltage decreases because part of the energy released by the chemical reaction is needed to overcome resistance inside the cell. The voltage applied to an electrolytic cell must be great enough to drive the chemical reaction and to overcome cell resistance. Lets denote the voltage of a galvanic cell with zero current as %<ernst which is a positive number, for a spontaneous reaction. If the reaction is reversed to make it an electrolytic cell, the voltage is 3%<ernst. In the absence of any other effects the voltage of a galvanic cell is decreased by I* and the magnitude of the applied voltage in an electrolytic cell must be increased by I* for current to flow. Effect of Oh"ic otential

1utput of galvanic cell4 %galvanic : %nernst F I*. Input to electrolysis cell4 %electrolysis : 3 %nernst FI* 5onsider the cell4 5d!s"05d5l/ !a$. >.,GM6"0#g5l!s"0#g in which the spontaneous chemical reaction is 5d!s" A /#g5l!s" = 5d/A A /#g!s" A /5l3 The <ernst e$uation tell us that the cell voltage is %nernst : >.MGBD !a" If the cell has a resistance of G.B/S and a current of /N.8m# is drawn, what will be the cell voltageT !b" 9hat voltage must be applied to operate the same cell in reverse as an electrolytic cell. +olution. with a current of /N.8m#, the voltage will decrease to. Concentration olari)ation 5oncentration polarization occurs when the concentration of a species created or consumed at an electrode is not the same at the surface of the electrode as it is in bulk solution. 5oncentration polarization decreases the magnitude of voltage available from a galvanic cell and increases the magnitude of the voltage re$uired for electrolytic cell. 5onsider the cadmium anode for which the o idation is 5d!s" = 5d/A A /e3 e$n .......................!," 'igure G &'I()*% G is not in this te t Iere !in this figure G". The potential of the 5d/A0 5d couple depends on the concentration of the 5d/A in the layer surrounding the electrode. If the 5d/A ions move rapidly away from the electrode by diffusion or convection, the concentration of 5d/A is uniform throughout the entire solution. The potential for reaction 5d!s" @ 5d/A A /e3 depends on K5d/ALs and not K5d/ALo. Lets write the <ernst e$uation for all half reactions as reductions. #nd reverse the direction of e$uation. The anode potential is. %!anode" : %o !anode" F !>.>CJ,G0/"logK!,0K 5d/ALs"L ..........................................................................!/" If K5d/ALs : K5d/ALo, the anode potential is consistent with bulk 5d/A concentration. If the current flows so fast that 5d/A cannot escape from the vicinity of the electrode as fast as it is made, K5d/ALs, will be greater than K5d/ALo. This is concentration polarization. The anode potential in e$n !M" becomes more positive and the cell voltage % : %!cathode" F %!anode" becomes more negative. 5onsider the 'igure !M" below. &'I()*% M is not in this te t This figure !M" shows the behaviour of a galvanic cell illustrating concentration polarization that occurs when K5d/ALs U K5d/ALo. The resistance of the cell is G.B/ S. The straight line shows the behaviour e pected from ohmic potential. 7eviation from the straight line at high currents is due to concentration polarization. 5oncentration polarization decreases the magnitude of voltage available !output" from a galvanic cell and increases the magnitude of the voltage re$uired !input" for electrolytic cell. <ote that when ions are not transported to or from an electrode as rapidly as they consumed or created, concentration polarization e ists and KVLs : KVLo where V is concentration of electro active species. Effects of Oh"ic #otential and Concentration #olari)ation 1utput of galvanic cell4 %galvanic : %nernst F I* F %conc. Input to electrolysis cell4 %electrolysis : 3 %nernst FI* 3 %conc.

9here %conc. : additional voltage. Ions move by diffusion, convection and electrostatic forces, raising the temperature increases the rate of diffusion and thereby decreases concentration polarization. 6echanical stirring transports species through the cell. Increasing ionic strength decreases electrostatic forces between ions and electrode. These factors all affect the degree of polarization. #lso the greater the electrode surface area, the more current can be passed polarization. To decrease concentration polarization. !a" *aise the temperature !b" Increase stirring !c" Increase electrode surface area !d" 5hange ionic strength to increase or decrease attraction between the electrode and the reactive ion. 'igure !N". &'I()*%s N is not in this te t This figure !N" is showing the behaviour of 2t and #g cathodes at which reduction of I81A occurs at pI 8./ in 1/3free, a$ueous I/+1B using saturated calomel electrode. The reaction is I81A A e3 = ,0/I/ A I/1 The reaction begins in earnest at appro imately 3>.8CD at a 2t cathode and at appro imately 3 >.ND at #g. Wuestion may be asked4 what is going on hereT If the chemistry is the same, why doesnt it re$uire the same voltage for different electrodesT To make matter worse, when a mercury electrode was used in the same e periment, reduction did not begin until 3,.8D. %ven when concentration polarization is absent and ohmic potential is taken into account, some electrolysis re$uires a greater than e pected applied voltage than one anticipated. The difference between the e pected voltage !after accounting for I* drop and concentration polarization" and the observed voltage is called the over potential !%over.". The faster you wish to drive on electrode reaction, the greater the over potential that must be applied. Effects of o%er #otential/ Concentration #olari)ation 1utput of galvanic cell4 %galvanic : %nernst F I* F %conc. F %over. Input to electrolysis cell4 %electrolysis : 3 %nernst FI* 3 %conc. F %over. 1ver potential can be traced to the activation energy barrier for the electrode reaction. The activation energy reactants can be converted to products. The higher the temperature, the greater the number of molecules with sufficient energy to overcome the barrier and faster the reaction proceeds. 'igure !Ja" and !Jb" &'I()*%+ Ja - b are not in this te t The above figures shows schematic energy profile for electron transfer from a metal to I81A !a" with no applied potential !b" after a potential is applied to the electrode. The over potential increases the energy of the electrons in the electrode. 'igure !a" shows a high barrier preventing electron transfer from a metal electrode to I81A, and the rate is very slow. If an electric potential !the over potential" is applied to the electrode, the energy of the electrons in the electrode is increased. In figure !b". The applied potential decreases the barrier that must be overcome and increase the rate of electron transfer. 1ver potential is the voltage needed to sustain a particular rate of electron transfer. The greater the rate, the higher the over potential must be. Thus over potential increases as current density !#0m/" increases. The activation energy for the chemical reaction is different for different metals, which e plains the different behaviours of a 2t and #g electrodes in 'igures !N".

his is the voltage that must be applied to drive the electrolysis in the absence of ohmic potential and over potential. It is called F %nernst !rather than %nernst" because, not the spontaneous galvanic reaction. The re$uired electrolytic voltage is %electrolysis : 3 %nernst FI* F over potentials 0'1' OLARO$RA 2Y olaro!ra" Diffusion current at dro##in! electrodes 2alf*wa%e otential Current otential Cur%es olaro!ra#h& In polarography, the current between the mercury !Ig" working electrode and an inert au iliary electrode e.g. platinum electrode is being measured. Doltage is measured between the mercury electrode and a reference electrode e.g. calomel electrode. # mercury electrode gives more reproducible behaviour that does a static surface !such as platinum electrode" whose characteristics changes with use. +econdly mercury electrode can operate at more negative potentials than most other electrodes. 2olarography is a techni$ue by which the relationship between current and voltage is observed during electrochemical processes which involved the use of dropping3mercury electrode. The classical dropping3mercury electrode consists of a long glass capillary tube connected to a mercury reservoir. The drop rate, which is typically one drop in ,3G sec, is controlled by raising or lowering the levelling bulb. The mercury drop grows continuously until it falls off4 then a new one begins. # mercury electrode is used because the freshly e posed mercury surface yields reproducible currentpotential behaviour. 9ith any other working electrode !such as 2t" current depends on the electrode surface condition. The vast majority of reactions studied with the mercury electrode are reductions. #t a 2t surface reduction of solvent competes with reduction of many analytes especially in acidic solutions. /IA A /e3= I/!g" %o : >. There is a large over potential for reduction of IA at the Ig surface. Therefore reactions that is thermodynamically less favourable than reduction of IA can be carried out without competitive reduction of IA. In neutral or basic solutions, even alkali metal !(roup I" cations are reduced more easily than IA, despite their lower standard potentials. This phenomenon is partly because of the over potential for IA reduction and partly because reduction of a metal into a mercury amalgam is more favourable than reduction to the solid state. e.g ;A A e3= ;!s", %o : 3/.J8GD ;A A e3 A Ig = ; !in Ig", %o : 3,.JMCD 6ercury is not very used for starting o idation reaction because Ig itself is easily o idized. In a non comple ing medium, Ig is o idized near A>./CD !versus +5%". If the concentration of 5l3 is ,6, Ig is o idized near >Dolt because Ig is stabilized by 5l3. Ig!l" A B 5l3 @ Ig5lB /3 A / e3 To study o idation reactions by voltammetry 2t, au, or 5 working electrodes in appropriate solvents provides a wide range of accessible redo potentials. OLARO$RAM The graph of current versus potential in polarography is called a polarogram.

The figure ,> below shows the reduction of 5d/A recorded by using the dropping3mercury electrode. &'I()*% ,> is not in this te t 'igure !,>" +hows classical direct current polarogramms !old one" of !a" Cm6 5d/A in ,6 I5l and !b" ,6 I5l alone. <ote that voltage becomes more negative to the right and the scale of current is in microamperes. The mercury electrode suspends a static drop of mercury with a fi ed size and then measures current and voltage with this drop. Then the ne t drop is suspended and the ne t measurements are made. The constant size drops give the smooth curve in the figure below. 'igure !,," shows a sampled current polarograms mercury of !a" Cm6 5d/A in ,6 I5l alone. &'I()*% ,, is not in this te t Diffusion current at dro##in! electrodes In deriving an e$uation for polarographic diffusion currents, it is necessary to take into account the rate of growth of the spherical electrodes, which is related to the drop time in seconds t and the rate of flow of mercury through the capillary m, in mg0s and the diffusion coeffiJcient of the analyte 7 in cm/0s and the diffusion variables are taken into account in the Ikovic e$uation4 !Id"ma : M>Gn7,0/m/08t,0G5 9here !Id"ma : 6a imum current in microamperes 5 : the analyte concentration in mill moles per litre. To obtain an e pression for the average current rather than the ma imum, the ma imum, the constant in the foregoing e$uation becomes G>M rather than M>G. That is !Id"avg : G>Mn7,0/m/08t,0G5 <ote that either the average or the ma imum current can be used in $uantitative polarography. The product m/08t,0G in the Ikovic e$uation called the capillary constant, described the influence of dropping electrode upon the diffusion current, both m and t are readily evaluated e perimentally. 5omparison of diffusion currents from the different capillaries is thus possible. 2alf*wa%e otential % : %,0/ F !>.>CJ/0n"logK!i0il3i"L 9here %,0/ : half3wave potential Il : limiting current # plot of % against logK!i0il3i"L gives a straight line with the slope : F !>.>CJ/0n" and the intercept : %,0/ Current otential Cur%es If both the o idant and reductant are initially present and both are in solution, then a Dolta metric wave would look like below. ! 'igure ,/" &'I()*% ,/ is not in this te t The anodic current !3id"a arises when the reduced form is being o idized at the electrode under these conditions the current potential relation assumes the form. % : %,0/ A !>.>CJ/0n"logK!!id"c3i0i3!id"aL Wuestion.3 The measurements shown in the table were made on a reversible dc polarographic wave for the reduction of 8.C ,>386 <itrate in dimethylformamide at /Co5. The limiting diffusion current was 8.8>X# on the plateau of the polarographic wave, the drop time was B8.M seconds for ,> drops and 8> drops had a mass of >.,JG/g. !a" 9hat number of electrons was involved in the electrode reactionT !b" 9hat is the half3wave potential for these reactionsT !c" 5alculate 7 for <itrate in the dimethylformamide.

%!D vs +5%" i0 X# 3>.C,J >.B> 3>.C/> ,.>/ 3>.C8, ,.CC 3>.C8N /.>, 3>.CBN /.CG 3>.CG> 8.>, 3>.CGN 8./> 3'1 EMF OF CELL Effect of Acti%it& on electrode otential Eo The -tandard Electrode otential Eo Effect of Acti%it& on electrode otential Ther"od&na"ic data fro" cell E'M'F The Te"#erature*de#endence of the E'M'F Effect of Acti%it& on electrode otential Let us consider the half3reaction p2 A $W A33333333333333333333333A ne3 @ r* A s+ 9here 2,W,*,+ are reacting species, e3 : no of electrons and p,$,r,s are number of moles. % : %o F !*T0n'"lnK!a*"r !a+"s0!a2"p !aW"$L333333333333333333333!," #t room temperature, !/JN;" *T0n' : >.>CJ,G0n Ience % : %o F !>.>CJ,G0n"logK!a*"r !a+"s0!a2"p !aW"$L33333333!/" %$uation !/" is a general statement of the <ernst e$uation which can be applied to both half3cell reaction or cell reactions The -tandard Electrode otential Eo 5onsider the potential for the process #gA A e3 @ #g!s", %o : A>.MJJD The nernst e$uation is4 % : >.MMJ F !>.>CJ,G0n"logKa#g0a#gAL333333333333!8" +ince the activity of #g is unity, since it is a solid e$n !8" becomes % : >.MMJ F !>.>CJ,G0n"logK,0a#gAL % ample ,. 9hat is the electrode potential for half3cell consisting of a cadmium electrode immersed in a solution that is >.>,C>6 in 5d. % ample /. 5alculate the potential for a platinum electrode immersed in a solution prepared by saturating a >.>,C>6 solution of ;Hr with Hr/. (iven that the half3cell reaction is.3 Hr/!l" A /e3 @ /Hr3, %o : ,.>GCD, and state any assumption made. 9here !L" indicates saturated solution % ample 8.3 5alculate the potential for a platinum electrode immersed in a solution that is >.>,C6 in ;Hr and ,.>> ,>38 in Hr/. (iven that the half3reaction Hr/!l" A /e3 @ /Hr3, %o : ,.>NMD, Ther"od&na"ic data fro" cell E'M'F To relate Y(o to %o, combine %o : !*T0'"ln; with the e pression Y(o m : 3*Tln;, the Y(o m : 3n'%o, where ' : 'araday, n : no of mole of electrons The Te"#erature*de#endence of the E'M'F

The variation of Y( with temperature is given by !d%0dT"p : Y+m0' The measurement of the gradient of the e.m.f of a cell with respect to temperature gives the values of the entropy change !Y+m" of the cell r n. +ince Y( : YI 3 TY+, the two results can be combined to give the enthalpy change in the reaction YIm : Y(m A TY+m : 3'K%3T!d%0dT"pL. Wuestion.3 #t />o5 the std e.m.f of the cell Ig0Ig/5l/!s" I5l!a$" I/, 2t is >./GJ/D and at 8>o5 it is >./GG>D. 'ind the values of Y(m, YIm, and Y+m at /Co5. The cell reaction is ,0/Ig/5l/!s" A ,0/I/!g" @ Ig!l" A I5l!a$" 5orresponding to a ,3electron transfer. #nswer.3 Y(o m : 3n'%o Y(o m!/J8;" : 3!J.GBJ ,>B" !>./GJ/D" : 3 /C.JNkEmol3, #nd Y(o m!8>8;" : 3!J.GBJ ,>B" !>./GG>D" : 3 /C.GM kEmol3, Ience Y(o m!/JN;" : Y(o m!/JN;" A Y(o m!8>8;" 0/ : 3 /C.N/ kEmol3, #nd KdY(o m0dTL/JN; : K3/C.GM3!/C.JN"L0K8>83/J8L : 8,.>>E;3,mol3, It follows that Y+o m : !dY(o m 0dT"/JN; : 38,.>>E;3,mol3, #nd YIo m : Y(o m A TY+o
m

: 3/C.N/ A !/JN" !38,.>>"0,>>> : 3 8C.>G kEmol3, <ote that. 'or the reaction Ig/5l/!s" A ,0/I/!g" @ /Ig!l" A /I5l!a$" simply these values by /. Then at /JN; Y(o m : 3C,.GB kEmol3,, YIo m : 3G/ kEmol3, and Y+o m : 3M>.,/ E;3,mol3,