AY Bate a Ae Lecturena L220 | es Wels as) Pash > > sya S50 Free energy and EMF Objectives After studying this Lecture you will be able to Distinguish between electrolytic cells and galyanic cells. Write the cell representation for electrochemical reactions, Derive the Nernst equation, Use the Nernst equation for calculating the electromotive force (emf) of a cell for any combination of activities of solution species. Evaluate ArG, ArH and ArS form dE. Introduction Both electrolytic cells and galvanic cells provide wonderful examples of conversion of one form of energy into another, In an electrolytic cell, a current is passed through a fluid medium (solutions, molten salts) causing migration of ions towards electrodes and the charge deposition by the ions at the electrodes. For example, if a current is passed through a solution of sodium chloride, the following reactions occur at the cathode and anode. Cathode: Na * +e 3 Na, reduction; The cathode Is connected to the ~ ve terminal of the battery oF ceil that is causing electrolysis. ‘Anode: C1~ 5 Vs Clz + €, oxidation; The anode Is connected to the + ve terminal of the ceil or battery (see Fg 1). ‘The complete reaction may be written as Na + + Cl” 5 Na(s) + 2 Cla (9) - ONG es AS NS ; E Figure 1: An electrolytic cell showing the migration of cations and anions. Kp ae ic cell pn the other hand, the two electrodes are present in differing chemical environments ical potentials / free energies) We have already seen in the earlier chapter that a imum non pressure volume work obtainable fromes Lbs ee cts b> NY Lecture #4 [arom Fe ) ENe ye Ce oy > pols, Nene ease 2. Call Representation and sign convention Te above Darel call my be convenient represered in» compact frm a5 Zn(s)| Zn** (Cy ) || Cu** (C2 ) | CUls) Anved cathed Here, the vertical ine denotes 2 boundary separating two phases. The double vertical lines indicate 2 salt Bridge. On ether side of the sat ridge are two haf eels, or electrodes, On the left hand side (L), oxidation (0) ecctre, Tis eletrode is referred to as the anode (A) and its the negative (N) terminal. A simple way {remember the arrangement is to. remember the word "LOAN" (let, oxidation, anode, negative). ‘Automabcaly ths implies that of the other electrode on te ight (R), reducson (R) occurs; the electrode is aiid te cathode (C) 2nd Wl the postive ternal), (RRCP). ‘The reactions atthe snode and the cathode are respective, Zn(s) = Zn?* + 28 cuP* + 2e = curs) The emf (electromotive force) of this cell is 1.103V. The potential (emf) of a single electrode or a half cei! ‘can not be measured; we always need to electrodes to obtain an emt. Instead of listing the potentials of all “pairs” of cells, t is far more convenient to take any one half cell as the standard and list all the other electrode potentials (actually reduction potentials, as recommended by the International Union of Pure and Applied Chemists, IUPAC) with reference to this standard. This reference electrode Is taken as the standard hydrogen electrode (SHE) whose emf is assigned a refererice value of OV Ht te 1/2H2(9),E° n+ z= 0 is ble 22.1 tats the standord electrode potentias of a number of hall eas In the standard eecrodes, eee in all forms (solids, liquids or gases) are present with unit activities, Le., in their standard states. Tt |g to be noted that emf Is an intensive property and that the half cell 2H* + 2e yH2 (g) will have the value for eq, (22.3), ‘same emf as eq (22.3) but the free energy change for this reaction will be twice the value for eq. (22 ‘A:G° = - nF £° and A,G° is an extensive property depending on the number of moles of transferred. ):Table 22.1 Standard electrode potentials at 298,15 KLecture #4 mies ee, = ich ts at any ‘stage of completion, the free energy ‘change Is given by he AG = AG°+ AT in (C] © [D} ara 1014/10) * (3) a nt. Using the relation between energy and emf, Le. coe wiser a < yeen the change In free energy and emf, | ern (ESE rary Ee AAIS va Bnd at eqlibrum, AG = 0, € = 0 and er nF am Ork =exp(wFE®seT}\ ——> Os Nes Car ‘The equation (22.6) / (22.7) is referred to as the Nemst equation. This Is the fundamental equation of ‘equilibrium electrochemistry. Using this equation, the cell potential at any stage of the reaction can be alculated. At 288K and 1 aim (101.3 KPa ) pressure, RT/ F= 8.314 3K“! mol! . 296 K / (96500 C/mol) 0.02569 V and the Nemst equation becomes Ps : eau NES ~ (0.02569 /n) in Q or E-E (22.9) E = E°~ (0.05916 /n ) log 19 (22.10) ‘The above equations are convenient forms of the Nemst equation for calculations done at room temperature of 25°C. Wee Example (1) Aroad Cat hed | y eis For the galvanic cell Cd | Cd *+ (0.05 M) || Cl” (0.10 M)| C17(1 atm) | Pt. E® = 1.76 V. Calculate ‘standard electrode potential of the cadmium electrode, b) the equilibrium constant for the cell ¢) the emfat 25 oCLecture #4 Solution: ‘The cell reaction is C4 (@) + Cl 2 (9, 1 atm) Cd * (0.05 M) + 2 C1” (0.1M) a The volue of E ® for the cel Is 1.76V, The standard electrode potential for the C12] Cl | PF call is 1.3595 V. Therefore the electrode (reduction) potential for the C4 2* | Cd cell is: 1.76V=E°=E%c yev2-E* ca? ya E° ca 2) cq = 1.3595 ~ 1.76 = - 0.4005 V ') The equilibrium constant forthe reaction (n = 2) Is K = exp [2 x 96500 x 1.76 / 8.314 x 298] = exp(137.1) = 3.49 x 10? ry = 5 Fag soe ©) The reaction quotient for the reaction is. Q= [Cd ** 1/ [Cd (s)] x 11-1? / C1 2(9)1 Both the denominators Cd(s) and Ci(q) at 1 atm pressure are in thelr standard states. SLs) “= 0.05 x (0.1) ? = 0.0005 — E=E°-(0.02569/n)InQ , = 1.76 - 0.012845 x (-76) vos ey = 1.858 Standard reduction potentials The standard reduction potential for a given electrode is defined to be the zero-cutrent potential for the galvanic cell that contains the standard hydrogen electrode (SHE) as the left-hand electrode and the given electrode as the right-hand electrode. All of the reacting species must be at unit activity. For example, for the Zn|Zn” electrode, the cell is Aut LS chsh! Patints, 1 banyt"(ag, a= 1)Iz02*(ag, a= 1)Z0(3) ‘The reaction for this cell is obtained by the rules, as follows: Znr*(aqanl) + 201 = Zn(s) +3 | HYaga=1) + & = 4 H,(g,1 bar) oats Zn2*(ag,a=1) + Hy(g,1 bar) = Zn(s) + 2 H*(aq,a=1).y Lecture #4 Similarly, the zero-current potential for the cell, PrlHo(g, 1 bar) Hag, a= 1)ICu2*(ag,a= Dieu) ts the standard reduction flows potential for the Cu| Cu2+ electrode. The reactions for this cell are as pe Cur*(ag,a=1) + 2e = Culs) Jett H¥(ag,a=1) + & = 4 Hy(g,! bar) Tight 2 left Cu?*(ag,a=1) + Ho(g,1 bar) = Cu(s) + 2H*(ag,e~1) Ifthe Pt electrodes of these two cells are connected together to make a combined cell as follows: Zn(s)|Zn2*(a= 1)> Ha = 1) | H,(1 bar) [Pt] #1,(1 bar) | H*(@= 1) Cu2*(a = 1)| Cufs) Then, because the potential of the Zn cell is reversed and the potentials of the two cells add, we must have E=E%Cu* Cu) — B%(Zn?* Zn) Ifthe reaction for the defining cell for the standard Zn| Zn2* electrode is subtracted from the fing cell reaction for the Cu| Cu2+ cell, the result will be found to be the cell reaction for the Daniell cell. This is consistent with the fact that in the center of the combined cell, H™ is reduced to H and then oxidized back to H*. We could therefore leave these cancelling half- reactions out of the cell to give the Daniell cell, as follows: tty}Lecture #4 Zn(s) | Zn2*(aq)r Cu2*(ag)|Culs) ‘What we have discovered is that to obtain the standard potential for an electrochemical cell from. the cell diagram, itis only necessary to subtract the standard reduction potential for the left-hand electrode from the standard reduction potential for the right-hand electrode. That is, F) = EXcight) - Alef) = £R-EP If this rule is applied to the defining cell for the standard reduction potential for the Zn |Zn?* electrode, we find that BO = EX(Zn2*Zn) - EOE Hy) But this £9 = £9(Zn2+ Zn), Evidently, our definition of the standard reduction potential is ‘equivalent to defining the standard reduction potential for the Pt | H| H* electrode to be zero. This can be seen another way by setting up the defining cell for the standard reduction potential for this cell. The right-hand and left-hand elctrodes of this cell are the same, so the the cell potential must be zero. That is, by definition, EO(H* a1 ,Hy(),1 bar) = 0 Itis worth noting that the standard potential for a cell is obtained by simple subtraction of the standard reduction potential for the left-hand electrode from the standard reduction potential for the right-hand electrode. There is no multiplication by integers to make the number of electrons equal, as is required to obtain the cell reaction. The reason for this is that electrode potentials are defined to be intensive properties, like the density and the molar volume, rather than extensive ‘properties, like the enthalpy, entropy, and fee energy (note then in the equation, AG? =-nFE°). — F9 is consistent with considerations of Gibbs free energy changes also, The rule that £°= ER Zn?*{aga-1) + 2e = Zn(s) AG? = AGP{(Zn(s))- AG7(Zn™* (aq)) Cu?*(aq,an1) + 2€ = Culs) AGg = AGCu(s))—AG7(Cu"* (ag))Lecture #a We have ignored the effect of in Welt te Of the electron in writing the Gibbs free energy changes. This can be lectrons cancel when the - = ‘equations are combined. Since subtracting the left- hhand equation from the right-hand equation gives the cell reaction, it must be tue thay AG’ = AG} -AG? Then, since AG? = —nFE°, AG = —nFE, and AG? =—nFEf, it must be truc that Eo = BR- Ey Another instructive example is provided by the cell, Seite op Pt| Fe? Fe3* | Zn? |Zn (The ag and s indications have been omitted for simplicity.) For this cell, the electrode reactions and standard Gibbs free energy changes are Fett tie = Fett AG] =-1FEZ and Zt + 2e = Zn AGB =-2FER because the number of electrons in the first reaction is 1, while the number of electrons in the second reaction is 2. To form the cell reaction, we must multiply the Fe**,Fe2* reaction by 2 before it is subtracted from the Zn2*,Zn reaction in order to eliminate electrons during the subtraction of the first reaction from the second, Therefore, the Gibbs free energy change for the cellis given by AG® = AG - 2AG? ‘After substitution of the electrode potentials, -2FE® = -2FER -2(-FE2) B? = BREE even when the two electrode reactions have differing numbers of electrons, the overall al is still the simple difference of the electrode potential for the right-hand electrode le ‘potential for the left-hand electrode. This shows again that electrode intensive properties (independent of the amount of substance), while Gibbs free t properties (proportional to the amount of substance).Lecture #4 3. Calculation of cell potentials The tables of standard reduction potentials simplify calculation of electrode : simple example to show two ways of carrying out the calculation. Consider the following cell Is. We use a Zo{s) | Zn?*(ag,2=0.02) | Fe?*(aq,a~0.05),Fe**(ag,a=0.10)| Pt hy For this cell he reaction for the right-hand electrode, written as a reduction, is, = ZN we Zrite Fe?*(aq,a=0.05) - Kettemley2 Fe¥(ag,e-0.10) + & While the reaction for the left-hand electrode, also written as a reduction, is Znu-rZntle Zo2*(ag,a-0.02) + 2e = Zn(s) ah ° ae Zhenve SC, For the cell reaction, we first multiply the equation for the right-hand (RH) electrode by 2 to Te balance the number of electrons in left-hand (LH) electrode reaction. Then, we subtract the LH reaction from the RH reaction to obtain & vw + Dee 2 Fe¥*(ag,a-0.10) + Zm(s) = 2Fe2*(ag,a-0.05) + Zn?*(ag,a=0.02) The activity quotient for this reaction istecture #4 g=StFet*yPatzn?*) _(005)2(002) a(Fe*Paten) (107) ‘Then, to obtain the cell potential we need the Nernst equation in one of the forms, 03 talhs) Adds Oo Lone We use £° = Ef ~ Ef to obtain £° and obi o tain the standard reducti i such as Table 6.1 in Atkins text, See aaa 25.7 mV B= po 2570 _ pe _S92mV 7 n= 22 8V og, 0 ER = E°(Fe* Fe2*)=0.77V Ef = E°(Zn?*,Zn)=-076V 0 that E° =0.77—(-0.76) =153V ‘Then, since v =2 for the cell reaction (after multiplication of the RH reaction by 2, both electrode reactions contained 2 ¢°), 257x103V. 2 E=153V— 1n(0.005) = 1598 V ‘A second technique allows one to bypass writing the cell reaction. Only the electrode reactions have to be written (or examined in a table of reduction potentials, such as Table 6.1 in Atkins text), We write for the right-hand electrode reaction RT 0.0257 V 7 ne Ea= ER pina = Eh The right-hand electrode reaction for our example is Fe3*(ag.a-0.10) +e = Fe?*(aqa-0.05) EZ =0.77V, vp=!,and a(Fe?* Or a(Fe™)Lectuer #5 ‘Surrent flow from or to its surface, Polarization can result fram either a slow step in an electrode Process or discharge of ions at an electrode surface, Distribution of anions and cations at a metal ~ Solution interface is shown as electrical double layer (Fig, 8.1). A compact layer (Helmholtz) closest to metal surface in which charge distribution and hence Potential varies linearly with distance (Fig. 8.2). A more diffuse innter layer (G. C. layer) where potential changes exponentially, Soooto og e090 z 2 Bx2088 © -@ Ses it i ntsc ety fee Rawonnar cnaionnanat Pata vane pentane tne metal surface involves forces such as convection, diffusion and migration, > or absence of electric field and flow conditions. Concentration by diffusion ‘gradients (Fick's law). Activation polarization involves |