(6422108. Chomical Equi and Mathematical Methods Dro Rogo MODULE 3 ELECTROCHEMISTRY ‘The material covered in this module based on the information contained in this ‘Study Guide and Chapler 17 ofthe set text book Chemistry” (Burrows ot a.) ‘The Study Guide for this module is important because the nomenclature used differs slighty from that of the set textbook but is consistent with the electrochemistry modue in Year 2. ‘Any part ofthis handout which isin Is not compulsory material and will not be included in any summative assessment. However, the material may be Useful and informative 0 you, see video 29 3.1 Oxidation ~ Reduction Reactions 3.2 Th trode potential EO,R 3.3 Voltaic cells - Practical aspects ‘34 Representing coll reactions (The “cell schematic”) ‘3.5 The spontaneous cell reaction 3.6 Thermodynamics of call reactions ‘Supplementary Reading PMWAIkins & J. De Paula, The Elements of Physical Chomisty (6° Ed), Oxtord University Pross, Oxford, 2013. P. Monk, The Fundamentals of Eletrosnalytical Chemistry, Wiley, Chichester, 2001, chapters 1-3. Department of Natural Sciences 1{6422103 Choma! Equlbrium and Mathomaico! Methods DrcARego 3:4 Oxidation — Reduction Reactions. ‘Chemical reactions in which the oxidation state of one or more substances changes are called oxidation-reduction (or redox) reactions. ‘Oxidation involves loss of electrons. Reduction involves gain of electrons OLL 2T G- Electrochemistry is the branch of chemistry that deals with the relationship between electricty ard chemical reactions. The reactions involved are redox reactions, Now read Section 161 of the set book 3.2 The electrode potential Eo, see video 30 In a previous unit we discussed the application of a DC and AC potential to an ‘aqueous solution, looking at is ionic conductviy, In this unit, we Took at electrochemical cols, for which we soe a voltage output. Such a coll comprises {wo half-celis, each cf which comprises an electrode in contact with a redox solution. The simplest ha cell comprises a metal electrode immersed in @ solution ofits own ions: (os, Ser wel in a selebim ok Cougs) xsl! weeded 08. ew” Cu2*(aq) +20 = Cine)” Lorem io) bain By convention, we write the reaction as a reduction (with the addition of electrons). 1@ He electrons we on Kelettr ck He equetrin If tho olectrode reaction is reversible, the half-coll exhibits an electrode potential. It is syrbolsed as Eo,R, where the subscrots identify the Composition ofthe couple, and represent, respectively the oxidised and reduced forms ofthe redox couple. We therefore write the electrode potential for reaction (1) a8 Equ2+,.cu. The onde Vets fem erm Department of Natural Sciences 2{8422108 Chomical Equlyium and Mathematica! Methods Or CARiG0 If all species exist in their standard states (Le, 298K, a prossure of ene ‘atmosphere 1.013 x 10°Pa, and solutions ata concentration of 1 mol dm-S) then \wo call this potontal the standard electrode potontial E®. Values of E® are based on an arbitrary value of E® = 0,000 V defined forthe standard hydrogen electrode (SHE). Example values of E® are listed belov. Tablo 1, Standard (reduction) electrode potentials at 298 K ean oy ctuchot elociode reaction fae was Nat + 2 Mg?" + 2e~ 2.38 me set oss pore na78 : Cmte 0.38 eee Sree “14 Poe 4 26+ 13 Eo Hees 0.00 SHE AgCl+ 6 0.22 Cu + 2e- 0.34 For re or Ag'+e ox, Reng) +6 108 hg at Ares 88 AF) +e 287 eset Si ‘Q. Write the reduction equation for silver in 2 solution of ts ions. o 2 : Ageaaye € = Asesy aren Department of Natural Sclences a{6422103 Chemical Equltsium and Mathomatial Methods DrGARege Types of half cell ‘see video 31 {A simple example of 2 redox couple is 2 metal electrode immersed in a solution of its own ions: e.g. the Cu®|Cu redox couple. The vertical line ‘| denotes a phase boundary because the copper is a solid metal and the Cu” ions are in solution. ‘Others simple redox couples include: 1, A gas together with a solution of fons, in contact with an inert metalic hh conductor: eyo) de ‘i ak ro eg. Ha PL Adin dee 9 H'(aq) | (Ha) | Hee ae where the electrode reduction reaction is H"(aq) + e- 2% He(a) ‘The ‘Pt here represents a platinum electrode; itis not part of the redox ‘couple but we include ito determine value of Ext na. We call ita probe. See figure 16.8 in Chemistry’. Ile pole comects He eledraletulle exlerrs! Cicer ct Stated arabnn a DRaH Cs [nek de TES a 2. -A-metal together witha sparingly soluble salt of the metal and an aqueous solution ofthe anion ofthe salt eg. Agi Aal(si| ea) ‘The electrode reaction is Ags) +e” = Ag(s) + Faq) AAS Agcy t o> Ayenr ° 3, A redox system: the oxidized and reduced forms of an ion residing together in soluton. Agaln, we need an Inert metallic conductor to act as a probe of EO.R. 2g. Fe (aq) lFe2*aq)lPt lectrode reacton: Fe?*(aq) + e° = Fe?" aq) Now read the section Standard Reduction (half cell) potentials in Section 16.3 of the set book. DDoparimont of Neal Sloncos 4(6F422103 Chemical Equiv and Mathematical Mothods Dre ARego 3.3 VOLTAIC CELLS - Practical aspects see video 32 (Gee electrochemistry experiment in laboratory session — Experiment P4) ‘When two half cells are connected together they form a voltaic cell (or battery) ‘The energy released in the spontaneous redox reaction may be used to perform electrical work (that isa voltage is created). ee on ee ean ace ee isle spire inp apo agence Cas uaa al focs anlage satel ee dash et ae ie ee ee ee experims P4). Although the hydrogen electrode is the primary reference eee ae bps it eprom ia Saas Joining two electrodes to form a cell creates a potential diference between them called the electromotive force or emf ofthe call. At equilibrium, the emis the difference between the two electrode potentials. The resulting emis defined ‘8 positive, s0 the least positive potential must be subtracted from the more positive potential Sal beg ‘emf = E(more postive) ~ E(more negative) voy , Department of Natural Sciences 5{422103 Chemical Equlbrium and Mathematical Methods DrGA Rego mace (tole ane Worked Example 2: Consider the Daniel cell Zn |Zn(aq)| |Cu"faq)|Cu EOcy2",cU=0.34VAND EON 2N=-OTEVIMI 22. CLE TE, Wat isthe emt of the call? DEC Bloy2+ cy ~ zn? 20 70.54 = - 076 =) 10V He gosbive sh code % wy He eg erive acide ane Now read Section 163 ofthe set book before attempting the SAQ's below ‘Self Assessment Questions When you have studied this section attempt the following Exercise from the set book: 1 Tutorial Question: 1 3.4 REPRESENTING CELL REACTIONS (The ‘cell schematic’) see video 33 ‘col schomatc’ must be witton according tothe IUPAC convention, The electrode withthe more postive electrode potential is always writen on the right-hand side. We say this electrode is has @ positive polarity? The stecrode on Tre Tet-tand’ ie has a negative polaty, that is, wi respect to the electode on the ight, (This isa rélatve argument: Eyaus) and E( Hs) can both be positive or both negative.) Eanes Bsus tific + Eneerve 7 Emeeve Doparimont of Natwal Slencos 6{8422108 Cherncal Equlvium and Mathematical Metiods rca Rego Worked Example 3: ito cll schematic forthe Daniel cali, Wie frst write zn. Cue Next we include a sit bridge inthe mide, writing ‘|| ezn...|| cue ‘The copper metal is in contact with a solution of Cu2* ions, so we include ‘another phase boundary, as Cu2*|Cu. We also note the phase boundary between the Zn electrcde and its solution of ions, this time writing Zn |Z2n2*, The escheat RTO pale die a < (921,20 aq! |Cv* aq)! ufo.) Alec\on How Se Meconerradrmat Vie ans rel S¢ecie) we erent Conterleeolive is in shendedd Londibion Now read Section 16.3 of the set book before attempting the SAQ's below ‘Self Assessment Questions When you have studied this section attempt the following Exercise from the set book: 2, 3 3.5 THE SPONTANECUS CELL REACTION 's00 video 34 Electrons low through the external circuit if we connect the two electrodes with ‘an electrical cable. They flow from the LHS to the RHS. We call this electron flow ‘2 current, /. The elecrons do not flow through the solution, but cause redox readions: we see a reduction reaction occuring at the RHS electrode and a concurrent oxidation fBaciion at the LHS electrode. Bacause both reduction and Deparment of Netual Slences 1{6F422103 Chemical Equlvium and Mathomatical Methods rc A Regs ‘oxidation occur within the cell, the concentrations of all redox species change, ‘causing total disruption of the equilibrium, To deduce the overall chemical reaction occurring in the cell, we add together the LHS oxid the RHS reduction reaction. nin the cell and Worked Example 4: Again consider the Daniel Cell, 02m |2n#(aq)| |Cu*aq)|Cu @. What is the reaction occuring nthe cot? We look first at the respective value of E0,. In this case, E®cy2+,cy = 0.34 V snd E®zn2+ zn = -0.76V, Te Cu2*| Cu couple has the more posive valve of ®, s0 we say Il Is the more positive electrode, The Zn2+\Zn couple is therefore the negative RHS electrode reaction (reduction): ("4 26° 2 Coy, LHS electrode reaction (oxidation): “2 sy Ung? ZANE a AYE F Coes tala YO nena es ical at = ‘a The an ebctmls wills etre the ore temicaleactonls, | Mee cane Cag t2ney = Cuesy + 2m Cagy ne He topr elec ‘The general case is O(RHS) + R(LHS)=R(RHS) + O(LHS) @) Lo. allowing a current flow through the cell causes zinc to dissolve oxidatively Into its respective aqueous solution, and Cu* ions will deposit reductively to form solid Cu metal. The extent to which this happens wil be governed by the value of ace. Gos ben . Cava Eu, von ha. E®z92+ zn =-0.78 Vand £c024co*-0277V 3. Consider the oot, © Pt|Sn#*, Sn2+||Ct-[ciggy Pt & Focp,cr = 1.36 V and EPs gl = 0.18 V at 298 K ‘2. Deduce the sxontaneous cel reaction and caleulate the B® Department of Natural Scionces 16{6422109 Chemical Equlium and Mathematical Methods DCA RENO 4, Consider the cal, 8 Cul Cu2*(10-$ mol dm-S)] |Ag*(10-S mol dor-3) Ag @ at 208K whare £2¢,2+,0)= 0.84 Vand Eat ag 0.80 Wee down the hat-osl eactions and he spontaneous ce reaction »b. Determine Zoot 4. Detorine the equilbrium constant K of the spontaneous chemical reaction that occurs at 298 K, 7. Rustings anton of wo processes cecrring on on Fe(s) + Fe2¥(aq)* 22° and YO gig) + Hp0 + 26°» 2O-fax) “Te overall process i, Feja)* 4Oz(q) +H0 -> Fe2* + 20H (aq) Flow by preciotaton, Fe(OH)a > FeCOWa-» #4 Fe0aHz0 (ust) Explain why, on scratching, tin cans {ton coated vith tn) rust easly but (galvanized buckets (ron coated with zine) do not. ‘Standard eleclrode potential: Epe2+ pe = 0.44 Vs E®zn2t zn = -D.76 V EPgn2t,gn=—0.414V. (Hint: Work out the equitixium constants forthe two systems) Deparment of Natural Sciences 6