LeQV/ fee Lecture #3 > > > > > Oph Cent cst= Equilibrium electrochemistry Half-reactions and electrodes Varieties of cells The electromotive force Standard potentials Applications of Mandar pOISHIA Soy 1. 5 Cats Us > “Electrochemical method” : The ability to make precise measuremenis of currents and potential differences (voltages PP & YUM ays cr OP B Oe Oks > “Electrochemical cell” : Consists of two electrodes contact with an clectr > “Galvanic eell” : An clectrochemica! cell that produces electricity as » result spontaneous reaction ASA) SEG G. BY Blist, 2s @ > “Electrolytic cell” ; An electrochemical cell in which a fionspontancous i an external source of current. e removal of electrons fro1 Oxidation : a species Reduction : The addition of electrons to @ species eos Redox reaction : Transfer of electrons from one species o another, <2 Ls spin Nese Dus Reducing agent ~The electron donor, Oxidizing agent = the eesti sega aa Redox couple : Expressed by the reduced and oxidized species in a half-reaction Ex) Ox+1e7 — Red . The redox couples : Ox/Red Mustration 7.7 (Expressing a reaction in terms of half-reactions) AgCl(s) > Ag (aq) + Cl" (aq) ‘A redox reaction can be expressed as the difference of the following two reduction half reactions. AgCl(s)+e" — Ag(s)+ CI (aq) Ag* (aq) +e" > Ag(s) The redox couples : AgCl/Ag,CI and Ag’/Ag est 43 ASLecture #3 ‘The reduction and oxidation processes responsible for the overall reaction in a cell Oxidation ; Electrons are released. Red,-> Ox, +ve- (at anode) yy Reduction ; Electrons are entered. Ox,+ve > Red, (at cathode) In a galvanic ceil (See Fig7.11) Cathode : Higher potential than the anode (reduction) Anode: Oxidation results in the mansfer of electrons to the electrode. (Oxidation) Isso te estore he Fig the unc ver eer rae 2) ne o DLN, ee arian? IaLecture #3 vole v » Tnumerse the electrodes in different electrolytes, as in the ‘Daniell cell" # The redox couple, Cu/Cu and Zn?*/Zn (see Fig7.12) » Electrolyte concentration cell The electrode compartments are identical except for the concentrations of the electrolytes, » Electrode concentration cell : The electrodes themselves have different concenitrations ex) Gas electrodes. Amtalgams (solutions in atercury) pipeicie seen a pin trngh de ype dace. (a) Liquid junction potentials (£,) » Definition : Potential difference across the interface of the two electrolytes. ex) Daniell cell a5 ~ Another example of junction potential (Different concentrations of hydrochloric acid) EH" ions diffuse into the more dilute solution Results in potential difference at the junction i r jal difference » A Salt bridge can reduce the potential differ cin Jmnerled Ube al of eons eee at nats bas two onesie jadcion poten is thot sinom cee seo : Nap elecle pte 0 ce Sau Ws zybay V3l2 je £,%0Lecture #3 (b) Notation for cells > Phase boundaries are denoted by a vertical bar, (see Fig 7.11) Pt(s) | Hx(g) | HClaq) | AgCl(s) | Ag(s) » Liquid junction (see Fig 7.12) Zu(s) ZnS$O,(aq) ? CuSO,(aq) | Cu(s) > A double vertical line, (see Fig 7.13) Zu(s) ZnSO, (aq) || CuSO,(aq) Cris) | . denotes an elimination of junction potential » Example of electrolyte concentration cell (liquid junction potential eliminated) Pr(s) | H,(@) | HCl(aq.b,) | HCI(aq. b,) | H,(e) | Pt(s) “The cell reaction’ : The reaction in the cell written on the assumption that the right-hand electrode is the cathode. so that the spontaneous renction is one in which reduction is taking place in the right-hand comparnnent €3) Za(s) Za50, (aa) |CuSO,eq) Cus) Right-hand electrode : Cu*(aq) +2e > Cus) as) Left-hand electrode : Zn?*(aq) +e > Zn(s) nai Ce) =AL+ - ad ‘The overall cell reaction is the difference : Cu’"(nq) +Zn(5) > Cu(s)+Zp"(aq) 2A 3d vc fore % 3,5 4 : SF ei (a) The nernst equation - ud aJolee artes oe he cell potential ; the potential difference between two electrodes, V (IV=1JC's) cell potential > a large amount of electrical work can be done I cell patential > only e small amount of electrical work can be done.Seats ol) cow Lary sae) Lecture #3 = The maxinium non-expansion work (see eqn 3 38) Wingy 40 (whete, 4G is defined with the Gibbs energy of the cell reaction, 4,6) To make use of 4G, the cell is operating reversibly at a specific, constant composition, (ad U aS. spec spos EY D9 a3 > The electromotive force (emf), Bias is | mye ae WEE 4G] P= Fareday’s constant, 5 AN | ee ae v= The soichiometic oefficiem ofthe electrons F \ss* Ge WX 4 Zepa|ee amae | Tiblonem be aivites = ‘Enare of reaction, ¢ aS us 27 \ 25\b) _ inti haltresetions imo which the eel » The driviue power of a cell (emf) is proportional to the slope of the Gibbs energy, (see Fig7.14) feiogpabuis nc ne Ifthe slope is steep, the cell reaction is far from equilibrium grime sme nnn If itis close to zero, the cell reaction is close to equilibrium, Tatiatedtese poaees The reduction and oxidation processes responsible for the overall seaction in a c# Oxidation : Electrons are released, Red, > Ox, +Ve- (at anode) ies Reduction : Electrons are entered, Ox+Ve" > Red, (at cathode) In a galvanic cell (See Fig7.11) Cathode : Higher potential than the anode sake (eduction) oo : ent ies poms min Anode; Oxidation results in the transfer of Beer electrons to the electrode. (Oxidation) eel emcee Be ie partes een nil cn been door Nate he sig afte ‘aayeds natn de stohetiom ene hevclosidiie= Tia otacannkawrereiedtans eetLecture #3 + Tminerse the electrodes in different electrolytes, a3 in the ‘Daniell cell’ ‘The redex couple, Cu*/Cu end Zn?/Zn (see Fig7 12) © Electrolyte concentration cell ae The electrode compartments are identieal exceyt Zee for the concentrations of the electrolytes, Peowey pet Copper > Electrode concentration cell apperty : The electrodes themselves have different peas concentrations ex) Gas electrodes. Te eet eel Te Amalganis (solutions in mercury) ‘derrod the ated, Pecos etree ‘apis ewig The toperlaceoe Varieties of cells (a) Liquid junction potentials ( E,) > Definition ; Potential difference across the interface of the two electrolytes, ex) Daniell call leorode Etcrode > Another exaniple of junction potential (Different concentrations of hydrochloric acid) =D ions cliffuse into the more dilute sohmtion Cl ions follow but so slowly Results in potential difference at the junction 2nS0,teq) 180,00 | Electrode i compartments » A Salt bridge can recice the potential difference Vig hth Theol bidge ese a8 between nwo electrolytes, inverted Usibe fil of concentrate st notion in ely. ss ws aos gai junction poteatas tat slot caneLecture #3, (b) Notation for cells > Phase boundaries are denoted by a vertical bar, (see Fig 7.11) Pt(s) | Hy(e) HCI(aq) AgCl(s) Ag’s) > Liquid junction (see Fig 7.12) Zn(s) Zn$O,(aq) | CuSO, (aq) | Cu(s) » A double vertical line. || . denotes an elimination of junction potential (see Fig 7.13) Za{s) ZnSO, (aq) || Cu8O,(aq) Cals) > Example of electrolyte concentration cell (liquid junction potential eliminated) Pixs) | H,(g) HCl(aq,b,) | HCK(aq. b,) | H,(e) | Pts) The electromotive force ‘The cell reaction’ : The reaction in the cell written on the assumption that the right-hand electrode is the cathode. so that the sportaneous reaction is one in which reduction is taking: place in the nght-hand compartment ex) Zils} | ZaSO, (aq) [eed Cu(s) Right-hand electrode : Cu**(aq) + 26 > Culs) Lefichand electrode : Zn™(aq) +2e > Znls) The overall cell reaction is the difference : Cu*(aq) +Zi1(s) > Cu(s) + Zn**(aq) (a) The nernst equation je cell potential : the potential difference berween two electrodes, V (IV-MCs) cell potential > a large amount of electrical work can be done, al cell potential > only a small amount of electrical work: can be done,Lecture #3 The maximum non-expanision work (see equi 238). FF, gq," 4G (here, AG is defined with the Gibbs energy of the cell reaction. 4.G) To make use of AG, the cell is operating reversibly at a specific. constant composition, » The electromotive force (emf), E WEE = 4G| : F = Faraday’s constant, Poa, V= The stoichiometric coefficient of the electrons in the hialfreactions into which the cell reaction can be divided, Et oirmcin? » The driving power of a cell (emf) is proportional to the slope ir trecitee kceniog Capaexr, of the Gibbs euerpy:'(see Fig? 14) Page Lead alithes Af the slope is steep, the cell reaction is far from equilibrium, If itis close to zero, the cell reaction is close to equilibrium eaves ‘oer eed pesi ere Relate the emf to the activities of the participants in the cell. ‘ g=-AS Ring (A,G=A,G +RTInQ)-eqn7.11 cm we 4 The first term on the right is Vine oe Ao ear : : Standard emf of the cell Nernst equation : predicts the dependence of cell potential on composition (see Fig?.15) > Application of Nemst equation : The determination of ca fr vii eae oe Seeman ees pH ofa solution and suitable choice ofelectodes ofthe smi ney ips napnv once woos ae entration of other ions. te standard emf : Interpreted as the emf when all the ceactants and products > ALN in the cell reaction ae in standard states, (Q=1, InQ=0) a aig, ¥ ntials cole ae pp : e potential of one of the electrodes as zero and then assign values asisLecture #3 ” Pi(s) H,(e) | H-(aq) 7 = E’ =0 (Standard hydrogen electrode (SHE)) activity of the hydrogen ions must bel @H=0 =0). : - The pressure of hydrogen gas must be 1 1 bar, i Measuring standard potential in the silver chloride cleetrode PH) HA(@) | HCHaq) | ARCIG) | Ag(s), $H:(E) + deGits) + HCIag)~ dete) Nemst equation E=E (Agel! dg cr) yea g, =] F Ep ~ ae ay, Aes; ae . AT --E is Hg, Ay. = ¥_D/banda, =y.8/5° (Section 5.9) E=E- Hyg yy! Replace b/b’ by ) E+ 2 ely, — 228l near 4c8 Illustration 7.12 (Determining the standard emf of a cell) ex) Pt(s) H2(g) | HCl(aq) | AgCl(s) | Ag(s) at25°C bHIO1bY 5.215 5.619 9.238 25.63 E/V 0.52053 0.49257 0.46860 0.41824 To determine the standard emf of the cell, draw up the following table 4710-3 b9 3215 $612 9.138 25.63 0110-3 b 2 1793 2.370 = 3,023 5.063 zy 052033 0.49237 0.40800 0.41824 0.2273 0.2299 0.051 39Inb 0.2256 0.2263Lecture #3 Table 19.3.1 Standard Potentials for Selected Reduction Hallf-Reactions at 25°C Half-Reaction = tiara [ey] Folg) + 2e°— 2F (aq) 2.87 H2Oz{aq) + 2H 'laq) 426 — 24,01) 178 Ce" (aq) +e Ce aq) 172 PbO2(8) + SQ, (a4) + 3H faq) + 26” — PbSOgls) + 2H,0U) 1169, Chg) + 26° + 2CF (aq) 136 | CrxO7" (09) + 44H faq) + 62 — CF loa) + 711,00) [723 | O2{g) + 4H (aq) + 4e — 2H,01) 123 MnO (5) + 4H (aq) 26° — Min” (aq) + 24,01) 1.22 Brolaq) +2e = 2r (aq) ue NOs (aq) + 3H (eq) + 22° — HNOa\eq) + H20(0 0.93 [Ag (eq) +e — Aals) eeu Fe leq) +e — Fe. (aq) Pie H,SeOslaq) +4H +42 — Sels) + 3H,01)) Oa On(g) + 2H (aq) +2e — H20.laq) oa MnO, (aq) + 2H201}) + Se, — MnO,(s} + 40H (aq) 0.60.liss)+2e 21 (eq) an os HSO.(aq) + 4H’ (aq) + 4e — Sis) +3H,0() rd ©2{g) + 2H201l)+4e <= 40H [aq) 0.40 Cu (aq) #26 = Cus) 034 AgCi{s)+e — Agts)+C! (aq) 0.22 Cu faq) +e — Cu"(aa) 0.15 $n (aq) +2e —» Sn (eq) 0.15 2H (aq) +2e — Hols) 0.00 Sn* (aq) +e — Sis) -0.14 280." (aq) + 4H+(aq)+2e = $;0, (aq) + 2,01) -0.22 Ni" fog) + 2e S Ni) -0.26 PbSO,is)+2e — Phis)+SO, (aq) -0.36 Cd tag) + 2e — Cats) -0.40 Cr agite Cr (eq) 041 Fe" (aq)+2e — Fels) -0.45 ‘AgsS(s)+2e — 2Agls) +S" faq) -0.69 Zn" (eq)+2e — Znls} 76 | Al’ laq)+3e — Alls} -1,662 Be’ aq) +26 —Bels) =1.85 Li(aq)+e — Lils) -3.04 SBP) Ue SU abt 2