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ELTCTROCHEMIsIRY

prepar-ccl rrr I i i-t b\ r'clrr.tll)g llt.(lr'(ie lrlo|tc itcld rvttli tttatlg:ltlcse clloxtcle. 2 HCI(aq) * l\!nL)rts) * ! l-{+(rzg} Cl2(g) + lrln2+(aq)+ 2 Hp(i(1)

N{no2 in acid {Ei,o: L208 \') rr';rs llre first oxidizing agent available to chentisrs rhat rlas ahnost as strorig as Cla (E;d : I.358 V). It rvas therefore the first oxidizing agent strong enotrgh to ch'ive tlris reaction to a point at which appreciable alllounts oi Cl, .oulcibe isoiatecl. -l-odav. cltlorine is prepared in the lab by reacting hvdyochloric acid u'ith potassiurir Pernlallgarlate :

l0 HCI(aq)* 2 N,lnOn-(aq]-l6H*(aq)+"$ clr(g) * 2lvln2+(ag)+ 8 HrO(/)

because the lr{nC)n- ion in :rcicl \Ei,a : 1 .491 V) is one of the feu' contmon oxidizing reagents that is actualh' stronger than Cl2. irude samples of alurnintrm were first prepared in 1825 bv reaction of aluminunr chloricls x,ith potassiirm nieuJ dissolved in mercury at temPeratures high er.rough to rnelt the reactants, and the first commercial preparation.of aluminurn in 1854-was basecl on the reaction betu'een sodium metal and aluminunr chloricie-

3 K(/) + '\lcll3(l)* Al(/) + 3 KCI(I) 3 Na(/) + AlCl3(/)---'---' Al(')* 3 NaCl{/)

This approach had the disadvantage of coupling the cost of aluminum metal rvith the coit'of sodium or porassir-rnr, which made aluminum in the 1850s more exPensive than silver. Ir rr'ls usecl because sodium {Ei"a:-2.7 1V) antl potassirrnr (Ei"o:-2.g2 \,) are iilnon!i rhe liandful of common reducing agents tltat are ,,r-]g.. than aluntinLrnt (E,"., : * I .7 i v) and thus strong enough to reduce A13+ ions to alunrinrrm metal. ln theorr., rr.e shorrlcl be able ro nrake sodium metal by reducing one of its salts' such as socliunr chloritle. Llnfbrttrnately, the potential for redrrcing Na+ ions to sodium metal is trnuspallv large, and this reaction is very unfavorable

Na+*e-+Na

Fo:-2.71 V

To dr.ive the reactiort ro cornpletit-,tl, we need a reducing agent witlr a Potelrtialof at least 3 volts. Sodium rvas theiefbre prepared for the firit time bv electrolvsis with a series of batteries thar producecl an electric current with enough Potellt;al to reduce tlte Na+ i<>ns to sot-liurrt metal.

19.14 THE ELECTROTYSIS OF MOIIEN HOCI

Let's take a closer look ;rt rr'hat happens when an electric current is used to reduce

the Na+ ions in soc.liLun ctrloricle to iodiunr metal. The first question is: Hor*'clo rr'e get the electric cr.rrrent into the sample? The answer is to connect tlre bltterv to inert electroclcs that calr concltrct an electric current and then insert the tlectr-odes

into the sample, as shorvn in Figure 19.9. One of the electrorles picks trp a net negative charge as the batretl P':l]i: eledrons onto this el"ct,'o,ie. The other electiode picks up a positive ( harge as tnc battery drarr,s electrons a\vay. 1'he positively charged-Na+. ions are tltrrcteo tou,arcl the negarive electrotle. antl the negatively ch"argert Cl- iorrs are atlracted towarcl the p.sirit'r. eiectr'rle . tlnfortunately, nothinglhappens if' ,r'e start rvith sodiuri chlor-ide ar roorn ternperirture, because the Na+ and Cl- ions are trappx:r-l in the crvstzrl lirttitc. \r-rrre o{ tlte ions are fl-ee to move through t}tc strrtLtlt' one ,,'a! oi solr'iilg this problem is to rnelt the sodium chj-oricle (lv{P : iJ(}i '(-) 19 1,1 TFt[ [i FCii

ltG. 19.9 i.lrcu,rir:rs ol rrroltt ri ,.;,,,.,, i,t,,,r,1, i,,,,,1.,.,r.i,,,, lrn rlc('tl ic crrrrcnt to t crlrrc c NaI iorrs to s(xliurrl nlet:rl :rt tll(catlro(le rn(l to o\idize (ll- rorrs tti Cln o'ts tt tlle attode- Bt'cattst' socliurrr rnetal lras a lori rrrclting poirtt ;-rrrrl :r rel.rtir rlr l.rr clensitr', it collects as a liquirl ab<xe thc rnolte n sodiurn clrloritle near tlle catllo(lc.

r.:,: ri

riert electrode

-l'he Na+ and Cl- ions are then free to nrove througli the rnolten salt, so rhev nligrate torvard tlre electrode rvith the ()Dl)osire charge. trlihat happens when one of the Na+ ions t.ollides u'ith the negative electrode?

The battery carries a potential large enough to force the Na+ ions to pick up elecrtrolis tci lorrn socliuni rnetal, rrhicir f (lllccls as l Iiquitl floating at the top of the nrolterl salt. The sodiuni produced irt tlris lrar tion is a iiqiricl becatrsc socliurrr rnelts ar relatively lorv temperatures (N{P:97.8"C). It lloars above rhe ntohen salr becattse its density (0.968 g,/cnr3) is ntuch slnaller than th;rt of sodiunr chloride Q.164 g/cm3). The overall reaction at the nef{i}tive electrode can be rr'rirrerr:rs lollort's.

Negative electrode (c;rrhorle )

Na+*c--Na

Sirrcc reduction alrvavs takes place at tilc cath.rcle. the negatir.,e electrode nrust be rlre cathode of this cell. \\'hat happens rllren one of'the Cl- itins coliicles rr'ith the positir.e electrode ., The st;irrclirrcl reclrrction potential frrr clrlorirre is aboul 1.36 rolts.

Cl2+ 2 e- + 2 Ol- E:,d: 1.3583 \'

This means that oxidizing chloride ions ro chlorine gas is an uphill battle.

2 Cl_-.--.-- Clr* 2 e, I::,:*(1.3593 \r)

But the batterl'carries enough potentiai to oxiclize the Cl- ions to Cl, gas, lvhich bubbles offat the positive electrode of'this cell. f he overall reacrion at the positive electrode can be written as fbllorr,s.

Positive electrocle (anocle ): 2 (.1- + Cl2 * 2 e'

.Since oxidation aln'at's takes place:rt thc'anock', the positive electrocle in this cell nrust be the anode. Students olten ask: "lVhat is the rnelrning of tlre dotted ver.tical line in clrau,ings of electrolytic cells?" One rvl,\,to ans\r'er this rlriestiorr is to thirrk aborrt the,',rn,litlons under rvhich tlre cell is operating. \,\'c krrorr' f hat it has to operate at high tetnperatrlres in order to keep the socliurrr chloride fronr crystallizing. We also

knorv that molten sodiurn nretal ctillects at onc encl of the cell and clilorine gas r:ollects at the other. ^.What rvould happerr if'the urolten socliunr rnctul canre in contact rvith (il, gas at 800'C? Socliurn reacrs violentlt rr'ith clrkrrinc:rr l'oonr te mperature. At 800'C, rhc reac[ion rvould be awesorlre.'l'he clotrecl iirre in Figure 19.9 svnrbolizes a rliaphragnr that keeps the (,1, gas frorrr conrirrg into coritact x,itlr the socliunr rrretal, ttlrilr allorr'ing iorrs to,,r,r,.lIi,,,', r)nr'\i{l( r,1'tlre rcl] t, t}ic otlrrr-.

l$ llrl.jielriiri.]de l-1 Lrij Battery

19 Ei-ECIROCHIMI5TRY

ll;.;:,itflt,t,.;l1i.rs;ilrg:rrtcllatiir(i,::.;;l:1.;,.trgl;;;1,;lii:;.:u'liillll.l:l';;..ltis rlcconrl.iose tliis conrpound into its ele nrertts. socliurrr rlietal al)d cliloririe gas.

Electrolysis of NaCl: Cathode (*): Na+ * e-- + N:r Anode (*): 2 CI- -- Cl2:-.2 cThe potential required to oxidize Cl- ions to Cl, is - I .36 volts, and the poterrtial needecl to redtrce Na+ ions to sodiunr metal is *2.71volts. The battery used to drive this reaction must therefore have a potential olat least 4.07 volts. "I'his exanipie explains why the process is called electrolysis. The suffix -lysis conles from the Greek stem meaning to loosen or split up. Electrolysis literally uses an eiectric current to split a compound into its elements. 2 NaCl(l) e-lecrrolvsis ' 2 Na(i) + clr(g)

This exantple also illustrates the difference between voltaic cells and elecroiytic cells. Voltaic cells use the energy given offin a spontaneous reaction to do electrical rvork. Elecrrolytic cells use electrical work as source of ertergy to drive rhe reaetion in the opposite direction.

t9.15 THE ELECTROTYSIS OF AQUEqIS I{oCI

What rvould happen if we dissolved sodium chloride in water and then tried to pass an elecrric currenr through this solution? Sodium chloride dissociates in rvater to give an aqueous solution of the Na+ and Cl- ions.

NaCI(s) I - Nu*(og) + Cl-(aq)

When rve connect a pair of inert electrodes to a battery and immerse thenr in this soiution, lve get the electrolysis cell shown in Figure 19.10' One of the electrodes picks up a net negative charge as it gains electrons froni the battery. The other picks up a positive charge as it loses electrons to the battery" The Na+ ions will migrate to*uid rhe negative electrode, and the Cl- ions will migrate torvard the positive electrode. Everything so far is the same as in the electrolysis of molten sodium chloride. But rvhen the tinre comes to predict what rr'ill happen when these ions come into contact rvith the electrocles, this system is nrore comPlex. There are llow two substances that can be reduced at the cathode, Na+ ions and water nrolecules.

Electrolysis of

m chloride results

of rvater to fornr

cathode and

Cl- ions to form

lnert electrode

iS g

anode

19 15 IHF ILECTROLYSIS OF AQUEOUS t'.to(t . ??*

l, - .r;l 1 L.rtd L.t t t

2 HrO * 2 e* - Hz + ? OH- [,?.a : *0.83 t' are also t\\,o substances that can be oxidiz-ed at tlie arxrdc, {,ll- ions:urd wate r

Anode (*): ) 2 Cl- ------ Cl, * 2 e- E].- - I.36 \/ 2 H2O-Oz+4II+ lle- lt;:- 1.23 \'

doesn't nrean that rve should xpect sodiurn metiil to accrrlnulate at the of this cell. Any sodium fornred at the cathode n ould inrrnediately react

r to fornr Na+ ions and Ftr, gas

2 Na(s) + 2 HzO(l) + / Na+(aq) * 2 OH-(aq) + Hr(e) product formed at the cathode is hvdrogerr gas. Cathode (-): 2 HrO(/) *2 e- * Hz(g) *2AH-{aq)

should we expect to see at the anode? There are tr\,o possible oxidation

ions in this cell.

2 Cl- * Clr* 2 e* 2H?O-*Oz+4H+*4e-

Ei,- * 1.36 \r Ei,-- 1.23 \'

rd-state reduction potentials for these half-reactions are so close to each

rve might expect to see a nrixture olCl2 and O, gas collect ar rhe anode.

, the only product of this reacrion is Clz.

the reaction produce onh' C12 ? Ar first glance, it would seern easier ro

ter {Ei : * 1.23 r'o}ts) to O, than to oxidize Cl* ions (Ej. : - 1.36 volts)

I factors must be kept in mind, however. Fir.st, the reaction is never

approach standard-state conditions. The concenrration of the Cl- ion is

hrge, which inffuences the reduction por.enrial ior the chloride ion. (The

b typically 2bTa NaCl by *'eight.)'I'he pH is also kept very high, rvhich

the reduction potential for n'ater

iding factor is a phenomenon knon,n as oaeraoltage.

: The difference between the theoretical and experimental volt-

red for the oxidation or reduction of a substance.

I conditions, a potentialof I .23 vohs is large enough ro oxidize lyater ro

Inder real conditions, horvever, it usually takes a much larger voltage to is reaction. The ove rvoltage for the oxidation of rvater can be as large as I

carefully choosirrg the electrode to nraxinrize the overvoltage for the r of water to O, gas and then carefully controlling the potential at which

s, we can ensure that only chlorine is produced-in this reaction

rmary, elecrolysis of aqueous solutions o[sodiunr chloride does not give products as electrolysis of nrolten sodiurrr chloride. Eleitroll'sis of moiten

this conpound into irs elerrrerrts. 2 Nacl(/) electrolvsis ' 2 Na(/) + Cl2(g)

of'aqueous NaCl s<ilLrtions givcs a rnixrure of hydrogerr and clrlorine dgueous sodiurrr hycir oxicle solrrtion,