You are on page 1of 90
Classico Atante nsots Bane ae ; es : * : ae Veg dL \qth cer 2 ongatRowct amr Re. Lease hah “econ extabidach. 3X, Connensoliorn Q mato — hay susur 1S3ie Maker con be adie Cmafah ast egkrayeh ley cvenieadl Ae Same chemieali compound ‘ : Seen o Rowena grec amie Kee Some Claws same tre frges, Ty QUE colon eodoncte , whdtlad eval, pnotlle. ot Qumestone — Wog arta Oa Ca) ad) bg O- (sore ielcacne sword Ws Atomic Thosra Yo 2x) Naan Eada — &s ees As Q an Darn t me pad fi Sua d one ea goons vim e j dnemicall guzalres Qi ; at b Reins & Rook dats bow crambend. Oe: ek. bgtap i sasastaha. particles calla airs. sens era-BBeD ) elms , ad Ba. Ye allows jpunina, Koggtiar simde aie noo: bo gute ‘ Comgoun’s tows, Loker ke ealag mdcorks. Woe era mdee 3 const Len Neiman Cano ements sugested, ae looove raory. The all venules 2 Qnese, exgers orem ate Surmmargek in Ee us ayesneknc Qos Las QR mele Rrogorions TY Soo clamor <2 5 Caw cowaenalion ocuute el Mow abemenks by, me Ko ET mae Kham one, comgourch, Whe Sing mas Qe dbich cardeime with a Yivd mom Q ae hy ate wo Si Qe dade newer talkin. » hw d Qacigtacehl Srogurtions = eegebivo VE Ae wma Mos Dames Aamdk © ubicla comearne vith a Awad onane om WX Bowen © de Wee same ob he. mosaes bn Senda Aor & Chomsclass comand ro Sind 2 wadkiges Chea}: ae : Dee, ; 2 Loker yeaaartedh cheval the fb aracimakric Lame are act a a eek, comectk. E=amct — moter Qek oo earn, esdoad. Ve Sodlide compounds, skoicdhiowakre — Q Yradk composts: fon ~ skovcthiowkere — ast Ysa comgo sition, ZB Wudrideo 2 catlorn — nk a dma Be. Lsoteaao. fs ees A Yao gare er ke gitication & Cae Akama “tneers iS 2) Bareeding anvetah Bre medam system Q chemical symecte Gard FA mele 2 che om Qe ewlodtance, which, cantslnn the same randear a, sqecpah qottices ot wtake os Hane at codon atmo wm tha d ej el. = The moar vedume Qo ogo Khe dune ocueed tay Verde & Bre aper(S 22K de? ok S.bG 5 Ueded ok trom Geng E aaa ol seinthstis i $- Buarrocenk Soran , codrell wih sac oulgude Le sna Damo : : W = woe ‘egeh Ska atta de ved sek. Realism de. aretacns, Ae Bilarieh dramarion es Hat . \ acpi deckros Yrown ce gutt oumduegy aan Iteowe otiund & a es eS dan ago. Te ome of Talim colt lew so Rote © aa S Wun Kons erdmcad Ua o gyn Lee sna Quin TA Pa ae Serta com Le counted, Fam thin koe Laroh no. Ryde ots emia mH Bde ene con ee ee Lreh. 1 Qroduad W kne soae Kime We wcoanted. Annee thas no. Yn 2S ok SER. Avegdds awe PRBS Nea gt a The, We eer mass Bo ase ot cng e Rae cvtrge wate Xb waves ona scale as wie alee hea AG Locker bese wens ae Qwik ‘ hast Po Sse So en veda aps? a ude eran ante at oKuegs hore Cong ou qrete- & Ars Kame. Sroudl I errodn oo clenk 32 ¢ cai + ged Bove Moo Ww cnn Edee, hte aX wadk rea! tana, Baga or os reve Kamp UW Bp Awe Bayh te Kee ee be Seok ge aekeee omgentns > Rik went cr ceosio te lee Sage Yo aloo 3, BAe An Nad tude a tren 2 eh y Are seer Jew re tear Khe & Bemoma — canal a rom L% Ka che | ohke. The st pede & scent hake setee Oc Cy Ya che Kee sawae oh Bede inver ee oy locket dels orks Ke Sak (fo & prs Uc lerestinng) amd, Mamadictcl, vaperrection 2 he Cig ad ccate ok Cre Saar G elaow ok Sas eee Y tre ware Low ealacka un the apedusel tule co 5 ae whume 2 Gece eoue woken. ache sa 7% on 3 wedded Ae. The orlawe 4 we on ae arladr tae & weasel Yar docs tne tlle Ws aiee ana. ook. aapokuns Qanedo . . Tre loreal oties. + adked anh the veges pitas due - waar Segre ok We ang: Arbo womr & set rcked, He Seay yt wrote s vogout soo Adienke Caan ye ame cconged oe rood RoW Nees ona sae wakine wets reads \ : ve 2261 Ro: Sc: s.k-a. . Nea yonder Qee wee a EN en Oh ae XY Dew re Whosiou® Q vesdanedus ondar cartane condense: Valine Wearada & cgi te ee +5 Cx Ran sen. -N.0.). Te Y an Yok Doan rom eb: as Tag 140 aoe ewe. CO) M0, SE 20, FS 2V9 + 02 vlna Wass Umdlargere Suerodclien, \—s at TY Wee rapociakion Khue ore U mdecbes d N20, we howe N04 == aN. NG 2h The randear Y snrdacdes Whe Reisen AT Ane dkall wader § mdeebss Mas Morodalinn » [ud -2Ned cc = O+4 For a geen meso Qago, Sandy v Loos gowtewl he condor Y molcedes grant. ck d, = Senn, to Mavodolin we da = sesame Jovan Ca. ths Maro calind Dra Ss op Cy Sat Le na a a aa rae Hg eRe, Wereento Yroor Vohane Lolawan. Yr omy SS Veoh aru Bis Se eens 2 k= Meee coe GA ea, The vege Samad § MO, ok 2EOFEIS & 3913. The vagaul dawnt, Qe wdlarodakeh NAD, & RG. Fonk Une degen Ldisecstion. \ Ae Saee - oro (20%). The Bia Wnre Meader Vase § Non dete SadliKoesbu gach ex a Baden he mathade oe cmaidod we deol Bak alk tetlkime onc POLS Ya ead et aseaaia erei (&s Liguak 2 O VARaT erraanle on SQaae ve aceon pubeuecddnued iapdh oh vege V Reckal roe velba Sngentenke malay ogo ee WEEE A Che Begph sek She re, We shal nos sa ee yak kee adduting yo none odleie sduke Woo on ie sake Leger Qreaouit a sue’, Ch pene vedakile seleike te ona whee oe vege eae to edionde). Thue mak be ve Keach creme lly eaten Se s anh wu: Exearimank shase thak che ereemcr a aon vedakede sduke Lowa kre vegor™ gta § ene sols So eX omy ogre emeanlite a detukien hoo a eer vagel Gt hon Khe ae selvewe. ag: iene pute Shinde = ~f SelySien Tanne. “Wis cee, aeglaceh oo les: gure sduew, a Jvve suk weloake © Sats sRwSe. oorkiclar. Aman Jae sel. evtide Since Oe me veliurm be weno are) Nay Che greaan 4 povtihas, XX eqpiltorum che aa greawte wey Syren allie” setakian Crom ¥ SS ene aeluewk. = Are ¥ Nip Taakisaim conenckraliion oh am vlk ok Kee neem, x vapert gece sxe eee Sates A, seearwewailia Roaoo\s pases sea a ee aaah selventa, En 1939 be The laline lewana QUhe Sager giana La &b groper seach: Ue $ caer Arve ae, 2 dB eae Bamietortne: ede Silos: Oy mdeoden sso 2 sdlsede Tha Whakiea Lewrreg A Che Loner queue V The odio Qarnma, vot seo) | ou saluank. \eke e= 2a were) a a he heen be: a = MY dole waeodus N= sdwonk wdeades ee e N«a (Neen Oke Reins Ear compare fo 0 plats “hed: eosees aug eacin conn Soe Simin} a Sa eee e “0 - Tlia com Non uaa to ek rabies See ame hon vRakSa sefar ao twlow i= 4 in \ eS waag Yacuenk, M.S MAO ade We ond. wore ade MW 2 Wh. rd mate by he sdeese cam ee WHER 805 dle =e} a, BEE sans on'? ol Loctligtl lt ae ee Avs d +. he oa eta, a alee anh setutin oe nr concen conn ‘ad tieagereks Wee rel. wed: mare 2 Many ee Sek 5 wuan: = Ma rgd eS the wine Lawrie, Ye wage qe (pe Yate, See Asa olden ie, Seeds cou ak veld: mekhela abe mole aceutesiy. Ons wallvalo ate bead ueon Khe le Che o rent oy Aone vote seo ian agen sn sr aS Bee archi, adultes do ut doa R Raoudkts ors exactly , bees Sica nie ae ae sed het Mie daviakiet® oc: oweray & seeiehe ea Kiweann shinies MG sedtenkes, we dele on id pa anal wad dues Vearonn Bact Se Reavis Nano our tha unde Tae mel oe cy. Bask ape: Resales Das and waking maddras Jet Sebermncng SP wd shoudS ‘a \ agech, Bree, ko uke te oN Oe a ceo eo = — rela te kre Nowra & Rae veges oT ome Ie + Geose: X he Ques goo 2\ Parelben X Rae \sobuns gawk, Anne Save welds loge fe Rae Qus'ss & Cae notte Sao stuke. frogatian Aegending on Se Anat X< parties are callah cal\igative. 3 Miedo Secs \e Degessimn A Daw, Treaseny, Cont: @ Bark Qeosen whan bre vogest, GRE Aehe Mak = epee RO WE : oa Chon Sor Bre gate adiwewk. Thus che vogeor Lae 2 Premnwe Are tk ade ote oom Qe veges aS laiiend fk lane ww he Yresrg gone hy xa Keaton lnellawd. AQ = vag. grmo.ane fer Bah Be = weg gem ame Yr slid BEG ork GM we Dead seer branches (Ssh. 2229 see ee Sa gttsoinn 2 Qwasea, ES oe bo tre Lauer, Lek To lee Syerns of chek Sc Q < Redeaaig eA an Rn Tea St 2 ert =k Cee) bok a os go ecto re gain saloank 4 Jo a ll ! . = Seer we ka Yes Trea vee A a. OZ See, =) he ee iit wa : ; mM re ae pee Tne Tha degsenoin sol ag do HG emgettinsd + cle vase ae ere soe ond one eT &S ne g aghere Lew The reaalen A Kao Yeo 2 cae LANA Qne soak eo cont & Sb £8 oe ued, Tra gwen ean ewes ee ye = J ve Bo : co Fom b-T = ha, ho gpen wa Qo Kewhot soewk , Kee Sa . y Le gory SUAS cs one Qae A Same ew eo ee SL Wow me ode % ogy ‘o ON sed ee \ Rey Se gues Sek 2 rood Bagieroun ec oly craoacagic. costes & Caro Ie reall ‘ea ), Crowing Wo ree Rae Walboe + woken dsl Wa shel, con Se Se pba ti Ler WO Re aoe Oso X mut Lake WA Ye web. male 2 okt A Lae & Ne. Souk 8 Sages Ny Lede EK lew crygecagic ewto’ & aed \ootds deen he veogrt awe ve eagwle Vago” greet dy re costa barge Ge ieeeQane we y S & Ae i arnecs Ke, Lowero Qe vag, GEES ae c sdublen Gall coh aba Whar Kon mine Keen xX ae Que colsemke (sere deere Meee ADS ab AEC ae Dnede similar browdes fey ote = £2 Re At 2 ieee c. Lrseera, § the ets hei CT Me Bkecace ha weg. greee. A sekven® a LO lee dling pak P Yeo veg press. of acbkan ak Cre Saat Ashe shen. Bren Tote = (Po =F) bubjon Raol&lac Lon@ = 1 buk % % o cosenk an © Yor a queen seven 1 nie Ro a oon ao a oo a sma veloas A. 0 Banda om oy Pa ean ears hase Qu od corena tha es Bakes J eh-md- wore Mi, Bion arene = (eel eee sg cr Ma ms Nay Ale Goo bus ooh Bro Kindo Tice plo) aor ra i sD ap ee dala Cano ls ys ee “a Bored Laws, Chettad Lars, Dats how M Parti Rerouies erabhae Lo 1 Goulds bow —Yick Q aps Lene — 1662 va, values Qo Yixad sane goa ak _contomk Komgantute Selena be Ves CH tonaFantel ey = conctowk feel ot aie Ais las dolds coxa wok Basiakins sf Wah grsoara anh eas nee joke 2 Chrorded baw Fw valame veh wrsen aod oK constant greasate & dieckhn etn Te Rae cesde Kenge tine: Mahurnd ee, tage 53 Aang (8) Vy xT. Conlaiang Gach och Chated bers, ee jo =; 101,325. U2 x R aps Oe Rete cde K = ae ST Kol a Dodkevla bas R Portiol Preauies. | Sepesce aon Weare tere Kkod Ye “wo asst k sum dene gattiod owroues Aw SORE a Bee a - Lek 0 = portil greaene 3 apo F jek 2 = betod grtanate A mnickine nom i= e Pq = tometer SA x P Koka a0. Jndecdao Tn mde Green’ Akg, wwe rove uate Q Wheenk cor wonder Boe, MS Oke Sarne, Con progtions Eo Kae Sqpoe Tose oe Cher Sewatoo. { - woe TYa oe the A sMutrm | X = = x apand Was dowalkian &, Ao eeqctnely a Wien eo Ce Yee iernahng a DL aoeen Wren Jaoht cde cow Wore veo aX Cre NA So mdecudas Yromnva Tayemn ed ee ee ee : a atte Becin & Rae Jrtng, J ogee ba gesewe Katey St sumo Gath foieg Bete SR OTE tae latin we Spee YB ours undar Cae same coniions ox Dae Mele, Thao X Gonos : Ais wee uk ai ty occqunk yr Rae ‘aloud Joscweh ex Ene aoe Vaasa: The Rrsory, odec greek Volrchde aaglaming Cre Wehasot A Qapabs oh slide oc wel oe gone) Ae wees eddates Ae reary a= Groaag of erode x xk in ene enduennnn keke CRawe X eee wadtcenles “a. Set = hea. Tne, Ta veaiiqhig comecteds Rae Sze cee JY Man Bre aso, Mdcenter Nee yb : . oe o Kone BBD cee van enone site, ZH Molochos & geaze seo consteK, ard cthastic matin wm IS o- skrak Unss Rekuson exQlistons, eeMlidivg with each ater onl ang Bounding sudsces UA Tandem Jodtien Croumtan mation): AQ mdsonder coWMimlore oe aaleckly eclectic — Le. no decresan ” toe amelie energy, om Eu ee. “anise! Ane avenge Knee, emmy a Ye wateues a oa me0 & cd, ¢ or yond Uw direct erqrioncd ieee close ~ Lorna liane. A Che Some Game. che ovetage Weeble eam re macedas FM apare & the sane, : Comadar a andecke Row Qo ono, on codea, a ee se S ae Lok hs teckel miong wy vdtedt, Cy uidh comer Meador oDong the 3 cperbinckes such Ent ateutssre ci’. mawenisnl wemiaircwdacthh nek Aaah) tlate Wena Contider Che tla, mara, mm ae we dedi only, Sana diskonae 2L the Oamnge ta women a be oe, i a 9 2 ees Peter = We Qokomse N enrormantuan = Senge Se rveenee Con 2p enone ier: Se Ne é 2 ene Gmetarrud 2 Mie, at Tere = Pew oukn Ea f Ricics = se ee oy : Be ° Tk wie Y dramas ¥ momerumlFar oe z z 2 ant amy ame Se SSE = = bee C™ lar thas nto sopne velo a ku, we ¥ ‘in Coe peed Mam saps valoda S Squae rect ob ere. onemae A Da square de valoatic. nu at coe motecsbas with veloatias C2)C3 ake. te the loox Che Gtk fore doe Ke a2 wsradgs Lal jie obven eee aS ame. x Rnes el Qian e z | wy an > Gt SCRE GI em oan Shy a a ssotcees | Anis —~ ax ermeue = aes tue WE NV ot CV =k mat Weidhin the dundarattal ace ayoSim. + Seuldo bevy The Winekic Crary Skokie avaase Woratic oy A Cre ceeds. 2 ape eeogettinalh te Sosdute mg T cama AS eee ss u “rh Kiake oven, Qitee wdesules at 7 a he ape Lanse com te dada Yon Ehka eatin as les = we. EM AT s cwtank Coaldoinn) a dered baw “ PY = Emad, Crem VE SOS BS Guk Saat Gad Tonk enn Yo contamdt Yorn Vrah wate L ged. So bet o rad mare dase ak condi Pate ja; Pare castor! . oy Vat (edotad be) Ze Woes haw x IE o Conardar (Yor sim eile) ao wixtie | ol Dasaic, ont Conadsting a My mdccnles 2 mous mn, anh tik wean syst vdoaky eS yre other aa nceedon 2 arse are an test wlan saps wadooky re chen, fame ad pee outs (see evs Saal Ss Bh a. Ae Bak VieVa CA ansas ot Oceugrying Se Some vemal) ent ocak tre Same Tenge Cote m Zt 2 bmads 07) SEs scan Poce or A= Oe nh 0 Ae n ee grease exo) 2 AHP. = ee m= eo (eh os — (92 \ «CP\+Pa) oo Poe (Be\ Che we, eadh aoe ears o eortil eracute 2apod & ae GGL gremwde mubticbe baids mde Qrckbion (one wand stating DedKals bend), atthe ‘Sao qnane we He Sendin Ss \ = \ = Rae INNO | Nay eS eet Se net zt => i ee Oo mi Ce TA : Bee a Tou under ne same condabims erroase of mctedas adenites L ae aeons ' | i =a c Pe Con are =e Conall oo © x ee Lees 6 Sina Che are eae corel. 2 anguimrkal coYrwabion, ey Bra etencies Whe Yenalte hoary oe red For Goo Sandoo X one ape ok Kee same Kame a. pees, = he onetoage sents x Khe mdacdes ot Kr saute, For ‘oo sanges 3 hee ages ak ne same Come, gonkeleas. pe he onerage Kinde eneraisa of@ Khe same bul Cre averse | Seeads oft ago Wre some. Heys 2a. 35h For tan, adie Ee seal ee readin Joddad, Nee rae x lo’c er Ane anamar & ndt simpy eeequar of Cre Gmeraane Tm Cee na. Q ceoQbintons . Calenlelsmns ‘ooadh mthe kinalic cas Rak Bre 00-3 codiarns ar secoh Tncdesito bu oan Reo 2 them Cre Ue incresand ley 10°C. Thus chs wv alto s Sang exdoraion coon, Yeocks, mak Ware art my Befpre a md Che febtivction Energy: Moleaas uiklk Cais anata oF Qeakar willl Yeadk, Croan wie ah Rnis emamp, will nat rack. 7 <1. E Kinaic Enators (ot sgced) N ish Curve, Lomrogne Ee the ackuakion oakguy, Yor Qhe meeees to rack. Mii a le ee | The ao Q molecule psonerane acini eae | posdanaamna, ener & W quien lex | re wader come Te wed eS ancl ogee Del AA tote fe | NO. R ond y ac gE hebos. tots am we Secs eras, i ang a al The Kinekic: hoor wek2o 2"rngortank esouaadtion IL he volume A the wrdeeudes Qrowrsallves to rralan le conngored ta a che bk volume dre ago. : a Ss ne sponses Nopeate eat any aktrckion oy pen Cots Ara qeolanse ate Cron only Wore ealdk dard) gos Ex a veel apo it Wa h er, reas anoumeliomes no \anagr Wah. nee Yea Qoaeo den cle ae apo lows. Heue fo. 20 Derwiakions Q aoann Yoon Bolds Las wee Tmnvediggeel by Prenoagl Ce 7). 2 Cakwos) A mnagals Cumes From Bods law OV = conctomlt Clemg corset) Fanoak Qouwd) Unsk CV iors adr coutenk calthe cleae cusves Show, En 83d vor dar Wiolbn came Mie Win Deena ha PY Vartan ce eranuie o a gyre nagar, 20 f A p A Wikguruies Che weraQae oe Sean Koger o's Cray ea no Leraar roaaille oe ke he volume g Bre apo Crue Uy \) whe volaad Behe aoe dnd Tb & Che space oceupia) nthe mises, She comprenatle ark Yee KEL volume > QUSR). A Daina Yor Ce vane QE eran Qnsf, P (Vb) = concord: . B rh ere mobeenBes okadt eada other a meee on Che outside Kosa cok abkmiin buotte, Buss Che wisauieh prtaoure [2 leo Baan Rae actaale Lacan meer For apie wresd of Gr, Che no x molecules strlanra Che wal? tm wnt Kine Tuam « Ades the to: & wmclectlen enating ap oth | akkrackion on Che. Vega wotdolly, of tome rk co oe ee alba & the cbservell pteaoute — “So corstank, ve wo Yr one mle L goo, Khe esd ass equstion camber wort 1— (p= S2)V-E) ERT - von Bar Wank’ eapration a NU cine ca oe earechianm Sper Khe mogukidea 2 PV wm ogpesite, waipt i wehbe & cmcrtean J; o tending b docresaa Uk. As the vyodue y ev Yer CO. Na decteaars ak Yuk w Ps moresacd; ne. ca Andee akimciims lo were impotent than the Y ene uedame 3 the wlecnlas alt le Gieaoure jaar ereanures Che poet tp warmed. > Ahe Crricol Stole da Goo Hemp My 2b Pray, on can he. Vapayeh ox akmoeghore grate) coda, emoudh. Nrgeng, apenas cam ee Ways ade oH irany ange log comgitasing drow, : 6 e Gadrensa Un 186° mvedinggal ae emndtion a eng. ont’ wander Whdh agers Lapel. He suddyecked CO, ts vorene Gitaoutes ox tons Kamps On Qa the cyeek & grasue or VRS The come odsTouek ot 2 cv eee Ye calla on isolnermall. As germonenk ano Viquid vagour 200 ‘Geealees) 130 100 So Rgothermas 2 CO. Ak WBC Che volume Secresans LR, Lertering ieee Or aceetbonce GA beds Lor. Mle Ve One veume Socresces Willy aan Soue’s has Brew ho gree: & doo $0 akweedraren Croets o lertale he Che ave ond Wap On ongaats . Tha, teas, eneine contort wh of era age roo Sinem convotdh oats drat. SL segnenk eee eenaey Ores) cartes grckcal ao Shomag wana, ae at Andress Qe thak ok Kenge: Melon BUC Ayuersctn coud ba, lomudnk alooukk and: Gekk dhe BWC Ra alackinn cok ak Qhe Torovank cloewK no nother hoo Qk haa gh Ww amg to calla Cre critics Kee. Yor CO.) The & ‘yy ft + (ZS oknen)| reagan % Dapel One age dk Rn cohen Gag, id cabal Oe enki graane ah Che vdune a me wake = Cheass o& Khe emKicnl Gane ok gees tw eh Cre enkiceR volume, 5 eave Rae : How'if theré’ is a decrease in potential energy in passing from reac- tants to products, then this energy must be lost from tie system in some way,presumably as heas, Towards the end of the nineteenth century Thomsén dnd Berthelot suggested that the change in energy es measured by the héat evolved in a chemical reaction was ti e driving force behind the reaction, To support this they were able to cite many reactions in which heat is evolved in passing from reactants to products, Such reac- tions are exothermic reactions, The decrease in energy in passing from reactants to products may be illustrated for any exothermic reaction as an energy, diagram As below. Total energy p. of reactants Wier were SS re Bp?- ErseAR “ "|" net energy evolved as heat smerey in the reaction, bs Total energy of products Reactanss Products Reaction Co-ordinate AM is the otal energy change for the reaction, It can be seen that the valus of A H depends only on the values of Ep and Er, It is independent of cny intermediate stages, Thus the proposition that the driving force behind a ckenical reaction is the decrease in energy in passing from reactants to products seems reasonable on the evidence presented so far, ~ many spontaneous chemical changes are accompanied by an absorption 2rease in the total energy of the system in of neat ie, there is an in passing from reactants to products, Such reactions are endothermic, as represented by the followiag diagram, gis Total energy of products Ep |= —— Enerey vow[-Bp > Be s AH net energy absorbed as heat meres! from the surroundings by the reaction, enerey 0: is reactant: Er Reactants Products Reaction Co-ordinate bvious that although the decrease in energy may be ind the reaction it is It thus © scomes @ contributory factor to %; driving force b. not a sufficient one for,all cases,, particularly endothermic 2 s.stions. fe must now look at morg, spontaneous reactions. or processes, perhaps of a different kind, todiscover vhat other factors may be involved, Since wo'have already e;tablished the energy factor in spontantous reactions, it is convenicns to look at systems where, there is little or no change in (totel energy juring.the reaction, A System in which the i>tal energy remains coristant is know as ‘én 0 gases separated by a partition in a lagged isolated system, Consider containor which is-closed, ie, no change in-total ‘energy of the system, eee ee ee TFI7F The two gases "a" and."b" tart as in A above. Upon removal of the partition diffusion of the to gases occurs ard we end up with the sit- uation as in B, The change is spontancous.as.it begins as soon as tie partition is removed, and t is irreversible. The system is’ becoming mixed-up. Z - jo may now formulate anther proposition concerning the nature’ of th more system to become nore. ase inthe ENPROpY ~~ of the system, A very diso-dered systemjhas,high entropy} avery ordered spontaneous processes, Thee is a tendency, fi disordered, For such’a chavge there has been an. inc system has low entropy, # sure crystalline substance at absolute ze¥o “of temperature has zero enzropy. Fora spontaneous charge inén isolated system there must be an injrease in, entropy, The universe ‘thay be con- sidered as an isolated sys sem of constant energy. It follows,therefore, a6 that for all changes in tho universe taken 2s a whole there must be a net increase in entropy, although in different parts of the universe there may be changes taking place which involve either en increase or a decrease in entropy, or no change. Thus, lthough the energy of the universe is constant, the cntropy must continually be increasing. The direction of spontaneous change is governed by these two factors: 1) change in enthalpy (to*al energy) 2) change in entropy (disorder). A new function G (change in FREE ENERGY) is defined, this new func- tion incorporating both the enthalpy and entropy ‘changes, | 4c .= AH — TAs T is the. absolute temperature, The product TAS (also an energy term) measures the ¢hange in energy which takes place.as a result of the rearrangement of’ the constituent atoms. This "internal" change in energy is always contained within the system and is therefore never available to do work outside it.AG is therefore the difference botween the total energy change and the ‘unavailable" energy chango and is thus a measure of the energy which ig available to do work outside the system,ie. a measure of the free energy. Ye are now in a positio: to suggest an answer to the original question "\mat is the driving force of a chemical reaction?" The driving force for a spontancous chemical reaction is the decrease in-free_onergy whioh tees place during the reaction, Standard Dathalpy (Heat) Changes There is no real meaning to the value of a heat change unless the exact conditions under which measurements took place are clearly stated, It is important to state physical conditions of reactants and products, To compare heat changes of different reactions, or to make use of heat changes in thermochemical salculations, it is convenient to quote the magnitude of the heat chanze at a chosen temperature, usually 25° C . When heat caanges are measured at 25° C, the heat change is’ said to be a Standard heat change, usually denoted by A x? Some Special Enthe py (eat) Changes 1) Standard Enthalpy of Reaction This may be defined as the enthalpy change which takes place at 25° C when the reactants and projucts are in the mole proportions as indicated by the equation for the reaction.(If gases are involved in the reaction, it is usual to stipulate tat these should be at one atmosphere pressure), 2) Standard Znthalpy' of Fé-mation This may be defined as she enthalpy change:when one mole of the compound is formed from its elements in the standard states. ( It is convention to take the actual heat content of all elements in their standard states as zero). 3) Standerd Unthelpy of Combustion ‘This may be defined as “he enthalpy change when one mole of a sub- stance is completely ~burnes-in-oxygen under standard conditions, Standard Dnthalpy of Ne :trelization This may be defined’as “he-enthalpy change (heat evolved) when that amount of acid or alkali noeded to form one mole of water is neutralized, under standard conditions. 5) Standard Unthalpy of So\ution This may be’ defined as ‘he enthalpy change which takes place when one mole of the substance is completely dissolved in a large enough volume of water so that no further enthalpy change takes.place, under standard conditions, The solution is now said to be at infinite dilution, Hess's Law of Constant Heit Summation If a system A is conversed into a system B, the enthalpy (heat) change is independent of the method of passing from A to B. og, From ammonia gas and hydrogen chloride gas we can make a solution of ammonium chloride in tw» ways, 1) React the gases and disuolve the resulting ammonium chloride in water, 2) First dissolve each gas in water, and mix the two solutions, From 1) WH, + HCL, —> i), C1 5(6)* HA (g) Be UCL (Gs) es's law the enthalsy change is the same in bo eeeennenne a kd = WH,Cl(,) + aq. WL (ngs) “soron ono Total enthalpy change = (ast) kJ Mis (aq. ) seas Hol(g) toa: ———> Holy gg) —> Beco) © eleCO) are a) (xey+z) kd Then by Hess's law:- (a+b) kd ber Cycle 3 This is a way of expressing the first law ‘of thermodynamics, which The Born-! state: The total amount of energy in an isolated system remains constant, Probably the best way of studying the Bor caber Cycle is to have a look at a question involving it. Q) Calculate a value for the lattice energy of potassium -chleride using a suitable thermochemical cycle “and the following data:- 1 eeenewnweenne = +90 kJ mol” 418 ko moa7's 1 enthalpy change of atomization of potassi first ionizetion energy o® potassium =. enthal nige of atoriz-tion of chlorine ~. = 54121 kJ nol (per nol of chlorine. ato::s) BS electron chlo=ine -. =364xI moi! the reaction:- Cl.) + e~ fe) 1 enthalpy chenge of fornat’on of potaésium-chioride -436kI mol’ Rig) + Me) --364 kJ | electron affinity i +121 kd | atomization of of chlorine sel seta K, Cl. day a (ahins +416 xs, | crepe son sation enerey . Me) * He) ePTnSea Lua Fe), © 2ihele)” | . +90 kJ, jheat of @ omization lattice energy of potas ium of Initial potassium chloride + Fel, State | (s) 2(e) ie : — 436 Ks enthalpy change of formation ‘$f potasium chloride “State [wae ) ‘ Applying Hess's law, ( -436) xs (90° ¥ kB 4 424 +A, - 364 ) ko “AW = 36 = 90 = *B-ut21 + 364 ) ko moi! 1 = -701 kJ mol” ae Dissolution of an Ionic Compound This can be represented as below:- x,., Gtsomtion ) Ti Nt X(aae) + A —\ v2 eee %() a i 5 Wie, 3 Oe Thus an ionic compound will dissolve if the hydration nergy is greater than the lattice energy. nh pe Factors Affect Such factors ave ag_@ Chemi :al_ Reaction Eeys Pg. 349 Chap. 15 (a) heat(tempesature) ; (0) light ; (c) physical state 5 (a) concentration 5 (e) c-talysts ; (f) pressure. a) Heat or Temperature This affects both the v:locity of a chemical reaction and the final position of equilibrium, ‘or a 10°C r ck se in temperature the rate of a ection is abou: doubled because there are far more molecules cal possessing activation enc -gy. Bffect on the position of Bquilibrium luaxwell distribution curve, Before we can Consider th s we need to be familiar with reversible (or balanced) reactions. Reversible Ree tions Consider th. reversibl» reaction for the aber process for the manufacture of ammonia. + 3E,;.)= > Mn qIN Ge = “o2 aspuors! 2(¢) = '3(e) “e(e) A reversible reaction ‘s one where the products of the reaction, (ammonia in the above cas:),once formed, react or break down again to give the reactants,(ni rogen and hydrogen in the above case). In a reversible reaction, the forvard reaction, No(g) + 383 (g) > 2¥¥5(g) in the above case, end the backward reac vion, 25 ¢g) —> Nag) + Face) in the above case, can be treated separately. ‘The greater the concen ration of reacting substances, the more collisions per second, th. more fruitful collisions per second, and the faster the reaction, If we start sith nitro en and hydrogen molecules in our reaction vessel ,the speUd of the f rvard reaction will be high to begin with and eraduaily #211 off. Tie speed of the backward reaction to begin with will be zero ,and cre ivally increase as core and more anmonia is formed, If the forward re ction starts off quickly and slows down, and the backward reaction ste-ts off at zero speed and quickens up, 2 point is reached when the forward and backward reactions are going at ieckly the same cpeed. At this p int the ammonia ic being produced as ¢ as it breaks dgwn,We now ave 2 state of DYNAMIC BQUILTERIUN and the composition of she mixtur from this point onvards will remain constant (tomperatuss conotant). This in of events u- to the arrivel of a state of dynamic equi briun car be Tepresentec by the following Se 2(e)~g— Maas 8 oe, assume another| 17 Ng 3.N, molecules 60 ¥, 2 51 ¥, : 2 | nave reacted > 2 | 20 ma, 26 NH, time 2.10 days time = 20 days Rp = 14 Ree Rp > Rp = 11 Thus,afte» 26 days for out reaction above, dynamic equilibrium has been rea end we can sey:- ei z X (temperature constant) K is known as the EQUILIBRIUM CONSTAI” Taof | brackets above .can "concentration", There is le reaction once equilibrium has been reached, Le Chatelier's Principle states:— TF something is done to a reversible reaction, once equilib- ri been reached, the composition of the mixturé will alter to oppose Thus aj eeoa ey this principle to the Haber synthesis above, we have :- Tethe ss is ifcreasea, : the compocition of the mixture will alter to reduce the teuperature in accords. ith Le Chotelier's Principle, this can eved by fomoving the heat, this is achicved by morc smmonia breal hydrogen, ng down into nitrogen and In nearly cli balanced reactions, the equilibrium point varies with according to bs Chatelier's Principle, ion of the offects of © change ii temperature on the ? ecullibrium-again lies in the change in the number of molecules posscssing activation energy, In a reversible or balanced reaction are different activation energies for the forward and backward reactions, 32, 2 Raising the temperature increases the number of molecules possessing these activation energies, but the number is not increased in the same proportion in both cases, The larger the activation energy, the larger the relative increase in the number of molecules having the pounsteatenr aes oe et, SES om; Ame onezer ei! RB A rise in temperature increases R, and R, but increases R, more than Rp. Thus the higher the témperature the smaller the % of HI molecules in the mixture, The @ of HI molecules in the equilibrium mixture is 79% at 400°C and 76% ‘at 500°C, The fraction ofthe total number of mol cules having ‘an énergy at vin temperature T is least equal to the activation energy, B, at given by 07!" tere davihe base of naturel Togs) Rife cerecieg gas constant (8,3 Jmoi~! 1) The above expression is called the Boltzmann factor.The activation energy for the combination of hydrogen and iodine at 400°C is 174 %J moi! and so the fraction pf molecules, with this energy is:- 3 97 174000/8,3 x 673 a2 10.'¢ aa 2.7 The activation energy for the- dissociation ef HI is 185 kJ mol’ The table below shows values of the Boltzmann factor for the two values of the activation energy at 400°C and 500°C", E/kS moi7! Bs ee ge 500°C 4th 3x 107!# 170 x 1071# 185 ter Om 300x407 eg Thus the larger the activation energy the larger the relative increase with rise of temperature in the number of molecules possessing this energy. b) Light All radiations from X-rays to infrared can exert a chemical effect, Photography, which is based on this fact, makes use of the suscepti- bility of silver halides to the action of these waves. Some reactions are accelerated by light, eg. the decomposition of 10,5 the combin- ation of H, and Cl,; the substitution of hydrogen by chlorine in CH, . Consider chlorine (or bromine) combining with hydrogen, The reaction is different to-that, between hydrogen and iodine, The rate of the reaction betweon chlorine and hydrogen is not directly pro- portional to the concentrations of hydrogen and chlorine, but depends ss 4 on the intensity of light, Nernst in 1916 put forward his theory of a ghain reaction, He put forward the theory that the absorption of a suitable quantum of light energy breaks the bond between the two. atoms in the chlorine molecule, producing freo radicals (chlorine atoms). cl—cl + hy —S 2ce . ---- -(1) h is Planck's constant, and v is the frequency of the radiation, The free Cis are very-reaétive and react as: Cle ew By S HCL 4+ He + Cl, ——> ECL. +. Cle oo. ae eso) H <---(3) Steps (2) and (3) are repeated over again, so that the absorption of a single cuantum of light energy may result in the combination of many thousands of H, and Cl, molecules, The sequence is eventually stopped when tvo free radicals form a stable molecule, — Evidence for the Above cg. He + When chlorine gas is exposed to ultraviolet light, the gas shows Also if the chlorine is ' the absorption spectrum of atomic chlorine. then passed into a blackened bulb containing hydrogen gas, the gases combine in complete darkness, Such a reaction taking place through the agency of light is called a photochemical reactio: The wavelength of the light is associated with a particular energy. ¢) Physical State The rate of a reaction is frequently affected by whether the substences are in solid state or in solution, eg, solid silver nitrate when mixed with solid sodium chloride «ives no reaction, but in: solut- ion the reaction is immediate. d) Concentration Concentration affects both reaction rate and position of equilib- rium(for a balanced reaction), i) Bffect on Reaction Rate The higher the concentration the faster the reaction, In 1867, Guldberg and Yaage suggested that " the rate at which 2 chemical reac- tion is proceeding at any instant is proportional to the active masses of the reacting substances at that instent", By "active masses" we now use "molar concentrations" We may regard an elementary reaction as a-oné stage reaction, In the'elementary reaction A + B—3C +-D; Ratecx [Al fel , where k is the rate constant oa the ShacttoNs pas 3 they proceed in a series Most reactions are not elementary, ‘ioveve! of stages. Zach stage has its own rate of reaction, Often one stage occurs more slowly than the rest and the rate of the overall reagtion is governed by the rate of the slowest stage-~called the rate deter- mining stage. In. many complicated reactions(not elementary) the overall reaction rate does not vary with molar concentrations of reactants in the way expected from Guldberg and : THE VAY IN WHICH THE laage's rate law. ; ATE OF A REACTION DEPENDS UFON THE VARIOUS CONCENTRATIONS CANNOT BE DEDUCED FROM THE EQUATION: IT HUST BE OBTAINED PROM SXPER é (4i) Berect on Position of Equilibrium The lav of mass action states that in a reversible reaction, there is a fixed relationship at a given temperature betveen the molar concéntrations of the products and those of the reactants in the equilibrium mixture, The above is deduced from many experiments, In the general balanced reaction:- AaB o+D it is found experimentally that at equilibrium B 5 Cain) K vhere [6] is the molar cone, of C (AB) s the ogu: rium constant(veries with temperature), The law of mass action can be expresse@ in the most general form a pA + QB + rC ——— xD + yE + 2F ep? By" a)? [a * fe] * Concentrations in gaseous reactions are sometimes expressed in terms of the partial pressures of the gases. Determination of iquilibrium Constants (leys Pg. 380 Liquid Systems --Zsterification of Ethanol Sc z CH,COOH + C,H,OH—=CH,COOC,H, + 1,0 cones, in equil- — (a=x) (b=x) x x ibrium mixture - v 2 7 hatmoles of ethanoic acid are mixed with"b"moles of ethanol. Vv total volume of mixture in m. ix x moles oz eaca have reacted at equilibrium, 6 c=, Cine 2g] es] _ GNIS) EH,cook] fo,u.on].. [le-x)/¥] [2/9] Saye 5 (a-z) (o-x) 2 Thus, "EM. con be/determined: from the.cpmposition of the equilibrium mixture, Tq general equi ‘brium constants vary with temperature(as do rate constants). Rate cor stants always: increase with. increasing temp- erature, Fquiljbrium constants may decrease or increase depending on whether the eaction is exothermic or endothermic, Bquilibrium constants (unlike rate constants) are not affected by catalysts, 4 known amount of acid and alcohol are put into a sealed tube. The tube is wotmed until caui librium is reached; The-tube is: then ‘broken’ uidor_wat@bian) the bemaiaing ethanoic acid estimated by-titration with standerd Sodium hydroxide -solution-using-phenok pl:thalein(why4)~ ~* ing the velue-of x found, Kis calouleted-ee above. + ~~ indicator: 60g of ethanoic acid, eg.(i) when 8.28 of ethanol were treated 4geT4e of acid remained at cquilibrium, Calculate the value of K at equili! dur 49.74 no, moles of ethanoic acid =. 760... =. 0,829moles.. i i ae Thus no. of moles of ethenoic acid’ reacted = (1-0,829) = 0,171moles. = no, of moles of ethanol reacted. 5 99 no. of moles of ethanol ct sgart = Sp Let volume of mixture be Vin, Thus no. of molés of ethsMol at equilibrium = (0,18 - 0,171) = 0,009mol, = 0,18 noheer = + ee BCC) Cet = fec008] 8,08] 2.829 x 0.909 . oi ¥ eg. (44) What mass of ethyl cthanoate should be present in the equil- ibrium mixture formed from 13,5¢ ethanol and 12g ethanoic ack Let 0H, + HCooR ethyt ethéne methanoic nethanoate acid Rate X [fic00c,H] , eo the reaction is a first order reaction as the rate is proportional t> the first, power of the concentration of a single substance, ai [kcooc, 1] at = ie. x, [le00c,H;] 5 x, » rate constant, Be eactions 3 Second Order ; : s Consider the reaction:- H, + I,——> 2HI The rate of disappearance of H, or I, is given by:- -afy} L at The rate of the above reaction is first order with respect to hydrogen, first order with respect to iodine, the overall reaction being second order, In_the General Case If the reactants are numberedt-" A, b, C, D, ete. and their concentrations are:- [A], (BJ, [el,{D], etc. If the rate of the reaction is separately proportional to[A]®,[z]° ete, Rate = Kfa}°{B][e]° [b)o ete. reaction = a # b +c +d ete, and the inetic order of the, But the order of a reaction is not, always ‘the same as the total no, of moles tak art as represented by the equation, x The order of a reaction cannot be deduced from the equation: only from experiment, ‘The ii tic order does agree with the no, of moles of reactants in the equation in some cases-- thes are.usually elemontary (ohe-step) reactions, In nost cases thére is no agreement. Consider Aecomposition of nydrogen p 2H,0,—> 28,0 + 0, This reaction is found to be first, not second order, showing hat the reaction does not take place simply by tvo molecules of hydrogen, peroxide collid ng together, °F = x[H,0] A possible reaction mechanism from the above facts is (4) ,0,—> #0 +0 vate determining slow step, (44) O + oo, -, fast Many second order reactions become first order when one of the reagents is in excess-~- such a reaction is called a "pseudo first order" reaction 38. 2 First Order Rezctions 5 A—3>B+C -------- first order elementary reaction, let initial cone. of "A" be "a" mol m7? : let"x" mol have disappeared after time "t" : then, dx k(a-x) ! rate constant at dx 2 fuat fe a". -In(a-x) = kt + cs when t = 03x = 03.°, c = -Ina Pee in (@=k) ila etc= sn ay etek etinvae-71n(a-x) : woke in( Boys ot, x = 22908 108; of8 units ttoe=! ax / + an3| In the above, decause concentrations are involved as a ratio, the actual concentrations need not be found--we need only the ratio ee so relative v: pressures will do instead of comcentrations. For a first order reaction the time for a given %.of a given substance to change(or decay) is independent of tie initial concentra~ tion, Yor a first order reaction the rate constant is the fraction of BG Ae ieectes wnueh “chuinige in ntt tine, ; fide inthe Seaction- Snie) 0, ime time t/- rommale Ge acto disappear ic the same vhevher ve start with 1mol m7? or 2uol m7? In both cases: 22303 log, at 2.303 log. 2 21203 Logy5 8° 5g 24303 1084, a half-life for radioactive decay, 9.693 K Radiocarbon Dating 4e 4s created continually in the atmosphere by bombardment of carbon dioxide by cossie rays, The resulting 'c becomes evenly distributed throughout the atmosphere, oceans, and all living things, a constant Seloosing loriatn ined notecen’Wo\ea) és aicintoeseiien wemee!2E: When plants and animals die, reneval of their radiocarbon ceases, and 1h, the '"c present degays at a known rate, The age of the specimen can be found by measuring the radioactivity of the remaining ''c, This is reliable for aces up to about 30,000 years, oS is = 40 To Show a Keaction is First Order. Heys Pg. 374 > Consider the reaction 2H,0,—> 2H,0 + 0, . } At intervals withdraw 10cm” and titrate with standard potassium mangeniate(V11) solution, At ttme ty let titre be Vg At time t, let titre be V, «", after time t,, amount of i #0, disappeared, ie, x, can be reptes- ented as (V, ~ V,)s acx can be represénted as V, . Hence for different values of t we can work out the corresponding values of (Vy-V, ies % 5 + anxe ata t and of V, From this wee ways of showing the reaction is a first order reaction, i) Calculation of zate constant caries BiDOD| 1p 2g orient tonal eroreativatucossantinstuceen they are constant indicating a first order reaction, ws (41) Graphical evaluation Rearrange the first order rate equation asi-~ Bearer . Ee 206, a eet = 2.303 = a constant. vs, t -- a straight line graph indicates a first order reaction, slope or cradient = k/2.303 (aii) Haif-1ite method Plot x against t..From the graph find the time for of H,0, to be ¢ initial cone, duced to half that value, then the time for it to be reduced to } th value etc, These times will be the same fora first order reacti Second Order Reactions A second order elementary reaction can be represented as:- ACsSB = 5.0 3 D Let the initial conc, of A and B be"a" mol m->, Let "x" mol of A have disappeared after time t, Rate = k{AJ[B), ie. after time t, ax k(a-x)? at : rearranging end integrating:- ax x 1 x kat 5 fists, eS (a-x)* a(a-x) € alarx) cone, Units of k = conc. time” ee cone. x time Here, the time,t/,for half the reaction to be comploted, is civen by!- Gf Led = , tc, t/ is inversely proportional to the initial concentration (ef, first order reaction). To Show a Heaction is Second Order. The same three methods as for a first order reaction are used. i) Calouratii Pind x for various values o2 t a1 of the rate constant i calculate k from the second order @ second order rate equation, The velues of k will be the reaction, ae ii) Graphical method real ofem vs, t -- a straight line indicates a Taoplot— action, k is the gradient, (444) Half-life method Plot x cecinst t; a'x t/ should be constant for a second order reaction, eo) Catalysts Heys Fa, 363 A catalyst is defined as a substance which alters rate of a reaction but remains the same in mass at ‘the end of the he speed or reaction or at equilibrium, homogeneous - when the catalyst and the reacting substances i are in the same physical state Reterogencous ~ when the catalyst and the reacting substances are in different physical stetesy Properties of Ca: Gene 1) Unchanged 2) Alter reaction rate but never the final position o ysts 2B ass at the ond of the reaction(or at equilibrium) sequilibriun 3) A small amount of cétalyst- influencds large amounts of reacting substances = 4) Age usually-specific in character 5) Tho efficiency is often.increased or decrtased by traces of other substances. The cfficicnéy is increased by a promoter, eg. in the --Eaber process aluminium oxide is 2 promoter for the iron catalyst. The efficiency is deersased by an inhibitor(catalyst poison) ce. HS; HON, Autocatalysis This is when one of © produets of a recetion acts as a catalyst for that reaction, eg, in the oxidation of cthancdioic cid by potassium nenganate (V11); tHe monganeso(11) sulphate(Vv1) produced acts as a catalyst and so the reaction speeds up. Explanation of Catalytic action : Catalytic action depends upon t! lowering of activation energy. This may be achieved in tvo weys, characteristic of homogeneous of hetero- gonoous catalysts, : Homogeneous Catalysis This ic ucuslly explained by the «intermediate compound theory Here the ca alyst takes e definite pert in the reaction by forming an intermediate compound which ic subsequently reconverted t the product the catalyst, eg. in the lead chamber process, the oxid- regenerating ation of S0, to S0, is catalysed by nitrogen sion The latter de(nitric oxide). © ts as oxygen carrier", 2NO + 0, 2H0, NO, + 80, —~.80, + m $0, + 1,0 > H,50, Heterogencous Catalysis This usually depends on a; ati sorption, Consider num atoms ot the surface of some platinum as having “free valencics", The lerger the surface area, the more "free valencies" for a giver mass of platinum, These "free valencies" are able to attach atomsof other substances to the surface, Thus when platinum catalyses the cont tion of hydrogen ané iodine vapour it i supposed that the bonds between the atons ne hydrogen atoms and the iodine atoms are broken and re adsorbed onto the surface of the platinum, AD ies If atoms of hydrogen and iodine occupy adjacent positions, an activa- ted complex of the form The complex consists of a hydrogen atom end an iodine atom joined to each other end to platinu: atoms by abnormally long,weak bonds, The activated coi has only a fleeting existence, Providing the hydrogen and iodine ateme have sufficient energy the bond between thom short the bonds witt the platinum are broken, and the newly formed molecule of hydrogen iodide vaporizes, leaving vacent sites for the adsorption of further tor £) Prossure Pressure affects only resctions in which gases are involved. i) Effect on Reaction Rate 4n increase in pressure on a gaseous system is equivalent to an inerease in concentration. Thus the recetion rate increases for an increase in ii) Brtec If there is no volume ch ressure. sition of Equilibrium re is no effect on the position of ge th equilibriun, wre is 2 volume change, the position of equilibrium ehenges according to Le Caatelier's principle. Heterogencou: Systoms These are systems where the different substances are not all in the 2 pecie ate i cece : game physical state, eg. CaC0,——>Ca0 + CO, 4 goi4a poheves in a reversible reaction as if it had a constant concentration, Apply the law of mess action te the above reaction » 88 the concentrations of Cad and CaCO, during the reaction rem in constant, thus the concentration or pressure of CO, is constant for a particular temperature, The value of this pressure at a given temperature is called the dissociation pressure at that temperature, PHASE EGUIISR IA, Heup Pa 25 | HASE EQUILIGRIA AB 4 = @)_Sinde Comgorenk Suptemo > 5 guid ; are (on poor Exceed under sack condakims only solid - veges | Seauass agent con ho ww equalibrum . 4 , Suakews Ww wich onda one ¢ Ahee ate 9 grates eee Hee sie Or DAS Aol to Torvalvel, gre calle one (since Coungonent syptows: . Aa eqpitecuam leokinean solid -vapoat of Liquid -vages on ee, Maced ‘ma Twas — bay olka, Saengentre ot ghaakle but “hese ot dagendonk on each othr Ale vdalimsie bekwer vogour presale on Kepagaotinnte a swlostamce. Vw kee sald: ond Regud ghokse com ‘ee reg enen bay oe grase equator Masyear. Ss Quan (N<*) LemeCel Arata ea ude Mactan © Sulastances, Pa regteaen Bre. wactsag, Un vageul gessule athe eBb uty wee vm Cmrorluie. Awe sdk webke ak &. QR Rortamnke Cee ‘mereoae —~ unpour” Pease grad \amed tds Vacktsan os ‘emgontane, \e Rewheate bing GR eda - wo the etal ek 3 el subbdtance ak ake huhar Kenearltites , Kash Ry usage Gee waditinguuball. 7 ak Q, add, Bayed on vapour reall tn ey fiu bra subd eee enndar Kb ousnls eee 2g he eri de gia. Onda ak bho Kemgariie, ik es ragreantal Lay com Khe KS gress cred ow ey doa Ane voraad medina ¢ sink oe fatceat, &We Kempentne a hea, eonk Q oa S Se need mahi, oo ws measwte 2S 9 grou} tol 3as Ww. : ; : 25 oe howe Ree eqpal aren gonk \eokiGern seu Ween Arad yeras wir oggneh, gana Rosse ea ilerians Maar Spr wssker es a’s Poae Tun Whee ogg diedkon 4 Brom Hast Ae Des waStonae Neca niea.! Leas? nadMeded\e docrtaarna, vole. NuWcomoraunt Sustens — Alea ole supreme wu ware Brow one cvewrieal Ua hwidua > wavdeed. “Sdide in Linde Aho sa. le diten aa sold wa dren, Leaps ammmk 2 he SOUL. Cin grand) dA ton Ragpad under queen corblias je gece ge Sete Ou $ wath Ot ee Scand cane Ss a nea Wehr > omcmieing simwt Geanmna k beual \aoodakon a en ake ues Spe Ane sddciiy a mote sodibs Vacttasas obthy Tagvacina S i. wn accede Gk he Chatebir Far wed ebidle wok ade sored. hon Khe sulattroue Mascluas Tn Ke pare, sdudion. at ha 2 ays Sore on saludor | preted, etre Onrowae Feltay clace cate ce The reak sesortaad. Fe ve Brew eae g sWhken ea. coudic soda, Moadveo an Ke searty solturite. suber Gtk Kee dosargtenn 3 heak , ek Dae enoduaiinn X coadandhe Wisk Shan Bee sQtb te abba be volar. SAdeiliey Caters sduleitey KO; alicog wetter | | Sdudeikiby oa, water Diserlinumse edsedste, ots aon ae f cohen, sepa ele sh aah ate. Sea Fackere Raduad ae Shue. z Enetay alosodeh ta erent Che Qo De eve Cans — hon sduenk wihcewdes. aKacn chemsedwer to 3, woke) AM -ve Sduatien 4 @ Rn grant Cnaghralins eran Ta whe corn 8 Ae ones, Youn & ke QWies, Teka Uae Wrcrenner Ene ake ey we system: Shoe. Eas plderuan Disotsws tn CuSd awoke Heyp fy 271 a\ composition Sivek Sy ee Sees con eee me ez Ss araponay Oo» Fig ea we Wn * ne wigs Uae abbar 2 vary. Chie © oe oo cue — apeume pies we Me code k ond e a sagin Kmart: 1A wird Sak’ Ekthk wells Bea 2 congonank sugtem: cece iste’ Cui) fore jee GRA Fa0, 3H0) +) 4 Ade upton 2 Mah as G50," 5129 on sm apelidoraae one om vagowd Bae vant Rt the vagoud prenare ee ean Kn gar Ba tan be 23 TV ra “r Or ey Yrg Khe com gnems ee SK Se da voroken es cor . ake ajo greens, aloha 8 San afage HH ite ©. The & eerttedarey waa)ul Ys andevaing chek negheme ikon, Che ertmowe of water ee So cea wile Re Or twledpate = 5s 9) & vorad ake 4 Enteckic daxtee eegie oe cra eee Condens, ayigte Sedum, oe adukion Qrom 20°C oo y Rerem| Ra, a Best X s QQ ba Ge Stee cil at keke OF ee eae ouk ond the Kon bacomes Mow in sak — Lia se AM icon Monto uabilig Crarsolaten! conbettn TUE cf ecatl wk otimankite 4 dbut~ave. AE Cisennk Salk sale emphiliae. oS Gygler os caked mike a = om Aaarky aetatka oolulinn A SOLE to coalal Yom 29°C the Yixk sod. be oggor te solk (RS in Aisarenl, oh pase Sure coalung ) mote, salir sagotaiins oak, uni) Rsodk Selah & 23-6% agen ak —2VC wha anh ico engr alice oul Cogakhor. The discakinuliy ot Cm dee fe direkt haresin- id “sedaklon, wikis vege? ond tex: Akena, mei CGiooen, sekardbed sellin wats vagewr anh sot onhadtnes: Alera CB hue io USsrum bakucnn sotumal sduten, wekss Uoeew oom N. adrota salk AL & satu aubo, Lea, waar usgeud and nada sok are addin aapaldordoes- Evkickle wintanis cam oso ba utah by 2wekels ot 2 craawe aedida. Provideng, Khe Kao subbstonag of& comeddrety misede when malta Regus ond the eure substance segosee o~ ‘ c~ cap ram Waarmes eee © wy py Hew ond : Ain modh& a 232°C ondlash ok 227°C. The wtrete hq — pcre eavltormra Gla le Ean, 36% load ) nadie aK 183°C. Thus om coding = waekyte An om Gah A tre Cram 26% Lah, go Be Yo dagosah Curae x). TY eee naxtyo® conto 36% Lasb gure aah segtalis oak oh sits (cee Ae S Che Maud ws solarbal kk weak be bey wctale. ane Baan For Zune oh Comer Oecd oo%le CL \o0rlstn O%> En A CG tine amb cadlmiunr 5: ok tagger anh Che compra Rice Uys ond Pere SE dre tes. Log ple od RaG~ Ugbh carve Close Oris ald io Linth Dee —sAd cane (lakes Wuoall Ge cot) Rakin the tion curves thee so nikine § sdih = Diab, The enacde & ot o chemical comgovnh “Seconst malinos gw oh comgos Shon vor wats geese Amare simde etectic Magners oe Somednes c comaicarel, Tea Bre groin 4s hie cweateds compeand hava, US oom Joa wabGng, goin: Ga exange ¥ Ras he CemngaraSinle composhen Leagan Myra magi Bene PARIS Aoaeht nr Gingget Sov Waar ae eyelet abe, Seo 6506 BSC = = Mai eea eras] aWiie x mento? On 100%o A — sh comgund Madan, + iquid G@— shh Za elignd — : Ee SAL com Mada. + eubeckic A D— sd Tae eukeckic A Are -mabtinng, pow 2X compouml Mata is ak ek =. Xie Che eubictic makita Q Ma + the compound, Matar. Y we Rre enlikic mixta of Zn + Che comgeumd Maeva: Thane Alcatams ott wae van shourrg Che exist Sd sodakion, sutectios poh coungourda: : Ane reunda maxim indicates eaok Rae comertend Mazny w ak vary skalde. A dnargir gaake indicatia a oot skalde comer. } S Kiawads we biaw su | Y Comeatate wioetle Lagade & iw alt prage tons, L Compatsly Vmanincila ids. » Portdly mucha Bape. LL Com@akal, Mucha Lowds Aq Wadi addin G ore tn whide 4, Bae, Joven oe che same vx Kae Solute os Choa ua Khe segoteke Uguide aoa Boe yodume Qene sul Xiq spade eqpods Cee A g Boe Shatin. eon eee on phan, ne Gog Re yada « Aa)e Khaw w vo sduvnans oe Wie}, Nos Prenoute Ram Tdasd Soduiion J who Fad & Asia hoe raph, a a es noe a dane I Same ode s our stoke. The uspeur petaale BiGeitaes SoS awk alee eens ae Ae Sotudin. the chomag @ wath compesdiimr Yer ideod solthono cael by Rawil's le a whads drves:— stad orseuie dA Gro sodulion, aka sui namie SOAS es ene doe frie See Gece 2 equa) Ee Coe vaoeur otaaude. ote. Ryak the some Bmastodet tous noe An he sok. 9. Sean of | wae OS me Fuh FO | 1 ends friction oF 0 Vapour pitsbute — Composition dhaataen fer on Sdeck Soutien pvat\eoe Fa oon “Baad SouuSun, componente Fam B have Ene Sam % gone ato Khe wageur ghana asim cote A ee Cageur gitaaule aa sesve Cae scltlnn % pagers’ Ywaddan YAH Che salation CSaally\. The, pars RG NMG 5 esis Xx Ss grees tenal t kee mde. Bretins a SB. Tok Ore sdelen = sum QL ported vagewt eee rer Bree x ee SG 50 Pardiol wap. Gres. adn. dua @ (whe Ypacilen 0+ Veg grea A gue A we 60 Rr Pork wag: geese: Le Qo uw to ACmda Sree S a: ws Cabot vag: gears Ao weer RA aL GS ok mde fockion ors OL. be (as +3e) v.55, (ey. z Raa Nece es a heen ond hegrane ak 30°C). Ane Dapet Renate & Noa Edasd Sone. d Soo Missile by The semiak Line reQelienship lackinenn Vogel GtsaNe ak nde Sordi Cem Soma Yor Sn dal olen $98 Dequide laneoman cutee, o Fee One, Maybe Basie Yoon acd “kebaviout: | Joe Dewratin Qrom Raoult’s bow 4 é 32) 2g 2s ee 2 =~! 100%A (00°, comgesiiion ——> Here Kho bod o rangure deme Vae Viguide & use Cron woe Ward. Tee Nee ones ae toa & Wadd sutsobiin Cie. gure Gaeda\. Cis diols shige skrct Yprena Ta Eee, tution Chan in Rae gat Linde. Thine vbied te o codtracien ta vw onl an eveluiien Qrack os woe egy Rae sada. Cag, vookar od eke) ach. Nd) Voting Devrodnan Imm Raoul bars EES competion ———> Rae ere eb o sremure dere the Laude 2 2RSar Bon Seca Gaia nes usleaern eae Suen Whe Solution, aan Brow he Que Uapids, Ts | aktrectwe § nea eetantnn Che wdeerdro ine sdution ewe Uapdee cha te o eRackanc be slic com@adalay. This i ersocaked wn am Wacktaan, in wlan, awk clesergton Q reek on Sear i: ¢ srixiang Cea, eXhomsl ond walir), Sn he obne Mogres, tre Ratko Reman show re gavtiol e > prepeatta A A ok Se aX tadenk Ene ungeur genet da mele & 2 emPakelsy woalbe guide wir tonkank, uk marae ohh comngras tian. Troe ol % tagen 4 wostotien. A. Someubnae. laekaneann See (2) Fer Werk sclas, — vag gress: & kee SA XS ns Avra % suerte guide. Lopes Sica () Voges Qrae- YX Qre Sta. mon, readrcantina twats adding Seriaiion Seeks Ros ilo) ew Q Ure sda. vos Madea maximum (cosicee 4 vias 3 Sy cs (2) Vege ge Stam Racull's Low) Co nea gordindss the oerbna, geen varae with co awgeainn So- Kok Ss a= (0) SemenKele belirsen Che bolling wads Qtha segante Laude, @ Wadhes o mazionmnr, © weecen @ ini - dag ot 3 mitre Ve Lene dona, QRDs L Condit 00- Fo: go 50 a tf, lon mone & meXwanel Kemgr= Comguentinn, Sizateen Yr method we a a witre f wabonk—unlir G Siatitleh ot arta qeaenty, ranges oceut gteqeasiveliy We leeildinn, gawk af the Ryd, “he Conngeas Fann Le Gaqud,, re co. at te i bet y. “ EA ee Suggesa Cee mie, Baadg AIAN conkains SOM maansl Cet mde. regtanctce Nag Lv. Gotling, comnancse ween She usgeu? graoule Q pk ho = akmaotare gerowe. Tia cote ok a Kang XQ £FOC. The BiXe awidus) tras ant Khe some Comgeation os Cae Yay jook Mwous contol a Waker gto Wien 2 the ono) Nelle constiinewk. 5 sae eS ae vageet ayven ay ok Onis time (FU) & pee - TY Wa vag > condansed ik gata 3 Uap ex =e na ee cakheah- EY due wh ba & vk orks eave SK ay MAN Neen oko Gg & abe 6F°C mh Kau vs ren \noo comgoueen NES aie ane candoncae apnea ow % x odwuk ante wahoo. By reacts is we can allan ink eo rads namal ON SNe eno Ta Nae Yosk Resomes wealar an eae Rake conddloant) and Yo edits eek Conkenuas Ko tae uml gute woke ty Daye i che Mack (lek 5m % wets ~\o0"¢): Ane lower re On the diaatem shave the oo & Toedina, eS a as og Jor thee a oltre La eocandiws - oe cune. Ane: 83 orn Soo comPakdl., miscilda Lagu vaima Che bRoen 3 Crus odin oe YencKroned dicts Woke. Thin grease & oa ok Bickldy i oo. Yronckine ee es whareds oes SEAT we comands mk oe onlin. The § pada: cama ® desrayah to ewan blur the seandiny vesaur |s brood ine Lnkimaee cantradk uk Jaramdivg LL wed ext) om eqpilopeun \oeKreann, Le oy aed ok uty Soge. Ta he (clootaltany, UF veh bn Wg the colin wots lose loka T. SONG en sien annie 0 waderes Fadl. Voges Jom Tre Yo condomsation onl udlotieation on Shae ere oa XK te Sutmawely nee os Wass Ne oacambina vegeus The aBedk ¢ Te We Sama ao Voto os he \eabing ye oes o rote fh eqpaiSarasan | a edelinah, Lmeck congas segerstion Ate camubaewta ges. aon wore volakd, cotta Bouse gow Cae Loe Ring eee inteen the (Gy wee eor Grate Wanowws Westtne, Wark, & Carls) the Se Didns aaa maxim oko eae Compecibionn : ° 20-2 To fe ACR Boiling gH compos bare lh Yr \udtechleric, acd oth wots Trio Maar leo Soo AN Bos ven The kre B vsolar ond Inagreclare SS Wooo cranium bode se BH NOBS7C hem Che waxKiie hes 202%. BWR. This w wpteatad buy geek &: Om SED a acbakten Y HOE carbnning Nase Chon -90°2% HL, elma connionces Rellos 08'S°C, ork Krav aon eben Wer Me washer Ben maibstra gti keny (ere Soe eget hota oak Jorn Une Waher "fe q- Whe eno VME cotnawt)) The Kauid wae WOT VA RO tL We shui coke 20:21, ROL. EE ARCH Crem at dh ak waste, cs atk ° LVS. } 5 X 20:27, Kel the a dat MLAg a Delien wee rt gabon Saou cemboims mde mubtaggn cWlarde Chen Khe ene Selon go yeas ce cmemirotien LEQ te Jemeoaas utd UC agin Wathes 20/2%l, how Whe AN, ogame Aes Suar uncdeamagh ok 108:5°C. Ane mcxGne conkaing 200%) HCL wedlel a contaut lorluna oko oT eoktogic WAKe, A som. conkaweina Wathen 20-210 HOL comer segatatel vuke pate cor om aredkragic Pxe. R sBu, corkeinina, marl Shon 20-27% ACR comlan sugerone ek ese \nehTegem eGR ank he aaeottogic aie Qe - Connie) Tha Sellen FE es mim of & COTS SOA DUS INT 62 Aone" FA ico Mody grigemnatnel_ = pana Yor otapancteol and wsekar A mndane J, ergom-\-oR anh volar Cees ane Caran. veg: gear ken Be Lash umkans 727s Nee east propnr= Tie wee ts segranrral Nog ger a Sa sada a wtere A Yoos ron 32's Gren leh A ‘crams aoave 88°C, The vogent cankaina & lorar Sle & qseem-\—R, Lam Rade Cre Sdn, Wdk “acowde wealth on ame eek We cow Wee Sepenee The eA vs kiNake, oh Lower leg Cazealrgc mente) aah oa ean Rapa x Wager hs a Oa Letty a mixtate H me Chon 72% gregenst wh, lectling, ‘onapne dome 28°C WYehong avagow” ¢ em gence chow Mae oven sn. Sey awk Waking the Bdtlliie, waco & = Ny . ate a rektatio db ome e\ne anh wae mR BOTIBLE MAGNE , Tn men’ 8G f CON a can ee segatarel boa odzovd Dakin whe Ure azzerm cAXTE ound Chol “coasts wade — wa exces. Here we darn ‘he areErtegic ee Yoon Soe, Vago aoe AY) Seees Yor See araciinian Deeded, geo’ oe, NS, OQ aic\ he oaadereic sdvtae & Rake os Chee pos. a Condabel, Suaiele Houde SB fee cada Reged GAL ear Ke our vogenr Meal whide Bapads othe Cewnganlnte buds ok nn fas gucaty tigi geal A\wa Kha BL vogew gaat Me Som Que segam vor qrapulte and WAL Tacttue wil sara ae Lean Bae coastina eee ge. eqpsde ok maadare Oe Kae Ne wy o Kenge Ge Grom Khe yedung, go X eshas oe : ete ata! wesaas) os= Wwe Brae 5 ca Whe ALL Ae QE bye ee cies a Wa yohue ae ae We OseRO 3 bre ee Dae she QUgeds \ ihe? yee oe re. vegont genaulte ie Wa se “pannaa 3 \iqyde \ads B.. pie WDa Sen Spr tne en oc R Wade Nooddana, GE 3 eee xX erate ee : cana, Rana Koc, t Jarome feat SHest. 0 . ditWokionr ape! xX Jone ewes 60 me & a ey ~ Gloee AS Y Sal Mocha Laps 1 Wher toe Ligade eg Qromd od wally, Lake oe goa a pardaly weisedhe, ale otbinary Kango, 2% Salen Keagdur Gx busskal sodwo, Whey coeuak Un gpnOOseanm ave getvarwas ee eres ee eae “hai coaristivg, Solan oR trawen a0 sonjuade solutions . Tne comes Ran R Cee \sygre WO voy eae Gengeetare - fs Rae Kenqariite tb Gncteasad) Coe potend AiG, X grenek ond wotar Ucreasne: Ts kre come. St grewed re : ager ok § wer Se re dremel Done Inca, ote & cartabn ong: ce Gao em ange selva, Reco mds sBaead Ae Rea pork Cre Cao extras sous, gare veld one Vromerapraana dela, art Ene, Cwqanlioe ak ack Sas occa & callah Gre exXicod sclkion Gmaariine a She canscluke, Komeretire. Tha sddodhiey dake Yor vast | Gham oa axgooadl oo wel i= a bor Rene Belg SS: so use ne? to 20 3 Rose 6 70 Slo Sawn vase 2 rend Rome 65+8S% chimed an welds oe wiaalle Sich sacl ot \nor ww oQh_ am eortons. Woon Wao eengartne ow) to a. Qo growed —wokar mixtne ot 8 mated eyo et: SA Che caper ame tae wheciie wo © Segoe, tte Eno conkvaer eee Than Some caneo, ea. ere See ae diel, @ sot, Wettsaee wily Luang Lenengeere snes 100 ome(%| 60 40 20 Lower erica seludin ager) Some ot ol Rasen jand re ey TAM, o Basualieats estas om wor Lower erkica Tangs — bore Veer exkica\ Gee = 210% 2 io 20 30 4 50 60 FO BO 4O Slo X icatine Conyuage, tiles, wed, Se dd Geng: on ado AM X condo competion. De cxrardar fudh sodas. co le Semlecilede Rrgurde ead eda carkwloukes US cum 1 a Wdne eee vageur presente, Ae take Saga BRARWE me qelr Xetra KR VOQet ehee X ok Reapik or way Vic O54. Nelcien che Yao, Bogan, Steam AUS tron He vaah. Eo eaclaagr the RENO UE aes NN Soy NER SE ea ee See ee él ZY, o woke 9 Goo Wmerioclde Bgpde ja scbsdanc wide aac oe ee te abba Ua vornyrs, ee eee aL Ser ele aan ta sudko wo Yrok Ye ke db congaakentiens mn Che Swe Layne & conan ob cotton Lewis , pee Nano na te. Sone SOS ees By sakake, mm gpd 8 uae os K vo Cre aidetlaNiim or cation colina Q Sok sugtem © Qrok® me: : Ais hedde wha Y Cre sduke & w Yee same wdaulst conditian ta bath solyatio - ta, conn have anacckotan of Auave colin Ae s A ype one & Phe sdvewsa. The apo a seus ok wnat agt Oxcad ao sual a ear seed) ad aapacdoressnn wank lee adel ladle concn Kroliens De cOmngo! . Kb qben las the ete 3 COWES. WIT Mandan. ey, wa “pelea Un cathon Misldude od woler Gere Saale Sx ao Cone. YL odene wm WO : \ | Electrical Properties of Solutions a dn: electrolyte is a substance which conducts electricity when dissolved or molten, Electrolysis is the conduction of electricity by an electrolyte. This type of conduction differs from metallic conduction as below:- 1) In electrolysis, chemical changes occur at the electrodes. In metallic conduction there are no chemical changes. 2) An electrolyte conducts electricity more readily at a higher temp- erature A metal conducts electricity less readily at a higher temperature. 3) Ions move throughout the electrolyte. Electrons move throughout the metal. Faraday's Laws In 1833 Faraday summarized his-experimental results in his laws of electrolysis. 1) The mass(m) of substance dissolved or liberated in electrolysis is directly proportional to the quantity of electricity which passes through the electrolyte. m= eIt I is the current in amps. e t is the time in seconds, e is a constant called the electrochemical equivalent. The electro- chemical equivalent is the mass of material liberated by 1 coulomb (1 amp for 1 second) of electricity, 2) The masses of different products set free by passing the same quantity of electricity through different electrolytes are directly propor- tional to their chemical equivalents, mi = ots “ma e. whereMandM, are the masses liberated by the same quantity of electricity from substances with chemical equivalents E, and £2. Thus the gram- equivalent of any product is liberated by the same quantity of electricity. This quantity of electricity is 96,487 coulombs and is known as the Zaraday, These laws are obeyed exactly over a very wide range of temper- ature, concentration, and current. Eis the charge on 1 mole of electrons, F is the quantity of electricity to liberate one gram-equivalent = 1 mole of univalent species. Thus F divided by the charge on an electron = the number of atoms in a mole ie, Avogadro's no. 63 22. ~ Sa = pte a acing — mol C (6602 x10" e is found by Millikan's experiment, a3 6023 x10 mol Ohm's Law Experiment shows that at a constant temperature the current flowing through a conductor (metallic or electrolytic) is directly proportional to the P.D. applied across its ends. zr MRD. PD. = RE The ratio of P.D. to current is the Resistance of the: conductor. The unit of resistance is the ohm —~.. A conductor has a resistance of 1 ohm when it allows a current of 1 amp. to pass through when subjected to a P.D. of 1 volt. * Q A ax rd At constant temperature, Rx Q= length Q = cross-sectional area resistivity (rho).(Constant for a given substance). P, is the resistance between two opposite faces of a unit cube. (F is then onsty,) Condu: In. electrochemistry we prefer to use the conductivity rather than resis- tivity. This is the reciprocal of resistivity and is defined as the con- ductance of a lcm, cube of the substance or solution, i seols_ ash k= Conductivity - K(kappa) is usually expressed in "om, - c =k 4 C = conductance eee ke = GL hence units 7! eat A a ? The conductivity of an electrolyte depends upon its nature and also on its concentration, The typical way k varies with concentration is shown below:~ & re conductivity goncentration Measurement of Conductivity This is normally carried out by the Kohlrausch method which uses the Wheatstone bridge circuit below:- Conductance Coll condenser (resistance Q, ) oscillator Q, = variable resistance leads 2 FE] sass somos electrolyte Bt electrodes Conductance Cell The resistance of a cell containing the electrolyte is compared to a known but vardable resistance Qa. The spacing apart of the electrodes is con- stant. Boe Le Alternating current from a valve oscillator or induction coil is used ( about 1000Hz ) to avoid polarization effects (ie. changes in the resis- tance of the cell due to formation of gas bubbles on the surface of the electrodes as a result of electrolysis), The null position is indicated by minimum sound in the headphones which are connected to a valve amplifier to increase their sensitivity, The sharpness of minimum sound is usually inereased by connecting a small variable condenser in parallel with the post office boxf,to balance the capacity of the cell. At minimum Q, pees As eRe cee E22 ST -wherefAC is a wire of uniform resistance and ® is a sliding contact. Sever- al values of Rj are found and the average taken. The experiment is then repeated with a salt solution (eg. KCl) of known concentration to find the cell constant (ie. a factor embodying the physical dimensions and spacing of the electrodes in the cell which rel- ates the resistance of the cell to the conductivity of the electrolyte). Throughout the experiment the temperature of the electrolyte must be kept constant, Also conductivity water must be used. Molar Conductance This is the conductance of a solution between two electrodes one centimetre apart which enclose one mole of the electrolyte between them, It is den- oted by A. Since the conductivity, K , is the conductance of tem? of solution between electrodes one centimetre apart, it follows that:- A = kv hilierel Vdiewth ol volemet tat cuchaontalniie one! molelorielectroseenee Nile ct measured directly but is determined from K using the above relationship. The molar conductance of a solution of any electrolyte depends upon temperature and concentration. Variation of Molar Conductance with Concentration The two general ways in which the molar conductance varies with concen- tration are shown below, where A is plotted against dilution. The dilution is the volume of solution in dm? which contains one mole of solute. alates ok 25° 120 100 80 60 ho 20 500 000 1500 Dilution (dm*) Curve Ais typical of most salts, HC1, H,S0,, HNO,, NaOH, KOH, In these cases the conductance is always high and increases only slightly on dilu- tion, soon reaching a maximum value known as the molar conductance at — infinite dilution and denoted by (Ae. Substances whose molar conductance varies in this way are known as strong electrolytes. Curve Bis typical of most organic acids, NH,OH, and certain mercury salts. In concentrated solutions the molar conductance is very low but it incre- ases steadily with dilution, Substances of this type are known as weak electrolytes, There is no sharp distinction between strong and weak elec= trolytes: some are of intermediate character. ‘The importance of molar conductance is that its variation with conc entration faithfully portrays the variation in the conducting power of the electrolyte since the quantity of electrolyte between the electrodes remains the same whatever the dilution, This is because on dilution, the volume of solution taken changes so that one mole of electrolyte is always present, This is not so with conductivity where the variation with conc= entration represents the resultant of two different changes: one in the conducting ability of the electrolyte and the other in the quantity of electrolyte contained in the cm? of solution between the two electrodes. Thus changes caused by dilution in the effectiveness of an electrolyte as a conductor of electricity are obscured in the case of conductivity, K . For a strong electrolyte, molar conductance at infinite dilution is best determined by plotting the molar conductance against square root of concentration. For very dilute solutions this gives a straight line(see graph below) which can then be extrapolated to cut the axis, the intercept being taken as /\co. & 6 Weak electrolytes also have a characteristic value for molar conductance at infinite dilution, but in their case it cannot be determined directly because the graph is not a straight line. It is calculated by applying Kohlrausch's law of independent migration of ions. Axo (20 Sodium chloride wee 80 40 ° O05 One OS 020 OF25) (concentredion| fariation of Molar Conductance with Square Root of Concentration The Simple Ionic Theory During the nineteenth century numerous attempts were made to explain the previous experimental facts. The most notable of these was the theory of electrolytic dissociation, generally known as the ionic theory. This was put forward by Arrhenius between 1883 and 1887, The theory postulates that in solution all electrolytes are spontaneously dissociated to some extent into positive and negative ions (or radicals).These ions have completely different properties fromthe atoms from which they are derived. The dissociation of an electrolyte into ions in solution is regarded as a reversible process, the extent of dissociation depending upon the nature of the electrolyte, concentration of the solution, and temperature, Arrhenius explained the variation in molar conductance with dilution by proposing that in a solution of a strong electrolyte the proportion diss- ociated is high at all concentrations and increases when the dilution is increased, soon reaching a maximum value when the dissociation is complete, He suggested that for a weak electrolyte the proportion which is dissociated in a solution of ordinary concentration is very small but that this proportion increases steadily with dilution so that the electr- olyte is completely dissociated at infinite dilution. Electrolytic conduction is explained by movement of the dissociated ions through the solution, According to Arrhenius's theory the amount of Product liberated at the electrodes during electrolysis is proportional to the number of ions discharged per second and to the time ie. to the 68 a z Similarly the masses of different products liberated by a given amount of electricity are related to their chemical equivalents because the masses of the different ions per unit of charge are proportional to their equiv~ alent weights. Arrhenius explained why electrolytic conduction obeyed Ohm's law by proposing that an electrolyte partially dissociates as soon as it dissolves. Thus ions are present in the solution all the time( even before the pot= ential difference is applied) and no electrical energy is consumed in donising the solute, Thus the dissociated ions move towards the electro- des and are discharged at a rate proportional to the attractive force acting upon them as a result of the applied potential difference. The Arrhenius theory also explains why solutions of electrolytes exert higher osmotic pressures, give larger freezing point depressions and boiling point elevations than expected from their relative molecular mass because they are dissociated. The abnormalities were used by Arrhenius and van't Hoff-to-calculate the extent -of- dissoctattons=~~—~ One of the achievements of Arrhenius's theory is the simple explana- tion it offers for common properties shown by.simpler compounds ie. all ___ copper (11) salts show similar properties due to Cu** ions, Arrhenius realised that the properties of all electrolytes - as far as their dilute solutions are concerned - are the same as the properties of the dissociated ions which they contain, Kohlrausch had already shown this to be true for conductance. The simple ionic theory can be used to explain many experimental observations ie. hydrolysis of salts, common - ion effect, precipitation, action of indicators etc. Indirectly they provide confirmation of the existence of ions, The most powerful evidence for the ionic theory came in the twentieth century as a result of X-ray analysis of solids- many salts are composed solely of ions in the solid state. The Degree of Dissociation The proportion of an electrolyte which is dissociated into ions in any given solution is known as the degree of dissociation, O.rt is expressed as a decimal or as a percentage. Arrhenius proposed that since all elec- trolytes are completely dissociated at infinite dilution, the degree of dissociation at any dilution is given by the ratio of its equivalent con~ ductance at that dilution to its equivalent conductance at infinite dilu- tion, ies = _A Neo je 6 About the same time, van't Hoff suggested the term i (known as the van't Hoff factor) to relate observed colligative value to the value calculated on the basis of no dissociation. Tae observed osmotic pressure calculated osmotic pressure observed freezing point depression Calculated freezing point depression observed boiling point elevation Calculated boiling point elevation and TTV = IAT for a given solution. Consider an electrolyte each molecule of which dissociates into n ions, and let C© be the degree of dissociation. Tus |[-%e& ——> NX Therefore total number of particles present = |+(q~|\ oC ,compared to only 1 if no dissociation. . + t+ Gale ~ =n oe (ea ; and ide aap Sa Arrhenius used this deduction to calculate the degree of dissociation of varius electrolytes at particular concentrations from the colligative properties of their solutions, and compared the values of & so obtained with those from measurements of equivalent conductance,In.most cases thero was good agreement for the two values of S%<, doing much to strengthen the confidence in the ionic theory. Kohlrausch's Law of Independent Migration of Ions In 1876 Kohlrausch noticed that pairs of sodium and potassium salts with the same anion showed a constant difference (| ~22' cm mol” in molar conductance at infinite dilution. There were similar results for other pairs of salts with a common anion or cation. Kohlrausch concluded that at infinite dilution each ion shows a characteristic conductance which is independent of the other ions present in the solution. Thus the molar conductance at infinite dilution for any electrolyte equals the sum of the molar conductances of its anion and cation at infinite dilution, Ka = AS & AS a 2 This law can be used to calculate molar conductances at infinite dilution (ie. for weak electrolytes which cannot be obtained by extrapolation) provided the values for three suitable strong electrolytes are known. eg. Calculate the molar conductance at infinite dilution of CH,COOH at 25°C, given that at that temperature the molar conductances at infinite dilution at 5 agosysl of HC1, NaCl, CH,COONa are 426, 126, 91 ns! cm mol” respectively. Netscooh = Nenjcoo" + Rat Ana = Ayt + Age Awect = Ana + Aer Nenscook = Ayer + Acuzcoo®a — Awaci (26 + 9) 12.6) A! em? endl - 3a Sasdcr seme Moderm Ionie Theories Im his theory of electrolytic dissociation, Arrhenius proposed that the degree of dissociation of an electrolyte at any dilution was equal to the ratio of its molar conductance at that dilution to its molar conduct= ance at infinite dilution, ie. = A/Aw When the degree of dissociation of a strong electrolyte is calculated in this way, the electrolyte is found not to obey Ostwald's dilution law(see later).Several other pieces of experimental evidence weigh against the Arrhenius theory as it applies to strong electrolytes. Studies of absorp- tion spectra show no evidence of undissociated molecules in solutions of salts, and heats of neutralization of strong acids and bases are so conc- ordant that they suggest, contrary to Arrhenius's theory, that all these electrolytes are dissociated to exactly the same extent in solution and this extent does not depend upon their concentrations. These findings have necessitated an important modification to the original Arrhenius theory as far as strong electrolytes are concerned, In relating the degree of dissociation to the ratio of molar conductivities, Arrhenius made the assumption that the number of ions present in solution was the only variable, This view is now no longer accepted and strong electrolytes are now regarded as being completely dissociated into ions in aqueous solutions at all dilutions. Ww i ‘The variation in their conductance and colligative effects on dilution is attributed solely, therefore, to changes in the velocities of their ions as a result of interionic attraction, and the ratio Afr <0, now known as the conductance ratio or apparent degree of dissociation, is really a measure of the way in which the velocities of ions from strong electrolytes change with concentration. The modern view devised by Debye and Huckel in 1923 and developed by Onsager in 1927, is that in a concentrated solution of a strong electrolyte, each ion is surrounded by an atmosphere of oppositely charged ions. Og 2o +0 ©} e eg. ° @ ° : ao en a © 38 2 a e aO +O no_electric fie. =_3 trical wnder potential gradient - asymmetr- ical Diagrams to Illustrate Ionic Atmosphere So the more concentrated is the solution, the greater the retarding effect of interionic attraction, For weak electrolytes, interionic attraction is slight since the con: centration of ions is never large therefore the velocity does not change much with dilution, Thus only a small error is incurred in taking the con= ductance ratio as the degree of dissociation for weak electrolytes and in general the Arrhenius theory accounts satisfactorily for their behaviour, Modern Ideas on Acids and Bases In 1923 Brdénsted and Lowry put forward independently the definition of an acid as any substance which donates protons to other substances. Similarly a base is defined as any substance which acts as a proton acc= eptor, Thus acids and bases are related as:- acid == Ht + base These are preferred to the narrower definitions ie, an acid yields H* ions, a base yields OH” ions, because they also apply to non-aqueous solvents and account for the way in which the strength of an acid varies with the nature of the solvent, The views of Bronsted and Lowry have been extended by Lewis who has defined a base as a substance possessing a lone pair of electrons capable of being used to link it to another atom, and an acid as a substance Ene willing to accept these electrons from a base. W es. #4 y—Ni— 4 \ 4 BASE acm Ostwald's Dilution Law Consider a solution containing 1 mole of a simple binary weak electrolyte AB in volume V of Solution. The temperature is kept constant. Applying the law of mass action(taking the active mass of each ion to be its ionic concentration) we have:= AG = Aree Amounts gueneat (- end e eee el eaney « x4 ualibriuws Concentra Wore test\nae Klaas? (<\dbe ssepiates EG | V vi Agduing Ure law of mass actions — [ati Ce] 5 ere (remgantate eBatkant\ Taek we TAD = Wr Fs ee oo Ee =) a . ott ie a Qeay = (ad K v 2 7 3 i SiS DEXNOD ES sec Oe ee Nave a To Sa! we [py] Grom the distectabion ofS wcker is icgorel as & is nadine comgated te he amount Hoon Phe acid. When of is small we can aggroxs mde, by calling (a) unity: Ba the doors X= 136 XIG vama Ci-x) =\ Wikh this AQTeKi mak ion Oskwad's Alukion lao becomes abe sas ie fo SU™ Beye deHocoeselee a 3 Thus chen Vel, o ETK te. Of of a weal cleckrelfe in midst sclukion ~E JK. K Sor ao week checkrelge Yemains umchangal ad’ only on dilukion buk abso on addikion of other alecktolyres to Khe solukion , even when the same ton (s \bokn equilibria. Common A For gdubasic oaks eg WS) we have -— WS SS Bt * AST Cad Cas) =k, a to? Chast HST SE east eC DELS) ie =e — <0) Tas} malbiQuing Ehee 2 eupremions Loggkbar :— ma Ay ee 6 IS Kaas. Lust rh 2 This is Ostwald's dilution law in symbols (1888), K is known as the dissociation constant of the weak electrolyte at that temperature, It is found that for weak electrolytes, Kis fairly constant, but for strong electrolytes there is a wide variation in its value with changing concen= tration. In fact a weak electrolyte is often defined as one which obeys Ostwald's law, and it was the inapplicability of the law to strong elec- trolytes which first raised doubts on the Arrhenius theory, K has no mean~ ing for strong electrolytes, which explains why when we meet K it always 2 mol. dmv? Since K varies with has a low value, usually less than 107 temperature the latter should always be stated unless it is 25°C, the arbitrary standard, The Strength of Acids and Bases K is an important index of the strength of an acid of base and is pre~ ferred to the degree of dissociation because K does not vary with concen= tration, Thus the relative strengths of weak electrolytes(acids and bases) can best be determined by comparing their dissociation constants at the same temperature. The degree of dissociation can be calculated at any concentration from K as below. eg. Calculate the degree of dissociation and concentration of H* in a decimolar solution of CH,COOH at 25°C, given K at 25°C is 1.85 x 1077 CH,cood SS — cH,cooo + OT \ eu\ ave Oe? AE K mde concoe WEan reank - ee nes Ke ees (s\~ he. elas Srom Ortiodlls dilubien lag Xt kK -s Ss au eugcoow = LBS md ho? ot = 8s x10" (\-s)V Vice Wel Galeesel (EEN containing, Vande dl sad = 10 here “ ~ gt = 188 xo (1L-si0 ot x bas whos — 185 xid* =0 = GaSe eles Oe Olin E : = Coasided an aqueows selukion of ae “Weak oak HA. RA * W1.0 2S WA0* + A Ko whe oddity castant SF Getto Bugera AZ|: Lua Dao) codderad bo lar coctant Loca kG on lang eee. Calling LUO) os Det) Ka = CHD Deas) Tacs d Simory \pr an ‘oyaeous sdudton do wealk \vere, B, Ww basicky cakerk jKb, yr 8+ Wo SB Kl = Lew*) Lowy Cet BH* = OH” B qQwea lay Ke = Cres) Low] Leased Ka xk = CHS Low] = 16" = (olen Ae net ae cal ig Kram oo Rha imc greduck \ cocker Ky. Ka ek EG oe scaly) negra ix Logarta: fave i ie See git = —Leqw Ko hence eke = ge ce The Lower He ge vole, He mae edhe “Eb, Tha lowe the gle vlan Eke mor loasic ev. .- The Dissociation of Water If water is purified of ions - by an exchange resin ~ its molar conductance falls to a steady, very low value, That this slight conduc- tance always remains indicates water always contains some ions, believ- ed to be formed as:— + 0H” ie, H,0 =—H* + On” Applying the lay of mass action at constant temp, and taking the conc, of ions (mole dm, ~) as their active masses:— Arad - « (eo Therefore fH lowq] = xih,o] Now {H ,G ig effectively constant. Thorofefe (Hl lon?| = Kiconatant = Kw (at constant temp.) Kw_= ionic product of water. Each molecule of water gives one H* and one OH”, Thus the concentra tion of these tvo igns musg be the same in pure water, Their conc, is about 10°! mol.dmy ” at,25°C. 5 _¢ 14 Bees Thus Kw = (10 10°") mol, "dm, = 10 mol,” dm, A solution containing [u* | greater than 1077 mol. dm.~? is acidic, A solution contajning "H* | 1ess than 1077 mol. dm.~2-is alkaline. At neutrality [H* ana lon” are equal. However much [H"] and |.0F are altered by the addition of acid or alkali, Kw remains constant at constant temp, but it varies with temperature. Hydrogen Ion Concentration and pH In describing the acidity.or alkalinity of a solution it is,gufficient to give! H* ! only since {OH i can be deduced from | on J = (at 25°C) In view of the large variation in [H*) it is convenient |fi*! to express it on a log, scale, The one suggested by Sorensen in 1909 is now in general use. The negative logarithm to the base 10 of the H* ion conc,(mol.dm.~ is called the pH of a soln, BD a eoy 1 fat] = 107PH ieeipt ='-tee,o ]" sadaeyg chy. snale'] = 10 = egs1 The conc. of H* ions in two solns, are (a) 1% 107? mol.dm,~ and 3 (b)5*107!° motsam.~9, what is the pH of each soln? (a) pH = 3 ()pH = 9.3 og. 2 A'soln, has a pH of 4.1 ans. H” ion conc, = 8x10’ Yhat is ity H* ion cone? nol.dm,-~, Hydrogen ion conc. of a soln, may be found in various ways. Yor a weak electrolyte it can be calculated from“as determined from the conduct- ivity ratio or the van't Hoff factor, It can also be deduced by a comp- arative colorimotric method, pH can be found by measuring the potential difference developed when a glass electrode and a standard electrode are in contact with the soln.(principle of pif meter). The Hydrolysis of Saits. a Consider a salt MA*dissociating completely in aqueous soln, asfoliows, ‘The position of equilibrium in the above depends on the strengths of MOH and FA, If KA is the salt of a strong acid/weak base (NH,CL) then an acid soin, results as HA is fully dissociated but MOH is énly: partially dissociated. : Hydrolysis can be regarded as the opposite process to neutralisation:- * neutralisation Acid + Bage— Salt + Vater = hydrolysis ‘The Common ion Effect If a strong electrolyte is added to a soln. of a weak electrolyte, so chosen such “that one of tite ions into which it dissociates is the same as one from the strong electrolyte, the degree of dissociation of the weak electrolyte i8 decreased as a result of the common ion effect. eg. Consider a sat, soln, of HS, Ignoring the ‘two stage dissociation we can éxpress the dissociatiof as:— 3 £ HS 22H" + s7 So thus 5 = fet] is= | : 1S ad i et (const. temp.) Ti . pes If a strong acid,HC1, is now added to the soln. the conc.,of H* is greatly. increased, thus:- fie) He1-) E* + cl” . Thus H* and S” combine so° that equals K, ¢ ; 80 the conc, of S ions decrease, The value of [H, iy : : relatively large and shows only little % change, thus the 4s approximately constant, Thus [s~] is approx.< and a 10 fold increase in 'H*' reduces |S” ! to 1/100 of its original value, The common ion effect is not limited to cases where the dissociation of the weak olectrolyte is decreased, cg. if NH,OH soln, is added to e saturated soln, of H,S, removal of H” ions by cémbining with OH ions from the Ni,0H cause8 the HS to dissociate more, This is made use of in systematic qualitative afialysis to separate the metals into various groups. NB:~ When HCl gas is bubbled into a nearly sat, soln. of NeCl, salt precipitates out,Is it the common ion effect? HEr gas will do the same as the HC1 gas-thus not wholly the common ion effect. when these very soluble gases dissolve and dissociate,a substantial no, of water mole- cules are used for hydrating the resulting ions, thus the effective conc. of the NaCl is i::creased and so salt is precipitated, Consider an aqueous soln, of a weak acid HA ref, hurray pe. 41 HA 2 He 0) eee Oe = * A cof) Tar Ka(acidity constant) = ES? zl & J (ha H,0}is considered constent because it is in large excess. ‘utting ino hs [i] ee [el Boel Similarly, for aqueous solns, of a weak base B, we havet- se + = A és ree B #80 2— BHY “+ “oH aw} for} _ facaaj fone Kb = Gy Bas¢j Ka x kb = (B4 fon 107! mo1.4am-=° at 25°C--the Jonie prdduct oF water, Ka”and Kb are usually represented in their logerithmic forms, pKa = -log,oiiay pb = -log, okb, hence pila + pkb = 14 the lower the pKa value, the more acidic. ELECTRODE POTENTIALS If a picce of metal is placed in a soln, of its ions, a potential diff erence is sect up between the metal and its solution, This potential difference is called the Zlectrode votential of the metal. oS Guexod - bon, of cu** ions The negatively charged Zn rod attracts an atmosphere of positively charged zinc ions round it to form an electrical double-layer, @n(s)=2 2n**(aq.) + 20 The threo principal factors affecting the position of equilibrium above are: 1) The nature of the electrode, 2) The concentration of the metal ions in tne solution, 3) The temperature of the system. The electrode potential of a metal/metal ion system cannot be measured directly because another electrode is needed to complete the circuit and will have an electrode potential of its owm, ‘tho standard electrode potential of hydrogen is taken as standard and is given the value of zero, Thus the standard electrode potential of any other element is then expressed in terms of the potential difference(in volts) oxi Gia beteesi 4 ts 61666SG0n hudsat ativan Bybbisen ea wetrede, pe Standard electrode potentials are when‘the element is in contact with @ Molar soln, of its ions at 25°C. When elements are arranged in order of their standard electrode potentials, the resulting list is i:nown as the electroctemical series. The equilibrium existing between an element and its ions, eg. reduction wet 4 2e—— saat is a redox system, o®idation The électrochemical series is part of.a much larger reduction-oxidation series called the Redox Series obtained by tabulating standard redox potentials, Redox Series(Standard redox potentials at 25°C | Oxidised form Reduced form Ee/v a Ne i -3.04 = ae increasing K* + e ——« 2.92 power of red- 7 24 5 s uced form as ns + 20 an 0.76 a reducing sn** + 20° Sn -0.14 foe eH oe Hy 0.00 e é sn'* + 26 sn** 40.15 dnereasing Cu** + 207 cu 40.34 ‘power of oxi- - - \@ised formas 2, + 26 oa Ses lan oxidising Fre’* + 6 Fe? 40.77 BSGE Bry + 26 Se 28r- +1,07 ae tasNereas Mno, + Wit + he + 2H,0 44.23 Gigante wee 3+. TH,0 41.33 2a s at : Clg + 26 201 41.36 "a at = WH, Moo, + SET 4 5a + 4HLO +152 ee oe 42,87 5, Sa In theory any reagent on the right will reduce any,gne on the left provided the latter is below it in the series, Thus Pe** ions reduce bromine to-Br=, but not iodine to I, Conversely, any reagent on the left will theoretically oxidise any one on the right provided the latter is above it in the series, Thus an acidified soln, of potassium permanganate, but not dichromate, will oxidise C1 ions to chlorine. Two points to note 1) The series is of standard redox potentials so if concentrations and temperatures differ, the order of the systems may differ. 2) The above gives.no indication of rat 2 "Standard Electric Cell Po Bsk.P, of Blectrochemical Celis. The Daniell cell consists of a Zn plate(cathode) in a solution of zinc sulphate and a Cu plate(anode) in a solution of copper(11) sulphate, the tvo solutions being separatec by @ porous partition, n_of flow of current er (11) sulphate soln, porous partition The current({not electrons) flows from the copper plate to the zinc plate in the external circuit, The process is accompanied by an inerease in concentration of the zinc sulphate soln, due to the dissolving of the zinc plate and the diffusing of sulphate(Vi) ions from the copper(11) sulphate(V1) soin., the latter becoming less con- centrated, with copper being deposited on the copper plato, The e,m.f, of the above cell is 1,10V. denoted by B, The standard e.m,f, of the cell is conventionally obtained by subtracting the standard electrode potential of the negative electrode(one on the left hand side le. oxidised state) from the standard electrode potential of the positive electrode\one on the right hand side ic, reduced stete). For the Daniell Cell:- Zn(s) an®*(aq) | cu**(eq) |cu(s) cathode i" anode ° e oxidised state Thus ae ‘cathode =e ‘hs = (40,34) - (-0.76) Vv = +1, 10V The sign of E is always the same as that of the rhs electrode in the cell diagram, a SOLUBILITY PRODUCT 1 . -Wa.can-determine- the conditions for precipitation-by-applying the law © avs edtion te the equilibrium that exists between a sparingly uble salt in*the solid state and its dons in solution, ce with an excess ‘af undissd\Wed solia at constant temperaturet-— MA(so1id) ==> asider a saturate3icolution of a binary electrolyte MA in contact mass ‘action and taking the cones, of individual Applying thd lew 4: dons as their active ood [Ea solid) But the active mass of any solid is constant at constant temp, = constant, therefore, [wt][f7] = constant = S.P.y,,the SOLUBILITY PRODUCT of the salt MA at that sear, a re pees Sel far x10713 = 6. 8.7 “hag =(bs‘T rd 4x107'3 mol, am. se eR Ag Seas GOP OP se of S.P. is that it indicates the maximum value of =a eolution.In an unsaturated solution, the domic pro oduct duct #21 have a lover value.S.P. can be applied to sparingly soluble lectrolytes only because in these cases only are ionic cones, suffic- to be teken as their active masses,Thus S.P%. are always very ao? S.P. vories with temp,, the latter always than 25°C, “9 of ae if ats sat, soln, contains 1.6 x 107 3g.dm.~ 3565 3 eGK1O mor.am. 9 75.3 Solubility of Ago seni? mol.dm,~> "10 mon,? am,"© at 20 c. SoP. “Dae Ter. Application of SP, to Qualitative Analysis iver chloride,mercury(1)chloride,and lead chloride at 15°C ars 1.2x107'°p017am, "©, 2.5x107'8mo1.2am.~*, 2,0 10~moid ams? eit Group 1 S.P respectively, T any of chese 3 metals are ‘present in the solution wi HCL is cet they will be precipitated as their chlorides because exceeded, S.P, of lead chloride increases with temp. 1 Soln, must be cooled before proceeding to ep. 11. ne pegoipttating agent is HS in the presenceof Hol. HoL suppresoes the S*7 gon cone, from bout: 1077362, dm, “3(its value ina F ‘sonuptitrty propuor ~~ 2" 84> a a ‘Since the-conc, saturated-soln, at'room temp.) to about 10”°°mol. dm, of metal ions:in gp: 11 “solns. wiil be about 107'mol, dm.7~3, only - the least soluble ‘sulphides with S.P, below 10776 wiil be pptd, The others will remain in soln.Thué ‘suipiiddes of Bi (1077?) ,He(11) (10754), ou(10745) ,ca(10729) ,Pb(10729),Sn(10728) appear in this gp, whereas those ‘of Ni (1072"), 2zn(10723) ;o(10727) and Nn(107') do not. This enables us to limit gp. 11 to 7or8 metals. If the cone, of HCL is too high, then dissociation of H,S may be suppressed to such an extent that even Pb,Cd,Sn, culphides may not be pptd, in this gp, Thus,after treatment with H,S,the gp. soln, should be diluted and tested again before going to ep. 111. Group i11 Hee the precipitating agent is NH,OK in the presence of @ high conc, of NH, Cl. The latter suppresses the conc, of OH” ions, thus the S.P. of more soluble hydroxides are not exceeded and their ppts. do not occur. S.P. of ‘Gry-A1; F6(111) hydroxides are low(1072°, 10739 410739) respectively. These 3 arb’ completely pptd. as their hydroxides. Group ZV a ‘The precipitating dgent here is either HS in the presence of NEJOK soin, or is ammonium.sulphide soln, In either case, the conc. of S*"ion ———an-soin,is high and those metals with insoluble sulphides which escaped ppin, in gp, II (Ni,Co,Zn,Nn) wiil-be pptd, here. Group ¥ = / ‘The precipitating agent here is ammonium carbonate, jhich gives @ high conc, of oa ion in soln, and brings about the complete pptn. of the carbonates of Ca,Sr,Ba,which have solubility products of 107°,1079, #167? respectively. bility of Salts of Weak Acids in Strong Acids It is an experimental fact that salts of weak acids are much more sol- uble in a soln, of a strong. acid than in water,Calcium phosphate is only sparingly-solnuble in water at room temp,,yet dissolves freely in dil. HCl.This can be explained by considering the equilibria existing in the soln.When solid calcium phosphate is added to water,we have;- Cas(PO, )gso1id e300 + 2P0p7 vara Loa TfO,2T* = 8.2006, (rj) 2 10°27 also HOP H* 5 on ; Under these circumstances, very little conbination af w* ana Pop” takes Place, because the expression CH") CP02 J soon attains the value , CRSP, T } a: sormesponding /to- Ky 9, HPO, 23H" + Pog 5 a a: ~~ Sowshien sha sbi toneadedy HO oe cry vaiaing-the-come.-of-H* ape paar eee a inten ca uecsp ial ons) eodicorg ions to wute in large nos, to form undissociated molecules of HyP0,,, 50 that uno expression Lit) [P02] is restored to ite original low value of . TasPoct Xu,P0,,- Im the process the cone, of Pop" ions is reduced to such a low 3a that the iconic product of. Ca, 13 (PO), 2 falls well below its S.P. causing more of the solid calcium arenes to dissolve.The interaction Rests the varicus equilibria continues until a high cone. of ortho- phosphoric acid molecules exists in soln, and much of the solid calcium “phosphate. has gone into soln, _ fe Thus the overall effect 6@ thé-HC1_is to suppress the already smali dissociation cf the weak orthophosphoric acid-by.means of the common jon effect and thereby to lower, the ‘cone, of PO?” ions in.the soln, eo that more of the salt dissolves. A similar explanation applies to the solubility of ‘salts of other weak acids,eg. oxalates and tartrates. *‘ryprcaTors Au indicator for acid/alk.li titrations is a substance showing different colours when the pifef its environment alters.It is usually-a weak organic acid or base and can be regarded simply as a substance which dissuciates thus:- AG ee eA * golour 1 colour 2 by Le Chatelier, in strongly acidic Soins., coléur 1 predyminates,and low cones. of H” colour 2 predominates. Indicators are weak electree ytes,varying greatly vheir dissociation constants, which means that they ohange colour over widely’ different bands of pe. _ : - . — ——- rine in aes eae > ce LOR gellow ted \lue phe asl Whalen es red H* ion conc, of the centre-pt. of each range is calculated from the walue of the dissociation constant, since CW BNE elae Duel ‘ind. Ceti = Rind ad so Se +e Ato-the-cemtre- Gistilled water is, alkaline to methyl orange(K,,4 = 2 10 moi.dms>) de. pH 3.7 ) PHT acid to phenol phthalein(K,.4 = 2 1071mo1.am7>) pH 9.7 neutral to 1itmus(K,,4 = 1077mo1.amy Titration Curves 1)Strong Acid/Strong Alkali If wo start with 50cm? of 0,1M HC1 and run in 0.1M NaOH, the results aze as below: 4 Volume 0, iM alkali acded(ez?) Be at E25 my i 2.3 ne QT 3.0 fe eS. 4, 49.95. 43 oe 50,00 7 50,05 967 50.1 10 51.0 " 55.0 Tis? 2)Weak Acid/Striam Alice eg. acetic acid titrated with sodium hydroxide soln, 3)Strong Acid/Veak Alkali eg. Hydrochloric acid titrated with ammonium hydroxide soln. Titration cucves cen be constructed for the titration of acid with alkali and are as shown below. at weak acd |strong, alk a . : Ze ckvong aed [strong ak ' : 2 cc wae -tttongacillwedleatt 5 6f--.-------- gS t : ~ 4 T