& CHAPTER1 THERMODYNAMICS OF ELECTROLYTES CONTENTS &WHAT IS ELECTROLYTE ty ee ee peso on oc en hr oy nr © en roe ELECTROLYTE SOLUTIONS oy i compostens cavern a enge {Con tow te aetcy caren 0 pass Soh con arp an “The sal in its slid ste or in the crystal stuctre are hed in & 3D ‘by very strong lone bonds, abd not remo free fons, they’ afte in the late structure ‘broken, and thus ions are free to move and more mobile > presence pees Tote nw mow nd ced cy offre ios. see noe : ELECTRO- ELECTROLYTE DISSOCIATION ‘SOLUTION Vigor Pressure Lowering ‘Osmotic Presa Dinan of cero prem Peter seat or cat mats nie compounds to generation Hos Beciel eonaor Cae arty oot nporsoutnerwaers wv patngrece pen eoDISSOCIATION a + Strong electrolyte soc oahy Hehay-+ Hg * Chay ELECTRO- DISSOCIATION (DISSOCIATION), A,B, VAP + BE + Weak elect: disor Dissociation constant Ky CH.COOH,, © CH,C00+ Hn, ‘monn cancntaton rs Hot dsocsted moked ot the tol dssted molec octae VAN'T HOFF FACTOR 5 ‘The vant Hof factor (the ratio of mele of paris in slution 1 ‘moles of formula wits dsoved les of pares ia solution ioe of formu nits disoed AT, = in % Kesing poi desicn) AM, = in x Ky ong pit evan) IMRT (smote pressure)ENG; DISSOCIATION Sea ABO VAT TYE: me cCrwnat the vayt Hot actor () for CaCl, ats concentration ow does i compare to the expected vaue of? THE RELATIVE PERMITTIVITY EFFECT OF SOLVENT ON IONIC DISSOCIATION ae, a a ng: Rd trey = CH,COOH agus ammonia > + Met (on) saan of benzene; hexane > ror-slctsh LUct Is a strong estoy in water ‘one nate of cent ax eo ‘buta weak letrotte i propane, (pert of te es «) OF THE MEDIUM +The relative poritvty can have a very significant fect on he sSrength ofthe mteractons between fons in slo, eau pasty oe mada (Ue el: ent Bot Gp) ‘gue gente. inTHE RELATIVE PERMITTIVITY “The ete purity ols sae pe ie ‘ola ep My puma. STATIC ELECTRICAL FORCE BETWEEN 2 IONS =e saticlercattone f= 52 (Coulomb law) +a a: charge of oppose ons “Note:The intescton (physcalchemical) beeen the solvent ‘and the electroite may ex SOLVATION/ HYDRATION & > imaracton soviet fom late stabs complex (ovation). ‘Sober: 10> nyeraon > Number of at moan he comple: oa. > For aga soos of tala! ig earth on: ome he n= ‘ates morass which doped on Ton eleetcal charge, lon radus, Sid ion weight SOLVATION/ HYDRATION £ ot pom Pee 0. 8: Hey” ge 938? tamer FQPa © «a3SOLVATION/ HYDRATION > Neartyieaionayrcorimasontont gg By (Stores eoneraie 9 SER > Farydaton yer weaksaiceecres Jy ay @ form else uretale, > ° ‘Solvation’ hydration 2 ate see net ~Bi ge ane? Ses etn (renkcpomeal os) * ror : inte acter 270 pn =f fo a ae Source (veo £6, S Pau, nd. Doser (1997) Classification of electrolytes 1. Stong! weak! non eletaytes: depen ono" 2 Tl pte ct: ped on eae tes foncninne mance en Tw ebstotytes: oni bond ~ x: HaCl, KCI, Cu€0,, Potential electrolytes: other bonds: ex: HCl, CH,COOK, Non- polar Polar polar aprotic protic solvents solvents solvents —_—_ Increase polarity - Proti solvents H" donor, form hyéroger- bond berween solvent solute (ectcytes) can delve! iocheel sohats to frm ons (FO.ecurol butanol.) ~ Aprotie solvents have commen & pairs cn solvate cation to form ons slutons (Acetone, Acetonitrile.)CHEMICAL POTENTIAL OF IONS Ay @). Gees) say eye Rha, 2 Ram, + RTI + Rha 2 4 Rom. + Rim ee ACTIVITY & RELATIVE EXPRESSIONS & erent setananr™ wet Qeerere tora RESIDUAL CHEMICAL-POTENTIAL bo he= RTM, Reason: Difference in interaction of ion ~ fon, ion ~ solvent, solvent ~ solvent =e "Vor ted slo Dterences are not sigifantDETERMINATION OF 7, BY EXPERIMENTAL METHODS IONIC STRENGTH (1) oa + For sohtons wi con 02 fons (1 anon, cat) (READ TEXTBOOK} Ty auetz4 m2) E= 13629) wnt de ay tnt) (Chthe ml cncrzaton (mses fk 1 Iter oslo) ‘What happen tol? eo Tonic strength (1) Tq, = 1/2.5(m,22) +Increase ion concentrations? *Increase ion charges? LEWIS-RANDALL EMPIRICAL LAW | SREOfien env cow coneennarony Extended Debye-Huckel equation & For H,0 solvent at 25°C: yea = (<0.1) 44(2296V1) (Second equation) 2 (nya of he hydrated on 0509 22, Tra2san *%! (1<0.5) «experimental constant _(hird equation) Ig Activity coefficient of fon in. hey, =-4z7i.] solutons: For H,0 solvent at 25 Ig7, =-0.509.Z) sso Ue Dt hw Correct for diute aqua solutions (C < 00 M: I= 0.01-0.03) and 1 eecrofes > 7, = 7,‘of onie activity coaficints: 7, OMA, OMe HAP HER ign = ver. +h => let * vl wey te s ter, fen eZ IZ fen ez Ze ForHOsoWert t 25°C: A=A'= 050% eats Mean of one activity coetilents: 7, ForH,Osohent at 25°C: gy. =-05091Z,Z 1] fen eZee oom | o5m | asst | oan | ao ter | ow | eos | osm | a3er ‘Mean of onic activity coufcims:, za (1<0.5) for estimation of y.+ Equlbcur constants + pH calculation + onic activity soeicient in solations containing many ions ee ‘owen ean) ase ‘stmt mae cate an mei aca * Conductor: nasa ond lactic engineer, «conductors ‘an cect or yoo ofmateral thal allows be Row af chara lec ‘men lone ormore drectons 7? Bea =: ‘lectrayte soliton orletELECTRICAL CONDUCTORS. oa + Tip mtn tec eect ann by evo role ‘ype ener mts tcc ‘anor enaon ane ELECTRICAL CONDUCTIVITY OF SOLUTION ingly + Conduct spciceondctnce,letic! conduct) of on eects sont ‘ows lem i's eames shy 16 aed eee. — Seen oy amigo eee a. eceote es Berl > — ia eo a anne ‘earone sec ordnen ‘ates {sae Tot lfm) i server conven pras| on ‘a Fe SFO ee 2HjO+ 16 34,4208 a K con-atoceoiea| Parafin 10% = . Tt CONDUCTANCE (3) & a Ma CONDE airy ore sia eee erated eae eae isaac reosance is xeon om, conan oSampe i exes ‘Te eoprocal on ud be cae eho, ut sol desgatan snow he ‘aang andinceses ws eesti aes A). (arte entsy Um te fcontcan ate ‘etme te oe conc, "The conductivity ofa scion depends on “he mumbe of on reson ow + te number aos nthe Slaton might not be preportonal oh lect 1 ect one ntact story wih one ates, the iememamtmea | eanaucuty of & soon 1 not enacty eecarketnaareiwte, propanol he nunber of ene presiWook lcs Low cone Range fw deraty on evs x= f(T) r= Yas [1 o(T-25) + BT-25)71 Empiialematon p= 0.0169 (o-0.0174) ty: lca condutly @T*C and 256 «fi: cana (depend on elect sles) Coa EQUIVALENT CONDUCTIVITY (2) — Euivalene condctity Conducviy| ‘fa yume conan aunt (alt ‘Saino Botwean 02 ft paral same 1000.7 gremtegt A= 1000-2 ic) ceaee : equivalent concentration (20.1), . Lome oe Aw cones ‘STRONG ELECTROLYTE SO.UTIONS. (KOHLRAUSCH'S LAW) Ag = Ay Kel? ‘syst ht nt th Sd ote Soros sie as& WEAK ELECTROLYTES. Kohirauseh’s law Set get man ARS VATA, Calan a iting mater conduct of aC), stton a 28 1272+ 27.63) msm mot'= 27.96 mS. mmol aa GK 7 Ostwala's dilution taw ii ELECTRICAL CONDUCTANCE + tt se gen cetmmecinniydainemind | Zet E ae ELECTRICAL CONDUCTANCE + Equivalent of can anion anspor YaSal gy Sac 1000 ogg through area $ (me) forts: Tota quently o elect () kenaported by cations, anions trough 8 of area (em) for 1 + Ohm's tw + Hence,MOBILITY & MOLAR CONDUCTIVITY, fy MOBILITY OF H* & OH" “The stun sein th lint of zoo corcantaion (when a i vy ih coping wh there ae no terion introns) rts aD A Cg) H.) MODI of ean & aion = | gee 2: Sena tcaton & anon Aan ee ene reece tat H naor ranspotnaga [HE | 368 : soins eewing eh mechanism 205 iy hn store | nc nod = Aastha Ulin einen on nos nga + bao Ho olga 79 Note: (acids) > 2. (bases) >> 2. (salts) d+ 8 > bend a Method for measurement a Electrical conductivity vs. solvent Ry Senate ae & Solvent | Relative | iz, = Using Whesstone dye permitvy | 2, Wired RRR Oy mo I a4 + (1) using conductivity meter: HON) 3a w7 cHor | 38 m2 5 goa [ms if it Uf eryot | 382 40 (ene | 4 oot & 7 ° xApplications Detain eer eat fr ay prcess + Inendyteal chem: lect! conuctly anys Electrical conductivity anelysis Pancine: ‘Due tc the especialy hgh conducity of H* and ‘OF the equivalent volume can be recognized, TRANSPORT NUMBER + The transport number, detned asthe faction of teal eurent cated by th on fa spect ype. ‘cy. axes stl on [oar] orTRANSPORT NUMBER ‘The limiting transport number." is dined in the same way but forthe mit ofzere concentration ofthe dectralyte solution HITTORF’S METHOD FOR a DETERMINAON OF TRANSPORT NUMBER: anc dann vatheconaniaonchngln nce nd cote ee Eco kor rane coer et oa] “Ta Tan = END