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    Ionic Equilibrium

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    Ionic Equilibrium

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    Ionic Equilibrium

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    Ut lonic Equilibria in Aqueous Solutions chemical equilibria In tonic equilibvs, te eslewlaton for concentrations of the dissolved substances from the esilibrium constant expresions is heguently canon oe by the use of valid approximations which isnot a comanOn preckes ie chemical equilibriun (Chapter 3) Such approximations become nectar te «ase the business of solving problems asthe systems generally pase theoegh simultaneous equilibrium reactions. The appronimations carried out can be verified by the exact treatment of ionic equlloria by considering the mater or smass balance and charge balance equston in addition to equilibrium constant expressions. In chemical equilibrium, we usd th equlitium constant both in termsol Ky and Kz but ‘here, in ionic equilib, only Ke is used in citioest terminologies. For example, acd disorston,conetant (K,). and. bese dissociation constant (Ky) for weak acs and weak bases roopectively, fone product of water (Kyy)in selfionisation of water and hydrolysis constant (Ry) hydrolysis of salts areal different forms ofthe equilbriu constant, K Hence, like K,, each of them depends only on temperature ‘There are various types of ionicequlibrinin aqueous solutions but most of them involve acids and bases. So we need to know frst how do the acids and the bases behave, 6 ACIDS AND Bases arene sn ‘yt wroup and produces OW hone Inangeoarecetng tg Rie wales fetaion HO" fort ncuallyreprncna "canes ho ease runberof water molecules, However, inviting tana! ctnoal neon, thenetation HO" fsimply epresnted ar a) because thereon later demical equations with extamclenen water Bransted-Lowry Concept Bose onthe fact that H” exists as HO" in agacous solos appt he lat abroad view of acids and bases than alot by the Acrharte coe ‘Seecesany Bronsted and Lowry presented loge exerion nthe Aer conceptof acids and bases. species having a tendency to secept or gains prt ne presence of water of bayer protonic solvent. Acording to Brod and Lowy ie mow reine Totapeesnt the dissociation of HA ae sates han HA eH Thus, a substance act as an acid only nthe presence fabase and acts ‘se aly inthe presence ofan aid. HA donates 3 proton to HyO since HA ts anacd, and HO is a base as it accepts te proton. For the reverse reaction, yO" and A~ acts an acid and a base respectively Since HA and A and also (Bronsted Lowry), + ethan 14y9" and HO. dilfor only by a protons th got an He Suter ly BY 9 roto, they ae led cng ac-base gate acid-base panne HICO5~COs", CHsCOOH-CH,COO™ “and Nit [ily An acid-base reaciion isthe wane af proton noosa “Ths there sa relationship between an acd and bse songerthenta aoe ‘siteconjgate bate and vie versa, —— Let us now see how the Bronsted-Lowry concept of ais an sen grater scope ban the Atheros concept. ae 1, According to Bronsted and Lowry, a bas is ay species that accepts roto; Arshenius says, OF ions the ony example of abse 2 Acids and bases ean be in molecu form an alsin ok form. 3. Some species can behave either as an aid ora bate depending on the tate othe other seactant oclven) |. Acd-base reactions are not retriced to aqueous elution cy Relative strengths f ocide and bates ‘According tothe Brensted-Lovrry concept th sent of nade governed ‘yt tendency to transfers proton to's mois of sven Surly, te Sltenginofe base is govesned by ts tendency to accept» proton oma slven More ceuly. te strength of tn acid depends botivon tne tendency ofthe ao [Mara protonandthatof the salvent to accept that proton. Snay the tenth tia bgedapend both on ts tendency tosccept proton and that ofthe solvent tw donate that proton. ° strong odds ond strong bares _ The acids such 5 HCL Hi 804, HNOs ad MGou aqueous medium dissodate completely becsure both te tendency of thse cede oloee a proton and that of the solvent watercecle to ecept thst * Moton are very sung, These acids are thus termed a tong acd ad Neer rane sung in water (Leveling effec), tet srengis cannot be vg agueous medium. However, ve acd ean na est co Og: whch has a ch Tess tendency tacept proton than such 35 Soe Spealed.stcong acids would dsp pasty to afferent rates te cosines atrengihe may be compared 1 interesting t0 note tat ete pave as eon acids in water and as weak ais in acetic 2 wm “The solvent pays the sn cle in dang the ote srergs of bse slo inthe sre way and lve we ae png ‘de dcuanon on the vole of solvent inte coo buses ‘Asin be Breated-Lowry concept the solvent sally water ow foes our dacsion on th elative steno wank cde and wea ssn queen Weok ods and weok bores Une he song asin water ics a Ide ete, tre are substances sich ss sete a ome add and hydrofluse aid which dsocate partly in water Such subiners ae ‘own 5 weak acd. Serlary, he substances, such ammonia danse ad imiduzol nie, having much laser tendency tan he tg oes to tect poton donated bythe ooivent wate, ace hnwnas weak es Hence, {be retve sng ofthe weak ace and week tows be enue 1 the ease of wen ade, say HE, the Sid srngh i ven by ald ein const Ry BPS HO o +r a) gh the ale of Ky higher i he aod sang Inthe ese of weak nes Ny tease stent shown noo mae ‘Acorn th Brat Lowry cancer Niy+ He Mi + OFF NMHO8") DONO to Stn > (Greate Lowey) -tocod ere base constant and not bie issocatn constant However acing to the Ahenis conepteeson septa a socio of HOH: NHLOH = NH «HF (anes), Modern Approach te Mya Cie Yt pce pect Wate i sdf amp ‘san both donate and accept protons, avon 64 snd 631201 nt nd see etre 404 seat pun > Ka ‘Tne because proton in sleaned mare edly by an aid molecule than 2 sinegatve fon. Thus protons ere mainly produced in the fist step of ‘dascation ofa polyprotieacid Proton concentatin centatbuted By the second ‘dition in therefore often neglected in the edation of foal proton ‘oncentetion in an aqueous solution os plyprotc ci In fhe case of 54055 sidnuch a HS0,, the ret diseociatoniralmost complet and ence H;50, is 2 song acid but ISO isa weak ai ‘Note (1) The values of Ky for strong aie are ot iste fa Table 6: 2 thet reactions with water do no tan equllcum in practic sense Such ‘cide undergo almost complete divacaon and their Ky values are ‘xttemely high On the sume grounds the values of trong Bases have ‘Also not Been inched in Tab 2. om Maer go he Chany Ve (2) Fora poypot i nly eit dado co strength of the aad at Ryo Say, for tase WH ny ‘rotors i mult-p ote akan canta Ry ves step Slthebere an oo hee ae Lets consider weakly, HA fr which weave he equi Lora, were Cis the nil concentration of HA and is degree of ds ‘Applying the lw of masacon we have nessa x, 25°C, Ky >1.0010" and py <1, and at T<25 °C, Ky <1.0%10" and py >. Hence, both pH and pOH can be even grester than 14 but the maxinnm value of py is 14 at 25 C. However, pkiy cn be greater than or ler than i temperature is less or greater than 25 °C respectively. BUMPLES Calculate the pH ofthe following aqueous saltions at 25°C. @ 10x10 MHCL GLI MCH;COOH K,(CHjCOOH)= 1810" r" Ts HCI = HO") 20-10, Inthe presence of HCL te dato 10s upped by ‘he crs ie 30" da w Hf wl Reto oe ‘ey smal ac cn be rghead companion 10 (9 CAACOOH iw weak ce (10 de dinoltion of CHS cOOH canto caeunes ty ei ae 7 SOO Ho weH,600"+ 1,0" hee tthe dere of donate sco ky -IGRcoo wo Tesco rare = oe a= PEE = gaeeto? ane Via . THO"1= 10.107 a = o.6? x00 = 424-10-4 PH = log H,0"}= eg tater 2AM alae he pH of 210-10? M50 sn ng Sotuion 1 S04)= 10-107 THj071= 20.10 Mt tog (20%30°) MENS NaOitanchange tts pltby one eit ‘ion Wel calculate the plo 00 MNGOH, NOH = [OH] = O001= 10510" A POH ~1og OF" plea RoghOt = M=10=-410H-1 = NOH = 19510-W Wino niole =m mV ea) of NAOT imimeltet ear nt natant 801-001 Non = C01 Boon ne Te ) su, (0080.00 es Coe or P2818 mt vollme of HCI added = 438 mt. EXAMPLE 12 Calcot the pH of 3.0120" Solution {HICH} = #150") 1010-2 4 INoOF= [OHI ~ 3.0% 10-2 04 lower than those produced by the eelelonsaion of water tats, EXAMPLES What Ic the pit of # 10%10°° M solution of ‘NAOH at 257 Solution For a solution having a very low concentration of OH” ons, we cannot neglect the OH concentration due tothe dissociation of water. Let us first ealculate [OH™] due to wate in the presence of 1010" MNaOH. Let it be + M. HO + H,0 #0" + OHM ee e.o0 dram nso) Ky = (Hs0°UOH7] by using Equation 612 or 10x10" = 2-(24 (1.010%) or x=95<10"9M ‘Thus, POH = ~log [OH] = —log 2.510% 1010) or pOH= 698. pH = 14-698-702 tan lian Aqueous Soins WosHOe HO", vole CO rete = 4g9" HOH Pits og HyO"b= log (95 10°" + 1.0-10°%) or piwame. ett te tg Te us cae the lt (as we did in the cate of CH3COOH (Game) stuming GHeOF asthe oly source of Hy fons. Initially, aaa? : : GiHJOH + HO = CyHO" + H50" 1, eIGHRONIHQO") _ 2.010% + euOHT zo=107 oe anto =20%10%a? or an 25sa30°, [H4j0"]= 20.20 x@55~10")= S210 M. pH =p 6104) = 73. But pH of a acd caret be greater than 7 and hence hs vale of PH not valid TRisinomect result isd to the very dilute sauton of avery weakacd (very love K, value)-To calculate pH corset we ‘Should not follow the method adopted for CHyCOOH. ‘We see that [H,0"] calculated is comparable to [Hy0°I produced by the disocton of HO. So we have to consider the fllowing qlibria exiting simeltaneousl. GAWOH +10 CHO” = Kyo" and H,0+#1,0 2 Hy0" + OH” respectively ategliiam: SABE AMON ag For thes eqn, we have IGMOMNO ys A TGROHT 300% ran0 2, Toa sys 26s) » ‘Alco Ay =[F1j0°HOH"]= 1010"! or nes10s10" C ‘There are three unimown quantities and two equations. We segues thd eyaton to lve these and oo Sl ae oS. ig ne Scent nth conavon of chon HO") = 684061087 ee reyes iS Now:eetisingy rm a= om in. we et . - 110? M snd pH = “tog H30"1= ~log (1.121077) or pHa ass. Un charge balan, the total number of positive charge ina claton is ‘qual tothe lta numberof negative charges (lecrnestall)] BUFFER SOLUTIONS So far we have discussed aqueous solutions of pure weak acid and weak bases. ‘The acidities of euch solutions were lao determined. Now we goto deal with Ue solutions which contains weakacid and ts salt and alco a weakbase andi salt. These solutions are known as buffer solutions. ‘A buffer solution sess changein pH when a small amount ofan aid ora base is added toi Buffer solutions are very important in chemical and biological ystems. The [pH of blood plasma is maintained at about 74 by several bulfer system inthe Fody, the most important of which isthe HyCOy-HCOs system. There are many other uses of buffers in industry. Se sod iors ar propre ymin) [e400 5 went baw ade [ulfer Solution of @ Weak Aeid ond its Salt CSepenntnansrenr ogc ei at co warpage neg pend yw cnn nen che none Sig a ie aces satiety Thane Sos Soon cpt copra Siesoe a ee oe ieee anne taneee pe ee sepehicroryeanieemeereet soars: ass ee HCOOH + gr c,COO" = 140 CHCOo + Ho" + cH,COOH- H.0 cpa” Adaliuad “Thus, athe added acd or the bce ie intataneously removed the pol the bulfler solution doesnot hangs nts cic fer. CHsCOOM chee the pH from rising whereas CHjCOO” ches the PH tor aling pH of an addi butler solution ‘Lets consider the acdc bulfer CH, COOH-CH,COONa Forth equlibiam, CH,COOH+ H,0e CH,COO + Ho wehave, {rscooHH,0°7 (exjc00H) [At equilibria, the concentration may be denote 29 (cH MOL TEHCOOH ati {[CH,COOM aah (ex or OK gcoo Ke compas eels seo contin CHsCOON wih done mon mir of moles of CHyCOO™ lone ‘fee EHSCOOH may be supp te be Tn tome tone the denon eee AY Me por cnn CHCOO™ fon rom [CHSCOO ogra * [CHSCOON Equation 6.16 becomes “ UHs0°1 K, {COOH (GHSCOONste Denoting the inital concentrations ofthe aid snd sea and theslt as (Alana (5} wH01- x, 4) . . wi cox STE 16 salt should be the concentation of the ‘Taking log ofboth sides ofthe equation, log 0"I= og K+ tog SAD of “leg fH30"}= 10g, ~1og 14) ee or pHl=pk, + tog (SL bs BAL 18) Equation 6:18 called Hlenderson-Hassetbalch equation ‘As the salt and the acid are presentin the same volume ofthe solution, we can write Equation 6.18 a2 pk, + log BUMBEE of moles (or mullimoes) ofthe salt (o19) PH= PK +126 number of moles (or milimeles) ofthe ace ae ‘As the salt CHjCOONa dissociates almost completely, 50 ICHCOON] = [CH COO], Thus Equation 6:18 may also be written os = pk, +log CHSCOO. PH PKs +195 iCHigCOOH) ‘Amore general form of this equation is a conjugate base) (620) saa! (620) K+ log se Equation 6.8 show tat epota 0 myc an ation Hence pH of lle slaton an 2 nar of he mane se HSER Fc dy teal CH{COONS, aso the nt eee caution shall not consume each oer utter Solution of a Weak Base and Its Salt Leos now Znsider abasic bufer solution that contains» weak bast 298 LAI MTclin nearly equimolar amounts, This basi Du sane aa ic ble des in maintaiug constant an othe strong dacrolyte NHC] which dissociates almost completly, ge daatn of Ny exiting in water a» NHL,OHD is repressed consider ly Be dete on ele (NiEy + HigO == Ng + OFF) The commoncion Si sn may now be mspponed to contain the base NH alt SE it cad NIQj Crome are also present inthe olution but does no SEettig er a ns an anion of a Strong seid. Than in general,» butter ‘SiSson can be sepresened ae = ase-oalt or base-conjupate acid. The Base TaN Sf awit te acid aded andthe aid component reacts withthe tended. Nit, + HOT + NU +O + OD + NHLOH “Thus both H,0* and OH fons added are removed instantaneously from the solution a resultofwhich the pH remains TInthie Dani baler, [Nilychecks the pl fom falling whereas NIM checks the pH from Hsing. Hof @ borle butler solution. ‘rus considera basic bulfer solution NH(NHOH)-NHg For the equibsum N+ HOA NH + OFF SIO UNH) tales or (Orr ny Naa, Lots IN Jequitibeiam Mare Approch to Physi Chemis V1 In the prosence of» sto song lectrolyte NHYCI wie dso ‘completely to give the sue mer of mole of x ‘remains practically undlsoiaied, ISTH ENF NHL = INH lorry Ky SMa TNFa ey teas fs a. oo vez {51 (dent te il concentrations ofthe si (noc, {Tecmo of te aang lo) ante ae epee, Noe thera S/o} 2 etameas ther ca eC tb) POH = py + 10g Justas the strength ofboth an acid and bases expressed by PK, cry. the ‘basicity of basic butler solution i also expressed by pH. To get Equation 622 In terme ofp, let us real he following equation: PH pOH = pw spin Equation 63 PK + Ky = Pw se Equation 67 Substituting pOH from Equation 615 and. pK fom Equation 67 in Equation 622, we get : ) = PK, + (623 pH= pK, +108 {5 eo) Each of the Equations 621, 622 and 623 is known a Hendesee-Hascibald equation which, ke Equation 619, cn be represented as number of motes (or millimoles) of the base, pk, +log RUmbEE of moles (or milinces of he Bas, pH = pK +105 Sof mole (or mimo) ofthese 629 “The most general form ofthese equations is _{basel__— (62) PH=pKa * 195 [conjugate acd] as(S]= (NHC INH']= loonjugate acid of NHS} ae Egle Aqueous Slaton tect of Temperature on the pH of Buffers “rnp expression fr bles Hderson-Hssebalch equation conta the ey anon ws epeanotengrnte Hs eal ined bene chreceo Re change wh durging epee reparation of « Buller Solution with a Specific pH. bela arovpamapnianeneeene ne let ean ye eee ta ea Oe es talon com Equation 618-og SL wo from Ba a5 = oan yuation 62: og from Ea og 0 snd hence, pits PK. rust prepare bur sltion ofa requied pH, we work bacoward ‘est we choose mach a weakacid Uo preparing a aid llr or eae Cepteparnga bese lle) hone pe, value is love to de denied pH The ane vals of pond pk in Equntions 613 and 629 rac nd CEDRUS Sipcoecly. tt ect Ow aso (51/(Al for ac ater and Tai toltos tase ater Now wesan prepare teller sluion of deeply (Ringe alana thea cthrbaeandthesaltineaieusted oink ee foauriese The sqm egtns MeCs0y+ OHO" + HCOG: Ky 956-8 MgPOqe OHO" HHGPO, 7K, = 6910 HcOOKATjOe HO" + HCO Ky =12 «10 o wien conjgate pir wosld be the best choice For epning 2 Daler sada PGES" 0 Yoweeatee teeta meses Sottion —_() Wefintaiatetbe pK values RAH 04) = ~log OP RH POD = —1og (69 *107 manna at etc tro tc ee moons Buffer Capacity A good butler solution must contain appreciable amounts ofboth a weak acid and its salt ora weak base and its salt so tha they are abe to modify the effect of an added acid or a base. This isthe origin of the term buffer. The larger the amount the greater isthe buffering capacity, thats, the effectvends of butler solution to sexist a change in pH. Batfer capacity is defined as the number of moles ofthe sido when added tone litre of a buffer solution, changes is pH by ne unit. ‘The condition for maximum butfer capacity i thatthe rato [S]/(A] or [BY/IS] should be unity. A buffer solution generally lores its usefulness vehen ‘one component of the Buffer pair isles than about one-tenth ofthe other. Weak {Sas and thei salty are better nu buffers for pH <7 weak Bases anc helt sls sre better as bullers for PH > 7 AMPLE? The pil of bloodatream it maintained by «proper balance of H3COs and NaHCO concentrations, What volume of 5 M NaHICOs solution Should be mixed witha 10 ml sample of blood whichis2 Min FigCOs, in onde to maintain a pH of 74? K, for HCO in blood is78 «107 ,COs-HCO} isan acid buller. Let the volume of NaFICOy sation tobemixed be » mt. Solution es of {E05 = 2 voy Henderson Hiasebalch equson. PH Bs + en of ACOs Dplitercis a0") oe pOH = og (15107) + log gS (ore ye 19-30 ‘A023 g sample af an unknown bar is isolved in water and tated Sithals8ht 1c elation. Alter the aiion of 835 mothe aca ‘Bite ater the advan of 39.62 mL of HC WHY? ‘Letthe molar mass of the base be M. “otal numberof male of the base = 222, mm of HC added = 0.135 «1825 = 247 [Asthebace and the acid combine in 1:1 ratio,2.4772 mom of HCL shall ‘peblie24772 mom of the Bact produce 24772 mm of the sl “The solution snow a butfer of a weak base and its sat. We apply the expression Sy ine Fain 2p ‘Aes applying Equation 618, we have “tog Ks + tog eNotes pit tag 10°)» hog 232 oo | Scie eran taceatecsunakocpesaier ee | Ripeceereeet ae rtmnsacibton ictsoutchermn tose en a Ee nce ancora Sitted with sutable mamples as follows, CH,COOH-GM | HCadded | , [NAOH: use Equations 614 and 2 = 005M a3 and 29 =50M. ‘Now, on mixing bufers X and Yin equal volume the concentration NHAOH—GM_ | Hcladded | <<, |NHJOH—NHCt we Egon Of HHA remains same, that i 05M; but concentration of Na willbe NH,CL—CaM~ |_ {623 for bute theaverage of = and 2, Ths, forthe mixture ofthe buffers Sey [NMACH st ydtolysi, we lal~ 05M , [7 equation 4 0.05450 2M, >, [ML use Equation 613 "| ‘or many meso Neb eginae prepare eof AMPLE 22 Sout] cr hecor etic cea pafageeenrs | eign af Nec ones solution of HCN and NACN. Batti mportant vo note Dat es Jens than O01 mole of NSGN because HCl wth > OO mole il nt ps Se Eos asceneem enemies mes | moles of HCN and moles of NSCN = (08 PH = py + Ing olsen 85 = og (41 -10")og 20 , soles ofsat by using Equation 618 or tog 28! oF 196 aging O88 Taking ang, ag 77sn= 0008 Moles of HCI = 0.0088 mote perlite. “The dissociation constant of an aid HA at 25 °C is 1.34 x10" How lt ofthis acid should be added to onelitreofan {002 mol of this acid to obtain a buffer pH of the solution fthe amount of ‘mol and (i) 0028201? ‘many moles of aqueous solution conta Solution of pH4732 What willbe the TiC aed otis buffers () 001 mol 0.015: Let the amount of NaA added be x mol I eee ee by sing ean < ptt pe oc : tants 04 twats 0a oot~ 003M nese apn ation 9, ‘oat pile pK 1 (Sa oe pte “log (13010) +108 5 aed, twill combine with the whole ‘Sore mot of HA. Ths the zr ODIs) mol of the weak ipl of the solution. oe ps4. (4) When g1s mol of HC Sais mal of NAA proton aera coat nose Wwe gas ae [Bey = o0nsa = 0605 ~195410 = 6825 «10+ tog (6825 "10° eH or pH esa. ‘When 0.025 mo of His ade, the whole of 0.015 mol of NAA «ay nos with O15 molof HCL, and 0.01 mol (0.025 ~ 0.015) of he 001 MHI determines the pH of the HCI remains. Here solution. pH =-log(000)=2 Modem Appronh Py Cems Vet 1 HYDROUSIs: acio-eas 2 PROPERTIES . ‘OF SALT SOLUTIONS Wehave discussed the ait ands fpr ed an ba ‘awe als discussed the acy and bs of ie slant cs and thei salts, and base and the als ‘base propertin of al solutions any Now 1h salt may be regarded ae an ienie compound cbtsined ‘eatalisation tention between anal and ase ale ca theo “tere types, namely slot) song ate and von bares Core ‘rnb 0) am ash and wah toy a 1) wet ha eree process of cid-bannealasdan ted hat i 2 eeathen proces, Beto hydro te ruling sluton may be aide bane re thay remain neutfal, When a sal undergaes hydrolyse een oy 10 +14,008110"« on vfs toward ight Because HO" or Oo eth get anne An ne cesar ibe oe conan Te tame can sn be rape! ty te Chunar principle Thashyarabys pta te 130" 701 blanc nwt Aconding tthe rose awry corps and en, en scr bois aldsand bses On fast oy as of aon cee a ers of aid oe hay oH nda or reve consider hydrlyat ntonsonly,myCR fms ACN anaes ate pan 6 oming tonya dN CN +1408 HEN + OFF 1 the OFF ton ea psu slat brome as, HCN. big een OE la agar dos notion ae nye onto, soy NN dre, ANNI on na Han mang ts congate bse NH VHOe Nye HC fo son ts pret the ston Booed The roe : sk base, does not ionise readily nase NE, ang 2 08 athe ean fan om with water 0 posit juga base and HO" vd and OH am orth tence hn »” esr dete hydra frye But bere tat we suc nmanter he fllaming import ft ‘The ane of wk ai a bak weith owe wes On the ter and trans of son oils hae any bearers hence Dey ‘Teint Fr amp ean Gof Hh pty (CF +#40-+ normcion ‘recto of wk bane ae acc wth ow y ales, The cations of soa as ov the oe hand, hve yay al hare td hence SEEING Hydinigee For stamp, te catlon No" of NOH does ot ‘Pyne with water. 1st of Strong Acids and Strong Boxes ‘lovnuhaaR, Ktand KNO3 contin ean fastongbaseand anion SIDED nd ence thee etna a nn vey ay ise ane ‘SiR ey ey eo om sth 10 1,08 HO" Om beer nat ata sures by he presente anc as ‘anaes ofthe type Nil Nether Na ofthese ase vO. noe cr aitengaci HCL erat opecvey wihOH and 1,0" prodiced ty descent of water The gO /OH banrisnotpst and 0 he creatine ype ofall remain neutl hep etch sitions will? mcr 8S Ho + 0 — rola 2. ats of Week Acids and Strong Boset sree cajcOOnSs ad KNO, proscar be ‘ot te pe eur new COON Seen EAN ser yay maaan rk mS Seep dosnt hye nthe cbt _Meden Approtch to Phycal Chemistry Vol SHSCOO-. to comugate tae ofthe weak acid HCOOH an wate ea em HO" on remeed tom the ston ening mene rng tndan cree acGHr butt Sotemtonetth asa ‘erycoons "°F Gsco0 z ae Dearee of hydrolysis and hydrolysis constant ‘Now, a ony the anions of ea hyrolye the equine acon eitalcomomemtis CH,COO + 0% CH,COOH OFF. Equllbtumconconon ett) ay 8 3 ‘Hore ka the degre of hry of CHCOO™ ln whlch ie dein he {ction ofthe tans undergoing yaya y= ICHSCOOHOETT foe HsCOOHOHTT «for ci4,COO ky is known as hydrolas constant In fat ydolysiconstat (fy) for he hydrolyse ofthe anion CHjCOO” isthe same asthe base constant (K) forthe Conjugate bse CHyCOO- ote wok acd CHSCOOH. oho pees (28 ae (628 the dogree of hydrolysis his very smal, Kye or ho [Ae Note that if i not that small to be neglected, Equation 6.28 has to be Jered. Also, Ky, is an equilibrium constant and hence depends only 62 Further, (628) temperature. Tn addition to the anionic hydrolysis equilibrium (Equation 626), thre ‘exists the equilibria for the dissociation of CHCOOH and HO: (CHjCOOH + 1,0 «* CHjCOO™+ H30", Anse quiet in Aaqurnts Setons ~ ¢ ae i Fa [EH;COOMT am | 10+ HO= HO" + OFF ra eter 08 an rm th Bee. on 60-0 Bit sy Ky (hoe CH,COC) from Equation owing tat on bye) az Nuno 631 bein os eo BIE oe Keke Kor hich i vali for any crotch a “These an ee Ry fr CH,COT “hydro from the K vale of curjcooma sco} smaaprie ace era tate ae Now ubtaing yom Eatin 631 Equation 286, we get Ke ain Equation 56, be oom ation 632 at (0 weaker hci hats smaller the valu of Ky) highrise degre hydrolysis, (3) lowe the concentration hati ore the Aon) higher the dese hydrolysis | (ay Righer the temperature higher isthe deren of drys. This ‘erase forthe same Hein temperature, Ky increses more rpily than Ky pH calculation ‘The equlbciam for he hy of CH COO” represented as CH;COO™ + HyOet CHJCOOH + OF, Mader Appr to Phy! Chey Vet 1 We see that wana ees bry “Taking og “og 1g y+ og og «) or pie okg ork +e 3) [Note that eis the concentration of CH, x [sCOO™ lon whichis same as thao the salt, CHjCOONe But if the salt is of the ‘concentration ¢ the concenraton of the lactate lon 3. Sal fof Strong Acids and Weak Bases type Callas), wuld be 22, te A salt ike NEf{Ctor NH4NOs produces an acidic olution. The cation of sich salt isthe conjugate acid ofa weak base which hydrolyate For example NM the conjugate acid of the weak base NH in the salt NCL, interacts wilt ‘OFT, thereby increasing HO" concentration and making the Slaton sce ‘On the other hand, as the anion CI” is of trong acd Ht doesnot combine with HO, that is, dose not hydrolyse. Thus the equlibum for self-donisation of water shifts towards right due to hydrolyse of NH on. Le CChateier’s principe says so. nua —%2 H+ HO esis “Danhed Degree of hydrolysis and hydrolysis constant “The equilbvium for NH; hydrolysis may be represented as NH! + H,0 «NH + 1,0" “Atequileium: (1-)) ot ow nt stat Ago Slatons Fy PELTEO' font ea aig) eta > ‘Te yds constart For hydrolysate fore congo ea Nis tthe weak oe seh ery ea, Kyo? or he (62) Inaditon othe outa Eqution 634 tee eis heer Ni + Oe NHS «OFF, ry NHGHOEE a ST 0+ H,0=1,0"- oF, Ke = MOLE (on From th Equations 635,637 an 638, we get Fer 5 (69 Knowing that Kj (for ction harass) = K, (lor NH) fom Egon 635, Equation 639 canbe waten as ole sinogutent leh i valid fr any coagate ai-base pais “Thus we can calclste Ky for NHj-Bydelysis frm the Kp vale of NH, @.8-10°), Ky 1210" 56.0%. Be a Re oF Now, subtitling Kf Equation 639 in Equation 636, we get ne [= (6a Kye ane ONG sia Eyton and cea nero M cotealoton ‘The hydrops for NH fon teprsent or eho fB - BeF ag -gK+6 9 oe pita Hep Pilg 0 eat Pei epee oe te se it sland highly crged tal cats chs A Cr Fe ae a aie aecian ne men ye a aii significantly acidic. The AI** ion gets strongly hydrated as AI(H,O),°", whichis Suyunrtnteclscoar etn nt piste Silenced wet ett ing cima ma mei SMITE ae i pine poor avec ‘AH, 012"(ag) + Hs00) + ANOHYEH:0} 09) + 50°C) hate san cen mo iin ot NE wt 4. Sots of Weok Acids and Weok Bases sn sta of weak acs and weak iss he CHACOON, NHN, so igen. bot te can and he anon ere The ting sotons een tee neu depending ene renive ai ue Seg oft eesti her conjugate parts For esanpie heaton of CHyCOON, owl Bsn (NHN 6 x10) = RCHCOO HEH. su tant eHHCOOH-CHIEOE A Fa rh 819) = RACHSCOOHNI BIT. m ™ TKS (INH 15.610") > KF 141"), sanig-Nis and EGF arco item rantyysset®)< Rye [CNis basic becuse (156-10 revlon oN | Ngee vas 1049 Bi Ae HeN-EN and NN ae consi D PS TN HI) KNEE ears o hyaysis ond yale constant aaa aera CH{COONH, bth eos ol wh rly Ge G00" + Ni + HHO = CHICOOH® NH + HO Reogutoumeeem)e-F) ee re an ae degrees of iyi of HCO” and NH fons a | ping lw of mast action we ge | wy HCOOH [CHCOOINH,T Ins sal soton he following equa abe CCHCOOH + HO CH,COO-+ OF, 1g, = [CHsCOO-HOH % = [ex COOH) Ny + Oe NERY + OFF j een ee INES) pees Ky =[Hj0°08). ee Ke a (47) 6) | for which on (645) And (646) ‘Now, applying the law of mas action in Equation 642 we pst ere as) (4) Sebotiuting Ki, rom Equation 647 in Equation 649, we get a (650) Equation 6.50 ells us thatthe degree of holy f the salt of weak sid and a weak base does not depend on the concentration of the solution “Moreover, weaker the acid and weaker the base, ore wilthe salt Ryarolyse “The Equations 6.47 and 6.50 have been expressed in terms of equilibrium constants f, (CHsCOOH) and K;, (NF) These oquationscanalso be expressed {terms of the equilibrium constants of their conjugate part, that i, Kp (CHyCOO? and Kz (NEI) reopectively For the conjugate acid-bare pair CH,COOI-CH,CO™ KeKiaKw or Ke asin Equation 66 and for conjugate acid-base pals NHZ-Ni KeKysky of Kyo Kit atin Bquation and pH coleuta ‘To derive an expression for pH, wecan start either from the equilibrium for the sneak acid of that of the weak bce. Assuming the salt tobe CH;COONHg, We tart here from the equilibrium ‘Modern Approach to Physical Chemisty Vol. y es) 63) teoeor mers sees B orien, Sengcooe eens Tovctometyaii esto Cypae Mit om caepOH «ray wo a mote Kg wa THO"]-K. JE (653) me" oe unos ER, oe io Htpke Pk) an Now, to getthe pH expressions in terms of and Kj forhydralysing NH sed CH{COO™ ions, substitute Ky and Ky fom Equations 66 and 651 ‘eepecively in Equation 653. kia ECEE wore BS i Ry > Kp, < pki pH <7: aide UK, pK: pH>7: bane TEKS = Ri pK; = pis pH = 7: newt t [EXAMPLES Calculate the pl of an agonous setin of 0M amienium oma SSRIS ge ego pt omit tm eno west wa on Hot, ae P= At P-) Solution aby ng Eguaton | 98-48) on pHad or pass, aqueous NaCh salon py of NHET What inte p Hof 850M NST amoare pen ea pK (HCN) = were ote Hee ‘solution 470293. by sing Basten cc pit Fete 93+ 505) or pH= ms. ie soe vter, the remington Me say ae de 10 yack of he dried ‘ANH O}?" + #0 ANOHN(HO” + 30" sn pl we pole, wicca bese yet to K(ANHHgOnd") = 14 «10°. pres -tg (4) 4854 espe ern pty oft oe t= Huta logan pH OF A SOLUTION OF AN ACID-BASE MIXTURE lution of an acid-base mixture depends Song o weak and also on thelr relative pot an aid anda base (3 «(edule amounts hati, the number of equvalnt of pete Lt denote strong acid strong bese, Weak Tops 0, WA and WS respectively for converse. by using Equon 64 ‘Themethod of calculating hepa nether the acid and the Base ae mounts, We Kove fom the lwo equivalence twoeectants eat ‘eal sequalto Aidan weak base 1 Appr toPayaiatChemiary Yo 69015436 o WB PH tog — | | eeauation i) srotsa Be "C00" i, (Guna sractare (Sinkinson) Fautomeric transformation of methyl orange can be explained se pee ons y aes orn 6 5-{ pf )a8 tat Quinonoa structure (odin acide solution) eo [EXAMPLE R® A SL siguat of 0.01 M solution of HCOOH was ated with [NsOHL Predict the pH of the solution atthe beginning ofthe reaction, i atthe haléequivatence point (Ge after TO mt ofthe base a ben aed (x, dtco0H = 178 ~10-4 fers quit in Aqueous Solutions cn ngdonrenicgor ott. pr}a en 00tx0:304 = 1396102. pit= tog (1 ee pita aHog 1.3410) ce pike 288 (9 Te widand tebe retin 1 ola Mile (na of HCOOH = 001 «50= 05, ‘in alegivalene point, mot NaOH added = 00125 = 025. ‘hs 025 um of NaOH evils 025 mm of HCOOH to SEES mot NCOONa te seiton wi iin Si Frtch ef HCOOH an HCOONe which = bail mitre pil pk + log BE OLESE . byusing Eaton 6a? or pik = tog (2.78 10-4) +g 2 or piteazs, (uy Abe cqlnce pint 0 mm of HCOOH i psd Oy isis Noort producing 08 mm of HCOON wich teres byes Now tsHCOOH snd NaOH rctin 1:1 molto tam of HCOOH = mot NaOH ce antss0= 9 +03, poset. toatolumesttheegurin po ata 80+ mmol Of IY oFHCOONS = eae Gal)” 5 ‘Now. appying the expression for pin he yay alt __ oleae and a strong base we ave Pe Hops pk log) by tgtnn 14 10g 0.78% 10- og $2) (6) Alar the egutvatence pointe atonal NAOH adn wey maom fone) = 225 ront= tog (585) = 20 —— Ee POLYPROTIC ACIDS AND THE ROLE OF AMPHOTERIC ANIONS {Letus consider asituaion in which a polyprotic aii aitation aginst abase liberates protons in succession. For example, easbonc sid, COs dooce intwostape HyS0y° Ox HCOS+ HO": Ky, 44007 HCO} HOM COR + HO K,, #47 10 Thus carbonic acd i actualy a mixture of two aide: HCO, and COS ‘As Ka, >> Kags the pi ofthis solution cam be cnculted by the fast ep Keg ABD) “ gibi > Kagt6B0 > Kool dose sgn > 3) ce equ slulein wer ; Nott A a Payee eran eae eg fB50) > Kf AB2CIOO tao 7 et <5th:C:00 eto pie becuase 9 SAS ve Re Fay ro et Bork rat awe merce em rectors Influencing Selbility rare bch muy prods and solbilty depend on embers aan epandsenly on termperatace whereas subiity My tsa Per aces Ike pH of the solution. commonon eet and aplocion formation tet fat trang soy ewer we set nd id sco PODS ace wer mato aataneoesy, io a iba mast nected when more ton on Suelo beasonerbe compos eae tec nns ect whe M40" oe wh ay Saar ay cama, Coir vo sgl cll sl se rica elm thes wo as ae shown excos Beats co? have assumed only the equilib spound and is tne inthe solution. But ‘we have to consider Is nL a HLS added. As \ Mode Approach to Fhyaical Chenty Vat 1302-1 decrease and both the sgt {Let hestuiy of B50, be x mot Kyeenetanio | Kyte? I502°), | or 220510 mat Lt | Fo 20610 mat | or inet eosge ss, 289 oe we BON 2239 og gt i e136 p00 | atc ne staiyprpductongsGi0e38'Citeeamceon | Seine NonsintsS Fade spt saonabaaneao ; fg -tae'FtGO2) soanwsp(2520%) Tasty ptt of AGC 3% Te iran ca gC) «Be vagy c- TAgoeay ro Ags 28 14-104, Cate Hay UAB. Wagtimcnerrn a e-20™ fiagchoys wr ciageaeiecr 7 ange ao passes ane” = LEoRAe SN To unc hon equnsne ant = - Coane akg ar 0081 anger nny 20°85 (shat) Conese wangmin SK = aap ns ng an (2a (0 TRasoveane TRE Ecakener semanas reer reer mm ety tein Pete Per I gee? Let the souby of TO FeOtD ey 208 Ke at HO aes, C2040) BB a* C07 Gh: toward loft due tothe increase in{Ca?*| pea ei Ezrlaton of CAC30, fm te mata due she eee ee by taturs pn Ne ty equa jst a8 ft docs Yo oh Selatan Before HCI is dae ete slpide lon concentration be =. EB oemos ny «HOt io or 10.19 = Gas ono or x= 107 00M for [S*TbeforeHCIis added « 1.07.10" YY a am fect esl the dere) ets Tin he presence of HCH 4 ORY canom mes 2 te OMe eae of HCL 5) cme frm 10710" M to 43: complexion formation Just acid ae ued to lower the concentration of anions in a solution the | Sptoing ents are ued in some casero lower the concentration of xtons | Nira toa saturted sotuson of AgCLitfors complexions. {Ag Tin | eesti, gc BE age +r ‘ereduced and 2o the equim sits towards ight in accordance with Le CGnters principe. Im other words, slut of AgCL increases due to compieion formation. AgCI fs gute aolble concentrated ammonia Ag" (age NH RACINE 9), _Ag( NF) (ag) « NHs (05) 2S. ANH) ig || __ ere he formation constant or stabi constant ofthe complex in, | sei tie denotes by Ry cd into oat oy ‘ovat of the complex on | tn solving sumesicl problems involving compton or precipitation atoms he rntons shou be fit smelt gotcompltion an then the | Sets solving proces should be coir Modern Approach 19 Physical Chemistry Vo. 1 vpn Mt xa Ve pivevsayeht ‘Consider the disocaton equtirum ABENIZ eAg™620N- ence a ~ Ky 0015 “56x10! for x=268410- Mag" KAAgOSH gta asia") EE RantRRD= 20 = 10° ant Solution 04 moleof AgCI diesolves to give 01 mole ofAg® and 0: mole of 0.4 mole of Ag" is frm supposed to combine with 9 mole of Nilo form Di mate of he compos Aa wh te dso {he solution isle ‘Let us fist ealculate[Ag"]érom the Ky vale of AgCL ‘AgCils) Ag 6 CI- Let the intial concentration of NH bey moles per ire, ut of which (0.2 M combines with 0.1 mole of Ag" the remaining NHg would be (y=0.2) moles per lire. Now, consider the dissociation equllbrium of Ag(NF3) ene ~ son? w “amon on site eS 1 oso%y-03? 1 ee ‘ar Tax?” y= 27 MINH iia ‘atin eae ny ing ta ain 2on mc n Tamneen cee "oe etn Aqua ee ‘Agtagh 505 tn gaya 74108 a ‘Mt iOu) gh 540 F pe gy! tage 1 Int meta tgp T= sapere a tact t= 0 Sic 1:0f I> tee! a be et some ceed nh ton ang mg ate em PEt hs emnren ecu maybe mont 0 ae TOF Tequal 0 286 M. of 290304 M ARSON ets nove sonar he Dat re eee ap hema beverg amano = agsogt OAC SOE Atequlibriom 27 iy) UP een - Gat eset Kem [agt&20502 1 for (Ag = 18810 19418305121 43020 ev cee ARO), cmler the fst compen Ateguivam yMB* SQE A Ano B= 7400 1 AE:0501 25410 date L1sI0-™ Me PAS prcpates but ZS remains ineslton. nett] com MGis I> 12-10% Seal precipitated and ZnS sare preci, Now we cau [P47] when 2 js stars procping. [Shen Za ant tarts pring = 110° Risen ssp, Ky = PIS oe 258007 =I PATIO, "=P Chama Yay FET the station = 256107 Ths perce Tt 227192, aR 0 PH noe 270 22300 $100 000095, Piaget | Solubility ultram of Ca inter maybe cane 2, Kop = 1a? M0 F = (nay? «4? AS Care ight soluble compound he coeation of Golubie sts wil pracuealy bese watntcop =a KofCaCO) (Cort ‘Again, considering the solubility the equim in the 13360 solution, we have tea cane SES Gr | Kyp= Ica" F emer hat Ka ems ap Er? : wie sen imate sy fai Te Sey a a | shan that of Ca ana ine | os the Kup VE ‘cate product values of eepectively- “The Key value of Sais golutich is practically om SiSery, assuming that [F 1érom exaurue ae such larger ety, We calculate (FT solution Caf negigble wo Looe Taps OUT P= aa 2 297107 Toa Rast pene can oa fen of Caf ey) a6 Se 075) arate kg rlPtnrh = 5 10810 3 Sd, a 3 aay "08107 ein oot ie 2on10? as nse “Tusprobemeanaboteclvedby considering hectare baarcremnton, fea eis l= FT 1 & ne steiny of Cath in lle slain comin, aM BCOOH and 02M NCOONE, (Ry Cah)= MA is MB ore cgoube tse ome Hume Fina eon evra" th burton Wears perks ys Boab oe pttenkg 7 0" +oe cago" 34078 JegltigQ*l= 3.4178 = 45822 coe “tjo"T= 5210, ‘Now we cel (HF rom ts vase HF +H,08 N30" OCH _ ¢s.<104 ar o Ke ae Tonkc Equilibria in Aqucoss a nee = than 14 at 25 C, yale an acid maybe rete Shore nay be Ty entot Fe i mand ato diferent coneentations may be compu oe state aay Tt Dereengholin ae ee enka ieee wit he increase in cONCEntaton = om 2h een pt sole With onl en many in he ay of a, we i ng | a ymin HO, aaaee eee ne namel CH Omtand EHNA a ‘Soc tn an cmc es we onl Sa mb 5 te ele A dig | soph SORTA S tzimete cl tan ic | he pofanaquens oon canbe ‘Pod ont Sh marble unwed eae 2ce™)

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