18-30 Contin Chaya Equilibrio. in Aqueous Solutions — Solubility, oduct We art now going 6 Casider compounds “Kat are only slighty soluble or “insoluble” in aguecus Solutions. Quotation ranks ave wed Suen, hreanly all compounds ane Soluble in taniee fo Some etext: Rie of thu’ used by Some (but dont wory abt it) + Ifa compourd duaroloes in wwoltt, fo give 0.020 moles JL im Solution , it 6 cmschud fo fe soluble. But there is a loge gray ana where Substameds are cmsidered slighty Soluble To work with, slightly soluble compounds , special equilibrium crrotert is wed + We SolusiLity PRoPucT: Corsider AgCt This compound appears on ¥e chau on back of exam envelope called Sowsitmry Products . So we knme it is “insoluble” o eh” Slightly soluble, In aguaone solactin Aqtiaze= Agia + W@) : Ke = Ksp = CAg*i(e] - 18x10" ot a5 S| . “oe Examples of solubility product expussins L N@Wsoe AP a + 3 Hag Ksp = Car} Cowl? = 2 Buse = 2 19 «10°33 : ABNeg + 3S @@ Key = Car P (sl - Lex io?18-2] In gentnol, My Nyce) =? n Magy + yX“fagy Kp = (MI Dxny” Note: ao the Kep value gel smaller, the solid becomes less soluble ao the Kop valu gel larger, the sotid becom more Soluble 2 What dato the solubility expussio mean 2 Ht allows us to Colculate the Concawhartions of the iono ot equdubrivm with the pant solid ix ogMtour sclutim at 25°C, provided we know the Kip value. shen he systim. is a equilibrium, Solid => ions G Agee Ap‘ee) + Hee and Kop = 18x10 = Cag I(r] the solution 's coMad SATURATED !/ How is Ksp diamine fr solids ? The soli is put in wader af a5%C andl stirred until sotid dusolute as muck ao it am forming a Safuiakeo ~ Solutin. “The molar Solububihy of the solid is meaounad + Kip is Collulatecl. So, vohat is motan Solublity ? molar solubility + the munber of melio of a. compound “Rat deszelue Yo que ohe Iie of sotwrakd solution. Example: The melar solbilty , sof barium sulfite (BaS0x) is 10510 M.~ What is Kep of BaS0y? 3 Ba S0y@ == Brey + SOiog, ee * Kop > (Oa J(So#J = s* = (los xiot)* = 1) x ior where S= rmolan Selub byaa Example: One lite of a Satuaitd solutim. of bauwm phosphate (Ba,0Oy), , : Mw= COLE g/mol) cortuno 3.94 * lo*g of Bas Poy),. the Kp fr Baz 0oy),. Plan: (1) colewlote s, molar (2) write the Kop expussion in terms of s ) solve fo kop. motto Bas (POd, _ (3,94 x10%9 / 01.8 gimel) . Tae CG) motor solubuity = titer soln @) Ba,(Pou)as) 2 3 Bag + 2 Poop if sis =» Bs Qs : ee rum. © Ksp = (Ba*PLPov*]* = (3s)'(as = 1s? 4s = 108 s* =655710'M @ Ksp = 108 (6.85107 = (108 )( 1.21 x16")= 130x106 Z Example: Guin a saturosed solution of Mg(0H), (Kep =15* 10°" ) 5 (0) What is the molan SolubLity of MqlOK)a ? What is solubility (PMeomL)? - (b) Whet are the eoncenhattons of Mg*tamd OH” avd the pH in sewed 2 on pr every | mole of (0H) (s) that dimolueo, we get mele of Mg" ions amd Q mules of OH" ions Mg(oh), G) =? Mg'tag + 20H) pe Oe > _ , Qs cy of MaQHla that ddsolve im VIR (malo solubibity) G@) Kepr is rio" = (Mer Ilow]* = (sy(asy* =4s° 4.5 x10 Oi UE @ rac en rrelan selubihity, s = [3,35210% (aasac®) PO ss ai0%18-23 Not: 40 take the third reot on calulaior (or any rect, ) Tien, 395x1IO* — Tienka 3.35*10™ T entra 3.75+10* pel yeaa en Sale ene 3 ent ¥ = 0.333 pwh +,3,= plane push = push inv leg + solubility (Bin) = LSSe10 moles, SP q_, Ole = 29x 10%, i T mete * (Comb = 3 donctdty 0” OR We Can reoom st we Rnow, 1.55 x10" mobo of Mg (OH), ant dissolved in | lites Solution 71.55% 107° molto of Mg (OM). we dusolved in ]OOmh O.1L) soln. ond 2q = LSS*1O" F rmotae x 58 glmot = 4x 104 4 Rep the solution is super saduvoste| - he obuby is ereatdedl a precipibite will fam and vill ondime fim until the conconhation. of tena in the Solution, teense Yo Such a. pnt Hat Qrp ~ Kp taken the systim ic of epuubibian. - Osp < Kep tthe Setudm is wnden satwioked : ho precipctatim will occur Exampla: If equal amounts of O-O10M KpS0y and 0.10M Pb(Nos), Soluhone axe mired, ull a precipchat, frm ? ; Skp 1: Whod could the preciputats be ? : “The ons present as Kt S04 Pb™ and NOs” - Possible, choicas (suntchung porters): KNOs ? rope - is Soluble _ PhSOy? yes Kp = 18 <10% * PbSOy may preeyulat. if Qsp > Kep Stp 2+ Writ the solubuity product expression : Kep = 1 xJo® = [Pb*I[Soy"] at equiletoium. Skp3: Calelati Qsp fp the final soluchin. Siew, equal voluires tae] Qe [r0*][S0,7] ote Tee wf = (0.050é)(0.005 M) “the conconttakin “ - = 25x 104 of each compound _ is haloed in. the Grol, Sabato.Blo a Step: Compare Qep with Kop in this case ep? Kop © the Soluhinis supersaduoted and © presale, will form wrt the concanhadions of #2 ions saiksfy —~ the solublity product expussion. - Aside - {Sr your interest + Whot ore the coesnhations of Pb and SOy remaining ix Solution afte the. syslom reached epuilibrivm. Kep = 18210 = [Pb*](Soy*] : sinea. Pb” + Soy*"> PESO, = (0.05 - x)(0.005- x) - #0 005 0.008 1% IO = x2-0055x + 2F*10" Thy 0.05% O0ns-x O= x-0.055x+ 25410" “Elle _ X= 9.95 ; 0,008 What dogo thio mean ? That at equilibrium , nearby al of te . S04" jams hawt Beon removed form Solution. X= 0.004999", * LetS soe for x elo" + (0.05~ 0.085 )(0.005 - x) i’ _ = (0.045 )(0.005~x) 0,008 -x = 4 x10"% x = 0.0049996 “concentrations still in solutim: [Pb] = 0.045 M - [SoyJ = 4%.0x10°7 M :Jemenshation, FB gin Example * @ fF equal amounts of 0.004 M Pb (NOs), and 0.001M NazSOy aw mixed Usill 0 precaprtote. ffrm ? (b) if equal amounts of 0.004 Pb(N0z), and O.00YM KF ane mixed Will 0 precaprfod frum ? Skp 1. What could the preupdate be ? (@ tons present: —Pb®* NOs No” S04?” possible choits GurikA pasture) + NaNOs ~ nope-is Solute PbSOq - ye Kp = L310 +if Qep > Kep, a preprints of PbSOy untl fim (b) tow present = PBY NOS KE OFT possible chirees (swtkh parturs) + KNO3 - hope - is soluble too PoA -yo Kep* 3.7 *10°* “f Qsp > Kop» a. precypulta of PA, will frm. Skp 2. Write the selubulity product evpressin. ) fA PbSOy Kips LB xlort = Leb? ILSoy*] ©) fr Pore Kp 33x10 = CeeICe Skp 3. Colabita Qsp fr final selutin, © [o.com | [o-008% @®) Jo.co4m] | 0.000% PoCNOWe| | NaaSoy | ebiNOds| | _KE Nai: since equal _ 7 v Y “Voluomas one odie stogeth, He (0.002 M PONDS) ©.002M Pb(NE)2, Seen fo.002 _NayS0y oa KF Qee~ Cpe ISoy*T Qsp= (Po*ICF-* = (6.002" > (6.002)(0.002* = Axio = Fx Qsp> Kep preaiplahm ——Qap < Kep “no prtcipdain18-28 In-Class_Quiz L. Wri he sclubuity product evpumsios fr (@) calcium hydroxide, ColH)s () Sep(PO4), , shonhim phesphote 2. Wri the above kop exprusions in toums of s, the molar solubdiity 3 Coluulati the molar solwoubity for Sta (Porn. Kips LO #10 4. If equal volumes of ‘the following Solukma are maied, will a preespctite farm? () BO*10%M Nid, amd b.0KI0YM Na,Co; (Kép nitoy* b.bx 10?) (by 2O% 107M NaF ond 20¥I0%M Malla — (Kip mats = bx IO") Answers # Lo @ Kep= (Ca2}Con-y ) Kept (Sr2*? [Oye]? 2.) GOW, @ 2 Ca'fegy + LOW ep Kp= Gy(asy? = As se mer: s as nk, CY Sta (PoD.G # BSr%ep +2 sera Poegy Kap (3s)* (8) = (28s 45%) Solubicby 3s ai = 108 s> 3. Ksp= LO*10%' = 108s* (see 2b) sh = 9.abx 10% s= a5*107M 4 (a) Qsp= CNMI COP] (IS *1076M)(20K10% M) = 4.5 x 107° sp S Ksp NiO; does NOT preciputati (bY Qsp: CMG ICR (1.0% 13 m)(L0*102 MY = 1.0 * 107 Qep > Rep MGE will. precipitate.a) Example {a)Whot coneonhostion of Cui is racessory fo Uniiotl preiprtaction from a. Solution containing O.COISM KOH? Ksp Culowa = Lox lon® (Hint preuprtation is initiated of equilibnim!!) (This is #45 in Ch20) CuloH), > = Cued + 20H%eR> & 0.0015 M do NOT double. The cmeswhatin of OH is what it is. Ksp = .6* 1078 = (eu Con] = [cut] (0.0015 4) 2 (G8: Zo M (1) Suppose more solid Cu(Nosda wao onlded untd (tut) = 0.0015 4, What would be [OH] in the solatim ? Whot io pH? Cigna eft of G2") a. weak od Cui), ©) = Cute) + 20H OQ 0.0015 M 2 Kap Lbxion® = (Cut*Jlou-? = (0.0015 m) fown* (ou-]? = 1.07 x10" 2 fou-J = LOx10%M; poH= ¥.00; pH boo - Exompla: If silver ions axe fo be removed firm solutim by prrcuretation, of AgaS, what final cmeanhation of Sulfide io ore required to reduce, the Ag* emeenhation fo 1.0 * 10° M? Ksp AgS = Loxio" I clubla, AqSG) 2 2Aq"@a)+ S*fo9) sis ce ie 2 oF c . Ksp= 1Oxlo = (Aq I*(S*] * oh : = (Ox lo)? [s7] a . [s*]+ Lox10-% Aa Wiles As more « more S* (fiom Na$) added, more «mae AqS Aa reabe $ preeipstoti out, but jhere is a tiny amount of S* and : Ag? ions that are in solution at oll times.(8-30 Fractional Recpation (For Intuest Only) Frachoral precipctotion is the process whumby some iors ave removed from solution while feaving other tons with simile propertis stil in solution Exompla: If sotid Natt is odded slowly 1 a solution thot is 0.010M each in Cot, Aq’ and Au’, which salt precipet oilto faut ? Cot Kop? (Cut Led = 19x oF Cather = Cu'Gogy + ep Ag’ Ksp= (Ag I(CrJ= 1@* 10 Ag&@)2 Aq’ (p+ CL'fog) oe Aull (se Autag) + Chee) We ore adding CL ims. In ‘which systim deeo Qep > Kop fat ? ANSWER! “The syslim unth the smallust kp (sith most insoluble salt) * Au preciptelio out first ao Auth, then Ag’, ten Cut Ag cute Further colwlohms cam be mode + - =