CHEM 301 Assignment #2 Provide solutions to the following questions in a neat and well organized manner. Reference data sources for any constants and state assumptions, if any. Due date: Tuesday, Oct 16", 2012 Only odd numbered questions will be graded. 1. Water from the hypolimnion of Maynard Lake has a measured pH of 5,81 and an ORP = -490 mV using an ORP probe with an internal silver/silver chloride reference electrode. Standard By values are referenced to a standard saturated hydrogen electrode (SHE). Look up the standard reduction potential for the AgC(s) + e- > Ag(s) + CT half reaction and correct the field ORP reading to an E, value. a) Calculate the E, and pe values and predict the dominant chemical speciation for iron, chromium and selenium in this water, using the appropriate pe-pH (Pourbaix) diagrams. b) Plot a log Cone (M) vs pH for reduced inorganic sulfur and nitrogen between pH 4 — 10, given the following information. [E2S}r=2.0x 10°M pK =7.0 pKa=12.0 9x 10° MpK, = 9.25 ©) Hydrogen sulfide (H2S) is considerably more toxic to fish than either HS" or S* Calculate the minimum safe pH, if the total sulfide concentration [S(-ID)}r is determined to be 20 uM and the safe threshold for fish health is 0.15 mg/L (as S) 5, = Loopy + 0-222 =~ AV 4 0.222 = -0.27%0 V Pe~ Fifosy = - 4.5% pH ere Iron - Fe deminowk Species = Fe aay 24 Chromiam= Cr olermtnont species = Cr OW Gag) Qohonium— Se — dominert Specter = HS2 cag) CHEM 301 Assign Sg 20'2.Eb-pH Speciation Diagrams for CHEM 301 Assign #2, Question 1 Iron Fe-O-H Species Considered Fe[2+], Fe(3+], Fe(OH):(aq)+ Fe(OH)3[+], Fe(OH)s(ag}, Fe(OH)a[-1, Fe(OH)s(—], Fes(OH)[ 44}, Fes(OH)A[5+], FeoH[+], FeoH[2+], Fe(Ol)2(ppd), Fe(OH), (Ppa), Feo(c) Goethite, Hematite, Magnetite, wustite | | Fe (LN) e(OFDAET Fela =098 - Figure 47: Eh-pH diagrams of the system Fe-O-H (1). [Fe = 10-!, 298.15K, 10° Pa. ‘The Atlas of Eh-pH Diagrams, Geological Survey of Japan, Open File Report No. 419 (2005)cx[2+}, cr[3t], CrO.[2-}, CxOrf GroH[2+], HCro.{-], Gr(s), Cr0.(s), CrO;(s), Cr20:(8), Crs04(8), CrsOa(s), Eh-pH Speciation Diagrams for CHEM 301 Assign #2, Question 1 (Cr-O-H Species Considered Cr (FACTIFACTSAGE) Eh(V) Figure 35: Eh-pl¥ diagrams of the system Cr-O-H (1). 5Cr= ‘The Atlas of Eh-pH Diagrams, Geological Survey of Tapan, Open File Report No. 419 (2005) 0-10, 298.15K, 10° Pa,Eh-pH Speciation Diagrams for CHEM 301 Assign #2, Question 1 Sek m ‘Se-O-H Species Considered Se0.[2-], Se[2-], Se03[2-], H:Se(aq), H,Se0;(aq), HSe[-], HSe0s[-], HSeO.[-}, Se, Se.0s, Se02, Se0; Se (HATCHESIFLASK-AQ) HSeOqh HySe0glem) 0.0 4 HoSetady Se0g(24 sf — 1 8 Bh 7 3 58 pH Figure 112: Eh-pHf diagrams of the system Se-O-H (2). 5>Se g-!°, 208.15K, 10° Pa. ‘The Atlas of Eh-pH Diagrams, Geological Survey of Japan, Open File Report No. 419 (2005)| by Avg, Cus] vs pH Log ys CHaSI, vs PH t t 2.0 x10 M A cHy™ HS = LHtD* ¢ Ka, CHA + Kay Ka, Sievtardy, oe doo Cus] vs pH dog Ans CHsST, vs pH * ay 2.0 xo“ OE CHO? +Ka,lHt] + Kas Ka, re dmc — for Jog CsI vs pH fag orinshe w #4 + zo xiooM Ka Kaz. Age CC + Kay Kaa aap otk ocledk speacds hot”puns woos pue wjuowue 1} uoneizeds WdHe 85 Bo} nying pur ueGosN s1UeBs0U] peonpey 405 Hd $a 9 B07 Jo 301d AeHEAO, oz (w 0 50112 Statey! We reed te carry ut a unt Conversion so thet we tan eonpare tool sulbde cone b safe tHreslold. We tan Han evoruacte, whet fraction of Hea totoh sith need to be ar the form of HS (toxic form) ond use sppropricte equililia expremion |S to solve fer Unit. ONS mg S 7 rol = se = LO BB,060mg = 4.bg x0" M = 4.63 AM AX. . Abs WS Bp 7 9:23y we see fom the gh SpeciohOn, Biagron hot ogg = 0-2 ot a pin t-8 Ak His pl romge, the dertamct forms of velscedt SulGwer ave HS ond HS™ lie, Sta ragligehle) eS ——— CHS Aus Cast + Lae] = O23,CHILHSI 70 HS = Ht + HS” Ka, ay 20 CHS] = Ka, EteS3 LHy So - F%SI : fe Xn = Chsd+ Kay Cast ~ 7 2 Kar cn Eng Th L£H7) ts = 0.234 LHY + Kay Sinee we Auow Ka,= 10%? we caw solve bO LH 22 Llbos, CH tT = 0:2 3y CHT + 0.234 Clo ~%°)) LHt - 0.234 CHOY = 0.234 Gio-7*) 1 EHD 0.23) (uO x7) ons cio"? (/ — 0.234) 0. Fey = 3.05 x10 * So pHs — beg CH F-522. Boric acid is a triprotic acid (HsBOs); pKa = 9.24, pK.2 = 12.74 and pKas = 13.80. a) Derive an expression for the fractional abundance of HsBOs as a function of pH ) Construct a fully labeled pH speciation diagram for boric acid over the pH range of 7 to 14 using Excel spreadsheet at a 0.2 pH unit interval ©) What is the total borate concentration ([HsBOs]r), if the concentration of BOs* is 1.0.x 10° Min a wastewater at pH 11.6? Ms Boy = Hi Bo = Hox = Gaz” % Lt HA represwt 1H, bd, LAL Cen ee ge Ate AT Ka, + and HATS Ht + HAR Ka, = HAA = Hee So Lit3AI CHI] LGA) Ligh) + LHe S+ CHAR) + LAPT LMT EH2AD ZA] CHAT =( cugcuey | CHAT J auch CURT = Keg CHOI (ka, Key £ LHW Lary= Ka, « ¥ and LAI~ Ka, Cun] Kay Ka, Kay CH5A3 CHy* / Cn LAT ba SHARD y LHt LHe ee eee LmgAl r Ka, CHA), Ka Ka, Sug) Ray ka, Kaz EWG hd LHF 2. (CHEM 301 Assign 9am 2.012.4 i) J+ Kay , Makes | Key big Kay Cue} CHE Dry _ Lupe LAD + Ka, CHIP Kai Ka,CHS + Kay Ka, Kay See athachiol C4a T= 10 x0 Mat PH WG 5 CHT Ha”! CHsbO,], = Cg Bds] tL HBA T+ £ 1 Bo,7T + £8033 t ft t t reghig ie 2 2 1:0 10-8 fy a pl tb et Few Kag expreroimn aaing CBQPI HbQe” = Ht + bax Kaz CATE be] LHba FT “Kes ~ 1B M10Simtlawty, Hz B0y = Ht + HBOS Ka = EXEL HeOST Try BOs J ", CM @og= LHTINBOZT (or) (1.5~ x10) a Tene ay = Big riot Therefore Prggogt = aig xo + \.Sgx1? + \0 a" = Q3,x10F MSs ak pHs , [H=lo P= hb x10 SM ioe > oma tre] = key cH (asco x07 5) Pree = (/.exios) * Lox toe =! Ie x 10-7 M converte +o ph (- ov ) Pl % psx tml , 55859, lobwy th 5 L po | 9 7 kg Lh ak pH = 5 LAs oF = 1 lo aed TED = (uaseat Oe” : (haem Oe has nia assuming E,5J=10 x53" cenver tng do pp ed e Gers ae elo ppb Fe* In other words, FeSuy 1o% (10 nillion) dimer fas voluble at pH thaw ot pHs |/3. The solubility of FeS(s) in marine sediments is expected to be affected by the pH and the [112S(aq)] in the surrounding pore water? Calculate the equilibrium concentration of Fe™ (ppb) at pH 5 and pH 8, assuming the HyS is 1.0 x 10° M. pK p(FeS) = 16.84. FeS(s) + 2H"(aq) <=> Fe™(aq) + LS * t t known a EtgS]= Lo x103M Strottgys We vill use He equclilenume xp rose ow foe “the renchin aleve +o solve Cre} Since He equiliovime eonstant Lor Win reockion “ro wot grew we ull nud to deve rit from Ha Kee ond grid dissociation conatactr tor HS. ose a hoe oy fee Ks = \0 y eat . Vie jo 2 a = H a ge 4 Ht S / oe wee e Ht 2S Ka = | ———— — _s Ksp_ e 31k Fes + ant = Fee HHS Keq= 2 = 10 fre lkss] CHty™ re 2. CA * Keg CH CHS 2 CHEM 301 Assign f S88 2012.This quiotin, da srmawhat arnbiguans 96 Gt do not char f we Abhl HS enc Ue Loxiot Mor Af we shovldl poke ety acemumt He affet of pm fuss]. ens IL we doke Yin he He case, we pace, Aug lo PH 2) cHye Aug = Cris Yo LH] + Kashar xt sy (uie®)* (edu ews) +O nels ™) + t Ft Keay (en an = 0.0% (4.19) oe EMaST pug = Os EST, © 0.041 x09 M fpr, Ha eee, [ee (asx?) ey) (01 x 1073) = ).6 xo tM b fet shill & 108 tims lero soluble a pH@ vs PHS4, At pCI = 2.0, Cd” and CdCT are the only dominant cadmium chloride species with a 50% fractional abundance of each. a) Calculate the equilibrium constant for the formation of CaCI” (B1), b) Derive an expression for the fractional abundance of CdCT’ as a function of [CI] and ~ B. for cadmium chloro species and calculate the fractional abundance of CdCI species at (CI ]ecawate a Cery=/0*? = pox 4 Aes = Loyoe = OF Lately Col ¢ cr =e CAT Ke he kar Her) 10 xi0*M —— =. CE £ caclty Aegoe = Led j, Lcacith = ceary + Lede] + LAC] + Lede] +Ledelt] 7 — : et subsite Ox deems reaerd 4 £6") of Lenard 4 Fens wing fr Manny Ba, Bs 4 Pa 2 CHEM.301 Assign e@ 201%gee EAST : yep, (LLL. - Lede pa are * Lod] = Bx Cole LAT? Led lery>= * Br LAVT LAT Al LAT = Aacoled tury? / = fs Leder Lery* | Bs- Loaded 3° Feat Ler fy = EES ro Led*] Co i Wf. fedele} =-B, ced* Lory - 6 rear] tert Ai 1 Rat * ase te 0), He. i Stee sso 4, Balada Ba (cattle? Py A - \ f A A fy EVI I+ pbery +f, Lerl*7BlOT +A £es* 1A 7 29x10! a= 32 x/0* textbook fa = 64 x/0™ Chap, 10 B 238 x/0* 4 EOTeeuatir = 0.56/ 1 Chpp. 3, tPhook.) (9x10) (0.56) ) HK eget SS : 1 49x10 OSD HBA T)VO SIF (6.4 018) (0.54)8 + & (3iexb*) (0.561) 4 = Lt F443 + 100,74 M34 33 #6 443 _ 9,1 ed IGS. , ie G %) cons) stint ute Fig. (0:2 Chex t book \5. Lime (calcium hydroxide) is sometimes added to wastewater to reduce the phosphate concentration to acceptable levels, In a pilot study, 10.0 g of Ca(OH)2 was dissolved in 100. L distilled water. Calculate the maximum total phosphate concentration [PO |r that this test solution could contain assuming that the concentration of PO,*>is controlled by precipitation of calcium phosphate, Ky = 1.3 x 10° Calo), ¢sy 2 Ca toq> + 2 OH” jag) t 2 L Le2*] = 1,35 Mn* + 21,0 pe°= 20.8 c) Caloulate the equation of the redox boundary between NOs /NHG" as a function of pH at 25°C and @ Capeces = 0.10 mM. a pe of air sakratiol wet, can be colermined by ye 22.6 art Or (40 redox couple Conerder the Kod f-rKr On + 4e7 + 4H4HH—% QMO E% 123Vv 7 Py bet ong? rearranging db isnbte LeJ geelds ! = . . + cant ~ Key OT tog ize = tog kg + og A, + tog LH7* ee ee 4 (tog tut) 4 0%! i POC game CG)d f+ (FG) dog 09 A Xo: P= O21 afm 2, CHEM 301 Assignd mgt 2012,by (123 ¥ sper Gar) +(4) dog (0-21) + 404 (or?) = 90.8 + (-0.17) —Bl = (BF peta EMP = 0S Hoge Mn Ops) + 4Ht + de Mn** + 2H20 Pe’ =20.8 ea pe. = P p Ne tog a Loney Whee Q= ae Lut " = “5 rr PR = 208-1 10 , ON tog (vo #)t pe = 203-1 (23) = 4.3couple Nos /wHyr Redox co) Toney = oe Vitiea ot te ase a ank pe= H eo Aw re pes Pe’— He Pp 0," OHt+ + 8e7 + 3H °= 0,882 V +t E°=0, Ng 3Ho “ 8 i No ook aes 510, Considering the following reactions and boundary conditions, construct pep speciation diagram forthe iron system consisting of Fe(s) ~ Fe” - Fe(OH)x(s) ~ Fe" Fe(OH) in freshwater. Use 1.0 x 10° M as the maximum soluble [Fe™] or [Re™] (Gee attached information) Reactions: Fet + & Fe* Fe* + 2¢ Fe(s) Fe(OH)(s) + 3H" + © == Fe* + 310 Fe(OH)s(s) + H’ ¢ === Fe(OH)xs) + 720 Fe(OH)As) + Fes) + 2H,0 Fe(OH)3(s)_ + + 310 Fe(OH)xs)_ + + 21,0 Thermodynamic Data for Fe(s) — —Fe* ~ Fe(OH),(s) — Fe** - Fe(OH) system: Ky Fe(OH), Ky (Fe(OH), Standard Free Energy of Formation (AG*) in ki/mol e | H | OH | H,00) | H,0%(aq) | Fe(s) | Fe"(aq) | Fe" (aq) | Fe(OH)Xs) | Fe(OH)s@) aq) | (aq) | (eq) o | o [-157.3 [2373 2372 | 0 | -789 | 460 | -4866 -699 Fe Ga) Felons} Fe G0) Fecsy Fetsy © pote Felts) 4a Move soluble thaw FeloH), és) Fe, Fi%tag, do more avcdie, Haw Fe ep CHEM 301 Assign SB 2012.Fetaay Fe low). csy pe Feria | Felorl el 2 OF PH Seven beundaries icdudltfiel o- 4° @: Fe + 3H0 = Felok), + ant AG? = cla] ~ C4. b0) +E) Cased] IR Lee AG? «= 13,200 7 A404 Ks 23RT ~ Zs (aawpczary. = 3-01 = CHP . : « Eresd cHte= Ki DRI “3 Aog CHI =40g K +Aag CRI Ag CH] = -301- 5 es =-Lb6F tog LHY = 26F (CHEM 301 Assign 29088 2012,® Ree ae se RY Be eotiy pe? =/3.05 | Bee ee | AG= CCAD] - LE4bd] =-743 KE | per = =ae ry \- +7F4,300 BERT MI Za aw Ran Q) = 13,02 L Lkert) = per-- 5 Lb | pe> P Ne 79 TA "at boundary CRM] = Lhe} = 0.5110 5 Dee eS © Felor\y + 3H pe7 = Fe7*+ 3th noes Cl Fea) + (s)62892) - [CLAD] = -41.5 is a e = 41,500 1 b.04 pe ZS oR ‘ Cre**) Pe = Pe — + Ang Q = bod — 5 deg Faas fp POF 10.0% = Log CHP? 09 CRI | = 1604-3pH +5 | pe =-Z1o4¢- 3.pH (CHEM, 301 Astign 2mm 2012.@ a) Rou), + Ht + em —e ROW, + HD Nee (486.0) + 62322)) - [eva] =-24.9 bo mal Oo. TAB L485 pe Zonet : ='pe? 7 1 pe = pe ~ 4 te Q = Acasa 4 doa Tat _\pesaasa ph Pet + ee —~ felow, + 2h aGe= Leased] - (Caad +2G2342)]=6.F dog K = GaSe = — W884 a Cre} Curl? = Cre #9 Q dog Lut] = 409 K + dog CFe*4) = ib? + E45) v1 hog Cat] = Vee 2 CHEM 301 Assige 2mm88 201@® Felow), + 2HY + 207 = Fees) HAMLO AG = LaGearay] - LEaebO | = 122 ke wal eee eee ca 23nRT = oy Pe= Pe. ne deg @ | =~ \0- 4 dog Fae = - oF -L@ fog LH! pe = hot —pH @ Fe + 2e~ © Fees E° =0.443V fe"=-%50 AG = Col -CCaaay l= 499 le mo\ AG? per= Gaere 7 GN oe pee~ ra 40g Q z (CHEM301 Assigh £2088 2042,pe a ue QZ Fe lo. 4), 15 CS)