TOP SCHOLAR NZ@A NEW ZEALAND QUALIFICATIONS AUTHORITY MANA TOHU MATAURANGA © ACTEAROA, Scholarship 2011 Chemistry 9.30 am Saturday 19 November 2011 Time allowed: Three hours Total marks: 40 Check that the National Student Number (NSN) on your admission slip is the same as the number at the top of this page. You should answer ALL the questions in this booklet. A periodic table is provided on page 2. Ifyou need more room for any answer, use the extra space provided at the back of this booklet. Check that this booklet has pages 2-26 in the correct order and that none of these pages is blank. You are advised to spend approximately 36 minutes on each question. YOU MUST HAND THIS BOOKLET TO THE SUPERVISOR AT THE END OF THE EXAMINATION. (© New Zealand Qualfications Authority, 2011, lights reserved, No pat of this publication may be reproduced by any means without the prior permission of the Naw Zealand Qualifcations Author,esz | 992 | Loz | zoz | ts | ore | vee | tee | Gee | zee | eez | tec | zez | uzz | soues on | pw | wi | sa | yo | xe | wo | ww | mg | dN | mn | ed | ue | ow | aplunoy zor} tor] ool] 66] 96; 26) 96/ 96) 6) 6) 26] 16) 06| 68 ezt | 69+ | zor | sor | eo: | esr | act | 2st | ost | art | vr | tv | ovr | Ger | soues aA wh 4a oH fg aL PS ng ws Wd PN dd 20 e7 | eplueqque] oz} 69, 99] 29] 99| s9| 9, 9) za} 19, 9] S| es] us ‘zie | we | a9z | soz | voz | e92 | coz | voz | coz | oz | ezz Sa | sa | w | sH | ua | 6s | ag | ww | on | ew | as tL] ObL] 60r| s0r| zor] gor) sor) vor] cor] sel ze zzz ] oz | oz | 6oz | z0z | voz | oz | zor | ser | zor | o6 | oer | var | ter | eer | sur | zen | eer va fw | od |e [aa | uw | 6H | wy | ad | a | so | ow | m | ee | aH | m | ee | so ge] se, ve} ee} ze) 18/08, ez) az| se} 92) se] ve} —ez| ze) a ver | Zs | et | zee | ow | sie | zu | aor | oor | cor | tor | ees | ese |eze | zie | eee | 9ze | soe x | 1 a | as | us | u | po | Sy | pa | we | ma | oe | ow | an | az | aA | as | aa | s| es} zs| ts) os| 6h] eh] zh] or, Sh] | ch, ze) | |e) we] ee ves | eez | oes | ers | ozz | 269 | vs9 | seo | res | ees | eas | ers | ozs | eos | ezb | Osr | Vor | ree Chemistry 93102, 2011 om | aa | es | sy |e | eo | uz | no | w | op | ed | uw | to | A | uw | os | eo | | ge| se] ve] cel ze] te] oe] ez] sz| sz) sz] sz] vz} ez) zz} zi oz) oF oor |sse ize fore [vez [ow | ze OF 66 8 Z 9 * € | eve | oz wim |s ais | w Sw | PN et; zb| ot] St] owt] a Le zoz | oer [oot [ov Joz | gor 06 en | a) | o | N | 90 | 8 °a Oo 6 8 Z 9 s v ov | 2b oF St Oh OL ,-low 6 yssew sejow | OF z + 2H H eg 1 | sequinu owory 8h SLNSWA31S SHL AO AISVL DIGOAd3 You have three hours to complete this examination. lsgesoes QUESTION ONE (@) (Discuss how the charges on subatomic particles contribute to the size of atoms and their ions. Subectomie_pockider (nor atorn induce _poritively wioece__proteas tha ant nel tn “the pqucleus, cheted_ehectrony hak ee orbit Amwnd “the Mctesia ond. neget thy fn Chiscrets energy eyes Hlectodtedic attractions between tr poartively outer, Clore eoh_ Qrsksas _ongh tha _.elvstscas. lin cfee yolias _sres_pdnealy define the s2* q atema ~ yeotir fhe slack -wstodie _ohloocUan betueea them, me Ahe___loyer_the enter _eloctwnrs oe te The nucle ond thus the apolar the cclom .. Greortar .eWrtvestedce cctlea tien anita from a _gyrtertar _pootive..cham ea the nuckeus, Wwh{ de prepa riioned the numba of probed. Slatelethag (sv wines gret of electvimd alse acl tone othe erem — legen, 03 Abe _cection = elset on repulsion. means thal the {EOE nucaar rome cebing A _voleAss €iatteona ys reclucse Sailor clacton = 2lect on_repualsion.1a. the walonss she area eloatge ctor, 0 the erred odomic. Tishaa \aureored foo vicluce..repvision ‘The some __Raclors..ply te the aide _of. Song =the py2nfar the ows ed charge, the smaliec the fon, O00 the Mere shielcting, (rom. omer tle ctens, castle andthe mere electron electron vepvleien frome elactrow -(Lupigi0§ “the ewer shell, _mthe _levRerntheion HSER. SEES Hence, fie _ genitive certivay , they eve compared _wnoilar son shee off0ma_dve fo (ow 4 electrons ach for -oni9P0__otheay 066. commporidiy Leimerflon shale. ama steppin |” : Gy ebeetrony “ Chemisty 93102, 20114 (ii) Explain the trends in the atom and ion sizes (in pm) in Figure 1 below. Relate your answer to your discussion in part (i). Be F To ig om oe 1 136, @s| Os O:| Ox) Ox, " "e-0 @:| ©. x Ox, Ke Cal, Se, Br @:/"@;, Ox) Ox, Rby Ses, In? Tey r «| Ox" Os, O:/ Ox|, ¥ Figure 1: Atomie and ionic radii (pm) Note. + The dark circles represent the ions. + The bolded numbers are the ionic radii. The tread acoso grace fer cromic. echii iy. dsyeosing be fron Li sho Ethos. et +The SOL sroiler, ond thin. bend ty commend 6/088 exh pene Ths 0 Ove the Sn erRatrg nuoleen _crewrqe 9RE ef fe nucle cee cleng. the geind (frome ee op) jondh or electrons ye _beiry dded do. the seme volenoe Shel thee eA a oytorter elestne tate. _exterctons Debwtan the onter 2tecbend ol the necte_povitine nudes. Cate) down the ofoaps., the _.qareed tread (4. atoonte ve VARA higher padi -0_sMaeaaigg Asp MeCons ot COM Pyyingy [MEG levels aA _-tRUS Grea ey Setar histones fro the Avoleus. (oGeared shielding (Am.tnter shells ole seduces mHhe .2ffertive sucker chage.., hence ceclusing Laclesteric edlecctort petucen volsnve leckerns. onc the _povilike nucteua. The ere pine othe rureeaire reek Jann fhe gpsuups. (ar _crtonnic feds 0 Ger, which beay on exlomicrodii_ef- 122, em _(smailler tho Aluminiuna oreo AGB pv). TRO oy ileal. ove to: the 4 cthak_cthe..erla cregy leuk (illed athe 3d svisheUonel othe. Gi) Chemistry 93102, 20115 Cs Subshetl, —Wnidat__comporaldng clove ln_enetyy levels of hus de ae..odd signi fleantey Ke. -tha rea. cocilas Pru the _poritive aucleam shonge op Grat_M_ mush _gyeorter =f hoa Mok of Al, AW thisappead 40 plowy oy op eoder rola ta. —rilucingycebomic edit de £5 gyeestar electrostonlic_ortle ctions.» a. soMnpaans, petro. Poa, We GO locke ct “tus 28 Pook, qorpl of lumens ~ the metals _cindh ths 000m edeals ta mtx meteal..clemedls,_certivas ace _.cluorgs foamed uproot ster valener otecvon. Thuy, os the onter valeme ole tron) ace. ot GQ loys energy Level [ako clove _ohiahe Meo the clus th foe lon, alt (sas q vseeillic_clomeds ous yyalles fon. hele _reipectire _ortomr....Ae _Aen= Aneto) element, eee, QAisnsove _fotned upon _qaicing electrons te complete the onter shell. Thus, makased electron -elesewa repulsiva. betuetA_ eletrmy ithe Oran shell _coure the lorie cadii op nore inetd ele Are Abs lye oywerker thon AGIA sy pe clive extents. Ging clonal the __gpeups, tonic _cectiisnurtoasa watence _2lectrerl ore _Cecupyyife neper_erezy tocels sing cress the pefnels, tents radii ereamm fo Mesos cry, os (20) -the scene period. ore ieetactopic, Yor nereosing ny fous gente _cucleen chovge ocd thet —4r_belel moe _otoreiy tote _puceny — Simailectey. Qa 22h = Metals onic adi, __ hewhoaey oro fe _poried ox Sum =the _eme._reeven -_plomever, 14 __eamp.ading meio inate nen-metel _(2aa__la_~R_ geone pened, Aen — tial lens ove __lerjer_oss__sths___ovter_shrella.c® 2-0. gyi _chiaenenprenn =the avelias (ocsplg athe men wat) = a toro Chemistry 93102, 20110) Cc co, . co 3 “ aq ee The Boudouard reaction is the name given to the oxidation-reduction reaction involving a mixture of carbon (graphite), carbon dioxide and carbon monoxide at equilibrium, at a given temperature, The reaction is an important process inside a blast furnace in the production of metals from metal oxides. ‘The graph below shows how the reaction mixture composition of the gases present changes with changing temperature at atmospheric pressure (101 kPa). a Boudouard Equilibrium Cc 5 co 5 co, 06 04 03 02 4 yp desucsy a Fraction of CO and CO, Ol 0 500 1000 < ‘Temperature / °C cpen tneboitlers oo ASR wivenses , Gore batkuerch , with justification, the product of the exothermic process in the Boudouard reaction. Use your answer to discuss the reaction products when the hot gases from a blast furnace reach the cooler air at the top of the chimney. Ax the stemearortinte inereenan the equilionwir..cf peeactler _keoks tina exe BWC nares the seks sp Ne endodlcmtic action .As shows in thy yep, mere CO priduced oo. eMpoertas. iyerGare.,dalcarting rat cerbo Meroe uel forthe gr0d UCR. of she. eoulo-thorme Machen... Thuy, WE Com Aarts athe presto ep the grothermic. poser flee Doudoverct _eattion 2 _CO.2_,o0.A oo preieak tn ngh. cenentrerGons ot lows _Aumpersctures wher €ojuilibawn Sai by toweets raceway athe cocks ay OA I athe excrthemmic_eactive. AL =ths Cooler _-Reanperesvuens te athe po -the_ chimney, pp a= the Squiltoawta ool stave Shel Ferecehs producing omore © @y..r-QreA fe =the .exeotomnle_eeo.e0.. Chemistry 93102, 2011Oy- DO 3c €+6, = ©, wo Baad 2 © TOT Cap 00 art! ae A large, heat-proof syringe with a freely moveable airtight piston initially contained 50 ml of carbon dioxide at 101 kPa and 25°C, plus 1 g of granular carbon. The apparatus was heated and maintained at a certain constant temperature until equilibrium ‘was reached. The pressure of the system remained constant at 101 kPa throughout. The apparatus was then cooled rapidly to 25°C. (At this temperature any farther change in composition was negligible.) A total of 60 mL. of gas was then present. Determine the temperature at which the reaction was caried out, ©7 S%~? 200 Note: + The same conditions apply to this experiment and to that represented by the graph on the previous page. + The volume ofa substance in its gas phase at a particular temperature and pressure is directly proportional to the amount in moles of the substance present, ____Bactien (co) = Ve - sn graph, the temp ek hid Greco (12,) 2 Ys —00A__Wattion (0) & Yaa eck expponiinertely — Chemistry 93102, 2011 49S" -QUESTION TWO (a) Account for the differences in the properties of the compounds in the table below. [Name | Structural Melting | Solubility in formula Point/°C_ | water at 25°C Cyclohexane ft ' 1 Insoluble 1, ChHp Mz Hemet OC | OH Cyclohexanol - ; 2. | ct, OH m= 05 Cy 25 | Sparingly soluble OH cis-cyclohexane-1,2-diol 98 Very soluble 3 CHjgOH) yA illo gmel! oA mae | 1 The methine, pot Of oubstane oe pereu ole ctl on the suo endenmetect exttrection, __partak Aetween moleales The. cofeaster the. irker md culer oflracti oD, The meat _21egg reejained “fo Sepeerte the anolecutled __frorn..elel_ phere te Wequidl.. prea _-fhd athe. lnghs the tua porture enquired ak __muatins ponk- f(a comparing cemprurels (2, and 3 (numbered adorns) 5 U cone Ake tak Hey precpeaiuely howe lexqer.riler Masses, 12. tre _enslar man... fF. doy geet fen fen 2, rhithare beth ei thon 2. i The pelercross <} _madeculea_si_e_abestortce. dlingelly Alek 42.-the seo, the 2lectron clovel_op. the molecule — ath _iawreens. site f the preportiorely .Thus,.ca p elect slaccl _saureasea from (=, Jo clea the _inetorrteneous_ctipste_extlections. 2etneen_maecules. initontoneas —ctlpsle_erfiaaction ere encesult of temporary eAipole — cipal _erflractionspcfivcer .moleeuler rhe to. drstemterecns clispryertionatce —citymlovitie «f chacpe this the —qyrerten ths woledtora cloud _yhe—_eycetterthe._passiloitetag ef uneeepaort clwieye—clisthlovation ~éhua_hx__Henrepr the tmtarforeevs_ctipele Chomistry 93102, 2011erttrarctions Purthomat, comparuncl 2 er) 3 cue chde te poor, Aujpleege Ipods betureem mde euler ober the peeseaw of. A Ayglegh opoup. The beg hly tor OM bond rete. the. bupleoqiA._vtay posite ond thar fete cta prem eva Unbarvedl pad of electrons oq © elo _neighbounng role cul, rho fooming, —_-ttreng___inyplaapee bonds As empenact 2. how or ve mek ryder gloponp.than. cenipand 60 foam mak 2... Conpornd 2 carer hnplrocy ee bones. cpetemeh flor _ compo ea be perm uplaeyen teat cy. then’ or 70. Hypa aly groups Thus, eve. compounds B_ toy. the Gscilea _premecuules OMIPACLINOS ow ore oo laear roe. meas. wed Irypiesqendonding Nyoroxy) group cvred bene eas othe highert pvellhney. pout. Cumposneh > cen foam ore pnplagen tend cord bes A nAer nev 7p LOOgrel-!, 92 hea the second highent_ telling paint. Cenpend A comet heplager 10d ond os ath vredlest lor Mod), .fhuy ray loratrt neiing gait. Solulailtty —_ceperts uper fhe _otoilitny ef. aceleoules “a & camped. pen hydreyen bead. usikh veto molecules — 4he fomotien. of yjeteqen farely wit) bela molecule relene eneqy ark hye thea Inypleone bones feed ne mac ene’ getocely fowouroble he olisolving prowis.,.omd._-thuy tha _rroeoolubte Hee compeourel . Composing .3...cen_ fom. tha meat nygleegen bends, on very soluble - Compound 2 en oly form mn lated frumoer of Inyetrogen hares , ond thus Uaperingly seleble (hydiertion NEKO Ade _Stgniflomy ey ecler thon _eneqay_reouiredt te sepoele. enstewlea iach ghege)).. Compare A. caving fem ery Ayplarjon Yesfeha OW tha a ty olurg,10 (b) A.year 11 student carried out an experiment to compare the energy released when octane and ethanol were burned as fuels. Octane was found to release considerably more energy than ethanol. The student concluded that this was because octane was a larger molecule, and so there were more chemical bonds to break, and hence more energy released in the reaction, Discuss the misconceptions in the student’s explanation and use appropriate data from the table below to provide your own answer for the observation. Moctane) = 114.0 g mol"! M(ethanol) = 46.1 g mol Bond enthalpy data/kJ mor CH 414 O-H 463 | ( co | 358 C=O | 1076 Co 7 804 | H-H 436 [iezestGz ose eee 6-C-0-4 Combvation. op Ocore = Cotte fg) FEO (a) PS CO2 lg) 4 AHr® (a) AW = (os4e) + [is aay) + (25x 408) = (tox $04) = (18x 463) = or — We = = SH emer / fh Comlattion of Ethenol CaMsotti) 302 (oy > 2CjayA ZH OHQ) AM? = Bab) 4 (sx) + (2x Gea) — (Gx se) — (oxaes) [4 (255) + (403) ] = GDB ee BI Nob bmsis| / Greet lensed fer fom. . octede = S= ta)* - 5004 = We 7% by (4) y mbeceed per gram of etherol = e> (az) x -re = 2 4e ks “ast) Chemistry 93102, 2011"1 (asthe. warbortion pcx fuel, Ue 0 impotent to under the pends looken end the. berets. fomed W—sthe. maction, ol here The stuck missonap fion Gert failing Fo eececpnre HA The aluck at eile inplica takin. fewite) fo. Neto noe boas, “mere enemy qu released whertes the peeling chemical boraly Oo etsthecmic.... protein that requir mas ene ° i 1) whe tee._cibpecke dom tha. ssurruneting “The. feamertica ot bros __r1_the_sexeathenmic pracy tok eit reece eneguy relensest (nthe... contortion op ocfevie, the teal energy) etepemmeel i the Comburlion op : POPE OM op the guibrtome is U2 ley - They elena srt CmouAl TAL. bree required te feale betes oaths. ROANKS, (ect ace ered axyener)., each the obbrequeAt 2Rey released yor. fence pores (the. prelucts(carboa ionic eel. peter). The erster mous othe furel dou alae Ped olsen ite ecco ,.00.. there or Leas mretes 4 eclene hone GON 4A The subHone flea A ere for etorel che 7 ts é tao, tien. asin band Litfolpies tome bec camed out for (gro of ethortel,, cbowung thok lev meqy beloved combating oe 20 Os) pO. (DP MO BP). Here POC os move Cxethecmie..procei hws. more... energy "a releqacd.- Rete tok calculertisnd rove been lore’ 0m The easumption Hak all eacterts ond prelueb Oe tn geo phase, andl thet Complete. wwmrlourt ian otews, The feTmer Gos pticn bd unlileely , By eclene and efhonal ore bath Liquids als room Lemperenture cd the product HO. ir _vynally. jn llquiel phous « The (erfler Qoumprion abe _uaralistic. as seme carbon ayencrice evel 3912 QUESTION THREE (a) A mixture contains oxalic acid, H,C,O,, sodium oxalate, Na,C,O,, and a water soluble impurity that does not react with solutions of sodium hydroxide or potassium permanganate, To determine the composition of the mixture, 2.496 g of the mixture was dissolved in water to give 100.00 mL of solution. In one test, 5.00 mL of the solution was titrated with 0.01803 mol L~ acidified potassium permanganate solution and needed 23,35 mL. to reach the equivalence point. In another test, 10.00 mL of the solution was titrated with 0.1040 mot L! sodium hydroxide solution and needed 17.30 mL to reach the equivalence point. Determine the mass fractions of oxalic acid, oxalate ion and the impurity. M(H,C,O,) = 90.04 g mol M(Na,C,0,) = 134.0 g mol SD TWHetion with potooiwy _pemereprede steals (ar Godt (vin 9 sorteiset to CO, ) oe oy —>.2C@xz tLem ee. mo «ant + Se7 int 4 Ue © Cot - { > (oc©, + Dwt+ SHO ewe Hy Og aah 2Mnogh st LOH (aay? 1OCOa pat. Dena SHO) n( mou) = 0.080% © .©2335 = 4.21 xto™ = [amet ).s = (He Jas = o.00le5% mel (%o-t) mol a(Qoer 1 (.Cy4* tn Wom) = ONCSS fgg = O-O29S me! D Threction wlth sectinm ydiexics feels for WO Oy H.C, Ou fag) EZ NACH fog) PNA OU fogs ZH (4) A (Neott) = -l04 x 6.00% = O_O DIA mel 0.20044 ee SE 6.996 IT mol BAG Ato a LO = €.44b xtom” mel A (HG O44 th bomb) (Chemistry 93102, 201113 1( Neg, 04 erica!) = a(G04%) = 0 ( Haley) =O. 2210S =O. GossGo ~ @.O1295 nel m_(_osalic_outd)) = 6.4462 107? _x 40.04. =O. 8 08% 9 Q.acerg fo Ub 0.3245 (4-8) ArGS3_. LACH oA _(OKCNe asic W = 2h. 45% im (wrote ion) = 0.0205 x Mm (Goytt = _©.©1205 x 3 = 1. bt OO) [roction 0 ( dm puritiq) = 2-44 — mm (Hela) — ml, GA) = W4% — 0 oA = (¢.6n85x 4) ~ 9.07076 g mrss fecction (orpurty) = 0.0707] 9 4Ie = ©. 9835. (4st) =_ 9.8354. —————— ‘Chemistry 93102, 201114 (b) Manganese is an element that exhibits a number of different oxidation states, Half-cell reactions and potentials for the different oxidation states vary depending on the conditions The table gives the standard reduction potentials for manganese species in aqueous solution ranging from Mn(II) to Mn(VII) at pH = 0 and at pH = 14, Conditions | _ Reduction half-equation pH=0 |- Mn?*(aq) + 2¢ —» Mn(s) 1.19 MnO,-(aq) + H'(ag) + & > MnO (aq) +090 | | MnO,(s) + 4H*(ag) + 26° MnO, (aq) + 8H"(aq) + Se —> Wh ~>| MnO,(aq) + 41*(aq) + 3e° >» MnO,(s) + 2H,0(2) | +1.69 | 2 >| HMn0,(aqg) + 3H(ag)% 2e —» MnO,(s) + 2H,0(0) © 42.10 | MnO, (s) + 4H"\(aq) + e& -» Mn°*(ag) + 2H,0@) +0.95 pH=14 2MnO,(s) + H,O(@) + 2e- —» Mn,0,(s) + 20H-(aq) +0.15 Mn,0,(s) + 3H,O(6) + 2e° —2Mn(OH),@) + 20H(ag) | -0.23 | Mn(OH),(s) + 2e — Mn(s) + 20H(ag) =1.19 | (Explain why Ma{JI) is not oxidised by O, in solutions at pH = 0, but is oxidised by O, solutions in which [OH] is 1 mol L~ 0,(@) + 211,09 # 4 > 401K) E® = 40.40 V (pH = 14) AS Og) + 4H*(aq) + de > 20,00) E°=+1.23 V (pH=0) Ak pH=O, Malt) canaet be enidlisest by Og. because the valuea foc redox rection betueen 02.060 M40 fog) are cod thiw._ore nck _sportenars_ reactions 33 ov 4.9. 1) Mo aq) 9 MMOrLs) 5 C°= GRE 28 = EST 23 =0.25 2) m0 (oa) > Maa) 5 C= GP - 151+ SS " = O-3iv Sa pony > Ma (agi) Here nore tre_alooie_reoictions ot pH =0.. (neretion 41s gust nok-sponteiesw) Hover, when Tot] ts terol’! ena ph IU, the E° velve Jor th. redluclsr a Oy 4o H_O b. O.MOV , ofel now on rex renetn con occur _sporeneously. ath fa (tHe (5) aa Malt). pedier Ama (ote(s) + Cola) zs oho - (- Chemistry”15 (i) _KMn0, is a common oxidant, and in acidic conditions may be reduced to MnO, or Mn, Discuss why the intermediate species HMnO,- does not accumulate during the reduction of MnO, to MnO,. Duding the _recletion of MaAQy te MAO, eis perriboe (or MaGy~ Ao. for. the _ulormecteie 2pesier HMAC 4 Homeser, HMMAI y=... Pc alee xen (24 —_ this doen _acturmmuterte 10 =the __ prow Oe 29. HM Ab4™ meng est with _Ma™ speries (aloo pomedl boyy the reduction 9g Mare” in aude. cerattians) He agp — Mfg) PDL p(S) tH pag) €2=_ O10 = 12% = O.87V > "0; here spanteaeas The __paduct Mavs (s).. Allerrertvely, HM Ay” mary react mith Ma te pat conenemts MA”, nich cos _subseeueacthy be etducel te MAD. +. BA MAO Tog) + 2MA™ (ogy SCPC) t 2M Ie) DALLA) Mag) @ = Ble = Siz 0 Sav > © j here speatnrend. HMADG” cea_ailse_rcege er _aurte «niciortiva _ceaction , thws pareluces MACY (on) ane __MnOp(oq') leasing re lM aby PRA pa jeluclion . 2 = — BHMAGG” (aa) H(ae,) MAD (2) +t 2 Madey (aq) ALMA) e°7 De = 64s aaeee = \.2N Po herce _ ypestertesest Chemistry 93102, 201116 Gi) Discuss the pH dependence of the stability of Mn(I11) in aqueous solution, AL fax _pbl ines __é2_.patelie. canelictien , saiirepenee. pascaaleg bb ue 5 pecan ——ealatleves Aa (It!) wrrlobi_1A_fhot tt ari uncle.goea _quurla exietortion _ceeCN 2 mith dime, fo foo Matt anol. MnO, 2a foe) K-22. > Ma Nag) M22 (3) =H ag) Ee Aet= 0.45 0 FW. SO hens ~ oponteriews ta. high ph cmdliciont Le. easel —_ Ma(lt) 6 prereat aa MA, O58) cre thse nel wrote dimilet cule eri AaOo1._ 286. cf eo». 0.23 0.15 The Chemistry 93102, 2011QUESTION FOUR (a) (The normal pH in blood plasma is 7.40, The pH of body fluids is regulated by the presence of CO,, HCO, and CO, dissolved in these fluids. At 25°C, K,(H,CO,) = 4.2 x 1077 and K(HCO,) = 4.7 x 107 Identify the components from the list above that would form the best buffer at this pH and calculate their ratio. Determine whether this buffer is more effective against added acid or base, THe,“ Dre") ES(MO,)= Tey wegen, GL = erate) (10%) = 10.55 w.L) Leos] rye") fet ay TRY ae ta Dro JE (10°79) (4) = 9 .0cll8] wonpgerk ue od cacich As the shania Cee pruent of pla? in mot appresave emouete (Ce. 2% LOA fertiv, > oppored to (OO) , these ore he tro cenymnents fhot fom ths ert bajler at Hin pH. The bufle- U mare effective coputtl oddecl audl os (ii) Lactic acid (HLac) is often said to be produced by the body during rapid exercise. move, corfpepete bea present. ‘Show by calculation that lactic acid is mainly present as the lactate ion (Lac’) at pH=7.40, pK,(lactic acid) = 3.86 ke llottie sid) = IpP*S = 126-104 by = 1tea tot = [we) (Y404) [eae] ce = Geox) = (10°) = 2467.37 Here as hueseuid etio iS very (ome, this indicones tha [ae] a pereatin._oigni ficontiy Gene. eNO ak -¢hy e Chemistry 99102, 2011 ACOs” fre) ondt_Hy@ (ests) 1CO5" (lore) ond18 (b) Predisposition for the condition known as gout occurs when the concentration of uric acid (HUr) and urate ions (Urr) in the blood becomes too high. Uric acid is a weak acid. pK, = 5.4 at37°C, ‘At37°C, the solubility of sodium urate is 8.00 x 10°? mol L"! and the solubility of uric acid is 5.00 x 10“ mol L*!, In blood serum, [Na*] = 0.130 mol Lt (ie at pH = 7.4 and temperature of 37°C). (i) Calculate the maximum urate concentration at which sodium urate will not precipitate, and show by calculation that uric acid will not precipitate at this concentration either. Hur yo — rt Hat PS = Tuc kyo) [recy lo {oy}. UE= {oq} = Nats} rot) (¥e) [090 o-?)2 a At0-9 0 ; > eal! O22, 2. Masimum vets oncesttrartion at wividh NAVE AU net precipitate GSES SEE U4 423 xlo melt! voll! Toe} [ROD Bods} A> [duc] << Ssetebi oh Wane eid UAC ciel wld or _peripteds Chemistry 93102, 201119 (ii) One form of kidney stone is made of crystals These can form when the concentration of uric acid and urate is high, and the pH of urine drops to around 5 to 6. Calculate the pH at which these stones can form. Assume that the total concentration of uric acid and urate is 2.00 x 103 mol L*, [Hue] + fur) = go xto™ nett! > [Hr] is 50x oS molt ren Ue enystatoea veneer. foc) = (22x07?) = (seonro™) = 9.0015 teytsed G.0S x C46") | _Beoxiot : Gantt «x OFS oo8s L397 21078 mett=! tn nt Chemistry 93102, 2011QUESTION FIVE (a) 20 Compound A has the molecular formula C,H,0,. Compound B is a stereoisomer of Compound A. The melting points of Compound A and Compound B are 135°C and 287°C respectively, due to the ability of Compound A to form an intramolecular hydrogen bond. Compound A reacts, on heating, with dilute H,SO, to form Compound C, C,H... Compound C is able to exist as enantiomers. Compound A will react with potassium permanganate fo form Compound D, C,H,0,. When Compound D is oxidised by periodate ions (IO,;), Compound Eis produced. Compound E has the molecular formula C,H,0, and gives a positive test with Tollens” reagent (ammoniacal silver nitrate). Bach molecule of Compound D produces 2 molecules of Compound E. (i) Identify the structures of Compounds A-E. Justify your choice of the stereoisomers A and B and write a balanced equation for the reaction of Compound E. with Tollens’ reagent. A A od Bore qeoretic a wares, ome AD “the cig QerTredton Ope mode as the 4u> covioayiit Sd frolenal gnu? Cee en fhe yee slot He dove tare! AG hod oA Cte on : to pom urbe neue \e : hydleogen hers between the tes OW eyoups Gl 2p Comperel 8, the trends ct ene. iganen) reise ts Ye ae Now Aha ad conboeylie oid — tiers os nokd Une coven) here CU bn an on oppeake sick 4 the doula bard. Thun, the “Od Groups oe ues to ebe te cht optial coldiny - . i HOY 2 fare bysvorpn lias lth Fe-6-6 —c% vther matcuules hence aera 6 e . Hor de dN syeler unternplealley - Daisy 4 Gries (1) Weg) (ii) Draw two other isomers of Compound A: one that has different functional groups from ‘Compound A, and another that has the same functional groups as Compound A. Explain why neither of these isomers meet the requirements to be Compound A as described in part (a). Orllewit pretsnal Grange + Sete _Fwrevcral_Gomp s chy “Ne ~bic# WO Son Compe FE __cloeai& 6 oeseihed req ciremerts because o> hve CFE two Covide Lends preset, upon reaction with ofilule Hy SO, _comparet with formater Cy gO, vill be produced ext cinrteceh (edidition op 2 he's) Compewach Ge deeant 7 sequozment® Beceure _upor reection nth dilute _M, S84, the (ellowing compen proud ~Sext= (Tia congo —cin eat 2 t or , Cry °Picol_ectwity , | Question Five continues sihal_corbon on the following page. O9_there “one — Chemisty 98102, 201122 (b) Discuss the potential for Compound C to form polymers fs comprwd__C._enly._ hen ___ene alcohol pep, deaple._the tw _.cerboeglic__ecel fanclierad Groups abayn chain ap_f\pelymee cat... formed 5.acicakehel poceenk (ctiatid) {a_needed to __ produc. polyenter Horeee 0 atientor conn _be_ formed ttt Compoosh Cr follrow « fs_indiceted lathe. pretveta chown, have ove tothe ~orl gyoup ath __peenk_in_tre_otlenber Ue Ailvvssponnilo for an enter \idleng2 —-to.repormed — with. ofthese auto} compound C Howes fhe poly dolor _artning _vitlt ach bs wepet_chasn ply Mar. 0d tunes. cate det te tetiehichel cxticgireal ¢..eoors_olpute the code orem fe whch the —Ot ayoup 8 crttoshe Chemistry 93102, 201125 Extra space if required. Write the question number(s) if applicable. Chemistry 93102, 2011oo en a — Question Mark ONE V ae oy Gg Two \ oO a (8) THREE %) 4 | FOUR FIVE » ; TOTAL 4 ( a