40 Hl Ky thi Olympic Hoa E U | hoc Quéc té [dn ther 40 Bai tap chuan bi 2008 Budapest, Hungary‘Bai tap chuan bi cho ky thi Olympic Hoa hoc Quoc Té lan thir 40 Téng bién tap: Gabor Magyarfalvi ISBN 978-963-463-065-7 ‘Ban quyén thudc vé ban td chute ky thi Olympic Hoa hoc Quéc Té lan thir 40. Mot vai chi tiét duoc bao hd ban quyén. Ban dich tiéng Viét nay thudc vé box Héa hoc — dién dan OlympiaVN. Moi ngu@i muén sir dung hay chia sé phai duoc sy déng y cla ban quan tri box Hoa Cong vie nay duge chimg nhn béi Creative Commons Attribution-Share Alike 3.0. 88 xem mot ban sao cla ‘ching ninan nay vui long truy cap dia chi http://creativecommons.orglicenses/by sa/3.0/ hay gir m6t birc th dén Creative Commons, 171 Second Street, Suite 300, San Francisco, Califomia, 94105, USA. Ban duge ty do + Chia sé —¢uge sao ai, due phan phat va git gu nay bao gbm cd vie sr dung a8 day hoc + Siva chira — a8 tao thanh céc phign ban Khe thich hep cho cong vige 'Phal tan tha céic cam két sau: ‘+ Quyén han. Ban phai xa dinh 16 vige nay la d8 tham kho Bai tap chudn bi cho ky thi Olympic Hoa hoc qué 8 tan thi 40, Budapest (nhung khdng bang cach ma céc.nha bién soan cho rng ban da vi pham hay vie lam cha ban da vi pham) ‘Chia ddu. Néu ban bién adi nay xay dng diva trén bai tap nay thi ban phai phan bé két qua cdng vige kh chirng ‘nhan aia ban la tzong ty va phi hop. ‘+ 861 bt ky si ding Iai hay phan bé ll thi nén edng b6 r6 ban durge chung nhan lam vige nay. Gch tt nhdt La hay dn dén trang web 6 tren + Nhung iu kien tren day 6 th8 dug b6 qua néu nhur ban duge sy dng ¥ cia ngudi git ban gée. iy thi Olympic Hoa hoc quée té lin thir 40 Vien Hoa Trung Dai hge Eotvos Lorand Pazmany Péter sétany 1/8 H-1117 Budapest Hungary ign thoal: +36-1-872-28-10 Fax: +36-1-372-29:31 E-mail: info@icho.hu Web: ww icho.huOlympic Hoa hoc quéc té lan ther 40, Bai tap chudn bi Muc luc Nhieng ngw@i bién soan bai tap 4 Loi néi dau 2 Cac hang sé va céng thie 6 Cac linh vue dac biét khé 7 Cac bai tap ly thuyét 9 Cac bai tap thc hanh 42 Cac bai giai 50 Cu trac dé cvong moi 98 Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét — box Héa hoc OlympiaVN 3Nhitng nguoi bién soan bai tap Zoltan Fekete Sarolta Igaz David Komaromy Andras Kotschy Gyorgy Kéczan Gabor Lente Gabor Magyarfalvi Attila Nagy Istvan Palinko Andras Stirling Laszl6 Turi Judit Zador University of Szeged Okker Education Ltd. Eotvés Lorand University Servier Research Institute for Medicinal Chemistry, Budapest Enzix LLC University of Debrecen Eétvés Lorand University Eotvos Lorand University University of Szeged Chemical Research Center of the Hungarian Academy of Sciences E®tvés Lorand University Edtvés Lorand University, currently at Sandia National Laboratories, USAOlympic Hoa hoc quéc té lan ther 40, Bai tap chudn bi Loi noi dau Ching t6i bién soan nhting bai tap nay véi myc dich lam cho sw chudn bi cho ky thi Olympic tr nén dé dang hon déi voi sinh vién va trréng doan. Myc dich cua chung t0i la chuyén sy tap trung clia cdc bai tap tur nhting tng dung co ban sang cac ting dung tha vi dya trén viéc 4p dung cac ly thuyét hoa hoc co ban & mirc do gido duc phé thong ‘Ching tdi nham dén viéc tuan tht dé cuong IChO hién hanh nhung ky thi Olympic ‘va bai tap chuan bi duoc bién soan voi tu tuéng Ia cau tric lai dé cwong. Chung toi khuyén nén str dung phién ban dé cvong méi sé cho & cudi tap bai tap nay trong qua trinh chuan bi Ching t6i d4 gidi han ban than chi dua vao mét sé it chi dé it gap & gido duc phd thong, Oday c6 6 linh vue dac biét khé ma chting tdi cho rang cdc doan tham dy vn da rat quen thuéc. Cac linh vuc nay duoc sap xép ré rang va cac eng dung cla chung sé dug mé ta trong bai tap. Trong nhting thir nghiém ctla chung tdi thi méi chii dé c6 thé dug gidi thiéu cho sinh vién nam vieng ly thuyét trong khoang tlr 2 — 3 gid. Dap 4n chinh thir chi co & trvéng doan tong lai clia méi nude vao thoi diém xuat bn tap bai tap nay. Dap n sé duoc dua lén mang vao thang Nam 2008. Chiing tdi chao dén cac Idi binh luan, stra I6i hay cau hdi vé céc bai tap nay qua email gmagyarf@chem.elte.hu Ching t6i rt thich bién soan cdc bai tap nay va chung tdi cling hy vong cae ban sé hizng thu khi gidi chung. Hen gap 6 Budapest! Loi cam on Téi chan thanh cém on dén tap thé ra dé. Ho da tirng tham gia cac ky thi Olympic hay cc truéng doan va ho sé hinh thanh lye lwong chu chét ctia hoi déng khoa hoc trong ky thi IChO. Toi rt vinh dur khi dug gid’ thigu cdc thanh vién trong héi ddng khoa hoc gdm Marton Boros, Zsolt Gengelicki, Dora K6halmi, Aron Kramarics, Krisztian Lérincz, Katalin sz, Zsuzsanna Santa va Zsofia Szalay khi dua ra nhting li khuyén v6 gia. Téi cing cam on Miklés Riedel cho cac y kién khi doc qua ban thao va Jon Baker khi stra tiéng Anh cho cdc bai tap nay Budapest, Ngay 20 thang 1 ném 2008 Gabor Magyarfalvi Téng chu bién Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét — box Héa hoc OlympiaVN 5Cac hang sé va cong thtrc Hang sé Avogadro Na = 6.022-10” mol Hang sé khi: Hang sé Faraday: Hang s6 Planck: Van téc anh sang Kh6ng 46 Celsius : Trong viéc tinh toan cac hang s6 can ban: thang néng d6 chuan la mét mole cho dm’. 273.15 K R=8.314 JK" mol F = 96485 C mol" h=6.626-10%Js = 3,000-10° ms Phuong trinh trang) _ thai khi ly tuéng pyaar Nang lvong Gibbs. G=H-TS A,G? = -RT Ink = -nFE2, Phuong trinh Ea 68 RT So Nernst ZF oa Phuong trinh = ain Arrhenius a Ao RT Binh luat Lambert 4 _ jg he Beer: =log ig thi toan b6 cdc ndng dé déu phai tham khdo Bang Hé théng tuan hoan véi khéi long nguyén tir tong tng 4 18 7 2 H He 1008 | 2 13141516 17 {4009 3 4 spTey7 Tepe] Li | Be BICI]N]|O]F [Ne 0% | 901 1021 | 1201 | 1401 | 1600 | 1900 | 2010 1] 2 sfufetolv] « Na | Mg all si] P| s | ci} ar noluo|s 4 5 6 7 8 9 10 11 12 |2608| 2800] 2097 | s206| 2645 |o005 s[>lajz],=]"|]=]=|z]=)]/=]=[u|luzlu|lu| =|» Kk |Ca]Sc] Ti | V | Cr] Mn] Fe | Co Ni | Cul Zn | Ga] Ge | As | Se | Br | Kr 28:10 | 40.08 fee 96] 47.27 | 0.96 | 52.00 | 54.04 | 5505 | 50.00 | 50.09 | 605s | 65.8 | 6972 | 7204 | 492 | 70.00 | 7990 | an00 wfefsfofatelolatsloela[alo)a]s to] = | « Rb | Sr} ¥ | Zr | Nb|Mo| Tc} Ru] Rh} Pd| Ag] Ca] in | Sn} Sb] Te] 1 | xe e547 | 76a fea os] 01.22 | 201 | e500 | |101.07| 102s |10s.4a| ror Br] 12.4 | 114 a2] 4.741217 12760] 8.90124 20 © | zfafu|[m,e,a7|n| «| o| a || o | eo | 0 | o Cs|Ba] | HE | Ta} W]Re]Os| Ir | Pt} Au} Hg] TI | Pb | Bi | Po} At | Rn 13291]197 99] “* [172.49 00:95) 103.04] 106,21] 19025 12.2165 00| 196.97 200 #0] 204 202072 [2006 5 a7 fae [| to | 10s | 0s [aor [ 10s | 109 [ rvo [am Fr | Ra] {| Rf | Db | Sg | Bh | Hs | Mt | Ds | Ro 7][=,=|o [a /e@ [a |e],e [ala [s,m lopn La|Ce| Pr | Nd |Pm|sm| Eu | Gd} Tb | Dy | Ho | Er | Tm] Yb | Lu 13091] 40.12]40 91] 144.24] - [15030151 90] 15725150 9 16280] 16499187 20 16699] 179.05] 174 27 eo | o | or | fo] o | os | o | or | om | oo | 100 | vos | vor | s00 Ac|Th| Pa] U | Np] Pu}Am|Cm| Bk | Cf} Es |Fm| Md | No | Lr 32.04201.04 239.09Olympic Hoa hoc quéc té lan thr 40, Bai tap chuan bi Nhitng Iinh vuc dac biét kho Ly thuyét Méi quan hé gitra cdc hang s6 cn bang, thé khir chudn va nang Iugng Gibbs tiéu chuan; Bign héa v6 co, chu&n dd oxy héa - khir va cn bang oxy héa - Khir; Biéu thtrc tich phan cla phan tng bac nhat, chu ky ban huy. Phuong trinh Arrhenius, xc dinh nang lugng hoat héa, dinh huéng phan tich co ché cdc phan ting phic tap CAu tric vat chat 6 trang thai ran Sy bién déi chon loc lap thé (ddng phan dia, dng phan di quang), hoat tinh quang hoc; Monosaccarit, can bang gitra dang vong va mach hd, pyranozo va furanozo. Céng thtrc chiéu Haworth va céng thire cau dang, cdc glycosit; Thyc hanh Chuan dé dinh lugng vé co nang cao; Ky thuat tng hop co’ ban: loc, lam khé két tua, chay sAc ky ban méng ; Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét— box Héa hoc OlympiaVN 7Olympic Hoa hoc quéc té lan thr 40, Bai tap chuan bi Cac bai tap ly thuyét Trong qua trinh trung tu lai khu nha s6 221 phd Baker thi ngudi ta da cé duoc mét kham pha thu vi. O day ngu@i ta da tim thay duoc mét chiéc td nhd ma trudc dé duge ding dé cAt git cdc ghi chép chua biét. No ndi lén rang Bac si Watson van ghi lai nhiyng cudc phiéu Ivu cia éng voi Mr. Sherlock Holmes cho dén nhiing nam 1950s. Nguoi ta doc urge mét cau chuyén thd vi nhung chua hoan chinh nhu sau: 1va nhy ngay lén xe taxi ri Idi dén phé Baker, lo sg mot phan rang t6i 06 thé da dén quai tré dé hd tro trong viée tim ra sy bi 4n nho nhé nay. Tor tim théy Sherlock Holmes mot minh, nhung trong trang thai niza thire niva ngu vei than hinh cao cao cudn trdn 6 mot goc chiée ghé banh. Trén ban day ry cac chai lo va éng nghiém dugc sép xép bira bai ccung v6i thir mai khé ngiri cia axit clohydric n6i Ién rng anh da dong nguyén ngay dé tién hanh cac cong viéc hoa hoc v6n da rat than quen voi anh. Hién nhién rang nguoi ban cca (01 Ga kiém tra cn than chiée hop kim loal dong kin ma Cchiing t0i da tim thay duoc 6 phia sau mot phién gach trot 6 ngay phia trén day chuéng phong khiich 6 ngoi nha nghéo ca Browning, ‘Anh néi: ‘Khong cé mot bang chizng nao cho thay cé tén t6i ham nao theo dai chiéc hop nay’. Ho da kham xét ti tang ham dén gac xép réi, Ti cé vé nh da danh mat chinh minh rnéu nu trudc do toi da khong gap Irene Adler...” ‘Sy chd y cla t6i hoain toan huéng vé phia chiéc hop a@ mr trén mat ld sui, No trédng khong. *Sé rt tt hon néu nhw gig nhtng gi cé trong hop khdi dau hoang”. Holmes gidi thich va dua cho toi mot cai chai. ‘Biéu nay sé lam cho n6 an toan hon dui téc dong cia khong khi nhung sé lam n6 dé chay hon.’ Chat léng mau vang trong cai chai dang bao quanh nhting vién ¢6 kich thuée nhé nhu ngén tay. “Day c6 phai la mot chat d6c nguy hiém khOng ?' Toi hdi. “khong han dau, Watson. bao gié’ anh thay mot chdc doc & dang vien ion nhu thé nay bao gid chua ? No sé rt khé nudt. Hay nhin day. ‘Anh ldy mot vign nhd, lam kh6 nd mot céch than trong r8i tha n6 vao trong nuée. Thay vi né tan cham hay cchim xuéng thi vin nhé nay “nhay" mot cach bat thudng trén mat nude. phat ra tiéng xU xi, cho cac bot kh ‘va mot s6 sn phdm c6 mui hoi, Ci mui cay nay lam cho toi cdm thdy dau hong va bat dau ho. “Holmes, thir nay sé giét chét ching ta mat,’ Toi gao len. “Anh nén xem phan ng cua no v6i axitclohydric. Buong nhién nhu t0i 48 n6i voi anh, phan nao 46 nd khong d0c,'Holmes vira néi vira ho. Va bat thin linh anh lay mot hop diém, cham lira rbi dua lai gan binh phan wing, céc bong bong khi béc chay voi ngon lira mau dé dep nhat ma tdi tirng dug thay. ‘CO dep khong? Moti ounce chat nay phan (ing véi nudc hay axit clohydric cho nhiéu hon ba cubic feet (cm*) khi, Toi da do duc 3.068 cubic feet 6 80.0 d9 va 4p suat tiéu chudn “Anh do duge dén thé u?' Toi gao én “DI nhién t0i xéc dinh no’ Holmes noi voi mot thai dO thiéu kién nhn, Anh lay mot cai chai dan nhan phenolphtalein va cho vai gigt vao trong chau nuéc thi ngay lap tizc chuyén sang mau hdng, ci mau goi tai cho toi mau sc cua ngon lira méi thay Ic nay. "Bay 06 phai la ly do ma chat nay rét quy khéng 2° "khong han,’ Holmes néi thm. 'Stic manh cia dia nguc da tao ra cdc vién nd nay hay t61 d& pham qua nhidu sai lam hé Watson. Tén toi pham & nha Browning khong quan tam gi dén cai hép kh6ng dang tién nay. TOi nhin vao nhdng vign nhé nhu cdm thach trong chai va cdm thay phan nao so’ hai Toi van chura hoan toan higu, anh Holmes.’ "Toi da tién hanh do dac chinh xac. Toi héa tan chinh xc mdt ounce chat nay vao nue, sau do dun soi dung dich thu dugc dé thu vé chat rén mau tréng ma tdi khong thé lam khé hoan toan dugc nén tdi hoa tan 16 lai trong nusée rdi thém vao mot it axt fohydric cho dén khi mét mau cla phenolphtalein. Toi dun soi Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét— box Héa hoc OlympiaVN 9phan nuéc [an nia va lam khé ba ran luc nay da khong con 1a van dé. Khéi long cia né dich xac la ba va vva mot phan tam ounce. Ba va mét phan tam, Ba thay chuva ho Watson ?” "Toi van con mi ma,’ T6i tra li voi mot sy bdi ri thay 6. "Toi khong muén tao ra mot bi an’, anh ndi, cudi mim, Van dé luc nay rAt don gidn. Anh con nhé chuyén phiéu Iuu nhé cila chung ta véi gido su Urey chur ? Cac ghi chép ngung & day. Sherlock Holmes sir dung cac don vi thudc hé théng do lvéng ci cla nuéc Anh: 1 foot bang 30.48 cm, 1 ounce la 28.350 g, ap suat khi quyén la hang dinh (101325 Pa) trong vai thé ky gan day. Nhiét d do 6 day la d6 Fahrenheit (°F): 0 °C bang 32 °F, trong khi 100 °C la 212 °F. Hay gip Watson tim ra chat gi trong hop. No dug ding dé lam gi ? Bai2 Hop chat A la mudi bén ciia kim logi H. Né chita 11.97 % N, 3.45 % H va 41.03 % O (ve khéi lugng) ngoai kim loai. So dd sau day mé té mot vai phan ung bat nguén tir A va H (A biéu dién dun néng). Phia trén mai tén biéu dién céc tac nhan cain thiét. Tat cd cdc chat déu cé mang nguyén t6 kim loai con san pham phy thi khéng (Khi mot chat duge xac nhan la tan trong nuéc thi né [a hgp chat ion va ban chi can viét ion kim loai) On By OHH o, og OZ0LH Ag, O10 Diy 2 H'/ HO © {sount Fat Ea fen ES e ®, fe |H20- |H20. H20 4 O24, jy Oa, 5, OH, K,, Less isx a) Xac dinh cac chat tiv A-K va viét cdc phan tng xay ra tir 1-14. b) Cho biét cdc phan tng nao trong sé cac phan Wng trén la oxy héa - khtr ¢) Cho biét chat nao trong sé cac chat tir A-K khéng co cap electron khéng lién két. d) Dva vao so dé da dua ra hay dé nghi phan tng diéu ché G tir F nhung khong dugc ‘str dung E. e) Hop chat B rt quan trong ctia né va cho g trong céng nghigp. Viét mét phan ding thé hign tinh quan st nd déng vai tro gi ? 10Olympic Hoa hoc quéc té lan thr 40, Bai tap chuan bi f) Tinh % cht I chtra *°CI néu khi clo ban dau duoc ding trong phan teng 8 chtra 99 % Elva 1 % Cl? g) Cho biét phn tram chat J sinh ra tir mau chat | chtra cl? Bai 3 Ban kinh cia kim loai crom du¢c uéc lwong la 126 pm. Khéi long riéng clia crom la 7.14 g/cm’. Crom tinh thé cé cau tric thuéc mang tinh thé lap phuong. a) XAc dinh kiéu mang tinh thé hang sé mang cia crom néu chi dya vao cac gid tri da cho. M6t thi nghiém dé xdc dinh sy cd mat cla ion Cl duge tién hanh nhu' sau: dun néng mot hén hop khé ctia mot vat ligu chu biét va kali dicromat voi axit sunfuric dc. San pham khi sinh ra dug dn qua dung dich NaOH, néu c6 sy xudt hién olla mau vang tic mAu ban dau cé mat clo. b) Hop chat bay hoi nao cla crom da dugc sinh ra trong phan tng trén? Vé céu tric ctia nd. Luu y rang trong phan tng dé sé oxy hda ctia clo va crom déu khong déi. ‘Axit hoa dung dich kali cromat dan dén sy tao thanh ion dicromat mau cam, sau dé la mau 6 dam clia cdc ion tri- va tetracromat. St dyng axit sunfuric dc chting ta nhan duoc mot két tla mau d6 khéng chwva kali. c) Viét cdc phan Ung xy ra va vé céu tric cdc ion. Ban cé thé 48 nghi ra mot cau tric ctia két tia khong? Gian d6 Latimer déi voi day cac tiéu phan chtra crom trong mdi trong axit (pH=0) va bazo (pH=14) dugc cho 6 duit 4.72 » 0.55 Cr,0F —— Cr(v) —— Cr(Iv) rt Cr | 0.95 | -0.74 3 -0.11 -1.33 Crop OH) cr 0.72 1.33 Cr(OH)- d) —Timba gia tri con thiéu. Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét - box Héa hoc OlympiaVN 11e) Cd phai Cr(V) va Cr(IV) bén déi voi phan teng di ly khong ? Dua vao gian dé Latimer hay chi ra xu huwéng cla chung. Tinh hang so can bang déi voi phan tng dj phan cua ion Cr"? f) Tinh tich sé tan cia crom (III) hydroxit va hang sé bén téng céng cia anion phtre tetrahydroxo-cromat({Il). Gian dé Latimer cla day cac tiéu phan clia oxy trong méi truéng axit (pH=0) va bazo’ (pH=14) duge cho 6 dudi 1.23 0.695 1.76 Oo. ——_—_—_—_———_- H2.02. ——— 20 0.13 1.51 U—___ HO 0.20 OF 9) Chuyén gi sé xdy ra néu pH cila dung dich chira cromat(V1), Cr(lIl) va hydropeoxit dugc dat la 0? Chuyén gi sé xay ra néu pH bang 14? Viét cdc phan tng xay ra va tinh cac gia tri thé chuan tuong Ung. Bai Silic oxit va thiy tinh silic c6 cdc don vi cdu tric néi véi nhau bdi lién két céng héa tri Si-O a) Cho biét s6 phdi tri cia cdc nguyén tt Si va O trong cdc cau tric nay Biét khdi lugng riéng ctia thliy tinh silic [a 2.203 g/om®. b) Cho biét thé tich trung binh cia mét don vj SiOz? Co bao nhiéu lién két trong mot don vi thé tich trung binh ? Mang tinh thé cila thiy tinh silic khéng hoan hao do sy thiéu hut oxy: cde nguyén tl oxy trong mang tinh thé da bi mat va cac nguyén ttr Si lang giéng cla nguyén tl Si mat oxy ty bén héa bang cach tao lién két Si-Si. Mau silic oxit v6 dinh hinh dugc dac trung béi céng thie SiO; 9. c) Tdng sé lién két Si-Si chiém bao nhiéu phan tram? 12Olympic Hoa hoc quéc té lan thr 40, Bai tap chuan bi d) Viét biéu thirc biéu dién ti Ié ng.s/ng.o trong mot mau SiO, nhu mét ham ciia x, voi Ng.si la 86 lién két Si-Si va ng.o la sé lién két Si-O. Tinh gia tri cla x khi trung binh tat cd cdc nguyén tir Si déu tao mot lién két Si-Si. Bai5 Pyrit (FeS2) tao mang tinh thé kiéu NaCl v6i cdc ion Fe** chiém cae vi tri cla Na* cn S* chiém cac vi tri cia ion CI’. Cac lién két S-S dinh hudng luan phién theo duéng chéo chinh. a) Fe duge phéi tri boi 8 nguyén tir lvu huynh. Nhu vay sé phéi tri cdia lvu huynh la bao nhiéu ? b) — Khdi lung riéng (p) ctia mét tinh thé pyrit ly twéng la 5.011 g/cm’. Tinh hang sé mang cla 6 mang co s0. Ngu®i ta da chimng minh duge rang hang s6 mang khéng phu thudc vao céng tha hyp thirc cda tinh thé tc la mang tinh thé van bén ving néu gia tri y trong céng thirc FeS, dao dng nhe xung quanh 2 (1.95-2.05). ¢) Tim phuong trinh thé hién méi lién hé gitra khdi long riéng vao y, cho rang chi co ham Iwong cla sat bién déi. Tim phuong trinh tuong ty néu nhu ham luong cua lvu huynh bién déi. a) Vé hai duéng cong trén cung hé truc y-p. Xac dinh cac vung sau trén dé thi: thiéu hut (Fe, hay S thiéu),khuyét tat dién ké (Fe, hay S du), mang tinh thé hoan hao. Trong quang pyrit thién nhién nguoi ta tim thay rang 99% vj tri cua nguyén ti sat bj chiém va 1% nguyén tir lu huynh dur ra xuat hién & cdc ché khuyét, ) —XAc dinh thanh phan ciia tinh thé. Tim cae diém twong ng 6 gidn dé y-p vira vé. Baié Cho dén thoi diém cudi thé ky 20 thi chi hai tiéu phan (mét phan td va mét anion) duge biét la tao thanh tir duy nhat cac nguyén ti nito, a) _Céng thive thye nghiém cua hai tiéu phan nay la gi ? Hopp chat vé cd dau tién chi chia duy nhat nito rat khdc biét so voi cdc chat trén da duoc tng hgp bdi Christe va céng sy vao nam 1999. Chat dau ctla phép téng hop nay la mét chat léng khéng bén A Ia axit yeu mot ndc. NO dug giai phéng khdi dang mudi natti (chia 35,36% natri vé khéi lung) bang lveng du lon axit stearic. b) _Xéc dinh céng thirc phan tir A va vé hai céng thre cOng huéng ciia phan tl nay (Chi ra cac cp electron héa tri lién két va khéng lién két trong phan tl.) Chat dau khac la chat (B) duoc diéu ché tir déng phan cis cla mét hop chat nito halogenua vén chira 42.44 % nito vé khdi lugng. Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét — box Héa hoc OlympiaVN 13,c) Xe dinh céng thive thyc nghiém cia halogenua nay. Vé céng thie Lewis d6i voi déng phan cis nay. Chi ra cac cp electron hda tri lién két va khOng lién két trong phan tur, Nito halogenua nay phan tng véi SbFs (Ia mot axit Lewis manh) voi ti Ié 1:1 6 -196 °C. Hop chat ion moi (B) nay duge xac dinh chia ba loai nguyén tw. Phép phan tich khéi lugng cho thay né chira 9.91 % N va 43.06 % Sb vé khdi lugng; xa hon thi né chira mét cation va mét anion, Hinh dang clia anion duge xac dinh la bat dién, d) — Xc dinh céng thc thyc nghiém cia hop chat ion B. ) Xe dinh céng thie thy nghiém ctia cation trong B va vé céng thire Lewis ciia nd, Vé cae cdu tric cong huéng néu c6. Chi ra cc cp electron hoa tr lién két va khong lién két trong phan tir. D8 nghi géc lién két cia cc tiéu phn tao thanh ion nay. B phan Ung mainh ligt voi nu6c: 0.3223 g hop chat nay cho 25.54 cm? (6 101325 Pa va 0°C) mét oxit nito khong mau va khéng mii chtva 63.65 % nito’ vé khdi long. f) Xe dinh nito’ oxit nao da sinh ra trong phan ting thiy pha va vé cdu tric Lewis cla n6. Vé cac cau tric céng hudéng néu cé. Chi ra cdc cp electron héa tri lién két va khéng lién két trong phan te. 9) _ Viét phuong trinh héa hoc khi B phan tng voi nude. Trong thi nghiém cia Christe va cac c6ng sy thi A dugc trén véi B trong hydro florua léng 0 -196 °C. Hén hop dug lac trong ba ngay trong mét ampun han kin 6 -78 °C, cudi cung 1nd lai dug lam lanh dén -196 °C nhan duoc hop chat C cling chira cling dang anion bat din nh B va dang cation dac biét hinh chi? V chi chira toan cdc nguyén tir N. C chira 22.90 % N vé khéi lung. h) — Xac dinh c6ng thtrc thyc nghiém ctia C. i) Cation C c6 kha nhiéu cau truc cong huéng. has many resonance structures. Vé céc cu tric céng huéng. Chi ra cac cap electron hda tri lién két va khong lién két trong phn tir. Dé nghi goc lién két ca cac tiéu phan tao thanh ion nay. i) Viét phuong trinh héa hoc cho sur tao thanh C. Sy tao thanh hop chat nao da lam cho qua trinh nay thuan Igi vé nhiét dng hoc ? Cation cia C 1a mét chat oxy hda manh. No oxy héa nuée, phan tng nay dan dén sy tao thanh hai don chat khi. Dung dich thu duge chtra san phdm giéng nhu sy thy phan B. k) _Viét phuong trinh phan tng thiy phan C. Vao nam 2004, ngudi ta di xa hon. Hop. chat ion E da dug ting hop chira 91.24 % nito vé khéi lugng. Buéc dau tién téng hgp E la phan tng gitra clorua ca mot nguyén t6 phan nhém chinh véi long dur muéi natri cua A (trong axetonitrin & -20 °C) dan dén su tao thanh hop chat D va NaCl. Trong qua trinh nay khéng ¢6 sy thoat khi. O' bude thw hai thi D phan wing vai C trong SO2 lng & -64 °C cho san phdm E. TiIé cation:anion trong E cing la 1:1 va né cling chia cing loai cation nhu trong C. D va E cling chira cung mét loai anion phirc vi nguyén tlr trung tam dug phéi tri bat dién. 1) Xac dinh céng thie thy nghiém cla E, néu biét no chia hai nguyén tl. 14Olympic Hoa hoc quéc té lan thr 40, Bai tap chuan bi m) _Xéc dinh céng thie thyc nghiém cia D va xéc dinh nguyén t6 phn nhém chinh d& duge ding. E duoc xem nhu la mét nguén nhién liéu tim nang cho nganh du lich vi tru trong trong lai do né tda rt nhigu nhiét. (No cing duge goi la “vat ligu dc nang lugng cao"). Mot log thé dé co thé dung né trong tvong lai la san pham sinh ra do E phan hiy khéng déc nén no khéng lam 6 nhiém khéng khi. n) Sdn pham phan wing phan hiy E trong khéng khi la gi? Bai7 Tinh néng dé chinh xac ctia méi dung dich sau: a) Dung dich HCI 66 pH = 4.00 (dung dich A), b) Dung dich axit axetic o6 pH = 4.00 (dung dich B), ¢) Dung dich axit sunfuric c6 pH = 4.00 (dung dich C), d) Dung dich axit xitric 06 pH = 4.00 (dung dich D). Tinh pH cia cac dung dich hén hyp sau: ) —Cing thé tich dung dich A va dung dich NaOH cé pOH = f)—Cing thé tich dung dich B va dung dich NaOH cé pOH = 4, g) _Cing thé tich dung dich C va dung dich NaOH cé pOH = 4, h) —Ciing thé tich dung dich D va dung dich NaOH cé pOH = i) Cling thé tich hai dung dich A va B i) Cling thé tich hai dung dich A va B. Axit axetic: pK, = 4.76 Axit sunfuric: ps2 = 1.99 Axit xitric: pK: = 3.10, pKaz = 4.35, pas = 6.39 Bais Nhiéu chat v6 co’ cé kha nang ty phan ly khi chting & trang thai Ing. O trang thai l6ng thi hydro florua (khéi long riéng, p = 1.002 glo’) thi can bang dui day biéu dién sy proton phan: 3 HF = HoF* + HF” Hang sé cén bang tong ting cia phan ting ld 8.0-10"", a) Tinh phan mol flo t6n tai trong tiéu phan cation trong HF Iéng, cho rang chi cé ba chat 6 lién quan tn tai trong hé. RAt nhigu phan ting khac nhau xay ra trong HF léng. Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét — box Héa hoc OlympiaVN 15b) _ Viét phan tng cia HF long voi cdc chat sau day: H2O, SiOz, axeton. Trong nue thi HF thé hién tinh axit trung binh va chi phan ly mot phan. Cac phan tng quan trong nhat bigu dién can bang phan ly clia HF trong dung dich dugc cho dui day: HF + H20 = H,0° + F (1) HF + = HF (2) Hang sé cn bang ctia hai can bang trén la Ky = 1.4-10% Ky = 2.6-10 ¢) Tinh ndng dO chinh xde cia HF trong dung dich cé pH = 2.00 Trong nhieng nghién cru dau tién vé dung dich nude cla HF thi ngudi ta bd qua can bang (2). Tuy nhién gid tri pH do duge khi chi xem xét cn bang (1) lai mau thudn voi thye nghiém d) Hay chi ra rang khi chi xem xét can bang (1) thi gid tri pH do duge dn toi sy phu thudc gitra ndng d6 vao hang 6 can bang cla (1). Hai nha hoa hoc muén xac dinh hang sé axit cla HF (K;) tle cing mét dung dich da biét truéc néng a6. Ho xac dinh pH ctla dung dich va tinh ton nhan dugc K;. Tuy nhién mot nha héa hoc gidi hon biét van tan tai can bang (2), c6 ciing biét hai ngudi cén lai khéng biét dén can bang nay. Nhu vay cé ay hét strc ngac nhién khi thay ho cling thu dug gid tri Ky. e) —Néng dé dung dich HF ban dau la bao nhiéu? f) Tinh hang sé cn bang ctia can bang sau: 2HF +H,0 = Hj0* + HF” Can bang phan ly cla chat tan trong dung dich cd thé dug dich chuyén bang cach thém vao mét chat khdc thich hyp vao dung dich. 9) _D&n ra ba hgp cht v6 co khdc nhau cé khd nding lam tang sy phan ly cla HF trong nude. Cac chat thich hop cling c6 thé lam dich chuyén can bang ty phan ly cia HF 6 trang thai long bang cach diéu chinh Iugng chat. Mét vi dy da dure nghién cizu nhiéu la SbF. h) Chia chat SbF dich chuyén can bang ty phan ly cla HF léng nhu thé nao ‘Sv dich chuyén cAn bang ty’ phan ly cling bao gém viéc tao ra mat bién déi quan trong vé tinh axit Bronsted clia dung méi. Nhu vay d6 solvat héa cia proton sinh ra tur sw ty phan ly anh huéng rat I6n dén tinh axit Bronsted cia dung méi. i) Tinh axit Bronsted ctia mot dung méi cho truée phy thude nhu thé nao vao sy gia tng khd nding solvat héa ciia proton ? Hén hop HF-SbFs thugc vé nhém superaxit do tinh axit rt cao cia chung. Cac axit nay co kha nding proton héa cac bazo rat yéu va nhw vay cho phép md ra khd nang proton héa ac tiéu phan bj dng voi kha nang nay. Diéu nay cling déng nghia voi viéc me ra cdc kha nang téng hop mdi. 16Olympic Hoa hoc quéc té lan thr 40, Bai tap chuan bi i) Viét phan eng xay ra khi cho metan va neopentan tong tc v6i superaxit HF-SbFs. Luu y trong ca hai trwéng hop déu tao ra duge san phdm khi. Bai 9 Amoni sunfua ((NH4)2S) la mét chat duoc str dyng rat réng rai trong phan tich dinh Iugng. é diéu ché tac nhan nay thi ngudi ta suc khi hydro sunfua qua dung dich amoniac 4-5 mol/dm®, réi sau dé thém vao mét it nudc. Dung dich dug chudn bi ttr phuong phdp nay hau nhu khéng tinh khiét.. NO c6 thé chia amoniac hay lveng du amoni hydro sunfua khi thé tich khi hap thy cao hon hay thap hon so voi hé s6 ti lung khi bi hap thu. © 10.00 cm? amoni sunfua duoc pha loding dén 1.000 dm®. Lay 10.00 cm® dung dich thu dugc nay chuyén vao binh cat ri thém vao dé ~40 cm? nude. Sau do lay 25.00 em? dung dich cadimi nitrat 0.1 mol/dm? duc thém vao binh htrng (noi ma cac phan ct ra duge ngung ty lai). Thém vao dé ngudi ta cho 20.00 om? dung dich axit sunfuric 0.02498 mol/dm® vao binh cat. ‘* Gan mot niva dung dich trong binh cat duge ngung ty lai & binh hing (Trong binh htyng thi ta cd thé dé dang nhan thay sy tao thanh két tua vang) ‘+ Phan con lai trong binh cét dugc chuyén hoan toan vao binh nén a8 chuan do. Sau khi thém vao do vai giot metyl dé thi tién hanh chun dO né bang dung dich NaOH 0.05002 mol/dm® NaOH. Thé tich chat chuan can 48 dat dén diém tong dong la 10.97 cm’, ‘* Dung dich nude brom dug thém vao binh hing (két tla tan ra) va long du’ brom bi loai di bang cach dun s6i dung dich trong vang 45 phut, Brom cé kha nang oxy héa céc hop chat chia anion sunfua thanh sunfat. Trung hoa hét Iuveng ion hydro sinh ra ti phan tng xay ra trong binh hung thay t6n hét 14.01 cm? dung dich NaOH 0.1012 molidm®, Tinh thanh phan chinhh xac cla dung dich amoni sunfua da diéu ché duge Bai 10 Dya vao nhiing théng tin & website cla ngan hang trung wong Hungary thi déng xu 2 forint Hungary mau sang bac duge ché tao tiv hop kim chi cia déng va niken, Mdt nha hoa hoc to mo (ligu ai biét dug rang chang ta co kha nang huy diét hét tién & Hungary hay khéng) can déng xu 2-Ft (3.1422 g) va héa tan hoan toan né trong axit nitric dac trong vong 4 gid trong td hut. Chi duy nhdt mot khi mau nau duge sinh ra trong qua trinh nay. a) _ Viét phyong trinh héa hoc cho phan tng hoa tan ‘Anh chang pha loang dung dich thu dug dén 100.00 cm? trong binh dinh murc. 8 xc inh thanh phan cla ddng xu thi anh ta 44 cd mt két hoach rat théng minh. Dau tién anh ta chun bj dung dich NazS2O3 bang cach hoa tan 6 g NazS203-5H20 trong 1.0 dm* nude. Sau dé anh ta cn 0.08590 g KIOs, héa tan vao née r8i dy 100.00 cm? trong mét binh dinh mirc. Anh ta l4y10.00 cm® ctia dung dich nay rdi thém vao dé 5 cm® 20 % axit clohydric va 2 g KI rén. Dung dich thu dug ngay lap ttre chuyén sang mau nau. Sau dé anh ta chuan d6 mu bang dung dich Na2S2O3 da pha sn. Tién hanh song song céc thi nghiém tuong ty anh ta xdc dinh diém tuong duong ciia phan tng [a 10.46 cm’, Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét — box Héa hoc OlympiaVN 17b) _ Viét tt ca cac phan tng xay ra va xc dinh néng dé cia dung dich NazS2Os. Anh ta nén sir dung chi thi nao trong phan @ng chuan dé ? Khi anh ta rira dung cu thi anh ta thay rang c6 mot Ivong két tia trang xuat hién & mau thr nhat. Anh ta nho rat r6 rang anh ta thém nhiéu hon lvgng Na2S2O3 can thiét so voi lugng can dé dat dén diém tuong duong. c) Viét phuong trinh héa hoc cila phan tng sinh ra két tua Tiép theo anh ta quay tr vé véi dung dich mau xanh da troi ma anh ta da chuain bj tu truéc. Anh ta lay 1.000 cm? dung dich nay cho vao binh nén, sau dé thém vao 20 cm* dung dich axit axetic 5 % va 2. KI. Anh ta doi trong vong 5 phut thi dung dich cé mau nau va xuat hién mét két ta cd mau sang. d) — Viét phuong trinh héa hoc gidi thich sy bién 46i mau cla dung dich va sy xuat hién két tua. Tai sao anh ta phdi dgi ? Tai sao lai la mot sai lm néu nhw anh ta doi lau hon ? Anh ta sau do chudn 46 mau bang dung dich Na2S2Os thu duge. Thé tich can dé dat dén diém tuong duong la 16.11 cm®, Bay gid’ anh ta co thé tinh dug thanh phan cla xu 2-Ft. ) Thanh phan phan trdm vé khéi long cia mdi kim loai trong déng xu ld bao nhiéu ? Do la mét nha héa phan tich gidi nén anh ta kh6ng thod man voi két qlia thu duge nén cd gang xc dinh thanh phan olla déng xu bang phuong phap tao phifc. Trong phuong phap nay anh ta khéng quan tam dén két qua da thu dugc bang phuong phap iot. Dau tién anh ta hoa tan 3.6811 g NaxEDTA:2H,0 (M = 372.25 gimol) dé tao 1.0000 dm? dung dich. Sau dé anh ta ldy 0.2000 cm’ ciia dung dich mau xanh da troi dau tién, thém vao dé 20 cm? nuée va 2 cm? dung dich amoniac 25 %. Dung dich chuyén sang mau tim dam. f) _Tidu phan nao gay ra mau dé ? Vai trd cila viée thém amoniac & day Ia gi ? Tur mét sé cdc thi nghiém tuong ty anh ta da xc dinh diém tuong duong cla phan wng 1a 10.21 cm’. g) Két qa nay liéu co sai léch so voi két luan truéc dé vé thanh phan cia dong xu khong ? Anh ta van chua théa man va bat dau nghi rang Idi & day la vao Ic anh ta can déng xu nén anh ta mé may phan tich tréc quang cti ca phong thi nghiém. Phong thi nghiém ma anh ta dang lam viéc 14 mét phdng thi nghiém tot nén anh ta dé dang tim thay, diéu ché va chuan héa duoc dung dich CuCl; 0.1024 mol/dm* va dung dich NiCl, 0,1192 mol/dm®. au tién anh ta do phé hap thy cia dung dich CuCl, bang cach ding cuvet thach anh day 1,000-cm va lvu y dén gid tri dé hdp thy & mét vai buéc séng ma theo anh ta la phi hop: Alnm]260 [395 [720 [815 A 0.6847 | 0.0110 | 0.9294 | 1.428 Sau dé anh ta do d6 hap thy cua dung dich NiCl, & cing mét buée séng trong cng mot cuvet: Ainm | 260 395 720 815 A 0.0597 | 0.6695 | 0.3000 | 0.1182 18Olympic Hoa hoc quéc té lan thr 40, Bai tap chuan bi Anh ta pha lodng 5.000 cm’ dung dich xanh da tréi ban dau dén 25.00 cm’ trong mét binh dinh mirc va do d6 hap thy. Anh ta doc duge gid tri la 1.061 & 815 nm va 0.1583 6 395 nm, h) Tai sao anh ta phai pha long dung dich. Néu chi dya vao nhing két quia cla phuong phap phan tich trac quang thi thanh phan cla déng xu nhu thé nao ? Tiép theo anh ta do d6 hdp thy quang 6 720 nm va nhan duge gia tri 0.7405. i) Gid tr nay co phu hyp véi nhiing két ludn tude dé khéng ? Cui cling anh ta chinh thiét bi dén 260 nm. Anh ta rat ngac nhién khi doc duge gia tri la 6.000. j) Anh ta muén thay gia tri bao nhiéu ? Anh ta quyét dinh do 46 h4p thy quang 6 budc séng nay trong cuvet thach anh nhd hon 6 d6 day 1.00-mm nhung anh ta van nhan duge gid tri la 6.000. k) — Giai thich su xuat hién gia tri nay va hay tim mét phuong phap dé xdc nhan diéu do bang cach str dung cac héa chat va dung cu da duge nha hda hoc clia ching ta sir dung, Bai 11 Vao ngay 30 thang 1 nam 2000, mét dap héng trong mét mé vang lam tran 100 000 m? nuéc thai chtva xianua xuéng dong séng Szamos. Nhiing dgt nuéc 6 nhiém nay sau dd lan dén cdc sng 6 trung tam chau Au Ia Tisza va Danube sé giét mét sé long lén ca, Vao ngay 15 thang 2 kénh tin tc cla dai truyén hinh trung wong Hungary phat sng mot thi nghiém don gidn: dau tién chudn bj dung dich NaCN, néng dé cila né cing tvong ty VOi néng 46 do duoc & dong nude 6 nhiém. Ca chét 6 ndng dé nay nhung sé séng duge khi thém vao dé sat (II) sunfat. Chuong trinh TV nay can gia thiét rng sat (II) sunfat nén sw dung dé lam gidm di phan nao sy pha hoai méi trvéng cla dung dich xianua. Tuy nhién khi mét thi nghiém tong ty dugc lap lai voi mot mau thyc lay tir dong nuéc 6 nhiém thi ca van bj chét sau khi thém vao do sat (II) sunfat. Dang tiéc rang thi nghiém ther hai nay khéng hé dug dé cap dén trong m6t ban tin budi t6i nao é lam sang té ban chat hda hoc ctia van dé thi mét nha hda hoc da lam mét chudi cac thi nghiém trong dé sy sir dung dién cy xianua lién hyp déng mot vai tro quan trong. Dau tién anh ta higu chinh dign oye bang cach str dung 3 néng d6 khac nhau 6 3 gia tri pH khac nhau. Nhiét d6 tién hanh tat ca cac thi nghiém la 25 °C. Két qua cla cac thi nghiém phan tich céng cu nay nhw sau! 4.00 ppm NaCN | 10.0 ppm NaCN | 100 ppm NaCN 0.01 mol/dm" NaOH 497.3 mV 438.2 mV 379.1 mV 0.001 mol/dm* NaOH 497.7 mV 438.6 mV 379.5 mV Bem pH=7.5| 598.9 mV 539.8 mV 480.7 mV a) Tinh hang sé phan ly axit cua HCN dua trén cac thi nghiém nay. Tur 100 om? dung dich thir nghiém chira 49.0 mg/dm? NaCN va c6 pH méi trudng dém la 7.5 thi 40.0 mg FeSO,-7H20 ran dug thém vao. © pH nay phan Ung gira ion sat (II) tan trong nude va oxy héa tan xay ra hoan toan dinh lvgng 6 cac diéu kién va cho két tha sat (Ill) hydroxit, Bé qua sy tao phirc gitra két ta va ion xianua. Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét - box Héa hoc OlympiaVN 19b) _Viét va cn bang phan tng oxy hoa - khir nay. TAt c cdc dung dich sir dung trong thi nghiém nay déu chwa long oxy héa tan ban dau la 8.00 mg/dm®. Gia tri doc dugte 6 dién cuc déi voi dung dich nay 1a 585.9 mV. lon sat (II) chi tao mét phic v6i ion xianua trong dé sat cé sé phéi tri 6. c) Viét phuong trinh ion mé ta sy tao phic. Xac dinh hang sé bén cla phire. Cac gid tri déc tinh sau (LCso: ligu chét mét niva sau 24 gid’ ngdm thudc) déi voi ca dug cho 6 bang: LCs ion xianua* 2.1 mg/dm® Naa[Fe(CN)s] “3H20 | 610° mgidm? t6ng long xianua khéng tao phire = [HCN] + [CN] ‘Sy hao hut Iugng oxy hea tan khong phai la van d& lon d6i véi cd Khi thé tich dung trong thi nghiém la rat bé, nhung nd sé la mot van a lon 6 didu kién ty nhién d) Co phai cac két qua thi nghiém va gia tri doc tinh dong y voi két qua thi nghiém da trinh dién trong phan tin tire & dai truyén hinh khong ? Mét diéu nho nén biét vé dong nue 6 nhiém nay la nd con chia cac ion kim loai chu yeu la déng (mét diéu rat hiém thay & cdc mé vang). Ding trong ty nhién thudng xuat hién & dang déng (I!) nhung trong dong nudc 6 nhiém thi né & dang déng (1) do c6 sy hién dién cia ion xianua. e) —Viét phuong trinh héa hoc ctia phan teng gitra déng (II) va ion xianua. Mét mau thy ldy tir nguén 6 nhiém cé pH bang 7.5, ting ndng dé xianua (bao gdm lvong tao phe, khéng tao phirc va da proton héa) dug xac dinh la 26 ppm, tng long dong la 21 ppm. Gia tri doc dug 6 dién cy xianua chon I9c d6i voi dung dich nay la 534.6 mV, va phuong phap dién héa cho thay gid tri ion dong (I) tyr do trong dung dich la khoang 2:10"® mol/dm”. lon déng (|) tao phic voi xianua theo ting ndc cho dén khi dat dugc sé phdi tri 3. Hang sé tao thanh [CuCN] la 6 thé bd qua duge khi so snh voi sy tao thanh hai ion phtrc. Oxy hda tan cé néng dé la 8.00 mg/dm*, cing tén tai voi phtrc déng (I) xianua. f) Ligu c6 déng (I) xianua két ta trong dung dich khéng? (Kspicucn) = 3.5°10") g) Xe dinh sé phi tri ca cdc phire ding (1) chiém wu thé trong m&u nghién ciru. Uoe lugng hang sé bén cla cac phic xianua dong (I) nay. Déc tinh cla phe xianua déng (1) cling tong ty nh NaCN; [Cu(CN)2]" 66 gid tri LCso laf 4.5 mg/dm®, Thém vao 100 em’ dung dich mau nuéc 6 nhiém 40.0 mg FeSO«'7H.0 ran, Bién cyc xianua chon loc cho ta gid tri 592.3 mV déi voi dung dich nay. h) U6 lung ndng dO cia céc phire khdc nhau trong mau. Ligu dung dich nay c6 doc khéng ? Liéu két qua nay c6 phu hgp voi thi nghiém khéng hé duge dua lén TV ? Bai 12 Cp Fe*/Fe* va hé HsAsO,/HsAsO3 la cac hé théng ‘oxy héa - khtr quan trong trong Hoa phan tich do nhizng can bang dién héa cla nd od thé duge dich chuyén boi su tao phir hay thay di gid tri pH 20Olympic Hoa hoc quéc té lan thr 40, Bai tap chuan bi a) Tinh thé khtr chudn E°, ctia phan ung Fe** + e~ — Fe**. Thé khw chudn cia hé Fe**/ Fe** trong dung dich HCI 1 mol/dm? HCI la 0.710 V. b) Dy doan vé hang sé bén déi voi sy tao phive [FeCl]. Ca Fe® va Fe” déu tao phire rat ban voi ion CN™ c) Tinh tilé cla cdc hang sé bén sinh ra trong sy tao thanh ion phtrc [Fe(CN)s]* va [Fe(CN)eJ™. d) HsAsO, va K4Fe(CN)s dug héa tan trong nuéc theo dung ti lwong. Vay tiIé cia [HsAsOx]/[HsAsOs] 6 thoi diém can bang la bao nhiéu néu pH do dug 6 thoi diém nay la 2.00 ? e) Cac ndng dé cn bang sau day c6 thé tén tai duoc trong dung dich nue khéng ? Néu duoc hay tinh pH cia dung dich. [HsAsO,] = [HsAsOs] = [Is] = [17] = 0.100 mol/dm®. Fe" /Fe 0.440 V Fe*/Fe = 0.036 V [Fe(CN)e]*fFe(CN)cJ~ +0.356 V HsASOs /HgASO3 +0.560 V BF +0.540V Bai 13 Gia tri tich sé tan cla bac clorua la 2.10-10"" & 9.7 °C va 1.56:10""° & nhiét do phong (25°C). a) Use lugng tich sé tan va dé tan (6 don vi mg/dm’) ca AgCl & 50 °C. Mac di AgCI khéng tan trong nude nhung né cé tan trong dung dich cd chia cdc tac nhan tao phic. Vi du trong sy cé mat alia ion CI & néng dé cao thi mét phan két tla AgCI 86 tan do tao thanh ion phirc [AgCl). Hang sé can bang cla phan teng Ag’(aq) + 2 Cr(aq) = AgCl2 (aq) la B = 2.50-10° & 25 °C, b) Tinh néng dé ciia dung dich KCI (@ nhiét d6 phong) can thém vao dé gid tri d6 tan cila AgCI bang v6i d6 tan cia né trong nude & 50 °C. Néu mét chat hién dién trong dung dich & nhiéu gi tri oxy hoa khac nhau thi né khong thé dug xac dinh true tiép bang chuan dé oxy héa - khir. Trong trudng hop nay thi dau tién mu phai dugc khtr. Ddi voi mét trudng hop nay thi ngudi ta stv dung cdc dung cu kh. Dung cu khtr thuéng Ia cét chia tac nhan khir manh 6 trang thai ran. Mau dugc axit hoa dug dan qua cét va dugc chun dé véi mot tac nhan oxy héa manh c6 néng do biét truéc (vi dy KMnO,). Phién ban thong dung nhat cia dung cy khir la c6t khi Jones chwva cdc hat hén héng kém. c) Phan tng nao sé xay ra néu ta khéng ding hén héng kém ? a) Viét phan tng xay ra khi cho céc dung dich sau day di qua cét khir Jones: Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét— box Héa hoc OlympiaVN 210.01 mol/dm® CuCl, 0.01 mol/dm? CrCl 0.01 mol/dm*® NH4VO3 (pH =1) e) Sw dung cdc gia tri thé khtr chudn cho & bang dui hay uéc Iugng hang sé can bang cia cdc phan trng nay. Khi str dyng mt tac nhan kht ém diu hon chang han nhu cét Ag/HCl (gdm cdc hat bac xOp va dung dich HCl). Diéu nay cé vé la ling do bac kim loai khong han la mét tac nhan khur tét, Chi xem xét vé thé chuan thi phan tng khi Fe® thanh Fe bang Ag la phan ung bat thuan nghich. f) Nhung chim mét thanh bac vao dung dich chiza 0.05 mol/dm? Fe(NO3)s. Tith ndng 46 cn baing ctia cdc ion kim loai. Phan tram ion Fe™ bi khtr la bao nhiéu? Bay gio’ chung ta sé gia thiét rang phan tng khtr Fe bang Ag dugc tién hanh trong méi trudng HC! 1.00 mol/dm?, g) Phan ting nao xay ra trong trudng hop nay? Tinh hang s6 can bang olla phan ung. h) Tinh néng dé ion [Fe] 6 thoi diém can bang néu biét ndng d6 dau cia ion Fe la 0.05 mol/dm?. i) Chat nao trong sé cac chat sau day sé bi khtr bang hé thong Ag/HCI ? 0.01 mol/dm? CrCl, 0.01 mol/dm? TiIOSO« (cuci= 1 mol/dm? ) IV PIV Cu /Cu 0.34 | Cr/Cr__ | -0.74 cucu’ | 0.16 | Cr /cr__ | -0.90 VO;*NO™ | 1.00 | Zn" /zn__ | -0.76 vor | 0.36 | TO" 7Ti™ | 0.10 VFN |=0.255 | Ag'/Ag | 0.80 VN ~1.13 | Fe*/ Fe” | 0.77 Bai 14 Mét thi nghiém do cdc nha gid kim thuat tién hanh & thdi xua da xac nhan duge rang hoi sinh ra khi nhiét phan protein (vi dy nhu nhéng khic thit thiva 6 1d md) véi da voi cé thém mét loai thudc tht? mau la axit tm trén mét thanh g6 sé chuyén sang mau dé dam. Hop chat c6 phan tng thu vi nay (B) c6 thé duge diéu ché nhu sau (mét vai phan tng dug chi ra & dudi day): 22Olympic Hoa hoc quéc té lan thr 40, Bai tap chuan bi H,0, heat heat protein. —2 ~~» H,.N-CH(C,H,-COOH)-COOH glutamic acid pyroglutamic acid H,0 — 1. Ca(OH), 2. heat multiple products (red) A-E la cdc chat khong mau(trang). B va E la cc chat lng co mui. a) Vé cu tric cdc chat tr A-E. b) _ Giai thich tinh bén cla B vdi bazo va kha nang phan hily nhanh ciia né khi phan ung voi axit. ¢) So sanh tinh bazo cia B va E. Gidi thich. d) Hay dua ra mét so dé phan tng phan hiy chat B bang axit. Gidi thich tai sao san pham lai cé mau. Bai 15 Tinh thom la mét khai niém quan trong trong héa hiru co. Hop chat chura vong thom thé hign cdc tinh chat ly — héa kha dac biét. Cé mot quy tac don gidn 1a quy téc Huckel gitip chung ta xac dinh dug cau tric nhu thé nao thi cé tinh thom. Quy tac nay néu lén rang cc hé théng lién hop vong chi thom khi s6 electron p tham gia trong hé théng lién két Tr bat dinh xu la 4n+2, voi n la mét sé nguyén khéng am. Quy tac nay cé thé dp dung cho cdc hé théng da vong dan trai cling nh hé théng vong ngung tu. a) Cho vi du vé cdc cu tric thom ting voi n= 0, 1, 2. Quy tac Hiickel cling duc ap dung cho cac hé théng vong ngung tu nhu la mot diéu kién bé sung dé xac nhan tinh thom cia chung, b) — Chira rang cdc hé théng ngung ty thang cla cac vong thom (ttre la mét vong thom dugc gan tiép tuc vao mach qua hai nguyén tir cacbon chung) la thom theo quy tac Hiickel. Vi du: OO On my Oo — YY Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét — box Héa hoc OlympiaVN 23,¢) — Chtrng minh rang cac hé théng ngung tu sinh ra khi gan hai mach ngung tu qua hai nguyén tt? cacbon chung cling dan dén mét hé thom theo Hiickel. Vi du: hy + OB, PROB d) Cho biét tiéu chun chung 48 sy ngung ty hai hydrocacbon thom sé tao thanh hé théng thom theo Hiickel. Vi dy: Thy . Oh — COC e) Bua ra vi du ching minh rang quy tc Hiickel khong phai la didu kin can thiét dé thé hién tinh thom. Tinh thom cing I mét sy dinh huéng manh trong tién trinh phan ng nhung cding khéng phai luc nao cing ludn la nhu vay. Chung ta sé xem xét cac vi dy sau: f)__Xiclopentadien cé pKa = 18, xiclopenten co pK, = 45. Giai thich sw khac biét nay ! g) Trong mét sé truéng hop thi sy tautome hda ciing dan dén két qiia [a su tao lap cac. hé thong thom. Hay chi ra con duéng nghich chuyén ma hop chat dui day phai trai qua dé tao lap duoc hé thing thom. r\ UN oO ~o h) Tuy nhién trong mét sé trudng hop khac thi cac cau tric thom lai chuyén thanh cdc cu truc khong c6 vong thom. Hay tim cdc cdu tric khong thom tng voi ac hé théng thom da cho va giai thich tai sao cac cau tric nay lai uu thé hon. Cho cac vi du khdc vé sy tautome héa ma trong dé phan tir wu tién ton tai & cdu tric khéng thom. OH Phan ti porphin la phan ti don gidn nhat trong ho chat porphyrin. Trong cau tric cla nd tan tai 4 vong pirole dat toi trang thai phang hoan toan. Tat ca cdc nguyén ti cacbon va nito dau lai héa sp’. Trong cdu tric nay ta odn tim thay hé théng néi dai lién hop. Khung lién két sigma ciia porphin dugc miéu ta duéi day: 24Olympic Hoa hoc quéc té lan thr 40, Bai tap chuan bi a) Co bao nhiéu electron tham gia vao hé théng néi déi lién hop ? Phan tl nay e6 thom khéng ? Vé hoan chinh cu tric porphin trong dé chi ré cc lién két doi tao thanh hé théng lién hop. Hai nguyén tir nito trung tam cé néi voi hydro. Cac nguyén tir hydro nay déu co tinh axit manh va @ diéu kién thong cac proton nay dé dang dich chuyén sang cac nguyeé tir N ké cn nh hinh dudi: b) I valll thugc loai déng phan nao ? Qua trinh dich chuyén nay anh hung nhu thé nao. én hé théng cc néi doi lién hop: sé electron rr tham gia dich chuyén 6 II nhiéu hay it hon 6 1? Vé cu tric porphin cia II voi sy chi rd cdc néi doi Cac nguyén tt hydro néi véi cacbon trong phan tir porphin cé thé bi thay thé bdi cdc nhém khac. Cho rang ta 6 thé gan mot nhém metyl vao vong porphin. O' diéu kién thuong thi sy dich chuy&n céc nguyén tl H trong vong (H gan voi nito) khéng hé bi anh huéng boi sy’ thé nay va sy dich chuyén xay ra lién tuc trong dung méi. ¢) C6 bao nhiéu déng phan monometyl cia porphin ? Tiép tyc gan thém mot nhém metyl khac vao phan tw porphin. d) —Trong truéng hop nay ta cé thé phan lap dug bao nhiéu déng phan ? Cac phirc kim loai cia porphin dugc diéu ché dé dang. Mét hog chat quan trong ciia loai phic nay la phirc magie vén la b6 khung ctia chlorophyll. Cau tric gém céc lién két sigma ca né dugc biéu dién nhu sau: ni e) Co bao nhiéu electron trong hé théng vong hvu co’ tham gia trong hé théng lién hop. & truéng hop nay. Cé bao nhiéu déng phan metyl-Mg-porphin ma cé mat nhém metyl trong vong hiru co’? Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét — box Héa hoc OlympiaVN 25Nguoi ta da tong hop dugc kha nhiéu dan xuat porphin cua sat (P). Cac mudi nay déu dc trung cho nhieng tinh chat cua dj vdng lon porphin nhung dong thdi nd cing co nhiing tinh chat cla cac vong lon. Ching co kha nang lién ket voi hai ligand, phdi tri voi 16 theo hai bén truc cua nguyén ti sat. Sy tao phire nay gém hai qua trinh lign tiép: Chat ban dau trong dé sat mang sé phdi tri 4 sé lién két voi mét ligand (L) dé tao thanh phirc phéi tri 5 (PL) va sé tiép tuc lién két voi mét ligand tiép theo d8 tao thanh phir phoi tri 6 (PL.). Trong dai da sé céc trvéng hop thi phan tng ngay lap ttc cho ra phizc PL2 trong khi phire PL lai rt kho phan lp. B6i voi sy’ tao phic clia mot phic st — porphin voi pytidin trong dung mdi hiru co tro’ thi dya vao dir kién phé cac nha khoa hoc xac nhan rang hai buo® nay co thé dug mé ta bang cac can bang tuong tng nhu’ sau: P+L=PL K,=1500 PL+L=Plo K2=19000 f) 0 day ching ta da thay mét trvdng hop khéng dién hinh K; < Ke relation. Tai sao diéu nay khéng bao gid’ xdy ra déi voi cdc axit nhiéu nac ? Cho rang chung ta thu hién dugc qua trinh tao phirc nay va dat dugc can bang 6 thoi diém ndng d6 can bang cua ligand L la 0.1 mol/dm*. g) Chtrng minh rang ta c6 thé bé qua dug Iuong phic phdi tri 5 trong dung dich. Cho rang chting ta cé thé phan lap dug phirc PL sinh ra trong tién trinh phan tng & trang thai tan trong dung méi va do tinh bén déng hoc cla né chung ta dat dugc néng dé PL la 0.1 mol/dm®. Bén thai diém xac dinh hé dat can bang. h) _Nhiét 46 anh hudng nhw thé nao dén tinh bén déng hoc ? i) Xac dinh néng dé ctia P, PL, PL2 va L & thoi diém can bang? Bai 17 a) Co bao nhiéu déng phan lap thé cia cdc hop chat cho duoi day ? 26Olympic Hoa hoc quéc té lan thr 40, Bai tap chuan bi b) Cho biét san phdm cilia cac phan trng sau va cho biét cd bao nhiéu déng phan lap thé khac dugc tao thanh ? 1, BH, 2,H,0; ce |. KI, NaHCO, OH ° ro + or ‘00H cl Oo 0s0, Bai 18 Ascaridol (A) la mét hop chat hiru co’ trong ty nhién cé cau tric exotic. Nd cd thé tim dug trong phan hoi ciia tinh dau cay goosefoot (Chenopodium album) va nhiéu cay khac. O day nguoi ta da xac nhan durge cdc théng tin sau: © A tinh khiét chi cé thé dug cat trong mai truéng chan khéng cao do Khi nang nhiét d6 no sé phat no. * Phé °C NMR chi ra trong A chi c6 mot lién két doi C=C. © Dung dich chat A (trong dietyl ete) khdng cho phan tng voi natri. Khir bang LiAIHs cho chat B. + Néu B phan tng voi NaBH, trong sy cé mat cla axit axetic, sau dé phan tng tiép véi HzO, trong méi truvéng bazo thi san pham la hdn hop hai déng phan céu tric. ‘* Phan Ung cila B voi mot dong Iveng trong sy cé mat clia xtic tac kim loai dan dén sy tao thanh C. A phan tng voi sé dong Ivong nhiéu gap di B cting trong phan ten tuong tu dé cho C. C khéng phan tng voi axit cromic trong axeton. Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét — box Héa hoc OlympiaVN 27* Su dehydrat héa C dan dén su tao thanh hai duong lugng H20 va hai hop chat hu co D va E. Xi ly D vi ozon tiép theo khiv bang Zn/H,0 dan dén sy tao thanh mot duong lugng glyoxal (etandial) va mét duong lyong 6-metyl-heptan-2,6-dion, Phan tng tuong ty déi véi chat E dan dén sy tao thanh mét duong Ivong 3-oxo-butanal va ling mét lung 4-metyl3-oxo-pentanal. ‘© Ciing da c6 thong bao xc nhan rag duéi nhing diéu kién ty nhién thi A dugc tao thanh khi chiéu sang D va F cd mat xc tac clorophin. Xéc dinh cu tric cac chat tr A-F. Bai 19 2,7-dimetyInaphtalen c6 thé duoc téng hop bang phan tng gitra tac nhan Grignard A va mot axetal (B). ) MgBr Hye CH; HAC A 1. Grignard react. 2. acid workup B N-chlorosuccinimide (2 eq.) Zn dust Pa, heat c ~D a) Dé nghi diéu kién phan tng cho su tao thanh A va B, b) _ Giai thich bang co ché su tao thanh 2,7-dimetyinaphtalen. c) _2,7-dimethyinaphtalen bj chuyén héa thanh E qua nhizng phan ng da néu 6 trén (E la mot hop chat thu vi c6 céng thire CasHy2.) Xe dinh C, D va E. Bai 20 a) De eet co ché ciia chuyén héa sau (sy vong héa Robinson). Oe Or 28Olympic Hoa hoc quéc té lan thr 40, Bai tap chuan bi b) Tilé héa sy xdy dyng bé khung gonan ie Co map = tt Mét a-clo xeton tién bat déi (prochiral) bi kh thanh halohydrin bang enzym (voi R la nhom ankyl). Mt enzym ancol dehydrogenaza (Rhodococcus ruber) sinh ra dong phan R va mét enzym odn lai (Lactobacillus brevis) cho ra déng phan S. Trong mdi trudng bazo thi cac epoxit tinh khiét quang hoc dug tao thanh tir cdc halohydrin. ) Cho biét cau tric lap thé cia cdc cac halohydrin trung gian va clia cac epoxit. Dé nghi co’ ché chi tiét cho sy déng vong nay. ° Bai 21 Cac xetozo la mot nhém dac biét trong cac dudng. Cac dn xuat ciia D-ribulozo dong mét vai tré quan trong trong tong hop quang héa. Mét a-metyl glycosit ctia D-ribulozo (A) c6 thé dugc diéu ché tl D-ribulozo’ bang cdc xt? ly voi metanol va xtc tac axit. Dun néng A trong axeton o6 mat HCI dan dén sy tao thanh B la mét dan xuat cla propyliden. Axeton tao thanh axetal véi cdc vic-diol néu hai nhém OH cé dinh hudng khéng gian thich hop. Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét - box Héa hoc OlympiaVN 29Hyg -O0CCHs Ow on Ho }-—0 90H, 4 CHZOH uly m : i wb 4 are D-ribulose F eco eae sttise aevonent EAN eat eet Gt op HOH OCH, HO HO. 1-O-methyl-o-D-ribulose<2.5> A a) Trong qua trinh ting hop B thi co thé tao thanh hai cdu tric. Vé cau tric cla ching va cho biét dau la san phdm chinh. B phan Ung voi anhydrit axetic (c6 mat xc tac) dé tao thanh C. D duge tao thanh C bang cach dun néng trong axit loang. D phan ting voi metanol cd mat axit tao thanh E. b) Vé cdu tric ctia cdc chat tir C-E. ¢) — Ligu cé thé xac dinh dug cau dang cia nguyén tir cacbon C1 trong E? Mac du sy tao thanh cdc axetonit la mét phuong phap gid tri dé bao vé nhém OH quan trong nhung trong nhiéu truéng hop no cho nhiéu san phdm (hay thanh phan san pham phy thudc nhiéu vao diéu kién phan tng). Noi chung day la truéng hop hay gap doi voi cac duéng cé cau triic vong 6 canh. Ngudi ta da chtrng minh rang khéng hé c6 sy tao thanh axetonit khi hai nhém OH ké nhau chiém vi tri axial, Tuy nhién cdc vic-diol cé nhém OH chiém hai vi tri equatorial hay mot axial mét equaorial déu phan tng duge voi axeton/HCl. d) Vé hai cdu dang ghé cilia 1-O-metyl-6-O-acetyl--D-galactozo<1.5> (F). Danh déu cc nhém OH 6 vi tri axial (a) hay equatorial (e). Xdc dinh cu dang bén nhat. ) Co bao nhiéu déng phan axetonit 06 thé dug tao thanh tir hop chat nay va 66 bao nhiéu cau dang ghé khac nhau ctia cdc axetonit nay tén tai duoc ? f) _Vé céng thre chiéu Haworth cia L-galactozo’ <1.5> Bai 22 © thai diém hién tai thi nhién ligu héa thach la ngudn nang lwgng quan trong nhat dé phuc vu loai ngudi. Ung dung cia nd dug phan thanh hai loai chinh. Trude hét, nang Ivong héa thach san sinh ra mét lweng lon cacbon dioxit thai vao bau khi quyén, va bay gio’ d& dug hiéu la nguyén nhan gay ra higu tng nha kinh. Thém vao dé voi toc do Khai thac nhién ligu nhu hién nay thi céc nguén nang lng héa thach sé sém bi can kit. Nhigu 30Olympic Hoa hoc quéc té lan thr 40, Bai tap chuan bi ngw®i tin rang cdc nguén nguyén liéu nhan tao nh hydro hay metanol sé som tim duoc tng dung réng rai do né than thién voi mdi tredng hon nhién ligu héa thach. Hydro khéng phai la nguén nang lugng so cap (cd sAn) ma nd phai duge téng hop tir cac ngudn nang long cé sn khdc nh nang Iuvgng hat nhan hay nang long maa trai. Cach tot nhat dé sAn xudt hydro [a tir nude trong mét qua trinh ma ngudi ta hay goi la phan tich nuée. a) Hay tinh xem phai tén bao nhiéu kWh dién nang dé san xuat ra 1 kg hydrog néu qua trinh dién phan xay ra & hiéu dién thé 1.6 V va hiéu suat dong dién la 90 %. Woe lugng xem qua trinh nay cé kinh té khéng dya vao gid dién nang va gid hydro (sir dung gia dién trung binh 1a 0.10 euro/kWh va 2 euro/kg H2). Thém vao dé trong qué trinh sén xuét thi vige chira va van chuyén hydro thinh thoang cing la mét van dé can tinh toi. Nhu vay thi van dé trong tam Ia gia tri nang long tinh theo ti 1é thé tich va ti Ié trong Iugng. TI 1é nang lung tinh theo thé tich Ia gia tri nang lugng cé thé tai sinh chia cho téng thé tich. Ti 1é nang lugng tinh theo trong Iugng Ia gid tri nang lu@ng cé thé tai sinh chia cho ting khdi lvong. b) Tinh gia tri ti I nding lwong tinh theo thé tich va trong lugng déi voi hydro & ap suat khi quyén va 298 K. (Cho rang 6 diéu kién nay hydro la khi ly tuéng) Hydro thudng due van chuyén trong cac binh hinh tru luc ap suati hydro trong binh dat adn 200 bar, Mot binh hinh try 68 Ton duge lam bang thép (khéi long riéng 7.8 g/cm?) cé thé tich str dung la 50 dm* va Itic réng nang 93 kg. O' ap suat cao thi hydro khéng con tuan theo cdc dinh luat vé khi ly tung nira. Luc nay né dugc mé ta t6t hon bang phuong trinh van der Waals: (of ]t%e-m =r voi pla ap suat, Vm la thé tich mol, R la hang sé khi, T la nhiét do tuyét déi, a va b la cac hang sé dac trung cho tirng khi. Voi hydro, a = 2.48-10° Pa m’mol? va b = 2.66-10°° mmol’. Hydro nén chi cé thé duge van chuyén trong binh hinh tru. ¢) _Uéc lugng gid tri ti Ié nang Ivong tinh theo thé tich va trong lung déi véi hydro nén. Hydro ciing c6 thé duge van chuyén & dang hydrua kim loai. NaBH, la mét chat htra hen duge ding nhiéu do né phan ting voi nuéc khi cé mat chat xc tac sé sinh ra hydro. d) Co bao nhiéu mol hydro duge sinh ra tir 1 mol NaBH,? Do nude luén c6 sén nén né khéng can phai van chuyén cling luc voi hydrua kim loai. . ©) _Xéc dinh gia tr ti 18 nang lugng tinh theo thé tich va trong lvong a6i v6i hydro duge cung cp tty NaBH, Biét khdi lvgng riéng cua né la 1.07 g/cm’, Mot diéu kh quan trong [a so sanh nguén nang Iuong nay véi nhing nguén nang lugng khac. f) Tir cdc két qua truéc d6, dé xem ngudn nang luong cua ching ta cé duoc xem la trin vong hay khéng thi hay tinh ti 16 nding Iuong tinh theo thé tich va khdi lvong cua cc ngudn nang Iugng sau i. Graphit l4 mét loai than dién hinh. Tinh khdi lugng riéng cla né néu biét 46 dai lién két trong graphit la 145.6 pm va khoang cach gira cdc lop Ia 335.4 pm. Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét — box Héa hoc OlympiaVN 31ii, n-Octane (CeHia) [4 mét thanh phan cia xang. Khéi long riéng cla né la 0.70 gicm®. iii, Metanol da dug ngudi doat giai Nobel nam 1994 Gyérgy Olah dé nghi la mot nguén nang lugng thay thé cho hydro. Khéi lugng riéng cla nd [a 0.79 gicm®. iv. M@t loai pin khé Ni-MH c6 kha nang nap dién duoc 6 thé tao ra dug cong 6 dong dién la 1900 mAh va hiéu dién thé 1.3 V, c6 dang hinh tru (dong kinh: 14.1 mm, chiéu cao: 47.3 mm, khdi luweng: 26.58 g). v. Nuéc la nguén cung cp hydro cho phan ting nhiét hach don gidn chuyén 'H thanh “He. Cac khdi lugng nguyén tt twong teng la: A,(H) = 1.00782, A,(“He) = 4.00260 Hydro ciing c6 thé dugc chiva & dang léng & nhiét do rat thap. Khdi lvgng riéng cua hydro. long & nhiét d6 s6i cia n6 (-253 °C) la 0.071 gicm®. g) Uc lugng gia tri ti Ié nding Iwong tinh theo thé tich va trong Ivong déi vei hydro long h) Hay cho biét Igi thé khi ta st dyng metanol long thay cho hydro léng khi ta dat gia thiét vé nén kinh té tuong lai 7 Metanol cing cé thé dug ding trong pin nhién ligu metanol. Phan tng chung cua pin nhién ligu nay la: CH;OH (I) + 1.5 Oz (g)> COz (g)+ 2 H20 (I) i) Viét phan tng xay ra & catot va anot. j) Tinh thé cue dai cla pin nhién ligu metanol 6 25 °C. k) Pin nhién liéu metanol hoat déng tét nhat & 120 °C. O nhiét 46 nay thi thé cla phan teng la 1.214 V. So sanh con sé nay véi sé thu dugc khi ta tinh toan. Cac théng sé nhiét dong & 298 K: H20(1)_| AH? = -286 kJ/mol_| | O2(k) S° = 205 J mol" K™ HzO(h) | AH = -242 kJimol_| | CO2(k)__ | AG? = -394.4 kJ/mol H20(|) | S°=70 J mol" K* CeHia(l) | AG? = 6.4 kJ/mol H,O(h) | S°= 189 J mol K™ | | CHsOH(I) | 4,G° = -166.3 kJ/mol | Ha{k) | S°= 131 J mol K™ Bai 23 Hau hét cdc nguyén t6 phan ting voi oxy dé tao thanh cac oxit trong dé sé oxy héa clia O la -2. Dau tién ta thay rang diéu nay khéng dung voi cac kim loai kiém von la nhiing chat Khir manh nhat, chung chay trong khéng khi dé tao thanh peroxit hay superoxit c6 tinh oxy héa manh. Tai sao oxy chi bi kht? mét phan trong cdc phan tng nay. Bé tim ra nguyén nhan thi phai bat dau tir nhiéng tinh chat co ban cla cc nguyén t6 nay. . Kim loai kim i Na K AvapH 148 kJ/mol | 99 kJ/mol | 79 kJ/mol Nang lwong ion héa | 520 kJ/mol | 496 kJ/mol | 419 kJ/mol 32Olympic Hoa hoc quéc té lan thr 40, Bai tap chuan bi Ban kinh ion M 76pm | 102pm | 138pm a) Gidi thich quy luat vé nding Iugng ion héa cia cdc kim loai Oxy anion OF OF Or ZH | 904 kdimot | $53 kJimol | —43 kJ/mol Ban kinhion| 40pm | 173pm | 158pm b) Gi tri entanpy hinh thanh cdc ion ty do tang dan theo thir ty: superoxit -> peroxit > oxit. Tai sao? Ching ta cing da biét rang can cung cap mét nang Iuong can thiét dé chuyén nguyén td thanh ion, Nhu vay cé bao nhiéu nang lugng d& duge gidi phéng khi cdc ion nay két hop lai voi nhau dé tao thanh tinh thé ion ? Nang lugng mang ludi cua chat ran ion co thé dug tinh boi phuong trinh Kapustinskii dang don gian nhat: AU(mang lw6i) = 107000 voi v 1a téng sé ion trong céng thie thue nghiém, z, va z_ la dién tich cac ion riéng biét, rs va la ban kinh ion (pm) va két qua cudi cling c6 don vj kJ/mol. ¢) Tinh nang lugng mang tinh thé mol cia oxit, peroxit va superoxit d6i voi ba kim loai kiém nhe nhat, Tinh nang lwgng giai phéng ra trong 9 qua trinh kha thi tao oxit, peroxit va superoxit clia cdc nguyén t6. Biét rang ludn o6 2 mol kim loai kiém ran phan ting voi oxy dé cho ra mét san pham. Phuong phap tiép cn don gian nay khéng cé nghia la cho ta mot su xac dinh gan ding vé entanpy hin thanh. Tuy nhién né phan anh chinh xéc céc nhan t6 chinh ctia céc phan (ng ma khéng can phai tinh toi bién thién entropy. Néu tinh todn cla ching ta mac Idi thi két luan thu dug sé mau thudn voi thye nghiém. d) di voi phan tng cia méi kim loai kiém voi lvgng du oxy thi sn pham wu tieé nhat vé mat nang long la gi? e) — Gidi thich ti lé két qia thu duoc dya vao cac thong sé co’ ban. Tai sao thanh phan cilia san pham wu tién nhat thay déi khi chung ta di tur trén xuéng dudi nhém IA. San phdm nao wu tién tao thanh khi Rb va Cs phan Ung véi oxy ? f) Co phi diéu nay o6 nghia rang cc chat oxy héa manh nhu peroxit va superoxit khéng thé bi kht? béi mét trong sé céc tac nhan khiy manh nhat la kali kim loai ? Bay gid’ ching ta sé chuyén sang phan cén lai clia bang tuan hoan. Hau hét céc nguyén td tao dugc oxit ion déu la cac cation c6 nhiéu dién tich duong clia cae tiéu phan kich thuée nhé duge wu tién trong nang lugng mang |udi 9) Cac kim loai kiém khéng 06 tinh chat nay. Tai sao ? h) — Xét mét kim loi tao dug cation M** véi ban kinh 100 pm (dai da sé cac cation déu bé hon).So sanh nang lugng mang lw6i cua oxit v6i peroxit. Dy doan san phdm cua kim loai nay voi oxy ? Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét — box Héa hoc OlympiaVN 33.Chi mét déng vi khéng phéng xa trong nhém IIA cé thé tao duoc peroxit khi dun néng trong khéng khi & ap suat khi quyén. B6 la kim loai nao ? Use lugng sy gidi han vé kich thuée cation trong mé hinh cia chting ta. Dé két luan hay cho biét ly do co ban chung nhat ma cdc chat khiy manh nhat nhw kim loai kiém va mét s6 kim loai khc khng thé khiy hoan toan oxy khi chay trong khong khi ? Bai 24 Chting ta sé khdo sat ba pin Galvanic: a) b) ¢) dq) e) Gid ching ta sé dinh nghia théng s 86 gira dién nang lam viéc va bién thién entanpy trong té bao. b) Pt(r) | Ha(k) | HCI(aq) | Cla(k) | Pt(r) Pb(r) | PbCh(r) | HCl(aq) | Hak) | Pt(r) Pb(r) | PbSOa(r) | K2SOx(aq) |] KNO3(aq) |] KCl(aq) | PbCl(r) | Pb(r) Viét phan ting xay ra trong té bao. Dya vao cdc dir kién vé nhiét hoa hoc hay usc Iugng thé chuan cia cdc pin Galvanic nay & 25 °C. Viét phan tng xay ra & catot va anot ciia céc pin Galvanic nay néu dién thé do dug cia pin bang ding thé khir chuan. Tinh hang sé can bang clla phan tng xay ra trong pin. Dién thé cia pin thay ddi nhu thé nao theo nhiét 46 ? iu suat nhiét” nhu la gia tri ly thuyét circ dai cua ti Tinh gia tri cla thong s6 nay trong cdc té bao da cho. Tur cdc con sé nay ta sé 06 nhieng két luan gi ? Bang gia tri nhiét hoa hoc & 25 °C: AW IkJ mor | S°/J mol "K Chalk) Ha(k HCl(aq) K2SO,(aq) KCl(aq) Pb(r) PbCI(r) PbSO,()Olympic Hoa hoc quéc té lan thr 40, Bai tap chuan bi Bai 25 Ban lanh dao mét doan thm hiém khéng gian dén khai phé mét hanh tinh dang cé ngudi ngoai hanh tinh sinh sng. Tuy nhién con tau khéng gian cla ban xuat hién lai khoi mao cho phan tng ha ap suat va sy phd hi nay tuan theo biéu thre déng hoc bac 1 va co chu ky ban hy la 13 gié. Tat ca moi ngudi can phai roi khdi tau khi Ap suat trong tau chi con 13 % . a) Tw day dén tic dé thi ban cén bao nhiéu thdi gian 2 Etyl-propionat thuy phan trong dung dich kiém theo phan ung: CzHsCOOC;Hs(aq) + OH (aq) = CzHsCOO"(aq) + CoHsOH(aq) Gid tr t6c 46 dau cua phan ing duge ghi & cac ndng do khac nhau nh trong bang [C:HsCOOC;H.] | [OH] | Téc 46 du (mmol dm-*s“*) 0.045 0.300 41.09 0.090 0.300 2.15 0.090 0.150 1.11 b) —_Xac dinh bac riéng phan clia cdc chat phan wng, bac déng hoc clla phan tng va hang sé van téc. Téc d6 dau cla phan tng tang gap déi khi tang nhiét d6 tr 25 °C dén 42 °C, khi gir nguyén néng dé chat dau. ¢) Theo Arrhenius thi nang long hoat héa cia phan tng la bao nhiéu 7 Co phan tng 2 NO(g) + O2(g) = 2 NO2(g) Tuan th phyong trinh dong hoc: r= k[NOF [Oz] d) — Giai thich sy thay ddi van téc phan Wng khi xay ra cc bién déi vé ndng dé sau day: i. [02] tang 4 lan ii, [NO] tang 4 lan iii, [NO] gidm mot nva iv. [02] gidm mét na va [NO] tang 4 lan v. [NO] gidm mét niva va [Oz] tang 4 lan. Téc d6 dau cla phan Ung trén hau nhu khéng déi khi nhiét 46 phan Ung tang tl 460 °C dén 600 °C, khi néng dé ctia cdc chat dau bi gidm di mét nwva. @) Theo Arrhenius thi nang Ing hoat héa cia phan tng la bao nhiéu ? ‘Su phan hiy bac nhat cla mét hop chat duoc quan sat bang phuong phap trac quang. Sau khi cho mét chat cd néng 46 0.015 mol/dm® vao mét cuvet day 0.99 cm thi d6 hap thu clia né (6 bude séng ma chi chat nay hap thy anh sang) duge ghi lai nh la mét ham cla thoi gian nhw sau: Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét - box Héa hoc OlympiaVN 350.15 o4 Absorbance 0.05 o 100 200 300 Time [s] f) Tir dé thi nay hay: i. Uéc lwong hé sé hap thu mol. ii, oc lwong téc 46 dau va hang sé téc 46 phan Ung. _ iii, Uoc lwong chu ky ban hiy cia phan teng tir gid tri hang sé téc dé. iv. Nhan xét chu ky ban hiy tinh dugc nhu vay cé phi hyp voi dé thi khong. v. Tinh thdi gian can thiét dé phan hiy 99 % va 99.99 % hop chat nay. Bai 26 © thuong tang khi quyén (tang binh Iwu) thi ozon bao vé ching ta khdi cac tia cue tim co hai do mat trdi chiéu toi. Tuy nhién & tng thap hon (tang sinh quyén) thi ozon gay anh huéng dén hé hé hap cia con ngudi cling nh clia cac loai thyc vat do ozon Ia chat oxy hoa manh. Sy tao thanh ozon & cdc khu dé thi c6 thé duc miéu ta theo co ché hai bude nhu sau: NO2 + hy NO +0 ky (1) O+0;,>03 ko (2) Buc dau tién la sy quang phan NOz la mét chat gay 6 nhiém khéng khi & thanh phd. (N.B.: k; bao gdm cudng dé anh sang mat trdi tinh trung binh vao nhiing ngay nang). Buc thir hai la phan Ung cila oxy nguyén ti voi oxy Khng khi. Dui nhimng diéu kién trong khi quy&n thi phan ting (2) xay ra nhanh hon nhiéu so v6i (1). Cho rang chung ta c6 mét lvgng nhé NO2 (Chang han 10~” phan mol trong khéng khi) duge dua vao bau khi quyén va chi xay ra phan ting (1) va (2). a) Tiéu phan nao sé 6 trang thai gid bén ? Viét biéu thwrc dai sé dé xac dinh ndng do cila né sau giai doan khoi mao, b) — Viét biéu thc vi phan va tich phan ctia van téc phan tng hinh thanh ozon. Hang s6 t6c d6 cila phan wing (1) la 0.0070 s“'. Néng d6 NOz ban dau la 2.5-10” phan ter. cm. 36Olympic Hoa hoc quéc té lan thr 40, Bai tap chuan bi ¢) Tinh ndng dé ozon sau 1 phtt. d) Chu ky ban hy cia NO; la bao lau ? e) —Nhiét dé anh huéng nhu thé nao dén téc dé phan tng hinh thanh ozon ? Tai sao ? Ozon khéng chi duge hinh thanh ma cdn dé bi loai di khdi tng binh Iuu, chi yéu ld do phan tng cua né voi NO: NO + O3 + NO2 + Oz ks (3) Cho rng trong phan ting (1-3), Os, NO va NO» dau dat can bang, Biét ks = 1.8:10- cm? phan tu"'s* f) _ Xac dinh ti lé [NOJ/[NOz], néu ndng dé ozon can bang la 9:10" phan tu.cm >? g) Cho rang ndng dé ozon can bang Ia git? nguyén. Cho biét ti lé trén thay déi nhu thé nao néu ta tang nhiét dé tle 10 °C lén 25 °C? Biét nang Iugng hoat héa cia phan tng (3) f& 10.8 ku/mol. Bai 27 Phan trng cla axeton voi brom sinh ra bromaxeton. a) Viét phuong trinh héa hoc cia phan Wng néu nhu axeton du. Khi nghién ctu co’ ché phan ting thi ngudi ta thy hién mét sé thi nghiém déng hoc sau & 25 °C trong dung dich nude bang cach do néng dé cia Br2 bang phuong phap trac quang. Duong cong déng hoc tuong tng dug ghi lai khi néng dé dau cla cdc chat la 0,520 mmol/dm?, [CsHsO]o = 0.300 molidm®, .050 molidm®, t(min) O[2[4]6] 8] 0] 12] 4 [Bra] (umol/dm*) | 520 | 471 | 415 | 377 | 322 | 269 | 223 | 173 | t (min) 16 | 18 | 20 | 22 | 24 | 26 | 28 | 30) [Bra] (umovam’) [424 | 69 | 20; 0 | 0) 0 {0/0 b) Tac nhdn phan dng hét trong thi nghiém nay ta? ¢) Bac clia phan tng déi véi tac nhan nay la 7 Thoi dim ma & dé xay ra buée gay vé tinh chat (characteristic break point) trén duéng cong d6ng hoc duge goi la théi gian phan tng va né duge do trong dung dich nudc 6 25 °C. Bang sau cho ta mét vai gid tri thoi gian phan tng trong mét vai thi nghiém khac nhau (‘chi phit, * chi gidy) Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét — box Héa hoc OlympiaVN 37Br], IC,H,O], | [HCIO,], | thdi gian phan Ging mmol/dm® | mmoldm® | mmol/dm? | 0.151 300 50 556" 0.138 300 100 244" 0,395 300 100 | 732" 0.520 100 100 | 30°37" 0.520 200 100 15713" 0.520 500 100 609" 0.520 300 200 | 4°55" 0.520 300 400 2728" d) Xd dinh bac phan wng tng voi ba chat tham gia. . e) —Viét biéu thirc toc dé tong quat. f) _ Néu gia tri va don vi cia hang sé van tc. Mét phyong phap dign héa khac cho phép ta str dung ndng d6 Bre bé hon. © mét dung cong dong hoc véi néng 4% cac chat dau [Brelo= 1.80 umol/dm?, [CoHyO = 1.30 mmol/dm’, va [HCIOzJo = 0.100 mol/dm? da dug cho 6 bang sau: t(s) 0 10 | 20 | 30 | 40 | 50 | 60 | 70 [Bra] (umol/dm®) | 1.80 | 1.57 | 1.39 | 1.27 | 1.06 | 0.97 | 0.82 [ 0.73 [t() 80_[ 90 | 100 | 410 | 120 | 130 | 140 | 150 [Bra] (umol/dm’) | 0.66 | 0.58 | 0.49 | 0.45 | 0.39 | 0.34 | 0.30 | 0.26 g) Tac nhan phan wing hét trong thi nghiém nay la 2 h) Bac clia phan tng déi voi tac nhan nay la? Chu ky ban hdy cla téc nhan phan ting hét duoc xde dinh béi mot vai thi nghiém va nd khéng hé phy thudc vao néng d6 cla tac nhan phan tng hét. [Bra (umoldm®) [GsHeOh (mmol) [HCIO.Jo (molidm’) | tx (8) 1.20 3.0 0.100 24 1.50 3.0 0.100 23 1.50 1.0 0.100 71 1.50 0.4 I 0.100 17 1.50 3.0 0.030 23 1.50 3.0) 0.400 24 i) X4c dinh bac phan tng tng voi ba chat tham gia. i) Viét biéu thre téc a6 ting quat. k) _ Néu gia tri va don vi clia hang sé van téc. 1) Tw cdc thong tin tim dugc hay dé nghi mat co ché hop ly cia phan Ung. 38Olympic Hoa hoc quéc té lan thr 40, Bai tap chuan bi Bai 28 Clo dioxit la mot phan tiv kha dc biét do nd cé mét electron déc than. a) Vé céng thre Lewis ctia clo dioxit. b) —_Xac dinh it nhat hai phan tu bén vieng khac khéng chtra kim loai ma cé 6 16 electron. Clo dioxit duoc si dung voi lveng ngay cang cao trong xi? ly nude. Ngudi ta da nghién citu phan ting cia clo dioxit vdi iot trong dung dich nuéc. Anh sang lam ting manh téc 46 phan tng, & day san pham cudi la ion clorua va iodat. ¢) _Viét va can bang phan teng xay ra. Thyc nghiém xac dinh rang ti 1@ 46 giam ndng dé cua clo dioxit va iot la 2.3. d) Phan teng phy nao cé thé gay ra su sai léch khdi hé sé tiluong ? e) Dé nghi mot phuong phap dé ngan phan teng phy nay. . Phuong phap phan tich dinh lugng déi voi phan ting quang héa stv dung mot den halogen céng suat l6n. Gidra dan va thiét bi quang héa thi ngudi ta dac mét kinh loc dé chi cac bude séng trong ving tir 455-465 nm co thé di qua. Day bude séng nay cé thé dugc xem la chim tia don sac cé bude séng 460 nm. lot c6 hé s6 hap thy mol Ia 740 dm* mol cm“' & 460 nm trong khi hé s6 hap thu mol cua clo dioxit thi Khong thé do duge 6 bude séng nay. Thiét bj phan tng quang héa c6 thé tich 25.00 cm’ voi d6 day la 5.00 cm duoc str dung trong tat cd céc th nghiem, Phan uimn duoc nghién ctu trong moi trong axit v6i néng 49 dau ciia ot la [lo = 8.1°10* mol/dm? va [C1Oz}p = 4.0:10* mol/dm®. Cac thi nghiém tham khdo d&u tién hanh duéi sy vang mat cua mét sé tac nhan. Khi dung dich chi chtra mdi clo dioxit thiu nguéi ta khong quan sat thay sw thay déi nao. . f) Tu didu nay ligu cd thé khang dinh rang clo dioxit khéng bi quang phan ? Khi dung dich chi chira iot ma khéng chtra clo dioxit thi ngudi ta quan sat thay 06 sy’ phan huy cham iot nhung t6c d6 ctia qua trinh nay rat nhé hon so véi khi cé mat clo dioxit. Trong nhinng thi nghiém c6 lién quan thi dung dich chira ca hai tac nhan, Trong méi thi nghiém thi ngudi ta do téc d6 dau cla sy mat clo dioxit (vo). Thi nghiém dau tién duoc tién hanh bang cach ding cac dir kién thi nghiém da duge mé ta 6 trén, © thi nghiém tiép theo thi mét kinh loc mau x4m dugc dua vao chim tia sang truéc thiét bj phan tng. Sy hp thy ctia kinh loc mau x4m & 460 nm duge do trong mét thi nghiém déc lap. O thi nghiém cudi cung thi mét tam thép dugc dua vao chum tia sang va no khéng cho bat ky nh sang nao di qua. Téc d6 dau duoc xdc dinh trong cac thi nghiém nay nh sau: Khéng kinh loc] Kinh loc 1 | Kinh Ioc2 | Kinh loc 3 [Tam thép | | Asso = 0.125 | Aago = 0.316 | Aago = 0.582 vo (nmol dm~ s ‘) 2.51 1.97 1.40 0.93 0.37 g) Tai sao 6 tm kim loai t6c a6 dau lai khong thé di vé 0 ? Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét - box Héa hoc OlympiaVN 39Cuong d6 anh sang duge xac dinh bang phép do 46 quang héa phitc ferioxalat. Mot dung dich Ks[Fe(C20,)s} 0.00600 mol/dm? dug pha v6i 0.05 molidm® HzSOx. Cho 25.00 cm? dung dich nay vao thiét bi quang héa. Truée dé thi d6 hap thy cia dung dich nay dugc xc dinh la 1.41 & 460 nm trong mot cuvet thach anh day 1.000 cm. Mau dug chiéu xa trong 30.00 phit. Phan tng sau day xay ra trong dung dich. 2 [Fe(CpO,)a* + hv 2 Fe + 2. COp +5 p02 Higu sudt long tt cila sy tao thanh sat (II) ka 1.12. ‘Sau khi chiéu xa thi ly 1.000 cm? mau tir dung dich cho vao binh dinh mirc 5.000 cm*. Sau day thém vao binh dinh mic dén vach dung dich 1,10-phenantrolin 0.0100 mol/dm? va 0.50 mol/dm® dung dich dém axetat/axit axetic 1:1 acetate/acetic. 86 hap thy cia dung dich nay 510 nm duge do trong cuvet day 1.000-cm la 0.3823. Hé sé hap thu mol cua phtrc Fe(phen);?*- 0) la € = 1.10-104 dm? mol! cm! & 510 nm & bude séng nay khong médt chat nao khac hp thy anh sang. h) Tinh ndng dé cua phic sat(|I) trong cuvet? i) Tinh wong sat(|!) tao thanh trong qua trinh nhiéu xa. i) Tinh cuéng dé anh sang & buée séng 460 nm 6 ca hai don vi la mol photon/s va W k) _ XAc dinh hiéu suat luong tir cia phan tng gitra clo dioxit va iot d6i voi sur mat ca clo dioxit va iot. Bai 29 Bang sau day biéu dién cac dir kién nang lvgng cla mét sé don nguyén tir va hai nguyén tl & don vi ku/mol: Trang thai kich thich | Nang lugng ion héa Nang lugng ion i le they nhat (Eex), ther nhat (Ei) héa ther hai (Ei) electron EA) Na 51.1 496 4564 : oa Hur 700.0 200 500 250.0 a_i 29.0 1251 | 1148 348.0 NaCl 860 70.1 *Nguyén ti gia thidt Cong thifc tinh nang luging tuong tac gitra hai dién tich diém (q; va qz) cach nhau mot khoang Fla e__Ka, R v6i k = 8.99-10° m/F. Bién tich clia electron (e) la 1602-107"? Cc. a) Cac nguyén tir Na va Cl tiép can gan nhau @ pha khi. Tim khoang cach nhé nhat ma 6 d6 chting khéng phan teng véi nhau. b) — Khodng cach nay bé hay lon hon néu nguyén tl Na @ trang thai kich thich thir nhat? Tinh toan ching minh, . 40Olympic Hoa hoc quéc té lan thr 40, Bai tap chuan bi X<ét tat cd cdc nguyén t6, ai luc electron dao déng trong khodng tir 4.6-348 kJ/mol va nang lung ion héa dao déng trong khoaing tt 375-2374 kJ/mol. c) Liéu cé kha thi dé tao phan ti hai nguyén tir cé thé phan ly tao thanh mot trang thai bén ving chira hai ion ? Tinh toan ching minh d) Mt nguyén ti Hu trung hoa va mét ion Hu" tiép cn ln nhau trong pha khi. Liéu chung c6 phan tng véi nhau khéng ? Xéc dinh bang tinh todn, Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét- box Héa hoc OlympiaVN 41DAP AN BAI TAP CHUAN BIOlympic Hoa hoc quéc té lan thr 40, Bai tap chuan bi R.299,82K ay chinh la long khi sinh ra tl 28,35g chat chua biét. Nhu vay 1 mol khi dug¢ sinh ra khi 8,028g chat nay phan tng véi nuéc. Cung voi tinh dé chay cia chat khi nay va mau ‘sc cla ngon lira cho phép chung ta két luan rang chat ban dau chinh la liti hydrua. LiH + HO = LiOH + He Khi trung hoa voi HF thi mét ai do bat ky ciing cé thé biét rang 7g + 19g = 26g LiF tir 8g LiH, ttrc la gdp 3,25 lan khoi lveng ban dau. Nhung Holmes chi quan sat duoc dé tang khdi lung la 3,125 lan, ttc la chi c6 25g LiF dugc sinh ra tir 1 mol LiH. Diéu nay khong thé dug giai thich néu nhu ta chi cho rang cdc nguyén té chi hién dién & trang thai dong vi thién nhién cla nd. Khéi lvong cla 1 mol LiF sé chi la 25g néu nh n6 chtva dong vi bén tinh khiét la °Li, chi chiém 7% trong liti thién nhién ("°F la déng vi bén duy nhat cuia F). Do khéi lvong cia chat dau van la 8 g/mol nén né han la hop chat cua °Li voi deuteri. °Li deuterua due diing (va hién nay a ding) lam nhién ligu phan ra chinh trong cc vi khi hat han. Sau qua trinh bat neutron dé bat du cdc chudi phan ra hat nhan thi xay ra cdc qué trinh sau: SLi+ \n—> }H+ $He iH+?H> tHe+ \n Bai 2: a) Thanh phan chat A: n(N) : n(H) : n(Q) = (11,97 / A(N)) : (3,45 / A(H)) : (41,03 /A(O)) = 14:3 Tir cdc ti 1é nay ta 06 thé biét duge trong A co chiza ion amoni Lugng kim loai H trong 100g A 1a 4,355g. Nhu vay ta cé thé gid thiét rang trong 1 mol A chiva 1 mol cila cd H va nito. Khéi long cia H sé la 43,559 / 0,8550 mol = 50,94 g/mol. Kim loai nay la Vanadi. Tw day ta 6 thé doan dug cdc chat tir AK theo ther ty A: NH,VOg HV B: 20s, IVC C: VO2" J: VC, D: VO K: VClz Ev F: vo" ove Cac phan ung xy ra nhu sau: + 2NH4VOs(F) — 2NHa(k) + V2Os(r) + H2O(k) V20s(r) + 2H30"(aq) > 2VO;"(aq) + 3H-0(!) }. 2VO2"(aq) + 3Zn(r) + 8H30*(aq) > 2V2"(aq) + 3Zn**(aq) + 12H2O(() |. NH4VOs(r) > NH¢’(aq) + VOs(aq) . VO3 (aq) + 2H30"(aq) > 2VOz'(aq) + 3H20(1) . 2VOs (aq) + $O2(k) + 4Hs0"(aq) > 2VO2'(aq) + SO.* (aq) + 6H2O(!) . VO2"(aq) + V*(aq) + 2H30" (aq) > 2V**(aq) + 3H20(1) . V(r) + 2Ch{k) > VEL) . AVC I) > 2VChs(r) + Chk) 10. 2VCla(r) + Ho(k) > 2VCl(r) + 2HCI(k) 114, VCli(l) + 3H20(1) > 2VO*"(aq) + 4Cr(aq) + 2H50° 12. 2VCh(r) > 2V"(aq) + 6CI(aq) OP PNOMAYNS Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét — box Héa hoc OlympiaVN 43,13. VCl(r) > V*"(aq) + 2CI(aq) 14, 2VCh(r) > 2VCh(r) + VELA) b) 3,6, 7, 8, 9, 10, 14 ¢) Do V 6 cau hinh la 48°3s° nén sy mat 2, 3 hay 4e dan dén cdc tiéu phan od electron d khong cap déi. Chi hop chat 6 trang thai oxy héa +5 thi khéng cé tinh chat nay: A, B, C, D d) Su khtr ion VO** bang kém trong méi trung axit cé thé divng lai & V" 2VOz"(aq) + 3Zn(r) + 8H30"(aq) >» 2V*(aq) + 3Zn*(aq) + 12H20(1) e) Qua trinh ting hop SOs dé san xudt H2SO4: 2SO2 + Oz = 2SOs diing xtic tac V2O5 1) Xac sudt ma khong c6 nguyén ti *Cl trong phan tt VC la 0.99% = 96,06%. Nhu vay sé cé Cl trong san pham tic ld phan mol ctia “Cl trong san phdm sé la 3,94% g) Ly do tuong ty cho ta biét xc sudt c6 mat nguyén tir *°Cl trong VCls la 2,97% Bai3 a) Trong mét hé lap phuong chung ta cé cac kiéu mang lap phuong don gidn, Jap phuong tam mat (fcc) va lap phuong tam khdi (bec). Tat cA cac 6 mang co’ sé nay chiva 1, 4 hay 2 nguyén tr trong trng. Chuing ta c6 thé xac dinh xem kiéu mang tinh thé thudc loai nao phy thudc vao gi tri ban kinh kim loai ap dung cho truéng hop cac nguyén tir tiép xue nhau. Chung ta sé thu dug cac biéu thtre déi voi mang lap phuong don gian la a = 2R, voi feo thi a = 2R-V2,, voi bec thia = 4R V3. Néu 6 mang tinh thé la lap phuong don gian thi ching ta cé 1 nguyén tu trong 6 mang co 6. Sit dung gia tr] Kh6i luong riéng ta 66 duoc gia tri thé tich 6 mang la M(Cr) / (p.Na) = 1,209.10" pm® . Hang s6 mang tinh thé luc nay Ia (1,209.10” pm)" = 229,5 pm. Tuy nhién gid tri nay khong dong nhat v6i 252 pm (a = 2R) déi vdi mot 6 mang lap phuong don gidn Néu 6 mang tinh thé [a fcc thi ching ta c6 4 nguyén tl trong 6 mang co s6. SW dung gid tri khdi long riéng ta 06 dug gid tri thé tich 6 mang la 4M(Cr) / (p.Na) = 4,838.10" pm’, Hang sé mang tinh thé Ic nay la (4,838.10" pm®)"® = 364,4 pm. Tuy nhién gid tri nay khong dang nhat voi 356 pm (a = 2R V2 ) déi voi fec. Néu 6 mang tinh thé la bcc thi chting ta cé 2 nguyén ti? trong 6 mang co sé. Str dung gid tri khéi Ivong riéng ta 06 duge gid tr thé tich 8 mang la 2M(Cr) / (p.Na) = 2,419.10" pm’ Hang sé mang tinh thé Ic nay la (2,419.10" pm*)"? = 289,2 pm gan khép voi gid tri thuc 6i v6i 6 mang bec ld a = 4R V3 = 29pm. Nhu vay kiéu mang tinh thé cla crom la lap phuong tam khdi b) CrO2Cl la cromyl clorua cé cau tric nhu sau: O° cree Viva cl oF ¢) Cac phuong trinh phan ung 2Cr0,? + 2H" = Cr,07* + HO 3CrO,* + 4H" = CrsOy0% + 220 44Olympic Hoa hoc quéc té lan thr 40, Bai tap chuan bi 4CrO,* + 6H" = CraO13* + 3H,O Cu tric cla cdc ion polycromat 7 sau: \ 7 VAN AN PA -_ BS oo jy 06 90 9 90 900 6 CrO3 c6 cAu tao mach polymer xuat phat tir cdc ion polycromat d) Ching ta sé str dung c6ng thire pon tiE} mE 1,35V déi voi qua trinh Cr(V) - Cr(IV), E® = 1,33V déi Tw biéu thirc nay ta nhan dugc E' V 0,90V déi voi qua trinh Cr?" - Cr vOi qua trinh Cr207” - Cr°*, E° e) Dé cho mét qua trinh ty phan ly c6 thé xay ra thi E°* < E, voi E™ la thé khiv cla qua trinh oxy héa va E* la thé khi ctia qua trinh khi?. Mét tiéu phan s&n sang bj dj phan néu nhu c6 sy chénh léch Ién trén gidn a6 Latimer gitra bén phdi so voi bén trai. Diéu nay dan dén két qua la Cr(V) va Cr(IV) khéng bén déi véi phan ng di phan 6i voi phan teng 3Cr** = 2Cr** + Cr thi hang sé can bang cé thé dugc tinh tur cdc gid tri thé khir chun A,G° =-2f( -0,90V — (-0,42V)) = 93 kJ/mol. Tu gia tri A,G° ta sé thu duge gid tri hang sé can bang bang cach diing cong thive: K = exp(-;G7/RT) = 6,91.10.7 ; 1) BE C6 thé tinh duge tich s6 tan clia Cr(OH)s ching ta chuyén sang gian dé Latimer voi pH = 14. S sdnh cdc gia tri thé khi? déi véi qué trinh Crilll) > Cr(0) déi véi pH = 0 va pH = 14 chiing ta co thé viet: 0,059 L Ig 7 3 “| Lor] Didu nay din dén két qua pL = 30 Tuong ty cho viéc tinh hang sé can bang téng ctia anion tetrahydroxo cromat (III) chung ta c6 thé vidt: foo 7p 082 059, _| [oxo] {ou} Thay 1,0 cho [Cr(OH)4] va [OH] ta co két quia pK = -30 -1,33=0,74+ Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét — box Héa hoc OlympiaVN 45g) Thé khir chuan cao nhat cé thé dat toi phu thudc vao cac tiéu phan trong méi trvdng axit la 1,33V — 0,695V = 0,635V. Nhu vay trong mdi trudng axit thi hydroperoxit sé bi oxy héa thanh O2 va Cr(VI) sé bi khir thanh Cr", Phan tng xdy ra theo phuong trinh Cr07** + 3H2O2 + 8H" = 2Cr** + 302 + 7H2O Trong méi truéng kiém thi OH’ sinh ra va su oxy héa Cr(Il) vé Cr(VI) xdy ra voi gid tri thé khir cao nhat c6 thé dat t67 la: 08,7V — (-0,72V) = 1,59V. Phan ung xdy ra theo phuong trinh: 2[Cr(OH)4] + 3HOz' = 2CrO,* + SH20 + OH Bai4 a)4va2 b) Trong tom? chung ta c6 p.Na / M(SiO2) = 2,208.10” don vi SiOz. Thé tich mét don vila 4,53.107°cm? MGi nguyén tir Si tao thanh 4 lién két Si-O. Nhu vay mét thé tich nguyén t6 co 1 don vi SiOz gdm 4 lién két Si-O c) Bay gia chung ta sé dinh Iai sé nguyén tt Si la n. Chung ta cé sé nguyén tir oxy la 1,9n dé tao ra 3,8n lién két Si — O. Gid tri 4n va 3,8n electron héa tri dug tao nén béi cdc. nguyén tl Si va O tao thanh (2 + 1,9)n lién két (Si — O va Si — Si). Gia tri con lai 3,9n — 3,8n chunh la sé lién két Si— Si. Ti 1é gita chung la: 3,9n-3,8n _ 0.1 _9 ons6 39n 3,9 Nhu vay 2,56% sé lién két la Si - Si d) Noi chung céng thtrc nhan dug cé thé dug viét tang quat dudi dang: Tw cau hdi ta 06 thé doan duge rang tilé "5 1 1/6, Diéu do dn dén két quia x = 1,5 Nsio Bai5 a) Nguyén ti lwu huynh dug phéi tri béi mét nguyén ti lu huynh khdc va ba ion Fe** trong mét sy sdp xép tu dién ) © mang nhé nhat ing véi hang sé mang la a chiza 4 nguyén tir Fe va 8 nguyén ti S. Bidu nay din dén: _ 4M(Fe)+8M(S) PN ,a Tw phuong trinh nay chung ta nhan dug két qua ao = 541,8pm_ =5,011g/cem* c) Déi voi cdc gia tri khac nhau cla st thi tinh toan sé tét hon néu lam nhu sau: Mét mol tinh thé cha 8 mol S va B/y mol Fe. Nhu vay méi quan hé gira khdi long riéng tinh thé va thanh phan ddi voi ham Ivgng sat khdc nhau sé la . 3M MEFe) (20 4A 7) sem! Naas a Déi voi cdc gia tri S khac nhau thi mét mol tinh thé chtra 4 mol Fe va 4y mol S. Nhu ay sv. phu thuéc giira khdi lung riéng vao y sé la: 46Olympic Hoa hoc quéc té lan thr 40, Bai tap chuan bi = MEF) Hy MOS) _(9,339+1,339y) gle’ Nay a) 5.98. Fe excess 5,08. 504. se *4 %Fe deficiency 500. 1 %S excess 498. p/g cm 498. sat $-deficiency Fe-deficiency 136 18820020208 e) Trong 6 mang co’ sé clia pyrit thién nhién thi sé c6 4.0,99= = 3,96 mol Fe va 8.1,01 = 8,08 mol S. Didu nay cho gia tri 8,08/3,96 = 2,04, N6 nam trong ving ma thong 86 mang khéng phy thugc vao thanh phan; nhu vay khdi lugng riéng c6 thé duge tinh toan tir cc gia tri 06 san: }6.M(Fe)+8,08.M(S) O14 glom? nao Diém (2,04 ; 5,014) duge chi ra & dé thi cia cau trén Bai 6: a) Na; No b) Mét mol mudi natri cia A chtra mét mol natri, nhu vay khéi lvgng phan tl la M(Na)/0,3536 = 65,02g/mol, Khdi lvgng phan tt? cla anion la 42,03 g/mol. Biu nay chi ra rng d6 la Ny. A sé la hydro azit. Céng thirc Lewis cua né la: ) Néu c6ng thie cla halogenua la NaXp (X la mot halogen cha biét) thi ta c6 phuong trinh sau aM(N) aM(N)+bM(X) Ti do ta cd bM(X) = 19a. Nhu’ vay X la flo, va b = a. Do NF khéng ton tai ma sé lién két cng héa tri ma nito cd thé tao ra tdi da la 4 nén halogenua nay sé la NzF2 c6 dang hinh hoc nhu sau: 0,4244 Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét — box Héa hoc OlympiaVN 47d) Do SbF la mét axit Lewis manh nén céng thire ca anion B sé la SbF... Do né chia mét anion nén B chi chtra mot nguyén tir Sb. Nhwr vay khdi long phan tir cla hop chat nay l& M(Sb)/0,4306 = 282,75 g/mol. Luong nito la 282,75.0,0991 = 28g, va 133g con lai la flo, TW cdc gia tri dé ta c6 céng thie thyre nghiém la SbNeF7 @) Anion B la SbF" nén céng thirc phan ti cia B la [N2F*][SbFe]. Cac c4u tric cong huéng ciia cation la: <-> W f) Gia sir cng thtrc cia nito’ oxit la NaOp thi co thé viét dugc phuong trinh sau — MN) __9 6365 aM(N)+bM(O) Tw day ta c6 a = 2b, céng thie cia oxit la N2O g) Lugng N2O sinh ra la 1,14 mmol. Long B la 0,3223g/282,75g.mol' = 1,14 mmol. Nguyén tir oxy dén tir phan tr nude. Biéu nay dan dén sy loai bd hai nguyén tir hydro dé tao HF voi ion flo: [NoF"][SbFe] + H2O = NzO + 2HF + SbFs ‘SbF; tham gia phan tng thi phan trong dung dich long, nhung phan tng nay dan dén nhiéu sdn phdm khéc nhau. Vi du nhu SbFs + H2O = SbOF + 2HF h) Anion cia C la SbF». Néu C chwa n anion cho méi cation va cation chira x nguyén tir N, nhu vay long nito va antimon sé la —_SMWN) ____9,2290 xM(N)+nM(SbF, ) nM(Sb) xM(N)+nM(SbE, ) Chia phuong trinh 1 cho 2 vé theo vé ta thu dug n = 5x. Tu day ta suy ra dugc cong thie ciia C la [Ns"][SbFe] =0,3982 ) NS _ 7 iNZN UNSW 2N N N oe : Noy NEN" NSyt neh ee hay hai cap electron khéng lién két & nite’ trung tam. Hai lién két cdn lai cé géc lién két 48Olympic Hoa hoc quéc té lan thr 40, Bai tap chuan bi phai la 180° trong cac céng thre cOng huéng & day thir nhat nhung sé bé hon 180° 6 day tht hai do c6 sy xuat hién cap electron khéng lién két trong céc nguyén tw nito’ J) (NoF*][SbF¢] + HNg = [Ns"][SbFe] + HF Phan tng nay thuan Igi vé nhiét déng hoe do tinh bén cao cla HF k) Néu C oxy hoa duc nuéc va cé sy tao thanh hai don chat khi thi mét trong sé ching phai la oxy. Khi cdn lai phai la nite’ do sw kém bén ctia cation C. Nhu vay phan Wing thiy phan xay ra nhu sau: 4[Ns']ISbF6] + 2H20 = 10N2 + Op + 4HF + 4SbFs )) Do anion D c6 kiéu phéi tri bat dign va né chia ion Ns (do né duge tao thanh tir A) nén didu kha thi duy nhat la nguyén tir D trung tam (va cd E nia) déu dug bao quanh béi sau ion Ns’. Do cation trong E la Ns" va ti Ié cation : anion la 1 : 1 nén céng thirc cla E la [Ns"][X(Ns)6]. Nhu vay céng thtrc phan tir la XNos (voi X la mét nguyén té phan nhom, chinh chua xac dinh). Ham lugng nito dug xac dinh theo biéu thirc sau: 23M(N) 23M(N)*MQO, Tw day ta xc dinh M(x) = 30,9g/mol. Nguyén t6 nay la photpho. Céng thive cila E Ie nay 86 la [Ns"][P(Ns)6] m) 86 oxy héa olia cdc nguyén tl? trong Na” va CI’ khéng ddi va sy thoat khi khong thé quan sat thay, diéu nay cho thay rang ion Ns khéng bi phan huy trong qué trinh tong hop. Nhw vay sy’ tao thanh E khéng phdi la phan ting oxy hda khi’. Photpho cé cling sé oxy hda nhu trong clo cing nhu trong E. Nhu vay clorua nay la PCls D chtra anion [P(Ns)s] . Con cation thi chi cé thé la Na*. Nhu’ vay céng thtre cia D la Na[P(Ns)e] 1n) Nito la san phdm khi. Do oxy ¢é sn trong khéng khi nén long photpho sé bi oxy hoa thanh POs. Phan ting héa hoc cho sw phan hily nay la: [Ns JIP(Ns)s] + 502 = 46N2 + 2P205 Bai7: a) [H,0°] = 10 molidm? [HCl}iéng = [30°] = 10 moldm® b) [H30"] = 10 mol/dm* Biéu thre can bang ndng dd: [HAching = [Ac] + [HAC] Cn bang dién tich: [H30°] = [Ac] [H,0° [ac] . [HAc] [Hac]... - [HAChing = 6,75.10% mol/dm® ) [Hs0*] = 10% mol/dm? Biéu thre cn bang néng do: [HeSOz}ting = [HSO.] + [SO.7] Cn bang dién tich: [H30"] = [HSO,] + 2[S0,7] >” THso; ] 2[H,80, ],,, [07] [H2SOsing = 5,024.10 mol/dm? Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét — box Héa hoc OlympiaVN 49d) [Hs0"] = 10% mova? Biéu thure can bang ndng dé: [HeAlkéng = [HyA] + [HoA'] + [HAP] + [AP] Can bang dién tich: [H30°] = [H2A] + 2[HA* “] + [Ae ] [i804] "ral [1,07 ][Ha*] [H2Ahing = 8.29.10 molidm? e) Tron hén hgp thi [HCl}éng = 5,00.10° mol/dm* va [NaOH}éng = 5.00.10 molidm* nén day la dung dich trung hoa voi pH = 7,00 ) Trong hdn hop [HAching = 3,375.10% molidm® va [NaOH}ing = 5.00.10 moldm® Can bang néng 46: [HAChing = [Ac'] + {HAc] va [NaOH]ting = [Na* ] Can bang dién tich: [Hs0"] + [Na*] = [Ac] [H,0° ][ Ac} THA] [Hs0"}iing = 4,46.10° molidm? pH = 4,35, g) Trong hén, hop [H2SOshtng = 2,512, 10° molidm? va [NaOH}téng = 5,00.10°° molidm? nén dung dich nay gan nhu trung h Can bang néng 46: [HSOsking = HSO4] + [SO.?] va NaOH} ing = [Na"] Gen an bang ign tich: [Hy0"] + [Na"] = [HSOx] + 2[80."] + [OH] = [HsO°][OH] = 10" To J[s * [Hs0; ] [H30*] = 2,76.107 mol/dm* pH = 6,56 h) Trong hén hop [HsA}ting = 4,145.10 molidm? va [NaOH]ting = 5,00. 10% mol/dm? nén dung dich chia [NaH2A}iing = 3,29.10° mol/dm® va [NazHAliing = 8,55.10° molidm? [H.0" JHA") [H,0" ]([Na,HA],__ +[H,0° }) [H.A"] [Nata], [ 10°] {H30*] = 2,00.10° mol/dm? pH=4,70 i) Trong hn hop [HAching = 3,375.10 molidm® va [HCl}ing = 5,00.10°° mol/dm? Can bang néng 46: [HAChing = [Ac'] + [HAc] va [HCIhting = [Cl] Can bang dién tich: [Hs0"] = [Ac] + [CI] [H,0" [Ac ] i [Hac] [H30"] = 9,99.10° mol/dm? pH = 6,00 50Olympic Hoa hoc quéc té lan thr 40, Bai tap chuan bi J) Trong hn hop [HeSOshing = 2,512.10° mol/dm va [HCl hing Can bang ndng dé: [H2SO4}ting = [HSO4] + (so. | va [HCl hing = Can bang dién tich: [HgO"] = [HSO«] + 2[S0,7] + [Cr] [110° ][50:| [Hso; ] {H30"] = 1,00.10% mol/dm* pH = 4,00 5,00.10° mol/dm® [cr] Bai 8: a) Tir cc sn phAm ion ta cé [HF] = [H2F*] = 8.0.10 = 2,8.10° mold? [HF] = p / M(HF) = 50,1 molidm? ‘Sy ty phan ly dan dén viéc bé qua sy thay ddi ndng d6 [HF] nén tilé dé bai yéu cdu sé la (H2F*]/ [HF] = 5,65.10° b) 2HF + H20 = H30° + HF SiO, + GHF = SiFe* + 2H30* CHsCOCH + 2HF = [CHsCOHCHs]" + HF? c) Cn bang trong hé dug mé ta béi cdc bidu thirc sau: (HF ]iéng = [HF] + [F] + 2[HF2|] (Sw cn bang flo) [F] + [HF2] = [HsO°] (Cn bang dién tich) Tw biéu thire cn bang dién tich ta c6 [F'] = [H30"] - [HF2] Thay thé vao biéu thie cn bang flo thi: [HF] = [HF lng ~ [H30"] - [HF2] Hang sé can bang: k _[H,0°][F jee ie Ee [HF] HF] [HE] _ [HF ' [HEI] [ar]((u,07] fine; )) [H30*] = 0,01 mol/dm? Giai phvong trinh nay nhan dugc [HF] = 0,0889 mol/dm? va [HF]ing = 0,0991 mol/dm* d) Biéu thurc hang s6 can bang cho (1) la mot ham cia [H30*], [HF ing va [HF2] _[240"](@40]-La:) [HF]... -[H,0" |-[HE] Khéng xét dén can bang (2) thi nhiing sy tinh todn sé dan dén: par, 7] Hai biéu thtrc trén sé chi bang nhau trong nhi?ng diéu kién hét strc dac biét chang han nhu cae phép do o6 thé chi ra hang s6 khéng can bang K;' e) Hai gia tri cla hang sé can bang dug xac dinh la nhu nhau do vay: [H.0'](#,07}-[H5))__[H.0"] [HF [HO] [HE] [HF [H.07] Tw phuong trinh nay ta c6 biéu thire [HF ting = 2[H30*] Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét — box Héa hoc OlympiaVN 51Thay biéu thirc nay vao biéu thie tinh K; ching ta nhan duge Ki = [Hs0°] Nhw vay [HF hing = 2K1 = 0,0022 molidm® f) K = Ky.Ke = 2,86.10% g) Vi dy: NaOH. CaCl, NazCOs, FeCls, AICls, van van h) 2HF + SbFs5 = SbFe’ + HF” i) Tinh axit tang khi kha nang solvat héa giam j) CHa + HSbF¢ = [CHs"[SbFe] — [CHs"][SbFe] + Hz CHs CH; Hc CHs + HSbF, ———»Hsc—c* SbFg + CH, CHs CH Bai 9: Dung dich axit sunfuric axit hoa dung dich nén tat c4 cdc ion sunfua va hydrosunfua déu chuyén héa hét thanh H2S dé ngung tu vao dung dich cadimi nitrat. Lyong axit sunfuric thém vao la 0,4996 mmol. Lyong NaOH phan tng voi lugng du axit sunfuric [a 0,5487 mmol . Nhu vay Iugng ion hydro phan Ung sé la 0,4505 mmol lon hydro do axt sunfuric phan ly o6 thé phan ting theo hai cach: S? + 2H,0* = HS + 2H20 NHs + H30" = NH." + H20 (trong trong hyp du amoniac) Dé xac dinh trvéng hop nao sé xay ra gitva hai trudng hop thi chung ta can phai xem xét chuyén gi da xay ra trong binh hing Ca** + HyS + 2H20 = CdS + 2H,0* CdS + 4Br2 + 12H,0 = Cd” + SO,” + 8Br + 8H,0" Nhu vay 1 mol HS dn dén sy tao thanh 10 mol HsO* (2 mol tir phan ng dau va 8 mol ciia phan tng sau) NaOH phan ting voi ion hydro sinh ra trong phan tng. Luong NaOH str dung la 1,418 mmol, Diu nay cé nghia la sé co 1,418/10 = 0,1418 mmol H2S trong binh hing Do long ion hydro sinh ra tir 0,1418 mmol HS (0,2836 mmol) thi it hon so v6i long ion hydro phan Ung voi dung dich axit sunfuric (0,4505 mmol) nén ching ta c6 thé két luan rng mét lvong axit sunfuric phan tng véi lugng du amoniac. Luong amoniac trong 10,00 cm? dung dich thu dug la 0,1669 mmol nén néng 46 amoniac trong dung dich dau (véi lueng gap 100 lan so véi dung dich mau) sé la 1,669 molidm’, Cui cling, néng 46 amoni sunfua trong dung dich tac nhan phan ting [a 1,418 molidm® Bai 10: a) Cu + 4HNOs = Cu(NOs)2 + 2NOz + 2H,O Ni + 4HNOs3 = Ni(NOs)2 + 2NO2 + 2H20_ b) IOs + 5 + 6H" = 3l, + 3H20 hel = ls bp + 28,03" ly + 28,0," 21 + SOc" 31 + S40q? 52Olympic Hoa hoc quéc té lan thr 40, Bai tap chuan bi 0,0895g___10,00cm* n(10 = 4,014.10 mol 214,00g. mol" "100,00em (lz) = 3n(103}) = 1,2042.10% mol 1n(S203*) = 2n(I2) = 2,4084.10% mol c= n(S203*) / V(S203*) = 2,4084.10% mol / 0,01046 dm? = 0,02302 mol/dm® dung dich Hd tinh bot c) S203” + H* = HSO3' +S. d) eeu +41 = 2Cul + Ip beta Phan ng khir gitva Cu®* va I’ khong phai xay ra ngay lap tire. ©! nhiing didu kién da néu thi phi cn dén 5 phut phan wing mdi hoan tat. Boi trong nhiéu gid 14 cd mét sai am do bj oxy cham boi oxy khéng khi e) n(S203*) = c.V = 0,02302 mol/dm®.0,01611 dm? = 3,7085.10* mol n(Cu**) (trong 1,000 om? dung dich mau) = 2n(l2) = n(S203”) = 3,709.10 mol m(Cu) = 3,709.10? mol = 63,55 g/mol = 2,357 g Luong ding trong dong xu 2-Ft la 2,357 / 3,1422 = 75,01% khdi lvong f) Mau sac phirc amin ctia cd Cu” va Ni** déu la mau tim (Thc ra mau sac cla phirc Cu** dam hon) Amoniac can dé chinh pH vé mét gia tri thich hop dé sy tao phtrc voi EDTA xay ra hoan toan 3,681 1g 10,21¢m?* 372.25g.mol" 1000,00em' n(Cu) + n(Ni) = 1,010.10% mol . 100,0 cm? / 0,2000 cm® = 0,05048 mol Tir khdi lugng cia déng xu: M(Cu).n(Cu) + M(Ni).n(Ni) = 3,1422g Giai phvong trinh déi voi n(Cu) va n(Ni) ta duoc 0,796g (¢ n 359 Két quia nay khép voi két quia ma true dé da duge tinh theo phuong php chuan dé iot g) (EDTA)= .010.10“mol +h) Dung dich mu chua pha loding sé cho gid tri 6 hdp thy In hon 2,0, vn khéng thé dé dang xac dinh Hé sé hp thy mol déi voi Cu” (260 nm) = 0,6847 / (0,1024 mol.dm® . 1,000 cm) e(395 nm) = 0,0110 / (0,1024 mol.dm* . 1,000 cm) = 0,107 dm’.mol.cm™* (720 nm) = 0,9294 / (0,1024 mol.dm* . 1,000 cm) = 9,076 dm®,molt.cm"* e(815 nm) = 1,428 / (0,1024 mol.dm’ . 1,000 cm) = 13,95 dm®.mol'.cm™ Hé sé hp thy mol déi voi Ni?* e(260 nm) = 0,0597 / (0,1192 mol.dm* . 1,000 cm) = 0,501 dm°.mol''.cm™ e(395 nm) = 0,6695 / (0,1192 mol.dm® . 1,000 cm) = 5,617 dm®.molt.cm* (720 nm) = 0,3000 / (0,1192 mol.dm’ . 1,000 cm) = 2,517 dm®.molt.cm* (815 nm) = 0,1182 / (0,1192 mol.dm* . 1,000 cm) = 0,9916 dm®.mol'.cm’t Néng 49 clia dung dich mau da pha loaing cé thé duge xac dinh bang cdc giai hé phuong trinh twong ting sau: 6,687 dm®.mol.cm™ Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét — box Héa hoc OlympiaVN 53.A (815 nm) = («(815 nm, Cu).c(Cu) + «(815 nm, Ni).c(Ni)).1,000 cm A (395 nm) = (2(395 nm, Cu).c(Cu) + (395 nm, Ni).o(Ni)) 1,000 om (Cu) = 0,07418 molidm? (Ni) = 0,02677 mol/dm’ déi voi dung dich lozing Nong 49 ca dung dich mau ban dau lon gap 5 lan: (Cu) = 0,3709 mol/dm? (Ni) = 0,1338 mold? 6i voi toan thé tich ota dung dich mau (100,0 om?) c(Cu) = 0,03709 mol/dm* c(Ni) = 0,01338 mol/dm® Két quia nay hoan toan khép voi két quia chudn do }) Gid tr ca 6 hap thy & 720 nm sé la: A (720 nm) = (¢(720 nm, Cu).c(Cu) + 2(720 nm, Ni).c(Ni)).1,000 cm = 0,7404 Két qa nay hoan toan khop voi gid tri da tinh 6 trén i) Gia tri cla d6 hap thy & 260 nm ‘A (260 nm) = (c(260 nm, Cu).o(Cu) + 2(260 nm, Ni).0(Ni)).1,000 cm = 0,5093 Két qua nay khong khdp vdi két qua thy nghié k) May pho ké trac quang dgc gia tri 4 6,000 c6 nghia la thyc té khéng hé cé anh sang di xuyén qua mau. Biéu nay van khéng thay ddi khi ta ding cuvet c6 46 dai nhé hon 6 hp thu mol cia Cu®* va Ni** Gury do bang cach str dung hai dung dich CuCl, va Nik. Axit nitric dug sir dung dé hoa tan déng xu nén néng 46 ctia anion nitrat sé rat cao trong dung dich mau. Quan sat thye nghiém o6 thé duge giai thich néu nhu ion nitrat hap thu & 260 nm. Biéu nay c6 thé duge xac nhan bang cach ghi phd UV-Vis cia mét mau axit nitric Bai 11: a) Cac dién cc sir dung déu cho thay cé sy tng voi phuong trinh Nernst voi hé s6 goc 1a 59,1 mV déi voi ca ba gid tri pH duoc stv dung trong phép do. Thé dién cue chuadn & don vi milivon dug tinh theo biéu thc. E = E°— 59,1.Ig(CN] Néng a6 cn bang clia CN’ cé thé dugc xem nhu la mét ham ila ndng 46 phan tich va Ap dung hai phuong trinh nay voi mét cap diém ma & dé xac dinh duoc néng dé phan tich cia ion xianua sé dan dén két qua H’] -x[H" XL he . x1 Ap dung phuong trinh nay aéi voi pH = = 12.va pH. = 7,5 (6 ba néng 46 cia NaCN thi Ein — Epti2 = -101,6 mV) sé cho ta két qua Ka = 6,195.10 b) 4Fe** + Op + 10H20 = 4Fe(OH)s + 8H” ¢) Fe** + 6CN’ = [Fe(CN)e]* Néng d9 clia NaCN trong dung dich la 0,0010 mol/dm®. Tu sy chun héa dién ce thi ta 06 E°= 220,0 mV vaOlympic Hoa hoc quéc té lan thr 40, Bai tap chuan bi [en"], =107" Gia tri dgc dug & trén dign oye la 585,9 mV & pH = 7,5. Tu 6 ta 06: [CN Jeg = 6,46.107 mol/dm? => [HCN]eq = [H"JeafCN leq / Ka = 3,32.10° molidm? Néng d6 cia phite xianua sé la: [CN Jpnac = [CN dng ~ [CN Jeq = [HCNeq = 9,66.10% mol/dm? Tat ca cac xianua tao phirc déu & dang hexaxianua sat (II) nén ndng d6 cia né sé la: [Fe(CN) 6" Jag = [CN Tpnic!6 = 1,61. 10° mol/dm? Luong sat (II) thém vao la 1,44.10 mol Lugng sat (II) phan tng véi oxy 1a 1,00.10 mot Luong sat (II) hién dién trong phir hexaxiano la 1,61.10° mol Néng dé ciia ion sat (II) ty do 1a 2,78.10% mol/dm* Hang so bén ctia phitc sé la Bo = [Fe(CN) 5" eq ([Fe*"JealCN Toa") = 99.10% @) Nong 46 ciia ion CN ty do va HCN la [CNJeg = 6,46.107 mol/dm? va [HCNleg = 3.32.10" * molidm®. Digu nay cé nghia la téng Ivong chat dc xianua sé bé hon mot ntva so voi gia tr LCso con gid tr] cua chat khong dOc [Fe(CN).“] rat cao. Cac gid tri nay hoan toan phi hop voi thi nghiém mac du sy ton tai lau dai cla cac chat nay sé gay ra nhizng anh huéng x4u nhat dinh d6i vdi strc khée cia loai ca e) 2Cu* + 2CN = 2Cu* + (CN)2 Cur + nCN’ = [Cu(CN)q] (n = 2-3) A) Tir gia tri doc dug & dién cyrc va gid tri pH ta 66 [CN Jeg 4,77.10° molidm? Do [Cu’] = 2.10 molidm® nén tich s6 tan ota hai néng dé luén bé hon Louon nén & day sé kh6ng c6 két tia CuCN 9) [Cu*}ing = 0,021 g/dm* / 63,55 g/mol = 3,30.10% mol/dm® nén sy két tia xay ra hoan toan [CN }ing = 0,026 g/dm? / 26,02 g/mol = 1,00.10° molfdm? Néng 49 cia ion xianua sé a [CN Jeg = 4.77.10 mol/dm* => [HCNJeq = 2.45.10 mol/dm?® {ON Ipnac = [CN Teng ~ [CN Jeq = [HCNleq = 7,50.10% molidm? S6 phi tty trung binh trong phite déng xianua: [Cu(CN)s"Jeq = [CN prac ~ 2[CUu" ing = 8,9.10° molidm? [CU(CN)s Jon = (ICN pic = SICU(CN):?Je)/2 = 2.4.10 mold? Nhu vay Bro = [Cu(CN)z'log / ([Cu"Jeg[CN Tea’) = 5.3.10" By = [Cu(CN)s"Jeq/ ([Cu"JealCN eq’) = 4,1.107° f) Tur gia tr doc durge 6 thé dign cc va gi tr pH: [CN Jeq = 5,04.10 mol/dm? => [HCN]eq = 2,59.10° mol/dm? [CN Toric = [CN hing - [CN'Jeq - [HCN]eq = 9,74.10% mol/dm® Téng lwgng sat (I) thém vao la 1,44.10 mol, trong 46 1,00.10* mol da tham gia phan teng voi oxy. Téng Iwong sat (II) cdn lai trong dung dich luc nay sé la 4,4.10% mol/dm? Tw dinh nghia cia Bo va sy bao toan néng dé ta co: Bo[CN ]eq’ = [Fe(CN) seg / ([Fe*"}ing ~ [Fe(CN)o* lea) Giai phuong trinh nay cho ta két qua [Fe(CN)o"Jeq = 5,04.10° mol/dm? va [Fe*"]aq = [Fe hing - [Fe(CN)s*Jeq = 3,9.10% mold? Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét - box Héa hoc OlympiaVN 55Két hop hai phuong trinh tao phtrc sé dan dén: 3{Cu(CN)J + Fe** = 3Cu’ + [Fe(CN)e*] Ket = Bo / Bo? = 5,34.107° Tir qua trinh trén ta c6 thé tinh duge ti 16 sau: : [Tre] Cu Fe (co), i FL aso [eweny, |, Y [Feenye J, Diéu nay cé nghia la toan bé Iugng déng da tham gia tao phirc trong dung dich Néng dé clia xianua trong phirc ding sé la [CN Jonite adng = [CN Jpnie - 6[Fe(CN)e* Jeq = 6.73.10 mol/dm® Nhu vay néng d6 clia phirc déng xianua sé la: [Cu(CN)s"Jeq = [CN Tone adng - 2[CU"héng = 1.10 molidm? [CU(CN)2'Jeq = ([CN Ipnuc abng - 3{Cu(CN)s” Jeq) / 2= 3,2.10% mol/dm? Luc nay cé kha nang cé két tia CuCN, va ta cé thé thi? kiém tra diéu nay: [Cu Jeq = 7.45.10" ; [Cu(CN)2'Jeq = 2.4.10? mol/dm? [CU"JeglCN Jeg = 1.2.10" < Loucn Tc la trong dung dich Ie nay sé chiza chat d0c [Cu(CN)2] & ndng dé cao lon hon so véi liu chét mot niva (37 mg/dm® > LCso) nén né sé rat déc hai. Biéu nay céng nh&n voi thi nghiém khéng duge biéu dién trén TV (3E°, — 2E°1) = 0,772V b) Es = E°s + 0,0591g({Fe*’] / [Fe*"]) = 0,710 V (Fe*"] / [Fe**] = 0,0890 Déi voi sy gan dung thé thi: Sig (Eccl aener0.9 11 “ [re ][cr'] 0,089.0,089 =115 c) Es = 0,356V __[Fe(CN)e ] [re* ][cen [Fe(cn): ] [Fe* ][cn °4, = E%s + 0,0591g(Bo(Fell) / Bs(Felll)) Bo(Fell) / Be(Felll) = 107 = 8,90.10° B,Fe(Ily B,Fe()= n,ELin, Ee nth, HsAsOs + 2H" + 2e = HsAsOs + HzO Es = E%s + (0,059/2)IgHs0" }* = E°s - 0,059pH = 0,442V E = (2.0,442 + 0,356)/3 = 0,413V 0,413 = 0,442 + 0,059/2Ig({HsAsO«)/[HsAsOs]) [HAsO«)/[HaAsOg] = 0,107 od) E= ) Es = E%s + 0,059/2Ig([Is V{I]°) = 0,540 + (0,059/2).2 = 0,599V 56Olympic Hoa hoc quéc té lan thr 40, Bai tap chuan bi ,599V = 0,560 — 0,059pH 282,85K va L; = 2,10.10"". Nhu vay A,G° 198, 15K va L; = 1,56.10"°. Nhu vay -RT2InL2 = 56,0 kJ/mol ‘St dung biéu thirc AG = AH - TAS cho két qtia A,S° = 119 J.mol.K" va AH? = 91,3 kJ.mot", gid thiét rang A,S° va A,H° khéng phy thudc vao nhiét dé trong mét khoaing he| Ngoai suy dén 50°C cho A,G°s = 53,0 kJ/mol, nhu vay Ls = exp(-A,GYRT) = 2,71.10°. tan sé lac= JZ, =5,2.10° molidm®, la 7,5 mg/dm? RTiInL = 57,8 kJ/mol b) Gia siv rang néng dé ion Cr rat cao & can bang. Diéu nay cé nghia la [Ag’] sé rat thap va 06 thé bé qua khi so sanh voi [AgCl]. [AgClling = 5,2.10° mol/dm? = [AgCl.] + [Ag’] = [AgClz] [Acc] _[AsCls pe oe [as er? ¥ler] |AgCl Nhu vay for] eC = 1,34 moldm? [Kling = [CI] + 2[AgCle] = [CI] = 1,34 mol/dm? c) Zn + 2H" = Zn* + Hp d) Voi ion Cu2* Do. E°(Cu"/Cu) > E°(Cu*"/Cu’) >> E°(Zn"/Zn) nén phan wng wu tién la: Cu?*(aq) + Zn(Hg) = Cu(r) + Zn?*(aq), Voi ion Cr** E(Cr"/cr 0,42V 1 Do E(Cr"/Cr**) > E(Cr°/Cr) >> E*(Zn"'I2n) > E°(Cr*/Cr) nén phan wng wu tién la: 2Cr**(aq) + Zn(Hg) = 2Cr**(aq) + Zn**(aq) n VO; (-0,74V)-2(-0,90V) Voi i VOz" + 2H" + e = VO + HO O' pH =1 thi EX(VOp" NO) = 1,00V + 0,059V. Ig0,1? = 0,88V VO*" + 2H" +e = V%" + HO. O pH = 1 thi E°(VO*/V™) = 0,36V + 0,059V. Ig0,1? = 0,24V Eves ,255V Do cd ba ban phan tng déu o6 thé chuan lon hon cap Zn"/Zn nén vanadi c6 thé dat dén 86 oxy héa +2. Thé chudn déi voi su khiv cao hon thi thép hon, vi thé nén phan tng uu tién sé la: 2V0;"‘(aq) + 3Zn(Hg) + 8H(aq) = 2V**(aq) + 3Zn**(aq) + 4H,0(I) e) Viéc hén héng hoa khéng lam thay déi thé chudn cla kém Cu**(aq) + Zn(Hg) = Cu(r) + Zn?*(aq) $6 electron trao déi lan = 2 Ein = 0,34 — (-0,76) = 1,10V K,-e ¥ =1,6.10" 2Cr*(aq) + Zn(Hg) = 2Cr**(aq) + Zn**(aq) Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét — box Héa hoc OlympiaVN 57$6 electron trao déi lan = 2 Erin = -0,40 — (-0,76) = 0,36V K,=e * =1,5.10" 2VOp" + 3Zn + BHY = 2V"* + 3Zn** + AHO $6 electron trao déi lan = 6 éi voi ban phan tng: VO2" + 4H" + 3e = V** + 2H20 00V+0,36V-0,255V E’=. Fi =0,368V O pH = 1 thi E° = 0,368+. 0,059 Ig0,1* = 0,290V 0,76) = 1,05V K,=e =2,9.10" f) Phan Wng xdy ra nhu sau: Fe*(aq) + Ag(r) = Fe**(aq) + Ag’(aq) E°sin = 0,77 — 0,80 = -0,03V K,=e ® =031 Néu [Ag‘] = [Fe®*] = x, [Fe®"] = 0,05 - x. Nhu vay: Tw day ta 6 x = [Ag’] = [Fe*’] = 4.4.10? mol/dm® va [Fe*] = 6.10° mol/dm®. Nhu vay 4 6 dén 88% luong ion Fe** bi khir g) Phan tng xdy ra nhu sau: Fe**(aq) + Ag(r) + Cl(aq) = Fe**(aq) + AgCl(r) Thé khw chuan ca phan wng AgCl(r) + e = Ag(r) + CI'(aq) la E*= 0,80V + 0,059V.Ig--2_ =0,22v [er] E%bin = 0,77 — 0,22 = 0,55V Ke 99.10" +h) Néu [Fe™] = y; [Fe*’] = 0,05 - y = 0,05 mol/dm® thi [Cr] cn bang 6 gia tri rat cao) ee tte] [Fe"][cr] y Tw day ta cd y = [Fe**] = 5,02.10° mol/dm* —y = 1 mol/dm® (do hang sé 1,99.10" i) Ca hai phan tng déu cé thé khtr du6i 0,22V nén cation sé khéng bi khur 58Olympic Hoa hoc quéc té lan thr 40, Bai tap chuan bi Bai 14 a) Br Br 1 wooo so cs (oS othe oS 4 H “Kt H H A B c D E b) Anion pyrole cé tinh thom, cation pyrole c6 hai néi dai lién hgp va khéng thom nén kém bén ving hon ) E c6 tinh bazo manh hon do cé cap e khéng lién két trén N d) Phan tng polymer héa xay ra trén hé théng ndi déi lién hop. Polymer thu dugc cé vai he lién hop x Bai 15 a) n=0 n=l n=2 b) Sy ngung ty cdc vong thom c6 6e x thanh cdc hé thom thang cé 4n + 2 electron x cho thay rang chung ta sé mat hai nguyén tir cacbon thom nén téng sé electron x sé 1a 4n+2+6 — 2 = 4(n+1) + 2. Tw la quy tac Huckel van dug bao toan c) Sw ngung tu cac vong thom ngung tu thang qua hai nguyén tir cacbon cd nghia la tng sé electron r Itic nay sé la 4ny + 2 + 4ng + 2-2 = 4(m + m2) + 2, quy tac Huckel van duoc bao toan d) Huéng kha thi nhat chinh la sy ngung tu phai 06 tat cd 4n + 2 s6 nguyén ti’ cacbon thom, véin la mét s6 khong 4m @) Mot vi dy la coronen: ) Bazo lién hyp cia xiclopentadien cé tinh thom Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét — box Héa hoc OlympiaVN 59\, HO: oO ° OCH, a wna NK, Ao Chat dau tién la xitozin, chat thir hai [a uraxin. Vai trd quan trong cia su tautomer héa nay chinh la sy tham gia cila cdc lién két hydro cla cc mach axit nucleic. Cau tric thom sé lam giém sé lién két hydro d6i voi cdc cp AND. Ta cé thé xem thém guanin va timin (con adenin van git? cdu tric thom) Bai 16: b) No la cac déng phan cdu tric hay cdc tautomer $6 electron x khéng bi 4nh hudng bai sy chuyén vi nay: ), Ching ta cé hai déng phan cdu tric. Sy dich chuyén ctia proton (va sy di chuyén tidy ndi cla cac electron thom) la qua nhanh dén ndi ma cac tautomer khac nhau khéng the phan lap duc d) Ching ta cé thé phan lap duoc 11 dong phan cau tric e) Sé electron x la hoan toan nhu nhau: 26 : Voi mét nhom thé metyl chting ta c6 thé cd dugc hai déng phan cau tric f) Vily do tinh dién g) Nong d6 can bang c6 thé duge tinh ter bidu thie: [Pal x, [L]=1900 va [Pt KK, [L] =285000 i 7 [P] 60Olympic Hoa hoc quéc té lan thr 40, Bai tap chuan bi Nhu vay [PL2] = 1900[PL] va [PL] = 285000[P]. Nhu vay cd [PL] va [P] déu rat bé so voi (PLe] h) Tinh bén déng hoc giém khi nhiét 46 giém (N6i céch khac dau hién tinh bén déng hoc sé xuat hién khi tang nhiét do) i) Ta c6 thé xét phan tng sau: PL + PL = P + Ply . Biéu nay 06 duge do méi phéi tl tham gia can bang aéu lam cn bang dich chuyén manh vé phia phdi tl bén hon. Can bang trén ciing co thé nhan dug tl’ cac can bang géc ban dau va tlr dé c6 thé viét biéu thire cho cac hang sé can bang tong teng nhu’ sau: K, _[PI[PE K [PL] Gol x mol/dm? la ndng d6 cia [PL] tham gia phan trng chuyén thanh P va PLz thi ndng 46 luc cn bang ctia [P] va [PL2] sé lé x/2 mol/dm®. Luc nay [PL] la 0,1 — x. Giai phuong trinh nay thi ta nhan dug gia tri ndng d6 can bang olla cdc chat la: = 12,67 = [PL2] = 0,0438 mol/dm® [PL] = 0,0123 mol/dm® PL []= L 0,000187 mol/dm? [PL]-«, 47: enantiome dp dia enantiome dp dia 1 dp dia 2 OH OH OH OH m Cor © enantiome Theo dinh nghia né la ding phan dia N~ Khéng c6 déng phan lap thé do su raxemic héa qua 2 nhanh & nguyén tw N hinh thap D Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét — box Héa hoc OlympiaVN 611 P. P. PO 96 E enantiome dpdia1—dpdia2 (‘e I b) Buéc so cp cila qua trinh nay [a sy hydrobo héa olefin. Bay la mét phan tng céng syn va 06 thé tao ra hai tiéu phan trung gian trong dé chi c6 mét la wu tién lap thé. Phan ting cila cdc tiéu phan trung gian nay véi hydroperoxit xay ra véi su bao toan céu hinh sé dan dén viéc tao san phdm chinh voi sy chon lgc lap thé cao. Mét lvgng nhé san pham phan ting hydrobo héa xay ra 6 phia bén kia dan dén sy tao thanh san phdm phy sau khi oxy héa wa 2, H,0, major Phan teng iodolacton héa olefin duoc bat dau béi sy hoat héa néi déi bang tac nhaén electrophin Ia iot tao thanh tiéu phan trung gian dudi. Do hudng phia trén cla néi déi chan khéng gian manh hon nén sy tan cong sé wu tién theo huvdng phia dudi. Sy tan c6ng nucleophin ngi phan tt? béi ion carboxylat déi véi tiéu phan iodonium dan dén sy chon loc lap thé tao thanh mét san pham duy nhat Ce |, Kl, NaHCO, CO- ore — 0 via "Oo ors Phan trng epoxy héa néi déi bang axit meta-cloperbenzoic bi anh hung kh6ng gian truc tiép. Huong tan céng chinh sé la hudng it bi chén khong gian hon dé tao thanh dong phan “threo”. Sy tan céng theo huéng ngugc lai sé it duge wu tién hon va chi tao mot lugng nho dong phan erythro. OH ° OH OH ( Gy OOH — 3 cl major minor 62Olympic Hoa hoc quéc té lan thr 40, Bai tap chuan bi Phan tng cis-dihydroxyl héa duéi anh hwéng cla osmi tetroxit sé tao thanh san phdm duge vé & dui, chat nay tdn tai & dang hén hop hai déi quang 9 Aen yho~en + Os0, ‘OH OH Sy hydro héa xiic téc trén b8 mat platin a mét qué trinh cOng syn vao néi doi. Hung tiép_ cn wu tién cla phan tir hydro gan trén bé mat xuc tac la huréng ma & dé c6 cdc nhom thé kich thuéc bé hon. Do anh huéng khong gian ctia nhém phenyl va metyl nén sé khong xay ra sy kh? nhém cacbonyl nén phan tng khtr la chon loc lap thé va chi tao duy nhat mét san ee PP \/ Bai 18: Do glyoxal c6 cu tric d6i xing nén cu tric ctia D 6 thé duge xae dinh: °. 2 of” Dya vao cu tric cdc san phdm ozon phan nén E cé kha nding tn tai hai cu tric: Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét — box Héa hoc OlympiaVN 63.i “ —— + A ° o a mh 0 o E, Do D va E la san pham dehydrat héa cia cling mét ancol nén chuing sé 06 cling b6 khung cacbon, Nhu vay cau tric cla E; phi hop hon: Cac cu tric 06 thé c6 cla C la: ewer sv defiyrat hoa C. vac Gs chi tao sin pham duy ana tuong ting la Ei va D nén chun khéng phai la cu triic ding. C khéng thé bi oxy héa bdi axit cromic nén né khéng th chiva bat ky nhém hydroxyl bac hai nao. Vi thé cAu tric C2 la chinh xac. B chi chira duy nhat mot ndi déi nén né cé thé 6 trong vong hay & nhém isopropyl:Olympic Hoa hoc quéc té lan thr 40, Bai tap chuan bi OH OH "OH ‘OH ‘Sw hydrobo héa B, dn dén hai cdu tric déi xteng cdn Bz chi mét nén chat phi hop Ia B;. OH OH OH 8, ——> + ‘OH a ‘OH OH 8; —__» HH HO, Thanh phn cila B la CigH;e02 trong khi A la CioH:sO2. Phd NMR chi ra trong A co mot lign két di duy nhat. Do A khéng phn ung duge véi natri nén A khéng c6 nhém hydroxyl nao. Két qua phan tich nguyén t6 bac bé rang A rat c6 kha nang chia nhém ete hay nhém hydroxyl. Nhu vay trong A khéng thé cé nguyén ti oxy lién két voi hydro, ma A lai it hon B hai hydro nén kha nang duy nhat o6 thé xay ra la hai oxy lién két voi nhau tw A cé chira nhém peroxit. Biéu nay giai thich duc kha nding né bi khiy bdi LiAIH, va He d& tao diol va tinh dé né cia né Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét - box Héa hoc OlympiaVN 65Vé hinh thirc A c6 thé duge tao thanh qua phan tng cOng gira D va oxy (F). Phan ting nay xay ra khi 06 sv chiéu xa dudi sy co mat cla mot chat cém quang (nhu clorophyll). Diéu nay cho thay rang phan Ung xay ra @ trang thai kich thich singlet cia oxy chtr khong phaii xy ra 6 trang thai co’ ban triplet. Phan tng nay la mét phan tng kiéu Diels — Alder VOi oxy singlet Ia tac nhan dienophin: oO hv ll as ° Bai 19: a) i, Phan ung brom héa géc ty do: Bro/as hay N-bromsucxinimit, sau dé la Mg + Et;0 (xuic tac iot) ii, etylenglycol xtc tac axit b) Q HSH OH ‘ Oe Oe Hye’ cH Non, OL COL, mye" “cH, me" c E, coronene 66Olympic Hoa hoc quéc té lan thr 40, Bai tap chuan bi Bai 20: Michael a) Ch base Ok» addition CO ‘oO o A i aldol addn, dehydration Co oS, ») °) Fa R R H R s Co ché phan wng déng vong: Ho H 9H OH + 7 — —_ 7 R cl Phan trng xay ra khong dung cham dén trung tam bat déi, vi thé nén cac san pham sé la: Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét — box Héa hoc OlympiaVN «67a) os Om ony Noctis ‘OCtH, Qo C v4 7 HC" CH s-sctoide 1 s-cetonide Sy tao thanh déng phan 1,3 it phd hep hon (do céc nhém thé 6 vi tri trans khéng thuan Igi cho viéc tao vong) nén san pham chinh sé la 3,4-acetonide b) GH,OH = Lo _,0H0-C0CH, Gots Hy ‘on acetic antyaride ©. PnOdee é eu Hoon Hye” SCH Hye” “ols cH,o-coch, cHOHN ‘ocHs wd c) Khéng, vi D co nhém OH chua bi khéa cho nén trong qua trinh téng hop E thi co thé tao thanh dugc ca hai déng phan a va B. Thanh phan cac déng phan nay phy thudc nhiéu vao diéu kién phan tng: 68Olympic Hoa hoc quéc té lan thr 40, Bai tap chuan bi d) (a) : dL pococrsocHs(®) HO () 4x(e), 1x(a) 4x(a), 1x(e) more stable e) CHZOCOCH3OCH: Ls 2 ay 8 | Pig0-COCHs C—__/ HO n— x wo, - \ 20%) H jl [So rr bu H 3,4-acetonide 2,3-acetonide Nhu vay déng phan 3,4-axetonide cé hai cau dang ghé khac nhau con déng phan 2,3 chi mot: Hye He Ho GHZOCOCH OCH 9 et pe Lape ep ee won —9, ne Ji? ‘o cm No, oN, oy 20H Ol ome Sor P7CHs\ ic \ x s 2 Hs Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét - box Héa hoc OlympiaVN 69Bai 22: a) Qua trinh dign phan nuéc: Anot: 2H,0 — 4H" + O, + 4e Catot: 4H,0 + 4e — 2H, + 40H” Nhu vay dién tich & 4 mol e [a can thiét dé giai phong 2 mol Ho i voi 1kg hydro thi 2.1,000g / M(H2) = 992 mol e, tic c&n c6 9,55.10"C dién tich E = 1,6V.9,55.10"C = 1,5.10° J : Dién Ivong can thiét dé dat duoc hiéu suat nh thé: 1,5.10° J / (0,90.3,6.10° J/kWh) = 47 kWh. Gia dign dé san xuat 1kg hydro nhu vay sé la 47 kWh.0,10 euro/kWh = 4,7 euro, nhiéu hon so véi gid céng nghiép can dé san xuat 1 kg hydro (2 euro), nhu vay phuong phap nay khéng kinh té lam. 1b) Nang lugng ty do cho phan tng chay ciia hydro & 298K: Ho(k) + 0,502(k) = HzO(I) A,G? = AWH°(H2O) — T(S%(H20) — S°(He) — 0,58°(O2)+ = -237 kJ/mol Tilg nang lugng theo khéi long sé la: 273 kJ/mol / 0,00202 kg/mol =1,17,10° ki/kg Thé tich mol ctia hydro 06 thé dug tinh tt phuong trinh khi ly tudng: Vm = RT/p = R.298K / 101325Pa = 0,02445 m°/mol Tilé nang Iyong theo thé tich sé la: 237 kJ/mol / 0,02445 m*/mol = 9,69.10° kJ/m* c) Bién ddi phuong trinh Van der Waals dan dén v_={b+ RT}. 4 2% fs pv, pv ‘Str dung lai céng thtrc nay dé tinh Vm d6i voi p = 200 bar & T = 298K 1,24.10°m'.mol® , 3,30.10""m*.mol? Vin (i) vai) Néu chting ta bat dau tién hanh phuong phap lap voi Vm(0) = 1.10? m®.molt Vn(1) = 1,50.10% m?,mol"; Vin(2) = 1,43.10% m°.mor Van 43.10% m®,molt Nhu vay du6i nhing digu kién nay thi Vp = 1,43.104 m®.mol'. Thé tich cia binh hinh try 1a 0,050 m°, vi thé nén né chtra 0,050 m*/ 1,43.10 m°/mol'' = 350 mol He Téng khdi lugng cia binh hinh try lic nay la 93kg + 350mol.0,00202 kg/mol = 93,7 kg TiIé nang lugng theo khdi lwgng sé la: 350 mol.237 kJ/mol / 93,7 kg = 8,85.107 ki/kg Thé tich cla mot binh try day khi sé la 50dm? + 93kg / 7,8 kg/dm? = 62 dm? Tilé nang Iugng theo thé tich sé la: 350mol . 237 kJ/mol / 0,062m* = 1,3.10° kJ/m® Vui + 1) = 1,50.10% m*/mol - S 4d) 1 mol NaBH cho 4 mol Hs. Phuong trinh héa hoc don gidn nhat ctia phan ung cho dui day (the ra ban chat héa hoc cla ion borat phic tap hon nhiéu) NaBH, + 2H,0 = NaBO>2 + 4H, ¢) TiI6 nang lugng theo khdi lugng sé la: 4 mol.237 kJ/mol / 0,03784 kg = 2,51.10* ku/kg TiIé nang wong theo thé tich sé la: 2,51.10* kJ/kg / 1070 kg/m? = 2,68.107 kd/m? 70Olympic Hoa hoc quéc té lan thr 40, Bai tap chuan bi ji. Bét chay graphit: C(r, gr) + Ox(k) = CO2(k) A,G? = AyG°(COz) = -394,4 kJ/mol TiIé nang lvgng theo khéi lung sé Ia: 394,4 kJ/mol / 0,01201 kg/mol = 3,28.10* kJ/kg Cu tric ciia graphit bao gdm cac luc giac déu sap xép theo ting Idp. Dién tich cla mot tt dign la: 6. V3 .(1,456.10"° m)? / 4 = 5,508,107" m* Thé tich cla mot cdu tric hinh luc gidc déu dugc tim thay gia hai lop: 5,508.107° m?.3,354.10"'°m = 1,847.10 m* Trong 6 mang nay (ta co thé hinh dung ra 6 mang nay mot cach dé dang nhung dé khong phai la 6 mang co’ s6’ cia graphit) thi c6 mai nguyén tl cacbon & mdi dinh, ma méi dinh lai chung cho 6 6 mang khdc. Nhu vay mdi 6 mang chwa 12.1/6 = 2 nguyén tr C Khéi lvong riéng & day sé la 2.M(C)/ (Na.1,847.107° m) = 2160 kg/m? TiIé nang lugng theo thé tich sé la 3,28.10* kJ/kg.2160 kg/m* = 7,08.10” kJ/m* ii, Bét chay n-octan: CeHia(l) + 12,5 On(k) = BCOr(k) + 9H20(!) A,G? = BAG%(COz) + BAG*(H20) - AG*(CeHia) = -5295 kJ/mol TiI6 nang lugng theo khdi lugng sé la: 5295 kJ/mol / 0,11426 kg/mol = 4,63.10* kJ/kg Tilé nang lwgng theo thé tich la: 4,63.10* Ku/kg.700kJ/m? = 3,24.10" kJ/m? iii, Dét chay metanol: CH3OH(I) + 1,502 = CO2(k) + 2H20(I) AG? = AyG°(COz) + 2AyG%(H20) - AyG°(CH;OH) = -702 kJ/mol Tig nang luong theo kh6i lang sé a: 702 kJmol / 0,03208 kg/mol = 2,19.10* kJ/kg Tilé nang lugng theo thé tich sé la: 2,19.10* kJ/mol .790 kg/m? = 1,73.10" kJ/kg iv. Nang long cia pin: E = 1,9A.3600s.1,3V = 8,9.10° J Til nang lugng theo khdi lugng sé Ia: 8,9 kJ / 0,02658 kg = 3,3.10? kiikg Thé tich cia pin: (7,05 mm)?. x .47,3 mm = 7386 mm? Tilé nang Iugng theo thé tich sé la: 8,9 kJ / 7,386.10° m° = v. D6 hut khdi trong phan tng hat nhan la: ‘Am = 4.1,000782 — 4,0,00260 = 0,02868 g/mol AE = Am.c? = 2,868.10° kJ/mol.(3,000.10° m/s)? = 2,581.10’? J/mol MBi phan tie née chira hai hat nhan hydro TiIé nang lung theo khdi luong sé la: 2,578.10"? J/mol / (2.0,01802 kg/mol) = 7,15.10"° kJikg TiIé nang lwgng theo thé tich sé la : 7,15.10" kd/kg . 1000 kg/m? = 7,15.10" kJ/m? :2.10° kJ/m? g) TIIg nang luong theo khéi lwong cla hydro éng bang voi hydro khi = 1,17.10° Jikg Tilé nang luong theo thé tich: 1,17.10° J/kg.71 kg/m? = 8,3.10° Jim? Tuy nhién can Iuu y rang chi phi cao cho phuong phap lam lanh khéng hé dug phan anh trong tilé nang lvong A) Ti lé nang lwgng vé thé tich va khdi long cla metanol la rat cao nén khdng can phai hoa long 1) Anot: CHsOH + HzO -» COz + 6H" + 6e" Catot: 1,502 + 6H” + 6e > 3H20 j) AG? = -2FE° AcG° = -702 kJ/mol , Z = 6, E°pin = 1,213 V k) Vé thuc nghiém la nhu nhau nhung vé hiéu luc cia pin nhién liéu thi sé cao hon khi tang nhiét 46 Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét — box Héa hoc OlympiaVN- 71Bai 23: a) Cac nguyén ti c6 cling c4u hinh electron I6p ngoai cing nén nang lung ion héa sé gidim khi tng kich thuée nguyén tl b) Superoxit rat dé dug tao thanh (qua trinh téa nhiét) bang cach thém mét e vao phan tir trung hda. Dé tao ion peroxit thi mét electron khac can dua thém vao mét ion am va diéu nay doi hi mét nang lugng lon. Trong ion oxit thi dién tich Am hai phai dugc didu tiét béi mét nguyén ti va thém vao dé lién kat O — O phai bj bé gay c) Két qua dugc dua vao trong ban sau. Tat cd cdc gid tri déu la kJ/mol Nang Iuong can thiét dé tao thanh Nang AH Sn pham | lon kim loai | lon oxy Téng lugng | (phan tng) | | [mang ludi omen s36| 904 [2240-2972 -732 LizO2 1336, 553 1889 -2578 -689 2LiO2 | 1336, -86 | 1250 | -1829 -579 NazO__| 1190 904 | 2094 | -2653 “559 NazO2 4190 553 1743 -2335 -592 2.NaQ2 1190 -86 1104 -1646 -542 K20. | 996 904 | 1900 |_-2309 -409 K202 | 996 553 | 1549 | -2064 “515 2KO2 996 -86 910 -1446 -536 d) LigO, NazO2, KO2 e) Nang long can thiét dé tao thanh anion tir O2 tang theo thir ty Oz > 02% > 07 va nang Ive@ng mang tinh thé gidi phong trong qua trinh tao thanh hop chat ion twong Ung cling t&ng lén (Peroxit c6 dién tich In hon superoxit va oxit c6 kich c bé hon peroxit).. Cation cang bé thi sy khdc biét gidva cac nding lugng mang tinh thé cang lén va cling twng ty cho su khdc biét gira sy tao thanh oxit, superoxit va peroxit. Trong truong hop cla Li thi sy khac biét gitra nang lugng mang lw6i lon dén mtrc ali bu cho nang lugng can thiét dé tao thanh oxit, nhu vay LizO sé la san phdm bén nhat. Déi voi cac cation lon hon thi cc nang lugng mang luéi khac sé bé hon va khéng dui bu triv nang lugng nén cdc anion 6 nhigt tao thanh khéng l6n sé duge wu tién hon, ‘San pham wu tién khi cho Rb va Cs phan ting voi Op sé ld superoxit voi lvong lon hon voi K. Didu nay dung, va ly do thi d& duge néi 6 trén f) Tat nhién la khéng. Nhéng sy tinh todn cia chting ta dé x4c nhan duge rang hop chat bén nhat khi oxy du’. Chung ta nén so sanh phan tng gitva 1 mol O2 voi nhieng long kim loai khac nhau thi oxit luén luén dan dau. Kali peroxit va superoxit dé dang bi kht khi ding du kim loai, Tire l& KO2 + 3K = 2K20 g) Déi v6i cdc kim loai kiém thi viéc tao cation M?* can phai ldy electron tir cdc lop bén trong, diéu nay can 06 mét nang long oye ky lon (trong khoang tir 3000 — 5000 kJ/mol) +h) MO: -3667 kJ/mol; MOz: -3136 kJ/mol. Sw kha biét nay Ion hon so v6i Li nén dé nhan thy rang san phdm wu tién la oxit i) Bari c6 ban kinh cation lén nhat. Theo mé hinh cla chung ta thi peroxit sé ben ving néu sy khac biet vé nang Itong mang lu6i gia oxit va superoxit bé han so voi sy khac biét gitra entanpy hinh thanh O* va 0, (351 ku/mol) 72Olympic Hoa hoc quéc té lan thr 40, Bai tap chuan bi 107000, -107000. 1 #140 1 H173 TW dé ching ta tinh duge r. > 127,7pm, diéu nay phi hop tét voi cdc gia tri thyre nghiém tim dug, ban kinh ion ciia Sr** la 118 pm, con & Ba™ la 135 pm <351 j) Kha nang hit e bé ctia cdc electron lop ngoai cing cia cc kim loai kiém thd. Két qua nay nhin tw mét phia thi do nang lung ion héa bé con & mot phia khadc la cation 6 kich thuOc lon. Nhu chung ta da biét, peroxit va superoxit sé hinh thanh néu cdc déi ion co kich thuée du én Bai 24: a) Ho(k) + Cla(k) = 2HCI (aq) Pb(r) + 2HCl(aq) — He(k) + PbCh(r) PbCla(r) + K2SO4(aq) = PbSO«(r) + 2KCI(aq) b) B6i voi pin thir nhat: AWH? = -334,4 kJ/mol; AS? = -240,8 J.mol".K" ; A,G° = -262,6 kJ/mol Esq = -A,G°/ (n.F) = 1,361 V ed v6i pin tht? hai 25 kJ/mol; A,S° = -127,3 J.mol".K" ; A,G° = -62,9 kJ/mol ey in = -A,G? | (n.F) = 0,326 V Oi voi pin thir ba: 14,4 kJ/mol; A,S° = 105,4 J.mol.K" ; A;G° = -17,0 kJ/mol -A,G° / (n.F) = 0,088 V c) Déi voi pin thir nhat: Anot: He = 2H" + 26 Catot: Cl, + 2r = 2Cr Déi voi pin ther hai: Anot: Pb + 2CI' = PbCl, + 2e Catot: 2H” + 2e = He Déi voi pin thr ba: Anot: Pb + SO,” = PbSO, + 2e Catot: PbClz + 2e = Pb + 2Cr aK= ol: Dé4i voi pin thtr nhat: K = 1,02.10% Voi pin thir hai: K = 1,05.10"" Oi voi pin thir ba: K = 952 ) Néu ching ta cho rang cdc gia tri nhiét dng hoc khéng phy thude nhiét 46 trong mot Khoang gidi han thi biéu thre sau: p= AH AST een nF chi ra rang sy phy thuéc gitia thé khiy pin vao nhigt d6 duigc xac dinh béi entropy ctia phan tng. B4i voi pin ther nhdt gia tri nay la am, nén sudt dién dong gidm khi tang nhiét déng. 86i v6i hai pin dn lai thi size dién dong tang khi tng nhiét do Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét — box Héa hoc OlympiaVN 73.AG AH ‘éi vdi pin thy nhat thi Nmax = 78,5% 6i voi pin thir hai thi max = 252% éi voi pin thir ba thi max = -118% Trong pin thir nhat thi qua trinh téa nhiét manh mac dui c6 sy gidm entropy do khong cé sy tao thanh chat khi . Entropy gidm trong tién trinh phan ting cé nghia la nang Iveng bi tiéu hao bét va hiéu suat sé thdp hon 100% O hai pin con lai thi cé sy tang entropy trong tién trinh phan ng (khi sinh ra hay sé ion hoa tan tang). Kha nang lam viéc cye dai luc nay sé lon hon so voi entanpy phan tng. Sy khac biét nay chdc han do méi truownfg, c6 nghia 4 mdi pin d&u o6 thé lay nhiét tir mai trwéng va chuyén no thanh dién nang O in ther ba thi mot pin tién hanh do phan trng thu nhiét dugc diéu khién do su tang entropy. Nang Iugng Idy tir méi trong do hoat déng cila pin galvani du bi cho entanpy phan ting, nén thong sé hiéu suat & day trd:nén kh6ng ré rang trong trudng hop nay A Mas = Bai 25: a) Thay cc gi tri vao biéu thtrc tich phan dan dén phuong trinh: 1 m2) t= -13h.In(0,13)/In(2) = 38,3 gid b) Khao sat cac gid tri cho & bang thi ta thay van t6c phan tng tang gp déi khi ndng do méi chat tang gap d6i. Nhu vay cac bac riéng phan déu bang don vi te phuong trinh van tdc luc nay cd dang: 1 = k{CoHsCOOCHs][OH] Hang sé van téc c6 thé dugc tinh tir bat ky hang nao trong bang, tirc la k = 0,00109 mol.dm*.s" / (0,05 mol.dm’*.0,3000 mol.dm*) = 0,081 dm*.mol".s. c) Ly ti I6 logarit ca hai phyong trinh Arrhenius cho hé thre re} e(a-a) ‘Sp xép lai va thay gid tri vao cho két qa Eq = 32 kd.mol" d) i. Van téc tang lén 4 lan ii, Van téc tang lén 4° = 16 lan ili, Van t6c gidm xudng 2 = 4 lan iv. Van téc tang Ién 47/2 = 8 lan v.. Van téc khong thay ddi do (1/2)°.4 e) Do bac chung ciia phan tng la 3 nén viée giam ndng dé di mét niva sé dan dén viée ndng dé chat san pham trong phuong trinh dong hoc gidm di mat Iuvong 2° van téc phan tng khéng thay déi thi k ciing phai tang lén mét lvgng: twong @ng E, nig 9k. mol! wr fi. Tw sy hap thy 6 t = 0, « = 0,138 / (0,015 mol.dm®.0,99cm) = 9,29 dm°.mol".cm™ 74Olympic Hoa hoc quéc té lan thr 40, Bai tap chuan bi ii. St dung sy bién ddi tir 0 dén 25s thi 0,138-0,102 0,015moldm” 0,138 = In(0,138/0,102)/25s = 1,2..107 s* iil, ty = In2/k = 57s iv. Thoi gian ban huy phi hop tét voi dé thi, tir né chung ta cé thé thdy dwoc dé hap thu (va néng 46) gidm manh di mot niva déi voi méi chu ky ban hoy v, (99%) = In(1-0,99)/k = 381s t(99,99%) = In(1-0,9999)/k = 762s 25s =1,57.10~ mol.dm>.s"' Bai 26 a) D6 la nguyén tir oxy, béi vi t6c 46 hinh thanh no cham hon nhiéu so voi téc dé loai bo né, digu nay gan nhu' thod man nguyén ly ndng 46 dizng eel =k, [NO,]-k, [O][0,], didu nay d&n an orto} b) Biéu thie vi phan del, [o][0.] bo 0} gan nhu 6 trang thai ding nén bai toan sé dugc don gidn héa thanh mét phuong trinh vi phan bac 0 (néng dé oxy lun la mét hang sé, chi cd mot lvgng rat nhé phan Wng). Ban dau thi khéng c6 ozon, tire la [Os] = 0. Bidu thtrc tich phan c6 dang: [Os] = k2[O][Oz]t c) Thay thé tir biéu thtrc tich phan cla nguyén tir ta sé 06: k,[NO,] (0,]-4 (0, ]t-k, [NO,]t [0.] ‘fol! ]-k,[NO,] Va sy phan hily NO» la mot qué trinh bac 1. [NO2h = [NOzoexp(-kit) = 1,64.10'? phan tir.cm’? Luong oxy nguyén ti hinh thanh & phan. ong dau tién thy té dug hinh thanh tu ozon [Os] = [NOz]o - [NOzh = 8,6.10"" phan td.cm ng dé ozon vao biéu thirc tinh ndng dé oxy o) ti = In2ik; = 99s e) Ching ta da ching minh duge rang néng dé cla ozon la mét ham cilia néng dé NO2 va k;, Do téc d6 phan ting quang phan (nhu k;) thudng it nhay déi voi nhiét d6 so voi cae phan ng nhiét (chang han phan tng luéng phan tt (2)) thi chi quan sat duge nhirng thay ddi nhé trong néng dé cia ozon. f) Dat can bang co nghia la sé khdng co san pham phu hay mat tiéu phan nao: ANOAI-.4, [No,]-&,[NO]fO, k, [NO], [NO}O,] [No] __k, [No,] &[0,] 432 Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét - box Héa hoc OlympiaVN- 75g) TiI6 nay sé gidm do theo phuong trinh Arrhenius ks téing theo nhiét do Tilé ndng 46 can phai duge nhan lén mot dai lugng la 1/1,26 = 0,79. Nhu vay gia tr) moi 1a 0,342 Bai 27: a) Phan tng fe} Jk + Bry ———> + Br +H b) Bra la tac nhan gidi han (chat phan Wng hét) ¢) BO thi dong hoc cua phan dng (dudng cong dong hoc) 600 K 2 3 8 ly = -24.945x + 520.64) R? = 0.9996 5 $ 3 [Br,] (mmol/dm*) NR 8 S28 Ses NI 0 Nt 0 5 10 15 20 25 30 35 7 (min), Dudng cong dong hoc luc nay 14 mét dong thangnén qua trinh nay la qua trinh bac O tia brom d) Do qua trinh la bac 0 déi v6i Bro va tat cA cac chat tac nhan khac déu 6 Ivong du nén gid tri t6c d6 la mét hang s6 trong mdi thi nghiém. No cd thé duge tinh mét cdch don gidn: V = [Broo / tphan enn V6 tphan ing [a thoi gian phan teng. Sy’ phy thudc gira téc 46 phan ting vao tac nh&n phan ting hét o6 thé dug khdo sat tryc tiép tl céng thie. Vé dé thi van téc nhu la mot ham cia néng dé axeton trong méi trudng axit (ndng dé khéng déi 0,100 mol/dm’) cho: 76Olympic Hoa hoc quéc té lan thr 40, Bai tap chuan bi 1.6 14 71 o y = 2.8363x| = 10 R’ = 0.9990 g 4 308 € 06 04 02 a 0.0 0 o4 02 03 04 05 06 [C3H_O] (mol/dm*) D6 thi la mOt dudng thang, phan Wng c6 bac 4 Wng voi axeton. Vé dé thi nhu la mét ham cla néng dé axit véi néng dé axeton git? khéng déi (0,300 molidm?) cho: 4 3 1 > y = 8.7672x % R? = 0.9997| 3 32 E > 1 0 0 o4 02 0.3 04 05 [HCIO,] (mol/dm?) 6 thi la mot dvdng thang, phan wg o6 bac 1 d6i voi [H"] @) V= ka[CsHeO][H"] f) Hang sé téc dO phan tng cé thé duge xdc dinh bang cach chia van téc tinh dugc trong méi thi nghiém voi néng do axeton va axit. Ti gia tri trung binh cila 8 thi nghiém cho trong bang ta 06 két quia k = 2,86.10° dm®.mol.s" (phan ting bac hai nén hang s6 t6c dé cing bac hai) g) Br2 [a téc nhan gidi han (chat phan ng hét) Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét — box Héa hoc OlympiaVN 77h) Budng cong dong hoe: 2.0 $ 154+ < . = . g 2 10 of = . a . © ies 05 TT ; “.] 0.0 0 25 50 75 100 125 150 t(s) Bung nay khéng han la dudng thang nén qua trinh nay khong phai bac 0. Kiém tra voi phan Gng bac 1 thi thay co khd nang bang cach xay dyng mot sy phy thudc vao logarit. Dé thi o6 dang digu nhw sau: “TN 05 = “MN -0.0128x + 0.0039] R’ = 0.9992 -2.0 IT 0 25 50 75 100 125 150 t(s) Cac diém cé thé thang hang voi nhau. Nhu vay qua trinh nay la bac 1 voi brom Met phuong phap khac la xac dinh théi gian ban huy tir nhiing cap gid tri néng do da cho. Tur dé rut ra duoc sy phan huy Bre tuan theo quy luat phan ting bac 1 6 S /) Qa trinh nay la bac 1 déi véi tac nhan gidi han Bro. Ti dé thi chu ky ban huy cia phan ng bac 1 thi m@t hang sé téc 46 phan Wing gid bac 1 (Kets) 06 thé duge tinh nhu sau ons = In2ftya. ‘Sy phy thudc cila kgis vao ndng d6 cdc tac nhan 6 Iwong lén gitip ta xdc dinh dyoc qu luat €éng hoc Ung voi cdc tac nhan con lai. Béi voi sy phy thuge néng d6 axeton khi néng d6 axit khong ddi (0,100 mol/dm*) 78Olympic Hoa hoc quéc té lan thr 40, Bai tap chuan bi 0.035 0.030 at 0.028 y = 0.00983x @ 0.020 R? = 0.99857| t 2 0.015 0.010 0.005 0.000 00 05 10 15 20 25 30 35 [C3H,O] (mmol/dm*) D6 thila dudng thang nén phan Ung Ia bac 1 eng voi axeton. D4i voi su phu thudc [H'] khi néng dé axeton khéng déi (3,0 mmmol/dm®) ta co: 0.03 -+—+ + 3 ge 0.02 ly = -0.0028x + 0.0300 < 0.01 0 0 0.1 02 03 04 [HCIO,] (mol/dm*) Hang sé téc dé phan tng gid bac 1 (kops) thu té khéng phy thuéc vao tinh axit nén phan tng c6 bac 0 véi [H"] DV= klCsHeOIBr] : k) Hang s6 van téc cé thé dug tinh bang cach chia van téc phan tng gid bac 1 tinh dugc voi ndng dé axeton. Tir gid tri trung binh cia 6 thi nghiém cho & bang ta tinh dugc: ky = 9,82 dm®,.mot".s" (phan ting bac hai Ung véi don vj hang s6 van tc bac hai) ) Bude 1 OH 9 Kk [H'] ky (H'] Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét - box Héa hoc OlympiaVN 79O néng a6 brom cao thi ky la bu’ xac dinh van téc, nhu vay ka = ki O néng dé brom thap thi bude 1 la can bang nhanh nén kk, ky = Keke as Bai 29: a) “or oF Sor b) NO, NO» ¢) 2CIO, + Ip + 2H2O = 2CI + 2103 + 4H" d) Phan wng phy xay ra chinh la phan tng di phan ClO2: 6CIO2 + 3H,0 = CI + 5CIO; + 6H" Mat kha nding khdc 6 thé xay ra la mét kidu di phan khac cia ClO, 8CIO2 + 4H,O = 3CI + 5CIO, + BH" Hay sy tao thanh ion iodat trong phan ting khi sau: 14CIO2 + 5lz + 12H20 = 14Cl + 1010, + 24H" ) Sy phan tich dinh tinh cdc ion clorat, perclorat va periodat cé thé duc dung 48 phan biét cdc phan tng phu 1) Khéng, 6 460 nm thi clo dioxit khéng hp thy anh sang; nhu vay mét tia sang 6 460 nm kh6ng thé gay sy quang phan dugc. Anh sang 6 buée séng thép hon cé thé khoi mao phan ting nay g) Phan teng cing cé thé xay ra trong su’ vang mat cia anh sang, nhu vay phan tng co. thé xay ra theo con dong nhiét phan hay quang phan 1h) Crean = 0,3823 / (1,10.10* dm°.mol.cm™.1,000 cm) = 3,48.10°° mol/dm? i) Lugng sat(I!) trong binh dinh mirc 5,000 om* la 1,74.107 mol Luong sat (II) hién dién trong 1,000 cm? mau dung dich nhiéu xa (thé tich toan bé cla mu [a 25,00 cm’), Nhu vay téng Iuong sat (II) tao thanh la 4,35.10° mol i) Higu suat lvong tl cla qua trinh tao sat (II) 1a 1,12. Nw vay trong 30,00 phut chiéu xa thi: 4,35.10° mol / 1,12 = 3,88.10° mol photon gay ra phan tng quang phan ‘Sy hdp thy cia dung dich trong cuvet 1,00cm la 1,41. B phan quang phan c6 quang dung anh séng di qua [a 5,00 cm, nh vay d6 hap thy dugc xem nhu a 7,05. Bigu nay c6 nghia la dung dich hap thu (1 - 10°7°*).100 = 100,00% anh sang (thyrc té coi nhu anh sang da bi hp thy). Cuéng d6 anh séng tl’ né va thoi gian chiéu xa sé la 3,88.10° mol 1800s = 2,16.10° mol/s 80Olympic Hoa hoc quéc té lan thr 40, Bai tap chuan bi Ning long cia mét photon 460 nm Ia hy, vai h la hang sé Planck va tan s6 cla photon c6 thé dug tinh bang cach sir dung biéu thirc van toc anh sang c voi v = c/a. 1= 2,16.10° mol/s.Nash.clh = 5,62.10“J.s = 0,562 mW k) Cudng dé anh sang sau Khi loc c6 thé dug tinh bang biéu thirc 10“"° Dé hap thy anh sdng ctia iot trong thiét bi quang hod sé la 5,1.10 mol/dm® . 740 dm®.mof"'.cny'.5,00 cm = 1,887 Nhu vay (1 — 10°87) = 98,7% anh sang bi hap thu bdi dung dich nay & 460 nm Khéng | Kinhigc 1. [Kinh loc 2 | Kinh loc 3. | Tm thép loc [Loc anh sang 0 | 0,125 O36 | 0,582 © Cudng 46 anh | 2,16.107 | 1,62.10° | 7,04.107 | 5.66.10 0 sng sau khi loc Luong iot hap | 2,13.10° | 1,60.10 1,03.10" | 5,59.10 0 thy vo(mol.dm™.s") | 2,51.10° | 1.97.10 1,40.10" | 9,3.10° 3,7.107 3.0 254 'y = 1.0036E+00x + 3.6836E-01 a R? = 9.9999E-01 1 15 rom Nn 6 Vo (nmolidm*/s) 0.0 05 1.0 1.5 2.0 25 | (nmol/s photon) He s6 géc cla duéng thang nay chinh la higu suat lung tir clia sy mét ClO; (1,00). Hé 86 6 chan dung thang chinh la t6c d6 dau cia phan ting 6 pha tdi Higu sudt long tt déi voi sy mat iot nhan duoc bang cach Iuu y dén hé sé ti long la 1,00/2,30 = 0,43 Bai 29: a) © mét khoang cach Na-Cl cho truéc thi mét e nhay tly Na dén Cl. O' diém nay thi nang lugng tang lén do sy tang lye hut tinh dién va di lye electron cua nguyén tl Cl chinh xdc bang v6i nang lwgng can thiét dé ion hoa nguyén tt Na Voi Ex, = 348 kJ/mol = 5,78.10°J, E; = 496 kJ/mol = 8,24.107% ‘Sp xép lai bidu thirc dé gidi tim R ta thu dugc gia tri R = 939pm Budapest, Hungary, 12-21/7 2008. Ban dich tiéng Viét — box Héa hoc OlympiaVN 81b) Khoaing cach sé Ién hon déi véi nguyén tty Na kich thich lam sy ion héa dé hon. Trong phuong trinh trén thi nang lwgng ion héa can phai thay bang gid tri E, - Eex = 445 kJ/mol. Khoaing cach sé la 1432 pm ) Céng thie tinh khoang céch cia sy nhay electron R’ nhu sau: aks E,-E, Gia tri nay sé t&ng khi gid tri E; — Ea gidm. Tuy nhién né luén ludn durong khi di lye eléectrn cuc dai cla nguyén t6 bé hon so vdi thé ion hdéa bé nhat. Nhu vay tat ca cdc hop chat ion hai nguyén ti (c6 thé tn tai) sé cd mét gia tri R xc dinh ma 6 dé ion phan ly it bén hon nguyén tu phan ly. ) Chung ta cé mét phan tng kht sau: Hu* + Hu = Hue" + Hur i voi tuong tac Coulomb chung ta c6 qi = 2.1,602.10" C, Ea(Hu) = 250 kJ/mol = 4,15.10"° J; IE = IE\(Hu) = 500 kJ/mol = 8,30.10""J. Khong cach phan ting sé la 1110p 82