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K thi Olympic Ha hc Quc t ln th 39

Ha hc: s kt hp gia khoa hc, ngh thut v bt ng

BI TP CHUN B (Phn l thuyt)

15-24/7, 2007 Moscow, Nga

MC LC Problem 1. ON THE BORDERS OF THE PERIODIC SYSTEM .................................................................................................... 3 Problem 2. SCHRDINGER CAT AND CHEMISTRY..................................................................................................................... 4 Problem 3. QUANTUM UNCERTAINTY ............................................................................................................................................ 6 Problem 4. QUANTUM CHEMISTRY OF VISION............................................................................................................................ 7 Problem 5. NANOPARTICLES AND NANOPHASES...................................................................................................................... 8 Problem 6. IN WHICH DIRECTION DOES A CHEMICAL REACTION PROCEED?............................................................... 10 Problem 7. LE CHATELIERS PRINCIPLE ...................................................................................................................................... 11 Problem 8. DMITRY IVANOVICH MENDELEEV: WHAT BESIDES THE PERIODIC TABLE?............................................. 13 Problem 9. KINETICS OF A FREE RADICAL REACTION ........................................................................................................... 14 Problem 10. ASYMMETRIC AUTOCATALYSIS AMPLIFICATION OF CHIRAL ASYMMETRY........................................ 16 Problem 11. RADIOCARBON DATING ............................................................................................................................................ 17 Problem 12. IRON DETERMINATION.............................................................................................................................................. 18 Problem 13. SULFUR DETERMINATION........................................................................................................................................ 21 Problem 14. MAGNESIUM DETERMINATION ............................................................................................................................... 22 Problem 15. INORGANIC PHOSPHATES: FROM SOLUTION TO CRYSTALS...................................................................... 23 Problem 16. FRUITS, VEGETABLES, ATOMS .............................................................................................................................. 26 Problem 17. CHAMELEONIC COBALT............................................................................................................................................ 29 Problem 18. THE FORMOSE REACTION ....................................................................................................................................... 32 Problem 19. THE ANALOGY IN ORGANIC CHEMISTRY............................................................................................................ 35 Problem 20. KETO-ENOL TAUTOMERISM .................................................................................................................................... 37 Problem 21. UNUSUAL PATHWAYS OF FATTY ACID OXIDATION: ALPHA-OXIDATION ................................................. 38 Problem 22. UNUSUAL PATHWAYS OF FATTY ACID OXIDATION: OMEGA- AND (OMEGA-1)-OXIDATION.............. 41 Problem 23. UNUSUAL PATHWAYS OF FATTY ACID OXIDATION: PEROXIDATION........................................................ 43 Problem 24. BIOLOGICALLY ACTIVE PEPTIDES AND THEIR METABOLIC PATHWAYS................................................. 45 Problem 25. RADICAL POLYMERIZATION .................................................................................................................................... 48 Problem 26. IONIC POLYMERIZATION .......................................................................................................................................... 50 Problem 27. CO-POLYMERIZATION ............................................................................................................................................... 53 Problem 28. TUNNELING IN CHEMISTRY ..................................................................................................................................... 56

Olympic Ha hc quc t ln th 39 Bi tp chun b

Bi 1. Bn v th t sp xp cc nguyn t trong bng h thng tun hon

Bng h thng tun hon u tin c nh ha hc Nga D. I. Mendeleev a ra nm 1869 vi cch sp xp cc nguyn t bit vo thi theo th t tng dn khi lng nguyn t. Nm 1871 Mendeleev cng b bi bo "H thng bn cht cc nguyn t v ng dng ca n xc nh tnh cht cc nguyn t cha bit" trn t Tp ch Ha hc Nga. Trong bi bo ny th Mendeleev miu t chi tit v tnh cht ca ba nguyn t vn cha c tm ra v c ng t tn l ekabo (Eb), eka nhm (Ea), v ekasilic (Es). Tt c chng u c tm ra 15 nm sau . 1. Tn hin ti ca c ba nguyn t c Mendeleev tin on l g ? Rt th v l tn ca cc nguyn t ny u c ngun gc a l. Bng H thng thun hon u tin ch gm 66 nguyn t v ba trong s vn cha c bit. Vo thi im hin nay th ngi ta bit c 118 nguyn t. Nguyn t th 118 c tm ra nm 2005 khi hai vin Nghin cu Ht nhn (Nga) v vin Livermore (M) tin hnh bn ph ht nhn 249Cf bng 48Ca th nguyn t th 118 c to thnh vi s khi A = 294 ng thi qu trnh bn ph ny lm gii phng ba ht . 2. Vit v cn bng phn ng ht nhn: i) tng hp nguyn t 118 v ii) S phn r ca nguyn t ny.

Olympic Ha hc quc t ln th 39 Bi tp chun b

3. Nguyn t th 118 thuc nhm no ca bng H thng tun hon ? Vit cu hnh electron ca n (vit phn kh him v cu hnh e lp ngoi cng). 4. Da vo tnh cht ca cc nguyn t cng nhm vi nguyn t th 118 v s dng kh nng suy lun hy d on cc tnh cht sau ca nguyn t th 118: i) nhit nng chy, ii) nhit si, iii) bn knh nguyn t, iv) th ion ha th nht, v) cng tc oxit cao nht ca.

Bi 2. Con mo ca Schrodinger v Ha hc Rt nhiu cc hin tng ha hc c th c gii thch bng cc l thuyt vt l. L thuyt chnh ca ha hc l l thuyt lng t, n l mt nn mng vng chc quan st c s bin i tun hon ca Ha hc. Mt trong s nhng hn tng ca c hc lng t l nguyn l chng cht trng thi c pht biu nh sau: Nu mt h lng t c th c xc nh trng thi 1 v 2 c miu t bi hai hm sng tng ng 1 v 2 th h cng c th c xc nh trng thi hn hp vi hm sng"

= c11 + c22,
vi c1 v c2 c trng cho s ng gp ca trng thi 1 v 2 ban u vo trng thi hn hp." Tng ca cc hm sng khc nhau vi cc h s khc nhau c gi l t hp tuyn tnh cc hm sng. Trong mt h lng t hn tp th h lng t tn ti c hai trng thi ban u mt cch ngu nhin. Khi chng ta ang tin hnh mt php o ca h ang trng thi hn hp th php o ny s phi chuyn h sang trng thi thun khit. Chng ta khng bao gi xc nh c trng thi cui ca h, n ch c th c xc nh bng cc nh lut xc sut. Xc sut ca mt h bt k trng thi cui c xc nh bng bnh phng modul ca cc h s t hp tng ng p1 ~ |c1|2, p2 ~ |c2|2. Tt nhin, xc sut tm thy mt h lng t trn ton khu vc bng n v: p1 + p2 = 1. 4

Olympic Ha hc quc t ln th 39 Bi tp chun b

Nguyn l chng cht trng thi ch c th p dng c cho cc h lng t v khng h c ngha khi p dng vo cc h v m. S dng mt my tnh Geiger c th d c electron i vo. My tnh c kt ni vi mt b phn c kh nng p v mt dng c cha cht c bng thy tinh khi c mt tiu phn i vo my d. Gn dng c thy tinh l mt con mo cn sng. Nu tiu phn i vo my d th con mo s b nhim c. Tuy nhin nu my d khng th xc nh c tn hiu v ang trng thi gia pht hin c v khng pht hin c th trng thi ca con mo l sng hay cht. D hiu hn, con mo c th sng hay cht tu thuc vo vic my d c xc nh c mt h lng t hay khng, iu ny l v l. Trong ha hc th nguyn l chng cht trng thi c s dng trong thuyt lai ha, cng hng v MO. Nguyn l chng cht trng thi i vi thuyt lai ha. 1. Mt AO lai ha sp3 l s t hp tuyn tnh gia mt AO s v 3 AO p

sp3 = c1 s + c2 px + c3 p y + c4 pz .
i) Gi s rng tt c cc AO u ng gp nh nhau vo AO lai ha th gi tr ca cc hng s t c1 c4 s l ? ii) Tng t, hy tm cc gi tr cho cc h s t hp c1 c3 i vi mt AO lai ha sp2. Nguyn l chng cht trng thi i vi thuyt MO. 2. MO i vi ion phn t H2+ trng thi c bn c dng:

1 a 1 b 1s + 1s , 2 2

vi a v b ch nguyn t hydro. Tnh xc sut tm thy electron obitan 1s ca nguyn t Ha ? Nguyn l chng cht trng thi i vi thuyt cng hng 3. Lin kt cng ha tr c mt phn tnh ion. Nh vy hm sng ca mt lin kt gia hydro v halogen c th c biu din bi s t hp tuyn tnh hai hm sng c trng cho trng thi ion (H+Hal) v cng ha tr (H:Hal):

HHal = ccov H:Hal + cion H+Hal


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Olympic Ha hc quc t ln th 39 Bi tp chun b

Trong cun sch ni ting "Bn cht ca lin kt ha hc" (1947) th L.Pauling ch ra rng lin kt trong HCl ch c 17% tnh ion. Tm cc gi tr ca ccht v cion i vi HCl. 4. Mt trong s cc hm sng ca benzen c th c m t bi s t hp tuyn tnh ca cc hm sng tng ng vi hai cng thc Kekule v ba cng thc Dewar:

C6H6

Vy th tng ca cc h s ng gp ca cc cng thc Kekule vo trng thi ca benzen l bao nhiu ? Trong cc phn ng ha hc th cu trc ca phn t thay i lin tc nn trng thi electron ca phn t l hm ca thi gian. Trong mt vi trng hp th cu trc ca phn t c th c biu din bi mt s chng cht trng thi gia trng thi u v cui vi s ph thuc thi gian. By gi chng ta xem xt mt phn t dao ng gia hai trng thi thun khit, mt vi hm sng 1, v trng thi cn li c hm sng 2, vi tn s . Ban u (t = 0) phn t trng thi thun khit th nht v sau mt na chu k (t = /) th trng thi thun khit th hai 5. Xc nh h s ph thuc thi gian ca s chng cht cc trng thi m t cu trc electron ca phn t. Vit biu thc ca hm sng tng qut sau mt phn t chu k.

Bi 3. S bt nh lng t Mt trong s nhng nh lut lng t chnh ni ln mi lin h gia s bt nh v tr x v v ng lng p ca tiu phn lng t. Tch cc bt nh ny khng c php b hn mt gi tr hng nh - mt na ca hng s Planck:

x p

h 2

Olympic Ha hc quc t ln th 39 Bi tp chun b

vi momen ng lng l tch ca khi lng v vn tc: p = mV, hng s Planck c gi tr h = 1.051034 Js. 1. Khng cn tnh ton, hy sp xp cc tiu phn sau theo th t tng dn bt nh v vn tc Vmin: a) mt e trong phn t H2 b) mt nguyn t H trong phn t H2 c) mt proton trong ht nhn cacbon d) mt phn t H2 chuyn ng trong ng nano; e) mt phn t O2 chuyn ng trong mt cn phng rng 5m. 2. i vi nhng tiu phn u tin v cui cng cu 1 hy tnh c th Vmin. Nhng d kin cn thit vui lng tm cc bng tra trn Internet.

Bi 4. Ha lng t ca th gic Bc u tin trong c mt c ch phc tp ca s nhn thy l phn ng ng phn ha cis trans ca cht tr mu retinal nm trong phn t rhodopsin. S hp th nh sng kh kin ca cis-retinal dn n s bin i cu dng ca lin kt i:
CH3 h CH3 CH3 O CH3 O trans-retinal

H3C

CH3

H3C

CH3

CH3 cis-retinal

H3C

1. Ch ra lin kt i no tham gia vo phn ng ng phn ha ny v ch ra i lng xc nh ta phn ng. 2. Nng lng ca cht phn ng v ca sn phm c xc nh nh l mt hm tun hon ca i lng xc nh ta phn ng x:

Olympic Ha hc quc t ln th 39 Bi tp chun b

Ecis ( x) = 1.79 (1 cos( x) ) ,


Etrans ( x) = 1.94 + 0.54 cos( x) .
n v nng lng l eV (1 eV = 1.601019 J = 96500 J/mol), x = 0 ng vi cht u, x = ng vi sn phm. V giin nng lng cho phn ng ny. Xc nh bin thin nng lng ca phn ng v nng lng hot ha n v kJ/mol. 3. Bc sng ln nht m cis retinal c th hp th l bao nhiu? By gi chng ta s p dng m hnh hp th mt chiu cho cc electron hin din trong h thng lin hp ca cis-retinal. Mc nng lng ca mt tiu phn c khi lng m c trong hp th mt chiu vi chiu di l c cho bi biu thc:

En =

h2n2 , n = 1, 2, 8ml 2

4. S electron trong cis-retinal l bao nhiu ? 5. Da vo p n ca cu (3)-(4) v s dng cng thc cho trn hy tnh l. So snh gi tr ny vi cu trc ca phn t retinal ta rt ra c iu g ?

Bi 5. Tiu phn nano v pha nano Ha nano thu ht c kh nhiu s quan tm trong nhng nm gn y v mt lng ln cc nghin cu ang i v hng nm r cc tnh cht ca vt liu nano. ng cacbon nano qun mt vng (SWNTs) c coi nh l mt th d in hnh v vt liu mi. SWNT c th c hnh dung l mt tm graphit qun quanh mt hnh tr kn (d 1.5 nm). Cc phn t cacbon hnh tr s l mt phn quna trng sn xut cc phn t in t trong tng lai. Tnh cht ca cc vt liu kch c nano ph thuc vo kch thc v hnh dng ca n p sut hi bo ha ca mt tiu phn hnh cu nh (dng tinh th hay lng) th cao hn so vi dng kt khi ca cng mt loi vt liu. cn bng th th ng p mol (G)

Olympic Ha hc quc t ln th 39 Bi tp chun b

ca pha ngng t (Gbulk) v pha hi (Gvap) bng nhau. Phng trnh (1) xc nh p sut hi bo ho p trn pha kt khi Gbulk = Gvap = Gvap + RT ln p, (1)

Gvap l th Gibbs tiu chun i vi s bay hi 1 mol cht p sut p = 1 bar. Cc cht bn trong nhng tiu phn hnh cu c sc cng ln c gy ra bi sc cng b mt: Pin = 2 / r r bn knh ca mu hnh cu, sc cng b mt ca "pha hi ngng t". S tng p sut ni l kt qa ca s bin i nng lng Gibbs ca mt cht bn trong tiu phn hnh cu. Nng lng Gibbs G*sph (nng lng Gibbs ca mt cht bn trong tiu phn hnh cu) th ln hn Gbulk. S kh bit nng lng Gibbs ca mt tiu phn hnh cu vi pha kt khi bng mt lng P V : (Pin : bin thin p sut ni) in G*sph = Gbulk + PinV = Gbulk + 2V / r, G*sph = Gbulk + 2V / r = Gvap = Gvap + RT ln p* p* l p sut hi bo ha ca tiu phn hnh cu bn knh r. 1. p sut hi bo ha ca nc T = 298 K l 3.15102 bar. Tnh p sut hi bo ha ca cc git nc hnh cu vi bn knh ln lt l: i) 1 m v ii) 1 nm. Sc cng b mt b mt phn cch lng hi ca nc l 0.072 J/m2. Khi xem xt tnh cht ca mt tiu phn dng kt khi vo thi im p sut hi bo ha ca pha hi v pha kt khi chnh lch nhau khong t hn 1%. Hy xc nh bn knh b nht ca mu hnh cu trong pha kt khi ? C bao nhiu phn t nc trong pha kt khi dng git lng? 2. Mt vi git thu ngn lng c t trong SWNT 400 K. p sut hi bo ha b nht ca thu ngn trong ng l bao nhiu ? p sut hi bo ha ca thu ngn kt khi l 1.38103 bar, khi lng ring ca thu ngn (Hg) = 13.5 g/cm3, sc cng b mt b mt phn cch lng hi ca thu ngn l 0.484 J/m2 nhit cho. (2) (3)

V l th tch mol ca cht lng hoc cht rn. Nh vy t phng trnh (1)

Olympic Ha hc quc t ln th 39 Bi tp chun b

3. Nhit si ca benzen p sut tiu chun l Ts = 353.3 K. Nhit ny ph thuc vo p sut hi bo ha ca benzen gn nhit si c cho bi phng trnh di y:

ln p(T ) =

H vap RT

+ const

(4)

vi Hvap = 30720 J/mol l entanpy bay hi ca benzen. Xc nh nhit si (T*) ca benzen lng p sut chun nu mu tn ti dng git lng vi bn knh r = 50 nm. Sc cng b mt ca benzen gn nhit si l 0.021 J/m2 v khi lng ring l 0.814 g/cm3. 4. Ni chung, tnh cht ca dng kt khi v vt liu kch thc i vi cng mt cht A l hon ton khc nhau. Hng s nhit ng no sau y s gim khi chuyn mt vt liu kt khi sang mt vt liu kch thc nano ? 1) tan ca A trong dung mi bt k 2) Nhit si ca mt cht p sut thng 3) p sut hi bo ha trn b mt pha rn ca cht A; 4) Hng s cn bng ca phn ng vi A l tc nhn; 5) Hng s cn bng ca phn ng vi A l cht sn phm.

Bi 6. Phn ng ha hc xy ra trong iu kin no? Xu hng t nhin ca bt k mt phn ng ha hc xy ra mt nhit v p sut xc nh ph thuc vo du ca bin thin nng lng Gibbs ca phn ng, G. y l mt nguyn l t nhin. Nu G < 0, phn ng xy ra theo chiu thun (chiu u tin to thnh sn phm). Nu G > 0 th phn ng xy ra theo chiu nghch (phn ng khng t xy ra). Trong trng hp G = 0 th phn ng t n trng thi cn bng. Bin thin nng lng Gibbs, G, c th c tnh ton t nng lng Gibbs ca s hnh thnh cht phn ng v sn phm (xem bng di).

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Olympic Ha hc quc t ln th 39 Bi tp chun b

1. Tnh hng s cn bng ca phn ng (1) 1627 C. Phn ng ny c th xy ra theo chiu thun hay khng nu nh p sut ban u ca O2 di 1.00 Torr? 2Ni(l) + O2(g) = 2NiO(s) 2. Th Gibbs tiu chun ca phn ng TiO2(s) + 3C(s) = 2CO(g) + TiC(s) (2) l dng 727 C. Tnh p sut cn bng ca CO 727 C. Phn ng ny nn c tin hnh trong nhng iu kin no nhit cho sao cho phn ng ny l t din bin? 3. Tnh bin thin nng lng Gibbs ca phn ng sau y 3H2 + N2 = 2NH3 (3) 300 K. Trong nhng iu kin di y th phn ng ny c phi l t din bin hay khng: p(NH3) = 1.0 atm, p(H2) = 0.50 atm, p(N2) = 3.0 atm? Trong thc t th phn ng ny khng xy ra 300K vi mt vn tc rt chm. Gii thch ? Bng 1. Nng lng Gibbs hnh thnh*. Cht NiO TiO2 TiC CO NH3 t, C 1627 727 727 727 27 (1)

f G o , kJ/mol
72.1 757.8 162.6 200.2 16.26

*p sut tiu chun 1atm, Bng JANAF.

Bi 7. Nguyn l Le Chatelier Nguyn l Le Charlelier ni rng Bt k mt h no trng thi cn bng khi chu nh hng ca yu t bn ngoi u thay i theo chiu lm gim s tc ng t (P.W. Atkins Physical Chemistry).

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Olympic Ha hc quc t ln th 39 Bi tp chun b

By gi chng ta s xt nh hng ca nguyn l ny. Xt mt h cn bng ha hc c hnh thnh bi phn ng gia cc kh l tng sau: 3H2 + N2 = 2NH3 bar, p(N2) = 0.125 bar, p(NH3) = 0.499 bar. Nhng yu t cho di y s lm cho cn bng b chuyn dch a) Tng p sut ca h nhng gi nguyn nhit b) Tng lng NH3 trong h phn ng trong khi gi nguyn p sut chung v nhit tin hnh phn ng c) a vo h phn ng mt lng nh N2 trong khi gi nguyn p sut chung v nhit tin hnh phn ng d) a vo h phn ng mt lng nh H2 trong khi gi nguyn p sut chung v nhit tin hnh phn ng. 1. Tnh nng lng Gibbs chun cho phn ng (1) T = 400 K. 2. Vit phng trnh tnh nng lng Gibbs cho phn ng (1) p sut bt k ca cht phn ng v sn phm sau khi chuyn dch cn bng. Phng trnh ny c gi l phng trnh ng nhit ca phn ng ha hc 3. S dng phng trnh ng nhit cu 2 hy xc nh xem trong s cc iu kin t (a)-(d) th iu kin no lm cho phn ng (1) t xy ra ? 4. Cu tr li ca cu hi 3 c thay i khng nu nh p sut u ca cc kh l tng l: p(H2) = 0.111 bar, p(N2) = 0.700 bar, p(NH3) = 0.189 bar? Gi thit rng nhit v p sut chung ca h vn c gi nguyn. (1) nhit T = 400 K th cc p sut ring phn ca cc kh o c l: p(H2) = 0.376

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Olympic Ha hc quc t ln th 39 Bi tp chun b

Problem 8. DMITRY IVANOVICH MENDELEEV cn cng trnh nghin cu no khc ngoi bng H thng tun hon Nh Ha hc Nga D. Mendeleev ni ting trn ton th gii nh cng trnh v bng H thng tun hon cc nguyn t ha hc. Ngoi ra th Mendeleev cng cn nhiu cng trnh nghin cu th v khc na. Chng ta s xem xt hai trong s chng 1. Mendeleev l ngi u tin a ra khi nim l mi cht c mt nhit si ti a". nhit cao hn nhit ny th "cht s lun tn ti pha kh bt k p sut cao bao nhiu". Theo Mendeleev th nhit si ti hn ca nc l 543 C. a) Th no l "nhit si ti a" ? b) Hy ch ra nhit si ti hn trn gin pha P-T ca nc. c) Tnh nhit si ti hn ca nc da vo phng trnh trng thi kh thc ca Van der Waals:

a p + 2 (V b) = RT , V
Vi H2O, a = 5.464 l2atmmol2, b = 0.03049 lmol1. 2. Nga th rt nhiu ngi tin rng D. Mendeleev l ngi pht minh ra cng thuc ch to mt thc ung ni ting "Vodka Nga". By gi chng ta s kim chng. Trong lun vn tin s ca mnh, Mendeleev m t vi tnh cht ca h hai cu t ethanol-nc. ng o t khi ca mt dy dung dch hai cu t ny ng vi s khc nhau ca W, vi W(%) l phn trm khi lng ca etanol trong hn hp. Kt qa d / dW c cho Hnh 1 di dng mt hm ca W.

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Olympic Ha hc quc t ln th 39 Bi tp chun b

d/dW
0

10

20

30

40

50

60

70

80

90

100

W% (C2H5OH)

Hnh 1. Kt qa th nghim m Mendeleev nhn c ng cong thu c c h s gc thay i ba ln. Theo D. Mendeleev th ba im c bit ny xut hin do c s hnh thnh nhng hp cht ha hc c lin kt yu c ng gi l "hydrat ca etanol". a) Cho bit cng thc ha hc ca hydrat ca etanol"? b) Liu thnh phn ca mt hydrat bt k c lin quan n cng thc ca vodka (40% th tch ca C2H5OH)? Bit t khi ca etanol l 0.794 gcm3. T rt ra kt lun liu Dmitry Mendeleev c phi l ngi c cng trong vic khm ph ra cng thc pha ch Vodka Nga hay khng ? Bi 9. ng hc ca phn ng gc t do Nhit phn l mt qu trnh cng nghip quan trng chuyn ha than thnh nhin liu lng v cc sn phm khc. Cu trc ca than cc c th c xem nh l mng li ba chiu ca cc hp cht thm a vng ngng t lin kt vi nhau qua cc cu ni l cc gc hydrocacbon mch thng, ngn. Trong nhng nghin cu mi y v nhit phn th cc , - diphenylankan c xem nh i din cho than cc

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Olympic Ha hc quc t ln th 39 Bi tp chun b

S phn hu nhit ca 1,3-diphenylpropan cho toluen v styren l sn phm chnh v cc sn phm ph gm etylbenzen v cc hydrocarbons khc. C ch phn ng phn hu ny c cp di y (giai on u l giai on chm nht):

1. Da vo nguyn l nng dng p dng cho gc t do 2, Hy vit biu thc vn tc i vi phn ng ph to thnh etylbenzen. 2. trng thi dng th t l gia cc gc t do 1 v 3 l bao nhiu ? Thm vo , hai gc t do c th kt hp li. Hng s tc ca phn ng kt hp kR c gi thit hon ton nh nhau i vi cc gc t do

3. Ti sao li chp nhn b qua nhng phn ng kiu nh th ny trong phng trnh trng thi dng cu 1 v 2 4. Mt trong s cc gc t do hin din trong hn hp phn ng c nng cao hn hn so vi cc gc cn li. Gc l

a) Ph CH CH 2CH 2 Ph , bi v n l gc bn vng nht;


. b) PhCH2 bi v hng s vn tc ca phn ng phn ct (4) cao hn so vi

hng s vn tc ca phn ng pht trin mch (3); . c) PhCH2CH2 , bi v n kch thch phn ng.

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Olympic Ha hc quc t ln th 39 Bi tp chun b

5. Tm phng trnh vn tc i vi s hnh thnh toluen. Xc nh bc phn ng. c tnh nng lng hot ha hiu lc da vo nng lng hot ha ca mi giai on trong c ch phn ng.

Bi 10. Phn ng t xc tc bt i xng - S khuch i bt i xng Cc c th sng u l cc hp cht bt i cng cu hnh. Hu ht cc aminoaxit u c cu hnh L, ng c cu hnh D. Mt trong s nhng khm ph ca hin tng ny bt ngun t s c mt ca cc cht t xc tc bt i xng.Trong mt vi phn ng t sn phm bt i c th ng vai tr xc tc cho phn ng to thnh n. Lng mt i quang to thnh cng ln khi phn ng xy ra cng nhanh. 1. Trng hp n gin nht cho phn ng t xc tc l: A + P 2P, vi P l sn phm. Phn ng c th c tin hnh di nhng iu kin khc nhau: c th trong h kn khi cc td nhn ch c trn ln vi nhau duy nht mt ln hay trong h h vi tc nhn A c lin tc thm vo hn hp phn ng cho nng ca n khng i. Vit biu thc ng hc v v ng cong ng hc i vi sn phm P trong h kn v h h. Gi thit rng nng ban u ca P khng bng 0 nhng rt b. Phn ng t xc tc bt i xng u tin c tm ra vo thi k u ca nhng nm 1990. Thm diisopropyl km vo pyrimidin-5-cacbandehit trong toluen dn n s hnh thnh hai i quang X1 v X2, sau khi thu phn chuyn thnh hai ancol i quang Y1 v Y2:
N N O (i-Pr) 2Zn toluene, 0 C
o

1 M HCl X1, X 2 Y 1, Y 2

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Olympic Ha hc quc t ln th 39 Bi tp chun b

2. V cng thc ca cp i quang X v Y, v ch ra cu hnh tuyt i cc trung tm bt i. Ngi ta nhn ra rng vi s c mt ca mt lng nh mt sn phm bt k (Y1 hay Y2) u xc tin cho phn ng dn n vic to thnh n nhiu hn trong hn hp phn ng. Gi thit rng hiu sut to thnh mi sn phm u ph thuc vo bnh phng phn mol ca mi ancol trong hn hp sau phn ng tng hp. 3. Vi 1 mmol hn hp Y1 v Y2, cha 55% Y1, Thm vi ln 1 mmol andehit v 1 mmol ca diisopropyl km. Gi thit hiu sut phn ng l 100%. Tnh xem phi thm tc nhn bao nhiu ln lm giu hn hp ancol ln: a) 70%, b) 90%, c) 99% Y1. Lu : Phi xy dng mt phng trnh hi quy gii bi ton ny

Bi 11. Xc nh nin i da vo ng v Cacbon phng x ng v cacbon-14 l mt ng v ca phng x ca cacbon thng c s dng trong kho c hc, a l v a cht thy vn. Chu k bn hu ca dng l, t1/2 = 5568 nm. ng v
14 14

C l t1/2 = 5730

nm, nhng trong vic tnh ton nin i cc mu c vt th mt gi tr khc c s C c sinh ra t nit trong khng kh di tc dng ca cc tia v tr. Sau n i vo cc c th sng ca thc vt v ng vt thng qua qu trnh quang hp v cc chui thc n. Lng ng v cacbon phng x trong c th sng gn nh l mt hng s vi phn r ca phn hu. 1. Vit phn ng hnh thnh v phn hu ca ng v 14C. 2. Trong mt mu y phc ca ngi Ai Cp c th ngi ta d c s phn r l 480 phn r i vi 1 gam cacbon trong mt gi. Xc nh tui ca mu y phc ny Trong mt thi i khc th ngi ta tm thy mt cht bt mu trng. Cc phng php phn tch cho thy rng cht ny l phenoxymetylenpenixilin (penixilin V) c cu to: 17
14

C l 230 Bq cho 1kg

cacbon. Sau khi sinh vt cht th qu trnh trao i cacbon dng li v 14C vn tip tc b

Olympic Ha hc quc t ln th 39 Bi tp chun b

O H HN O O OH O N S

Hin nay th phenoxymetylpenixilin c sn xut bng cch cy vi khun trong mi trng gm cc cacbohydrat (lactoz, glucoz, saccaroz), dung dch bp ngm (ngm bp vo nc), mt s mui khong v axit phenoxyaxetic. Khi p dng phng php s dng ng v cacbon phng x o tui mu bt ny th bng phng php ph khi ngi ta xc nh c t s khi lng cc ng v
14

C/12C xp x 6.01013.

3. Nh kho c hc quyt nh kho st tui ca mu bt ny bng cc nh lut phng x. Vy mu bt ny c sn xut t lc no ? 4. Gii thch kt qa v hy cho bit thi gian thc m mu bt ny c sn xut ? Cc thng tin lin quan c ly t Lloyd A. Currie. The Remarkable Metrological History of Radiocarbon Dating. // J. Res. Natl. Inst. Stand. Technol. 109, 185-217 (2004)

Bi 12. Xc nh St St l mt trong s nhng nguyn t quan trng nht v rt cn thit cho qu trnh trao i cht ca cc c th sng. S thiu ht st c th gy ra bnh thiu mu, bnh ny 18

Olympic Ha hc quc t ln th 39 Bi tp chun b

thng c cha tr bng cch b sung thm vo c th Fe(II). nh hng ca cc hp cht Fe(III) khng ln lm. Fe(II) l mt cht kh mnh v c kh nng b oxy ha ngay thnh Fe(III). Vn chng ta gp phi y l lm th no tch Fe(II) khi Fe(III) cng nh xc nh tng hm lng st cn thit trong vic kim tra tiu chun cht lng dc phm. By gi chng ta s xem xt cch gii quyt vn ny. 1. Phng php thng dng xc nh tng nng st l chuyn hon ton nh lng Fe(II) thnh Fe(III). S dng bng th kh chun cho di y xc nh xem iu kin tiu chun th cht oxy ha no c th oxy ha Fe(II) ln Fe(III). Vit v cn bng cc phn ng lin quan dng ion.

Dng oxy ha Fe3+ HNO3 H2O2 (+H ) I2 Br2


+

Dng kh Fe2+ NO (+H2O) H2O I

E, V +0.77 +0.96 +1.77 +0.54 +1.09

Br

2. Sau khi oxy ha hon ton lng st thnh Fe(III) th tng lng st c th c xc nh bng cch kt ta st di dng Fe(OH)3 sau nung kt ta ny n khi lng khng i chuyn thnh dng cn Fe2O3 . a) Xc nh pH ca dung dch FeCl3 0.010M. Gi thit rng cation Fe(OH2)63+ l axit mt nc vi hng s phn ly Ka = 6.3.103. b) Tnh pH cn thit bt u xy ra s kt ta Fe(OH)3 t dung dch trn. Bit tch s tan ca Fe(OH)3 l Ksp = 6.3.1038. c) pH no th s kt ta Fe(OH)3 t 100.0 mL dung dch FeCl3 0.010M xy ra hon ton? S kt ta c coi l hon ton khi hm lng st cn li trong dung dch di 0,2mg.

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Olympic Ha hc quc t ln th 39 Bi tp chun b

Lu . Ton b gi tr pH tnh c u phi chnh xc n 0.1 n v pH. B qua lc ion ca dung dch. 3. Fe(II) c th c xc nh trong s c mt ca Fe(III) bng cch nh phn vi dung dch KMnO4 trong mi trng axit. V dung dch KMnO4 c xu hng phn hu chm khi bo qun nn nng chnh xc ca KMnO4 cn c xc nh li ngay trc khi tin hnh nh phn Fe(II). iu ny c thc hin mt cch d dng khi tin hnh nh phn KMnO4 bng cht chun gc (l mt cht tinh khit vi thnh phn c xc nh). Cc dung dch chun c th c chun b bng cch pha mt lng chnh xc cht chun vo nc trong bnh nh mc hoc dng c khc bit chnh xc th tch. i vi s nh phn 10.00 mL dung dchu chun cha 0.2483 g As2O3 trong 100.0 mL nc th tn ht 12.79 mL dung dch KMnO4. Trong khi nh phn 15.00 mL dung dch c hm lng 2.505 g Fe trong 1 lt th cn 11.80 mL dung dch KMnO4 trn. Hi hm lng phn trm Fe(II) trong mu ban u l bao nhiu? 4. i vi mt dung dch cha Fe(II) v Fe(III) th ngi ta thm vo axit tactric. Dung dch ny sau c trung ho bi amoniac v thm KCN cho n d. S ding in cc platin o th ca dung dch ny th thu c th l +0.132 V so vi in cc tiu chun calomel. a) Gi thit rng ton b lng st trong dung dch sau cng u dng Fe(CN)6n . Tnh hm lng phn trm Fe(III) trong mu ban u. Chi bit th kh chun ca cp Fe(CN)63/Fe(CN)64 l +0.364 V. Th kh chun ca in cc calomel l +0.241 V. Nhit ca dung dch l 25 C. b) Phn ng no xy ra khi thm axit tactric v amoniac vo dung dch trn. Vit v cn bng cc phng trnh phn ng lin quan dng ion.

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Olympic Ha hc quc t ln th 39 Bi tp chun b

Bi 13. Xc nh lu hunh Cc hp cht cha lu hunh s oxy ha thp thng xut hin trong nc thi ca rt nhiu ngnh cng nghip (luyn kim, giy, ha cht) v u l nhng cht nguy him. Cc hp cht c s oxy ha thp ca lu hunh trong dung dch l cc ion S2, SO32 v S2O32. Cc tiu phn ny c th c xc nh bng phng php chun oxy ha - kh 1. Ly 20.00 mL mu dung dch cha S2, SO32 v S2O32, thm vo lng d huyn ph ZnCO3 trong nc. Khi phn ng xy ra hon ton th dch lc thu c cho vo bnh nh mc 50.00mL v nh mc cho n vch. Ly 20.00 mL dung dch mi ny ri thm vo mt lng d HCHO. Dung dch hn hp ny c axit ha bng axit axetic ri chun tn ht 5.20 mL dung dch chun iot 0.01000M. a) Vit phng trnh ion cc phn ng xy ra trong qu trnh phn tch. b) Ion no, S2, SO32 hay S2O32, c th c xc nh bng phng php ny ? c) Tnh nng ca ion (ppm) trong dung dch ban u. 2. Ly 20.00 mL dung dch iot 0.01000 M em axit ha bng dung dch axit axetic ri vo 15.00 mL dung dch lc cu trn. nh phn hn hp ny tn ht 6.43 mL dung dch chun natri thiosunfat 0.01000 M. a) Vit phng trnh ion cc phn ng xy ra trong qu trnh phn tch. b) Ion no, S2, SO32 hay S2O32, c th c xc nh bng phng php ny da vo kt qa ca th nghim 1? c) Tnh nng ca ion ny (ppm) trong dung dch ban u. 3. Ly 10.00 mL dung dch iot 0.05000 M em axit ha bng dung dch axit axetic sau thm vo 10.00 mL dung dch mu ban u cha S2, SO32 v S2O32. nh phn hn hp ny tn ht 4.12 mL dung dch chun natri thiosunfat 0.05000 M .

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Olympic Ha hc quc t ln th 39 Bi tp chun b

a) Vit phng trnh ion cc phn ng xy ra trong qu trnh phn tch b) Ion no, S2, SO32 hay S2O32, c th c xc nh bng phng php ny da vo kt qa ca hai th nghim trc? c) Tnh nng ca ion ny (ppm) trong dung dch ban u.

Bi 14. Xc nh magie xc nh hm lng magie trong dung dch th u tin dung dch ny cn phi c axit ha bng HCl, tsau kim ha bng cch thm NH3 v cui cng l thm lng d dung dch (NH4)2HPO4. Kt ta MgNH4PO4 c lc b, ra bng dung dch amoniac bo ha ri nung 1000 C n khi lng khng i ri em cn. Tr li cc cu hi di y, s dng cc gi tr cho cui bi nu cm thy cn thit. 1. Vit v cn bng cc phn ng dng ion xy ra trong qu trnh phn tch. 2. Vit phn ng ho hc xy ra trong qu trnh nung. 3. Khi xc nh lng magie trong thuc calmagin bng phng php trn th t 1.8005g calmagin ta nhn c 0.1532g mu qua nung. Xc nh phn trm hm lng MgO trong kt ta. 4. Trong qu trnh kt ta MgNH4PO4 mt s tp cht khc cng tham gia cng kt nh MgHPO4, Mg(NH4)4(PO4)2, Mg3(PO4)2, Mg(OH)2, (NH4)2HPO4 v NH4Cl. Mt vi cht trong s cc cht ny chu s phn hu nhit khi nung. Vit cc phn ng phn hu nhit ca cc tp cht ny. 5. Ch ra tp cht no trong s cc tp cht cho bng di y c th gy ra sai s khi tin hnh xc nh hm lng magie bng phng php trn. Ghi s 0 vo bng nu khng gy sai s, tng ng l du + nu gy ra sai s dng v du - nu gy sai s m. 22

Olympic Ha hc quc t ln th 39 Bi tp chun b

Tp cht MgHPO4 Mg(NH4)4(PO4)2 Mg3(PO4)2 Mg(OH)2 (NH4)2HPO4 NH4Cl

Sai s

6. Tm gi tr pH cc i c th tch hon ton MgNH4PO4 m trnh c s ng kt ta ca Mg(OH)2? Bit lc u th tch ca dung dch mu l 200 mL v lng magie trong mu l 0.10 g. 7. xc nh tch s tan (Ksp) ca MgNH4PO4 th thm tng git NaOH vo 100mL dung dch u cha 0.010 M MgCl2, NH4Cl v NaH2PO4 cho n khi bt u kt ta. Gi tr pH thi im y l 6.48. Tnh Ksp. B qua s thay i th tch din ra trong qu trnh th nghim. Mt s gi tr tham kho H3PO4 hng s axit Ka1 Ka2 Ka3 NH3 Mg(OH)2 H2 O hng s baz tch s tan Hng s ion ha Kb Ksp Kw 7.1.103 6.2.108 5.0.1013 1.8.105 6.0.1010 1.0.1014

Bi 15. Photphat v c: t dung dch n tinh th Cc axit v c cha photpho, oxy v hu ht cc mui ca nhng axit ny u c hnh thnh t cc t din oxy lin kt vi nhau v tm ca t din l nguyn t photpho. Cc t din ny c th ring bit hoc dng chung nguyn t oxy to cu lin kt POP.

23

Olympic Ha hc quc t ln th 39 Bi tp chun b

1.

a) V cng thc cu to cc anion t din trong cc mui trung tnh ca cc axit sau: H3PO4, H3PO3, H3PO2. b) i vi dy cc axit ni trn hy: 1) So snh tnh axit ca chng (ch xt cc gi tr pKa1), 2) Gc ha tr OPO.

2. Cng thc ca axit metaphotphoric c th c vit dng (HPO3)n. Axit ny cng c cu to t cc t din photpho oxy. Vit cng thc cu to ca hp cht ny v t xc nh s nguyn t photpho ti thiu cn phi c trong axit ny l bao nhiu. 3. a) xc nh in tch ca anion PnOk(2k5n), chng ta s s dng mt thng s th hai Ai ca nguyn t i bng cch ly s oxy ha ca nguyn t ny, Zi, chia cho s phi tr ca n trong anion, CNi,:
Ai = Zi . CN i

Tng ca cc s oxy ha (ZN) ca mt nguyn t N (trng hp ny l nguyn t photpho) v gi tr Ai ca nguyn t lm mi trng phi tr (trong trng hp ny l oxy) i vi nguyn t N dn n vic xc nh in tch Q(N) ca nguyn t N:

Q( N ) = Z N +

Zi . i =1 CN i

Tnh Qm(P) i vi cc t din PO4 c m = 1, 2, 3 v 4 nguyn t oxy chung cho cc t din PO4 khc. b) Tnh tng t cho cc t din TO4 khc khi cc t din ny lin kt vi nhau theo ng thng vi T l 1) T = Si, 2) T = S. 4. By gi chng ta s xt mt t din vi gi tr Qm(P) nh nht v cng l tiu phn bn vng nht i vi phn ng thu phn.

24

Olympic Ha hc quc t ln th 39 Bi tp chun b

a) Gi tr no ca m ph hp vi t din photpho-oxy bn vng nht khng b thu phn ? b) Gi tr no ca m ph hp vi t din TO4 (T = Si, S) bn vng nht khng b thu phn? 5. Cc t din photpho-oxy bit lp (khng c lin kt POP) c th c tm thy trong cc tinh th. Cc photphat hn tp (V) MaPOb c bit n do s pha trn gia hai loi t din PO4- v MO4- vi mi nguyn t oxy u c cng s nguyn t M v P xung quanh n. a) Xc nh gi tr Q(O) ca hp cht trn. b) Cho bit cng thc hp thc ca hp cht ny. 6. Floapatit Ca5(PO4)3F l mt thnh phn trong rng ngi. N c th c tng hp bng cch s dng phng php khuch tn hai ln vi mng gelatin phn tch dung dch cha cc ion F, HPO42 v Ca2+. S tng hp ny dn ti s hnh thnh mt loi vt liu lai tp gia photphat v polymer hu c to thnh chn rng. a) Nu mt l do hai dung dch hp phn ny hai pha khc nhau ca mng gelatin t cho php s kt ta floapatit nh l cht ch trong th nghim khuch tn hai ln. 5 mM Ca(NO3)2 Dung dch 1 Dung dch 2 b) Vit v cn bng phn ng dn n s kt ta floapatit c cp phn trn. c) Tnh p sut thm thu tc dng ln mng thi im bt u tin hnh th nghim (nhit 25 C, hot ca tt c cc ion bng 1). 1 mM NaF 3 mM Na2HPO4

25

Olympic Ha hc quc t ln th 39 Bi tp chun b

Bi 16. T tri cy v rau qu n nguyn t


Khi gii bi tp ny hy nh khng c tri cy hay rau qu no b ph hy!

Nm 1611 nh Ton hc v thin vn hc ngi c Johannes Kepler quan st c cch sp xp cc qu n pho thnh hnh kim t thp. ng xc nh c rng ch c mt cch c th sp xp cht xt nht cc khi cu c th tch nh nhau, cho khng c mt cch sp xp no khc c th xp c nhiu khi cu hn trn cng mt n v th tch. ng l ngi u tin cng thc ha mt vn nh l phng on Kepler. Nm 1998 Gio s Thomas Hales1 cng b mt cch gii cho phng on Kepler v tt c chng u nm trong mt lot bi bo "Tin hc v gii hn hnh hc" bt u t nm 1997. ng xt nhiu hn 150 cc gi tr khc nhau ca cch sp xp khng gian cht xt bn cnh nhng gi thit ca Kepler. Cch gii quyt ca Hales tn 250 trang in v d liu my tnh ca n khong 3 Gb. Nh vy th khi nim sp xp cht xt cc khi cu (c.p.s) c chp nhn mt cch rng ri trong lnh vc ho hc cht rn sau khi c kim chng cht ch bng ton hc v bng cc gi tr d. trong bi ton ny th chng ti khng yu cu cc em t ra cch gii quyt cho vn ny. Tuy nhin chng ti s hng dn cc em cc em c th t bit c nhng nh lut c bn ca vic sp xp cht xt c ng dng trong i sng hng ngy. 1. trnh lm v nhng qa c chua khi vn chuyn th cch tin nht l sp xp chng trn mt k to thnh h n lp ng b. Xt hai cch sp xp (hnh 2). a) Tnh mt cc qa c chua () i vi cch A v B da trn cng thc sau y: = Stomato / (Svoid + Stomato). b) Kiu sp xp no s tn t din tch hn?

Hin lm vic i hc Pittsburgh, PA

26

Olympic Ha hc quc t ln th 39 Bi tp chun b

2R R R

2R

A
Fig. 2. Two possible types of packing tomatoes.

2. Cc loi rau qu cng nh c chua hay bp ci u c th c sp xp trn cc container. Ta s xt cc cch sp xp sau: (1) Lp u tin xp theo cch A (Hnh. 2). Lp th hai c xp y nh lp th nht, tc rau qa lp th hai nm ngay trn lp th nht (kiu sp xp ny c gi l lp phng n gin, k hiu s.c.) (2) Lp u tin xp theo cch A. Lp th hai c xp ngay trn cc khong trng c to ra bi lp th nht (lp phng tm khi, k hiu b.c.c.). (3) Lp th nht xp theo kiu B. Lp th hai xp chng ngay pha trn lp th nht. Kiu sp xp ny c gi l cch sp xp lc phng (K hiu h.p). (4) Lp th nht xp theo kiu B. Lp th hai c sp xp trn cc khong trng c to ra bi lp th nht (kiu sp xp ny c gi l lc phng cht xt, k hiu h.c.p) a) Tnh mt ca cc cch sp xp t (1) (4). b) Cch sp xp no l cht xt nht ? c) C hai cch sp xp lp th ba i vi cch sp xp B: i) Cc rau qu lp th ba nm trc tip trn cc qu cu lp th nht (xp chng cc khong trng sinh ra lp th hai) hay ii) Cc rau qu lp th ba c xp sao cho khng trng vi cc qu cu lp th nht v th hai (nhn cch sp xp B Hnh. 2). Tnh mt cht xt i vi trng hp th hai (gi l cch sp xp lp phng tm din. K hiu f.c.c).
27

Olympic Ha hc quc t ln th 39 Bi tp chun b

d) Mt ngi nng dn mun sp xp lp th ba theo kiu f.c.c nhng by gi khng th hnh dung c rau qu lp th nht nh th no. Do sai lm ny m cc gi tr khc nhau nh th no ? 3. By gi th bc nng dn li quyt nh t nhng qa cu vo toa hng cng vi da hu. Bc ta c nh s sp xp cc qu l vo nhng l hng c to ra khi sp xp cc qa da hu. a) Xc nh t l Rl / Rda hu ti a trnh lm cho cc qa l b v trong nhng trng hp sau: (1) Xp cc qa l vo nhng l lp phng ca mng s.c (2) Xp cc qu l vo nhng l bt din ca mng b.c.c. (3) Xp cc qa l vo nhng l bt din ca mng f.c.c. b) Nu bc nng dn s dng cc cch sp xp c.s, h.c.p, b.c.c, f.c.c th vi mt qu da hu s c bao nhiu qu l xung quanh n ? c) Gi tr cc i i vi c.s, b.c v f.c.c khi cc qa l nm trong l trng l bao nhiu ? 4. Tri cy s b hng do trong thng thiu ch thng gi. a) gi cho cch sp xp cc loi tri cy l b.c.c v f.c.c th bc nng dn s t cc qu l vo l bt din c to bi cc qu da hu m khng nm st nhau theo hng cnh hay mt. Nh vy i vi mt qa da hu th xp c my qa l ? b) Bc nng dn li c mt tng khc: Lp y cc l bt din trong mng f.c.c bng nhng qa l cn l t din bng nhng qu to (mt tng xut sc). Vy i vi mi qa da hu s c my qa to theo cch sp xp ny? Vic sp xp trong t nhin cng tun theo nguyn l phng on Kepler. Opal l mt loi trong t nhin c hnh thnh t cc n v nh l cc phn t SiO2 theo kiu cc qa cu sp xp cht xt (c.p.s). Tnh cht chnh ca Opal l s tn sc nh
28

Olympic Ha hc quc t ln th 39 Bi tp chun b

sng khi b chiu x. Hin tng ny c gii thch b s phn x ca nh sng nhn thy theo nh lut Bragg: = 2d sin vi l bc sng nh sng, d l khong cch gia cc lp trong cu trc c.p.s, 2 l gc to thnh gia tia ti v tia phn x (hay ni mt cch khc, l gc ti). Opal l cht in hnh nht ca tinh th photon, l loi vt liu c cu thnh bng cch sp xp nhng qu cu rt nh nhng loi vt liu ny c kh nng phn x rt cao. Quang ph ca vt liu ny chng minh tnh cht ni bt ca n v d vng photon (nh vng electron trong vng dn ca cht dn in). Tinh th photon c xem nh vt liu cu thnh chnh ca ngnh vt liu quang hc, l cng ngh thng tin ca tng lai. 5. a) Tm gi tr ch s Miller b nht (h k l) ca lp "c php" phn x th nht trong mng f.c.c. b) Tnh bc sng nh sng nu g phn x quan st c l 2 = 60. Bn knh ca cc khi cu siu nh SiO2 l 450 nm. S phn x ca SiO2 (ph thuc vo bc sng) c th c b qua.

Bi 17. S i mu ca mui coban Thng tin lin lc lun c xem l sn phm c gi tr nht bt ngun t nhng hot ng ca con ngi. Vi vic nhn ra cc thng tin th xut hin mt vn cng quan trng khng km l lm th no bo mt thng tin. M ha l mt con ng tin ch tip cn vic bo mt thng tin t vic khng xc nh c thi gian ghi tin. Mt m khng th c nhn ra khi ta vit n bng mt loi mc c bit ch c th nhn ra trong nhng qu trnh c bit. Trong lch s cng c vi cng thc ch to mc vit mt m v hu ht trong s chng u da trn nhng tnh cht ca mui coban (II). Do c mu hng nht nn mc coban s tr nn khng mu khi vit ln giy. Tuy nhin khi un nng th nhng dng ch mu xanh sng s xut hin.

29

Olympic Ha hc quc t ln th 39 Bi tp chun b

Chng ta cng bit c mt s ng dng ca mui coban (II) cng ph thuc vo s bin i mu nh trn. Nhng vin silica-gel c thm vo mui Co(II) c mu xanh sng trong cc thit b lm kh s nhanh chng tr thnh mu hng khi ht nc. a chnh l tn hiu tin hnh hot ha li silica-gel (lm kh li v n hp th qu nhiu nc). n gin hn th mt t giy c tm mui CoCl2 bo ha s chuyn thnh mu xanh trong khng kh kh do c s hnh thnh CoCl24H2O, v li chuyn v mu hng ca CoCl26H2O trong mi trng m t. Nh vy t giy c th ng vai tr nh mt vt ch th trong cc m k (dng c xc nh m) 1. S dng cc gi tr nhit ng cho bng di hy xc nh ngng m (%) m m k c th pht hin c.

Hp cht CoCl26H2O(tt) CoCl24H2O(tt) H2O(l) H2O(k

o o f H 298 , kJ mol1 S298 , J mol1 K1


2113.0 1538.6 285.8 241.8 346.0 211.4 70.1 188.7

S chuyn mu t hng (thnh thong tm) xanh da tri c m t trn c gii thch do c s xy dng li kiu phi tr quanh ion Co2+: t bt din (octahedral) t din (tetrahedral). cu trn th s chuyn cu trc xy ra gia cc cht [Co(H2O)6]oct2+ [Co(H2O)4]tetr2+. Nh mt quy lut, cc hp cht c kiu phi tr t din u t bo ha hn so vi bt din. Tuy nhin by gi ta s th so snh iu ny i vi phc t din v bt din trong cc hp cht Co2+ 2. hiu c l do v tnh cht th chng ta hy so snh cc phc: a) [Cr(H2O)6]3+ v [Cr(H2O)4]3+, b) [Co(H2O)6]2+ v [Co(H2O)4]2+. V gin tch mc nng lng ca ion trung tm theo l thuyt trng tinh th. Ch ra s tch mc nng lng trong cc obitan 3d ca kim loi; ch ra thng s tch mc nng lng cc obitan d: . i vi mi ion trn hy cho bit cu hnh electron c mt phn lp obitan d ca kim loi. Th nng lng bn ha trng tinh th (CSFE) ca mi ion , so snh v rt ra kt lun

30

Olympic Ha hc quc t ln th 39 Bi tp chun b

3. Cho phn ng sau y: [Co(H2O)6]2+ + 4X = [CoX4]2 + 6H2O, (1) vi X = Cl, Br, I, SCN, c s dng trong mt s sch bi tp minh ho cho nguyn l chuyn dch cn bng Le Chatelier. Nu thm vo h mt lng mui cha X, dung dch chuyn sang mu xanh da tri cn nu thm vo lng d nc th dung dch c mu hng nht tr li.

a) Hy xc nh du ca bin thin entanpy ( r H 298 ) v entropy ( r S 298 ) i vi phn ng (1). b) Nhit nh hng nh th no n cn bng (1)? c) Xt phn ng (1) vi ngun cung cp X- l KCl v KSCN. Mui no trong s hai mui trn khi tc ng vi cng mt nng s chuyn dch cn bng (1) mnh hn v pha phi ? Gii thch bng cch s dng nguyn l axit baz cng v mm (HSAB). 4. Xt cn bng (2): [CoX2L4] = [CoX2L2] + 2L. (2)

a) Nu L = pyridin (py), th ligand X no (Cl hay I) lm cn bng dch chuyn mnh hn v pha phi ? Gii thch bng cch s dng nguyn l axit baz cng v mm (HSAB). b) Nu L = PH3, th ligand X no (Cl hay I) lm cn bng dch chuyn mnh hn v pha phi ? Gii thch bng cch s dng HSAB. c) Hp cht phc vi cng thc [CoX2L2], vi L = py, X = Cl tn ti hai dng tm v xanh da tri. Cu trc ca cc phc ny nhn bn ngoi th ging nhau tuy nhin vi cht sau th c khc bit nh. i vi dng mu tm, hy v phng to mt phn cu trc ca n c th nhn ra c hnh dang phi tr quanh ion coban Vi mt s nhng hiu bit nht nh v ha hc cc hp cht phc ca Co(II) c cp trn, cc em c th nm c nhng bin i c m t di y.
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Olympic Ha hc quc t ln th 39 Bi tp chun b

Tng git dung dch NaOH c thm vo dung dch mui Co(II) iu kin lnh (0 C) dn n xut hin kt ta xanh da tri. Nu kt ta ny nhit phng (25 C) trong mt lc th s c mu hng. Nu thm mt lng d kim vo kt ta th kt ta s tan i cho dung dch mu xanh da tri. 5. Hy vit cc phng trnh phn ng biu din chuyn ha trn.

Bi 18. Cc phn ng formo ha (FORMOSE REACTION ) Andehit c kh nng phn ng rt cao v l mt cht khng th thiu c trong tng hp hu c. Nguyn t cacbon trong nhm cacbonyl l trung tm electrophin. Trong phn ng ngng t andol th tc nhn nucleophin enol (hay enolat) tn cng nhm cacboyl electrophin ca phn t andehit (hay xeton) khc. 1. in vo cc trng di trong phn ng andol ha cp, v nh E hay N tng ng vi trung tm electrophin v nucleophin tham gia phn ng.
CH3CHO OH CH3CHO

Cc andehit mt nguyn t hydro- thng c xem l khng tham gia phn ng andol ha nh mt tiu phn nucleophin. Nh vy cc andehit ny u khng th tham gia phn ng ngng t c. 2. Cc andehit no khng th enol ha c ? Ti sao ? Hy cho th d v ba andehit nh vy. Trong dy cc andehit th fomandehit l cht ni ting nht. N c tm ra bi mt trong s nhng v cha ca ha hu c, Alexander M. Butlerov vo u nhng nm 1859. Nghin cu v hp cht ny th Butlerov khm ph ra mt tnh cht rt th v ca dung dch nc foamdehit trong s c mt ca vi to

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Olympic Ha hc quc t ln th 39 Bi tp chun b

thnh xir ngt. Mt nh ha hu c v i khc l Emil Fischer khi nghin cu chi tit hn v phn ng ny vo khong 50 nm sau xc nh rng hn hp ny gm cc raxemic cacbohydrat. Hn hp ny c mang tn formose; Phn ng chuyn ha trn c gi l phn ng formo ha. Phn ng ny l phn ng rt th v do n c th gii thch c s hnh thnh ng trn tri t vo thi k mi hnh thnh. i vi ngnh cng ngh sinh hc th s dng fomandehit l mt cch n gin c th sn xut ra cht ng vi gi thnh h v mt phn na l fomandehit c sn xut vi s lng ln t cacbon v nc. 3. ngh mt phng php c th dng trong cng nghip sn xut fomandehit t cacbon v nc m khng qu ba phn ng. Cch m fomandehit tham gia phn ng ngng t ch c hiu ra bng nhng cng trnh nghin cu ca Fischer. Mt trong s nhng cha kha dng gii quyt vn l khi nim Umpolung2 (chuyn ha lng cc). S quan trng ca qu trnh tng hp ny c th c nhn ra nu ta xem xt qa trnh ngng t benzoin:
PhCHO CN CN Ph O

CN Ph OH

PhCHO

NC Ph

OH

O Ph HCN Ph Ph OH

OH

4. nh du vo v tr ca sn phm (benzoin) cc phn c to thnh t benzandehit v t nhng ch ci E v N cc trung tm nucleophun v electrophin. Trng thi chyun tip ca mt tc nhn nucleophin t cht ban u ng vai tr nh mt tc nhn electrophin (hay vice versa) c gi l nguyn l Umpolung trong ha hu c hin i. trnh vic s dng cht c xianua th c th dng nhng hp cht khc n gin c nhm CH axit trong cc mui thiazolium. Thng l nhng hp cht c nhng tnh cht bt thng khi nghin cu nhng hp cht c cng khung cu to. Mt trong s cc mui thiazolium - dn xut ca vitamin B1 hay thiamin pyrophotphat c c th s dng nh l mt cht ng tr lc cho enzym trans xetolaza xc tc cho cc phn ng c dng nh ngng t benzoin trong c th sng bng cch chuyn gc axyl thnh mt tc nhn nucleophin th tt hn so vi electrophin.
2

T ting c c dch sang ting Anh mt cch khng c chnh xc lm.

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Olympic Ha hc quc t ln th 39 Bi tp chun b


CH3 N CH3 N N
+

NH2 S

O O O P O P O O O

5. nh du vo cc nhm CH- axit trong thiazolium c tc dng nh HCN. V cng thc ca cacbanion tng ng v vit cc cng thc cng hng c th gii thch c tnh axit ca nhm CH-axit. 6. Gii thch ti sao ngi ung ru nhiu thng thiu vitamin B1 ? Mt loi phn ng fomo ha hin i c nghin cu. Formo ha fomandehit trong s c mt ca canxi hydroxit v vitamin B1 (k hiu HZ s pha di) cho xetotrioza n gin nht (dihydroxyaxeton, DHA) vi hiu sut cao.
CH2O Z Z O Z OH CH2O

Z O OH

7. Hon thnh s ny cho n sn phm cui cng Vi tt c cc thng tin c th chng ta c th tin hnh gii m c nhng b n ca phn ng formo ha. Mt thng tin quan trng l phn ng ca dung dch nc fomandehit trong s c mt ca vi l phn ng t xc tc, ngha l phn ng xy ra chm giai on u (giai on cm ng), sau tc phn ng tng dn cho n khi c s thot ra fomandehit. S c mt ca mt cacbohydrat bt k d ch lng vt cng tng tc phn ng v ngay lp tc bt u khng qua giai on cm ng. Qu trnh ny xy ra theo mt chu trnh xc tc gm phn ng ngng t (AC), ng phn ha xeto enol (KET), chuyn proton to thnh enolat (E), ng phn ha enolat hay enol (EI). 8. in vo nhng trng di y hon thnh s mt phn ng formo n gin 9. Ch ra cc giai on cm ng ca phn ng. 10. Ch ra chu trnh xc tc v hy cho bit nhng cht no ng vai tr xc tc

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Olympic Ha hc quc t ln th 39 Bi tp chun b

CH2O

H2O

OH

CH2O

H2O O AC HO KET OH

AC KET

CH2O

CH2O AC EI

OH

Bi 19. S tng t trong Ha hc hu c Nu suy ngh thong hn bng trc gic th nhng s tng t (v cu trc, v electron, v ha lp th) c cc nh ha hc s dng rng ri gii thch nhiu l do. V d cc nh ha hc hu c thng to ra c nhiu tc nhn mi hay cc phn ng mi bng s tng t vi nhng g bit. Mt dng quan trng ca s tng t l s tng t d nguyn t ca cc hp cht hay phn ng m ch khc nhau bi s thay th mt nguyn t hay mt nhm nguyn t bi nguyn t hay nhm khc c cng kiu lin kt so vi nhm b thay th. Nh vy, nhm tng t d nguyn t ca andehit l mui iminium. V d mui Eschenmoser c bit nhiu nht vi cng thc CH2=NMe2+I.

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Olympic Ha hc quc t ln th 39 Bi tp chun b

1. Cation mui Eschenmoser thuc loi tc nhn no? Electrophin t do , axit Lewis , cht oxy ha , nhm bo v

, nucleophin

, gc

2. Vit phn ng gia mui Eschenmoser vi axeton. Gii thch ti sao phn ng ny xy ra khng cn n xc tc ? Xa hn chng ta s xt s tng t ng vi loi phn ng. V d phn ng chuyn v Cope xy ra khi un nng 1, 5 dien. Phn ng ny xy ra cng vi s lun chuyn 6e to thnh hai lin kt v mt lin kt , y l mt loi phn ng chuyn v sigma.

3. Khi thay th mt nguyn t hydro C1 trong 1,5-hexadien bng mt nguyn t deuteri ri tin hnh phn ng Cope trong mi trng tr th sn phm l g (b qua hiu ng ng v) Nu chng ta s dng vinyl allyl ete CH2=CHOCH2CH=CH2 thay th dien th cng xy ra kiu phn ng chuyn v tng t nhng sn phm thu c c cha nhm chc khc l xeton cha no. Nh vy s tng t d nguyn t (oxy-) c gi l chuyn v oxo Cope hay phn ng chuyn v Claisen. Phn ng ny c tm ra bi nh ha hc v i ngi c Ludwig Claisen. 4. Hon chnh phn ng sau
O D t

Phn ng chuyn v ny thu ht c kh nhiu s quan tm v c th to thnh nhm chc mi vi kh nng phn ng cao ch qua mt qu trnh n gin v nhng nhm chc mi sinh ra ny c th tham gia vo cc phn ng tip theo trong cng iu kin hn hp phn ng m khng cn tch ra cht trung gian. Phn ng dy chuyn kiu ny c gi l phn ng domino, nh mt xo thut bin mt cht mch di thnh mch ngn hn ch bng mt tc ng n gin.

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Olympic Ha hc quc t ln th 39 Bi tp chun b

5. Cu hi cho em l hy th hnh dung th no l mt qu trnh domino khi phn ng di y xy ra bng cch cho mt git axit mnh v mt tc nhn loi nc mnh nh HC(OEt)3
CHO HN H+ N H

ngh mt c ch cho phn ng trn

Bi 20. H bin xeto - enol Dung dch nc hay dung dch ancol ca xeton v andehit c th c chun bng dung dch halogen hay lin halogen. c th thu c kt qa tt th s chun phi c din ra nhanh trong s c mt ca mt mui lng tnh nh NaHCO3. T 10 g dung dch xiclohexanonanon trong metanol ta thm vo 2.00 mmol NaHCO3, v 1.00 ml 2.00 N ICl trong metanol. Sau khi khuy trn th mt lng d NaI c thm vo, tip theo l chun thy tn ht 1.594 ml dung dch 1.00 N Na2S2O3 vi ch th h tinh bt. 1. Vit cc phn ng xy ra trong qu trnh phn tch 2. Hp cht no phn ng vi ICl? Xc nh thnh phn cht ny trong xiclohexanon. 3. Vai tr ca mui lng tnh l g ? Nu ta s dng Na2CO3 thay th cho NaHCO3 th chuyn g s xy ra ? Mt cht khng mu A vi cng thc thc nghim C2H2O cho hai tn hiu 34ppm v 159ppm trn ph
13

C NMR. Phn ng ca A vi halogen v lin halogen xy ra ngay

lp tc nhng phn ng chun trn khng hiu qa nu nh thm nhiu hn 1 mol halogen / 1 mol A to ra kt ta. A phn ng ngay lp tc vi andehit trong s c mt ca xc tc axit hay baz sinh ra cc sn phm theo t l hp thc l 1:1, 1:2 hay 1:3 (ph thuc vo t l tc nhn
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Olympic Ha hc quc t ln th 39 Bi tp chun b

phn ng). Cc sn phm thng c mu v thng c s dng phn tch nh lng cc cht c cha nhm andehit. V d, cacbohydrat cho mu khi phn ng vi A v mt git HCl. Trong kim th cht A phn ng vi metyl iodua cho ra hn hp sn phm. Vi mt lng d MeI th ch to ra duy nht B. B d dng b chuyn ha thnh sn phm ging nh sn phm trime ha dimetylxeton trong s c mt ca baz. Mt khc, nu phn ng ca A vi lng d MeI xy ra vi s c mt ca NaHCO3 th mt hp cht khc C c hnh thnh. Hp cht ny c trong thnh phn ca hng hoa hng. Trong ph 1H NMR th hp cht B ch cho duy nht mt tn hiu cng hng, cn C cho hai vch n nhn vi tir l cng tng ng l 1:3. Phn ng gia A vi NaHSO3 khi un nng cho ra dung dch nc khng mu c cng thc nguyn C6H5NaO5S, cho mu tm vi dung dch FeCl3. Ph cho 4 tn hiu 157, 144,106,105 ppm. Phn ng gia A vi hydroxylamin cho hp cht D c cng thc nguyn C2H3NO. Kh hon ton cht ny bng H2 xc tc Ni-Raney cho ra mt hp cht E c cng thc nguyn C2H3N nhanh chng b sm trong khng kh. Hp cht ny rt t tan trong nc nhng tan v hn trong dung dch HCl. un si dung dch ny thu li A. 4. Xc nh cu trc ca A, B, C, D, E. 5. Vit tt c cc phn ng xy ra Bi 21. Mt con ng oxy ha axit bo him gp: oxy ha v tr alpha
13

C NMR trong D2O

Qu trnh oxy ha ph hy cu trc ca axit bo l mt qu trnh sinh hc ph bin xut hin trong tt c cc c th sng. Qu trnh ny l qu trnh oxy ha l qu trnh thoi phn axit bo trong vi khun. N c m t bi s di y:
R O S CoA 1.3.

4.2.

1.1.

2.3.

R O

CoA + O

CoA

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Olympic Ha hc quc t ln th 39 Bi tp chun b

Trong tt c cc bc ca qu trnh oxy ha th gc axyl lin kt vi coenzym A bng lin kt thioeste. Trong qu trnh trn cc nhm v h nhm (subclasses) (s trn mi tn) ca enzym xc tc tng ng theo ng vi cc nhm c phn loi bi IUB. Lu rng trong sut mt qu trnh oxy ha th nhm R khng thay i. 1. Vit cng thc cu to (khng cn quan tm n lp th) ca cc cht trung gian X, Y v Z s dng k hiu R i vi phn gc axyl khng thay i. Axit phytanic A l mt axit bo bo ha c tm thy trong t nhin di dng hn hp hai ng phn dia. N khng tham gia vo phn ng oxy ha do n c mt cu trc k l. Tuy nhin cc loi ng vt c v c th chuyn ha n thnh axit pristanic B vi s thay i cu hnh ca nguyn t cacbon bt i. Qa trnh cui cng (c coi nh l oxy ha ) xy ra trong mt t bo hu c phc tp l, peroxisomes. Phng trnh phn ng di y th hin qu trnh trao i cht ca A:
O NTP NMP+PPi E1 HS-CoA O2 E2 CO2 H S CoA E3 NAD+ NADH + H+ E4

A1 HOOC

A2
HOOC COOH

A3
H2O

COOH

NMP v NTP l cc mono v triphotphat tng ng ca ribonucleotit N (A, C, G hay U), PPi pyrophotphat, CoA-SH coenzym A, NAD+ v NADH tng ng l dng oxy ha v dng kh ca dinucleotit adenin, E1-E4 cc enzym xc tc cho cc phn ng tng ng. Qu trnh sinh tng hp A1 c xc tc bi E1 l mt qu trnh hai giai on. Trng thi trung gian cha photpho v oxy vi t l cc nguyn t trong phn t l 1:8. 2. T cc phn ng lit k di y, chn nhng thng tin tng ng vi cc phn ng c xc tc bi E1 v E3. a) Hnh thnh este ca ribonucleotit photphat v axit cacboxylic b) Chuyn gc axit photphoric thnh mt cht khc do c s ct mt lin kt c nng lng cao ca mt cht khc (phn ng kinaza: kinase reaction), c) Thu phn lin kt este
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Olympic Ha hc quc t ln th 39 Bi tp chun b

d) To thnh thioeste ca axit cacboxylic e) Decacboxyl ha oxy ha. f) Ct t mt lin kt cacbon cacbon. 3. V cng thc cu to ca trng thi chuyn tip sinh ra trong phn ng c xc tc E1 . Xem cng thc ca axit phytanic l RCOOH, vi R l phn gc hydrocacbon. B chu s chuyn ha tip theo ca cc chu trnh chuyn ha oxy ho . Cc d liu ca phn ng oxy ha thoi phn axhit pristanic c cho bng di

Bc Hnh thnh pristanoyl CoA Chu trnh oxy ha th nht Chu trnh oxy ha th hai Chu trnh oxy ha th ba Chu trnh oxy ha th t Chu trnh oxy ha th nm Chu trnh oxy ha th su Chu trnh oxy ha th by

Sn phm ct mch Khng Propionyl CoA Axetyl CoA Propionyl CoA Axetyl CoA Propionyl CoA Axetyl CoA Propionyl CoA + Fomyl CoA (sn phm thoi phn cui cng)

4. Xc nh cng thc thc nghim v cng thc phn t ca axit pristanic A m khng da vo d kin ca s oxy ha v tm ra cng thc cu to ca axit pristanic. 5. Vit cng thc cu to ca A v B vi y cc thng tin lp th. Lu cu hnh ca trung tm bt i gn nhm cacboxyl nht trong cc axit bo lun tn ti cu dng R. 6. Gii thch ti sao axit phytanic khng th tham gia vo qu trnh oxy ha c. Enzym xc tc cho phn ng u tin ca chu trnh oxy ha l c th lp th. Axyl CoA chu s chuyn ha ca enzym ny ch khi cu hnh nguyn t cacbon bt i xa nht so vi nguyn t cacbon- c cu hnh S. Nh vy tn ti mt loi enzym c bit l AMCAR raxemaza (xut hin trong mt vi qu trnh bnh l) c kh nng chuyn ha axit pristanic v mt vi sn phm trong qu trnh oxy ha ca n t cu hnh R sang S trung tm bt i c khong cch xa nht so vi nguyn t cacbon-.

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Olympic Ha hc quc t ln th 39 Bi tp chun b

7. ngh mt c ch cho s raxemic ha pristanoyl CoA. 8. V (ghi r cc thng tin lp th) cc bc trong qu trnh trao i axit pristanic (AMCAR). Trong qu trnh oxy ha ca A trong ng vt c v th ch c mt cp ng phn dia c sinh ra trong qu trnh m E2 lm xc tc. 9. Da vo nhng thng tin v mt lp th hy ngh cu hnh (R hay S) cho cc trung tm bt i ng phn dia A2.

Bi 22. Mt con ng him gp oxy ha axit bo: oxy ha Omega- v (Omega-1) Ch gii bi ny sau khi gii c bi 21

Qu trnh oxy ha l mt trong s cc qu trnh oxy ha axit bo t ph bin, t hn c qu trnh oxy ha . Con ng him gp ny bt u bng qu trnh oxy ha nhm metyl ca mt axit bo to thnh nhm cacboxyl mi. Kt qa l axit dicacboxylic sinh ra b oxy ha tip to thnh mt chui cc chu trnh oxy ha c pht trin dn v pha nhm cacboxyl c sn trong phn t ban u. Tt c cc phn ng trong qu trnh oxy ha ny u khng c tnh c th lp th. Do c nhng im c bit trong cu trc, s tng hp axit bo bo ha D c th c xc tin trong cc loi ng vt c v ch duy nht bng con ng oxy ha (khng c s tham gia ca qu trnh oxy ha - hay -). Sn phm l axit dicacboxylic E chu chuyn ha tip thnh dng axyl CoA tng ng, cht ny s chu 7 chu trnh oxy ha tip theo cho ra by phn t CoA khc. Cng thc ca sn phm chuyn ha trung gian F1 l C27H39N7P3SO195. F1 tn ti dng anion vi gi tr pH khng gy nh hng n sinh l. Qu trnh thu phn n to hai sn phm, mt trong s l F2, khng h cha mt nguyn t cacbon bt i no
omegaoxidation

acyl CoA of E

7 beta-oxidation cycles

F1

H2O

F2 + ...

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Olympic Ha hc quc t ln th 39 Bi tp chun b

1. V cng thc cu to ca cc hp cht D, E, F2 v anion F1 pH 7. Chng minh y l cu tr li ph hp. 2. Gii thch ti sao axit bo D khng th tham gia vo qu trnh oxy ha - hay -. 3. Xy dng cng thc cu to (khng ch n lp th) ca axit tng hp G, l mt ng phn ca cht D, cha cng s nguyn t cacbon mch chnh v cng khng th tham gia vo qu trnh oxy ha - hay - v l do cu trc. Qu trnh oxy ha (-1)- cng l mt qu trnh thoi phn axit bo khc trong cc loi ng vt c v. N ng mt vai tr quan trng trong qu trnh trao i prostaglandin v trong qu trnh gy bnh tt do bin i gen. Mt chu trnh oxy ha (-1)- bao gm nm phn ng oxy ha nhn 2e ca axit bo. Axit bo monocacboxylic H cha 75.97% C, 12.78% H, v 11.25% O v khi lng c rt nhiu trong t nhin. N to thnh hp cht J l sn phm cui cng trong qu trnh oxy ha (-1)-. Hp cht I (72.42% C, 11.50% H, 16.08% O v khi lng) l mt trong s cc cht trung gian trong qu trnh chuyn ha H thnh J. Ph 1H NMR ca cht I cha hai vn n vi chiu cao khc nhay v mt s lng cc vn a. Cng ca cc vn a ny khc so vi vn n. Mt trong s cc vn n c c trng bi cng hp th cao nht trong tt c cc tn hiu ph. 4. V cng thc cu to H v I. Chng minh y l cu tr li ph hp. 5. Xc nh c bao nhiu bc ca qu trnh oxy ha nhn 2e ca cht H to ra cht I nu bit rng con ng ch l mt phn ca con ng (-1)-. 6. Xc nh cng thc cu to J Qu trnh oxy ha - khng th thc hin c i vi nhng bnh l di truyn ca ngi trng thnh (ARD) do enzym xc nh thng tin di truyn b mt trong qu trnh oxy ha ny. Qu trnh oxy ha axit phytanic A (hn hp ca hai ng phn dia trongd ng phn R nhiu hn, xem cu 21) trong cc c th sng nh ca nhng ngi bnh dn n s to thnh axit dicacboxylic C (cng c lng ng phn R nhiu hn).

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Olympic Ha hc quc t ln th 39 Bi tp chun b

7. Xc nh xem cn c bao nhiu bc oxy ha di y nhn c cht C t A trong cc c th bnh nhn b ARD, nu chng ta bit rng malonyl CoA khng c to thnh t chu trnh oxy ha - u tin. Oxy ha Oxy ha ____ _____

Oxy ha (-1)- _____ AMCAR lm mt enzym epimeraza duy nht c s dng trong qu trnh chuyn ha A thnh C (xem cu 21 bit thm thng tin v AMCAR). 8. V cng thc cu to (ghi y thng tin lp th) ca hp cht trung gian trong qu trnh oxy ha A cc c th ngi b ARD, cht ny c th chnh l AMCAR.

Bi 23. Mt con ng him gp khi oxy ha axit bo: qu trnh peroxy ha Qu trnh peroxy ha cht bo c tm thy trong cc mng sinh hc v lipoprotein c xem nh l mt bc quan trng trong s pht trin ca nhiu chng bnh, bao gm c chng tch m lm dy thnh ng mch. Lipit cha cc nhm axit bo khng bo ha (PUFA) l nhng th phm chnh trong ca qu trnh oxy ha loi ny. X l mt trong s nhng sn phm cui cng ca s peroxy ha cc axit bo khng bo ha trong cc ng vt c v. X c th c tng hp bng cch ozon phn PUFA. 1. Vit phn ng chung xy ra khi tin hnh ozon phn axit timnodonic c ho tan trong dimetyul sunfua.
COOH timnodonic acid (without stereochemical information)

X c kh nng phn ng rt cao vi cc phn t c hot tnh sinh hc bao gm c protein. Mt phn l n c tng tc khng enzym vi cc phn t aminoaxit c trong anbumin, mt phn quan trng trong s vn chuyn serum. Kt qa l cc mch nhnh trong phn t aminoaxit c lin kt li vi nhau. Lin kt hnh thnh trong phn ng c m t di y (R1 v R2 l cc phn ca mch polipeptit trong protein).
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Olympic Ha hc quc t ln th 39 Bi tp chun b


R1 H N HN N HN R2

2. Vit cng thc cu to X (vi y cc thng tin lp th) v cc aminoaxit chnh, cc nhnh c lin quan n s ghp mch. 3. ngh c ch ca qu trnh to lin kt nn chng ta bit rng ch c duy nht phn t nc b loi ra trong qu trnh ghp mch. Y l mt sn phm khc trong qu trnh peroxy ha lipit. N c cng s cacbon vi X v tng tc c vi c protein v axit nucleic. Tng tc gia Y vi lysin trong protein dn n kt qa l to thnh mt aminoaxit khng chnh tc N-(3-fomyl-3,4-dehydropiperidino) lysin (FDP-lysin):
N COOH NH2

OHC

4. V cng thc cu to Y, lu rng mt lng ng s mol nc b loi ra trong qu trnh hnh thnh FDP-lysin. 5. ngh mt c ch cho s hnh thnh FDP-lysin. Nu lysin ban u l mt phn ca protein. Lu rng phn ng Michael l mt bc c trong qu trnh ny. Tng tc gia Y vi nucleosit Z trong phn t axit nucleic sinh ra sn phm cng l nucleotit Z1. Ph khi ca Z1 thu c bng phng php bn ph nguyn t nhanh (FAB-MS) gm hai pic chnh ng vi cc mnh c monoproton ha (M+H+) vi gi tr m/z tng ng l 191 v 307. 6. Xc nh cu trc ca Z, nu phn ng vi cht Y ch cho duy nht sn phm Z1. Z1 cha mt baz v mt phn baz ny c cu to nh sau:

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Olympic Ha hc quc t ln th 39 Bi tp chun b

OH N N

7. Xc nh cu trc ca Z1.

Bi 24. Cc peptit c hot tnh sinh hc v chu trnh trao i cht ca chng (Lu : Trong bi ny th tin tnh ton, tt c cc khi lng nguyn t u l s nguyn) H oligopeptit Angiotensins (Ang) c hot tnh sinh hc ht sc quan trng i vi c th ngi. Chng ng mt vai tr quan trng trong qu trnh iu chnh p sut mu, duy tr cn bng mui-nc v iu chnh cc qu trnh suy ngh. Decapeptit angiotensin I (Ang I) l cht u ca h peptit ny, l tin cht cho tt c cc cht cn li. Thu phn hon ton Ang I thu c hn hp gm 9 aminoaxit: axit aspactic; araginin, valine, histidin, isoleuxin, leuxin, prolin, tyrosin v phenylalanin. Asparagin b thu phn cho ra axit aspactic trong iu kin tng t nh khi tin hnh thu phn hon ton peptit. 1. Vit v cn bng phn ng thu phn asparagin trong mi trng axit. Enzym ca mt vi nhm cng c tham gia vo qa trnh chyun ha angiotensin. Nhm u tin bao gm aminopeptidaza (AMA v AMN), ct mch aminoaxit hay peptit thnh cc phn mnh t u N ca oligopeptit. Nhm th hai i din bi enzym cacboxipeptidaza (enzym chuyn i Angiotensin, ACE v cht tng ng ACE2), ct mch aminoaxit thnh cc phn mnh t ui C ca oligopeptit. Nhm th ba bao gm cc peptidaza (enopeptiaza trung tnh (NEP) v prolyl endopeptidaza (PEP)), chng phn ct lin kt peptit c hnh thnh bi cc n v aminoaxit c bit.

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Olympic Ha hc quc t ln th 39 Bi tp chun b

Ang I c chuyn ha thng qua s di:

Nonapeptit X M=1182 Da
3

Ang I M=1295 Da
ACE

Heptapeptit Y
5

Ang II M = 1045 Da

Nonapeptit Z

1-5 l cc peptidaza xc tc cho cc phn ng tng ng. Mi cc peptidaza xc tc cho s thu phn ca ch duy nht mt lin kt peptit. Mt vi peptidaza c th c xc nh bi cc con s khc nhau. gi tn cc angiotensin, mt loi danh php c bit c xut. Cc n v aminoaxit ca Ang I c nh s t N- n C- cui cng. Khi tt c cc angiotensin u cha cc mnh Ang I th t angiotensin xut hin tn ca n v tip theo l ch s rp nm trong ngoc n ch v tr ca N- u v C- cui trong Ang I. V d Ang I c tn theo danh php nh trn l angiotensin (1-10). 2. Vit tn cc gi tr c bn ca cc aminoaxit v cc oligopeptit c th b ct b khi hnh thnh Ang II t Ang I. 3. Xc nh tn cc oligopeptit X, Y v Z theo danh php Angiotensin. Xc nh enzym 1-3 l cc enzym aminopeptidaza hay cacboxipeptidaza. 4. Xc nh thnh phn s lng cc aminoaxit c trong Ang I. Chng minh y l cu tr li ph hp. Qu trnh chuyn ha sinh hc dn xut Ang I c ch ra trn s sau:

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Olympic Ha hc quc t ln th 39 Bi tp chun b

Heptapeptide Y
ACE 6 5

Ang II M =1045 Da
7

NEP

Tetrapeptide X1 M = 512 Da

Pentapeptide Y2 M = 664 Da

Oligopeptide Y1
10

Ang III
11

Nonapeptide Z
AM-N

Pentapeptide Y3 M = 627 Da

PEP

Ang IV M=774 Da

12

Octapeptide Z1

6-12 l cc peptidaza xc tc cho cc phn ng tng ng. Mt hay nhiu peptit c th c nh s khc nhau. Pancreatic proteaza trypsin xc tc cho phn ng thu phn lin kt peptit sinh ra bi nhm cacboxyl ca araginin hay lysine. Z1 c khi lng phn t cao nht trong s cc peptit sinh ra khi enzym trypsin xc tc cho s proton phn Ang I. 5. Xc nh nhng mnh no b ct ra trong qu trnh chuyn ha t Ang II n Ang IV. PEP ch ct chn lc nhng lin kt peptit c sinh ra t nhm cacboxyl ca prolin. 6. Xc nh aminoaxit ui C- Ang II v cu trc ca dipeptit sinh ra khi x l heptapeptit Y vi ACE. Pancreatic proteaza chymotripsin xc tc cho cc phn ng thu phn lin kt peptit sinh ra bi nhm cacboxyl ca aminoaxit thm nh phenylalanin, tyrosin hay tryptophan. Thng th chymotrypsin cng ct nhng lin kt sau leuxin cng tng t nh cc aminoaxit cp trn v tnh a nc. Ch c hai tetrapeptit c to thnh khi Ang II c x l vi chymotrypsin. 7. Xc nh chnh xc th t sp xp cc aminoaxit trong Ang I. 8. Gi tn cc oligopeptit X1, Y1 v Z1 theo danh php Angiotensin.

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Olympic Ha hc quc t ln th 39 Bi tp chun b

Bi 25. Phn ng polyme ha theo c ch gc t do Polyme ha c ch gc l mt trong s nhng phng php hay dng nht trong qu trnh tng hp polyme. N bao gm cc giai on sau: Khi mo Cc tiu phn hot ng thng u tin to gc t do xut hin trong qu trnh tin hnh phn ng ha hc hoc bin i tnh cht vt l ca h (nh un nng, chiu x). Pht trin mch Gc t do cng vo phn t monomer to thnh mt gc t do mi ln hn. Thng th hng s tc ca bc ny c lp vi polyme ha ca mt gc t do ang pht trin (cho rng n bng kh nng phn ng). Tt mch Bc pht trin mch dng li khi hai gc t do kt hp li vi nhau. S t hp v d ly l nhng cch hu hiu tt mch phn ng. Chuyn mch Mt phn t polyme km hot ng c sinh ra do tng tc ca mt gc t do ang ln tng tc vi mt tc nhn chuyn mch. Qu trnh ny i cng vi s chuyn ha cc cht chuyn mch thnh cc gc t do mi. Cht ny c th xc tin phn ng m cng c th lm tt mch. Phn t monomer, dung mi hay cc cht thm vo u c kh nng phn ng nh mt cht chuyn mch. iu ch c poly-(metyl metacrylate) (poly-MMA) th 9,4g monomer c un nng n 60 C trong s c mt ca 0.1 g of ,-azodiisobutyronitrin (AIBN) v 0.5 g clotoluen. Khi lng ring ca hn hp phn ng l 0.91 g/cm3. Hng s tc ca cc bc l: kin = 7.2104 s1 (khi mo), kp = 7.1102 lmol1s1 (pht trin mch), kt = 2.6107 lmol1s1 (tt mch). Hiu sut khi mo l fin = 0.8. Hng s chuyn mch l: CA = 4.2104 (vi -clotoluen) v CM = 1.0105 (i vi monomer) Lu : Hng s chuyn mch c nh ngha l t s ca hng s tc chuyn mch v pht trin mch i vi cng mt tiu phn (C = ktr / kp).

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Olympic Ha hc quc t ln th 39 Bi tp chun b

CH3 H2C O O CH3 N CH3 CH3 N N CH3 CH3 N

MMA

AIBN

1. Trnh by c ch phn ng trn hp ca h cho vi y cc bc: khi mo, pht trin mch, tt mch v pht trin mch. 2. Vit phn ng c kh nng lm gim kh nng khi mo fin. 3. Vit biu thc tc phn ng cho: a) Bc to gc t do b) Tiu th monomer c) Thay i nng gc t do 4. p dng nh lut phng nh trng thi dng hy vit biu thc xc nh nng gc t do thi im cn bng nh l mt hm ca cc thng s ng hc bc c s. 5. Xc nh tc bc tiu th monomer (tc polyme ha) nh l mt hm ca nng cc cht trung gian ca monomer, cht u, v cc thng s ng hc ca bc c s. Tm bc phn ng polymer ha vi monomer v cht khi mo phn ng polyme ha. Polyme nhn c bng cch nh trn c chuyn ha rt thp (ch khong t hn 10% vi nng monomer a vo) v c polymer ha Pn l 125. 6. Xc nh gi tr ca hng s tc ca bc tt mch thng qua qu trnh d ly. Sp xo cc qu trnh sau y theo th t gim dn gi tr Pn . a) Tt mch b) Chuyn mch t monomer c) Chuyn mch t -clotoluen
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Olympic Ha hc quc t ln th 39 Bi tp chun b

Ph 1H NMR ca polymer nhn c nh qu trnh c m t phn trn c cho di y: 7. Xc nh cu trc ca polymer da vo cc thng tin v cng ca cc pic tng ng cho bng sau:. Tn hiu a b c d e f g h Cng vch ph 5.0 1.0 1.0 42 2.0 27 39 4.5

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Olympic Ha hc quc t ln th 39 Bi tp chun b

Bi 26. Phn ng polymer ha theo c ch ion Phn ng polymer ha c th khi mo bng cc tc nhn ion. Ph thuc vo in tch ca nhm ng cui ca mch ang pht trin th c th phn bit c c ch trng hp l cationic, anionic hay c ch gc (khi mo, tt mch v chuyn mch). Phn ng polymer ha theo c ch cationic c khi mo bi cc axit mnh v cc tc nhn electrophin trong khi c ch anionic c khi mo b baz mnh v cc cht nhn electron. 1. Vi cc monomer cho di y hy xc nh hnh thc trng hp m n c th tham gia c (gc, anionic, cationic)
O O O CH3 CH3 H2C

H2C

H2C

CH2 H2C

CH3 H2C O S O CH3 O O CH3

O H2C

CH3 H2C CH3

NO2

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Olympic Ha hc quc t ln th 39 Bi tp chun b

Phn ng trng hp anionic c khi mo bi xc tc c kim v c th c miu t bi cc biu thc ng h, trong bao gm cc bc khi mo, pht trin mch v tt mch. Bc sau cng l cacbanion phn ng vi tc nhn tt mch l mt axit HA.
+

C4H9Li
+

C4H9 Li

C4H9 Li

H 9C 4 H2C R

Li CH
-

H2C R

H 9C 4 n R HA CH R
-

Li

kin

kp kt
H 9C 4 n R

+
R

LiA

2.

a) Vit biu thc tc phn ng tiu th monomer theo nng monomer v mch phn t hot ng tng ng l (cc anion ln) [M] v [M]. b) S polymer ha theo c ch anionic cho php tng hp c cc polymer c cu trc gn nh ng nht. Da trn im ny ta so snh mt cch nh lng hng s tc phn ng khi mo v pht trin mch. c) Tnh khi lng phn t ca mt polymer nhn c khi polymer ha 100 g styren trong 600 ml 1,4-dioxan di s c mt ca 0.234 g naphthalen v 0.042 g kim loi natri. Cho rng ch 58.9% lng monomer b chuyn ha trong qu trnh polymer ha.

Phn ng polymer ha l mt qu trnh y trin vng tin hnh vic xy dng cc mch phn t vi nhiu hnh dng v kch thc khc nhau. Ch c bc ct mch l bt li trong phng php ny do n khng gn thm mt n v monomer mi no. 3. a) Bc ct mch no l c kh nng xy ra vi qu trnh polymer ha bng gc t do v anionic. Hy in vo bng.

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Olympic Ha hc quc t ln th 39 Bi tp chun b

Loi ct mch D ly Kt hp li Chuyn mch n dung mi Chuyn mch n monomer

Polyme ha gc t do Polyme ha anionic

b) Gii thch ti sao mt polymer nhn c bng con ng anionic li c khi lng phn t thp hn so vi phng php gc t do. c) Nhng dung mi no sau y c s dng to ra cc polyme c khi lng phn t trung bnh bng cn ng anionic: (a) benzen; (b) 1,4-dioxan; (c) tetrahydrofuran; (d) 1,2-dimetoxyetan. Sp xp cc dung mi ny theo th t tng dn tc polymer ha. d) So snh tc polymer ha anionic vi kim loi natri, kali v cesi vi cht khi mo s dng trong cc trng hp l naphtalen.

Bi 27. Phn ng ng trng hp


tng hp c cc phn t ln vi cu trc phc tp th c th s dng cch sau: dng cc loi phn ng polymer ha khc nhau, cc cht khi mo khc nhau, dung mi v iu kin phn ng khc nhau, ng trng hp cc monomer khc nhau cng nh b sung cc polymer thu c. Mt s v d v polymer ng trng hp cho bng

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Olympic Ha hc quc t ln th 39 Bi tp chun b

Dng polymer ng trng hp Block: polymer ghp li) Alternating: (Cc n v (hai hon mch

S cu trc

K hiu vit tt poly(A)-blockpoly(B) poly(A-alt-B), poly(AB)

chnh AAAAAAAAAAABBBBBBBBBBBBB

monomer sp xp lun ABABABABABABABAB phin) Statistical (Cc n v monomer sp xp ngu AABABAABBBAABBBABAABABAAB nhin)
AAAAAAAAAAAAAAAAAAAAAAAAAAAA

poly(A-stat-B)

Graft

(Mch

polymer

ny l nhnh ca mch polymer khc) Gradient (Cc monomer

B B B B B B

B B B B B B

B B B B B B

poly(A)-graftpoly(B)

sp xp theo mt quy AAAAABAAABAABBABABBBBABBBB lut nht nh)

poly(A-grad-B)

Khi pht trin k thut ng trng hp th mt iu quan trng l nh c kh nng phn ng tng i ca cc monomer. ng hc ca phn ng ng trng hp c th c miu t bng mt lot cc phn ng c s vi cc hng s tc phn ng tng ng. Trong trng hp ny hai gc t do c th tin hnh 4 phn ng ng trng hp pht trin mch nh di (m hnh n v cui cng end-unit model)

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Olympic Ha hc quc t ln th 39 Bi tp chun b

R1

+ +

k11
M1 R1

k21
M1 R1

R2

R1

k12
M2 R2

R2

k22
M2 R2

Tc phn ng ca cc monomer trong phn ng ng trng hp c c trng b t l cc hng s tc cc phn ng cng to gc t do ln:: r1 =

k11 k , v r2 = 22 . k12 k21

Cc t l nycoi nh l thng tin cho hng s ng trng hp ( Gi tr r lun nm gia 0 v 1). V d phn ng trng hp gia styren v anhydrit maleic c cc hng s ng trng hp tng ng ln lt l 0.04 v 0.01. Thnh thong mt vi hng tip cn tng t c s dng nh hng s ca phn ng ng trng hp hai ion. 1. Hon thnh cc phn ng polyme ha di y v v cng thc cu to ca cc hp cht t X1 X7. Ghi r cc chi tit v cng thc cu to ngn gn ca cc polymer ng trng hp. Trong cc cng thc thu gn th n v styren c k hiu St, etylenoxit l EO, ancol vinylic l VA v anhydrit maleic l MA. S dng cc k hiu vit tt t bng trn nu cn. a)
H2C H2C Na X1 X2 X3 X4 O

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Olympic Ha hc quc t ln th 39 Bi tp chun b

b)
1) a Na (a << n) n 2) H2C X5

OH

c)
H2C
H3 C N H3 C N CH3 N CH3 N

X6

NaOH/H2O T

X7

2. Tnh di trung bnh ca mt n v A trong mt polymer bt k nhn c bng cch ng trng hp ng s mol hn hp hai monomer c hot tnh nh nhau.

Bi 28. Hiu ng ng hm trong Ha hc

ng hm i qua hng ro nng lng l mt hiu tng lng t thun tu. iu ny c gii thch bng hm sng c th khc 0 trong nhng khu vc b cm (l nhng khu vc m nng lng ca tiu phn b hn hng ro nng lng):

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Olympic Ha hc quc t ln th 39 Bi tp chun b

S nghch chuyn ca amoniac l mt minh chng rng ri v hiu ng ng hm:

Trong qu trnh ny th phn t amoniac c bin i thnh dng bung ra nh mt cy d trong gi mnh. Tn s ng hm l 24 GHz, v hng ro nng lng gia hai trng thi ny l 25 kJ/mol. 1. V gin nng lng (biu din s ph thuc ta phn ng vo nng lng) i vi s nghch chuyn ca amoniac. Th no l ta phn ng v ta no ng vi cc i nng lng ? 2. vng no th ph cng hng t electron c th quan st c hiu ng ng hm amoniac ? 3. Tm s khc bit v nng lng ph hp vi tn s ng hm. Tnh t l ca nng lng ny so vi hng ro nng lng? 4. Bng cch no tn s ng hm thay i nu chng ta tin hnh thay th ln lt mt vi nguyn t hydro bng deuteri. Gii thch.

57

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