KY THI CHON HOC SINH GIOI QUOC GIA TRUNG HOC PHO THONG AM HOC 2022 - 2023 Mon: HOA HOC ‘Thoi gian: 180 phiit (khdng ké thai gian giao dé) Negaiy thi: 24/02/2023 Dé thi gdm 05 trang, 06 cau Cho: H= 1,0; N= 14,0; 0 = 16,0; F = 19,0; Na = 23,0; Cl= 35,5; Co = 58,9; Br = 79,9; Ziy= 1; Zee = 26; Zco = 27; 381107 IK; 0,0592; 1 bar = 105 Pa; 0 °C = 273 K. €=3.10'ms'e= 1,6.10 C; F = 96485 C mol; R= 8,314 J K mol; hang s6 Boltzmann ky = is 2,303RT fh = 6,626.10" J s; Na = 6,02.10° mol"; & 298 K: Ki higu: r: rin; |: long; k: khi; he hoi. Cau 1 (3,0 diém) 1, Nang lwong cua electron (£;) trong nguyén tir hydrogen durgc tinh theo céng thite: nsl23l0s (kJ mol") n trong d6, 1 1a s6 Iugng tir chinh (= J, 2, 3, ..). Biét ring sw chuyén dich electron giita céc trang thai cua nguyén tir hydrogen chi duge phép khi chénh léch s6 lurong tir orbital (Al) gitta cae trang thai bling +1 a) Mot nguyén tir hydrogen 6 trang thai ban dau (71 =n.) chuyén vé trang thai n = 1 thi phat ra mt photon cd bude song 102,57 nm, Xée dinh n. va viét céu hinh electron cua nguyén tit hydrogen 6 trang thai ban dau. b) Neuyén tir hydrogen 6 ¥ L1.a cé thé chuyén vé mite nang Itong thap hon khdc. Lap luan va viét cau hinh electron cia nguyén tir hydrogen 6 mite nding lgng thap hon nay. ©) Cae nguyén tir hydrogen 6 trang thai tng v6i » rat lon duge goi la cde nguyén tir kiéu Rydberg. Cho ring, khi mot nguyén tir hydrogen kiéu Rydberg (n= 110) va cham nhigt voi mot nguyén tir khée thi nhan durge mot ning luong ¢=k,7 (J), trong dé ky 1a hang sé Boltzmann, 7 (K) ld nhiét d6. Tinh ton dé chi ra xem nang lugng va cham nhiét 6 0 °C cé du dé ion héa nguyén tir Rydberg nay khong? 2. Lién két hydrogen 1a mét loai twong tac quan trong. Mét két qua tinh toan nang lugng lién két hydrogen ‘utt) kiéu X-H~-OH2 va dign tich cia nguyén tir H (gu) trong lién két X-H (X = C, O, N) trong pha khi (tuong tic CA ORD cing duge xét 1a mgt lién eu) nhu sau: O--OIh | N-H-OFb - trong CHy trong H20--OH2 | trong NHy'--OF | Bua (ki mot") 3.0 20,0 [800 | t gale) 0,066 0,165 [0352 | a) Sir dung ba cap s6 ligu (Eicn, qu) 6 bang trén, xac dinh phurong trinh bac mOt mé ta tét nhat mdi lién hé gira Ex (kJ mol!) vai gu (e). +2, 20). Trong proton b) Lién két hydrogen cé trong cau tric cla cae proton hydrate dang H(H20),, (m= hydrate HsO} c6 hai lién két hydrogen, mdi lién két c6 d6 dai 1,22 A; bon lién két O-H, mdi lién két cd dd dai 0,98 A va khoang cach gitta hai nguyén tur O la 2,44 A. ave cng thite cdu tao cla HO} va quy gan (cé giai thich) cde d6 dai lién két. ii) Giai thich tai sao nang lung lién két hydrogen trong Hs0} (138 kJ mol) cao hon so véi cdc gid tri Ein trong bang trén ¢) Nghién ciru the nghigm xéc dinh duge khoang cach gitta 2 nguyén tir oxygen cdch nhau 2 lign két trong proton hydrate H;O} la 2,43 A va 2,73 A. Vé (co giai thich) cng thite cu tao ca H70} phu hop voi két qua thue nghiém. Trang 1/5CAu 11 (4,0 diém) Cac gia tri nhiét hinh thanh chudn (A ,//$,, ) va nhigt dung Cy (coi la khéng phy thuge nhigt d9) cia cae chat duge cho trong bang sau Chat Ox® | Nox) | He [| HOM) | CHONG) | HCHOM) L A, HS KI molt 0 0 0 241,83 | -201,00 108,60 | C.K" mol! 29,40 29,10 28,84 33,60 44,10 35,40 Goi: Cae khi, hon hop khi xir su nhur khi ly tong; khong khi chi gm Op vi No trong d6 O2 chiem 20% thé tich. Ap suat chun p0= 1 bar. C2 (khOng khi) = 29,16 J K mol". Thiéu nhiét (nhiét chy) chuan eta CHa(k) 14 -890,57 kJ mot! Formaldehyde (HCHO) duge téng hop tir methanol (CH;OH) va oxygen khi 6 mat mot cha theo phurong trinh sau: xite tae chon loc CHOH (&) + 1/202 (k) +» HCHO () + H20 (Hi) a 1. Néu phan img (1) tao ra nude 6 thé léng thay vi nude 6 thé hoi theo phuong trinh: (CH3OH (k) + 1/202 (k) ++ HCHO (k) + H20 (2) (Ib) Khdng tinh ton, chi ra (c6 gi ich) & 298 K cdc gid tr A, H°(Ib) va A,S°(Ib) cha phan img (1b) Am hon hay duwong hon céc gid tri tong tmg cia phan img (1) 2. Xét bai toan sau véi cae gia thiét: ’) trong thiét bj phan tng t téng duge On dinh 6 1 bar; ii) thiét bi phan img va buéng cap nhiét duge thidt ké sao cho eéch nhiét tuyét ddi va c6 hé s6 hap thu nhigt khéng dang ke. ‘Thue 16, ludn c6 phan img (2) xy ra déng thi phan ing (1): (CH3OH (k) > HCHO (k) + Ho (4) (2) ‘a) Cho biét hing s6 can ae K cia phan émg (1) va (2) lan ligt A. Kg9¢(1) = 3,95.10;, Ky99(2) = 3.37.10"! 1f, ,0(1 4) Ten - 1, ching minh ring tn Ky = In Ky, + aT) saci{in EB ‘] dink aT #) Tir biéu thite trong d6 Ky, va Ky lan lugt la hing s6 can bang nhigt d6 T: va nhigt 46 T; A,Hy, la bién thién enthalpy ctia phan img 6 Ti, ACp la bién th nhigt dung ding 4p cia phan img, Bo qua anh hudng cia ap sua ii) Xe dinh hing s6 can bing ctia phan ting (1) va (2) 6 700 K. b) Dan x mol methanol (298 K, x > 1) theo m6t dung dan, va khéng khi (298 K, chita 0,5 mol O2) theo mot dung din khée vao thiét bi phan img chira xi tée & nhigt 46 700 K duoc gidt khong doi, Xéc dinh thinh phan can bang (% mol) cia hén hop khi 6 nhiét d6 700 K. Biét ring hén hgp khi can bang khéng chita O2; nhigt ta ra tir phan img (1) chi diang dé nang nhiét d6 hon hop khi ban dau lén 700 K va dé xay ra phan img (2). ¢) Trong cong nghiép, toin bé ra tir thiét bi phan ting 6 y IL2cb duge Lim ngudi ding ap dén 298 K. Cho rang, toa b@ Itong nhigt 6a ra (Q) tir sy lm ngudi nay duge ding dé lim néng khong khi trong budng cap nhiét lén nhigt 4 Ta, Xéc dinh nhigt d6 T2 néu budng cp nbiét la hinh tru kin c6 ban kinh la 1,3 m, cao 2,0 m chifa sin mot lrgng khong khi & 1,013 bar, 298 K, 3. Khi te nhién duge tim thay 6 thém luc dia trong dé thanh phan chi yéu la methane 6 dang methane hydrate. Trong methane hydrate, phan tir methane bi “nhét” trong mot long clathrate duge tao nén tir cde phan tir nude. Hinh bén 1a mot lng clathrate. Méi dinh cia Jong 1a mt nguyén tir oxygen. Mi canh cia léng duuge tao boi lién két cong héa tri va lign két hydrogen gitta cde nguyén tir oxygen vi hydrogen (O-H~O). a) Xac dinh sé phan tir nude, s6 lién két hydrogen cia cdc canh va sé mat cla mot long clathrate b) Xac dink sé m' methane hydrate can dé cung cp dit lugng nhigt Q 6 y 11.2. ring 1 m’ methane hydrate giai phong hoan toin 164 m* khi methane (6 di chun); sin phim dét chay chi tao ra khi CO2 va nude; higu suat ciia qua trinh chay la 80%. Néu hoe sinh khéng tinh duoc Q 6 ¥ H.2.¢, c6 thé sit dung long nhiét Or = 5,0.10° kJ dé tinh To va ¥ IL3.b Ling clathrate Trang 2/5CAw III (3,0 diem) Mot loai pin nhién ligu sir dung methanol (direct methanol fuel cell - DMFC) ¢6 phan img xay ra trong pin theo phuong trinh héa hoe sau: (CH3OH (J) + 3/202 (k) + CO2 (k) + 2H2O (1) () Cho bide: Thigu nhigt (nhigt chiy) chun cia CHOH() =~726,07 kJ mot va entropy: $,, (CHsOH, |)= 126,80 J K-' mol 8%, (Of) =205,15 JK"! mot !; $8, (COs, ) = 213,78 JK mol! S$, (HzO, 2) = 69,95 JK! mot 1. a) Viét phuong trinh céc ban phan tig xdy ra trén cde dign eye ctia pin. . 1b) Cho biét (c6 giai thich) nhimg sy thay d6i duéi day c6 Lim ting sie dign dong ly thuyét ctia pin nhién ligu trén hay khong? i) Chat xiic tc duge sir dung trén cae dign cue. ii) San phm 1a nude & thé hoi thay cho thé long. 2. a) Xac dinh cong cut dai c6 thé thu duge tir pin DMEC 6 diéu kign chudn cho sy tao thanh 2,0 mol H20 (!) 625°C. Tirdé, xac dinh site dign dng cue dai ly thuyét ma pin nay c6 thé dat duge trong cing mot diéu kién xd dinh cng cue dai. b) Tinh nhigt kém theo phan img (1) khi pin lam vige. ©) Tir méi quan hé gitta bién thién nang Iugng tyr do Gibbs ciia phan img véi site dign dng cua pin, rat ra phuong trinh biéu dien sy phy thude cua sire dign dng chuan (E*) vao nbigt 4. Dya vio phuong trinh thu duge, chi ra v6i digu kign nao thi E° sé it phy thude vao nhigt d6 nbat? d) Si dung phuong trinh thu duge 6 y HIIL.2.c, xac dinh sire dién d6ng chuan cua pin 6 80°C, Bo qua anh hung ctta nhiét d6 dén cae gid tri ca AH va 4,5" 4d) Higu sudt cia pin nhién ligu duge tinh tir ti s6 gitta bién thidh céng dign va bién thién enthalpy cua phan ting. Xac dinh higu st 3. Phuong sin thye hanh Mot hoc sinh muén xac dinh hang s6 bén ca phite chit [Cu(NHs)«J°* bing phuong phap dign hoa trong phong thi nghiém. Dé dat duge muc dich 46, c&n thigt Lap mot pin dign hoa tir hai dign cue: Cu | Cu", Cr va Zn | Zn", Cs trong 6 C; va C2 lin lot 1a ndng a6 mol cita dung dich CuSO, va dung dich ZnSO,, Sau 46, tién hanh do site dién déng cia pin. Mét sé thao tac thye hanh chinh nhu sau: Buéc I: Ding gidy rip (gidy nhim) kim sach bé m3t cia hai I ddng va kém. Lay chinh xée cing mot thé tich ¥; dung dich CuSOy va dung dich Zn$Os, Lin lugt cho vao c6e dung li déng (Coe 1) va e6e dung la kém (Cée [). Ding dita thity tinh khuay nhe dung dich. Buse 2: Thiet lap pin va ding day dan néi céc dign eye cita pin véi von ké c6 dign tro rat lon. Bude 3: Bat von ké va doc gid tri site dién dGng cua pin (E)) tren von ké. Bude 4: Lay chinh xe mét thé tich V2 dung dich NH c6 néng d@ Cs (mol L“) cho vao Coc I. Ding dita thay ing lwong cue dai cia qué trinh dusi dang cla pin 6 diéu kign chuan. tinh khuay nhe dung dich. . Ven ké Bude 5: Doc gid tri site dign dng cla pin (£2) trén von ke. a) Tra li cde edu hoi sau day: Pi Pa. (_ ) Tai sao can kim sach bé mat la ding va la kém (bude 1) true: 4 1 hi cho tigp xite voi dung dich CuSOy va dung dich ZnSO? | C4 >, ean ii) Cée thé tich V7; va V2 néu khOng lay chinh xic s@ true tiép 5 i gily ra sai s6 cua dai luong nao trong qué trinh tinh todn hing pk 86 bén cia phite chat? ; . ) Dé lip hé do site dign dng cita pin (bude 2) can ding mot Chet Chel Dydd OAy xanh fay dan boc nhua day din boc nhya mau xanh, mot d i) Chi ra (cé gid thich) vi ti can noi if) Dung cu Y la gi va vai trd cia n6? Cho biét: E210, = 034 Vi ‘do ndi voi von ké (nhu hinh trén) va mét dung cu Y. dan mau xanh va mau dé v6i cde diém P1, P2 trong hinh trén. con lai cia d 0,76 V. Cau TV (3,0 diém) Phan tmg thé phdi tir trong phite chat [ML4]* bing tac nhan X trong mi trudng acid. yéu xay ra theo phuong. trinh phan img: 2X + [MLs]> — [ML2X2] + 2L (a) Ki higu [ML] la Phd va [ML2Xa] la Ph2. Trang 3/5Quy luat dong hoe cla phin img duge viet nhu sau: thd’ gian(phan,x AC} ChiC& , trong d6 ni, n2, n3 Tan hrgt la bac riéng phan cita phan img theo H’, Ph] va X. Dé nghién ctru dng hoc ctia phan tng trén, ngui ta thue hign cc thi nghiém J, 2 vi 3. Céc thi nghiém nay chi khac nhau & néng dé dau cia cae chat va pH, con cdc khae duge gidt én dinh nhur nhau. 1. Thi nghigm 1 vi 2 duge én hinh dong thoi 6 pH én eng phin cia phan img doi vi Ph va X dra a A Yn OSt61x-§ ét qua the nghiém duge biéu dién trong do thj 6 hinh bén. 2. Trong thi nghiém 3, néng 46 cia cae chat trong hon hop phan ing duge xée dinh bang phuong phip do 46 hap thy quang. Co la néng 6 Ph/ tai thoi diém t = 0, O mot bude séng xe dink: goi 1, ¢2 va es lan lugt 1a he sé hap thy mol ciia X, Phd va Ph2; Ao, Ac va Aw lain Iugt la d6 hdp thu quang cia dung dich tai thai diém ¢= 0, thoi diém / va thoi diém phan tg két thie, t. BO hdp thu quang cla dung dich tudn theo biéu thite: A=YeilC,, "2241-59614 trong dé / 1a hang sé. a) Thiét lap biéu thite tinh hing s6 téc 46 phan img theo As, As, Av, Co va fnéu X va Ph/ durge lay theo ding hé s6 ti long trong phuong trinh h6a hgc, bac ctia phan img khong thay d6i so véi thi nghigm 69 IV.1 b) Trong dieu kign: Co(PA/) = 5,0 mmol L™; Co(X) 10,0 mmol L~', pH én dinh bang 53; 6 hap thy quang cia dung dich hin hop phan tng theo thoi gian nhw sau: 1, phit o [25 | 50 | 10 | 15 | 20 | « 6 hap thu quang [0,632 | 0,600 | 0,571 | 0,522 | 0,481 | 0,451 [ 0,120 Viét phurong trinh lug tée d6 dy dui cho phan img (1) va xée dinh hang s6 tbe d6 cia phan ting, 3. Mot ca ché eta phn ng (1) due d& xt nh sau: [ML,P + X —— [ML,X]* nhanh (bude 1) [ML,xP> > [ML,xP + LD (bude 2) [ML,X} + X —S5 [ML,x,>° (bude 3) ([ML,X,]" “Ks [ML,X,] + Lo (buée 4) Bién ludn va chi ra trong céc bude 2, 3 va 4, bude nao quyét dinh téc 46 phan ting va gid thich duge quy Int Ong hoc thyc ngh ‘Cfiu V (3,0 diém) 1. Khi cho Al (la chat khi 6 diéu kign thuong) phan img véi khi hydrogen trong diéu kién thich hgp thu duge khi A2. Tir A2, qua mét sé giai doan chuyén héa, thu duge acid A3. Khi cho A2 tac dung véi A3 thu duge muoi A4. Phan tng gitta A2 & dang long vai sodium (Na) theo ti Ié 1 : 1 tao ra sn phim AS. Khi nhigt phan ‘Ad 6 150°C thu duge kh A6. Cho AS tée dung v5i A6 187°C thu duge mudi A7 (66 phan trim khéi hugng nitrogen 14 64,62%) va A2. Khi cho A2 dur tac dung véi khi fluorine 6 mat xtc tc thu duge khi khong mau AB chita 19,72% nitrogen vé Khoi lugng. Dun nong A8 v6i dong 6 398 °C thu duge A9 chi chita hai nguyén 10 voi ti 1G nguyén tir gidta chiing 1a 1 ; 2. Phan img gira A9 voi AICIs 6-70 °C tao ra A10 (c6 cdu tric trans va momen lung cue bing 0) va AL a) Xac dinh cong thite héa hoe cita cae chat tir AI dén A10, biét ching déu chisa nguyén td nitrogen. b) Viet cac phuong trinh héa hoe tgo ra A7 dén A10 durge mo ta 6 trén, 2. D6 bOi M ciia mot nguyén tir hoc ion duge tinh theo céng thite M = sé electron déc than + J. Trong phite cht, sur chuyén electron tir orbital d e6 mite ning hueng thip dén orbital 6 mie nang long cao cia nguyén tir trung tm trong truéng tinh thé li khong duge phép vé mat spin néu lam thay di d6 bGi M cita no a) Phite chat [Fe(CN)s(NHs)}* nghich ti 6 ap suat thép, nhung lai thudin tir 6 Ap suat cao. Trang 4/5i) Vé gian dé tach mire nang long obital d va viét cau hinh electron cia nguyén tir trung tam trong truong tinh thé cua phite chat (Fe(CN)s(NHs)]* 6 ap suat thap va 6 ap suat cao. ii) Cho biét (c6 gidi thich) sy chuyén clectron gitta cdc mite nang lrgng orbital d cita nguyén tt trung tam trong phite chat [Fe(CN)s(NHs)]* ki duge phép hay khéng duge phép vé mat spin 6 ap suit thap va 6 ap suat cao? b) Phite chat [Co(NHs)e]** la phite chat spin cao. Dua vao thuyét trudng tinh thé, hay cho biét sy chuyén clectron gitta cae mite nang Iugng orbital d ctia nguyén tir trung tm trong phite chat [Co(NHs)]** la duge phép hay khéng duge phép vé mat spin. 3. Phite chat PI c6 cong thite phan tir Co2(COs)3(NHs)e. Khi cho P1 téc dung véi acid HNOs trong dié thich hop tao ra khi COs va hai phite chat P2, P3. Hai phite chat nay déu c6 ion céu ndi dang bat dién cau ngoai chi chia ion nitrate. Biét: PI chita cdu ndi cua phite chat P3; P3 chita 16,98% Co vé khdi lung. Xée dinh cng thite héa hoc eta cae phite chat P1, P2, P3 va déng phan phoi tri ctia PL. CAu VI (4,0 diém) 1. o-Phthalic acid (M = 166,132 g mol) li mét acid 2 nac, ki higu li HoA, ¢6 pKi = 2,95 va pKa = 5,41. Hoa tan hoain toan 0,8307 g H2A thinh 100,0 mL dung dich X. a) Tinh pH ciia dung dich X. ) Xac dinh bidu thie tinh va danh gid % déng gép ca cée can bang dén néng dé cn bing cia H” trong dung dich X. Coi sur ding gop la khdng dang ké néu % dong gop 1a nho hon 1%, 2. Dung dich Y Ia dung dich ciia L-leucine (ki higu L-leucine la HB) co néng 46 trong khong tir 0,01 M dén 0,02 M. Mot thi nghiém durge thye hign theo cdc bude nhur sau: 10,00 mL dung dich ¥ tron v6i 10,00 mL dung dich HCI 0,025 M Buée 2: Thém 1 giot chi thi methyl 46 va 1 giot chi thi phenolphthalein, Bude 3: Thém dan dén hét 15,00 mL dung dich NaOH 0,035 M. a) Dua vao khoang chuyén mau cua chi thj hay cho mau cia hén hop methyl dé va phenolphthalein sé thay di theo céc khoang pH nhu thé nao? b) Giai thich su thay di mau ctia dung dich trong bude 3 bing tinh toan. ©) G buée 3, khi thém dén 10,90 mL dung dich NaOH thi 80% chi thi phenolphthalein tn tai 6 dang base, tinh ndng dé L-leucine trong dung dich Y. Cho biét: © 298 K, dang proton héa cia L-leucine (H2B") c6 pKai = 2,33, pKa = 9,60; Kw= 10"; methyl do 6 pK, = 4,95, dang acid mau do, dang base mau vang, khoang d6i mau tir 4,4 — 6,2; phenolphthalein c6 pK, =9,4, dang acid khong mau, dang base mau dé, khoang chuyén mau tir 8,0 — 10,0; coi thé tich vi néng 46 cia chi thi khéng anh hudng dén pH cia hé. 3. Phuong an thye hanh Dung dich NaOH thutdmg durge ding lam dung dich chuan trong phuong phap chuan d@ acid-base va durge pha tir hoa chat rin NaOH, Mot quy trinh chuan bi dung dich NaOH duge thy hign nhu sau: can 0,4 g NaOH rin va pha vao muéc cat thinh 1 L dung dich NaOH. Dé dung dich vita pha trong binh kin. Nong 46 cua dung di NaOH vita pha duge xie dinh bing phép chun 46 v6i dung dich potassium hydrogen o-phthalate da biét nong 44 chinh xic sir dung chi thi la dung dich phenolphthalein, ‘a) Gidi thich tai sao edn dé dung dich NaOH vita pha trong binh kin. b) Dung cu sir dung cho chuan d6 gm: binh tam gide-250 mL, buret-25 mL, c6c-50 mL, pipet-10 mL va cae dung cu cn thiét khac. 1) Cho biét nhing dung cu nao duge diing dé do thé tich chinh xdc? ii) Cho biét buret dung dung dich gi trong phép chuan d6 @ trén? ©) Trong mot phép chuan 46, tai thoi diém dung dich trong binh tam gic di mau, thé tich doe duge trén buret 1 7,54 mL va c6é m6t gigt dung dich cdn treo 6 dau dudi ciia buret. Mét hoc sinh cho rang can lay giot dung, dich nay vao binh tam giée. Mot hgc sinh khac lai cho ring nén bo gigt dung dich nay. #) So snh anh huong eiia hai cach lam nay dén néng d} NaOH duge tinh tir két qua phép chudn 46 tren, ii) Tin sai s6 twong d6i ding gop cua gigt dung dich dén két qua doc thé tich trén buret, biét | giot dung dich 66 thé tich 14 0,05 mL. - HET © Thi sinh KHONG duege ste dung tai lieu; © Gidm thi KHONG gidi thich gi thém. Trang 5/5KY THI CHON HQC SINH GIOI QUOC GIA TRUNG HOC PHO THONG NAM HOC 2022 - 2023 Mén: HOA HOC ‘Thoi gian: 180 phiit (khdng ké thoi gian giao dé) Ngiy thi: 25/02/2023 Dé thi gdm 04 trang, 06 cau Cie chit va ki higu viét tit: Ac: acetyl; AIBN: azoisobutyronitrile; Bn: benzyl; n-Bu: n-butyl; DIPEA: N,N-diisopropylethylamine; DMAP: 4-dimethylaminopyridine; DMF: N,-dimethylformamide; DMSO: dimethylsunfoxide; Et: ethyl; Me: methyl; NBS: N-bromosuccinimide; Ph: phenyl; ‘Pr: isopropyl; ‘TE: trifluoromethanesulfonyl; THE: tetrahydrofuran; Ts: tosyl; dd: dung dich; dk: digu kign; k: khi; xt: xtc tae; VSEPR: luc day gitta cic cap electron v6 héa tr). Cho: O = 16,0; F = 19,0; As = 74,9; |= 126,9; Zi = 53. Trong cc quy trinh tng hop hitu co, c6 di eée cl V6 co, dung méi, xc tac va dieu kién can thiét, Cau I (3,5 diém) 1. Cho ede chat 06 cdng thite sau “oO oor ae Ch Al A2 a) Vé can bang giita 2 dong phan cau dang oe xde dinh cau a bén hon va gan He higu R, G om ting ding phan lap thé ctta Al. Biét: twong tac cia 2 nhém methyl in dm quyét dinh dén d6 bén cua cau dang. b) Cho gid tri pX, cia acid lin hop véi A2 va A3 Kan lugt li 5,1 va 12,1. Gidi thich tinh base cao bat thudng cita A3 so voi A2. ©) Cho gia tri p& (img véi nhém -NH-) cua A4, AS va A6 trong dung moi DMSO (xép ngdu nhién) 1a 25,4; 20,7; 26,6. Gan gia tri pX, cho timg chat A4, AS va AG. 2. Tong hop va nghién ciru tinh chat de bigt ctia cae phan ti c6 site c’ing 16n la thach thite va thu hit sir quan tam, cia cae nha hoa hoc a) Cho so dé sau HCI ° N, " =C1 NS ENHy HNO, 2H,C=CH, Ne en 2 1 B2 + 3N, +HCI Ong thite phan ttr CsHs va chi chita 1 loai hydrogen a0 cita BI va cong thite cau tric ctia B2. Goi tén B2 theo danh phap TUPAC. b) Hydrocarbon [4,5 Jeoronane B3 chisa ving e6 stie eang lén duge tong hgp theo so dé sau: Oreo - roel ‘SeMe AgBF, by CHO CiHy0 Cyt, VE céng thite cau tao clia cdc chat tir B4 dén B6, Biét: BS chita mét vong 5 canh (duge tao thanh twong ty chuyén vi pinacol). 3. Illudinine cd ngudn géc thién nhién va duge téng hop theo quy trinh sau day: OMe acyl héa hydrocarbon thom C1 véi 3-chloropropanoy! chloride (CsHsClO) c6 y# mat AICIs, thu duge C2 (Ci2Hi3Cl0). Bun néng C2 co mat H2SO4, thu duge oO HCI va C3. Alkyl ha C3 véi lugng dur Mel, e6 mit K2COs, sau do Khir hoa Clemmensen vi Zn va ACOH, thu duge C4 (CiaHis). Brom hoa C4 voi lugng dur Bry c6 mat AIBrs, thu duge C5 (CiHieBr2). Cho CS phan img véi n-BuLi B3 coon ca illudinine Trang 1/4theo ti 1é mol 1:1, sau d6 véi B(OH); va cudi cing véi H2O2, thu duge C6 (C\4Hi7BrO). Methyl héa C6 boi Me:$Os ¢6 mit K2COs, thu durge C7. Cho C7 phan img voi Mg trong dung m6i tro, sau dé v6i CICOOMe, thu duoc C8. Oxi hoa C8 bang CrOs, sau d6 khtr hoa voi NaBHs, thu duge C9 (C)7H2204). Dur ng C9 co mat H2S0, din dén tach H20, thu duge C10. Oxi héa cit mach C10 sir dung hé tac nhain OsO4/HIOy, thu duge C11 CI phan img véi NH,OAc, sau dé thay phan trong dung dich KOH, r0i acid h6a, thu duge illudinine, Vé cong thite cdu tao cita cdc chat tir C2 dén CH. Cau II (2,5 diém) VE co ché dé xudt cho cic qué trinh chuyén hod sau: ; mm OOH 7 Oo On y on ey 7" Ok, ae NL N Me coon nO x ‘er Biét: MeCOCOOH nim can bing véi dang enol khi tham gia end img véi imine trung gian. a of 2) e-Buti nok IEietad we HSOynS0, + Ch ee H,SO¢nS0,_ wo’ : wo (.00 ok (Khong yéu edu v8 chi tit co ché phan ing véi oxygen) bu Biét: giai doan dau tién n-BuLi phan mg véi hydrogen cia _| Biét: chuyén hoa 6 tao thanh trung gian chira nhém n-c=c- nhém chite alkene va trung gian SOsH’. CA IIL (3,0 diem) 1. Quy trinh téng hop D1 duge mé ta nhu sau: Cho D2 phan img véi AczO c6 mat KxCOs, thu duge D3 (C1iHyNO.). Thuy phin D3 bing dung dich NaOH sau 6 acid héa, thu duge D4 (Ci/HiiNOs). D4 tham gia phan tng dong vong véi sur c6 mat ciia AlCl, thu duge DS (Cui HyNO,). DS phan img véi PCls, thu duge D6 (Ci H7ChNO2). D6 phan ing voi D7 (D7 duge tong hop tit diethylamine va aziridine), thu duge D8 (Ci7Hz2CINsOz). D8 phan img voi MeOCH2CHCH2ONa, thu duge D1. Og NH OA Et x 4 hh x 5 LN MeO” N70 oe BI aziridine Vé céng thite cau tao ctia cae chat tir D3 dén DB. a 2 a) Ve eo ché dé xuat cho phin img cia phenol véi oh aD 2-(chloromethyljoxirane (CsHsCIO) €6 mat KCOs oA b) DE xuat mot quy trinh téng hop EL tir 2-hydroxyphenol, Mel, Ac. kL 2-(chloromethyloxirane, piperazine (CsHisNo, chira vong 6 canh va 2 he nguyén tir nitrogen 6 vi tri 1,4), 2-chloroacetic acid va aniline L 3. Dé xuat mot con during tong hop B2 tr ethanol, acetic acid va benzene _ 0 ‘au IV (4,0 diém) 1, Pumiliotoxine C duge phan lip tir da cia loai éch Dendrobates pumilio va ciing durge tang hop theo so dé sau: Met ieee @ ud qo co CyHaNO, "2 CyyHasNO, 4 L ° Me nON NA ca NN mar gest eon aN, oo y CisHyyNOz wich ogi YN CisHy3Ns0,8 AIBN, sH1,,NO. x Nol ter pumiliotoxine C Ve cong thite céu tao cilia cde chat tir G1 dén G6, Biét: phan img khir héa GS thanh G6 xay ra theo co ché géc tudo Trang 2/42. Alkaloid H9 1d mt hoat chat sir dung trong nghién eiru y duge. H9 duge tng hop theo so dé sau: 20: nM : oT uN. a : MeLiCut ud” Yo \e =CHMgtir Cotte Oe a “in 7 a ‘coon W Gris C,1H,;NO, yH1,,0 C380 thay thé nhom OH Nuon bing nn Ns yoy 3 ial, H4 . ‘HS = He y ge HS BA 2 Nabi, ‘ou Coglls202 Cy7Hy,0> CirHaN0 7" Cy HyNjOz — CygHy;NOy A Vé cong thie edu tao ca céic chat tir H1 dén HB. Biét: HS chita nhém chic ketone; H8 la sin phim chuyén_ vi va c6 chita 2 vong 6 canh. 3. Berberine duge phan lap tir cay Vang ding, Hoang ba va Hoang Ii Q Berberine li thudc thio duge ciia Vigt Nam, duge sit dung lam thude chong tigu cha vit thude nho mat, gan day duge phit hign 6 khé ning) ln chong vigm va bito v6 thin kink, Berberine va din xuat cia n6 eting wo MeO” SN duge téng hgp theo so dé sau: aed on 1) MeOCHPPh;C1 5 chu, PP : Q rath yy Ny MIS yg SM, Ls ° 5 THF One 10 2) HICVH,O. ¢ CoHlyg0s ‘CopHlygBrNOs PaOAC), 1) Khit ha NaBH, 1) BBry, CHCl, DIPEA, PPh, 2 HcIH,o” berberine aan 2 HO is ee" CagHy7NOs * CygHy)NO, 7" CygHp)NOg a) Vé cng thite céu tao cita cae chat tir L1 dén L8. Biér: Pd(OAc)x/DIPEA/PPhs xtc tac cho phan ung dong vong ndi phan tir. b) Dé xuat so d6 téng hgp L tir cae chat 2,3-dimethoxybenzoic acid va 2,2-diethoxyethan-1-amine. 4. Daldinin A tach tir nm Daldinia concentrica o6 hoat tinh khing virus HIV va gay doc té bio ung thu. Daldinin A cling duge tong hgp theo so dé sau: oO. O . Je _ NaH cH,c00C oxi hin NaBH, Meo7 ~~ ~“~om Mi BCHCOOCH, yyy hi Ms Ml THF KO; ; : onc—==cycr,cn, 1HygOs Me CyeH2007 CyeHis0s Me. ou i" Me’ 0, 0 M4 _CHLONs, Mg. __LiOn M6 —_DCHCOCH,, Abo. Cis) CHON” Cy4H1,,0g DMSO.” Cy311,404 2 Heat Ho Bt daldinin A V8 cing thite edu tao cia c MB tai lign c chat tir M1 dén M6, Biét: M1 chira ving 6 canh, phan ing oxi héa M2 thinh *t C-H no cita nhém benzyl. Cau V (3,0 diém) 1. Cyanoglycoside X 1a chat phéng vé ciia mot sé thue vat chéng lai cn trling theo co ché giai phong HCN. Thiiy phin hoan toan X trong méi om i gt trudg acid, phin lap duge carbohydrate X1 (CsHioOs) va X2 (CoHi206). ee Ko > VM a) Vé cng thie chiéu Fischer (Fiso) dang mach ho eiia X1 va X2. ou On OF b) Dang mach hé ciia X1 nim trong can bing véi cae dang mach vong x of hemiacetal furanose tuong img. V8 cdng thie Haworth (Havooe) cia cic dang mach ving furanose ¢6 thé c6 cia X1. ¢) X1 phan (mg vi phenylhydrazine tao thanh phenylosazone X3. Vé cong thitc chiéu Fischer cita X3 va cho biet X3 c6 hoat déng quang hoc khéng? . 2, Alkaloid thién nhign vindoline (CasHssNz0s) c6 hoat tinh chéng ung thu, Vindoline due ting hgp theo so 6 sau: Trang 3/4NH-NH, pt s O boone yy BME yp tooo yy Le eo Ay? Mb Bs ; a YD ChotlawNsOs—— CyeltagNsOs CyollsyNsOs Tt . t S 1) HyPd NaBH,CN MeOTE Bt oe ys 7 Y6 _—__. vindoline Me" an ‘OBn 2 ~, NaBHy . ‘ DAO —— CosHypNzO7 CasHlyN2O; CasHyaN 05 Y4 Me CooMe . a) VE cng thite cu tao eta cdc chat Y1, ¥2, Y3, YS, Y6 va vindoline. Biét: phan img chuyén YI thinh Y2 18 qua trinh dng vong 5 canh chira oxygen va nitrogen; Y6 va vindoline chira nhém chite alcohol bac 3 bén, b) Vé co ché dé xuat cho phan img chuyén Y3 thanh Y4, Biér: phan img di qua giai doan (4+2], sau d6 hinh thinh trung gian 1,3-Luéng eye do tach loai Nz 3. Mot sO tien chat thude vugt qua cée enzyme phan hiy thude trong hé tiéu hoa va tuan hoan dé dén té bao dich. Tai 6, ching chuyén héa thanh thudc hoat dng. Sau khi thye leon hign ede chite ning, hoat chat thuée durge chuyén héa va dio bi thai ra khdi co thi . ot Z 1a tién chat thude qua duémg uéng, Z. bj thity phan chon n“H.NY™ on loc, sau dé déng vong tao thanh Z1 (CisHi2ClN20, c6 hoat Zz ZA tinh an than). Z1 bj oxi héa 6 lién két C-H tai carbon a ciia nh6m carbonyl, tao thanh Z2 (CisH:2Cl2N2O>, chita nhém -OH). ZA tao lién két f-glycoside v6i Z2 thinh Z3. Z3 duge dio thai qua dudng bai tiét. VE cong thite cau tao eiia cde chat tir ZI den Z3. Chu VI (4,0 did) 1, a) Dua vao thuyét orbital phan tir ‘) Vietcau hinh electron, tinh bac lin két cua I va ion Ia’ (coi gin d6 orbital phan tir cla h va ion bo twong te giiin d6 cia F2). So sinh 46 dai lién két HI trong bs va ion Ia’. ii) Gidi thich tai sao ion 12° c6 thé dimer héa tao thanh ion 1°" va ion L* ¢6 2 loai d6 dai lién két IH khac nhau. U6, U7 b)Cho so do ben: Biét. UL UL0 déu_chita nguyén t6 halogen U; UI la don chat & thé ran trong diéu ki thudng va lam doi mau hé tinh P.do, nude Us bot; U4 c6 dang hinh chit T (theo " CuSO, thuyét VSEPR); U7 c6 mau ving, a @ Gy U2“ Gy > UI US ittan trong nude; U9 chira 22,10% oxygen vé khdi Ivong; U10 chi yy 28 HCLloing |g AsFs trong S02 ong, chiza mot cation chiém 57,33% ) 1) Vé khdi Iuong, cation nay duge tao nén tir 4 nguyen tir halogen U. us 4) Xée dinh cong thite héa hoe cita cde chat tir UI dén UIO. 4a) Viet cic phuong trinh phan img ti (1) dén (10) vat cho biét vai trd cla UI trong timg phan tmg (4), (5), (6), (7), (9). (10) 2. Dung dich Fe*" dé trong kh6ng khi c6 thé bi oxi héa thinh Fe** bai oxygen hea tan. a) Dung dich A chira Fe*’ 0,010 M va H” 0,50 M. Biing tinh todn hay danh gid kha ning oxi héa Fe** trong dung dich A khi dé cn bing véi khéng khi. Coi sy oxi héa ld hoan toan khi nong dé can bang ciia Fe’ nho hon 10° M. Cho: 6 298 K, £°,. 9. =0,771 Vi B® ,229 V; 2,303RTIF = 0,0592; Oxy) = Oriaa) K =1072; (02, 11° 11,0 ~ p suat riéng phan cita O2 trong khong khi la 0,208 atm. : b) Dung dich A sau mot thoi gian dé trong khong khi duge diing Lim thi nghigm. Suc dong khi No dé duéi hét kh On trong dung dich A. ‘Thay ring, khi them ti tir dén 0,50 mL. dung dich chita SCN” 0,01 M vio 10,00 mL. dung dich A thi dung dich chuyén thanh mau héng cua phite FeSCN?'. Tinh %Fe?* trong dung dich A di bj oxi héa thinh Fe" 6 thai diém lay kam thi nghigm. Cho: [FeSCN*"] > 9.10-° M thi quan sat thay mau hing; FeSCN?* ¢6 lg = 3,03; HSCN c6 pK, = 0,89. Gia thiet cde thanh phan khéc va cae qué trinh khdc la khong anh husmg dén he. © Thi sinh KHONG duoc sit dung tai liéu, © Gitim thi KHONG gidi thich gi thém. Trang 4/4KY THI CHON HQC SINH GIOI QUOC GIA TRUNG HQC PHO THONG NAM HQC 2022 - 2023 Mén: HOA HOC ‘Thoi gian: 180 phi (Khdng ké thai gian giao dé) Nea thi: 24/02/2023 Hudng din cham thi gdm 10 trang 1. HUONG DAN CHUNG 1. Gidm khao cham ding nhu dap an, biéu diém cia BO Gido duc va Dao tao. 2. Néu thi sinh cé cach tra loi khac dap an nhung ding thi van cham theo biéu diém ctia huéng dan cham thi. 3. Gidm khao khéng quy trén diém thanh phan cua timg cau, diém cua bai thi IL DAP AN, BIEU DIEM s Ciu Noi dung Chi ¥: Néu thi sinh khong ghi don vj ciia ede dai lwgng m9t cach hg thong trong cau tra loi, thi trir 1/4 digm tir ting sé diém cia cau. Cau I | 1.a) Khi electron trong nguyén tir H chuyén tir mite nang hrgng ne ve n= GB,0 peteeloes he 1 heN , [aa =]1- SENS een a x1 312x10° x10 diém) | AE 6,626x10-™ x3x10" x 6,02 x10" (a = 0,8892 => 1, =3 | 102,57%107 x1,312%10" x10" O mite n = 1, chi c6 gia tri / = 0, nén trang thai ban dau cia nguyén tir H phai c6 / = 1. Cau hinh | electron cia nguyén tir H 6 trang thai ban dau li 3p! | 1.b) Electron 6 thé chuyén tir» = 3 vé mite ning lugng thp hon khdc la n = 2. Theo quy tic chon loc Al=21, electron tr 3p (= 1) chi chuyén vé duge 2s (= 0). Cau hinh electron ctia nguyén tir H 6 mire nang lugng thap hon khac li 2s! | Thi sinh vé cau hinh electron duéi dang 6 lugng tir van cho diém t6i da. Néu xéc dinh thita cae trang | thai ctia nguyén tie H thi khong cho diém todn bo J. | 1.6) Nang long ion héa (IF) nguyén tir H tir trang thai ting véi nm = 110 la: 1,312x10°x10° 1 } IE 12 By = 0-| — — |=1,800x107 N, 110° Nang Iugng nguyén tir H nhan duge tit va cham nhigt 6:0 °C €=k, xT =1,381x10 x 273 =3,770x107) | Do ¢> IE , nén va cham nhigt cé thé gay ra sw ion héa nguyén tir H 6 trang thai img voi n = 110. a) Phuong trinh bac m6t mé ta moi lién hé gitta Liq va qu: | En =-19,29+275,94xqy, (KI mot) hoke 4, =0,0722 + 0,0036% | 2.b) i) Lon HsO>" 06 hai lién két hydrogen tong duong nhau va bén liGn két cOng héa tr} OH twong duong nhau. Tir dit ligu vé d6 dai lién két O-H va khoang céch O-O, suy ra eée nguyén tir tham gia ‘go hai lién két hydrogen O ~ H- © phai thing hang, Cau tao etia HsO2": Naa a 4 09d, Giai thich: Lién két hydrogen OH O trong HsOz" la tong tac lién phan tir, yéu hon lién két cng | hoa tri O-H théng thudng trong H2O do mat dé electron gitta céc nguyén tir trong lién két thap hon. | Do do lién két O--H dai hon lién ket O-H. | thi sinh ve cdu tao dang H2O"H-“OHo nhung m6 té va quy gén diing dé dai lién két van cho diém t6i da. Néu ve dang géc thi khong duegc diem. Trang 1/10ii) Tw ya) nhan thay dién tich trén nguyén ur H tham gia tao lién két hydrogen cing cao (lién két X— H céng phan cue) thi nding lurgng lign két hydrogen cang l6n. Eyy trong HsO2" cao hon Ens trong bang do dign tich duong trén nguyén ti H cao hon (cé thé coi 1a proton mang dign tich +1 bj hydrate héa). 2.e) Vi khoang cach gitta hai nguyén tir O trong H7Os" bing 2,43 A, xap xi bang khoang cach gitta hai nguyén tir O trong HsO2* nén trong HxOs° c6 lién két hydrogen manh kiéu O--H- O twong ty nhw trong HsO2" hoac cé thé 1a lién két hydrogen manh kiéu H3O*--OH)2 (nguyén tir H trong H30* c6 dién tich duong l6n); va lign két hydrogen thong thuimg dang H2O™-OHb cé nang lugng lién két thap hon, 49 dai lién két lin hon, do d6 Khoang cach gitta hai nguyén ti O Ién hon. Céng thite cau tao cla H7O3* iL é . 302". H20: hoje Hx0".2H20: Néu thi sinh ve I nguyén tic H lién két voi 3 phan tic nude thi khong duoc Giu IL 4.0 diém) . Xét cdc phan img: CH3OH (4) + 1/202 (k) > HCHO (k) + H20 (h) (1) 120 (h) > H20 (I) a’) CH3OH (k) + 1/202(k) + HCHO (k) + 120 (2) (1b) A,H(Ib) = A.4(1)+4,4 (I) A,S(Ib) = A,S(1)+4,5(0°) A-H (1’) am, do qua trinh ngung ty toa nhiét, nén A,H (1b) am hon A,H(1) hay AcH (1b) wH(1) A;S (1) 4m, do H2O(/) cé entropy nho hon H20(h), nén A;S (1b) 4m hon A,S (Lhay AcS (1b)< AS(L) (Néu hoc sinh chi dwa ra két qué mé khong gidi thich thi khéng cho diém toan bé ¥, 2a) i) dink _a,H° pee at RT? 30° r TAH r 7 faink = 4) [Se ar sac? [Lar—act <7 JLar 1, Ry ai 5 ela ae "oa? Ink, -InK;, Ink, =n, +] 4,4 i = dpem ii) A, Hy (1) = A, Hy, (HCHO,K) + A, Hyg (H;0,h)— A Hy (CH,OH,K) = (—108, 60) + (—241, 83) — (201,00) = -149, 43 kJ mol"! = -149430 J mol! | ACH) = C) x (HCHO, k) + C? x (HO, h) —C, x (CH OH, k)— 0,3 C(0,,4) | = 35,40 +33, 60~44,10-0,5%29,40=10,20)K” mol” Thay vao phyong trinh & trén thu durge In Koo(1 Tuong ty, doi vi phan ing (2): A, H3,4(2)= 92400 J mol! = 92,40 kJ mol! AC} (2) = C)(HCHO,k) + C)(H,,k)— C2(CH,OH, k) 3,856 => Kroo(1) = 35,40 + 28,84—44,10 = 20,14) K! mol! In Kro0(2) = -2,020 => Kro0(2) = 0.1327 Trang 2/102.b) Khi ban diu: CH;OH: x (mol); Oz: 0,5 mol; No: 2,0 mol duge dua vio budng phan img ti 2 duong hac nhau, gap xite téc 6 700 K sé c6 cde phan tg sau CHOH (4) + 1/20) (k) > HCHO (k) + H20 (h) (dy) CH3OH (k) > HCHO (k) + He (k) Q) © 700 K, vi Kr( 1) rat 16n nén ¢6 thé coi phan img (1) xay ra hoan toan, Kroo(2) nho nén phan ting (2) xay ra dat dén cin bing 6 nhigt dé phan img, A,Hs()=A,Hy+ [ A,C'dT =A, HE, +A,C! XAT | A.A) = 149430 +10,2 (700-298) = 145329, 6 mot"! =—145,33k mol" A, Hyyo(2) = 92400 + 20,14 x (700-298) = 100496,3 J mol = 100,50 kJ mol" Goi y 1a s6 mol HCHO due sinh ra tir phan img (2). Hn hop khi cin bing 6 700K. gém: Ne: 2 mol, H20: 1 mol, HCHO: (1+y) mol, Hz: y mol, CH;OH: (x—1- y’) mol. ‘Téng s6 mol khi trong he: (3+.x+y) mol Phuong trinh can bing nhigt: A, Hy (I) + YA, Hyp (2)+[0,5%C, (O, XxC,(CHOH,K) XAT + yA, Hoy (2) AH (1) = -145329,6 Jmol" AH yo (2) = 100496,3 Jmol! AT = 700-298 = 402K 17728,2x+100496,3y = 116023,8 1116023,8~100496,3y *17728,2 ~ V6i phan ting (2): k) +2,0%C, (N,.k) +2 C,(CH,OH,k)]x AT = ‘A, Hy (1)-[0,5xC,(O,,&)+2,0%C,(N, ,A)] XAT ‘Thay x tir phuong trinh can bang nhiét vao phurong trinh K(2) cia phan tmg (2): ~3,134y* +12,888y-7,026=0 y=0,6469 mol; x=2,8770mol Thanh phan hén hgp can bing: No: 2,0 mol (30,66%), HzO: 1,0 mol (15,33%), HCHO: 1,6469 mol (25,24%), Hz: 0,6469 mol (9,92%), CH,OH: 1,2300 mol (18,85%). | 2.¢) Luong nhigt t6a ra khi lam ngugi ding ap hon hgp khi tir 700 K xudng 298 K. Q=[1,2300% C) (CH,OH) + 1,6469% C3 (HCHO) + 0,6469xC8(H,)+ +1,0%C} (HO) + 2,0% C2 (N,)] (298 700) = -89645,9 3 Thé tich buéng cap nhigt ¥ = 3,1416x(1,3 m)*x2,0 m=10,619 m° vo * «1,013 x10° mol khng khi ban di; n, = 2% = 10.619 mL 013110" Pa _ 434 16 poy R 8,314J"'mol'K"' x 298K Bung cap nhiét kin: V = const C’, (khéng khi) = 29,16 JK“ mol! G 7p ~ R= 29,163 K ‘mol! ~8,314) ‘mol = 20,846) K"'mol” Nhigt d6 72: Qy = nC/AT = 434,16 mol 20,846 JK“ mot x(7, -298) K = 89645,9J > T, =307,9K =34,9°C Néu ldy Qs = 5X10" kd thi Ts 3.a) Trong mot long clathrate: 850.4 K (577,4°C) Trang 3/10tr, do dodecahedron 6 20 diém giao = 20 dinh la 20 nguyén ti O. -anh = 30 ign két nude = 20 pl ~ S6 lign két hydrogen = it = 12 mat 3.b) CHa (K) + 2028) > CO.(h}+ 2H20 (1) ‘Thigu nhiét cla CHs: AH°29s = -890,57 kJ mol! =~ 890570 J mot! . Dé c6 89645,9 J nang hgng can; 0,1007 mol CHs. Vi higu suat dét chay la 80%, nén sé mol CHs can 14 0,1258 mol. Thé tich CHy ki _0,1258 molx8,314)K | mol’ x 298K 10° Pa Thé tich methane hydrate la: v 5 3\12107 m* 9010 m* 164 Néu sir dung gia tri Q, = 5,0%10° kJ thi can 5,614 mol CI tich methane hydrate 1a 8.476% 104 m’. Higu suat 80% nén can 1,059%107 m?, wong durong vai 0,139 m3 methane. Thé iu Mm G0 diém) 1.a) Anode: CHsOH (I) + 60H (aq) -> SH2O(1) + CO2(K) + 6e Cathode: O2(k) + 2H:0() +4e > 40H eq) Hoge Anode: CHsOH (1) + H:0(aq) > 6H (oa) + CO2() + 6e Cathode: O2(k) + 4H” + 4e > 2H:0()) 1.b) ’) AG’ =-nFE° . Bién thién cua cac dai lwong nhigt dong xc dinh & diéu kién can bang nhiét dong nén xc tac khéng lim thay d6i site dign dong ly thuyét cua pin ii) Xét cae phan img CH3OH (1) + 3/202 > CO2(k) +2H20 (2) (1) H20 (/) — H20 (h) qa’) CHSOH () + 3/202 CO2(k) +220 (4) (2) 2 Co: £°(2) = E"()-—ae"(1) Q)=B-AaGr(ty ‘Neu pin Lim vige 6 nhigt dé thap hon nhiét d6 s6i cua nude, thé hoi kém bén hon 6 thé ling, AG°(1°) > 0 nén E*(2) gidm so véi £°(1). Néu pin lam vige & nhigt 49 cao hon nhiét d6 s6i ca nude, thé hoi sé bén hon thé long, AG*(1’) <0, nén £° (2) ting so voi £°(1). Néu thi sinh bién ludn truéng hop pin lam viée 6 298 K vé riit ra duege E° (2) giém so voi E° (1) van cho diém toi da. Néu chi tra loi la “khong” hay “cé" ma khéng gidi thich, thi khéng cho diém toan bd y 1b) 2.a) CH3OH () + 3/202(K) > 2H20() + COx(8) Céng eure dai A, Gig =A Hogg -TA,Sy A, Gig, = ~726,07 kJ mol"! — 298 K x(—80,845)x107kJ Kol! ‘ong cue dai =| AGS, 701,978 kJ mol! 701,978 kJ mol" (mot: tinh cho mét mol phen ting) 701,978%10° 96485%6 A,Gyy =—nFE" = E' 1,213V 2.b) Nhigt kém theo qua trinh khi pin lam viée Q= TAS G mhigt d6 298 K: Q = 298 x (80,845) = -24,092 kJ mol 2.6) Coz AG? = -nFE" = AH ~TAS° = e¢ = AS p_ AH” nF nF V6i pin nbién ligu trong bai: E" = -1,3965%10°7 +1,2542 Khi 4,S° gin 0 thi E*it phy thude vio nhigt d6, Trang 4/10| 3.0 diém) 353x(-80,845) _(-726,07x10°) .d)Ta +273 2.d) Tai T = 80 + 27 696485 6% 96485 53 K=>E°= 2.4) Higu suat tai diéu kign chuan: SG. 701,978 3a) Vi kim logi thing o6 lép oxide aged néa ein dinh gidy rap dé loai bo l6p oxide nay. - Thé tich Vi, V2 khong chinh xée sé gay sai s6 trac tiép dén tinh ndng d6 cua cde chat trong can bing tao phite. 3.b) Ta co: rE Boog 0,0592 HS = 28 100% In[Zn?"]; Es Vi Ebinc, =034V > BE? =-0,76 V nén dé thay Zn| Zn* dong vai trd anode 1a hgp ly. Néu mudn. anode Ia Cu] Cu?" t Eoxpsian > Beoniey Wie li: nl), 2(Bosmicr Foire) Ge 17 0,0592 phéng thi nghigm, So d6 pin nhur sau: =37,16= [Zn ]>1,38%10"[Cu"]: khong thye hign duge trong (anode) ZnjZn*', CaCu?’, Ci|Cu ( ¢ Dé do site dign déng cua pin can mac di xung: noi dau (+) trén von ké voi cathode ciia pin va ndi déu (-) trén v6n ké véi anode cia pin. Do 46, can ndi cathode (P1) vai dau day d6; anode (P2) ndi véi dau day xanh, ~ Dung cu Y a cau mudi, cé vai tro két ndi dung dich gitra hai bin nguyén t6 dé dong ion dich chuyén, hop v6i ding electron dich chuyén bén ngoai tir anode sang cathode tao thanh mach khép kin. Néu hoe sinh chi ndi ndi PI v6i dau a6, P2 voi dau xanh ma khdng gidi thich vi PI la cathode va P2 1a anode thi khéng cho diém 1, Dat k" = ACN CY > v= k"Cp, Do str phu thude cia InCry: vao # 18 tuyén tinh nén phan img 6 bac 1 véi Phl =>n2 G pH = 5,0: C,(X) = 0,20 M,k"=0,5461 phit™ Sn C,00) = 0,45 M, k"=1,2241 phat ke Ce => k'=2,725M" phat! 2.a) Vi cde chat phin img duge lay theo ding hé so ti long trong phuong trinh hoa hoc nén 2¢, | on | Bac ciia phan ting khdng ddi nén: v=k'C,,,Cy = 2k'C2, voik' = KCN Goi C la ndng d6 ctia Phil tai thoi diém ¢ thi cd: . (@) Theo bigu thite d hdp thy quang A, = (26, +8,)xC, xl A, =£,xC, x1 A, =[(2e,xC +6, xC+e, x(C,—C))x1 = (26, +8, -€,) x Cxl-+6xC, xd (b) Tir dé c6 thé viet: 4, -( Trang 5/10Tir (a) va (b) suy ra: & b) Ta c6 bang sau: - [e(phay) 25 | 5,0 10 15 20 LAO phir) 2,667 2,705 2,736 2,788 2,734 => k'=2,726 M phiit O thi nghigm | va 2: k'= KC"! = 2,725 M“ phat” v6i pH = 5,0 thi nghigm 3: k'= kC7. = 2,726 M“ phat" véi pH = 5,5 O hai pH khé Phuong trinh luat toc d6 day du: nhau cing ra mot gid tr) C3" nén bac phan img voi H” bing 0 (nl = Ch CyCx 5 = 2, 7255 M™ phat 3. Dé don gidn hoa, trong ¥ ny, nong dé C cita cde phite chat duege ki hiéu bang ngoae [ ] va heoe bo méc vuing ctia phitc chdt trong cdc phuong trinh déng hoc. Buse | thuan nghich, nhanh nén khéng la bude quyét toc d6 phan img. = Trudng hop 1: Néu bude 2 1a bude chim quyét dinh tée a phan img. v=k[ML,X*] Vi bude 1 thudn nghich, nhanh dat can bing, ap dung nguyén IY cn bang én dinh cho (1) 48 rt ra bigu thite tinh [ML«X]? AIML,* JX] [ML,X*] = KML? IX] [ML UX] =>phii hop vi qui ludt tim ra tirthye nghigm, . Néu thi sinh bign lun dua trén nguyén ly nong d6 dn dinh: Gia si [ML«X]* la tigu phan trung gian hoat dong, ap dung nguyén ly néng 46 n dinh cho [MLX]° ae = KML? JX]-k. [(ML.X*]- d CMe ke +k Vi bude (1) nhanh dat can bang nén_k >> ke, v= K\k,[ML.> JX] (ineong hop nay néu khong bign ludn dé dua vé két qua cudi ciing thi khong cé diém do [ML4X]* duge tao thinh nhiéu tie bude 1 nhueng lai tiéu thu chdm theo bude 2 nén khéng dp dung duoc nguyén by nong dg én dinh cho [MLsX]*) . . sae hop 2: Néu bude 3 1a bude chim, quyét dinh tée d6 phan tng, = ky[MLX~ LX] Néu bude 3 cham quyét dinh téc d6 phan img, [MLsX]° duge tao thanh nhiéu 6 bude 2 va tigu thy chim 6 buée 3 nén khéng ap dung nguyén ly néng 46 én dinh cho tiéu phan nay. Ap dung nguyén ly can bing én dinh L (2) = khong ph hop véi qui luat dng hoe tim ra tr thye nghigm. ~ Trrdng hop 3: Néu bude 4 la bude cham, quyét dinh t6c d6 phan ung: v=k[ML,X,] Tuong ty, 4p dung nguyén ly can bang én dinh cho [ML3X2] (Mi => [MLyXy |= Ky[ML,X- JX] => v= ky K[MLXJLX Trang 6/10| ag, Ree RIML ET =n, KikaKo Mls ICP [4] =khdng phii hop véi qui luat dng hoc thye nghigm. Két lun: trudmg hop 1 véi bude 2 la bude quyét dinh tée dé phin tng la phit hop véi qui lugt dong hoc thye nghiém. Co ché dé xudt sé nhw sau: (ML, + X = [ML,xP nhanh (Bude 1) (ML,xe 25 IMLxP 4 (Buse 2) (ML,XT + X —5 [MLx,)> nhanh (Buée 3) [ML;X,. = —» [ML,X,] +L” nhanh (Bude 4) | Trong edie tring hop 2, 3, néu thi sinh gid thiét [ML3X]° va (ML3X2]° la tiéu phan trang gian hoat ding va dp dung nguyén bf néng dé on dink nhueng bién ludn duoc ket qué cudi cing khong phi hop di thure nghiém van diege dic diém, Thi sink phai lam dit 3 trudmg hop méi diege diém t6i da cho ¥ 3. Gu G0 diém) 1.a) Vi AI chita nitrogen va la chat khi 6 diéu kign thug phan img duoc voi hydrogen nén AI co thé la Nz. Khi d6 khi A2, acid A3, mudi Ad, sin pham AS, khi AG lan lot li: NHs; HNOs, NH:NOs, NaNHs, N:O, A7 la mudi etia Na véi anion chita nitrogen (c6 thé la mudi NOs, NO+’, Ne..). Theo bai ra A7 chita 64,62% nitrogen vé khdi lwgng nén A7 li NaNs, Nhu vay Al li No la phi hgp. Vi NH3 du + F2 > A8 (chita 19,72% nitrogen vé khoi lugng) nén A8 1a NF; NF; + Cu — A9 (chi chtta hai nguyén to voi ti 1é 1 : 2) va tir A9 thu duge A10 (cé céu tric trans va momen ludng cuc bang 0) nén A9 li NoFy va A10 1a trans-NoF2 Vay: Al: No; A2: NH3; A3: HNO; Ad: NHsNOs; AS: NaNH2; | NoFs: 10: trans-NoF AG: N2O; A7: NaNa; A8: NF3; A9: NaN3 + NH3 + NaOH 4NHG (du) +3F2 28. NF) + 3NHGE 2NFi+ Cu2™S NGF y+ Cure 2N2Fa+ 2AICL 2S. trans-NoF2 + 2AIFs + No +3Ch Khéng can bang phuong trinh thi tric mia sé diém 2. a) i)- O ap suat thap, phite chat [Fe(CN)s(NHs)> nghich tirnén sy tach mife ning long cde orbital d cia nguyén tir trung tim trong trudmg tinh thé nhw sau: nang long Fe?*: 346 AA) Fe” trong (Fe(C) u hinh electron ciia nguyén tir trung tam: (t2e)"(es)” ~ 6 Ap suit cao, phite chat [Fe(CN)s(NH3)]> thudin tir nén sy tach mite nang lugng cdc orbital d cua nguyén tir trung tim trong trudng tinh thé nhur sau: ning lugng )s(NH5) Fe™ trong [Fe(CN),(NH3)]}° Cau hinh electron cita nguyén tit trung tam:_(t3,)*(e,)? Trang 7/104 su phan bé electron dé ma khong vie diém ii) Sy chuyén electron gitta céc mite nang long orbital d cua nguyén tir trung tam trong phite [Fe(CN)s(NHs)]> 6 Ap suat thap la khéng duge phép vé mat spin vi d6,b6i_M bi thay doi ti 1 1én 3 hung duge phép vé spin 6 ap suat cao vi d@ bi M khOng thay doi va déu bing 5. Néu khOng gidi thich thi chi dwgc ntia so diém. b) [Co(NHs)o]" la phite chat spin cao nén su tach mite nding Iugng celia nguyén tir trung tam trong truéng tinh thé nhw sau: (O tren gi ning Inong eer ces BT , : Co trong [Co(NH3),]”" Chuyén mite d-d eta ion Co® duge phép vé mit spin vi d6 boi M khong bj thay di loai phdi tur CO3*, NH, H2O vi NOs. Vi P2 va P3 1a phite chat bat iy chi chia mét loai phdi tr, ctu ngoai eta 2 phire chat niy chi NOs nén ching la cae phire chat cation. Vi phan img ra khi CO: do d6 P2 va P3 tao ra c6 the li [Co(Hs0)s](NOs)s (chita 16,69% Co vé khéi lung) va [Co(NHs)s(NOs)s (chita 16,98 % Co vé khdi luong). Tir dir kign dau bai P3 chira 16,98% Co vé khéi long nén P3 1a [Co(NH3)s](NO3)s. Vi PI chira cau noi cua phite chét P3 nén Co cén lai trong PI phai li Co™, do vay P2 1a [Co(H20).](NOs)s va PI Li [Co(NHs)s][Co(COs)3). Vay c6ng thire héa hoe: PI: [Co(NHs)s][Co(COs)s], P2:[Co(H20)s](NOs)s; P3: [Co(NH3)s](NOs)s P16 | dong phan phdi tri véi cng thire héa hge: [Co(COs)(NH3)«][Co(COs)a(NH3)2]. Néu viet thiéu méc vuéng trong tat céc phite chat thi duoc mita so diém. Cau VI 40 diém) 0,8307 1.a) Dung dich H2A néng dg: C= —-—_ = 0,05 M ') Dung dich HA nong 49: C= +e 01 Cée ean bing HLA = HAT +H Ku = 10795 a HAS A> +H! Ka= 10%" (2a) hoje HA = A> + 2H" KaiKia = 10° (2b) H20 =H’ + OH” Ku= 10" @) M6 ta it nhdt 2 cén bang trong dé phai cd 1 va 2a hode 2b thi duge ati diém Cich 1 Dinh gié Kai >> Keo va KC >> Ky ; nén cin bing (1) la chinh Tinh theo ean bang (1) A = HA+H Ky = 107 Cc 005 1 0,05—x x x = 0,00695 => pH = 2,16 (2,158) Cich 2 ‘Theo dinh ludt bio toin dign tich hode theo diéu kign proton [H'] = [HA] + 2[A*] + [017] HK, 42K, K, tHe] = E28 Ke o05 4 Ai (HY +[H'1K, +K,K,, [H’) ) Thiét lap biéu thitc % déng gop cia cae can bang I > [H'] = 0,00695 M + pH = 2,16 1 Trang 8/10| Su dong gop H’ tir edn bing Qa) ting véi [A*]; su ding gop H™tir ein bang | img v6i tong ((HA] + [A*); su déng g6p ca can bing (3) img voi [OH] . ; AE % dong gop cia cén bang (1) = mre 100% ; % dong gop cia can bang (2a) = a J o0rs % dong gop ca can bing (3) = th 100% | Néu cn bing mé ta la (2b) «done va me THA] oe ne Yoding pip cba cia bing (1) =F 100% ; % déng gop cita cn bing (2b) = : |OH™ % dong gop cua can bing (3) = an 00% Néu cde biéu thie va can bang mé té la khong khép nhau thi chi duge nita 86 diém Tinh % va danb gid (chit yeu hay khong dang ké) [HA-] = 0,00695 [A*] = Cxa.q2- = 3,89%10-° M [OH] = 1,44*10-? (HA }HA™] 0,00695 fA") 0,00695 [OH] 8 100% =2x10°% ; ké 000s 10%; khong dang ké % dong gop cita can bang (1 100% = 100% ; chit yéu % dong gop ciia can bing (2a) = 100% = 0,06% ; khong dang ké | | % dong gop cia ean bang 3) => De | Néu ean bing m6 ta 1a (2b) (HA) | % bing (1) = 100% = 100% ; chi | % dong gop cita en bing (1) = itaces cha yéu % dong gop cita can bin; (2b) = 2477 09% = 0,12% Khéng dang ké % dong gop ct i (2b) =F ggp 100% = 0.12% ; khong ding | 2a) | Hén hop chi thi d6i mau theo pH tir d6 (pH < 4,4) > da cam (d6+vang) (4,4 ~ 6,2) -> vang (6,2 ~ 8) | da cam (héng+vang) (8 ~ 10) ~> do da cam (hoge do hoe da cam hoie dé + vang) (pH>10) | Néu chi néu su bién d6i mau khong gan v6i khoding pH thi chi cho niea so diém. 2.b) Tinh gidi han pH cua dung dich thu duge & bude 1 Phan img: HB + H* — H2B* ‘Thanh phan sau bude 1: H” du vi HoB™ dur > (10%0,25 ~ 10*0,02)/20 = 0,0025 M; ing: 1B! = HB +H" Ka HB=B-+H" Ka 120 = OH +H Kw [H’] > C(H") du — pH < 2,6 > khi thém chi thi methyl do va phenolphthalein thi mau ciia dung ich dau bude 3 ki mau do Tinh gidi han pH ciia dung dich & cudi bude 3 Phan img: H* + OH-—> H20, HB" + 20H 2H20 + B- Thanh phan cudi buée 3: OH du va B C(OH') dur > (15%0,035 ~ 10*0,025 ~ 10%0,02)/35 = 2,14*10° M; Cin bing. B> +H,0 = HB+OH- Ku Trang 9/10HB + H2O = H2B™ + OH™ Kor 120 = OH + Ht Ky [OH"] > C(OH-) > pH > 11,3 > Mau cia dung djch cudi bude 3 1a mau do/dé da cam/da cam/(d6+vang) Mau ctia dung dich trong bude 3 sé bién ddi tir dé — da cam ~ ving ~ da cam — d6/do da cam/da cam/(do+vang) Néu thi sinh chi dia ra sw bién déi mau nhw ya ma khong tinh todn thi khéng cho diém ©) Hon hop g6m: 10,9 mL dung dich NaOH 0,035 M, 10 mL dung dich HB CM, 10 mL dung dich HCI 0,025 M; hén hgp 6 thanh phan ban dau truée khi phan img 1a: Coxon = 0,035%10,9/30,9 M Cuacy = 0,025%10/30,9 M Cuz = 10*C/30,9 M Khi chi thi phenolphthalein (ki higu li Hin) ton tai 80% 6 dang base, trong dung dich tdn tai can bang celia chi thi la: Hin = In- +H" K,=10°4 Theo dinh luat tic dung khdi Ivong: ee ae a K, jan) > I iey he gl? =9,95x10""' =10 M Theo dinh Iuat bao toan dign tich: O'] + [Na‘] + [HeB‘] = [OH] + [B>] + [Cr] pH = 10,0 nén bé qua [H’], [H2B"] so voi [Na’}; [Na‘] = C(NaOH); [Cl-] = C(HC) ue 5 1), Ke HTH") | 30,9 30,9 * Caren C= (Cowon ~Cyrcy “LOH. wee Cosson = [OH] + =— K,+[H x10,9-0,025x1 6 +10" 9,02510 _jg.4) 107 +10 30,9 10°* Nong d6 ctia HB trong dung dich ¥ li C = 0,018 M 3.a) Giai thich: Dung dich vira pha can duge dé trong binh kin dé tanh CO> trong khong khi hoa tan vao dung dich phan tmg voi NaOH. 3.b) - Buret, pipet ld dung cu do thé tich chinh xc. ~ Buret dung dung dich NaOH 3.) #) Hai céch lam déu kh6ng anh huong dén két qua tinh ndng a> NaOH duge tinh tir két qua chuan 6, vi gid tri 7,54 1a da bao gém ca giot dung dich can treo 6 dau buret. it) Sai s6 twong d6i la (0,05/7,54)*100% = 0,7% FET —__________ Trang 10/10BQ GIAO DUC VA DAO TAO KY THI CHON HQC SINH GIOI QUOC GIA TRUNG HQC PHO THONG NAM HOC 2022 - 2023 HUONG DAN CHAM THI Mén: HOA HOC Dé thi chinh thire ‘Thoi gian: 180 phi (khdng ké thai gian giao dé) Ngay thi: 25/02/2023 cham thi gdm 09 trang Hung 1. HUONG DAN CHUNG 1. Giém khio chim ding nhur dap 4n, biéu diém ciia BO Gido due vi Dao tao. 2. Néu thi sinh c6 cach tra Ii khac dap an nhung ding thi van cham theo biéu diém cita hudng dan ch: thi, 3. Giam khao khéng quy tron diém thanh phan cua timg cau, diém ciia bai thi. Céc chit va ki higu viét tét: Ac: acetyl; AIBN: azoisobutyronitrile; Bn: benzyl; n-Bu: n-butyl; DIPEA: N,N-diisopropylethylamine; DMAP: 4-dimethylaminopyridine; DMF: N,N-dimethylformamide; DMSO: dimethylsulfoxide; Et: ethyl; Me: methyl; NBS: V-bromosuccinimide; Ph: phenyl; ‘Pr: isopropyl; ‘TE tifluoromethanesulfonyl; THF: tetrahydrofurane; Ts: tosyl; dd: dung dich; dk: digu kign; k: khis xt xtic tac; VSEPR: lute day gitta cac cp electron v6 héa tr), Cho: O ‘Trong IL DAP AN, BIEU DI 16,0; F = 19,0; As = 74,9; I= 126,9; Zi = 53. ic quy trinh tng hop hitu co, c6 di cdc chat v6 co, dung méi, xite tae va diéu kign can thiét. 4 cau Noi dung 1 (3.5 | 1. a) Vé can bang gitra 2 dng phin cdu dang ghé, xc dinh cdu dang bén hon va gan ki higu R, diém) | § cho timg dng phan lap the cua A1. Biét: twong tic cha 2 nhém methyl in dm quyét dinh | dén d6 bén tia Dap an: dang. ue Oo a ben ton Me | le TI Me eM fw Mey Me Me bat thuong cia A3 so véi A2. | Dap dn: Trong A3 cé thé nang cao do hiéu img lap thé ctia cc nhém methyl khién cho cac cap e tu do trén nitrogen khé lién hgp vao vong thom va 2 cp electron tu do trén 2 nguyén tir nitrogen diy nhau vi 6 gin nhau, Qua trinh proton héa A3 tao ra acid lién hgp FLA3* da lam ben hod hé do mot cp electron ty do trén mét nitrogen lién két véi proton va cAp electron ty do cita nguyén tir nitrogen con lai tao lién két hydrogen N-H---N. Cau triic “2 cang” gitt proton nay rat bén nén acid lién hop HA3* duge bén hoa, din dén tinh base cia A3 manh hon A2 (acid lign hop HA2" khong 06 cau tric git proton “2 cing” va A2 it bj tong téc khong gian manh ciia cic nhom Trang 1/9‘methyl nén anh hyong khGng nhiéu dn su lign hgp ca ep e ty do vao ving thom) rat nhieu, MeN Nee, Me” yates 1? OO = OO ‘A3 (Néu thi sinh chi giai thich qua higu ting khéng gian ctia cée nhém methyl trén A3 kim cho cée cip ¢ ty do khéng lién hgp vao vong thom duge thi cho nita tng s6 diém) ©) Cho gid tri p&s (img voi nhém -NH-) cia A4, AS va AG trong dung moi DMSO (xép ngiu nhién) la 25,4; 20,7; 26,6. Gan gia trj p&y cho timg chat Ad, AS va A6, Dap an: 7 AS AG 20,7 25,4 26,6 2. a) VE cong thite cau tao cia BI va cong thire edu tric cia B2. Goi tén B2 theo danh phip TUPAC. pa spiro[2.2]pentane Dap an: BI Bz +b) VE cng thite edu tao cia ede chat ti B4 dn BG. Bier. BS chita mot vong 5 canh (dugc tao thanh tuong ty chuyén vi pinacol). ® ay SN Nie Dap an: BA (CH ,0) BS (GoHin0) BE (CyHla.0) 3. Vé cong thite céu tao ctia cde chat tir C2 dén C11 Dap an, oo a i =a 180. So0d DML K:CO. pmo IOC be ‘ich ie cco ‘Acom AB CXC MC! C3 (C,:H,0) CaCl) Be €5 (Cyl yB) on Me ome ho OMe Dats MeS0y My 110s 2 HOM, Kc, 2) C1C00Me 2 NaBH, SHO: be be CooMe boone €6(Cye11,,B10) o cs 9 (CH, OMe pa Mme _ uso. hon eee NH,oAe xe “Ho, 7 ONG, iN 10 Coome ci one amo" illudinine COOH Trang 2/9125] 1. pn COOH diém) ou J One. YT 1 o ' + WA Pe ie] 5 . ‘Pr Biét: MeCOCOOH nam can bing véi dang enol khi tham gia phan img véi imine trung gian. Dap an: | | po r, "bAe coon Noy (Gs oe - wow d vi yt — “ye i rr A ‘Pr Bre PHOT (SH Sone 2 ° 1) mai Bi T p = THF, -78°C i Ss . NUN Bo,” N, 20; Meo” So plete Lo) (a B o WW (Khéng yéu cau vé chi tiét eo ché phan tg voi oxygen) ‘Biét: giai doan dau tién n-BuLi phan img voi hydrogen ca nhém 1 kene va trung gian SOsH | Trang 3/9a Et Me. Et Me. Bt Ae =e Ae, Mss Me Me i Me ud WF 7° oot Hos Con BH Gon Feu WL G0 diém) chat tir D3 dén D8. 1. Vé cbng thite clu tgo etia Dap an: ° cost ° ° A Lo -0 Aso ioe) yaanson ore ACh loot “Mc0” N 70; MeO" N 2) acid hoa MeO” ‘NH “Mc” yoo | - a \ D3 (CyHyNO,) D4 (Cj,Hy,NOs) DS (Cj\HyNO,) a ON A, ¥ OCI Ey NW of. AE : Bay Uh x ay Pers { i 07 Ss MeO. AON AN Ft MoO” N7Scr Meo" Nc i wo omte D6 (CH ClNO») DB (C,sHy:CIN302) D1 o re, Oo ) fe wo. F savin, 4 ‘hay am OF gah Ny é 4 (Chults:03) HS (C)03) H6 (C sH3)N,0) OyMes _non_ Litt 2) Nab, ‘on “ on ’ bu o 17 Clty H8 (CgHly)NO.) 1 3. a) Vé cong thite cau tao cuia cae chat tir L1 dén L8. ql Dip an: Bs one 1) MeOCH,PPhsCl ‘0 6S 2yncu,0."" pom” par TF L2cathaoy Ls L4 (CH,Br,0,) ° Meo” mal Sy Br > C3,C0,.0° eee ‘0 DIPEA, DHCHO bw LS (Coglt),BrNO) dMe J 16 (CaoHyNOs) 4b on Y Ee NaBH Cr 2x A Meo" 3 Meo" Meo” Me OOCl bate Ome berberine 7 (CgHa)NO,) L8 (C\gH2\NO4) Trang 5/9b) Dé xuat so dé téng hop L tir cdc chat 2,3-dimethoxybenzoic acid va 2,2-diethoxyethan- om Bi, ee SoC Eo NN 1,80, dae Na 2 oe nn ee Meo" "COOH" MeO” ‘cocl Bae MeO’ 0° MeO’ ome Ome OMe 0 Ome 0 4. Vé cing thite cu tao eta ce chat tir MI dén M6. Biét: MI chira vong 6 canh, phan ting oxi hoa M2 thinh M3 tai lién két C-H no cua nhém benzyl. Dap an: oo 8 nomen nee en nycooe A ’coocit, MFA ME nat sic.cooct, _oxihia na ‘ THF a ‘K,CO; a wa CHOW onie—=Henen,en, =H Os CuatasOs CuathOs sconce C006 - Jo _crors_ HO Lott nen,coct,. alo, CHO oss0.1,0 2) Hy xt ae Ho re ne dalinin A cast, Cull, CialuOg V (3,0 | 1.a) Vé céng thite chiéu Fischer (Fiso) dang mach ho cua X1 va X2. diém) | Dap an: cHo utton HOH,C—}-oH CHAOH cH,0n X1(CsHyO5) X2 (CgH)20,) ) Dang mach hg ctia X1 nim trong cn bing véi cée dang mach vong hemiacetal furanose tong ting. Vé cOng thire Haworth (Havoc) ciia cdc dang mach ving furanose cé thé c6 celia X1. Dap An: on ott on oH dd uo cno si on On HOH non oh, bn Hou,c—-ou Ho—-cH,0n CHOI CHO : | oN a sad oo 0 Tow XI x1 fi oH ou On" noch, of ©) X1 phan ing véi phenylhydrazine tao thinh phenylosazone X3. Vé cdng thae chiéu Fischer (Fiso) ciia X3 va cho biét X3 c6 hoat dong quang hoc khong? Dap ain: HOH,C on cH,OH Con X3 Khéng quang hoat 2. a) Ve céng thire cau tao ctia cde chit VI, V2, V3, Y5, Y6 va vindoline, Biér: phn ang chuyén YI thinh Y2 la qua trinh déng vong 5 canh chita oxygen va nitrogen; Y6 va vindoline chita nhém chite alcohol bac 3 bén. Trang 6/9.Coome te Y2 (CyghlysNsO2) ° Ft wo0c Ee ¢ Lyra oe Jy ac ee 2D Mo Meo” 2 Aes Me COOME Me ome v3 aaa or hs Namiicn Meore AR | ye eo One N “OAc MeO COOMe Me Come Ne HOCOOMe YS (CysHyN20;) Y6(CasHy3N20;) vindoline (CagH34N20¢) ) VE ca ché dé xuat cho phan ting chuyén V3 thanh V4, Bier: phan img di qua giai dogn [42], sau d6 hinh thanh trung gian 1,3-ludng cue do tach loai No. Bap an: ° binge ea } oe Be " a % oO cat) * Toone Meo" On Meo N’ tn MEOr vo ope ns COOMe Me Stowe es 3. Vé cing thite cau tao ciia cdc chat tir Z1-Z3. p an. coon yt ’ = ow oe C 7 sa us ‘1 a Z1 i 22 2B VI 40 diém) 1. a) 1) Viet edu hinh electron, tinh bic lign két cua T2 va jon l° (coi gidn d6 orbital phan tr cua 1 va ion 1 tuong ty gidn dé cia F2), So sénh d6 dai lin két -T trong b va ion I Dap an: Si dung ede AO ha tr cua 1 dé hop tao MO, 06: Cau hinh electron eta a: (635)(os5 (csp) (rspx* Ry"Nensps tn) Cau hinh electron ciia 12°: (655)(oss")P(65p2) (5p Hspy)?(Aespx"? Tspy"") Bac lién két cua I va Ip’ Han Iuot 1a 1 va 1,5 nén d6 dai lign két euia [2 lim hon ota (viét cdiu hinh ma khong ghi ro AO tham gia t6 hop tao MO (5s, Sp) thi dieoe mira sé diém) ii) Giai thich tai sao ion In" ¢6 thé dimer héa tao thanh ion Le vi 6 2 logi dé dai lién két [1 khae nhau. Dap an. M6i ion Ie* c6 1 MO phan lién két spy* chita 1 electron déc than, nén hai ion Is’ cé thé twong tae v6i nhau tao thinh lign két, hinh thanh ion 12°. Sy t6 hop gitta hai MO mespy* cia hai ion I>° S@ 30 ra 2 MO, trong d6 1 MO €6 ning Iuong thap chita 2 electron vi 1 MO ¢6 nang lurgng cao trong. Trong ion 1a, lign két I-I duge hinh thanb tir sy t6 hop cia céic AO Sp sé bén hon va do Trang 7/946 c6 d6 dai ngin hon lién két IT duge tao thanh tir su t8 hgp etia 2 MO phan lign kat 5p," (Gidi thich theo eich khéc diing van duge dit diém) b) i) Xéc dinh céng thtre héa hoc cua cac chat tir UI dén U0. Dap an: Vi_ UI la don chat chita halogen 6 thé rin trong digu kign thudng va lam déi mau hé tinh bot nén la Ip, khi dé U2 la KI. Tay theo diéu kign, [2 phan ting véi Fz e6 thé cho sin phim IF, khde nhau, vi Ud cé dang hinh chir T nén phai li IF3. Khi I> phan img véi AgF 6 0°C tao ra U6 va U7 trong dé U7 mau vang it tan trong nude nén U7 1d Agi va U6 la IF. Khi [2 phan img voi Os tao Fa 10, trong d6 oxygen chiém 22,10% phan tram vé khoi Iuong nén U9 la Os. Vi U10 chi c6 mt cation chia 4 nguyén ti U (U li 1) chiém 57,33% vé khdi lung nén UL0 Ia (14)(AsFo)2 chat phan img trong so d6. ; UT: Agh; U8: HIOs; U9: 1.05; UL0: Vay UL: Is; U2: KI; U3: Cul, U4: (La)(AsFo)2 ii) Viét cae phuong trinh phan ting tir (1) dén (10) va cho biét va (4), (5), (©), (7), (9), (10). Dap an: 1) b+ 2K2S203— K28s0¢+ 2KI 2) 4KI + 2CuSOs I+ 2Cul + 2K2S0« dk thich hop Seibich hon oir, tro cia UI trong timg phan img 3) b+3F2 4) 2 + NaHs—> No + 4HI bb c6 vai tro 1a chat oxi hé 5) 3le+ 2P4s + 6H20 —> 2H5POs + 6H 1h c6 vai tro 1a chat oxi hi 6) b+ AgF “S IF + Agi Ib vita la chat oxi héa vita la chat khit 7) lo+ SCls + 6H20 — 2H105 + 10HCI 1 c6 vai tro la chat khir 8) 2HIO3 + 5SnCl + OHI» 2+ SSnCly + 6120 9) 2+ 303 > LO» 1h €6 vai trd 1a chat khir 10) 21) + 3AsFs S85. (14)(AsFa)2 + AsFs Ip 6 vai tro la chat khit, 2. a) Dung dich A chira Fe** 0,010 M va H’ 0,50 M. Bang tinh toan hay danh gid kha nang oxi héa Fe** trong dung dich A khi dé can bing véi kh6ng khi. Dap an: Phan ting > SPT _ 1 y3095 4Pe* + Ong) +4 = 4Fe +220 K = 10 06 = 107 ‘Thanh phan gidi han sau phan ting (1) la: C(Fe*') = 0,01 M, C(H") = 0,49 M can bing v6i Oza) Ciich 1: Tink theo can bing véi Oza) Tinh theo cin bing Fe? + 2H20 = 4Fe? + O2qy + 4H" K = 10399 001 p(O2) 0,49 0 (0,01-4x) 4x plz) (0,49+4x) ‘Theo dinh luat tac dung khdi lrgng (4x)" po, (0,49+ 4x)" 10° ; v6i p(O2) = 0,208 va gia thiét 4x<<0,01 53.10" << 10-°M. Vly Fe?’ c6 thé bj oxi héa hoan toan, Clich 2: Tinh theo can bing véi O2 trong dung dich Theo can bang O2jx) = Oras) K= 102? {0,] 729 * — [0,]= 107" 0,208 = 2,50x10*M Trang 8/9Can bang véi O2 trong dung dich APE + 2H20 = Fe + Ona + 4H" K = 107095292 =19-987 Cc ool 2,5x104 0,49 0 (0,01-4x) 4x 25x10 (0,49+4x) (4x)'2,5*10 “(0,49 +4x)* (0,01= 4x)" Vay Fe* 06 thé bj oxi héa hoan todn. | Néu khéng lam tron céc phép tinh trung gian thi [Fe?*] = 5,54x10-"° M b) Tinh %Fe** trong dung dich A da bi oxi héa thanh Fe 6 thoi diem lay lim thi nghiém. Dap an. Thanh phan ban dau cua dung dich C(Fe*} M; C(Fe?*) = (0,01%10/10,5 — x) M; CCH’) = (0,5%10/10,5 — x) = (5/10,5 — x) M; (SCN) = 0,01%0,5/10,5 = 1/2100 = 4,76%10-4 M Can bang Fe + SCN’ = FeSCN* 6 =10°" > (4x) = [Fi 53x10" M << 10“ M SCN’ +H” = HSCN Ky" Theo dinh luat bao toan nong do C(Fe**) = [Fe’'] + [FeSCN?"] qa (SCN) = 1/2100 = [FeSCN**] + [HSCN] + [SCN] @) C(H’) = 5/10,5 — x= [H"] + [HSCN] @) Theo dinh luat tac dung khéi luong tasen}=""iseny 4) [FeSC —LFeSCN’] 5 sen rey? a Vi [HSCN] < C(SCN’) = 4.76104 << CCH) = 0,5/10,5 va gid thiét x << CCH’) Nén tir (3) —+ [H"] = 5/10,5 M Thay vio (4) —» [HSCN] = To 10,5 5N ]=3,696x[SCN-] = 9x10 won © = (3,696+1)[SCN"] Thay vao (2) véi [FeSCN’ [SCN] =9,9510°M, [HSCN] = 3,68x10~ M. _[FeSCN 9x10" [SCN]8 — 9,95x10° 10> Thay vio (1): C(Fe**) = [Fe**] + [FeSCN*] = 8,44x10% + 9x10° = 9,34x10-5 M = x << (5/10,5), nén gia thiét ding, %Fe** bj oxi hoa = 9,34%10°(0,01«10/10,5)*100% = 0,98% Thay vio (5) — [Fe*] =8,44x10°M Néu giai 6 hop cac phuong trinh (2 - 5) ra4 4 tong ty, la [Fe*'], [HSCN], [SCN7], [H"] cing ra dap én HET Trang 9/9