KY THI CHỌN HỌC SINH GIỎI QUỐC GIA THPT NAM 2015 - MÔN HÓA HỌC

BQ GIAO D1)C vA DAo T~o KY THI CHQN HQC SINH GI()J ouoc GIA THPT NA.M2015 Mon: HoAHOC Thoi gian: 180 phut (kh6ng ki thai gian giao d€) Ngay thi thir nhat: 08/0112015 ~iN.-H~ I BANCHINH BAN C ~TTT I I (f)€ thi co 03 trang, g6m 05 cdu) I Cho: H = 1; C = 12; = 16; Na = 23; Cl }rnor1X-1 = 0,082 atm·L·rnorIX-I = 35,5; K = 39; Mn = 55; T(K) = t(°C) + 273; R = 8,314 Csu I (3,0 diim) Cho ch~t N=SF3 long tac dung voi [XeF][AsF6], thu duoc san pham la [F3SN-XeF][AsF6] (1) trang thai ran, bi dun nang, (1) chuyen [F4SN-Xe][AsF6] (2) Phan irng cua (2) voi HF, thu duoc san pham [FsSN(H)-Xe][AsF6] (3), [F4SNH2][AsF6] (4) va XeF2 a) Sir dung mo hinh su dAy cua cac c~p electron hoa tri (YSEPR), d~ xu~t cciu true cua anion o 6r, cation cac hop chat (1), (2), (3), (4) va cho biet (co giai thich) cation nao co lien k~t [AsF giira S va N ngan nhat, dai nhat b) Cho bi~t trang thai lai hoa ella nguyen nr hru huynh cac hop chftt (1), (2), (3) va (4) SU dung thuyet obitan phan nr (thuyet MO) d~ giai thich tai nang hrong ion hoa thu nh~t cua phan tu nitO' (1501 kJ·rnor1) l&n hon nang luqng ion hoa thu nh~t Clla nguyen tu nitO' (1402 klrnor1) Cau II (4, diim) D6t chay hOM toan 3,6 gam hqp ch~t hfru cO'X th~ b~ng rnQt luqng du oxi rnQt born nhi~t luqng kS Ban dfiu, nhi~t luqng kS chua 600 gam nu&c, 25°C Sau phan ilng, nhi~t dQ Cllah~ la 28°C; co 11 gam CO2(k) va 5,4 gam H20(1) duqc ti;lothanh Gia thiSt, luqng nhi~t bi h~p th\l boi oxi du va cac san phfun phan ilng la khong dang k~ Xac dinh cong thue phan tu Clla X Xac dinh nhi~t dung clla nhi~t luqng kS (khong bao g6m 600 gam nu&c) Xac dinh nhi~t sinh tieu chuAn (!lH~.298) Clla X Cho biit: !lH2.298 Clla CO2(k) va H20(l) lfin luqt la -393,51 va -285,83 kJ'mor1; Nhi~t dung rieng Clla nu&c la 4,184lg-1'K-1; BiSn thien nQi nang Clla phim ilng d6t chay mol X {y 2SoC, /).Ui98 = -2070,00 kJ·morl Cau III (4,0 diim) Trong rnoi truemg axit, r bi oxi hoa boi BrO~ thea phan ung: 9r + BrO~ + 6H+ ) 31~ + Br- + 3H20 (I) Thvc nghi~m cho biSt, a mQt nhi~t dQ xac dinh, bi~u thuc t6c dQ clla phan ilng co d~ng: v= d[BrO~] = k[H+]2[BrO~][r] (II) dt v&i k la hkg s6 t6c di) Clla phan ilng a) Cho bi~t b?c Clla phan ilng (I) B?c clla phan ung b~ng bao nhieu n~u phan ilng duqc th\Ic hi~n dung dich d~m co pH = 3? b) NSu th\Ic hi~n phan ilng dung dich d~m co pH < thi nang luqng hOi;lthoa clla phim ilng co thay d6i khong? Ti;lisao? trang 113 Co ch~ cua phan img (I) diroc d~ nghi nhir sau: H2BrO; + IBr02 r + 1- IBr02 k2) + H20 12 + BrO; kJ (I) (nhanh, can bang) (2) (cham) (3) (nhanh) BrO; + 21- + 2H+ k4) 12 + BrO- + H20 (4) (nhanh) zr ks 12 + Br- + H20 (5) (nhanh) (6) (can bang) BrO- + + 1- k6) k_6 + 2H+ r a) Co th~ ap dung nguyen li nong dQ dirng eho cac ti~u pharr trung gian H2BrO; va IBr02 diroc khong? Tai sao? b) Chung minh rang co che phu hQ'Pvoi bieu thirc t6c dQ (II) tren, tir tim bieu thirc cua k Cau IV (5,0 didm) Cac kim loai nhom IA nhir Li, Na, co heat tinh hoa hoc cao MQt s6 hQ'Pch~t cua chung co irng dung rong rai nhieu linh V\lC a) Vi~t cac phirong trinh hoa hoc xay d6t chay tirng kim loai Li, Na khong b) Hien nay, mot s6 hQ'P chat chua kim loai kiem la cac v~t li~u tiem nang cho pin nhien lieu boi kha nang hru trfr hidro cao, LhN la mot nhfrng hQ'Pch~t nhir vay MQt pharr tfr LhN co kha nang phan (mg v6i hai phan tu H2 qua hai phan (mg thea sa d6 sau: LhN + H2 A + B A+H2 C+B Hoan cac phuang trinh hoa hQCva cho bi~t cong thuc pharr tU cac hQ'Pch~t A va B c) MQt hQ'Pch~t khac vCriham luqng hidro cao cling thu hut nhiSu S\l quan tam va nghien CUula NH3BH3 Tuy nhien, mQt nhuQ'c di~m Clla hQ'Pch~t 1£1chi b~t d~u giai phong hidro nhi~t dQ kha cao (khoang 150°C), kh6ng thich hQ'Pcho cac phan (mg pin nhien li~u D~ kh~c ph\1c nhuQ'c di~m nay, nguai ta cho NH3BH3 phan (mg v6i hQ'Pch~t B thea t1 l~ moll: I, thu duQ'cmQt mol H2 va mQt mol hQ'Pch~t m6i D Vi~t phuang trinh hoa hQc t~o D phan (mg tren Cho bi~t cong thuc du t~o CllaD va tr~ng thai lai hoa clla cac nguyen tfr B, N hQ'Pch~t d) Cac tinh toan Ii thuySt va th\lc nghi~m d~u chi rkg, hQ'Pch~t D co kha nang d~ hidro hoa o nhi~t dQ th~p han dang k~ so v6i NH3BH3 (khoang 90°C), nha co S\l tham gia Clla Li hQ'Pch~t Hay d~ xu~t ca chS hai bu6c cho S\l giai phong mQt pharr tu H2 tir mQt phan tfr D MQt lo~i qu~g chi chua Mn02 va t~p ch~t tra Can chinh xac 0,5000 gam qu~g tren r6i cho vao binh c~u co nhanh Them tir ill vao binh khoang 50 mL dung dich HCI d~c Dun nong dSn m~u qu~g tan hSt, chi l~i t~p ch~t tra H~p th\1 hoan toan Ch thoat bkg luqng du dung dich KI, thu duQ'c dung dich X Chuy~n toan bQ X vao binh dinh muc 250 mL, them nu6c dt d~n v~ch muc, l~c d~u Chu~n dQ 25,00 mL dung dich bkg dung dich chuk Na2S203 0,05 M (chi tm h6 tinh bQt) thi hSt 22,50 mL a) Vi~t cac phuang trinh hoa hQc xay b) Tinh ham luqng % thea kh6i luqng Clla Mn02 qu~ng tren Cau V (4,0 didm) MQt nhUng thu6c thu d~c trung d~ tim ion Pb2+ (trong dung dich) la Na2Cr04 Cho bi~t, kSt tlla PbCr04 mau vang, tan dUQ'ctrong dung dich NaOH du; do, k~t rna PbS mau den, khong tan duQ'c dung dich NaOH trang 2/3 ,Them til til 0,05 mol Pb(N03)2 vao 1,0 L dung dich X gorn 0,02 mol Na2S va 0,03 mol Na2Cr04, thu duoc h6n hop Y gbm phan k~t tua va phk dung dich (coi th~ tich khong thay d6i them Pb(N03h vao dung dich X) 1.Tinh pH cua dung dich X 2, Bang l~p luan va danh gia hop li, chimg to rang, pH phan dung dich cua Y x§.pxi bang 7,0 3, Tinh [Cr20~-] va [Pb2+] phan dung dich cua Y 4, Trinh bay each thiet l~p sa db pin duoc ghep boi dien cue chi (Pb) nhung h6n hop Y va di~n eire hidro tieu chuan Cho bdt: pKa1(H2S)= 7,02; pKa2(H2S)= 12,90; pKa(Hcr04") = 6,50; E~b2+!Pb = -0,126 V pKs(PbS)= 26,60; pKs(PbCr04)= 13,70; pKs(Pb(OHh)= 14,90 2CrO!- + 2H+ ~ , (VC1l Cr20~- + H20 K= 3,13.1014 Ig'P, = Ig'Ppb(OH)"" = -7,80 = 19'PPb(OHh= -17,20 Pb2++ 2H20 ~ Pb(OH)2(dd) + 2H+ 19'P2 Pb2+ + 3H20 ~ Pb(OH); + 3H+ 19'p = 19'p = -28 00 Pb(OH)3" ' , pKa = -lgKa; pKs = -lgKs; a 25 C: 2,303RT F = 0,0592 V) H~T * Thi sinh khong duoc su dung tid lieu; thi khong giai thich gi them * Giam trang 3/3 " _', KY THI CHON HOC SINH GIOI QUOC GIA THPT NAM2015 , Mon: HoA HQC Thai gian: 180 phut (khong ke thai gian giao Ngay thi thir hai: 09/0112015 (f)~ thi 03 trang, g6m 05 cdu) ' ae) co M{}t s6 ki hi~u vi~t t~t: dd: dung dich, I: loang, Me: metyl, Et: etyl, Ac: axetyl, t-Bu: tert-butyl, Ph: phenyl, Py: piridin Call 1(4,5 adm) Cho cac chat sau: Al A2 A3 A4 AS A6 A7 a) M6i ch~t tren phan (rug cong electrophin v61 hQ'Pch~t loai E-Nu (E+: tac nhan electrophin, Nu': tac nhan nucleophin) thea ti l~ moll: (; nhiet dQ th~p va (; nhiet dQ cao tao cac san pham khac Hay cho biet cong thirc du tao san pham chinh va giai thich Gia thiet qua trinh phan ling, khung cacbon cua cac ch~t ban dfiu khong thay d6i b) Nhirng chit nao phan (rug cong duoc voi anhidrit maleic thea ti l~ moll: (; nhiet dQ cao? Ve cong thirc lap th~ cua san pham thu diroc Bi~t rang phan (rug cong dong vong co sir tham gia d6ng thai cua 4n+2 electron 1t (n = 1,2, ) thi dS xay Hidrocacbon H (CI4HIO)tach tu nhva than da, chi g6m eac vang c~, t6n t~i (; d~g tinh th~ hinh la, khong mau, nong chay (; 101°C Dung dich cua H benzen co kha nang phcit huynh quang mau xanh Khu H bfulg NalC2HsOH, thu duQ'c chit I (CI4HI2)' Khi cho H phan Ung v6i HN03/H2S04, thu duQ'c h6n hQ'Pcac mononitro co cling cong thuc phan ill CI4H9N02 Khi cho H phan Ung v6i Br2/CCl4 (; nhi~t dQ th~p, thu duQ'ch6n hQ'Pkhong quang ho~t g6m ba ch~t Xl, X2 va X3 co clmg cong thuc phan tu CI4HIOBr2.Du6i tac d\l11geua nhi~t, ca Xl, X2 va X3 d~u t~o chit X (CI4H9Br) Oxi hoa H bfulg K2Cr207/H2S04 di~u ki~n thich hQ'P,thu duQ'cch~t K (CI4Hg02) (; d~ng tinh th~ hinh kim, mau da cam, khong mlii va nong chay (; 207°C Xu Ii K v61 dung dich ki~m, sau axit hoa h6n hQ'P san ph~ thi thu dUQ'cch~t L (CI4HIO03) khong quang ho~t Dun nong L co m!).tH2S04 d!).c,thu duQ'c mQt cac san ph~m la ch~t M (C2gHI604)' a) Xac dinh cac hQ'Pch~t H, I, K, L, M, X, Xl, X2 va X3., HO b) Khi xu Ii 9-fluorencacbinol (cong thuc hinh ben) moi truang axit thi thu dUQ'cH D~ xu~t cO'ch~ giai thich qua trinh t~o H c) Vi~t sa d6 di~u ch~ H (cac tac nhan vo cO'co s~n): (i) Til o-nitrobenzandehit va axit phenylaxetic (ii) Til naphtalen va anhidrit sucxinic, 9-Fluorencacbinol Call II(3,0 aiJm) Cho cae hQ'Pch~t cacbonyl sau: * H1) " 0 H, )lMe Me/! Me H, Ph/f o )lMe Me~OEt o Me~Me Ph ABC D E F Cac h9'P ch~t cacbonyl co nguyen tu hidro (; vi tri a co th~ chuy~n hoa sang d~ng enol thea can b~ng sau: o )l RI/ Y/R2 H Nguyen tu hidro nhom OH enol phan Ii t~o anion enolat thea can bfulg sau: Trang 1/3 (A~> OH Rl~R2 + H+ Rl~R2 Ka(OH) a) So sanh (co giai thich) gia tri pKe cua cac hQ'Pch~t A, B, C va D d6i voi qua trinh enol hoa xay voi cac nguyen nr hidro dtroc danh d~u (*) b) Cho: F E D Chat -0,41 1,00 8,33 pKe 9,41 10,00 10,94 pKa(OH) Tinh gia tri pKa(CH) d6i voi sir phan li nguyen nr hidro linh d9ng nh~t thuoc lien k~t C-H cua cac hQ'Pch~t D, E va F c) Dira tren cac gia tri cho cau (b), tinh g§n dung gia tri pKe, pKa(OH) va pKa(CH) cua dietyl malonat Enamin co thS diroc tao cho andehit hoac xeton phan irng voi amin b~c hai co xuc tac axit a) Xiclohexanon phan ung voi pirolidin tao enamin H thea sa db sau: +6~ CN-OH DS xu~t co che giai thich qua trinh tao enamin H b) Longifolen la mot sesquitecpen co phan nhua thong va tinh d~u cua mot s6 cay la kim, duoc dung cong nghiep huang li~u, mi pham, Chat Y diroc su dung dS t6ng hQ'P longifolen Til' xiclopentadien, ch~t Y duqc t6ng hQ'Pthea sa db sau: ~ O _ ({o o +HCl I - :::::: Mg/ete, to CO2+ K 3.HP SOCI2 I Enamin X (C9HJSNO) clf) 2.HP+ PhCH20COCl M hv - '''~ CH2Ph [2+2] - ::::::: L Y - XaC dinh cac ch~t I, K va M _Xac dinh cong thuc c~u tdung dich h6n hop bang dung dich chuan HCl voi chi thi thimolphtalein thi phan irng xay nhir sau: H+ + OR ~ H20 H+ + pol- ~ HPO/ Khi chuan d(>h6n hop bang dung dich chuan HCl voi chi thi metyl thi phan ling xay nhir sau: H++OR~H20 2H+ + pol- ~ H2P04- K~t hop phep chuan d(>se tinh duoc nong d(>m6i ch~t KOH va Na3P04 dung dich h6n hop III each ti~n hanh Chudn bi mJu Dung pipet l~y 10,00 mL dung dich mftu can phan tich (trong 19 miu), chuyen vao binh dinh rmrc dung tich 100 mL Them mroc dt vao binh d~n vach dinh mire, l~c d~u diroc dung dich A Phep chudn Bmrc 1: Chuyen dung dich chuan HCllen buret va di€u chinh d~n vach O B1f()'C2: Dung pipet l~y 10,00 mL dung dich A cho vao binh tam giac 250 mL, them 2-3 giot chat chi thi thimolphtalein, dung dich co mau xanh Nho til tir dung dich chuan HCI 0,05028 M tir tren buret d~n dung dich binh tam giac chuyen sang khdng mau thi dirng l baa Truong: Chtr ki cua thi sinh: HQi d6ng coi thi: Can hi} coi tbi thrr nhat (Ki va ghi ro ho ten) danh: / Can hi) coi tbi thrr bai (Ki va ghi ro ho ten) So phach (Do HE) cham thi ghi) 1/2 DQ GIAo DVC vA DAo T~o KY THI CHQN HQC SINH GI()I ouoc GIA THPT NAM 2015 Mon thi: Thtrc hanh Hoa hoc Ngay thi: 10/0112015 DE THI CHiNH THUC Lm THI THUC HANH PHIEU DANH GIA vA TRA • (D~ thi chinh thirc) sa phach (Do HD cham thi ghi) Liru y: Thi sinh: KHONG ghi s6 baa danh, ho ten, chtr kY vao phieu - Bi tnr diem: NSu xin lai m~u (chi duoc lfin) hoac xin them dung dich chuan hoac lam va dung cu (buret, pipet, binh dinh mire, binh tam giac) thai gian lam bai, Can b9 coi thi: phai ghi "co" hoac "khfmg" vao Phin PhAn 1: Ph§n ky nang thuc hanh (0,4 di~m) Ghi chu C6/Khong TT Xin lai m~u Xin them dung dich chuan HC1 Lam va dung cu PhAn 2: Ph§n k~t qua thi nghiem (1,6 di~m) Thi sinh viSt ki hieu m~u ghi tren 19dung m~u tuong ling voi kSt qua bao cao Ph§n danh cho can hi} ch~m thi Diem (toi da 0,8 Sai so tirong doi (%) diSm/mQt chi tieu) Ph§n danh cho thi sinh Nong dQcac chat m~u (mollL) CKOH Ki hi~u m~u = CNa,PO, = Ph§n 3: Di~m bai thi th,!c hanh: Ph~n ky nang th\fc hanh Ph~n kSt qua thi nghi~m ? ? "' , " d'" lem: b'"ang so" Tong , hang ch-u: ••••••••• •.••••••••••••••• 212 [...]...BO GIAo DUC vA DAo TAO DE THI CHiNH THUC KY THI CHQN HQC SINH GIOI ouoc GIA THPT NAM 2015 Mon thi: Tb,!c hanh Hoa bQC Thai gian: 90 phut (khong k€ thai gian giao d€) Ngay thi: 10/01 12015 PHIEU DANH GIA VA TRA LOI THI 'rmrc • HANH (D~ tbi chinh thirc) HQ va ten thi sinh: sf> baa Truong: Chtr ki cua thi sinh: HQi d6ng coi thi: Can hi} coi tbi thrr nhat (Ki va ghi... (Ki va ghi ro ho ten) So phach (Do HE) cham thi ghi) 1/2 DQ GIAo DVC vA DAo T~o KY THI CHQN HQC SINH GI()I ouoc GIA THPT NAM 2015 Mon thi: Thtrc hanh Hoa hoc Ngay thi: 10/01 12015 DE THI CHiNH THUC Lm THI THUC HANH PHIEU DANH GIA vA TRA • (D~ thi chinh thirc) sa phach (Do HD cham thi ghi) Liru y: Thi sinh: KHONG ghi s6 baa danh, ho ten, chtr kY vao phieu nay - Bi tnr diem: NSu xin lai m~u (chi duoc 1... binh dinh mire, binh tam giac) trong thai gian lam bai, Can b9 coi thi: phai ghi "co" hoac "khfmg" vao Phin 1 PhAn 1: Ph§n ky nang thuc hanh (0,4 di~m) Ghi chu C6/Khong TT 1 Xin lai m~u 2 Xin them dung dich chuan HC1 3 Lam va dung cu PhAn 2: Ph§n k~t qua thi nghiem (1,6 di~m) Thi sinh viSt ki hieu m~u ghi tren 19dung m~u tuong ling voi kSt qua bao cao Ph§n danh cho can hi} ch~m thi Diem (toi da 0,8 Sai... danh cho can hi} ch~m thi Diem (toi da 0,8 Sai so tirong doi (%) diSm/mQt chi tieu) Ph§n danh cho thi sinh Nong dQcac chat trong m~u (mollL) CKOH Ki hi~u m~u = CNa,PO, = Ph§n 3: Di~m bai thi th,!c hanh: 1 Ph~n ky nang th\fc hanh 2 Ph~n kSt qua thi nghi~m ? ? "' , " d'" lem: b'"ang so" Tong , hang ch-u: ••••••••• •.••••••••••••••• 212