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8/7/2019 Tuyen Tap de Thi Hoc Sinh Gioi Hoa 2010 Part 2
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THPT CHUYN H N I
Cu I: ( 2.0 i m)M t terpen X th ng g p trong thin nhin c t ng h p theo s sau
4metylpentan1,4diol d n xu t dibromua bromanken Mgete khan
Grignard G X
Cho ch t G ph n ng v i s n ph m sinh ra khi cho isopren ph n ng v i but3en2on s thu c ch t c nt ng h p X.
1. Hon thnh chuy n ha ny b ng cc cng th c c u t o t ng ng.2. Cho bi t tn thng th ng v ng d ng c a s n ph m.
Cu II: (2.0 i m)
Hydrocacbon A l m t ch t r n c tnh d o, n h i (11,76% H theo kh i l ng) c trong m cy cao su. Ozonphn A cho C16H16O6, khi cho m t mol ch t ny vo n c nng thu c 2 mol andehit levulinicHOC(CH2)2COCH3.
Hydrocacbon B (11,11% H theo kh i l ng) l ch t t ng h p u tin c thnh phn gi ng A nh ng khng ctnh d o v tnh n h i gi ng nh A. B c t o thnh khi un nng hydrocacbon C c m t natri ; C c thnhph n nh tnh gi ng B
1. Cho bi t CTCT c a A, B, C2. S v ng m t c a axetylaxeton trong s n ph m c a chng ch ng t A c c tr ng g ?
Cu III: (2.0 i m)Qu trnh t ng h p ph c Pt(CH3NH2)(NH3)[CH2COO]2 l thu c ch ng ung th m i c hi u q a cao l i t c
v t cho ph n ng ph . Qu trnh t ng h p thu c ny nh sau:
K2PtCl4 oKIdu
70 C A (dung dch nu)3 2+ CH NH
1:2 B (tinh th sng)4 2 5HClO v C H OH
C (r n nu)3 2NH /H O D (tinh th vng kim, phn c c) 2 3Ag CO du v axit malonic E (tinh th vng nh t)
Ph ng php ph IR cho bi t trong h p ch t C c hai lo i lin k t Pt I khc nhau v C c tm i x ng. Bi tMC = 1,88MB. Cho bi t s ph i tr c a platin lun khng i trong qu trnh t ng h p v platin lun gi d ng laiha dsp2 trong cc ph c
1. Vi t CTCT cc s n ph m A, B, C, D, E.2. Trong s n ph m E th khng c ch a iot. Nh v y t i sao lc ban u ph i chuy n K2PtCl4 thnh A.3. M c ch c a vi c s d ng Ag2CO3 trong ph n ng cu i l g ?
Cu IV: (2.0 i m)L thuy t lai ha do Carl Linus Pauling xu t v n l l thuy t chu n xc nh t trong vi c gi i thch d ng hnh
h c c a cc ch t v c . V y y chng ta s th gi i quy t nh ng m hnh sau y
1. Gi i thch d ng hnh h c c a TiCl4 theo thuy t lai ha ?2. Gi i thch d ng hnh h c c a ph c Fe(CO)5 theo thuy t lai ha ?
Cu V: (2.0 i m)Kh NO k t h p v i h i Br2 t o ra m t kh duy nh t trong phn t c ba nguyn t1. Vi t ph ng trnh ph n ng2. Bi t Hp < 0; Kp(25
oC) = 116,6. Tnh KP 0oC, 50oC. Gi thi t r ng t s gi a tr s cn b ng gi a 0oC v
25oC c ng nh 25oC v i 50oC u b ng 1,543. Xt t i 25oC, lc cn b ng ha h c c thi t l p th cn b ng s chuy n dch th no n u
a. Tng l ng NOb. Gi m l ng h i Br2
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c. Gi m nhi t d. Thm kh N2 vo khi
(1) V = const ;(2) Pchung = const
Cu VI (4.0 i m)Guaiol (C15H26O) l m t ancol r n tr ng thi tinh th c c u trc terpen. Ancol ny c phn l p t tinh d u
cy g Bulnesia sarmienyi. Khi dehydrat ha guaiol b ng l u hu nh th thu c m t hydrocacbon th m mu xanh
da tr i khng ch a vng benzen X (C15H18). Khi ha tan hydrocacbon th m ny vo axit sunfuric c th mu xanhbi n m t. Cho n c vo dung dch ny th X c ph c h i nguyn d ng. R t kh hydro ha guaiol b ng hydroc xc tc. Qua m t lo t cc chuy n ha d i y ta nh n c m t d n xu t c a naphtalen (A l s n ph m duynh t c a qu trnh ozon phn)
1. Xc nh c u trc c a guaiol v X n u bi t trong phn t guaiol th nhm hydroxyl g n v i nguyn tcacbon b c ba exocyclic c a h vng
2. Gi i thch mu xanh da tr i c a X v nu l do n b m t mu trong dung dch axit sunfuric c3. Xc nh CTCT A, B v gi i thch s t o thnh A. C bao nhiu m nh isopren trong ch t XCu VII (2.0 i m)
C th tch c rhodi ra kh i cc kim lo i qu khc b ng cch sau: M t m u b t qu ng rhodi c tr n v iNaCl v un nng trong dng kh clo. B r n thu c ch a m t mu i ch a 26,76% Rhodi v kh i l ng. B r nny sau c ha tan vo n c, l c dung dch thu c r i c bay h i thu c tinh th B ch a 17,13% rhodi.Tinh th c lm kh 120oC n kh i l ng khng i (kh i l ng m t i l 35,98%) r i un nng t i 650oC.R a b r n thu c b ng n c ta c rhodi tinh khi t
1. Xc nh cng th c A, B2. Khi m t l ng d H2S c s c qua dung dch mu i A th t o thnh k t t a C. Thnh ph n h p th c c a
h p ch t ny ch a 47,59% S. Xc nh cng th c C3. Gi i thch t i sao c n ph i r a b ng n c nng b c cu i cng. Vi t cc ph n ng x y ra
Cu VIII: (4.0 i m)Cc cacbohydrat t nhin u c t ng h p quang ha trong cy xanh. Tuy nhin cc cacbohydrat khng c
trong t nhin c th c t ng h p b ng con ng nhn t o. S d i y l s t ng h p L-riboz . Honchnh s t ng h p sau:
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THPT CHUYN H N I
Cu I: (2.0 i m)
1. Cng th c c u t o cc ch t lin quan (1,75 i m)
2. Ch t ny l -bisabolol th ng dng trong cng nghi p m ph m (0,25 i m)
Cu II: (2.0 i m)1. Cng th c th c nghi m c a A l (C5H8)x, n l cao su t nhin. Cc cng th c th c nghi m c a B v C l n
l t l (C2H3)y. B l cao su t ng h p polibutadien cn C l buta-1,3-dien (1,5 i m, m t i m cho m i c ut o).
2. Ta c:
Nh v y s v ng m t c a axetylaxeton trong s n ph m ozon phn ch ng t cao su thin nhin c c u trc u - u (0,5 i m cho l p lu n)
Cu III: (2.0 i m)1. Cng th c c u t o cc ch t lin quan (1,25 i m ; 0,25 i m cho m i c u t o)
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2. ch c ch n thu c s n ph m cu i th bu c B ph i d ng cis nn K2PtCl4 ph i c chuy n thnh A(0,25 i m)
3. Ag2CO3 ph n ng v i D theo ph n ng D + Ag2CO3 = DCO3 + 2AgI sau DCO3 ph n ng v i axitmalonic t o thnh E (0,5 i m)
Cu IV: (2.0 i m)1. Do i v i Ti lc ny th nng l ng c a AO 3d gi m th p h n so v i AO 4p nn s c s t h p gi a 1
AO 4s v 3 AO 3d t o thnh 4 AO lai ha sd3 h ng v 4 nh c a m t t di n u (1 i m)2. Do CO l ph i t tr ng m nh nn s y cc electron c a Fe v tr ng thi c p i. Lc ny 1 AO 3d tr ng
s t h p v i 1 AO 4s tr ng v 3 AO 4p tr ng thnh 5 AO lai ha dsp3 h ng v 5 nh c a m t l ng thptam gic.(1 i m)
Cu V: (2.0 i m)1. 2NO(k) + Br2(h i) 2NOBr(k) H > 0 (0,25 i m)2. Do ph n ng thu nhi t nn c lin h KP t i 0
oC < KP (25oC) < KP (50
oC)V y KP t i 0
oC = 1/1,54.KP = 116,6 / 1.54 = 75,71KP t i 50
oC = 1,54.KP = 116,6.1,54 = 179,56 (0,25 i m)3. Xt s chuy n d i cn b ng ha h c t i 25oC
Tr ng h p a v b v nguyn t c c n xt t s :
2NOBr
NO
PQ
P
Sau so snh Q v i KP k t lu nTuy nhin y khng c i u ki n l p lu n theo bi u th c ny nn ta s d a vo nguyn l LeCharteliera. N u tng l ng NO th cn b ng dch chuy n sang ph i (0,25 i m)b. N u gim l ng Br2 th cn b ng ha h c dch chuy n sang tri (0,25 i m)c. N u gi m nhi t th cn b ng dch chuy n sang tri ch ng l i chi u gi m nhi t (0,25 i m)d. Thm N2 l kh tr+ N u V = const th khng nh h ng t i cn b ng ha h c do N2 khng gy nh h ng lin h no (theo
nh ngha p su t ring ph n)+ N u P = const ta xt lin h
N u ch a c N2 th P = PNO + PBr2 + PNOBr (a)N u c N2 th P = PNO + PBr2 + PNOBr + PN2 (b)
V P = const nn Pi = PiLc xt Q theo bi u th c lin h trn v so snh t ng quan v i KP
- Q = KP: khng nh h ng- Q > KP: cn b ng chuy n dch sang tri Q gi m t i KP- Q < KP: cn b ng chuy n d i sang ph i Q tng t i KP (1,25 i m)
Cu VI (4.0 i m)
1. Ta c th suy lu n cng th c c a guaiol d a trn nh ng d ki n sau:- Dehydrat ha ancol ny b ng l u hu nh thu c hydrocacbon th m X mu xanh da tr i khng ch a vng
benzen. Nh v y X ch c th l d n xu t c a azulen.- b t bo ha c a guaiol l 3, t c ng v i hai vng v n cn m t n i i. V tr c a n i i s n m
i m ti p gip hai vng do v tr kh b hydro ha nh t, v khi ozon phn v tr ny s d cho s n ph mchuy n v l hai vng 6 gip nhau. M t vng sinh ra do s m r ng vng 5, m t vng sinh ra do s thu h pvng 7
- Ta d dng nh n th y r ng qu trnh chuy n ha c a guaiol khng h nh h ng t i cc m ch nhnh, vv y t v tr cc m ch nhanh trong d n xu t naphtalen ta c th suy ra c v tr c a cc m ch nhnh nytrong guaiol.
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- Do nhm OH c a guaiol n m cacbon b c ba nn cng th c c u t o c a guaiol ch c th l:
L lu n d n ra CTCT ng c 1,0 i m, c u t o 0,5 im- Cng th c c u t o X s l (0,5 i m)
2. Mu xanh da tr i c a X c c do s lin h p gi a cc n i i trong phn t X. (0,25 i m)Khi ha tan X vo axit sunfuric c mu xanh s bi n m t do s bi n m t c a h th ng lin h p trong h p
ch t c t o thnh nh hnh v : (0,5 i m)
3. Cng th c c u t o hai ch t A, B nh sau. ng CTCT m i ch t c 0,25 i m
OH
OH
O O
A B
S t o thnh ch t A c gi i thch nh sau (0,5 im)
Do cng th c phn t c a A l C15H26O nn trong A s c 3 m nh isopren (0,25 i m)Cu VII (2.0 i m)
1. Na3[RhCl6] (0,375 i m) ; Na3[RhCl6].12H2O (0,375 i m)2. Rh2S3.2H2S (0,5 i m)3. lo i b cc mu i tan, ch y u l NaCl (0,25 i m).
M i ph n ng ng c 0,125 i m2Rh + 6NaCl + 3Cl2 = 2Na3[RhCl6]
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http://vn.myblog.yahoo.com/volcmttl K THI CH N H C SINH GI I QU C GIA THI TH L P 12 THPT NM 2010
Mn: HO H CTh i gian : 180 pht (khng k th i gian giao )
( thi g m 3 trang, c 10 cu)
CU 1: (2,0 i m)1. Oleum l h n h p c t o ra khi cho SO3 tan trong H2SO4 tinh khi t. Trong h n h p c cc axit d ng
poli sunfuric c cng th c t ng qut H2SO4.nSO3 hay H2Sn+1O3n+4 ch y u ch a cc axit sau: axit sunfuricH2SO4, axit isunfuric H2S2O7, axit trisunfuric H2S3O10 v axit tetrasunfuric H2S4O13. Cho bi t cng th cc u t o c a cc axit trn.
2. Gi i thch t i sao SO3 l i d dng ph n ng v i H2O, HF, HCl, NH3 hnh thnh nn nh ng phn t tdi n t ng ng. Vi t ph ng trnh ph n ng v cng th c c u t o s n ph m.
3. Kim c ng v than ch l hai d ng th hnh c a nguyn t cacbon. Tnh kh i l ng ring v th tch molc a chng. Bi t r ng: di lin k t CC (kim c ng) l 154 pm, CC (than ch) l 141 pm, kho ng cchgi a cc l p than ch l 336 pm. NA = 6,02.10
23. Kim c ng c c u t o t ng t silic v s nguyn t Ctrong m t m ng tinh th c a kim c ng g p 4 l n s nguyn t C trong m t m ng tinh th than ch.
CU 2: (2.0 i m)
1. Vi t cng th c c u t o Lewis, nu tr ng thi lai ha v v d ng hnh h c c a cc phn t v ion sau: B2H6,XeO3, NO2
+, NO2.
2. Ph n ng c a NaNO3 trong n c v i h n h ng Na/Hg c ng gi ng nh ph n ng c a etylnitrit C2H5NO2v i hydroxylamine NH2OH c m t Natrietoxit cho cng m t s n ph m. S n ph m ny l mu i c a m t axity u khng b n ch a Nit , axit ny ng phn ha t o thnh m t s n ph m c ng d ng trong thnh ph nnhin li u tn l a. Vi t cc ph ng trnh ph n ng x y ra v vho bi t cng th c c u trc c a axit ng phnni trn.
CU 3: (2.0 i m)Cho ph n ng: A B C D (1) l ph n ng n gi n. T i 27oC v 68oC, ph ng trnh (1) c h ng s t c t ng ng l n l t l k1 = 1,44.10
7 mol-1.l.s-1 v k2 = 3,03.107 mol-1.l.s-1, R = 1,987 cal/mol.K
1. Tnh nng l ng ho t ha EA (cal/mol) v gi tr c a A trong bi u th cE
RTk A e
mol-1.l.s-1.2. T i 119oC, tnh gi tr c a h ng s t c ph n ng k3.3. N u CoA = CoB = 0,1M th 1/2 nhi t 119oC l bao nhiu.
CU 4: (2,0 i m)1. Clobenzen c momen l ng c c 1 = 1,53 D (1 h ng t nhn ra ngoi) ; anilin c momen l ng c c 2 =
1,60D (2 h ng t ngoi vo nhn benzen). Hy tnh momen l ng c c c a cc ch t sau: ortho cloanilin ; meta cloanilin v para cloanilin.
2. Tnh pH c a dung dch NH4HCO3 0,1M. Bi t r ng H2CO3 c h ng s phn li axit K1 = 4,5.10-7 ; K2 =
4,7.10-11, NH3 c pKb = 4,76.
CU 5: (2,0 i m)C th i u ch tinh th FeCl3.6H2O theo cch sau: Ho tan s t kim lo i vo trong dung dch axit clohydric 25%.Dung dch t o thnh c oxy ha b ng cch s c kh clo qua cho n khi cho k t qu m tnh v i K3[Fe(CN)6].Dung dch c c bay h i 95oC cho n khi t tr ng c a n t chnh xc 1,695 g/cm3 v sau lm l nh n4oC. Tch k t t a thu c b ng cch ht chn khng r i cho vo m t d ng c ch a c nim kn.
1. Vi t cc ph n ng d n n s k t t a FeCl3.6H2O2. C bao nhiu gam s t v bao nhiu mL dung dch axit clohydric 36% (d=1,18g/cm3) c n i u ch
1,00kg tinh th ny. Bi t r ng hi u su t qu trnh ch t 65%3. un nng 2,752g FeCl3.6H2O trong khng kh n 350
oC thu c 0,8977g b r n. Xc nh thnh ph n
nh tnh v nh l ng c a b r n.
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CU 6: (2,0 i m)1. A l ch t b t mu l c khng tan trong axit v ki m long. Khi n u ch y A v i KOH c m t khng kh thu
c ch t B c mu vng, d tan trong n c. Ch t B tc d ng v i axit sunfuric chuy n thnh ch t C cmu da cam. Ch t C b l u hu nh kh thnh ch t A v c th oxi ha axit clohiric thnh kh Clo. Vi t ccph ng trnh ph n ng x y ra.
2. T cc ch t A, B, C trn, hon thnh s sau:
- Xot A + N2 + H2O
- C + (NH3)2S + H2O Y + S + NH3 + KOH
- B + (NH4)2S + KOH + H2O Z + S + NH3- C + H2SO4 + H2S T + S + K2SO4 + H2O
CU 7: (2,0 i m)1. Vi t cng th c c u trc cc d ng enol c a dietylmalonat (1), Etylaxetoaxetat (2). Trong cc c u trc c a
(2), cho bi t d ng no b n nh t, d ng no km b n. Gi i thch?2. Cho bi t cng th c m ch h c a cc ch t sau:
O OH
OHOO
OCH3CH2
CH3
Brevicomin
O
C2H5
O
HOCH2
OH
Talaromicin A
a. b. c. d.
CU 8: (2,0 i m)1. Cho bi t s n ph m t o thnh t cc ph n ng sau v g i tn s n ph m :
a. Furan + (CH3CO)2O + (C2H5)2O: BF3o0 C
Ab. Thiophen + C6H5COCl + SnCl4 B
c. Pyrol + C6H5N2+Cl C
d. Pyrol + CHCl3 + KOH D2. Vi t s i u ch izatin (indolin-2,3-dion) t 2-nitrobenzoyl clorua
CU 9: (2,0 i m)1. Khi cho amoniac ph n ng c ng v i axetanehit thu c s n ph m khng b n A, s n ph m ny d b tch
n c thnh B. B d dng trime ha cho s n ph m C l triazin. M t khc n u cho amoniac ng ng t v ifomanehit s thu c s n ph m D (urotropin) c CTPT l C6H12N4. Ch t D c kh nng tc d ng v i axitnitric trong anhirit axetic t o ra E (hexogen hay xiclonit) l ch t n m nh c dng trong i chi n th gi i th II: C6H12N4 + 3HNO3 E + 3HCHO + NH3. Xc nh A, B, C, D, E v vi t cc ph ng trnhph n ng x y ra.
2. Gi i thch s khc nhau v nhi t si trong dy cc ch t sau:(1) (2) (3) (4)
N
N
S
N
N
H
NN
H
115oC 117oC 256oC 187oC
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- T ng t trong m ng tinh th than ch
Di n tch m t y = 23
3 d2
(d = CC (than ch))
Th tch m ng = 23
3 d h2
(h l kho ng cch gi a cc l p)
=> Kh i l ng ring D = 2,297 (g/cm3) v th tch mol = 5,224 (cm3/mol)
CU 2: (2.0 i m)1. (1,0 i m) M i cng th c ng c 0,25 i m- B2H6: B lai ha sp
3, g m 2 t di n l ch c m t c nh chung, lin k t BHB l lin k t 3 tm nh ng ch c 2electron, 1 electron c a H v 1 electron c a B- XeO3: Xe lai ha sp
3, phn t d ng thp y tam gic- NO2
+: N lai ha sp, c u trc on th ng- NO2
: N lai hoa sp2, c u trc g p khc (ch V)- Cng th c Lewis
XeO
O
OB
H
B
HHH
H H
N
O O
N
O ONO O NO O
2. (1,0 i m)- Cc ph n ng (m i ph n ng 0,25 im)
2NaNO3 + 8Na(Hg) + 4H2O Na2N2O2 + 8NaOH + 8Hg
NH2OH + C2H5NO2 + 2C2H5ONa Na2N2O2 + 3C2H5OH- Na2N2O2 l mu i c a axit hyponitr H2N2O2 (2.0,125 = 0,25)
N N
OHHO
N N
OH
HO
- C u trc ng phn: H2N NO2 (nitramit) (0,25)
N N
O
O
H
H
CU 3: (2.0 i m)1. (1,0 i m)Ph n ng ng h c b c hai, p d ng ph ng trnh Archnius ta c:
A1
1
Eln k ln ART ; A2
2
Eln k ln ART
A A2 1
2 1
2 A
1 1 2
2 1 2A
2 1 1
E Eln k ln k ln A ln A
RT RT
k E 1 1ln
k R T T
T T kE R ln 3688,2(cal /mol)
T T k
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2 11 3 a 4 2 3 w2 a 4 2 3 w
11 3
a 4 2 3 w1
1 3
[H ] 1 K .[HCO ] K .[NH ] K .[HCO ] K
K .[NH ] K .[HCO ] K[H ]
1 K .[HCO ]
K .[NH ] K .[HCO ] K[H ]
1 K .[HCO ]
Thay cc gi tr g n ng: 4 3[NH ] [HCO ] 0,1M 8[H ] 1,6737.10 M
pH lg[H ] 7, 78
CU 5: (2,0 i m)1. Cc ph ng trnh ph n ng: (4.0,125 = 0,5 i m)
Fe + 2HCl FeCl2 + H22FeCl2 + Cl2 2FeCl33FeCl2 + 2K3[Fe(CN)6] Fe3[Fe(CN)6]2 + 6KCl
FeCl3 + 6H2O FeCl3.6H2O
2.3,270
1000 = 3,7mol FeCl3.6H2O
Nh v y c n mL9780,65.1,18.0,36
36,5.2.3,7 dung dch HCl 36% (0,5 i m)
3. Khi un nng th FeCl3.6H2O phn hu theo ph ng trnh sau:
FeCl3.6H2O FeOCl + 5H2O + 6HClKhi nhi t tng th FeOCl s ti p t c phn hu :
3FeOCl FeCl3 + Fe2O3 (H i FeCl3 bay ra)
L ng FeCl3.6H2O trong m u l3,270
752,2= 10,18 mmol
i u ny ng v i kh i l ng FeCl3 l 107,3. 0,01018 = 1,092g FeOClDo kh i l ng thu c c a b r n b h n nn ta bi t c FeOCl s b phn h y m t ph n thnh Fe2O3.
Kh i l ng FeCl3 m t mt do bay h i l:162,2
0,89771,902 = 1,20mmol => B r n cu i cng ch a (0,01018
3.0,00120) = 6,58 mmol FeOCl v 1,20 mmol Fe2O3. (1,0 i m)CU 6: (2,0 i m)1. (1,0 i m) m i ph ng trnh ng c 0,25
- A l Cr2O3, B l K2CrO4, C l K2Cr2O7- Cc ph ng trnh ph n ng:
2Cr2O3 + 3O2 + 8KOH 4 K2CrO4 + 4H2O
2K2CrO4 + H2SO4 K2Cr2O7 + K2SO4 + H2O
S + K2Cr2O7 Cr2O3 + K2SO414HCl + K2Cr2O7 3Cl2 + 2CrCl3 + 2KCl + 7H2O
2. (1,0 i m) m i ph ng trnh ng c 0,25- X l (NH4)2Cr2O7, Y l Cr(OH)3, Z l K3[Cr(OH)6], T l Cr2(SO4)3- Cc ph ng trnh ph n ng:
(NH4)2Cr2O7ot Cr2O3 + N2 + 4H2O
K2Cr2O7 + 3(NH3)2S + H2O 2Cr(OH)3 + 5S + 6NH3 + 2KOH
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2K2CrO4 + 3(NH4)2S + 2KOH + 2H2O 2K3[Cr(OH)6] + 3S + 6NH3K2Cr2O7 + 4H2SO4 + 3H2S Cr2(SO4)3 + 3S + K2SO4 + 7H2O
CU 7: (2,0 i m)1. (1,0 i m) Cc c u trc
CH
OEt
OH
O
EtO CH
OEt
O O
EtO
H
OEt
O O
EtO
Trong :
- D ng A t b n do n i i khng lin h p- D ng B b n nh ng khng c c ng h ng este- D ng C b n nh t do c n i i lin h p v c ng h ng este
CH3COCH
2COOEtCH
2OEt
OH
O
CH
CH3 OEt
O O
CH
CH3 OEt
OH
O
H
A
B
C
2. (1,0 i m) M i cng th c ng c 0,25 i ma. CH2OHCH2CH2CH2=CHO
5-hidroxipentanal
b. CHOCH2CH2CHOHCH=CHCH=CH24-hidroxiocta-5,7-dienalc. CH3CH2CHOHCHOH(CH2)3COCH3
6,7-dihidroxinonan-2-ond. (HOCH2)2CHCHOHCH2CO(CH2)2CH(C2H5)CH2OH
2,8-di(hidroxometyl)-1,3-dihidroxidacan-5-onCU 8: (2,0 i m)1. (1,0 i m) M i cng th c ng c 0,25 i m
O
COCH3
2-acetylfuran
A
S
COC6H5
2-benzoylthiophen
B
N
N=NC6H5
H
2-(phenylazo)pyrol
C
N
CHO
H
2-pyrolcacboxandehit
D
2. (1,0 i m)
NO2
C
O
ClKCN
-HClNO2
C
O
CN H3O+
-NH3NO2
C
O
COOH 6H
-H2O
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NH2
C
O
COOH to
-H2O NHO
O
CU 9: (2,0 i m)
1. (1,5 i m)- Andehit bo c th tham gia ph n ng c ng v i amoniac t o thnh m t s n ph m t b n l Andehit-amoniac
CH3CHO + NH3 Axetandehit-amoniac (tnc = 97oC) A
CH3 CH
OH
NH2- Axetandehit-amoniac d b tch n c thnh B l CH3CH=NH v B d trime ha thnh h p ch t d vng Clo i triazin
CH3 CH
OH
NH2
-H2O CH3CH=NH trime ha NH NH
NH CH3
CH3
H3C
B C
- M t khc n u cho amoniac ng ng t v i fomanehit s thu c s n ph m D (urotropin) c CTPT lC6H12N4
6HCHO + 4NH3 C6H12N4 + 6H2O
N
N
N
N
Urotropin- Urotropin c kh nng tc d ng v i axit nitric trong anhirit axetic t o ra E (hexogen hay xiclonit) l ch t nm nh c dng trong i chi n th gi i th II theo ph n ng:
C6H12N4 + 3HNO3 + 3HCHO + NH3N N
N
NO2
NO2O2N
E2. (0,5 i m)- Ta c nhi t si c a (1) < (2) l do hai ch t ny khng t o c lin k t hydro nn nhi t si ph thu cvo kh i l ng phn t .
- L i c, nhit si c a (4) < (3) l do m c d c hai ch t u c lin k t hydro lin phn t nh ng lin k thydro c a (3) d ng polyme cn c a (4) d ng dimeCU 10: (2,0 i m)1. (1,0 i m)a. Anion c hnh thnh b i s tch H enolic l b n v i n tch c gi i t a n O c a C=O qua lin k t iC=C
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C
CHO
HO C
O
H+-C
C-O
HO C
O
C
CO
HO C
O
b. S i u ch
D-GlucoseNaBH4
D-Socbitol (A)[O]
enzymL-Socbose (B) endiol B'
2CH3COCH3
Diaxetonua (C)1. KMnO4/OH
-
2. dd H+(D)
H+
toaxit L-ascobic
Trong :
CH2OH
HO H
HO H
H OH
HO H
CH2OH
A
CH2OH
C O
HO H
H OH
HO H
CH2OH
B
CH2OH
CHO
CHO
H OH
HO H
CH2OH
B'
CH2OH
C
C
H O
HO H
CH2 O
C
CH3
CH3
O
OC
CH3
CH3
C
COOH
C
CH O
HO H
CH2 O
C
CH3
CH3
O
O
CCH3
CH3
D
2. (1,0 i m)Salixin l ng khng kh v l glucozit do b th y phn b i elmuxin
RO HOH
HO
OH
CH2OH
OH2O
enzimD-Glucose + ROH (Saligenin)
C7H8O2
Salixin
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Trong cng th c C7H8O2, ROH xu t hi n nhn th m. Tch c andehit salixylic, i u ch ng t qu trnh oxiha nhm CH2OH thnh nhm CHO
D-Glucose +
CHOHO
H2O, H+
OHOHO
OH
OHOH2C
CHO
Saligenin l o-(hidroximetyl)phenol. Cng th c c u trc c a salixin l
OHOHO
OH
OHOH2C
CH2OH
- - - - - - - - - - H T - - - - - - - - - - -Th sinh lm cch khc n u ng v n cho i m t i a
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http://vn.myblog.yahoo.com/volcmttl K THI H C SINH GI I QU C GIA L P 12 THPT THI TH NM H C 2008 2009
MN THI: HA H C I C NGTh i gian lm bi: 180 pht (Khng k th i gian pht )
( thi g m c 2 trang)
Cu 1: (2.0 i m)
1. T i sao ion ph c spin th p [Co(NH3)6]3+ l i c mu. Gi i thch d a vo 1o 22900(cm ) . Cho bi t:1 11 cm 11,962 J.mol .
2. D a trn m hnh VSEPR, gi i thch d ng hnh h c c a NH3, ClF3, XeF4.
3. Qu trnh: O O 1e c I1 = 13,614 (eV). D a vo ph ng php Slater xc nh h ng s ch n c a ccelectron trong nguyn t i v i electron b tch. So snh b n t ng i c a hai c u hnh electron c a Ov O+, gi i thch.
Cu 2: (2.0 i m)1. Thi t l p bi u th c ph thu c gi a th oxi ha kh v i pH c a mi tr ng trong 2 tr ng h p sau:
2. 2 32 7
2 32 7 2 Cr O /2Cr
Cr O 14H 6e 2Cr 7H O 1,33V o; E . pH = 7, 2
2 7Cr O c oxi ha c I
khng?Bi t r ng:
2
o
I / 2 I
E 0,6197V ;3 2
3 2 Co(OH) / Co(OH)Co(OH) 1e Co(OH) OH 0,17V o; E
3. Bi t tch s ion c a n c KW = 10-14 v RT2,303 ln x 0,0592lgx
F ( t i 25
oC, 1atm)
Cu 3: (1.5 i m)Cho ph n ng: A B C D (1) l ph n ng n gi n. T i 27oC v 68oC, ph ng trnh (1) c h ng s t c
t ng ng l n l t l k1 = 1,44.107 mol-1.l.s-1 v k2 = 3,03.10
7 mol-1.l.s-1, R = 1,987 cal/mol.K
1. Tnh nng l ng ho t ha EA (theo cal/mol) v gi tr c a A trong bi u th c E
RTk A e
mol-1.l.s-1.2. T i 119oC, tnh gi tr c a h ng s t c ph n ng k3.3. N u CoA = CoB = 0,1M th 1/2 nhi t 119oC l bao nhiu.
Cu 4: (2.5 i m)i n phn dung dch NaCl dng i n c c Katode l h n h ng Hg dng ch y u v dng c c titan b c ruteni vroi l Anode. Kho ng cch gi a Anode v Katode ch vi mm
1. Vi t ph ng trnh ph n ng x y ra t i i n c c khi m i b t u i n phn pH = 7. Tnh cc gi tr th i nc c v th phn gi i
2. Sau m t th i gian, pH tng ln n gi tr pH = 11. Gi i thch t i sao. Vi t cc ph ng trnh x y ra t i pH. Tnh th in c c v th phn gi i
3. Cho bi t:2 23 2
o o oO / H ONa / Na 2H O / H
E 2,71V ; E 0,00V ; E 1, 23V . V i dung dch NaCl 25% v 0,2% Na
trong h n h ng Na/Hg: oNa / Na(Hg)
E 1,78V .2
o
Cl /ClE 1,34V cho dung dch NaCl 25% theo kh i l ng
2H1,3V trn Hg ;
2O0,8V trn Ru/Rd
Cu 5: (1.5 i m)
Trong cc tinh th (c u trc l p ph ng tm kh i) cc nguyn t cacbon c th chi m cc m t c a m ng c s
1. Bn knh kim lo i c a s t l 1,24o
A . Tnh di c nh a c a m ng c s
2. Bn knh c ng ha tr c a cacbon l 0,77o
A . H i di c nh a s tng ln bao nhiu khi s t c ch acacbon so v i c nh a khi s t nguyn ch t
3. Tnh di c nh m ng c s cho s t (c u trc l p ph ng tm di n) v tnh tng chi u di c nh m ng bi t r ng cc nguyn t cacbon c th chi m tm c a m ng c s v bn knh kim lo i s t l
1,26o
A . C th k t lu n g v kh nng xm nh p c a cacbon vo 2 lo i tinh th s t trn
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Cu 6: (1.5 i m)K t qu phn tch m t ph c ch t A c a Platin (II) cho bi t c: 64,78 % kh i l ng l Pt, 23,59 % l Cl, 5,65 % lNH3 v 5,98 % cn l i l H2O
1. Tm cng th c phn t c a ph c ch t bi t r ng A l ph c ch t 1 nhn v Pt c s ph i tr l 4. Vi t cngth c c u t o 2 ng phn cis v trans c a n
2. Entanpi t do chu n t o thnh 25oC c a cc ng phn cis, trans l n l t l: -396 v -402 kJ.mol-1. Tnhh ng s cn b ng K c a ph n ng sau: cis(A) trans(A)
3. Tnh n ng mol/lit m i ng phn trong dung dch, bi t r ng lc u ch c ng phn cis n ng 0,01M. Cho Pt = 195 ; Cl = 35,5 ; N = 14 ; O = 16 ; H = 1Cu 7: (2.0 i m)Nitramit c th b phn h y trong dd H2O theo ph n ng: NO2NH2 N2O(k) + H2O
Cc k t qu th c nghi m cho th y v n t c ph n ng tnh b i bi u th c: 2 23
[NO NH ]v k
[H O ]
1. Trong mi tr ng m b c c a ph n ng l bao nhiu2. Trong cc c ch sau c ch no ch p nh n c:
a. C ch 1: 1k2 2 2 (k) 2NO NH N O + H O
b. C ch 2:2
3
k +2 2 3 2 3 2
k+ +2 3 2 3
NO NH H O NO NH + H O
NO NH N O + H O
c. C ch 3:4
5
6
k +2 2 2 2 3
k2 2
k+3 2
NO NH H O NO NH + H O
NO NH N O + OH
H O OH 2H O
Cu 8: (3.0 i m)1. C 3 nguyn t A, B v C. A tc d ng v i B nhi t cao sinh ra D. Ch t D b thu phn m nh trong
n c t o ra kh chy c v c mi tr ng th i. B v C tc d ng v i nhau cho kh E, kh ny tan ctrong n c t o dung dch lm qu tm ho . H p ch t c a A v i C c trong t nhin v thu c lo i ch t c ngnh t. H p ch t c a 3 nguyn t A, B, C l m t mu i khng mu, tan trong n c v b thu phn. Vi t tn c aA, B, C v ph ng trnh cc ph n ng nu trn.
2. kh o st s ph thu c thnh ph n h i c a B theo nhi t , ng i ta ti n hnh th nghi m sau y: L y3,2 gam n ch t B cho vo m t bnh kn khng c khng kh, dung tch 1 lt . un nng bnh B ho h ihon ton. K t qu o nhit v p su t bnh c ghi l i trong b ng sau:
Nhi t (oC) p su t (atm)444,6 0,73554450 0,88929500 1,26772900 4,80930
1500 14,53860Xc nh thnh ph n nh tnh h i n ch t B t i cc nhi t trn v gi i thch.
Cu 9: (1.5 i m)
C th vi t c u hnh electron c a Ni2+
l:Cch 1: Ni2+ [1s22s22p63s23p63d8] Cch 2: Ni2+ [1s22s22p63s23p63d64s2].p d ng ph ng php g n ng Slater, tnh nng l ng electron c a Ni2+ v i m i cch vi t trn (theo n v eV).Cch vi t no ph h p v i th c t . T i sao.Cu 10: (2.5 i m)
1. Phng th nghi m c m u phng x Au198 v i c ng 4,0 mCi/1g Au. Sau 48 gi ng i ta c n m t dungdch c phng x 0,5 mCi/1g Au. Hy tnh s gam dung mi khng phng x pha v i 1g Au c dungdch ni trn. Bi t r ng Au198 c t1/2 = 2,7 ngy m.
2. Hy ch ng minh r ng ph n th tch b chi m b i cc n v c u trc trong m ng tinh th kim lo i thu c cch l p ph ng n gi n, l p ph ng tm kh i, l p ph ng tm di n tng theo t l 1 : 1,31 : 1,42.
- - - - - - - - - - H T - - - - - - - - - -
m
m
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http://vn.myblog.yahoo.com/volcmttl K THI H C SINH GI I QU C GIA L P 12 THPT THI TH NM H C 2008 2009
H NG D N CH M MN HA H C I C NG
Cu N i dung i m
1
1 Tnh c: 437nm . S h p th nh sng n m trong ph nhn th y nn c mu. 0,5
2
C u t o c a NH3 cho th y quanh nguyn t N trung tm c 4 vng khng gian khu trelectron, trong c 1 c p electron t do (AB3E) nn phn t NH3 c d ng thp y tam gic
v i gc lin k t nh h n o109 28' (c p electron t do i h i m t kho ng khng gian khu trl n h n)
N H
H
H N
H
HH
C u trc thp y tam gic tm l nguyn t NPhn t ClF3 c 5 kho ng khng gian khu tr electron, trong c 2 c p electron t do(AB3E2) nn phn t c d ng ch T (Cc electron t do chi m v tr xch o)
Cl F
F
F ClF
F
F
Phn t XeF4 c 6 vng khng gian khu tr electron, trong c hai c p electron t do(AB4E2) nn c d ng vung ph ng (trong c u trc ny cc c p electron t do phn b xanhau nh t)
Xe
F
FF
F
XeFF
F F
0,25 3= 0,75
3
- C u hnh electron: O 1s22s22p4 km b n h n O+ 1s22s22p3 do l c y l n nhau c a 2 trong m t orbital c a phn l p 2p v do O+ t c u hnh bn bo ha phn l p 2p nnb n
- t b l h ng s ch n c a cc electron trong nguyn t i v i electronb tch. Ta c:*2
*2 2 21 2
ZI 13,6 13,614 Z n 4 (8 b) 4 b 6
n
0,25
0,5
2.0
2 1
2 3 2 32 7 2 7
2 32 7
2 32 7
1422 7
2Cr O / 2Cr Cr O / 2Cr 3
214 2 7
2Cr O /2Cr 3
22 7
2Cr O /2Cr 3
Cr O H0,0592lg
6 Cr
Cr O0,0592 0,0592lg H lg
6 6 Cr
Cr O0,05920,138pH lg
6 Cr
o
o
o
E = E
E
E
t:2 3 2 3
2 7 2 7Cr O / 2Cr Cr O / 2Cr0,138pH
' oE E
2 32 7
'
C r O / 2CrE l th i u ki n v ph thu c vo pH. pH cng gi m th dung dch cng c mi
tr ng axit th E cng tng, tnh oxi ha c a 22 7Cr O
cng m nh.
- T i pH = 0, [H+] = 1M th E = Eo = 1,33V- T i pH = 7 th E = 0,364
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