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b gio dc v o to k thi chn hc sinh gii quc gialp 12 thpt nm hc 2000-2001
hng dn chm thi chnh thc
ho hc v c (Bng A)Cu I(4 im):
1. Phng php sunfat c th iu ch c cht no: HF , HCl , HBr , HI ? Nuc cht khng iu ch c bng phng php ny, hy gii thch ti sao?
Vit cc phng trnh phn ng v ghi r iu kin (nu c) minh ho.2. Trong dy oxiaxit ca clo, axit hipoclor l quan trng nht. axit hipoclor c
cc tnh cht: a) Tnh axit rt yu, yu hn axit cacbonic; b) C tnh oxi ho mnh lit;c) Rt d b phn tch khi c nh sng mt tri, khi un nng. Hy vit cc phngtrnh phn ng minh ho cc tnh cht .
3. C cc dung dch (b mt nhn) : a) BaCl2 ; b) NH4Cl ; c) K2S ; d) Al2(SO4)3 ;e) MgSO4 ; g) KCl ; h) ZnCl2 . c dng thm dung dch phenolphtalein (khong pHchuyn mu t 8 - 10) hoc metyl da cam (khong pH chuyn mu t 3,1 - 4,4).
Hy nhn bit mi dung dch trn, vit cc phng trnh ion (nu c) giithch.
4. Tm cch loi sch tp cht kh c trong kh khc v vit cc phng trnhphn ng xy ra: a) CO c trong CO2 ; b) H2S c trong HCl ; c) HCl c trong H2S ;d) HCl c trong SO2 ; e) SO3 c trong SO2 .Cch gii1. Phng php sunfat l cho mui halogenua kim loi tc dng vi axit sunfuric c,nng iu ch hirohalogenua da vo tnh d bay hi ca hirohalogenua.Phng php ny ch p dng iu ch HF , HCl, khng iu ch c HBr v HI vaxit H2SO4 l cht oxi ho mnh cn HBr v HI trong dung dch l nhng cht kh
mnh, do p dng phng php sunfat s khng thu c HBr v HI m thu cBr2, I2.
Cc phng trnh phn ng:CaF2 + H2SO4 , nng = 2 HF + CaSO4
NaCl + H2SO4 , nng = HCl + NaHSO4
2 NaCl + H2SO4 , nng = 2 HCl + Na2SO4NaBr + H
2
SO4
, nng = NaHSO4
+ HBr
2 HBr + H2SO4 , nng = SO2 + 2 H2O + Br2
NaI + H2SO4 , nng = NaHSO4 + HI
6 HI + H2SO4 , nng = H2S + 4 H2O + 4 I22. Axit hipoclor :
- Tnh axit rt yu, yu hn axit cacbonicNaClO + CO2 + H2O = NaHCO3 + HClO
Tnh oxi ho mnh lit, a cht phn ng c s oxi ho cao nht+6
4 HClO + PbS-2 = 4 HCl + PbSO4
- D b phn tch :a s to
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HClO = HCl + O ; 3 HClO = 2 HCl + HClO3
3. Dng phenolphtalein nhn ra K2S
S-2 + H2O = HS- + OH -
pH > 10 dung dch phenolphtalein c mu Dng K2S lm thuc th. Cho K2S vo cc dung dch cn li:
to
- Vi NH4Cl : S-2 + NH4+ = NH3 + HS
-Nhn ra NH3 nh mi khai, hoc ho giy lc tm phenolphtalein ( v NH3 c
pH > 9 ).- Vi Al2(SO4)3 : Cho kt ta keo trng Al(OH)3
Al3+ + 3 S-2 + 3 H2O = Al(OH)3 + 3 HS-
- Vi MgSO4 : Cho kt ta trng Mg(OH)2
Mg2+ + 2 S2- + 2 H2O = Mg(OH)2 + 2 HS-- Vi ZnCl2 : Cho kt ta trng ZnS
Zn2+ + 2 S2- = ZnS Dng NH4Cl nhn ra MgSO4: kt ta Mg(OH)2 tan c trong NH4Cl ; trong khi
cc kt ta Al(OH)3 v ZnS khng tan.to
Mg(OH)2 + 2 NH4+ = Mg2+ + 2 NH3 + H2O
Dng MgSO4 nhn ra BaCl2:
Ba2+ + SO42- = BaSO4trng
Dng BaCl2 nhn ra Al2(SO4)3 :Cn li l KCl. Ba2+ + SO4
2- = BaSO4trng(Hoc dng metyl da cam lm thuc th:
Nhn ra Al2(SO4)3
Al2(SO4)3 2 Al3+ + 3 SO4
2-
Al3+ + 3 H2O = AlOH2+ + H+
Dung dch c phn ng rt axit ( pH < 4 ) lm cho metyl da cam c mu da camhoc hng.
Cc dung dch cn li u c pH > 4,4 nn metyl da cam c mu vng. Dng
Al2(SO4)3 lm thuc th:- Vi BaCl2 cho kt ta trng tinh th Ba
2+ + SO42- = BaSO4trng
- Vi K2S cho kt ta keo trng Al(OH)3
Al3+ + 3 S-2 + 3 H2O = Al(OH)3 + 3 HS-
Dng K2S lm thuc th:to
- Vi NH4Cl : S-2 + NH4+ = NH3 + HS
-Nhn ra NH3 nh mi khai, hoc ho giy lc tm phenolphtalein.
- Vi MgSO4 : Cho kt ta trng Mg(OH)2
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Mg2+ + 2 S2- + 2 H2O = Mg(OH)2 + 2 HS-
- Vi ZnCl2 : Cho kt ta trng ZnSZn2+ + 2 S2- = ZnS - Vi KCl khng c du hiu g.
phn bit MgSO4 vi ZnCl2 , cho NH4Cl vo 2 kt ta Mg(OH)2 v ZnS thch c kt ta Mg(OH)2 tan trong NH4Cl khi un nng
to
Mg(OH)2 + 2 NH4+ = Mg2+ + 2 NH3 + H2O
cn ZnS khng tan.4. to
a) CO + CuO = CO2 + Cub) H2S + CuCl2 = CuS + 2 HClc) HCl + NaHS = NaCl + H2Sd) HCl + NaHSO3 = NaCl + SO2 + H2O
e) SO3 + H2SO4 = H2S2O7 (oleum)Cu II(3,5 im):1. Hy dng k hiu lng t biu din cc trng hp s lng electron trong
mt obitan nguyn t.2. Mi phn tXY3 c tng cc ht proton, ntron, electron bng 196; trong ,
s ht mang in nhiu hn s ht khng mang in l 60, s ht mang in ca X thn s ht mang in ca Y l 76.
a) Hy xc nh k hiu ho hc ca X,Y v XY3 .b) Vit cu hnh electronca nguyn tX,Y.c) Da vo phn ng oxi ho - kh v phn ng trao i, hy vit phng trnh
phn ng (ghi r iu kin, nu c) cc trng hp xy ra to thnh XY3.Cch gii1. C ba trng hp: hoc
Obitan nguyn t trng c 1 e c 2 e2. a) K hiu s n v in tch ht nhn ca X l Zx , Y l Zy ; s ntron (htkhng mang in) ca X l Nx , Y l Ny . Vi XY3 , ta c cc phng trnh:
Tng s ba loi ht: 2 Zx + 6 Zy + Nx + 3 Ny = 196 (1)2 Zx + 6 Zy Nx 3 Ny = 60 (2)6 Zy 2 Zx = 76 (3)
Cng (1) vi (2) v nhn (3) vi 2, ta c:
4 Zx + 12 Zy = 256 (a)12 Zy 4Zx = 152 (b)
Zy = 17 ; Zx = 13Vy X l nhm, Y l clo. XY3 l AlCl3 .b) Cu hnh electron: Al : 1s2 2s2 2p6 3s2 3p1 ; Cl : 1s2 2s2 2p6 3s2 3p5Cc phng trnh phn ng to thnh AlCl3:
to2Al + 3 Cl2 = 2 AlCl3
to
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2Al + 3 CuCl2 = 2 AlCl3 + 3 CuAl2O3 + 6 HCl = 2 AlCl3 + 3 H2OAl(OH)3 + 3 HCl = AlCl3 + 3 H2OAl2S3 + 6 HCl = 2 AlCl3 + 3 H2SNaAlO2 + 4 HCl = AlCl3 + NaCl + 2 H2O
Al2(SO4)3 + 3 BaCl2 = 2 AlCl3 + 3 BaSO4Cu III(5 im):
1. Hon thnh phng trnh phn ng a) , b) sau y. Cho bit cc cp oxi ho -kh lin quan n phn ng v so snh cc gi tr Eo ca chng.
a) Zn[Hg(SCN)4] + IO3-
+ Cl- ICl + SO4
2- + HCN + Zn2+ + Hg2+
b) Cu(NH3)m2+ + CN
-+ OH
- Cu(CN)2-
+ CNO- + H2O
2. Dung dch X c cht tan l mui M(NO3)2 . Ngi ta dng 200ml dung dchK3PO4 va phn ng vi 200ml dung dch X, thu c kt ta M3(PO4)2 v dungdch Y. Khi lng kt ta ( c sy kh) khc khi lng M(NO3)2 ban u l
6,825 gam.in phn 400 ml dung dch X bng dng in I = 2 ampe ti khi thy khilng catt khng tng thm na th dng, c dung dch Z. Gi thit s in phn chiu sut 100%.
a) Hy tm nng ion ca dung dch X, dung dch Y, dung dch Z. Cho bitcc gn ng phi chp nhn khi tnh nng dung dch Y, dung dch Z.
b) Tnh thi gian (theo giy) in phn.c) Tnh th tch kh thu c 27,3oC , 1atm trong s in phn.
Cch gii: 1.a) Zn[Hg(SCN)4] + 16 H2O Zn
2+ + Hg2+ + 4 HCN + 4 SO42- + 24 H+ + 24 e
6 IO3- + Cl- + 6 H+ + 4 e ICl + 3 H2O
Zn[Hg(SCN)4] + 6 IO3-
+ 6 Cl- + 8 H+ Zn2+ + Hg2+ + 4 HCN + 4 SO4
2- ++ 6 ICl + 2 H2O
Eo IO3-/ ICl > Eo SO42-, HCN / Zn[Hg(SCN)4]
b) 2 Cu(NH3)m2+ + 2 CN - + e Cu(CN)2
-+ m NH3
CN - + 2 OH- CNO- + H2O + 2 e2 Cu(NH3)m
2+ + 5 CN-
+ 2 OH- 2 Cu(CN)2
-+ 2m NH3 + CNO
-+ H2O
Eo Cu(NH3)m2+/Cu(CN)2- > Eo CNO-/ CN -2. a) Phng trnh phn ng:
3 M(NO3)2 + 2 K3PO4 M3(PO4)2 + 6 KNO3 (1)
Dung dch Y: dung dch KNO3 KNO3 K+ + NO3- (2)
Theo (1), 6mol NO3- phn ng to ra 2mol PO4
3- lm thay i khi lng 372 190 =182 (g)
x mol NO3- phn ng to ra x/3mol PO4
3- lm thay i khi lng 6,825 (g)
)mol(1125,0182
825,6x3x == )l/mol(2625,0
200
1000x115,0Cddx ==
Theo (1), nK+ = nNO3- = nKNO3 = 2 nM (NO3)2 = 2 0,1125 = 0,225 (mol).
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Coi VddY VddX + Vdd K3PO4 400 (ml) (3)
0,225 1000Vy C K+ = C NO - = = 0,5625 (mol/l)3 400
Dung dch Y c nng : C K+ = C NO3- = 0,5625 (mol/l)
Cc gn ng chp nhn khi tnh nng dung dchY
:- B qua s thay i th tch khi tnh (3) v s c mt M 3(PO4)2
- B qua s tan M3(PO4)2 = M2+ + PO4
2- (4)
- B qua s phn li H2O = H+ + OH -
Xt s in phn, s in phn:K M(NO3)2 A
H2O
M2+ + 2 e = M 2 H2O - 2 e = 1/2 O2 + 2 H+
Phng trnh in phn:M(NO3)2 + H2O M + 1/2 O2 + 2 HNO3 (5)
Dung dch Z c cht tan HNO3 .
Coi VddZ VddX 400 (ml) (6)0,5625 400
Theo (5) nHNO = 2 nM(NO3)2 = 2 31000
nHNO3 1000Vy C H+ = C NO - = = 1,125 (mol/l)3 400
(hoc theo(6) v (5) nH+
= nNO3-
= 2 C dd x = 1,125)Cc gn ng chp nhn khi tnh nng dung dch Z:
- Coi VddZ VddX, b qua s thay i th tch do s in phn gy ra.
- B qua s phn li H2O = H+ + OH - v Z l dd HNO3.
Nng ion dd X: CM+ = 0,5625 M ; CNO3- = 1,125 M
dd Y: CK+ = CNO3- = 0,5625 M
dd Z: CH+ = CNO3- = 1,125 M.
b) Tnh thi gian in phn:
m nThay s vo (7) l = M(NO3)2 = 0,5625 0,4 = 0,025 (mol)A
n = 2 ; I = 2Vy t = 0,225 96500 = 21.712,5 (giy)
c) Tnh th tch kh thu c 27,3oC , 1atm trong s in phn dung dch Y, Z.
22,4 0,1125 300,3 nVo = = 2,772 (lt)2 273 1
)mol(1125,02
225,0n
2
1n
232 )NO(MO===( ) :5Theo
Cu IV(4 im):
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1. Sunfuryl iclorua SO2Cl2 l ho cht ph bin trong phn ng clo ho. Ti350oC, 2 atm phn ng
SO2Cl2 (kh) = SO2 (kh) + Cl2 (kh) (1)C Kp = 50 .
a) Hy cho bit n v ca tr s v gii thch: hng s cn bng Kp ny phic n v nhvy.
b) Tnh phn trm theo th tch SO2Cl2(kh) cn li khi (1) t ti cn bng iu kin cho.
c) Ban u dng 150 mol SO2Cl2(kh), tnh s mol Cl2(kh) thu c khi (1) tti cn bng.
Cc kh c coi l kh l tng.2. a) Tnh in li ca dung dch CH3NH2 0,010M.
b) in li thay i ra sao khi- Pha long dung dch ra 50 ln.- Khi c mt NaOH 0,0010M.
- Khi c mt CH3COOH 0,0010M.- Khi c mt HCOONa 1,00M.
Bit: CH3NH2 + H+ CH3NH3 ; K = 10
10,64
CH3COOH = CH3COO- + H+ ; K = 10-4,76
Cch gii:1. a) Gi s mol SO2Cl2 ban u l 1, phn li l , ta c:
SO2Cl2 (kh) = SO2 (kh) + Cl2 (kh) (1)Ban u 1 0 0Phn li
Cn bng (1 ) pSO (atm) pCl (atm)2 2Kp = = 50 atm (2)
pSO2Cl2(atm)b) V cc kh u l kh l tng nn pi = P . xi (3)
nim xi = (4)
nj y : nSO2 = nCl2 = ; nSO2Cl2 = (1 ) ; cn nj = 1 + (5)b) T hp (5) v (4) , (3) v (2) ta c:
S mol SO Cl cn l (1 ) 0,0194 (mol)2 20,0194
Do SO Cl cn li chim 100% 0,98%2 21,9804
2
2
1
.PKp
=
502
50
KpP
Kp
+
=
+
= 9806,0=
y l % theo s mol, cng l % theo th tch. Vy khi (1) t ti cn bngSO2Cl2 cn li chim 0,98%v s mol hay th tch ca h.
(Hoc SO2Cl2 (kh) = SO2 (kh) + Cl2 (kh) Kp = 50 (1)2 atm2 - (P + p) p p
0100p100p50p22
p 22 =+=
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pSO2Cl2
= 2 - 2 0,9902 = 0,0196 (atm)pSO2Cl2 = P . nSO2Cl2 nSO2Cl2= 0,0196 : 2 = 0,0098 hay 0,98%
% theo s mol cng l % theo th tch. Vy khi (1) t ti cn bng SO2Cl2 cnli chim 0,98%v s mol hay th tch ca h.)
c) Ban u dng 150 mol (kh), tnh s mol Cl2(kh) thu c khi (1) t ti cn bng:Theo (1) ta c: nSO2 = nCl2 = nSO2Cl2 98,06 = 150 0,9806
nCl2 = 147,09 mol2. a) Tnh in li ca dung dch CH3NH2 0,010M:
CH3NH2 + H2O = CH3NH3+ + OH- 10-14
c c Kb = = 10-3,36
[] c-x x x 10-10,64
336,3
2
b
2
10.88,1x10
x010,0
xK
xc
x ==
=
%8,1810
10
10.88,1 22
3
==
b) in li thay i ra sao khi- Pha long dung dch ra 50 ln:
42
NHCH 10.250
10C
23
== 436,34
2
10.49,1x10x102
x
==
%5,7410102
1049,1 24
4
=
=
-Khi c mt NaOH 0,0010M:
NaOH = Na+ + OH-CH3NH2 + H2O = CH3NH3
+ + OH- 10-3,36 (1)
c 0,01 1. 10-3
[] 0,01 - x x 1. 10-3 + x336,3
3
1049,1x10x01,0
)x10(
==
+x%9,1410
10
1049,1 22
3
=
=
gim v OH- ca NaOH lm chuyn dch cn bng (1) sang tri.- Khi c mt CH3COOH 0,0010M:
CH3COOH = CH3COO- + H+ ; Ka = 10
-4,76
CH3NH2 + H+ = CH3NH3
+ ; Ka-1 = 1010,64
CH3COOH + CH3NH2 = CH3NH3+ + CH3COO
- ; K = Ka.Ka-1 = 105,88
K rt ln, phn ng xy ra hon ton CCH3NH3
+ = CCH3COOH = 1,0 10-3 ; CCH3NH2 = 9 10-3
CH3NH2 + H2O = CH3NH3+ + OH- ; Kb= 10
-3
c 9.10-3 1.10-3[] 9.10-3 - x 10-3 + x x
[CH3NH3+] = (1,39 + 1).10-3 = 2,39 10-3
336,3
3
3
10.39,1x10x10.9
)x10(
==
+x
%9,231010
1039,2 22
3
=
=
tng v CH3NH
2tng tc vi CH
3COOH.
- Khi c mt HCOONa 1,00M:
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HCOONa HCOO- + Na+
HCOO- + H2O = HCOOH + OH- (1)
25,1075,3
14
b, 1010
10K
==
KaHCOOH > KaCH3COOH ( = 10-4,76
) nnK,b < 10-14 / 10-4,76 = 10-9,24
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b bgio dc v o to k thi chn hc sinh gii quc gialp 12 thpt nm hc 2000-2001
hng dn chm thi chnh thc
ho hc hu c Bng A
Cu I(5 im):1. Xut pht t brombenzen cha 14 C v tr 1 v cc ho cht v c cn thit
khng cha 14 C, hy iu ch cc hp cht thm cha 14 C v tr 3 : a) Anilin ;b) Iotbenzen ; c) Axit benzoic.
2. Hon thnh s cc phn ng sau v gi tn cc sn phm tA n F :Na2Cr2O4 2 H
Cl2 (1 mol) H2O C D
Benzen (1 mol)A
B
FeCl3 tO , p HNO3 (1 mol) Fe, HCl
E F
3. Khi oxi ho etylenglicol bng HNO3 th to thnh mt hn hp 5 cht. Hyvit cng thc cu to phn t ca 5 cht v sp xp theo trt t gim dn nhit si ca chng (c gii thch).Cch gii:1. Br MgBr COOMgBr COOH
14 14 14 14
Mg CO2 H3O+
ete COOH14 14 14
NaOH/CaO HNO3/ H2SO4
NH2 NO2 NO2
0-5oC NaNO2
14 HCl 14 14 14
KI CuCN H3O+
I N2(+)Cl(-) CN COOHa)
Br MgBr MgBr COOMgBr14 ete khan 14 14 14
+ Mg (1) ; + CO2 (2)
COOMgBr COOH14
+ H3O+ + MgBr+ + H2O (3)
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COOH COOH14 H2SO4
14
+ HNO3 + H2O (4)
NO2
COOH COONa14 142 + Na2CO3 2 + H2O + CO2 (5)
NO2 NO2
COONa14 CaO
14
+ NaOH rn + Na2CO3 (6)
NO2 NO214 14
+ 3 Fe + 7 HCl + 3 FeCl2 + 2 H2O (7)
NO2 NH3Cl14 14
+ NaOH + NaCl + H2O (8)
NO2 NH2
14 14
b) + NaNO2 + 2 HCl + NaCl + 2 H2O
NH2 N N Cl
14 14
+ KI + N2 + KCl
N N Cl I
14 14
+ CuCN + N2 + CuCl
N N Cl C N
14 14
c) 2 + 2 H2O + H+ 2 + NH4
+
C N COOHO OH
2. Cl OH Na2Cr2O4 2 HCl2 (1 mol) H2O
FeCl3 tO , p O OH
OH OH OHNO2 Fe, HCl
HNO3
NO2 NH3Cl
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ClFeCl3
+ Cl2 + HCl (1)
A: ClobenzenCl OH
to, p+ H2O + HCl (2)
B: PhenolOH O O OH
[O] 2 H(3) ; (4)
O O OHC: p-Benzoquinon D: Hiroquinon
OH
OH + H2O (5)
+ HNO3 NO2 E:p-Nitrophenol
OHNO2
+ H2O
OH OH(6)
+ 3 Fe + 7 HCl F: p-Aminophenol
NO2 NH3Cl
3. (B)CH2OH CHO HOCH2- COOH COOH COOH
[O] [O] [O] [O]CH2OH CH2OH OHC - CHO CHO COOH
(E) (A) (C) (D) () > B > D > A > C
(Gii thch bng hiu ng electron v lin kt hiro).
Cu II(4 im): NXinconiin (X) c cng thc cu to :
CH=CH2C9HOH
l ng phn lp th C9 ca xinconin (Y). N1. Hy ghi du vo mi nguyn t cacbon bt i v khoanh vng trn nguyn
t nit c tnh baz mnh nht trong phn tX.2. Cho t t dung dch HBr vo X nhit phng ri un nng nh, sinh ra cc
sn phm chnh l A (C19
H23
BrON2) , B (C
19H
24Br
2ON
2) , C (C
19H
25Br
3ON
2) , v
D (C19H24Br4N2). Ch ho D vi dung dch KOH trong ru 90o thu c E (C19H20N2)
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Hy vit cng thc cu to ca A , B , C , D , E. Ghi du vo mi nguyn tcacbon bt i trong phn tD v E.
3. Cho C6H5COCl vo X v Y thu c sn phm u c cng thc C26H26N2O2(t l F v G). F v G c ng nht (cng l mt cht) hay khng? Chng c nhit nng chy ging hay khc nhau? ti sao?Cch gii: . .1. N
CH=CH2CHOHN : H
2. N N(+)Br(-)
CH=CH2 CH=CH2
CHOH CHOHBr(-)(+)NH Br(-)(+)NH(A) (B)
H HN(+) Br(-) N(+) Br(-)
CHBr-CH3 CHBr-CH3
CHOH CHBr Br(-) (+)NH Br(-) (+)NH(C) (D)
3. N N
CH-CH3 CH=CH2CH= C6H5COO-9CH
(E) N (F) N
F v G l ng phn cu hnh C9 (tng t X v Y) v phn ng viC6H5COCl khng lm t lin kt C9-O v vy F v G khng ng nht, chng lnhng ng phn i quang ca nhau, nn tnc ging nhau.
Cu III(4 im):1.C mt hn hp protit gm pepsin (pHI = 1,1), hemoglobin (pHI = 6,8) v
prolamin (pHI = 12,0). Khi tin hnh in di dung dch protit nu trn pH = 7,0 th thuc 3 vt cht (xem hnh):
Xut pht
Cc CcA B C
Cho bit mi vt cht c tr
ng cho protit no ? Gii thch.
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2. Khi thu phn hon ton 1 mol tripeptit X thu c 2 mol axit glutamic( HOOC(CH2)2CH(NH2)COOH ), 1 mol alanin ( CH3CH(NH2)COOH ) v 1 mol NH3.X khng phn ng vi 2,4-initroflobenzen v X ch c mt nhm cacboxyl t do.Thu phn X nh enzim cacboxipeptiaza thu c alanin v mt ipeptit Y.
Vit cng thc cu to ca X , Y v gi tn chng.Cch gii:1. Vt A: Pepsin, v Pepsin l protit c tnh axit mnh (pH I = 1,1) nn tn ti dnganion, do chuyn v cc dng.
Vt B: Hemoglobin (pHI = 6,8), hu nh dng ion lng cc.Vt C: prolamin (pHI = 12,0), v l protit c tnh baz mnh nn dng cation, do
chuyn v cc m.2. Tripeptit X c cu to theo trt t Glu-Glu-Ala. V theo d kin u bi aminoaxitui (ui C) l Ala, nhm -NH2 ca aminoaxit u (u N) to thnh lactam vi
nhm -COOH ca n v Glu th nht, nhm -COOH ca n v th Glu hai dngchc amit -CONH
2
(do thu phnto ra NH3
). Vy:
O OX: NH - CH - C - NH - CH - C - NH - CH - COOH ;
O=C (CH2)2-CONH2 CH3
CH2 - CH2 -Glutamolactam--ylglutaminylalaninO
Y: NH - CH - C - NH - CH - COOHO=C (CH2)2-CONH2
CH2 - CH2 -Glutamolactam--ylglutamin
Cu IV(4,5 im):Melexitoz (C18H32O16) l ng khng kh, c trong mt ong. Khi thu phn
hon ton 1 mol melexitoz bng axit s nhn c 2 mol D-glucoz v 1 mol D-fructoz. Khi thu phn khng hon ton s nhn c D-glucoz v isaccaritturanoz. Khi thu phn nh enzim mantaza s to thnh D-glucoz v D-fructoz, cnkhi thu phn nh enzim khc s nhn c saccaroz.
Metyl ho 1 mol melexitoz ri thu phn s nhn c 1 mol 1,4,6-tri-O-metyl-D-fructoz v 2 mol 2,3,4,6-tetra-O-metyl-D-glucoz.
1. Hy vit cng thc cu trc ca melexitoz. Vit cng thc cu trc v gi tnh thng ca turanoz.
2. Hy ch ra rng, vic khng hnh thnh fomanehit trong sn phm oxi hobng HIO4 chng t c cu trc furanoz hoc piranoz i vi mt xch fructoz vpiranoz hoc heptanoz (vng 7 cnh) i vi mt xch glucoz.
3. Cn bao nhiu mol HIO4 phn hu hai mt xch glucoz c cu trcheptanoz v s nhn c bao nhiu mol axit fomic?Cch gii:1. T cc d kin u bi suy ra melexitoz:
- Khng cn -OH semiaxetan- L trisaccarit c cu thnh t 2 dn v D-glucoz v 1 n v D-fructoz,
trong 1 n v D-glucoz lin kt vi D-fructoz to thnh isaccarit turanoz, n
v D-glucoz th hai cng lin kt vi D-fructoz to thnh isaccarit saccaroz.- Thu phn 1 mol sn phm metyl ho melexitoz thu c:13
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1
1 mol CH3OCH2 H v 2 mol6CH3OCH2
2 5 H HHO3 4 CH2OCH3 4 1
OH H CH3
O 3 2 OH
H OCH3
T suy ra n v D-fructoz dng furanorit, 2 n v D-glucoz u dngpiranorit; 2 n v D-glucoz u to ra lin kt glicorit vi C2 v C3 ca D-fructofuranozit.Cu trc: 4 H2
6COH O1CH2OH HO
HO 5 O HHO 3 2 1 2 5
OH O H 46CH2OH
4
H2COH O
3
HHO 5
HO 3 2 1 H
H O Melexitoz (C18H32O16)H
4 H26COH O H2
1COH O H
HO 5 2 5
HO 3 2 1H HO H HO 6CH2OH
H OH 3 4 H
O3-O-(-D-glucopiranozyl)-D-fructofuranoz
(Turanoz)hoc: 4 6C H2OH O
HO 5 HHO 3 2 1
H OH O H
4 H2COH O
HO 5 H 3 4 OH
HO 3 2 OH 1 H 2 O 5 6CH2OHH 1CH2OH
H Melexitoz(C18H32O16)
4 H26COH O
HO 5 HHO 2 1 4 H
3 HO O 3 OHH H 6CH2OH
HO 25 H (Turanoz)
1CH2OH3-O-(-D-glucopiranozyl)-D-fructofuranoz
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2. Mt xch fructoz Mt xch glucoz
7 7
CH2OH CH2OH O - CH O-CH
O - C O - C CHOH CHOH O - CH O - CH O CHOH O CHOH O
CHOH O CHOH CHOH CHOH
CHOH CH CHOH CH
CH2 CH2OH CH2 CH2OH
Piranoz Furanoz Heptanoz Piranozkhng c HCHO khng c HCHO khng c HCHO khng c HCHO
T fructoz T glucoz
V V(do khng c nhm 1,2-itol kiu -CHOH-CH2OH)
3. O - CH O - CH
CHOH O=CH2 CHOH O + 6 HIO4 2 O + 4 HCOOH
CHOH + 6 HIO3
CHOH O=CH + 2 H2O
CH2 CH2
Cu V(2,5 im):
1. Clorofom tip xc vi khng kh ngoi nh sng s b oxi ha thnh photgenrt c. nga c ngi ta bo qun clorofom bng cch cho thm mt lng nhancol etylic chuyn photgen thnh cht khng c.
Vit phng trnh phn ng oxi ha clorofom bng oxi khng kh thnhphotgen, phn ng ca photgen vi ancol etylic v gi tn sn phm.
2. un nng vi git clorofom vi lng d dung dch NaOH, sau nh thmvi git dung dch KMnO4 thy hn hp xut hin mu xanh. Vit cc phng trnhphn ng v gii thch s xut hin mu xanh.
3. Khi tin hnh iu ch axit lactic t anehit axetic v axit xianhiric, ngoisn phm mong mun ta cn thu c hp cht X (C6H8O4). Vit cng thc cu to caX v cc phng trnh phn ng xy ra.Cch gii: as1. 2 CHCl3 + O2 2 COCl2 + 2 HCl
COCl2 + 2 C2H5OH O=C(OC2H5)2 + 2 HCl
ietyl cacbonatto
2. CHCl3 + 4 NaOH HCOONa + 3 NaCl + 2 HOH
HCOONa + 2 KMnO4 + 3 NaOH Na2CO3 + K2MnO4 + Na2MnO4 + 2 HOH
Anion MnO42- cho mu xanh.
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3. Axit lactic l -hiroxiaxit, trong iu kin tin hnh phn ng D chuyn thnhlactit X:
OHCH3CH=O + HCN CH3CH
CNOH to OH2 CH3CH + 2 HOH + H
+ CH3CH + NH4+
CN COOHOH H+,to COO
2 CH3CH CH3CH CHCH3 + 2 HOH
COOH OOClactit X
Cu IV(4,5 im): (thay cu IVbng A, dng cho bng B)1. Vit phng trnh phn ng iu ch D-fructoz t D-glucoz, bit rng
D-glucozazon khi tc dng vi benzanehit to thnh ozon ca D-glucoz(HOCH2(CHOH)3COCHO).
2. Chitin (tch t v tm, cua...) c coi nh l dn xut ca xenluloz,trong cc nhm hiroxyl cc nguyn t C2 c thay th bng cc nhmaxetylamino ( -NH-CO-CH3 ).
a) Vit cng thc cu to mt on mch ca phn t chitin.b) Gi tn mt mt xch ca chitin.c) Vit phng trnh phn ng xy ra khi un nng chitin vi dung dch HCl
c (d), un nng chitin vi dung dch NaOH c (d).Cch gii:1. CH=O CH=N-NHC6H5
C=N-NHC6H5 + C6H5NHNH2 + NH3
+ 3 C6H5NHNH2 (CH3OH)
CH2OH D-Glucozazon
CH2OH
CH=N-NHC6H5 H+ CH=O
C=N-NHC6H5 + 2 H2O CH=O + 2 C6H5NHNH2
(CH3OH) (CH3OH)CH2OH CH2OH
CH=O CH2OH (nhm -CH=O d b kh
CH=O + 2 [H] C=O hn nhm C=O )(CH3OH)
CH2OH
CH2OH D-Fructoz
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Cu III(5 im): (thay cu III bng A, dng cho bng B)1. Cho hn hp ng phn t gm axit benzoic v axitp-metoxibenzoic tc dng
vi hn hp HNO3 c v H2SO4 c.Vit cng thc cu to hai sn phm mononitro chnh v cho bit cht no to
thnh vi s mol nhiu hn? Hy so snh tnh axit ca cc cht gm hai axit u v hai
sn phm, gii thch.2. C cc hp cht sau: H3NCH2COO
(A) , H2NCH2CONH2 (B) ,H2N-CO-NH2 (C) , CH3CHOHCOOH (D). Cho bit tng hp cht trn thuc loihp cht c chc hu c no? Vit phng trnh phn ng ca tng hp cht trn vi:
a) Dung dch HCl (d, nng) ; b) Dung dch NaOH (d, nng).Cch gii:1. HNO3
COOH + CH3O COOH COOH + CH3O COOHH2SO4
(A) (B) O2N (C) O2N (D)- S mol D nhiu hn s mol C , v B c nhm CH3O- y electron lm nhn
thm giu electron hn.- Tnh axit gim dn theo chiu : C > D > A > B .
(gii thch bng hi ng electron ca cc nhm th)2. A l aminoaxit c nhm chc cacboxyl v nhm chc amino
B l dn xut ca aminoaxit c nhm chc amit v nhm chc aminoC l dn xut ca axit cacbonic c nhm chc amit (iamit)D l - hiroxiaxit c nhm chc cacboxyl v nhm chc hiroxyl
toa) H3NCH2COO + HCl [ H3NCH2COOH]Cl
toH2NCH2CONH2 + HCl + H2O Cl[ H3NCH2COOH] + NH4Cl
toH2N-CO-NH2 + 2 HCl + H2O 2 NH4Cl + CO2
H+CH3CHCOOH + HCl CH3CHCOOH + H2O
OH Clto
b) H3NCH2COO + NaOH H2NCH2COONa + H2O
toH2NCH2CONH2 + NaOH H2NCH2COONa + NH3
toH2N-CO-NH2 + 2 NaOH Na2CO3 + 2 NH3
CH3CHCOOH + NaOH CH3CHCOOH + H2O
OH Cl
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b gio dc v o to k thi chn hc sinh gii quc gialp 12 thpt nm hc 2000-2001
thi chnh thc
Mn : Bng B
Thi gian : 180 pht ( khng k thi gian giao )Ngy thi : 13 / 3 / 2001
Cu I(5 im):1. Xut pht t brombenzen cha 14 C v tr 1 v cc ho cht v c cn thit
khng cha 14 C, hy iu ch cc hp cht thm cha 14 C v tr 3 : a) Anilin ;b) Iotbenzen ; c) Axit benzoic.
2. Hon thnh s cc phn ng sau v gi tn cc sn phm tA n F :Na2Cr2O4 2 H
Cl2 (1 mol) H2O C D
Benzen (1 mol) A BFeCl3 t
O , p HNO3 (1 mol) Fe, HClE F
3. Khi oxi ho etylenglicol bng HNO3 th to thnh mt hn hp 5 cht. Hyvit cng thc cu to phn t ca 5 cht v sp xp theo trt t gim dn nhit si ca chng (c gii thch).
Cu II(3,5 im): NXinconiin (X) c cng thc cu to :
CH=CH2
C9HOH l ng phn lp th C9 ca xinconin (Y). N
1. Hy ghi du vo mi nguyn t cacbon bt i v khoanh vng trn nguynt nit c tnh baz mnh nht trong phn tX.
2. Cho t t dung dch HBr vo X nhit phng ri un nng nh, sinh ra ccsn phm chnh l A (C19H23BrON2) , B (C19H24Br2ON2) , C (C19H25Br3ON2) , vD (C19H24Br4N2). Ch ho D vi dung dch KOH trong ru 90
o thu c E (C19H20N2)Hy vit cng thc cu to ca A , B , C , D , E. Ghi du vo mi nguyn t
cacbon bt i trong phn tD v E.
Cu III(5 im):1. Cho hn hp ng phn t gm axit benzoic v axitp-metoxibenzoic tc dng
vi hn hp HNO3 c v H2SO4 c.Vit cng thc cu to hai sn phm mononitro chnh v cho bit cht no to
thnh vi s mol nhiu hn? Hy so snh tnh axit ca cc cht gm hai axit u v haisn phm, gii thch.
2. C cc hp cht sau: H3NCH2COO (A) , H2NCH2CONH2(B) ,
H2N-CO-NH2 (C) , CH3CHOHCOOH (D). Cho bit tng hp cht trn thuc loi hpcht c chc hu c no? Vit phng trnh phn ng ca tng hp cht trn vi :
a) Dung dch HCl (d, nng) ; b) Dung dch NaOH (d, nng).
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Cu IV(4,5 im):
1. Vit phng trnh phn ng iu ch D-fructoz t D-glucoz, bit rngD-glucozazon khi tc dng vi benzanehit to thnh ozon ca D-glucoz(HOCH2(CHOH)3COCHO).
2. Chitin (tch t v tm, cua...) c coi nh l dn xut ca xenluloz, trong cc nhm hiroxyl cc nguyn t C2 c thay th bng cc nhm axetylamino( -NH-CO-CH3 ).
c) Vit cng thc cu to mt on mch ca phn t chitin.d) Gi tn mt mt xch ca chitin.c) Vit phng trnh phn ng xy ra khi un nng chitin vi dung dch HCl
c (d), un nng chitin vi dung dch NaOH c (d).Cu V(2 im):
1. Clorofom tip xc vi khng kh ngoi nh sng s b oxi ha thnh photgenrt c. nga c ngi ta bo qun clorofom bng cch cho thm mt lng nh
ancol etylic chuyn photgen thnh cht khng c.Vit phng trnh phn ng oxi ha clorofom bng oxi khng kh thnhphotgen, phn ng ca photgen vi ancol etylic v gi tn sn phm.
2. un nng vi git clorofom vi lng d dung dch NaOH, sau nh thmvi git dung dch KMnO4 thy hn hp xut hin mu xanh. Vit cc phng trnhphn ng v gii thch s xut hin mu xanh.
______________________
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b gio dc v o to k thi chn hc sinh gii quc gialp 12 thpt nm hc 2000-2001
thi d b Mn : Bng AThi gian : 180 pht ( khng k thi gian giao )
Ngy thi th nht : ( theo quyt nh v thng bo ca B)
Cu I:1. Vit cc phng trnh ho hc t Na2Cr2O7 , C (than ), Al (bt nhm) v
cc iu kin cn thit thu c Cr.2. CrO2Cl2 (cromyl clorua) l mt ho cht quan trng. Hy vit cc phng
trnh ho hc to ra CrO2Cl2 t:a) CrO3 tc dng vi axit HCl.b) Cho K2Cr2O7 tc dng vi KCl tronh H2SO4 c, nng.3. Thm cht thch hp v hon thnh phng trnh ho hc sau:a) KNO
2
+ KNO3
+ ? K2
CrO4
+ NOb) NaNO2 + ? + NaI I2 + NaHSO4 + NO + H2Oc) HNO3 + P2O5 ? + N2O5
Cu II:1. Vn dng l thuyt Bronstet v axit baz hy gii thch tnh axit baz trong
dung dch nc ca cc cht sau:a) BaCl2 ; b) K2S ; c) NH4HS ; d) NaHSO32. Hy trnh by 3 th nghim minh ho tnh cht axit baz trong mi dung
dch : a) NH4HSO4 ; b) Na2CO3 (m t cch th nghim v gii thch).3. Cho NaOH (d) vo hn hp X gm c Zn2+ ; Pb2+ ; Fe3+ ; Cu2+ ;
Mg2+ ; NO3- s c kt ta A v dung dch B.
Hy nu phng php ho hc xc nhn cc cht c mt trong kt ta A vdung dch B(nu r nhn bit) Vit phng trnh ion ca cc phn ng xy ra.Cu III:
1. Thm dn dung dch NaOH vo dung dch cha H+ 0,100M ; Fe3+ 1,0.10-3Mv Mg2+ 0,100M cho n d. Cho bit c hin tng g xy ra?
2. Gi s tng nng NaOH cho vo l 0,2030 M. Hy tnh nng cc iontrong dung dch (khi tnh khng k s to phc hiroxo ca cc ion kim loi).
Cho: Tch s tan Mg(OH)2: 10 10,95
Fe(OH)3 : 10 37,5.
Cu IV:
1. Hai mui ca cng mt axit lm i mu khc nhau i vi giy qu tm, tokt ta trng vi nc vi trong v to kt ta vng vi dung dch AgNO3 l nhngmui no? Vit cc phng trnh phn ng chng minh.
2. a) Nu dn chng c th cho thy Cu2O bn vi nhit hn CuO v CuCl bnvi nhit hn CuCl2 , gii thch nguyn nhn.
b) Nu dn chng c th cho thy trong nc CuCl km bn hn CuCl2 , giithch nguyn nhn.
c) Th in cc chun ca cp Cu2+/ Cu+ l 0,15V, ca cp I2/ 2I- l 0,54V nhng
ti sao ngi ta c th nh lng ion Cu2+ trong dung dch nc thng qua tc dngca ion vi dung dch KI? Cho bit dung dch bo ho ca CuI trong nc nhit
thng c nng l10-6
M.
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Cu V:
1. Hy thit lp s pin sao cho khi pin phng in th xy ra phn ng kh ionFe3+ bi Cu . Vit phng trnh cc na phn ng xy ra ti cc in cc.
2. Tnh sc in ng tiu chun ca pin (Eopin) khi pin mi bt u hot ng.
3. Tnh nng cc cht cn li trong cc dung dch khi pin phng in honton (gi s nng cc cht trc phn ng u bng 0,010M).
4. Sc in ng ca pin s tng hay gim nu:- Thm mt t KI- Thm t NH3
vo dung dch cc ng (dung dch A).- Thm mt t KMnO4 (mi trng axit)- Thm t NaF- Thm t NaOH
vo dung dch ca cc cha Fe3+ (dung dch B).
Cho Eo
Cu2+
/ Cu+
= 0,34V ; Eo
Cu+
/ Cu = 0,52VEoFe3+/ Fe2+ = 0,77V ; EoFe2+/ Fe = - 0,40V
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b gio dc v o to k thi chn hc sinh gii quc gialp 12 thpt nm hc 2000-2001
thi d b Mn : Bng BThi gian : 180 pht ( khng k thi gian giao )
Ngy thi th nht : ( theo quyt nh v thng bo ca B)Cu I:1. Vit cc phng trnh ho hc t Na2Cr2O7 , C (than ), Al (bt nhm) v
cc iu kin cn thit thu c Cr.2. CrO2Cl2 (cromyl clorua) l mt ho cht quan trng. Hy vit cc phng
trnh ho hc to ra CrO2Cl2 t:a) CrO3 tc dng vi axit HCl.b) Cho K2Cr2O7 tc dng vi KCl tronh H2SO4 c, nng.3. Thm cht thch hp v hon thnh phng trnh ho hc sau:a) KNO2 + KNO3 + ? K2CrO4 + NO
b) NaNO2 + ? + NaI I2 + NaHSO4 + NO + H2Oc) HNO3 + P2O5 ? + N2O5Cu II:
1. Vn dng l thuyt Bronstet v axit-baz hy gii thch tnh axit-baz trongdung dch nc ca cc cht sau:
a) BaCl2 ; b) K2S ; c) NH4HS ; d) NaHSO32. Hy trnh by 3 th nghim minh ho tnh cht axit baz trong mi dung
dch : a) NH4HSO4 ; b) Na2CO3 (m t cch th nghim v gii thch).3. Cho NaOH (d) vo hn hp X gm c Zn2+ ; Pb2+ ; Fe3+ ; Cu2+ ;
Mg2+ ; NO3- s c kt ta A v dung dch B.Hy nu phng php ho hc xc nhn cc cht c mt trong kt ta A v
dung dch B(nu r nhn bit) Vit phng trnh ion ca cc phn ng xy ra.Cu III:
1. Thm dn dung dch NaOH vo dung dch cha H+ 0,100M ; Fe3+ 1,0.10-3Mv Mg2+ 0,100M cho n d. Cho bit c hin tng g xy ra?
2. Gi s tng nng NaOH cho vo l 0,2030 M. Hy tnh nng cc iontrong dung dch (khi tnh khng k s to phc hiroxo ca cc ion kim loi).
Cho: Tch s tan Mg(OH)2: 10 10,95
Fe(OH)3 : 10 37,5.
Cu IV:1. Hai mui ca cng mt axit lm i mu khc nhau i vi giy qu tm, to
kt ta trng vi nc vi trong v to kt ta vng vi dung dch AgNO3 l nhngmui no? Vit cc phng trnh phn ng chng minh.
2. a) Nu dn chng c th cho thy Cu2O bn vi nhit hn CuO v CuCl bnvi nhit hn CuCl2 , gii thch nguyn nhn.
b) Nu dn chng c th cho thy trong nc CuCl km bn hn CuCl2 , giithch nguyn nhn.
c) Th in cc chun ca cp Cu2+/ Cu+ l 0,15V, ca cp I2/ 2I- l 0,54V nhng
ti sao ngi ta c th nh lng ion Cu2+ trong dung dch nc thng qua tc dngca ion vi dung dch KI? Cho bit dung dch bo ho ca CuI trong nc nhit thng c nng l10 -6M.
b gio dc v o to k thi chn hc sinh gii quc gia
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lp 12 thpt nm hc 2000-2001 thi d b Mn : Bng A
Thi gian : 180 pht ( khng k thi gian giao )
Ngy thi th hai : ( theo quyt nh v thng bo ca B)
Cu I:1.Vit cc phng trnh phn ng (nu c) ca:a) Axit axetic (pKa = 4,76) , phenol (pKa = 10) vi :- Dung dch NaHCO3- Dung dch Na2CO3Bit H2CO3 c pKa1 = 6,4 v pKa2 = 10,3b) Dung dch CH3COONa , dung dch C6H5ONa vi CO22. Hon thnh cc phng trnh phn ng (cc sn phm vit dng cng thc
cu to) theo cc s chuyn ho sau:CH
3OH(dung mi)
a) C6H5CH=CH2 + Br2 A + BH2SO4 , t
o
b) C6H5CH=CH2 C(C16H16)Nu tn cc c ch ca phn ng a) v b).
COOHCO2 H
+ (CH3CO)2O OCOCH3e) C6H5ONa M N
6 at, 125oC(Aspirin)
Cu II:
Hp cht thin nhin X cha 66,67% cacbon; 6,67% hiro; cn li l oxi. Bitphn t khi ca X l 180.
X tc dng vi (CH3CO)2O cho A(C14H16O5), vi HBr lnh cho B (C10H11BrO2,gm hai ng phn c to B1 v B2), vi CH3I (c mt baz) cho D (C11H14O3), vi HInng cho CH3I , v vi O3 ri Zn / HCl (dung dch) cho E (C8H8O3).
E tc dng vi HI nng cng cho CH3I, ngoi ra E cn kh c AgNO3. X , B ,v E tan trong dung dch NaOH nhng khng tan trong dung dch NaHCO3.
A v D khng tan trong dung dch NaOH nhng d lm mt mu KMnO4 longngui v brom long.
1. Xc nh cng thc phn t v cc nhm chc c trong phn t X.
2. Xc nh cng thc cu to ca X , A , B , D v E ; bit rng E l ng phnc pKa gn thp nht.3. Dng cc cng thc cu to thu gn vit cc phng trnh phn ng xy ra.
Gii thch ti sao sinh ra hai ng phn ca B.4. Gi tn X , B1 , E.
Cu III:1. Vit phng trnh phn ng monoclo ho sec-butyl clorua, gi tn cc sn
phm to thnh.2. Nu xut pht t (S)-sec-butyl clorua th s nhn c bao nhiu hp cht
quang hot? Vit cng thc cu to v gi tn theo danh php R , S.
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3. Hon thnh s cc phn ng sau v gi tn cc sn phm :Cl2 (1 mol) HNO3(1 mol) HN(C2H5)2 Fe, HCl
a) Benzen (1 mol) A B C DAlCl3 H2SO4
CH3I (1 mol)
HNO3(1 mol) Fe, HCl Gb) Phenol (1 mol) E F
ClCH2COOHH
Cu IV:Thnh phn chnh ca tinh du hi l anetol (C10H12O). Cho anetol phn ng vi
dung dch KMnO4 trong nc th to thnh kali axetat, kalip-metoxi benzoat v MnO2.1. Xc nh cng thc cu to ca anetol, vit cng thc cu trc cc ng phn
khng gian c th c v gi tn IUPAC ca chng.2. Vit cc phng trnh phn ng xy ra v ngh cch tch ly axitp-metoxi
benzoic t hn hp sau phn ng.3. Dng cng thc cu to, hy vit cc phng trnh phn ng ca anetol vi: a)
Br2/ CCl4 ; b) HCl ; c) Cl2 + H2O4. Khi un nng vi xc tc, anetol thng b ho nha. Hy gii thch.
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b gio dc v o to k thi chn hc sinh gii quc gialp 12 thpt nm hc 2000-2001
thi d b Mn : Bng BThi gian : 180 pht ( khng k thi gian giao )
Ngy thi th hai : ( theo quyt nh v thng bo ca B)
Cu I:1.Vit cc phng trnh phn ng (nu c) ca:a) Axit axetic (pKa = 4,76) , phenol (pKa = 10) vi :- Dung dch NaHCO3- Dung dch Na2CO3Bit H2CO3 c pKa1 = 6,4 v pKa2 = 10,3b) Dung dch CH3COONa , dung dch C6H5ONa vi CO22. Hon thnh cc phng trnh phn ng (cc sn phm vit dng cng thc
cu to) theo cc s chuyn ho sau:CH3OH(dung mi)
a) C6H5CH=CH2 + Br2 A + BH2SO4 , t
o
b) C6H5CH=CH2 C(C16H16)Nu tn cc c ch ca phn ng a) v b).
COOHCO2 H
+ (CH3CO)2O OCOCH3f) C6H5ONa M N
6 at, 125oC(Aspirin)
Cu II:Hp cht thin nhin X cha 66,67% cacbon; 6,67% hiro; cn li l oxi. Bit
phn t khi ca X l 180.X tc dng vi (CH3CO)2O cho A(C14H16O5), vi HBr lnh cho B (C10H11BrO2,
gm hai ng phn c to B1 v B2), vi CH3I (c mt baz) cho D (C11H14O3),vi HInng cho CH3I , v vi O3 ri Zn / HCl (dung dch) cho E (C8H8O3).
E tc dng vi HI nng cng cho CH3I, ngoi ra E cn kh c AgNO3. X , B ,v E tan trong dung dch NaOH nhng khng tan trong dung dch NaHCO3.
A v D khng tan trong dung dch NaOH nhng d lm mt mu KMnO4 longngui v bom long.
1. Xc nh cng thc phn t v cc nhm chc c trong phn t X.2. Xc nh cng thc cu to ca X , A , B , D v E ; bit rng E l ng phn
c pKa gn thp nht.Cu III:
1. Vit phng trnh phn ng monoclo ho sec-butyl clorua, gi tn cc snphm to thnh.
2. Hon thnh s cc phn ng sau v gi tn cc sn phm :Cl2 (1 mol) HNO3 (1 mol) HN(C2H5)2 Fe, HCl
a) Benzen (1 mol) A B C DAlCl3 H2SO4
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CH3I (1 mol)
HNO3 (1 mol) Fe, HCl Gb) Phenol (1 mol) E F
ClCH2COOH
HCu IV:
Thnh phn chnh ca tinh du hi l anetol (C10H12O). Cho anetol phn ng vidung dch KMnO4 trong nc th to thnh kali axetat, kalip-metoxi benzoat v MnO2.
1. Xc nh cng thc cu to ca anetol, vit cng thc cu trc cc ng phnkhng gian c th c v gi tn IUPAC ca chng.
2. Vit cc phng trnh phn ng xy ra v ngh cch tch ly axitp-metoxibenzoic t hn hp sau phn ng.
3. Dng cng thc cu to, hy vit cc phng trnh phn ng ca anetol vi: a)Br2/ CCl4 ; b) HCl ; c) Cl2 + H2O
4. Khi un nng vi xc tc, anetol thng b ho nha. Hy gii thch.
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