K THI LP I TUYN QUC GIA

P N V THANG IM
Mn : Ho hc
(gm 9 trang)

Kho ngy 29 thng 12 nm 2009

Cu 1 : (2 im)
C 3 hp cht khc nhau ca Cr (III) vi nc v ion clorua c cng thnh phn l
19,51% Cr ; 39,92% Cl v 40,57%H2O.
- Hp cht th nht c mu tm tan nhanh trong nc cho ion phc c in tch 3+
v 3 ion Cl. Tt c ion Cl ny kt ta ngay khi thm AgNO3 vo dung dch.
- Hp cht th 2 c mu xanh tan nhanh trong nc cho ion phc c in tch l 2+
v 2 ion Cl. C 2 ion Cl ny u cho kt ta AgCl.
- Hp cht th 3 c mu lc tan nhanh trong nc cho ion phc c in tch l 1+
v cho 1 ion Cl. Ion Cl ny cho kt ta AgCl.
1) Vit cng thc, v cu trc v gi tn 3 phc cht .
2) Dung dch mui Cr (III) c c im mu sc thay i. Gii thch nguyn nhn
gy nn hin tng .
p n
19,51 39,92 40,57
1) nCr : nCl : nH2O =
:
:
= 0,375 : 1,125 : 2,25 = 1 : 3 : 6
35,5
52
18
=> 3 hp cht ca crom c cng thc l CrCl3.6H2O
(0,50 )
- Cht (I) :
[Cr(H2O)6]Cl3 mu tm, hexaaqucrom(III)clorua
[Cr(H2O)6]Cl3 [Cr(H2O)6]3+ + 3Cl
- Cht (II) :
[Cr(H2O)5Cl]Cl2.H2O pentaaquclorocrom(III)clorua
[Cr(H2O)5Cl]Cl2 [Cr(H2O)5Cl]2+ + 2Cl
- Cht (III) :
[Cr(H2O)4Cl2]Cl.2H2O tetraaquiclorocrom(III)clorua
[Cr(H2O)4Cl2]Cl [Cr(H2O)4Cl2]+ + Cl
(0,50 )
- Cu trc ca ba phc trn u c hnh bt din.
Cl

H2O
H2O
H2O

Cr
H2O

H2O

(I)

Cl
H2O

H2O H2O

Cr
H2O

H2O

(II)

H2O
H2O H2O

Cr
H2O

H2O

Cl

(III)

(0,50 )
2) Mu sc ca dung dch thay i do cc electron d c thn hp th nh sng
vng trng thy v chuyn dch trong trng ca phi t. Phi t c trng mnh yu
khc nhau nn hp cht th hin mu khc nhau.
(0,50 )
Cu 2 : (2 im)
1) Tnh nng mol/l ca dung dch amoniac ha tan va ht 0,01 mol kt ta
AgCl bng 100 ml dung dch NH3. Bit AgCl c tch s tan T = 10 9,75, cc phc
[AgNH3]+ v [Ag(NH3)2]+ c cc hng s to phc ln lt l 1 = 103,32; 2 = 103,92.
Trang 1/10

2) Tnh in li ca CO32 trong dung dch Na2CO3 c pH =11,60. Bit H2CO3 c

pKa1 = 6,35 v pKa2 = 10,33.
p n
+

1) AgCl Ag + Cl
T = 109,75
(a)
+
+
3,32
Ag
+ NH3 [AgNH3]
1 = 10
(b)
+
+
3,92
[AgNH3] + NH3 [Ag(NH3)2]
2 = 10
(c)
=> AgCl
+ 2NH3 [Ag(NH3)2]+ + Cl Kcb
(d) (0,25 )
Ho tan ht 0,01 mol AgCl, cn 0,02 mol NH3, to thnh 0,01 mol [Ag(NH3)2]+;
v 0,01 mol Cl
=> [Ag(NH3)2+] = [Cl] = 0,01 : 0,1 = 0,1M; [NH3] to phc = 0,2M
(0,25 )
Kcb = T. 1 . 2 = 10 9,75.103,32.103,92 = 102,51
[Ag(NH3 ) 2 + ][Cl ]
0,1.0,1
2,51
Kcb =
=
2 = 10
2
[NH
]
[NH ]
3
3

=> [NH3] = 1,8 M

(0,25 )
=> tng nng mol/l ca NH3 = 1,8 trong dung dch + 0,2 trong phc = 2,0 M.
(0,25 )
2,4
2) pH = 11,6 => pOH = 2,4 => [OH] = 10 M
CO32 + H2O HCO3 + OH (1)
Kb1 = 1014/1010,33 = 103,67
HCO3 + H2O H2CO3 + OH (2)
Kb2 = 1014/106.35 = 107,65
Kb1 >> Kb2 , cn bng (1) l ch yu.
(0,25 )
2

3,67
CO3 + H2O HCO3 + OH
Kb1 =10
C
C
[ ]
C - 102,4
102,4 102,4
(102,4 ) 2
3,67
=> Kb1 =
=> C = 0,0781 M
(0,50 )
2,4 = 10
C - 10
102,4
2
=> (CO3 ) = 0,0781 .100 = 5,1(%)
(0,25
)
Cu 3 : (2 im)
Ngi ta tin hnh xc nh tc ca phn ng 250C :
CH3Br + KOH CH3OH + KBr
Cc s liu thc nghim nh sau :
Nng u (mol.l1)
Tc phn ng
Th nghim
CH3Br
KOH
(mol.l1 .s1)
1
0,10
0,10
2,80.106
2
0,10
0,17
4,76.106
3
0,033
0,20
1,85.106
1. Hy xc nh bc ring i vi tng cht ban u v bc chung ca phn ng.
2. Hy tnh hng s tc ca phn ng (ghi r n v)
3. Sau my gi th th nghim 1 ch cn 0,05 mol.l1 mi cht trong bnh?
Trang 2/10

1)

p n
t biu thc ca tc phn ng l : v = k.CaCH3Br.CbKOH
v1 = k.0,1a . 0,1b
= 2,8 .106 (1)
v2 = k.0,1a . 0,17b = 4,76 .106 (2)
v3 = k.0,033a . 0,2b
= 1,85 .106 (3)
Lp cc t s :

(0,50 )

v1
0,1b
2,8
=
=
=> b = 1
v2
4, 6
0,17b
v1
0,1a.0,1 b
2,8
=
=
=> a = 1
v3
0, 033a.0, 2 b 1,85

Bc phn ng i vi CH3Br v KOH u bng 1, bc chung bng 2. (0,50 )

2,8.10 6
2) v = k.CCH3Br.CKOH => k =
= 2,8.104. (mol1.l.s1)
(0,50 )
0,1.0,1
3) Nng mi cht u bng nhau v u gim mt na
1
1
=> t1/2 = k.C =
= 9,92 gi
(0,50 )
2,8.10 4.0,1
o
Cu 4 : (2 im)
n mn kim loi thng i km vi cc phn ng in ha. Vic n mn g st
trn b mt cng theo c ch ny. Phn ng in cc ban u thng l :
(1) Fe(r) Fe2+(aq) + 2e
(2) O2 + 2H2O + 4e 4OH (aq)
T bo in ha ng vi cc phn ng trn c biu din nh sau (t=25oC) :
Fe(r)Fe2+(aq)OH(aq), O2 (k)Pt(r).
Th in cc chun 25oC :
Fe2+(aq) + 2e Fe(r)
Eo = 0,44V.
O2 + 2H2O + 4e 4OH(aq)
Eo = 0,40V.
1. Tnh Eo ca phn ng 25oC.
2. Vit PTHH ca phn ng xy ra khi pin hot ng v tnh hng s cn bng K
ca phn ng.
3. Phn ng xy ra trong 24 gi v I = 0,12A. Tnh khi lng Fe chuyn thnh
2+
Fe sau 24 gi.
4. Tnh E ca phn ng bit:
[Fe2+] = 0,015M; pHna pin phi = 9,00; p(O2) = 0,700 bar. (1 atm = 1,013 bar)
p n
o
o
o
1. E pin = E phi E tri = 0,40 (-0,44) = 0,84V
(0,50 )
2. 2Fe + O2 + 2H2O 2Fe2+ + 4OH
o
K = 10nE /0,059=104.0,84/0,059= 8,9.1056
(0,50 )
3. Q = It = 10368 C => ne = Q/F = 0,1075 mol => mFe = 3,01 g.
(0,50 )
[Fe 2+ ]2 [OH ]4
0,059
o
log
4.
Epin = E pin 4
PO
2

Trang 3/10

pH = 9,00 [H+] = 10 9M => [OH] = 10 5M

PO2 = 0,7/1,013 = 0,69 atm
0,0152.(105 )4
0,059
=> E = 0,84
log
= 0,49V
(0,50 )
4
0,69
Cu 5 : (2 im)
iu ch Cl2 trong cng nghip bng phng php in phn mui n, do iu
kin khng m bo ngoi Cl2 thu c cn to thnh mt lng ClO2 v mt s cht
khc. Trong phng th nghim, ClO2 c iu ch nhanh chng bng cch cho hn
hp KClO3, H2C2O4 tc dng vi H2SO4 long, cn trong cng nghip ClO2 c iu
ch bng cch cho NaClO3 tc dng vi SO2 c mt H2SO4 4M. Vit cc phng
trnh phn ng gii thch s to thnh cc cht trn. So snh cc phn ng v cc sn
phm khi cho mi cht Cl2 v ClO2 tc dng vi H2O, vi dung dch NaOH.
p n
iu ch Cl2 trong cng nghip :
in phn nng chy :
2NaCl 2Na + Cl2
in phn dung dch NaCl c mng ngn :
2NaCl + 2H2O H2 + Cl2 + 2NaOH
(0,50 )
S to ClO2 do :
4Cl2 + 3O2 + 2H2O 4ClO2 + 4HCl
2KClO3 + H2C2O4 + 2H2SO4 2ClO2 + 2KHSO4 + 2CO2 + 2H2O
2NaClO3 + SO2 + H2SO4 2ClO2 + 2NaHSO4
(0,50 )
Cc phn ng vi H2O, vi dung dch NaOH
6ClO2 + 3H2O HCl + 5HClO3
Cl2
+ H2O HCl
+ HClO
2ClO2 + 2NaOH NaClO2 + NaClO3 + H2O
Cl2
+ 2NaOH NaCl
+ NaClO + H2O
(0,50 )
Bn cht ca cc phn ng ny ging nhau : u l phn ng t oxi ho - kh.
Khc nhau : Cl Cl2 Cl+ cn Cl3+ Cl4+ Cl5+
(0,50 )
Cu 6 : (2 im)
Mt hp cht v c cha bit A c mt s c im v tnh cht sau :
- A l mt cht rn mu trng hi vng, d chy ra v thng hoa khi un nng. A
c phn t khi l 267.
- A phn ng mnh lit vi nc cho dung dch B.
- Khi mt dung dch hn hp gm NH3 v NH4Cl c thm vo dung dch B th
nhn c kt ta keo mu trng.
- Mt mu dung dch B phn ng vi dung dch hn hp axit nitric v bc nitrat
cho kt ta mu trng C. Kt ta trng ny tan i khi thm vo dung dch NH 3, khi
NH3 d th li xut hin kt ta trng D.
- Lc kt ta D, em ho tan trong NaOH thu c dung dch trong sut E.
Trang 4/10

- Khi cho kh CO2 li qua dung dch E th li sinh ra kt ta D.

- Cht A ho tan khng in li trong ete khan. Khi dung dch ny phn ng vi
LiH th s to thnh sn phm F. Nu dng d LiH th F s chuyn thnh G.
Xc nh cht A v cc cht t B n G. Vit cc PTHH ca cc phn ng xy ra.
p n
T cc d kin bi => A l hp cht ca Al v Cl, phn t khi 267 => Al2Cl6
(0,25 )
Cc PTHH :
H2O AlCl3 (dung dch B)
Al2Cl6
Al3+ + 3NH3 + 3H2O Al(OH)3 + 3NH4+
(0,25 )

+
Cl
+ Ag
AgCl (kt ta C)
AgCl + 2 NH3 [Ag(NH3)2]Cl
(0,50 )
3+
+
Al
+ 3NH3 + 3H2O Al(OH)3 (kt ta D)+ 3NH4
Al(OH)3
+ OH [Al(OH)4](dung dch E)
[Al(OH)4] + CO2 Al(OH)3 + HCO3
(0,50 )
ete 6LiCl + 2AlH3 (F)
Al2Cl6 + 6LiH
AlH3 + LiH
LiAlH4 (G)
(0,50 )
Cu 7 : (2 im)
1) Vit cng thc cu to ca cc ng phn cis v trans ca imin N2H2. Trong
mi cu to , nguyn t N dng lai ha no ? ng phn no bn hn? Ti sao?
2) 3-metylbut-1-en tc dng vi axit clohiric to ra cc sn phm, trong c A
l 2-clo-3-metylbutan v B l 2-clo-2-metylbutan. Bng c ch phn ng, hy gii
thch s to thnh hai sn phm A v B.

1)

Trans-imin

p n
Cis-imin

H
N

N
H

H
N

(0,50 )
C 2 ng phn u phng, mi nguyn t N u trng thi lai ha sp . Ti N c
3 obitan lai ha sp2 v 1 obitan p cha lai ha (to lin kt pi), trong c 1 obitan
sp2 cha 1 i electron t do.
(0,25 )
Dng trans bn hn v 2 m my e t do khc pha, tng tc yu hn dng cis.
(0,25 )
2) Do cacbocation bc hai (II) c kh nng chuyn v hirua to thnh cacbocation
bc ba (III) nn to thnh hai sn phm A, B.
2

Trang 5/10

CH3

CH3
CH3-CH-CH=CH2

H+

+
CH3-CH-CH2-CH2 (I)
CH3
CH3-CH-CH-CH3 (II)
+
Cl
CH3

chuyn v

CH3
CH3-C-CH2-CH3 (III)
+
ClCH3

CH3-CH-CH-CH3

CH3-C-CH2-CH3

Cl
2-Clo-3-metylbutan

Cl
2-Clo-2-metylbutan

(0,25 )
Cu 8 : (2 im)
1. Mt hc sinh tng hp glixeranehit theo hai giai on (1a, 1b) sau:
KOH/alcol
KMnO4 (l)
Glixerandehit
Cl
CH2 CH2 CHO
CH2 CH
CHO
1a
1b
(A)
(A2)
(A1)
a. Nhn xt 2 phn ng trn (1a, 1b) l ng hay sai? Ti sao?
b. T A1, ngh cch khc tng hp A?
2. Cho bit cc cng thc ha hc lp th cho cc hp cht t E n J?
CN/H+ E + F
R-(+)-glixeranehit
(u c cng thc C4H7O3N)
1) OH , H2O, to
E + F
G+H
(u c cng thc C4H8O5)
2) H+
G + HNO3 I (C4H6O6)
H + HNO3 J (C4H6O6)

(hot ng quang hc)

(khng hot ng quang hc)

p n
1.a. Phn ng (1a) sai do trong mi trng baz (KOH) ngoi phn ng tch E2
cn c th cho phn ng aldol ho trn nhm CHO.
(0,25 )
Phn ng (1b) sai v ngoi lin kt i >C=C<, nhm CHO cng c th b oxi
ho trong KMnO4 long to COOH.
(0,25 )
b. Phng php tng hp A t A1:
Cl

CH2 CH2
(A1)

C2H4(OH)2
CHO
CH2 CH2
HCl

O
CH

KOH
Alcol

O
CH2

CH2 CH
OH

OH
(A)

CHO

H+/H2O

CH

O
KMnO4 (l)

Cl

CH

O
CH2 CH
OH

OH

CH
O

(0,50 )

Trang 6/10

2. Hc sinh c th trnh by theo cng thc phi cnh hoc Newman u c

im nu xc nh ng cu trc sau :

CHO
H

CN ,H+

HO

HO
H

OH
CH2OH
G

2) H+

CN

+
-,H

CN

(R)-(+)-Glixerandehit

OH

CH2OH
E
1) OH-, H2O, toC

OH
CH2OH

HO

COOH

COOH

CN

H
OH
COOH
I

HNO3

COOH

COOH

OH

OH

OH

OH

OH

OH

CH2OH
H

CH2OH
F

COOH
J (Meso)

(1,00 )
Cu 9 : (2 im)
Hp cht hu c A c cng thc phn t C7H9N.
- Cho A phn ng vi C2H5Br d, sau vi NaOH thu c hp cht B c cng
thc phn t C11H17N. Nu cng cho A phn ng vi C2H5Br c xc tc AlCl3 khan
th to ra hp cht C c cng cng thc phn t vi B.
- Cho A phn ng vi H2SO4 c 180oC to hp cht D c cng thc phn t
C7H9O6S2N, sau khi ch ho D vi NaOH 300oC ri vi HCl s cho sn phm E c
phn ng mu vi FeCl3.
- Nu cho A phn ng vi NaNO2 / HCl 5oC, ri cho phn ng vi -naphtol
trong dung dch NaOH th thu c sn phm c mu G.
Xc nh cng thc cu to ca A, B, C, D, E, G v vit cc phng trnh phn
ng (nu c).
p n
- A phn ng vi C2H5Br (d) nn sn phm B C11H17N c nhm N,N-ietyl
-A phn ng vi NaNO2 / HCl 5oC, ri cho phn ng vi -naphtol trong dung
dch NaOH th thu c sn phm c mu G => A c nhm chc amin bc I v c
nhm metyl.
-A phn ng vi H2SO4 (c) 180oC to hp cht D c cng thc phn t
C7H9O6S2N, y l phn ng sunfo ho nhn thm, c 2 nhm -SO3H => nhm metyl
s v tr para so vi nhm amin.
- Sau khi ch ho D vi NaOH 300oC ri trung ho bng HCl s cho sn phm E
(E c phn ng mu vi FeCl3) => E c nhm chc phenol.
-A phn ng vi C2H5Br c xc tc AlCl3 (khan) hp cht C c cng cng thc
phn t vi B (C11H17N), l sn phm th vo nhn benzen, v v tr para so vi
nhm -NH2 c nhm -CH3 nn nhm -C2H5 s th vo v tr ortho.
(1,00 )
Trang 7/10

C2H5

C2H5

(1) C2H5Br (du)

(2) NaOH

(B)
CH3

NH2

C2H5Br

NH2
C2H5

C2H5
(C)

AlCl3 khan

CH3

H2SO4 dac
o
180 C

NH2

HO3S

(D)
o
NaNO2 + HCl, 5 C
-naphtol/ NaOH

CH3

SO3H

o HO
1) NaOH, 300 C

OH

2) H+

(E)

CH3

H3C

NH2

NaO

N N

CH3
(G)

(1,00 )
Cu 10 : (2 im)
Trong mt ma c mt cht ng khng c tnh kh l rafinoz c cng thc phn
t C18H32O16 (A). Thy phn hon ton (A) c D-glucoz (B), D-fructoz (C) v
D-galactoz (D) l ng phn epime ca D-glucoz cacbon s 4.
a. Vit cng thc Fisher v Haworth dng vng 6 cnh ca D-galactoz.
b. Thy phn khng hon ton (A) nh enzim -galactozidaza (enzim xc tc cho
phn ng thy phn cc -galactozit) thu c -D-galactoz v saccaroz. Nu
thy phn (A) bng enzim invecta (men thy phn saccaroz) li cho D-fructoz v
mt isaccarit.
Metyl ha hon ton (A) nh hn hp CH3I v Ag2O, sau thy phn sn phm
metyl ha thu c 1,3,4,6-tetra-O-metyl-D-fructoz (E); 2,3,4,6-tetra-O-metyl-Dgalactoz (G) v 2,3,4-tri-O-metyl -D-glucoz (H). Xc nh cng thc cu trc ca
(E), (G), (H) v (A).
p n

Trang 8/10

a. Cng thc chiu Fisher v Haworth dng vng 6 cnh ca D-galactoz

CHO
OH
H
H
OH
CH2OH

H
HO
HO
H

OH

H2C

H2C
O H

HO
OH

OH
OH

OH

-D-galactopiranoz

O OH

HO

OH

H
H

OH

-D-galactopiranoz

(0,25 3)
b. Theo bi rafinoz khng c tnh kh => khng c nhm OH hemiaxetal.
(A) b thy phn to ra D-fructoz + D-galactoz + D-glucoz nn (A) cu to t 3
monosaccarit trn. (A) b thy phn di tc dng ca men -galactozidaza to ra
-D-galactoz v saccaroz vy (A) c -D-galactoz mt u mch.
(A) b thy phn bi men invecta to D-fructoz v isaccarit vy (A) c Dfructoz u mch cn li, vy trong (A) D-glucoz nm gia.
Do saccaroz c cu to t -D-fructoz v -D-glucoz nn phn t -Dfructoz v -D-glucoz vi -D-galactoz to ra (A) theo trt t : -Dgalactoz- -D-glucoz- -D-fructoz.
T cc v tr O-metyl ca E, H, G => cu to ca (A) rafinoz :
CH2OH
OH

O
OH
O
OH

CH2
O
OH

OH
O

OH

CH2OH

OH

HO

HOCH2
CH2OCH3
CH3O

CH3OCH2

O
CH2OH

CH3O

OCH3

HO
OH
OCH3

OCH3

OCH3
CH2OCH3 CH O
3

OH
OCH3

(0,25 5)
Trang 9/10

-------------ooOoo------------(Th sinh c th lm theo cch khc. Gim th khng c gii thch g thm.)

Trang 10/10