UBND TNH BC NINH

S GIO DC V O TO




THI CHN HC SINH GII CP TNH
NM HC 2012 2013
MN THI : HA HC-LP 12-THPT
Thi gian lm bi: 180 pht (khng k thi gian giao )
Ngy thi: 29 thng 3 nm 2013
===========
Bi 1 (3,0 im): Da vo c im cu to ca cc phn t NH
3
, H
2
S v H
2
O. Hy cho bit.
a) Ti sao gc ha tr ca cc phn t li khc nhau: Gc (HNH) = 107
0
, gc (HSH)=92
0
, gc
(HOH) = 104,5
0
. Gii thch.
b) Ti sao iu kin thng H
2
S v NH
3
l cht kh cn H
2
O l cht lng.
c) Ti sao H
2
O c khi lng ring ln nht 4
0
C v P = 1 atm.
Bi 2 (3,0 im): Mt dung dch cha 4 ion ca 2 mui v c, trong c mt ion l SO
4
2-
, khi tc
dng va vi Ba(OH)
2
t nng cho 1 cht kh, kt ta X, dung dch Y. Dung dch Y sau khi axit
ha bng HNO
3
to vi AgNO
3
kt ta trng ha en ngoi nh sng. Kt ta X em nung n khi
lng khng i thu c a gam cht rn Z. Gi tr a thay i ty theo lng Ba(OH)
2
dng: nu va
a t cc i, cn nu ly d th a gim dn n cc tiu. Khi cho cht rn Z vi gi tr cc i
a=8,51g thy Z ch phn ng ht vi 50 ml dung dch HCl 1,2M v cn li mt b rn nng 6,99 gam.
Hy lp lun xc nh hai mui trong dung dch.
Bi 3 (4,0 im): Cho hn hp A gm ba oxit ca st Fe
2
O
3
, Fe
3
O
4
v FeO vi s mol bng nhau. Ly
m
1
gam A cho vo mt ng s chu nhit, nung nng ri cho mt lung kh CO i qua ng, CO phn
ng ht, ton b kh CO
2
ra khi ng c hp th ht vo bnh ng lng d dung dch Ba(OH)
2
thu
c m
2
gam kt ta trng. Cht cn li trong ng s sau phn ng c khi lng l 19,20 gam gm
Fe, FeO v Fe
3
O
4
, cho hn hp ny tc dng ht vi dung dch HNO
3
d un nng c 2,24 lt kh
NO duy nht ( ktc).
a) Vit phng trnh ha hc ca cc phn ng.
b) Tnh khi lng m
1
, m
2
v s mol HNO
3
phn ng .
Bi 4 (4,0 im): Chia 2,24 lt ( ktc) hn hp X gm hai anken (phn t khi hn km nhau 28u)
thnh hai phn bng nhau.
Phn 1: em t chy hon ton ri cho sn phm chy qua dung dch cha 0,1 mol Ca(OH)
2
thu c 7,5 gam kt ta.
Phn 2: cho tc dng hon ton vi nc c xc tc thu c hn hp 2 ancol . un nng hn
hp 2 ancol vi H
2
SO
4
c 140
0
C mt thi gian thu c 1,63 gam hn hp 3 ete. Ho hi lng ete
thu c 0,532lt 136,5
0
C v 1,2atm.
a) Xc nh CTCT hai anken v tnh phn trm theo khi lng mi cht.
b) Xc nh hiu sut mi ancol thnh ete.
Bi 5 (3,0 im): Hp cht hu c A cha C, H, O thuc loi hp cht no, mch h v cha hai loi nhm
chc. Khi thy phn A trong mi trng axit v c long, thu c ba cht hu c B, D, E.
Bit B, D u thuc loi hp cht n chc, c cng s nguyn t cacbon trong phn t v u
tc dng vi Na gii phng H
2
. Khi t chy hon ton B thu c kh CO
2
v hi nc c th tch
bng nhau. Mt khc, t chy hon ton mt t D th thu c CO
2
v H
2
O c t l mol bng 2:3.
Khi cho 1,56 gam E tc dng ht vi dung dch AgNO
3
trong NH
3
d (hay [Ag(NH
3
)
2
]OH) th
thu c 3,24 gam Ag v cht hu c F. Bit phn t khi ca F ln hn phn t khi ca E l 50 (u).
Cc th tch kh v hi o cng iu kin nhit v p sut.
a) Xc nh CTCT ca B, D, E, t suy ra cu to ca A.
b) Vit cc phng trnh ho hc xy ra?
Bi 6 (3,0 im): Khi thy phn khng hon ton mt loi lng th, ngi ta thu c mt oligopeptit
X. Kt qu thc nghim cho thy phn t khi ca X khng vt qu 500 (u). Khi thy phn hon ton
814 mg X th thu c 450mg Gly, 178mg Ala v 330mg Phe (axit 2-amino-3-phenylpropanoic).
a) Xc nh CTPT ca oligopeptit .
b) Khi thy phn khng hon ton X th trong hn hp sn phm thy c cc ipeptit Gly-Ala,
Ala-Gly m khng thy c Phe-Gly. Xc nh CTCT c th c ca X.

============== Ht ==============
( thi gm 02 trang)
Th sinh c s dng bng HTTH v my tnh cm tay thng thng.
CHNH THC
HNG DN CHM
THI CHN HC SINH GII CP TNH NM HC 2012 2013
MN THI : HA HC-LP 12
Bi 1 (3,0 im): Da vo c im cu to ca cc phn t NH
3
, H
2
S v H
2
O. Hy cho bit.
a) Ti sao gc ha tr ca cc phn t li khc nhau: Gc (HNH) = 107
0
, gc (HSH) = 92
0
, gc
(HOH) = 104,5
0
. Gii thch.
b) Ti sao iu kin thng H
2
S v NH
3
l cht kh cn H
2
O l cht lng.
c) Ti sao H
2
O c khi lng ring ln nht 4
0
C v P = 1 atm.
NI DUNG IM
a Trong phn t NH
3
v H
2
O. Nguyn t N v O u trng thi lai ha sp
3
. nn
gc ha tr gn vi gc 109
0
28.
Nhng do cp electron t do khng tham gia lin kt trn obitan lai ha khuch
tn kh rng trong khng gian so vi cp electron lin kt, nn n c tc dng y my
electron lin kt v do gc lin kt thc t li thua gc lai ha sp
3
. Trong phn t
NH
3
nguyn t N c mt cp electron khng lin kt, cn trong phn t H
2
O nguyn t
O cn 2 cp electron khng lin kt. V vy gc lin kt (HOH) nh hn gc lin kt
(HNH) v nh hn 109
0
28.
Trong phn t H
2
S. S chu k 3 kh nng to lai ho km nn trong H
2
S mc
d c cu to tng t H
2
O nhng S khng lai ho sp
3
.
Nguyn t S b ra 2 electron c thn trn 2 obitan p (p
x
, p
y
) xen ph vi 2
obitan 1s c electron c thn ca nguyn t H to 2 lin kt S H. Gc to bi trc
ca 2 obitan p
x
v p
y
l 90
0
. Nhng do to 2 lin kt S H lm tng mt electron
khu vc gia nhn hai nguyn t S, H. Hai cp electron lin kt ny y nhau lm cho
gc lin kt HSH ln hn 90
0
v thc t l 92
0
.
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b iu kin thng NH
3
, H
2
S l cht kh; H
2
O l cht lng. H
2
O v NH
3
cng
to c lin kt hidro lin phn t nhng H
2
O c kh nng to lin kt hiro mnh
hn so vi NH
3
do hidro linh ng hn.
H
2
S khng to c lin kt hidro lin phn t, phn t phn cc km nn c
nhit si thp.

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0,5
c C hai l do:
Th nht, khi nc nng chy lin kt hiro b t i to thnh nhng lin hp phn
t n gin hn. Suy ra, th tch nc gim nn khi lng ring tng dn t 0 4
0
C.
Th hai, t 4
0
C tr i do nh hng ca nhit, khong cch gia cc phn t
tng dn lm cho th tch nc tng ln v lm khi lng ring gim dn. Do lin
quan gia hai cch bin i th tch ngc chiu nhau, nn nc c khi lng ring
ln nht 4
0
C.


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Bi 2 (3,0 im): Mt dung dch cha 4 ion ca 2 mui v c, trong c mt ion l SO
4
2-
, khi tc
dng va vi Ba(OH)
2
t nng cho 1 cht kh, 1 kt ta X, 1 dung dch Y. Dung dch Y sau khi
axit ha bng HNO
3
to vi AgNO
3
kt ta trng ha en ngoi nh sng. Kt ta X em nung c a
gam cht rn Z. Gi tr a thay i ty theo lng Ba(OH)
2
dng: nu va a t cc i, cn nu ly
d th a gim dn n cc tiu. Khi cho cht rn Z vi gi tr cc i a = 8,51g thy Z ch phn ng ht
vi 50 ml dung dch HCl 1,2M v cn li mt b rn nng 6,99 gam.
Hy lp lut xc nh 2 mui trong dung dch.
NI DUNG IM
*) Mt dung dch mui khi tc dng vi dung dch Ba(OH)
2
un nng cho kh bay ra
th kh l NH
3
. Vy trong dung dch mui c ion NH
4
+
.
NH
4
+
+ OH
-
NH
3
+ H
2
O
Kt ta X ti thiu c BaSO
4
do: Ba
2+
+ SO
4
2-
BaSO
4

Dung dch Y sau khi axit ha bng HNO
3
to vi AgNO
3
kt ta trng ngoi
nh sng ha en l AgCl nn trong dung dch Y c ion Cl
-
do:
Ag
+
+ Cl
-
AgCl ; 2AgCl
as
2Ag + Cl
2

*) Dung dch u cha 4 ion ca 2 mui v c l: NH
4
+
, Cl
-
, SO
4
2-
, A
n+
.
Nu kt ta X ch c BaSO
4
thi khi nung Z cng ch l BaSO
4
khng phn ng
c vi HCl, nh vy X phi c thm mt kt ta na do A
n+
to ra. l
A
n+
+ n OH
-
A(OH)
n


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0,5

Nung X gm BaSO
4
v A(OH)
n
. 2A(OH)
n

0
t
A
2
O
n
+ n H
2
O
*) Khi dung dch u tc dng vi Ba(OH)
2
c 2 trng hp:
- Nu va th Z c khi lng cc i.
- Nu Ba(OH)
2
dng d th Z c khi lng cc tiu iu ny chng t trong X
cht A(OH)
n
phi tip tc tan bi Ba(OH)
2
nh th A(OH)
n
l hiroxit lng tnh.
2A(OH)
n
+ (4- n)Ba(OH)
2
Ba
4
-
n
[A(OH)
4
]
2

Khi Z c khi lng cc i tc Z gm BaSO
4
v A
2
O
n
, phn ng vi HCl.
A
2
O
n
+ 2nHCl 2ACl
n
+ n H
2
O
0,03/n 0,06
B rn cn li l BaSO
4
.
Khi lng A
2
O
n
= (2A + 16n).0,03/n = 8,51 6,99 = 1,52 (g)
A =
52
.
3
n n = 3; A = 52 (tha mn). A l Cr, A
2
O
n
l Cr
2
O
3
.
Vy dung dch ban u gm cc ion: NH
4
+
, Cl
-
, SO
4
2-
, Cr
3+
.
Hai mui ban u l NH
4
Cl v Cr
2
(SO
4
)
3
hoc (NH
4
)
2
SO
4
v CrCl
3





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Bi 3 (4,0 im): Cho hn hp A gm ba oxit ca st Fe
2
O
3
, Fe
3
O
4
v FeO vi s mol bng nhau.
Ly m
1
gam A cho vo mt ng s chu nhit, nung nng n ri cho mt lung kh CO i qua ng, CO
phn ng ht, ton b kh CO
2
ra khi ng c hp th ht vo bnh ng lng d dung dch
Ba(OH)
2
thu c m
2
gam kt ta trng. Cht cn li trong ng s sau phn ng c khi lng l
19,20 gam gm Fe, FeO v Fe
3
O
4
, cho hn hp ny tc dng ht vi dung dch HNO
3
un nng c
2,24 lt kh NO duy nht (ktc).
a) Vit phng trnh ha hc ca cc phn ng.
b) Tnh khi lng m
1
, m
2
v s mol HNO
3
phn ng .
NI DUNG IM
a
CO + 3Fe
2
O
3

0
t
2Fe
3
O
4
+ CO
2
(1)
CO + Fe
3
O
4

0
t
3FeO + CO
2
(2)
CO + FeO
0
t
Fe + CO
2
(3)
Sau phn ng (1, 2, 3) thu c hn hp gm Fe, FeO, Fe
3
O
4

CO
2
+ Ba(OH)
2
BaCO
3
+ + H
2
O (4)
3Fe
3
O
4
+ 28HNO
3
9Fe(NO
3
)
3
+ NO + 14H
2
O (5)
3FeO + 10HNO
3
3Fe(NO
3
)
3
+ NO + 5H
2
O (6)
Fe + 4HNO
3
Fe(NO
3
)
3
+ NO + 2H
2
O (7)


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b Ta c s phn ng sau:
2
3
( )
2 3 2
2 3 3 4 3 3
3 4
( )
, ,
( )
19, 2 ( , , )
Ba OH
CO
HNO
CO BaCO m gam
FeO Fe O Fe O
Fe NO
g Fe FeO Fe O
NO
+
+

S dng phng php qui i: Coi hn hp (Fe, FeO, Fe
3
O
4
) l hn hp ch c
(Fe, Fe
2
O
3
). Ta c:
S mol Fe = s mol NO = 2,24/22,4 = 0,1 mol
S mol Fe
2
O
3
=
19, 2 56.0,1
0, 085
160

= (mol)
t s mol FeO = s mol Fe
2
O
3
= s mol Fe
3
O
4
= a mol
p dng nh lut bo ton nguyn t cho Fe ta c:
a + 2a + 3a = 0,1 + 0,085.2 a = 0,045 (mol)
m
1
= 0,045. (72 + 232 + 160) = 20,88 gam
p dng nh lut bo ton khi lng ta c:
20,88 + 28.n
CO
= 19,2 + 44.n
CO2
n
CO2
= n
BaCO3
= 0,105 mol (v n
CO
=n
CO2
)
m
2
= m
BaCO3
= 0,105.197 = 20,685 gam
S mol HNO
3
p = 3.n
Fe(NO3)3
+ n
NO
= 3. (0,1 + 0,085.2) + 0,1 = 0,91 (mol)












0,75
0,75


0,75
0,75
Bi 4 (4,0 im): Chia 2,24 lt ( ktc) hn hp X gm hai anken (phn t khi hn km nhau 28u)
thnh hai phn bng nhau.
Phn 1: em t chy hon ton ri cho sn phm chy qua dung dch cha 0,1 mol Ca(OH)
2
thu
c 7,5 gam kt ta.
Phn 2: cho tc dng hon ton vi nc c xc tc thu c hn hp 2 ancol . un nng hn
hp 2 ancol vi H
2
SO
4
c 140
0
C mt thi gian thu c 1,63 gam hn hp 3 ete. Ho hi lng ete
thu c 0,532lt 136,5
0
C v 1,2atm.
a) Xc nh CTCT hai anken v tnh phn trm theo khi lng mi cht.
b) Xc nh hiu sut mi ancol thnh ete.
NI DUNG IM
Cng thc chung ca hn hp hai anken l C
n
H
2n
vi n l s nguyn t C trung
bnh.
Phn 1:
0
t
n 2n 2 2 2
3n
C H + O nCO + nH O
2
(1)
S mol CO
2
= 0,05.n > 0,05.2 = 0,1 (mol). Vy khi cho CO
2
tc dng vi
Ca(OH)
2
to ra 2 mui.
CO
2
+ Ca(OH)
2
CaCO
3
+ H
2
O (1)
0,1 0,1 0,1
CO
2
+ CaCO
3
+ H
2
O 2Ca(HCO
3
)
2
(2)
0,025 (0,1 0,075)
S mol CO
2
= 0,05.n = (0,1 + 0,025) n = 2,5. Vy hai anken l C
2
H
4
v C
4
H
8
.
V n = 2,5 s mol C
2
H
4
= 0,0375; s mol C
4
H
8
= 0,0125 (mol).
Do 2 anken ch to 2 ancol nn chng l
CH
2
=CH
2
v cis-but-2-en
hoc
CH
2
=CH
2
v trans-but-2-en

%
2 4
60%
C H
m =
%
4 8
40%
C H
m =
Phn 2: C
2
H
4
+ H
2
O
H
+
CH
3
CH
2
OH (3)
C
4
H
8
+ H
2
O
H
+
C
4
H
9
OH (4)
S mol C
2
H
5
OH = s mol C
2
H
4
= 0,0375 (mol);
S mol C
4
H
9
OH = s mol C
4
H
8
= 0,0125 (mol).
2C
2
H
5
OH
2 4
0
c
140
H SO
C
2
H
5
OC
2
H
5
+ H
2
O (5)
2C
4
H
9
OH
2 4
0
c
140
H SO
C
4
H
9
OC
4
H
9
+ H
2
O (6)
C
2
H
5
OH + C
4
H
9
OH
2 4
0
c
140
H SO
C
2
H
5
OC
4
H
9
+ H
2
O (7)
Gi a, b ln lt l s mol C
2
H
5
OH v C
4
H
9
OH tham gia phn ng ete ha.
Theo bi, theo (5), (6), (7) ta c.
S mol ete = s mol H
2
O =
. 0, 532.1, 2
0,019
22, 4
.
.(136, 5 273)
273
P V
R T
= =
+
(mol)
S mol ancol phn ng = 2.s mol ete = 2.0,019 = 0,038 (mol).
Khi lng hn hp ancol phn ng = m
ete
+ m
H2O
= 1,63 + 0,019.18 = 1,972 (gam).
Ta c:
0,038 0,03
46 74 1, 972 0,008
a b a
a b b
+ = =

+ = =


Hiu sut chuyn ha C
2
H
5
OH thnh ete = 0,03.100%/0,0375 = 80%
Hiu sut chuyn ha C
4
H
9
OH thnh ete = 0,008.100%/0,0125 = 64%








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0,5

0,5

0,25
0,25


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0,25




0,25


0,25


0,5

0,25
0,25

Bi 5 (3,0 im):
Hp cht hu c A cha C, H, O thuc loi hp cht no, mch h v cha hai loi nhm chc. Khi
thy phn A trong mi trng axit v c long, thu c ba cht hu c B, D, E.
Bit B, D u thuc loi hp cht n chc, c cng s nguyn t cacbon trong phn t v u tc
dng vi Na gii phng H
2
. Khi t chy hon ton B thu c kh CO
2
v hi nc c th tch bng
nhau. Mt khc, t chy hon ton mt t D th thu c CO
2
v H
2
O c t l mol bng 2 : 3.
Khi cho 1,56 gam E tc dng ht vi dung dch AgNO
3
trong NH
3
d (hay [Ag(NH
3
)
2
]OH) th
thu c 3,24 gam Ag v cht hu c F. Bit phn t khi ca F ln hn phn t khi ca E l 50 (u).
Cc th tch kh v hi o cng iu kin nhit v p sut.
a) Xc nh CTCT ca B, D, E, t suy ra cu to ca A.
b) Vit cc phng trnh ho hc xy ra?
NI DUNG IM
a T p thy phn suy ra A cha chc este; B l axit no mch h hoc ancol mch h
c mt lin kt i n chc : C
n
H
2n
O
2
hoc C
n
H
2n
O.
t D thu c s mol H
2
O ln hn CO
2
v D p vi Na to H
2
nn D l ancol no,
mch h, n chc c s C trong phn t bng : n = 2/(3-2) = 2. Vy D l C
2
H
5
OH
=> B c CTPT C
2
H
4
O
2
(Loi C
2
H
4
O v khng tn ti CH
2
=CH-OH v A no).
CTCT l CH
3
-COOH.
V khi 1 nhm CHO COONH
4
th phn t khi tng 33u, m 33 < 50 < 33.2
Nn trong E ngoi 1 nhm CHO cn c 1 nhm COOH(v COOH COONH
4
c
tng phn t khi l 17u)
+ V A c chc este m khi thy phn to ra CH
3
-COOH v C
2
H
5
OH nn E phi c
nhm COOH v OH. C n
E
= n
Ag
/2 = 0,015 mol M
E
=
1, 56
0, 015
=104u. Gi cng
thc E (HO)
a
R(CHO)-COOH 17a + R = 30 a= 1, R = 13(CH)
Vy E c CTCT : HOOCCH(OH)CHO.
CTCT ca A l : C
2
H
5
OOCCH(OOC-CH
3
)CHO


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0,5
0,5
b C
2
H
5
OOCCH(OCOCH
3
)CHO +2H
2
OOHC-CH(OH)COOH+CH
3
COOH + C
2
H
5
OH
CH
3
COOH + Na CH
3
COONa + 1/2H
2

C
2
H
5
OH + Na C
2
H
5
ONa + 1/2H
2

C
2
H
5
OH + 3O
2
2CO
2
+ 3H
2
O
HOOC-CH(OH)-CHO + 2[Ag(NH
3
)
2
]OH HO-CH(COONH
4
)
2
+ 2Ag +2NH
3
+ H
2
O


0,5
Bi 6 (3,0 im):
Khi thy phn khng hon ton mt loi lng th, ngi ta thu c mt oligopeptit X. Kt qu
thc nghim cho thy phn t khi ca X khng vt qu 500 (vC). Khi thy phn hon ton 814 mg
X th thu c 450mg Gly, 178mg Ala v 330mg Phe (axit 2-amino-3-phenylpropanoic).
a) Xc nh CTPT ca oligopeptit .
b) Khi thy phn khng hon ton X th trong hn hp sn phm thy c cc ipeptit Gly-Ala,
Ala-Gly m khng thy c Phe-Gly. Xc nh CTCT c th c ca X.
NI DUNG IM
a T s mol cc amino axit thu c khi thy phn chnh l t s cc mt xch
amino axit trong phn t oligopeptit X. Ta c:
450 178 330
: : : : 3: 1: 1
75 89 165
Gly Ala Phe = =
Cng thc n gin nht ca oligopeptit X l (Gly)
3
(Ala)(Phe).
Cng thc phn t l [(Gly)
3
(Ala)(Phe)]
n
vi M s 500u
V 5 phn t aminoaxit tch i 4 phn t nc.
(3.75 + 89 + 165 4.18).n s 500 n = 1.
Cng thc phn t ca oligopeptit l (Gly)
3
(Ala)(Phe) hay C
18
H
25
O
6
N
5

l mt pentapeptit gm 3 mt xch glyxin, mt mt xch alanin v mt mt xch
phenylalanin.


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b Khi thy phn tng phn thy c Gly-Ala v Ala-Gly chng t mt xch ala
gia 2 mt xch Gly: .. Gly- Ala Gly
Khng thy c Phe-Gly chng t Phe khng ng trc Gly. Nh vy Phe ch
c th ng cui mch (amino axit ui). Vy oligopeptit c th l
Gly-Gly-Ala-Gly-Phe
Gly-Ala-Gly-Gly-Phe
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Ch : Nu th sinh c cch gii khc, kt qu ng th vn cho im ti a tng ng.