Part 1

TUYN TP THI HC SINH
GII MN HA HC
[Ti liu tng hp t cc thi HSG]
[copyright2010 http://vn.myblog.yahoo.com/volcmttl]
YDS
Phan Cuong Huy
Copyright 2010 http://vn.myblog.yahoo.com/volcmttl
2 TUYN TP THI HC SINH GII MN HA HC
PHN 1: CC THI HC SINH GII THNH PH NNG
(Ngun: Thy ng Cng Anh Tun GV Trng THPT Chuyn L Qu n Nng)
S 1
S GIO DC V O TO
THNH PH NNG
HNG DN CHM THI HC SINH GII THNH PH
NM HC 2007 - 2008
MN: HA HC LP 1O
Thi gian: 150 pht (khng k thi gian giao )
Cu I (4 im)
X v Y l cc nguyn t nhm A, u to hp cht vi hiro c dng RH (R l k hiu ca nguyn t X hoc Y).
Gi A v B ln lt l hiroxit ng vi ha tr cao nht ca X v Y. Trong B, Y chim 35,323% khi lng. Trung
ha hon ton 50 gam dung dch A 16,8% cn 150 mL dung dch B 1M.
1. Xc nh cc nguyn t X v Y.
2. B l anion tng ng ca phn t B. (a) Hy cho bit (c cng thc minh ha) dng hnh hc ca B v B. (b)
So snh (c gii thch) di lin kt Y-O trong phn t B v B.
3. Bit X c cu trc tinh th lp phng tm khi v mt sp xp tng i c nh ngha bng t l gia
th tch chim bi cc hnh cu trong t bo c s v th tch t bo c s. Hy tnh mt sp xp tng i
trong tinh th ca X.
P N IM
1. Hp cht vi hiro c dng RH nn Y c th thuc nhm IA hoc VIIA.
Trng hp : Nu Y thuc nhm IA th B c dng YOH
Ta c : 284 , 9 Y
677 , 64
323 , 35
17
Y
= = (loi do khng c nghim thch hp)
Trng hp 2 : Y thuc nhm VIIA th B c dng HYO
4
Ta c : 5 , 35 Y
677 , 64
323 , 35
65
Y
= = , vy Y l nguyn t clo (Cl).
B (HClO
4
) l mt axit, nn A l mt baz dng XOH
gam 4 , 8 gam 50
100
8 , 16
m
A
= =
XOH + HClO
4
XClO
4
+ H
2
O
mol 15 , 0 L / mol 1 L 15 , 0 n n
4
HClO A
= = =
mol 15 , 0
gam 4 , 8
mol / gam 17 M
X
= +
M
X
= 39 gam/mol, vy X l nguyn t kali (K).
2. B l HClO
4
, B l ClO
4
-
(a) Dng hnh hc :
Axit pecloric
(dng t din)
Ion peclorat
(dng t din u)
(b) Bc lin kt cng ln di lin kt cng nh, do vy :
3. Gi a l di cnh mng c s v R l bn knh nguyn t, ta c R 4 a 3 =
S nguyn t c trong mt mng c s bng : 2 1
8
1
8 = +
Vy % 68
a
R
3
4
2
f
3
3
v
=
t
=
Cu II (4 im)
1. Cho bit s oxi ha ca mi nguyn t lu hunh (S) trong phn t axit thiosunfuric (H
2
S
2
O
3
) v ca mi
nguyn t cacbon trong phn t axit axetic (CH
3
COOH)
2. Thm lng d dung dch KI (c pha h tinh bt) vo 5,00 mL dung dch K
2
Cr
2
O
7
c nng a M trong
H
2
SO
4
, th dung dch thu c c mu xanh. Thm tip dung dch Na
2
S
2
O
3
0,10 M vo cho n khi mu xanh
bin mt th dng 15,00 mL dung dch ny. Vit cc phng trnh phn ng v tnh a. Bit sn phm oxi ha
S
2
O
3
2-
l S
4
O
6
2-
.
3. Ha tan hon ton 9,06 gam mt mu hp kim Al-Mg (gi thit khng c tp cht no khc) bng dung dch
H
2
SO
4
c, thu c 12,22 L kh SO
2
(o 136,5
o
C; 1,1 atm) v 0,64 gam cht rn mu vng. Xc nh phn
trm khi lng mi kim loi trong mu hp kim trn.
P N IM
1. S oxi ha ca cc nguyn t S v C :
1.0
2. Phng trnh phn ng :
6KI + K
2
Cr
2
O
7
+ 7H
2
SO
4
3I
2
+ Cr
2
(SO
4
)
3
+ 4K
2
SO
4
+ 7H
2
O (1)
2Na
2
S
2
O
3
+ I
2
2NaI + Na
2
S
4
O
6
(2)
0,5
T (1) v (2) ta c : mol 10 . 5 , 2 L / mol 1 , 0 L 015 , 0
6
1
n
6
1
n
4
O S Na O Cr K
3 2 2 7 2 2
= = =
M 05 , 0
L 10 . 5
mol 10 . 5 , 2
a
3
4
= =

0,5
3. Gi x, y ln lt l s mol cc kim loi Mg v Al.
) mol ( 4 , 0
5 , 1 273
273
4 , 22
22 , 12 1 , 1
n
2
SO
=

= ; Cht rn l S, ) mol ( 02 , 0
32
64 , 0
n
S
= =
0
02 . 0 12 , 0
6
y
4
4 , 0 8 , 0
6
y 3
3 0
y
x 2
2 0
x
S e 6 S
S e 2 S
e 3 Al Al
e 2 Mg Mg
+
+
+
+
+
+ +
+
+
1,5
Ta c :
= =
= +
= +
22 , 0 y ; 13 , 0 x
92 , 0 y 3 x 2
06 , 9 y 27 x 24
% 44 , 34 % 100
gam 06 , 9
mol / gam 24 mol 13 , 0
m %
Mg
=
= v % 56 , 65 m %
Al
=
0,5
Cu III (4 im)
1. Nguyn t ca nguyn t X c tng s ht cc loi l 60, s ht mang in trong ht nhn bng s ht khng mang
in; Nguyn t ca nguyn t Y c 11 electron p ; nguyn t nguyn t Z c 4 lp electron v 6 electron c thn.
a) Da trn cu hnh electron, cho bit v tr ca cc nguyn t trn trong bng h thng tun hon.
b) So snh (c gii thch) bn knh ca cc nguyn t v ion X, X
2+
v Y
-
.
2. V hnh m t cch tin hnh th nghim iu ch dung dch HCl bng nhng ha cht v dng c n gin c sn
trong phng th nghim sao cho an ton. Ghi r cc ch thch cn thit.
3. Sc Cl
2
vo dung dch KOH long thu c dung dch A, ha tan I
2
vo dung dch KOH long thu c dung
dch B (tin hnh nhit phng).
a) Vit phng trnh ha hc xy ra v cho nhn xt.
b) Nu hin tng v vit phng trnh ha hc xy ra khi cho ln lt cc dung dch hn hp HCl v FeCl
2
,
dung dch Br
2
, H
2
O
2
vo dung dch A (khng c Cl
2
d).
P N IM
1. a) Xc nh v tr da vo cu hnh electron:
X X X X X
2Z N 60 ; Z N Z 20 + = = = , X l canxi (Ca), cu hnh electron ca
20
Ca:[Ar] 4s
2
Y c 11 electron p nn cu hnh ca Y l 1s
2
2s
2
2p
6
3s
2
3p
5
hay [Ne] 3s
2
3p
5
Y l Cl
Theo gi thit th Z chnh l crom, cu hnh electron ca
24
Cr: [Ar] 3d
5
4s
1
STT Chu k nguyn t Nhm nguyn t
Ca 20 4 IIA
Cl 17 3 VIIA
Cr 24 4 VIB
Trt t tng dn bn knh nguyn t:
Ca
Cl Ca
R R R
2
< <
+
b) Bn knh nguyn t t l vi thun vi s lp electron v t l nghch vi s n v in
tch ht nhn ca nguyn t . Bn knh ion Ca
2+
nh hn Cl
-
do c cng s lp electron (n
= 3), nhng in tch ht nhn Ca
2+
(Z = 20) ln hn Cl
-
(Z = 17). Bn knh nguyn t Ca ln
nht do c s lp electron ln nht (n = 4).
2,0
2. iu ch HCl t dung dch H
2
SO
4
m c v NaCl rn, hnh 5.5 trang 128 SGK Ha hc 10
nng cao.
0,75
3. a) nhit thng:
2KOH + Cl
2
KCl + KClO + H
2
O
6KOH + 3I
2
5KI + KIO
3
+ 3H
2
O
Gii thch: Trong mi trng kim tn ti cn bng: 3XO
-
X
-
+ XO
3
Ion ClO
-
phn hy rt chm nhit thng v phn hy nhanh khi un nng, ion IO
-
phn
hy tt c cc nhit .
b) Cc phng trnh ha hc:
Ion ClO
-
c tnh oxi ha rt mnh, th hin trong cc phng trnh ha hc:
- Khi cho dung dch FeCl
2
v HCl vo dung dch A: c kh vng lc thot ra v dung dch t
1,25
khng mu chuyn sang mu vng nu:
2 FeCl
2
+ KClO + 2HCl 2 FeCl
3
+ Cl
2
+ H
2
O
- Khi cho dung dch Br
2
vo dung dch A : dung dch brom mt mu :
Br
2
+ 5KClO + H
2
O 2HBrO
3
+ 5KCl
- Khi cho H
2
O
2
vo dung dch A: c kh khng mu, khng mi thot ra:
H
2
O
2
+ KClO H
2
O + O
2
+ KCl
Cu IV(4 im)
1 Cho bit: nng lng lin kt ca cc lin kt H-H, O-O, O=O, H-O ln lt l 436, 142, 499, 460 ( kJ/mol).
Hy vit phng trnh nhit ha hc ca phn ng gia kh hiro v kh oxi to ra hiropeoxit.
2 Cho phn ng: 2SO
2
(k) + O
2
(k) 2SO
3
(k) H = - 198 kJ
a) tng hiu sut qu trnh tng hp SO
3
, ngi ta c th s dng bin php no lin quan n p sut, nhit
v cht xc tc? Gii thch?
b) Cho 10,51 mol kh SO
2
v 37,17 mol khng kh (20% v th tch l O
2
cn li l N
2
) c xc tc l V
2
O
5
. Thc
hin phn ng 427
0
C, 1 atm th phn ng t hiu sut 98%. Tnh hng s cn bng K
C
, K
P
ca phn ng
427
0
C.
3 A l mt oxit ca st. Ly mt lng A chia lm 2 phn bng nhau. Phn I tc dng va vi a mol H
2
SO
4
trong dung dch H
2
SO
4
long. Phn II tc dng va vi b mol H
2
SO
4
trong dung dch H
2
SO
4
c nng to
SO
2
(sn phm kh duy nht). Bit b = 1,25a, xc nh cng thc oxit st ban u.
P N IM
1. H
p
= E
H-H
+ E
O=O
- 2E
O-H
- E
O-O
H
p
= 436 + 499 -2.460 142 = -127 (kJ)
H
2
(k) + O
2
(k) H
2
O
2
(k) H = - 127 kJ
1,0
- Gim nhit ca h phn ng, nhng khong 500
0
C l thch hp v: nu gim thp qu th
tc phn ng chm.
- Thi lin tc SO
2
v khng kh c nn p sut cao vo l phn ng v phn ng xy ra
theo chiu thun lm gim p sut ca h.
- Dng V
2
O
5
lm xc tc phn ng mau chng t trng thi cn bng.
0,75
2. nO
2 b
= 7,434 (mol), nN
2 b
= 29,736 (mol)
2SO
2
(k) + O
2
2SO
3
(k) H = - 198 kJ
Ban u: 10,51 (mol) 7,434 (mol) 0
Lc phn ng: 10,3 (mol) 5,15 (mol) 10,3 (mol)
Lc CB: 0,21 (mol) 2,284 (mol) 10,3 (mol)
s mol hn hp TTCB = 0,21 + 2,284 + 10,3 + 29,736 = 42,53 (mol)
P
i
= x
i
.P = x
i
.1 = x
i
1,25
2
3
P 2
2 2
(Pso )
K =
(Pso ) .Po
v
- n
C P
K =K (RT)
A
(R = 0,082, T = 427 + 273 = 700
0
K, n = -1)
2
4
P 2
(10,3) .42,53
K = >> 4,48.10
(0,21) .2,284
v
4 -(-1) 4
C
K =4,48.10 .(0,082.700) 257.10 ~
3. Gi Fe
x
O
y
l cng thc ca A
( 1) 2Fe
x
O
y
+ 2yH
2
SO
4
xFe
2
(SO
4
)
2y/x
+ 2y H
2
O
n ny
(2) 2Fe
x
O
y
+ (6x-2y) H
2
SO
4
xFe
2
(SO
4
)
3
+ (3x-2y) SO
2
+ ( 6x-2y) H
2
O
n n (3x-y)
Theo gi thit : n(3x-y) = 1,25 ny
x 2, 25 3
y 3 4
= = A l Fe
3
O
4
1,0
Cu V ( 4 im)
1. T dung dch H
2
SO
4
98% ( D= 1,84 g.mL
-1
) v dung dch HCl 5 M, trnh by phng php pha ch c
200 mL dung dch hn hp H
2
SO
4
1M v HCl 1M .
2. t chy hon ton a gam S ri cho sn phm sc qua 200 mL dung dch NaOH b M thu c dung dch X.
Chia X lm hai phn bng nhau. Phn 1 cho tc dng vi dung dch CaCl
2
d thy xut hin c gam kt ta .
Phn 2 tc dng vi dung dch nc vi d thy xut hin d gam kt ta . Bit d >c. Tm biu thc quan h
gia a v b.
3. Cho cc dung dch ring bit mt nhn sau: Na
2
SO
4
, AlCl
3
, FeSO
4
, NaHSO
4
, FeCl
3
. Mt hc sinh cho rng nu
dng dung dch Na
2
S th c th phn bit cc dung dch trn ngay ln th u tin. Kt lun ca hc sinh
c ng khng ? V sao?
P N IM
1.
* Phn tnh ton :
S mol H
2
SO
4
cn ly = s mol HCl cn ly =
200 1
0, 2 (mol)
1000
=
Khi lng dung dch H
2
SO
4
cn ly : m
dd
=
0, 2 98 100
20 (gam)
98

=
Th tch dung dch H
2
SO
4
cn ly = 20 : 1,84 = 10,87 (mL)
Th tch dung dch HCl cn ly = 0,2 : 5 = 0,04 (L) = 40 mL
* Cch tin hnh: Ly khong 100 - 120 mL nc cho vo bnh th tch 200 mL c chia vch.
1,0
Cn 20 gam dung dch H
2
SO
4
hoc ong 10,87 mL dung dch H
2
SO
4
, sau cho t t vo
bnh cha nc khuy u. i dung dch H
2
SO
4
tht ngui, ong 40 mL dung dch HCl 5M
thm vo bnh, sau thm nc vo cho n vch 200 mL
2. Phng trnh :
(1) S + O
2
SO
2
(2) SO
2
+ NaOH NaHSO
3
(3) SO
2
+ 2 NaOH Na
2
SO
3
+ H
2
O
Phn I tc dng vi dung dch CaCl
2
sinh kt ta, chng t dung dch X c cha Na
2
SO
3
, phn
II tc dng vi dung dch Ca(OH)
2
sinh nhiu kt ta hn chng t dung dch X c mui
NaHSO
3
(4) Na
2
SO
3
+ CaCl
2
CaSO
3
+ 2NaCl
(5) NaHSO
3
+ Ca(OH)
2
CaSO
3
+ Na
2
SO
3
+ 2H
2
O
n
s
= a/32 (mol) , n
NaOH
= 0,2 b ( mol)
Theo (2),(3), SO
2
tc dng vi dung dch NaOH sinh 2 loi mui th :
2
NaOH NaOH
SO S
n n
1 2
n n
< = < 1 <
0, 2b 6, 4b
a
a
32
= < 2
Vy :
a a
b
6, 4 3, 2
< <
1,5
3. Kt lun ca hc sinh trn ng, v khi cho dung dch Na
2
S ln lt vo mu th ca cc
dung dch trn th:
- Mu th khng c hin tng cha dung dch Na
2
SO
4
- Mu th xut hin kt ta trng keo v c hin tng si bt kh cha AlCl
3
: 2AlCl
3
+ 3
Na
2
S + 3H
2
O 6NaCl + 2Al(OH)
3
+ 3H
2
S
- Mu th c hin ttng si bt kh cha dung dch NaHSO
4
2 NaHSO
4
+ Na
2
S 2Na
2
SO
4
+ H
2
S
Mu th xut hin kt ta en cha FeCl
2
: Na
2
S + FeCl
2
FeS + 2NaCl
- Mu th xut hin kt ta en v vng c cha FeCl
3
2FeCl
3
+ 3Na
2
S 6NaCl + S + 2FeS
1,5
S 2
S GIO DC V O TO
THNH PH NNG
K THI CHN HC SINH GII LP 10
NM HC 2008-2009
MN THI: HA HC
Thi gian lm bi : 150 pht (khng k thi gian giao )
CHNH THC
( ny gm c hai trang)
Cu I: ( 2,0 im)
1. (a) X,Y u l hai nguyn t nhm A. Nguyn t X c tng s electron s l 7, Y l nguyn t p, c s electron
ln hn 15, c 3 lp electron v c 2 electron p c thn trng thi c bn. Xc nh X, Y v gi tn. (b) So
snh bn knh ca ion A
+
, B
2-
v gii thch. (c) Vit s hnh thnh lin kt trong oxit bc cao nht ca X. Vit
cng thc cu to v cho bit dng hnh hc ca oxit bc cao nht v hiroxit tng ng ca Y.
2. (a) Xc nh x, y v hon thnh phng trnh ht nhn
238 206 4 0
92 82 2 1
U Pb x He y e
+ +
(b) Mt mu cha 35 mg
238
92
U v 3 mg
206
82
Pb . Tnh thi gian tn ti ca mu , bit chu k bn hy ca
238
92
U l 4,51.10
9
nm.
3. M l mt kim loi c khi lng nguyn t l 1,0550817.10
-22
gam. Trong t nhin M c hai ng v hn km
nhau 2 ntron. T l % s nguyn t ca ng v nh hn trong t nhin l 73%. Xc nh s khi hai ng v
v tnh % v khi lng ca ng v nh trong oxit MO. (Cho: 1u = 1,6605.10
-24
gam, O = 16, gi tr nguyn t
khi ca mi ng v bng s khi.)
Cu II: ( 2,0 im)
1. a) Xc nh s oxi ho ca P, S, Pb trong cc cht sau : POCl
3
; Na
2
S
2
O
3
; Pb
3
O
4
.
2. Hon thnh v cn bng cc phn ng sau theo phng php cn bng electron:
a) Fe
3
O
4
+ HI FeI
2
+ I
2
+ ?
b) CrI
3
+ KOH + Cl
2
K
2
CrO
4
+ KIO
4
+ ? + ?
3. Ha tan 1,0 gam mt qung st cha Fe
2
O
3
v tp cht tr trong dung dch HCl d, loi tp cht, thu c dung
dch A. Dung dch A phn ng va vi mt lng dung dch KI thu c dung dch B v cht rn C. Cht
rn C tc dng va vi 25 ml dung dch Na
2
S
2
O
3
0,2 M. Tnh % khi lng Fe
2
O
3
trong qung st ni trn.
Cho cc phn ng xy ra hon ton.
Cu III: ( 2,0 im)
1. a) Vit phng trnh ha hc thc hin chuyn ha sau, ghi r iu kin phn ng.
1 2 3 4
3 2 2 3
KCl KClO Cl Br BrF
( ) ( ) ( ) ( )

b) (SCN)
2
l mt halogen gi. Bit tnh oxi ha ca Br
2
> (SCN)
2
> I
2
. Vit phng trnh ha hc minh ha kt
qu so snh trn .
2. Ti sao c s khc bit v gc lin kt ca Cl
2
O (111
0
) v OF
2
(105
0
) ?
3. tch brom c trong 1m
3
nc bin di dng NaBr, ngi ta cho mt lng dung dch H
2
SO
4
vo mt
lng nc bin; tip n sc kh clo vo dung dch mi thu c; sau dng khng kh li cun hi brom
vo dung dch Na
2
CO
3
ti khi bo ho brom. Cui cng cho H
2
SO
4
vo dung dch bo ho brom, thu hi
brom ri ho lng, c 28,05 ml Br
2
c khi lng ring 3,12 g/ml 20
0
C. Vit phng trnh ho hc ch yu
xy ra trong qu trnh v cho bit vai tr ca H
2
SO
4
. Tnh % khi lng ca brom trong nc bin bit khi
lng ring ca nc bin l 1,25 g/ml.
Cu IV: ( 2,0 im)
1. Cho hn hp Fe v FeS tc dng vi dung dch H
2
SO
4
m c nng thu c dung dch X lm mt mu dung
dch K
2
Cr
2
O
7
trong H
2
SO
4
long. Vit phng trnh ha hc ca cc qu trnh th nghim trn.
2. A l hp cht ca lu hunh, tan rt tt trong nc to dung dch X cha mt cht tan. Ha tan 25,8 gam A vo
nc thu c 200 ml dung dch X ( D = 1,15 g/ml). Chia dung dch X lm hai phn bng nhau. Phn 1 trung ha
va vi 100 ml dung dch NaOH 10% (D = 1,2 g/ml). Phn 2 tc dng vi dung dch BaCl
2
d thu c mt
kt ta trng khng tan trong axit. Xc nh cng thc phn t v vit cng thc cu to ca A.
Cu V: (2,0 im)
1. Hng s cn bng K
C
25
0
C ca phn ng Cl
2
(k) 2Cl (k) l 1,4.10
-18
. Tnh nng Cl 25
0
C lc cn
bng bit nng ca Cl
2
lc cn bng l 0,896 M. T cho bit 25
0
C, clo tn ti ch yu dng phn t
hay nguyn t ?
2. Cho bit cn bng 2FeCl
2 (aq)
+ Cl
2 (aq)
FeCl
3 (aq)
s chuyn di theo chiu no khi sc mt lng kh H
2
S
thch hp vo dung dch? Cho V 36 , 1 E , V 77 , 0 E
Cl 2
Cl
0
Fe
Fe
0
2
2
3
+ = + =
+
+
.
3. Phn ng chuyn ho mt loi khng sinh trong c th ngi nhit 37
0
C c hng s tc bng 4,2.10
-5
(s
-1
). Vic iu tr bng loi khng sinh trn ch c kt qu nu hm lng khng sinh lun lun ln hn 2,00
mg trn 1,00 kg trng lng c th. Mt bnh nhn nng 58 kg ung mi ln mt vin thuc cha 300 mg
khng sinh .
a) Hi bc ca phn ng chuyn ho?
b) Khong thi gian gia 2 ln ung thuc k tip l bao lu?
c) Khi bnh nhn st n 38,5
0
C th khong cch gia 2 ln ung thuc thay i nh th no? Bit nng
lng hot ho ca phn ng bng 93,322 kJ.mol
1
.
----------------HT ---------------
Ch : Hc sinh c s dng H thng tun hon cc nguyn t ha hc v my tnh c nhn n gin theo quy
nh ca B Gio dc v o to. Gim th khng gii thch g thm.
S 3
S GIO DC V O TO
THNH PH NNG
HNG DN CHM K THI HC SINH GII THNH PH
NM HC 2004 - 2005
MN: HA HC LP 11
CU I (3 im)
1. Hy so snh v gii thch s khc nhau v phn cc phn t, nhit si v mnh tnh baz gia NH
3
v
NF
3
.
2. N
2
O
4
phn li 20,0% thnh NO
2
27
o
C v 1,00 atm. Hy xc nh (a) gi tr K
p
; (b) phn li ca N
2
O
4
ti 27
o
C
v 0,10 atm; (c) phn li ca 69g N
2
O
4
trong bnh 20 L 27
o
C.
3. Tnh pH ca dung dch thu c khi thi ht 224 mL kh CO
2
vo 200 mL dung dch NaOH 0,05M, bit axit
cacbonic c 35 , 6 pK
1 a
= , 33 , 10 pK
2 a
= .
P N IM
1. Cu to:
N
H
H
H
N
F
F
F
- NH
3
phn cc hn NF
3
do trong NH
3
lng cc lin kt v lng cc electron t do cng
chiu, cn trong NF
3
lng cc lin kt v lng cc electron t do ngc chiu.
- Nhit si ca NH
3
cao hn do NH
3
to c lin kt H lin phn t.
- NH
3
l mt baz cn NF
3
th khng, do trong NF
3
cc nguyn t F ht electron lm gim
mt electron trn nguyn t N.
2. Xt phn ng phn li:
N
2
O
4
2NO
2
n 0
no 2no
n-no 2no
Phn mol:
o +
o
1
1
o +
o
1
2
, P
1
4
P
P
P
K
2
2
O N
2
NO
O N
2
NO
P
4 2
2
4 2
2
o
o
=
= =
(a) 17 , 0 1
) 2 , 0 ( 1
) 2 , 0 ( 4
P
1
4
K
2
2
2
2
P
=
=
o
o
=
(b) %) 6 , 54 ( 546 , 0 17 , 0 10 , 0
1
4
2
2
= o =
o
o
(c) mol 75 , 0
92
69
n = =
0,75
(0,253)
) 1 ( 9225 , 0
20
300 082 , 0 ) 1 ( 75 , 0
P
4 2
O N
o =
o
=
o =
o
= 845 , 1
20
300 082 , 0 . 75 , 0 . 2
P
2
NO
17 , 0
) 1 ( 9225 , 0
) 845 , 1 (
K
2
P
=
o
o
= %) 27 , 19 ( 1927 , 0 = o
3. 01 , 0 05 , 0 2 , 0 n , mol 01 , 0
4 , 22
224 , 0
n
NaOH CO
2
= = = =
V s mol CO
2
v NaOH bng nhau nn h ch cha NaHCO
3
. C th tnh pH ca h lng tnh
ny bng cng thc:
, ) 3 , 8 33 , 10 35 , 6
2
1
) pK pK (
2
1
pH
2 1
= + = + =
1,50
(0,503)
0,75
(0,25+0,5)
CU II (3 im)
2. Vit phng trnh phn ng xy ra khi cho NH
4
Cl tc dng vi CuO v vi ZnO. Cho bit ng dng thc t ca
NH
4
Cl tng ng vi cc phn ng ny.
3. Ha tan 10,00 g hn hp gm Cu
2
S v CuS bng 200,0 mL dung dch MnO
4
-
0,7500 M trong mi trng axit.
Sau khi un si ui ht kh SO
2
sinh ra, lng MnO
4
-
cn d trong dung dch phn ng va ht vi 175,0
mL dung dch Fe
2+
1,000 M.
(a) Vit cc phng trnh phn ng xy ra (dng phng trnh ion thu gn).
(b) Tnh phn trm khi lng CuS trong hn hp ban u.
P N IM
1. Trong thc t, NH
4
Cl c dng nh sch b mt kim loi trc khi hn:
4CuO + 2NH
4
Cl N
2
+ 3Cu + CuCl
2
+ 4H
2
O
ZnO + 2NH
4
Cl ZnCl
2
+ 2NH
3
+ H
2
O
2. (a) Phng trnh phn ng:
5Cu
2
S + 8MnO
4
-
+ 44H
+
10Cu
2+
+ 5SO
2
+ 8Mn
2+
+ 22H
2
O (1)
5CuS + 6MnO
4
-
+ 28H
+
5Cu
2+
+ 5SO
2
+ 6Mn
2+
+ 14H
2
O (2)
5Fe
2+
+ MnO
4
-
+ 8H
+
5Fe
3+
+ Mn
2+
+ 4H
2
O (3)
(b) Xc nh %
(1) mol 035 , 0 1 175 , 0
5
1
n
5
1
n
2
4
Fe ) 3 ( MnO
= = =
+
1,50
(0,503)
0,75
(0,253)
mol 115 , 0 035 , 0 75 , 0 2 , 0 n
) 2 , 1 ( MnO
4
= =
t s mol Cu
2
S v CuS ln lt l x v y, ta c:
=
=
= +
= +
0625 , 0 y
025 , 0 x
115 , 0 y
5
6
x
5
8
10 y 96 x 160
% 60 % 100
10
96 0625 , 0
m %
S Cu
=
=
0,75
CU III (4 im)
1. Ch dng cht ch th phenolphtalein, hy phn bit cc dung dch NaHSO
4
, Na
2
CO
3
, AlCl
3
, Fe(NO
3
)
3
, NaCl,
Ca(NO
3
)
2
. Cc phn ng minh ha vit di dng ion thu gn.
2. Ha tan ht 2,2 g hn hp kim loi A gm st v nhm trong 150 mL dung dch HNO
3
2M thu c dung dch
B v 448 mL (ktc) kh C gm N
2
O v N
2
c t khi so vi khng kh bng 1,2414. Thm 13,6 g NaOH nguyn
cht vo dung dch B thu c kt ta D, lc kt ta D thu c dung dch nc lc E.
(a) Tnh phn trm khi lng mi kim loi trong hn hp A ban u.
(b) Nung kt ta D n khi lng khng i th thu c bao nhiu gam cht rn khan?
(c) Tnh th tch dung dch HCl 0,5M cn thm vo dung dch E thu c 2,34 g kt ta.
P N IM
1. Trch mu th cho mi ln th nghim:
Cho phenolphtalein vo mi mu th. Mu th c mu hng l dung dch Na
2
CO
3
, cc mu
th cn li khng mu.
CO
3
2-
+ H
2
O HCO
3
-
+ OH
-
Dng Na
2
CO
3
lmthuc th cho vo cc mu th cn li.
Mu th c si bt kh khng mu l NaHSO
4
CO
3
2-
+ 2H
+
H
2
O + CO
2
Mu th to kt ta trng keo v si bt kh khng mu l AlCl

3
2Al
3+
+ 3CO
3
2-
+ 3H
2
O 2Al(OH)
3
+ 3CO
2
Mu th to kt ta nu v si bt kh khng mu l Fe(NO
3
)
3
2Fe
3+
+ 3CO
3
2-
+ 3H
2
O 2Fe(OH)
3
+ 3CO
2
Mu th to kt ta trng l Ca(NO
3
)
2
Ca
2+
+ CO
3
2-
CaCO
3
Mu th khng to hin tng l NaCl.

2. (a) t s mol N
2
O v N
2
ln lt bng a v b, ta c:
1,50
(0,256)
= =
= =
+
= = +
01 , 0 b a
36 29 2414 , 1
02 , 0
b 28 a 44
02 , 0
4 , 22
448 , 0
b a
t s mol Fe v Al ln lt bng x v y
Cht kh Cht oxi ha
Fe - 3e Fe
3+
10H
+
+ 2NO
3
-
+ 8e N
2
O + 5H
2
O
3x x 0,10 0,08
Al - 3e Al
3+
12H
+
+ 2NO
3
-
+ 10e N
2
+ 6H
2
O
3y y 0,12 0,10
V mol 3 , 0 ) bd ( n mol 22 , 0 ) pu ( n
H H
= < =
+ +
nn axit d, phn ng khng to Fe
2+
.
Ta c:
=
=
= +
= +
04 , 0 y
02 , 0 x
18 , 0 y 3 x 3
2 , 2 y 27 x 56
Vy % 9 , 50 % 100
2 , 2
56 02 , 0
m %
Fe
=
= v % 1 , 49 m %
Al
=
(b) Thm NaOH vo dung dch B [H
+
(0,15.2-0,22 = 0,08 mol), Fe
3+
(x = 0,02 mol), Al
3+
(y = 0,04
mol) v NO
3
-
]
H
+
+ OH
-
H
2
O (1)
Fe
3+
+ 3OH
-
Fe(OH)
3
(2)
Al
3+
+ 3OH
-
Al(OH)
3
(3)
Al(OH)
3
+ OH
-
AlO
2
-
+ 2H
2
O (4)
mol 34 , 0
40
6 , 13
n mol 3 , 0 n 4 n 3 n n
) bd ( OH Al Fe H ) 4 , 3 , 2 , 1 ( OH
3 3
= = < = + + =
+ + +
sau (1), (2), (3), (4) vn cn d OH
-
, kt ta D l Fe(OH)
3
(0,02mol)
2Fe(OH)
3
Fe
2
O
3
+ 3H
2
O, m
rn
= g 6 , 1 160 01 , 0 m
3 2
O Fe
= =
(c) Thm HCl vo dung dch E [Na
+
, OH
-
(0,04 mol), AlO
2
-
(0,04 mol) v NO
3
-
]
OH
-
+ H
+
H
2
O (5)
AlO
2
-
+ H
+
+ H
2
O Al(OH)
3
(6)
Al(OH)
3
+ 3H
+
Al
3+
+ 3H
2
O (7)
1,00
0,50
mol 03 , 0
78
34 , 2
n
3
) OH ( Al
= =
Trng hp 1: Xy ra (5), (6) v AlO
2
-
d
mol 07 , 0 03 , 0 04 , 0 n n n
3
) OH ( Al
OH H
= + = + =
+
, L 14 , 0
5 , 0
07 , 0
V = =
Trng hp 2: Xy ra (5), (6), (7)
mol 01 , 0 03 , 0 04 , 0 n
) 7 ( ) OH ( Al
3
= =
mol 11 , 0 03 , 0 04 , 0 04 , 0 n 3 n n n
) 7 ( ) OH ( Al
AlO OH H 3
2
= + + = + + =
+
L 22 , 0
5 , 0
11 , 0
V = =
1,00
(0,502)
CU IV (3 im)
1. Tnh hiu ng nhit phn ng hidro ha etilen to etan, bit nhit chy ca C
2
H
6
v C
2
H
4
ln lt bng -368,4
kcal/mol v -337,2 kcal/mol [sn phmchy l CO
2
(k) v H
2
O (l)], nhit hnh thnh H
2
O (l) l -68,32 kcal/mol.
2. (a) Vit cng thc cu to v gi tn anken t cacbon nht ng thi c ng phn hnh hc v ng phn
quang hc. (b) Vit cc ng phn hnh hc v quang hc ng vi cu to (s dng cng thc Fisher) v xc
nh cu hnh mi ng phn (Z/E v R/S). (b) Vit cu to cc sn phm chnh hnh thnh khi cho anken trn
tc dng vi dung dch nc brom c lng nh mui natri clorua.
P N IM
1. (1) C
2
H
6
(k) + 7/2O
2
(k) 2CO
2
(k) + 3H
2
O (l) kcal 4 , 368 H = A
(2) C
2
H
4
(k) + 3O
2
(k) 2CO
2
(k) + 2H
2
O (l) kcal 2 , 337 H = A
(3) H
2
(k) + 1/2O
2
(k) H
2
O (l) kcal 32 , 68 H = A
Ly (2) - (1) + (3) ta c:
C
2
H
4
(k) + H
2
(k) C
2
H
6
(k) kcal 1 , 37 ) 32 , 68 ( ) 4 , 368 ( ) 2 , 337 ( H = + = A
2. (a) Cu to:
CH
3
CH CH C
H
CH
3
C
2
H
5
(4-metylhex-2-en)
(b) Cu hnh:
1,00
0,25
C
C
CH
3
H
C
2
H
5
C
H
H
CH
3
C
C
H CH
3
C
2
H
5
C
C
CH
3
H
C
2
H
5
C
CH
3
H
H
C
C
H CH
3
C
2
H
5
H
H
C
CH
3
H
CH
3
C
H
(E)(R) (E)(S)
(Z)(R)
(Z)(S)
(c) Cu to cc sn phm:
CH
3
CH CH CH
CH
3
C
2
H
5
CH
3
CH CH CH
CH
3
C
2
H
5
Br Br
CH
3
CH CH CH
CH
3
C
2
H
5
OH Br
CH
3
CH CH CH
CH
3
C
2
H
5
Cl Br
1,00
(0,254)
0,75
(0,253)
CU V (3 im)
1. Hidrocacbon A c khi lng phn t bng 80. Ozon phn A ch to andehit fomic v andehit oxalic.
C H
O
H C H
O
C
O
H
andehit fomic andehit oxalic
a. Xc nh cu to v gi tn A.
b. Dng c ch gii thch cc sn phmhnh thnh khi cng Br
2
vo A theo t l mol 1:1, gi tn cc sn phm
ny.
2. Hp cht A c cng thc phn t C
9
H
8
. A lmmt mu Br
2
trong CCl
4
; hidro ha A trong iu kin m du to
ra C
9
H
10,
cntrong iu kin nhit v p sut cao th to ra C
9
H
16
; oxi ha mnh lit A sinh ra axit phtalic
[1,2-C
6
H
4
(COOH)
2
]. Lp lun xc nh cu to ca A.
P N IM
1. (a) Cng thc tng qut cho A l C
x
H
y
Ta c
=
=
+ s
= +
8 y
6 x
2 x 2 y
80 y x 12
, cng thc phn t C
6
H
8
) 3 ( = A
T sn phmozon phn ta thu c cu to ca A:
0,50
CH
2
CH CH CH CH CH
2
H
2
C O O
H
C
H
C O O
H
C
H
C O O CH
2
A (hexa-1,3,5-trien)
(b) C ch v sn phm:
CH
2
CH CH CH CH CH
2
Br
2
CH
2
CH CH CH CH CH
2
CH
2
CH CH CH CH CH
2
Br
Br
CH
2
CH CH CH CH CH
2
Br
CH
2
CH CH CH CH CH
2
CH
2
CH CH CH CH CH
2
Br
Br
CH
2
CH CH CH CH CH
2
Br
Br
Br
Br
(X) 5,6-dibromhexa-1,3-dien; (Y) 3,6-dibromhexa-1,4-dien;
(X)
(Y)
(Z)
(Z) 1,6-dibromhexa-2,4-dien
2. A (C
9
H
8
) c bt bo ha 6 = A
A lm mt mu Br
2
v cng m du 1 phn t H
2
cho thy A c 1 lin kt i.
A cng ti a 4 phn t H
2
v khi oxi ha to axit phtalic cho thy A c vng benzen v ngoi ra
cn mt vng 5 cnh na.
Cng thc ca A:
0,50
(0,252)
1,50
(0,503)
0,50
CU VI (4 im)
Chia 3,584 L (ktc) hn hp gm mt ankan (A), mt anken (B) v mt ankin (C) thnh 2 phn bng nhau. Phn 1
cho qua dung dch AgNO
3
d trong NH
3
thy th tch hn hp gim 12,5% v thu c 1,47g kt ta. Phn 2 cho
qua dung dch brom d thy khi lng bnh brom tng 2,22g v c 13,6g brom tham gia phn ng. t chy
hon ton kh ra khi bnh brom ri hp th sn phm chy vo dung dch Ba(OH)
2
d th thu c 2,955g kt ta.
1. Xc nh cng thc cu to A, B v C.
2. T A vit dy chuyn ha (ghi r iu kin phn ng) iu ch 1,1-dibrompropan v 2,2-dibrompropan.
3. Vit phng trnh phn ng xy ra khi cho C tc dng vi dung dch KMnO
4
trong (i) mi trng trung tnh
nhit phng v (ii) mi trng axit (H
2
SO
4
) c un nng.
P N IM
1. Trong mt phn, ta c: mol 08 , 0
4 , 22
584 , 3
2
1
n
C , B , A
= = . Dung dch AgNO
3
/NH
3
ch hp th ankin,
t cng thc ankin l RCCH (gi s khng phi l C
2
H
2
).
RCCH + AgNO
3
+ NH
3
RCCAg + NH
4
NO
3
(1)
mol 01 , 0 08 , 0
100
5 , 12
n n
ankin
= = != (R + 132) 0,01 = 1,47
R = 15 (CH
3
-), cng thc ca ankin l CH
3
CCH
Dung dch brom hp th anken (C
n
H
2n
) v ankin
C
n
H
2n
+ Br
2
C
n
H
2n
Br
2
(2)
C
3
H
4
+ 2Br
2
C
3
H
4
Br
4
(3)
g 82 , 1 40 01 , 0 22 , 2 m
n 2 n
H C
= = , mol 065 , 0 2 01 , 0
160
6 , 13
n
) 2 ( Br
2
= =
T
065 , 0
1
82 , 1
n 14
= n = 2, cng thc ca anken l CH
2
=CH
2
.
Kh ra khi bnh brom l ankan (C
m
H
2m+2
), mol 005 , 0 065 , 0 01 , 0 08 , 0 n
2 n 2 n
H C
= =
+
C
m
H
2m+2
+
2
O
2
1 n 3
|
.
|
\
| +
nCO
2
+ (n+1)H
2
O (4)
CO
2
+ Ba(OH)
2
BaCO
3
+ H
2
O (5)
015 , 0
197
955 , 2
n n
3 2
BaCO CO
= = = T (4): 3 n
015 , 0
n
005 , 0
1
= = , cng thc ankan l CH
3
CH
2
CH
3
.
2. iu ch:
C
3
H
8
C
3
H
7
Cl CH
3
CH=CH
2
CH
3
CHBr-CH
2
Br
CH
3
C CH
CH
3
CH
2
CHBr
2
CH
3
CBr
2
CH
3
Cl
2
,as KOH/ROH
KOH/ROH
Br
2
HBr
HBr
peoxit
3. Phn ng ca C:
+ 2KMnO
4
CH
3
C CH CH
3
C C
O O
+ 2MnO
2
+ KOH OK
5CH
3
CCH + 8KMnO
4
+ 12H
2
SO
4
5CH
3
COOH + 5CO
2
+ 8MnSO
4
+ 4K
2
SO
4
+ 12H
2
O
0,75
0,75
0,50
1,00
(0,502)
1,00
(0,502)
S 4
S GIO DC V O TO
THNH PH NNG
NM HC 2005 - 2006
MN: HA HC LP 11
CU I (4 im)
1. Nu hin tng xy ra v vit phng trnh phn ng minh ha trong cc trng hp sau:
(a) Ha tan t t cho n d dung dch NaOH vo dung dch AlCl
3
, sau thm HCl vo dung dch thu c
n d.
(b) Thm dung dch K
2
CO
3
vo dung dch Fe(NO
3
)
3
2. A l dung dch Na
2
CO
3
0,1M; B l dung dch hn hp Na
2
CO
3
0,1M v KHCO
3
0,1M v C l dung dch KHCO
3
0,1M.
(a) Tnh th tch kh CO
2
(ktc) thot ra khi cho t t tng git n ht 50 mL dung dch HCl 0,1M vo 100 mL
dung dch A v khi cho ht 100 mL dung dch B vo 200 mL dung dch HCl 0,1M.
(b) Xc nh s mol cc cht c trong dung dch thu c khi thm 100 mL dung dch Ba(OH)
2
0,1M vo 150
mL dung dch C.
(c) Tnh pH ca cc dung dch A v C, bit axit cacbonic c pK
1
= 6,35 v pK
2
= 10,33.
(d) ngh phng php nhn bit cc anion c trong dung dch B.
P N IM
1. (a) Thmdung dch NaOH vo dung dch AlCl
3
thy xut hin kt ta trng keo, sau tan li:
Al
3+
+ 3OH
-
Al(OH)
3
Al(OH)
3
+ OH
-
Al(OH)
4
-
Thm HCl vo dung dch thu c li thy xut hin kt ta trng keo, sau tan
li:
Al(OH)
4
-
+ H
+
Al(OH)
3
+ H
2
O
Al(OH)
3
+ 3H
+
Al
3+
+ 3H
2
O
0,50
(b) Thm dung dch K
2
CO
3
vo dung dch Fe(NO
3
)
3
thy xut hin kt ta nu v si bt kh
khng mu: 2Fe
3+
+ 3CO
3
2-
+ 3H
2
O 2Fe(OH)
3
+ 3CO
2
0,25
2. (a) Cho t t tng git n ht 50 mL dung dch HCl 0,1M vo 100 mL dung dch Na
2
CO
3
0,1M
CO
3
2-
+ H
+
HCO
3
-
0,01 0,005
0,005 0,005
0,005 0
0,50
Do CO
3
2-
d nn khng c giai on to CO
2
, 0 V
2
CO
=
Cho ht 100 mL dung dch Na
2
CO
3
0,1M v KHCO
3
0,1M vo 200 mL dung dch HCl 0,1M:
CO
3
2-
+ 2H
+
H
2
O + CO
2
(1)
HCO
3
-
+ H
+
H
2
O + CO
2
(2)
V
+
> +
H HCO CO
n n n 2
3
2
3
nn H
+
phn ng ht.
Gi s (1) xy ra trc th ta c mol 01 , 0 n
2
1
n
H
CO
2
= =
+
Gi s (2) xy ra trc th t (1) v (2) ta c mol 015 , 0 n
2
CO
=
Thc t (1) v (2) ng thi xy ra nn:
L 336 , 0 4 , 22 015 , 0 V 4 , 22 01 , 0 L 224 , 0
2
CO
= < < =
1,00
(b) Thm 100 mL dung dch Ba(OH)
2
0,1M vo 150 mL dung dch KHCO
3
0,1M
HCO
3
-
+ OH
-
CO
3
2-
+ H
2
O
0,015 0,02
0,015 0,015
0 0,005 0,015
Ba
2+
+ CO
3
2-
BaCO
3
0,01 0,015
0,01 0,01
0 0,005
Dung dch cn 0,005 mol KOH v 0,005 mol K
2
CO
3
0,50
(c) Dung dch A c cc cn bng:
CO
3
2-
+ H
2
O HCO
3
-
+ OH
-
K
b1
= 10
-3,67
HCO
3
-
+ H
2
O H
2
O + CO
2
+ OH
-
K
b2
= 10
-7,65
H
2
O H
+
+ OH
-
K
N
= 10
-14
V K
b1
>> K
b2
>> K
N
nn cn bng (1) l ch yu:
0,75
pH = 14 -
2
1
(pK
b1
+ pC) = 14 -
2
1
(3,67 + 1) = 11,67
Dung dch C l dung dch lng tnh nn:
pH =
2
1
(pK
1
+ pK
2
) =
2
1
(6,35 + 10,33) = 8,34
(d) Trch mu th, thm BaCl
2
d vo mu th thy xut hin kt ta trng (tan trong axit),
nh vy mu th c CO
3
2-
.
Ba
2+
+ CO
3
2-
BaCO
3
Lc tch kt ta, thm HCl vo dung dch nc lc thy si bt kh khng mu (lm c nc
vi trong), vy dung dch c HCO
3
-
HCO
3
-
+ H
+
H
2
O + CO
2
.
0,50
CU II (4 im)
1. (a) Amoniac c tnh oxi ha hay tnh kh? Vit phng trnh phn ng minh ha. (b) Trong dung mi amoniac
lng, cc hp cht KNH
2
, NH
4
Cl, Al(NH
2
)
3
c tnh axit, baz hay lng tnh ? Vit cc phng trnh phn ng
minh ha.
2. Ha tan 4,8 gam kim loi M bng dung dch HNO
3
c nng d, hay ha tan 2,4 gam mui sunfua kim loi ny
cng trong dung dch HNO
3
c nng, th u cng sinh ra kh NO
2
duy nht c th tch bng nhau trong cng
iu kin.
(a) Vit cc phng trnh phn ng di dng phng trnh ion.
(b) Xc nh kim loi M, cng thc phn t mui sunfua.
(c) Hp th kh sinh ra c hai phn ng trn vo 300 mL dung dch NaOH 1M, ri thm vo mt t
phenolphtalein. Hi dung dch thu c c mu g? Ti sao?
P N IM
1. (a) NH
3
va c tnh oxi ha, va c tnh kh :
Tnh oxi ha: K + NH
3 (l)
KNH
2
+ 1/2H
2
Tnh kh: 2NH
3
+ 3CuO 3Cu + N
2
+ 3H
2
O
0,75
(b) KNH
2
l mt baz, NH
4
Cl l axit v Al(NH
2
)
3
c tnh lng tnh.
Phn ng trung ha: KNH
2
+ NH
4
Cl KCl + 2NH
3
Phn ng ca cht lng tnh vi axit: Al(NH
2
)
3
+ 3NH
4
Cl AlCl
3
+ 6NH
3
Phn ng ca cht lng tnh vi baz: Al(NH
2
)
3
+ KNH
2
K[Al(NH
2
)
4
]
075
2. (a) Phng trnh phn ng:
M + 2mH
+
+ mNO
3
-
M
m+
+ mNO
2
+ mH
2
O
(1)
M
2
S
n
+ 4(m+n)H
+
+ (2m+6n)NO
3
-
2M
m+
+ nSO
4
2-
+ (2m+6n)NO
2
+ 2(m+n)H
2
O (2)
1,00
(b) V s mol NO
2
hai trng hp l bng nhau nn ta c:
) n 6 m 2 (
n 32 M 2
4 , 2
m
M
8 , 4
+
+
=
=

=
3 , 2 , 1 m , n
m 2 n 6
mn 64
M
, nghim thch hp l n = 1, m = 2 v M = 64.
Vy M l Cu v cng thc mui l Cu
2
S.
0,75
(c) mol 075 , 0
64
8 , 4
n
Cu
= =
Cu + 4HNO
3
Cu(NO
3
)
2
+ 2NO
2
+ 2H
2
O
NaOH NO
n mol 3 , 0 075 , 0 2 2 n
2
= = =
xy ra va phn ng:
2NO
2
+ 2NaOH NaNO
3
+ NaNO
2
+ H
2
O
Dung dch thu c c mu hng do NO
2
-
to mi trng baz:
NO
2
-
+ H
2
O HNO
2
+ OH
-
0,75
CU III (4 im)
1. (a) Tnh t l cc sn phm monoclo ha (ti nhit phng) v monobrom ha (ti 127
o
C) isobutan. Bit t l
kh nng phn ng tng i ca nguyn t H trn cacbon bc nht, bc hai v bc ba trong phn ng clo
ha l 1,0 : 3,8 : 5,0 v trong phn ng brom ha l 1 : 82 : 1600.
(b) Da vo kt qu tnh c cu (a), cho nhn xt v cc yu t nh hng n hm lng cc sn phm
ca phn ng halogen ha ankan.
2. Dng c ch phn ng gii thch ti sao khi x l 2,7-imetylocta-2,6-dien vi axit photphoric th thu c
1,1-imetyl-2-isopropenylxiclopentan.
3. Hiro ha mt hirocacbon A (C
8
H
12
) hot ng quang hc thu c hirocacbon B (C
8
H
18
) khng hot ng
quang hc. A khng tc dng vi Ag(NH
3
)
2
+
v khi tc dng vi H
2
trong s c mt ca Pd/PbCO
3
to hp cht
khng hot ng quang hc C (C
8
H
14
).
4. Lp lun xc nh cu to (c lu cu hnh) v gi tn A, B, C.
5. Oxi ha mnh lit A bng dung dch KMnO
4
trong H
2
SO
4
.Vit phng trnh ho hc.
P N IM
1. (a) T l sn phm:
CH
3
CH CH
3
+ Cl
2
- HCl
CH
3
CH CH
2
Cl
CH
3
C CH
3
Cl
1-clo-2-metylpropan
2-clo-2-metylpropan
CH
3
CH
3
CH
3
(9x1,0)
(9x1,0) + (1x5,0)
= 64,3%
(1x5,0)
(9x1,0) + (1x5,0)
= 35,7%
CH
3
CH CH
3
+ Br
2
- HCl
CH
3
CH CH
2
Br
CH
3
C CH
3
Br
1-brom-2-metylpropan
2-brom-2-metylpropan
CH
3
CH
3
CH
3
(9x1,0)
(9x1,0) + (1x1600)
= 0,56%
(1x1600)
(9x1,0) + (1x1600)
= 99,44%
0,50
0,50
(b) Hm lng sn phm halogen ha ph thuc ba yu t:
Kh nng tham gia phn ng th ca ankan: Phn ng halogen ha u tin th hidro trn
nguyn t cacbon bc cao hn.
Kh nng phn ng ca halogen: Brom tham gia phn ng yu hn so vi clo, nhng c
kh nng chn lc v tr th cao hn so vi clo.
S nguyn t hidro trn cacbon cng bc: Khi s hidro trn cc nguyn t cacbon cng
nhiu th hm lng sn phm cng ln.
0,75
2. C ch:
H
+
-H
+
0,75
3. (a) A c bt bo ha 3
2
12 8 . 2 2
=
+
= A , B c 0
2
18 8 . 2 2
=
+
= A v C c
2
2
14 8 . 2 2
=
+
= A .
V A cng 3 phn t hidro to ra B nn A c cc lin kt bi hoc vng ba cnh.
A cng 1 phn t H
2
to ra C v A khng tc dng vi Ag(NH
3
)
2
+
nn A c mt lin kt ba
dng -CC-R.
A cng phi cha mt lin kt i dng cis- (Z) v tr i xng vi lin kt ba, v khi A cng
1 phn t H
2
(xc tc Pd lm cho phn ng chy theo kiu cis-) to C khng hot ng
quang hc.
0,50
Cu to ca A, B, C l:
CH
3
C C
H H
H
C
CH
3
C
*
C CH
3
2Z-4-metylhept-2-en-5-in (A)
CH
3
CH
2
CH
2
CH(CH
3
)CH
2
CH
2
CH
3
4-metylheptan (B)
CH
3
C C
H H
H
C
CH
3
C C CH
3
2Z,5Z-4-metylhepta-2,5-dien (C)
H H
0,75
(b) Phng trnh phn ng:
5CH
3
CH=CHCH(CH
3
)CC-CH
3
+ 14KMnO
4
+ 21H
2
SO
4

10CH
3
COOH + 5CH
3
CH(COOH)
2
+ 14MnSO
4
+ 7K
2
SO
4
+ 16H
2
O
0,25
CU IV(4 im)
1. Limonen (C
10
H
16
) l tecpen c trong v qu cam, chanh v bi. Oxi ha limonen bng kalipemanganat to
cht A.
CH
3
C
O
CH
2
CH
2
CH
CH
2
COOH
C O
H
3
C
(A)
(a) Dng d kin trn v qui tc isopren xc nh cu trc ca limonen.
(b) Vit cng thc cc sn phm chnh hnh thnh khi hidrat ha limonen.
2. iu ch nitrobenzen trong phng th nghim v tnh hiu sut phn ng, ngi ta tin hnh cc bc sau:
Cho 19,5 ml axit nitric vo mt bnh cu y trn c 200 mL lm lnh bnh v lc, sau thm t t 15 mL
H
2
SO
4
m c, ng thi lc v lm lnh n nhit phng. Lp ng sinh hn hi lu (nc hay khng kh),
cho tip 13,5 mL benzen qua ng sinh hn vi tc chm v gi nhit khng qu 50
0
C, ng thi lc lin
tc (a).
Sau khi cho ht benzen, tip tc un nng bnh phn ng trn bp cch thu trong 30-45 pht v tip tc lc.
Sau lm lnh hn hp phn ng v qua phu chit. Tch ly lp nitrobenzen trn. Ra nitrobenzen
bng nc ri bng dung dch Na
2
CO
3
(b). Tch ly nitrobenzen cho vo bnh lm kh c cha cht lm kh A
th rn (c). Chng ct ly nitrobenzen bng bnh Vuy-c trn bp cch thu thu ly nitrobenzen sch. Cn
lng nitrobenzen thy c 15 gam (d).
(a) Vit phng trnh ho hc chnh v cc phng trnh th hin c ch ca phn ng. Cho bit v sao cn
phi lc bnh lin tc v gi nhit phn ng 50
0
C? Nu khng dng H
2
SO
4
m c, phn ng c xy
ra khng?
(b) V sao cn phi ra nitrobenzen bng nc, sau bng dung dch Na
2
CO
3
?
(c) A c th l cht no?
(d) Tnh hiu sut phn ng nu khi lng ring ca benzen 0,8g/mL.
P N IM
1. (a) Cu to:
O + O=C=O
O
O
OH
limonen
0,75
(b) Cc sn phm chnh khi hidrat ha:
OH
OH OH
OH
0,75
4. (a) Phn ng:
C
6
H
6
+ HONO
2

4 2
SO H
C
6
H
5
NO
2
+ H
2
O (1)
C ch phn ng:
HO - NO
2
+ H
2
SO
4
H - O - NO
2
+ HSO
4
H
(+)
(-)
H - O - NO
2
+ H
2
SO
4
H
(+)
H
3
O
(+)
+ HSO
4
(-)
+ NO
2
(+)
0,75
+ NO
2
(+)
H NO
2
+
NO
2
+ H
(+)
chm nhanh
Hn hp phn ng h d th nn cn phi lc u hay khuy mnh lin tc to thnh
nh tng, bo m s tip xc tt gia cc tc nhn.
Phi gi 50
0
C v nu nhit cao hn s tng lng sn phm initrobenzen.
Nu khng dng H
2
SO
4
, phn ng vn xy ra do vn c s hnh thnh NO
2
+
theo phng
trnh sau:
HO-NO
2
+ HNO
3
H
2
O
+
-NO
2
+ NO
3
-
H
2
O
+
-NO
2
+ HNO
3
H
3
O
+
+ NO
3
-
+ NO
2
+
(1)
Tuy nhin khi khng c H
2
SO
4
phn ng xy ra chm v hiu sut to NO
2
+
sinh ra trong (1)
rt thp. Khi c mt H
2
SO
4
m c, cn bng chuyn di v pha thun nn phn ng xy
ra nhanh hn.
0,75
(c) Cn phi ra bng nc loi axit, sau ra bng dung dch Na
2
CO
3
loi ht axit d
v d kim tra kt qu do phn ng gia axit v Na
2
CO
3
sinh kh.
0,25
(b) A l cht ht nc dng rn, nn A c th l CaCl
2
, ... khan 0,25
(d) Hiu sut phn ng:
gam 512 , 9
123
78 15
m
) 1 ( H C
6 6
=
= % 88
mL / g 8 , 0 mL 5 , 13
g 512 , 9
H =
=
0,50
CU VI
A l hidrocacbon khng lm mt mu dung dch brom. t chy hon ton 0,02 mol A v hp thu sn phm chy
vo dung dch cha 0,15 mol Ca(OH)
2
thu c kt ta v khi lng bnh tng ln 11,32 gam. Cho dung dch
Ba(OH)
2
d vo dung dch thu c kt ta li tng ln, tng khi lng kt tu hai ln l 24,85 gam. A khng vi
dung dch KMnO
4
/H
2
SO
4
nng, cn khi monoclo ha trong iu kin chiu sng th ch to mt sn phm duy
nht.
1. Xc nh cng thc cu to v gi tn A.
2. Ngi ta c th iu ch A t phn ng gia benzen v anken tng ng trong axit sunfuric. Dng c ch
phn ng gii thch phn ng ny.
3. Mononitro ha A bng cch cho phn ng vi axit nitric (c mt axit sunfuric c) th sn phm chnh thu
c l g? Ti sao?
P N IM
1. Dung dch Ca(OH)
2
hp th ht sn phm chy ca A cha CO
2
v H
2
O
CO
2
+ Ca(OH)
2
CaCO
3
+ H
2
O (1)
2CO
2
+ Ca(OH)
2
Ca(HCO
3
)
2
(2)
Ca(HCO
3
)
2
+ Ba(OH)
2
CaCO
3
+ BaCO
3
+ 2H
2
O (3)
0,50
t s mol CO
2
tham gia cc phn ng (1) v (2) ln lt l x v y, ta c:
mol 1 , 0 y x
85 , 24
2
y
197
2
y
x 100
15 , 0
2
y
x
= =
= + |
.
|
\
|
+
= +
, mol 2 , 0 y x n
2
CO
= + =
T mol 14 , 0
18
44 . 2 , 0 32 , 11
n g 32 , 11 m m m
O H CO O H
2 2 2
=
= = + = A
0,50
t cng thc tng qut ca A l C
x
H
y
:
C
x
H
y
+ (x+y/4)O
2
xCO
2
+ y/2H
2
O
Ta c 14 y , 10 x
14 , 0 . 2
y
2 , 0
x
02 , 0
1
= = = =
Cng thc phn t ca A l C
10
H
14
, ) 4 = A
0,50
V A khng lm mt mu dung dch brom (cu trc thm), khng tc dng vi dung dch
KMnO
4
/H
2
SO
4
(ch c mt nhm th) v monoclo ha (nh sng) ch to mt sn phm duy
nht (nhm th c cu trc i xng cao) nn cu to ca A l:
C
CH
3
CH
3
CH
3
(t-butylbenzen)
1,00
2. C ch:
(CH
3
)
2
C=CH
2
+ H
2
SO
4
(CH
3
)
2
C
+
-CH
3
+ HSO
4
-
+
C(CH
3
)
3
H
+ H
(+)
chm nhanh
+ (CH
3
)
3
C
+
C(CH
3
)
3
1,00
3. Nhm ankyl ni chung nh hng th vo cc v tr ortho- v para-. Tuy nhin, do nhm t-butyl
c kch thc ln gy n ng khng gian nn sn phm chnh l sn phm para-:
C
CH
3
CH
3
CH
3
O
2
N
0,50
S 5
S GIO DC V O TO
THNH PH NNG
CHNH THC
ny c hai (2) trang
HNG DN CHM THI HC SINH GII THNH PH
NM HC 2006 - 2007
MN: HA HC LP 11
CU I (4 im)
1. Tnh pH ca dung dch thu c khi trn ln 50,0 mL dung dch NH
4
Cl 0,200 M vi 75,0 mL dung dch NaOH
0,100 M. Bit K
b
(NH
3
) = 1,8.10
-5
.
2. Phn l mui sunfat kp ca mt cation ha tr mt (nh K
+
hay NH
4
+
) v mt cation ha tr ba (nh Al
3+
, Fe
3+
hay Cr
3+
). Phn st amoni c cng thc (NH
4
)
a
Fe(SO
4
)
b
.nH
2
O. Ha tan 1,00 gam mu phn st vo 100 cm
3
H
2
O, ri chia dung dch thu c thnh hai phn bng nhau. Thm dung dch NaOH d vo phn mt v un
si dung dch. Lng NH
3
thot ra phn ng va vi 10,37 cm
3
dung dch HCl 0,100 M. Dng km kim loi
kh ht Fe
3+
phn hai thnh Fe
2+
. oxi ha ion Fe
2+
thnh ion Fe
3+
tr li, cn 20,74 cm
3
dung dch KMnO
4
0,0100 Mtrong mi trng axit.
(a) Vit cc phng trnh phn ng dng ion thu gn v xc nh cc gi tr a, b, n.
(b) Ti sao cc phn khi tan trong nc u to mi trng axit ?
P N IM
1. M 08 , 0
L 125 , 0
L . mol 200 , 0 L 050 , 0
C
1
o
Cl NH
4
=
=

; M 06 , 0
L 125 , 0
L . mol 100 , 0 L 075 , 0
C
1
o
NaOH
=
=

NH
4
Cl + NaOH NaCl + NH
3
+ H
2
O
0,08 0,06
0,06 0,06 0,06
0,02 0 0,06
Xt cn bng :
NH
3
+ H
2
O NH
4
+
+ OH
-
0,06 0,02
x x x
0,06x 0,02+x x
5
3
4
b
10 . 8 , 1
x 06 , 0
x ) x 02 , 0 (
] NH [
] OH ][ NH [
K

+
=
+
= = , gn ng M 10 . 4 , 5
02 , 0
06 , 0
10 . 8 , 1 x
5 5
= =
73 , 9 )] 10 . 4 , 5 lg( [ 14 pH
5
= =

0,50
1,00
2. (a) t s mol ca phn st (NH
4
)
a
Fe(SO
4
)
b
.nH
2
O trong mi phn l x mol.
Phng trnh phn ng phn mt :
NH
4
+
+ OH
-
NH
3
+ H
2
O
ax
0 ax
Fe
3+
+ 3OH
-
Fe(OH)
3
NH
3
+ H
+
NH
4
+
ax ax
Phng trnh phn ng phn hai :
Zn + 2Fe
3+
Zn
2+
+ 2Fe
2+
x
0 x
5Fe
2+
+ MnO
4
-
+ 8H
+
5Fe
3+
+ Mn
2+
+ 4H
2
O
x x/5
10,25
Ta c : mol 10 . 037 , 1 L . mol 100 , 0 L 01037 , 0 ax
3 1
= =
mol 10 . 037 , 1 L . mol 010 , 0 L 02074 , 0 5 x
3 1
= =
a = 1
Cng thc ca phn c vit li l NH
4
+
Fe
3+
(SO
4
2-
)
b
.nH
2
O
b = 2
T M = 18 + 56 + 96.2 + 18n =
mol 10 . 037 , 1
gam 5 , 0
3
n = 12
Cng thc ca phn st amoni l NH
4
Fe(SO
4
)
2
.12H
2
O
(b) Phn tan trong nc to mi trng axit v cc ion NH
4
+
, Al
3+
, Fe
3+
v Cr
3+
u nhng ion
axit (cc ion K
+
c tnh trung tnh, cn SO
4
2-
c tnh baz rt yu).
NH
4
+
+ H
2
O NH
3
+ H
3
O
+
M
3+
+ H
2
O M(OH)
2+
+ H
+
CU II (4 im)
1. Vit phng trnh phn ng xy ra khi ln lt cho cc n cht As v Bi tc dng vi dung dch HNO
3
(gi
thit sn phm kh ch l kh NO).
2. So snh (c gii thch) tnh tan trong nc, tnh baz v tnh kh ca hai hp cht vi hidro l amoniac (NH
3
)
v photphin (PH
3
).
3. Mt giai on quan trng trong qu trnh tng hp axit nitric l oxi ha NH
3
trong khng kh, c mt Pt xc
tc.
(a) Xc nh nhit phn ng ca phn ng ny, bit nhit hnh thnh cc cht NH
3
(k), NO (k) v H
2
O (k) ln
lt bng 46 kJ/mol; + 90 kJ/mol v - 242 kJ/mol.
(b) Trong cng nghip, ngi ta s dng nhit v p sut th no qu trnh ny l ti u ? Ti sao ?
P N IM
1. Phng trnh phn ng :
3As + 5HNO
3
+ 2H
2
O 3H
3
AsO
4
+ 5NO
Bi + 4HNO
3
Bi(NO
3
)
3
+ NO + 2H
2
O
1,00
2. Tnh tan :
NH
3
tan tt hn PH
3
trong nc, do phn t phn cc hn v c kh nng to lin kt hidro
vi nc.
H N
H
H
H O
H
H N
H
H
... ... ... ...
Tnh baz :
NH
3
c tnh baz mnh hn PH
3
, do lin kt N-H phn cc mnh hn lin kt P-H, lm cho
nguyn t N trong phn t NH
3
giu electron hn, d dng nhn proton hn (mt nguyn
nhn na gii thch cho iu ny l ion NH
4
+
bn hn PH
4
+
).
Tnh kh :
PH
3
c tnh kh mnh hn nhiu so vi NH
3
, do nguyn t P l mt phi kim c m in
nh v phn t PH
3
kmbn hn NH
3
.
3. (a) 4NH
3
(k) + 5O
2
(k) 4NO (k) + 6H
2
O (k)
= A A + A = A
3 2
NH O H NO
H 4 H 6 H 4 H
kJ 908 ) kJ 46 ( 4 [ )] kJ 242 ( 6 [ ) kJ 90 4 ( H = + = A
(b) V phn ng l ta nhit, nn tng hiu sut cn gim nhit . Tuy nhin nu h
nhit qu thp s lm gim tc phn ng, nn thc t phn ng ny c tin hnh
850-900
o
C v c xc tc Pt. V phn ng thun l chiu lm tng s phn t kh, nn tng
hiu sut phn ng cn gim p sut. Tuy nhin, iu kin p sut gy tng gi thnh cng
ngh sn xut, nn ta ch dng p sut thng (1 atm).
CU III (4 im)
1. Dng hnh v, m t th nghim c tin hnh trong phng th nghim xc nh s c mt ca cc nguyn
t C v H c trong glucoz.
2. Hon thnh cc phn ng di y. Xc nh sn phm chnh ca mi phn ng v dng c ch gii thch s
hnh thnh sn phm chnh .
(a) CH
3
-CH=CH
2
(propilen) + HCl
(b) CH
3
-CH
2
-CH(OH)-CH
3
(ancol s-butylic)
C 180 , SO H
o
4 2
(c) C
6
H
5
CH
3
+ HNO
3

o
4 2
t , SO H
3. Dng s xen ph obitan nguyn t m t cc phn t CH
3
-CH=C=CH-CH
3
(phn t A) v CH
3
-
CH=C=C=CH-CH
3
(phn t B). Cho bit A, B c ng phn hnh hc hay khng ? Ti sao ?
P N IM
1. Th nghim xc nh s c mt ca cc nguyn t C v H c trong glucoz :
1,5
2. Phn ng v c ch phn ng:
(a) Phn ng :
CH
3
CH CH
2
+ HCl
CH CH
3
CH
3
Cl
CH
2
CH
3
CH
2
Cl
(sn phm chnh)
C ch (cng A
E
) :
CH
3
CH CH
2
H
+
o
CH
3
CH CH
3
CH
3
CH
2
CH
2
Cl
-
CH CH
3
CH
3
Cl
(X)
(Y)
Sn phm chnh hnh thnh theo hng to cacbocation trung gian bn vng hn. D
thy rng cacbocation (X) bn hn (Y) (do in tch c gii ta nhiu hn, vi 6H
),
nn sn phm chnh l isopropyl clorua.
0,50
(b) Phn ng :
CH
3
CH
2
H
2
SO
4
(sn phm chnh)
CH CH
3
OH
CH
3
CH CH CH
3
+ H
2
O
CH
2
CH CH
2
CH
3
+ H
2
O
C ch (tch E1) :
CH
3
CH
2
CH CH
3
OH
CH
3
CH CH CH
3
CH
2
CH CH
2
CH
3
H
+
CH
3
CH
2
CH CH
3
+
OH
2
-H
2
O
(X)
(Y)
Sn phm chnh c hnh thnh theo hng to sn phm bn hn. y, (X) bn hn
(Y) do c s nguyn t H
tham gia lin hp, lm bn ha lin kt nhiu hn.

0,50
(c) Phn ng :
+ HONO
2
H
2
SO
4
+ H
2
O
CH
3
CH
3
NO
2
+ H
2
O
CH
3
NO
2
C ch (th S
E
2Ar) : HONO
2
+ H
2
SO
4
HSO
4
-
+ H
2
O +
+
NO
2
+
NO
2
+
NO
2
-H
+
CH
3
CH
3
CH
3
CH
3
-H
+
CH
3
CH
3
H
NO
2
H
NO
2
NO
2
NO
2
Phn ng dnh hng th vo v tr meta-, do mt electron v tr ny trong phn t
toluen giu hn cc v tr ortho-, para-. ng thi phn ng th vo v tr ny to s gii
ta in tch tt nht phc .
0,50
3. M hnh phn t :
H
CH
3
H
CH
3
Trong trung hp ny, cc nhm th khng ng phng, nn phn t khng xut hin hin
tng ng phn hnh hc.
H
CH
3
H
CH
3
Trong trng hp ny, cc nhm th ng phng, nn phn t xut hin hin tng ng
phn hnh hc.
1,00
CU IV (4 im)
1. Thi 672 mL (ktc) hn hp kh A gm mt ankan, mt anken v mt ankin (u c s nguyn t cacbon trong
phn t bng nhau) qua dung dch AgNO
3
/NH
3
, th thy c 3,4 AgNO
3
tham gia phn ng. Cng lng hn
hp kh A trn lm mt mu va ht 200 mL dung dch Br
2
0,15 M.
(a) Xc nh thnh phn nh tnh v nh lng cc cht trong A
(b) ngh phng php tch ring tng cht ra khi hn hp A.
2. Oxi ha m gam hp cht hu c A bng CuO ri cho sn phm sinh ra gm CO
2
v hi H
2
O ln lt i qua bnh
1 ng Mg(ClO
4
)
2
v bnh 2 ng 2 lt Ca(OH)
2
0,0 2 M th thu c 2 gam kt ta. Khi lng bnh 1 tng
1,08 gam v khi lng CuO gim 3,2 gam, M
A
< 100. Oxi ha mnh lit A, thu c hai hp cht hu c l
CH
3
COOH v CH
3
COCOOH.
(a) Xc nh cng thc cu to v gi tn A.
(b) Vit cc dng ng phn hnh hc tng ng ca A.
(c) Khi cho A tc dng vi Br
2
theo t l mol 1:1, th to c nhng sn phm no ? Gii thch.
P N IM
1. (a) Nu ankin c dng RCCH :
RCCH + AgNO
3
+ NH
3
RCCAg + NH
4
NO
3
mol 02 , 0
mol / gam 170
gam 4 , 3
) ankin ( n = = v mol 04 , 0 ) ankin ( n 2 n
2
Br
= >
iu ny tri gi thit, v s mol Br
2
ch bng mol 03 , 0 L / mol 15 , 0 L 2 , 0 =
Vy ankin phi l C
2
H
2
v nh vy ankan l C
2
H
6
, anken l C
2
H
4
.
T phn ng :
C
2
H
2
+ 2AgNO
3
+ 2NH
3
C
2
Ag
2
+ 2NH
4
NO
3
n(C
2
H
2
) = 1/2n(AgNO
3
) = 0,01 mol
T cc phn ng :
C
2
H
2
+ 2Br
2
C
2
H
2
Br
4
C
2
H
4
+ Br
2
C
2
H
4
Br
2
n(C
2
H
4
) = 0,01 mol
0,50
n(C
2
H
6
) = = mol 01 , 0 mol 01 , 0
mol / L 4 , 22
L 672 , 0
0,01 mol
(b) Thi hn hp qua binh cha dung dch AgNO
3
/NH
3
d. Lc tch kt ta, ha tan kt ta
trong dung dch HCl d thu c kh C
2
H
2
.
C
2
H
2
+ 2AgNO
3
+ 2NH
3
C
2
Ag
2
+ 2NH
4
NO
3
C
2
Ag
2
+ 2HCl C
2
H
2
+ 2AgCl
Kh ra khi bnh cha dung dch AgNO
3
/NH
3
, thi tip qua dung dch nc brom d. Chit ly
sn phmv un nng vi bt Zn (trong CH
3
COOH) thu c C
2
H
4
:
C
2
H
4
+ Br
2
C
2
H
4
Br
2
C
2
H
4
Br
2
+ Zn C
2
H
4
+ ZnBr
2
Kh ra khi bnh cha dung dch brom l kh C
2
H
6
1,00
2. (a) n(H
2
O) = 0,06 mol n(H) = 0,12 mol
T cc phn ng :
CO
2
+ Ca(OH)
2
CaCO
3
+ H
2
O
2CO
2
+ Ca(OH)
2
Ca(HCO
3
)
2
vi mol 045 , 0 n
2
) OH ( Ca
= v mol 02 , 0 n
3
CaCO
= n(CO
2
) bng 0,02 mol hoc 0,07 mol.
n(O) tham gia phn ng bng mol 2 , 0
mol / gam 16
gam 2 , 3
=
Vy s mol O trong A bng :
n(O) = 0,02mol 2 + 0,06 mol 0,2 mol < 0 (loi)
n(O) = 0,07mol 2 + 0,06 mol 0,2 mol = 0 mol
A l hidrocacbon c cng thc n gin C
7
H
12
V M
A
< 100, nn cng thc phn t ca A chnh l C
7
H
12
( 2 = A )
Cu to ca A ph hp vi gi thit l:
CH CH
3
C
CH
3
CH CH CH
3
(3-metylhexa-2,4-dien)
1,00
0,50
(b) Cc dng ng phn hnh hc :
CH
3
C C
CH
3
C C
CH
3
H H
H
H
3
C
C C
CH
3
C C
H
CH
3
H
H
H
C C
CH
3
C C
CH
3
H H
CH
3
H
C C
CH
3
C C
H
CH
3
H
CH
3
cis-cis cis-trans trans-cis trans-trans
0,50
(c) Tc dng vi brom theo t l mol 1:1 th to c cc sn phm:
CH CH
3
C
CH
3
CH CH CH
3
+ Br
2
- Br
-
CH CH
3
C
CH
3
H
C CHBr CH
3
H
C CH
3
C
CH
3
CH CHBr
H
C CH
3
C
CH
3
CH CH CH
3
CH
3
Br
+ Br
-
CH
3
CH=C(CH
3
)-CHBr-CHBr-CH
3
CH
3
-CHBr-C(CH
3
)=CH-CHBr-CH
3
CH
3
-CHBr-CBr(CH
3
)-CH=CH-CH
3
0,50
CU V( 4 im)
1. Trnh by phng php phn bit mi cp cht di y (mi trng hp ch dng mt thuc th n gin,
c vit phn ng minh ha) :
(a) m-bromtoluen v benzylbromua
(b) phenylaxetilen v styren
2. T benzen v cc cht v c, xc tc cn thit khc c , vit cc phng trnh phn ng ha hc iu ch :
(a) meta-clonitrobenzen
(b) ortho-clonitrobenzen
(c) axit meta-brombenzoic
(d) axit ortho-brombenzoic
3. Hidrocacbon X c phn t khi bng 128, khng lm nht mu dung dch Br
2
. X tc dng vi H
2
(xc tc Ni, t)
to cc sn phm Y v Z. Oxi ha mnh lit Y to sn phm l axit o-phtalic, o-C
6
H
4
(COOH)
2
.
(a) Xc nh cu to v gi tn X, Y, Z.
(b) Vit phn ng to ra sn phm chnh, khi cho X ln lt tc dng vi dung dch HNO
3
c (H
2
SO
4
c xc
tc) v Br
2
(xc tc bt st). Bit mi phn ng, t l mol cc cht tham gia phn ng l 1:1.
P N IM
1. Phn bit cc cht :
(a) Dng AgNO
3
, benzyl bromua cho kt ta vng :
C
6
H
5
CH
2
Br + AgNO
3
+ H
2
O C
6
H
5
CH
2
OH + AgBr + HNO
3
(b) Dng dung dch AgNO
3
/NH
3
, phenylaxetilen cho kt ta vng xm:
C
6
H
5
CCH + AgNO
3
+ NH
3
C
6
H
5
CCAg + NH
4
NO
3
1,00
2. iu ch :
NO
2
+ HONO
2
H
2
SO
4
+ Cl
2
Fe
NO
2
Cl
(a)
Cl
+ HONO
2
H
2
SO
4
+ Cl
2
Fe
Cl
(b)
+H
2
SO
4
SO
3
H
Cl
SO
3
H
t
Cl
NO
2
NO
2
CH
3
+ CH
3
Cl
AlCl
3
+ Br
2
Fe
COOH
(c)
+ KMnO
4
COOH
Br
CH
3
+ Br
2
Fe
+CH
3
Cl
AlCl
3
CH
3
(d)
+H
2
SO
4
SO
3
H
CH
3
SO
3
H
t
CH
3
Br
Br
+ KMnO
4
COOH
Br
0,25
0,50
0,25
0,50
3. (a) X (C
x
H
y
), c 12x + y = 128 (y s 2x + 2) c hai nghim thch hp l C
10
H
8
v C
9
H
20
. Tuy nhin, v
X tc dng c vi hidro, nn cng thc ng l C
10
H
8
( 7 = A ).
V X khng lm nht mu nc brom nn cu to thch hp ca X l naphtalen v ph hp vi
gi thit th Y l tetralin v Z l decalin :
(naphtalen)
(tetralin) (decalin)
1,00
(b) Phn ng :
+ HONO
2
H
2
SO
4
+ H
2
O
NO
2
+ Br
2
Fe
+ HBr
Fe
0,50
S 6
S GIO DC V O TO
THNH PH NNG
NM HC 2004 - 2005
MN: HA HC LP 12 - BNG A
Cu I (3 im)
1. T l triti so vi tng s nguyn t hidro trong mt mu nc sng l 8.10
-18
. Triti phn hy phng x vi chu k
bn hy 12,3 nm. C bao nhiu nguyn t triti trong 10gam mu nc sng trn sau 40 nm.
2. (a) Gi tn v vit ng phn cho cc hp cht phc [Pt(NH
3
)
4
Cl
2
]
2+
v [Co(en)
2
Cl
2
].H
2
O.
(b) Gii thch s hnh thnh lin kt trong [CoF
6
]
3-
(cht thun t) v [Co(CN)
6
]
3-
(cht nghch t) theo thuyt
lin kt ha tr VB.
3. Vit phng trnh phn ng minh ha qu trnh iu ch cc cht sau y t cc n cht halogen tng
ng: (a) HClO
4
, (b) I
2
O
5
, (c) Cl
2
O, (d) OF
2
, (e) BrO
3
.
p n im
1. S nguyn t T
3
1
trong 10g mu =
18 23
10 . 8 10 . 02 , 6 2
18
10

= 5,35.10
6
nguyn t
T kt
n
n
ln
o
= v
2 / 1
t
693 , 0
k =
s nguyn t T
3
1
cn li sau 40 nm:
40
3 , 12
693 , 0
6
e 10 . 35 , 5 n

= = 5,8.10
5
nguyn t T
3
1
2. (a) Tn gi v ng phn:
[Pt(NH
3
)
4
Cl
2
]
2+
: ion diclorotatraaminplatin (IV)
[Co(en)
2
Cl
2
].H
2
O: diclorobis(etilendiamin)coban(II) monohidrat
H
3
N
H
3
N NH
3
NH
3
Cl
Cl
H
3
N
H
3
N Cl
NH
3
Cl
NH
3
trans- cis-
2+ 2+
Cl
Cl
Cl
Cl
trans- cis-
en en
en
en
cis-
en
en
(b) Phc [CoF
6
]
3-
thun t cho thy cc ion F
-
phi tr vo cc obitan lai ha ngoi sp
3
d
2
cn
trng ca Co(III):
F
-
F
-
F
-
F
-
F
-
F
-
lai ha sp
3
d
2
Phc [Co(CN)
6
]
3-
nghch t cho thy cc ion CN
-
phi tr vo cc obitan lai ha trong d
2
sp
3
cn trng ca Co(III):
CN
-
CN
-
CN
-
CN
-
CN
-
CN
-
lai ha d
2
sp
3
3. (a) 3Cl
2
+ 6NaOH
t
5NaCl + NaClO
3
+ 3H
2
O
4NaClO
3

t
NaCl + 3NaClO
4
NaClO
4
+ H
2
SO
4
NaHSO
4
+ HClO
4
(chng ct)
(b) 3I
2
+ 6OH
-
5I
-
+ ClO
3
-
+ 3H
2
O
IO
3
-
+ H
+
HIO
3
2HIO
3

t
I
2
O
5
+ H
2
O
(c) 2Cl
2
+ HgO Cl
2
O + HgCl
2
(d) 2F
2
+ 2OH
-
2F
-
+ OF
2
+ H
2
O
(e) Br
2
+ 2O
3

C 0
o
2BrO
3
Cu II (4 im)
1. Tnh khi lng amoniclorua v th tch dung dch natri hidroxit 3,0M cn thm vo 200mL nc v sau
pha long n 500mL iu ch dung dch m c pH = 9,5 vi nng mui l 0,1M. Bit pK
b
(NH
3
) = 4,76.
2. Cho cc thy tinh th nht cha dung dch hn hp KMnO
4
0,02M, MnSO
4
0,005M v H
2
SO
4
0,5M; cc th hai
cha dung dch hn hp FeSO
4
0,15M v Fe
2
(SO
4
)
3
0,0015M. t in cc platin vo mi cc v ni hai cc vi
nhau bng cu mui. Ni cc in cc vi nhau qua mt Vol k. Gi thit rng H
2
SO
4
in li hon ton v th
tch dung dch trong mi cc bng nhau. Cho V 771 , 0 E
o
Fe / Fe
2 3
=
+
v V 51 , 1 E
o
Mn / H , nO M
2
4
=
+ +
.
(a) Tnh th mi in cc trc khi phn ng xy ra. Vit s pin v tnh hiu th pin.
(b) Tnh hng s cn bng v th mi in cc ti cn bng.
3. Cho 1L dung dch HClO
4
0,003M cha 2,0.10
-4
mol mi ion Mn
2+
v Cu
2+
. Bo ha dung dch ny bng H
2
S, gi
thit nng H
2
S lun bng 0,1M khng ph thuc s c mt ca cc cht khc.
(a) Hy cho bit c th tch ring hai ion Mn
2+
v Cu
2+
khng? Bit H
2
S c pK
1
= 7 v pK
2
= 14. T
MnS
= 2,5.10
-10
v T
CuS
= 8,5.10
-36
.
(b) Kt lun trn c thay i khng nu thay HClO
4
bng dung dch m c [H
+
] = 10
-9
M?
p n im
1. T
] NH [
] NH [
lg pK pH
4
3
a
+
+ =
] NH [
] NH [
lg ) 76 , 4 14 ( 5 , 9
4
3
+
+ = 8 , 1
] NH [
] NH [
4
3
=
+
Trong dung dch cui: M 1 , 0 NH
4
=
+
nn M 18 , 0 M 1 , 0 8 , 1 NH
3
= =
mol 05 , 0 ) L 5 , 0 ( ) L . mol 1 , 0 ( n
1
NH
4
= =

+
v
mol 09 , 0 ) L 5 , 0 ( ) L . mol 18 , 0 ( n
1
NH
3
= =

T phn ng NH
4
+
+ OH
-
NH
3
+ H
2
O ta thy rng s mol NaOH cn dng bng s mol NH
3
v
tng lng mui amoni cn ban u l 0,05mol + 0,09mol = 0,14mol.
L 03 , 0
) L . mol 0 , 3 (
) mol 09 , 0 (
V
1
ddNaOH
= =

, g 49 , 7 ) mol / g 5 , 53 ( ) mol 14 , 0 ( m
Cl NH
4
= =
2. (a) V 671 , 0
15 , 0
003 , 0
lg 059 , 0 771 , 0
] Fe [
] Fe [
lg 059 , 0 E E
2
3
o
Fe / Fe
Fe
2 3
= + = + =
+
+
+ +
V 52 , 1
005 , 0
) 1 )( 02 , 0 (
lg
5
059 , 0
51 , 1
] Mn [
] H [ ] MnO [
lg
5
059 , 0
E E
8
2
8
4 o
Mn / nO M
Mn
2
4
= + = + =
+
+
+
S pin:
Pt|Fe
2+
(0,150M), Fe
3+
(0,003M)||MnO
4
-
(0,02M), Mn
2+
(0,005M), H
+
(1M)|Pt
Hiu th pin:
E
pin
= E
Mn
- E
Fe
= 1,52V - 0,671V = 0,85V
(b) Hng s cn bng:
63 , 62 059 , 0
) 771 , 0 51 , 1 .( 5
059 , 0
E n
10 10 10 K = = =
A
V hng s cn bng ln nn phn ng sau c coi l hon ton:
5Fe
2+
+ MnO
4
-
+ 8H
+
5Fe
3+
+ Mn
2+
+ 4H
2
O
0,15 0,02 0,003
0,1 0,02 0,1
0,05 0 0,103
Ti cn bng:
V 79 , 0
05 , 0
103 , 0
lg 059 , 0 771 , 0
] Fe [
] Fe [
lg 059 , 0 E E E
2
3
o
Fe / Fe
Fe Mn
2 3
= + = + = =
+
+
+ +
3. (a) Coi s ng gp H
+
ca H
2
S l khng ng k ta c [H
+
] = 0,003M
T
21
2 1
2
2 2
10 K . K
] S H [
] S [ ] H [
= =
+
[S
2-
] =
, )
M 10 . 1 , 1
003 , 0
1 , 0
10
17
2
21
=
[Cu
2+
][S
2-
] = (2.10
-4
)(1,1.10
-17
) = 2,2.10
-21
> T
CuS
= 8,5.10
-36
Cu
2+
kt ta di dng CuS
[Mn
2+
][S
2-
] = (2.10
-4
)(1,1.10
-17
) = 2,2.10
-21
< T
MnS
= 2,5.10
-10
Mn
2+
khng kt ta di dng mui sunfua.
Nng S
2-
thay i khng ng k khi Cu
2+
kt ta ht, nn khi Mn
2+
vn cha kt ta.
Vy c th tch ring hai ion ny.
(b) [S
2-
] =
, )
M 0
10
1 , 0
10
4
2
9
21
=
[Mn
2+
][S
2-
] = (2.10
-4
)(10
-4
) = 2.10
-8
> T
MnS
= 2,5.10
-10
Mn
2+
cng kt ta, vy khng th tch ring hai ion ny.
Cu III (3 im)
1. Tnh G A v nhn xt chiu t xy ra cho phn ng: H
2
O (l) H
+
(aq) + OH
-
(aq)
ti 25
o
C trong mi iu kin sau:
(a) [H
+
] = 10
-3
M v [OH
-
] = 10
-4
M
(b) [H
+
] = 10
-12
M v [OH
-
] = 2.10
-8
M
2. Hng s cn bng (K
C
) ca mt phn ng ha hp:
A(k) + B (k) AB (k)
l 1,8. 10
3
L.mol
1
ti 25
o
C v 3,45.10
3
L.mol
1
ti 40
o
C.
(a) Gi s H A khng ph thuc nhit , hy tnh
o
H A v
o
S A
(b) Hy tnh cc hng s cn bng K
P
v K
X
ti 298K v p sut ton phn l 1 atm.
3. (a) Thit lp biu thc xc nh chu k bn hy phn ng mt chiu bc hai dng A sn phm
(b) Tnh chu k phn ng bc hai: buta-1,3-dien (k) xiclobuten (k). Bit nng ban u ca butadien l
0,272M; ti 500K hng s vn tc phn ng l 0,0143M
-1
s
-1
.
p n im
1. Ti cn bng ta c: [H
+
] = [OH
-
] = 10
-7
M v K
N
= 10
-14
1 4 14 1 1
N
o
mol . J 10 . 8 ) 10 ln( ) K 298 )( mol . K . J 314 , 8 ( K ln RT G

= = = A
(a) ]) OH ][ H ln([ RT G G
o +
+ A = A
1 4 4 3 1 1 1 4
mol . J 10 . 4 ) 10 10 ln( ) K 298 )( mol . K . J 314 , 8 ( mol . J 10 . 8 G

= + = A
V 0 G > A nn phn ng khng t xy ra theo chiu thun.
(b)
1 4 8 12 1 1 1 4
mol . J 10 . 2 , 3 ) 10 . 2 10 ln( ) K 298 )( mol . K . J 314 , 8 ( mol . J 10 . 8 G

= + = A
V 0 G < A nn phn ng t xy ra theo chiu thun.
2. (a) T
|
|
.
|
\
|
A
=
2 1
o
1
2
T
1
T
1
R
H
K
K
ln
|
.
|
\
|

A
=
313
1
298
1
314 , 8
H
10 . 8 , 1
10 . 45 , 3
ln
o
3
3
AH
o
= 33,77 kJ/mol
T AG
o
= RT ln K = AH
o
TAS
o
1 1
2
2 2
o
o
mol . K . J 6 , 175
T
K ln RT H
S

=
+ A
= A
(b) Ti 298K:
1
3
1
C P
atm 726 , 0
298 . 314 , 8
10 . 8 , 1
) RT ( K K

= = =
726 , 0 P K K
P x
= =
3. (a) k[A]
2
=

t
A
A
A

kt
A
1
A
1
o
+ =
khi t =
2
1
t th:

2
A
A
0
=

0 0
0
2 / 1
A k
1
A
1
2
A
1
k
1
t =
|
|
|
|
.
|
\
|
=
(b)

s 257
) M 272 , 0 )( s M 0143 , 0 (
1
A k
1
t
1 1
o 2
1
= = =

Cu IV (3 im)
1. Hon thnh cc dy chuyn ha di y:
axetilen + CH
3
MgBr G + CH
4
G + CO
2
H
+
H
I (C
3
H
2
O
2
)
I
4 4 2 2
HgSO , SO H , O H
J (C
3
H
4
O
3
)
J + KMnO
4
sn phm ch cha mt cht hu c K.
2. So snh (c gii thch) mnh tnh axit ca K vi (a) axit oxalic v (b) axit sucxinic.
p n im
1. Hon thnh dy chuyn ha
CHCH + CH
3
MgBr CHCMgBr + CH
4
CHCMgBr + CO
2
CHCCO
2
MgBr
+
H
CHCCOOH
CHCCOOH
4 4 2 2
HgSO , SO H , O H
HOCCH
2
COOH
HOCCH
2
COOH
4
KMnO
HOOCCH
2
COOH
2. (a) K
1
(axit oxalic) > K
1
(axit malonic) do khi mch cacbon tng, hiu ng (-I) ca nhm cacboxyl
gim lm phn cc ca lin kt O-H v gim bn ca baz lin hp. K
2
(axit oxalic) > K
2
(axit malonic) do ion oxalat c bit bn nh s cng hng.
(b) K
1
(axit malonic) > K
1
(axit sucxinic) do khi mch cacbon tng, hiu ng (-I) ca nhm cacboxyl
gim lm phn cc ca lin kt O-H gim v bn ca baz lin hp gim. K
2
(axit malonic)
< K
2
(axit sucxinic) do ion sucxinat bn hn ion malonat nh mch cacbon ln hn, th nng
tng tc gia cc nhm COO
-
nh hn.
C
O O
C
OH HO
C
O O
C
O
-
HO
C
O O
C
O O
2-
HOOC(CH
2
)
n
COOH HOOC(CH
2
)
n
COO
-
-
OOC(CH
2
)
n
COO
-
Cu V (3 im)
Citral, C
10
H
16
O, l mt tecpen ng vai tr cu t chnh cho du c chanh. N phn ng vi hidroxylamin sinh ra
mt hp cht c cng thc C
10
H
7
ON, v vi thuc th Tollens cho kt ta bc cng hp cht c cng thc
C
10
H
16
O
2
. Oxi ha mnh lit citral sinh ra axeton, axit oxalic v axit levulinic (CH
3
COCH
2
CH
2
COOH).
1. ngh cu to cho citral ph hp vi cc d liu trn v ph hp vi quy tc isopren.
2. Trong thc t citral gm hai ng phn l citral a v citral b. Oxi ha m du geraniol sinh ra citral a (geranial),
cn t nerol th sinh ra citral b (neral). Trong axit sunfuric, c geraniol v nerol u chuyn ha thnh o-
tecpineol nhng kh nng chuyn ha ca geraniol chm hn nhiu so vi nerol. Xc nh cu trc ph hp v
gi tn theo IUPAC cho hai ng phn ny. Vit c ch phn ng to thnh o-tecpineol t nerol.
3. Khi cho citral phn ng vi olivetol trong axit long thu c mt hn hp cc sn phm trong cha (I) .
Cho bit c ch hnh thnh (I) v gi tn tng giai on ca c ch.
OH
HO C
5
H
11
-n
Olivetol
OH
C
5
H
11
-n
A
1
-3,4-trans-tetrahidrocannabinol (I)
O
OH
o-tecpineol
p n im
1. Citral C
10
H
16
O c bt bo ha 3 = A ; Phn ng vi hidroxylamin v thuc th Tollens cho
thy n l mt andehit; Oxi ha to ba phn mnh cho thy phn t c hai lin kt i. Xp cc
phn mnh theo quy tc isopren ta c cu to ca citral:
CH
3
C
CH
3
OH
O
C
OH
CH
2
CH
2
C
OH
CH
3
O
C
OH
C
OH
OH
CH
3
C
CH
3
CH CH
2
CH
2
C
CH
3
CH CH O
2. Citral a v b l ng phn hnh hc lin kt i C
2
: Nerol phn ng d dng hn, vy nerol v
neral l ng phn cis- (Z) cn geraneol v geranial l ng phn trans- (E).
C C
H CH
3
CH
3
CH
2
CH
2
C C
H
CH
3
CHO
C C
H CH
3
CH
3
CH
2
CH
2
C C
CHO
CH
3
H
Citral a
(E)-2,7-dimetylocta-2,6-dienal
Citral b
(Z)-2,7-dimetylocta-2,6-dienal
C ch phn ng (A
E
):
OH
CH
2
OH CH
2
OH
2
+
CH
2
+ H
+
- H
2
O
+ H
2
O
- H
+
3. C ch to (I)
HO
HO
C
5
H
11
-n
CHO
H
+
CHOH
olivetol
C
OH
H
H
+
(3)
HO
HO
C
5
H
11
-n C
H
-H
2
O
HO
HO
C
5
H
11
-n
HO
OH
C
5
H
11
-n
-H
+
(6)
HO
O
C
5
H
11
-n
(5)
(4)
(2) (1)
(1) Proton ha andehit, (2) Th S
E
Ar, (3) Proton ha v tch nc to ion dn alylic, (4) Cng A
E
ca cacbocation vo lin kt i, (5) Cng to ete proton ha, (6) Tch proton to (I).
Cu VI (4 im)
1. Ngi ta xc nh cu to cht khng sinh gramicidin S (cht A) bng cc qu trnh sau:
Phn tch sn phm thy phn cho thy t l ng phn t cc aminoaxit Leu H
3
N
+
CH(i-Bu)COO
-
(M = 131),
Orn H
3
N
+
(CH
2
)
3
CH(NH
2
)COO
-
(M = 132), Phe PhCH
2
CH(
+
NH
3
)COO
-
(M = 165), Val H
3
N
+
CH(i-Pr)COO
-
(M =
117), Pro (M = 115). Khi lng phn t A khong 1300.
N
H H
H
COO
- Pro:
Th nghim xc nh aminoaxit C-cui mch cho kt qu m; th ngim xc nh aminoaxit N-u mch
bng DNFB ch thy sinh ra DNP-NHCH
2
CH
2
CH
2
CH(
+
NH
3
)COO
-
.
Thy phn khng hon ton gramicidin S to thnh cc dipeptit v tripeptit sau: Leu-Phe, Phe-Pro,
Phe-Pro-Val, Val-Orn-Leu, Orn-Leu, Val-Orn, Pro-Val-Orn.
Cho bit trt t cu to ca phn t gramicidin S.
2. Qu trnh oxi ha metyl glycosit Q bng HIO
4
to sn phm ging nh sn phm oxi ha metyl -glycosit ca
D-andohexoz. Tuy nhin, qu trnh oxi ha Q ch tiu tn 1 mol HIO
4
v khng to ra axit fomic. Metyl ha Q,
thy phn, sau oxi ha mnh lit thu c axit dicacboxilic di-O-metylete ca axit (-)-tartaric. Lp lun vit
cu hnh y cho Q (dng cng thc chiu).
p n im
1. T 1300 ) 117 115 165 132 131 ( n M ~ + + + + = n = 2
Theo gi thit gramicidin S khng c C-cui mch. Sn phm DNP-NHCH
2
CH
2
CH
2
CH(
+
NH
3
)COO
-
cho thy DNFB ch phn ng vi c-NH
2
, ngha l gramicidin S cng khng c N-u mch. Vy
gramicidin S c cu trc vng.
T kt qu thy phn khng hon ton: Leu Phe
Phe Pro
Phe Pro Val
Val Orn Leu
Orn Leu
Val Orn
Pro Val Orn
ta c trt t: Leu-Phe-Pro-Val-Orn-Leu, vy trt t cu to ca gramicidin S l:
Val Orn Leu Phe
Pro
Val Orn Leu Phe
Pro
2. Cu hnh y :
OMe
HO
OH
CH
2
OH
O
OMe
MeO
OMe
CH
2
OH
O
CHO
MeO
OMe
CH
2
OH
OH
COOH
MeO
OMe
COOH
OMe
CHO
CHO
CH
2
OH
O
(Q)
S 7
S GIO DC V O TO
THNH PH NNG
P N K THI HC SINH GII THNH PH
NM HC 2004 - 2005
MN: HA HC LP 12 - BNG B
Cu VII (3 im)
4. Nguyn t ca nguyn t X c 10 electron thuc phn lp p. Thm n cht X hot ng phng x vo dung
dch cha
2
3
XO thu c ion A hot ng phng x. Thm dung dch cha Ba
2+
th thu c kt ta B. Lc
tch kt ta B, sy kh ri x l vi dung dch axit clohidric th thu c cht rn c hot ng phng x, cht
kh khng hot ng phng x v nc.
(a) Vit cc phng trnh ion thu gn minh ha (k hiu X
*
cho nguyn t X hot ng phng x).
(b) Vit cng thc cu to cho ion A v cho bit cu to, dng hnh hc cc hp kh vi H, oxit bc cao nht,
hidroxit bc cao nht ca X.
5. Sn xut ure t nguyn liu u l NH
3
v CO
2
qua hai cng on chnh sau:
(a) 2NH
3
(k) + CO
2
(k) H
2
NCOONH
4
(r) + 159,1kJ (tng hp amoni cacbamat)
(b) H
2
NCOONH
4
(r) H
2
NCONH
2
(r) + H
2
O (l) - 258kJ (dehidrat ha to ure)
Cho bit cc bin php c th p dng lmtng hiu sut mi qu trnh trn.
p n im
1. (a) Cu hnh electron ca X: 1s
2
2s
2
2p
6
3s
2
3p
4
Z = 16, X l lu hunh (S)
S
*
+
2
3
SO
2
3
*
SO S (
2
3 2
O S )
Ba
2+
+
2
3
*
SO S
3
*
SO BaS !
3
*
SO BaS ! + 2H
+
SO
2
| + S
*
! + Ba
2+
+ H
2
O
(b) Cu to ca A:
O
S
S
O
O
2- *
V SO
2
khng c hot tnh phng x nn S
*
ch tham gia lin kt S-S, m khng tham gia
lin kt S-O.
Cu to cc hp cht cha H, oxit bc cao nht, hidroxit bc cao nht ca X:
HO
HO
S
H
S
H
S
O
O O
O
O
d ng ch V d ng tamgi c phng d ng tdin
2. (a) Dng d NH
3
hoc CO
2
(thc t ch dng d NH
3
), tng p sut v h nhit .
(b) un nng (khng qu cao nu khng s gy phn hy ure) v chng ct nc.
Cu VIII (4 im)
4. Mi hn hp gm hai cht sau y c th tn ti c hay khng ? Nu c tn ti th hy cho bit iu kin,
nu khng tn ti th gii thch r nguyn nhn: (a) H
2
v O
2
, (b) SO
2
v NO
2
, (c) Na
2
O
2
v H
2
O, (d) dd FeCl
2
v
Br
2
, (e) dd FeCl
3
v KI
5. X l hp cht ho hc to ra trong hp kim gm Fe v C trong c 6,67% C v khi lng. Ho tan X trong
HNO
3
c nng thu c dung dch A v hn hp kh B. Cho A, B ln lt tc dng vi NaOH d th A to kt
ta A
1
, B to hn hp B
1
c 3 mui. Nung A
1
v B
1
nhit cao A
1
to oxit A
2
, B
1
to hn hp B
2
gm hai
mui. Cho B
2
tc dng vi H
2
SO
4
long thu c kh B
3
v axit B
4
. Cht B
4
lm mt mu dung dch KMnO
4
(trong mi trng axit). Vit cc phng trnh phn ng (cc phn ng trong dung dch vit dng ion thu gn).
6. Tnh th tch amoniac m c (14,8M) v khi lng amoni clorua cn dng pha ch 100mL dung dch
mc pH = 10, nu nng ca mui l 0,2M. Bit pK
b
(NH
3
) = 4,76.
p n im
1. (a) Tn ti iu kin thng, phn ng khi un nng : H
2
+
2
1
O
2

o
t
H
2
O.
(b) Khng : SO
2
+ NO
2
SO
3
+ NO
(c) Khng: Na
2
O
2
+ H
2
O2NaOH +
2
1
O
2
(d) Khng : 6FeCl
2
+ 3Br
2
4FeCl
3
+ 2FeBr
3
(e) Khng : FeCl
3
+ KI 2FeCl
2
+ 2KCl + I
2
2. Vi Fe
x
C
y
, ta c 3
y
x
67 , 6
33 , 93
y 12
x 56
= = , cng thc Fe
3
C
Fe
3
C + 22H
+
+ 13NO
3
-
3Fe
3+
+ CO
2
+ 13NO
2
+ 11H
2
O
Fe
3+
+ 3OH
-
Fe(OH)
3
CO
2
+ 2OH
-
CO
3
2-
+ H
2
O
2NO
2
+ 2OH
-
NO
2
-
+ NO
3
-
+ H
2
O
2Fe(OH)
3

t
Fe
2
O
3
+ 3H
2
O
NaNO
3

t
NaNO
2
+ 1/2O
2
CO
3
2-
+ 2H
+
CO
2
+ H
2
O
NO
2
-
+ H
+
HNO
2
5HNO
2
+ 2MnO
4
-
+ H
+
5NO
3
-
+ 2Mn
2+
+ 3H
2
O
A: Fe(NO
3
)
3
B: CO
2
, NO
2
A
1
: Fe(OH)
3
B
1
: Na
2
CO
3
, NaNO
3
, NaNO
2
A
2
: Fe
2
O
3
B
2
: Na
2
CO
3
, NaNO
2
B
3
: CO
2
B
4
: HNO
2
3. g 07 , 1 ) mol . g 5 , 53 ( ) L . mol 2 , 0 ( ) L 1 , 0 ( m
1 1
Cl NH
4
= =

+
+ =
4
3
b
NH
NH
lg ) pK 14 ( pH , 10 = (14 - 4,76) +

1
3
L . mol 2 , 0
NH
lg
[NH
3
] = 1,15 (mol.L
-1
), mol 115 , 0 ) L 1 , 0 ( ) L . mol 15 , 1 ( n
1
NH
3
= =

L 10 . 8 , 7
L . mol 8 , 14
mol 115 , 0
V
3
1
ddNH
3
= =
Cu IX (3 im)
Cho 2,16gam hn hp gm Al v Mg tan ht trong dung dch axit HNO
3
long, un nng nh to ra dung dch A v
448mL (o 354,9K v 988mmHg) hn hp kh B kh gm 2 kh khng mu, khng i mu trong khng kh. T
khi ca B so vi oxi bng 0,716 ln t khi ca CO
2
so vi nit. Lm khan A mt cch cn thn thu c cht rn
D, nung D n khi lng khng i thu c 3,84 gam cht rn E. Vit phng trnh phn ng, tnh lng cht D
v % lng mi kim loi trong hn hp ban u.
p n im
i. Phng trnh phn ng: Kh B theo gi thit cha N
2
v N
2
O.
5Mg + 12H
+
+ 2NO
3
5Mg
2+
+ N
2
| + 6H
2
O
4Mg + 10H
+
+ 2NO
3
4Mg
2+
+ N
2
O| + 5H
2
O
10Al + 36H
+
+ 6NO
3
10Al
3+
+ 3N
2
| + 18H
2
O
8Al + 30H
+
+ 6NO
3
8Al
3+
+ 3N
2
O| + 15H
2
O
4Al(NO
3
)
3
2Al
2
O
3
+ 12NO
2
| + 3O
2
|
2Mg(NO
2
)
2
2MgO + 4NO
2
| + O
2
|
Vi KL mol TB ca 2 kh = 36 v tng s mol 2 kh = 0,02 ta c th tnh c:
S mol N
2
= 0,01 mol v s mol N
2
O = 0,01mol
Al 3e
3
Al
+
2
5
N
+
+ 10 e N
2
.
x 3x 0,1 0,01
Mg 2e
2
Mg
+
2
5
N
+
+ 8 e N
2
O
y 2y 0,08 0,01
Bo ton electron ta c: 3x + 2y = 0,18 v 27x + 24y = 2,16 x = 0.
T y ny sinh tnh hung c vn ? Theo nh lut bo ton khi lng: 3,84 gam cht E chc
chn l Al
2
O
3
v MgO. T lng 2 kim loi v lng 2 oxit tnh c s mol Al = 0,04 v s mol Mg
= 0,045. Lp li tnh ton nh trn :
Al 3e
3
Al
+
2
5
N
+
+ 10 e N
2
0,04 0,12 0,1 0,01
Mg 2e
2
Mg
+
2
5
N
+
+ 8 e N
2
O
0,045 0,09 0,08 0,01
ta thy : tng s mol e nhng (0,21) > tng s mol e thu (0,18) chng t cn mt phn
5
N
+
= 0,21
0,18 = 0,03 mol tham gia phn ng khc, khng gii phng kh.
l phn ng: 4Mg + 10H
+
+ NO
3
4Mg
2+
+ NH
4
+
+ 3H
2
O
8Al + 30H
+
+ 3NO
3
8Al
3+
+ 3NH
4
+
+ 9H
2
O
2NH
4
NO
3
N
2
| + O
2
| + 4H
2
O|
Vy cht D gm: Al(NO
3
)
3
(8,52 gam); Mg(NO
3
)
2
(6,66 gam); NH
4
NO
3
(2,4 gam) c khi lng 17,58
gam. Hn hp ban u c 50% khi lng mi kim loi.
Cu X(3 im)
3. Cho 6 dung dch : glucoz, axit fomic, axit axetic, andehit axetic, etylenglicol v ru etylic. Phn bit 6 dung
dch trn bng phng php ho hc v vit s phn ng chuyn ho glucoz thnh 5 cht cn li.
4. Trong cc dy chuyn ha iu ch axit picric t benzen di y, dy no hp l v dy no khng hp l. Gii
thch r s hp l v khng hp l .
(a) benzen
) 1 (
phenyl clorua
) 2 (
phenol
) 3 (
axit picric
(b) benzen
) 1 (
phenyl clorua
) 2 (
1-clo-2,4-dinitrobenzen
) 3 (
2,4-dinitrophenol
) 4 (
axit
picric
p n im
1. Tmtt cch gii:
glucoz axit fomic axit axetic and axetic etylenglicol ru
etylic
qu tm - (B) (A) (A) - (B) - (B) - (B)
(A) AgNO
3
trong NH
3
kt ta
trng bc
-
(B) Cu(OH)
2
trong OH
-
, t
dd xanh
! gch
! gch dd xanh -
C
6
H
12
O
6

men
C
2
H
5
OH
t , CuO
CH
3
CHO
+ 2
2
Mn , O
CH
3
COOH
C
2
H
5
OH
t , SO H
4 2
CH
2
=CH
2

4
KMnO
CH
2
(OH)CH
2
(OH)
CH
3
COOH
t , CaO , NaOH
CH
4

o
600 400 , NO
HCHO
+ 2
2
Mn , O
HCOOH
2. (a) benzen
) 1 (
phenyl clorua
) 2 (
phenol
) 3 (
axit picric
Dy ny khng hp l do khi nitro ha phenol (3), HNO
3
c tnh oxi ha mnh s oxi ha ng
thi oxi ha phenol.
(b) benzen
) 1 (
phenyl clorua
) 2 (
1-clo-2,4-dinitrobenzen
) 3 (
2,4-dinitrophenol

) 4 (
axit picric
Dy ny hp l. Giai on (2) do Cl- v -NO
2
u l nhmphn hot ha nn ch th dinitro. Giai
on (4), hai nhm-NO
2
lmbn ha phenol, trnh c qu trnh oxi ha xy ra khi nitro ha.
Cu XI (4 im)
4. Hidrocacbon mch thng A c 7 : 36 m : m
H C
= . Xc nh cng thc cu to A v hon thnh dy chuyn
ho:
A A
2
A
3
Phenol
+ Ni , H
2
A
4

+CuO
A
5

+
H , KMnO
4
A
6
t nilon 6,6
5. Tin hnh th nghim nh sau: Cho 1mL CHCl
3
ra sch ion halogenua vo ng nghim c sn 3mL dung
dch NaOH 10% trong ng nghim, lc u v un si hn hp mt cch cn thn. Lm lnh hn hp phn
ng, gn ly phn dung dch trong pha trn ri chia lmba phn:
Phn 1: Cho thm vi git dung dch HNO
3
, sau thm tip vi git dung dch AgNO
3
1% .
Phn 2: Cho 1mL dung dch AgNO
3
/NH
3
vo phn 2 ri un nng nh.
Phn 3: Cho vi git dung dch KMnO
4
1% vo phn 3.
Nu hin tng xy ra trong 3 th nghim 3 phn dung dch trn, gii thch, vit phng trnh phn ng
minh ha.
6. Vit c ch phn ng dehidrat ha 3,3-dimetylbutan-2-ol v xiclobutylmetanol trong H
2
SO
4
c.
p n im
(a) 7 : 3
1
7
:
12
36
n : n
H C
= =
Cng thc nguyn: (C
3
H
7
)
n
Ta c iu kin: 7n s 6n + 2 v 7n l s chn
n = 2, cng thc phn t ca A C
6
H
14
Cng thc cu to: CH
3
(CH
2
)
4
CH
3
(n-hexan)
Dy chuyn ha:
Cl OH OH
O
n-C
6
H
14
Al
2
O
3
/Cr
2
O
3
Cl
2
, as
H
2
O
425
o
H
2
, Ni
CuO, t
KMnO
4
, H
+
HOOC(CH
2
)
4
COOH
H
2
N(CH
2
)
6
NH
2
Tnilon-6,6
(b) CHCl
3
+ 3 NaOH
0
t
HCOONa + 3 NaCl + 2 H
2
O
phn 1 xut hin kt ta trng do :
NaCl + AgNO
3
AgCl + NaNO
3
phn 2 xut hin kt ta Ag ( phn ng trng gng) do :
HCOONa + 2 [Ag(NH
3
)
2
]OH
0
t
NaHCO
3
+ 2Ag + 4NH
3
+ H
2
O
phn 3 , dung dch mu tmhng ca KMnO
4
chuyn sang mu xanh l cy do:
HCOONa + 2 KMnO
4
+ 3 NaOH Na
2
CO
3
+ K
2
MnO
4
+ Na
2
MnO
4
+ 2 H
2
O
(c) C ch:
CH
3
C
CH
3
CH
3
CH
OH
CH
3
CH
3
C
CH
3
CH
3
CH
OH
2
CH
3
CH
3
C
CH
3
CH
3
CH CH
3
CH
3
C
CH
3
CH CH
3
CH
3
H
+
- H
2
O
-H
+
CH
3
C
CH
3
C CH
3
CH
3
CH
2
OH CH
2
OH
2
H
+
- H
2
O
- H
+
Cu XII (3 im)
Hn hp Y gm hai cht hu c A v B cng chc ho hc. Nu un nng 15,7 gam hn hp Y vi NaOH d th thu
c mui ca mt axit hu c n chc v 7,6 gam hn hp hai ru no n chc bc nht k tip nhau trong
cng dy ng ng. Nu t 15,7 gam hn hp Y th cn dng va ht 21,84 lt O
2
v thuc 17,92 lt CO
2
(cc th
tch kh oiukintiu chun). Xcnh cng thc cu to ca A v B.
p n im
Este n chc k tip c dng chung C
x
H
y
O
2
mol 975 , 0 n
2
O
= ; mol 8 , 0 n
2
CO
=
mol 65 , 0
18
44 8 , 0 32 975 , 0 7 , 15
n
O H
2
=
+
=
mol 15 , 0
2
2 975 , 0 2 8 , 0 65 , 0
n
Y
=
+
=
33 , 5
15 , 0
8 , 0
C = = (5 < 5,33 < 6)
66 , 8 2
15 , 0
65 , 0
H = = (8 < 8,66 < 10)
Cng thc phn t 2 este l C
5
H
8
O
2
v C
6
H
10
O
2
66 , 50
15 , 0
6 , 7
MROH = =
Hai ru k tip l C
2
H
5
OH (M = 46) v n-C
3
H
7
OH (M = 60)
Cng thc ca hai este l CH
2
=CHCOOC
2
H
5
v CH
2
=CHCOOC
3
H
7
-n
S 8
S GIO DC - O TO
THNH PH NNG
K THI HC SINH GII THNH PH
NM HC 2005 - 2006
HNG DN CHMMN HC LP 12 - BNG A
Cu 1 (3,0 im)
1. Da vo phng php gn ng Slater, tnh nng lng ion ha I
1
cho He (Z = 2).
2. Da trn m hnh VSEPR, gii thch dng hnh hc ca cc phn t NH
3
, ClF
3
v XeF
4
.
3. Hot tnh phng x ca ng v Po
210
84
gim i 6,85 % sau 14 ngy. Xc nh hng s tc ca qu
trnh phn r, chu k bn hy v thi gian cho n b phn r 90 %.
P N IM
Cu 1 (3,0 im)
1. He c cu hnh 1s
2
,
, )
eV 6 , 78
1
3 , 0 2 6 , 13
2
n
Z 6 , 13
2 E
2
2 *
2 *
*
He
=

=
|
|
.
|
\
|
=
He
+
c cu hnh 1s
1
, eV 4 , 54
1
2 6 , 13
n
Z 6 , 13
E
2
2
2
*
He
=
= =
+
Qu trnh ion ha He - e He
+
;
eV 2 , 24 ) eV 6 , 78 ( ) eV 4 , 54 ( E E I
*
He
*
He
1
= = =
+
0,75
2. Cu to ca phn t NH
3
cho thy quanh N c 4 khng gian khu tr, trong c 1
cp electron t do (AB
3
E) nn phn t NH
3
c dng thp y tam gic vi gc lin
kt nh hn 109
o
28
'
(cp electron t do i hi mt khong khng gian khu tr ln
hn):
N H
H
H
..
H
N
H
H
0,50
Phn t ClF
3
c nm khong khng gian khu tr, trong c hai cp electron t do
(AB
3
E
2
) nn c dng ch T (cc electron t do chim v tr xch o):
0,50
Cl F
F
F
.
. .
.
F Cl
F
F
Phn t XeF
4
c su khong khng gia khu tr, trong c hai cp electron t do
(AB
4
E
2
) nn c dng vung phng (cc cp electron t do phn b xa nhau nht):
Xe
F
F
F
F
.
.
.
.
F
Xe
F F
F
0,50
3. T
, )
00507 , 0
85 , 6 100
100
ln
14
1
k kt
m
m
ln
t
0
=
= = ngy
-1
137
00507 , 0
693 , 0
k
2 ln
t
2 / 1
= = = ngy
Thi gian Po
210
84
b phn r 90% l:
, )
454
90 100
100
ln
00507 , 0
1
t =
= ngy
0,75
Cu 2 (3,0 im)
1. Trn 15,00 mL dung dch CH
3
COONa 0,030 M vi 30,00 mL dung dch HCOONa 0,15 M. Tnh pH ca
dung dch thu c. Bit pK
a
(CH
3
COOH) = 4,76 v pK
a
(HCOOH) = 3,75.
2. Tnh nng ban u ca HSO
4
-
(K
a
= 10
-2
), bit gi tr sc in ng ca pin:
Pt|I
-
0,1 M; I
3
-
0,02 M||MnO
4
-
0,05 M, Mn
2+
0,01 M, HSO
4
-
C M|Pt
25
o
C o c bng 0,824 V. Cho V 51 , 1 E
o
Mn / MnO
2
4
=
+
v V 5355 , 0 E
o
I / I
3
=

.
3. Tnh nng ion H
+
lm gim nng Ag(NH
3
)
2
+
0,10 M xung cn 1,0.10
-8
M. Bit pK
b
(NH
3
) =
4,76 v hng s bn [Ag(NH
3
)
2
+
] = 7,24.
P N IM
Cu 2 (3,0 im)
1. M 010 , 0
45
15 03 , 0
C
-
3
O CO CH
=
= ; M 100 , 0
45
30 15 , 0
C
-
O HCO
=
=
Cc cn bng:
H
2
O H
+
+ OH
-
K
w
= 10
-14
(1)
CH
3
COO
-
+ H
2
O CH
3
COOH + OH
-
K
b
= 10
-9,24
(2)
HCOO
-
+ H
2
O HCOOH + OH
-
K
b
= 10
-10,25
(3)
Do
25 , 11
HCOO
'
b
24 , 11
O CO CH
b
10 C K 10 C K
-
3

= ~ =

cho nn khng th tnh gn
ng theo mt cn bng.
iu kin proton: h = [H
+
] = [OH
-
] - [CH
3
COOH] - [HCOOH]
] O HCO [ ) K ( ] O CO CH [ K 1
K
h
- 1 '
a
-
3
1
a
w

+ +
= (4)
Chp nhn [CH
3
COO
-
]
o
= 0,010; [HCOO
-
]
o
= 0,10 v thay vo (4) tnh h
1
:
9
1 75 , 3 2 76 , 4
14
1
10 . 96 , 2
10 . 10 10 . 10 1
10
h

=
+ +
=
T gi tr h
1
tnh li [CH
3
COO
-
]
1
v [HCOO
-
]
1
theo cc biu thc:
o
-
3
9 76 , 4
76 , 4
1
-
3
] O CO CH [ 010 , 0
10 . 96 , 2 10
10
010 , 0 ] O CO CH [ = ~
+
=

o
-
9 75 , 3
75 , 3
1
-
] O HCO [ 10 , 0
10 . 96 , 2 10
10
10 , 0 ] O HCO [ = ~
+
=

Kt qu lp li.
Vy h = 2,96.10
-9
= 10
-8,53
pH = 8,5
1,00
2. in cc phi: MnO
4
-
+ 8H
+
+ 5e Mn
2+
+ 4H
2
O
in cc tri: 3I
-
I
3
-
+ 2e
01 , 0
] H [ 05 , 0
lg
5
059 , 0
51 , 1
] Mn [
] H ][ MnO [
lg
5
059 , 0
E E
8
2
8
4 o
Mn / MnO
p
2
4
+
+
+
+ = + =
+
V 574 , 0
) 1 , 0 (
02 , 0
lg
2
059 , 0
5355 , 0
] I [
] I [
lg
2
059 , 0
E E
3 3
3 o
I 3 / I
t
3
= + = + =

E = E
phi
- E
tri
0,824 = 1,51 +
5
059 , 0
lg(5[H
+
]
8
) 0,574
Suy ra h = [H
+
] = 0,053 M
Mt khc t cn bng:
H
2
SO
4
-
H
+
+ SO
4
2-
K
a
= 10
-2
[] C h h h
Suy ra C h
K
h
K
h C
h
a
2
a
2
= + =
Thay gi tr h = 0,053 v K
a
= 1,0.10
-2
, tnh c M 334 , 0 C
4
HSO
=
1,00
3. Do [Ag(NH
3
)
2
+
] = 1,0.10
-8
M << 0,10 M, suy ra phc b phn hy hon ton. Hn na
mi trng axit, nn c th b qua qu trnh to phc hidroxo ca Ag
+
. Phn ng
phn hy phc:
Ag(NH
3
)
2
+
+ 2H
+
Ag
+
+ 2NH
4
+
K = 10
-7,24
.(10
9,24
)
2
= 10
11,24
C
o
0,1 C
C
o
- C 0,2 0,1 0,2
V mi trng axit v
24 , 9
NH
10 K
4
=
+
nh nn s phn li ca NH
4
+
c th b qua.
Xt cn bng:
Ag
+
+ 2NH
4
+
Ag(NH
3
)
2
+
+ 2H
+
K
-1
= 10
-11,24
C 0,1 0,2 C 0,2
[] 0,1-10
-8
0,2 - 2.10
-8
10
-8
C-0,2 + 2.10
-8
1,00
M 2015 , 0 C 10
) 2 , 0 .( 1 , 0
10 . ) 2 , 0 C (
24 , 11
2
8 2
= =
Cu 3 (4,0 im)
1. Cho 100 gam N
2
nhit 0
o
C v p sut 1 atm. Tnh nhit Q, cng W, bin thin ni nng U v
bin thin entanpi H trong cc bin i sau y c tin hnh thun nghch nhit ng: (a) nung
nng ng tch ti p sut bng 1,5 atm; (b) gin ng p ti th tch gp i th tch ban u. Chp
nhn rng N
2
l kh l tng v nhit dung ng p khng i trong qu trnh th nghim v bng 29,1
J.K
-1
.mol
-1
.
2. Hy xc nh bc ca phn ng:
(CH
3
)
3
CBr (aq) + H
2
O (l) (CH
3
)
3
COH (aq) + H
+
+ Br
-
t cc d kin thc nghim sau y 298K:
t, (s) 0 15000 35000 55000 95000 145000
[(CH
3
)
3
CBr], (mol.L
-1
) 0,0380 0,0308 0,0233 0,0176 0,0100 0,00502
3. Cn bng: N
2
(k) + 3H
2
(k) 2NH
3
(k)
s chuyn dch chiu no khi (a) thm Ar vo hn hp cn bng nhng gi cho th tch khng i; (b)
thm Ar vo hn hp cn bng nhng gi cho p sut khng i?
P N IM
Cu 3 (4,0 im)
1. (a) Nung nng ng tch ti p sut bng 1,5 atm
V V = const nn W = 0
, ) , ), ) , ), )
1 2
p
1 2
p
1 2
V
V
T T R C n T T R C n T T C n Q U = = = =
, ) , ) J 74 , 10138 15 , 273 15 , 273
1
5 , 1
314 , 8 1 , 29
28
100
T T
P
P
R C n
1 1
1
2
p = |
.
|
\
|
=
|
|
.
|
\
|
=
, ) J 05 , 14194 15 , 273 15 , 273
1
5 , 1
1 , 29
28
100
T T
P
P
C n T T C n H
1 1
1
2
p
1 2
p = |
.
|
\
|
=
|
|
.
|
\
|
= =
0,75
(b) Gin ng p ti th tch gp i
, ) =
|
|
.
|
\
|
= = =
1 1
1
2
p
1 2
p
p
T T
V
V
C n T T C n H Q
, ) J 09 , 28388 15 , 273 15 , 273 . 2 1 , 29
28
100
= =
, ) J 60 , 8110 15 , 273 . 314 , 8 .
28
100
T T
V
V
nR T T nR V P W
1 1
1
2
1 2
= =
|
|
.
|
\
|
= = =
J , 20278 8110 28388 W Q U = = + =
0,75
2. Phng trnh ng hc ca phn ng:

o o
= = CBr ) CH ( O H k
dt
CBr ) CH ( d
v
3 3 2
3 3
Do nng ca cht tan rt nh, nn c th coi [H
2
O] ~ const, phng trnh trn
tr thnh:

o
= = CBr ) CH ( k
dt
CBr ) CH ( d
v
3 3
3 3
vi k = k[H
2
O]
= const
0,75
Th cc d kin thc nghim vo cc biu thc ca k i vi cc phn ng n
gin bc 0, 1, 2 ta c cc kt qu sau y:
= 0 = 1 = 2

t
A A
k
1 o 1

=

1
o 1
A
A
ln
t
1
k =

1 o 1
1 o 1
A A
A A
t
1
k
=
4,80.10
-7
1,4.10
-5
4,10.10
-4
4,20.10
-7
1,4.10
-5
4,70.10
-4
3,70.10
-7
1,4.10
-5
5,50.10
-4
2,95.10
-7
1,4.10
-5
7,80.10
-4
2,27.10
-7
1,4.10
-5
1,19.10
-4
Vy phn ng c bc 1 i vi (CH
3
)
3
CBr.
0,75
3. (a) Ta c:
2
n
2
3
H N
2
NH
3
H N
2
NH
P
RT
V
K
RT
V
n n
n
P P
P
K
2 2
3
2 2
3
|
.
|
\
|
= |
.
|
\
|
= =
V V, K
P
v T = const nn const
n n
n
K
3
H N
2
NH
n
2 2
3
= = . Nh vy c s tng p sut
ca h nhng khng c s chuyn dch cn bng.
(b)
2
n P
RT
V
K K |
.
|
\
|
=
Vi T, P v K
p
= const, khi thmAr lmV tng nn K
n
phi gim. S thm
agon lmcn bng chuyn dch theo chiu nghch (chiu lm phn li NH
3
).
Ch thch:
Trong trng hp ny, ta khng th da vo nguyn l Le Chatelier d on
chiu din bin ca phn ng.
0,50
0,50
Cu 4 (3,0 im)
1. Streptimidon l mt loi khng sinh c cng thc sau:
H
NH
H
CH
3
H
3
C
H
OH H
O
O
O
H
(a) M t cc trung tm lp th ca streptimidon bng k hiu E, Z v R, S.
(b) Streptimidon c bao nhiu ng phn lp th, trong c bao nhiu ng phn enan v bao
nhiu ng phn dia?
2. So snh v gii thch:
(a) Nhit si ca cc cht xyclopentan, tetrahidrofuran v pirolidin.
(b) mnh tnh baz ca dimetylamin, piperidin v piridin.
P N IM
Cu 4 (3,0 im)
1. (a) Streptimidon c ba trung tm lp th:
H
NH
H
CH
3
H
3
C
H
OH H
O
O
O
H
E
S
R
*
*
0,75
(b) Streptimidon c 2
3
= 8 ng phn lp th, trong streptimidon v i quang ca
n to cp ng phn enan, cn su ng phn lp th cn li l ng phn dia ca
streptimidon.
0,75
2. (a) Trt t tng dn nhit si:
O N
H
khng phn cc c phn cc to c kin kt H lin
phn t
0,75
(b) Trt t tng dn mnh tnh baz:
N
N
H N
H
N lai ha sp
2
N lai ha sp
3
N lai ha sp
3
v cu trc
vng t gy n ng
khng gian vi N
0,75
Cu 5 (3,0 im)
1. (-)-Nicotin, ankaloit c trong thuc l, c th c tng hp theo cch sau:
axit nicotinic (3-pyridincacboxilic) + SO
2
Cl
2
, t
o
nicotinyl clorua (C
6
H
4
ONCl)
nicotinyl clorua + C
2
H
5
OCH
2
CH
2
CH
2
CdCl G (C
11
H
15
O
2
N), mt xeton
G + NH
3
, H
2
, xc tc H (C
11
H
18
ON
2
)
H + HBr + nhit cao I (C
9
H
12
N
2
) + etyl bromua
I + CH
3
I, NaOH ( )-nicotin (C
10
H
14
N
2
)
Xc nh cu trc ca ( )-nicotin v hon thnh cc phn ng trn.
2. Cht li cun bn tnh ca loi bm m c th c tng hp bng cch di y. Hy cho bit
cu trc v tn gi ca hp cht ny. Hon thnh cc phng trnh phn ng.
1-heptin + LiNH
2
S (C
7
H
11
Li)
S + 1-clo-3-brompropan T (C
10
H
17
Cl)
T + Mg, sau n-C
10
H
21
CHO, sau H
+
U (C
21
H
40
O)
U + H
2
, xc tc Lindlar V (C
21
H
42
O)
V + CrO
3
cht li cun bn tnh (C
21
H
40
O)
P N IM
Cu 5 (3,0 im)
1. Cu trc v phn ng:
SOCl
2
EtO(CH
2
)
3
CdCl
N
COOH
N
COCl
N
C
O
C
H
2
CH
2
CH
2
EtO
G
Amin bc 2
NH
3
, H
2
Ni
HBr
I H
N
CH
C
H
2
CH
2
CH
2
EtO
NH
2
N
CH
C
H
2
CH
2
CH
2
Br
NH
2
N
*
N
H
H
(+)-Nicotin
Alkyl ha
CH
3
I, OH
-
N
*
N
H
3
C
H
1,50
2. n-C
5
H
11
CCH
2
LiNH
n-C
5
H
11
CCLi (S)

Cl CH CH BrCH
2 2 2
n-C
5
H
11
CCCH
2
CH
2
CH
2
Cl (T)

Mg
n-C
5
H
11
CC(CH
2
)
3
MgCl

+
H , CHO H C n
21 10
n-C
5
H
11
CC(CH
2
)
3
CH(OH)C
10
H
21
-n
(CH
2
)
3
C
H
C
n-C
5
H
11
H
CH
OH
C
10
H
21
-n
H
2
Lindlar
(CH
2
)
3
C
H
C
n-C
5
H
11
H
C
O
C
10
H
21
-n
CrO
3
(Z)-6-henicosen-11-on
1,50
Cu 6 (4,0 im)
1. .(+)-Raffinoz, mt ng khng kh c tm thy trong ng c ci, c cng thc C
18
H
32
O
16
.
Thy phn trong mi trng axit to ra D-fructoz, D-galactoz v D-glucoz. Thy phn di tc
dng ca enzim |-galactosidaza to ra D-galactoz v saccaroz. Thy phn di tc dng ca
invertaza (mt enzim phn ct saccaroz) to thnh D-fructoz v disaccarit melibioz. Metyl ha
raffinoz, sau thy phn to ra 1,3,4,6-tetra-O-metyl-D-fructoz, 2,3,4,6-tetra-O-metyl-D-
galactoz v 2,3,4-tri-O-metyl-D-glucoz. Cho bit cu trc ca raffinoz v melibioz.
2. Mt gii php bo v nhm amin hiu qu l tin hnh phn ng axyl ha bng anhydrit phtalic
hnh thnh mt phtalimit c nhm th trn nguyn t N. Nhm bo v sau c th g b d dng
bng hidrazin m khng nh hng n cu ni peptit. p dng gii php ny vit s tng hp
Gli-Ala v Ala-Gli.
P N IM
Cu 6 (3,0 im)
Melibioz
Raffinoz
O
HO
OH
O
HO
CH
2
OH
OH
O
OH
O
HO
CH
2
CH
2
OH
HOH
2
C
O
H
HO
HO
Galactoz
Saccaroz
Fructoz Glucoz
1,50
Melibioz
6-O-(o-D-Galactopyranosyl)-D-glucopyranoz
(|-anomer)
O
OH
OH
O
HO
CH
2
OH
OH
O
OH
HO
CH
2
HO
0,50
N
2
H
4
Gly-Ala
+
Phtalhydrazua
Kali phtalimit
+
H
3
NCH
2
C NHCHCOO
-
CH
3
O
NH
NH
O
O
NCH
2
C
O
O
NHCHCOO
-
O
CH
3
NCH
2
COCl
O
O
Ala SOCl
2
NCH
2
COOH
O
O
H
+
H
2
O
NCH
2
COOEt
O
O
BrCH
2
COOEt
NK
O
O
i v i Ala-Gly: bt u v i BrCHCOOEt, vsau d ng
+
H
3
NCH
2
COO
-
CH
3
1,00
1,00

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TUYN TP THI HC SINH

Mu th to kt ta trng keo v si bt kh khng mu l AlCl

Mu th khng to hin tng l NaCl.

tham gia lin hp, lm bn ha lin kt nhiu hn.

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