Tuyen Tap de Thi Hs Gioi Môn Hóa THPT

TUYN TP D THI HC SINH
CI0I MN HuA HC
[Ti liu tng hp t cc thi HSG]
[copyrlght2010 http://vn.myblog.yahoo.com/volcmttl]
?uS
han Cuong Puy
Copyrlght 2010 http://vn.myblog.yahoo.com/volcmttl
2 1u?Ln 1 uL 1Pl PCC SlnP ClCl MCn PCA PCC
nN 1: CC L 1nI nC SINn GICI 1nNn nC NNG
(ngun: 1hy ung Cng Anh 1un - Cv 1rung 1P1 Chuyn L Cuy un - u nng)
L SC 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
uL SC 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.
L SC 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 dlm)
1. Py so snh v glal thlch su khc nhau v d phn cuc phn t, nhlt d sl v d manh tlnh bazo glua nP
3
v
nl
3
.
2. n
2
C
4
phn ll 20,0 thnh nC
2
o 27
o
C v 1,00 atm. Py xc dlnh (a) gl trl k
p
, (b) d phn ll ca n
2
C
4
tal 27
o
C
v 0,10 atm, (c) d phn ll ca 69g n
2
C
4
trong blnh 20 L o 27
o
C.
3. 1lnh pP ca dung dlch thu duoc khl thl ht 224 mL khl CC
2
vo 200 mL dung dlch naCP 0,03M, blt axlt
cacbonlc c 35 , 6 pK
1 a
= , 33 , 10 pK
2 a
= .
P N IM
1. Cu tao:
N
H
H
H
N
F
F
F
- nP
3
phn cuc hon nl
3
do trong nP
3
lung cuc lln kt v lung cuc electron tu do cung
chlu, cn trong nl
3
lung cuc lln kt v lung cuc electron tu do nguoc chlu.
- nhlt d sl ca nP
3
cao hon do nP
3
tao duoc lln kt P lln phn t.
- nP
3
l mt bazo cn nl
3
thl khng, do trong nl
3
cc nguyn t l hut electron lm glam
mt d electron trn nguyn t n.
2. xet phan ung phn ll:
n
2
C
4
2nC
2
n 0
no 2no
n-no 2no
hn 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 = =
0,7S
(0,233)
) 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
= = = =
vl s mol CC
2
v naCP bng nhau nn h chl chua naPCC
3
. C th tlnh pP ca h lung tlnh
ny bng cng thuc:
, ) 3 , 8 33 , 10 35 , 6
2
1
) pK pK (
2
1
pH
2 1
= + = + =
1,S0
(0,303)
0,7S
(0,23+0,3)
CU II (3 dlm)
2. vlt phuong trlnh phan ung xay ra khl cho nP
4
Cl tc dung vl CuC v vl ZnC. Cho blt ung dung thuc t ca
nP
4
Cl tuong ung vl cc phan ung ny.
3. Pa tan 10,00 g hn hop gm Cu
2
S v CuS bng 200,0 mL dung dlch MnC
4
-
0,7300 M trong ml trung axlt.
Sau khl dun sl d dul ht khl SC
2
slnh ra, luong MnC
4
-
cn du trong dung dlch phan ung vua ht vl 173,0
mL dung dlch le
2+
1,000 M.
(a) vlt cc phuong trlnh phan ung xay ra (dang phuong trlnh lon thu gon).
(b) 1lnh phn trm khl luong CuS trong hn hop ban du.
P N IM
1. 1rong thuc t, nP
4
Cl duoc dung d dnh sach b mt klm loal truc khl hn:
4CuC + 2nP
4
Cl n
2
+ 3Cu + CuCl
2
+ 4P
2
C
ZnC + 2nP
4
Cl ZnCl
2
+ 2nP
3
+ P
2
C
2. (a) huong trlnh phan ung:
3Cu
2
S + 8MnC
4
-
+ 44P
+
10Cu
2+
+ 3SC
2
+ 8Mn
2+
+ 22P
2
C (1)
3CuS + 6MnC
4
-
+ 28P
+
3Cu
2+
+ 3SC
2
+ 6Mn
2+
+ 14P
2
C (2)
3le
2+
+ MnC
4
-
+ 8P
+
3le
3+
+ Mn
2+
+ 4P
2
C (3)
(b) xc dlnh
(1) mol 035 , 0 1 175 , 0
5
1
n
5
1
n
2
4
Fe ) 3 ( MnO
= = =
+
1,S0
(0,303)
0,7S
(0,233)
mol 115 , 0 035 , 0 75 , 0 2 , 0 n
) 2 , 1 ( MnO
4
= =
ut s mol Cu
2
S v CuS ln luot 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
=
=
0,7S
CU III (4 dlm)
1. Chl dung cht chl thl phenolphtaleln, hy phn blt cc dung dlch naPSC
4
, na
2
CC
3
, AlCl
3
, le(nC
3
)
3
, naCl,
Ca(nC
3
)
2
. Cc phan ung mlnh hoa vlt dul dang lon thu gon.
2. Pa tan ht 2,2 g hn hop klm loal A gm st v nhm trong 130 mL dung dlch PnC
3
2M thu duoc dung dlch
8 v 448 mL (dktc) khl C gm n
2
C v n
2
c tl khl so vl khng khl bng 1,2414. 1hm 13,6 g naCP nguyn
cht vo dung dlch 8 thu duoc kt ta u, loc kt ta u thu duoc dung dlch nuc loc L.
(a) 1lnh phn trm khl luong ml klm loal trong hn hop A ban du.
(b) nung kt ta u dn khl luong khng dl thl thu duoc bao nhlu gam cht rn khan?
(c) 1lnh th tlch dung dlch PCl 0,3M cn thm vo dung dlch L d thu duoc 2,34 g kt ta.
P N IM
1. 1rlch mu th cho ml ln thl nghlm:
Cho phenolphtaleln vo ml mu th. Mu th c mu hng l dung dlch na
2
CC
3
, cc mu
th cn lal khng mu.
CC
3
2-
+ P
2
C PCC
3
-
+ CP
-
uung na
2
CC
3
lm thuc th d cho vo cc mu th cn lal.
Mu th c sl bot khl khng mu l naPSC
4
CC
3
2-
+ 2P
+
P
2
C + CC
2
^
Mu th tao kt ta trng keo v sl bot khl khng mu l AlCl
3
2Al
3+
+ 3CC
3
2-
+ 3P
2
C 2Al(CP)
3
j+ 3CC
2
^
Mu th tao kt ta do nu v sl bot khl khng mu l le(nC
3
)
3
2le
3+
+ 3CC
3
2-
+ 3P
2
C 2le(CP)
3
j+ 3CC
2
^
Mu th tao kt ta trng l Ca(nC
3
)
2
Ca
2+
+ CC
3
2-
CaCC
3
j
Mu th khng tao hln tuong l naCl.
2. (a) ut s mol n
2
C v n
2
ln luot bng a v b, ta c:
1,S0
(0,236)
= =
= =
+
= = +
01 , 0 b a
36 29 2414 , 1
02 , 0
b 28 a 44
02 , 0
4 , 22
448 , 0
b a
ut s mol le v Al ln luot bng x v y
Cht kh Cht oxl ha
le - 3e le
3+
10P
+
+ 2nC
3
-
+ 8e n
2
C + 3P
2
C
3x x 0,10 0,08
Al - 3e Al
3+
12P
+
+ 2nC
3
-
+ 10e n
2
+ 6P
2
C
3y y 0,12 0,10
vl mol 3 , 0 ) bd ( n mol 22 , 0 ) pu ( n
H H
= < =
+ +
nn axlt du, phan ung khng tao le
2+
.
1a 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) 1hm naCP vo dung dlch 8 [P
+
(0,13.2-0,22 = 0,08 mol), le
3+
(x = 0,02 mol), Al
3+
(y = 0,04
mol) v nC
3
-
]
P
+
+ CP
-
P
2
C (1)
le
3+
+ 3CP
-
le(CP)
3
(2)
Al
3+
+ 3CP
-
Al(CP)
3
(3)
Al(CP)
3
+ CP
-
AlC
2
-
+ 2P
2
C (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 du CP
-
, kt ta u l le(CP)
3
(0,02mol)
2le(CP)
3
le
2
C
3
+ 3P
2
C, m
rn
= g 6 , 1 160 01 , 0 m
3 2
O Fe
= =
(c) 1hm PCl vo dung dlch L [na
+
, CP
-
(0,04 mol), AlC
2
-
(0,04 mol) v nC
3
-
]
CP
-
+ P
+
P
2
C (3)
AlC
2
-
+ P
+
+ P
2
C Al(CP)
3
(6)
Al(CP)
3
+ 3P
+
Al
3+
+ 3P
2
C (7)
1,00
0,S0
mol 03 , 0
78
34 , 2
n
3
) OH ( Al
= =
1rung hop 1: xay ra (3), (6) v AlC
2
-
du
mol 07 , 0 03 , 0 04 , 0 n n n
3
) OH ( Al
OH H
= + = + =
+
, L 14 , 0
5 , 0
07 , 0
V = =
1rung hop 2: xay ra (3), (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
(0,302)
CU IV (3 dlm)
1. 1lnh hlu ung nhlt phan ung hldro ha etllen tao etan, blt nhlt chy ca C
2
P
6
v C
2
P
4
ln luot bng -368,4
kcal/mol v -337,2 kcal/mol [san phm chy l CC
2
(k) v P
2
C (l)], nhlt hlnh thnh P
2
C (l) l -68,32 kcal/mol.
2. (a) vlt cng thuc cu tao v gol tn anken lt cacbon nht dng thl c dng phn hlnh hoc v dng phn
quang hoc. (b) vlt cc dng phn hlnh hoc v quang hoc ung vl cu tao d (s dung cng thuc llsher) v xc
dlnh cu hlnh ml dng phn (Z/L v 8/S). (b) vlt cu tao cc san phm chlnh hlnh thnh khl cho anken trn
tc dung vl dung dlch nuc brom c luong nho mul natrl clorua.
P N IM
1. (1) C
2
P
6
(k) + 7/2C
2
(k) 2CC
2
(k) + 3P
2
C (l) kcal 4 , 368 H = A
(2) C
2
P
4
(k) + 3C
2
(k) 2CC
2
(k) + 2P
2
C (l) kcal 2 , 337 H = A
(3) P
2
(k) + 1/2C
2
(k) P
2
C (l) kcal 32 , 68 H = A
Ly (2) - (1) + (3) ta duoc:
C
2
P
4
(k) + P
2
(k) C
2
P
6
(k) kcal 1 , 37 ) 32 , 68 ( ) 4 , 368 ( ) 2 , 337 ( H = + = A
2. (a) Cu tao:
CH
3
CH CH C
H
CH
3
C
2
H
5
(4-metylhex-2-en)
(b) Cu hlnh:
1,00
0,2S
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 tao cc san 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
(0,234)
0,7S
(0,233)
CU V (3 dlm)
1. Pldrocacbon A c khl luong phn t bng 80. Czon phn A chl tao andehlt lomlc v andehlt oxallc.
C H
O
H C H
O
C
O
H
andehit fomic andehit oxalic
a. xc dlnh cu tao v gol tn A.
b. uung co ch glal thlch cc san phm hlnh thnh khl cng 8r
2
vo A theo tl l mol 1:1, gol tn cc san phm
ny.
2. Pop cht A c cng thuc phn t C
9
P
8
. A lm mt mu 8r
2
trong CCl
4
, hldro ha A trong dlu kln m dlu tao
ra C
9
P
10,
cntrong dlu kln nhlt d v p sut cao thl tao ra C
9
P
16
, oxl ha mnh llt A slnh ra axlt phtallc
[1,2-C
6
P
4
(CCCP)
2
]. Lp lun xc dlnh cu tao ca A.
P N IM
1. (a) Cng thuc tng qut cho A l C
x
P
y
1a c
=
=
+ s
= +
8 y
6 x
2 x 2 y
80 y x 12
, cng thuc phn t C
6
P
8
) 3 ( = A
1u san phm ozon phn ta thu duoc cu tao ca A:
0,S0
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) Co ch v san 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
P
8
) c d bt bo ha 6 = A
A lm mt mu 8r
2
v cng m dlu 1 phn t P
2
cho thy A c 1 lln kt dl.
A cng tl da 4 phn t P
2
v khl oxl ha tao axlt phtallc cho thy A c vng benzen v ngol ra
cn mt vng 3 canh nua.
Cng thuc ca A:
0,S0
(0,232)
1,S0
(0,303)
0,S0
CU VI (4 dlm)
Chla 3,384 L (dktc) hn hop gm mt ankan (A), mt anken (8) v mt ankln (C) thnh 2 phn bng nhau. hn 1
cho qua dung dlch AgnC
3
du trong nP
3
thy th tlch hn hop glam 12,3 v thu duoc 1,47g kt ta. hn 2 cho
qua dung dlch brom du thy khl luong blnh brom tng 2,22g v c 13,6g brom d tham gla phan ung. ut chy
hon ton khl ra khol blnh brom rl hp thu san phm chy vo dung dlch 8a(CP)
2
du thl thu duoc 2,933g kt ta.
1. xc dlnh cng thuc cu tao A, 8 v C.
2. 1u A vlt dy chuyn ha (ghl r dlu kln phan ung) dlu ch 1,1-dlbrompropan v 2,2-dlbrompropan.
3. vlt phuong trlnh phan ung xay ra khl cho C tc dung vl dung dlch kMnC
4
trong (l) ml trung trung tlnh o
nhlt d phng v (ll) ml trung axlt (P
2
SC
4
) c dun nng.
P N IM
1. 1rong mt phn, ta c: mol 08 , 0
4 , 22
584 , 3
2
1
n
C , B , A
= = . uung dlch AgnC
3
/nP
3
chl hp thu ankln,
dt cng thuc ankln l 8C=CP (gla s khng phal l C
2
P
2
).
8C=CP + AgnC
3
+ nP
3
8C=CAg + nP
4
nC
3
(1)
mol 01 , 0 08 , 0
100
5 , 12
n n
ankin
= = != (8 + 132) 0,01 = 1,47
8 = 13 (CP
3
-), cng thuc ca ankln l CP
3
C=CP
uung dlch brom hp thu anken (C
n
P
2n
) v ankln
C
n
P
2n
+ 8r
2
C
n
P
2n
8r
2
(2)
C
3
P
4
+ 28r
2
C
3
P
4
8r
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
= =
1u
065 , 0
1
82 , 1
n 14
= n = 2, cng thuc ca anken l CP
2
=CP
2
.
khl ra khol blnh brom l ankan (C
m
P
2m+2
), mol 005 , 0 065 , 0 01 , 0 08 , 0 n
2 n 2 n
H C
= =
+
C
m
P
2m+2
+
2
O
2
1 n 3
|
.
|
\
| +
nCC
2
+ (n+1)P
2
C (4)
CC
2
+ 8a(CP)
2
8aCC
3
+ P
2
C (3)
015 , 0
197
955 , 2
n n
3 2
BaCO CO
= = = 1u (4): 3 n
015 , 0
n
005 , 0
1
= = , cng thuc ankan l CP
3
CP
2
CP
3
.
2. ulu 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. han ung ca C:
+ 2KMnO
4
CH
3
C CH CH
3
C C
O O
+ 2MnO
2
+ KOH OK
3CP
3
C=CP + 8kMnC
4
+ 12P
2
SC
4
3CP
3
CCCP + 3CC
2
+ 8MnSC
4
+ 4k
2
SC
4
+ 12P
2
C
0,7S
0,7S
0,S0
1,00
(0,302)
1,00
(0,302)
S 4
S GIO DC V O TO
THNH PH NNG
NM HC 2005 - 2006
MN: HA HC LP 11
CU I (4 dlm)
1. nu hln tuong xay ra v vlt phuong trlnh phan ung mlnh hoa trong cc trung hop sau:
(a) Pa tan tu tu cho dn du dung dlch naCP vo dung dlch AlCl
3
, sau d thm PCl vo dung dlch thu duoc
dn du.
(b) 1hm dung dlch k
2
CC
3
vo dung dlch le(nC
3
)
3
2. A l dung dlch na
2
CC
3
0,1M, 8 l dung dlch hn hop na
2
CC
3
0,1M v kPCC
3
0,1M v C l dung dlch kPCC
3
0,1M.
(a) 1lnh th tlch khl CC
2
(dktc) thot ra khl cho tu tu tung glot dn ht 30 mL dung dlch PCl 0,1M vo 100 mL
dung dlch A v khl cho ht 100 mL dung dlch 8 vo 200 mL dung dlch PCl 0,1M.
(b) xc dlnh s mol cc cht c trong dung dlch thu duoc khl thm 100 mL dung dlch 8a(CP)
2
0,1M vo 130
mL dung dlch C.
(c) 1lnh pP ca cc dung dlch A v C, blt axlt cacbonlc c pk
1
= 6,33 v pk
2
= 10,33.
(d) u nghl phuong php nhn blt cc anlon c trong dung dlch 8.
P N IM
1. (a) 1hm dung dlch naCP vo dung dlch AlCl
3
thy xut hln kt ta trng keo, sau d tan lal:
Al
3+
+ 3CP
-
Al(CP)
3
Al(CP)
3
+ CP
-
Al(CP)
4
-
1hm PCl vo dung dlch thu duoc lal thy xut hln kt ta trng keo, sau d tan
lal:
Al(CP)
4
-
+ P
+
Al(CP)
3
+ P
2
C
Al(CP)
3
+ 3P
+
Al
3+
+ 3P
2
C
0,S0
(b) 1hm dung dlch k
2
CC
3
vo dung dlch le(nC
3
)
3
thy xut hln kt ta do nu v sl bot khl
khng mu: 2le
3+
+ 3CC
3
2-
+ 3P
2
C 2le(CP)
3
+ 3CC
2
0,2S
2. (a) Cho tu tu tung glot dn ht 30 mL dung dlch PCl 0,1M vo 100 mL dung dlch na
2
CC
3
0,1M
CC
3
2-
+ P
+
PCC
3
-
0,01 0,003
0,003 0,003
0,003 0
0,S0
uo CC
3
2-
du nn khng c glal doan tao CC
2
, 0 V
2
CO
=
Cho ht 100 mL dung dlch na
2
CC
3
0,1M v kPCC
3
0,1M vo 200 mL dung dlch PCl 0,1M:
CC
3
2-
+ 2P
+
P
2
C + CC
2
(1)
PCC
3
-
+ P
+
P
2
C + CC
2
(2)
vl
+
> +
H HCO CO
n n n 2
3
2
3
nn P
+
phan ung ht.
Cla s (1) xay ra truc thl ta c mol 01 , 0 n
2
1
n
H
CO
2
= =
+
Cla s (2) xay ra truc thl tu (1) v (2) ta c mol 015 , 0 n
2
CO
=
1huc t (1) v (2) dng thl xay ra nn:
L 336 , 0 4 , 22 015 , 0 V 4 , 22 01 , 0 L 224 , 0
2
CO
= < < =
1,00
(b) 1hm 100 mL dung dlch 8a(CP)
2
0,1M vo 130 mL dung dlch kPCC
3
0,1M
PCC
3
-
+ CP
-
CC
3
2-
+ P
2
C
0,013 0,02
0,013 0,013
0 0,003 0,013
8a
2+
+ CC
3
2-
8aCC
3
0,01 0,013
0,01 0,01
0 0,003
uung dlch cn 0,003 mol kCP v 0,003 mol k
2
CC
3
0,S0
(c) uung dlch A c cc cn bng:
CC
3
2-
+ P
2
C PCC
3
-
+ CP
-
k
b1
= 10
-3,67
PCC
3
-
+ P
2
C P
2
C + CC
2
+ CP
-
k
b2
= 10
-7,63
P
2
C P
+
+ CP
-
k
n
= 10
-14
vl k
b1
>> k
b2
>> k
n
nn cn bng (1) l ch yu:
0,7S
pP = 14 -
2
1
(pk
b1
+ pC) = 14 -
2
1
(3,67 + 1) = 11,67
uung dlch C l dung dlch lung tlnh nn:
pP =
2
1
(pk
1
+ pk
2
) =
2
1
(6,33 + 10,33) = 8,34
(d) 1rlch mu th, thm 8aCl
2
du vo mu th thy xut hln kt ta trng (tan trong axlt),
nhu vy mu th c CC
3
2-
.
8a
2+
+ CC
3
2-
8aCC
3
Loc tch kt ta, thm PCl vo dung dlch nuc loc thy sl bot khl khng mu (lm duc nuc
vl trong), vy dung dlch c PCC
3
-
PCC
3
-
+ P
+
P
2
C + CC
2
.
0,S0
CU II (4 dlm)
1. (a) Amonlac c tlnh oxl ha hay tlnh kh? vlt phuong trlnh phan ung mlnh hoa. (b) 1rong dung ml amonlac
long, cc hop cht knP
2
, nP
4
Cl, Al(nP
2
)
3
c tlnh axlt, bazo hay lung tlnh ? vlt cc phuong trlnh phan ung
mlnh hoa.
2. Pa tan 4,8 gam klm loal M bng dung dlch PnC
3
dc nng du, hay ha tan 2,4 gam mul sunlua klm loal ny
cng trong dung dlch PnC
3
dc nng, thl du cung slnh ra khl nC
2
duy nht c th tlch bng nhau trong cung
dlu kln.
(a) vlt cc phuong trlnh phan ung dul dang phuong trlnh lon.
(b) xc dlnh klm loal M, cng thuc phn t mul sunlua.
(c) Pp thu khl slnh ra o ca hal phan ung trn vo 300 mL dung dlch naCP 1M, rl thm vo d mt lt
phenolphtaleln. Pol dung dlch thu duoc c mu gl? 1al sao?
P N IM
1. (a) nP
3
vua c tlnh oxl ha, vua c tlnh kh :
1lnh oxl ha: k + nP
3 (l)
knP
2
+ 1/2P
2
1lnh kh: 2nP
3
+ 3CuC 3Cu + n
2
+ 3P
2
C
0,7S
(b) knP
2
l mt bazo, nP
4
Cl l axlt v Al(nP
2
)
3
c tlnh lung tlnh.
han ung trung ha: knP
2
+ nP
4
Cl kCl + 2nP
3
han ung ca cht lung tlnh vl axlt: Al(nP
2
)
3
+ 3nP
4
Cl AlCl
3
+ 6nP
3
han ung ca cht lung tlnh vl bazo: Al(nP
2
)
3
+ knP
2
k[Al(nP
2
)
4
]
07S
2. (a) huong trlnh phan ung:
M + 2mP
+
+ mnC
3
-
M
m+
+ mnC
2
+ mP
2
C
(1)
M
2
S
n
+ 4(m+n)P
+
+ (2m+6n)nC
3
-
2M
m+
+ nSC
4
2-
+ (2m+6n)nC
2
+ 2(m+n)P
2
C (2)
1,00
(b) vl s mol nC
2
o hal trung hop 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
, nghlm thlch hop l n = 1, m = 2 v M = 64.
vy M l Cu v cng thuc mul l Cu
2
S.
0,7S
(c) mol 075 , 0
64
8 , 4
n
Cu
= =
Cu + 4PnC
3
Cu(nC
3
)
2
+ 2nC
2
+ 2P
2
C
NaOH NO
n mol 3 , 0 075 , 0 2 2 n
2
= = =
d xay ra vua d phan ung:
2nC
2
+ 2naCP nanC
3
+ nanC
2
+ P
2
C
uung dlch thu duoc c mu hng do nC
2
-
tao ml trung bazo:
nC
2
-
+ P
2
C PnC
2
+ CP
-
0,7S
CU III (4 dlm)
1. (a) 1lnh tl l cc san phm monoclo ha (tal nhlt d phng) v monobrom ha (tal 127
o
C) lsobutan. 8lt tl l
kha nng phan ung tuong dl ca nguyn t P trn cacbon bc nht, bc hal v bc ba trong phan ung clo
ha l 1,0 : 3,8 : 3,0 v trong phan ung brom ha l 1 : 82 : 1600.
(b) uua vo kt qua tlnh duoc o cu (a), cho nhn xet v cc yu t anh huong dn hm luong cc san phm
ca phan ung halogen ha ankan.
2. uung co ch phan ung glal thlch tal sao khl x ly 2,7-dlmetylocta-2,6-dlen vl axlt photphorlc thl thu duoc
1,1-dlmetyl-2-lsopropenylxlclopentan.
3. Pldro ha mt hldrocacbon A (C
8
P
12
) hoat dng quang hoc thu duoc hldrocacbon 8 (C
8
P
18
) khng hoat dng
quang hoc. A khng tc dung vl Ag(nP
3
)
2
+
v khl tc dung vl P
2
trong su c mt ca d/bCC
3
tao hop cht
khng hoat dng quang hoc C (C
8
P
14
).
4. Lp lun xc dlnh cu tao (c luu y cu hlnh) v gol tn A, 8, C.
5. Cxl ha mnh llt A bng dung dlch kMnC
4
trong P
2
SC
4
.vlt phuong trlnh ho hoc.
P N IM
1. (a) 1l l san 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,S0
0,S0
(b) Pm luong san phm halogen ha phu thuc ba yu t:
kha nng tham gla phan ung th ca ankan: han ung halogen ha uu tln th hldro trn
nguyn t cacbon bc cao hon.
kha nng phan ung ca halogen: 8rom tham gla phan ung yu hon so vl clo, nhung c
kha nng chon loc vl trl th cao hon so vl clo.
S nguyn t hldro trn cacbon cung bc: khl s hldro trn cc nguyn t cacbon cng
nhlu thl hm luong san phm cng ln.
0,7S
2. Co ch:
H
+
-H
+
0,7S
3. (a) A c d bt bo ha 3
2
12 8 . 2 2
=
+
= A , 8 c 0
2
18 8 . 2 2
=
+
= A v C c
2
2
14 8 . 2 2
=
+
= A .
vl A cng 3 phn t hldro d tao ra 8 nn A c cc lln kt bl hoc vng ba canh.
A cng 1 phn t P
2
tao ra C v A khng tc dung vl Ag(nP
3
)
2
+
nn A c mt lln kt ba
dang -CC-8.
A cng phal chua mt lln kt dl dang c|s- (Z) o vl trl dl xung vl lln kt ba, vl khl A cng
1 phn t P
2
(xuc tc d lm cho phan ung chay theo klu c|s-) tao C khng hoat dng
quang hoc.
0,S0
Cu tao ca A, 8, 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
0,7S
(b) huong trlnh phan ung:
SCP
3
CP=CPCP(CP
3
)CC-CP
3
+ 14kMnC
4
+ 21P
2
SC
4

10CP
3
CCCP + SCP
3
CP(CCCP)
2
+ 14MnSC
4
+ 7k
2
SC
4
+ 16P
2
C
0,2S
CU IV(4 dlm)
1. l|mooeo (C
10
P
16
) l tecpen c trong vo qua cam, chanh v buol. Cxl ha llmonen bng kallpemanganat tao
cht A.
CH
3
C
O
CH
2
CH
2
CH
CH
2
COOH
C O
H
3
C
(A)
(a) uung du kln trn v qul tc lsopren xc dlnh cu truc ca llmonen.
(b) vlt cng thuc cc san phm chlnh hlnh thnh khl hldrat ha llmonen.
2. u dlu ch nltrobenzen trong phng thl nghlm v tlnh hlu sut phan ung, ngul ta tln hnh cc buc sau:
Cho 19,3 ml axlt nltrlc vo mt blnh cu dy trn c 200 mL lm lanh blnh v lc, sau d thm tu tu 13 mL
P
2
SC
4
dm dc, dng thl lc v lm lanh dn nhlt d phng. Lp ng slnh hn hl luu (nuc hay khng khl),
cho tlp 13,3 mL benzen qua ng slnh hn vl tc d chm v glu nhlt d khng qu 30
0
C, dng thl lc lln
tuc (a).
Sau khl cho ht benzen, tlp tuc dun nng blnh phan ung trn bp cch thuy trong 30-43 phut v tlp tuc lc.
Sau d lm lanh hn hop phan ung v d qua phu chlt. 1ch ly lp nltrobenzen o trn. 8a nltrobenzen
bng nuc rl bng dung dlch na
2
CC
3
(b). 1ch ly nltrobenzen cho vo blnh lm kh c chua cht lm kh A
o th rn (c). Chung ct ly nltrobenzen bng blnh vuy-c trn bp cch thuy d thu ly nltrobenzen sach. Cn
luong nltrobenzen thy duoc 13 gam (d).
(a) vlt phuong trlnh ho hoc chlnh v cc phuong trlnh th hln co ch ca phan ung. Cho blt vl sao cn
phal lc blnh lln tuc v glu nhlt d phan ung o 30
0
C? nu khng dung P
2
SC
4
dm dc, phan ung c xay
ra khng?
(b) vl sao cn phal ra nltrobenzen bng nuc, sau d bng dung dlch na
2
CC
3
?
(c) A c th l cht no?
(d) 1lnh hlu sut phan ung nu khl luong rlng ca benzen 0,8g/mL.
P N IM
1. (a) Cu tao:
O + O=C=O
O
O
OH
limonen
0,7S
(b) Cc san phm chlnh khl hldrat ha:
OH
OH OH
OH
0,7S
4. (a) han ung:
C
6
P
6
+ PCnC
2

4 2
SO H
C
6
P
3
nC
2
+ P
2
C (1)
Co ch phan ung:
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
(+)
0,7S
+ NO
2
(+)
H NO
2
+
NO
2
+ H
(+)
cham nhanh
Pn hop phan ung o h dl th nn cn phal lc du hay khuy manh lln tuc d tao thnh
nh tuong, bao dam su tlp xuc tt glua cc tc nhn.
hal glu o 30
0
C vl nu o nhlt d cao hon s tng luong san phm dlnltrobenzen.
nu khng dung P
2
SC
4
, phan ung vn xay ra do vn c su hlnh thnh nC
2
+
theo phuong
trlnh sau:
PC-nC
2
+ PnC
3
P
2
C
+
-nC
2
+ nC
3
-
P
2
C
+
-nC
2
+ PnC
3
P
3
C
+
+ nC
3
-
+ nC
2
+
(1)
1uy nhln khl khng c P
2
SC
4
phan ung xay ra chm vl hlu sut tao nC
2
+
slnh ra trong (1)
rt thp. khl c mt P
2
SC
4
dm dc, cn bng chuyn dl v phla thun nn phan ung xay
ra nhanh hon.
0,7S
(c) Cn phal ra bng nuc d loal axlt, sau d ra bng dung dlch na
2
CC
3
d loal ht axlt du
v d klm tra kt qua do phan ung glua axlt v na
2
CC
3
slnh khl.
0,2S
(b) A l cht hut nuc o dang rn, nn A c th l CaCl
2
, ... khan 0,2S
(d) Plu sut phan ung:
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,S0
CU VI
A l hldrocacbon khng lm mt mu dung dlch brom. ut chy hon ton 0,02 mol A v hp thu san phm chy
vo dung dlch chua 0,13 mol Ca(CP)
2
thu duoc kt ta v khl luong blnh tng ln 11,32 gam. Cho dung dlch
8a(CP)
2
du vo dung dlch thu duoc kt ta lal tng ln, tng khl luong kt tua hal ln l 24,83 gam. A khng vl
dung dlch kMnC
4
/P
2
SC
4
nng, cn khl monoclo ha trong dlu kln chlu sng thl chl tao mt san phm duy
nht.
1. xc dlnh cng thuc cu tao v gol tn A.
2. ngul ta c th dlu ch A tu phan ung glua benzen v anken tuong ung trong axlt sunlurlc. uung co ch
phan ung d glal thlch phan ung ny.
3. Mononltro ha A bng cch cho phan ung vl axlt nltrlc (c mt axlt sunlurlc dc) thl san phm chlnh thu
duoc l gl? 1al sao?
P N IM
1. uung dlch Ca(CP)
2
hp thu ht san phm chy ca A chua CC
2
v P
2
C
CC
2
+ Ca(CP)
2
CaCC
3
+ P
2
C (1)
2CC
2
+ Ca(CP)
2
Ca(PCC
3
)
2
(2)
Ca(PCC
3
)
2
+ 8a(CP)
2
CaCC
3
+ 8aCC
3
+ 2P
2
C (3)
0,S0
ut s mol CC
2
tham gla cc phan ung (1) v (2) ln luot 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
= + =
1u 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,S0
ut cng thuc tng qut ca A l C
x
P
y
:
C
x
P
y
+ (x+y/4)C
2
xCC
2
+ y/2P
2
C
1a c 14 y , 10 x
14 , 0 . 2
y
2 , 0
x
02 , 0
1
= = = =
Cng thuc phn t ca A l C
10
P
14
, ) 4 = A
0,S0
vl A khng lm mt mu dung dlch brom (cu truc thom), khng tc dung vl dung dlch
kMnC
4
/P
2
SC
4
(chl c mt nhm th) v monoclo ha (nh sng) chl tao mt san phm duy
nht (nhm th c cu truc dl xung cao) nn cu tao ca A l:
C
CH
3
CH
3
CH
3
(t-butylbenzen)
1,00
2. Co ch:
(CP
3
)
2
C=CP
2
+ P
2
SC
4
(CP
3
)
2
C
+
-CP
3
+ PSC
4
-
+
C(CH
3
)
3
H
+ H
(+)
cham nhanh
+ (CH
3
)
3
C
+
C(CH
3
)
3
1,00
3. nhm ankyl nl chung dlnh hung th vo cc vl trl ottbo- v poto-. 1uy nhln, do nhm t-butyl
c klch thuc ln gy n ngu khng glan nn san phm chlnh l san phm poto-:
C
CH
3
CH
3
CH
3
O
2
N
0,S0
uL SC 3
S GIO DC V O TO
THNH PH NNG
L CnINn 1n0C
u ny c hal (2) trang
HNG DN CHM THI HC SINH GII THNH PH
NM HC 2006 - 2007
MN: HA HC LP 11
CU I (4 dlm)
1. 1lnh pP ca dung dlch thu duoc khl trn ln 30,0 mL dung dlch nP
4
Cl 0,200 M vl 73,0 mL dung dlch naCP
0,100 M. 8lt k
b
(nP
3
) = 1,8.10
-3
.
2. hen l mul sunlat kep ca mt catlon ha trl mt (nhu k
+
hay nP
4
+
) v mt catlon ha trl ba (nhu Al
3+
, le
3+
hay Cr
3+
). hen st amonl c cng thuc (nP
4
)
a
le(SC
4
)
b
.nP
2
C. Pa tan 1,00 gam mu phen st vo 100 cm
3
P
2
C, rl chla dung dlch thu duoc thnh hal phn bng nhau. 1hm dung dlch naCP du vo phn mt v dun
sl dung dlch. Luong nP
3
thot ra phan ung vua d vl 10,37 cm
3
dung dlch PCl 0,100 M. uung km klm loal
kh ht le
3+
o phn hal thnh le
2+
. u oxl ha lon le
2+
thnh lon le
3+
tro lal, cn 20,74 cm
3
dung dlch kMnC
4
0,0100 M trong ml trung axlt.
(a) vlt cc phuong trlnh phan ung dang lon thu gon v xc dlnh cc gl trl a, b, n.
(b) 1al sao cc phen khl tan trong nuc du tao ml trung axlt ?
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
=
=

nP
4
Cl + naCP naCl + nP
3
+ P
2
C
0,08 0,06
0,06 0,06 0,06
0,02 0 0,06
xet cn bng :
nP
3
+ P
2
C nP
4
+
+ CP
-
0,06 0,02
x x x
0,06-x 0,02+x x
5
3
4
b
10 . 8 , 1
x 06 , 0
x ) x 02 , 0 (
] NH [
] OH ][ NH [
K

+
=
+
= = , gn dung 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) ut s mol ca phen st (nP
4
)
a
le(SC
4
)
b
.nP
2
C trong ml phn l x mol.
huong trlnh phan ung phn mt :
nP
4
+
+ CP
-
nP
3
+ P
2
C
ax
0 ax
le
3+
+ 3CP
-
le(CP)
3
nP
3
+ P
+
nP
4
+
ax ax
huong trlnh phan ung phn hal :
Zn + 2le
3+
Zn
2+
+ 2le
2+
x
0 x
3le
2+
+ MnC
4
-
+ 8P
+
3le
3+
+ Mn
2+
+ 4P
2
C
x x/3
10,25
1a 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 thuc ca phen duoc vlt lal l nP
4
+
le
3+
(SC
4
2-
)
b
.nP
2
C
b = 2
1u M = 18 + 36 + 96.2 + 18n =
mol 10 . 037 , 1
gam 5 , 0
3
n = 12
Cng thuc ca phen st - amonl l nP
4
le(SC
4
)
2
.12P
2
C
(b) hen tan trong nuc tao ml trung axlt vl cc lon nP
4
+
, Al
3+
, le
3+
v Cr
3+
du nhung lon
axlt (cc lon k
+
c tlnh trung tlnh, cn SC
4
2-
c tlnh bazo rt yu).
nP
4
+
+ P
2
C nP
3
+ P
3
C
+
M
3+
+ P
2
C M(CP)
2+
+ P
+
CU II (4 d|m)
1. vlt phuong trlnh phan ung xay ra khl ln luot cho cc don cht As v 8l tc dung vl dung dlch PnC
3
(gla
thlt san phm kh chl l khl nC).
2. So snh (c glal thlch) tlnh tan trong nuc, tlnh bazo v tlnh kh ca hal hop cht vl hldro l amonlac (nP
3
)
v photphln (P
3
).
3. Mt glal doan quan trong trong qu trlnh tng hop axlt nltrlc l oxl ha nP
3
trong khng khl, c mt t xuc
tc.
(a) xc dlnh nhlt phan ung ca phan ung ny, blt nhlt hlnh thnh cc cht nP
3
(k), nC (k) v P
2
C (k) ln
luot bng - 46 k!/mol, + 90 k!/mol v - 242 k!/mol.
(b) 1rong cng nghlp, ngul ta d s dung nhlt d v p sut th no d qu trlnh ny l tl uu ? 1al sao ?
P N IM
1. huong trlnh phan ung :
3As + 3PnC
3
+ 2P
2
C 3P
3
AsC
4
+ 3nC
8l + 4PnC
3
8l(nC
3
)
3
+ nC + 2P
2
C
1,00
2. 1lnh tan :
nP
3
tan tt hon P
3
trong nuc, do phn t phn cuc hon v c kha nng tao lln kt hldro
vl nuc.
H N
H
H
H O
H
H N
H
H
... ... ... ...
1lnh bazo :
nP
3
c tlnh bazo manh hon P
3
, do lln kt n-P phn cuc manh hon lln kt -P, lm cho
nguyn t n trong phn t nP
3
glu electron hon, d dng nhn proton hon (mt nguyn
nhn nua glal thlch cho dlu ny l lon nP
4
+
bn hon P
4
+
).
1lnh kh :
P
3
c tlnh kh manh hon nhlu so vl nP
3
, do nguyn t l mt phl klm c d m dln
nho v phn t P
3
kem bn hon nP
3
.
3. (a) 4nP
3
(k) + 3C
2
(k) 4nC (k) + 6P
2
C (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) vl phan ung l toa nhlt, nn d tng hlu sut cn glam nhlt d. 1uy nhln nu ha
nhlt d qu thp s lm glam tc d phan ung, nn thuc t phan ung ny duoc tln hnh o
830-900
o
C v c xuc tc t. vl phan ung thun l chlu lm tng s phn t khl, nn d tng
hlu sut phan ung cn glam p sut. 1uy nhln, dlu kln p sut gy tng gl thnh cng
ngh san xut, nn ta chl dung p sut thung (1 atm).
CU III (4 dlm)
1. uung hlnh v, m ta thl nghlm duoc tln hnh trong phng thl nghlm d xc dlnh su c mt ca cc nguyn
t C v P c trong glucozo.
2. Pon thnh cc phan ung dul dy. xc dlnh san phm chlnh ca ml phan ung v dung co ch glal thlch su
hlnh thnh san phm chlnh d.
(a) CP
3
-CP=CP
2
(propllen) + PCl
(b) CP
3
-CP
2
-CP(CP)-CP
3
(ancol s-butyllc)
C 180 , SO H
o
4 2
(c) C
6
P
3
CP
3
+ PnC
3

o
4 2
t , SO H
3. uung so d xen ph obltan nguyn t d m ta cc phn t CP
3
-CP=C=CP-CP
3
(phn t A) v CP
3
-
CP=C=C=CP-CP
3
(phn t 8). Cho blt A, 8 c dng phn hlnh hoc hay khng ? 1al sao ?
P N IM
1. 1hl nghlm xc dlnh su c mt ca cc nguyn t C v P c trong glucozo :
1,S
2. han ung v co ch phan ung:
(a) han ung :
CH
3
CH CH
2
+ HCl
CH CH
3
CH
3
Cl
CH
2
CH
3
CH
2
Cl
(san pham chnh)
Co ch (cng A
L
) :
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)
San phm chlnh hlnh thnh theo hung tao cacbocatlon trung glan bn vung hon. u
thy rng cacbocatlon (x) bn hon (?) (do dln tlch duoc glal toa nhlu hon, vl 6P
o
),
nn san phm chlnh l lsopropyl clorua.
0,S0
(b) han ung :
CH
3
CH
2
H
2
SO
4
(san pham chnh)
CH CH
3
OH
CH
3
CH CH CH
3
+ H
2
O
CH
2
CH CH
2
CH
3
+ H
2
O
Co ch (tch L1) :
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)
San phm chlnh duoc hlnh thnh theo hung tao san phm bn hon. C dy, (x) bn hon
(?) do c s nguyn t P
o
tham gla lln hop, lm bn ha lln kt n nhlu hon.
0,S0
(c) han ung :
+ HONO
2
H
2
SO
4
+ H
2
O
CH
3
CH
3
NO
2
+ H
2
O
CH
3
NO
2
Co ch (th S
L
2Ar) : PCnC
2
+ P
2
SC
4
PSC
4
-
+ P
2
C +
+
nC
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
han ung dlnh hung th vo vl trl meto-, do mt d electron o vl trl ny trong phn t
toluen glu hon cc vl trl ortho-, para-. ung thl phan ung th vo vl trl ny tao su glal
toa dln tlch tt nht o phuc n.
0,S0
3. M hlnh phn t :
H
CH
3
H
CH
3
1rong trung hop ny, cc nhm th khng dng phng, nn phn t khng xut hln hln
tuong dng phn hlnh hoc.
H
CH
3
H
CH
3
1rong trung hop ny, cc nhm th dng phng, nn phn t xut hln hln tuong dng
phn hlnh hoc.
1,00
CU IV (4 dlm)
1. 1hl 672 mL (dktc) hn hop khl A gm mt ankan, mt anken v mt ankln (du c s nguyn t cacbon trong
phn t bng nhau) qua dung dlch AgnC
3
/nP
3
, thl thy c 3,4 AgnC
3
d tham gla phan ung. Cng luong hn
hop khl A trn lm mt mu vua ht 200 mL dung dlch 8r
2
0,13 M.
(a) xc dlnh thnh phn dlnh tlnh v dlnh luong cc cht trong A
(b) u nghl phuong php tch rlng tung cht ra khol hn hop A.
2. Cxl ha m gam hop cht huu co A bng CuC rl cho san phm slnh ra gm CC
2
v hol P
2
C ln luot dl qua blnh
1 dung Mg(ClC
4
)
2
v blnh 2 dung 2 llt Ca(CP)
2
0,0 2 M thl thu duoc 2 gam kt ta. khl luong blnh 1 tng
1,08 gam v khl luong CuC glam 3,2 gam, M
A
< 100. Cxl ha mnh llt A, thu duoc hal hop cht huu co l
CP
3
CCCP v CP
3
CCCCCP.
(a) xc dlnh cng thuc cu tao v gol tn A.
(b) vlt cc dang dng phn hlnh hoc tuong ung ca A.
(c) khl cho A tc dung vl 8r
2
theo tl l mol 1:1, thl tao duoc nhung san phm no ? Clal thlch.
P N IM
1. (a) nu ankln c dang 8CCP :
8CCP + AgnC
3
+ nP
3
8CCAg + nP
4
nC
3
mol 02 , 0
mol / gam 170
gam 4 , 3
) ankin ( n = = v mol 04 , 0 ) ankin ( n 2 n
2
Br
= >
ulu ny trl gla thlt, vl s mol 8r
2
chl bng mol 03 , 0 L / mol 15 , 0 L 2 , 0 =
vy ankln phal l C
2
P
2
v nhu vy ankan l C
2
P
6
, anken l C
2
P
4
.
1u phan ung :
C
2
P
2
+ 2AgnC
3
+ 2nP
3
C
2
Ag
2
+ 2nP
4
nC
3
n(C
2
P
2
) = 1/2n(AgnC
3
) = 0,01 mol
1u cc phan ung :
C
2
P
2
+ 28r
2
C
2
P
2
8r
4
C
2
P
4
+ 8r
2
C
2
P
4
8r
2
n(C
2
P
4
) = 0,01 mol
0,S0
n(C
2
P
6
) = = mol 01 , 0 mol 01 , 0
mol / L 4 , 22
L 672 , 0
0,01 mol
(b) 1hl hn hop qua blnh chua dung dlch AgnC
3
/nP
3
du. Loc tch kt ta, ha tan kt ta
trong dung dlch PCl du thu duoc khl C
2
P
2
.
C
2
P
2
+ 2AgnC
3
+ 2nP
3
C
2
Ag
2
+ 2nP
4
nC
3
C
2
Ag
2
+ 2PCl C
2
P
2
+ 2AgCl
khl ra khol blnh chua dung dlch AgnC
3
/nP
3
, thl tlp qua dung dlch nuc brom du. Chlt ly
san phm v dun nng vl bt Zn (trong CP
3
CCCP) thu duoc C
2
P
4
:
C
2
P
4
+ 8r
2
C
2
P
4
8r
2
C
2
P
4
8r
2
+ Zn C
2
P
4
+ Zn8r
2
khl ra khol blnh chua dung dlch brom l khl C
2
P
6
1,00
2. (a) n(P
2
C) = 0,06 mol n(P) = 0,12 mol
1u cc phan ung :
CC
2
+ Ca(CP)
2
CaCC
3
+ P
2
C
2CC
2
+ Ca(CP)
2
Ca(PCC
3
)
2
vl mol 045 , 0 n
2
) OH ( Ca
= v mol 02 , 0 n
3
CaCO
= n(CC
2
) bng 0,02 mol hoc 0,07 mol.
n(C) tham gla phan ung bng mol 2 , 0
mol / gam 16
gam 2 , 3
=
vy s mol C trong A bng :
n(C) = 0,02mol 2 + 0,06 mol - 0,2 mol < 0 (loal)
n(C) = 0,07mol 2 + 0,06 mol - 0,2 mol = 0 mol
A l hldrocacbon c cng thuc don glan C
7
P
12
vl M
A
< 100, nn cng thuc phn t ca A chlnh l C
7
P
12
( 2 = A )
Cu tao ca A phu hop vl gla thlt l:
CH CH
3
C
CH
3
CH CH CH
3
(3-metylhexa-2,4-dien)
1,00
0,S0
(b) Cc dang dng phn hlnh hoc :
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,S0
(c) 1c dung vl brom theo tl l mol 1:1 thl tao duoc cc san 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,S0
CU V( 4 dlm)
1. 1rlnh by phuong php phn blt ml cp cht dul dy (ml trung hop chl dung mt thuc th don glan,
c vlt phan ung mlnh hoa) :
(a) m-bromtoluen v benzylbromua
(b) phenylaxetllen v styren
2. 1u benzen v cc cht v co, xuc tc cn thlt khc c d, vlt cc phuong trlnh phan ung ha hoc dlu ch :
(a) meto-clonltrobenzen
(b) ottbo-clonltrobenzen
(c) axlt meto-brombenzolc
(d) axlt ottbo-brombenzolc
3. Pldrocacbon x c phn t khl bng 128, khng lm nhat mu dung dlch 8r
2
. x tc dung vl P
2
(xuc tc nl, t)
tao cc san phm ? v Z. Cxl ha mnh llt ? tao san phm l axlt o-phtallc, o-C
6
P
4
(CCCP)
2
.
(a) xc dlnh cu tao v gol tn x, ?, Z.
(b) vlt phan ung tao ra san phm chlnh, khl cho x ln luot tc dung vl dung dlch PnC
3
dc (P
2
SC
4
dc xuc
tc) v 8r
2
(xuc tc bt st). 8lt o ml phan ung, tl l mol cc cht tham gla phan ung l 1:1.
P N IM
1. hn blt cc cht :
(a) uung AgnC
3
, benzyl bromua cho kt ta vng :
C
6
P
3
CP
2
8r + AgnC
3
+ P
2
C C
6
P
3
CP
2
CP + Ag8r + PnC
3
(b) uung dung dlch AgnC
3
/nP
3
, phenylaxetllen cho kt ta vng xm :
C
6
P
3
CCP + AgnC
3
+ nP
3
C
6
P
3
CCAg + nP
4
nC
3
1,00
2. ulu 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
0,2S
0,S0
0,2S
0,S0
3. (a) x (C
x
P
y
), c 12x + y = 128 (y s 2x + 2) c hal nghlm thlch hop l C
10
P
8
v C
9
P
20
. 1uy nhln, vl
x tc dung duoc vl hldro, nn cng thuc dung l C
10
P
8
( 7 = A ).
vl x khng lm nhat mu nuc brom nn cu tao thlch hop ca x l naphtalen v phu hop vl
gla thlt thl ? l tetralln v Z l decalln :
(naphtalen)
(tetralin) (decalin)
1,00
(b) han ung :
+ HONO
2
H
2
SO
4
+ H
2
O
NO
2
+ Br
2
Fe
+ HBr
Fe
0,S0
L SC 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. 1l l trltl so vl tng s nguyn t hldro trong mt mu nuc sng l 8.10
-18
. 1rltl phn hy phng xa vl chu kl
bn hy 12,3 nm. C bao nhlu nguyn t trltl trong 10gam mu nuc sng trn sau 40 nm.
2. (a) Col tn v vlt dng phn cho cc hop cht phuc [t(nP
3
)
4
Cl
2
]
2+
v [Co(en)
2
Cl
2
].P
2
C.
(b) Clal thlch su hlnh thnh lln kt trong [Col
6
]
3-
(cht thun tu) v [Co(Cn)
6
]
3-
(cht nghlch tu) theo thuyt
lln kt ha trl v8.
3. vlt phuong trlnh phan ung mlnh hoa qu trlnh dlu ch cc cht sau dy tu cc don cht halogen tuong
ung: (a) PClC
4
, (b) l
2
C
3
, (c) Cl
2
C, (d) Cl
2
, (e) 8rC
3
.
p n im
1. S nguyn t T
3
1
trong 10g mu =
18 23
10 . 8 10 . 02 , 6 2
18
10

= 3,33.10
6
nguyn t
1u kt
n
n
ln
o
= v
2 / 1
t
693 , 0
k =
s nguyn t T
3
1
cn lal sau 40 nm:
40
3 , 12
693 , 0
6
e 10 . 35 , 5 n

= = 3,8.10
3
nguyn t T
3
1
2. (a) 1n gol v dng phn:
[t(nP
3
)
4
Cl
2
]
2+
: lon dlclorotatraamlnplatln (lv)
[Co(en)
2
Cl
2
].P
2
C: dlclorobls(etllendlamln)coban(ll) monohldrat
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) huc [Col
6
]
3-
thun tu cho thy cc lon l
-
phl trl vo cc obltan lal ha ngol sp
3
d
2
cn
trng ca Co(lll):
F
-
F
-
F
-
F
-
F
-
F
-
lai ha sp
3
d
2
huc [Co(Cn)
6
]
3-
nghlch tu cho thy cc lon Cn
-
phl trl vo cc obltan lal ha trong d
2
sp
3
cn trng ca Co(lll):
CN
-
CN
-
CN
-
CN
-
CN
-
CN
-
lai ha d
2
sp
3
3. (a) 3Cl
2
+ 6naCP
t
3naCl + naClC
3
+ 3P
2
C
4naClC
3

t
naCl + 3naClC
4
naClC
4
+ P
2
SC
4
naPSC
4
+ PClC
4
(chung ct)
(b) 3l
2
+ 6CP
-
3l
-
+ ClC
3
-
+ 3P
2
C
lC
3
-
+ P
+
PlC
3
2PlC
3

t
l
2
C
3
+ P
2
C
(c) 2Cl
2
+ PgC Cl
2
C + PgCl
2
(d) 2l
2
+ 2CP
-
2l
-
+ Cl
2
+ P
2
C
(e) 8r
2
+ 2C
3

C 0
o
28rC
3
Cu II (4 im)
1. 1lnh khl luong amonlclorua v th tlch dung dlch natrl hldroxlt 3,0M cn thm vo 200mL nuc v sau d
pha long dn 300mL d dlu ch dung dlch dm c pP = 9,3 vl nng d mul l 0,1M. 8lt pk
b
(nP
3
) = 4,76.
2. Cho cc thy tlnh thu nht chua dung dlch hn hop kMnC
4
0,02M, MnSC
4
0,003M v P
2
SC
4
0,3M, cc thu hal
chua dung dlch hn hop leSC
4
0,13M v le
2
(SC
4
)
3
0,0013M. ut dln cuc platln vo ml cc v nl hal cc vl
nhau bng cu mul. nl cc dln cuc vl nhau qua mt vol k. Cla thlt rng P
2
SC
4
dln ll hon ton v th
tlch dung dlch trong ml 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) 1lnh th ml dln cuc truc khl phan ung xay ra. vlt so d pln v tlnh hlu th pln.
(b) 1lnh hng s cn bng v th ml dln cuc tal cn bng.
3. Cho 1L dung dlch PClC
4
0,003M chua 2,0.10
-4
mol ml lon Mn
2+
v Cu
2+
. 8o ha dung dlch ny bng P
2
S, gla
thlt nng d P
2
S lun bng 0,1M khng phu thuc su c mt ca cc cht khc.
(a) Py cho blt c th tch rlng hal lon Mn
2+
v Cu
2+
khng? 8lt P
2
S c pk
1
= 7 v pk
2
= 14. 1
MnS
= 2,3.10
-10
v 1
CuS
= 8,3.10
-36
.
(b) kt lun trn c thay dl khng nu thay PClC
4
bng dung dlch dm c [P
+
] = 10
-9
M?
p n im
1. 1u
] NH [
] NH [
lg pK pH
4
3
a
+
+ =
] NH [
] NH [
lg ) 76 , 4 14 ( 5 , 9
4
3
+
+ = 8 , 1
] NH [
] NH [
4
3
=
+
1rong dung dlch cul: 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
= =

1u phan ung nP
4
+
+ CP
-
nP
3
+ P
2
C ta thy rng s mol naCP cn dung bng s mol nP
3
v
tng luong mul amonl cn ban du l 0,03mol + 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
= + = + =
+
+
+
So d pln:
t|le
2+
(0,130M), le
3+
(0,003M)||MnC
4
-
(0,02M), Mn
2+
(0,003M), P
+
(1M)|t
Plu th pln:
L
pln
= L
Mn
- L
le
= 1,32v - 0,671v = 0,83v
(b) Png s cn bng:
63 , 62 059 , 0
) 771 , 0 51 , 1 .( 5
059 , 0
E n
10 10 10 K = = =
A
vl hng s cn bng ln nn phan ung sau duoc col l hon ton:
3le
2+
+ MnC
4
-
+ 8P
+
3le
3+
+ Mn
2+
+ 4P
2
C
0,13 0,02 0,003
0,1 0,02 0,1
0,03 0 0,103
1al 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) Col su dng gp P
+
ca P
2
S l khng dng k ta c [P
+
] = 0,003M
1u
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
> 1
CuS
= 8,3.10
-36
Cu
2+
kt ta dul dang CuS
[Mn
2+
][S
2-
] = (2.10
-4
)(1,1.10
-17
) = 2,2.10
-21
< 1
MnS
= 2,3.10
-10
Mn
2+
khng kt ta dul dang mul sunlua.
nng d S
2-
thay dl khng dng k khl Cu
2+
kt ta ht, nn khl d Mn
2+
vn chua kt ta.
vy c th tch rlng hal lon 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
> 1
MnS
= 2,3.10
-10
Mn
2+
cng kt ta, vy khng th tch rlng hal lon ny.
Cu III (3 im)
1. 1lnh G A v nhn xet chlu tu xay ra cho phan ung: P
2
C (l) P
+
(aq) + CP
-
(aq)
tal 23
o
C trong ml dlu kln sau:
(a) [P
+
] = 10
-3
M v [CP
-
] = 10
-4
M
(b) [P
+
] = 10
-12
M v [CP
-
] = 2.10
-8
M
2. Png s cn bng (k
C
) ca mt phan ung ha hop:
A(k) + 8 (k) A8 (k)
l 1,8. 10
3
L.mol
-1
tal 23
o
C v 3,43.10
3
L.mol
-1
tal 40
o
C.
(a) Cla s H A khng phu thuc nhlt d, hy tlnh
o
H A v
o
S A
(b) Py tlnh cc hng s cn bng k
P
v k
X
tal 298k v p sut ton phn l 1 atm.
3. (a) 1hlt lp blu thuc xc dlnh chu kl bn hy phan ung mt chlu bc hal dang A san phm
(b) 1lnh chu kl phan ung bc hal: buta-1,3-dlen (k) xlclobuten (k). 8lt nng d ban du ca butadlen l
0,272M, tal 300k hng s vn tc phan ung l 0,0143M
-1
s
-1
.
p n im
1. 1al cn bng ta c: [P
+
] = [CP
-
] = 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
vl 0 G > A nn phan ung khng tu xay ra theo chlu 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
vl 0 G < A nn phan ung tu xay ra theo chlu thun.
2. (a) 1u
|
|
.
|
\
|
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
AP
o
= 33,77 k!/mol
1u AC
o
= 81 ln k = AP
o
1AS
o
1 1
2
2 2
o
o
mol . K . J 6 , 175
T
K ln RT H
S

=
+ A
= A
(b) 1al 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
+ =
khl t =
2
1
t thl:

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. Pon thnh cc dy chuyn ha dul dy:
axetllen + CP
3
Mg8r C + CP
4
C + CC
2
P
+
H
l (C
3
P
2
C
2
)
l
4 4 2 2
HgSO , SO H , O H
! (C
3
P
4
C
3
)
! + kMnC
4
san phm chl chua mt cht huu co k.
2. So snh (c glal thlch) d manh tlnh axlt ca k vl (a) axlt oxallc v (b) axlt sucxlnlc.
p n im
1. Pon thnh dy chuyn ha
CPCP + CP
3
Mg8r CPCMg8r + CP
4
CPCMg8r + CC
2
CPCCC
2
Mg8r
+
H
CPCCCCP
CPCCCCP
4 4 2 2
HgSO , SO H , O H
PCCCP
2
CCCP
PCCCP
2
CCCP
4
KMnO
PCCCCP
2
CCCP
2. (a) k
1
(axlt oxallc) > k
1
(axlt malonlc) do khl mach cacbon tng, hlu ung (-l) ca nhm cacboxyl
glam lm d phn cuc ca lln kt C-P v glam d bn ca bazo lln hop. k
2
(axlt oxallc) > k
2
(axlt malonlc) do lon oxalat dc blt bn nh su cng huong.
(b) k
1
(axlt malonlc) > k
1
(axlt sucxlnlc) do khl mach cacbon tng, hlu ung (-l) ca nhm cacboxyl
glam lm d phn cuc ca lln kt C-P glam v d bn ca bazo lln hop glam. k
2
(axlt malonlc)
< k
2
(axlt sucxlnlc) do lon sucxlnat bn hon lon malonat nh mach cacbon ln hon, th nng
tuong tc glua cc nhm CCC
-
nho hon.
C
O O
C
OH HO
C
O O
C
O
-
HO
C
O O
C
O O
2-
PCCC(CP
2
)
n
CCCP PCCC(CP
2
)
n
CCC
-
-
CCC(CP
2
)
n
CCC
-
Cu V (3 im)
c|ttol, C
10
P
16
C, l mt tecpen dng val tr cu t chlnh cho du co chanh. n phan ung vl hldroxylamln slnh ra
mt hop cht c cng thuc C
10
P
7
Cn, v vl thuc th 1ollens cho kt ta bac cung hop cht c cng thuc
C
10
P
16
C
2
. Cxl ha mnh llt cltral slnh ra axeton, axlt oxallc v axlt levullnlc (CP
3
CCCP
2
CP
2
CCCP).
1. u nghl cu tao cho cltral phu hop vl cc du llu trn v phu hop vl quy tc lsopren.
2. 1rong thuc t cltral gm hal dng phn l cltral a v cltral b. Cxl ha m dlu geranlol slnh ra cltral a (qetoo|ol),
cn tu nerol thl slnh ra cltral b (oetol). 1rong axlt sunlurlc, ca geranlol v nerol du chuyn ha thnh o-
tecplneol nhung kha nng chuyn ha ca geranlol chm hon nhlu so vl nerol. xc dlnh cu truc phu hop v
gol tn theo luAC cho hal dng phn ny. vlt co ch phan ung tao thnh o-tecplneol tu nerol.
3. khl cho c|ttol phan ung vl ol|vetol trong axlt long thu duoc mt hn hop cc san phm trong d chua (l) .
Cho blt co ch hlnh thnh (l) v gol tn tung glal doan ca co 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. c|ttol C
10
P
16
C c d bt bo ha 3 = A , han ung vl hldroxylamln v thuc th 1ollens cho
thy n l mt andehlt, Cxl ha tao ba phn manh cho thy phn t c hal lln kt dl. xp cc
phn manh theo quy tc lsopren ta c cu tao ca c|ttol:
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. Cltral a v b l dng phn hlnh hoc lln kt dl C
2
: nerol phan ung d dng hon, vy nerol v
neral l dng phn c|s- (Z) cn geraneol v geranlal l dng phn ttoos- (L).
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
Co ch phan ung (A
L
):
OH
CH
2
OH CH
2
OH
2
+
CH
2
+ H
+
- H
2
O
+ H
2
O
- H
+
3. Co ch tao (l)
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) roton ha andehlt, (2) 1h S
L
Ar, (3) roton ha v tch nuc tao lon dan alyllc, (4) Cng A
L
ca cacbocatlon vo lln kt dl, (3) Cng tao ete d proton ha, (6) 1ch proton tao (l).
Cu VI (4 im)
1. ngul ta xc dlnh cu tao cht khng slnh qtom|c|J|o 5 (cht A) bng cc qu trlnh sau:
hn tlch san phm thy phn cho thy tl l dng phn t cc amlnoaxlt Leu P
3
n
+
CP(|-8u)CCC
-
(M = 131),
Crn P
3
n
+
(CP
2
)
3
CP(nP
2
)CCC
-
(M = 132), he hCP
2
CP(
+
nP
3
)CCC
-
(M = 163), val P
3
n
+
CP(|-r)CCC
-
(M =
117), ro (M = 113). khl luong phn t A khoang 1300.
N
H H
H
COO
- Pro:
1h nghlm xc dlnh amlnoaxlt C-cul mach cho kt qua m, th nglm xc dlnh amlnoaxlt n-du mach
bng unl8 chl thy slnh ra un-nPCP
2
CP
2
CP
2
CP(
+
nP
3
)CCC
-
.
1hy phn khng hon ton gramlcldln S tao thnh cc dlpeptlt v trlpeptlt sau: Leu-he, he-ro,
he-ro-val, val-Crn-Leu, Crn-Leu, val-Crn, ro-val-Crn.
Cho blt trt tu cu tao ca phn t gramlcldln S.
2. Cu trlnh oxl ha metyl glycoslt C bng PlC
4
tao san phm glng nhu san phm oxl ha metyl -glycoslt ca
u-andohexoz. 1uy nhln, qu trlnh oxl ha C chl tlu tn 1 mol PlC
4
v khng tao ra axlt lomlc. Metyl ha C,
thy phn, sau d oxl ha mnh llt thu duoc axlt dlcacboxlllc dl-C-metylete ca axlt (-)-tartarlc. Lp lun vlt
cu hlnh dy d cho C (dang cng thuc chlu).
p n im
1. 1u 1300 ) 117 115 165 132 131 ( n M ~ + + + + = n = 2
1heo gla thlt qtom|c|J|o 5 khng c C-cul mach. San phm un-nPCP
2
CP
2
CP
2
CP(
+
nP
3
)CCC
-
cho thy unl8 chl phan ung vl c-nP
2
, nghla l qtom|c|J|o 5 cng khng c n-du mach. vy
qtom|c|J|o 5 c cu truc vng.
1u kt qua thy phn khng hon ton: Leu he
he ro
he ro val
val Crn Leu
Crn Leu
val Crn
ro val Crn
ta c trt tu: Leu-he-ro-val-Crn-Leu, vy trt tu cu tao ca qtom|c|J|o 5 l:
Val Orn Leu Phe
Pro
Val Orn Leu Phe
Pro
2. Cu hlnh dy d:
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)
L SC 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. 1hm don cht x hoat dng phng xa vo dung
dlch chua
2
3
XO thu duoc lon A hoat dng phng xa. 1hm dung dlch chua 8a
2+
thl thu duoc kt ta 8. Loc
tch kt ta 8, sy kh rl x ll vl dung dlch axlt clohldrlc thl thu duoc cht rn c hoat dng phng xa, cht
khl khng hoat dng phng xa v nuc.
(a) vlt cc phuong trlnh lon thu gon mlnh hoa (kl hlu x
*
cho nguyn t x hoat dng phng xa).
(b) vlt cng thuc cu tao cho lon A v cho blt cu tao, dang hlnh hoc cc hop khl vl P, oxlt bc cao nht,
hldroxlt bc cao nht ca x.
5. San xut ure tu nguyn llu du l nP
3
v CC
2
qua hal cng doan chlnh sau:
(a) 2nP
3
(k) + CC
2
(k) P
2
nCCCnP
4
(r) + 139,1k! (tng hop amonl cacbamat)
(b) P
2
nCCCnP
4
(r) P
2
nCCnP
2
(r) + P
2
C (l) - 238k! (dehldrat ha tao ure)
Cho blt cc bln php c th p dung d lm tng hlu sut ml qu trlnh trn.
p n im
1. (a) Cu hlnh electron ca x: 1s
2
2s
2
2p
6
3s
2
3p
4
Z = 16, x l luu huynh (S)
S
*
+
2
3
SO
2
3
*
SO S (
2
3 2
O S )
8a
2+
+
2
3
*
SO S
3
*
SO BaS !
3
*
SO BaS ! + 2P
+
SC
2
| + S
*
! + 8a
2+
+ P
2
C
(b) Cu tao ca A:
O
S
S
O
O
2- *
vl SC
2
khng c hoat tlnh phng xa nn S
*
chl tham gla lln kt S-S, m khng tham gla
lln kt S-C.
Cu tao cc hop cht chua P, oxlt bc cao nht, hldroxlt 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) uung du nP
3
hoc CC
2
(thuc t chl dung du nP
3
), tng p sut v ha nhlt d.
(b) uun nng (khng qu cao nu khng s gy phn hy ure) v chung ct nuc.
Cu VIII (4 im)
4. Ml hn hop gm hal cht sau dy c th tn tal duoc hay khng ? nu c tn tal thl hy cho blt dlu kln,
nu khng tn tal thl glal thlch r nguyn nhn: (a) P
2
v C
2
, (b) SC
2
v nC
2
, (c) na
2
C
2
v P
2
C, (d) dd leCl
2
v
8r
2
, (e) dd leCl
3
v kl
5. x l hop cht ho hoc tao ra trong hop klm gm le v C trong d c 6,67 C v khl luong. Po tan x trong
PnC
3
dc nng thu duoc dung dlch A v hn hop khl 8. Cho A, 8 ln luot tc dung vl naCP du thl A tao kt
ta A
1
, 8 tao hn hop 8
1
c 3 mul. nung A
1
v 8
1
o nhlt d cao A
1
tao oxlt A
2
, 8
1
tao hn hop 8
2
gm hal
mul. Cho 8
2
tc dung vl P
2
SC
4
long thu duoc khl 8
3
v axlt 8
4
. Cht 8
4
lm mt mu dung dlch kMnC
4
(trong ml trung axlt). vlt cc phuong trlnh phan ung (cc phan ung trong dung dlch vlt dang lon thu gon).
6. 1lnh th tlch amonlac dm dc (14,8M) v khl luong amonl clorua cn dung d pha ch 100mL dung dlch
dm c pP = 10, nu nng d ca mul l 0,2M. 8lt pk
b
(nP
3
) = 4,76.
p n im
1. (a) 1n tal o dlu kln thung, phan ung khl dun nng : P
2
+
2
1
C
2

o
t
P
2
C.
(b) khng : SC
2
+ nC
2
SC
3
+ nC
(c) khng: na
2
C
2
+ P
2
C2naCP +
2
1
C
2
(d) khng : 6leCl
2
+ 38r
2
4leCl
3
+ 2le8r
3
(e) khng : leCl
3
+ kl 2leCl
2
+ 2kCl + l
2
2. vl le
x
C
y
, ta c 3
y
x
67 , 6
33 , 93
y 12
x 56
= = , cng thuc le
3
C
le
3
C + 22P
+
+ 13nC
3
-
3le
3+
+ CC
2
+ 13nC
2
+ 11P
2
C
le
3+
+ 3CP
-
le(CP)
3
CC
2
+ 2CP
-
CC
3
2-
+ P
2
C
2nC
2
+ 2CP
-
nC
2
-
+ nC
3
-
+ P
2
C
2le(CP)
3

t
le
2
C
3
+ 3P
2
C
nanC
3

t
nanC
2
+ 1/2C
2
CC
3
2-
+ 2P
+
CC
2
+ P
2
C
nC
2
-
+ P
+
PnC
2
3PnC
2
+ 2MnC
4
-
+ P
+
3nC
3
-
+ 2Mn
2+
+ 3P
2
C
A: le(nC
3
)
3
8: CC
2
, nC
2
A
1
: le(CP)
3
8
1
: na
2
CC
3
, nanC
3
, nanC
2
A
2
: le
2
C
3
8
2
: na
2
CC
3
, nanC
2
8
3
: CC
2
8
4
: PnC
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
[nP
3
] = 1,13 (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 hop gm Al v Mg tan ht trong dung dlch axlt PnC
3
long, dun nng nhe tao ra dung dlch A v
448mL (do o 334,9k v 988mmPg) hn hop khl 8 kh gm 2 khl khng mu, khng dl mu trong khng khl. 1y
khl ca 8 so vl oxl bng 0,716 ln ty khl ca CC
2
so vl nlto. Lm khan A mt cch cn thn thu duoc cht rn
u, nung u dn khl luong khng dl thu duoc 3,84 gam cht rn L. vlt phuong trlnh phan ung, tlnh luong cht u
v luong ml klm loal trong hn hop ban du.
p n im
l. huong trlnh phan ung: khl 8 theo gla thlt chua n
2
v n
2
C.
3Mg + 12P
+
+ 2nC
3
3Mg
2+
+ n
2
| + 6P
2
C
4Mg + 10P
+
+ 2nC
3
4Mg
2+
+ n
2
C| + 3P
2
C
10Al + 36P
+
+ 6nC
3
10Al
3+
+ 3n
2
| + 18P
2
C
8Al + 30P
+
+ 6nC
3
8Al
3+
+ 3n
2
C| + 13P
2
C
4Al(nC
3
)
3
2Al
2
C
3
+ 12nC
2
| + 3C
2
|
2Mg(nC
2
)
2
2MgC + 4nC
2
| + C
2
|
vl kL mol 18 ca 2 khl = 36 v tng s mol 2 khl = 0,02 ta c th tlnh duoc:
S mol n
2
= 0,01 mol v s mol n
2
C = 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
C
y 2y 0,08 0,01
8ao ton electron ta c: 3x + 2y = 0,18 v 27x + 24y = 2,16 x = 0.
1u dy nay slnh tlnh hung c vn d? 1heo dlnh lut bao ton khl luong: 3,84 gam cht L chc
chn l Al
2
C
3
v MgC. 1u luong 2 klm loal v luong 2 oxlt tlnh duoc s mol Al = 0,04 v s mol Mg
= 0,043. Lp lal tlnh ton nhu 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
C
0,043 0,09 0,08 0,01
ta thy : tng s mol e nhung (0,21) > tng s mol e thu (0,18) chung to cn mt phn
5
N
+
= 0,21 -
0,18 = 0,03 mol d tham gla phan ung khc, khng glal phng khl.
u l phan ung: 4Mg + 10P
+
+ nC
3
4Mg
2+
+ nP
4
+
+ 3P
2
C
8Al + 30P
+
+ 3nC
3
8Al
3+
+ 3nP
4
+
+ 9P
2
C
2nP
4
nC
3
n
2
| + C
2
| + 4P
2
C|
vy cht u gm: Al(nC
3
)
3
(8,32 gam), Mg(nC
3
)
2
(6,66 gam), nP
4
nC
3
(2,4 gam) c khl luong 17,38
gam. Pn hop ban du c 30 khl luong ml klm loal.
Cu X(3 im)
3. Cho 6 dung dlch : glucozo, axlt lomlc, axlt axetlc, andehlt axetlc, etylengllcol v ruou etyllc. hn blt 6 dung
dlch trn bng phuong php ho hoc v vlt so d phan ung chuyn ho glucozo thnh 3 cht cn lal.
4. 1rong cc dy chuyn ha dlu ch axlt plcrlc tu benzen dul dy, dy no hop ll v dy no khng hop ll. Clal
thlch r su hop ll v khng hop ll d.
(a) benzen
) 1 (
phenyl clorua
) 2 (
phenol
) 3 (
axlt plcrlc
(b) benzen
) 1 (
phenyl clorua
) 2 (
1-clo-2,4-dlnltrobenzen
) 3 (
2,4-dlnltrophenol
) 4 (
axlt
plcrlc
p n im
1. 1m tt cch glal:
glucozo axlt lomlc axlt axetlc and axetlc etylengllcol ruou
etyllc
qul tlm - (8) do (A) do (A) - (8) - (8) - (8)
(A) AgnC
3
trong nP
3
kt ta
trng bac
-
(8) Cu(CP)
2
trong CP
-
, t
dd xanh
! do gach
! do gach dd xanh -
C
6
P
12
C
6

men
C
2
P
3
CP
t , CuO
CP
3
CPC
+ 2
2
Mn , O
CP
3
CCCP
C
2
P
3
CP
t , SO H
4 2
CP
2
=CP
2

4
KMnO
CP
2
(CP)CP
2
(CP)
CP
3
CCCP
t , CaO , NaOH
CP
4

o
600 400 , NO
PCPC
+ 2
2
Mn , O
PCCCP
2. (a) benzen
) 1 (
phenyl clorua
) 2 (
phenol
) 3 (
axlt plcrlc
uy ny khng hop ll do khl nltro ha phenol (3), PnC
3
c tlnh oxl ha manh s oxl ha dng
thl oxl ha phenol.
(b) benzen
) 1 (
phenyl clorua
) 2 (
1-clo-2,4-dlnltrobenzen
) 3 (
2,4-dlnltrophenol

) 4 (
axlt plcrlc
uy ny hop ll. Clal doan (2) do Cl- v -nC
2
du l nhm phan hoat ha nn chl th dlnltro. Clal
doan (4), hal nhm -nC
2
lm bn ha phenol, trnh duoc qu trlnh oxl ha xay ra khl nltro ha.
Cu XI (4 im)
4. Pldrocacbon mach thng A c 7 : 36 m : m
H C
= . xc dlnh cng thuc cu tao A v hon thnh dy chuyn
ho:
A A
2
A
3
henol
+ Ni , H
2
A
4

+CuO
A
3

+
H , KMnO
4
A
6
to nllon 6,6
5. 1ln hnh thl nghlm nhu sau: Cho 1mL CPCl
3
d ra sach lon halogenua vo ng nghlm c sn 3mL dung
dlch naCP 10 trong ng nghlm, lc du v dun sl hn hop mt cch cn thn. Lm lanh hn hop phan
ung, gan ly phn dung dlch trong o phla trn rl chla lm ba phn:
hn 1: Cho thm vl glot dung dlch PnC
3
, sau d thm tlp vl glot dung dlch AgnC
3
1 .
hn 2: Cho 1mL dung dlch AgnC
3
/nP
3
vo phn 2 rl dun nng nhe.
hn 3: Cho vl glot dung dlch kMnC
4
1 vo phn 3.
nu hln tuong xay ra trong 3 thl nghlm o 3 phn dung dlch trn, glal thlch, vlt phuong trlnh phan ung
mlnh hoa.
6. vlt co ch phan ung dehldrat ha 3,3-dlmetylbutan-2-ol v xlclobutylmetanol trong P
2
SC
4
dc.
p n im
(a) 7 : 3
1
7
:
12
36
n : n
H C
= =
Cng thuc nguyn: (C
3
P
7
)
n
1a c dlu kln: 7n s 6n + 2 v 7n l s chn
n = 2, cng thuc phn t ca A C
6
P
14
Cng thuc cu tao: CP
3
(CP
2
)
4
CP
3
(o-hexan)
uy 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) CPCl
3
+ 3 naCP
0
t
PCCCna + 3 naCl + 2 P
2
C
C phn 1 xut hln kt ta trng do :
naCl + AgnC
3
AgCl + nanC
3
C phn 2 xut hln kt ta Ag ( phan ung trng guong) do :
PCCCna + 2 [Ag(nP
3
)
2
]CP
0
t
naPCC
3
+ 2Ag + 4nP
3
+ P
2
C
C phn 3 , dung dlch mu tlm hng ca kMnC
4
chuyn sang mu xanh l cy do:
PCCCna + 2 kMnC
4
+ 3 naCP na
2
CC
3
+ k
2
MnC
4
+ na
2
MnC
4
+ 2 P
2
C
(c) Co 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)
Pn hop ? gm hal cht huu co A v 8 cung chuc ho hoc. nu dun nng 13,7 gam hn hop ? vl naCP du thl thu
duoc mul ca mt axlt huu co don chuc v 7,6 gam hn hop hal ruou no don chuc bc nht k tlp nhau trong
cung dy dng dng. nu dt 13,7 gam hn hop ? thl cn dung vua ht 21,84 llt C
2
v thuduoc 17,92 llt CC
2
(cc th
tlch khl doodluklntlu chun). xcdlnh cng thuc cu tao ca A v 8.
p n im
Lste don chuc k tlp c dang chung C
x
P
y
C
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 = = (3 < 3,33 < 6)
66 , 8 2
15 , 0
65 , 0
H = = (8 < 8,66 < 10)
Cng thuc phn t 2 este l C
3
P
8
C
2
v C
6
P
10
C
2
66 , 50
15 , 0
6 , 7
MROH = =
Pal ruou k tlp l C
2
P
3
CP (M = 46) v o-C
3
P
7
CP (M = 60)
Cng thuc ca hal este l CP
2
=CPCCCC
2
P
3
v CP
2
=CPCCCC
3
P
7
-o
L SC 8
SC GIC DC - C 1AC
1nNn nC NNG
kI 1nI nC SINn GICI 1nNn nC
NM nC 200S - 2006
nUCNG DN CnMMCN nC LC 12 - 8NG A
Cu 1 (3,0 dlm)
1. uua vo phuong php gn dung Slater, tlnh nng luong lon ha l
1
cho Pe (Z = 2).
2. uua trn m hlnh vSL8, glal thlch dang hlnh hoc ca cc phn t nP
3
, Cll
3
v xel
4
.
3. Poat tlnh phng xa ca dng vl Po
210
84
glam dl 6,83 sau 14 ngy. xc dlnh hng s tc d ca qu
trlnh phn r, chu ky bn hy v thl glan d cho n bl phn r 90 .
N ILM
Cu 1 (3,0 dlm)
1. Pe c cu hlnh 1s
2
,
, )
eV 6 , 78
1
3 , 0 2 6 , 13
2
n
Z 6 , 13
2 E
2
2 *
2 *
*
He
=

=
|
|
.
|
\
|
=
Pe
+
c cu hlnh 1s
1
, eV 4 , 54
1
2 6 , 13
n
Z 6 , 13
E
2
2
2
*
He
=
= =
+
Cu trlnh lon ha Pe - e Pe
+
,
eV 2 , 24 ) eV 6 , 78 ( ) eV 4 , 54 ( E E I
*
He
*
He
1
= = =
+
0,7S
2. Cu tao ca phn t nP
3
cho thy quanh n c 4 khng glan khu tru, trong d c 1
cp electron tu do (A8
3
L) nn phn t nP
3
c dang thp dy tam glc vl gc lln
kt nho hon 109
o
28
'
(cp electron tu do dl hol mt khoang khng glan khu tru ln
hon):
N H
H
H
..
H
N
H
H
0,S0
hn t Cll
3
c nm khoang khng glan khu tru, trong d c hal cp electron tu do
(A8
3
L
2
) nn c dang chu 1 (cc electron tu do chlm vl trl xlch dao):
0,S0
Cl F
F
F
.
. .
.
F Cl
F
F
hn t xel
4
c su khoang khng gla khu tru, trong d c hal cp electron tu do
(A8
4
L
2
) nn c dang vung phng (cc cp electron tu do phn b xa nhau nht):
Xe
F
F
F
F
.
.
.
.
F
Xe
F F
F
0,S0
3. 1u
, )
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
1hl glan d Po
210
84
bl phn r 90 l:
, )
454
90 100
100
ln
00507 , 0
1
t =
= ngy
0,7S
Cu 2 (3,0 dlm)
1. 1rn 13,00 mL dung dlch CP
3
CCCna 0,030 M vl 30,00 mL dung dlch PCCCna 0,13 M. 1lnh pP ca
dung dlch thu duoc. 8lt pk
a
(CP
3
CCCP) = 4,76 v pk
a
(PCCCP) = 3,73.
2. 1lnh nng d ban du ca PSC
4
-
(k
a
= 10
-2
), blt gl trl suc dln dng ca pln:
t|l
-
0,1 M, l
3
-
0,02 M||MnC
4
-
0,03 M, Mn
2+
0,01 M, PSC
4
-
C M|t
o 23
o
C do duoc bng 0,824 v. Cho V 51 , 1 E
o
Mn / MnO
2
4
=
+
v V 5355 , 0 E
o
I / I
3
=

.
3. 1lnh nng d lon P
+
d d lm glam nng d Ag(nP
3
)
2
+
0,10 M xung cn 1,0.10
-8
M. 8lt pk
b
(nP
3
) =
4,76 v hng s bn [Ag(nP
3
)
2
+
] = 7,24.
N ILM
Cu 2 (3,0 dlm)
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:
P
2
C P
+
+ CP
-
k
w
= 10
-14
(1)
CP
3
CCC
-
+ P
2
C CP
3
CCCP + CP
-
k
b
= 10
-9,24
(2)
PCCC
-
+ P
2
C PCCCP + CP
-
k
b
'
= 10
-10,23
(3)
uo
25 , 11
HCOO
'
b
24 , 11
O CO CH
b
10 C K 10 C K
-
3

= ~ =

cho nn khng th tlnh gn
dung theo mt cn bng.
ulu kln proton: h = [P
+
] = [CP
-
] - [CP
3
CCCP] - [PCCCP]
] O HCO [ ) K ( ] O CO CH [ K 1
K
h
- 1 '
a
-
3
1
a
w

+ +
= (4)
Chp nhn [CP
3
CCC
-
]
o
= 0,010, [PCCC
-
]
o
= 0,10 v thay vo (4) d tlnh h
1
:
9
1 75 , 3 2 76 , 4
14
1
10 . 96 , 2
10 . 10 10 . 10 1
10
h

=
+ +
=
1u gl trl h
1
tlnh lal [CP
3
CCC
-
]
1
v [PCCC
-
]
1
theo cc blu thuc:
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 qua lp lal.
vy h = 2,96.10
-9
= 10
-8,33
pP = 8,3
1,00
2. C dln cuc phal: MnC
4
-
+ 8P
+
+ 3e Mn
2+
+ 4P
2
C
C dln cuc trl: 3l
-
l
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 = L
phal
- L
trl
0,824 = 1,31 +
5
059 , 0
lg(3[P
+
]
8
) - 0,374
Suy ra h = [P
+
] = 0,033 M
Mt khc tu cn bng:
P
2
SC
4
-
P
+
+ SC
4
2-
k
a
= 10
-2
[] C - h h h
Suy ra C h
K
h
K
h C
h
a
2
a
2
= + =
1hay gl trl h = 0,033 v k

a
= 1,0.10
-2
, tlnh duoc M 334 , 0 C
4
HSO
=
1,00
3. uo [Ag(nP
3
)
2
+
] = 1,0.10
-8
M << 0,10 M, suy ra phuc bl phn hy hon ton. Pon nua
ml trung axlt, nn c th bo qua qu trlnh tao phuc hldroxo ca Ag
+
. han ung
phn hy phuc:
Ag(nP
3
)
2
+
+ 2P
+
Ag
+
+ 2nP
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
vl ml trung axlt v
24 , 9
NH
10 K
4
=
+
nho nn su phn ll ca nP
4
+
c th bo qua.
xet cn bng:
Ag
+
+ 2nP
4
+
Ag(nP
3
)
2
+
+ 2P
+
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 dlm)
1. Cho 100 gam n
2
o nhlt d 0
o
C v p sut 1 atm. 1lnh nhlt C, cng W, bln thln nl nng U v
bln thln entanpl H trong cc bln dl sau dy duoc tln hnh thun nghlch nhlt dng: (a) nung
nng dng tlch tl p sut bng 1,3 atm, (b) gln dng p tl th tlch gp dl th tlch ban du. Chp
nhn rng n
2
l khl ll tuong v nhlt dung dng p khng dl trong qu trlnh thl nghlm v bng 29,1
!.k
-1
.mol
-1
.
2. Py xc dlnh bc ca phan ung:
(CP
3
)
3
C8r (aq) + P
2
C (l) (CP
3
)
3
CCP (aq) + P
+
+ 8r
-
tu cc du kln thuc nghlm sau dy o 298k:
t, (s) 0 13000 33000 33000 93000 143000
[(CP
3
)
3
C8r], (mol.L
-1
) 0,0380 0,0308 0,0233 0,0176 0,0100 0,00302
3. Cn bng: n
2
(k) + 3P
2
(k) 2nP
3
(k)
s chuyn dlch chlu no khl (a) thm Ar vo hn hop cn bng nhung glu cho th tlch khng dl, (b)
thm Ar vo hn hop cn bng nhung glu cho p sut khng dl?
N ILM
Cu 3 (4,0 dlm)
1. (a) nung nng dng tlch tl p sut bng 1,3 atm
vl 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 = |
.
|
\
|
=
|
|
.
|
\
|
= =
0,7S
(b) Cln dng p tl th tlch gp dl
, ) =
|
|
.
|
\
|
= = =
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 = = + =
0,7S
2. huong trlnh dng hoc ca phan ung:

o o
= = CBr ) CH ( O H k
dt
CBr ) CH ( d
v
3 3 2
3 3
uo nng d ca cht tan rt nho, nn c th col [P
2
C] ~ const, phuong trlnh trn
tro thnh:

o
= = CBr ) CH ( k
dt
CBr ) CH ( d
v
3 3
3 3
vl k = k'[P
2
C]
o'
= const
0,7S
1h cc du kln thuc nghlm vo cc blu thuc ca k dl vl cc phan ung don
glan bc 0, 1, 2 ta duoc cc kt qua sau dy:
o = 0 o = 1 o = 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
-3
4,10.10
-4
4,20.10
-7
1,4.10
-3
4,70.10
-4
3,70.10
-7
1,4.10
-3
3,30.10
-4
2,93.10
-7
1,4.10
-3
7,80.10
-4
2,27.10
-7
1,4.10
-3
1,19.10
-4
vy phan ung c bc 1 dl vl (CP
3
)
3
C8r.
0,7S
3. (a) 1a 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
|
.
|
\
|
= |
.
|
\
|
= =
vl v, k
v 1 = const nn const
n n
n
K
3
H N
2
NH
n
2 2
3
= = . nhu vy c su tng p sut
ca h nhung khng c su chuyn dlch cn bng.
(b)
2
n P
RT
V
K K |
.
|
\
|
=
vl 1, v k
p
= const, khl thm Ar d lm v tng nn k
n
phal glam. Su thm
agon d lm cn bng chuyn dlch theo chlu nghlch (chlu lm phn ll nP
3
).
Chu thlch:
1rong trung hop ny, ta khng th dua vo nguyn ll Le Chateller d du don
chlu dln bln ca phan ung.
0,S0
0,S0
Cu 4 (3,0 dlm)
1. 5ttept|m|Joo l mt loal khng slnh c cng thuc sau:
H
NH
H
CH
3
H
3
C
H
OH H
O
O
O
H
(a) M ta cc trung tm lp th ca streptlmldon bng kl hlu L, Z v 8, S.
(b) Streptlmldon c bao nhlu dng phn lp th, trong d c bao nhlu Joq pbo eooo v bao
nhlu Joq pbo J|o?
2. So snh v glal thlch:
(a) nhlt d sl ca cc cht xyclopentan, tetrahldroluran v plrolldln.
(b) u manh tlnh bazo ca dlmetylamln, plperldln v plrldln.
N ILM
Cu 4 (3,0 dlm)
1. (a) Streptlmldon c ba trung tm lp th:
H
NH
H
CH
3
H
3
C
H
OH H
O
O
O
H
E
S
R
*
*
0,7S
(b) Streptlmldon c 2
3
= 8 dng phn lp th, trong d streptlmldon v dl quang ca
n tao cp dng phn enan, cn su dng phn lp th cn lal l dng phn dla ca
streptlmldon.
0,7S
2. (a) 1rt tu tng dn nhlt d sl:
O N
H
khng phn cuc c phn cuc tao duoc kln kt P lln
phn t
0,7S
(b) 1rt tu tng dn d manh tlnh bazo:
N
N
H N
H
n lal ha sp
2
n lal ha sp
3
n lal ha sp
3
v cu truc
vng lt gy n ngu
khng glan vl n
0,7S
Cu 5 (3,0 dlm)
1. (-)-N|cot|o, ankalolt c trong thuc l, c th duoc tng hop theo cch sau:
axlt nlcotlnlc (J-pyt|J|ococbox|l|c) + SC
2
Cl
2
, t
o
nlcotlnyl clorua (C
6
P
4
CnCl)
nlcotlnyl clorua + C
2
P
3
CCP
2
CP
2
CP
2
CdCl C (C
11
P
13
C
2
n), mt xeton
C + nP
3
, P
2
, xuc tc P (C
11
P
18
Cn
2
)
P + P8r + nhlt d cao l (C
9
P
12
n
2
) + etyl bromua
l + CP
3
l, naCP ( )-nlcotln (C
10
P
14
n
2
)
xc dlnh cu truc ca ( )-nlcotln v hon thnh cc phan ung trn.
2. Cht ll cun ban tlnh ca lol bum dm c th duoc tng hop bng cch dul dy. Py cho blt
cu truc v tn gol ca hop cht ny. Pon thnh cc phuong trlnh phan ung.
1-heptln + LlnP
2
S (C
7
P
11
Ll)
S + 1-clo-3-brompropan 1 (C
10
P
17
Cl)
1 + Mg, sau d o-C
10
P
21
CPC, sau d P
+
u (C
21
P
40
C)
u + P
2
, xuc tc Llndlar v (C
21
P
42
C)
v + CrC
3
cht ll cun ban tlnh (C
21
P
40
C)
N ILM
Cu 5 (3,0 dlm)
1. Cu truc v phan ung:
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,S0
2. o-C
3
P
11
CCP
2
LiNH
o-C
3
P
11
CCLl (S)

Cl CH CH BrCH
2 2 2
o-C
3
P
11
CCCP
2
CP
2
CP
2
Cl (1)

Mg
o-C
3
P
11
CC(CP
2
)
3
MgCl

+
H , CHO H C n
21 10
o-C
3
P
11
CC(CP
2
)
3
CP(CP)C
10
P
21
-o
(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,S0
Cu 6 (4,0 dlm)
1. .(+)-koff|oozo, mt dung khng kh duoc tlm thy trong dung c cal, c cng thuc C
18
P
32
C
16
.
1hy phn trong ml trung axlt tao ra u-lructozo, u-galactozo v u-glucozo. 1hy phn dul tc
dung ca enzlm |-galactosldaza tao ra u-galactozo v saccarozo. 1hy phn dul tc dung ca
lnvertaza (mt enzlm phn ct saccarozo) tao thnh u-lructozo v dlsaccarlt mel|b|ozo. Metyl ha
ralllnozo, sau d thy phn tao ra 1,3,4,6-tetra-C-metyl-u-lructozo, 2,3,4,6-tetra-C-metyl-u-
galactozo v 2,3,4-trl-C-metyl-u-glucozo. Cho blt cu truc ca ralllnozo v mellblozo.
2. Mt glal php bao v nhm amln hlu qua l tln hnh phan ung axyl ha bng anhydrlt phtallc d
hlnh thnh mt phtallmlt c nhm th trn nguyn t n. nhm bao v sau d c th g bo d dng
bng hldrazln m khng anh huong dn cu nl peptlt. p dung glal php ny vlt so d tng hop
Cll-Ala v Ala-Cll.
N ILM
Cu 6 (3,0 dlm)
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,S0
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,S0
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 D THI HC SINH

1hay gl trl h = 0,033 v k

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