Tuyen Tap de Thi HSG Hoa Hoc p2

2010
Phan Cuong Huy

TUYN TP THI HSG
MN HA HC
Copyright 2010 http://vn.myblog.yahoo.com/volcmttl
2 TUYN TP THI HSG MN HA HC
PHN 2: CC N THI HC SINH GII QUC GIA
S 1
THPT CHUYN H N I K THI CHN HC SINH GII QUC GIA
THI TH LP 12 THPT NM 2010
Mn: HO HC
Thi gian : 180 pht (khng k thi gian giao )
( thi gm3 trang, c 8 cu)
Cu I: ( 2.0 i m)
M t terpen X th ng g p trong thin nhin c t ng h p theo s sau
4metylpentan1,4diol d n xu t dibromua bromanken
Mg
ete khan
Grignard G X
Cho ch t G ph n ng v i s n ph m sinh ra khi cho isopren ph n ng v i but3en2on s thu c ch t c n
t ng h p X.
1. Hon thnh chuy n ha ny b ng cc cng th c c u t o t ng ng.
2. Cho bi t tn thng th ng v ng d ng c a s n ph m.
Cu II: (2.0 i m)
Hydrocacbon A l m t ch t r n c tnh d o, n h i (11,76% H theo kh i l ng) c trong m cy cao su. Ozon
phn A cho C
16
H
16
O
6
, khi cho m t mol ch t ny vo n c nng thu c 2 mol andehit levulinic
HOC(CH
2
)
2
COCH
3
.
Hydrocacbon B (11,11% H theo kh i l ng) l ch t t ng h p u tin c thnh phn gi ng A nh ng khng c
tnh d o v tnh n h i gi ng nh A. B c t o thnh khi un nng hydrocacbon C c m t natri ; C c thnh
ph n nh tnh gi ng B
1. Cho bi t CTCT c a A, B, C
2. S v ng m t c a axetylaxeton trong s n ph m c a chng ch ng t A c c tr ng g ?
Cu III: (2.0 i m)
Qu trnh t ng h p ph c Pt(CH
3
NH
2
)(NH
3
)[CH
2
COO]
2
l thu c ch ng ung th m i c hi u q a cao l i t c
v t cho ph n ng ph . Qu trnh t ng h p thu c ny nh sau:
K
2
PtCl
4 o
KI du
70 C
A (dung dch nu)
3 2
+ CH NH
1:2
B (tinh th sng)
4 2 5
HClO v C H OH
C (r n nu)
3 2
NH / H O
D (tinh th vng kim, phn c c)
2 3
Ag CO du v axit malonic
E (tinh th vng nh t)
Ph ng php ph IR cho bi t trong h p ch t C c hai lo i lin k t Pt I khc nhau v C c tm i x ng. Bi t
M
C
= 1,88M
B
. Cho bi t s ph i tr c a platin lun khng i trong qu trnh t ng h p v platin lun gi d ng lai
ha dsp
2
trong cc ph c
1. Vi t CTCT cc s n ph m A, B, C, D, E.
2. Trong s n ph m E th khng c ch a iot. Nh v y t i sao lc ban u ph i chuy n K
2
PtCl
4
thnh A.
3. M c ch c a vi c s d ng Ag
2
CO
3
trong ph n ng cu i l g ?
Cu IV: (2.0 i m)
L thuy t lai ha do Carl Linus Pauling xu t v n l l thuy t chu n xc nh t trong vi c gi i thch d ng hnh
h c c a cc ch t v c . V y y chng ta s th gi i quy t nh ng m hnh sau y
1. Gi i thch d ng hnh h c c a TiCl
4
theo thuy t lai ha ?
2. Gi i thch d ng hnh h c c a ph c Fe(CO)
5
theo thuy t lai ha ?
Cu V: (2.0 i m)
Kh NO k t h p v i h i Br
2
t o ra m t kh duy nh t trong phn t c ba nguyn t
1. Vi t ph ng trnh ph n ng
2. Bi t H
p
< 0; K
p
(25
o
C) = 116,6. Tnh K
P
0
o
C, 50
o
C. Gi thi t r ng t s gi a tr s cn b ng gi a 0
o
C v
25
o
C c ng nh 25
o
C v i 50
o
C u b ng 1,54
3. Xt t i 25
o
C, lc cn b ng ha h c c thi t l p th cn b ng s chuy n dch th no n u
a. Tng l ng NO
b. Gi m l ng h i Br
2
c. Gi m nhi t
d. Thm kh N
2
vo khi
(1) V = const ;
(2) P
chung
= const
Cu VI (4.0 i m)
Guaiol (C
15
H
26
O) l m t ancol r n tr ng thi tinh th c c u trc terpen. Ancol ny c phn l p t tinh d u
cy g Bulnesia sarmienyi. Khi dehydrat ha guaiol b ng l u hu nh th thu c m t hydrocacbon th m mu xanh
da tr i khng ch a vng benzen X (C
15
H
18
). Khi ha tan hydrocacbon th m ny vo axit sunfuric c th mu xanh
bi n m t. Cho n c vo dung dch ny th X c ph c h i nguyn d ng. R t kh hydro ha guaiol b ng hydro
c xc tc. Qua m t lo t cc chuy n ha d i y ta nh n c m t d n xu t c a naphtalen (A l s n ph m duy
nh t c a qu trnh ozon phn)
1. Xc nh c u trc c a guaiol v X n u bi t trong phn t guaiol th nhm hydroxyl g n v i nguyn t
cacbon b c ba exocyclic c a h vng
2. Gi i thch mu xanh da tr i c a X v nu l do n b m t mu trong dung dch axit sunfuric c
3. Xc nh CTCT A, B v gi i thch s t o thnh A. C bao nhiu m nh isopren trong ch t X
Cu VII (2.0 i m)
C th tch c rhodi ra kh i cc kim lo i qu khc b ng cch sau: M t m u b t qu ng rhodi c tr n v i
NaCl v un nng trong dng kh clo. B r n thu c ch a m t mu i ch a 26,76% Rhodi v kh i l ng. B r n
ny sau c ha tan vo n c, l c dung dch thu c r i c bay h i thu c tinh th B ch a 17,13% rhodi.
Tinh th c lm kh 120
o
C n kh i l ng khng i (kh i l ng m t i l 35,98%) r i un nng t i 650
o
C.
R a b r n thu c b ng n c ta c rhodi tinh khi t
1. Xc nh cng th c A, B
2. Khi m t l ng d H
2
S c s c qua dung dch mu i A th t o thnh k t t a C. Thnh ph n h p th c c a
h p ch t ny ch a 47,59% S. Xc nh cng th c C
3. Gi i thch t i sao c n ph i r a b ng n c nng b c cu i cng. Vi t cc ph n ng x y ra
Cu VIII: (4.0 i m)
Cc cacbohydrat t nhin u c t ng h p quang ha trong cy xanh. Tuy nhin cc cacbohydrat khng c
trong t nhin c th c t ng h p b ng con ng nhn t o. S d i y l s t ng h p L-riboz . Hon
chnh s t ng h p sau:
_________________ HT _________________
- Th sinh khng c s dng ti liu.
- Gim th khng gii thch g thm.
THPT CHUYN H N I K THI CHN HC SINH GII QUC GIA
P N THI TH LP 12 THPT NM2009 2010
Mn: HO HC
(p n thi gm4 trang, c 8 cu)
Cu I: (2.0 i m)
1. Cng th c c u t o cc ch t lin quan (1,75 i m)
2. Ch t ny l o-bisabolol th ng dng trong cng nghi p m ph m (0,25 i m)
Cu II: (2.0 i m)
1. Cng th c th c nghi m c a A l (C
5
H
8
)
x
, n l cao su t nhin. Cc cng th c th c nghi m c a B v C l n
l t l (C
2
H
3
)
y
. B l cao su t ng h p polibutadien cn C l buta-1,3-dien (1,5 i m, m t i m cho m i c u
t o).
2. Ta c:
Nh v y s v ng m t c a axetylaxeton trong s n ph m ozon phn ch ng t cao su thin nhin c c u trc
u - u (0,5 i m cho l p lu n)
Cu III: (2.0 i m)
1. Cng th c c u t o cc ch t lin quan (1,25 i m ; 0,25 i m cho m i c u t o)
2. ch c ch n thu c s n ph m cu i th bu c B ph i d ng cis nn K
2
PtCl
4
ph i c chuy n thnh A
(0,25 i m)
3. Ag
2
CO
3
ph n ng v i D theo ph n ng D + Ag
2
CO
3
= DCO
3
+ 2AgI sau DCO
3
ph n ng v i axit
malonic t o thnh E (0,5 i m)
Cu IV: (2.0 i m)
1. Do i v i Ti lc ny th nng l ng c a AO 3d gi m th p h n so v i AO 4p nn s c s t h p gi a 1
AO 4s v 3 AO 3d t o thnh 4 AO lai ha sd
3
h ng v 4 nh c a m t t di n u (1 i m)
2. Do CO l ph i t tr ng m nh nn s y cc electron c a Fe v tr ng thi c p i. Lc ny 1 AO 3d tr ng
s t h p v i 1 AO 4s tr ng v 3 AO 4p tr ng thnh 5 AO lai ha dsp
3
h ng v 5 nh c a m t l ng thp
tam gic.(1 i m)
Cu V: (2.0 i m)
1. 2NO
(k)
+ Br
2(h i)
2NOBr
(k)
H > 0 (0,25 i m)
2. Do ph n ng thu nhi t nn c lin h K
P
t i 0
o
C < K
P
(25
o
C) < K
P
(50
o
C)
V y K
P
t i 0
o
C = 1/1,54.K
P
= 116,6 / 1.54 = 75,71
K
P
t i 50
o
C = 1,54.K
P
= 116,6.1,54 = 179,56 (0,25 i m)
3. Xt s chuy n d i cn b ng ha h c t i 25
o
C
Tr ng h p a v b v nguyn t c c n xt t s :
2
NOBr
NO
P
Q
P
=
Sau so snh Q v i K
P
k t lu n
Tuy nhin y khng c i u ki n l p lu n theo bi u th c ny nn ta s d a vo nguyn l Le
Chartelier
a. N u tng l ng NO th cn b ng dch chuy n sang ph i (0,25 i m)
b. N u gi m l ng Br
2
th cn b ng ha h c dch chuy n sang tri (0,25 i m)
c. N u gi m nhi t th cn b ng dch chuy n sang tri ch ng l i chi u gi m nhi t (0,25 i m)
d. Thm N
2
l kh tr
+ N u V = const th khng nh h ng t i cn b ng ha h c do N
2
khng gy nh h ng lin h no (theo
nh ngha p su t ring ph n)
+ N u P = const ta xt lin h
N u ch a c N
2
th P = P
NO
+ P
Br2
+ P
NOBr
(a)
N u c N
2
th P = P
NO
+ P
Br2
+ P
NOBr
+ P
N2
(b)
V P = const nn P
i
= P
i
Lc xt Q theo bi u th c lin h trn v so snh t ng quan v i K
P
- Q = K
P
: khng nh h ng
- Q > K
P
: cn b ng chuy n dch sang tri Q gi m t i K
P
- Q < K
P
: cn b ng chuy n d i sang ph i Q tng t i K
P
(1,25 i m)
Cu VI (4.0 i m)
1. Ta c th suy lu n cng th c c a guaiol d a trn nh ng d ki n sau:
- Dehydrat ha ancol ny b ng l u hu nh thu c hydrocacbon th m X mu xanh da tr i khng ch a vng
benzen. Nh v y X ch c th l d n xu t c a azulen.
- b t bo ha c a guaiol l 3, t c ng v i hai vng v n cn m t n i i. V tr c a n i i s n m
i m ti p gip hai vng do v tr kh b hydro ha nh t, v khi ozon phn v tr ny s d cho s n ph m
chuy n v l hai vng 6 gip nhau. M t vng sinh ra do s m r ng vng 5, m t vng sinh ra do s thu h p
vng 7
- Ta d dng nh n th y r ng qu trnh chuy n ha c a guaiol khng h nh h ng t i cc m ch nhnh, v
v y t v tr cc m ch nhanh trong d n xu t naphtalen ta c th suy ra c v tr c a cc m ch nhnh ny
trong guaiol.
- Do nhm OH c a guaiol n m cacbon b c ba nn cng th c c u t o c a guaiol ch c th l:
L lu n d n ra CTCT ng c 1,0 i m, c u t o 0,5 i m
- Cng th c c u t o X s l (0,5 i m)
2. Mu xanh da tr i c a X c c do s lin h p gi a cc n i i trong phn t X. (0,25 i m)
Khi ha tan X vo axit sunfuric c mu xanh s bi n m t do s bi n m t c a h th ng lin h p trong h p
ch t c t o thnh nh hnh v : (0,5 i m)
3. Cng th c c u t o hai ch t A, B nh sau. ng CTCT m i ch t c 0,25 i m
OH
OH
O O
A
B
S t o thnh ch t A c gi i thch nh sau (0,5 i m)
Do cng th c phn t c a A l C
15
H
26
O nn trong A s c 3 m nh isopren (0,25 i m)
Cu VII (2.0 i m)
1. Na
3
[RhCl
6
] (0,375 i m) ; Na
3
[RhCl
6
].12H
2
O (0,375 i m)
2. Rh
2
S
3
.2H
2
S (0,5 i m)
3. lo i b cc mu i tan, ch y u l NaCl (0,25 i m).
M i ph n ng ng c 0,125 i m
2Rh + 6NaCl + 3Cl
2
= 2Na
3
[RhCl
6
]
Na
3
[RhCl
6
].12H
2
O = Na
3
[RhCl
6
] + 12H
2
O
2Na
3
[RhCl
6
] = 2Rh + 6NaCl + 3Cl
2
2Na
3
[RhCl
6
] + 3H
2
S = Rh
2
S
3
.3H
2
S + 6NaCl + 6HCl
Cu VIII (4.0 i m)
Cng th c c u t o cc s n ph m trung gian (Cc ch t A, B m i ch t 0,5 i m, cn C, D, E, F m i ch t 0,75 i m).
L u qu trnh chuy n t D sang ch t dng th hai bao g m nhi u h n m t giai o n
_________________ HT _________________
Th sinh c th lm cch khc, nu ng vn c im ti a
http://vn.myblog.yahoo.com/volcmttl K THI CH N H C SINH GI I QU C GIA
THI TH L P 12 THPT NM 2010
Mn: HO H C
Th i gian : 180 pht (khng k th i gian giao )
( thi g m 3 trang, c 10 cu)
CU 1: (2,0 i m)
1. Oleum l h n h p c t o ra khi cho SO
3
tan trong H
2
SO
4
tinh khi t. Trong h n h p c cc axit d ng
poli sunfuric c cng th c t ng qut H
2
SO
4
.nSO
3
hay H
2
S
n+1
O
3n+4
ch y u ch a cc axit sau: axit sunfuric
H
2
SO
4
, axit isunfuric H
2
S
2
O
7
, axit trisunfuric H
2
S
3
O
10
v axit tetrasunfuric H
2
S
4
O
13
. Cho bi t cng th c
c u t o c a cc axit trn.
2. Gi i thch t i sao SO
3
l i d dng ph n ng v i H
2
O, HF, HCl, NH
3
hnh thnh nn nh ng phn t t
di n t ng ng. Vi t ph ng trnh ph n ng v cng th c c u t o s n ph m.
3. Kim c ng v than ch l hai d ng th hnh c a nguyn t cacbon. Tnh kh i l ng ring v th tch mol
c a chng. Bi t r ng: di lin k t CC (kim c ng) l 154 pm, CC (than ch) l 141 pm, kho ng cch
gi a cc l p than ch l 336 pm. N
A
= 6,02.10
23
. Kim c ng c c u t o t ng t silic v s nguyn t C
trong m t m ng tinh th c a kim c ng g p 4 l n s nguyn t C trong m t m ng tinh th than ch.
CU 2: (2.0 i m)
1. Vi t cng th c c u t o Lewis, nu tr ng thi lai ha v v d ng hnh h c c a cc phn t v ion sau: B
2
H
6
,
XeO
3
, NO
2
+
, NO
2
.
2. Ph n ng c a NaNO
3
trong n c v i h n h ng Na/Hg c ng gi ng nh ph n ng c a etylnitrit C
2
H
5
NO
2
v i hydroxylamine NH
2
OH c m t Natrietoxit cho cng m t s n ph m. S n ph m ny l mu i c a m t axit
y u khng b n ch a Nit , axit ny ng phn ha t o thnh m t s n ph m c ng d ng trong thnh ph n
nhin li u tn l a. Vi t cc ph ng trnh ph n ng x y ra v vho bi t cng th c c u trc c a axit ng phn
ni trn.
CU 3: (2.0 i m)
Cho ph n ng: A B C D + + (1) l ph n ng n gi n. T i 27
o
C v 68
o
C, ph ng trnh (1) c h ng s t c
t ng ng l n l t l k
1
= 1,44.10
7
mol
-1
.l.s
-1
v k
2
= 3,03.10
7
mol
-1
.l.s
-1
, R = 1,987 cal/mol.K
1. Tnh nng l ng ho t ha E
A
(cal/mol) v gi tr c a A trong bi u th c
E
RT
k A e
= mol
-1
.l.s
-1
.
2. T i 119
o
C, tnh gi tr c a h ng s t c ph n ng k
3
.
3. N u C
oA
= C
oB
= 0,1M th t
1/2
nhi t 119
o
C l bao nhiu.
CU 4: (2,0 i m)
1. Clobenzen c momen l ng c c
1
= 1,53 D (
1
h ng t nhn ra ngoi) ; anilin c momen l ng c c
2
=
1,60D (
2
h ng t ngoi vo nhn benzen). Hy tnh momen l ng c c c a cc ch t sau: ortho
cloanilin ; meta cloanilin v para cloanilin.
2. Tnh pH c a dung dch NH
4
HCO
3
0,1M. Bi t r ng H
2
CO
3
c h ng s phn li axit K
1
= 4,5.10
-7
; K
2
=
4,7.10
-11
, NH
3
c pK
b
= 4,76.
CU 5: (2,0 i m)
C th i u ch tinh th FeCl
3
.6H
2
O theo cch sau: Ho tan s t kim lo i vo trong dung dch axit clohydric 25%.
Dung dch t o thnh c oxy ha b ng cch s c kh clo qua cho n khi cho k t qu m tnh v i K
3
[Fe(CN)
6
].
Dung dch c c bay h i 95
o
C cho n khi t tr ng c a n t chnh xc 1,695 g/cm
3
v sau lm l nh n
4
o
C. Tch k t t a thu c b ng cch ht chn khng r i cho vo m t d ng c ch a c nim kn.
1. Vi t cc ph n ng d n n s k t t a FeCl
3
.6H
2
O
2. C bao nhiu gam s t v bao nhiu mL dung dch axit clohydric 36% (d=1,18g/cm
3
) c n i u ch
1,00kg tinh th ny. Bi t r ng hi u su t qu trnh ch t 65%
3. un nng 2,752g FeCl
3
.6H
2
O trong khng kh n 350
o
C thu c 0,8977g b r n. Xc nh thnh ph n
nh tnh v nh l ng c a b r n.
CU 6: (2,0 i m)
1. A l ch t b t mu l c khng tan trong axit v ki m long. Khi n u ch y A v i KOH c m t khng kh thu
c ch t B c mu vng, d tan trong n c. Ch t B tc d ng v i axit sunfuric chuy n thnh ch t C c
mu da cam. Ch t C b l u hu nh kh thnh ch t A v c th oxi ha axit clohiric thnh kh Clo. Vi t cc
ph ng trnh ph n ng x y ra.
2. T cc ch t A, B, C trn, hon thnh s sau:
- X
o
t
A + N
2
+ H
2
O
- C + (NH
3
)
2
S + H
2
O Y + S + NH
3
+ KOH
- B + (NH
4
)
2
S + KOH + H
2
O Z + S + NH
3
- C + H
2
SO
4
+ H
2
S T + S + K
2
SO
4
+ H
2
O
CU 7: (2,0 i m)
1. Vi t cng th c c u trc cc d ng enol c a dietylmalonat (1), Etylaxetoaxetat (2). Trong cc c u trc c a
(2), cho bi t d ng no b n nh t, d ng no km b n. Gi i thch?
2. Cho bi t cng th c m ch h c a cc ch t sau:
O OH
O
HO
O
O
CH
3
CH
2
CH
3
Brevicomin
O
C
2
H
5
O
HOCH
2
OH
Talaromicin A
a.
b.
c. d.
CU 8: (2,0 i m)
1. Cho bi t s n ph m t o thnh t cc ph n ng sau v g i tn s n ph m :
a. Furan + (CH
3
CO)
2
O + (C
2
H
5
)
2
O: BF
3
o
0 C
A
b. Thiophen + C
6
H
5
COCl + SnCl
4
B
c. Pyrol + C
6
H
5
N
2
+
Cl
C
d. Pyrol + CHCl
3
+ KOH D
2. Vi t s i u ch izatin (indolin-2,3-dion) t 2-nitrobenzoyl clorua
CU 9: (2,0 i m)
1. Khi cho amoniac ph n ng c ng v i axetanehit thu c s n ph m khng b n A, s n ph m ny d b tch
n c thnh B. B d dng trime ha cho s n ph m C l triazin. M t khc n u cho amoniac ng ng t v i
fomanehit s thu c s n ph m D (urotropin) c CTPT l C
6
H
12
N
4
. Ch t D c kh nng tc d ng v i axit
nitric trong anhirit axetic t o ra E (hexogen hay xiclonit) l ch t n m nh c dng trong i chi n th
gi i th II: C
6
H
12
N
4
+ 3HNO
3
E + 3HCHO + NH
3
. Xc nh A, B, C, D, E v vi t cc ph ng trnh
ph n ng x y ra.
2. Gi i thch s khc nhau v nhi t si trong dy cc ch t sau:
(1) (2) (3) (4)
N
N
S
N
N
H
N
N
H
115
o
C 117
o
C 256
o
C 187
o
C
C
CH
2
OH
HO
H
O
HO OH
O
axit L ascobic
-
CU 10: (2,0 i m)
1. Vitamin C (axit L-ascobic, pK
a
= 4,21) l endiol v c c u trc nh sau:
a. Hy gi i thch tnh axit c a axit L-ascobic v cho bi t nguyn t H no
c tnh axit.
b. i u ch L-ascobic t D-glucoz
2. Salixin C
13
H
18
O
7
b th y phn b i elmusin cho D-glucoz v Saligenin
C
7
H
8
O
2
. Salixin khng kh thu c th Tolen. Oxi ha Salixin b ng HNO
3
thu
c m t h p ch t h u c X m khi th y phn th cho D-Glucoz v anehit
Salixylic. Metyl ha Salixin thu c pentametylsalixin, th y phn h p ch t
ny cho ta 2,3,4,6-tetra-O-metyl-D-Glucoz . Xc nh CTCT c a Salixin
_________________ H T _________________
- Th sinh khng c s d ng ti li u.
- Gim th khng gi i thch g thm.
http://vn.myblog.yahoo.com/volcmttl K THI CH N H C SINH GI I QU C GIA
THI TH L P 12 THPT NM 2010
H NG D N CH M THI TH MN HA H C
(p n ny c 8 trang)
CU 1: (2,0 i m)
1. (0,5 i m) M i cng th c ng c 0,125 i m
HO
S
HO
O
O
S
O
O
HO O
S
O
O
O
S
O
O
O
S
OH
O
O
S
O
O
HO O
S
OH
O
O
S
O
O
HO O
S
O
O
O
S
OH
O
O
H
2
SO
4
H
2
S
2
O
7
H
2
S
3
O
10
H
2
S
4
O
13
2. (0,5 i m) Gi i thch ng + vi t ng 4 ph ng trnh v c u trc
- Gi i thch: Phn t SO
3
d ng tam gic phng v i nguyn t S tr ng thi lai ha sp
3
, d dng ph n ng
chuy n sang th ng thi lai ha sp
3
b n, l tr ng thi c tr ng c a l u hu nh
- Ph ng trnh ph n ng: SO
3
+ H
2
O H
2
SO
4
SO
3
+ HF H[SO
3
F] SO
3
+ HCl H[SO
3
Cl]
SO
3
+ NH
3
H[SO
3
NH
2
]
- C u trc cc s n ph m
S
O
O
O H
O H
S
O
O
O H
F
S
O
O
O H
Cl
S
O
O
O H
NH
2
3. (1,0 i m)
- Kim c ng (t ng t Silic) c c u trc l p ph ng tm di n ngoi ra cn c 4 nguyn t Cacbon n m trong 4
h c (site) t di n nn s nguyn t cacbon trong m t m ng c s tinh th kim c ng l:
1 1
8 6 4 8
8 2
+ + =
- Do v y suy ra cacbon than ch trong m t m ng tinh th c 2 nguyn t cacbon
- Trong m ng tinh th kim c ng:
di c nh m ng tinh th : a =
4d
3
(d = CC (kim c ng)) => Th tch m ng = a
3
=
3
4d
3
|
|
\ .
Kh i l ng ring c a tinh th kim c ng:
3
10
A
23
8 M 8 12
D = 3, 545
N V
4 154 10
6, 02 10
3

= =
|

|
\ .
(g/cm
3
)
=> Th tch mol c a kim c ng =
M
D
=3,385 (cm
3
/mol)
- T ng t trong m ng tinh th than ch
Di n tch m t y =
2
3
3 d
2
(d = CC (than ch))
Th tch m ng =
2
3
3 d h
2
(h l kho ng cch gi a cc l p)
=> Kh i l ng ring D = 2,297 (g/cm
3
) v th tch mol = 5,224 (cm
3
/mol)
CU 2: (2.0 i m)
- B
2
H
6
: B lai ha sp
3
, g m 2 t di n l ch c m t c nh chung, lin k t BHB l lin k t 3 tm nh ng ch c 2
electron, 1 electron c a H v 1 electron c a B
- XeO
3
: Xe lai ha sp
3
, phn t d ng thp y tam gic
- NO
2
+
: N lai ha sp, c u trc o n th ng
- NO
2
: N lai hoa sp
2
, c u trc g p khc (ch V)
- Cng th c Lewis
Xe
O
O
O
B
H
B
H
H H
H H
N
O O
N
O O
N O O
N O O
2. (1,0 i m)
- Cc ph n ng (m i ph n ng 0,25 i m)
2NaNO
3
+ 8Na(Hg) + 4H
2
O Na
2
N
2
O
2
+ 8NaOH + 8Hg
NH
2
OH + C
2
H
5
NO
2
+ 2C
2
H
5
ONa Na
2
N
2
O
2
+ 3C
2
H
5
OH
- Na
2
N
2
O
2
l mu i c a axit hyponitr H
2
N
2
O
2
(2.0,125 = 0,25)
N N
OH HO
N N
OH
HO
- C u trc ng phn: H
2
N NO
2
(nitramit) (0,25)
N N
O
O
H
H
CU 3: (2.0 i m)
1. (1,0 i m)
Ph n ng ng h c b c hai, p d ng ph ng trnh Archnius ta c:
A
1
1
E
ln k ln A
RT
= + ;
A
2
2
E
ln k ln A
RT
= +
A A
2 1
2 1
2 A
1 1 2
2 1 2
A
2 1 1
E E
ln k ln k ln A ln A
RT RT
k E 1 1
ln
k R T T
T T k
E R ln 3688, 2(cal / mol)
T T k

= + +
|
=
|
\ .
= ~

, ,
, ,
, ,
E
RT
E
E
RT
RT
1
9 1 1 1
k k
k A e A 7 10 (mol .l.s )
e
e

= = = =
2. (0,5 i m)
, ,
E
RT
3
7 1 1
3
k A e 6,15 10 (mol .l.s )

= =
3. (0,5 i m)
7
1/ 2
3 oA
1
1, 63 10 (s)
k .C
t = =
CU 4: (2,0 i m)
1. (1,0 i m)
Clo c m i n l n,
1
h ng t nhn ra ngoi nhm NH
2
c c p e t do lin h p v i h e t c a vng benzen
hai momen l ng c c cng chi u
ortho meta para
C ng vect s d ng h th c l ng trong tam gic a
2
= b
2
+ c
2
2bc cos

A
D n xu t ortho:
2
O
=
2
1
+
2
2
2
1
2
cos 60
0
=
2
1
+
2
2

1
2
= 2,45
o
= 2, 45 = 1,65D
D n xu t meta:
2
m
=
2
1
+
2
2
2
1
2
cos 120
0
=
2
1
+
2
2
+
1
2
= 7,35
m
= 7, 35 = 2,71D
D n xu t para:
2
p
=
1
+
2
= 1,60 + 1,53 = 3,13D
2. (1,0 i m)
Ta c cc qu trnh sau:
4 3 4 3
4 3 a
1
3 2 3 1
2
3 3 2
14
2 W
NH HCO NH HCO
NH NH H ; K
HCO H H CO ; K
HCO H CO ; K
H O H OH ; K 10
+
+ +
+
+
+
+
+ =
Trong :
14
9,24
a
b
10
K 10
K
= =
p d ng i u ki n proton ta c:
2
3 3 2 3
1 a 4 2 3 w
1 3
2 1 2
a 4 2 3 w 1 3
2 1 2
1 3 a 4 2 3 w
[H ] [NH ] [CO ] [OH ] [H CO ]
K .[NH ] K .[HCO ] K
[H ] K .[H ].[HCO ]
[H ] [H ] [H ]
[H ] K .[NH ] K .[HCO ] K K .[H ] .[HCO ]
[H ] K .[H ] .[HCO ] K .[NH ] K .[HCO ] K
+
+
+ +
+ + +
+ + +
+ + +
= + +
= + +
= + +
+ = + +
, ,
2 1
1 3 a 4 2 3 w
2 a 4 2 3 w
1
1 3
a 4 2 3 w
1
1 3
[H ] 1 K .[HCO ] K .[NH ] K .[HCO ] K
[H ]
1 K .[HCO ]
[H ]
1 K .[HCO ]
+ +
+
+

+
+

+ = + +
+ +
=
+
+ +
=
+
Thay cc gi tr g n ng:
4 3
[NH ] [HCO ] 0,1M
+
= =
8
[H ] 1, 6737.10 M
pH lg[H ] 7, 78
+
+
=
= =
CU 5: (2,0 i m)
1. Cc ph ng trnh ph n ng: (4.0,125 = 0,5 i m)
Fe + 2HCl FeCl
2
+ H
2
2FeCl
2
+ Cl
2
2FeCl
3
3FeCl
2
+ 2K
3
[Fe(CN)
6
] Fe
3
[Fe(CN)
6
]
2
+ 6KCl
FeCl
3
+ 6H
2
O FeCl
3
.6H
2
O
2.
3 , 270
1000
= 3,7mol FeCl
3
.6H
2
O
Nh v y c n mL 978
0,65 . 1,18 . 0,36
36,5 . 2 . 3,7
~ dung dch HCl 36% (0,5 i m)
3. Khi un nng th FeCl
3
.6H
2
O phn hu theo ph ng trnh sau:
FeCl
3
.6H
2
O FeOCl + 5H
2
O + 6HCl
Khi nhi t tng th FeOCl s ti p t c phn hu :
3FeOCl FeCl
3
+ Fe
2
O
3
(H i FeCl
3
bay ra)
L ng FeCl
3
.6H
2
O trong m u l
3 , 270
752 , 2
= 10,18 mmol
i u ny ng v i kh i l ng FeCl
3
l 107,3. 0,01018 = 1,092g FeOCl
Do kh i l ng thu c c a b r n b h n nn ta bi t c FeOCl s b phn h y m t ph n thnh Fe
2
O
3
.
Kh i l ng FeCl
3
m t mt do bay h i l:
162,2
0,8977 1,902
= 1,20mmol => B r n cu i cng ch a (0,01018
3.0,00120) = 6,58 mmol FeOCl v 1,20 mmol Fe
2
O
3
. (1,0 i m)
CU 6: (2,0 i m)
1. (1,0 i m) m i ph ng trnh ng c 0,25
-
A l Cr
2
O
3
, B l K
2
CrO
4
, C l K
2
Cr
2
O
7
- Cc ph ng trnh ph n ng:
2Cr
2
O
3
+ 3O
2
+ 8KOH 4 K
2
CrO
4
+ 4H
2
O
2K
2
CrO
4
+ H
2
SO
4
K
2
Cr
2
O
7
+ K
2
SO
4
+ H
2
O
S + K
2
Cr
2
O
7
Cr
2
O
3
+ K
2
SO
4
14HCl + K
2
Cr
2
O
7
3Cl
2
+ 2CrCl
3
+ 2KCl + 7H
2
O
2. (1,0 i m) m i ph ng trnh ng c 0,25
- X l (NH
4
)
2
Cr
2
O
7
, Y l Cr(OH)
3
, Z l K
3
[Cr(OH)
6
], T l Cr
2
(SO
4
)
3
- Cc ph ng trnh ph n ng:
(NH
4
)
2
Cr
2
O
7
o
t
Cr
2
O
3
+ N
2
+ 4H
2
O
K
2
Cr
2
O
7
+ 3(NH
3
)
2
S + H
2
O 2Cr(OH)
3
+ 5S + 6NH
3
+ 2KOH
2K
2
CrO
4
+ 3(NH
4
)
2
S + 2KOH + 2H
2
O 2K
3
[Cr(OH)
6
] + 3S + 6NH
3
K
2
Cr
2
O
7
+ 4H
2
SO
4
+ 3H
2
S Cr
2
(SO
4
)
3
+ 3S + K
2
SO
4
+ 7H
2
O
CU 7: (2,0 i m)
1. (1,0 i m) Cc c u trc
C
H
OEt
O
H
O
EtO
C
H
OEt
O O
EtO
H
OEt
O O
EtO
Trong :
- D ng A t b n do n i i khng lin h p
- D ng B b n nh ng khng c c ng h ng este
- D ng C b n nh t do c n i i lin h p v c ng h ng este
CH
3
COCH
2
COOEt
C H
2
OEt
O
H
O
C
H
C H
3
OEt
O O
C
H
C H
3
OEt
O
H
O
H
A
B
C
a. CH
2
OHCH
2
CH
2
CH
2
=CHO
5-hidroxipentanal
b. CHOCH
2
CH
2
CHOHCH=CHCH=CH
2
4-hidroxiocta-5,7-dienal
c. CH
3
CH
2
CHOHCHOH(CH
2
)
3
COCH
3
6,7-dihidroxinonan-2-on
d. (HOCH
2
)
2
CHCHOHCH
2
CO(CH
2
)
2
CH(C
2
H
5
)CH
2
OH
2,8-di(hidroxometyl)-1,3-dihidroxidacan-5-on
CU 8: (2,0 i m)
O
COCH
3
2-acetylfuran
A
S
COC
6
H
5
2-benzoylthiophen
B
N
N=NC
6
H
5
H
2-(phenylazo)pyrol
C
N
CHO
H
2-pyrolcacboxandehit
D
2. (1,0 i m)
NO
2
C
O
Cl
KCN
-HCl
NO
2
C
O
CN
H
3
O
+
-NH
3
NO
2
C
O
COOH
6H
-H
2
O
NH
2
C
O
COOH
t
o
-H
2
O
NH
O
O
CU 9: (2,0 i m)
1. (1,5 i m)
- Andehit bo c th tham gia ph n ng c ng v i amoniac t o thnh m t s n ph m t b n l Andehit-amoniac
CH
3
CHO + NH
3
Axetandehit-amoniac (t
nc
= 97
o
C) A
CH
3
CH
OH
NH
2
- Axetandehit-amoniac d b tch n c thnh B l CH
3
CH=NH v B d trime ha thnh h p ch t d vng C
lo i triazin
CH
3
CH
OH
NH
2
-H
2
O
CH
3
CH=NH
trime ha
NH NH
NH CH
3
CH
3
H
3
C
B C
- M t khc n u cho amoniac ng ng t v i fomanehit s thu c s n ph m D (urotropin) c CTPT l
C
6
H
12
N
4
6HCHO + 4NH
3
C
6
H
12
N
4
+ 6H
2
O
N
N
N
N
Urotropin
- Urotropin c kh nng tc d ng v i axit nitric trong anhirit axetic t o ra E (hexogen hay xiclonit) l ch t n
m nh c dng trong i chi n th gi i th II theo ph n ng:
C
6
H
12
N
4
+ 3HNO
3
+ 3HCHO + NH
3
N N
N
NO
2
NO
2
O
2
N
E
2. (0,5 i m)
- Ta c nhi t si c a (1) < (2) l do hai ch t ny khng t o c lin k t hydro nn nhi t si ph thu c
vo kh i l ng phn t .
- L i c, nhit si c a (4) < (3) l do m c d c hai ch t u c lin k t hydro lin phn t nh ng lin k t
hydro c a (3) d ng polyme cn c a (4) d ng dime
CU 10: (2,0 i m)
1. (1,0 i m)
a. Anion c hnh thnh b i s tch H enolic l b n v i n tch c gi i t a n O c a C=O qua lin k t i
C=C
C
C HO
HO C
O
H
+
-
C
C
-
O
HO C
O
C
C O
HO C
O
b. S i u ch
D-Glucose
NaBH
4
D-Socbitol (A)
[O]
enzym
L-Socbose (B) endiol B'
2CH
3
COCH
3
Diaxetonua (C)
1. KMnO
4
/OH
-
2. dd H
+
(D)
H
+
t
o
axit L-ascobic
Trong :
CH
2
OH
HO H
HO H
H OH
HO H
CH
2
OH
A
CH
2
OH
C O
HO H
H OH
HO H
CH
2
OH
B
CH
2
OH
C HO
C HO
H OH
HO H
CH
2
OH
B'
CH
2
OH
C
C
H O
HO H
CH
2
O
C
CH
3
CH
3
O
O
C
CH
3
CH
3
C
COOH
C
C
H O
HO H
CH
2
O
C
CH
3
CH
3
O
O
C
CH
3
CH
3
D
2. (1,0 i m)
Salixin l ng khng kh v l glucozit | do b th y phn b i elmuxin
RO H
OH
HO
OH
CH
2
OH
O
H
2
O
enzim
D-Glucose + ROH (Saligenin)
C
7
H
8
O
2
Salixin
Trong cng th c C
7
H
8
O
2
, ROH xu t hi n nhn th m. Tch c andehit salixylic, i u ch ng t qu trnh oxi
ha nhm CH
2
OH thnh nhm CHO
D-Glucose +
CHO
HO
H
2
O, H
+
O HO
HO
OH
O
HOH
2
C
CHO
Saligenin l o-(hidroximetyl)phenol. Cng th c c u trc c a salixin l
O HO
HO
OH
O
HOH
2
C
CH
2
OH
- - - - - - - - - - H T - - - - - - - - - - -
Th sinh lm cch khc n u ng v n cho i m t i a
http://vn.myblog.yahoo.com/volcmttl K THI H C SINH GI I QU C GIA L P 12 THPT
THI TH NM H C 2008 2009
MN THI: HA H C I C NG
Th i gian lm bi: 180 pht (Khng k th i gian pht )
( thi g m c 2 trang)
Cu 1: (2.0 i m)
1. T i sao ion ph c spin th p [Co(NH
3
)
6
]
3+
l i c mu. Gi i thch d a vo
1
o
22900(cm )
A = . Cho bi t:
1 1
1 cm 11, 962 J.mol

= .
2. D a trn m hnh VSEPR, gi i thch d ng hnh h c c a NH
3
, ClF
3
, XeF
4
.
3. Qu trnh: O O 1e
+
+ c I
1
= 13,614 (eV). D a vo ph ng php Slater xc nh h ng s ch n c a cc
electron trong nguyn t i v i electron b tch. So snh b n t ng i c a hai c u hnh electron c a O
v O
+
, gi i thch.
Cu 2: (2.0 i m)
1. Thi t l p bi u th c ph thu c gi a th oxi ha kh v i pH c a mi tr ng trong 2 tr ng h p sau:
2.
2 3
2 7
2 3
2 7 2
Cr O / 2Cr
Cr O 14H 6e 2Cr 7H O 1, 33V
+
+ +
+ + + = +
o
; E . pH = 7,
2
2 7
Cr O

c oxi ha c I
khng?
Bi t r ng:
2
o
I / 2I
E 0, 6197V
=
;
3 2
3 2 Co(OH) / Co(OH)
Co(OH) 1e Co(OH) OH 0,17V
+ + = +
o
; E
3. Bi t tch s ion c a n c K
W
= 10
-14
v
RT
2, 303 ln x 0, 0592lg x
F
=
( t i 25
o
C, 1atm)
Cu 3: (1.5 i m)
Cho ph n ng: A B C D + + (1) l ph n ng n gi n. T i 27
o
C v 68
o
C, ph ng trnh (1) c h ng s t c
t ng ng l n l t l k
1
= 1,44.10
7
mol
-1
.l.s
-1
v k
2
= 3,03.10
7
mol
-1
.l.s
-1
, R = 1,987 cal/mol.K
1. Tnh nng l ng ho t ha E
A
(theo cal/mol) v gi tr c a A trong bi u th c
, ,
E
RT
k A e

= mol
-1
.l.s
-1
.
2. T i 119
o
C, tnh gi tr c a h ng s t c ph n ng k
3
.
3. N u C
oA
= C
oB
= 0,1M th t
1/2
nhi t 119
o
C l bao nhiu.
Cu 4: (2.5 i m)
i n phn dung dch NaCl dng i n c c Katode l h n h ng Hg dng ch y u v dng c c titan b c ruteni v
roi l Anode. Kho ng cch gi a Anode v Katode ch vi mm
1. Vi t ph ng trnh ph n ng x y ra t i i n c c khi m i b t u i n phn pH = 7. Tnh cc gi tr th i n
c c v th phn gi i
2. Sau m t th i gian, pH tng ln n gi tr pH = 11. Gi i thch t i sao. Vi t cc ph ng trnh x y ra t i pH
. Tnh th i n c c v th phn gi i
3. Cho bi t:
2 2
3 2
o o o
O / H O
Na / Na 2H O / H
E 2, 71V ; E 0, 00V ; E 1, 23V
+ +
= = = . V i dung dch NaCl 25% v 0,2% Na
trong h n h ng Na/Hg:
o
Na / Na(Hg)
E 1, 78V
+
=
.
2
o
Cl / Cl
E 1, 34V
= cho dung dch NaCl 25% theo kh i l ng

2
H
1, 3V = trn Hg ;
2
O
0, 8V = trn Ru/Rd
Cu 5: (1.5 i m)
Trong cc tinh th o (c u trc l p ph ng tm kh i) cc nguyn t cacbon c th chi m cc m t c a m ng c s
1. Bn knh kim lo i c a s t l 1,24
o
A. Tnh di c nh a c a m ng c s
2. Bn knh c ng ha tr c a cacbon l 0,77
o
A . H i di c nh a s tng ln bao nhiu khi s t o c ch a
cacbon so v i c nh a khi s t o nguyn ch t
3. Tnh di c nh m ng c s cho s t (c u trc l p ph ng tm di n) v tnh tng chi u di c nh
m ng bi t r ng cc nguyn t cacbon c th chi m tm c a m ng c s v bn knh kim lo i s t l
1,26
o
A . C th k t lu n g v kh nng xm nh p c a cacbon vo 2 lo i tinh th s t trn
Cu 6: (1.5 i m)
K t qu phn tch m t ph c ch t A c a Platin (II) cho bi t c: 64,78 % kh i l ng l Pt, 23,59 % l Cl, 5,65 % l
NH
3
v 5,98 % cn l i l H
2
O
1. Tm cng th c phn t c a ph c ch t bi t r ng A l ph c ch t 1 nhn v Pt c s ph i tr l 4. Vi t cng
th c c u t o 2 ng phn cis v trans c a n
2. Entanpi t do chu n t o thnh 25
o
C c a cc ng phn cis, trans l n l t l: -396 v -402 kJ.mol
-1
. Tnh
h ng s cn b ng K c a ph n ng sau: cis
(A)
trans
(A)
3. Tnh n ng mol/lit m i ng phn trong dung dch, bi t r ng lc u ch c ng phn cis n ng
0,01M. Cho Pt = 195 ; Cl = 35,5 ; N = 14 ; O = 16 ; H = 1
Cu 7: (2.0 i m)
Nitramit c th b phn h y trong dd H
2
O theo ph n ng: NO
2
NH
2
N
2
O
(k)
+ H
2
O
Cc k t qu th c nghi m cho th y v n t c ph n ng tnh b i bi u th c:
2 2
3
[NO NH ]
v k
[H O ]
+
=
1. Trong mi tr ng m b c c a ph n ng l bao nhiu
2. Trong cc c ch sau c ch no ch p nh n c:
a. C ch 1:
1
k
2 2 2 (k) 2
NO NH N O + H O
b. C ch 2:
2
3
k
+
2 2 3 2 3 2
k + +
2 3 2 3
NO NH H O NO NH + H O
NO NH N O + H O
+
+
c. C ch 3:
4
5
6
k
+
2 2 2 2 3
k
2 2
k +
3 2
NO NH H O NO NH + H O
NO NH N O + OH
H O OH 2H O
Cu 8: (3.0 i m)
1. C 3 nguyn t A, B v C. A tc d ng v i B nhi t cao sinh ra D. Ch t D b thu phn m nh trong
n c t o ra kh chy c v c mi tr ng th i. B v C tc d ng v i nhau cho kh E, kh ny tan c
trong n c t o dung dch lm qu tm ho . H p ch t c a A v i C c trong t nhin v thu c lo i ch t c ng
nh t. H p ch t c a 3 nguyn t A, B, C l m t mu i khng mu, tan trong n c v b thu phn. Vi t tn c a
A, B, C v ph ng trnh cc ph n ng nu trn.
2. kh o st s ph thu c thnh ph n h i c a B theo nhi t , ng i ta ti n hnh th nghi m sau y: L y
3,2 gam n ch t B cho vo m t bnh kn khng c khng kh, dung tch 1 lt. un nng bnh B ho h i
hon ton. K t qu o nhi t v p su t bnh c ghi l i trong b ng sau:
Nhi t (
o
C) p su t (atm)
444,6 0,73554
450 0,88929
500 1,26772
900 4,80930
1500 14,53860
Xc nh thnh ph n nh tnh h i n ch t B t i cc nhi t trn v gi i thch.
Cu 9: (1.5 i m)
C th vi t c u hnh electron c a Ni
2+
l:
Cch 1: Ni
2+
[1s
2
2s
2
2p
6
3s
2
3p
6
3d
8
] Cch 2: Ni
2+
[1s
2
2s
2
2p
6
3s
2
3p
6
3d
6
4s
2
].
p d ng ph ng php g n ng Slater, tnh nng l ng electron c a Ni
2+
v i m i cch vi t trn (theo n v eV).
Cch vi t no ph h p v i th c t . T i sao.
Cu 10: (2.5 i m)
1. Phng th nghi m c m u phng x Au
198
v i c ng 4,0 mCi/1g Au. Sau 48 gi ng i ta c n m t dung
dch c phng x 0,5 mCi/1g Au. Hy tnh s gam dung mi khng phng x pha v i 1g Au c dung
dch ni trn. Bi t r ng Au
198
c t
1/2
= 2,7 ngy m.
2. Hy ch ng minh r ng ph n th tch b chi m b i cc n v c u trc trong m ng tinh th kim lo i thu c cc
h l p ph ng n gi n, l p ph ng tm kh i, l p ph ng tm di n tng theo t l 1 : 1,31 : 1,42.
- - - - - - - - - - H T - - - - - - - - - -
Nhanh
Ch m
Nhanh
Ch m
Nhanh
THI TH NM H C 2008 2009
H NG D N CH M MN HA H C I C NG
Cu N i dung i m
1
1 Tnh c: 437nm = . S h p th nh sng n m trong ph nhn th y nn c mu. 0,5
2
C u t o c a NH
3
cho th y quanh nguyn t N trung tm c 4 vng khng gian khu tr
electron, trong c 1 c p electron t do (AB
3
E) nn phn t NH
3
c d ng thp y tam gic
v i gc lin k t nh h n
o
109 28' (c p electron t do i h i m t kho ng khng gian khu tr
l n h n)
N H
H
H N
H
H
H
C u trc thp y tam gic tm l nguyn t N
Phn t ClF
3
c 5 kho ng khng gian khu tr electron, trong c 2 c p electron t do
(AB
3
E
2
) nn phn t c d ng ch T (Cc electron t do chi m v tr xch o)
Cl F
F
F
Cl
F
F
F
Phn t XeF
4
c 6 vng khng gian khu tr electron, trong c hai c p electron t do
(AB
4
E
2
) nn c d ng vung ph ng (trong c u trc ny cc c p electron t do phn b xa
nhau nh t)
Xe
F
F F
F
Xe
F F
F F
0, 25 3
= 0,75
3
- C u hnh electron: O 1s
2
2s
2
2p
4
km b n h n O
+
1s
2
2s
2
2p
3
do l c y l n nhau c a 2
trong m t orbital c a phn l p 2p v do O
+
t c u hnh bn bo ha phn l p 2p nn
b n
- t b l h ng s ch n c a cc electron trong nguyn t i v i electronb tch. Ta c:
*2
*2 2 2
1 2
Z
I 13, 6 13, 614 Z n 4 (8 b) 4 b 6
n
= = = = = =
0,25
0,5
2.0
2 1
2 3 2 3
2 7 2 7
2 3
2 7
2 3
2 7
14
2
2 7
2 Cr O / 2Cr Cr O / 2Cr
3
2
14
2 7
2 Cr O / 2Cr
3
2
2 7
2 Cr O / 2Cr
3
Cr O H
0, 0592
lg
6
Cr
Cr O
0, 0592 0, 0592
lg H lg
6 6
Cr
Cr O
0, 0592
0,138pH lg
6
Cr
+ +
+
+
+
+
+
+
+
1 1
] ]
+
1
]
1
]
1 = + +
]
1
]
1
]
= +
1
]
o
o
o
E = E
E
E
t:
2 3 2 3
2 7 2 7
Cr O / 2Cr Cr O / 2Cr
0,138pH
+ +
=
' o
E E
2 3
2 7
'
Cr O / 2Cr
E
+
l th i u ki n v ph thu c vo pH. pH cng gi m th dung dch cng c mi

tr ng axit th E cng tng, tnh oxi ha c a
2
2 7
Cr O

cng m nh.
- T i pH = 0, [H
+
] = 1M th E = E
o
= 1,33V
- T i pH = 7 th E = 0,364 <
2
o
I / 2I
E 0, 6197V
=
nn khng oxi ha c I
-
0,5
0,25
0,25
2
3 2 3 2
Co(OH) / Co(OH) Co(OH) / Co(OH)
1
0, 0592lg
[OH ]
+
o
E = E
. Thay
W
K
[OH ]
[H ]
+
= ta c:
3 2 3 2
3 2
3 2
Co(OH) / Co(OH) Co(OH) / Co(OH)
W
Co(OH) / Co(OH) W
Co(OH) / Co(OH) W
[H ]
0, 0592lg
K
0, 0592lg[H ] 0, 0592lg K
0, 0592pH 0, 0592lg K
+
+
+
= +
=
o
o
o
E = E
E
E
. Thay
3 2
o
Co(OH) / Co(OH)
14
W
0,17
K 10
+
=
E =
3 2
Co(OH) / Co(OH)
0, 996 0, 0592pH E =
pH cng tng th E cng gi m ngha l tnh oxi ha c a Co(OH)
3
gi m, tnh kh c a Co(OH)
2
tng
0,25
0,5
0,25
2.0
3
1
- Ph n ng ng h c b c hai, p d ng ph ng trnh Archnius ta c:
A
1
1
E
ln k ln A
RT
= +
;
A
2
2
E
ln k ln A
RT
= +
A A
2 1
2 1
2 A
1 1 2
2 1 2
A
2 1 1
E E
ln k ln k ln A ln A
RT RT
k E 1 1
ln
k R T T
T T k
E R ln 3688, 2(cal / mol)
T T k

= + +
|
=
|
\ .
= ~
-
, ,
, ,
, ,
E
RT
E
E
RT
RT
1
9 1 1 1
k k
k A e A 7 10 (mol .l.s )
e
e

= = =
0,5
0,25
0,25
2
, ,
E
RT
3 7 1 1
3
k A e 6,15 10 (mol .l.s )

= =
0,25
3
7
1/ 2
3 oA
1
1, 63 10 (s)
k .C
t = =
0,25
1.5
4 1
Trong dung dch NaCl c: NaCl Na
+
+Cl
-
; 2H
2
O H
3
O
+
+ OH
-
Khi i n phn c th c cc qu trnh sau x y ra:
Catode: Na
+
+ Hg + e Na(Hg) 1 (1)
2H
2
O H
3
O
+
+ OH
-
2
2 H
3
O
+
+ 2e H
2
+ 2H
2
O 1
2H
2
O + 2e H
2
+ OH
-
(2)
Anode: 6 H
2
O O
2
+ 4H
3
O
+
+ 4e (3)
2 Cl
-
Cl
2
+ 2e (4)
Na / Na(Hg)
E 1, 78V
+
= ,
3 2
7
2H O / H
E 0, 00V 0, 0592lg10 0, 413V
+

= + =
2
3 2 3 2
' o
H
2H O / H 2H O / H
E E 1, 713
+ +
= + = . Do
3 2
' o
2H O / H Na / Na(Hg)
E E
+ +
> nn khi m i b t u
i n phn, Katode qu trnh (2) s x y ra, c H
2
thot Anode
Anode: T (3) ta c:
2 2 2 2 2 2 2 2 2
o '
O / H O O / H O 3 O / H O O / H O O
E E 0, 0592lg[H O ] 0, 817V ; E E 1, 617V
+
= + = = + =
B i v:
2 2
2
'
O / H O
Cl / 2Cl
E E
< nn Anode x y ra qu trnh (4) v c Cl

2
bay ra
Ph ng trnh i n phn: 2Cl
-
+ 2H
2
O H
2
+ Cl
2
2OH
-
4.0,125
= 0,5
0,25
0,25
0,25
Th phn gi i: V =
' '
A K
E E = 3,053V
0,25
2
Sau m t th i gian, do [OH
-
] tng nn pH c ng tng. Khi pH = 11, ph n ng i n phn x y ra
nh sau:
T i Catode: [H
+
] =10
-11
.
3 2 3 2
' o
2H O / H 2H O / H Na / Na
E 0, 649V ; E 1, 949V E
+ + +
= = > nn
Anode c qu trnh (1) x y ra
T i Anode:
2 2 2 2 2 2
o '
O / H O O / H O 3 O / H O
E E 0, 0592lg[H O ] 0, 581V ; E 1, 381V
+
= + = =
Do
2 2
2
'
O / H O
Cl / 2Cl
E E
< nn Anode v n c Cl
2
bay ra
Ph ng trnh i n phn: 2Na
+
+ 2Cl
-
+ 2Hg Cl
2
+ 2Na(Hg)
Th phn gi i: V =
' '
A K
E E = 3,12V
0,25
0,25
0,25
0,25
2.5
5
1
di c nh a c a m ng c s c a s t o l:
o
4r 4 1, 24
a 2, 86A
3 3
= = =
0,25
2.
Khi s t o c ch a cacbon, tng chi u di c nh a c a m ng c s l:
o
Fe C
2 (r r ) a 2(1, 24 0, 77) 2, 86 1,16A
o
A = + = + =
0,25
3
di c nh a c a m ng c s c a s t l:
o
4r 4 1, 26
a 3, 56A
2 2
= = =
Khi s t c ch a cacbon, tng chi u di c nh a c a m ng c s l:
o
Fe C
2 (r r ) a 2(1, 26 0, 77) 3, 56 0, 5A
A = + = + =
K t lu n: Kh nng xm nh p c a cacbon vo s t o kh h n vo s t , do c ha tan
c a C trong s t o nh h n trong s t
0,25
0,25
0,5
1.5
6
1
t CTPT c a A l: Pt
x
Cl
y
(NH
3
)
z
(H
2
O)
t
. V ph c ch t A l ph c 1 nhn nn phn t kh i c a
A:
Pt
A
M 100% 195 100
M 301(g / mol)
%Pt 64, 78

= = = . T % c a cc thnh ph n c trong A
x = 1, y = 2, z = 1, t = 1 CTPT l: PtCl
2
(NH
3
)(H
2
O)
CTCT 2 ng phn cis, trans:
Cis Trans
0,25
0,125.2
= 0,25
2
Xt ph n ng chuy n ha:
Cis Trans
Cn b ng: 10
-2
x x
o
298K
G 402 396 6kJ A = + = = -6000J ;
6000
8,314 298
K e 11, 27
= =
0,5
3
Xt ph n ng chuy n ha:
Cis Trans K = 11,27
Cn b ng: 10
-2
x x
[trans]
K
[cis]
=
=
3 4
2
x
11, 27 x [trans] 9, 2 10 [cis] 8 10
10 x

= = = =
0,25.2
= 0,5
1.5
7
1
Do trong mi tr ng m [H
3
O]
+
= const nn bi u th c t c ph n ng l:
2 2
v k[NO NH ] = l ph n ng b c nh t theo th i gian
0,5
2
- C ch 1:
1 2 2
v k [NO NH ] = lo i
- C ch 2:
3 2 3
v k [NO NH ]
+
=
M:
2 2 3
2 3 2
2
[NO NH ][H O ]
[NO NH ] k
[H O]
+
+
=
V y:
2 2 3
3 2
2
[NO NH ][H O ]
v k k
[H O]
+
=
lo i
- C ch 3:
5 2
v k [NO NH ]
=
M:
2 2 2
2 4
3
[NO NH ][H O]
[NO NH ] k
[H O ]
+
=
V y:
2 2 2
5 4
3
[NO NH ][H O]
v k k
[H O ]
+
=
Trong mi tr ng dung dch n c [H
2
O] = const. Ch n c ch 3
0,25
0,25
0,25
0,25
0,5
2.0
8
1
- H p ch t A
x
B
y
l m t mu i. Khi b thu phn cho thot ra H
2
S.
- H p ch t A
n
C
m
l Al
2
O
3
nhm oxi
- V y A l Al nhm, B l S l u hu nh, C l O oxi
- H p ch t A
o
B
p
C
q
l Al
2
(SO
4
)
3
nhm sunfat
2 Al + 3 S Al
2
S
3
Al
2
S
3
+ 6 H
2
O 2 Al(OH)
3
+ 3 H
2
S
4 Al + 3 O
2
2 Al
2
O
3
S + O
2
SO
2
Al
3+
+ 2 H
2
O Al(OH)
2+
+ H
3
O
+
5 ch t
0,125.5
= 0,625
5 ptrnh
0,125.5
= 0,625
2
S mol nguyn t S trong 3,2 gam l u hu nh:
S
3, 2
n 0,1mol
32
= =
Dng cng th c:
PV
n
RT
=
tnh c s mol cc phn t l u hu nh tr ng thi h i t i cc
nhi t :
* 444,6
o
C: n
1
= 0, 0125 mol g m cc phn t S
8
v 0, 0125 8 = 0,1 mol
* 450
o
C: n
2
= 0,015 mol, s nguyn t S trung bnh trong 1 phn t :
0,1
6, 67
0, 015
~
Thnh ph n h i l u hu nh nhi t ny c th g m cc phn t l u hu nh c t 1 n
8 nguyn t .
* 500
o
C: n
3
0,1
5
0, 02
=
8 nguyn t ho c ch g m cc phn t S
5
.
* 900
o
C: n
4
0,1
2
0, 05
=
8 nguyn t ho c ch g m cc phn t S
2
.
* 1500
o
C : n
5
= 0,1 mol : H i l u hu nh ch g m cc nguyn t S.
0,25
0,25
0,25
0,25
0,25
0,25
0,25
3.0
9
Nng l ng c a m t electron phn l p l c s l ng t chnh hi u d ng n* c tnh theo
bi u th c Slater:
1
= -13,6 x (Z b)
2
/n* (theo eV)
H ng s ch n b v s l ng t n* c tnh theo quy t c Slater. p d ng cho Ni
2+
(Z=28, c
26e) ta c:
V i cch vi t 1 [Ar]3d
8
:
1s
= -13,6 x (28 0,3)
2
/1
2
= -10435,1 eV
2s,2p
= -13,6 x (28 0,85x2 0,35x7)
2
/ 2
2
= - 1934,0 eV
3s,3p
= -13,6 x (28 1x2 0,85x8 0,35x7)
2
/3
2
= - 424,0 eV
3d
= - 13,6 x (28 1x18 0,35x 0,35x7)
2
/3
2
= - 86,1 eV
E
1
= 2
1s
+ 8
2s,2p
+ 8
3s,3p
+ 8
3d
= - 40423,2 eV
V i cch vi t 2 [Ar]sd
6
4s
2
:
1s
,
2s,2p
,
3s,3p
c k t qu nh trn . Ngoi ra:
3d
= -13,6 x (28 1x18 0,35x5)
2
/3
2
= - 102,9 eV
4s
= - 13,6 x (28 1x10 0,85x14 0,35)
2
/3,7
2
= - 32,8 eV
Do E
2
= - 40417,2 eV.
E
1
th p (m) h n E
2
, do cch vi t 1 ng v i tr ng thi b n h n. K t qu thu c ph h p
v i th c t l tr ng thi c b n ion Ni
2+
c c u hnh electron [Ar]3d
8
.
0,25
0.125.5
= 0,625
0,125.3
= 0,375
0,25
1.5
10
1
- t = 48 h = 2 ngy m.
- p d ng bi u th c t c c a ph n ng m t chi u b c m t cho ph n ng phng x , ta
c: = 0,693/t
1/2;
V i t
1/2
= 2,7 ngy m, = 0,257 (ngy m)
-1
.
T pt ng h c p. m t chi u b c nh t, ta c: =(1/t) ln N
0
/N.
V y: N/N
0
= e
- t
= e
-0,257 x 2
= 0,598.
Nh v y, sau 48 gi phng x c a m u ban u cn: 0,598 x 4 = 2,392 (mCi).
Do s gam dung mi tr c n dng l: (2,392 : 0,5) 1,0 = 3,784 (g)
0,25
0,25
0,25
0,25
2
Ph n th tch b chi m b i cc nguyn t trong m ng tinh th c ng chnh l ph n th tch m
cc nguyn t chi m trong m t t bo n v ( m ng c s ).
- i v i m ng n gi n:
+ S nguyn t trong 1 t bo: n = 8 x 1/8 = 1
+ G i r l bn knh c a nguyn t kim lo i, th tch V
1
c a 1 nguyn t kim lo i:
V
1
= 4/3 x r
3
(1)
+ G i a l c nh c a t bo, th tch c a t bo l:
V
2
= a
3
(2)
Trong t bo m ng n gi n, t ng quan gi a r v a c th hi n trn hnh sau:
hay a = 2r (3).
Thay (3) vo (2) ta c: V
2
= a
3
= 8r
3
(4)
Ph n th tch b chi m b i cc nguyn t trong t bo l:
V
1
/V
2
= 4/3 r
3
: 8r
3
= /6 = 0,5236
i v i m ng tm kh i:
0,5
r
a
- - - - - - - - - - - H T - - - - - - - - - -
Th sinh c th lm cch khc, n u ng v n cho i m t i a
+ S nguyn t trong 1 t bo: n = 8 x 1/8 + 1 = 2. Do V
1
= 2x(4/3) r
3
.
+ Trong t bo m ng tm kh i quan h gi a r v a c th hi n trn hnh sau:
Do : d = a 3 = 4r. ra a = 4r/ 3
Th tch c a t bo:
V
2
= a
3
= 64r
3
/ 3 3
Do ph n th tch b chi m b i cc nguyn t trong t bo l:
V
1
: V
2
= 8/3 r
3
: 64r
3
/3 3 = 0,68
i v i m ng tm di n:
+ S nguyn t trong 1 t bo: n = 8 x 1/8 + 6 x = 4. Do th tch c a cc
nguyn t trong t bo l:
V
1
= 4 x 4/3 r
3
+ Trong t bo m ng tm di n quan h gi a bn knh nguyn t r v c nh a c a t bo
c bi u di n trn hnh sau:
T d ta c: d = a 2 = 4r, do a = 4r/ 2
Th tch c a t bo: V
2
= a
3
= 64r
3
/2 2
Ph n th tch b cc nguyn t chi m trong t bo l:
V
1
/V
2
= 16/3 r
3
: 64r
3
/ 2 2 = 0,74
Nh v y t l ph n th tch b chi m b i cc nguyn t trong 1 t bo c a cc m ng n gi n,
tm kh i v tm di n t l v i nhau nh 0,52 : 0,68 : 0,74 = 1 : 1,31 : 1,42.
0,5
0,5
2.5
a
d
THI TH NM H C 2008 2009
MN THI: HA H C
Th i gian lm bi: 180 pht (Khng k th i gian pht )
( thi g m c 2 trang)
Cu 1: (2.5 im)
1. Cho bng sau:
Nguyn t Ca Sc Ti V Cr Mn
Nng lng ion ho I
2
(eV) 11,87 12,80 13,58 14,15 16,50 15,64
Hy gii thch s bin i nng lng ion ho th hai ca cc nguyn t trong bng.
2. Vit cng thc Lewis v xc nh dng hnh hc ca cc phn t v ion sau: BCl
3
, CO
2
, NO
2
+
, NO
2
, IF
3
3. Ti sao bo triclorua tn ti dng monome (BCl
3
) trong khi nhm triclorua li tn ti dng ime (Al
2
Cl
6
)?
Cu 2: (2.5 im)
Silic c cu trc tinh th ging kim cng.
1. Tnh bn knh ca nguyn t silic. Cho khi lng ring ca silic tinh th bng 2,33g.cm
-3
; khi lng mol
nguyn t ca Si bng 28,1g.mol
-1
.
2. So snh bn knh nguyn t ca silic vi cacbon (r
C
= 0,077 nm) v gii thch.
3. Vit tt c cc ng phn ca phc cht [Co(bipy)
2
Cl
2
]
+
vi bipy (hnh bn)
Cu 3: (2.5 im)
1. i vi phn ng : A
k1
k2
B. Cc hng s tc k
1
= 300 giy
-1
; k
2
= 100 giy
-1
.
thi im t = 0 ch c cht A v khng c cht B. Hi trong bao lu th mt na lng ban u cht A bin
thnh cht B.
2. Cho 2 cap oxi hoakh: Cu
2+
/ Cu
+ 0
1
0,15 E V = ; I
2
/ 2I
- 0
2
0, 62 E V =
a. Vi et cac phng trnh phan ng oxi hoakhvaphng trnh Nernst tng ng. iu kin chuan co
th xay ra soxi hoaI
-
bang i on Cu
2+
?
b. Khi odung dch KI vao dung dch Cu
2+
thay cophan ng:
2+ -
2
1
Cu + 2I CuI + I
2
!
Hay xac nh hang socan bang cua phan ng tren . Bi et tch sotan T cua CuI l a10
-12
Cu 4: (2.5 im)
1. Trong bnh chn khng dung tch 500cm
3
cha m gam HgO rn. un nng bnh n 500
0
C xy ra phn ng:
2HgO
(r)
2Hg
(k)
+ O
2(k)
. p sut khi cn bng l 4 atm
a. Tnh K
P
ca phn ng
b. Tnh khi lng nh nht ca thu ngn oxit cn ly tin hnh th nghim ny. Cho Hg = 200.
2. t chy etan ( C
2
H
6
) thu sn phm l kh CO
2
v H
2
O ( lng ) 25C.
a. Vit phng trnh nhit ho hc ca phn ng xy ra. Hy xc nh nhit hnh thnh etan v nng lng
lin kt C=O. Bit khi t chy 1 mol etan to ra lng nhit l 1560,5KJ. V :
H
ht
( KJ.mol
-1
) Lin kt Nng lng lin kt ( KJ.mol
-1
)
CO
2
-393,5 CC 347
H
2
O (l) -285,8 HC 413
O
2
0 HO 464
O=O 495
b. Phn ng c G = -1467,5 ( KJ.mol
-1
). Hy tnh bin thin entropi ca phn ng cho theo n v
J.mol
-1
.K
-1
.
N N bipy
Cu 5: (2.5 im)
1. Thm 1 ml dung dch
4
NH SCN 0,10 M vo 1ml dung dch
3
Fe
+
0,01 M v F
1M. C mu ca phc
2+
FeSCN hay khng? Bit rng mu ch xut hin khi
2+
6
FeSCN
C 7.10 M
> v dung dch c axit ha

s to phc hidroxo ca Fe (III) xy ra khng ng k. Cho
1 13,10
3 eF
3
10
F

= ;
1
2 3,03
eSCN
10
F
+
= ( l hng
s bn).
2. nh gi thnh phn cn bng trong hn hp gm Ag
+
1,0.10
-3
M;
3
NH 1,0 M v Cu bt. Cho
3 2
7,24
2
Ag(NH )
10
+
= ;
3
2 12,03
4Cu( NH )4
10
+
= ;
2
0 0
Ag / Ag Cu / Cu
E 0, 799V; E 0, 337V
+ +
= = ( 25
0
C)
Cu 6: (2.5 im)
1. Khi cho PVC tc dng vi Zn trong ru th tch ra c ZnCl
2
v thu c polime c cha 20,82% clo. Polime
khng cha ni i v khng c tnh do nh PVC. Kt qu trn cho bit g v cu to ca polime mi thu
c. Tnh % mc xch vinyl clorua b tch clo bi Zn.
2. X l o- halogen xeton vi baz mnh to thnh cc sn phm chuyn v. S chuyn v ny gi l phn ng
Favorski. o- cloxiclohexanon s chuyn v thnh metylxiclopentancacboxilat khi c mt CH
3
ONa trong ete.
Hy xc nh c ch ca phn ng ny.
Cu 7: (2.0 im)
1. Vit s iu ch cc cht sau y:
a. 1,2,3 tribrmbenzen t axtilen v cc ho cht cn thit khc.
b. Axit mtoluic t benzen v cc ho cht cn thit khc.
2. Hy ngh c ch phn ng kh nc (H
+
) ca
a. Butan1ol to (trans)but 2en
b. 3,3imetylbutan2ol to 2,3imtylbut 2en
Cu 8: (3.0 im)
1. Axit fumaric v axit maleic c cc hng s phn li nc 1 (k
1
), nc 2 (k
2
). Hy so snh cc cp hng s phn li
tng ng ca hai axit ny v gii thch.
2. So snh kh nng phn ng ca cc ancol sau vi hirobromua HBr v gii thch: p-CH
3
-C
6
H
4
-CH
2
OH,
p-CH
3
O-C
6
H
4
-CH
2
OH, p-CN-C
6
H
4
-CH
2
OH v p-Cl-C
6
H
4
-CH
2
OH.
3. Oxi ho hirocacbon thm A (C
8
H
10
) bng oxi c xc tc coban axetat cho sn phm B. Cht B c th tham gia
phn ng: vi dung dch NaHCO
3
gii phng kh CO
2
; vi etanol (d) to thnh D ; un nng B vi dung dch
NH
3
to thnh E. Thu phn E to thnh G, un nng G nhit khong 160
0
C to thnh F. Mt khc, khi
cho B phn ng vi kh NH
3
(d) cng to thnh F. Hy vit cc cng thc cu to ca A, B, D, G, E v F.
4. Cho s cc phn ng sau:
HCHO H
2
O
OH
OH
-
A
B
NaCN
DMF
C
O
Cl
D1 + D2 + E (sn phm ph)
Hy vit cng thc cu to ca A, B, C, D1, D2 v E. Bit E c cng thc phn t C
19
H
22
O
5
N
2
.
.........................................................................................................Ht.........................................................................................................
O
Cl
COOCH
3
NaCl
CH
3
ONa
ete
THI TH NM H C 2008 2009
H NG D N CH M MN HA H C
Cu 1: (2,5 im)
1 (0,5 im). Cu hnh electron ca cc nguyn t:
Ca [Ar]4s
2
; Sc [Ar]3d
1
4s
2
; Ti [Ar]3d
2
4s
2
; V [Ar]3d
3
4s
2
; Cr [Ar]3d
5
4s
1
; Mn [Ar]3d
5
4s
2
.
Nng lng ion ho th hai ng vi s tch electron ho tr th hai. T Ca n V u l s tch electron 4s th
hai. Do s tng dn in tch ht nhn nn lc ht gia ht nhn v cc electron 4s tng dn, do nng lng
ion ho I
2
cng tng u n. i vi Cr, do cu hnh electron c bit vi s chuyn 1 electron t 4s v 3d
sm t c phn lp 3d
5
y mt na, electron th hai b tch nm trong cu hnh bn vng ny cho nn s
tch n i hi tiu tn nhiu nng lng hn nn I
2
ca nguyn t ny cao hn nhiu so vi ca V. Cng chnh v
vy m khi chuyn sang Mn, 2 electron b tch nm phn lp 4s, gi tr I
2
ca n ch ln hn ca V va phi,
thm ch cn nh hn gi tr tng ng ca Cr.
2. a (0,5 im). Cng thc Lewis:
BCl
3
:
.
.
B
Cl
.
.
:
: :
: :
: :
. .
Cl
.
.
.
.
.
.
:
.
. .
B
Cl
Cl
.
.
.
Cl
.
. .
.
.
.
.
:
. .
.
B
Cl
.
.
.
.
.
.
.
.
Cl
.
.
.
.
.
.
Cl
.
.
.
.
Cl
.
.
.
.
.
.
CO
2
NO
2
+
NO
2
IF
3
.
. .
. .
N
O
.
.
.
.
.
.
.
O
.
.
.
.
.
.
.
.
+
O : : N : : O
. .
. . . .
. .
. .
. .
. .
. .
. .
. .
.
O
.
.
.
.
. .
.
N
.
.
.
.
O
.
.
.
.
. .
. .
O : : C : : O
.
.
.
.
.
.
.
.
.
.
I
.
. .
:
:
F
F
F
.
.
.
b (1 im). Dng hnh hc:
BCl
3
: Xung quanh nguyn t B c 3 cp electron (2 cp v 1 "siu cp") nn B c lai ho sp
2
, 3 nguyn t Cl lin kt
vi B qua 3 obitan ny, do phn tc dng tam gic u.
CO
2
: Xung quanh C c 2 siu cp, C c lai ho sp, 2 nguyn t O lin kt vi C qua 2 obitan ny. Phn t c dng
thng.
NO
+
: Ion ny ng electron vi CO
2
nn cng c dng thng.
NO
2
: Xung quanh N c 3 cp electron quy c |gm 1 cp + 1 siu cp (lin kt i) + 1 electron c thn| nn N
c lai ho sp
2
. Hai nguyn t O lin kt vi 2 trong s 3 obitan lai ho nn phn t c cu to dng ch V (hay gp
khc). Gc ONO < 120
o
v s y ca electron c thn.
IF
3
: Xung quanh I c 5 cp electron, do I phi c lai ho sp
3
d, to thnh 5 obitan hng n 5 nh ca mt
hnh lng chp ng gic. Hai obitan nm dc trc thng ng lin kt vi 2 nguyn t F. Nguyn t F th ba lin
kt vi 1 trong 3 obitan trong mt phng xch o. Nh vy phn t IF
3
c cu to dng ch T. Nu k c n s y
ca 2 cp electron khng lin kt, phn t c dng ch T cp.
. .
. .
. .
. . . .
. .
. .
F
F
F I
C O O
N O O
Cl
B
Cl
.
.
.
.
.
.
.
. .
.
.
.
Cl
O
N
.
.
.
.
. .
.
.
.
O
+
. . . .
. . . .
. .
. . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
. .
.
3 (0,5 im). BCl
3
: B c 3 electron ho tr. Khi to thnh lin kt vi 3 nguyn t Cl, nguyn t B ch c 6
electron, phn t khng bn. c bt t nguyn t B s dng 1 obitan p khng lai ho to lin kt vi 1
trong 3 nguyn t Cl. Kt qu l to thnh phn t BCl
3
c dng tam gic u nh trnh by trn.
AlCl
3
: AlCl
3
cng thiu electron nh BCl
3
, nhng Al khng c kh nng to thnh lin kt kiu p
-p
nh B.
c bt t, 1 trong 4 obitan lai ho sp
3
ca nguyn t Al nhn 1 cp electron khng lin kt t 1 nguyn t Cl
phn t AlCl
3
bn cnh. Phn t AlCl
3
ny cng x s nh vy. Kt qu l to thnh mt ime.
Cu 2: (2,5 im)
1 (0,5 im). Trong cu trc kiu kim cng (Hnh bn)
di ca lin kt C-C bng 1/8 di ng cho d ca t bo n v (unitcell).
Mt khc, d a 3 = , vi a l di ca cnh t bo.
Gi l khi lng ring ca Si.
T nhng d kin ca u bi ta c:
=
nM
NV
=
23 3
8.28,1
6, 02.10 .a
= 2,33
suy ra: a = [8 . 28,1 / 6,02.10
23
. 2,33]
1/3
cm = 5,43.10
-8
.
d = a \ 3 = 9,40.10
-8
cm; r
Si
= d : 8 = 1,17.10
-8
cm = 0,117nm
2 (0,5 im). r
Si
= 0,117 nm > r
C
= 0,077 nm. Kt qu ny hon ton ph hp vi s bin i bn knh nguyn t ca
cc nguyn t trong bng h thng tun hon.
3 (1im). Quy c biu din bipy bng mt cung li.
a (0,25 im). ng phn cis, trans:
b (0,75 im). ng phn quang hc:
Cu 3: (2,5 im)
1. A
k1
k2
B
t = 0 a 0
t
2
a
2
a
p dng cng thc cho :
e
1 2
e
x 1
k k ln
t x x
+ =
y nng lc cn bng x
e
c xc nh thng qua hng s cn bng K :
| |
| |
e
e
B x
K
A a-x
= =
Sau khi bin i ta c :
K 1
aK
x
e
+
= v
e
aK-x(1+K)
x x
1 K
=
+
Cui cng
Kx - x - aK
aK
lg
t
303 , 2
k k
2 1
= +
Trans
Co
Cl
Cl Cis
Co
Cl
Cl
Co
Cl
Cl Co
Cl
Cl
V
2
a
x = Nn
2
a
K -
2
a
- aK
aK
lg
t
303 , 2
k k
2 1
= +
K - 1 - 2K
2K
lg
t
303 , 2
=
1 - K
2K
lg
t
303 , 2
=
V K = k
1
/ k
2
Nn
2 1
1
2 1
k - k
2k
lg
k k
303 , 2
t
+
= giy 10 . 7 , 2
100 - 300
300 . 2
lg
100 00 3
303 , 2
3
=
+
=
2. a. Xet 2 cap oxi hoakh:
Cu
2+
+ e

Cu
+
2
0
1 1
0, 059lg
Cu
E E
Cu
+
+
1
]
= +
1
]
I
2
+ 2e

2I
-
| |
2 0
2 2 2
0, 059
lg
2
I
E E
I
= +
1
]
0 0
1 2
E E ( : Khong thecophan ng gi a Cu
2+
vaI
-
c.
b. Gi asodung dch KI vao dung dch cha Cu
2+
vamot t Cu
+
. V CuI rat
t tan nen [ Cu
+
] rat nho, do oE
1
cothel n hn E
2
.
Nh vay ta co: Cu
2+
+ e

Cu
+
I
-
+ Cu
+
CuI !
1
2
I
2
+ e

I
-
Phan ng oxi hoakhtong quat l a:
Cu
2+
+ 2I
-
CuI ! +
1
2
I
2
(1)
Luc can bang ta co:
2
1
0,15 0, 059lg
[ ]
Cu
E
T
I
+
1
]
= +
=
| |
2
2 2
0, 059
0, 62 lg
2
I
E
I
= +
1
]
: 0,62 0,15
| |
2
2
1
2
2
1
0, 059lg 0, 059lg
.
Cu I
T K
T I
+
1 1
] ]
= =
0,62 0,15
4 0,059
1
.10 10
+
= = K
T
Nh vay vi K rat l n, phan ng (1) xay ra hoan toan.
Cu 4: (2.5 im)
1.a. 2HgO (r)

2Hg(k) + O
2
(k)
[ ]
0
a mol 0 0
[ ]
cb
a 2x 2x x
2
2
3
2 3
2 1 4 4.4
. 9, 48
3 3 27 27
p Hg O
K P P P P P
|
= = = = =
|
\ .
b. S mol Hg nh nht khi a = 2x. T cng thc
HgO
4.0, 5
3 0, 0105
0, 082.773
Vay a = 0,021 mol
m 0, 021.216 4, 53
PV
n x x
RT
g
= = = =
= =
2. Ta c cc phng trnh:
C
2
H
6
+
2
7
O
2
2CO
2
+ 3H
2
O H = - 1560,5 KJ
( 2C
2
H
6
+ 7O
2
4CO
2
+ 6H
2
O H = - 3121 KJ )
H
p
= 4 H
ht
CO
2
+ 6 H
ht
H
2
O - 7H
ht
O
2
- 2 H
ht
C
2
H
6
H
ht
C
2
H
6
=
, , , , , , | |
2
3121 8 , 285 6 5 , 393 4 +
= - 83,9 ( KJ.mol
-1
)
H
p
= 2 E
C C
+ 12 E
C H
+ 7E
O=O
- 8 E
C = O
- 12 E
H O
E
C = O
=
, , | |
8
3121 464 x 12 495 x 7 413 x 12 347 x 2 + +
= 833( KJ.mol
-1
)
b. AG = AH - TAS
=> AS =
, , | |
, , 273 25
5 , 1467 5 , 1560
+

= - 0,312 (kJ.mol
-1
K
-1
) = -312 J.mol
-1
.K
-1
Cu 5: (2.5 im)
1. Ta c:
3
Fe
C
+
<<
F
C ( 1)
=
3
FeF
| rt ln.
V vy trong dung dch, Fe
3+
tc dng ht vi F
-
to ra phc
3
FeF .
3+
3
Fe 3F FeF
+
Ban u 0,01 1
Sau phn ng __ 0,97 0,01
Sau khi trn vi
4
NH SCN :
3
FeF
C = 5.10
-3
M;
F
C

= 0,485M;
2
SCN
C 5.10 M

=
FeF
3
Fe
3+
+ 3F
-
10
-13,10
Fe
3+
+ SCN
-
FeSCN
2+
10
+3,03
FeF
3
+ SCN
-
FeSCN
2+
+ 3F
-
K = 10
-10,07
C 5.10
-3
5.10
-2
0,485
[ ] (5.10
-3
-x) (5.10
-2
-x) x 0,485+3x
3
10,07
3 2
x(0, 485 3x)
10
(5.10 x)(5.10 x)

+
=

Vi x << 5.10
-3
ta c :
, ,
6 13
3
07 10 5
10 x 7 10 x 86 1
485 0
10 x 10 x 25
x

< = = ,
,
,
Vy mu ca phc
2+
FeSCN khng xut hin, ngha l F
-
che hon ton Fe
3+
2. Cc qu trnh xy ra:
- To phc
2+
3
Ag(NH ) (
+
>
Ag
NH
C C
3
)
Ag
+
+ 2NH
3
Ag(NH
3
)
2
+ 7,24
2
10 =
1,0.10
-3
1,0
__ 1,0-2,0.10
-3
1,0.10
-3
- Kh
2+
3
Ag(NH ) bi Cu:
2x Ag(NH
3
)
2
+
Ag
+
+ 2NH
3
1 7,24
2
10

= (1)
2Ag
+
+ Cu 2Ag + Cu
2+ 15,61
0
10 K = (2)
- To phc ca Cu
2+
vi
3
NH (
+
>
2
3 Cu
NH
C C )
Cu
2+
+ 4NH
3
Cu(NH
3
)
4
2+ 12,03
4
10 = (3)
T hp (1)(2) v (3):
2Ag(NH
3
)
2
+
+ Cu 2Ag + Cu(NH
3
)
4
2+
;
4 0
2
2
K K | | =

. . = 10
13,16
1,0.10
-3
----- 5,0.10
-4
TPGH:
2
3 4
Cu(NH )
+
: 5,0.10
-4
M ;
3
3
NH : 1, 0 2.10 1, 0M
~
Cn bng Cu(NH
3
)
4
2+
+ 2Ag 2Ag(NH
3
)
2
+
+ Cu 10
- 13,16
C 5,0.10
-4
[ ] 5,0.10
-4
-x 2x
2
13,16
4
(2x)
10
(5, 0.10 x)

x = 5.10
- 4
2x =
4 23 8 16 13 4
10 x 5 10 10 10 x 5

< =
, ,
.
Vy:
+ -8,23 9
3 2
[Ag(NH ) ]=2x=10 5, 9.10 M
=
2+ -4
3 4
[Cu(NH ) ]=5,0.10 M
Mc d Ag
+
tn ti di dng phc
3 2
Ag(NH )
+
nhng vn b Cu kh hon ton.
Cu 6: (2.5 im)
1. PVC clo chim 66,8% (theo khi lng). Sau phn ng vi Zn, clo gim cn 20,82%, lng clo gim nhiu m
polime to thnh khng cha ni i. vy PVC c cu to u n, c mt nhm CH
2
- li n 1 nhm CHCl-, v
nu c 2 nhmCHCl- cnh nhau th to ni i.
Phn ng tch clo khi PVC c th biu din theo s :
Trong polime to thnh, nu c x mc xch cn li 1 nguyn t clo th cng thc l [-(C
2
H
3
)
x
Cl-]
n
Ta c:
35, 5
27x 35, 5 +
= 0,2082 x = 5.
Vy c 5 mc xch ch c 1 mc xch cn clo.
Suy ra % s mc xch b loi clo l:
4
5
.100% = 80%
2. C ch:
O
Cl
CH
3
O
CH
3
OH
O
Cl
O
CH
3
O
O
OCH
3
2 Zn
CH
CH
2
CH
CH
2
CH
2
CH
CH
2
CH
Cl Cl
Cl Cl
CH
CH
2
CH
CH
2
CH
2
CH
CH
2
CH
ZnCl
2
2
H
2
O
OH
O O
OCH
3
OCH
3
Cu 7: (2.5 im)
1a.
b.
2. C ch :
a.
b.
CH
3
CHCCH
3
C C
CH
3
CH
3
H
3
C
H
H
2
O
H
CH
3
CH
3
OH
CH
3
CHCCH
3
CH
3
CH
3
CH
3
CHCCH
3
CH
3
CH
3
H
3
C
Cu 8: (2.5 im)
1 (0,75 im).
H
H HOOC
COOH - H
+
H
H HOOC
COO
-
- H
+
F
F
,
F
,,
Axit fumaric
H
H
-
OOC
COO
-
H H
O OH
OH O
- H
+
- H
+
H
COO
- -
OOC
H
...
H H
O O
O OH
.
.
.
. ....
...
M Axit maleic M
,
M
,,
k
1
(M) > k
1
(F) l do M c kh nng to lin kt hidro ni phn t, lin kt O-H ca M trong qu trnh phn li th
nht phn cc hn so vi F v baz lin hp M' cng bn hn F'.
CH
3
CH
3
NO
2
CH
3
NH
2
CH
3
NHCOCH
3
CH
3
NHCOCH
3
Br
NH
2
Br
CH
3
N
2
Cl
Br
Br
CH
3
MgBr
CH
3
CH
3
COOH
CH
3
CH
3
Cl
AlCl
3
HNO
3
H
2
SO
4
[H]
Fe/HCl
CH
3
COCl Br
2
H
2
O
NaNO
2
C
2
H
5
OH
Mg/ete CO
2
/ete
/HCl
0 5 C
0
C
2
H
2
NO
2
NH
2
NH
2
Br
Br
Br
N
2
Cl
Br
Br
Br
Br
Br
Br
600 C
0
C
HNO
3
H
2
SO
4
[H]
Fe/HCl
Br
2 NaNO
2
/HCl C
2
H
5
OH
CH
3
CH
2
CH
2
CH
2
OH CH
3
CH
2
CH
2
CH
2
CH
3
CH
2
CHCH
3
C C
H
CH
3
H
H
3
C
H
H
2
O
H
k
2
M < k
2
F ) l do lin kt hidro ni phn t lm cho M' bn, kh nhng proton hn so vi F'. Ngoi ra, baz lin
hp M'' li km bn hn (do nng lng tng tc gia cc nhm-COO
-
ln hn) baz lin hp F''.
2 (0,75 im). Phn ng gia cc ancol cho vi HBr l phn ng th theo c ch SN. Giai on trung gian to
cacbocation benzylic. Nhm OCH
3
y electron (+C) lm bn ho cacbocation ny nn kh nng phn ng tng.
Nhm CH
3
c (+I) nn cng lm bn ha cacbocation ny nhng km hn nhmOCH
3
v (+C) > (+I) . Cc nhmCl
(-I > +C) v CN (-C) ht electron lm cacbocation tr nn km bn do vy kh nng phn ng gim, nhm CN
ht electron mnh hn nhmCl.
Vy sp xp theo trt t tng dn kh nng phn ng vi HBr l:
p-CN-C
6
H
4
-CH
2
OH < p-Cl-C
6
H
4
-CH
2
OH < p-CH
3
-C
6
H
4
-CH
2
OH < p-CH
3
O-C
6
H
4
-CH
2
OH.
3 (0,75 im).
A B
CH
3
CH
3
C
C
O
O
O
D
C
O
C
O
O
C
C
O
O
OC
2
H
5
OC
2
H
5
+ C
2
H
5
OH
ftalimit F
C
C
O
O
O
+ NH
3
(kh, d)
C
C
O
O
N H
C
C
O
O
NH
2
OH
F
C
C
O
O
N H
160
O
C
G
4. (0.75)
S iu ch p-hiroxiphenylaxetamit
HO HO
CH
2
CN
HO
CH
2
OH
HO
CH
2
CONH
2
HCHO
OH
-
H
2
O NaCN
DMF
A B C
OH
C D1 D2
H
2
NCOCH
2
+ O
Cl
O
H
2
NCOCH
2
O
O
H
2
NCOCH
2
Cl
OH
Sn
phm ph:
C
19
H
22
O
5
N
2
O
H
2
NCOCH
2
O
OH
CH
2
CONH
2
- - - - - - - - - - - H T - - - - - - - - - -
Th sinh c th lm cch khc, n u ng v n cho i m t i a

Tuyen Tap de Thi HSG Hoa Hoc p2

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Tuyen Tap de Thi HSG Hoa Hoc p2

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2010

Phan Cuong Huy

Copyright 2010 http://vn.myblog.yahoo.com/volcmttl

= cho dung dch NaCl 25% theo kh i l ng

l th i u ki n v ph thu c vo pH. pH cng gi m th dung dch cng c mi

< nn Anode x y ra qu trnh (4) v c Cl

> v dung dch c axit ha

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