Tuyển tập đề thi hsg hóa

2010
han Cuong Puy

?uS
Copyrlght http://vn.myblog.yahoo.com/volcmttl
TUYN TP D THI HSC
MN HuA HC
Copyrlght 2010 http://vn.myblog.yahoo.com/volcmttl
2 1ULN 1 L 1nI nSG MCN nCA nC
nN 2: CC L CN 1nI nC SINn GICI UCC GIA
L SC 1
THPT CHUYN H NI kI 1nI CnN nC SINn GICI UCC GIA
L 1nI 1n0 LC 12 1n1 NM 2010
Mn: nC nC
1hl glan : 180 pht (kboq k tb| q|oo q|oo J)
(u tb| qm J ttooq, c 8 cu)
Cu I: ( 2.0 im)
Mt terpen X thng gp trong thin nhin c tng hp theo s sau
4metylpentan1,4diol dn xut dibromua bromanken
Mg
ete khan
Grignard G X
Cho cht G phn ng vi sn phm sinh ra khi cho isopren phn ng vi but3en2on s thu c cht cn
tng hp X.
1. Hon thnh chuyn ha ny bng cc cng thc cu to tng ng.
2. Cho bit tn thng thng v ng dng ca sn phm.
Cu II: (2.0 im)
Hydrocacbon A l mt cht rn c tnh do, n hi (11,76% H theo khi lng) c trong m cy cao su. Ozon
phn A cho C
16
H
16
O
6
, khi cho mt mol cht ny vo nc nng thu c 2 mol andehit levulinic
HOC(CH
2
)
2
COCH
3
.
Hydrocacbon B (11,11% H theo khi lng) l cht tng hp u tin c thnh phn ging A nhng khng c
tnh do v tnh n hi ging nh A. B c to thnh khi un nng hydrocacbon C c mt natri ; C c thnh
phn nh tnh ging B
1. Cho bit CTCT ca A, B, C
2. S vng mt ca axetylaxeton trong sn phm ca chng chng t A c c trng g ?
Cu III: (2.0 im)
Qu trnh tng hp phc Pt(CH
3
NH
2
)(NH
3
)[CH
2
COO]
2
l thuc chng ung th mi c hiu qa cao li t c
v t cho phn ng ph. Qu trnh tng hp thuc 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 (rn nu)
3 2
NH / H O
D (tinh th vng kim, phn cc)
2 3
Ag CO du v axit malonic
E (tinh th vng nht)
Phng php ph IR cho bit trong hp cht C c hai loi lin kt Pt I khc nhau v C c tm i xng. Bit
M
C
= 1,88M
B
. Cho bit s phi tr ca platin lun khng i trong qu trnh tng hp v platin lun gi dng lai
ha dsp
2
trong cc phc
1. Vit CTCT cc sn phm A, B, C, D, E.
2. Trong sn phm E th khng c cha iot. Nh vy ti sao lc ban u phi chuyn K
2
PtCl
4
thnh A.
3. Mc ch ca vic s dng Ag
2
CO
3
trong phn ng cui l g ?
Cu IV: (2.0 im)
L thuyt lai ha do Carl Linus Pauling xut vn l l thuyt chun xc nht trong vic gii thch dng hnh
hc ca cc cht v c. Vy y chng ta s th gii quyt nhng m hnh sau y
1. Gii thch dng hnh hc ca TiCl
4
theo thuyt lai ha ?
2. Gii thch dng hnh hc ca phc Fe(CO)
5
theo thuyt lai ha ?
Cu V: (2.0 im)
Kh NO kt hp vi hi Br
2
to ra mt kh duy nht trong phn t c ba nguyn t
1. Vit phng trnh phn ng
2. Bit H
p
< 0; K
p
(25
o
C) = 116,6. Tnh K
P
0
o
C, 50
o
C. Gi thit rng t s gia tr s cn bng gia 0
o
C v
25
o
C cng nh 25
o
C vi 50
o
C u bng 1,54
3. Xt ti 25
o
C, lc cn bng ha hc c thit lp th cn bng s chuyn dch th no nu
a. Tng lng NO
b. Gim lng hi Br
2
c. Gim nhit
d. Thm kh N
2
vo khi
(1) V = const ;
(2) P
chung
= const
Cu VI (4.0 im)
Guaiol (C
15
H
26
O) l mt ancol rn trng thi tinh th c cu trc terpen. Ancol ny c phn lp t tinh du
cy g Bulnesia sarmienyi. Khi dehydrat ha guaiol bng lu hunh th thu c mt hydrocacbon thm mu xanh
da tri khng cha vng benzen X (C
15
H
18
). Khi ha tan hydrocacbon thm ny vo axit sunfuric c th mu xanh
bin mt. Cho nc vo dung dch ny th X c phc hi nguyn dng. Rt kh hydro ha guaiol bng hydro
c xc tc. Qua mt lot cc chuyn ha di y ta nhn c mt dn xut ca naphtalen (A l sn phm duy
nht ca qu trnh ozon phn)
1. Xc nh cu trc ca guaiol v X nu bit trong phn t guaiol th nhm hydroxyl gn vi nguyn t
cacbon bc ba exocyclic ca h vng
2. Gii thch mu xanh da tri ca X v nu l do n b mt mu trong dung dch axit sunfuric c
3. Xc nh CTCT A, B v gii thch s to thnh A. C bao nhiu mnh isopren trong cht X
Cu VII (2.0 im)
C th tch c rhodi ra khi cc kim loi qu khc bng cch sau: Mt mu bt qung rhodi c trn vi
NaCl v un nng trong dng kh clo. B rn thu c cha mt mui cha 26,76% Rhodi v khi lng. B rn
ny sau c ha tan vo nc, lc dung dch thu c ri c bay hi thu c tinh th B cha 17,13% rhodi.
Tinh th c lm kh 120
o
C n khi lng khng i (khi lng mt i l 35,98%) ri un nng ti 650
o
C.
Ra b rn thu c bng nc ta c rhodi tinh khit
1. Xc nh cng thc A, B
2. Khi mt lng d H
2
S c sc qua dung dch mui A th to thnh kt ta C. Thnh phn hp thc ca
hp cht ny cha 47,59% S. Xc nh cng thc C
3. Gii thch ti sao cn phi ra bng nc nng bc cui cng. Vit cc phn ng xy ra
Cu VIII: (4.0 im)
Cc cacbohydrat t nhin u c tng hp quang ha trong cy xanh. Tuy nhin cc cacbohydrat khng c
trong t nhin c th c tng hp bng con ng nhn to. S di y l s tng hp L-riboz. Hon
chnh s tng hp sau:
_________________ nL1 _________________
- 1bl s|ob kboq Juoc su Juoq t| l|u.
- C|m tb| kboq q|o| tblcb q tbm.
THPT CHUYN H NI kI 1nI CnN nC SINn GICI UCC GIA
N L 1nI 1n0 LC 12 1n1 NM 2009 - 2010
Mn: nC nC
(up o J tb| qm 4 ttooq, c 8 cu)
Cu I: (2.0 im)
1. Cng thc cu to cc cht lin quan (1,75 im)
2. Cht ny l o-bisabolol thng dng trong cng nghip m phm (0,25 im)
Cu II: (2.0 im)
1. Cng thc thc nghim ca A l (C
5
H
8
)
x
, n l cao su t nhin. Cc cng thc thc nghim ca B v C ln
lt l (C
2
H
3
)
y
. B l cao su tng hp polibutadien cn C l buta-1,3-dien (1,5 im, mt im cho mi cu
to).
2. Ta c:
Nh vy s vng mt ca axetylaxeton trong sn phm ozon phn chng t cao su thin nhin c cu trc
u - u (0,5 im cho lp lun)
Cu III: (2.0 im)
1. Cng thc cu to cc cht lin quan (1,25 im ; 0,25 im cho mi cu to)
2. chc chn thu c sn phm cui th buc B phi dng cis nn K
2
PtCl
4
phi c chuyn thnh A
(0,25 im)
3. Ag
2
CO
3
phn ng vi D theo phn ng D + Ag
2
CO
3
= DCO
3
+ 2AgI sau DCO
3
phn ng vi axit
malonic to thnh E (0,5 im)
Cu IV: (2.0 im)
1. Do i vi Ti lc ny th nng lng ca AO 3d gim thp hn so vi AO 4p nn s c s t hp gia 1
AO 4s v 3 AO 3d to thnh 4 AO lai ha sd
3
hng v 4 nh ca mt t din u (1 im)
2. Do CO l phi t trng mnh nn s y cc electron ca Fe v trng thi cp i. Lc ny 1 AO 3d trng
s t hp vi 1 AO 4s trng v 3 AO 4p trng thnh 5 AO lai ha dsp
3
hng v 5 nh ca mt lng thp
tam gic.(1 im)
Cu V: (2.0 im)
1. 2NO
(k)
+ Br
2(hi)
2NOBr
(k)
H > 0 (0,25 im)
2. Do phn ng thu nhit nn c lin h K
P
ti 0
o
C < K
P
(25
o
C) < K
P
(50
o
C)
Vy K
P
ti 0
o
C = 1/1,54.K
P
= 116,6 / 1.54 = 75,71
K
P
ti 50
o
C = 1,54.K
P
= 116,6.1,54 = 179,56 (0,25 im)
3. Xt s chuyn di cn bng ha hc ti 25
o
C
Trng hp a v b v nguyn tc cn xt t s:
2
NOBr
NO
P
Q
P
=
Sau so snh Q vi K
P
kt lun
Tuy nhin y khng c iu kin lp lun theo biu thc ny nn ta s da vo nguyn l Le
Chartelier
a. Nu tng lng NO th cn bng dch chuyn sang phi (0,25 im)
b. Nu gim lng Br
2
th cn bng ha hc dch chuyn sang tri (0,25 im)
c. Nu gim nhit th cn bng dch chuyn sang tri chng li chiu gim nhit (0,25 im)
d. Thm N
2
l kh tr
+ Nu V = const th khng nh hng ti cn bng ha hc do N
2
khng gy nh hng lin h no (theo
nh ngha p sut ring phn)
+ Nu P = const ta xt lin h
Nu cha c N
2
th P = P
NO
+ P
Br2
+ P
NOBr
(a)
Nu 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 biu thc lin h trn v so snh tng quan vi K
P
- Q = K
P
: khng nh hng
- Q > K
P
: cn bng chuyn dch sang tri Q gim ti K
P
- Q < K
P
: cn bng chuyn di sang phi Q tng ti K
P
(1,25 im)
Cu VI (4.0 im)
1. Ta c th suy lun cng thc ca guaiol da trn nhng d kin sau:
- Dehydrat ha ancol ny bng lu hunh thu c hydrocacbon thm X mu xanh da tri khng cha vng
benzen. Nh vy X ch c th l dn xut ca azulen.
- bt bo ha ca guaiol l 3, tc ng vi hai vng vn cn mt ni i. V tr ca ni i s nm
im tip gip hai vng do v tr kh b hydro ha nht, v khi ozon phn v tr ny s d cho sn phm
chuyn v l hai vng 6 gip nhau. Mt vng sinh ra do s m rng vng 5, mt vng sinh ra do s thu hp
vng 7
- Ta d dng nhn thy rng qu trnh chuyn ha ca guaiol khng h nh hng ti cc mch nhnh, v
vy t v tr cc mch nhanh trong dn xut naphtalen ta c th suy ra c v tr ca cc mch nhnh ny
trong guaiol.
- Do nhm OH ca guaiol nm cacbon bc ba nn cng thc cu to ca guaiol ch c th l:
L lun dn ra CTCT ng c 1,0 im, cu to 0,5 im
- Cng thc cu to X s l (0,5 im)
2. Mu xanh da tri ca X c c do s lin hp gia cc ni i trong phn t X. (0,25 im)
Khi ha tan X vo axit sunfuric c mu xanh s bin mt do s bin mt ca h thng lin hp trong hp
cht c to thnh nh hnh v: (0,5 im)
3. Cng thc cu to hai cht A, B nh sau. ng CTCT mi cht c 0,25 im
OH
OH
O O
A
B
S to thnh cht A c gii thch nh sau (0,5 im)
Do cng thc phn t ca A l C
15
H
26
O nn trong A s c 3 mnh isopren (0,25 im)
Cu VII (2.0 im)
1. Na
3
[RhCl
6
] (0,375 im) ; Na
3
[RhCl
6
].12H
2
O (0,375 im)
2. Rh
2
S
3
.2H
2
S (0,5 im)
3. loi b cc mui tan, ch yu l NaCl (0,25 im).
Mi phn ng ng c 0,125 im
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 im)
Cng thc cu to cc sn phm trung gian (Cc cht A, B mi cht 0,5 im, cn C, D, E, F mi cht 0,75 im).
Lu qu trnh chuyn t D sang cht dng th hai bao gm nhiu hn mt giai on
_________________ nL1 _________________
1bl s|ob c tb lm ccb kbc, ou Juoq vo Juoc J|m t| Jo
http://vn.myblog.yahoo.com/volcmttl 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 gm 3 trang, c 10 cu)
CU 1: (2,0 im)
1. Oleum l hn hp c to ra khi cho SO
3
tan trong H
2
SO
4
tinh khit. Trong hn hp c cc axit dng
poli sunfuric c cng thc tng qut H
2
SO
4
.nSO
3
hay H
2
S
n+1
O
3n+4
ch yu cha 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 bit cng thc
cu to ca cc axit trn.
2. Gii thch ti sao SO
3
li d dng phn ng vi H
2
O, HF, HCl, NH
3
hnh thnh nn nhng phn t t
din tng ng. Vit phng trnh phn ng v cng thc cu to sn phm.
3. Kim cng v than ch l hai dng th hnh ca nguyn t cacbon. Tnh khi lng ring v th tch mol
ca chng. Bit rng: di lin kt CC (kim cng) l 154 pm, CC (than ch) l 141 pm, khong cch
gia cc lp than ch l 336 pm. N
A
= 6,02.10
23
. Kim cng c cu to tng t silic v s nguyn t C
trong mt mng tinh th ca kim cng gp 4 ln s nguyn t C trong mt mng tinh th than ch.
CU 2: (2.0 im)
1. Vit cng thc cu to Lewis, nu trng thi lai ha v v dng hnh hc ca cc phn t v ion sau: B
2
H
6
,
XeO
3
, NO
2
+
, NO
2
.
2. Phn ng ca NaNO
3
trong nc vi hn hng Na/Hg cng ging nh phn ng ca etylnitrit C
2
H
5
NO
2
vi hydroxylamine NH
2
OH c mt Natrietoxit cho cng mt sn phm. Sn phm ny l mui ca mt axit
yu khng bn cha Nit, axit ny ng phn ha to thnh mt sn phm c ng dng trong thnh phn
nhin liu tn la. Vit cc phng trnh phn ng xy ra v vho bit cng thc cu trc ca axit ng phn
ni trn.
CU 3: (2.0 im)
Cho phn ng: A B C D + + (1) l phn ng n gin. Ti 27
o
C v 68
o
C, phng trnh (1) c hng s tc
tng ng ln lt 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 lng hot ha E
A
(cal/mol) v gi tr ca A trong biu thc
E
RT
k A e
= mol
-1
.l.s
-1
.
2. Ti 119
o
C, tnh gi tr ca hng s tc phn ng k
3
.
3. Nu C
oA
= C
oB
= 0,1M th t
1/2
nhit 119
o
C l bao nhiu.
CU 4: (2,0 im)
1. Clobenzen c momen lng cc
1
= 1,53 D (
1
hng t nhn ra ngoi) ; anilin c momen lng cc
2
=
1,60D (
2
hng t ngoi vo nhn benzen). Hy tnh momen lng cc ca cc cht sau: ortho
cloanilin ; meta cloanilin v para cloanilin.
2. Tnh pH ca dung dch NH
4
HCO
3
0,1M. Bit rng H
2
CO
3
c hng 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 im)
C th iu ch tinh th FeCl
3
.6H
2
O theo cch sau: Ho tan st kim loi vo trong dung dch axit clohydric 25%.
Dung dch to thnh c oxy ha bng cch sc kh clo qua cho n khi cho kt qu m tnh vi K
3
[Fe(CN)
6
].
Dung dch c c bay hi 95
o
C cho n khi t trng ca n t chnh xc 1,695 g/cm
3
v sau lm lnh n
4
o
C. Tch kt ta thu c bng cch ht chn khng ri cho vo mt dng c cha c nim kn.
1. Vit cc phn ng dn n s kt ta FeCl
3
.6H
2
O
2. C bao nhiu gam st v bao nhiu mL dung dch axit clohydric 36% (d=1,18g/cm
3
) cn iu ch
1,00kg tinh th ny. Bit rng hiu sut 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 rn. Xc nh thnh phn
nh tnh v nh lng ca b rn.
CU 6: (2,0 im)
1. A l cht bt mu lc khng tan trong axit v kim long. Khi nu chy A vi KOH c mt khng kh thu
c cht B c mu vng, d tan trong nc. Cht B tc dng vi axit sunfuric chuyn thnh cht C c
mu da cam. Cht C b lu hunh kh thnh cht A v c th oxi ha axit clohiric thnh kh Clo. Vit cc
phng trnh phn ng xy ra.
2. T cc cht 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 im)
1. Vit cng thc cu trc cc dng enol ca dietylmalonat (1), Etylaxetoaxetat (2). Trong cc cu trc ca
(2), cho bit dng no bn nht, dng no km bn. Gii thch?
2. Cho bit cng thc mch h ca cc cht 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 im)
1. Cho bit sn phm to thnh t cc phn ng sau v gi tn sn phm :
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. Vit s iu ch izatin (indolin-2,3-dion) t 2-nitrobenzoyl clorua
CU 9: (2,0 im)
1. Khi cho amoniac phn ng cng vi axetanehit thu c sn phm khng bn A, sn phm ny d b tch
nc thnh B. B d dng trime ha cho sn phm C l triazin. Mt khc nu cho amoniac ngng t vi
fomanehit s thu c sn phm D (urotropin) c CTPT l C
6
H
12
N
4
. Cht D c kh nng tc dng vi axit
nitric trong anhirit axetic to ra E (hexogen hay xiclonit) l cht n mnh c dng trong i chin th
gii th II: C
6
H
12
N
4
+ 3HNO
3
E + 3HCHO + NH
3
. Xc nh A, B, C, D, E v vit cc phng trnh
phn ng xy ra.
2. Gii thch s khc nhau v nhit si trong dy cc cht 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 im)
1. Vitamin C (axit L-ascobic, pK
a
= 4,21) l endiol v c cu trc nh sau:
a. Hy gii thch tnh axit ca axit L-ascobic v cho bit nguyn t H no
c tnh axit.
b. iu ch L-ascobic t D-glucoz
2. Salixin C
13
H
18
O
7
b thy phn bi elmusin cho D-glucoz v Saligenin
C
7
H
8
O
2
. Salixin khng kh thuc th Tolen. Oxi ha Salixin bng HNO
3
thu
c mt hp cht hu c X m khi thy phn th cho D-Glucoz v anehit
Salixylic. Metyl ha Salixin thu c pentametylsalixin, thy phn hp cht
ny cho ta 2,3,4,6-tetra-O-metyl-D-Glucoz. Xc nh CTCT ca Salixin
_________________ HT _________________
- Th sinh khng c s dng ti liu.
- Gim th khng gii thch g thm.
http://vn.myblog.yahoo.com/volcmttl K THI CHN HC SINH GII QUC GIA
THI TH LP 12 THPT NM 2010
HNG DN CHM THI TH MN HA HC
(p n ny c 8 trang)
CU 1: (2,0 im)
1. (0,5 im) Mi cng thc ng c 0,125 im
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 im) Gii thch ng + vit ng 4 phng trnh v cu trc
- Gii thch: Phn t SO
3
dng tam gic phng vi nguyn t S trng thi lai ha sp
3
, d dng phn ng
chuyn sang thng thi lai ha sp
3
bn, l trng thi c trng ca lu hunh
- Phng trnh phn 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
]
- Cu trc cc sn phm
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 im)
- Kim cng (tng t Silic) c cu trc lp phng tm din ngoi ra cn c 4 nguyn t Cacbon nm trong 4
hc (site) t din nn s nguyn t cacbon trong mt mng c s tinh th kim cng l:
1 1
8 6 4 8
8 2
+ + =
- Do vy suy ra cacbon than ch trong mt mng tinh th c 2 nguyn t cacbon
- Trong mng tinh th kim cng:
di cnh mng tinh th: a =
4d
3
(d = CC (kim cng)) => Th tch mng = a
3
=
3
4d
3
|
|
\ .
Khi lng ring ca tinh th kim cng:
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 ca kim cng =
M
D
=3,385 (cm
3
/mol)
- Tng t trong mng tinh th than ch
Din tch mt y =
2
3
3 d
2
(d = CC (than ch))
Th tch mng =
2
3
3 d h
2
(h l khong cch gia cc lp)
=> Khi lng ring D = 2,297 (g/cm
3
) v th tch mol = 5,224 (cm
3
/mol)
CU 2: (2.0 im)
- B
2
H
6
: B lai ha sp
3
, gm 2 t din lch c mt cnh chung, lin kt BHB l lin kt 3 tm nhng ch c 2
electron, 1 electron ca H v 1 electron ca B
- XeO
3
: Xe lai ha sp
3
, phn t dng thp y tam gic
- NO
2
+
: N lai ha sp, cu trc on thng
- NO
2
: N lai hoa sp
2
, cu trc gp khc (ch V)
- Cng thc 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 im)
- Cc phn ng (mi phn ng 0,25 im)
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 mui ca axit hyponitr H
2
N
2
O
2
(2.0,125 = 0,25)
N N
OH HO
N N
OH
HO
- Cu trc ng phn: H
2
N NO
2
(nitramit) (0,25)
N N
O
O
H
H
CU 3: (2.0 im)
1. (1,0 im)
Phn ng ng hc bc hai, p dng phng 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 im)
, ,
E
RT
3
7 1 1
3
k A e 6,15 10 (mol .l.s )

= =
3. (0,5 im)
7
1/ 2
3 oA
1
1, 63 10 (s)
k .C
t = =
CU 4: (2,0 im)
1. (1,0 im)
Clo c m in ln,
1
hng t nhn ra ngoi nhm NH
2
c cp e t do lin hp vi h e t ca vng benzen
hai momen lng cc cng chiu
ortho meta para
Cng vect s dng h thc lng trong tam gic a
2
= b
2
+ c
2
2bc cos

A
Dn xut 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
Dn xut 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
Dn xut para:
2
p
=
1
+
2
= 1,60 + 1,53 = 3,13D
2. (1,0 im)
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 dng iu kin 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 gn ng:
4 3
[NH ] [HCO ] 0,1M
+
= =
8
[H ] 1, 6737.10 M
pH lg[H ] 7, 78
+
+
=
= =
CU 5: (2,0 im)
1. Cc phng trnh phn ng: (4.0,125 = 0,5 im)
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 vy cn mL 978
0,65 . 1,18 . 0,36
36,5 . 2 . 3,7
~ dung dch HCl 36% (0,5 im)
3. Khi un nng th FeCl
3
.6H
2
O phn hu theo phng trnh sau:
FeCl
3
.6H
2
O FeOCl + 5H
2
O + 6HCl
Khi nhit tng th FeOCl s tip tc phn hu:
3FeOCl FeCl
3
+ Fe
2
O
3
(Hi FeCl
3
bay ra)
Lng FeCl
3
.6H
2
O trong mu l
3 , 270
752 , 2
= 10,18 mmol
iu ny ng vi khi lng FeCl
3
l 107,3. 0,01018 = 1,092g FeOCl
Do khi lng thu c ca b rn b hn nn ta bit c FeOCl s b phn hy mt phn thnh Fe
2
O
3
.
Khi lng FeCl
3
mt mt do bay hi l:
162,2
0,8977 1,902
= 1,20mmol => B rn cui cng cha (0,01018
3.0,00120) = 6,58 mmol FeOCl v 1,20 mmol Fe
2
O
3
. (1,0 im)
CU 6: (2,0 im)
1. (1,0 im) mi phng 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 phng trnh phn 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 im) mi phng 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 phng trnh phn 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 im)
1. (1,0 im) Cc cu trc
C
H
OEt
O
H
O
EtO
C
H
OEt
O O
EtO
H
OEt
O O
EtO
Trong :
- Dng A t bn do ni i khng lin hp
- Dng B bn nhng khng c cng hng este
- Dng C bn nht do c ni i lin hp v cng hng 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 im)
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 im)
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 im)
1. (1,5 im)
- Andehit bo c th tham gia phn ng cng vi amoniac to thnh mt sn phm t bn 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 nc thnh B l CH
3
CH=NH v B d trime ha thnh hp cht d vng C
loi 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
- Mt khc nu cho amoniac ngng t vi fomanehit s thu c sn phm 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 dng vi axit nitric trong anhirit axetic to ra E (hexogen hay xiclonit) l cht n
mnh c dng trong i chin th gii th II theo phn 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 im)
- Ta c nhit si ca (1) < (2) l do hai cht ny khng to c lin kt hydro nn nhit si ph thuc
vo khi lng phn t.
- Li c, nhit si ca (4) < (3) l do mc d c hai cht u c lin kt hydro lin phn t nhng lin kt
hydro ca (3) dng polyme cn ca (4) dng dime
CU 10: (2,0 im)
1. (1,0 im)
a. Anion c hnh thnh bi s tch H enolic l bn v in tch c gii ta n O ca C=O qua lin kt i
C=C
C
C HO
HO C
O
H
+
-
C
C
-
O
HO C
O
C
C O
HO C
O
b. S iu 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 im)
Salixin l ng khng kh v l glucozit | do b thy phn bi 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 thc C
7
H
8
O
2
, ROH xut hin nhn thm. Tch c andehit salixylic, iu chng 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 thc cu trc ca salixin l
O HO
HO
OH
O
HOH
2
C
CH
2
OH
- - - - - - - - - - HT - - - - - - - - - - -
Th sinh lm cch khc nu ng vn cho im ti a
http://vn.myblog.yahoo.com/volcmttl K THI HC SINH GII QUC GIA LP 12 THPT
THI TH NM HC 2008 2009
MN THI: HA HC I CNG
Thi gian lm bi: 180 pht (Khng k thi gian pht )
( thi gm c 2 trang)
Cu 1: (2.0 im)
1. Ti sao ion phc spin thp [Co(NH
3
)
6
]
3+
li c mu. Gii thch da vo
1
o
22900(cm )
A = . Cho bit:
1 1
1 cm 11, 962 J.mol

= .
2. Da trn m hnh VSEPR, gii thch dng hnh hc ca NH
3
, ClF
3
, XeF
4
.
3. Qu trnh: O O 1e
+
+ c I
1
= 13,614 (eV). Da vo phng php Slater xc nh hng s chn ca cc
electron trong nguyn t i vi electron b tch. So snh bn tng i ca hai cu hnh electron ca O
v O
+
, gii thch.
Cu 2: (2.0 im)
1. Thit lp biu thc ph thuc gia th oxi ha kh vi pH ca mi trng trong 2 trng hp 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?
Bit rng:
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. Bit tch s ion ca nc K
W
= 10
-14
v
RT
2, 303 ln x 0, 0592lg x
F
=
( ti 25
o
C, 1atm)
Cu 3: (1.5 im)
Cho phn ng: A B C D + + (1) l phn ng n gin. Ti 27
o
C v 68
o
C, phng trnh (1) c hng s tc
tng ng ln lt 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 lng hot ha E
A
(theo cal/mol) v gi tr ca A trong biu thc
, ,
E
RT
k A e

= mol
-1
.l.s
-1
.
2. Ti 119
o
C, tnh gi tr ca hng s tc phn ng k
3
.
3. Nu C
oA
= C
oB
= 0,1M th t
1/2
nhit 119
o
C l bao nhiu.
Cu 4: (2.5 im)
in phn dung dch NaCl dng in cc Katode l hn hng Hg dng chy u v dng cc titan bc ruteni v
roi l Anode. Khong cch gia Anode v Katode ch vi mm
1. Vit phng trnh phn ng xy ra ti in cc khi mi bt u in phn pH = 7. Tnh cc gi tr th in
cc v th phn gii
2. Sau mt thi gian, pH tng ln n gi tr pH = 11. Gii thch ti sao. Vit cc phng trnh xy ra ti pH
. Tnh th in cc v th phn gii
3. Cho bit:
2 2
3 2
o o o
O / H O
Na / Na 2H O / H
E 2, 71V ; E 0, 00V ; E 1, 23V
+ +
= = = . Vi dung dch NaCl 25% v 0,2% Na
trong hn hng Na/Hg:
o
Na / Na(Hg)
E 1, 78V
+
=
.
2
o
Cl / Cl
E 1, 34V
= cho dung dch NaCl 25% theo khi lng

2
H
1, 3V = trn Hg ;
2
O
0, 8V = trn Ru/Rd
Cu 5: (1.5 im)
Trong cc tinh th o (cu trc lp phng tm khi) cc nguyn t cacbon c th chim cc mt ca mng c s
1. Bn knh kim loi ca st l 1,24
o
A. Tnh di cnh a ca mng c s
2. Bn knh cng ha tr ca cacbon l 0,77
o
A . Hi di cnh a s tng ln bao nhiu khi st o c cha
cacbon so vi cnh a khi st o nguyn cht
3. Tnh di cnh mng c s cho st (cu trc lp phng tm din) v tnh tng chiu di cnh
mng bit rng cc nguyn t cacbon c th chim tm ca mng c s v bn knh kim loi st l
1,26
o
A . C th kt lun g v kh nng xm nhp ca cacbon vo 2 loi tinh th st trn
Cu 6: (1.5 im)
Kt qu phn tch mt phc cht A ca Platin (II) cho bit c: 64,78 % khi lng l Pt, 23,59 % l Cl, 5,65 % l
NH
3
v 5,98 % cn li l H
2
O
1. Tm cng thc phn t ca phc cht bit rng A l phc cht 1 nhn v Pt c s phi tr l 4. Vit cng
thc cu to 2 ng phn cis v trans ca n
2. Entanpi t do chun to thnh 25
o
C ca cc ng phn cis, trans ln lt l: -396 v -402 kJ.mol
-1
. Tnh
hng s cn bng K ca phn ng sau: cis
(A)
trans
(A)
3. Tnh nng mol/lit mi ng phn trong dung dch, bit rng lc u ch c ng phn cis nng
0,01M. Cho Pt = 195 ; Cl = 35,5 ; N = 14 ; O = 16 ; H = 1
Cu 7: (2.0 im)
Nitramit c th b phn hy trong dd H
2
O theo phn ng: NO
2
NH
2
N
2
O
(k)
+ H
2
O
Cc kt qu thc nghim cho thy vn tc phn ng tnh bi biu thc:
2 2
3
[NO NH ]
v k
[H O ]
+
=
1. Trong mi trng m bc ca phn ng l bao nhiu
2. Trong cc c ch sau c ch no chp nhn 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 im)
1. C 3 nguyn t A, B v C. A tc dng vi B nhit cao sinh ra D. Cht D b thu phn mnh trong
nc to ra kh chy c v c mi trng thi. B v C tc dng vi nhau cho kh E, kh ny tan c
trong nc to dung dch lm qu tm ho . Hp cht ca A vi C c trong t nhin v thuc loi cht cng
nht. Hp cht ca 3 nguyn t A, B, C l mt mui khng mu, tan trong nc v b thu phn. Vit tn ca
A, B, C v phng trnh cc phn ng nu trn.
2. kho st s ph thuc thnh phn hi ca B theo nhit , ngi ta tin hnh th nghim sau y: Ly
3,2 gam n cht B cho vo mt bnh kn khng c khng kh, dung tch 1 lt. un nng bnh B ho hi
hon ton. Kt qu o nhit v p sut bnh c ghi li trong bng sau:
Nhit (
o
C) p sut (atm)
444,6 0,73554
450 0,88929
500 1,26772
900 4,80930
1500 14,53860
Xc nh thnh phn nh tnh hi n cht B ti cc nhit trn v gii thch.
Cu 9: (1.5 im)
C th vit cu hnh electron ca 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 dng phng php gn ng Slater, tnh nng lng electron ca Ni
2+
vi mi cch vit trn (theo n v eV).
Cch vit no ph hp vi thc t. Ti sao.
Cu 10: (2.5 im)
1. Phng th nghim c mu phng x Au
198
vi cng 4,0 mCi/1g Au. Sau 48 gi ngi ta cn mt dung
dch c phng x 0,5 mCi/1g Au. Hy tnh s gam dung mi khng phng x pha vi 1g Au c dung
dch ni trn. Bit rng Au
198
c t
1/2
= 2,7 ngy m.
2. Hy chng minh rng phn th tch b chim bi cc n v cu trc trong mng tinh th kim loi thuc cc
h lp phng n gin, lp phng tm khi, lp phng tm din tng theo t l 1 : 1,31 : 1,42.
- - - - - - - - - - HT - - - - - - - - - -
nhanh
Chm
nhanh
Chm
nhanh
HNG DN CHM MN HA HC I CNG
Cu Ni dung im
1
1 Tnh c: 437nm = . S hp th nh sng nm trong ph nhn thy nn c mu. 0,5
2
Cu to ca NH
3
cho thy quanh nguyn t N trung tm c 4 vng khng gian khu tr
electron, trong c 1 cp electron t do (AB
3
E) nn phn t NH
3
c dng thp y tam gic
vi gc lin kt nh hn
o
109 28' (cp electron t do i hi mt khong khng gian khu tr
ln hn)
N H
H
H N
H
H
H
Cu trc thp y tam gic tm l nguyn t N
Phn t ClF
3
c 5 khong khng gian khu tr electron, trong c 2 cp electron t do
(AB
3
E
2
) nn phn t c dng ch T (Cc electron t do chim 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 cp electron t do
(AB
4
E
2
) nn c dng vung phng (trong cu trc ny cc cp electron t do phn b xa
nhau nht)
Xe
F
F F
F
Xe
F F
F F
0, 25 3
= 0,75
3
- Cu hnh electron: O 1s
2
2s
2
2p
4
km bn hn O
+
1s
2
2s
2
2p
3
do lc y ln nhau ca 2
trong mt orbital ca phn lp 2p v do O
+
t cu hnh bn bo ha phn lp 2p nn
bn
- t b l hng s chn ca cc electron trong nguyn t i vi 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 iu kin v ph thuc vo pH. pH cng gim th dung dch cng c mi

trng axit th E cng tng, tnh oxi ha ca
2
2 7
Cr O

cng mnh.
- Ti pH = 0, [H
+
] = 1M th E = E
o
= 1,33V
- Ti 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 gim ngha l tnh oxi ha ca Co(OH)
3
gim, tnh kh ca Co(OH)
2
tng
0,25
0,5
0,25
2.0
3
1
- Phn ng ng hc bc hai, p dng phng 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 in phn c th c cc qu trnh sau xy 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 mi bt u
in phn, Katode qu trnh (2) s xy 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
+
= + = = + =
Bi v:
2 2
2
'
O / H O
Cl / 2Cl
E E
< nn Anode xy ra qu trnh (4) v c Cl

2
bay ra
Phng trnh in phn: 2Cl
-
+ 2H
2
O H
2
+ Cl
2
2OH
-
4.0,125
= 0,5
0,25
0,25
0,25
Th phn gii: V =
' '
A K
E E = 3,053V
0,25
2
Sau mt thi gian, do [OH
-
] tng nn pH cng tng. Khi pH = 11, phn ng in phn xy ra
nh sau:
Ti 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) xy ra
Ti 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 vn c Cl
2
bay ra
Phng trnh in phn: 2Na
+
+ 2Cl
-
+ 2Hg Cl
2
+ 2Na(Hg)
Th phn gii: V =
' '
A K
E E = 3,12V
0,25
0,25
0,25
0,25
2.5
5
1
di cnh a ca mng c s ca st o l:
o
4r 4 1, 24
a 2, 86A
3 3
= = =
0,25
2.
Khi st o c cha cacbon, tng chiu di cnh a ca mng 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 cnh a ca mng c s ca st l:
o
4r 4 1, 26
a 3, 56A
2 2
= = =
Khi st c cha cacbon, tng chiu di cnh a ca mng c s l:
o
Fe C
2 (r r ) a 2(1, 26 0, 77) 3, 56 0, 5A
A = + = + =
Kt lun: Kh nng xm nhp ca cacbon vo st o kh hn vo st , do c ha tan
ca C trong st o nh hn trong st
0,25
0,25
0,5
1.5
6
1
t CTPT ca A l: Pt
x
Cl
y
(NH
3
)
z
(H
2
O)
t
. V phc cht A l phc 1 nhn nn phn t khi ca
A:
Pt
A
M 100% 195 100
M 301(g / mol)
%Pt 64, 78

= = = . T % ca cc thnh phn 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 phn ng chuyn ha:
Cis Trans
Cn bng: 10
-2
x x
o
298K
G 402 396 6kJ A = + = = -6000J ;
6000
8,314 298
K e 11, 27
= =
0,5
3
Xt phn ng chuyn ha:
Cis Trans K = 11,27
Cn bng: 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 trng m [H
3
O]
+
= const nn biu thc tc phn ng l:
2 2
v k[NO NH ] = l phn ng bc nht theo thi gian
0,5
2
- C ch 1:
1 2 2
v k [NO NH ] = loi
- 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]
+
+
=
Vy:
2 2 3
3 2
2
[NO NH ][H O ]
v k k
[H O]
+
=
loi
- 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 ]
+
=
Vy:
2 2 2
5 4
3
[NO NH ][H O]
v k k
[H O ]
+
=
Trong mi trng dung dch nc [H
2
O] = const. Chn c ch 3
0,25
0,25
0,25
0,25
0,5
2.0
8
1
- Hp cht A
x
B
y
l mt mui. Khi b thu phn cho thot ra H
2
S.
- Hp cht A
n
C
m
l Al
2
O
3
nhm oxi
- Vy A l Al nhm, B l S lu hunh, C l O oxi
- Hp cht 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 cht
0,125.5
= 0,625
5 ptrnh
0,125.5
= 0,625
2
S mol nguyn t S trong 3,2 gam lu hunh:
S
3, 2
n 0,1mol
32
= =
Dng cng thc:
PV
n
RT
=
tnh c s mol cc phn t lu hunh trng thi hi ti cc
nhit :
* 444,6
o
C: n
1
= 0, 0125 mol gm 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 phn hi lu hunh nhit ny c th gm cc phn t lu hunh c t 1 n
8 nguyn t.
* 500
o
C: n
3
0,1
5
0, 02
=
8 nguyn t hoc ch gm cc phn t S
5
.
* 900
o
C: n
4
0,1
2
0, 05
=
8 nguyn t hoc ch gm cc phn t S
2
.
* 1500
o
C : n
5
= 0,1 mol : Hi lu hunh ch gm cc nguyn t S.
0,25
0,25
0,25
0,25
0,25
0,25
0,25
3.0
9
Nng lng ca mt electron phn lp l c s lng t chnh hiu dng n* c tnh theo
biu thc Slater:
1
= -13,6 x (Z b)
2
/n* (theo eV)
Hng s chn b v s lng t n* c tnh theo quy tc Slater. p dng cho Ni
2+
(Z=28, c
26e) ta c:
Vi cch vit 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
Vi cch vit 2 [Ar]sd
6
4s
2
:
1s
,
2s,2p
,
3s,3p
c kt 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
thp (m) hn E
2
, do cch vit 1 ng vi trng thi bn hn. Kt qu thu c ph hp
vi thc t l trng thi c bn ion Ni
2+
c cu 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 dng biu thc tc ca phn ng mt chiu bc mt cho phn ng phng x, ta
c: = 0,693/t
1/2;
Vi t
1/2
= 2,7 ngy m, = 0,257 (ngy m)
-1
.
T pt ng hc p. mt chiu bc nht, ta c: =(1/t) ln N
0
/N.
Vy: N/N
0
= e
- t
= e
-0,257 x 2
= 0,598.
Nh vy, sau 48 gi phng x ca mu ban u cn: 0,598 x 4 = 2,392 (mCi).
Do s gam dung mi tr cn dng l: (2,392 : 0,5) 1,0 = 3,784 (g)
0,25
0,25
0,25
0,25
2
Phn th tch b chim bi cc nguyn t trong mng tinh th cng chnh l phn th tch m
cc nguyn t chim trong mt t bo n v ( mng c s).
- i vi mng n gin:
+ S nguyn t trong 1 t bo: n = 8 x 1/8 = 1
+ Gi r l bn knh ca nguyn t kim loi, th tch V
1
ca 1 nguyn t kim loi:
V
1
= 4/3 x r
3
(1)
+ Gi a l cnh ca t bo, th tch ca t bo l:
V
2
= a
3
(2)
Trong t bo mng n gin, tng quan gia r v a c th hin trn hnh sau:
hay a = 2r (3).
Thay (3) vo (2) ta c: V
2
= a
3
= 8r
3
(4)
Phn th tch b chim bi cc nguyn t trong t bo l:
V
1
/V
2
= 4/3 r
3
: 8r
3
= /6 = 0,5236
i vi mng tm khi:
0,5
r
a
- - - - - - - - - - - HT - - - - - - - - - -
Th sinh c th lm cch khc, nu ng vn cho im ti 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 mng tm khi quan h gia r v a c th hin trn hnh sau:
Do : d = a 3 = 4r. ra a = 4r/ 3
Th tch ca t bo:
V
2
= a
3
= 64r
3
/ 3 3
Do phn th tch b chim bi cc nguyn t trong t bo l:
V
1
: V
2
= 8/3 r
3
: 64r
3
/3 3 = 0,68
i vi mng tm din:
+ S nguyn t trong 1 t bo: n = 8 x 1/8 + 6 x = 4. Do th tch ca cc
nguyn t trong t bo l:
V
1
= 4 x 4/3 r
3
+ Trong t bo mng tm din quan h gia bn knh nguyn t r v cnh a ca t bo
c biu din trn hnh sau:
T d ta c: d = a 2 = 4r, do a = 4r/ 2
Th tch ca t bo: V
2
= a
3
= 64r
3
/2 2
Phn th tch b cc nguyn t chim trong t bo l:
V
1
/V
2
= 16/3 r
3
: 64r
3
/ 2 2 = 0,74
Nh vy t l phn th tch b chim bi cc nguyn t trong 1 t bo ca cc mng n gin,
tm khi v tm din t l vi nhau nh 0,52 : 0,68 : 0,74 = 1 : 1,31 : 1,42.
0,5
0,5
2.5
a
d
MN THI: HA HC
Thi gian lm bi: 180 pht (Khng k thi gian pht )
( thi gm c 2 trang)
Cu 1: (2.3 dlm)
1. Cho bang sau:
nguyn t Ca Sc 1l v Cr Mn
nng luong lon ho l
2
(ev) 11,87 12,80 13,38 14,13 16,30 13,64
Py glal thlch su bln dl nng luong lon ho thu hal ca cc nguyn t trong bang.
2. vlt cng thuc Lewls v xc dlnh dang hlnh hoc ca cc phn t v lon sau: 8Cl
3
, CC
2
, nC
2
+
, nC
2
, ll
3
3. 1al sao bo trlclorua tn tal odang monome (8Cl
3
) trong khl nhm trlclorua lal tn tal odang dlme (Al
2
Cl
6
)?
Cu 2: (2.3 dlm)
Slllc c cu truc tlnh th glng klm cuong.
1. 1lnh bn klnh ca nguyn t slllc. Cho khl luong rlng ca slllc tlnh th bng 2,33g.cm
-3
, khl luong mol
nguyn t ca Sl bng 28,1g.mol
-1
.
2. So snh bn klnh nguyn t ca slllc vl cacbon (r
C
= 0,077 nm) v glal thlch.
3. vlt tt ca cc dng phn ca phuc cht [Co(blpy)
2
Cl
2
]
+
vl blpy (hlnh bn)
Cu 3: (2.3 dlm)
1. ul vl phan ung : A
k1
k2
8. Cc hng s tc d k
1
= 300 gly
-1
, k
2
= 100 gly
-1
.
C thl dlm t = 0 chl c cht A v khng c cht 8. Pol trong bao lu thl mt na luong ban du cht A bln
thnh cht 8.
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 phuong trlnh phan ng oxi hoakhvaphng trnh Nernst tng ng. C dlu kln 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: (2.3 dlm)
1. 1rong blnh chn khng dung tlch 300cm
3
chua m gam PgC rn. uun nng blnh dn 300
0
C xay ra phan ung:
2PgC
(r)
2Pg
(k)
+ C
2(k)
. p sut khl cn bng l 4 atm
a. 1lnh k
ca phan ung
b. 1lnh khl luong nho nht ca thuy ngn oxlt cn ly d tln hnh thl nghlm ny. Cho Pg = 200.
2. ut chy etan ( C
2
P
6
) thu san phm l khl CC
2
v P
2
C ( long ) o 23C.
a. vlt phuong trlnh nhlt ho hoc ca phan ung xay ra. Py xc dlnh nhlt hlnh thnh etan v nng luong
lln kt C=C. 8lt khl dt chy 1 mol etan toa ra luong nhlt l 1360,3k!. v :
AP
ht
( k!.mol
-1
) Lln kt nng luong lln kt ( k!.mol
-1
)
CC
2
-393,3 C-C 347
P
2
C (l) -283,8 P-C 413
C
2
0 P-C 464
C=C 493
b. han ung c AC = -1467,3 ( k!.mol
-1
). Py tlnh d bln thln entropl ca phan ung d cho theo don vl
!.mol
-1
.k
-1
.
N N blpy
Cu S: (2.3 dlm)
1. 1hm 1 ml dung dlch
4
NH SCN 0,10 M vo 1ml dung dlch
3
Fe
+
0,01 M v F
1M. C mu do ca phuc
2+
FeSCN hay khng? 8lt rng mu chl xut hln khl
2+
6
FeSCN
C 7.10 M
> v dung dlch duoc axlt ha d d

su tao phuc hldroxo ca le (lll) xay ra khng dng k. Cho
1 13,10
3 eF
3
10
F

= ,
1
2 3,03
eSCN
10
F
+
= ( l hng
s bn).
2. unh gl thnh phn cn bng trong hn hop 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
+ +
= = (o 23
0
C)
Cu 6: (2.3 dlm)
1. khl cho vC tc dung vl Zn trong ruou thl tch ra duoc ZnCl
2
v thu duoc pollme c chua 20,82 clo. ollme
khng chua nl dl v khng c tlnh do nhu vC. kt qua trn cho blt gl v cu tao ca pollme ml thu
duoc. 1lnh mc xlch vlnyl clorua d bl tch clo bol Zn.
2. x ll o- halogen xeton vl bazo manh tao thnh cc san phm chuyn vl. Su chuyn vl ny gol l phan ung
lavorskl. o- cloxlclohexanon s chuyn vl thnh metylxlclopentancacboxllat khl c mt CP
3
Cna trong ete.
Py xc dlnh co ch ca phan ung ny.
Cu 7: (2.0 dlm)
1. vlt so d dlu ch cc cht sau dy:
a. 1,2,3 - trlbrmbenzen tu axtllen v cc ho cht cn thlt khc.
b. Axlt m -tolulc tu benzen v cc ho cht cn thlt khc.
2. Py d nghl co ch phan ung kh nuc (P
+
) ca
a. 8utan-1-ol tao (trans)-but- 2-en
b. 3,3-dlmetylbutan-2-ol tao 2,3-dlmtylbut- 2-en
Cu 8: (3.0 dlm)
1. Axlt lumarlc v axlt malelc c cc hng s phn ll nc 1 (k
1
), nc 2 (k
2
). Py so snh cc cp hng s phn ll
tuong ung ca hal axlt ny v glal thlch.
2. So snh kha nng phan ung ca cc ancol sau vl hldrobromua P8r v glal thlch: p-CP
3
-C
6
P
4
-CP
2
CP,
p-CP
3
C-C
6
P
4
-CP
2
CP, p-Cn-C
6
P
4
-CP
2
CP v p-Cl-C
6
P
4
-CP
2
CP.
3. Cxl ho hldrocacbon thom A (C
8
P
10
) bng oxl c xuc tc coban axetat cho san phm 8. Cht 8 c th tham gla
phan ung: vl dung dlch naPCC
3
glal phng khl CC
2
, vl etanol (du) tao thnh u , dun nng 8 vl dung dlch
nP
3
tao thnh L. 1huy phn L tao thnh C, dun nng C o nhlt d khoang 160
0
C tao thnh l. Mt khc, khl
cho 8 phan ung vl khl nP
3
(du) cng tao thnh l. Py vlt cc cng thuc cu tao ca A, 8, u, C, L v l.
4. Cho so d cc phan ung sau:
HCHO H
2
O
OH
OH
-
A
B
NaCN
DMF
C
O
Cl
D1 + D2 + E (san pham phu)
Py vlt cng thuc cu tao ca A, 8, C, D1, D2 v L. 8lt L c cng thuc phn t C
19
P
22
C
3
n
2
.
.........................................................................................................Pt.........................................................................................................
O
Cl
COOCH
3
NaCl
CH
3
ONa
ete
HNG DN CHM MN HA HC
Cu 1: (2,S d|m)
1 (0,5 J|m). Cu hlnh electron ca cc nguyn t:
Ca [Ar]4s
2
, Sc [Ar]3d
1
4s
2
, 1l [Ar]3d
2
4s
2
, v [Ar]3d
3
4s
2
, Cr [Ar]3d
3
4s
1
, Mn [Ar]3d
3
4s
2
.
nng luong lon ho thu hal ung vl su tch electron ho trl thu hal. 1u Ca dn v du l su tch electron 4s thu
hal. uo su tng dn dln tlch hat nhn nn luc hut glua hat nhn v cc electron 4s tng dn, do d nng luong
lon ho l
2
cng tng du dn. ul vl Cr, do cu hlnh electron dc blt vl su chuyn 1 electron tu 4s v 3d d
sm dat duoc phn lp 3d
3
dy mt na, electron thu hal bl tch nm trong cu hlnh bn vung ny cho nn su
tch n dl hol tlu tn nhlu nng luong hon nn l
2
ca nguyn t ny cao hon nhlu so vl ca v. Cng chlnh vl
vy m khl chuyn sang Mn, 2 electron bl tch nm o phn lp 4s, gl trl l
2
ca n chl ln hon ca v vua phal,
thm chl cn nho hon gl trl tuong ung ca Cr.
2. a (0,5 J|m). Cng thuc Lewls:
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 J|m). uang hlnh hoc:
8Cl
3
: xung quanh nguyn t 8 c 3 cp electron (2 cp v 1 "slu cp") nn 8 c lal ho sp
2
, 3 nguyn t Cl lln kt
vl 8 qua 3 obltan ny, do d phn tc dang tom q|c Ju.
CC
2
: xung quanh C c 2 slu cp, C c lal ho sp, 2 nguyn t C lln kt vl C qua 2 obltan ny. hn t c Jooq
tboq.
nC
+
: lon ny dng electron vl CC
2
nn cng c Jooq tboq.
nC
2
: xung quanh n c 3 cp electron quy uc |gm 1 cp + 1 slu cp (lln kt dl) + 1 electron dc thn| nn n
c lal ho sp
2
. Pal nguyn t C lln kt vl 2 trong s 3 obltan lal ho nn phn t c cu tao Jooq cb v (boy qp
kbuc). Cc CnC < 120
o
vl su dy ca electron dc thn.
ll
3
: xung quanh l c 3 cp electron, do d l phal c lal ho sp
3
d, tao thnh 3 obltan hung dn 3 dlnh ca mt
hlnh lung chp ng glc. Pal obltan nm doc truc thng dung lln kt vl 2 nguyn t l. nguyn t l thu ba lln
kt vl 1 trong 3 obltan trong mt phng xlch dao. nhu vy phn t ll
3
c cu tao Jooq cb 1. nu k ca dn su dy
ca 2 cp electron khng lln kt, phn t c Jooq cb 1 cup.
. .
. .
. .
. . . .
. .
. .
F
F
F I
C O O
N O O
Cl
B
Cl
.
.
.
.
.
.
.
. .
.
.
.
Cl
O
N
.
.
.
.
. .
.
.
.
O
+
. . . .
. . . .
. .
. . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
. .
.
3 (0,5 J|m). 8Cl
3
: 8 c 3 electron ho trl. khl tao thnh lln kt vl 3 nguyn t Cl, o nguyn t 8 chl c 6
electron, phn t khng bn. u c bt t nguyn t 8 s dung 1 obltan p khng lal ho d tao lln kt n vl 1
trong 3 nguyn t Cl. kt qua l tao thnh phn t 8Cl
3
c dang tam glc du nhu d trlnh by o trn.
AlCl
3
: AlCl
3
cng thlu electron nhu 8Cl
3
, nhung Al khng c kha nng tao thnh lln kt n klu p
n
-p
n
nhu 8. u
c d bt t, 1 trong 4 obltan lal ho sp
3
ca nguyn t Al nhn 1 cp electron khng lln kt tu 1 nguyn t Cl o
phn t AlCl
3
bn canh. hn t AlCl
3
ny cng x su nhu vy. kt qua l tao thnh mt dlme.
Cu 2: (2,S d|m)
1 (0,5 J|m). 1rong cu truc klu klm cuong (Plnh bn)
d dl ca lln kt C-C bng 1/8 d dl dung cheo d ca t bo don vl (unltcell).
Mt khc, d a 3 = , vl a l d dl ca canh t bo.
Col p l khl luong rlng ca Sl.
1u nhung du kln ca du bl ta c:
p =
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 = 3,43.10
-8
.
d = a \ 3 = 9,40.10
-8
cm, r
Sl
= d : 8 = 1,17.10
-8
cm = 0,117nm
2 (0,5 J|m). r
Sl
= 0,117 nm > r
C
= 0,077 nm. kt qua ny hon ton phu hop vl su bln dl bn klnh nguyn t ca
cc nguyn t trong bang h thng tun hon.
3 (1J|m). Cuy uc blu dln blpy bng mt cung ll.
a (0,25 J|m). ung phn cls, trans:
b (0,75 J|m). ung phn quang hoc:
Cu 3: (2,S d|m)
1. A
k1
k2
8
t = 0 a 0
t
2
a
2
a
p dung cng thuc d cho :
e
1 2
e
x 1
k k ln
t x x
+ =
C dy nng d luc cn bng x

e
duoc xc dlnh thng qua hng s cn bng k :
| |
| |
e
e
B x
K
A a-x
= =
Sau khl bln dl ta duoc :
K 1
aK
x
e
+
= v
e
aK-x(1+K)
x x
1 K
=
+
Cul cung
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
vl
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
=
vl 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.S d|m)
1.a. 2PgC (r)

2Pg(k) + C
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 Pg nho nht khl a = 2x. 1u cng thuc
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. 1a c cc phuong trlnh:
C
2
P
6
+
2
7
C
2
2CC
2
+ 3P
2
C AP = - 1360,3 k!
( 2C
2
P
6
+ 7C
2
4CC
2
+ 6P
2
C AP = - 3121 k! )
AP
pu
= 4 AP
ht
CC
2
+ 6 AP
ht
P
2
C - 7AP
ht
C
2
- 2 AP
ht
C
2
P
6
AP
ht
C
2
P
6
=
, , , , , , | |
2
3121 8 , 285 6 5 , 393 4 +
= - 83,9 ( k!.mol
-1
)
AP
pu
= 2 L
C - C
+ 12 L
C - P
+ 7L
C=C
- 8 L
C = C
- 12 L
P - C
L
C = C
=
, , | |
8
3121 464 x 12 495 x 7 413 x 12 347 x 2 + +
= 833( k!.mol
-1
)
b. AC = AP - 1AS
=> AS =
, , | |
, , 273 25
5 , 1467 5 , 1560
+

= - 0,312 (k!.mol
-1
k
-1
) = -312 !.mol
-1
.k
-1
Cu 3: (2.3 dlm)
1. 1a c:
3
Fe
C
+
<<
F
C ( 1)
=
3
FeF
| rt ln.
vl vy trong dung dlch, le
3+
tc dung ht vl l
-
tao ra phuc
3
FeF .
3+
3
Fe 3F FeF
+
8an du 0,01 1
Sau phan ung __ 0,97 0,01
Sau khl trn vl
4
NH SCN :
3
FeF
C = 3.10
-3
M,
F
C

= 0,483M,
2
SCN
C 5.10 M

=
lel
3
le
3+
+ 3l
-
10
-13,10
le
3+
+ SCn
-
leSCn
2+
10
+3,03
lel
3
+ SCn
-
leSCn
2+
+ 3l
-
k = 10
-10,07
C 3.10
-3
3.10
-2
0,483
[ ] (3.10
-3
-x) (3.10
-2
-x) x 0,483+3x
3
10,07
3 2
x(0, 485 3x)
10
(5.10 x)(5.10 x)

+
=

vl x << 3.10
-3
ta duoc :
, ,
6 13
3
07 10 5
10 x 7 10 x 86 1
485 0
10 x 10 x 25
x

< = = ,
,
,
vy mu do ca phuc
2+
FeSCN khng xut hln, nghla l l
-
d che hon ton le
3+
2. Cc qu trlnh xay ra:
- 1ao phuc
2+
3
Ag(NH ) (
+
>
Ag
NH
C C
3
)
Ag
+
+ 2nP
3
Ag(nP
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 ) bol Cu:
2x Ag(nP
3
)
2
+
Ag
+
+ 2nP
3
1 7,24
2
10

= (1)
2Ag
+
+ Cu 2Ag + Cu
2+ 15,61
0
10 K = (2)
- 1ao phuc ca Cu
2+
vl
3
NH (
+
>
2
3 Cu
NH
C C )
Cu
2+
+ 4nP
3
Cu(nP
3
)
4
2+ 12,03
4
10 = (3)
1 hop (1)(2) v (3):
2Ag(nP
3
)
2
+
+ Cu 2Ag + Cu(nP
3
)
4
2+
,
4 0
2
2
K K | | =

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

x = 3.10
- 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 du Ag
+
tn tal dul dang phuc
3 2
Ag(NH )
+
nhung vn bl Cu kh hon ton.
Cu 6: (2.3 dlm)
1. vC clo chlm 66,8 (theo khl luong). Sau phan ung vl Zn, clo glam cn 20,82, luong clo glam nhlu m
pollme tao thnh khng chua nl dl. vy vC c cu tao du dn, cu mt nhm -CP
2
- lal dn 1 nhm -CPCl-, vl
nu c 2 nhm -CPCl- canh nhau thl tao nl dl.
han ung tch clo khol vC c th blu dln theo so d:
1rong pollme tao thnh, nu cu x mc xlch cn lal 1 nguyn t clo thl cng thuc l [-(C
2
P
3
)
x
Cl-]
n
1a c:
35, 5
27x 35, 5 +
= 0,2082 x = 3.
vy cu 3 mc xlch chl c 1 mc xlch cn clo.
Suy ra s mc xlch bl loal clo l:
4
5
.100 = 80
2. Co 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.S d|m)
1a.
b.
2. Co 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: (2.3 dlm)
1 (0,75 J|m).
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
(l) l do M c kha nng tao lln kt hldro nl phn t, lln kt C-P ca M trong qu trlnh phn ll thu
nht phn cuc hon so vl l v bazo lln hop M' cng bn hon l'.
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
l ) l do lln kt hldro nl phn t lm cho M' bn, kh nhung proton hon so vl l'. ngol ra, bazo lln
hop M'' lal kem bn hon (do nng luong tuong tc glua cc nhm -CCC
-
ln hon) bazo lln hop l''.
2 (0,75 J|m). han ung glua cc ancol d cho vl P8r l phan ung th theo co ch Sn. Clal doan trung glan tao
cacbocatlon benzyllc. nhm -CCP
3
dy electron (+C) lm bn ho cacbocatlon ny nn kha nng phan ung tng.
nhm CP
3
c (+l) nn cng lm bn ha cacbocatlon ny nhung kem hon nhm -CCP
3
vl (+C) > (+l) . Cc nhm -Cl
(-l > +C) v -Cn (-C) hut electron lm cacbocatlon tro nn kem bn do vy kha nng phan ung glam, nhm -Cn
hut electron manh hon nhm -Cl.
vy sp xp theo trt tu tng dn kha nng phan ung vl P8r l:
p-Cn-C
6
P
4
-CP
2
CP < p-Cl-C
6
P
4
-CP
2
CP < p-CP
3
-C
6
P
4
-CP
2
CP < p-CP
3
C-C
6
P
4
-CP
2
CP.
3 (0,75 J|m).
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, du)
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)
So d dlu ch p-hldroxlphenylaxetamlt
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
San
phm phu:
C
19
H
22
O
5
N
2
O
H
2
NCOCH
2
O
OH
CH
2
CONH
2
- - - - - - - - - - - HT - - - - - - - - - -
Th sinh c th lm cch khc, nu ng vn cho im ti a

Tuyển tập đề thi hsg hóa

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2010

han Cuong Puy

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

= cho dung dch NaCl 25% theo khi lng

l th iu kin v ph thuc vo pH. pH cng gim th dung dch cng c mi

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

> v dung dlch duoc axlt ha d d

C dy nng d luc cn bng x

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