MỘT SỐ ĐỀ THI CHỌN ĐỘI TUYỂN QG CÁC TỈNH MÔN HÓA

2010
TUYN TP THI HSG
MN HA HC
TUYN TP THI HSG MN HA HC
PHN 2: CC N THI HC SINH GII QUC GIA

S 1
K THI CHN HC SINH GII QUC GIA
THPT CHUYN H NI
THI TH
LP 12 THPT NM 2010
Mn: HO HC
Thi gian : 180 pht (khng k thi gian giao )
( thi gm 3 trang, c 8 cu)
Cu I: (2.0 im)
Mt terpen X thng gp trong thin nhin c tng hp theo s sau
4-metylpentan-1,4-diol --------- > dn xut dibromua -------- > bromanken j^Mkg> Grignard G ------- > X
Cho cht G phn ng vi sn phm sinh ra khi cho isopren phn ng vi but-3-en-2-on 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 C16H16O6, khi cho mt mol cht ny vo nc nng thu c 2 mol andehit levulinic
Hoc(ch2)2coch3.
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(CH3NH2)(NH3)[CH2COO]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:
K2PtCl4 KIodcu > A (dung dch nu) + CHfH 2 > B (tinh th sng) H Clv C2H jH > C (rn nu)
___ NH3/H2O ____V T tnl-1 tli \7nn l/rn nlin /"V/'A
Ag CO
2 3 du v axit malonic
> D (tinh th vng kim, phn cc) ------ 3 umaonlc > E (tinh th vng nht)
Phng php ph IR cho bit trong hp cht C c hai loi lin kt Pt -1 khc nhau v C c tm i xng. Bit MC
= 1,88Mb. 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 2PtCl4 thnh A.
3. Mc ch ca vic s dng Ag2CO3 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 TiCl4 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 Br2 to ra mt kh duy nht trong phn t c ba nguyn t
1. Vit phng trnh phn ng
2. Bit AHp < 0; Kp(25oC) = 116,6. Tnh KP 0oC, 50oC. Gi thit rng t s gia tr s cn bng gia 0oC v
25oC cng nh 25oC vi 50oC u bng 1,54
3. Xt ti 25oC, lc cn bng ha hc c thit lp th cn bng s chuyn dch th no nu
a. Tng lng NO
Copyright 2010 http://vn.myblog.yahoo.com/volcmttl
b.
Gim lng hi Br2
c. Gim nhit
d. Thm kh N2 vo khi
(1) V = const ;
(2) Pchung= const
Cu VI (4.0 im)
Guaiol (C15H26O) 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 (C15H18). 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)
_
03
- 2H20 _ Guaiol
A (C-h^C^) ^ B
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 120oC n khi lng khng i (khi lng mt i l 35,98%) ri un nng ti 650 oC. Ra b rn thu c
bng nc ta c rhodi tinh khit
1. Xc nh cng thc A, B
2. Khi mt lng d H2S 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:
CO2M6
r-0
\
Ky
1 1
100c 0s04
_ Me2C(OMe)2
''
03
- 7- - - ^ - -
cD
H ; CH 3COCH 3
CO2M6
MCPBA 1) MeOH/H E
H
2) UAIH4
3) H20
HT
Th sinh khng c s dng ti liu.

Gim th khng gii thch g thm.
- - - - - - -
* -
THPT CHUYN H NOI
K THI CHN HC SINH GII QUC GIA
P N THI TH
LP 12 THPT NM 2009 - 2010
n: HO HC
(p n thi gm 4 trang, c 8 cu)

Cu I: (2.0 im)
1. Cng thc cu to cc cht lin quan (1,75 im)
,OH
2. Cht ny l a-bisabolol thng dng trong cng nghip m phm (0,25 im)
Cu II: (2.0 im)
1. Cng thc thc nghim ca A l (C5H8)x, n l cao su t nhin. Cc cng thc thc nghim ca B v C ln lt
l (C2H3)y. B l cao su tng hp polibutadien cn C l buta-l,3-dien (1,5 im, mt im cho mi cu to).
2. Ta c:
andehit
levulinic
"dau - duoi"
0,
axetylaxeton
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-
k nh2ch3
r 'NH2CH3
CH3H2N rk .1
r 'r 'NH2CH3
,NH2CH3
k ,nh2ch3 r 'nhI
Z. chc chn thu c sn phm cui th buc B phi dng cis nn KptCl 4 phi c chuyn thnh A (0,25
im)
3. Ag2CO3 phn ng vi D theo phn ng D + Ag2CO3 = DCO3 + 2AgI sau DCO3 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 sd3 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) + Br2(hi) ^ 2NOBr(k) AH > 0
(0,25 im)
2. Do phn ng thu nhit nn c lin h K p ti 0oC < Kp (25oC) < Kp (50oC)
Vy Kp ti 0oC = 1/1,54.Kp = 116,6 / 1.54 = 75,71
Kp ti 50oC = 1,54.Kp = 116,6.1,54 = 179,56
(0,25 im)
3. Xt s chuyn di cn bng ha hc ti 25oC
Trng hp a v b v nguyn tc cn xt t s:
P
Q _ rNOBr
P2
Q
NO
Sau so snh Q vi Kp 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 Br2 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 N2 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 N2 th p = pNO + pBr2 + pNOBr
(a)
Nu c N2 th P = PnO + PBr2 + PNOBr + pN2 (b)
V P = const nn Pi = pi
Lc xt Q theo biu thc lin h trn v so snh tng quan vi Kp
- Q = Kp: khng nh hng
- Q > Kp: cn bng chuyn dch sang tri Q gim ti Kp
- Q < Kp: cn bng chuyn di sang phi Q tng ti Kp (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)
/ OH
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
S to thnh cht A c gii thch nh sau (0,5 im)
Do cng thc phn t ca A l C15H26O nn trong A s c 3 mnh

Cu VII (2.0 im)
1. Na3[RhCl6] (0,375 im) ; Na3[RhCl6].12H2O (0,375 im)
2. Rh2S3.2H2S (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 + 3C2 = 2Na3[RhCl6]
isopren (0,25 im)
Na3[RhCl6].12H2O = Na3[RhCl6] + 12H2O
2Na3[RhC6] = 2Rh + 6NaCl + 3Cl2

2Na3[RhCl6] + 3H2S = Rh2S3.3H2S + 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
HT
Th sinh c th lm cch khc, nu ng vn c im ti a
10
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THI TH
K THI CHN HC SINH GII QUC GIA 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 SO3 tan trong H2SO4 tinh khit. Trong hn hp c cc axit dng poli
sunfuric c cng thc tng qut H2SO4.nSO3 hay H2Sn+1O3n+4 ch yu cha cc axit sau: axit sunfuric H2SO4,
axit isunfuric H2S2O7, axit trisunfuric H2S3O10 v axit tetrasunfuric H2S4O13. Cho bit cng thc cu to ca
cc axit trn.
2. Gii thch ti sao SO3 li d dng phn ng vi H2O, HF, HCl, NH3 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 C-C (kim cng) l 154 pm, C-C (than ch) l 141 pm, khong cch gia cc lp than
ch l 336 pm. NA = 6,02.1023. 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:
B2H6, XeO3, NO2+, NO2-.
2. Phn ng ca NaNO3 trong nc vi hn hng Na/Hg cng ging nh phn ng ca etylnitrit C 2H5NO2 vi
hydroxylamine NH2OH 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 27oC v 68oC, phng trnh (1) c hng s tc
tng ng ln lt l kj = 1,44.107mol-1.l.s-1 v k2 = 3,03.107 mol-1.l.s-1, R = 1,987 cal/mol.K
1. Tnh nng lng hot ha EA (cal/mol) v gi tr ca A trong biu thc k = A X e Ekt mol-1.l.s-1.
2. Ti 119oC, tnh gi tr ca hng s tc phn ng k3.
3. Nu CoA = CoB = 0,1M th X 1/2 nhit 119oC l bao nhiu.
CU 4: (2,0 im)
1. Clobenzen c momen lng cc 1^4 = 1,53 D (1J4 hng t nhn ra ngoi) ; anilin c momen lng cc |J ,2 =
1,60D (|a2 hng t ngoi vo nhn benzen). Hy tnh momen lng cc |a ca cc cht sau: ortho - cloanilin ;
meta - cloanilin v para - cloanilin.
2. Tnh pH ca dung dch NH4HCO3 0,1M. Bit rng H2CO3 c hng s phn li axit K = 4,5.10 -7 ; K2 = 4,7.10 ,
NH3 c pKb = 4,76.
CU 5: (2,0 im)
C th iu ch tinh th FeCl3.6H2O 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 95oC cho n khi t trng ca n t chnh xc 1,695 g/cm3 v sau lm lnh n
4oC. 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 FeCl3.6H2O
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 FeCl3.6H2O trong khng kh n 350oC thu c 0,8977g b rn. Xc nh thnh phn nh
tnh v nh lng ca b rn.
11
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 A + N2 + H2O
C + (NH3) 2S + H2O ------ > Y + S + NH3 + KOH
B + (NH4)2S + KOH + H2O ------ > Z + S + NH3
C + H2SO4 + H2S ------ > T + S + K2SO4 + H2O
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:
a
b.
d.
C22HH5
HO.
'O"
'OH
HOCH
Talaromicin A
Brevicomin
CU 8: (2,0 im)
1. Cho bit sn phm to thnh t cc phn ng sau v gi tn sn phm :

a.
Furan + (CH3CO)2O + (C2H5)2O: BF3
b.
Thiophen + C6H5COCl + SnCl4 ---------------- > B
c.
Pyrol + C6H5N2+Cl- -------------- > C
0oC
d. Pyrol + CHCs + 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 C6H12N4. 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: C6H12N4 + 3HNO3 ^ E + 3HCHO + NH3. 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)
N^\
N-
0
N
115oC
117oC
(4)
(
N
I
H
256oC
\\
N
X
187oC
12
CU 10: (2,0 ' im)

.
.
1. Vitamin C (axit L-ascobic, pKa = 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
H
HO'
CH2OH
-C
tnh axit.
Q
b. iu ch L-ascobic t D-glucoz
2. Salixin C13H18O7 b thy phn bi elmusin cho D-glucoz v Saligenin C7H8O2.
<K
Salixin khng kh thuc th Tolen. Oxi ha Salixin bng HNO 3 thu c mt
HO OH axit L-
hp cht hu c X m khi thy phn th cho D-Glucoz v anehit Salixylic.
ascobic
Metyl ha Salixin thu c pentametylsalixin, thy phn hp cht ny cho ta
HT
13
2,3,4,6-tetra-O-metyl-D-Glucoz. Xc nh CTCT ca Salixin

Th sinh khng c s dng ti liu.
Gim th khng gii thch g thm.
14
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K ' THI CHN HC SINH GII QUC GIA LP

12 THPT NM 2010
THI TH
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
O
O
HO
xSÔH
HO
\/ HO^ Ô
OO
H2SO4
H S O
22 7
O
X XX XX
S^
O O
O O O O HO. II ^11 ^11

,OH HO. II .O. II /O^ II /O^
II /OH ^S^ S^ S^ S^
15
TUYN TP THI HSG

HA HCO
O MN O
16
H S O
2 3 10
2.
3.
H2S4O13
(0,5 im) Gii thch ng + vit ng 4 phng trnh v cu trc

Gii thch: Phn t SO3 dng tam gic phng vi nguyn t S trng thi lai ha sp 3, d dng phn ng
chuyn sang thng thi lai ha sp3 bn, l trng thi c trng ca lu hunh
Phng trnh phn ng: SO3 + H2O --------- > H2SO4 SO3 + HF ---------> H[SO3F] SO3 + HCl -------- > H[SO3Cl]
SO3 + NH3 ------- > H[SO3NH2]
Cu trc cc sn phm
OH
OH
OÎIÔH O^||XF
S.
O
Ss O
OH
O^||XCl
SN O
OH
O^||XNH2
Ss O
(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: 8 X + 6 X + 4 = 8

82
Do vy suy ra cacbon than ch trong mt mng tinh th c 2 nguyn t cacbon

Trong mng tinh th kim cng:
4d
di cnh mng tinh th: a = = (d = C-C (kim cng)) => Th tch mng = a3 =
-\/3
(4d ^3
Khi lng ring ca tinh th kim cng:

D=
3
8XM
8 X12
= 3,545 (g/cm3)
NA X V
6,02X1023 X(4X154X10^10
Vs
M
=>
Th tch mol ca kim cng = =3,385 (cm /mol)
17
Tng t trong mng tinh th than ch

Din tch mt y = 3 V3 X d2 (d = C-C (than ch))
,
3 2
Th tch mng = v3 X d X h(h l khong cch gia cc lp)
=> Khi lng ring D = 2,297 (g/cm3) v th tch mol = 5,224 (cm3/mol)
CU 2: (2.0 im)
1. (1,0 im) Mi cng thc ng c 0,25 im
-
B2H6: B lai ha sp3, 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
-
XeO3: Xe lai ha sp3, phn t dng thp y tam gic
NO2+: N lai ha sp, cu trc on thng
NO2-: N lai hoa sp2, cu trc gp khc (ch V)
Cng thc Lewis
N=O
O=
2.
:N-
(1,0 im)
OO
Cc phn ng (mi phn ng 0,25 im)

2NaNO3 + 8Na(Hg) + 4H2O --------------- > Na2N2O2 + 8NaOH + 8Hg
NH2OH + C2H5NO2 + 2C2H5ON ----------------- > Na2N2O2 + 3C2H5OH
Na2N2O2 l mui ca axit hyponitr H2N2O2 (2.0,125 = 0,25)
HO
HO.
OH
N=N
Cu trc ng phn: H2N - NO2 (nitramit) (0,25)
H
O
N ------ N
H
CU 3: (2.0 im)
1. (1,0 im)
Phn ng ng hc bc hai, p dng phng trnh Archnius ta c:

-E
-E
lnk, =-=A- + ln A 1 RT
lnk, = -=^ + ln A 2 RT,
-E
-E
^ ink, - ink, = -=A + ln A-^=A + lnA
RT,
RT
Ea
11
^ ln^2 =
k, R
TT
V 11 2 y
T_ X T ..
k,
1T
X ln 3688,2 (cal/mol)
T2 - Ti ki
'
XO
N=N
OH
18
2.
k = A X e( ERt^ ^ A = ( k - = k' = 7 X109 (mol 1.l.s 1)

v
e(-E/W e(-Er)
(0,5 im)
'
k3 = A X e( = 6,15 X107 (mol-1.l.s-1)

3.
(0,5 im)
1
= 1,63 X10 (s)

k C
3- oA
CU 4: (2,0 im)
1.
(1,0 im)
Clo c m in ln, 1^4 hng t nhn ra ngoi - nhm NH2 c cp e t do lin hp vi h e % ca vng benzen ^
hai momen lng cc cng chiu
X
1/2 _
ortho
Cng vect s dng h thc lng
meta
trong tam gic a2 =
b2 + c2 - 2bc cos A Dn xut ortho: |aO = M-1 + M-2 - 2^41^ cos 600 = ^2 + |a2
- M'1^2 = 2,45 |a0 = V 2,45 = 1,65D Dn xut meta: |a2 = ^2 + |a2 -2p,1^2cos
120 = ^2 + |a2 + ^1M'2 = 7,35 |am= -7735 = 2,71D Dn xut para: |a2 = 1^4 +
|J,2 = 1,60 + 1,53 = 3,13D
2.
(1,0 im)
Ta c cc qu trnh sau:
NH4HCO3 ---------> NH+ + HCO3 NH+ NH3 + H + ;Ka HCO3 + H+ <
---------------------- H2CO3;K-1 HCO3 <=
IH ++ CO2;K2
H2O < ----- > H+ + OH-;KW = 10-14 10-14
Trong : Ka = = 10-9'24
a
Kb
p dng iu kin proton ta c:

[H+ ] = [NH3] + [CO2-] + [OH] - [H2CO3] ^ [H+ ] = 3 + K2.[HCO3] +
^T-K-1.[H+ ].[HCO3] [H + ] [H + ] [H+ ] 1
^ [H+ ]2 =
Ka.[NH+ ] + K2.[HCO-] + Kw -K-1.[H + ]2.[HC3] ^ [H+ ]2 + K-1.[H

+ ]2.[HCO3] = Ka.[NH+ ] + K2.[HC3] + Kw
19
^ [H+ ]2 (1 + K-".[HCO-]) = Ka.[NH+] + K2.[HCo + K ^ [H + ]2 =

Ka.[NH+ ] + K2.[HCO3] + Kw [ ]
1 + K 1.[HCO;]
Ka.[NH+ ] + K2.[HCO3] + K
1 + K-1.[HCO3]
Thay cc gi tr gn ng: [NH+ ] = [HCO- ] = 0,1M ^ [H+ ] = 1,6737.108
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 --------> FeCl2 + H2
2FeCl2 + Cl2 ------- > 2FeCl3
3FeCl2 + 2K3[Fe(CN)6] ------- > Fe3[Fe(CN)6]2 + 6KCl

FeCl3 + 6H2O ------- > FeCl3.6H2O
2.
1000
= 3,7mol FeCl3.6H2O 270,3
32
Nh vy cn ------ ---- 978 mL dung dch HCl 36% (0,5 im)

0,36.1,18.0,65
3.
Khi un nng th FeCl3.6H2O phn hu theo phng trnh sau:

FeCl3.6H2O ------- > FeOCl + 5H2O + 6HCl
Khi nhit tng th FeOCl s tip tc phn hu:
3FeOCl ------ > FeCl3 + Fe2O3 (Hi FeCl3 bay ra)
2,752
Lng FeCl3.6H2O trong mu l 3- = 10,18 mmol g 3 2 g
270,3
iu ny ng vi khi lng FeCl3 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 Fe2O3.
1,902 - 0,8977
,
,
Khi lng FeCl3 mt mt do bay hi l: -------------- ------- = 1,20mmol => B rn cui cng cha (0,01018 162,2
3.0,
00120) = 6,58 mmol FeOCl v 1,20 mmol Fe2O3. (1,0 im)
CU 6: (2,0 im)
1.
(1,0 im) mi phng trnh ng c 0,25 _ A l Cr 2O3, B l
K2CrO4, C l K2Cr2O7
Cc phng trnh phn ng:
2Cr2O3 + 3O2 + 8KOH ------- > 4 K2CrO4 + 4H2O
2K2CrO4 + H2SO4 -------- > K2Cr2O7 + K2SO4 + H2O
S + K2Cr2O7 ------ ^ Cr2O3 + K2SO4
2.
-
14HCl + K2&2O7 --------> 3Cl2 + 2CrCl3 + 2KCl + 7H2O

(1,0 im) mi phng trnh ng c 0,25
X l (NH4)2Cr2O7, Y l Cr(OH)3, Z l K3[Cr(OH)a], T l Cr2(SO4)3
Cc phng trnh phn ng:
(NH4)2Cr2O7 -> Cr2O3 + N2 + 4H2O
K2Cr2O7+ 3(NH3)2S + H2O ------ > 2Cr(OH)3 + 5S + 6NH3 + 2KOH
20
2K2&O4 + 3(NH4)2S + 2KOH + 2H2O ---------------- > 2K3[Cr(OH)6] + 3S + 6NH3
K2Cr2O7 + 4H2SO4 + 3H2S --------------- > Cr2(SO4)3 + 3S + K2SO4 + 7H2O

CU 7: (2,0 im)
1. (1,0 im) Cc cu trc
H
O'"H O
EtO^^CÔEt
H
_ \_ OO
OO
E,ÔEt
EtO
OEt
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
/H
OO
H2C^^^ÔEt
\_
H
OO
CH3COCH2COOEt
H3C C 3H
OEt
B
O''1"1 O
XX
H3C C OEt 3H
C
a.
CH2OH-CH2CH2CH2=CHO 5-hidroxipentanal
b.
CHOCH2CH2CHOHCH=CH-CH=CH2 4-hidroxiocta-5,7-
c.
CH3CH2CHOHCHOH(CH2)3COCH3
dienal
6.7d.
dihidroxinonan-2-on
(HOCH2)2CH-CHOHCH2CO(CH2)2CH(C2H5)CH2OH
2.8-
di(hidroxometyl)-1,3-dihidroxidacan-5-on
CU 8: (2,0 im)
COCH 3
O
2-acetylfuran 2. (1,0
COCRH
6H5
N=NC6H6H5
'N-H
NH
2 - (phenylazo) pyrol
2 -benzoylthiophen
CHO
2-pyrolcacboxandehit
im)
O
11
C^
CN
HsO+>
COOH 6H
-NH3
NO2
-H2O
2
21
O
\
COOH
O
-H2O
'NH2
^/-^NH
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
CH3CHO + NH3 ------- > Axetandehit-amoniac (tnc = 97oC) A
,OH
CH3 ------ CH
'NH2
Axetandehit-amoniac d b tch nc thnh B l CH3-CH=NH v B d trime ha thnh hp cht d vng C loi
triazin
HsC^ NH /CH3
OH
-H?O
^-ch3ch=nh
CH3 ------- CH
'NH 2
trime ha -
NH NH
CH3 C
- Mt khc nu cho amoniac ngng t vi fomanehit s thu c sn phm D (urotropin) c CTPT l C6HN4
6HCHO + 4NH3 ------------ > C6HN4 + 6H2O
^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:
NO2
C6H12N4 + 3HNO
rS
+ 3HCHO + NH:
/N. /N^
_ 2.N^
O
N^ no
2
ON
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
22
O
II
HOCC* II
HOC
b.
S iu ch
NaBH4
D-Glucose
Ov
l-'
HOC-T-C-
C
-O-C?-
-H+
HOC=C- 1
0=C
[O]
D-Socbitol (A) --------- L-Socbose (B)-
, 2CH3COCH3>
endiol B
enzym
1. KMnO4/OH
Diaxetonua (C)
(D)
2. dd H+
>- axit L-ascobic

t
H+
Trong :
C
H2OH
HO
HO
HO
CH2OH 1
HOC
Iu
HOC
CH2OH
12
H
H
C
H =
o
H
HO
HO
OH
H
HO
HO
OH
H
HO
HO
OH
HO
H
CH2OH
CH2OH
CH2OH
B'
CH O
\/ -C
C
CH/ V
C
-O. CH3
-H \
C
/ XCH3
-O, C 3
-H C\
CH/ V H
HO
HO
1 CH3
CH2-O
CH2-O
D
C
2.
COOH
CH2OH 1
2
C 11 C
CH^ O-
OH
(1,0 im)
Salixin l ng khng kh v l p glucozit do b thy phn bi elmuxin
D-Glucose + ROH (Saligenin)

C7H8O2
O
H2O
enzim
23
CH2OH
Salixin
24
Trong cng thc C7H8O2, ROH xut hin nhn thm. Tch c andehit
salixylic, iu chng t qu trnh oxi
HO CHO
7H8O2
ha nhm -CH2OH thnh nhm -CHO
HO
D-Glucose +
HOH2C
h2o, h+
HHVÂ r
Saligenin l o-(hidroximetyl)phenol. Cng thc cu trc ca salixin l

HOH2C
HO^*Hr
HH2C
HT
Th sinh lm cch khc nu ng vn cho im ti a
25
K Thi hc sinh gii quc gia lp 1Z tHpT

NM HC ZOOS - Z009
http://vn.mvblog.vahoo.com/volcmttl "
THI TH
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(NH3)6]3+ li c mu. Gii thch da vo A = 22900(cm-1). Cho bit:
1 cm-1 = 11,962 J.mol-1.
Z. Da trn m hnh VSEPR, gii thch dng hnh hc ca NH3, ClF3, XeF4.
S. Qu trnh: 0 ^ 0+ + 1e c I1 = 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 0+, gii thch.
Cu Z: (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. Cr202-+ 14H ++ 6e ^ 2Cr3++ 7H20 ; EC 02-/2c3+ =+1,33V. pH = 7, Cr207- c oxi ha c I - khng?
Bitrng: E/2r = 0,6197V;Co(0H)3 + 1e^Co(0H)2 + OH- ; ECo(0H)3/Co(0H)2 =+0,17V S. Bit tch s
ion ca nc Kw = 10-14 v 2 303RTlnx = 0 0592lgx ( ti 25oC, 1atm)
Cu S: (1.5 im)
Cho phn ng: A + B ^ C + D (1) l phn ng n gin. Ti 27 oC v 68oC, phng trnh (1) c hng s tc tng ng ln
lt l k1 = 1,44.107 mol-1.l.s-1 v k2 = 3,03.107 mol-1.l.s-1, R = 1,987 cal/mol.K
1. Tnh nng lng hot ha EA (theo cal/mol) v gi tr ca A trong biu thc k = A X e(RE) mol-1.l.s-1.
2. Ti 119oC, tnh gi tr ca hng s tc phn ng k3.
S. Nu CoA = CoB = 0,1M th X 1/2 nhit 119oC 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
S. Cho bit: Eo =-2,71V ; Eo = 0,00V ; Eo n = 1,23V . Vi dung dch NaCl 25% v 0,2% Na
Na+ /Na
0 /H 0
2H 3 0+ /H 2
trong hn hng Na/Hg: E
=-1 78V. E /c - = 1,34V cho dung dch NaCl 25% theo khi lng
% = 1,3V trn Hg ; ^0 = 0,8V trn Ru/Rd

Cu 5: (1.5 im)
Trong cc tinh th a (cu trc lp phng tm khi) cc nguyn t cacbon c th chim cc mt ca mng c s
o
1. Bn knh kim loi ca st l 1,24 A . Tnh di cnh a ca mng c s
o
2. Bn knh cng ha tr ca cacbon l 0,77 A . Hi di cnh a s tng ln bao nhiu khi st a c cha cacbon so vi
cnh a khi st a nguyn cht
S. Tnh di cnh mng c s cho st y (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 y l
o
1,26 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 H2O
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
26
to 2 ng phn cis v trans ca n

2. Entanpi t do chun to thnh 25oC 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 H2O theo phn ng: NO2NH2 ^ N2O(k) + H2O Cc kt qu thc nghim cho thy vn
tc phn ng tnh bi biu thc: v = k [NO2NH2]
[H
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: NO2NH2 ^N2O(k) + H2O
b. C ch 2:
3 ]
NO2NH2 + H3O+ NO2NH+ + H2O Nhanh NO2NH+

c.
Chm
N2O + H3O+
C ch 3:
NO2NH2 + H2O ^ NO2NH- + H3O+ Nhanh NO2NH-

N2O + OH-
Chm
H3O+ + OH- 2H2O
Nhanh
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 (oC)
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 Ni2+ l:
Cch 1: Ni2+[1s22s22p63s23p63d8]
Cch 2: Ni2+Us^s^p^s^p^d^s2].
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 Au198 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 Au198 c t1/2 = 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 -------------- - - -
27
http://vn.mvblog.vahoo.com/volcmttl
K THI HC' SINH GII QUC GIA LP 12 THPT NM HC 2008 -
THI TH
2009
HNG DN CHM MN HA HC I CNG

Cu
1
Ni dung
im
1 c: X = 437nm. S hp th nh sng nm trong ph nhn thy nn c mu.

Tnh
2
0,5
Cu to ca NH3 cho thy quanh nguyn t N trung tm c 4 vng khng gian khu tr electron, trong c 1 cp
0,25 X 3
electron t do (AB3E) nn phn t NH3 c dng thp y tam gic
= 0,75
vi gc lin kt nh hn 109o28' (cp electron t do i hi mt khong khng gian khu tr ln hn)

H-N-H 9..,
1/VH
HHV
H
H Cu trc thp y tam gic tm l nguyn t N
Phn t ClF3 c 5 khong khng gian khu tr electron, trong c 2 cp electron t do (AB3E2) nn phn t c dng
ch T (Cc electron t do chim v tr xch o)
F
FCl-F F C,^
C C'^
FF
Phn t XeF4 c 6 vng khng gian khu tr electron, trong c hai cp electron t do (AB4E2) nn c dng vung
phng (trong cu trc ny cc cp electron t do phn b xa nhau nht)
F
^.. /F F............................................... ,,,,F
Xe' .............................................. Xer
FF
-3 Cu hnh electron: O 1s22s22p4 km bn hn O+ 1s22s22p3 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:
Z*2
I1 = 13,6^ = 13,614 ^ Z*2 = n2 = 4 ^ (8-b)2 = 4 ^ b = 6 n
0,25
0,5
2.0
2
E1
| 0,0592 lg[
Cr O2 H+ 14
3+
0,5
][ ]
Cr2O2 /2Cr ^C^ /2Cr + ^ 6
lg
[c 3 ]
+
[ C r ]
=E^,,C,+Tlg [ H+]"+Tlg [ COj
= Ect;Oj- C,* 0,138pH + 0,06592lg ^y1

t: E
Cr2O2 /2Cr3+ = EC,Or /2Cr=+ 0,138pH

^ E' l th iu kin v ph thuc vo pH. pH cng gim th dung dch cng c mi
Cr2O2 /2Cr3+
trng axit th E cng tng, tnh oxi ha ca Cr2O2 cng mnh.
Ti pH = 0, [H+] = 1M th E = Eo = 1,33V
Ti pH = 7 th E = 0,364 < Eo = 0 6197V nn khng oxi ha c I-
0,25
28
29
0,25
2
0 0592 lg
Co(OH)3/Co(OH)2 Co(OH)3/Co(OH)2 + ,
[OH_
j'
Thay[OH
] [H+ ] ta c
0,25
Co(OH)3/Co(OH)2 _ ECo(OH)3/Co(OH)2 + 0,0592lg K

= E0Co(OH)3/Co(OH)2 + 0,0592lg[H+]-0,0592lgKw . Thay ECo(OH)3/Co4H)2 = +0,17 _C( ( )2 " " .. Kw=10-14
= ECo(OH)3/Co(OH)2 - 0, 0592pH - 0, 0592 lg Kw ^ ECo(OH)3/Co(OH)2 = 0, 996 - 0, 0592pH
pH cng tng th E cng gim ngha l tnh oxi ha ca Co(OH)3 gim, tnh kh ca Co(OH)2 tng
0,5
0,25
2.0
Phn ng ng hc bc hai, p dng phng

trnh Archnius
ta c:
A
A
1
2
-E -E lnk = + lnA ; lnk2 = + lnA RT1 RT2
-E -E
0,5
^ lnk2 lnk = A + lnA A + lnA 2 1 RT2 RT1
0,25
1 2 Ea f 1 1
^ ln = _ ; --------
k R
1 ^ T1 T2 J
0,25
^ Ea = RT2 x T' X lnk2 * 3688,2(cal/ mol)

T -T
2 1 1
k=AXÂ=
,kE) k
- = 7 X 109(mor'.l.s-1)
elRT e,RT|)
k3 = Ax JRT3^ = 6,15 xio7 (morM.s-1)
1 / 2
0,25
= = 1,63x10-7(s)
0,25
3.CoA
1.5
Trong dung dch NaCl c: NaCl ^ Na++Cl' ; 2H2O ^ H3O + + Khi in phn c
OH"
4.0,125
= 0,5
th c cc qu trnh sau xy ra:

X1 (1)
Catode: Na+ + Hg + e ^ Na(Hg)
2H2O ^ H3O+ + OH"
XI
2 H3O+ + 2e ^ H2 + 2H2O
0,25
2H2O + 2e ^ H2+ OH (2)
Anode: 6 H2O ^ O2 + 4H3O+ + 4e (3)

2 Cl- ^ CI2 + 2e (4)
E
Na+
0,25
/N(Hg) = -1,78V E2H3O+ /H. = 0,00V + 0,0592lg10-7 = -0,413V

E
-1 713 Do
2H3O^/H2 = V /H2 + %2 = ,
E'2H3O+ /Hz > E0Na+ /Na(Hg)
nn khi mi bt u
0,25
in phn, Katode qu trnh (2) s xy ra, c H2 thot Anode Anode: T (3) ta c:
E
O2/H2O = EO2/h2o + 0,0592lg[H3O ] = 0,817V ; EO2/H2O = EO2/H2O +%2 = 1,617V Bi v: ECl /2Cl- < EO /H O nn Anode xy ra
qu trnh (4) v c Cl2 bay ra Phng trnh in phn: 2Cl" + 2H2O ^ H2 + Cl2 2OH"
30
Th phn gii: V = EA - EK = 3,053V

2
0,25
Sau mt thi gian, do [OH ] tng nn pH cng tng. Khi pH = 11, phn ng in phn xy ra nh sau:
E
+ =10'". E2H30-/H2 = -0,649V ; e2H30+ /H2 = -1,949V> Na+ /Nann Anode c qu trnh (1) xy ra
T i Catode: [H ]
Anode: E02/H2O = EO2/H2O + 0,0592lg[^0+ ] = 0,581V ; E02/H2O = 1.381V Do EC1 /2cr < E0 /H 0 nn Anode
0,25
0,25
vn c Cl2 bay ra Phng trnh in phn: 2Na+ + 2Cl + 2Hg ^ Cl2 + 2Na(Hg)
0,25
Th phn gii: V = EA - EK = 3,12V
0,25
2.5
1
2.
^ ^ ' 4r 4X1 24 o
di canh a ca mang c s ca st a l: a = = = 2 86 A ' V a/3
Khi st a c cha cacbon, tng chiu di cnh a ca mng c s l: A = 2 X (rFc_a + rc) - a = 2(1,24 + 0,77) -
0,25
0,25
2,86 = 1.16
5
r Ar 4x1 26 0 di canh a ca mang c s ca st Y l: a = = = 3 56A
' - Tz
0,25
Khi st Y c cha cacbon, tng chiu di cnh a ca mng c s l:

A =
(r Fe - Y + r C )
2(1,26
0,77)
3,56
0,5 A
0,25
Kt lun: Kh nng xm nhp ca cacbon vo st a kh hn vo st Y, do c ha tan ca C trong st a nh hn

0,5
trong st Y
1.5
1
t CTPT ca A l: PtxCly(NH3)z(H2O)t. V phc cht A l phc 1 nhn nn phn t khi ca
0,25
A A/T MPt X100% 195 X100 ( , *

A: MA = P -------------- = -------- = 301(g/ mol) . T % ca cc thnh phn c trong A
A
%Pt 64,78 s
^ x = 1, y = 2, z = 1, t = 1 ^ CTPT l: PtCl2(NHs)(H2O)
CTCT 2 ng phn cis, trans:
0,125.2
= 0,25
Cis Trans
2
Xt phn ng chuyn ha:
0,5
Cis ^ Trans Cn bng: 10-2 - x x

AG298K =402 + 396 = 6kJ = -6000J ; K = e8 314x298 = 1 1, 27
Xt phn ng chuyn ha:
0,25.2 =
Cis ^ Trans K = 11,27 Cn bng: 10-2 - x x

K=
[trans]
- x = 11,27 ^ x = [trans] = 9,2 X10

[cis] 10 x
^ [cis] = 8 X10
0,5
4
31
1.5
+
Do trong mi trng m [H3O] = const nn biu thc tc phn ng l: v = k[NO2NH2] l phn ng bc nht
1
0,5
theo thi gian

C ch 1: v = kj[NO2NH2] ^ loi C ch 2:
0,25
0,25
v = k3[NO2NH+] V3L1NW21>IAA3 J
+
+1 = ,_ [NO2NH2][H3O ]
M: [NO2NH+] = k2
[H2O]
0,25
Vy: v = k3k2[NO2NTH2][H3O+] ^ loi 3 2 [H2O]
7
2
C ch 3: v = k5[NO2NH]
0,25
[NO2NH2][H2O]
M: [NO2NH ] = k
[H3O ]
[NO2NH2][H2O]
V :
y v = k 5k 4
0,5
[H3O+]
Trong mi trng dung dch nc [H2O] = const. Chn c ch 3
2.0
Hp cht
thu
phn cho thot ra H2S.
Hp
cht A
AxxBByy llmt
mtmui.
mui.Khi
Khibb
Hp
cht AnCm l Al2O3 nhm oxi Vy A l Al
0,125.5
nhm, B l S lu hu
Hp cht AoBpCq l Al2(SO4)3
= 0,625
nhm sunfat
cht
2 Al
Al2S3
+
+
3S
6 H2O
Al2S3
2 Al(OH)3
4 Al
3 O2
2 Al2O3
0,125.5
SO2
= 0,625
Al
3+
2 H2O
+ 3 H2S
Al(OH) +
5 ptrnh
+ H3O+
0,25
S mol nguyn t S trong 3,2 gam lu hunh: nS = ^- = 0,1mol

32
PV
Dng cng thc: n = tnh c s mol cc phn t lu hunh trng thi hi ti cc RT
0,25
nhit :
8
* 444,6oC: n1 = 0, 0125 mol gm cc phn t S8 v 0, 0125 X 8 = 0,1 mol

0,1
o
450 C: n2 = 0,015 mol, s nguyn t S trung bnh trong 1 phn t:
6,67
0,25
0,25
0,015
^ Thnh phn hi lu hunh nhit ny c th gm cc phn t lu hunh c t 1 n 8 nguyn t.
2
500oC: n3 = 0,02 mol, s nguyn t S trung bnh trong 1 phn t:
0,1
0,02
=5
0,25
^ Thnh phn hi lu hunh nhit ny c th gm cc phn t lu hunh c t 1 n 8 nguyn t hoc ch

gm cc phn t S5.
* 900oC: n4 = 0,05 mol, s nguyn t S trung bnh trong 1 phn t:
0,1
0,05
=2
0,25
^ Thnh phn hi lu hunh nhit ny c th gm cc phn t lu hunh c t 1 n 8 nguyn t hoc ch

gm cc phn t S2.
* 1500oC : n5 = 0,1 mol : Hi lu hunh ch gm cc nguyn t S.
0,25
32
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:
S1 = -13,6 x (Z - b)2/n* (theo eV)
0,25
Hng s chn b v s lng t n* c tnh theo quy tc Slater. p dng cho Ni2+ (Z=28, c 26e) ta c:
Vi cch vit 1 [Ar]3d8:
1s = -13,6 x (28 - 0,3)2/12 = -10435,1 eV 2s,2p = -13,6 x (28 - 0,85x2 - 0,35x7)2/ 22 = - 1934,0 eV ^ 3s,3p = -13,6
2
x (28 - 1x2 - 0,85x8 - 0,35x7) /3 = - 424,0 eV 3d = - 13,6 x (28 - 1x18 - 0,35x - 0,35x7) /3 = - 86,1 eV
E
1 = 21s + 8 2s,2p + 8 3s,3p + 8 3d = - 40423,2 eV
0.125.5 =
0,625
Vi cch vit 2 [Ar]sd64s2:
is, 2s 2p, 3s 3p c kt qu nh trn . Ngoi ra:

3d = -13,6 x (28 - 1x18 - 0,35x5)2/32 = - 102,9 eV 4s =- 13,6 x (28 - 1x10 - 0,85x14 - 0,35)2/3,72 = - 32,8 eV Do
E2 = - 40417,2 eV.
E1 thp (m) hn E2, do cch vit 1 ng vi trng thi bn hn. Kt qu thu c ph hp vi thc t l trng
2
0,125.3 =
0,375
thi c bn ion Ni + c cu hnh electron [Ar]3d .
0,25
1.5
10
- t = 48 h = 2 ngy m.
0,25
- p dng biu thc tc ca phn ng mt chiu bc mt cho phn ng phng x, ta c: A = 0,693/t1/2- Vi t1/2 =
2,7 ngy m, = 0,257 (ngy m)-1.
0,25
T pt ng hc p. mt chiu bc nht, ta c: =(1/t) ln N0/N.
0,25
Vy N/N0 = e t = e'0257 x 2 = 0,5 98.

Nh vy, sau 48 gi phng x ca mu ban u cn: 0,598 x 4 = 2,392 (mCi).
0,25
Do s gam dung mi tr cn dng l: (2,392 : 0,5) - 1,0 = 3,784 (g)

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 V1 ca 1 nguyn t kim loi:
V1 = 4/3 x^r3 (1)
+ Gi a l cnh ca t bo, th tch ca t bo l:
V2 = a3 (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: V2 = a3 = 8r3 (4)

Phn th tch b chim bi cc nguyn t trong t bo l:
V1/V2 = 4/3 ^r3: 8r3 = n/6 = 0,5236
i vi mng tm khi:
0,5
33
+ S nguyn t trong t bao: n - 8 X 1/8 + - 2. Do V~1 = 2x(4/3) n ? . + Trong t bo mng tm khi

quan h gia r v a c th hin trn hnh sau:
Do : d = aV3 = 4r. ^ ra a = 4r/V3 Th tch ca t bo:

V2 = a3 = 64r3/ 3 V Do phn th tch b chim bi cc nguyn t trong t bo l:
Vi : V2 = 8/3 nr3 : 64r3/3V = 0,68 i vi mng tm din:
0,5 l:
+ S nguyn t trong 1 t bo: n = s x 1/8 + x */2 = 4. Do th tch ca cc nguyn t trong t bo
Vi = 4 x 4/3 n r3
+ 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:
Th tch ca t bo
d = a V2 = 4r, do a = 4r/ V2 V2 = a3
ih tch ca t bo: V2 = a =
b4r/2V2 Phn th tch b cc nguyn t chim trong
= 64r3/2 V2
t bo l:
V1/V2 = 16/3 nr3: 64r3/ 2 V2 = 0,74 Nh vy t l phn th tch b chim bi cc nguyn t trong
0,5 1,42.
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 :
2.5
------------------ HT ------------- : - - Th sinh c th lm cch khc, nu ng vn cho im ti a
34
http://vn.mvblog.vahoo.com/volcmttl
K THI HC SINH GII QUC GIA LP 12 THPT NM

HC 2008 - 2009
MN THI: HA HC
Thi gian lm bi: 180 pht (Khng k thi gian pht ) ( thi gm c 2 trang)
Cu 1: (2.5 im) 1. Cho bng sau:
THI TH
Nguyn t
Nng lng ion ho I2 (eV)
Ca
Sc
Ti
Cr
Mn
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: BCl3, CO2, NO2+, NO2, IF3
3. Ti sao bo triclorua tn tidng monome (BCl3) trong khi nhm triclorua li tn tidng ime (Al 2Cl6)?
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 (rC = 0,077 nm) v gii thch.
\rf -----bipy
+
3. Vit tt c cc ng phn ca phc cht [Co(bipy)2Cl2] vi bipy (hnh bn)
Cu 3: (2.5 im)
1. i vi phn ng : A > 1(1 > B. Cc hng s tc k1 = 300 giy-1; k2 = 100 giy-1.
k2
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 cp oxi hoa kh : Cu2+/ Cu+ E = 0,15 V ; I2/ 2I- E = 0,62V
a. Vit cc phng trnh phan ng oxi ho kh v phng trnh Nernst tng ng. iu kin chun co th xay
ra s oxi ho I- bang ion Cu2+ ?
b. Khi dung dich KI vo dung dich Cu2+thy co phan ng: Cu2+ + 2I- ^ CuI ^ + 1I2
2
Hay xc nh hang s" cn bng ca phan ng trn . Bit tch s" tan T cua CuI l 10 Cu
4: (2.5 im)
1. Trong bnh chn khng dung tch 500cm3 cha m gam HgO rn. un nng bnh n 5000C xy ra phn ng:
2HgO(r) ^ 2Hg(k) + O2(k).p sut khi cn bng l 4 atm
a. Tnh KP 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 ( C2H6) thu sn phm l kh CO2 v H2O ( 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 :
-12
AHht ( KJ.mol-1)
Lin kt
Nng lng lin kt ( KJ.mol-1)
CO2
-393,5
C-C
347
H2O(l)
-285,8
H-C
413
H-O
464
O=O
495
O2
b.
Phn ng c AG = -1467,5 ( KJ.mol-1). Hy tnh bin thin entropi ca phn ng cho theo n v
J.mol-1.K-1.
35
Cu 5: (2.5 im)
1. Thm 1 ml dung dch NH4SCN 0,10 M vo lml dung dch Fe3+ 0,01 M v F_ 1M. C mu ca phc FeSCN2+
hay khng? Bit rng mu ch xut hin khi C SCN2+ > 1 .10 6M v dung dch c axit ha
s to phc hidroxo ca Fe (III) xy ra khng ng k. Cho3 1FeF = 10 13,10 ; iFSCN2+ = 10303 ( l hng s bn).
2. nh gi thnh phn cn bng trong hn hp gm Ag+ 1,0.10 -3 M; NH3 1,0 M v Cu bt. Cho
2 += 101,24 ; 4Cu(NH)4+= 1012,03 ; E0 + = 0,199V;E0 2+ = 0,331V (250C)
2
4Cu(NH )4
Ag(NH3 )+
3
Ag+ /Ag
Cu2+ /Cu
'
'
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 a - halogen xeton vi baz mnh to thnh cc sn phm chuyn v. S chuyn v ny gi l phn ng
Favorski. a - cloxiclohexanon s chuyn v thnh metylxiclopentancacboxilat khi c mt CH 3ONa trong ete. Hy
xc nh c ch ca phn ng ny.
O
CHaONa
e t
e > (
OOCH
a
+
NaCI
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 m -toluic t benzen v cc ho cht cn thit khc.
2. Hy ngh c ch phn ng kh nc (H+) ca
a. Butan-1-ol to (trans)-but-2-en
b. 3,3-imetylbutan-2-ol to 2,3-imtylbut- 2-en Cu 8: (3.0 im)
1. Axit fumaric v axit maleic c cc hng s phn li nc 1 (k1), nc 2 (k2). 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-CH3-C6H4-CH2OH, p-CH3OC6H4-CH2OH, p-CN-C6H4-CH2OH v p-Cl-C6H4-CH2OH.
3. Oxi ho hirocacbon thm A (C8H10) bng oxi c xc tc coban axetat cho sn phm B. Cht B c th tham gia
phn ng: vi dung dch NaHCO3 gii phng kh CO2 ; vi etanol (d) to thnh D ; un nng B vi dung dch
NH3 to thnh E. Thu phn E to thnh G, un nng G nhit khong 1600C to thnh F. Mt khc, khi cho B
phn ng vi kh NH3 (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:
OH
C
HCHO
p , , , , X
A NaCN B H2O C O
OH- A DMF B ----------------- C --------------------- 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 C19H22O5N2.

.......................................................................Ht .......................................................................
36
K THI HC SINH GII QUC GIA LP 12 THPT NM

HC 2008 - 2009
http: //vn.mvblog.vahoo.com/volcmttl
THI TH
HNG DN CHM MN HA HC
Cu 1: (2,5 im)
1 (0,5 im). Cu hnh electron ca cc nguyn t:
Ca [Ar]4s2; Sc [Ar]3d*4s2; Ti [Ar]3d24s2; V [Ar]3d34s2; Cr [Ar]3d54s*; Mn [Ar]3d54s2.

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 I2 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 3d5 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 I2 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 I2 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:
BCl3
::
:q:
. . .. . .
.Ql... ..
B
Cl. .Cl.
C: l :
. . .B... .
. C. .l.. ...C. l.
.
N2+
C2
N2+
: : N : : ol
N2
::C::
.N ..;. .0.
IF:3 : F:
... . .F.
. F.
. . .N... .
.../ .....
b (1 im). Dng hnh hc:

BCl3: Xung quanh nguyn t B c 3 cp electron (2 cp v 1 "siu cp") nn B c lai ho sp2, 3 nguyn t Cl lin kt vi B qua 3 obitan
ny, do phn t c dng tam gic u.
CO2: 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 CO2 nn cng c dng thng.
NO2: 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 sp2. 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 < 120o v s y ca
electron c thn.
IF3: Xung quanh I c 5 cp electron, do I phi c lai ho sp3d, 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 IF3 c cu to dng chT. Nu k c n s y ca 2 cp electron khng lin kt, phn t c dng ch Tcp.
qr
. B.
. ...
. Cl. ..Cl.
= C=
= N=
.F------1 ----- F.
N
..
.
.
.F.
37
3 (0,5 im). BCl3: 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 n vi 1 trong 3 nguyn t
Cl. Kt qu l to thnh phn t BCl3 c dng tam gic u nh trnh by trn.
AlCl3: AlCl3 cng thiu electron nh BCl3, nhng Al khng c kh nng to thnh lin kt n kiu p n-pn nh B. c
bt t, 1 trong 4 obitan lai ho sp3 ca nguyn t Al nhn 1 cp electron khng lin kt t 1 nguyn t Cl phn t
AlCl3 bn cnh. Phn t AlCl3 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).
khc, d = a>/3, vi a l di ca cnh t bo.
Mt
p l khi lng ring ca Si.
Gi
nhng d kin ca u bi ta c:
T
nM
8.28,1
: 2,33
p:
23 3
NV
6,02.10 .a suy ra: a = [8 . 28,1 /
6,02.1023. 2,33]1/;i cm = 5,43.10" d = a V F=
11/3,
9,40.10-8 cm; r Si = d : 8 = 1,17.10"8
2 (0,5 im). rSi = 0,117 nm > rC = 0,077 nm . Kt qu ny hon
nguyn t ca cc nguyn t trong bng h thng tun hon.
3 (1im). Quy c biu din bipy bng mt cung li.
cm = 0,117nm
ton ph hp vi s bin i bn knh
a (0,25 im). ng phn cis, trans:
Cl
Cl
Cl
Co
Cl Trans
b (0,75 im). ng phn quang hc:
Ci
C
s
Cl ------- Co
Cl
Co -------- Cl
Cu 3: (2,5 im) 1.
t=0
t
kl
2"
p dng cng thc cho : k1 + k2 = ln- e
tX-x
y nng lc cn bng xe c xc nh thng qua hng s cn bng K
K = [B] = X.
[A]
a-x
Sau khi bin i ta c :
aK
.=1+K
aK-x(1+K)
v x -X = ------------- -------e
1+K
, 2,303 aK Cui cng

k1 + k2 = ----------- lg
aK - X - Kx
38
aK
a , . 2,303
V x = Nn k, + k2 =---------------- lg
12
2 t
2,303
a
aK- -K
!g
2K
2K - 1- K
2,303 2K
. lgK-i
22
K = ki / k2
Nn
k -k
2 1
2.300 O T 1 n _ 3 ^ 'Igonn nn =
2,7.10 giy
300 + 100 300 -100
2,303 , 2k1
t = lg ki + k
2,303
2. a. Xt 2 cp oxi hoa kh :
Cu2+ +
E = E + 0,059 lg
Cu+
E = Ei+0.059i^_^
0
[ I- ]2
I2 + 2
E(E: Khong th co phan ng gia Cu2+ va I- c.

b. Gia s o dung dch KI vao dung dch cha Cu2+ va mt t Cu+. V CuI rt t
ln hn E2.
tan nn [Cu+] rt nho, do o El co th
Cu+
Nh vy ta co : Cu + +
I- + Cu+
-- I2 + < ^ I
2
<
Phan ng xi ha kh tng quat la :
2
C2+ + 2I- < ----------------- > CI
(1 )
Lc can bang ta c:
"] = E = 0,62 + M5?igL
E = 0,15 + 0,059lg
T [ I- ]
^ 0,62- 0,15 = 0,059lg
= 0,059lg
-0,62+0,15
1
^ K = ^~.10 0 0 5 9 =
104 T
Nh vay vi K rt ln, phan ng (1) xay ra hoan toan. Cu
4: (2.5 im)
a.
2HgO (r)
2Hg(k) + O2 (k)
[ ] 0 a mol
[ ]cb a - 2 x
K
p
b.
Hg
p .P0
0
=
j
p1 -p
2x
= p = =
9,48
3 27
S mol Hg nh nht khi a = 2x. T cng thc
27
T.K
39
PV 4 0 5 n =
2.
4 0,5
3x^ x = 0,0105 RT 0,082.773 Vay a = 0,021 mol m HgO =

0,021.216 = 4,53^
Ta c cc phng trnh:
7
C2 H6 + -O2 ------------> 2CO2 + 3H2O AH =- 1560,5 KJ
( 2C2 H6 + 7O2 -------- > 4CO2 + 6 H2O AH =-3121 KJ )
AHp= 4 AHhtCO2 + 6 AHhtH,O - 7AHhtO, - 2 AHhtC,H6
2 + 6 OHhtH2 O - /OHhtO2 - 2 OHhtC
^ AHhtC2H6 = l"v
[4(- 393,5) + 6(- 285,8)-(- 3121)]

v
= - 83,9 ( Kl.mol"1)
b.
AHp = 2 Ec-c + 12 Ec-h + 7Eo=o - 8 Ec = O - 12 Eh-o

^ c _ [2x347 + 12x413 + 7x495-12x464-(-3121)] _ 0, _ .-1. ^ EC = O= i =
833( KJ.mol )
8
AG = AH - TAS
[-1560,5-(-1467,5)]
,
,.1 .
=> AS = i ------- 7 v _ ,= - 0,312 (kl.mol K ) = -312 J.mol'1.K'1
(25 + 273)
Cu 5: (2.5 im)
1. Ta c: CFe3+ << CF-(= 1) ppep3 rt ln.
V vy trong dung dch, Fe3+tc dng ht vi F" to ra phc FeF3.
Fe3+ + 3F- ^ FeF3 Ban u 0,01 1
Sau phn ng ___ 0,97 0,01
Sau khi trn vi NH4SCN : CF F = 5.10"3M; C - = 0,485M; C - = 5.10-2M
4
FeF
F-
' SCN-
Fe3+ + SCN" s FeSCN2+
10+3,03
FeF3 + SCN" s FeSCN2+ + 3F'

C 5.10" 5.10"2
0,485
3
2
[ ] (5.10" -x) (5.10" -x) x 0,485+3x
K = 10'10'07
^ x(0,485 + 3x)3 = 10-10,07 (5.10-3 -x)(5.10-2 -x)

-5
-10 07
-3 ...... 25x10 x10 '
in 13 _ in 6
Vi x << 5.10"3 ta c : x =--------- ---------------- = 1'86x10 < 7x10
(0'485)3
Vy mu ca phc FeSCN2+ khng xut hin, ngha l F" che hon ton Fe3+
2. Cc qu trnh xy ra:
-To phc Ag(NH3)2+ ( CNH3 > CAg+ )
Ag+ + 2NH3 5 Ag(NH3)2+
1,0.10-3 1,0 __ 1,0-2,0.10-3 1,0.10-3
2+ I
Kh Ag(NH3)2+ bi Cu:
p2 = 107,24
40
2x Ag(NH3)2+ s Ag+ + 2NH3
2Ag+ + Cu 2Ag + Cu1+

To phc ca Cu2+ vi NH3 (CNH > CC 2+)
Cu2+ + 4NH3 s Cu(NH3)42+
T hp (1)(2) v (3):
1 C ch:
= 10w-24 (1) K0 =
1015,61 (2)
p, = 1012 03 (3)
2Ag(NH3)2+ + Cu 5 2Ag + Cu(NH3)4 + ; K = p-2.K0.p4 = 1013'16

1,0.10-3
5,0.10-4
----
TPGH: Cu(NH3)4+ : 5,0.10-4M ; NH3: 1 ,0-2. 1 0-3 * 1 ,0M

Cu(NH3)42+ + 2Ag s 2Ag(NH3)2+ + Cu
Cn bng
10-
2x
-4
-4
-4
= 10-13 16
(5,0.10 - x) x = 5.10 ^ 2x =45x10 .10 ' = 10

-9
' < 5x10-4 Vy: [Ag(NH3)+]=2x=10-8,23 = 5,9.10 M
8 23
[Cu(NH3)4+]=5,0.10-4M
Mc d Ag+ tn ti di dng phc Ag(NH3)+ 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
to thnh
khng
ni i.
PVC c cu to u n, c mt nhm -CH2- li n 1 nhm -CHCl-, v nu
41 polime
TUYN
TP
THI cha
HSG MN
HAvy
HC
c 2 nhm -CHCl- cnh nhau th to ni i.
Phn ng tch clo khi PVC c th biu din theo s :
CH2 CH2
"CH^ "CH^ "
ch2 ch2
CH2
Cl
Cl
Cl
Cl
CH
CH
"CH^ CH^ " CH CH

" ^ch2" ^
2 Zn
2 ZnCl2
CH2
CH2
Trong polime to thnh, nu cx mc xch cn li 1 nguyn t clo th cng thc l [Ta c:
(C2H3)xCl-]n 35'5
0,2082 ^ x = 5.
27x + 35'5
xch ch c 1 mc xch cn clo.
Vy c 5 mc
C 5,0.10 [ ]
,
Suy ra % s mc 5,0.10-4-x
O
xch b loi clo l: -7.100% = 80%
(2x)2
O
Cl
CH3O
O
C
l
CH3O
H
OCH3
Q
C H 3O
42
Cu 7: (2.5 im) 1a.
C22HH2
HNO3
600 C?
SO
H2SO
4
nh2
NO2
NH2
J H1 I _ B r Brv 1 ..Rr " ...-.Br,
3 1 [H] 1 Br2
V-NY - NaNO2/HCl
OJ ------------- >- 0 2 5
Fe/HCl
Br
N2Cl
Br C2H5OH
Br^^Br
Br
Br
b.
CH
CH 3
CH3C1 hno3
ch3
ch3
ch3
Br2
CH3COCl
[H1
Br
Fe/HCl NO2 NH2

Nhcoch3 NHCOCH3
H2O
CH3
CH3
CO /ete
CH3
CH3
CH3
1 Mg/ete I c2h5Oh1 NaNO2/HCl
BrTVC
OOH ^^MgBr ^Br ^^Br0-50c
Br
N2Cl
NH2
2. C ch:
a.
+ H
CH3CH2CH2CH2OH h o C H 3C H 2C H 2C H 2
H CX
-H
C=C H /
ch3ch2chch3
CH3
b.
CH3
CH3
CH3
I
+ Hl
ch3chCch3
-^
CH3' ,Chch3
ch3chcch3
H2O
H C
3 \
CH3
CH3
H3C
CH3
OhCh3
CH3
C=C
Cu 8: (2.5 im)
1 (0,75 im).
HOOC H
HOOC
H COOH "-H+ F Axit fumaric
OOC
H+
H COO- F
H
COO-
F
OH O
OH-O
COO-
OOC
O
H+
H+
H H M Axit
HH
maleic
HH
ki(M) > ki(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'.
43
k2M < k2F ) 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 -OCH3 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 nhm -OCH3 v (+C) > (+I) . Cc nhm -Cl (-I > +C) v -CN (-C) ht electron lm cacbocation tr nn
km bn do vy kh nng phn ng gim, nhm -CN ht electron m n h hn nhm -Cl.
Vy sp xp theo trt t tng dn kh n n g phn ng vi HBr l: p-CN-C6H4-CH2OH < p-Cl-C6H4-CH2OH < p-CH3-C6H4-CH2OH < pCH3O-C6H4-CH2OH.
3 (0,75 im).
;O
O
COC 2 H 5
:O
C 2 H5OH
C- OC 2 H 5
O
D
O
O
C
C
O
;O + NH3 (kh, d)
C-nh2
O
C
C
O
160 C
COH
O
:N-H
:N-H
4. (0.75)
S iu chp-hiroxiphenylaxetamit
,CH 2 OH
------- )
OH -
HO
,CH 2 CN
H2 O
DMF
HO
HO
HO
,OH
O
O
H2NCOCH
, CH 2 CONH 2
NaCN
HCHO
Cl
+
H2NCOCH2
H2NCOCH2
D1
D2
Sn
phm ph:
C19H22O5N2
H2NCOCH
CH2CONH
-- ------------------- ht ----------------- - - - Th sinh c th

Jm cch khc, nu ng vn cho im ti a

MỘT SỐ ĐỀ THI CHỌN ĐỘI TUYỂN QG CÁC TỈNH MÔN HÓA

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MỘT SỐ ĐỀ THI CHỌN ĐỘI TUYỂN QG CÁC TỈNH MÔN HÓA

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2010

TUYN TP THI HSG

TUYN TP THI HSG MN HA HC

PHN 2: CC N THI HC SINH GII QUC GIA

K THI CHN HC SINH GII QUC GIA

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TUYN TP THI HSG MN HA HC

Gim lng hi Br2

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TUYN TP THI HSG MN HA HC

1. Xc nh cu trc ca guaiol v X nu bit trong phn t guaiol

Th sinh khng c s dng ti liu.

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TUYN TP THI HSG MN HA HC

THPT CHUYN H NOI

K THI CHN HC SINH GII QUC GIA

LP 12 THPT NM 2009 - 2010

(p n thi gm 4 trang, c 8 cu)

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TUYN TP THI HSG MN HA HC

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TUYN TP THI HSG MN HA HC

Sau so snh Q vi Kp kt lun

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TUYN TP THI HSG MN HA HC

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

2. Mu xanh da tri ca X c c do s lin hp gia cc ni i trong phn t X. (0,25 im)

3. Cng thc cu to hai cht A, B nh sau. ng CTCT mi cht c 0,25 im

S to thnh cht A c gii thch nh sau (0,5 im)

Do cng thc phn t ca A l C15H26O nn trong A s c 3 mnh

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isopren (0,25 im)

TUYN TP THI HSG MN HA HC

Na3[RhCl6].12H2O = Na3[RhCl6] + 12H2O

2Na3[RhC6] = 2Rh + 6NaCl + 3Cl2

Cu VIII (4.0 im)

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TUYN TP THI HSG MN HA HC

http: //vn .myblog.yahoo.com/vol cmttl

K THI CHN HC SINH GII QUC GIA LP 12 THPT NM 2010

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TUYN TP THI HSG MN HA HC

C + (NH3) 2S + H2O ------ > Y + S + NH3 + KOH

B + (NH4)2S + KOH + H2O ------ > Z + S + NH3

C + H2SO4 + H2S ------ > T + S + K2SO4 + H2O

1. Cho bit sn phm to thnh t cc phn ng sau v gi tn sn phm :

Furan + (CH3CO)2O + (C2H5)2O: BF3

Thiophen + C6H5COCl + SnCl4 ---------------- > B

Pyrol + C6H5N2+Cl- -------------- > C

d. Pyrol + CHCs + KOH -------------- > D

Gii thch s khc nhau v nhit si trong dy cc cht sau:

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TUYN TP THI HSG MN HA HC

CU 10: (2,0 ' im)

Hy gii thch tnh axit ca axit L-ascobic v cho bit nguyn t H no c

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

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TUYN TP THI HSG MN HA HC

2,3,4,6-tetra-O-metyl-D-Glucoz. Xc nh CTCT ca Salixin

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TUYN TP THI HSG MN HA HC