S GIO DC V O TO

PH TH

K THI CHN HC SINH GII CP TNH LP 12

Nm hc: 2009 - 2010
MN: HO HC
Thi gian lm bi: 180 pht (khng k thi gian giao )
CHNH THC
---------------------------------------------------------

Cu 1: (4,0 im)
1) C 5 kh A, B, C, D, E. Kh A c iu ch bng cch nung KMnO4 nhit cao;
kh B c iu ch bng cch cho FeCl2 tc dng vi hn hp KMnO4 v H2SO4 long;
kh C c iu ch bng cch t st sunfua trong oxi; kh D c iu ch bng cch
cho st pirit vo dung dch HCl trong iu kin thch hp, kh E c iu ch bng cch
cho natri nitrua vo nc.
Cho kh A, B, C, D, E ln lt tc dng vi nhau, trng hp no c phn ng xy
ra? Vit phng trnh ho hc biu din cc phn ng. (Ghi r iu kin nu c)
2) Vit phng trnh ho hc biu din cc phn ng xy ra (nu c) v nu hin tng khi
cho t t ure ln lt vo cc cha:
a) Dung dch Na2CO3.
b) Dung dch Ba(OH)2.
3) Mui X nguyn cht, mu trng, tan trong nc. Dung dch X khng phn ng vi dung
dch H2SO4 long m phn ng c vi dung dch HCl cho kt ta trng, kt ta ny li
tan trong dung dch NH3. Khi axit ho dung dch to thnh bng dung dch HNO3 li c
kt ta trng tr li. Cho Cu vo dung dch X, thm dung dch H2SO4 v un nng th c
kh khng mu, ho nu trong khng kh thot ra, ng thi c kt ta en xut hin. Bin
lun xc nh cng thc ca X. Vit cc phng trnh ho hc biu din cc phn ng
xy ra.
Cu 2: (5,0 im)
1) Vit phng trnh ho hc biu din cc phn ng (nu c) v nu hin tng xy ra
trong cc qu trnh sau:
a) Cho dung dch brom vi dung mi nc c mu vng vo cht lng hexan.
b) Cho dung dch brom t t n d vo dung dch phenol (u dung mi nc).
c) Sc kh C2H2 vo dung dch KMnO4 sau thm CaCl2 vo.
d) un nng anlyl iotua vi nc, sau thm dung dch brom va vo.
2) A, B, C, D c cng cng thc phn t C4H6O4 u phn ng vi NaOH theo t l mol
1:2. Trong :
- A, B u to mt mui v mt ancol.
- C, D u to mt mui, mt ancol v nc.
Bit rng khi t chy mui do A, C to ra th trong sn phm chy khng c nc.
Xc nh A, B, C, D v vit phng trnh ho hc biu din phn ng xy ra vi NaOH.
3) C th tn ti mi lin kt hiro khc nhau no trong ancol etylic c ho tan phenol.
Vit cng thc biu din cc mi lin quan ny v cho bit trong s lin kt vit th lin
kt no bn nht, lin kt no km bn nht? Gii thch.
Cu 3: (4,0 im)
Ho tan hon ton 1,62 gam nhm vo 280 ml dung dch HNO3 1M c dung dch
A v kh NO (sn phm kh duy nht). Mt khc, cho 7,35 gam hai kim loi kim thuc
1

hai chu k lin tip vo 500 ml dung dch HCl, c dung dch B v 2,8 lt kh H2 (ktc).
Khi trn dung dch A vo dung dch B thy to thnh 1,56 gam kt ta.
a) Xc nh tn hai kim loi kim.
b) Tnh nng mol/l ca dung dch HCl dng.
Cu 4: (4,0 im)
1) cho 9,2 gam mt hp cht hu c n chc X tc dng va vi dung dch cha 0,4
mol AgNO3 trong NH3 thu c 21,6 gam Ag. Xc nh cng thc cu to ca X. Vit
phng trnh ho hc xy ra.
2) A l hp cht hu c cha C, H, O. t chy hon ton 3,08 gam A. Hp th ton b
sn phm thu c vo bnh ng 5000 ml dung dch Ca(OH)2 0,02M thy xut hin 6
gam kt ta, phn nc lc c khi lng ln hn dung dch Ca(OH)2 ban u l 1,24
gam.
a) Vit cng thc phn t ca A bit rng khi lng mol phn t ca A nh hn
khi lng mol phn t ca glucoz.
b) Bit A phn ng c vi NaOH theo t l mol A v NaOH l 1 : 4 ; A c phn
ng trng gng. Xc nh cng thc cu to ca A v vit phng trnh ho hc xy ra
ca cc phn ng trn.
Cu 5: (3,0 im)
1) C 6 dung dch khng nhn gm: Zn(NO3)2, FeSO4, MnSO4, NiSO4, CuSO4,
Pb(CH3COO)2 v 6 l ng bt kim loi: Cu, Zn, Fe, Pb, Mn, Ni. Khng dng thm thuc
th no khc, hy dng phng php ho hc kt hp vi th in cc tiu chun sau y
nhn ra cc cht ni trn?
Cho bit:
M2+/M
Zn2+/Zn
Fe2+/Fe
Mn2+/Mn
Ni2+/Ni
Cu2+/Cu
Pb2+/Pb
E0 (V)
- 0,76
- 0,44
- 1,18
- 0,25
+ 0,34
- 0,13
2) Mui st (III) thu phn theo phn ng:
Fe3+ + H2O Fe(OH)2+ + H+
K = 4.10-3
a) Tnh pH dung dch FeCl3 0,02M.
b) Tnh pH m dung dch phi c 95% mui st (III) khng b thu phn.
-------------------------------- HT --------------------------------

Ghi ch:
- Cn b coi thi khng gii thch g thm.
- H tn th sinh: ............................................................................SBD..................................

S Gio dc v o to
Ph Th

Hng dn chm thi chn hc sinh gii cp tnh

Lp: 12
Nm hc: 2009 - 2010
Mn: Ho hc

chnh thc

----------------------------------------------------------Cu
Cu 1
1.

Ni dung

im
4,0
1,5

2KMnO4 K2MnO4 + MnO2 + O2(A)

10FeCl2+6KMnO4+24H2SO4 5Fe2(SO4)3+3K2SO4+6MnSO4+24H2O+10Cl2(B)
t C
4FeS + 7O2
2Fe2O3 + 4SO2 (C)
0

FeS2 + 2HCl FeCl2 + S + H2S (D)

..........................................................................

0,5

Na3N + 3H2O 3NaOH + NH3 (E)

Cho cc kh A, B, C, D, E ln lt tc dng vi nhau:
O2 + 2SO2

V2O5 ,t C

2 SO3

t C
3O2 + 2H2S
2SO2 + 2H2O hoc O2 + 2H2S 2S + 2H2O
.................................
0

0,5

t C
Pt ,t C
3O2 + 4NH3
2N2 + 6H2O hoc 5O2 + 4NH3
4NO + 6H2O
0

Cl2 + SO2 SO2Cl2

Cl2 + H2S S + 2HCl
t C
3Cl2 + 2NH3
N2 + 6HCl
SO2 + 2H2S 3S + 2H2O
.........................................................................................
0

2.

3.

0,5

1,0
a) Khi cho ur vo cc dung dch Na2CO3 , Ba(OH)2 th trc ht c phn ng:
(NH2)2CO + 2H2O (NH4)2CO3
C phn ng Na2CO3 + (NH4)2CO3 2CO2 + 2NH3+ 2NaOH
Vy cho ure vo s thy xut hin si bt kh CO2 v NH3 (mi khai)
(Hay Na2CO3 +
(NH4)2CO3

2NH3+ 2NaHCO3 )
0,5
..................................................
b) C phn ng Ba(OH)2 + (NH4)2CO3 BaCO3 + 2NH3 + 2H2O
0,5
Vy cho ure vo s thy xut hin si bt kh NH3 (mi khai) v kt ta
...................
1,5
X khng phn ng vi H2SO4 trong X khng c Ba2+, Ca2+, Pb2+...
X + HCl kt ta trng, vy trong X c th c Ag+; Hg+ ...
3

Kt ta trng tan trong dung dch NH3 sau li kt ta tr li khi axit ho.
Vy
kt
ta

l
AgCl

dung
dch
X
c
cha
0,5
Ag+.......................................................
Cho Cu vo un nng trong dung dch axit c kh khng mu, ho nu
trong X c cha NO 3 v kt ta en sau cng l Ag. X l AgNO3
Cc phng trnh phn ng:
Ag+ + Cl AgCl trng
0,5

AgCl
+
2NH3

Ag(NH3)
+
Cl
2
....................................................................
Ag(NH3) 2 + Cl + 2H+ AgCl + 2NH 4
2NO 3 + 3Cu + 8H+ 3Cu2+ + 2NO + 4H2O
2NO + O2 2NO2
2Ag+ + Cu Cu2+ + 2Ag
.............................................................................
Cu 2

5,0

1.

2,0
a. Pthh:
Khng c phn ng xy ra
Htng: - Ban u dung dch tch 2 lp: trn l hexan khng mu, di l dung
dch brom mu vng.
- Sau mu vng ca brom chuyn dn t lp di ln trn do brom tan
vo hexan tt hn tan vo nc.
.............................................................................................
b. Pthh: C6H5OH + 3Br2 C6H2Br3OH + 3 HBr
Br
Br
C6H2Br3OH + Br2
O + HBr
Br
Br
Htng: - Ban u c kt ta trng xut hin, brom mt mu
- Khi brom d kt ta trng chuyn sang mu vng.
.........................................
c. Pthh:
3C2H2 + 8KMnO4 3KOOC-COOK + 8MnO2 + 2KOH + 2H2O
KOOC-COOK + CaCl2 CaC2O4 + 2KCl
2KOH + CaCl2 Ca(OH)2 + 2KCl
Htng: - Dung dch KMnO4 mt mu, c kt ta mu en.
- Thm CaCl2 c kt ta trng xut hin.
................................
....................
d. Pthh:
CH2=CH-CH2I + H2O CH2=CH-CH2-OH + HI
CH2=CH-CH2-OH + Br2 CH2Br-CHBr-CH2-OH
2HI + Br2 2HBr + I2
Htng: - Ban u to ra dung dch ng nht
- Khi thm dung dch brom vo th dung dch sm mu hn do to ra I2
.........

2.

0,5

0,5

0,5

0,5

0,5

1,0
A, B tc dng vi NaOH theo t l mol 1: 2 to ra mt mui v mt ancol suy ra
A, B l 2 este 2 chc.
H3COOC-COOCH3 + 2 NaOH NaOOC-COONa + 2 CH3OH.
(A)
0,5
HCOOCH2 - CH2OOCH + 2 NaOH 2HCOONa + HOCH2-CH2 OH
........................
(B)
C, D tc dng vi NaOH theo t l mol 1: 2 to ra mui, ancol v nc suy ra C, D
4

l este axt . Mui do C to ra chy khng to ra nc do C l

HOOC - COOC2H5 ; cn D l HOOC - CH2 - COOCH3.
HOOC - COOC2H5 + 2 NaOH NaOOC - COONa + C2H5OH + H2O
HOOC - CH2 - COOCH3 + 2 NaOH NaOOC - CH2 - COONa + CH3OH + H2O
......
3.

0,5

2,0
Trong hn hp ancol - phenol c 4 loi lin kt hiro nh sau:

O H ... O H

..................................
C2H5
C2H5

(I)

O H ...

C2H5

OH

C6H5

(II)

O H ... O H
O H ... O H

(III)

(IV)
C6H5
C6H5
C6H5
C2H5
................................
+ Lin kt hyr bn nht l kiu (IV) do: gc C6H5 - ht electron do H trong
nhm OH ca phenol linh ng hn (d in tch dng nhiu hn). Cn gc
C2H5- y electron nn O trong nhm OH ca C2H5OH d phn in tch m nhiu
hn. .......
+ Lin kt hiro km bn nht llin kt kiu (II): do H trong nhm OH ca ancol
d phn in tch dng t hn, cn O trong nhm OH ca phenol d phn in
tch m t hn.
.......................................................
Cu 3

Phng trnh ho hc: Al + 4HNO3 Al(NO3)3 + NO + 2H2O (1)

2M + 2HCl 2MCl + H2
(2)
2M + 2H2O 2MOH + H2
(3)...........................
Ban u: s mol Al: 0,06 mol ; s mol HNO3: 0,28 mol
Sau phn ng HNO3 cn d: 0,04 mol
...........................................................................
Khi cho hn hp hai kim loi kim vo dung dch HCl th xy ra phn ng (2) v
c th c phn ng (3):
a).............. Theo pthh: s mol M = s mol H = 0,25 mol M =
2
.
29,4..........................................
b)............. V hai kim loi kim thuc hai chu k lin tip nn Na, K tho mn
..
(23 < 29,4 <
39)...........................................................................................................
Khi trn hai dung dch A v B c kt ta to ra chng t ban u c phn ng (3),
ta c phng trnh ho hc:
HNO3 + MOH MNO3 + H2O
(4)
Al(NO3)3 + 3MOH Al(OH)3 + 3MNO3
(5)...................................
S mol kt ta: Al(OH)3 = 0,02 mol nh hn s mol Al(NO3)3. Nn c 2 kh nng:
.....
TH1: Al(NO3)3 cn d th s mol MOH = 0,04 + 0,02.3= 0,1 mol
s mol M phn ng(2) = 0,25 - 0,1 = 0,15 mol
s mol HCl = 0,15 mol CM(HCl) = 0,3M
...........................................................
TH2: MOH cn d, Al(OH)3 tan tr li mt phn:

0,25

0,25
0,5
0,5
4,0

0,75
0,5

0,5
0,5

0,5
0,25
0,5
0,25
0,25
5

Al(OH)3 + MOH MalO2 + 2H2O (6)

.......................................
S mol Al(OH)3 tan = 0,06 - 0,02 = 0,04 mol. T cc phng trnh(4,5,6) ta c:
S mol MOH = 0,04 + 0,06.3 + 0,04 = 0,26 mol (loi - v ln hn s mol M ban
u)..
Cu 4
1.

4,0
1,5
+ Theo bi ra X l hp cht hu c n chc tc dng vi ANO3/ NH3 to ra Ag
nn X l anht n chc.
21,6
Ta c: n Ag
= 0,2 mol < n Ag (c trong AgNO3 cn dng = 0,2 . 2 = 0,4 mol)
108
t cng thc phn t ca X l R 0,25
CHO.........................................................................
RCHO + +2AgNO3+3NH3+H2ORCOONH4+2Ag+2NH4NO3
0,1mol
0,2
0,1
0,2
9,2
MX =
= 92 MR = 92 - 29 = 63
0,1
............................................................................
Mt khc ta c: s mol AgNO3 tc dng vo kin kt 3 u mch l 0,2
=> s nguyn t H c trong X c th thay th vi Ag l 2
trong X c 2 lin kt 3 u mch (CH C - ).
...........................................................
m MR = 63 nn CTCT ca X phi l:
HC C CH CHO

C
|||
CH
.................................................................................................

0,25

0,5

0,5

2.
a.

3,0
1,5
Gi cng thc phn t ca A l CxHyOz.
(x nguyn 1; 2 y nguyn 2x+2; z nguyn 1)
Phn ng chy:
CxHyOz + ( x

y z
y
)O2 xCO2 + H2O (1)
4 2
2

Sn phm chy c CO2 v nc, khi hp th vo dung dch Ca(OH)2, c phn ng:
CO2 + Ca(OH)2 CaCO3 + H2O
(2)
C th c phn ng:
................................

2CO2 + Ca(OH)2 Ca(HCO3)2

nCa (OH )2 = 5.0,02 = 0,1 (mol);

nCO2 (2) = nCaCO3 =

(3) 0,5

6
= 0,06 (mol)
100

Do khi lng phn nc lc tng so vi khi lng dung dch Ca(OH)2 ban u:
mCO2 + mH 2O - 6 = 1,24 (g)
Trng hp 1. Khng c phn ng (3) th: mH 2O = 1,24 + 6 - 0,06.44 = 4,6 (g)

=> nH 2O =

0,5

n CO2 2 x 0,06.18
4,6
. Theo (1) th
1,08y = 9,2x

n H 2O
y
4,6
18

=> 9,2x 1,08(2x+2) 7,04x

..............................................
Trng hp 2. C phn ng (3) ta c:

2,16

0,3

(loi)

nCO2 = nCO2 (2) + nCO2 (3) = 0,06+(0,1-0,06).2 = 0,14 (mol)

=> nH 2O = 1,24 + 6 - 0,14.44 = 1,08 (gam) => nH 2O = 1,08/18 = 0,06 mol.
Trong 3,08 gam A c: nC = 0,14 (mol); nH = 0,06.2 = 0,12 (mol);
nO = (3,08 - 0,14.12 - 0,12)/16 = 0,08;=> x : y : z = 0,14 : 0,12 : 0,08 = 7 : 6 : 4

0,5

=> Cng thc thc nghim ca A l (C7H6O4)n

Theo gi thit th MA < Mglucoz => 154n < 180 => n = 1. Vy cng thc phn t
ca
A
lC7H6O4.....................................................................................................................
.....
b.

1,5
Vi cng thc phn t C7H6O4 tho mn iu kin bi ra th A c th c cc cng
thc cu to sau:
OH

OH
OH

HCOO

OH

HCOO

HCOO
OH
OH

OH
OH

HCOO

OH

HCOO

HCOO
OH
HO

.................

OH

........

0,75

Phng trnh phn ng:

HCOOC6H3(OH)2 + 4NaOH HCOONa + C6H3(ONa)3 + 3H2O

HCOOC6H3(OH)2+2AgNO3+3NH3+H2O
NH4OCOC6H3(OH)2+2Ag+2NH4NO3......

Cu 5
1.

0,5

3,0
1,5

Trch mu th,da vo th in cc chun v nhn bit cc cht theo bng sau:

Zn2+

Fe2+

Mn2+

Ni2+

Cu2+

Pb2+

Cu

Zn

Fe

M2+
M

Pb

Mn

Ni

0,5
.............
.

- Mu khng c phn ng g th kim loi em th l Cu

- Mu ch c mt kt ta (Cu) bm trn b mt mt kim loi xm en(Pb) th
kim loi em th l Pb v dung dch chnh l CuSO4.

- Nu thy xut hin hai ln kt ta th kim loi em th l Ni, dung dch nghin
cu l Cu2+ v Pb2+. V trong cc dung dch cho ch c hai dung dch mu xanh
nn
ta
nhn
ra
dung
dch
NiSO4. 0,5
...........................................................................................................
.............
- Nu c 4 trng hp c kt ta xut hin th kim loi em th l Zn. Ta nhn .
ra dung dch Fe2+ v bit dung dch Cu2+, Pb2+, Ni2+.
- Nu c 5 trng hp kt ta xut hin th kim loi em th l Mn, dung dch
khng c tn hiu l Mn2+.
- Cn li l dung dch Zn2+
.......................................................................................

pthh:........
0,5

2.

1,5

a.

0,75
Ta c Ka(Fe3+) = 4.10-3 >> 14-14 nn b qua s ph li ca nc.
FeCl3 Fe3+ + Cl
0,02

0,02

Fe + H2O Fe(OH)2+ + H+
3+

K = 4.10-3

T: 0,02
[ ] (0,02 - x)
.....................................................

x 0,5

0,25
x2
= 4.10-3 x = 7,165.10-3 pH = 2,145.
0, 02 x
......................................
Ta c: K =

0,75
95% mui st (III) khng b phn hu, ngha l c 5% mui b thu phn
Fe3+ + H2O Fe(OH)2+ + H+

K = 4.10-3

T: 0,02
[ ]
(0,02 - 10-3)
....................................................

10-3 0,5

H .103
Ta c: K = 3 = 4.10-3 [H+] = 0,076 pH = 1,12
0, 02 10

0,25

Vy pH m dung dch phi c 95% mui st (III) khng b phn hu l 1,12.

8

............

Ch khi chm thi:

- Trong cc phng trnh ha hc nu vit sai cng thc ha hc th khng cho im,
nu khng vit iu kin phn ng hoc khng cn bng phng trnh hoc c hai th cho 1/2
s im ca phng trnh .
- Nu lm cc cch khc m ng vn cho im ti a ng vi mi , cu ca ra.

-----------------------------Ht ----------------------------------