UBND TNH BC NINH

THI CHN HC SINH GII CP TNH

S GIO DC V O TO

NM HC 2009 2010
MN THI : HA HC-LP 12-THPT

CHNH THC

Thi gian lm bi: 180 pht (khng k thi gian giao )

Ngy thi: 14 thng 4 nm 2010
===========

Bi 1(3,0 im):
1. Cng thc n gin nht ca axit cacboxylic A mch h, khng nhnh l (CHO) n. Bit
rng c 1,0 mol A tc dng ht vi NaHCO3 gii phng ra 2,0 mol CO2; dng P2O5 tch nc
t mt phn t A to ra cht B c cu to mch vng. Vit cng thc cu to ca A, B, gi
tn ca A v vit phn ng to ra B.
2. C nhng loi hp cht no, mch h cha mt loi nhm chc c cng thc C nH2n-2O2?
Vit cc loi hp cht di dng cng thc tng qut cha nhm chc.
3. Vi n bng bao nhiu th c c hp cht X c cng thc phn t C nH2n-2O2 m khi un
nng vi dung dch NaOH c hp cht A (cha C, H, O, Na) tho mn s sau: A

[O]

+NaOH
D +NaOH
CH4

Vit cng thc cu to ca A, B, D.

Bi 2 (2,0 im): Cho m gam hn hp gm NaBr, NaI phn ng vi dung dch H 2SO4 c
nng thu c hn hp kh A ( ktc). iu kin thch hp A phn ng va vi nhau
to cht rn c mu vng v mt cht lng khng chuyn mu qu tm. Cho Na d vo phn
lng c dung dch B. Dung dch B hp th va vi 2,24 lt CO 2 ( ktc) c 9,5 gam
mui. Vit phng trnh ha hc ca cc phn ng xy ra v tnh m.
Bi 3 (2,0 im): C 5 cht hu c X, Y, Z, T, H mch h, thnh phn cha C, H, O v u
c phn t khi bng 60 vC. em trn tng cp cht vi nhau theo t l 1:1 v khi lng
c cc hn hp sau: hn hp A 1 gm X v Y; hn hp A2 gm Y v Z; hn hp A3 gm T
v H; hn hp A4 gm X v H. Bit rng khi ly cng mt khi lng cc hn hp A 1, A2,
A3, A4 ln lt cho tc dng vi lng d kim loi Na v NaOH th cho kt qu sau:
S mol hiro sinh ra trong phn ng ca cc hn hp trn vi Na phn ng c t l tng
ng l: 2:1:1:1
S mol NaOH phn ng vi tng hn hp trn c t l tng ng l: 1:1:0:1
Hy xc nh cng thc cu to ca 5 cht trn.
Bi 4 (2,0 im):

1. Dung dch X c cha cc ion sau: Na+, NH 4+ , NO3 ,

S 2 .

Hy nhn ra s c mt ca tng

ion trong hn hp X. Vit cc phng trnh ha hc xy ra (nu c) trong qu trnh nhn bit.
2. Gii thch qu trnh hnh thnh hang ng v qu trnh hnh thnh thch nh trong cc ni
vi.
Bi 5 (4,0 im): Hn hp X gm Fe v mt kim loi R c ho tr khng i. Ho tan hon
ton 3,3 gam X trong dung dch HCl d thu c 2,9568 lt kh 27,3oC, 1 atm. Mt khc,
ho tan hon ton cng 3,3 gam X trong dung dch HNO 3 1,0M (ly d 10%) th thu c
896 ml hn hp kh Y gm N2O, NO ( ktc) c t khi so vi hn hp gm NO, C 2H6 l
1,35 v dung dch Z.
a) Xc nh kim loi R v tnh phn trm khi lng ca cc kim loi trong X.
b) Cho dung dch Z tc dng vi 400 ml dung dch NaOH thy xut hin 4,77 gam kt ta.
Tnh nng mol ca dung dch NaOH, bit Fe(OH)3 kt ta hon ton.
Bi 6 (4,0 im): t chy hon ton 4,3 gam mt cht hu c X thu c hn hp kh
CO2, H2O. HCl. Dn hn hp ny vo bnh ng dung dch AgNO 3 d c mt HNO3 0oC
thu c 5,74 gam kt ta v khi lng bnh dung dch AgNO 3 tng thm 2,54 gam. Kh
thot ra khi bnh dung dch AgNO3 dn vo 5 lt dung dch Ca(OH)2 0,02M thy xut hin
kt ta, lc tch kt ta, dung dch cn li cho tc dng vi dung dch Ba(OH) 2 d li thy
xut hin thm kt ta, tng khi lng kt ta 2 th nghim l 13,94 gam.
a) Tm CTPT ca X bit Mx < 230 g/mol.
b) A, B, D l cc ng phn ca X tha mn cc iu kin sau:
* 43,0 gam A + NaOH d 12,4 gam C2H4(OH)2 + 0,4 mol mui A1 + NaCl
* B + NaOH d Mui B1 + CH3CHO + NaCl + H2O
* D + NaOH d Mui A1 + CH3COONa + NaCl + H2O
Tm cng thc cu to ca A, B, D v vit cc phng trnh phn ng xy ra.
Bi 7 (3,0 im): Cho 88,2 g hn hp A gm FeCO 3, FeS2 cng lng khng kh (ly d
10% so vi lng cn thit t chy ht A) vo bnh kn dung tch khng i. Nung bnh
mt thi gian xy ra phn ng, sau a bnh v nhit trc khi nung, trong bnh c
kh B v cht rn C (gm Fe2O3, FeCO3, FeS2). Kh B gy ra p sut ln hn 1,45% so vi p
sut kh trong bnh trc khi nung. Ha tan cht rn C trong lng d H 2SO4 long, c
kh D ( lm kh); cc cht cn li trong bnh cho tc dng vi lng d dung dch KOH
thu c cht rn E. E ngoi khng kh cho n khi khi lng khng i, c cht rn
F. Bit rng: Trong hn hp A mt mui c s mol gp 1,5 ln s mol ca mui cn li; gi

thit hai mui trong A c kh nng nh nhau trong cc phn ng; khng kh cha 20% oxi v
80% nit v th tch.
a) Vit phng trnh ha hc ca cc phn ng xy ra.
b) Tnh phn trm khi lng ca cc cht trong hn hp F.
c) Tnh t khi ca kh D so vi kh B.
============== Ht ==============
Th sinh c php mang bng tun hon cc nguyn t ha hc vo phng thi.
H v tn th sinh ......................................................................... SBD ............................
Ch k gim th 1 .............................

Ch k gim th 2 ........

HNG DN CHM THI CHN HSG CP TNH MN HO 12 NM 2010

Cu
1

NI DUNG

im
3,0

1.

V 1 mol A tc dng c vi NaHCO3 gii phng 2 mol CO2 A l

mt axit 2 nc CTPT ca A phi l C 4H4O4 hay C2H2(COOH)2. ng
vi mch thng c 2 ng phn cis-trans l:
HOOC

H
C

H
C

COOH

HOOC

C
COOH

axit trans-butenioic

axit cis0,5

butenioic
(axit fumaric)

(axit maleic)

Ch c ng phn cis mi c kh nng tch nc to anhirit:

O
C

P2O5

C
H

COOH

COOH

+H2O

C
O

2.

S lin kt pi trong hp cht trn l (2n+2)-(2n-2)/2 = 2 hp cht

c th l:
* Axit khng no (c 1 ni i C=C), n chc: Cn-1H2n-3COOH (n 2)
* Ancol hai chc, khng no (cha 2 lin kt pi): CnH2n-4(OH)2 (n 4)
* Anehit hoc xeton no hai chc: Cn-2H2n-4(CHO)2 (n 2)
* Este n chc, khng no (c 1 ni i C=C): Cn-1-xH2n-yCOOCxHy (x
1, ...)

0,5
1,0

3.

T d kin B l CH3COONa hoc CH2(COONa)2, C c cha chc

axit, A c cha chc ancol hoc anehit. Mt khc, cng thc phn t
ca X l CnH2n-2O2 v X tc dng NaOH X l axit khng no c 1 ni
i hoc X l este vng no. tho mn ho tnh ca A, B, D th X l
este vng c cu to l:
CH2

CH2

0,5
(ng vi n = 3)

Cng thc cu to ca A, B, D l:
(A) HO-CH2-CH2-COONa ;

(B) HOOC-CH2-COONa; (D)

CH2(COONa)2
2

0,5
2,0

V A iu kin thch hp thu c rn mu vng A gm SO2 v

H2S, m NaBr c tnh kh yu hn NaI nn cc phn ng xy ra l:
2NaBr + 2H2SO4

Na2SO4 + Br2 + SO2 + 2H2O

0,15

(1)

0,075

8NaI + 5H2SO4

4Na2SO4 + 4I2 + H2S + 4H2O

1,2

(2)

0,15

ktc, Br2 th lng v I2 th rn, nn A ch c H2S v SO2:

2H2S + SO2 2H2O + 3S
0,15 0,075

(3)

0,15

Cht lng l H2O: Na + H2O NaOH + 1/2H2

0,15

(4)

0,15

dung dch B l NaOH:

CO2 + NaOH = NaHCO3
CO2 + 2NaOH = Na2CO3 + H2O

(5)
(6)

Gi x, y ln lt l s mol hai mui NaHCO3 v Na2CO3, ta c h:

84x + 106 y = 9,5

x = y = ,0 05 n

x + y = 0,1

NaOH

1,0

= 0,15

Theo cc phng trnh (4), (3), (2), (1) ta c khi lng hai mui ban
u l:
m = 0,15.103 + 150.1,2 = 195,45 g

1,0

2,0
Xc nh CTCT c th c ca cc hp cht X, Y, Z, T, H:
Gi cng thc l CnHmOz, ta c: 12n + m + 16z = 60.
+ Nu z = 1 12n + m = 44 n = 3, m = 6. CTPT l C 3H8O, ng vi
cng thc ny ch c th l ancol C3H7-OH hoc ete CH3-O-C2H5.
+ Nu z = 2 12n + m = 28 n = 2, m = 4 CTPT l C2H4O2, CTCT
c th l
1,0

CH3-COOH, HCOO-CH3, HOCH2-CHO

+ z = 3 khng c cng thc tha mn.
Bin lun tm cc cht X, Y, Z, T, H:
+ Khi cho cc hn hp tc dng vi Na v NaOH:
Hn hp :

X,Y Y,Z T,H X,H

Na

NaOH

1,0

X l axit : CH3COOH; Y v T l C3H7OH hoc HO-CH2-CHO ;

Z l este : HCOO-CH3 ; H l ete : CH3-O-C2H5
4
1.

Nhn ra ion Na bng cch t, cho ngn la vng ti.

+

2,0
1,0

Nhn ra ion S2 bng dung dch cha ion Pb2+ hoc Ag+ hoc Cu2+, .. v
du:
S2 + Pb2+ PbS en
Nhn ra ion NH4+ bng OH/t0 v giy qu m:
NH4+ + OH
Nhn ra ion

H2O + NH3 qu tm m xanh

NO3 :

axit ha dung dch bng H2SO4 un nh loi b

ion sunfua, sau cho Cu vo:

2.

S2 + 2H+ H2S

3Cu + 2NO3 + 8H+ 3Cu2+ + 2NO + 4H2O

Qu trnh hnh thnh hang ng l do s ha tan vi bi nc ma
c ha tan kh cacbonic:

1,0

CaCO3 + CO2 + H2O Ca2+ + 2HCO3

Qu trnh hnh thnh thch nh trong hang ng l do s phn hy ca

canxi hirocacbonat to thnh CaCO3 : Ca2+ + 2HCO3 CaCO3 +
CO2 + H2O
5

4,0

a)

Cc pthh:
+ X tc dng vi HCl:
2R + 2nHCl 2RCln + nH2

(1)

Fe + 2HCl FeCl2 + H2

(2)

+ X tc dng vi HNO3
Fe Fe3+ + 3e;

Qu trnh oxi ha:

Qu trnh kh:

R Rn+ + ne

2NO3 + 10H+ + 8e N2O + 5H2O

NO3 + 4H+ +3e NO + 2H2O

0,5

Gi x, y ln lt l s mol N2O v NO trong hn hp Y, ta c:

0,896
x = 0,03
x+ y=

22,4
44x + 30 y = 30. ,1 35(x + y) y = 0,01

0,5

Gi a, b ln lt l s mol ca R v Fe trong 3,3 gam hn hp X. Theo

d kin cho v cc phng trnh, ta c h:

aR + 56b = 3,3
b = 0,03 n = 3 R = 27(Al)

2,9568
an + 2b = 2. an = 0,18 a = 0,06
0,082(273+ 27,3) R = 9n b = 0,03
an + 3b = 0,03.8+ 0,01.3
b)

0,5

0,5

trong X c %Al = 49%; %Fe = 51%

Dung dch Z gm: Al3+ (0,06 mol); Fe3+(0,03 mol); NO3
H+ d:

10
100

0,034 mol
Cho NaOH vo dung dch Z th:
H+ + OH H2O

(3)

(3.0,06 + 3.0,03 + 0,03.2 + 0,01) =

0,5

Fe3+ + 3OH Fe(OH)3 (4)

Al3+ + 3OH Al(OH)3 (5)

0,5

Al(OH)3 + OH [Al(OH)4] + 2H2O

(6)

Ta c khi lng kt ta Fe(OH)3 l 0,03.107 = 3,21 gam

s mol ca Al(OH)3 l

4,77 3,21
= 0,02
78

(mol) < s mol Al3+

Xt hai trng hp:

* TH (1): NaOH khng kt ta ht Al3+:
S mol OH cn dng l: (0,034 + 0,02.3 + 0,03.3) = 0,184 mol

0,5

Nng ca dung dch NaOH l: CM = 0,184/0,4 = 0,46 M

* TH (2): Al3+ phn ng sinh ra c Al(OH)3 v [Al(OH)4]
S mol NaOH = 0,034 + 0,03.3 + 0,06.3 + (0,06 0,02) = 0,344 mol

0,5

Nng : CM(NaOH) 0,344/0,4 = 0,86 M

6

4,0
a)

Tm CTPT ca X:
+ t X to ra CO2, H2O, HCl X c C, H, Cl, c th c O.
+ Cho hn hp CO2, H2O, HCl qua dung dch AgNO3 th HCl, H2O b
gi li.
AgNO3 + HCl AgCl + HNO3

(1)

5,74

nHCl = nAgCl = 143,5 = 0,04 mol nH2O = 0,06 mol

0,5

+ Kh thot ra khi bnh l CO2 cho tc dng vi dung dch Ca(OH)2:

CO2 + Ca(OH)2 CaCO3 + H2O (2)
2CO2 + Ca(OH)2 Ca(HCO3)2

(3)

Dung dch nc lc tc dng vi Ba(OH)2

Ca(HCO3)2 + Ba(OH)2 BaCO3 + CaCO3 + 2H2O (4)

0,5

Gi a, b ln lt l s mol Ca(OH) 2 tham gia (2) v (3), theo cc pthh

(2), (3), (4) ta c:

a + b = ,0 02.5
a = ,0 08

100a + (100 + 197)b = 13,94 b = ,0 02

CO2: 0,12 mol

0,5
0,5

Vy trong 4,3 gam X c: n C = 0,12 mol; nH = 2.0,06 + 0,04 = 0,16 mol;

nCl = 0,04 mol; nO = (4,3 0,12.12 0,16 0,04.35,5)/16 = 0,08 mol.
nC : nH : nO : nCl = 0,12: 0,16: 0,08: 0,04 = 3:4:1:2 CTPT ca X
dng:
b)

(C3H4O2Cl)n 230 n = 1 (loi); n = 2 c CTPT l C6H8O4Cl2.

Lp lun tm cng thc cu to ca A, B, D v vit cc phng trnh
phn ng xy ra.
+ Tm A:

C6H8O4Cl2 + NaOH d C2H4(OH)2 + mui A1 + NaCl

0,2 mol

0,2 mol

0,4 mol

1,0

A c th l: ClCH2-COO-CH2-CH2-OOC-CH2Cl
hoc ClCH2-COO-CH2-COO-CH2-CH2Cl
Phng trnh:
ClCH2-COO-CH2-CH2-OOC-CH2Cl + 4NaOHC2H4(OH)2 + 2HOCH20,5

COONa + 2NaCl
ClCH2-COO-CH2-COO-CH2-CH2Cl+ 4NaOHC2H4(OH)2 + 2HOCH2COONa + 2NaCl
+ Tm B: B + NaOH d Mui B1 + CH3CHO + NaCl + H2O

0,5

B l: CH3-CHCl-OOC-COO-CHCl-CH3
CH3-CHCl-OOC-COO-CHCl-CH3 + 4NaOHNa2C2O4+ 2CH3CHO +
2NaCl + 2H2O
+ Tm D: D + NaOH d Mui A1 + CH3COONa + NaCl + H2O
D l: CH3-COO-CH2-COO-CCl2-CH3
CH3COO-CH2COO-CCl2-CH3+5NaOH2CH3-COONa+
HOCH2COONa+2NaCl+ 2H2O
7

3,0
a)

- Pthh ca cc phn ng xy ra
4FeCO3 + O2 2Fe2O3 + 4CO2

(1)

4FeS2 + 11O2 2Fe2O3 + 8SO2

(2)

0,5

+ Kh B gm: CO2, SO2, O2, N2; cht rn C gm: Fe2O3, FeCO3, FeS2.
+ C phn ng vi dung dch H2SO4 long:
Fe2O3 + 3H2SO4 Fe2(SO4)3 + 3H2O

(3)

FeCO3 + H2SO4 FeSO4 + H2O + CO2 (4)

FeS2 + H2SO4 FeSO4 + S + H2S

(5)

0,5

+ Kh D gm: CO2 v H2S; cc cht cn li gm:FeSO4, Fe2(SO4)3,

H2SO4 d v S, khi tc dng vi KOH d:
2KOH + H2SO4 K2SO4 + 2H2O

(6)

2KOH + FeSO4 Fe(OH)2

(7)

+ K2SO4

6KOH + Fe2(SO4)3 2Fe(OH)3

+ 3K2SO4

(8)

+ Kt ta E gm Fe(OH) 2, Fe(OH)3 v S, khi ra khng kh th ch c

phn ng:
4Fe(OH)2 + O2 + 2H2O 4Fe(OH)3
b)

0,5
(9)

Vy F gm Fe(OH)3 v S
- Nhn xt: So snh h s cc cht kh trong (1) v (2) ta thy: p sut
kh sau phn ng tng ln chng t lng FeCO 3 c trong hn hp A
nhiu hn FeS2.
Gi a l s mol ca FeS2 s mol ca FeCO3 l 1,5a, ta c:
116.1,5a + 120a = 88,2 a = 0,3.
+ Vy trong A gm : FeS2 (0,3 mol), FeCO3 (0,45 mol).

0,5

+ Nu A chy hon ton th cn lng O2 l : (0,45/4 + 11.0,3/4) =

1,03125 mol s mol N2 l 4.1,03125 = 4,125 mol ; s mol khng kh
l (1,03125 + 4,125) = 5,15625 mol.
- V hai mui trong A c kh nng nh nhau trong cc phn ng nn gi
x l s mol FeS2 tham gia phn ng (1) th s mol FeCO 3 tham gia phn
ng (2) l 1,5x.
+ Theo (1), (2) v theo cho ta c : nB = (5,15625 + 0,375x)

0,5

+ V p sut sau phn ng tng 1,45% so vi p sut trc khi nung, ta

c :
(5,15625 + 0,375x) = 5,15625. 101,45/100 x = 0,2
- Theo cc phn ng (1), ...(9) ta c cht rn F gm : Fe(OH)3 (0,75 mol)
c)

v S (0,1 mol). Vy trong F c %Fe(OH)3 = 96,17% ; %S = 3,83%

- B gm: N2 (4,125 mol), O2 (0,40625 mol), CO2 (0,3 mol), SO2 (0,4
mol) MB = 32.
- Kh D gm CO2 (0,15 mol), H2S (0,1 mol) MD = 40. Vy dD/B = 1,25

Lu : Nu th sinh lm cch khc ng, cho im ti a tng ng.

0,5

===============================