S GIO DC V O TO

THNH PH NNG

HNG DN CHM K THI HC SINH GII THNH PH

NM HC 2004 - 2005
MN: HA HC LP 12 - BNG A
Thi gian: 180 pht (khng k thi gian giao )

Cu I
(3 im)
1. T l triti so vi tng s nguyn t hidro trong mt mu nc sng l 8.10 -18. Triti phn hy phng
x vi chu k bn hy 12,3 nm. C bao nhiu nguyn t triti trong 10gam mu nc sng trn sau
40 nm.
2. (a) Gi tn v vit ng phn cho cc hp cht phc [Pt(NH3)4Cl2]2+ v [Co(en)2Cl2].H2O.
(b) Gii thch s hnh thnh lin kt trong [CoF 6]3- (cht thun t) v [Co(CN) 6]3- (cht nghch t)
theo thuyt lin kt ha tr VB.
3. Vit phng trnh phn ng minh ha qu trnh iu ch cc cht sau y t cc n cht halogen
tng ng: (a) HClO4, (b) I2O5, (c) Cl2O, (d) OF2, (e) BrO3.
p n

im

10
2 6,02.10 23 8.10 18 = 5,35.106 nguyn t
1. S nguyn t 31T trong 10g mu =
18
n
0,693
kt v k
T ln
no
t1/ 2

s nguyn t 31T cn li sau 40 nm:

n 5,35.10 6 e

0, 693
40
12 ,3

= 5,8.105 nguyn t 31T

2. (a) Tn gi v ng phn:
[Pt(NH3)4Cl2]2+:
ion diclorotatraaminplatin (IV)
[Co(en)2Cl2].H2O:
diclorobis(etilendiamin)coban(II) monohidrat
2+

Cl
H3N

NH3

H3N

H3N

NH3

H3N

Cl
trans-

Cl
NH3
cis-

en

Cl
en

2+

Cl
NH3
en

Cl

en

Cl

Cl
en
en
cistranscis3(b) Phc [CoF6] thun t cho thy cc ion F phi tr vo cc obitan lai ha ngoi
sp3d2 cn trng ca Co(III):
F-

F-

F-

F-

F-

F-

3 2
lai ha sp
d

Phc [Co(CN)6]3- nghch t cho thy cc ion CN - phi tr vo cc obitan lai ha

1

trong d2sp3 cn trng ca Co(III):

CN-

CN- CN-

CN- CN- CN-

lai ha 2dsp3

3. (a) 3Cl2 + 6NaOH t 5NaCl + NaClO3 + 3H2O

4NaClO3 t NaCl + 3NaClO4
NaClO4 + H2SO4 NaHSO4 + HClO4 (chng ct)
(b) 3I2 + 6OH- 5I- + ClO3- + 3H2O
IO3- + H+ HIO3
2HIO3 t I2O5 + H2O
(c) 2Cl2 + HgO Cl2O + HgCl2
(d) 2F2 + 2OH- 2F- + OF2 + H2O
(e) Br2 + 2O3 0 C 2BrO3
o

Cu II
(4 im)
1. Tnh khi lng amoniclorua v th tch dung dch natri hidroxit 3,0M cn thm vo 200mL nc
v sau pha long n 500mL iu ch dung dch m c pH = 9,5 vi nng mui l 0,1M.
Bit pKb (NH3) = 4,76.
2. Cho cc thy tinh th nht cha dung dch hn hp KMnO 4 0,02M, MnSO4 0,005M v H2SO4
0,5M; cc th hai cha dung dch hn hp FeSO 4 0,15M v Fe2(SO4)3 0,0015M. t in cc platin
vo mi cc v ni hai cc vi nhau bng cu mui. Ni cc in cc vi nhau qua mt Vol k. Gi
thit rng H2SO4 in li hon ton v th tch dung dch trong mi cc bng nhau. Cho
o
Eo 3
0,771V v E MnO ,H / Mn 2 1,51V .
Fe / Fe 2
4
(a) Tnh th mi in cc trc khi phn ng xy ra. Vit s pin v tnh hiu th pin.
(b) Tnh hng s cn bng v th mi in cc ti cn bng.
3. Cho 1L dung dch HClO4 0,003M cha 2,0.10-4 mol mi ion Mn2+ v Cu2+. Bo ha dung dch ny
bng H2S, gi thit nng H2S lun bng 0,1M khng ph thuc s c mt ca cc cht khc.
(a) Hy cho bit c th tch ring hai ion Mn2+ v Cu2+ khng? Bit H2S c pK1 = 7 v pK2 = 14.
TMnS = 2,5.10-10 v TCuS = 8,5.10-36.
(b) Kt lun trn c thay i khng nu thay HClO4 bng dung dch m c [H+] = 10-9M?
p n
1. T pH pK a lg

[ NH 3 ]
[ NH 4 ]

9,5 (14 4,76) lg

im
[ NH 3 ]
[ NH 4 ]

[ NH 3 ]
[ NH 4 ]

1,8

Trong dung dch cui: NH 4 0,1M nn NH 3 1,8 0,1M 0,18M

1

n NH 4 (0,1mol.L ) (0,5L) 0,05mol v

n NH3 (0,18mol.L1 ) (0,5L) 0,09mol

T phn ng NH4+ + OH- NH3 + H2O ta thy rng s mol NaOH cn dng bng s
mol NH3 v tng lng mui amoni cn ban u l 0,05mol + 0,09mol = 0,14mol.
VddNaOH
o
2. (a) E Fe E Fe

(0,09mol)
0,03L , m NH 4Cl (0,14mol) (53,5g / mol) 7,49g
(3,0mol.L1 )
[ Fe 3 ]
0,003

0
,
059
lg
0,771 0,059 lg
0,671V
2
/ Fe
0,15
[ Fe ]
2

E Mn E oMnO / Mn 2
4

0,059 [MnO 4 ][H ]8

0,059 (0,02)(1) 8
lg

1
,
51

lg
1,52V
5
5
0,005
[Mn 2 ]

S pin:
Pt Fe2+ (0,150M), Fe3+ (0,003M) MnO4- (0,02M), Mn2+ (0,005M), H+ (1M) Pt
Hiu th pin:
Epin = EMn - EFe = 1,52V - 0,671V = 0,85V
(b) Hng s cn bng:
nE
0 , 059

5.(1, 51 0 , 771)
0 , 059

K 10
10
10 62, 63
V hng s cn bng ln nn phn ng sau c coi l hon ton:
5Fe2+ + MnO4- + 8H+ 5Fe3+ + Mn2+ + 4H2O
0,15
0,02
0,003
0,1
0,02
0,1
0,05
0
0,103
Ti cn bng:
E Mn E Fe E oFe3 / Fe2 0,059 lg

[ Fe 3 ]
0,103
0,771 0,059 lg
0,79V
2
0,05
[ Fe ]

3. (a) Coi s ng gp H+ ca H2S l khng ng k ta c [H+] = 0,003M

[H ] 2 [S 2 ]
K 1 .K 2 10 21
T
[H 2S]
0,1
21
1,1.10 17 M

[S2-] = 10
0,003 2

[Cu2+][S2-] = (2.10-4)(1,1.10-17) = 2,2.10-21 > TCuS = 8,5.10-36

Cu2+ kt ta di dng CuS

[Mn2+][S2-] = (2.10-4)(1,1.10-17) = 2,2.10-21 < TMnS = 2,5.10-10

Mn2+ khng kt ta di dng mui sunfua.

Nng S2- thay i khng ng k khi Cu2+ kt ta ht, nn khi Mn2+ vn cha
kt ta. Vy c th tch ring hai ion ny.
21
(b) [S2-] = 10

0,1

10

9 2

0 4 M

2+

[Mn ][S2-] = (2.10-4)(10-4) = 2.10-8 > TMnS = 2,5.10-10

Mn2+ cng kt ta, vy khng th tch ring hai ion ny.

Cu III
(3 im)
1. Tnh G v nhn xt chiu t xy ra cho phn ng: H2O (l) H+ (aq) + OH- (aq)
ti 25oC trong mi iu kin sau:
(a) [H+] = 10-3M v [OH-] = 10-4M
3

(b) [H+] = 10-12M v [OH-] = 2.10-8M

2. Hng s cn bng (KC) ca mt phn ng ha hp:
A(k) + B (k) AB (k)
3
1
o
3
l 1,8. 10 L.mol ti 25 C v 3,45.10 L.mol 1 ti 40oC.
(a) Gi s H khng ph thuc nhit , hy tnh H o v S o
(b) Hy tnh cc hng s cn bng KP v KX ti 298K v p sut ton phn l 1 atm.
3. (a) Thit lp biu thc xc nh chu k bn hy phn ng mt chiu bc hai dng A sn phm
(b) Tnh chu k phn ng bc hai: buta-1,3-dien (k) xiclobuten (k). Bit nng ban u ca
butadien l 0,272M; ti 500K hng s vn tc phn ng l 0,0143M-1s-1.

1.

p n
Ti cn bng ta c: [H ] = [OH ] = 10 M v KN = 10-14
G o RT ln K N (8,314J.K 1 .mol 1 )(298K ) ln(10 14 ) 8.10 4 J.mol 1
(a) G G o RT ln([H ][OH ])
+

im

-7

G 8.10 4 J.mol 1 (8,314J.K 1 .mol 1 )( 298K ) ln(10 3 10 4 ) 4.10 4 J.mol 1

V G 0 nn phn ng khng t xy ra theo chiu thun.

(b)
G 8.10 4 J.mol 1 (8,314J.K 1 .mol 1 )(298K ) ln(10 12 2.10 8 ) 3,2.10 4 J.mol 1

V G 0 nn phn ng t xy ra theo chiu thun.

2.

(a) T ln
ln

K 2 H o 1
1

K1
R T1 T2

3,45.10 3
1,8.10 3

H o 1
1

8,314 298 313

Ho = 33,77 kJ/mol
T Go = RT ln K = Ho TSo
H o RT2 ln K 2
o
175,6J.K 1 .mol 1
S
T2
(b) Ti 298K:
K P K C ( RT ) 1

3.

K x K P P 0,726
A
(a) k[A]2 =

khi t =

t1
2

1,8.10 3
0,726atm 1
8,314.298

1
1

kt
A A o

A 0
th: A
2

t 1/ 2

1
1
A 0 A 0

1

k

1
k A 0

257s
(b) t 1 k A
(0,0143M 1s 1 )(0,272M )
o
2

Cu IV
(3 im)
1. Hon thnh cc dy chuyn ha di y:
axetilen + CH3MgBr G + CH4
G + CO2 H H I (C3H2O2)

H 2O , H 2SO 4 , HgSO 4 J (C H O )
3

J + KMnO4 sn phm ch cha mt cht hu c K.

2. So snh (c gii thch) mnh tnh axit ca K vi (a) axit oxalic v (b) axit sucxinic.
p n

im

1. Hon thnh dy chuyn ha

CHCH + CH3MgBr CHCMgBr + CH4
CHCMgBr + CO2 CHCCO2MgBr H CHCCOOH

CHCCOOH

H 2O , H 2SO 4 , HgSO 4 HOCCH COOH

2

HOCCH2COOH KMnO
4 HOOCCH2COOH

2. (a) K1 (axit oxalic) > K1 (axit malonic) do khi mch cacbon tng, hiu ng (-I) ca nhm
cacboxyl gim lm phn cc ca lin kt O-H v gim bn ca baz lin hp. K 2
(axit oxalic) > K2 (axit malonic) do ion oxalat c bit bn nh s cng hng.
(b) K1 (axit malonic) > K1 (axit sucxinic) do khi mch cacbon tng, hiu ng (-I) ca
nhm cacboxyl gim lm phn cc ca lin kt O-H gim v bn ca baz lin hp
gim. K2 (axit malonic) < K2 (axit sucxinic) do ion sucxinat bn hn ion malonat nh
mch cacbon ln hn, th nng tng tc gia cc nhm COO- nh hn.
HO
OH
HO
OO
O 2C C
C C
C C
O
O
O
O
O
O
HOOC(CH2)nCOOH HOOC(CH2)nCOO- -OOC(CH2)nCOOCu V
(3 im)
Citral, C10H16O, l mt tecpen ng vai tr cu t chnh cho du c chanh. N phn ng vi
hidroxylamin sinh ra mt hp cht c cng thc C10H7ON, v vi thuc th Tollens cho kt ta bc
cng hp cht c cng thc C10H16O2. Oxi ha mnh lit citral sinh ra axeton, axit oxalic v axit
levulinic (CH3COCH2CH2COOH).
1. ngh cu to cho citral ph hp vi cc d liu trn v ph hp vi quy tc isopren.
2. Trong thc t citral gm hai ng phn l citral a v citral b. Oxi ha m du geraniol sinh ra citral a
(geranial), cn t nerol th sinh ra citral b (neral). Trong axit sunfuric, c geraniol v nerol u
chuyn ha thnh -tecpineol nhng kh nng chuyn ha ca geraniol chm hn nhiu so vi
nerol. Xc nh cu trc ph hp v gi tn theo IUPAC cho hai ng phn ny. Vit c ch phn
ng to thnh -tecpineol t nerol.
3. Khi cho citral phn ng vi olivetol trong axit long thu c mt hn hp cc sn phm trong
cha (I) . Cho bit c ch hnh thnh (I) v gi tn tng giai on ca c ch.
OH
OH
OH
-tecpineol

HO

C5H11-n
Olivetol

O
C5H11-n
-3,4-trans-tetrahidrocannabinol (I)
1

p n
1. Citral C10H16O c bt bo ha 3 ; Phn ng vi hidroxylamin v thuc th

im
5

Tollens cho thy n l mt andehit; Oxi ha to ba phn mnh cho thy phn t c hai
lin kt i. Xp cc phn mnh theo quy tc isopren ta c cu to ca citral:
CH3
CH3
OH
CH3

OH

CH2 CH2

OH

OH

OH

OH

CH3

CH3

CH3 C CH CH2 CH2 C CH CH O

2. Citral a v b l ng phn hnh hc lin kt i C 2: Nerol phn ng d dng hn, vy
nerol v neral l ng phn cis- (Z) cn geraneol v geranial l ng phn trans- (E).
CH3
H
CH3
H
C
CH3

CH2
CH2

H
C

CH3

CH3

CH2OH2+

CH2OH

CHO

H
(1)

CHOH

CHO
C

CH3

Citral b
(Z)-2,7-dimetylocta-2,6-dienal

+ H2O
- H+

CH2

- H2O

3. C ch to (I)
+

CH2
CH2

CHO

Citral a
(E)-2,7-dimetylocta-2,6-dienal
C ch phn ng (AE):
+ H+

H
C
OH

olivetol
(2)

OH

HO
C5H11-n
HO

H+
-H2O
(3)

H
C

HO

HO
C5H11-n

C5H11-n

(4)

HO

HO

HO

HO
C5H11-n

(5)

OH

-H+
(6)

C5H11-n
O

(1) Proton ha andehit, (2) Th S EAr, (3) Proton ha v tch nc to ion dn alylic, (4)
Cng AE ca cacbocation vo lin kt i, (5) Cng to ete proton ha, (6) Tch
proton to (I).
Cu VI
(4 im)
1. Ngi ta xc nh cu to cht khng sinh gramicidin S (cht A) bng cc qu trnh sau:
6

Phn tch sn phm thy phn cho thy t l ng phn t cc aminoaxit Leu H3N+CH(i-Bu)COO(M = 131), Orn H3N+(CH2)3CH(NH2)COO- (M = 132), Phe PhCH2CH(+NH3)COO- (M = 165), Val
H3N+CH(i-Pr)COO- (M = 117), Pro (M = 115). Khi lng phn t A khong 1300.
H
Pro:
COON
H
H
Th nghim xc nh aminoaxit C-cui mch cho kt qu m; th ngim xc nh aminoaxit Nu mch bng DNFB ch thy sinh ra DNP-NHCH2CH2CH2CH(+NH3)COO-.
Thy phn khng hon ton gramicidin S to thnh cc dipeptit v tripeptit sau: Leu-Phe, PhePro, Phe-Pro-Val, Val-Orn-Leu, Orn-Leu, Val-Orn, Pro-Val-Orn.
Cho bit trt t cu to ca phn t gramicidin S.
2. Qu trnh oxi ha metyl glycosit Q bng HIO 4 to sn phm ging nh sn phm oxi ha metyl glycosit ca D-andohexoz. Tuy nhin, qu trnh oxi ha Q ch tiu tn 1 mol HIO 4 v khng to ra
axit fomic. Metyl ha Q, thy phn, sau oxi ha mnh lit thu c axit dicacboxilic di-Ometylete ca axit (-)-tartaric. Lp lun vit cu hnh y cho Q (dng cng thc chiu).

p n

im

1. T M n (131 132 165 115 117 ) 1300 n = 2

Theo gi thit gramicidin S khng c C-cui mch. Sn phm DNPNHCH2CH2CH2CH(+NH3)COO- cho thy DNFB ch phn ng vi -NH2, ngha l
gramicidin S cng khng c N-u mch. Vy gramicidin S c cu trc vng.
T kt qu thy phn khng hon ton: Leu

Phe
Phe

Pro

Phe

Pro

Val
Val

Pro

Orn

Leu

Orn

Leu

Val

Orn

Val

Orn

ta c trt t: Leu-Phe-Pro-Val-Orn-Leu, vy trt t cu to ca gramicidin S l:

Val

Orn

Leu

Pro
Phe

2. Cu hnh y :
OMe
CHO
CHO O
CH2OH

Pro
Leu Orn

MeO
OH O
CH2OH

Val

OMe

OMe
HO

Phe

CHO
MeO

OMe O
CH2OH

COOH
MeO

OMe
OH
CH2OH

OMe
COOH

(Q)