Chemistry:OurLife,OurFeature

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CHEMISTRY
2011
OlympiaVN
PH LC 1. CC HNG S V CNG THC CN THIT
Hng s Avogadro NA = 6,022 x 10
23
mol
1

Phng trnh trng
thi kh l tng
pV = nRT
Hng s kh R = 8,314 J K
1
mol
1
Nng lng Gibbs: G = H TS
Hng s Faraday F = 96485 C mol
1

o
cell r
nFE K RT ln
o
G
Hng s Planck h = 6,626 x 10
34
J s Phng trnh Nernst
red
ox o
c
c
zF
RT
E E ln

Vn tc nh sng c = 2,998 x 10
8
m s
1
Nng lng photon

h
hc
E

0
o
Celcius 273,15 K
nh lut
Lambert-Beer
l c
I
I
A
0
10
log


Trong tnh ton hng s cn bng cc gi tr nng phi c chun ha vi 1 mol L
-1
. Coi
tt c cc kh l l tng.

PH LC 2. Bng tun hon v khi lng nguyn t
1 18
1
H
1.01 2

13 14 15 16 17
2
He
4.00
3
Li
6.94
4
Be
9.01
5
B
10.81
6
C
12.01
7
N
14.01
8
O
16.00
9
F
19.00
10
Ne
20.18
11
Na
22.99
12
Mg
24.30 3 4 5 6 7 8 9 10 11 12
13
Al
26.98
14
Si
28.09
15
P
30.97
16
S
32.06
17
Cl
35.45
18
Ar
39.95
19
K
39.10
20
Ca
40.08
21
Sc
44.96
22
Ti
47.87
23
V
50.94
24
Cr
52.00
25
Mn
54.94
26
Fe
55.85
27
Co
58.93
28
Ni
58.69
29
Cu
63.55
30
Zn
65.38
31
Ga
69.72
32
Ge
72.64
33
As
74.92
34
Se
78.96
35
Br
79.90
36
Kr
83.80
37
Rb
85.47
38
Sr
87.62
39
Y
88.91
40
Zr
91.22
41
Nb
92.91
42
Mo
95.96
43
Tc
-
44
Ru
101.07
45
Rh
102.91
46
Pd
106.42
47
Ag
107.87
48
Cd
112.41
49
In
114.82
50
Sn
118.71
51
Sb
121.76
52
Te
127.60
53
I
126.90
54
Xe
131.29
55
Cs
132.91
56
Ba
137.33
57-
71
72
Hf
178.49
73
Ta
180.95
74
W
183.84
75
Re
186.21
76
Os
190.23
77
Ir
192.22
78
Pt
195.08
79
Au
196.97
80
Hg
200.59
81
Tl
204.38
82
Pb
207.2
83
Bi
208.98
84
Po
-
85
At
-
86
Rn
-
87
Fr
-
88
Ra
-
89-
103
104
Rf
-
105
Db
-
106
Sg
-
107
Bh
-
108
Hs
-
109
Mt
-
110
Ds
-
111
Rg
-



57
La
138.91
58
Ce
140.12
59
Pr
140.91
60
Nd
144.24
61
Pm
-
62
Sm
150.36
63
Eu
151.96
64
Gd
157.25
65
Tb
158.93
66
Dy
162.50
67
Ho
164.93
68
Er
167.26
69
Tm
168.93
70
Yb
173.05
71
Lu
174.97

89
Ac
-
90
Th
232.04
91
Pa
231.04
92
U
238.03
93
Np
-
94
Pu
-
95
Am
-
96
Cm
-
97
Bk
-
98
Cf
-
99
Es
-
100
Fm
-
101
Md
-
102
No
-
103
Lr
-



Bi 1:
1. Kho st phn t CO.
a) V gin MO ca phn t ny.
LUMO l MO khng cha electron c mc nng lng thp nht. HOMO l MO cha electron
c nng lng cao nht. Mi MO khc nhau li c ng gp t cc AO ban u vi t l khc nhau
(V d: MO 2pz ca 1 phn t AB c ng gp t 70% bi AO 2p ca nguyn t A v 30% bi AO
2p ca nguyn t B).
b) Hy nhn xt mc ng gp ca Carbon v Oxy vo HOMO ca CO. T cho bit lin kt
ca CO vi Fe
3+
trong phc [Fe(CO)6]
3+
c to thnh bi C vi Fe hay O vi Fe?
c) Chiu di ca lin kt CO trong phc trn s thay i th no. Gii thch ngn gn.
2. Thuyt MO trong phc cht c th c p dng vo vic gii thch s tch mc nng lng
ging nh thuyt trng tinh th, nhng a ra li gii thch chi tit hn. Cng nh thuyt
trng tinh th, HOMO v LUMO ca phc bt din c phn b nh sau:

Trong eg mang bn cht phn lin kt (LUMO), t2g mang bn cht khng lin kt (HOMO),
v c 2 phn mc nng lng ny u mang c tnh ca kim loi nhiu hn c tnh ca phi t.
Gin trn l gin chung cho trng hp ligand ch l thun ty cho.
i vi trng hp ligand l cho hay nhn, cc MO ca ligand c th to lin kt vi
kim loi s tng tc vi MO t2g ni trn ca kim loi. Gi s nhng MO to ca ligand c th
c biu din nh sau:
FORUMOLYMPIAVN
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Hy v s t hp gia hai mc t2g ca ligand v ca kim loi trong trng hp cho v
nhn. Ch nng lng tng i ca t2g ca ligand so vi t2g ca kim loi (cao hn hay thp hn)
trong hai trng hp trn. T gii thch th t ca dy ph ha hc ca ligand:
I < Br

< S
2
< SCN

< Cl

< OH

< H2O < NCS

< < NH3 < < NO2

< PPh3 < CN

CO

Bi 2:
1. Cho cc d kin sau:
Qu trnh H
o
(kJ/mol)
Thng hoa ca Li (r) 161
Nng lng ion ha ca Li 520
Nng lng lin kt F2 158
i lc electron ca F 328
Nhit hnh thnh ca LiF (r) 618
a) Tnh Uml ca LiF
b) Chng minh rng i vi mng tinh th kiu NaCl, ta lun c 2 1

3 1.
Vi r(+) l bn knh cation, r() l bn knh anion. Xem hp cht AB l hp cht ion hon ton.
c) Ngi ta o c khi lng ring ca LiF rn l 2.64 g/cm
3
v chiu di cnh mng c s
l 402 pm. D on loi mng da vo tnh ton. Cho bit r(Li
+
)= 76 pm; r(F

) = 133 pm.
2. Carbon14 c thi gian bn hy 5730 nm.
Nm 1930, mt mu vt A c em gim nh tui. Ngi ta nhn thy hm lng tng
i ca
14
C trong mu vt ch cn 0.000558% so vi hm lng tng i ca
14
C trong
khng kh. Mt khc, ngi ta nhn thy mu vt ny c cha
238
U v
206
Pb, vi t l nguyn
t l 32257 : 1 . Chu k bn hy ca
238
U l 4.47 t nm. Hm lng cc nguyn t khc trong
chui phng x rt nh v hu nh khng i.
a) nh gi tui ca mu vt bng phng php
14
C v
238
U . T kt lun phng php no
cho kt qu hp l hn?
b) Vo nm 1970 ngi ta tm thy mt mu vt B cho kt qu phn tch tng t nh mu vt
A. Lc ny phng php no s cho d on hp l hn? Bit rng khong t 19451960 xy
ra kh nhiu th nghim ht nhn trn mt t.

Bi 3:
Cho bng gi tr nhit ng ca mt s cht nh sau (P
o
= 1,013.10
5
Pa). Cc gi tr ny
khng ph thuc nhit .
Cht

1 0
298
. ,

mol kJ H
1 1 0
298
,

K Jmol S
Na2SO4 1384,6 149,5
Na2SO4.10H2O 4324,7 591,9
H2O (lng) 285,8 70,1
H2O (kh) 241,8 188,7
1. C hin tng g xy ra khi 2 mui trn ra ngoi khng kh c m tng i bng 67%
v nhit 25
o
C .
2. Cc kt qu thu c trn c thay i khng khi h nhit xung 0
o
C.
3. m tng i no ca khng kh c hai cht song song tn ti 25
o
C.
4. Ni Na2SO4 l cht ht m tt c ng khng?

Bi 4:
1. Mt trong nhng phn ng quan trng trong phc cht l phn ng oxi ha kh ngoi
cu. C ch ca phn ng oxi ha kh ngoi cu vi hai cht A v B c m t nh sau:

a) Trong hai cht A v B, cht no l cht oxi ha, cht no l cht kh?
Bc (1) v (3) tng i ging nhau, l cc qu trnh hai cht tin li gn nhau bi s
khuch tn v phn ly. Phc hp [A, B] c gi l tin phc hp, cn phc hp [A
+
,B

]
c gi l hu phc hp. Ring bc (2) l bc chnh ca phn ng, l qu trnh cho
nhn electron gia A v B. Ngi ta cho rng bc (2) l bc chm, v do l bc tc
nh, ca c ch trn.
b) ngh phng trnh ng hc cho phn ng trn vi gi thit s dng trng thi dng.
c) Thu gn hng s tc phn ng t biu thc thu c cu b vi gi thit kd xp x kr.
d) V mt nguyn tc, bc th hai l bc cho nhn electron, m theo nguyn l Franck
Condon th s cho nhn electron l tc thi so vi s dao ng ca lin kt.
iu g lm cho bc (2) tr thnh bc chm? GI : trc ht nh gi s
nhanh/chm ca qu trnh khuch tn, sau cn ch n nng lng hot ha ca bc
(2). Ni mt cch khc, iu g khin ro cn nng lng ca bc (2) cao hn nhiu so
vi nhng bc khc.
2. Phn ng oxi ha kh gia hai phc cht cn c th c din ra theo kiu ni cu. Khi
hai phc cht tin li gn nhau ch yu do s khuch tn, ligand ca phc cht ny thay th
mt trong cc ligand ca phc cht kia to thnh tin phc hp, sau qu trnh
electron cho nhn din ra, ri ligand b thay th ban u tc kch vo hu phc hp thay
th ligand cu ni mt trong hai trung tm kim loi cho ra hai phc cht sn phm.
Qu trnh trn c m t nh sau:


Trong hai cp phc cht sau y, cp no c th thc hin phn ng oxi ha kh ni cu?
a) [Fe(H2O)6]
3+
v [Cr(H2O)6]
2+
b) [Co(NH3)5Cl]
2+
v [Cr(H2O)6]
2+


Bi 5:
Trong nc ion Pb
2+
to kt ta PbO l mt oxit lng tnh. Trong mi trng axit th ch c
duy nht Pb
2+
, nhng khi tng pH th c PbO v Pb(OH)3

u hin din lng c th o c.
Nhng cn bng quan trng ca cc tiu phn ch trong dung dch nc c cho di:
Phn ng 1 PbO(s) + H2O(l) Pb
2+
(aq) + 2 OH

(aq) Ksp = 8.010

16
Phn ng 2 PbO(s) + 2H2O(l) Pb(OH)3

(aq) + H3O
+
(aq)

Ka = 1.010
15

a) Oxit lng tnh PbO tan hon ton khi pH rt thp. Vi nng u ca Pb
2+
l 1.0010
2

molL
1
th pH bt u xut hin kt ta PbO l bao nhiu?
b) T gi tr pH tnh c cu trn, tng dn pH n mt gi tr xc nh s thy kt ta tan
dn. gi tr pH no kt ta tan hon ton?
c) Vit biu thc tnh tan ca PbO (r).
d) V l thuyt, tan cc tiu t c pH 9.40. Tnh nng mol ca tt c cc tiu phn
v gi tr tan cc tiu pH ny.
e) Xc nh vng pH gi tr tan nh hn hoc bng 1.010
3
molL
1
.

Bi 6:
A l mt oxit ca nit c mu nu. A tham gia vo cc phn ng sau y:
1) SO2 + A + H2O = H2SO4 + B 4) A + H2O + O2 = ... 7) D + A = C + ...
2) A + H2O (lnh) = ... 5) A + SO2 + H2O = C + ... 8) C + H2O = ...
3) A + H2O (nng) = ... 6) A + SO2 + H2O = D + ...
Bit rng phn ng 6 t l mi cht l 1:1:1. C nhiu hn D ng mt nguyn t hydro.
Xc nh cu trc cc cht cha bit v v cng thc cu to hp cht D.




Bi 1:
1. So snh tnh base ca cc hp cht sau

2. Trong cc hp cht sau, hp cht no l hp cht thm, phn thm v khng thm

3. So snh nhit nng chy v tan (trong dung mi l nc) ca hai hp cht
NH2COCONH2 (X) v NH2CONH2 (Y).

Bi 2:
Benzyne l mt trong nhng cht trung gian rt hot ng c tim nng rt ln trong tng
hp hu c. Cch iu ch benzyne ph bin nht l s tch loi 1,2 trn vng benzene. Gn y,
nhm nghin cu ca Gio s Hoye (trng i hc Minnesota Hoa K) tm ra mt cch khc
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iu ch benzyne in situ da vo phn ng Diels Alder. Trc ht, benzyne c th c biu
din bi mt cu trc cng hng A.

1. Gii thch kh nng phn ng cao ca benzyne.
2. ngh cu trc ca A, t ngh tin cht to thnh A da trn phn ng Diels Alder.
Benzyne rt hot ng, chng c th phn ng vi hng lot nucleophin hoc dien.
3. Da vo cc thng tin trn, hy ngh tin cht cho sn phm di y:


Bi 3:
Ty vo cch x l khc nhau i vi hn hp phn ng gia xiclohexen vi ozon 78
o
C
trong metanol v diclometan, sn phm thu c s khc nhau:
Cch 1: Nu ngay lp tc cho pMeC6H4SO3H (TsOH) ri trung ha bng NaHCO3, sau
cho Me2S (ng vai tr l cht kh) vo hn hp phn ng s thu c cht A. 1 ng lng A c
th phn ng vi 1 ng lng TsNHNH2. Mt khc, thy phn A trong mi trng axit mnh
to thnh B c th phn ng vi 2 ng lng TsNHNH2.
Cch 2: Nu cho hn hp phn ng x l vi anhydrit axetic (Ac2O) trong s c mt ca
Et3N s to thnh C. Cht ny cng c th phn ng vi 1 ng lng TsNHNH2. Cht C khc cht
A ch n va c th b thy phn trong mi trng axit, va c th b thy phn trong mi
trng kim (nhng trong mi trng kim C b thy phn nhanh v hiu qu hn). Tuy nhin sn
phm sau khi thy phn vn ch c th phn ng vi 1 ng lng TsNHNH2.
Cch 3: Nu cho hn hp phn ng x l vi TsOH nhng khng trung ha bng NaHCO3 v
cho phn ng vi Ac2O v Et3N th s cho ra D. Cht D khng c kh nng phn ng vi TsNHNH2,
nhng sn phm thy phn ca D trong mi trng axit c th phn ng vi 1 ng lng Ts
NHNH2, cn sn phm thy phn ca D trong mi trng kim khng th phn ng vi TsNHNH2.
1. C ba cch x l nu trn u i qua cng mt trung gian X. ngh c ch phn ng cho s
to thnh cht trung gian ny.
2. Xc nh A, B, C, v D. T X, ngh c ch phn ng to thnh B.
3. Bc quan trng nht trong cch x l u tin l phi trung ha hn hp phn ng
bng NaHCO3 trc khi cho Me2S. Chuyn g s xy ra nu ngi thc hin phn ng qun
trung ha dung dch trc?

Bi 4:
1. T 1,3xiclohexadion, MeI, EtI, v
i
PrMgBr cng vi cc cht cn thit khc hy ngh s
tng hp cht sau y.

2. Vo nm 2010, cc nh khoa hc vin Hi dng hc Nha Trang kt hp vi i hc
Illinois (Hoa K) c lp thnh cng t vnh Nha Trang cht nhatrangin A (Journal of
Natural products, 2010) c cu trc nh sau:

Cht ny c cc nh ha tng hp n cng b tng hp thnh cng ln u tin

vo thng 4/2013 theo s tng hp ngc nh sau:
OH
OMe O
OH
O
O
HO
OH
OH
OMe OH
OH
O
A
C
7
H
6
O
2

a) Lp lun xc nh A
b) A c chuyn ha theo s di y. Hy xc nh cu trc cc cht cha bit vi lp
th chnh xc. Cho bit: Phn ng t B ra C l phn ng cng Michael, phn ng t C ra D l
phn ng kh xeton, cn phn ng t E sang F l phn ng andol ha xc tc DProlin.


Bi 5:
1. Glucoz phn ng vi metanol trong HCl sinh ra metyl glucopyranoz.
a) ngh c ch phn ng ny.
b) Trn l thuyt, sn phm thu c s l hn hp gia hai ng phn v metyl glycozit.
Tuy nhin thc t ch thu c glycozit. Hy gii thch iu ny.
c) ngh mt phng thc tng hp chn lc Dmetyl glucopyranoz t glucoz.
2. Hon thnh cc phn ng sau:
a. Leu-Gly-Ser + 1-Flo-2,4-initrobenzen A
b. Ile-Glu-Phe B B
c. Asn-Ser-Ala + benzyloxycacbonyl clorua D
d. D + p - nitrophenol E
e. E + este etyl ca valin F
f. F
Pd , H
2
G

DCC
2. HBr, nitrometan
1. PhNCS