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I.

1

( )
, ,
( )

Ca10(PO4)6(OH)2 (
1004 /). , .
:

.
1 3 ,
,
7. :
7.1103, 6.2108, 5.01013. :
1.

a = [] / cPO4 (cPO4 )?
2.

Ks .

3.

, , 4.0.


, ,
10 ?
4.

(160 / ),

.
a.

, ,

-1-

2
,
, . ,
MnO4 + 8H+ + 5e = Mn2+ + 4H2O :
E MnO 4

E 0MnO 4

Mn 2+

=E

0
MnO -4 Mn 2+

0.059
5

[MnO 4- ][H + ]8
0
lg
= EMnO
2+
4
[Mn ]

Mn 2+

0.059
5

0
MnO 4 /Mn2+, EMnO

Mn 2+

[MnO 4- ]
lg
,
[Mn 2 + ]
Mn 2+

, .
0
EMnO

1.

Mn 2+

- ?
:
2H+ + 2e = H2 (pH < 7)

E 0H + H = 0.00
2

4H+ + O2 + 4e = 2H2O (pH < 7) E O0

H 2O

= 1.23 ( 2 = 0.21 ;

0 , lg p2)
2.

KMnO4 6?

E 0MnO 4

3.

Mn 2+

= 1.51 .

FeSO4 (NH4)2SO4 6H2O

0.100 . K2Cr2O7
( ) KMnO4.
7.42 K2Cr2O7 8.00 KMnO4.
KMnO4 .
4.

, ,
. (II)
. Fe2+ ,
Fe3+/Fe2+, MnO 4 /Mn2+.
(,
), , .
,
Fe2+ 2,
1%. E 0MnO

Mn 2+

= 1.51 , E 0Fe

3+

Fe 2+

= 0.77 .

-2-

3
, :
O

O
N

N
O

HN
O

H
N

N
O


: ,
( = 287 /),
( = 287 /),
. , ,
20 0.1 AgNO3.
( m1 = 0.0975 ).
FeNH4(S4)2
9.75 0.104 .
- .
1.

AgNO3,

.
2.

(),
(tR),
, ,
, .
3 ,
(tR = 5.47 ), (tR = 4.15 ) (tR = 11.15 ).
S (. .)
1= 0.05 /.
.
-

( )

( )

( )

( )

( )

( )

()

2.45

1.16

12.66

3.67

0.58

11.45

7.72

3.

, ,

cA = B = 5.93104 .
-3-

II.
1


(E). ,
d- (- ), (. ). D,
, , .
1.

2+

) Ni; ) Ni .
2.

Ni
3.

Ti3+

[Ar]3d1. ( D) -

d-


d- .

?
4.

2+

3
D
5
2
D
5

, D. , n d-
m .

(DhydH) M2+(.) M2+(.).

298.15K. ()
, .
5.

, .

H2O D = 8500 -1. :


. 1 -1.
: 1 -1 = 11.9627 -1.
-4-

Mn2+ Zn2+ ,
.
6.

d- (. )

, .
7.

2
.

,
.
1.

1.000 , 40%

. ,
? :
= 0.946 /3, = 0.789 /3, = 1.00 /3.
-.

( ). I
, II
, III . ()
.
C2, T1 ( D)
C4 C2.
(. ) .
T2 ( E) C1, C3 ( L
-5-

G). T3 ( F) 2.
2.

C1?

, C2?
3.

100 ,

40% ( ) E?
(
) , .
4.

50% 100 40%

? .
5.

, 40% 60% , .


.
?
30% ? .
,
1.9 , .

3
Haim A. Satin N. JACS ,
ABD, ,
A D, :
[Cr(H2O)5ABD]2+ [Cr(H2O)5DBA]2+

i(298) = 3.00105; i(318) = 1.35105.

[Cr(H2O)5ABD]2+ HClO4 ()
, (k) [H+]:
k = (k a + k i ) +

(k 'a + k i' ) K a
,
[H + ]

ka ka' ( 2); ki ki'


; [Cr(H2O)5ABD]2+.
[H+], /
k105,
([Cr(H2O)5ABD]2+) = C0
A292

1.00
7.75
102
0.105

0.500
9.20

0.100
20.8
102
0.105

0.0500
35.3

0.0100
151
5.00103
0.0525

C([Cr(H2O)5DBA]2+) = 292 ; l = 1
292 = C l (292 = 2.90103). k,
-6-

, ,
:

[Cr(H2O)5ABD]2+ + 2 [Cr(H2O)6]3+ + ABD

(k1)

[Cr(H2O)5ABD]2+ [Cr(H2O)4(OH)ABD]+ + H+

' ;K )
(k2' ; k2
a

[Cr(H2O)4(OH)ABD]+ + H2O [Cr(H2O)5(OH)]2+ + ABD

[Cr(H2O)5ABD]2+ [Cr(H2O)5]3+ + ABD

(k4; k4)

[Cr(H2O)5]3+ + ABD [Cr(H2O)5DBA]2+

(k5)

[Cr(H2O)5ABD]2+ [Cr(H2O)4(OH)ABD]+ + H+

1.

(k3' )

' ;K )
(k2' ; k2
a

[Cr(H2O)4(OH)ABD]+ [Cr(H2O)4(OH)]2+ + ABD

(k6' )

[Cr(H2O)4(OH)]2+ + ABD [Cr(H2O)4(OH)DBA]+

(k7' )

, A B , ,

S = 1, D II , + 2 = 4D.
ABD (lAB = 1.68 ; lBD = 1.16 ) DBA (lAB = 1.56 ; lBD = 1.22 ).
.
2.

H0, S0 G0 (T = 298K).

3.

, () i (298).

[Cr(H2O)5ABD]2+ [Cr(H2O)5DBA]2+ 1102 /


, , .
4.

(ka + ki) Ka(k a' + k i' ).

.
5.

[Cr(H2O)6]3+ [Cr(H2O)5DBA]2+,

. ,
[H+].
[[Cr(H2O)6 ]3+ ]
k a k 'a
=
=
[[Cr(H2 O)5 DBA]2+ ] k i k 'i

6.

ka, ki, Kaka' Kaki' ,

7.

, Wa = k1C([Cr(H2O)5ABD]2+) + k'3C([Cr(H2O)4(OH)ABD]+) Wi =

= k5C([Cr(H2O)5]3+)C(ABD) + k'7C([Cr(H2O)4(OH)]2+)C(ABD), , .
8.

k.

-7-

III.
1
, , ...
..

1967
Y. (. .),
( . equus
), : ) ;
) Harry the Horse.
t
A + B
C6H10 C6H4O2

C1

C12H14O2

C2

Zn
D
t
O

hn

hn

+ H'

Br2
E
CCl4 C H Br
12 14 2
Br
KOH
N
C2H5OH
O

Zn

G
C12H10Br2

1.

2.

I Y, , :
) ,

-; )
1

13; ,

2, ;
) G 4 ; ) ( = 93.5%)
, ,
, ; ) Y
-.
3.

Z. .
4.

F G?

2
,

(Nu)

:
X

Nu

E+
Nu

Nu

-8-

(+)

1.

I II,

, ,
:
O
+

O
O

1) CH3ONa / CH3OH
2) HCl / H2O, t

O
+

I
O

1) CH3ONa / CH3OH
2) HCl / H2O, t

II

- (+)
:
-.
2.

III. ,

,

( )
O

MgBr / CuI, -78oC

1)
2) Br

COOC(CH3)3 25oC

H+ / H2O

III

.
-
. , (IV)
( R = t-BuMe2Si ,
):
O

1) LiCu
2

OR
RO

2)

COOCH3

LiBHBu3
1 .

1) PdCl2(PhCN)2

2) HCOONH4

Bu4NF

OH
O

HOOC

IV
OH

3.

1) HO / H2O
2) H3O+

B .

IV.
:
t-BuMe2SiCl
OH
HC CH

4.

CH2O
KOH

Bu3SnH

1) BuLi

LiCu

2) CuI, R3P

1)

, H+
O
J
H
2) PBr3

1) BuLi
2) H2C CHCOOCH3
3) H+ / H2O

CH3OH
+

F L.
-9-

1) PBr3/
2) NaI/

OR
I
H3COOC

3
, ,
:
Cl

[2+2]
hn

A+B+C+D

KOEt
EtOH

150oC

D, 4--1 [2+2]- , .
D .
KMnO4
.
1.

C E .
Y

. Z
X,

, -
Z.
2.

Y Z.

, Y Z.
[n] [M(acac)2]
, [M(acac)2] :
O

O
M
O

.
.

Q, 10.6% Al 56.7% .
3.

n? , , [n]

(C) = 69.9%. [MXn].


4.

Q, .
,

.
[3]:
- 10 -

[MXn]

I J K, :
CHCl3
NaOH

CH3Li

CHCl3
G
NaOH

CH3Li

[MXn]

5.

F K, , H,

1 , :
I : MJ : MK = 1:2:3.

- 11 -

IV.
1

Y
Annales de chimie
Gl, .
Y: ,
Y (NH4)2CO3, K2SO4,
H2SO4. Gl
30 , (A),
70 Na Gl (B):
C + Cl2, t0

Gl

X
NaHF2, t0

, Gl M ( Y)
, Ar(Gl) 13.8,
, 1884
, Gl
, .
1.

Gl, X Y.

2.

3.

Gl M

Y: B Y,
. Y.
4.

Gl,

.
5.

Gl ?

2
,
(N) FSR =

lMe-Me
.
lMe-Me

Cln,
- 12 -

92.00% 28.80 Cl2,


(MeCl2)m (w = 5.04%, ). (m = 79.49 )
MeCln

,
72.86 , -

= 1920 1

= 2145,

~ 1700 1).

3 ,
HCl 00 D ,
500 .

MeCln (.)

MeCln ()
(MeCl2)m

D
E
1.

wMe, .% lMeMe,

H 0f ,

528

S0 ,

3.84

225

446

395

44.86
40.34
40.25

2.70
~4
2.11
2.13
2.38

, MeCln (MeCl2)m. ,

(MeCl2)m Cl ,
1/3 Cl ,
1 4103 /.
2.

MeCln (MeCl2)m.

3.

, , D , .

4.

D.

N: N =

e - e*
2

5.

FSR, lMeMe = 2.78 N.

6.

.
7.

( ).

- 13 -

3
.,
X, ,
.
SXa+n PtXa+n
Yd E (, X).
Xd + PtYb

PtXa+n (wPt = 63.1%) + Yd


SXa
SXa+n

Xd +

E (wPt = 57.2%) + YXa-1 (wX = 41.6%)

,
PtXa+n Z
.
Z

ZPtXa+n (wPt = 44.3%)

PtXa+n
Z

ZPtXa+n+1

Z ZPtXa+n+1
R (wX = 36.7%),
ZXa 2 ZXa + 2 .
1.

, PtYb.

2.

3.

AXa AXa + n ( A S, Pt).

4.

ZPtXa + n. ,


1.229 3.386.
.

- 14 -

V.
1
,
, ,
, , .
,

,
.

.
1.

, .
.
,
, F , G .
O

E SH CoA SH
CoA
A1
S

CoA SH A1
S

H2O E SH NADPH,H+ NADP+

CoA
A
B

NADPH,H+ NADP+
HO
E (C6H10O4)

CoA SH
D

HO
F

C
S-

2ATP 2ADP ATP ADP+Pi+CO2


G
CO2H

OPiPi
H

SH , SH
, NADPH NADP+ , ATP ADP ,
Pi .
2.

, .
, , H
- , , 4
: (1), (2), (3), (4,
).
3.

H H1,

-. H1 DrG0(298)
- 15 -

H H1, H1
1.9 .., ,
19% .
4.

H1

. ,
H1 ROH.
5.

H1 .

M N,
: M (N) + NADPH + H+ + NADP+.
M N, M ,
, , , N
.
P1 (4.93% O
) .
-

HO

O
R2

O O
P O
O
R3
R1
O

P1 + P2

(42H80NPO8), ,
(R1) (R2) ,
(R3). , P1
;

, 342 C612. R3
.
6.

, R1 R3,

P1, ,
16 .

2
(In) ,
. In ( ),
(SS) , . In
(pIn), N- -
, ;
-.
- 16 -

1.

-, - - pIn.
In pIn
.
2.

, 1, ?
.


. (Ala, 89 /); (Val, 117 /); (Gly, 75 /);
(Ile, 131 /); (Ser, 105 /) D H.
? D H / (Thr, 119 /).

3.

8
Thr
D
?
D
Thr


-
-
9
10
30
E
G
Thr
E
H
D
E
G
E
?
?
F
?
G
D

In () In (),
/
0
74
14
74
30

D H,

(G) > (H). .


4.

In 10- 30- ?
(X, Y Z) ,

, ,
,
. X Z
(1) (2):
Y + NAD++ + NAD+ (1)
5.

Y Z + CO2 (2)

X Z, Z 15.0% (

), Y, Z 50 70 /.
6.

Y . ,

(1), ,
.

( ) -
: (2.2 ..) (1.2 ..).
- 17 -

7.

X, Y Z ?
Y

. Y K ( ):
6126 () + 2L + 2M
8.

K, L M,

: O K L 2:1 1:2, .
9.

K, .


(dXMP), ( = A, T, G, C).

OO
P
O

5'

3'
4'
dXMP OH

1'
2'


().
: = ( ) G ( ).
dRib (Pi), Pi ,
3'- 5'- dRib.
1.

a)

(3'- 5'-) ,

(dXTP),
?
b)

( ) dRib, .
()
. ,


- 5' 3'- (. .).
, 3'- ( ).
, : , .
- 18 -

- ( ):

3'- ;

(,

),

(),

- dXTP .

. , 3'- , ,
b. , .
2.

?
3.

, 2- 3- .

a b .
4.

( n ) :
a)

b)

, ;

c)

, .

.
, .
.
5.

, 30 :
)

a, 231 62;
b)

32,

- 19 -