IV

51

2014

..

..
..

..
..
..
..

..

..

- : .,
., ., ., .,
., . :
























2014 -
51-

Web- :
http://www-chemo.univer.kharkov.ua/olympiad.htm
Web-
. -
.

1. 4 . .
5 .

2. !
3.
.

4. ,
. ,
. , ,
, - , , .

5. ,
.

6. . , , .
. , .

7. , . ,
, . ,
, .

8. .
.

9. ,
.

18

1
H
1.008

13

14

15

16

17

2
HE
4.003

3
LI
6.941

4
BE
9.012

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
24.31

10

11

12

13
AL
26.98

14
SI
28.09

15
P
30.97

16
S
32.07

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
[98]

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
LA
138.91

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
(209)

85
AT
(210)

86
RN
(222)

87
FR
(223)

88
RA
226.0

89
AC
(227)

104
RF
(261)

105
HA
(262)

58
CE
140.12

59
PR
140.91

60
ND
144.24

61
PM
(145)

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

90
TH
232.04

91
PA
231.04

92
U
238.03

93
NP
237.05

94
PU
(244)

95
AM
(243)

96
CM
(247)

97
BK
(247)

98
CF
(251)

99
ES
(254)

100
FM
(257)

101
MD
(256)

102
NO
(254)

103
LR
(257)

23

NA = 6,022110
1
:

= 8,314 K
1
1 = = 0,08205
K-11

= 96485 1

= 6,6310

34

PV

= nRT

E = hc /

= H TS

0
r G 0 RT ln K nF E

H = U + nRT

:
1
1
:

(..):

Q = It

273,15 K

E
a
RT
k = Ae

1 -2

Kw = 1,010-14

25 C

= 3,00108 1

1,60210
1,60210

-19

-19

R T (Ox i ) i
ln
n F (Red i ) i

: = l

1 .

: E E 0

0 ,

1 = 10

ln p H const
0

RT

1 = 760 = 1,0132510

0
ln K a H

T p RT 2

4
V r3
3

29 /

ln Ka (T )

H 0
RT

const

8 . 1 .
1.
: (IO2)2(S2O7)
1, (NO)6[Ni4(NO3)14].2HNO3 2, ClO2AsF6 3.
1-1 , : ) ;
) ; ) ;
) .
) 2; ) 3; ) 1; ) 3.
1-2 , 2 1?
3.661013 .
1-3 1 3.
27.72 %.
1-4 .
62.62 %.
2. .
,
.
,
, .
:
, . ,
(n, l, ml)
.
..
.
2-1 2
.
:
n = 1, 2, 3, ;
l = 0, 1, 2, 3, n1 ;
ml = 0, 1, 2, 3, l .
He 1s12s1, Li 1s12s12p1, Be 1s12s12p2 B 1s12s12p3.
2-2 , 2
.
:

2-3 , ,
? ' ?
.
.
3. !
,
, ,
. - ,
- .

(D(C) = 5.511).
D (D(D) = 4.255),
- ,
-100, .
3-1 , , , D ,
, 0.0968
15.00 NaOH
0.150 /.
A BrN3, B NBr3, C Br2, D NH3, X HN3.
3-2 ,
. ?

, , ,
1811 . . , .
3-2 , ,
, 11.64 %. .
NCl3

 , ,
, .
3-3 HCl.
3HN3 + 11HCl + 2Au = 2H[AuCl4] + 3NH4Cl + 3N2
4.
... '
, ...
, ,
, , ,
.
4-1 (
):

( )

4-2 ,
?
? ?
.
4-3 ,
.
, ( < 0) .
,
, , , .
( ) .
4-4 ?
.
()
().
5.
100
, ,
, (), ( . .).
74.25 %.
5-1 , ,
, .
Co(NO3)26H2O, CoO, 2, NO2, 2.
(
52.93 %), .
, . ,
2:1, ,
36.18 %.
5-2 , , . .
l, Al2O3. CoAl2O4.
2(NO3)26H2O = 2CoO + 4NO2 + O2 + 12 H2O,
2Al2(SO4)3 = 2Al2O3 + 6SO2 + 3O2,
CoO + Al2O3 = CoAl2O4.
5-3 : ) ; )
.
2Al + 2NaOH + 10H2O = 2Na[Al(OH)4(H2O)2] + 3H2,
2Al + 6HCl = 2AlCl3 + 3H2.
6.
,

, ,
, 2014. : ,
-, -,
, . 4 ,

 , 0 , . - 1 , -
2 , 3
. : 60 /
0 , 20 60 / 5 , 20 / 10 .
8 , D.
, .

-
-

SF2
0
?
0
6
0
8
CS2
?
?
?
0
0
?
BF3
4
?
?
?
?
?
ClF3
0
3
?
?
?
?
4
?
?
0
10
?
A
?
?
?
3
10
?
B
?
4
0
?
?
7
C
?
?
0
0
0
9
D
6-1 D, 2 . ,
,
. .
6-2 ? , .

-
-

SF2
0
2
0
6
0
8
CS2
4
2
4
0
0
10
BF3
4
3
0
0
0
7
ClF3
0
3
0
6
0
9
A (4)
4
4
0
0
10
18
B (NH3)
0
3
0
3
10
16
C (SF4)
0
4
0
3
0
7
D (PF5)
4
5
0
0
0
9
4, NH3, CS2.
6-3 8- , ,
(, , ,
), .

F
F

sp2

sp3

H
H

H
sp3

N H
H
H
sp3

sp

F
sp3d

F
H

Cl

S
F

F
F

sp3d

P
F

F
F

sp3d

,
, . , CS2, ,
.
6-4 ? .
CO2.

8 . 2 .
1.

, . ,
.
,
Y ,
. Y , Z,
( . atramentarius -).
Y:

,
, . .
.
,
.
.
. ,
,
. ,
, '
.
- .
Y .
1-1 ,
, 0.100 3.3 Hl (wl = 10.52 %, - = 1.05 /3)
22.04 3.609 ( 26.85 = 202.6 ).
Fe. Z FO, Y Fe2O3.
1-2 X Y, Y Z, Z Y,
, , ( 900), 70%-
( ).
4Fe + 3O2 = 2Fe2O3,
Fe2O3 + Fe = 3FeO,
4FeO + O2 = 2Fe2O3,
2Fe + 3Cl2 = 2FeCl3,
Fe + S = FeS,
3Fe + 4H2O = Fe3O4 + 4H2,
2Fe + 6H2SO4 = Fe2(SO4)3 + 3SO2 + 6H2O.
'

(w(N) = 27.07 %) .
1-3 .
Na2[Fe(OH)4].
1-4 Y ?
.
: , , ,
.
Fe2O3: , (), .
2.


. ,
. ,
.

( ) (
). ,
, .
1.0
, , 1.015 ,
- .
2-1 , ,
, ,
.
Cu(NO3)2, AgNO3, Cu(OH)2, Ag2O, [Cu(NH3)4](OH)2, - [Ag(NH3)2]OH,
CuI, AgI, I2.
Cu(NO3)2 + 2NH3 + 2H2O = Cu(OH)2 + 2NH4NO3,
2AgNO3 + 2NH3 + H2O = Ag2O + 2NH4NO3,
Cu(OH)2 + 4NH3 = [Cu(NH3)4](OH)2,
Ag2O + 4NH3 = 2 [Ag(NH3)2]OH,
AgNO3 + KI = AgI + KNO3,
2Cu(NO3)2 + 4KI = 2CuI + I2 + 4KNO3.
2-2
?
.
2-3 ? , ,
.
AgI AgNO3 .
2-4
.
2Ag + 2NO3 = AgNO3 + NO2 + 2.
3.
, (47.01 %). ,
(39.95 %). ,
, , - .
, ,
1.25:1.
3-1 .
S, Ca, A CaSO4, B CaSO3.
( 49.60 % )
D ( 55.76 % ).
3-2 D.
CaSO40.5H2O. D CaSO42H2O.
3-3 AD.
CaSO4 , ,
CaSO40.5H2O , ,
CaSO42H2O .
3-4 , C D?
, .

 4.
- ,
,
'.
.
, .
10 3 ( 25
1 ). , , 21 %, , ,
16 % ( '), ' , , .
4-1 , .
n(O2) = 20.45 .
:
O2 + H2O C6H12O6 + O2.
4-2 , ,
. , '
((H2O) = 1 /3)?
V(H2O) = 369 .
m() = 614 .
.
4-3 , ,
(w(C) = 69.03 %), (w(H) = 4.64 %),
(w(O) = 13.14 %), (w(N) = 9.20 %) 1 ,
40 /.
M(35285N4Mg) = 608.97 /.
, , , ,
.
4-4 , .
, .
4-5 ,
, .
2KMnO4 = K2MnO4 + MnO2 + O2 ( ),
2KNO3 = 2KNO2 + O2 ( ),
2H2O2= 2H2O + O2 ( (nO2, Cu2+ .) ),
2lO3 = 2Cl + 3O2 ( ).
5.
, ,
. ,
, .
5-1 : , ,
, .
[P] = , [T] = , [V] = 3, [m] = .
, .
,
. ,
.
, B X,
D, E F . D, E F

G, ,
H, I, , , .
, G ( = 1 /),
, , , ,
. 1 , 77F
6.546, 3.986 4.688 .
, , .
G. ,
+32F (F ), +212F.
.
, G 3784 , G
' 7.492103 .
5-2 G.
G 2.
5-3 ' .
F = 1.8K 459.67
5-4 , .
1 = 28.35 , 1 = 3.784 .
5-5 .
Li, Na, K, X O2, D Li2O, H LiOH, Y H2, E Na2O2, I NaOH, F KO2 , K
KOH.
5-6 , .
4Li + O2 = 2Li2O,
2Na + O2 = Na2O2,
K + O2 = KO2,
Li2O + H2O 2LiOH,
Na2O2 + 2H2O 2NaOH + H2O2,
2KO2 + 2H2O 2KOH + H2O2 + O2.
6. -
(,
, ),
, . ,
, , , ,
.
, , ,
. , , , ,
!
6-1 ,
. ,
, .


, ,

,
, , .
6-2 ,
.



Fe(OH)2
()

FeSO47H2O
()
()-

KCr(SO4)212H2O

NaHCO3


CuCl2
()

Fe(OH)3
()

NaOH

K2CO3


CuSO45H2O
()

CuCl
()
20- , ,
. , ,
,
,
.
6-3 ,
, , .
.

N
N N

sp2 sp
+

sp3
+
N
O
2
H
O sp

O N
O

N N N

sp2

O O

O O
O

CO

O
O

Co CO
OC

CO

dsp3
O

Co
Co

O
O

- sp

( )

9 . 1 .
1.
0,2 ,
. ,
, , , 1,466 .
,
.
1.1. , .
CF4. , , .
1.2. , , 1,45 20
2 ( 100%).
KF.
1.3. ?
. .
1.4. ,
.
: + + 1 = 0. : 2F- - 2 = F2; F2 + C = CF4.
1.5. ? .
: 2SiC + 2F2 = 2Si + CF4; 2 + SF4 = CF4 + SO2.
2.
(Ho 298)
. ,
12,544 2 H3PO4 (=1,1 /) 0.01 NaOH ( 10 M ).
2,52 ( C=265,4 /,
). ,
=2.06.
Ho HCl NaOH. ,
0,01 582
.
2.1. Ho HCl. .
Ho = -58.2 /
2.2. Ho H3PO4. ?
Ho=-66.88 /. : H3PO4+OH-=H2PO4-+H2O.
2.3. Ka1 H3PO4.
Ka1 = 6,810-3.
2.4. Ho1 So1 H3PO4.
o
H 1 = -8.6 /; So1 = -70.35 /.
3.
. ,
Sa (I) Sb (II), .
3.1. a b, MI/MII = 0.875. I II.
I II S7 S8. 8S7
7S8.
3.2. rH I II, ' S S
260,0 / I 263,3 / II.
rH = -184.8 .
3.3. , 66,
S6 ( = 0,32%), S7 ( = 0,76%) S8 ( = 98,92%).

 %.
(S6) = 0.43%; (S7) = 0.87%; (S8) = 98.70%.
3.4. Kc S6 S8, [S6] = 0,0018
/.
= 4.31019 2/2.
3.5. 8- , ,
S4N4. S4N4, S N ;
N 3, S 2 (2 ) 4 (2 ).
, S4N4:

4.
, 1
(0,050 ) 5,010-7 NaOH
17,7, .
, :
NaOH, : n(NaOH) = (5,010-7 /) (5,010-5 ) =
2,510-11 .
1,371021 ( ).
: [NaOH] = n(NaOH)/V() = (2,510-11 )/(1,371021 ) = 1,8210-32 M = [OH]. [H3O+][OH-] = Kw, [H3O+] : [H3O+] = Kw/[OH-] =
(1,0010-14)/(1,8210-32) = 5,481017 . = - lg[H+] = lg[H3O+], = lg(5,481017) = 17,7 !!!
5.1 ,
. ,
, .
pH = 7,00, .
5.2 ,
, 1.
8,1.
mNaOH = 6,191014 .
5.3 pH .
pH = 7,71.
5.4 ? .
.
5.5 pH NaOH, KOH, CsOH, Ca(OH)2 B(OH)3
( = 1 m)? ,
pH .
B(OH)3 > (NaOH, KOH, CsOH) > Ca(OH)2
5. .
, , , ,
(() = 39,10 %, () = 12,94 %).
.
, ,
, ,
I ( )
. I ,
' .

5.1 , ,
96,11 %. .
=
=
=
B=
=
=
=
=
As2S3
Ag2S
S
H2
Ag
AsH3
As
S
5.2 , .
3Ag2S + 8HNO3 (., .) = 6AgNO3 + 2NO + 3S + 4H2O,
3As2S3 + 10HNO3 (., .) + 4H2O = 6H3AsO4 + 10NO + 9S,
Zn + H2SO4 (.) = ZnSO4 + H2,
2AsO43- + 11H2 = 2AsH3 + 8H2O,
2 + 2AgNO3 = 2Ag + 2HNO3,
AsH3 + 6AgNO3 + 3H2O = 6Ag + H3AsO3 + 3HNO3.
2AsH3 = 2As + 3H2
5.3 ?

.
5.4 ?
S8 , AsH3 .
6. .
0,300 0,508
0,338 ,
, .
, , ,
1:, :1.
,
1990 .
30 C, .
, 86,98%.
, ,
( )
.
6.1 , , .
.
B=
=
=
=
=
=
=
A=
AgN3
I2
IN3
AgI
NI3
BN
IF
BF3
6.2 , .
B:
:
sp3
sp2 sp
+

N N N

N N N
I

I
I

9 . 2 .
1. .
.
1.1 .
CaO+CO2 = CaCO3 ( )
ClO2+H2O=HClO2+HClO3 ( )
N2O+CO=N2+CO2 (- )
FeO+CO=Fe(CO)5+CO2 (- + )
NO+NO2=N2O3 ( )
1.2 2012 X2On YOz ( ..).
, ,
80 24 .
(w(X) =
6.54 %,w(Y) = 29.91%), .
, X2On HXO3,
H2YO4.
X2On YOz .
.
X2On N2O5; YOz SO3; A (NO2)2(S4O13).

- sp, - sp3
1.3 ,
X2On YOz, ( ).
(NO2)2(S4O13)+5H2O=2HNO3+4H2SO4
N2O5 SO3 , , :
2NO2 + O3 = 2N2O5 + O2, 2HNO3 + P2O5 = N2O5 + 2HPO3
2SO2 + O2 = 2SO3 ( ), Na2S2O7 = Na2SO4 + SO3 (
)
1.4 8 YOz 100 . ?
.
w(H2SO4) = 8.89%
2.
, ,
17,39 % Mg, 19,57 % ,
21,62 % Mg. 4,6 4
, 20 % Mg,
.
2.1 . .
=
=
=
=
MgHPO4H2O
Mg2P2O73H2O
Mg2P2O7
MgHPO4
2.2 ,
2MgHPO4H2OMg2P2O7+3H2O
Mg2P2O73H2OMg2P2O7+3H2O
MgHPO4H2OMgHPO4+H2O
2.3 .

O
O

O
O

3.
' ,
. , ,
, .
, ,
, , , .
'
CxHyNzOn 0,1
, ,
(N) = 12,17 %.
, , 4 %- 2 .
' 1
. 12,6
HCl.
3.1 ,
, '
5 , 1 Cl, 2,3 , 2,6 2,6 0,1
.
(HCl) = 0,05 .
3.2 .
NH4HSO4 + 2NaOH = NH3H2O + Na2SO4,
NH3 + H2O + H3BO3 = NH4[B(OH)4].
NH4[B(OH)4] + HCl = NH4Cl + H3BO3 + H2O.
3.3 , .
(N) = 17,64 %.
3.4 (, ,
)? ,
?
. , .

 4.

, 1 5.
, 1 3, ,
2 3 , . 3 4
. ,
. Y ,
, (Y) = 36,81 %.
4.1 Y, 1 5 . .
1 =
2 =
A3 =
A4 =
A5 =
=
MnO2
2MnO4
MnSO4
Mn(OH)2
KMnO4
H2SO4
B=
=
=
=
=
Y=
O2
H2O

2SO4
Mn
O
4.2 .
2MnO2 + 2H2SO4 = 2MnSO4 + O2 + 2H2O,
MnSO4 + 2 = Mn(OH)2 + K2SO4,
2Mn(OH)2 + O2 = 2MnO(OH)2,
MnO(OH)2 (t) = MnO2 + H2O,
2MnO2 + O2 + 4KOH = 2K2MnO4 + 2H2O,
2KMnO4 (t) = K2MnO4 + MnO2 + O2,
K2MnO4 + 2H2SO4 + 2Na2SO3 = K2SO4 + 2Na2SO4 + MnSO4 + 2H2O (
- ).
4.3 1, 4, 5.
1
2
5

MnO2
K2MnO4
KMnO4

4.4 2 1 ? .
. (
) :
K2MnO4 (t) = K2O + MnO2 + O2.

 5. .
1869 , .. ,
.
"-", "-" ( "") "-".
- .
5.1 -, - -?
, ...
- , AG = 68 ... ( 69,72 ...);
- , AGe = 72 ... ( 72,61 ...);
- , A = 99 ... ( 98,91 ...).
5.2 , , .. - ,
,
? ,
-, -, -? ,
, .
, , ,
.
5.3 , -, .
, CO2 - , SiO2 - .
CO2 SiO2. 2,
.
CO2: O=C=O, sp-, . SiO2: , Si4+
.
5.4 ..
, , .
?
, , , .
5.5 36Ar 38Ar, 40Ar
99,600%. 36Ar, 38Ar 40Ar 35,970, 37,960 39,960
..., .
(mp=1.007 ..., mn=1.009 ...)?
36
Ar = 0,00101 ( 0,101 %);
38Ar = 0,00299 ( 0,299 %).
,
( ).

 6.
, Y,
. , ,
Y . .
, , :
Q ( (X) = 65,26%) R,
Q 1:2.
, ,
( ).
,
.
6.1 , Y, , B, Q R,
. .
=
=
Q=
Y=
R=
=

2
H2SO4

22
H2S2O8
2H2 + O2 = 2H2O
2H2SO4 = H2S2O8 + 2
2S2O8 + 2H2O = 2H2SO4 + H2O2
1000 ,
, 40 .
6.2 , , ',
96%. .
H2O3; 22 + 3 = H2O3 + O2.

10 11 . 1 .
1.
(D2=14). 1908
,
. 1923 C ,
D , ,
. D 1959 ,
. D Td ( ),
C3v ( ).
, ( C3v):
F

Na
H2

ZCl3

H
C3v

C
t

D + E
Td

C3v

D E

F
G
H
, % 73,42
100,00
34,47
41,22
30,38
24,49
27,72
1.1 , , D, E, H
( ).
18- . ,
.
A Co3O4
B Co
C Co2(CO)8
D E o4(CO)12
Z Bi
G
H
F Na[Co(CO)4]
X CO
Bi[Co(CO)4]3
BiCo3(CO)9
1.2 C?
0.
1.3 .
Co3O4 + 4H2 3Co + 4H2O
2Co + 8CO Co2(CO)8
Co2(CO)8 Co4(CO)12 + 4CO
Co2(CO)8 + 2Na 2Na[Co(CO)4]
3Na[Co(CO)4] + BiCl3 Bi[Co(CO)4]3 + 3NaCl
Bi[Co(CO)4]3 BiCo3(CO)9 + 3CO
1.4 D, E H, ,
, .

 2.
1877 ..
,
.
. ,
B . , B C .
B C ,
(, ).
,
D (15,79% H).
(17,24% H).
2.1 A-E, , -
9:1.
.
H3C
CH3

CH2
H3C

CH3

H3C

CH3

H2C
CH3

CH3

H3C

CH3

H3C
CH3
H3C

H3C

CH3
D

CH3
C

H3C

H3C
CH3

H2SO4
H3C

CH3

H2C
CH3

CH3

H3C

H2C
CH3

CH3

CH3
H3C
CH3

H2, Ni/Re
CH3

H3C

H3C

Br

CH2

CH3

H3C

H2C
CH3
H3C

CH3

CH2

CH3

H2, Ni/Re

CH3

H3C

CH3

CH3

CH3

H3C
CH3

CH3

H3C

CH3

H3C
CH3

H3C

CH3

H3C

CH3

CH3

H3C
CH3

Br2
CH3

H3C

H3C

CH3
Br

CH3 Br

CH3

CH2

Br2

H3C

Br

CH3

Br
H2C Br
CH3
CH3
CH3

2.3 B C.
:
CH2

H3C

CH3

H3C

H3C
CH3 C+

CH2

CH3

H+

CH3

H3C

H3C

CH3

CH3 H
G

F
H3C
CH3
H3C
CH3

CH3

H2C
CH3
H3C
CH3

CH3

CH3

CH3
E

2.2 .
CH2

CH3

CH3

-H+

 , ,
, ,
.
2.4 ,
. , .
, . ,
I J H.
H3C
H3C
CH3 C+
H3C
CH3 H
G

CH3

CH2

H3C

H3C
H3C
H3C

CH3

H3C
H3C

H3C CH3 CH3

+

CH3

-H+

H3C CH3 CH3

CH3
H

H
H

H3C
H3C
H3C

H3C CH3 CH2

CH3
H
J

2.5 .

?
CH2

CH3
CH3

CH3

CH3

CH3

2.6 ,
?
().
3.
,
.
.
, . ,
IV . ..,
1846
. 25 .. (
).
1000 (p=1 ):
(.) + 0,52(.) (.)
(.) + 2(.) 2(.)
:

2
0
0
0
-110,4
-393,5
H f, /
0
5,7
205,2
197,6
213,6
S , /K
3
3.1 /
31,36 /3.
3.2
1000, , .
G1 = -199,8 /
1 = 2,7 1010
G2 = -396,2 /
2 = 5,2 1020

3.3 ) , ) ,
) ? .
) ; ) ; ) .
(Hb) , ,
. ,
, :
CO() + HbO2() O2() + HbO() ; Kc=230
, HbO 2%
HbO2.
3.4 ,
,
..
7,76 10 7 / .
(II)
. .
I2O5, Na2S2O3.
3.5 , .
CO + PdCl2 + HOH Pd + CO2 + 2HCl
5CO + I2O5 5CO2 + I2
I2 + 2Na2S2O3 2NaI + Na2S4O6
4. E-

,
.
, ,
:

,
39,34 %
N

X
171

59,93 %
Y

20,72 %

27,37 %
500(II)

N ( = 5,64 , = 2,16 /3) 171 (

= 4,59 , = 2,96 , = 4,25 /3). ,
, , 4, .
450(I)

4.1 N 171?

 N 4 .
171 2 .
4.2 ,
N 171
Mr (N) = 58,44
Mr (E171) = 79,87
4.3 X Y N, 171.
X Na
Y Ti
N NaCl
171 TiO2
4.4 A D, 450(I) 500(II). , . . D
.
AD450(I) 500(II) B - TiOSO4 C TiO(OH)2
FeTiO3
TiCl4
Na2H2P2O7
NaHCO3
4.5 .
FeTiO3+2H2SO4=TiOSO4+FeSO4+2H2O
TiOSO4+2KOH=TiO(OH)2 +K2SO4
TiO(OH)2 =TiO2+H2O
2FeTiO3+7Cl2+3C=2TiCl4+2FeCl3+3CO2
TiCl4+O2=TiO2+2Cl2
2NaH2PO4=Na2H2P2O7+H2O
NaCl+NH3+CO2+H2O=NaHCO3+NH4Cl
450(I), 500(II) , ,

.
4.6 ,
.
2NaHCO3+Na2H2P2O7= Na4P2O7+2CO2+2H2O
5.
-
Na2S Na2SO4 .
"
" . , '
, , 100 1
CuSO4. , Na2S,
.
: = 298 , (CuS) = 610-36
5.1 , Na2SO4
.
Na2SO4 + 4C = Na2S + 4CO
CuSO4 + Na2S = CuS() + Na2SO4.
5.2 , . ,
. ,
Na2S . ,
CuS .
2+
Cu + 2 = Cu
:
RT
E = E o 2+
+
lna 2+ = E o 2+
+ 0,013lna 2+
Cu
Cu
Cu / Cu
Cu / Cu
zF
, Cu2+.
5.3 ,
6,00 Na2S. .
0,02 .

5.4 ,
12,00 Na2S. .
0,986 .
5.5 -, Cu|CuSO4
Ag|AgNO3 ? , :
) Na2S CuSO4
) Na2S CuSO4
) ; ) .
5.6 Cu|CuSO4
Ag|AgNO3 Na2SO4?
; .
Cu|CuSO4 .
6.
: ( 232Th 208Pb), ( 237Np
209Bi), ( 238U 206Pb, T,238=4,47109 ) ( 235U 207Pb,
T,235=7,038108 ).
6.1 , ?
, .
- ( 4). ,
4 .
4, 4 : 232Th (4n), 237Np (4n+1), 238U (4n+2), 235U (4n+3).
6.2 , - --
.
6 - 4 --.
,
206Pb/207Pb.
204Pb .
6.3 , 206Pb/207Pb
.
n(X) X.

6.4 , ,
: 238U/235U=137,88,
206
Pb/207Pb=1,09. ,
.

, 208Pb/232Th.
6.5 , 208Pb/232Th=910-5, (Th-232) = 4,9510-11 -1.
1,82 .
7.

, - .

 .
.
50 6,42 % ( ,
1 /3) , , :
1. ' 10
. '

0,1314 ( 70%). .
2. ,
.
3. ' 10
1,0332 .
C 0,8328 ( 36,3%
).
4.
HCl, D (
15,74% ).
5. , ,

( ,
1 ).

NaCl
BaCl2
AlCl3
K4[Fe(CN)6]
A
,
113
224
342
432
346
121
7.1 -D, .
35,5,
.

B
C
D
[Co(NH3)6]Cl3
oO1,27
[Co(NH3)6](NO3)3
[Co(NH3)6]2(SO4)3
7.2 , .
2[Co(NH3)6]Cl3 + 6NaOH 2CoO1,2 + 6NaCl + 3H2O + 12NH3+ 0,3O2
[Co(NH3)6]Cl3 + 3AgNO3 3AgCl + [Co(NH3)6](NO3)3
2[Co(NH3)6]Cl3 + 3H2SO4 6HCl + [Co(NH3)6]2(SO4)3
7.3 . , ?
: [Co(NH3)6]3+, Cl-. [Co(NH3)6]3+ ,
, . .
7.4 Fe(NH4)2(SO4)26H2O?
, ,
.
5 . ,
440.

10 . 2 .
1.

, '
() ()
():
C 2
K
1
,
.
1.1 KCl?
.
1.2
0 ?
0 1 .
,
.
1.3
2 .
4 2 3
K
1
, ,
C 2
K
.
1
1.4 ,
H .
.
1.5 0,
+ .
:
) d = 10-4 /
) d = 10-7 /
) d = 10-10 /
) = 99,9 %; ) = 50,0 %; ) = 0,10 %.
2.
A (D2 = 21) 100
.
2.1 A .
A

Al2O3

2.2 ,
.

 :
Cl2/400 0C

Cl

HBr

Cl

Br

Zn

ROOR

2.3 () ()
(H0 = 53,1 /; S0 = 238 /()) (H0 = 20,5
/; S0 = 267 /()) 100 0.
K = 1,2106; ~ 100%.
2.4 100 0 6,8 15%.
1/2 .
1/2 = 28,8 .

, , .
. 100 0 Al2O3
, .
2.5 . , Al2O3
H+, .

3.
, , .
. (1971-1867)

.
. 120,000 ,
4,812%.
2,500. 4 : -D.
t3.
:
. ( ) 35,5.

3.1 m=f(t)?
() tg .

M I
F
3.2 -D, , t2/t1=1,60, ,
.
A H2; B O2; Cl2; D Cu.
3.3
t3. , -D .
: CuSO4, (2,4 , 2,00%).
: H2SO4, (1,29%).
3.4 t1, t2 t3 .
t1 = 1930 ;
t2=3088; t3 = 8106 .
3.5 ,
.
H2O:
CuCl2:
CuSO4:
2+
2+
Ka: 2H2O +2e H2 +
Ka: u +2e Cu Ka: u +2e Cu
+
2OH: 2Cl -2e Cl2
: 2H2O -4e 4H + O2
:
:
: 2H2O -4e 4H+ + O2
CuCl2 Cu + Cl2
2CuSO4 + 2H2O 2Cu + 2H2SO4 + O2
: 2H2O 2H2+ O2
tg

4.
,
. , , ,
.
4,4 ( 18,2 %)
5,4 .
4.1 - .
512
4.2 , -
, ( *),
, ,
.
O
O
O
O

*
4.3 ?
RS .
O
O
O

S
4.4 , ,
.
:

, ,
, - .
4.5 ,
, .
:
:

:
O

4.6 , .
() ()
( , * ,
).

()
*
O

.
5. ?
,
.
, , . 2012
,
.

 , .
2+ 1,000
, 0,100
.
5.1 2+ ,
55,000 . ,
, .
2+
w(Ca ) = 22%
5.2 2+ .
, ,
0,20 % 18,50 % ,
-.
Ca5(PO4)3(OH).
5.3 ,
.
w(Ca5(PO4)3(OH)) = 55,25 %.
5.4 2+ Ca3(PO4)2,
Ks(Ca3(PO4)2) = 210-29 (/)5.

5.5 , 100
0,5 400 0,1 .
Kb(NH4OH) = 1,810-5 /.
5.6 , 0,04
?
= 8,95.
6.
,
. ,
.

 A2
B
D
K
L
G
W(A), % 100 82,35 30,45 30,41 28,77 43,74
6.1 . .
, ,
.
A2 N2
B NH3 C Mg3N2 D NO2
E HNO3
F NH4NO3
G
H N2 O K
L
M Ca3[Fe(CN)6]2
NH4NO2
Ca(CN)2
Ca2[Fe(CN)6]
6.2 , .
N2 + 3H2 = 2NH3
6Ca(CN)2 + 2FeCl3 = Ca3[Fe(CN)6]2 + 3CaCl2
2NH3 + 3Mg = Mg3N2 + 3H2
Ca3[Fe(CN)6]2 + aI2 = 2Ca2[Fe(CN)6] + I2
N2 + 3Mg = Mg3N2
3Ca2[Fe(CN)6] = 6Ca(CN)2 + Fe3C + 5C + 3N2
4NH3 + 7O2 = 4NO2 + 6H2O
NH3 + HNO3 = NH4NO3
4NO2 + O2 + 2H2O = 4HNO3
NH4NO3 + Zn + 2HCl = NH4NO2 + ZnCl2 + H2O
12HNO3 + 5Sn = 5Sn(NO3)2 + N2 + 6H2O NH4NO2 = N2 + 2H2O
CaC2 + N2 = Ca(CN)2
NH4NO3 = N2O + 2H2O
3N2O + 2NH3 = 4N2 + 3H2O
6.3 2.
.

n=3
6.4 + + +.
K(BH+) = 1,75109. 0,10
.
pH = 11,12.
6.5 0,100 .
= 1,3%.
7.
G (w(Sn)=72.02%)
. , PXa.
PXbYa-b. , PXbYa-b
,
, : PXb-1 D
(MD=1,183M(PXb-1)).
LiAlH4 F (w(C)=18.08%,
w(Sn)=59.57%) .
7.1 .
F (CH3)3SnCl; G (CH3)3SnH, Y H; F; D SiF4.
7.2 ,
4(CH3)3SnCl+LiAlH4=4(CH3)3SnH+LiCl+AlCl3
(CH3)3SnH+PF5=(CH3)3SnF+HPF4
4HPF4+SiO2=SiF4+4PF3+2H2O
7.3 PXa, PXbYa-b PXb-1.
.

sp3d
sp3d
sp3
, PXbYa-b :
PXbYa-b :
7.4 T PXbYa-b ( )
= 237,2 K; =176,2 K.
7.5 H H. .

 = 11,04 /

11 . 2 .
1.
, ,
.
, ,
. S-
1989 ,
.

S
A (C7H10N2O)

SK

EtO

OH
O

B (C8H7N2OSK)

C (C9H12NOCl.HCl)
NaOH

D (C17H19N3O2S)

N
N

CH3

S O
NH

1.1 D.
A

B
SK

NH2

NH2

NH

D
O

Cl

. HCl
N

N
H

N
Cl

S
N

NH

Cl
O

: = 2
105 .
= 11.

. ,
: ,
.
1.2 .

SH

OH
S

O
+

N
N

S O

NH

NH

NH

O
O

1.3 : 1 = 3,98, 2 = 8,7. ,

, ( )
= 2; 7; 11.
= 2
= 7
= 11
O
+

N
H

S O

N
NH

1.4 , .
(S-)
.
.
O
N
O
S
N

..

NH
O

1.5 , MgEs23H2O (Es

). 3,5104 /.
, .
= 1,71010
1.6 , ,
pH (
1).
pH = 9.8; = 3.5104(6.4104)2 = 1.41010.
2.

 .
(
( ), -33.
(
: = 0,583 , = 0,3181 , 4 ) 7,29 /3.

2.1 .
118,7 ; Sn.
.
0,182 .
2.2 . .
5,770 / 3 ; - ; .
.
2.3 .
-Sn -Sn 25,6%,
.
.
2.4 K , ,
- ;
- ,,F,G,H ;
- , F G, D I, J .
HCl(k)

O2

HCl (p)

HNO3 (k)

NH3xH2O

Cl2

O2
OH2

Li Al H4

A
HSnCl3
H2SnCl4
G

KOH

FeCl3

KOH

HNO3 (p)

KOH

E
vakuum, t

HCl

Cl2

SnCl2

SnCl4

HNO3

D
H2[Sn(OH)6]
Sn(OH)4
J

E
K2[Sn(OH)6]

I
K
H2SnO3
SnO
SnH4
Sn(NO3)2
Sn(OH)2
SnO2nH2O
2.5 .

Sn + 3HCl(.) HSnCl3 + H2 Sn + 4HCl(.) H2SnCl4 + H2

Sn + 2HCl(.) SnCl2 + H2
SnCl2 + 2FeCl3 SnCl4 + 2FeCl2
SnCl4 + 4NH3 + 6H2O H2[Sn(OH)6] + 4NH4Cl
H2[Sn(OH)6] + 2KOH K2[Sn(OH)6] +2H2O

F
SnO2
M
Sn(NO3)4


Sn + O2 SnO2
SnO2 + Sn 2SnO
SnO + 2HCl(.) SnCl2 + H2O
SnCl2 + Cl2 SnCl4
SnCl4 + Li[AlH4] SnH4 + LiCl + AlCl3.
SnH4 Sn + 2H2

Sn + 4HNO3(.) H2SnO3 + 4NO2 + 2H2O

3Sn + 8HNO3(.) 3Sn(NO3)2 + 2NO + 4H2O
Sn(NO3)2 +2KOH Sn(OH)2 +2KNO3
Sn(OH)2 SnO + H2O

Sn + 2Cl2 SnCl4
SnCl4 + 22 Sn2 + 4Cl
2Sn + O2 2SnO2
SnO2+ 2H2O + 2KOH K2[Sn(OH)6]
K2[Sn(OH)6] + 6HNO3 2KNO3 + Sn(NO3)4 + 6H2O
3.
, , , .
.
, :
o
o
f H 298
f S 298
.
o
o

f H 298
f S 298
, /
, /
1
2 Ag + O2 = Ag2O
31,13
66,67
2
Cu + O2 = CuO
157,03
93,20
3
Fe + O2 = FeO
264,85
68,92
4
Ti + O2 = TiO2
943,87
185,33
5
C + O2 = CO
110,53
89,29
6
CO + O2 = CO2
282,98
86,39
3.1 , , 5 , 5
.
14 , ,
, . 6
,
. 5
, .
3.2 , ,
1000
(, ,
0,2 ).
Ag2O; 518.
3.3 ?
255 .
3.4 ?
. ?
. Ti :
: TiO2 + C + Cl2 = TiCl4(g.) + CO2;

850o C

: TiCl4(g.) + 2Mg Ti + 2MgCl2.

3.5 ( %) ,
FeO 1000 1 .
?
x( CO 2 ) 0.52 , x( CO ) 0.48 .
.
4.
0
0,1 /
:
,

30

55

100

200

420

720

950

0,094
0,090
0,084
0,072
0,055
0,042
0,035
NaOH, /
4.1 .
0,0197 11.
20 ,
C0 :
C0 , /

0,08

0,1

0,5

1 / 2 ,

114,7
91,7
18,4
4.2 .
56,9 /.
-
20 ,
( ):
C0 , /

0,05

0,1

0,15

1 / 2 ,

246,9

123,5

82,3

4.3 -.
-
.
0,00135 11.
- 20

- ( ):
C0 , /

0,05

0,1

0,15

1 / 2 ,

38,75
38,75
38,75
4.4 -.
-
-.
0,0179 1. SN1 .
5. Du Pont
30- XX Du Pont ,
, .


(, , ), (, ),
Du Pont .
Y, ,
,
. 1,000 (
) 2,337 2, 0,876 2 0,124 N2.
F CrO3 .
H2SO4

NH2OH
D

C
H2/Ni

O2
B

A
150 0C
2 MPa

E
100 0C

HNO3
NH4VO3

145 0C
0,7 MPa

H2/Co

NH3

G
55 0C

X
250 0C

I
200 0C
58 MPa

400 0C

G
- H2O
Y

J
280 0C

5.1 - X, Y E.
6H11NO.
5.2 J, G , I .
C

D
N

OH

OH
NH

G
O

H
OH

HO

H2 N

NH2

J
+H N(CH ) NH +
3
2 4
3
-O C(CH ) CO 2
2 4
2

5.3 X Y
.

 :
X

Y
O

H
N

n*

H
N

*
N n
H

*
O

5.4 D ? .
:
:
H
N

OH

N
H+

H
- H2O

+ H2O HO

H
N

6.
0,975 200 .
-
( )
. (
) 2 (I = 0,1072 , 100 %).
.
, , ,
( ).
0,552 - Y (, 100 %,
Y ).
6.1 Y, , Y 36,9 % .
- VCl2
Y - VOCl2
6.2 , . ,
.
:
: VCl2 -2e + H2O = VOCl2 + 2H+
: 2H+ + 2e = H2
:
2VCl2 + O2 = 2VOCl2
, V 2+
.

.
KMnO4, !
6.3 , .
5VCl2 + 3KMnO4 +14HCl = 5VOCl3 + 3KCl + 3MnCl2 + 7H2O
2KMnO4 + 16HCl = 2KCl + 2MnCl2 + 5Cl2 + 8H2O

6.4 ( ),
. ' 0,05
25 (
, )?
-, .
- :
AgNO3 + HCl = AgCl + HNO3
2AgNO3 + VCl2 = 2AgCl + V(NO3)2.
V(KMnO4) = 0,012 (12 ).
7. E-

,
. ,
,
:

C21H20O6

100

C6H8O2

200

???
C3H6O3

270
???
C6H8O7 ,
330
???
C2H6O
,
1510
???
C
H
O

8 8 3

Vanilla planifolia,
,
.
1 .
OH
O

OH 1. OH

O
O

2. H+

B
C9H10O5

1. O2
2. H+, -CO2

(500 MHz, DMSO-d6).

7.1 A, B. 1 .
,
, .
A

B
D

HO

OH

B
HO

O
E

OH

-100 Curcuma longa,

.
:
B2O3
B(Osec-C4H9)3

A +

n-C4H9NH2

"E 100"

7.2 100, , 13 11 .
/,
100.
B2O3?
100

100

+
O
O
B
O
O

OH

HO
O

H2BO3-

B2O3:
O

HO
O

E 200 Sorbus aucuparia (),

E 200.
1 .
O

OHH

H2C C O

H+

C
C4H8O2

D
C4H6O

BF3

H+

"E 200"

C6H8O2

7.3 - E 200. 1
E 200.
E 200
, .

E 200 (500 MHz, DMSO-d6).

200

OH
OH
C

E
O

O
O

270, 330, 1510 ,

.
7.4 270, 330, 1510, :
270 - , L(+) ;

 330 - ,
;
1510 = 78.4 0, .
270
330

OH

HO

OH

OH
O

OH
1510

OH

OH O