Теоретические задачи

1.
,
,
,
(e),
(p)
,
,
.
(
(p)
,
,
:
)
.
,
2002
,
.
(Nature 419, 456
(2002)).
(p p ).
1-1.
,
pp
,
.
1-2.
?
2.
[18]
C18H18
(Acta Cryst. 19, 227 (1965)).
:
–3
1 e⋅Å .
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
.
«
,
En =
h–
,
:
, me –
,L–
0, ±1, ±2, ±3,
;
h2n2
,
2me L2
,n–
.
».
n
…,
,
,
.
2-1.
,
1.40 Å,
,
.
3.
O22+
.
O22+,
,
.
,
+
O,
,
.
1960-
O22+
,
.
,
,
O+
: [O≡O]2+.
.
,
pO22+,
«
-
».
3-1.
O+,
O22+?
3-2.
3-3.
3-4.
3-5.
O22+
O22+
?
(
)?
2+
O2 ?
,
O2
2+
.
,
2+
O2 ?
3-6.
3-7.
O+−O+?
O+,
O22+?
4.
.
Ni-Cd
(«
:
»)
,
,
,
,
.
.
2000
:
.
-
Cd(OH)2( ) + 2e– → Cd( ) + 2OH–
E1° = –0.809
2NiO(OH)( ) + 2H2O + 2e– → 2Ni(OH)2( ) + 2OH–
E2° = –0.490
E1° E2° –
4-1.
25
.
?
.
?
4-2.
.
,
4-3.
.
4-4.
4-5.
E
25
.
700
⋅ .
5.
(
116
4
3
.
.
,
,
– 0.73 /
5-1.
).
3
43000
/ ,
.
,
: ( ) 5 ; ( ) 2.2
; ( ) 2.1
.
5-2.
CO2
?
( ) 300 ; ( ) 1 ; ( ) 5
; ( ) 10
; ( ) 30
.
; ( ) 12
; ( ) 3.3
6.
.
80 NH4NO3 1
0
.
:
6.01
25.69
⋅ ⋅
–1
6-1.
H2O.
⋅
76
⋅
–1
–1
⋅
–1
⋅
–1
,
,
,
1.86
.
: ( ) 1.86 ; ( ) 3.72 ; ( ) 3.72
; ( ) 1.86
;
( ) –3.72 ;
( ) –3.72 ; ( ) –1.86 K; ( ) –1.86 ; ( ) –3.83 .
6-2.
:( )
;
( )
;( )
;( )
; ( )
; ( )
; ( )
.
6-3.
(
):
;
;
;
;
,
;
;
;
;
;
;
;
.
6-4.
: ( ) ∆S > 0; ( ) ∆S = 0; ( ) ∆S < 0; ( ) ∆S
.
7.
,
CO2
CO2:
– Pc = 73.75
5.1850
, T3 = 216.58 .
7-1.
1
.
, Tc = 304.14 ;
25 .
,
CO2? ( ) 2
( ) 20
; ( ) 73.8
;( )
7-2.
5.1850
;( )
100
;( )
20
– P3 =
;( )
63
; ( ) 5.185
.
,
CO2? ( )
; ( ) 73.8
.
2
;( )
;
;( )
8.
– α-Fe –
2.87 Å.
7.86 /
3
.
25
– γ-Fe –
,
3.59 Å.
α-Fe
8-1.
,
α-Fe
,
.
γ-Fe
8-2.
γ-Fe,
γ-Fe
,
.
,
8-3.
(
)
α-Fe ( . .,
(1/2, 0, 1/2)),
,
.
?
,
8-4.
,
γ-Fe.
,
8-5.
. 8.3
,
8.4?
0.077
,
(200)
8-6.
.
(
,
α-Fe,
32.6 .
.
.
,
).
9.
–
: α-, β-, γ-
,
6, 7
,
8
.
β(
,
–
.
,
:
Dacus Oleae
,
,
;
,
.
,
)
.
,
C42H70O35⋅C12H12N2⋅12H2O.
P21.
(
): a = 15.394(7) Å, b = 31.995(12) Å, c = 15.621(7) Å,
o
β = 103.738(15) , α = γ = 90o.
4
(2
–
).
3
9-1.
( Å)
.
10.
: CO, H2O,
,
: ( ) 1; ( )
30; ( ) 54; ( ) 120; ( ) 174; ( ) 720; ( )
10-1.
C60?
2; ( ) 3; ( ) 4; ( )
.
10-2.
.
XY
,
WZ.
?
(1) XY WZ –
(2) XY
(3) XY
(4)
.
,
WZ.
,
WZ.
XY
,
WZ.
: ( ) 1; ( ) 2; ( ) 3; ( ) 4; ( ) 1 2; ( ) 1 3; ( )
1 4; ( ) 2 3; ( ) 2 4; ( ) 3 4; ( ) 1, 2 3; ( ) 1, 2 4; ( ) 1, 3
4; ( ) 2, 3 4; ( ) 1, 2, 3 4; ( )
.
11.
11-1.
(1)
« »
«
»
:
γ?
(2)
83?
(3)
82?
(4)
?
(5)
?
12.
14
C – β-
t1/2 = 5700
.
.
,
14
,
14
.
12
C
.
13
C
C
C
CO2
,
14
12
C/ C
.
,
12
14
.
C
,
14
C.
0.277
C
(1
).
,
12-1.
0.25
14
12
,
,
C /
.
,
14
12-2.
12-3.
C
14
C,
?
12-4.
14
C
?
(
.),
C/
14
14
C,
18.5%.
C
75
,
,
13.
U (Z = 92) –
238
U (99.3%, t1/2 = 4.47⋅109
α.
(Z = 82).
235
)
,
U (0.7%, t1/2 = 7.04⋅108
α- (4He2+)
(
).
β– 206
Pb
)
,
,
Pb
. γ-
207
,
.
235
U
238
,
U,
;
,
.
235
:
U + n → U* →
+ 2-3 n + 200
α-
13-1.
β-
235
/
U.
,
(
238
U → 206Pb
235
U → 207Pb).
,
13-2.
.
13-3.
,
(235U :
, . .
238
U = 1 : 1),
,
.
(
13-4.
),
,
1
:
C + O2 → CO2 + 393.5
/
(
4.1
/
).
235
U.
14.
(Pb(NO3)2)
(KI)
(PbI2).
,
5.000 .
:
,
.
:
,
,
1
0.500
0.692
2
1.000
1.388
3
1.500
2.093
4
3.000
2.778
5
4.000
1.391
PbI2 ( ),
5,00
4,00
3,00
2,00
1,00
0,00
0,00
1,00
2,00
3,00
4,00
5,00
Pb(NO3)2 ( - ),
:
14-1.
.
.
14-2.
PbI2
Pb(NO3)2.
15.
IV
1
2
9
d , d , …, d
ML62+ (L –
:
»
M( )2+;
,
«
.
15-1.
).
«
»
,
,
t2g
(
,
)
∆,
eg
,
P,
.
:
.
16.
.
,
,
.
100
(
1913 .)
,
,
Co(NH3)63+,
,
,
.
,
,
CoCl3⋅4NH3,
450-200
.
Rh(py)3Cl3 (py –
.
–1
).
.
,
≡ σ,
-
S2 ≡ i
,
.
[Co(NH3)4Cl2]Cl,
,
)
S1
,
[Co(en)2Cl2]Cl (en –
,
.
16-1.
16-2.
Co(NH3)63+.
Co(NH3)63+
NH3
3–
CoF6 ?
F–
.
16-3.
.
Rh(py)3Cl3.
16-4.
,
16-5.
.
[Co(en)3]I3?
17.
4-
,
,
-
.
,
.
MA2B2,
.
sp
,
– dsp
Ni
17-1.
4p
2
3
sd
.
2+
[Ar]3d 8.
NiCl42–,
Ni(CN)42–.
3d, 4s
–
.
3
18.
.
(PC) –
.
.
,
PC
,
PC
Cu(I)
Cu(II).
PC
:
(
http://www.rcsb.org/,
: 1PNC).
18-1.
18-2.
18-3.
Cu, Cu(I), Cu(II).
PC,
PC,
?
10500 /
PC
–1
«
597
3
⋅ –1).
0.700.
⋅
.
(PC
»), . .
(
4500
PC
PC (
1
)
Cu(II)
5
3
.
,
18-4.
–
.
Ni(II), Zn(II)
,
,
Cd(II),
.
-
?
Co(II),
,
19.
,
,
10
(100 Å).
,
,
.
«
»
.
: (1)
; (2)
; (3)
; (4)
.
,
.
),
(
(
)
,
.
.
,
(
,
.
1 ).
.
,
(
. 1.
. 1 ).
:( )
( )
.
.
«
, y,
»,
n-
,
.
: y = 10n + 2 (n = 1, 2, 3, …) (
2
,
«
»
1
2
3
4
5
. 2).
. 2.
«
»
.
,
.
(TEM),
–
(HR-TEM).
,
–
,
,
.
. 3. ( )
Pd(0),
. ( )
Pd(0)
.
Pd(0)
)
19-1.
Pd(II)-
(1
:
nPd(II) + nH2 → Pd(0)n + 2nH+.
,
Pd(0)n
,
,
2.05
.
(N)
.
(n)
ρ = 12.02 /
.
3
?
.
Pd(0)n,
19-2.
,
,
:
+ H2
Pd(0)n
Pd(0)n,
3
50
;
3
400
50
5
3
H2
Pd(0)
.
4
H2
.
30
.
. 4.
. 4.
.
30
(%)
.
, 50
Pd(0), 5
3
.
i
ii
,
Pd(0),
,
: ( )
(TON): TON =
Pd(0) (
19-3.
H2 (
Pd(0) (
H2 (
(
).
)/
Pd(0)n,
) /
(TOF):TOF =
); ( )
) /
C6H10: ρ = 0.81 /
,
3
.
-1.
Pd(0)n
CH3(CH2)3CH CH2 + H2
CH3(CH2)4CH3
,
.
-1
30
).
,
Pd(0)n
.
. 5.
(
.
. 5. 1H
(300
): )
-1; )
30
.
,δ/ . .
-1 (
(
.5 )
.5 )
0.88-0.96
3
1.15-1.32
4
1.99-2.08
2
4.85-4.98
2
5.65-5.79
1
0.88-0.96
9
1.12-1.37
12
1.99-2.08
2
4.85-4.98
2
5.65-5.79
1
-1
30
.
20.
,
.
,
.
[A]s –
,
[A]s.
,
, [A]b.
[A]s
20-1.
d[A]b/dt.
75% [A]s
20-2.
[A]s
.
?
21.
Br2 + CH4
:
Br2 + CH4 → CH3Br + HBr.
:
k1
Br2 + M → 2Br + M
Br + CH4 → CH3 + HBr
Br2 + CH3 → CH3Br + Br
HBr + CH3 → CH4 + Br
2Br + M → Br2 + M
M–
,
k3
(1)
(2)
(3)
(4)
(5)
k2
k3
k4
k5
k4
.
:
21-1.
CH3
Br.
,
.
.
: d[CH3] / dt = 0
,
d[Br] / dt = 0.
CH3Br
k1 – k5 .
21-2.
.
,
,
CH3
Br
.
k11 / 2 k 2 [Br2 ]1 / 2 [CH 4 ]
⋅
k 4 [HBr]
k 51 / 2
+1
k 3 [Br2 ]
(I)
k11 / 2 k 2
v' = 1 / 2 ⋅ [Br2 ]1 / 2 [CH 4 ]
k5
(II)
k11 / 2 k 2 k 3 [Br2 ]3 / 2 [CH 4 ]
⋅
v' ' = 1 / 2
[HBr]
k5 k 4
(III)
v=
,
.
(I), (II)
21-3.
,
(III)
,
.
:
22.
,
CH3COOH/CH3COO–)
.
(
,
, NH3/NH4+).
(
.
,
.
pH
,
pH = pK a + lg
Ka –
A–,
HA
:
[A − ]
[HA]
HA,
.
pH
22-1.
–4
2.1×10 )
,
0.150 M
,
22-2.
0.200 M
.
pH
.
0.01000 M
,
0.200 M
22-3.
100.0
3
(Ka =
,
(CH3COOH, Ka = 1.8×10–5),
0.150 M
pH = 5.00.
22-4.
pH
(C6H5COOH, Ka =6.6×10–5)
4.18; ( ) 9.82; ( ) 9.00.
,
0.0100 M
0.0100 M
.
A B.
22-5. A: 0.100 M CH3COOH (Ka = 1.8×10 ), B: 0.0500 M NaOH.
:
i
: ( )
; ( )
;( )
;( )
ii
pH
: ( ) 3.02; ( ) 4.74; ( ) 3.17; ( ) 7.00.
22-6. A: 0.100 M CH3COOH (Ka = 1.8×10–5), B: 0.150 M NaOH.
:
i
: ( )
; ( )
;( )
;( )
ii
pH
: ( ) 12.00; ( ) 12.70; ( ) 13.18; ( ) 12.40.
22-7. A: 0.150 M CH3COOH, B: 0.100 M NaOH.
i
: ( )
; ( )
;( )
;( )
ii
pH
: ( ) 3.17; ( ) 7.00; ( ) 5.05; ( ) 13.00.
22-8. A: 0.100 M CH3COOH, B: 0.100 M NaOH.
: ( ) 5.00; ( )
–5
;
;
:
;
:
: ( )
i
;( ) ii
pH
; ( )
;( )
: ( ) 7.00; ( ) 13.00; ( ) 8.72; ( ) 3.02.
;
23.
(
).
250
(
3
).
,
.
pH
.
–
,
.
.
-
-
.
,
23-1.
3
50.00
0.1000 M
Ka =1.8×10–5)
1.
,
(CH3COOH,
0.1000 M
;
1.
, pH
3.2 – 4.4
4.2 – 6.2
6.0 – 7.6
6.8 – 8.2
8.0 – 9.8
9.3 – 10.5
(
23-2.
-
C, C6H8O6) –
,
:
C6H8O6 ς C6H7O6– + H+
C6H7O6– ς C6H6O62– + H+
Ka1 = 6.8×10–5
Ka2 = 2.7×10–12
,
. 50.00
3
0.1000 M
.
i
ii
:
: ( ) 7.00; ( ) 2.58; ( ) 4.17; ( ) 1.00.
pH
( ) 50.00
iii
pH
( ) 4.58.
iv
pH
v
0.2000 M
3
,
; ( ) 35.00
:
3
3
; ( ) 25.00
; ( ) 20.00
12.5 3
3
.
: ( ) 4.17; ( ) 2.58; ( ) 7.00;
: ( ) 7.00; ( ) 8.50; ( ) 8.43; ( ) 8.58.
(
. 1): ( )
;( )
;( )
;( )
.
vi
pH
( ) 11.42.
26.00
3
: ( ) 13.30; ( ) 11.30; ( ) 11.00;
24.
–
.
,
,
.
–
–
,
,
,
,
.
,
.
S
1
2,
:
KD
(S)1
,
KD –
(S)2
a
S
:
KD =
( aS ) 2
( aS )1
(1)
S,
.
. 1.
(
.
. 1).
(1)
,
.
S
,
,
,
KD
D:
D=
CS –
(
(CS ) 2
(CS )1
(2)
)
S
,
–
.
,
(2)
,
D–
S
(
,
,
S
S,
S
V1
V2
n
,
.
).
W0
1
–
,
pH
1,
2,
,
S
Wn
S,
:
n

 V1
 W0
Wn = 
 DV2 + V1 
(3)

 V1
W

f n = n = 
W0  DV2 + V1 
fn –
S,
n
(4)
n
1
.
(3)
,
(4)
,
.
(3).
24-1.
24-2.
D = 3.2.
S
S,
50
S: ( )
3
100
3
25
3
;( )
.
99%
24-3.
3
100
,
25.0
3
0.500
X,
KD = 9.5?
Ka (
)
,
HA
24-4.
X
.
,
HA
(
KD),
.
+
D
.
[H ]
.
–
24-5.
6.6×10
–5
1×10–10,
.
.
D / KD
i
ii
,
24-6. 8, C9H6(OH)N (
+
C9H6(OH)NH (OxH2+),
.
.
OxH)
–
K1
C9H6(O–)N (Ox–).
K2
N
H
pH
N
N
O-
OH
OH
OxH2+
Ox-
OxH
: K1 = 1×10–5, K2 = 2×10–10.
KD = 720.
,
[H ]
i
D 8-
+
ii
iii
.
D
pH,
D
pH
.
.
25.
-
-
-
,
.
.
(m/z)
,
z = 1,
.
-
,
R = m / ∆m,
∆m –
, m –
,
C2H4+ CH2N+,
(28.0313
28.0187,
,
R = 28 / (28.0313 – 28.0187) ≈ 2200.
(R ≈ 300-1000)
.
28),
.
,
(m =
),
-
,
,
15 (12C1H3+)
.
,
CH3+
19 (13C2H3+).
,
,
: 98.90% 12C
(M = 15)
(M + 1 = 16)
13 2
C H3+,
.
1.10%
13
: 99.985% 1H
0.015% 2H.
12 1
C H3+,
: 13C1H3+ 12C1H22H+,
, . .
C,
,
M + 4,
.
CH2Cl+
C, H
Cl (75.77% 35Cl
24.23% 37Cl).
C1H235Cl:
0.989×(0.99985)2×0.7577 =
M + 1 = 50
13
C1H235Cl:
12 2 1 35
C H H Cl:
12 1 2 35
C H H Cl:
0.011×(0.99985)2×0.7577 =
0.00833
0.989×0.00015×0.99985×0.7577 = 0.00011
0.989×0.99985×0.00015×0.7577 = 0.00011
0.00855
M + 2 = 51
13
0.011×0.00015×0.99985×0.7577 = 1.25×10–6
0.011×0.99985×0.00015×0.7577 = 1.25×10–6
0.989×(0.99985)2×0.2423 =
0.240
0.240
M = 49
12
C2H1H35Cl:
13 1 2 35
C H H Cl:
12 1
C H237Cl:
0.7491
M + 3 = 52
13
C2H235Cl:
13 1
C H237Cl:
12 1 2 37
C H H Cl:
12 2 1 37
C H H Cl:
0.011×(0.00015)2×0.7577 =
0.011×(0.99985)2×0.2423 =
0.989×0.99985×0.00015×0.2423 =
0.989×0.00015×0.99985×0.2423 =
M + 4 = 53
13
C2H1H37Cl:
13 1 2 37
C H H Cl:
12 2
C H237Cl:
0.011×0.00015×0.99985×0.2423 = 4.0×10–7
0.011×0.99985×0.00015×0.2423 = 4.0×10–7
0.989×(0.00015)2×0.2423 =
5.4×10–9
8.1×10–7
13
0.011×(0.00015)2×0.2423 =
M + 5 = 54
C2H237Cl:
M
1.9×10–10
0.00266
3.59×10–5
3.59×10–5
0.0027
6×10–11
M + 5
,
.
,
.
,
(
CH2Cl+),
(
M = 49
100%).
M = 49:
M + 1 = 50:
M + 2 = 51:
M + 3 = 52:
M + 4 = 53:
M + 5 = 54:
:
100%
(0.00855/0.7491)×100% = 1.14%
(0.240/0.7491)×100% =
31.98%
(0.0027/0.7491)×100% = 0.36%
(8.1×10–7/0.7491)×100% = 1×10–4%
(6×10–11/0.7491)×100% = 8×10–9%
(
,
http://www.chem.uoa.gr/applets/appletMS/appl_MS2.html)
25-1.
–
:
35
Cl,
37
,
: 28Si, 29Si, 30Si,
Cl.
+
25-2.
SiCl2 ?
: 10B 19.9%, 11B 80.1%,
(A – E)
: 35Cl 75.77%, 37Cl 24.23%.
BCl+?
: ( ) N2+, ( ) CO+, ( ) CH2N+, ( ) C2H4+
25-3.
M = 28
.
,
M + 1,
.
H:
C:
N:
O:
M+1
H: 99.985%
12
C: 98.9%
14
N: 99.634%
16
O: 99.762%
1
1.15%.
H: 0.015%
13
C: 1.1%
15
N: 0.366%
17
O: 0.038%
,
:
2
18
O: 0.20%
26.
–
,
,
.
.
26-1.
.
A, B, C.
26-2.
1. CH3I (
.
)
A (C10H21N)
2. Ag2O, H2O, ∆
1. CH3I (
.
)
A
1,4-
+ 1,5-
2. Ag2O, H2O, ∆
C6H5CH2OCOCl
o
NaOH, 0 C
B
KMnO4
∆
C
H2 / Pd / C
(S)-5-
-
27.
.
.
.
–
:
OH
8
HO
1
3"
1'
O
6'
5
OH
4"
4
O
:
27-1.
1. NaH /
B
2.
MeI
(
.)
C
,
27-2.
C-5,
1
,
C-4
H-
.
C-5
:
( )
;( )
2M
27-3.
D
;( )
NaOH
.
,
,
E:
NaOH 2M
D+E
D (C6H6O3)
(C9H12O2)
FeCl3,
(
FeCl3.
:
,
(
II).
D
E.
1
1
I).
H-
HE
,
27-4.
13
C
B.
C-
,
28.
–
L(
α-
,
)
S-
.
L-
28-1.
L-
?
.
,
28-2.
(
N-
).
.
ROCO-,
.
(
)
-
?
.
H.
.
.
-
.
.
.
28-3.
.
.
28-4.
(1)
(2)
(3)
(4)
(5)
C-
),
(
(1)
(2)
(3)
(4)
(5)
,
(
C6H5CH2OCOCNH2
C6H5CH2OCO2CH3
C6H5CH2OCO2C(CH3)3
C6H5CH2OCOCl
C6H5OCOCl.
-
)?
.
,
28-5.
,
R OCO NH
:
H+
:
[R+] + CO2 + H2N
O
O
O
N
O
N
C.
A.
O
O2N
O
O
B.
H
N
D.
CH3O
CH3O
O
N
29.
-
,
-
.
,
,
,
(A),
(R –
):
COOCH3
O
R
O
O
O
O
OH
HO
OH
OH
A
,
29-1.
–
( )
(A1),
:
,
,
–
(A2).
,
,
A1;
( )
-
,
.
-
29-2.
154.
A1
1
H-
A1
.
:
1
-
-
A1:
OH
OH
OH
HO
OH
CH3
HO
CH2OH
OH
CH3
OH
C
B
A
A1
29-3.
a, b, c
d
,
1
H-
.
30.
,
-
C
Br
Br2 / CCl4
C
:
C
C
Br
30-1.
.
.
H
C
à)
C
C
Br
H
C
á)
CH3
H
H
C
Br
C
C
H
CH3
C
H
Br
H
H3C
H
C
C
ã)
H
Br
H
H3C
C
â)
C
H
CH3
Br
H3C
H3C
H
C
H
C
H3C
Br
H
34.
2,5-
-1-
.
,
.
–
.
-
1,4.
2,5-
,
(1) (N-
2,5-
-1-
).
3
.
.
:
2,5-
.
,
.
.
.
–
1.
,
,
1:
.
2,5-
-1-
:
,
,
2,5-
,
. HCl,
0.5 M HCl
.
,
25
3
,
,
,
10 3,
5 3,
5
,
,
,
10
5
,
,
,
(
1c ,
10 c ),
100
3
,
,
(254
),
(
-
1:3),
.
.
2,5-
-1-
)
228
1
(2.0
HCl.
186
(2.0
3
, 0.5
) 2,5-
15
.
.
5.0
3
0.5 M HCl,
3
1
/
1
-
.
.
3
.
.
.
(
3-5
)
(~5)
.
.
(
1:3.
(254
)
-
).
.
.
.
I.
II.
III.
IV.
:
.
.
.
.
.
.
.
Rf
.
1
.
H(CDCl3)
:
= 2.04 ( , 6H), 5.91 ( , 2H), 7.22 ( , 2H)
7.44 ( , 3H)
δ,
,
.
.
.
II.
III.
IV.
.
:
:
:
:
:
178
342
: 52%
48°C (
. 50-51°C)
.
.
Rf
: 0.85
H(CDCl3)
:
= 2.04 ( , 6H), 5.91 ( , 2H), 7.22 ( , 2H)
1
7.44 ( , 3H)
35.
DEET
.
DEET –
N,N-
- ,
. DEET,
,
,
, 1957 .
.
230
DEET
DEET.
70
.
,
.
DEET
•
:
N,N•
- -
:
(25oC)
0.996
,
(1
19
DEET
DEET
,
-
-
( -
-
).
.
(NaOH)
:
)
,
111 C
)
(160oC)
.
,
-
(SOCl2);
.
)
.
,
.
,
,
:
.
(0.55
(0.5 , 3.7
3
, 7.6
),
3
(0.2
)
),
(2
)
99.5% SOCl2
8
3
5
.
.
3
(1.3
25
)
, 12
. .
10% NaOH (5
3
1
MgSO4
Na2SO4
)
SOCl2
0 oC.
15
,
3
.
3
1
,
.
.
.
I.
II.
III.
DEET
.
:
.
.
.
.
-
3
[
]:
;
,
,
,
;
,
50%
-
.
,
;
, 50%
-
3,
-
,
,
I.
II.
III.
1763
C−
H
C− H
C=O
–1
1720
–1
.
[
].
.
~3065
~2987-2880
:
:
;
–1
;
~
–1
I.
II.
III.
:
0.68
0.70
: 97%
:
.
-
3
[
]:
;
,
,
;
,
50%
-
.
-
, 50%
.
1763
.
–1
–1
1720
,
C=O
36.
.
. .
(
1984
α-
.)
-
.
K.
2-
,
,
.
,
,
,
.
Fmoc-
,
N-α .
,
.
,
C,
).
(
,
.
. 1. 2-
,
,
.
–
1%
.
H2N-Ser-Ala-OH
,
Fmoc-
,
.
. 2.
2-
. 2 .
H2N-SER-ALA-OH
Fmoc-
2-
H2N-SER-ALA-OH
.2 .
(
1).
(
2-5).
Fmoc-
2.
11.
.
.
2.
2
Fmoc-
3
20%
3.
2-3
.
5.
(3
)
.
(Asample)
,
3
3
.
,
4.
6.
.
20%
(Ablank)
290
.
n–
Fmoc-
(
),
( ),
,m–
.
.
Fmoc-Ala-OH (62 , 0.2
) (139
, 0.8
).
1.
(N,N-
)
3
CH2Cl2 (2
)
DIPEA
,
,
(200
30
, 0.2
;
Cl 1.0
2-
/
),
1
CH2Cl2.
.
3
0.2
«
»
,
–
3
CH2Cl2
,
.
20%
Fmoc.
.
,
5
(
3
2
Fmoc-Ser(O-t-Bu)-OH (383
.
20
.
:
3.
1
,
1
(
,
,
)
)
HOBt (135
DIC (156
3
.
2
3
3
2
CH2Cl2 (
, 1
,
).
15
.
CH2Cl2/MeOH/DIPEA=17/2/1,
KOH.
,
3
3
3
2
2
2.
3
3
3
)
,
3
).
, 1
, 1
)
)
CH2Cl2 (
(
2
).
:
:
1.
5
2.
80
3.
2
100
3
EtOH.
3
20
3
0.001 M
EtOH.
KCN 98
3
.
4.
2
.
5.
5
(
)
(
4.
5.
.
,
).
Fmoc-
,
(
2.
2
3
)
-
10
(3
.
2
3
)
(
(5
3
3
.
0.5% TFA/CH2Cl2)
,
).
.
.
5
.
Ala-OH
3
.
.
10
,
H2N-Ser-
–
.
:
I.
: 8
II.
(
:
12.3
0.35)
III.
: 65%
IV.
:
210-213°C
.
(
CHCl3/MeOH=9/1)
i) Fmoc-Ala-OH,
ii) Fmoc-Ser(O-t-Bu)-OH,
iii) H2N-Ser-Ala-OH
.
Rf
:
i) 0.25, ii) 0.40, iii) 0.
α
.
[α
t–
/100
(25
3
]Dt.
:
), D
HCl.
: α = 1.91° , [α ]Dt = –31.8°
(589.0
–1⋅ –1⋅
3
.
), l = 1
, c=6
37.
.
-
,
,
.
.
.
,
,
1
.
= 101 325
(= 1.013
).
(
).
,
(
,
,
,
),
.
dP ∆H
=
,
dT T∆V
, ∆H –
dP / dT –
, ∆V –
–
,
.
,
-
: )
, )
.
:
d ln P
∆H
=−
.
d (1 / T )
R
ln P
,
1/ .
,
.
(100-200
0-20
),
),
0-200 °C,
(
–
,
, H2O.
:
)
(
.
.
.
16
,
,
180 °C.
,
.
80
(
,
,
.
,
),
(
).
P
(
),
.
ln P, T, 1/T.
)
ln P, T, 1/T.
(
ln P
1/T.
.
–
,
.
–
.
.
,
6
.
3
38.
.
–1
+7,
,
.
+7
+5
+3
+1
0
–1
HClO4, ClO4–
HClO3, ClO3–
HClO3, ClO2–
HClO, ClO–
Cl2
HCl, Cl–
F2
HF, F–
HBrO3, BrO3–
H5IO6, IO4–
HIO3, IO3–
HBrO, BrO–
Br2
HBr, Br–
HIO, IO–
I2
HI, I–
,
.
,
.
.
.
.
.
.
13×100
,
II .
–
1-2
3
5
.
,
,
.
3-4
–
.
:
,
I2
,
.
,
,
.
I.
. 2
I–
3
0.1
KI
AgNO3.
0.1
.
.
2
3
3
. 2
3% H2O2.
KI 5 3
(5% NaOCl).
,
?
3
KI 5
.
0.1
.
0.1
II.
.
1.
3
3
3
.
.
0.1 M KI
,
?
,
2.
3
?
3.
H2SO4 3-4
5
IO3–
5
.
3
III.
.
3
2
3
6M
I2
(
10
,
0.5 )
6 M KOH.
,
KOH.
6 M KOH.
0.1 M Na2SO3, 2
?
.
.
.
.
0.1 M KI
3
3
KIO3
2 3 6 M H2SO4.
.
.
,
6M
.
.
,
6
HNO3 (10
),
.
.
?
.
KOH.
,
, ,
6M
,
.
.
.
,
. .
,
.
,
. (2).
(1).
2
3
,
6M
H2SO4
5
3-4
.
3
.
3
5
.
1M
.
Na2SO3,
.
. II .
(2).
AgNO3,
5-10
.
,
0.1 M
.I .
1.
2. .
,
.I ,I ,I .
,
. III (1)
,
. II .
.
0.1 M
,
AgNO3
. III (2)
.I .
.
,
KOH
I2
6M
. III ?
3.
.
,
.
4.
?
.
5.
?
,
.
6.
,
–
–
–
5–
ClO2 , ClO4 , BrO3 , IO6 .
1. I : I– (aq) + Ag+ (aq) → AgI↓ (
).
–
–
+
–
I : 2I (aq) + OCl (aq) + 2H (aq) → I2 + Cl (aq) + H2O
.
I2 + OCl (aq) + H2O → IO3– (aq) + 5Cl– (aq) + H+ (aq).
NaOCl
–
.
2I– (aq) + H2O2 + 2H+ (aq) → I2 + 2H2O.
I :
.
2. .
2–
.II
SO3
KIO3)
.
–
2–
–
2–
IO3 + 3SO3 → I + 3SO4 ,
5I– + IO3– + 6H+ → I2 + 3H2O.
(
. III
.
.
-
IO3–
-
:
-
-
:
IO3– + 3SO32– → I– + 3SO42–,
5I– + IO3– + 6H+ → I2 + 3H2O,
3I2 + 3SO32– + 3H2O → 6I– + 6H+ + 3SO42–.
–
.
,
.
. III (2)
(
)
,
.I :
–
+
I (aq) + Ag (aq) → AgI↓.
I2 6 M
KOH (
. III )
.
3.
:
3I2 + 6OH → 5I + IO3 + 3H2O.
:
–
–
+
5I + IO3 + 6H → 3I2 + 3H2O.
(–1).
–
2
5
: ns np .
–
4.
.
X–
–
–
5.
F2
,
KF
KF + HF → F2 + H2 (
6. ClO2–:
IO65–:
.
HF:
)
2F– → F2 + 2e
2H+ + 2e → H2
E° = –2.87
E° = 0.00
2F– + 2H+ → F2 + H2
∆E = 2.87
, ClO4–:
; BrO3–:
;
39.
Cu(NH3)4SO4·H2O
.
(Cu(H2O)4(H2O)22+,
.
.
,
.
Cu2+(aq)
:
2+
Cu(H2O)6 ,
CuSO4⋅5H2O,
Cu(H2O)4SO4⋅H2O,
NH3
Cu2+ (aq) + 4NH3 → Cu(NH3)42+ +
2
0.01
Cu2+(aq))
-
.
5M
2+
Cu(NH3)4 .
2+
2+
Cu(NH3)3(H2O) , Cu(NH3)2(H2O)2
Cu(NH3)(H2O)3
5M
Cu(NH3)5(H2O)2+.
Cu(NH3)42+.
[Cu(NH 3 ) 24+ ]
K form =
2+
[Cu aq
][ NH 3 ] 4
NH3,
.
:
2+
NH3
,
, Kinst =
Kform
1 / Kform,
.
Cu(NH3)42+
, . .
,
.
Cu(NH3)42+
, . .
.
.
,
Cu(NH3)42+
NH3,
2+
Cu ,
NH3,
(
,
).
1. 6.25 CuSO4⋅5H2O
NH3 6 3
2.
,
3
10
.
Cu(NH3)4SO4⋅H2O
(
,
,
Cu(NH3)42+.
).
10
.
3
–
–
-
?
3.
:( )
,( )
( )
.
4.
.
NH3,
,
CaCl2,
- .
CaO.
,
5.
: 0.3
,
NH3,
Cu(II) NH3
CuSO4⋅5H2O
Na2CO3
2
CuCO3.
Cu(NH3)4SO4⋅H2O
Cu(NH3)42+.
,
10
2
3
,
Na2CO3
Cu(II)
CuCO3
,
Cu(NH3)4SO4·H2O?
Cu(NH3)42+ → Cu2+ (aq) + 4NH3.
NH3:
( )
( )
( )
,
CaCl2,
HCl.
(- )
(- ).
,
?
40.
,
.
:
2HCO3– ς H2O + CO2↑ + CO32–,
Ca2+ + CO32– = CaCO3↓.
.
,
,
.
–
.
o
, D ),
3
H2O (
(
CaCO3 / 1000
3
CaO / 100
3
CaCO3 / 100
H2O (
H2O
, Fo)
).
.
(
1.
3
50
)
«
H2O.
»
2+
2+
,
Mg
Ca .
NH3 – NH4Cl pH = 10 3-4
0.5%T(
).
Mg2+
,
2.
1).
Ca
2+
0.01 F (
Mg2+
1
.
3
,
.
1:1.
Ca
Mg
CaCO3 /
3
2-3
2+
2+
Mg ,
2+,
.
.
pH = 10
,
.
V–
,
CaCO3,
50
,
3
1
CaCO3 / 100
3
.
3
H2O
Fo = 2VC.
= 0.01 F ~ 1
CaCO3 / 1
3
,
Fo = 2V.
–
1.
CaCO3
,
1
0.01 F
3
1
.
2.
3.
25
Do
F°,
CaCO3 /
3
3
?
H2O.
4.
,
2+
Ca ,
Mg
2+
?
?
5.
.
1
1.0×10–3 M
CaF2 1.7×10–10.
(1 ppm)
CaF2?