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Термодинамика органических соединений сурьмы(V)

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ФИО соискателя: Летянина Ирина Александровна Шифр научной специальности: 02.00.04 - физическая химия Шифр диссертационного совета: Д 212.166.08 Название организации: Нижегородский государственный университет им.Н.И.Лобачевского Адрес организации: 60
(V)
02.00.04
2012
"
. . .
:
"
,
:
(
. . .
)
(
. . .
)
:
.
" "
212.166.08
.
. . .
, . 23,
.2
. .
2012 .
: 603950, .
,
. . .
"
"
2012 .
,
,
. .
.
.
,
,
:
,
,
,
,
.
-
.
.
,
-
,
,
.
,
.
,
,
,
,
,
,
-
,
,
-
,
-
.
-
.
,
.
-
.
,
(
11-03-09436-
_)
:
:
В«
-
-
,
,
В».
.
-
;
.
:
ONCPhMe, O2CCH=CH2,
ONCPh2, ONCPhMe)
O2CCMe=CH2,
3
Ph3SbX1X2 (
X1 = X2 = Ph,
O2CC10H15; X1 = Ph, X2 =
,
-
Sb(V),
;
(T < 50 K)
-
;
T = 298.15 K;
T = 298.15 K;
.
.
-
Sb(V),
Ph4SbR,
Ph3SbR2
T
,
Ph5Sb,
0
.
-
: C po ( ), HВ°(T) HВ°(0), SВ°(T), GВ°(T) HВ°(0)
.
D,
,
.
(
)
(V)
T = 298.15 K.
)
T = 298.15 K,
,
(
T = 298.15 K.
(V)
.
-
,
(
)
(T = 298.15 K)
,
,
-
.
4
.
-
,
,
,
,
.
.
,
.
.
,
,
,
,
,
.
.
"
-2009" (
, 2008
2011), 1-
2009), XVII
-
"
-
XVIII
(
, 2009
(
,
-2008"
,
(
, 2011), 19(
,
,
, 2011), XIII, XIV, XV XVI
, 2008, 2009, 2010
2011).
.
:
,
;
;
:
1.
Markin A.V., Letyanina I.A., Smirnova N.N., Sharutin V.V., Senchurin
V.S. Thermodynamic properties of triphenylantimony bis(1-adamantanecarboxylate)
// J. Chem. Thermodyn. 2012 (to be published).
2.
Markin A.V., Letyanina I.A., Smirnova N.N., Sharutin V.V., Molokova
O.V. Standard thermochemical characteristics of formation of triphenylantimony
bis(acetophenoneoxymate) // J. Therm. Anal. Calorim. 2012 (to be published).
3.
. .,
. .,
. .,
. .
//
. . .
. 2012. 3 (
).
5
169
,
,
-
,
,
(119
33
),
.
33
,
1.
7
.
(
)
(
)
.
-
.
,
,
, . .
,
.
,
-
,
,
.
.
.
-
/
Ph3SbO/P4S10,
,
,
. .
,
,
-
Sb.
,
.
,
: Me3Sb, Et3Sb, Ph3Sb, Ph3SbO.
,
.
,
,
,
,
,
,
.
6
Et3Sb.
-
2.
,
,
-
,
.
-
6 (320 370) K,
3,
"
"(
.
.).
-
300 530 K
DSC 204 F1 Phoenix
Netzsch Geratebau,
.
300 540 K
TG 209 F1, Netzsch Geratebau,
.
-08
.
3
.
,
-
"
-6".
(
10
.
.
)
-
5 10-3 K
-3.
-90.
-
-
.
1.5
3
1.6 .
C po
,
K-3.
,
C po
15 40 K
В±2%
В±0.2%
15 K, В±0.5%
40 370 K;
-
0.01 K,
В±0.2%.
.
7
-
,
.
:
,
(
),
,
,
-
,
" 2 36",
.
,
,
,
-
.
,
В±1.5%,
C po
0.3 K,
-
.
-
В±0.8%.
330 350 K
,
K
,
,
100%-
.
T
C po
,
,
350 K
-
,
(0.5 1.5)%.
,
300 450 K
0.8 K/
.
90
-
1000 K
,
,
DSC 204 F1 Phoenix
-
,
3%.
,
,
,
.
-
,
0.5 K,
.
1%.
.
C po
Netzsch Software Proteus.
5 K/
.
-08.
-08
.
,
-
.
8000
-
,
30 .
8
(R = 50
),
.
.
~0.5
.
,
,
-
,
.
.
,
.
(II)
,
.
(6 10
-6
)
.
.
,
Sb(V)
Sb2O4
)
Sb2O3 (
Sb
.
.
.
. .
. .
-
. .
-
,
.
,
,
.
,
-
,
-
,
-
-
.
.
99.5
-
.%.
3.
Ph5Sb,
Ph4SbONCPh2,
Ph4SbONCPhMe
C po = f(T)
Ph4SbONCPhMe
Ph5Sb, Ph4SbONCPh2
6 (415 450) K.
.1
9
.
Cpo ,
/(K
)
1200
. 1.
-
800
B
Ph5Sb
C
400
o
Tfus
A
0
100
200
300
400
T, K
500
,
-
= 370 K (
,
C po
. 1,
B),
Ph5Sb.
.
.
-
,
,
Ph5Sb
405 K.
,
(
. 1,
ABC)
.
-
, . .
.
(
)
Ph3Sb(ONCPhMe)2
,
,
(
)
(
. 2,
(
.
20
(
. 2).
)
B)
(
,
. 2,
DE)
-
.
,
(
)
85 110 K (
. 3).
10
Cpo ,
/(K
)
2000
C C
1600
. 2.
1200
B
DE
(
)
Ph3Sb(ONCPhMe)2
800
400
A
0
100
300
200
500
400
T, K
/(K
Cpo ,
350
)
. 3.
300
(
)
Ph3Sb(ONCPhMe)2
250
200
50
100
T, K
150
Ph3Sb(O2CCH=CH2)2
Ph3Sb(O2CCMe=CH2)2
.4
.
.
,
o
C p = f(T)
150 167 K (
11
. 5).
/(K
Cpo ,
1000
)
2
800
1
. 4.
-
600
2
400
Ph3Sb(O2CCH=CH2)2 (1)
-
1
Ph3Sb(O2CCMe=CH2)2 (2)
200
0
100
200
300
400
500
T, K
/(K
Cpo ,
450
)
. 5.
350
Ph3Sb(O2
250
100
160
Me=CH2)2
220
T, K
. 1.
-
-
.
-
,
.
,
,
:
.
,
.
,
.
12
-
1.
-
Ph3Sb(ONCPhMe)2
Ph3Sb(O2CCMe=CH2)2
,K
85 110
150 167
(1-
trHВ°,
Ttro , K
-
/
99.5В±0.5
159.5В±0.5
/(KВ·
86.8В±0.2
216.5В±0.4
)
.
trSВ°,
)
0.883В±0.002
1.370В±0.003
Ph3Sb(O2CC10H15)2
6
(1-
)
Ph3Sb(O2CC10H15)2.
,
,
Cpo ,
/(K
.
)
C
C
1500
D
I
1250
E
H
. 6.
B
G
1000
-
(1-
F
)
Ph3Sb(O2CC10H15)2
750
500
Tgo
250
o
Tfus
A
100
0
200
300
400
500
T, K
6 320 K,
300
526 K
-
.
(
(
BCC D),
DE).
T = 526 K (
)
5 K/
-
.
(
13
FGH).
403 444 K (
HI)
.
,
IDE
526 K (
,
)
444 K (
I)
T = 526 K.
Tgo = 334В±1 K,
Cpo ( Tgo ) = 122В±2
/(K
),
Ph3Sb(O2CC10H15)2 Sgo (0) = 27В±1
/(K
).
:
-
. 2,
,
,
.
.
-
,
.
2.
Ph5Sb
Ph4SbONCPh2
Ph4SbONCPhMe
Ph3Sb(ONCPhMe)2
Ph3Sb(O2CCH=CH2)2
Ph3Sb(O2CCMe=CH2)2
Ph3Sb(O2CC10H15)2
370
400
390
423
390
400
485
o
Tfus
В±0.5,
K
403.3
443.4
409.6
434.5
428.4
418.7
495.1
,K
420
450
430
453
430
440
515
fusHВ°,
fusSВ°,
/
/(K
)
42.0В±0.6
96.7В±1.4
47.2В±0.6
95.4В±1.2
(V)
D
max
(20
T/K
50)
.
-
D
.
D
.
C po
,
1
3
2
,
, . .
D
14
1, 2, 3.
,
-
20 50 K
D(
. 3)
-
.
,
,
,
,
-
,
.
.
-
.7
.
Ph4SbONCPh2
C HВ·В·В·
1
. 7.
Ph4SbONCPh2
.
1
,
D
.
-
max
(1),
,
,
(1max(Ph3Sb(O2CC10H15)2)
<
1
)
max(Ph3Sb(ONCPhMe)2)
max(Ph4SbONCPhMe)
.
max(Ph4SbONCPh2)
< max(Ph3Sb(O2CCMe=CH2)2) <
< max(Ph3Sb(O2CCH=CH2)2)
. .,
. .,
. .
. //
15
.
max(Ph5Sb)
. 2001. . 71.
<
<
(1)
8. . 1317 1321.
3.
D
max
D
1.3
1.5
1.5
1.6
1.4
1.5
1.6
Ph5Sb
Ph4SbONCPh2
Ph4SbONCPhMe
Ph3Sb(ONCPhMe)2
Ph3Sb(O2CCH=CH2)2
Ph3Sb(O2CCMe=CH2)2
Ph3Sb(O2CC10H15)2
max,
K
246.7
202.8
218.7
194.8
251.1
227.6
201.6
: 20 50 K
: n = 28
,%
1.0
0.5
1.0
0.9
0.6
0.6
0.8
o
p
: C (T), HВ°(T) HВ°(0), SВ°(T)
T
0
. 4
GВ°(T) HВ°(0)
.
T = 298.15 K.
:
SВ°(Ph3Sb(O2CC10H15)2) > SВ°(Ph3Sb(ONCPhMe)2) > SВ°(Ph4SbONCPh2) >
> SВ°(Ph4SbONCPhMe) > SВ°(Ph3Sb(O2CCMe=CH2)2) > SВ°(Ph5Sb) >
> SВ°(Ph3Sb(O2CCH=CH2)2)
(2)
(1), . .
(
)
(1-
(
,
)
)
.
4.
T = 298.15 K
C po ( ),
Ph5Sb ( )
Ph4SbONCPh2 ( )
Ph4SbONCPhMe ( )
Ph3Sb(ONCPhMe)2 ( )
Ph3Sb(O2CCH=CH2)2 ( )
Ph3Sb(O2CCMe=CH2)2 ( )
Ph3Sb(O2CC10H15)2 ( )
Ph3Sb(O2CC10H15)2 ( )
/(K
531.0
646.4
595.6
672.5
510.5
555.9
734.7
784.4
HВ°(T) HВ°(0),
/
)
83.96
101.0
94.73
106.6
84.66
92.71
111.8
119.4
16
SВ°(T),
/(K
584.8
690.1
649.2
725.5
582.4
636.3
741.2
818.2
)
[GВ°(T) HВ°(0)],
/
90.38
104.8
98.83
109.7
88.97
97.00
109.1
124.5
,
-
(
)
,
C po ( ),
SВ°(T),
HВ°(T) HВ°(0)
( [GВ°(T) HВ°(0)])
( . 8, 9).
Cpo (298.15),
/(K
740
SВ°(298.15),
/(K
)
)
740
SВ°(T) = 1.2331M
R2 = 0.9976
42.702
. 8.
(T = 298.15 K)
660
660
Ph5Sb Ph4SbONCPhMe
Ph3Sb(ONCPhMe)2
580
Cpo = 1.2401M
580
100.13
R2 = 0.9975
500
500
550
HВ°(298.15) HВ°(0),
/
600
500
650
M, /
[GВ°(298.15) HВ°(0)],
/
110
110
[GВ°(T) HВ°(0)] =
= 0.1693M + 4.0845
R2 = 0.9948
. 9.
100
100
90
80
500
(T = 298.15 K)
90
HВ°(T) HВ°(0) =
= 0.1984M 16.875
R2 = 0.9992
550
600
M, /
80
650
17
Ph5Sb Ph4SbONCPhMe
Ph3Sb(ONCPhMe)2
T = 298.15 K
(Ph5Sb, Ph4SbONCPh2,
Ph4SbONCPhMe
Ph3Sb(ONCPhMe)2)
,
(
-
. 5).
,
Sb2O4
Sb2O3 (
.), Sb2O3 (
.)
Sb
-
.
,
.
.
= 298.15 K
,
-
.
= 298.15 K.
5.
T = 298.15 K
HВ°,
Ph5Sb ( )
Ph4SbONCPh2 ( )
Ph4SbONCPhMe ( )
Ph3Sb(ONCPhMe)2 ( )
Ph3Sb(O2CCH=CH2)2 ( )
Ph3Sb(O2CCMe=CH2)2 ( )
Ph3Sb(O2CC10H15)2 ( )
fSВ°,
fHВ°,
/
16637.0В±19.0
20137.6В±20.0
17794.2В±22.2
18967.1В±32.7
/
805.0 25.7
836.5В±27.7
746.5 29.2
703.6В±40.1
fGВ°,
/(K
)
1266.6В±6.2
1726.5В±7.4
1608.1В±6.6
1937.7В±7.1
1383.5В±5.4
1602.5В±5.8
2884.7В±7.9
/
1182.7 25.7
1351.3В±27.7
1226.0В±29.7
1281.3В±40.1
,
(1)
.
-
.
,
(
)
18
-
,
(
fHВ°,
/
/(K
/
fSВ°,
fGВ°,
2000
. 10).
)
fSВ° = 5.8811M
R2 = 0.9999
1714.8
fGВ°
2
= 0.8646M + 742.09
R = 0.9951
1500
1000
fHВ°
2
= 0.8889M + 1253.4
R = 0.9992
500
500
550
600
650
M, /
. 10.
(T = 298.15 K)
,
Ph5Sb
Ph4SbONCPhMe
Ph3Sb(ONCPhMe)2
,
,
-
.
1.
.
2.
,
.
3.
(T < 50 K)
,
-
,
.
19
-
4.
HВ°(T) HВ°(0), SВ°(T), GВ°(T) HВ°(0)
.
T
0
: C po ( ),
(400 526) K
5.
T = 298.15 K.
6.
fH
,
fS
:
-
fG
T = 298.15 K.
7.
"
".
:
1.
2.
3.
4.
5.
6.
7.
8.
Smirnova N.N., Letyanina I.A., Larina V.N., Markin A.V., Sharutin V.V., Senchurin V.S. Thermodynamic properties of pentaphenylantimony Ph5Sb over the
range from T
0 to 400 K // J. Chem. Thermodynamics. 2009. V. 41.
1. P. 46 50.
. .,
. .,
. .,
. .,
. .,
. .
0 450 K //
.
. 2009. . 79.
4.
. 553 559.
Letyanina I.A., Smirnova N.N., Markin A.V., Ruchenin V.A., Larina V.N., Sharutin V.V., Molokova O.V. Thermodynamics of tetraphenylantimony acetophenoneoxymate // J. Therm. Anal. Calorim. 2011. V. 103. P. 355 363.
. .,
. .,
. .,
. .,
. .
(
)
//
.
. 2011. . 85. 8. . 1427 1434.
Markin A.V., Letyanina I.A., Ruchenin V.A., Smirnova N.N., Gushchin A.V.,
Shashkin D.V. Heat capacity and thermodynamic functions of triphenylantimony
dimethacrylate over the temperature range from (0 to 400) K // J. Chem. Eng.
Data. 2011. V. 56. P. 3657 3662.
. .,
. .,
. .,
. .,
. .
//
.
. 2012. . 86. 8. . 1329 1335.
. .
Ph5Sb //
.
. XV
,
В«
-2008В».
. 2008.
. 635.
. .
(V) //
.
. XVI
,
В«
-2009В».
. 2009. . 30.
20
9.
10.
11.
12.
Letyanina I.A., Smirnova N.N. Thermodynamics of Ph3Sb(ONCPhMe)2 // Abstr.
XVII International Conference on Chemical Thermodynamics in Russia
RCCT2009. Kazan. 2009. V. II. P. 52.
Letyanina I.A., Markin A.V., Smirnova N.N., Gushchin A.V., Shashkin D.V.
Thermodynamic properties of antimony(V) organic derivatives with a general
formula Ph3SbR2, where R -Ph, -O2CCH=CH2, -O2CCMe=CH2 // Abstr. XVIII
International Conference on Chemical Thermodynamics in Russia
RCCT2011. Samara. 2011. V. I. P. 194.
Letyanina I.A., Markin A.V., Gushchin A.V., Shashkin D.V. Thermodynamics of
triphenylantimony dimethylacrylate // Abst. 19th European Conference on
Thermophysical properties. Greece. Thessaloniki. 2011. P. 371.
Letyanina I.A., Markin A.V., Smirnova N.N., Zakharova Yu.A., Gushchin
A.V. Thermodynamics of triphenylantimony diacrylate // Abstr. 1st Central
and Eastern European Conference on Thermal Analysis and Calorimetry.
Romania. Craiova. 2011. P. 126.
21
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