2016, . 158, . 3 ISSN 1815-6169 (Print)
. 381–390 ISSN 2500-218X (Online)
381
541.8
. .
1,
. . Ф
2,
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1,
. . Ш
1,
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11
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2
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и
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в в : , - ,
.
,
,
,
,
,
.
.
,
Д1, 2Ж,
.
,
–
(
α
1) [3].
,
,
.
.
Д4Ж,
;
. .
,
,
-HSO
4–10
Д5Ж.
,
,
,
.
,
-,
,
.
.
,
SO
42−-
.
,
.
,
-.
,
.
-
,
M + L = ML.
-
,
–
Li
+, Na
+, K
+, NH
4 +–
Br
−, CI
−,
SO
42−-
,
--
(
SO
4−solv).
-
25
°
,
(
HBr, HNO
3),
–
-.
0,5; 1,0; 2,0; 3,0; 4,0.
. 1 2
.
(1÷3)·10
–5/ .
-4·10
–5/ .
:
,
SO
Sr
SrSO
solv 24 solv2 4
(1)
solv 4 solv
solv 2
4
H
HSO
. 1
(L, / )
HBr, / L, /
(Li, H)Br (Na, H)Br (K, H)Br
I = 0.5
0 2.51 2.55 2.58
0.3 5.62 5.68 5.74
0.4 6.33 6.36 6.40
0.5 6.85 6.85 6.86
I = 1.0
0 3.70 3.80 3.79
0.2 5.64 5.73 5.76
0.4 6.97 6.98 7.01
0.6 7.94 7.92 8.02
0.8 9.02 8.92 9.08
1.0 9.72 9.72 9.75
I = 2.0
0 4.49 4.58 4.60
0.25 5.89 6.02 6.84
0.5 6.67 6.86 6.86
1.0 8.36 8.40 8.39
1.5 9.24 9.24 9.22
2.0 9.88 9.86 9.86
I = 3.0
0 4.70 4.87 4.90
0.5 6.46 9.03 7.94
1.0 7.95 10.05 10.20
1.5 8.12 11.23 12.30
2.0 9.18 11.45 12.20
2.5 9.23 11.25 11.98
3.0 10.04 10.04 10.00
I = 4.0
0 4.80 4.98 5,02
0.5 6.10 8.02 10.02
1.0 6.86 9.02 10.23
2.0 8.25 10.46 12.68
3.0 9.12 10.97 11.98
4.0 10.42 10.40 10.44
,
,
(
):
],
SO
][
Sr
[
242 SO
SO
,
(3)
1 1 2 4 4
1 [HSO ][SO ] [H ]
.
(4)
(3) (4)
“
solv
”
-,
Θ
. 2
(L, / )
H l, / (Li, H) L, /
l (Na, H)Cl (K, H)Cl
I = 0.5
0 2.90 2.60 3.26
0.3 6.03 5.84 6.58
0.4 6.53 6.55 6.70
0.5 6.78 6.83 6.81
I = 1.0
0 3.68 3.80 4.86
0.2 6.03 6.09 7.12
0.4 7.19 7.50 8.23
0.6 8.21 8.34 8.98
0.8 8.81 8.95 9.53
1.0 9.70 9.76 9.70
I = 2.0
0 1.77 4.48 5.79
0.25 6.01 6.70 8.19
0.5 8.05 8.82 10.3
1.0 9.78 10.41 12.13
1.5 11.29 11.65 13.04
2.0 12.14 12.17 12.15
I = 3.0
0 4.73 4.73 7.84
0.5 7.10 8.67 13.49
1.0 8.64 10.37 14.29
1.5 8.12 11.23 12.30
2.0 10.33 11.90 14.38
2.5 9.23 11.67 12.77
3.0 11.47 11.50 11.47
I = 4.0
0 3.45 4.09 8.03
0.5 5.94 8.50 13.77
1.0 7.06 10.40 14.26
2.0 8.50 11.49 13.80
3.0 9.44 11.07 12.42
4.0 10.60 10.65 10.68
,
(2)
:
.
HSO
Sr
H
SrSO
solv 4solv2 solv 4
(5)
:
1 4
2
1
[
Sr
][
HSO
][
H
]
s
.
(6)
,
-,
:
1 0 1
1
(
)
(1
)
–
(
6)
(
L
)
]).
H
[
)
(
1
(
]
Sr
[
])
[
1
](
SO
[
]
][
SO
[
]
SO
[
]
HSO
[
]
SO
[
1 0 1 1 2 0 1 2 4 2 4 1 2 4 4 2 4
s s sH
H
L
(8)
Sr
2+S0
42–
,
,
,
SЫS
O
4,
Д
Sr
2+
] =
L
.
])
H
[
1
(
]
H
[
0 11 0
2
s s
s
L
,
(9)
-
( )
,
)
exp(
1
]
H
[
])
H
[
exp(
1
H H 1 1 1 1 2 0 2
C
C
L
L
(10)
L0
–
;
α0
–
(1)
α1
–
(5).
.
(10)
,
lg
]
)
(
)
1
Φ
lg[(
H 1
1
1 H
C
C
(11)
β
1α
1.
Д6Ж
SrS
4( , ) ,
–
Li
+, Na
+,
+Б –
Br
−, CI
−.
β
1,
,
(
α
1),
.
. 3 4.
α
10.5÷4.0,
.
-.
,
.
-
-
,
-SrSO
4.
I
= 0.5;
1.0 2.0
;
,
3,
,
.
.
LТ
+. 3 α1, lgβ1 (Li, H)Br, (Na, H)Br, (K, H)Br
= 298
I (Li, H)Br (Na, H)Br (K, H)Br
1 ±
0.03 lgβ1
±
0.04
±
0.06
1 ±
0.03 lgβ1
±
0.04
±
0.06
1 ±
0.06 lgβ1
± 0.04 ± 0.06 0.5 1 2 3 4 0.11 0.09 0.08 0.11 0.09 1.12 0.80 0.40 0.23 0.40 5.11 4.84 4.67 4.63 4.60 0.17 0.14 0.14 0.14 0.18 1.08 0.90 0.63 0.75 1.50 5.20 4.85 4.69 4.63 4.62 0.22 0.27 0.20 0.29 0.20 1.23 0.94 0.63 0.42 0.86 5.20 4.89 4.75 4.64 4.64
1 0.09 0.15 0.24
. 4 α1, lgβ1 (Li, H)CI, (Na, H) CI, (K, H)CI
= 298
I (Li, H) CI (Na, H)CI (K, H)CI
1 ±
0.05
lgβ1 ±
0.04
±
0.06
1 ±
0.03
lgβ1 ±
0.04
±
0.06
1 ±
0.06
lgβ1 ±
0.04 ± 0.06 0.5 1 2 3 4 0.35 0.19 0.09 0.08 0.11 1.13 0.94 0.80 0.44 0.63 5.07 4.87 4.75 4.65 4.92 0.33 0.24 0.16 0.19 0.20 1.16 0.95 0.83 0.77 1.93 5.10 4.84 4.70 4.65 4.78 0.51 0.30 0.24 0.39 0.38 1.12 0.78 0.73 0.78 0.79 4.97 4.63 4.47 4.21 4.19
1 0.12 0.20 0.33
,
.
(
+)
I
=
4 (
.
1).
,
-
-
.
-α
1(
Li, H)Br
;
LiBr, NaBr, KBr
α
1,
(
. 5).
,
-,
-,
.
lg
β
1
,
Д7Ж:
, lg 6 . 1 1
lg 10
2
1 bI
I I A
Z
(12)
. P 6 . 1 1 0 2 bI I I A
Z
(13)
∆
Z
2–
,
-,
4
lg
β
10
8
0. 1. +
-I = 4
. 5
(α1) (Li, H)Br,
(Na, H)Br, (K, H)Br (Li, H)CI, (Na, )CI, (K, H)CI
(Li, H)Br (Na, H)Br (K, H)Br
α1
0.09 0.15 0.24
(Li, H)CI (Na, )CI (K, H)CI
0.12 0.20 0.33
,
,
,
,
lg
β
10 0
( ,
)
Br (1.07
±
0.02; 6.52
±
0.07) (
M, H)CI
(1.62
±
0.05; 6.45
±
0.08
)
-.
,
--
-,
я
.
и
1. Ш Е. .
IIIA // . . . – 2008. –
.81, № 9. – . 1428–1431.
2. И. .
-. – : - , 2003. – 238 .
3. Ф . ., .И., . .
SO42– - // . . . –
2006. – . 80, № 2. – . 263–268.
4. Bjerrum J. Determination of small stability constants. A spectrophotometric study of copper(II) chloride complexes in hydrochloric acid // Acta Chem. Scand. A. – 1976. – V. 41, No 6. – P. 328–334.
5. Fletcher A.N. Bisulphate dissociation quotient in mixed electrolytic solutions // J. Inorg. Nucl. Chem. – 1964. – V. 26, No 6. – P. 955–960.
6. . . -
-: . … . . . – , 2006. – 117 .
7. . . . – .: . ., 1982. –
317 .
04.06.16
в в и в , ,
-. , . 79, . , 660041,
E-mail: Lera0727@yandex.ru
в и в и ви , ,
-. -. « », . 31, . , 660049,
E-mail: chem@sibstu.kts.ru
и и ви , ,
-. , . 79, . , 660041,
E-mail: Vladimirganzha@yandex.ru
Ш в ви , ,
-. , . 79, . , 660041,
E-mail: shram18rus@mail.ru
и в и в , ,
-. , . 79, . , 660041,
ISSN 1815-6169 (Print) ISSN 2500-218X (Online)
UCHENYE ZAPISKI KAZANSKOGO UNIVERSITETA. SERIYA ESTESTVENNYE NAUKI
(Proceedings of Kazan University. Natural Sciences Series)
2016, vol. 158, no. 3, pp. 381–390
Formation of Hydrogen-Ion in Isomolar Solution of Hydrochloric and Hydrobromic Acids and Their Salts
M.A. Kovalevaa*, V.A. Fedorovb**, V.A. Ganjaa***,
V.G. Shrama****, N.N. Lysyannikovaa***** a
Siberian Federal University, Krasnoyarsk, 660041Russia
bSiberian State Technological University, Krasnoyarsk, 660049Russia
E-mail:*Lera0727@yandex.ru, **chem@sibstu.kts.ru, ***Vladimirganzha@yandex.ru,
****
shram18rus@mail.ru, *****nataly.nm@mail.ru
Received June 4, 2016
Abstract
Despite the presence of a large amount of factual material on thermodynamic parameters of com-plexation of agents in different solvents, including mixed ones, obtained knowledge is specific in nature. In order to identify more general patterns, studies are relevant that would allow to interpret the obtained data taking into account the interaction between chemical forms in solutions.
This paper presents a general approach to studying weak ionic interactions in solutions that allows to simultaneously determine the constants of these interactions and the parameters characterizing the influence of changes in the ionic environment on these constants by the example of chlorides and bromides of alkali metals.
The obtained constants for hydrosulfate-ion formation and the imperfection parameters can be a reference material for more accurate calculation of the concentration of hydrogen ions in sulfuric acid solutions. The developed approach and patterns identified in the work can be used to study the balanced states for formation of low and medium stable complexes.
Keywords: solubility, hydrosulfate ion, environmental effects
Figure Captions
Fig. 1. Dependence of the complexation function F on + for the bromide and chloride system atI = 4. References
1. SСФoХ’nТФoЯ E.V. Thermodynamic calculation of the solubility of solid hydroxides of group IIIa elements in water and aqueous media. Russ. J. Appl. Chem., 2008, vol. 81, no. 9, pp. 1503–1507. 2. Mironov. I.V. The Effect of Environment and Complex Formation in Solutions of Electrolytes.
Novosibirsk, Izd. INKh Sib. Otd. Ross. Akad. Nauk, 2003, 238 p. (In Russian)
3. Fedorov V.A., Belevantsev V.I., Batalina L.S. Secondary environment effects on the first step of the protonation of SO4
in saline aqueous solutions. Russ. J. Phys. Chem., 2006, vol. 80, no. 2, pp. 200–204.
4. Bjerrum J. Determination of small stability constants. A spectrophotometric study of copper(II) chloride complexes in hydrochloric acid. Acta Chem. Scand., Ser A, 1976, vol. 41, no. 6, pp. 328–334. 5. Fletcher A.N. Bisulphate dissociation quotient in mixed electrolytic solutions. J. Inorg. Nucl.
Chem., 1964, vol. 26, no. 6, pp. 955–960.
6. Batalina L.S. Effects of environment in the formation of hydrosulphate ion in water-salt solutions.
7. VКЬТХ’ОЯ V.P. TСОЫmoНвnКmТМ PЫopОЫЭТОs of Electrolytes. Moscow, Vyssh. Shk., 1982. 317 p. (In Russian)
Для цитир ва ия: . ., Ф . ., . ., Ш . ., я
-. -. -
// . . . - . . . . –
2016. – .158, .3. – . 381–390.
For citation: Kovaleva M.A., Fedorov V.A., Ganja V.A., Shram V.G., Lysyannikova N.N.
