ЕЛЕКТРОХІМІЧНІ ВЛАСТИВОСТІ ВОДНИХ РОЗЧИНІВ АМІНОМЕТАНСУЛЬФОНАТІВ НАТРІЮ
The pH and conductometric study of the electrochemical properties of aqueous solutions (1∙10-4 ÷ 9∙10-3 М) YNHCH2SO3Na (Y = H, CH3, HOCH2CH2, (CH3)3C and C6H5CH2) was carried out. The values of the limiting electrical conductivity were calculated by extrapolation according to Shidlovsky. The activat...
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Ukrainian Chemistry Journal| _version_ | 1871465647597158400 |
|---|---|
| author | Khoma, Ruslan Ennan, Alim Chebotaryov, Alexandr Vodzinskii, Sergey Dlubovskii, Ruslan Toporov, Sergey |
| author_facet | Khoma, Ruslan Ennan, Alim Chebotaryov, Alexandr Vodzinskii, Sergey Dlubovskii, Ruslan Toporov, Sergey |
| author_institution_txt_mv | [
{
"author": "Ruslan Khoma",
"institution": "Одесский национальный университет имени И.И. Мечникова"
},
{
"author": "Alim Ennan",
"institution": "Физико-химический институт защиты окружающей среды и человека МОН Украины и НАН Украины"
},
{
"author": "Alexandr Chebotaryov",
"institution": "Одесский национальный университет имени И.И. Мечникова"
},
{
"author": "Sergey Vodzinskii",
"institution": "Одесский национальный университет имени И.И. Мечникова"
},
{
"author": "Ruslan Dlubovskii",
"institution": "Physical-Chemical Institute for Environment and Human Protection of MES of Ukraine and NAS of Ukraine"
},
{
"author": "Sergey Toporov",
"institution": "Odessa I.I. Mechnikov National University"
}
] |
| author_sort | Khoma, Ruslan |
| baseUrl_str | https://ucj.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-22T08:23:45Z |
| description | The pH and conductometric study of the electrochemical properties of aqueous solutions (1∙10-4 ÷ 9∙10-3 М) YNHCH2SO3Na (Y = H, CH3, HOCH2CH2, (CH3)3C and C6H5CH2) was carried out. The values of the limiting electrical conductivity were calculated by extrapolation according to Shidlovsky. The activation parameters of the electrical conductivity of the systems “sodium aminomethanesulfonate – H2O” at 293-313 K were obtained. |
| doi_str_mv | 10.33609/2708-129X.86.11.2020.51-64 |
| first_indexed | 2025-09-24T17:43:36Z |
| format | Article |
| fulltext |
51
УДК 54-45:547.436.3 doi: 10.33609/2708-129X.86.11.2020.51-64
ELECTROCHEMICAL PROPERTIES OF AQUEOUS SOLUTIONS OF SODIUM
AMINOMETHANESULFONATES
R. E. Khoma1,2*, A. A.-A. Ennan1, A. N. Chebotarev2, S. V. Vodzinskii1,2,
R. M. Dlubovskii1, S. V. Toporov2
1Physico-Chemical Institute of Environment and Human Protection, Preobrazhenskaya str., 3,
Odessa 65082, Ukraine
2Odessa I.I. Mechnikov National University, Dvoryankaya str., 2, Odessa 65082, Ukraine
*e-mail: rek@onu.edu.ua
The pH and conductometric study of the electrochemical properties of aqueous solutions
(1∙10-4 ÷ 9∙10-3 М) YNHCH2SO3Na (Y = H, CH3, HOCH2CH2, (CH3)3C and C6H5CH2) was car-
ried out. The values of the limiting electrical conductivity were calculated by extrapolation ac-
cording to Shidlovsky. The activation parameters of the electrical conductivity of the systems
“sodium aminomethanesulfonate – H2O” at 293-313 K were obtained.
Key words: aminomethanesulfonic acids, aqueous solutions, hydrolysis, conductivity.
INTRODUCTION. The theoretical inte
rest in aminomethanesulfonic acid and its
N-alkylated derivatives is be explained by their
specific physicochemical properties and a wide
spectrum of biological activity [1–5]. Under
physiological conditions (pH = 6.8 – 7.8), the
degree of dissociation of the sulfo group, in
contrast to α-aminocarboxylic acids, is 100%,
and the рKа values of the amino group are in
the range of physiological pH values [6–9]. The
sulfo group can act as an anionic fragment and
a hydrogen bond acceptor when interacting
with a potential biological target [10].
Solubility and permeability are two bio-
pharmaceutical parameters responsible for
effective bioavailability and good correlation
between in vitro and in vivo studies [11]. The
improvment of solubility and dissolution rate,
as well as bioavailability of amino acids, con-
tinues to be a challenge for pharmaceutical
technologists. The hydrotropic action of sul-
fonates and amino acids is considered as one
of the important methods of solubilization [12,
13]. Conductometric studies of aminometh-
anesulfonates at a definite and infinite dilution
in a solvent system provide valuable informa-
tion about ion-ion (complexation, association)
and ion-solvent (solvation) interactions.
Therefore, the determination of the tem-
perature and concentration dependences of
the molar electrical conductivity of aqueous
solutions of sodium aminomethanesulfonates
and monoethanolammonium is, of course,
an actual task. To determine the factors af-
fecting the electrical conductivity of aqueous
solutions of sodium aminomethanesulfonates,
ELECTROCHEMICAL PROPERTIES OF AQUEOUS SOLUTIONS OF SODIUM AMINOMETHANESULFONATES
52 ISSN 2708-129X. Укр. хім. журн., 2020
PHISICAL CHEMISTRY
a pH and conductometric study of their be
havior was carried out in the temperature
range of 293–313 K.
EXPERIMENTAL PART. The studies used
AMSA, its N-methyl (MeAMSA), N-(2-
hydroxyethyl) (HEAMSA), N-tert-butyl
(t-BuAMSA) and N-benzyl (BzAMSA) de-
rivatives synthesized according to original
methods [3, 14]. Aqueous solutions of sodi-
um salts YNHCH2SO3Na (Y = H (AMSNa),
CH3 (MeAMSNa), HOCH2CH2 (HEAMSNa),
(CH3)3C (t‑BuAMSNa) and C6H5CH2
(BzAMSNa)) were prepared by NaOH react-
ing with the corresponding acids in equimolar
amounts.
Potentiometric measurements were carried
out using a universal ЭВ-74 ionomer and a
pH-meter of the pH-150M type. The pH measu
rement accuracy was ± 0.05 units (ЭВ-74) and ±
0.02 units (pH-150M), and for the redox poten-
tial ± 1 mV (ЭВ-74). Conductometric measu
rements were performed on an Expert-002 con-
ductometer (the relative error was ≤ 0.5%).
Electrochemical properties of aqueous solu-
tions of sodium aminomethanesulfonates
Fig. 1–5 show the results of pH and conduc-
tometric studies of aqueous solutions (1∙10-4
÷ 1∙10-2 М) AMSNa, MeAMSNa, HEAMSNa,
t-BuAMSNa and BzAMSNa in the temperature
range 293 ÷ 313 K. Judging by the results of
conductometric study of the systems АМSNa –
Н2О (Fig. 1b) and YАМSNa – Н2О (Fig. 2b –
5b), an increase in temperature from 293 to
313 K is accompanied by an increase in the
electrical conductivity of the systems (similar
to aqueous solutions of AMSA [15], YAMSA
[16] and glycine [11]) due to an increase in the
degree of dissociation of electrolytes and (or)
the mobility of the resulting ions. In this case,
for all the systems under study, acidic proper-
ties decrease with an increase in temperature
from 293 to 308 K (Fig. 1a – 5a).
Aminosulfonic acids, like amino-carboxylic
acids, belong to the class of organic ampholy-
tes and in solution can be in several ionic forms.
The qualitative and quantitative composition of
amino acid forms depends on the type of amino
acid and the pH of the solution [6, 10, 11, 15].
Fig. 1. рН (а) and molar conductivity (b) of
aqueous solutions of AMSNa. Т (К): 293–1; 298–2;
303–3; 308–4; 313–5.
Even in the simplest case of an aqueous
solution of an individual amino acid, a com-
plex mixture is formed, consisting of zwitter-
R. E. Khoma, A. A.-A. Ennan, A. N. Chebotarev, S. V. Vodzinskii, R. M. Dlubovskii, S. V. Toporov
53https://ucj.org.ua
UCJ № 11 / Vol. 86
ions, amino acid cations and anions, protons,
and hydroxyl anions. The mutual influence of
all components of the system on each other
determines the complexity in the study of the
electrochemical behavior of solutions of amino
acids and their salts.
Fig. 2. рН (а) and molar conductivity (b) of
aqueous solutions of MeAMSNa. Т (К): 293–1;
298–2; 303–3; 308–4; 313–5.
In aqueous solutions of YАМSNa рН > 7.0
is due to hydrolysis of aminomethanesulfonate
ions (reaction 1) with the formation of zwitte-
rions:
YNHCH2SO 3
− + H2O
→
←
→
← Y
+
N H2CH2SO 3
−
+ OH-,
(1)
Kh =
- -
2 2 2
-
2 2
[Y N H CH SO O ] [OH ]
[YNHCH SO O ]
+
⋅ . (2)
Fig. 3. рН (а) and molar conductivity (b) of
aqueous solutions of HeAMSNa. Т (К): 293–1;
298–2; 303–3; 308–4; 313–5.
With equations (1), (3), we have a system
of equations that take into account the law
of effective masses (2), material balance ac-
cording to YAMSA (4) and the condition of
electroneutrality (5).
ELECTROCHEMICAL PROPERTIES OF AQUEOUS SOLUTIONS OF SODIUM AMINOMETHANESULFONATES
54 ISSN 2708-129X. Укр. хім. журн., 2020
PHISICAL CHEMISTRY
H2O →← H
+ + OH- (3)
QYAMSA =
= [Y N
+
H2CH2SO 3
− ] + [YNHCH2SO 3
− ] (4)
[YNHCH2SO 3
− ] + [OH-] =
= [H+] + [Na+]
(5)
Fig. 4. рН (а) and molar conductivity (b) of
aqueous solutions of t‑BuAMSNa. Т (К): 293–1;
298–2; 303–3; 308–4; 313–5.
N-alkylation of aminomethanesulfonate
anions promotes hydrolytic decomposi-
tion by reaction (6) [17]. At pH < 7.0, in
aqueous solutions of YAMSNa (Y – CH3,
HOCH2CH2, (CH3)3C and C6H5CH2), un-
like AMSNa, hydrolytic decomposition of
N-alkylaminomethanesulfonate ions occurs
with the formation of alkylaminomethanol
and hydrosulfite ions:
YNHCH2SO 3
− + H2O →←
→
← YNHCH2OH + HSO 3
− .
(6)
Fig. 5. рН (а) and molar conductivity (b) of
aqueous solutions of BzAMSNa. Т (К): 293–1;
298–2; 303–3; 308–4; 313– 5.
R. E. Khoma, A. A.-A. Ennan, A. N. Chebotarev, S. V. Vodzinskii, R. M. Dlubovskii, S. V. Toporov
55https://ucj.org.ua
UCJ № 11 / Vol. 86
Along with this, dissociation (7) of HSO5
occurs, as well as protonation (8) and (9) at
the nitrogen atoms of N-alkylaminomethane
sulfonate ions and alkyl-aminomethanol, re-
spectively:
HSO 3
−
→
← H
+ + SO 2
3
− , (7)
YNHCH2SO 3
− + H+ →← Y N
+
H2CH2SO 3
− , (8)
YNHCH2OH + H+ →← Y N
+
HCH2OH. (9)
In this case, the material balance according
to YAMSNa takes the form (10), and the con-
dition of electroneutrality - (11). In addition,
equation (12) must be taken into account.
QYAMSA = [YNHCH2SO 3
− ] +
+ [YNHCH2OH] + [Y N
+
H2CH2SO 3
− ] +
+ [Y N
+
HCH2OH]
(10)
[YNHCH2SO 3
− ] + [OH-] + [HSO 3
− ] +
+2[SO 2
3
− ] = [H+] + [Na+]+[Y N
+
HCH2OH]
(11)
[YNHCH2OH] + [Y N
+
HCH2OH] =
= [HSO 3
− ] + [SO 2
3
− ]
(12)
Due to the lack of data on equilibrium (9),
we calculated, similarly to [6, 8], the ion-mo-
lecular composition of aqueous solutions
of YAMSNa only at pH > 7.0 on the basis of
pH-metric data (Fig. 1a-5a).
The ionic strength of sodium aminometh-
ane sulfonate solutions at pH > 7.0 is deter-
mined by the following expression:
µ = 1
2
∙([YNHCH2SO 3
− ]∙(-1)2 +
+ [OH-]∙(-1)2 + [H+]∙(-1)2 + [Na+]∙(-1)2
+
+ [Y N
+
H2CH2SO 3
− ]∙|2|2)
(13)
Due to the fact that the degree of hydro
lysis of aminomethanesulfonate anions and
N-alkylaminomethanesulfonate anions by
reaction (1) does not exceed 2.0 %, then µ is
practically equal to СYAMSNa for all studied so-
dium aminomethanesulfonates in the region
СYAMSNa = (2.0 ÷ 10∙10-3 mol∙l-1 in the investiga
ted temperature range.
Using the obtained data, the constants
of hydrolysis (2) of aminomethanesulfonate
and N-alkylaminomethanesulfonate anions
were calculated.
pKh = -lg Kh (14)
Dependences of pKh = f (µ) are described
by the equation (15), coefficients of which are
in the Table 1.
pKh = Ai + Bi∙ µ + Сi∙µ
(15)
Analyzing the data in the table. 1, it should
be noted that for the studied acids the constants
of equation (15) are related to each other by di-
rectly proportional dependences (16) - (19).
BAMS = -731.2 + 157.6∙AAMS –
–8.148∙(AAMS)
2; R2 = 0.9985
(16)
CAMS = 4902 + 1039∙AAMS +
+ 53.66∙(AAMS)
2; R2 = 0.9980
(17)
BBzAMS = -165.3 + 45.31∙ABzAMS –
–2.550∙(ABzAMS)
2; R2 = 0.9879
(18)
CBzAMS = 1129 + 292.5∙ABzAMS +
+ 16.60∙(ABzAMS)
2; R2 = 0.9846
(19)
According to the definition [18], the coeffi-
cient Aі in equation (15) is the negative decimal
logarithm of the thermodynamic hydrolysis
constant Kh. The pKh = f (T) dependences are
shown in Fig. 6.
−
3
ELECTROCHEMICAL PROPERTIES OF AQUEOUS SOLUTIONS OF SODIUM AMINOMETHANESULFONATES
56 ISSN 2708-129X. Укр. хім. журн., 2020
PHISICAL CHEMISTRY
The observed straight-line dependen
ces (Fig. 7) of the thermodynamic constants
of hydrolysis of N-methyl, N-tert-butyl and
N-benzyl-aminomethanesulfonate anions on
the thermodynamic constants of hydrolysis of
aminomethanesulfonate anions are described
by the equation (20), the parameters of which
are given in the Table 2, and testify to the simi
larity in these processes.
pKh
T (YNHCH2SO 3
− ) =
= Ai + Bi∙ pKh
T(NH2CH2SO 3
− )
(20)
Table 1
The values of the coefficients in equation (15) for aqueous solutions of YAMSNa.
CYAMSNa = (0.1 ÷ 10.0)∙10-3 mol∙l-1; n = 9
T, K Ai Bi Ci R2
NH2CH2SO 3
−
293 10.63 23.06 -76.68 0.9999
298 10.31 27.03 -102.4 0.9997
303 10.04 29.59 -119.1 0.9992
308 9.87 30.18 -122.8 0.9991
313 9.71 30.49 -124.6 0.9991
H3CNHCH2SO 3
−
298 10.72 16.66 -39.07 0.9992
303 10.52 17.35 -42.37 0.9999
308 10.27 19.63 -56.03 0.9998
313 10.15 19.10 -52.63 0.9997
HOCH2CH2NHCH2SO 3
−
293 10.74 20.05 -57.10 0.9998
298 10.40 24.28 -83.49 0.9999
303 10.20 24.97 -87.45 0.9997
308 10.38 17.04 -40.03 0.9999
313 10.14 19.16 -51.87 0.9999
(CH3)3CNHCH2SO 3
−
298 10.19 29.48 -116.9 0.9992
303 10.15 26.04 -94.36 0.9999
308 9.91 28.34 -109.6 0.9996
313 9.75 28.63 -111.5 0.9993
C6H5CH2NHCH2SO 3
−
293 10.36 29.78 -119.5 0.9994
298 10.13 31.45 -130.9 0.9995
303 9.94 32.25 -136.3 0.9995
308 9.74 33.73 -147.1 0.9992
313 9.58 33.99 -148.6 0.9991
R. E. Khoma, A. A.-A. Ennan, A. N. Chebotarev, S. V. Vodzinskii, R. M. Dlubovskii, S. V. Toporov
57https://ucj.org.ua
UCJ № 11 / Vol. 86
Thus, the molar electrical conductivity of
aqueous solutions of sodium aminometh-
anesulfonates is determined by the equation
(21):
λ = λ +
0
Na
· +Na
a + λ -
0
OH
· -OH
a +
+ λ -
2 3
0
YNHCH SO
· -
2 3YNHCH SO
a +
+ λ +
-
2 2 3
0
Y NH CH SO
· +
-
2 2 3Y NH CH SO
a .
(21)
Data on the electrical conductivity of aque-
ous solutions of sodium aminomethanesul-
fonates given in the Table 3, represent the result
of a correlation analysis of the dependence of λ
(Ohm-1∙sm2∙mol-1) on the molar concentration
of YAMSNa in a four-parameter dependence
according to Shidlovsky (22), which describes
the behavior of solutions of weak 1:1 electrolytes
at a concentrations more than 10-3 mol∙l-1 [19].
λ = B0 + B1∙C
0.5 + B2∙C + B3∙C
1.5 (22)
Fig. 6. Temperature dependence of thermody-
namic hydrolysis constants of YNHCH2SO −
3 .
Fig. 7. Mutual dependences of thermodynamic
hydrolysis constants of YNHCH2SO −
3 .
Y – H (1), CH3(2), HOCH2CH2 (3), (CH3)3C (4) and C6H5CH2 (5).
Table 2
Coefficient values in the equation (20)
Y Ai Bi R2
CH3 0.5854 0.9847 0.9804
(CH3)3C 2.6621 0.7332 0.9571
C6H5CH2 1.4430 0.8413 0.9883
R-squared values (R2 ≥ 0.98) indicate a satis
factory nature of the correlation according to
equation (22), and the values of the limiting
electrical conductivity (λ0) are numerically
equal to the coefficients В0. Thus, the experi-
mental values of the limiting molar electrical
conductivity of aqueous solutions of sodium
aminomethanesulfonates obtained by extrapo-
lation according to Shidlovsky, like λ0 of aque-
ous solutions of N-derivatives of amino-meth-
anesulfonic acid [16], increase with increasing
temperature.
According to Kohlrausch’s law for weak elec-
trolytes [20], the limiting electrical conductivity
of aqueous solutions of sodium aminometha
nesulfonates is determined by expression (23).
λ
2 3
0
YNHCH SO Na = λ +
0
Na
+ h0(λ -
0
OH
+
+ λ +
-
2 2 3
0
Y NH CH SO
) + (1 - h0)λ -
2 3
0
YNHCH SO
,
(23)
ELECTROCHEMICAL PROPERTIES OF AQUEOUS SOLUTIONS OF SODIUM AMINOMETHANESULFONATES
58 ISSN 2708-129X. Укр. хім. журн., 2020
PHISICAL CHEMISTRY
where h0 – the degree of hydrolysis of ami-
nomethanesulfonate ions at infinite dilution.
In infinitely dilute solutions of hydrolyzed
YNHCH2SO3Na, hydrolysis occurs at the ani-
on (1). The degree of hydrolysis will be deter-
mined, like [20], by the following equation:
h0 =
T
w
h w
K
K K+
. (24)
Then the limiting molar electrical conduc-
tivity of sodium aminomethanesulfonates is:
λ
2 3
0
YNHCH SO Na = λ +
0
Na
+
T
w
h w
K
K K+
(λ -
0
OH
+
+ λ +
-
2 2 3
0
Y NH CH SO
) +
+ (1 -
T
w
h w
K
K K+
)λ -
2 3
0
YNHCH SO
,
(25)
Table 3
Parameters of Shidlovsky equation (22) for aqueous solutions
YАМSNa. CYAMSNa = (1.0 ÷ 10.0)∙10-3 mol∙l-1; n = 15
T, K B0 -B1 B2∙10-5 -B3∙10-5 R2
AMSNa
293 1364 54663 7.8136 40.00 0.9789
298 1384 54526 7.7048 40.00 0.9814
303 1447 56444 7.9312 40.00 0.9841
308 1546 60086 8.4271 40.00 0.9841
313 1759 70660 100.00 50.00 0.9805
MeAMSNa
298 131.5 1757 0.2402 1.160 0.9783
303 174.7 2021 0.1345 0.160 0.9912
308 296.5 8141 1.1200 5.110 0.9965
313 295.4 7788 1.0800 5.010 0.9936
HEAMSNa
293 183.5 2524 0.0826 0.517 0.9802
298 235.0 4356 0.3286 0.606 0.9874
303 242.5 4991 0.2946 0.445 0.9879
308 264.2 4595 0.4183 1.440 0.994
313 309.4 5860 0.5500 1.730 0.9937
t‑BuАМSNa
298 105.5 1410 0.0200 1.000 0.9393
303 136.4 2602 0.3833 1.890 0.9798
308 171.9 3859 0.5636 2.770 0.9940
313 201.3 4456 0.5930 2.650 0.9740
BzАМSNa
293 112.1 2192 0.2724 1.220 0.9947
298 125.0 2443 0.2951 1.310 0.9951
303 123.9 2232 0.2709 1.220 0.9918
308 149.2 3154 0.3921 1.750 0.9907
313 147.3 2696 0.0309 1.330 0.9910
R. E. Khoma, A. A.-A. Ennan, A. N. Chebotarev, S. V. Vodzinskii, R. M. Dlubovskii, S. V. Toporov
59https://ucj.org.ua
UCJ № 11 / Vol. 86
The observed linear dependences (Fig. 8)
of the limiting molar electrical conductivity
of aqueous solutions of N-methyl, N-2-hydro
xyethyl, N-tert-butyl and N-benzyl-amino-
methanesodium sulfonates on the limiting
molar conductivity of aqueous solutions of
sodium aminomethanesulfonate are described
by equation (26), the parameters of which are
given in the Table 4, and testify to the simila
rity in these processes.
λ
2 2 3
0
YNH CH SO Na = Ai + Bi∙ λ 2 2 3
0
NH CH SO Na
(26)
Judging by the data in the Table 3, N-alky
lation of sodium aminomethanesulfonate leads
to a decrease in the values of the limiting molar
electrical conductivity of its aqueous solutions.
This fact is indicated by negative values of the
coefficient Ai in equation (26) (Table 4).
Considering the fact that the limiting mo-
bility of hydroxide ions and Na+ at 298 K are
respectively equal to 199.2 Ohm-1∙sm2∙mol-
1and 50.1 Ohm-1∙sm2∙mol-1 [21], then
λ0(AMSNa) > λ0(HEMSNa) > λ0(OH–) >
> λ0(MeAMSNa) ≈ λ0(BzAMSNa) >
> λ0(tBuАМSNa) > λ0(Na+) and
λ0(AMSNa) > λ0(OH–) + λ0(Na+) >
> λ0(HEMSNa) > λ0(MeAMSNa) ≈
≈ λ0(BzAMSNa) > λ0(tBuАМSNa).
The latter, obviously, indicates a decrease in
the mobility of hydroxide ions in solutions of
MeAMSNa, HEAMSNa, t-BuAMSNa, BzAM-
SNa, compared with the value of mobility
during the transfer along the chains of water
H-bonds. A similar situation occurs with the
mobility of hydroxonium ions in aqueous solu-
tions of MeAMSA, HEAMSA, t-BuAMSNa
[16] and aspartic acid [22], as well as with the
mobility of hydroxyl ions in HEAMSA solu-
tions [16].
Fig. 8. Mutual dependences of the limiting mo-
lar electrical conductivity of aqueous solutions
YNHCH2SO3Na. Y – CH3(2), HOCH2CH2 (3),
(CH3)3C (4) and C6H5CH2 (5).
Table 4
Coefficient values in the equation (26)
Y Ai Bi R2
CH3 -48.623 7.3949 0.9964
HOCH2CH2 -3.0572 1.1761 0.9948
(CH3)3C -26.707 4.3399 0.9798
C6H5CH2 -9.4619 1.9683 0.8684
Activation parameters of electrical conduc-
tivity of aqueous solutions of sodium ami-
nomethane sulfonates
The dependences of lnλ on 1/T are li
near, which makes it possible to determine
the effective activation energies of electrical
conductivity [19] (Table 5). Transferring the
analogy between the Arrhenius equations
(27) and Eyring (28) from kinetics to elec-
trical conductivity, we calculated the activa-
tion enthalpy of electrical conductivity using
equation (29) and the activation entropy us-
ing equation (30) [19], the values of which are
given in the Table 5.
ELECTROCHEMICAL PROPERTIES OF AQUEOUS SOLUTIONS OF SODIUM AMINOMETHANESULFONATES
60 ISSN 2708-129X. Укр. хім. журн., 2020
PHISICAL CHEMISTRY
k = A∙
aE
RTe− (27)
λ = A∙
aE
RTe− (28)
∆H# = Ea – RT (29)
∆S# = -205.8 + 19.15∙lgλ/T + Ea/T
(30)
The processes of formation of activated
complexes 0.001 ≤ QYAMSA ≤ 0.009 М are en-
dothermic (Table 5). Negative values of ΔS#
indicate that atoms in activated complexes are
located more “compactly” than in initial sys-
tems [23], that is, during the formation of acti-
vated complexes, the number of rotational and
vibrational degrees of freedom decreases. For
the reactions of association and dimerization,
the activation entropies have large numerical
values [24]. The same is observed for the molar
electrical conductivity of aqueous solutions of
N-alkylaminomethanesulfonic acids [16].
The entropic and enthalpy components of
the studied processes mutually compensate
each other (Table 5). The compensatory effect
is expressed by equation (31), the parameters
of which are given in the Table 6, which corre-
sponds to the presence of a compensation ef-
fect similar to the usual kinetic effect with the
temperature Tiλ similar to the isokinetic one.
∆H# = αi + Tiλ∙∆S# (31)
In the case of the parameters of equation
(30), a compensation effect is also observed
[25] (Table 5), expressed by equation (32), the
parameters of which are given in the Table 7.
ln(A) = αi + Ea/(R∙Tiλ) (32)
Table 5
Activation parameters of electrical conductivity of YAMSNa water
solutions according to Eyring. T=298 K
CYAMSNa∙10-3, M Ea, kJ∙mol-1 ln(A) R2 ∆H#, kJ∙mol-1 ∆S#, J∙mol-1∙K-1
AMSNa
0.5 10.6 10.52 0.9647 8.14 -170
0.6 9.82 10.05 0.9918 7.34 -173
0.7 9.60 9.84 0.9939 7.13 -173
0.8 9.73 9.78 0.9760 7.26 -173
0.9 9.89 9.77 0.9996 7.41 -172
1.0 9.14 9.58 0.9954 6.67 -175
2.0 10.9 9.56 0.9701 8.43 -169
3.0 11.0 9.36 0.9846 8.54 -169
4.0 10.2 8.87 0.998 7.74 -171
5.0 10.5 8.87 0.9919 8.03 -170
6.0 10.6 8.83 0.9929 8.09 -170
7.0 10.0 8.53 0.9897 7.51 -172
8.0 9.67 8.34 0.9939 7.19 -173
9.0 10.0 8.43 0.9279 7.55 -172
R. E. Khoma, A. A.-A. Ennan, A. N. Chebotarev, S. V. Vodzinskii, R. M. Dlubovskii, S. V. Toporov
61https://ucj.org.ua
UCJ № 11 / Vol. 86
MeAMSNa
2.0 13.2 9.85 0.9973 10.7 -161
3.0 10.3 8.67 0.9990 7.85 -171
4.0 12.1 9.34 0.9996 9.66 -165
5.0 12.7 9.59 0.9919 10.2 -163
6.0 12.4 9.44 0.9975 9.88 -164
7.0 11.7 8.53 0.9897 9.23 -166
8.0 12.5 9.45 0.9995 10.0 -164
9.0 11.3 8.96 0.9916 8.78 -168
HEAMSNa
1.0 13.8 10.5 0.9947 11.4 -159
2.0 19.9 12.6 0.9702 17.4 -139
3.0 20.1 12.6 0.9502 17.6 -138
4.0 21.6 13.1 0.9617 19.2 -133
5.0 20.0 12.4 0.9513 17.5 -139
6.0 23.1 13.6 0.9534 20.6 -128
7.0 17.8 11.4 0.9365 15.3 -146
8.0 20.0 12.3 0.9528 17.5 -139
9.0 21.6 12.9 0.9325 19.1 -133
t-BuAMSNa
1.0 17.2 11.3 0.9716 14.8 -148
2.0 12.1 9.21 0.9904 9.66 -165
3.0 20.1 12.6 0.9502 9.69 -165
4.0 12.3 9.24 0.9933 9.84 -164
5.0 12.9 9.44 0.9973 10.4 -163
6.0 12.7 9.36 0.9934 10.2 -163
7.0 13.0 9.50 0.9974 10.6 -162
8.0 12.8 9.39 0.9815 10.4 -163
9.0 12.9 9.40 0.9691 10.4 -162
BzAMSNa
1.0 10.2 8.36 0.9894 7.73 -171
2.0 11.4 8.74 0.9955 8.88 -168
4.0 9.71 7.94 0.9954 7.23 -173
5.0 8.90 7.58 0.9876 6.43 -176
6.0 9.68 7.86 0.9826 7.20 -173
7.0 8.29 7.26 0.9790 5.81 -178
8.0 8.49 7.32 0.9934 6.01 -177
9.0 8.68 7.37 0.9755 6.21 -177
Table 5 continuation
ELECTROCHEMICAL PROPERTIES OF AQUEOUS SOLUTIONS OF SODIUM AMINOMETHANESULFONATES
62 ISSN 2708-129X. Укр. хім. журн., 2020
PHISICAL CHEMISTRY
Table 6
Values of parameters of equation (31) and physicochemical properties
of sodium aminomethanesulfonates
Acid αi, kJ·mol-1 Til R2 MR, Å [7] lgPow [7] V, Å3 [7]
MeMSNa 58.81 298.0 0.999 24.15 -0.27 506.8(3)
HEAMSNa 58.85 298.0 0.999 30.44 -0.71 637.32(8)
t-BuAMSNa 58.81 298.0 0.999 37.95 0.57 825.9(5)
BzAMSNa 58.88 298.0 0.999 48.76 1.51 946.93(17)
Keys: R2 – approximation confidence value; MR – molar refractionя; Pow – partition coeffi-
cient in the octanol – water system; V – molar volume.
Table 7
Values of parameters of equation (32)
Salt αi, kJ∙mol-1 Til R2
MeAMSNa -1.444 310.9 0.999
HEAMSNa -1.860 343.0 0.974
t-BuAMSNa -1.177 288.4 0.999
BzAMSNa -0.750 242.2 0.998
Thus, by processing the data of conducto-
metric studies, the activation parameters of the
electrical conductivity of the systems “sodium
aminomethanesulfonate – water” at 293–313 K
were obtained. The obtained data on the ac-
id-base and electrochemical properties of the
YAMSNa – H2O systems are recommended for
use in chemical analysis, microbiological and
biochemical studies, as well as in the simula-
tion of chemisorption processes of capturing
acid gases (CO2 and SO2).
Acknowledgement. The work was
carried out with financial support from
the Ministry of Education and Science of
Ukraine.
ЕЛЕКТРОХІМІЧНІ ВЛАСТИВОСТІ ВОДНИХ
РОЗЧИНІВ АМІНОМЕТАНСУЛЬФОНАТІВ
НАТРІЮ
Р. Є. Хома1,2*, А. А.-А. Еннан1,
О. М. Чеботарьов2, С. В. Водзінський,
Р. М. Длубовський1, С. В. Топоров2
1Фізико-хімічний інститут захисту навко
лишнього середовища і людини, вул. Преоб
раженська, 3, Одеса 65082;
2Одеський національний університет імені
І. І. Мечникова, вул. Дворянська, 2, Одеса
65082
*e-mail: rek@onu.edu.ua
Здійснено рН- і кондуктометричне до-
слідження електрохімічних властивос-
тей водних розчинів (1∙10-4 ÷ 9∙10-3 М)
YNHCH2SO3Na (Y = H (AMSNa), CH3
(MeAMSNa), HOCH2CH2 (HEAMSNa),
(CH3)3C (t-BuAMSNa) и C6H5CH2
(BzAMSNa)) в області температур 293–
313 К. За результатами кондуктометрич-
ного дослідження систем YNHCH2SO3Na –
Н2О збільшення температури від 293 до
R. E. Khoma, A. A.-A. Ennan, A. N. Chebotarev, S. V. Vodzinskii, R. M. Dlubovskii, S. V. Toporov
63https://ucj.org.ua
UCJ № 11 / Vol. 86
313 К супроводжується підвищенням мо-
лярної електропровідності систем внас-
лідок зростання ступеня дисоціації елек-
тролітів і/або рухливості утворених іонів.
При цьому для всіх досліджуваних систем
кислотні властивості з ростом температу-
ри від 293 до 308 К знижуються. Оцінено
концентраційні та температурні залежно-
сті констант гідролізу амінометансульфо-
нату та N-алкіламінометансульфонатів
(алкіл: метил, 2-гідроксиетил, трет-бу-
тил і бензил). Спостережувані прямолі-
нійні залежності термодинамічних кон-
стант гідролізу N-метил, N-трет-бутил
і N-бензил-амінометансульфонат аніонів
від термодинамічних констант гідролізу
амінометансульфонат аніонів свідчать про
подібність в зазначених процесах. Роз-
раховано значення граничної молярної
електропровідності шляхом екстраполяції
за Шидловським. З урахуванням літератур-
них даних встановлено, що граничні рух-
ливості зменшуються в рядах: λ0(AMSNa) >
λ0(HEMSNa) > λ0(OH–) > λ0(MeAMSNa) ≈
λ0(BzAMSNa) > λ0(tBuАМSNa) > λ0(Na+)
та λ0(AMSNa) > λ0(OH–) + λ0(Na+) >
λ0(HEMSNa) > λ0(MeAMSNa) ≈ λ0(BzAMSNa)
> λ0(t-BuАМSNa). Відзначено відносне зни-
ження рухливості іонів водню в розчинах
MeAMSNa, HEMS, t-BuАМSNa та BzАМSNa
порівняно з величиною рухливості при
перенесенні по ланцюгах Н-зв’язків води.
Виявлено компенсаційні ефекти в актива-
ційних параметрах молярної електропро-
відності системи aмінометансульфонат на-
трію – вода в області температур 293–313 К.
Ключові слова: амінометансульфокис-
лоти, водні розчини, гідроліз, електропро-
відність.
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Стаття надійшла 26.11.2020.
|
| id | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-258 |
| institution | Ukrainian Chemistry Journal |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-07-23T01:05:22Z |
| publishDate | 2020 |
| publisher | V.I.Vernadsky Institute of General and Inorganic Chemistry |
| record_format | ojs |
| resource_txt_mv | ucjorgua/34/9430fd38948fc4dc817c2655df050534.pdf |
| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-2582026-07-22T08:23:45Z ELECTROCHEMICAL PROPERTIES OF AQUEOUS SOLUTIONS OF SODIUM AMINOMETHANESULFONATES ЕЛЕКТРОХІМІЧНІ ВЛАСТИВОСТІ ВОДНИХ РОЗЧИНІВ АМІНОМЕТАНСУЛЬФОНАТІВ НАТРІЮ Khoma, Ruslan Ennan, Alim Chebotaryov, Alexandr Vodzinskii, Sergey Dlubovskii, Ruslan Toporov, Sergey aminomethanesulfonic acids, aqueous solutions, hydrolysis, conductivity. The pH and conductometric study of the electrochemical properties of aqueous solutions (1∙10-4 ÷ 9∙10-3 М) YNHCH2SO3Na (Y = H, CH3, HOCH2CH2, (CH3)3C and C6H5CH2) was carried out. The values of the limiting electrical conductivity were calculated by extrapolation according to Shidlovsky. The activation parameters of the electrical conductivity of the systems “sodium aminomethanesulfonate – H2O” at 293-313&nbsp;K were obtained. V.I.Vernadsky Institute of General and Inorganic Chemistry 2020-12-15 Article Article Physical chemistry Физическая xимия Фізична xімія application/pdf https://ucj.org.ua/index.php/journal/article/view/258 10.33609/2708-129X.86.11.2020.51-64 Ukrainian Chemistry Journal; Vol. 86 No. 11 (2020): Ukrainian Chemistry Journal; 51-64 Украинский химический журнал; ##issue.vol## 86 ##issue.no## 11 (2020): Украинский химический журнал; 51-64 Український хімічний журнал; Том 86 № 11 (2020): Український хімічний журнал; 51-64 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/258/142 Copyright (c) 2020 Ruslan Khoma, Alim Ennan, Alexandr Chebotaryov, Sergey Vodzinskii, Ruslan Dlubovskii, Sergey Toporov https://creativecommons.org/licenses/by-nc/4.0 |
| spellingShingle | Khoma, Ruslan Ennan, Alim Chebotaryov, Alexandr Vodzinskii, Sergey Dlubovskii, Ruslan Toporov, Sergey ЕЛЕКТРОХІМІЧНІ ВЛАСТИВОСТІ ВОДНИХ РОЗЧИНІВ АМІНОМЕТАНСУЛЬФОНАТІВ НАТРІЮ |
| title | ЕЛЕКТРОХІМІЧНІ ВЛАСТИВОСТІ ВОДНИХ РОЗЧИНІВ АМІНОМЕТАНСУЛЬФОНАТІВ НАТРІЮ |
| title_alt | ELECTROCHEMICAL PROPERTIES OF AQUEOUS SOLUTIONS OF SODIUM AMINOMETHANESULFONATES |
| title_full | ЕЛЕКТРОХІМІЧНІ ВЛАСТИВОСТІ ВОДНИХ РОЗЧИНІВ АМІНОМЕТАНСУЛЬФОНАТІВ НАТРІЮ |
| title_fullStr | ЕЛЕКТРОХІМІЧНІ ВЛАСТИВОСТІ ВОДНИХ РОЗЧИНІВ АМІНОМЕТАНСУЛЬФОНАТІВ НАТРІЮ |
| title_full_unstemmed | ЕЛЕКТРОХІМІЧНІ ВЛАСТИВОСТІ ВОДНИХ РОЗЧИНІВ АМІНОМЕТАНСУЛЬФОНАТІВ НАТРІЮ |
| title_short | ЕЛЕКТРОХІМІЧНІ ВЛАСТИВОСТІ ВОДНИХ РОЗЧИНІВ АМІНОМЕТАНСУЛЬФОНАТІВ НАТРІЮ |
| title_sort | електрохімічні властивості водних розчинів амінометансульфонатів натрію |
| topic_facet | aminomethanesulfonic acids aqueous solutions hydrolysis conductivity. |
| url | https://ucj.org.ua/index.php/journal/article/view/258 |
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