BEHAVIOR OF AMINOMETHANESULPHONIC ACID – 3D-METAL SALT – WATER SOLUTIONS.
Based on direct pH, redox and conductometry data, the features of the acid-base and electrochemical behavior of aqueous solutions of aminomethanesulfonic acid (AMSA) with 3d metal salts (manganese(II), iron(II), cobalt(II), nickel(II), copper(II) sulfates and cobalt(II), nickel(II), copper(II) chlor...
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| Дата: | 2026 |
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V.I.Vernadsky Institute of General and Inorganic Chemistry
2026
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Репозитарії
Ukrainian Chemistry Journal| _version_ | 1871466202546569216 |
|---|---|
| author | Khoma, Ruslan Vodzinskii, Sergey Karych, Anastasiya Kovtun, Vasyl |
| author_facet | Khoma, Ruslan Vodzinskii, Sergey Karych, Anastasiya Kovtun, Vasyl |
| author_institution_txt_mv | [
{
"author": "Ruslan Khoma",
"institution": "Одесский национальный университет имени И.И. Мечникова"
},
{
"author": "Sergey Vodzinskii",
"institution": "Одесский национальный университет имени И.И. Мечникова"
},
{
"author": "Anastasiya Karych",
"institution": "Odessa I. I. MechnikovNationalUniversity"
},
{
"author": "Vasyl Kovtun",
"institution": "Odessa I. I. MechnikovNationalUniversity"
}
] |
| author_sort | Khoma, Ruslan |
| baseUrl_str | https://ucj.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-22T08:23:57Z |
| description | Based on direct pH, redox and conductometry data, the features of the acid-base and electrochemical behavior of aqueous solutions of aminomethanesulfonic acid (AMSA) with 3d metal salts (manganese(II), iron(II), cobalt(II), nickel(II), copper(II) sulfates and cobalt(II), nickel(II), copper(II) chlorides) were established. The behavior of aqueous solutions of AMSA – 3d metal salts was studied by the ligand saturation method (equilibrium shift) at CM2+ = 0.025 mol/l; CAMSA/CM2+ = 0.08 ¸ 4.00. The composition of the formed complexes was judged by the positions of extrema and kinks in the integral pH, redox-metric curves, and extrema in the corresponding differential curves, as well as by kinks in the conductometric curves. In the studied solutions, complex compounds of the composition [M(NH2CH2SO3)]+ (I), [M2(NH2CH2SO3)3]+ (II), M(NH2CH2SO3)2 (III), [M2(NH2CH2SO3)5]- (IV), [M(NH2CH2SO3)3]- (V), are realized.  So, as the products of the reaction of metal ions with AMSA, in addition to the above-mentioned complex compounds, including hydroxonium ions, which are characterized by increased movability, the value Dk (Dk = k3 - k2 - k1, where k1 - k2 - k3 – specific of the electrical conductivity of water solutions MzAn2, AMSA and MzAn2 from AMSA, respectively) acquire positive values. Based on a developed physicochemical model taking into account the law of mass action, the material balance of AMSA and the metal, and the principle of electroneutrality, the ion-molecular composition of the studied solutions was calculated, and the concentration constants of complexation were estimated.
Correlations were found between the formation constants of these complexes. The relative stabilities of 3d-metal ion complexes with AMSA correlate with literature data on similar values for taurine and its derivatives. The highest stability is predominantly demonstrated by compounds of Cu2+ ions with the studied ligand.
  |
| doi_str_mv | 10.33609/2708-129X.92.1.2026.45-60 |
| first_indexed | 2026-04-01T01:00:19Z |
| format | Article |
| fulltext |
45
УДК 54-386:546.302: 547.436.3 doi: 10.33609/2708-129X.92.1.2026.45-60
BEHAVIOR OF AMINOMETHANESULPHONIC ACID –
3d-METAL SALT – WATER SOLUTIONS.
A. M. Karych, R. E. Khoma*, S. V. Vodzinskii, V. S. Kovtun
Odessa I.I. Mechnikov National University,
2 Vsevoloda Zmienkа str., 65082 Odesa, Ukraine
*e-mail: rek@onu.edu.ua
Based on direct pH, redox and conductometry data, the features of the acid-base and elec-
trochemical behavior of aqueous solutions of aminomethanesulfonic acid (AMSA) with 3d
metal salts (manganese(II), iron(II), cobalt(II), nickel(II), copper(II) sulfates and cobalt(II),
nickel(II), copper(II) chlorides) were established. The behavior of aqueous solutions of
AMSA – 3d metal salts was studied by the ligand saturation method (equilibrium shift) at
CM
2+ = 0.025 mol/l; CAMSA/CM
2+ = 0.08÷4.00. The composition of the formed complexes was
judged by the positions of extrema and kinks in the integral pH, redox-metric curves, and
extrema in the corresponding differential curves, as well as by kinks in the conductometric
curves. In the studied solutions, complex compounds of the composition [M(NH2CH2SO3)]
+ (I),
[M2(NH2CH2SO3)3]
+ (II), M(NH2CH2SO3)2 (III), [M2(NH2CH2SO3)5]
- (IV), [M(NH2CH2SO3)3]
-
(V), are realized. So, as the products of the reaction of metal ions with AMSA, in addition to
the above-mentioned complex compounds, including hydroxonium ions, which are charac-
terized by increased movability, the value Dk (Dk = k3 - k2 - k1, where k1 - k2 - k3 – specific of
the electrical conductivity of water solutions MzAn2, AMSA and MzAn2 from AMSA, respec-
tively) acquire positive values. Based on a developed physicochemical model taking into ac-
count the law of mass action, the material balance of AMSA and the metal, and the principle
of electroneutrality, the ion-molecular composition of the studied solutions was calculated,
and the concentration constants of complexation were estimated.
Correlations were found between the formation constants of these complexes. The relative
stabilities of 3d-metal ion complexes with AMSA correlate with literature data on similar
values for taurine and its derivatives. The highest stability is predominantly demonstrated by
compounds of Cu2+ ions with the studied ligand.
Keywords: aminomethanesulfonic acid, 3d-metal cations, complexation, acid-base inter-
actions, complexation constants, stability.
46 ISSN 2708-129X. Укр. хім. журн., 2026
BEHAVIOR OF AMINOMETHANESULPHONIC ACID – 3D-METAL SALT – WATER SOLUTIONS.INORGANIC CHEMISTRY
INTRODUCTION. Aminomethanesulfonic
acid (AMSA) and its N-alkylated derivatives
(YAMSA) are easily synthesized from inexpen-
sive reagents; the pKa values of amino groups
are in the range of physiological pH values
(6.8–7.8); their salts are easily soluble in water
and poorly soluble in non-polar solvents [1–4].
That is, they meet four of the seven criteria that
were put forward for the components of buffer
solutions that can be used in biological and bio-
chemical research [5]. Unlike aminoethanesul-
fonic acid (taurine, Tau), AMSA and YAMSA
exhibit antibacterial and antiviral properties
[2, 11, 12]. Despite the fact that AMSA (sul-
fur analog of glycine) is the first representative
in the homologous series of aminoalkanesul-
fonic acids, data on the complexing ability of
this ligand are absent in the literature. Only the
results of studying the reactivity of Tau in re-
actions with metal cations are known [6–10].
Metal complexes based on aminoalkanesulfon-
ic acids are promising precursors for the crea-
tion of new antibacterial and antiviral agents.
AMSA complexes with 3d-metal cations can
be used as models for studying the interaction
of metal ions with amino acids in living orga
nisms. They may have antitumor, antibacterial,
and antifungal activity.
The aim of this work is to identify the fea-
tures of the acid-base and electrochemical
behavior of AMSA during complexation with
salts (chlorides and sulfates) of 3d metals in
aqueous solutions.
EXPERIMENT AND DISCUSSION OF
THE RESULTS. In the studies, MnSO4×H2O,
FeSO4×7H2O, CoSO4×7H2O, CoCl2×6H2O,
NiCl2×6H2O, CuSO4×5H2O, CuCl2×2H2O
and ZnSO4×7H2O of analytical grade were
used; AMSA was synthesized according to an
original method [13]. Working solutions were
prepared with a concentration of 0.05 M of
the specified salts and 0.20 M AMSA. This is
due to the limited solubility of AMSA in wa-
ter, which at 298 K is 0.41 M. The preparation
of a saturated AMSA solution is energetically
complicated and requires preliminary heating
(to ~333 K) of the mixture of a given content
of components (AMSA and H₂O) for complete
dissolution of aminosulfonic acid, followed by
cooling to a given temperature. The behavior
of aqueous solutions of AMSA – 3d metal salts
was studied by the ligand saturation method
(equilibrium shift). From the working solu-
tions of AMSA and M2+ a series of solutions
was prepared (CM
2+ = 0.025 M; CAMSA/CM
2+ =
0.08÷4.00). Conductometric and pH-metric
studies were carried out similarly to [14] at
298 K.
Initial solutions of 3d-metal salts have pH
2.70 (FeSO4)¸ 6.40 (MnSO4) due to cation hyd
rolysis [15]:
M2+ + H2O ⇌ M(OH)+ + H3O
+ (1)
Kg =
[M(OH)+]∙[H3O
+]
(2)
[M2+]
According to the obtained data (Fig. 1), an
increase in the CAMSA/CM
2+ ratio leads to a de-
crease in the pH of the studied solutions due
to the course of reaction (3), except for solu-
tions with MnSO4, CuCl2, and ZnSO4. In the
case of CuCl2 solutions, initially with an in-
crease in CAMSA/CM
2+ (up to 1.0:1.0), a decrease
in pH is observed, then pH stepwise acquires
constant values in the sections CAMSA/CM
2+
1.0:(1.0÷2.0), 1.0:(2.5÷3.0), and 1.0:(3.5÷4.0).
kM2+ + nN
+
H3CH2SO-
3+ nH2O ⇌
[Mk(NH2CH2SO3)n]2k-n + nH3O
+, (3)
where k and n are stoichiometric coefficients.
47https://ucj.org.ua
A. M. Karych, R. E. Khoma, S. V. Vodzinskii, V. S. Kovtun UCJ № 1/ Vol. 92
K =
[Mk(NH2CH2SO3)n
2k-n]∙[H3O
+]n
(4)
[M2+]k ∙ [N
+
H3CH2SO-
3]
AMSA solutions at CAMSA/CM
2+
< 1.0 by de-
creasing pH values, cations in the presence of
sulfates and chlorides can be arranged in the
following series, respectively:
Co2+ > Mn2+ > Zn2+ > Ni2+ > Cu2+ > Fe2+;
Co2+ > Ni2+ > Cu2+.
Fig. 1. Integral curves of pH dependence on the ratio CAMSA/CM
2+. CM
2+ = 0,025 M. M2+: Mn2+ (1),
Fe2+ (2), Co2+ (3), Ni2+ (4), Cu2+ (5), Zn2+ (6). Anz-: SO -2
4 (а), Cl- (b).
The composition of the formed complexes
(n:k ratio) was determined by the positions of
extrema and inflection points on the integral
pH-metric curves (Fig. 1) and extrema on the
differential curves (Fig. 2), the characteristics
of which are presented in Table 1.
According to pH-metry data for MnSO4
solutions, the formation of three compounds
with CAMSA/CM
2+ ratios of 1.5:1.0, 2.0:1.0, and
3.0:1.0 was observed; for NiSO4 and NiCl2 –
three compounds with CAMSA/CM
2+ ratios of
1.0:1.0, 1.5:1.0, and 2.0:1.0. For FeSO4, CoSO4,
and ZnSO4, the formation of four compounds
is characteristic. In solutions of CoCl2, CuCl2,
and CuSO4, five compounds are formed.
The data from redox-metric study of the in-
teraction in AMSA – M2+ – H2O solutions are
presented in Figs. 3 and 4. At CAMSA/CM
2+
< 4.0,
the redox potential values of the studied solu-
tions decrease in the following sequence de-
pending on the cation: Fe2+ > Cu2+ > Zn2+ ³ Mn2+
(for sulfates; i.e., the same series as for pH, but
in reverse order) and Co2+ > Ni2+ (for chlorides).
For MnSO4 solutions, redox-metry pro-
vides little information about the composition
of the formed compounds (Fig. 3). In the case
48 ISSN 2708-129X. Укр. хім. журн., 2026
BEHAVIOR OF AMINOMETHANESULPHONIC ACID – 3D-METAL SALT – WATER SOLUTIONS.INORGANIC CHEMISTRY
of NiCl2, it allows the detection of an addition-
al compound with CAMSA/CM
2+ = 2.5 : 1.0, be-
sides the indicated 1.5 : 1.0 and 2.0 : 1.0 ratios
(Figs. 3, 4; Table 2). For CuSO4, extrema on the
differential redox-metric curves were also ob-
served at CAMSA/CM
2+
= 1.0:1.0 and 2.5:1.0. In
FeSO4 and CoCl2 solutions, all five compounds
are formed.
Fig. 2. Differential curves of dpH/
dCAMSA dependencies on the CAMSA/
CM
2+
ratio.
CM
2+ = 0.025 M. Salts: MnSO4 (1),
NiSO4 (2).
Table 1
pH-metry characteristics of aqueous AMSA solutions with 3d-metal salts
Effect CAMSA/CM
2+
Integral curve Differential curve
type pH type dpH/dCAMSA, L/mol
MnSO4
I 1.5 - 3.50 maximum 35.0
II 2.0 minimum 3.35 second-kind
discontinuity 0
III 3.0 minimum 2.26 maximum 27.5
FeSO4
I 1.0 maximum 2.40 maximum 2.5
II 1.5 maximum 2.40 maximum 2.5
III 2.0 second-kind
discontinuity 2.33¸2.38 - -3.0
IV 2.5 - 2.38 maximum 12.5
CoSO4
I 1.0 - 4.15 maximum -24.0
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A. M. Karych, R. E. Khoma, S. V. Vodzinskii, V. S. Kovtun UCJ № 1/ Vol. 92
Effect CAMSA/CM
2+
Integral curve Differential curve
type pH type dpH/dCAMSA, L/mol
II 1.5 - 3.74 minimum -35.5
III 2.0 break point 3.39 minimum -5.0
IV 2.5 - 3.21 minimum -20
NiSO4
I 1.0 break point 3.55 minimum -32.5
II 1.5 - 3.43 minimum -25.8
III 2.0 3.06 maximum -16.5
CuSO4
I 1.0 - 2.62 plateau -7.5
II 1.5 second-kind
discontinuity 2.57¸2.95 maximum 95
III 2.0 minimum 3.00 minimum -7.5
IV 2.5 maximum 3.04 maximum 10
V 3.0 minimum 3.00 minimum -12.5
ZnSO4
I 1.5 second-kind
discontinuity 3.03¸4.36 maximum 333
II 2.0 second-kind
discontinuity 4.23¸3.16 minimum -268
III 2.5 maximum 4.01 maximum 208
IV 3.0 jump 3.93 minimum -263
CoCl2
I 1.0 break point 4.15 maximum -24
II 1,5 - 3.74 maximum -5
III 2.0 break point 3.39 minimum -35.5
IV 2.5 - 3.21 minimum -20
V 3.0 break point 3.04 minimum -18.5
NiCl2
I 1.0 break point 3.70 minimum -32.5
II 1.5 - 3.33 minimum -25
III 2.0 break point 3.06 minimum -25.8
CuCl2
I 1.0 plateau 2.73 maximum 2.5
II 1.5 plateau 2.73 maximum 2.5
III 2.0 plateau 2.72 maximum 2.5
IV 2.5 plateau 2.76 maximum 10
V 3.0 plateau 3.00 plateau 0
Table 1
50 ISSN 2708-129X. Укр. хім. журн., 2026
BEHAVIOR OF AMINOMETHANESULPHONIC ACID – 3D-METAL SALT – WATER SOLUTIONS.INORGANIC CHEMISTRY
Fig. 3. Integral curves of E (mV) dependencies
on CAMSA/CM
2+. CM
2+ = 0.025 M. M2+: Mn2+ (1),
Fe2+ (2), Co2+ (3), Ni2+ (4), Cu2+ (5), Zn2+ (6). Anz-:
SO -2
4 (1, 2, 5, 6); Cl- (2, 3).
Fig. 4. Differential curves of E (mV) dependen-
cies on CAMSA/CM
2+. CM
2
+ = 0.025 M. M2+: Fe2+ (1),
Ni2+ (2), Cu2+ (3). Anz-: SO -2
4 (1, 3); Cl- (2).
Table 2.
Redox-metry characteristics of aqueous AMSA solutions with 3d-metal salts.
Effect CAMSA/CM
2+
Integral curve Differential curve
type E, mV type dE/dCAMSA,
mV×L/mol
FeSO4
I 1.0 minimum 510 minimum -30000
II 1.5 maximum 550 maximum 5500
III 2.0 minimum 515 - 0
IV 2.5 minimum 490 minimum -8750
V 3.0 plateau 500 minimum -5000
CoCl2
I 1.0 minimum 355 minimum -1250
II 1.5 maximum 370 - 0
III 2.0 maximum 285 maximum 6250
IV 2.5 minimum 375 - 0
V 3.0 maximum 400 - 0
51https://ucj.org.ua
A. M. Karych, R. E. Khoma, S. V. Vodzinskii, V. S. Kovtun UCJ № 1/ Vol. 92
NiCl2
I 1.0 minimum 290 minimum -2500
II 2.0 maximum 325 minimum -2500
III 2.5 maximum 340 plateau 150
CuSO4
I 1.0 plateau 525 minimum -1250
II 2.0 plateau 500 minimum -2500
III 2.5 - 510 maximum 2500
IV 3.0 plateau 500 maximum 0
ZnSO4
I 1.0 maximum 425 - 0
II 1.5 maximum 430 - 0
III 2.0 minimum 390 maximum 2500
Table 2.
The results of conductometric study of
complex formation in AMSA – M2+ – H2O
solutions are presented in Fig. 5. The specific
conductivity values of the studied solutions de-
crease for sulfates in the following sequence of
metal cations:
Zn2+ > Cu2+ > Fe2+ > Ni2+ > Co2+ » Mn2+
(at CAMSA/CM
2+
< 1.0),
Zn2+ > Cu2+ > Ni2+ > Fe2+ > Co2+ » Mn2+
(at CAMSA/CM
2+
> 1.0).
The products of interaction of the studied
cations with AMSA are aminomethanesul-
fonate complexes and hydronium ions (re-
action 3). The latter are characterized by en-
hanced mobility. This causes Δκ to acquire
positive values (Fig. 5b).
Conductometry detects only three com-
pounds with MnSO4 (similar to pH-metry),
NiSO4 and NiCl2 (analogous to pH- and re-
dox-metry); four compounds with FeSO4,
CoSO4 and ZnSO4 (similar to pH-metry); five
compounds with CuSO4 and CuCl2 (similar
to pH-metry) (Fig. 5; Table 3). In CoCl2 solu-
tions, five compounds are registered, similar to
redox-metry.
Table 3.
Conductometry characteristics of aqueous AMSA solutions with 3d-metal salts.
Effect CAMSA/CM
2+ Type k, mS/cm Dk, mS/cm
MnSO4
I 1.5 plateau 3.02 0.35
II 2.0 break point 3.32 0.52
52 ISSN 2708-129X. Укр. хім. журн., 2026
BEHAVIOR OF AMINOMETHANESULPHONIC ACID – 3D-METAL SALT – WATER SOLUTIONS.INORGANIC CHEMISTRY
Effect CAMSA/CM
2+ Type k, mS/cm Dk, mS/cm
III 3.0 minimum 3.76 0.61
FeSO4
I 1.0 maximum 2.59 0.02
II 1.5 break point 2.76 0.04
III 2.0 break point 2.96 0.04
IV 2.5 break point 3.08 0.01
CoSO4
I 1.0 break point 2.74 0.12
II 2.0 break point 3.39 0.42
III 2.5 break point 3.54 0.42
IV 3.0 break point 3.83 0.57
NiSO4
I 1.0 break point 3.14 0.50
II 1.5 break point 3.51 0.72
III 2.0 break point 3.88 0.95
CuSO4
I 1.0 break point 2.90 0.43
II 1.5 break point 3.33 0.68
III 2.0 break point 3.75 0.95
IV 2.5 break point 4.06 0.95
V 3.0 break point 4.49 1.38
ZnSO4
I 1.0 break point 4.09 1.20
II 2.0 break point 5.25 2.34
III 2.5 break point 5.74 2.50
IV 3.0 second kind break
point 6.57¸4.92 3.04¸1.50
CoCl2
I 1.0 break point 4.66 0.70
Table 3.
53https://ucj.org.ua
A. M. Karych, R. E. Khoma, S. V. Vodzinskii, V. S. Kovtun UCJ № 1/ Vol. 92
Effect CAMSA/CM
2+ Type k, mS/cm Dk, mS/cm
II 1.5 break point 5.02 0.91
III 2.0 break point 5.53 1.22
IV 2.5 break point 5.75 1.29
V 3.0 plateau 6.17 1.60
NiCl2
I 1.0 break point 3.90 0.13
II 1.5 break point 4.22 0.28
III 2.0 plateau 4.53 0.40
CuCl2
I 1.0 break point 5.00 1.08
II 1.5 plateau 5.80 1.73
III 2.0 plateau 6.63 2.37
IV 2.5 plateau 7.18 2.70
V 3.0 plateau 7.92 3.37
Fig. 5. Curves of κ (a) and Δκ (b) dependencies on the CAMSA/CM
2+ ratio.
CM
2+
= 0.025 M. M2+:Mn2+ (1), Fe2+ (2), Co2+ (3), Ni2+ (4), Cu2+ (5), Zn2+ (6). Anz-: SO4
2-
Table 3.
54 ISSN 2708-129X. Укр. хім. журн., 2026
BEHAVIOR OF AMINOMETHANESULPHONIC ACID – 3D-METAL SALT – WATER SOLUTIONS.INORGANIC CHEMISTRY
Physicochemical model
Thus, the formation of five complex com-
pounds [M(NH2CH2SO3)]+ (I), [M2(N-
H2CH2SO3)3]
+ (II), [M(NH2CH2SO3)2] (III),
[M2(NH2CH2SO3)5]
- (IV) and [M(NH2CH-
2SO3)3]
- (V) was detected in the studied solu-
tions, which are described by equation (5). In
addition, reactions of water autoprotolysis (7),
AMSA dissociation (8) [2, 16, 17], and cation
hydrolysis (1) occur. A mathematical model
was developed that takes into account the law
of mass action (2), (4), (6), (9), material bal-
ance for AMSA (10) and metal (11), as well as
the principle of electroneutrality (12), similar
to [2, 3, 14, 16, 17].
Complex formation
kM2+ + nNH2CH2SO -
3 ⇌ [Mk(NH2CH2SO3)n]2k-n (5)
b =
[Mk(NH2CH2SO3)n
2k-n]
(6)
[M2+]k ∙ [NH2CH2SO -
3 ]n
Autoprotolysis H2O
2H2O ⇌ H3O
+ + OH- (7)
AMSA dissociation +
N H3CH2SO -
3 + H2O ⇌ NH2CH2SO -
3 + H3O
+ (8)
KAMSA =
[NH2CH2SO -
3 ] ∙ [H3O
+]
(9)
[
+
NH2CH2SO -
3 ]n
CAMSA = [
+
N H3CH2SO -
3 ] + [H2NCH2SO -
3 ] + n[Mk(NH2CH2SO3)n]2k-n (10)
CM
2+ = [M2+] + [M(OH)+] + k[Mk(NH2CH2SO3)n]2k-n (11)
[H3O
+] + [M(OH)+] + 2×[M2+] + (2k-n)[Mk(NH2CH2SO3)n] =
= [H2NCH2SO -
3 ] + [OH-] + 2×CM
2+
(12)
Based on pH-metry data, the ion-molecular
composition of the studied systems was cal-
culated (for example, Fig. 6). With increasing
CAMSA/CM
2+
ratio, the content of the zwitterion
mole fraction (curve 4) increases from 67% to
98%. At the same time, the relative content of
unbound Cu2+ (curve 1) and complexed forms
of AMSA (curve 6) decrease. The relative con-
tent of complexed forms of copper (curve 3)
initially increases, reaching a maximum val-
ue (about 10%) at CAMSA/CM
2+ 1.0, and then
decreases. Meanwhile, the relative content of
the hydrolyzed form of Cu2+ (basic salt – cop-
per(II) hydroxide sulfate) and aminometh-
anesulfonate anion (curves 2 and 5, respective-
ly) is less than 0.01%.
55https://ucj.org.ua
A. M. Karych, R. E. Khoma, S. V. Vodzinskii, V. S. Kovtun UCJ № 1/ Vol. 92
Fig. 6. Partial distribution diagrams of different forms of interaction in CuSO4 – AMSA–H2O
solutions depending on CAMSA/CM
2+. CM
2+ = 0.025 M. Ni – mole fraction.
N1 = [Cu2+]
CCu
; N2 = [CuOH+]
CCu
; N3 = [I] + 2[II] + [III] + 2[IV] + [V]
CCu
;
N4 =
[+H3NCH2SO-
3]
CAMSA
; N5 =
[H2NCH2SO-
3]
CAMSA
; N6 = [I] + 3[II] + 2[III] + 5[IV] + 3[V]
CAMSA
.
According to calculations, the ionic strength
of the solutions, which is determined by equa-
tion (13), depends on the charge of the counte-
rion in the d-metal salt and the ratio of AMSA
to metal. The concentration dependencies m =
f(CAMSA/CM
2+) are described by an equation of
the form (14).
μ = 1/2([H3O
+] + [M(OH)+] + 4×[M2+] +
+ (2k-n)2×Mk(NH2CH2SO3)n] + 4×
×[
+
N H3CH2SO -
3 ] + [H2NCH2SO -
3 ] +
+ [OH-] + |z|×2× CM
2+) (13)
μ = Ai + Bi×CAMSA/CM
2+
(14)
According to the calculation results, for
chloride salts (of cobalt, nickel, and copper)
Ai ≅ 3×CM
2+; in the case of sulfates (of all stud-
ied metals) Ai ≅ 4×CM
2+. The nature of the
metal itself has almost no effect on this. The
Bi values do not depend on the nature of the
anion and cation and are approximately equal
to 2×CM
2+.
The concentration constants of hydrolysis
(equation 2) and complex formation (equa-
tion 6) were calculated, the numerical values
of which are presented in Table 4. For sulfates,
the following was noted:
pβII = -12.05 + 1.77×pβI; R
2 = 0.9472
(except CoSO4); (15)
56 ISSN 2708-129X. Укр. хім. журн., 2026
BEHAVIOR OF AMINOMETHANESULPHONIC ACID – 3D-METAL SALT – WATER SOLUTIONS.INORGANIC CHEMISTRY
pβIII = 1.35 + 0.665×pβ II; R
2 = 0.9015
(except ZnSO4); (16)
pβIV = -4.58 + 1.46×pβ II; R
2 = 0.9093
(except ZnSO4); (17)
pβV = -1.30 + 0.88×pβ II; R
2 = 0.8879
(except ZnSO4). (18)
A dependence of the stability constants of
complexes on the counterion of the salt used
is observed (Table 4). Regardless of the nature
of the complex (Co2+, Ni2+, Cu2+), complexes
with sulfates are more stable than those with
chlorides. Judging from equations (5) and (8),
during the formation of neutral complexes III
from sulfate and chloride salts, the by-products
are sulfuric and hydrochloric acids, respective-
ly. Moreover,
pβIII(HCl) = 34.49 + 3.15×pβIII(H2SO4);
R2 = 0.9419. (19)
The presence of correlations (15) – (19)
indicates a uniform type of ligand coordina-
tion with the central atoms. The deviations of
CoSO4 and ZnSO4 from correlations (15) and
(16) – (18), respectively, are due to differenc-
es in the coordination modes of Co2+ and Ni2+
compared to other cations. The observed sta-
bilization of complexes III by sulfate anions,
compared to chlorides, may be caused by the
salt effect (the ionic strength of sulfate salt
solutions is higher than that of chlorides (Ta-
ble 4)). This may also be caused by the fact that
the reactivity of Cl- toward competing coordi-
nation with M2+ cations is higher than that of
SO -2
4 . For a more detailed explanation of the
observed stabilization, additional experiments
involving other physicochemical and quantum
chemical methods are necessary.
Table 4.
Values of concentration constants of hydroxylation and complex formation in AMSA –
M2+ – H2O solutions.
Complex
(m, M)
M2+ Mn2+ Fe2+ Co2+ Ni2+ Cu2+ Zn2+
MSO4
pKg 11.18 3.76 9.62 9.44 6.32 7.54
I (0.14) pβ -5.74 -7.43 -5.76 -7.07 -7.42 -6.26
Δpβ 0.01 0.16 0.46 0.06 0.03 0.18
II (0.17) pβ -21.93 -24.95 -23.66 -24.56 -25.38 -23.60
Δpβ 0.32 0.33 0.36 0.14 0.17 0.27
III (0.19) pβ -13.01 -14.98 -14.87 -15.04 -15.47 -11.41
Δpβ 0.43 0.08 0.86 0.78 0.03 0.57
IV (0.21) pβ -36.26 -40.59 -40.25 -40.25 -41.81 -35.80
Δpβ 0.12 0.27 0.72 0.72 0.83 0.73
V (0.24) pβ -20.28 -22.77 -22.75 -22.84 -23.65 -17.19
Δpβ 0.20 0.07 0.21 0.27 0.07 0.30
MCl2
pKg - - 8.96 9.82 7.04 -
57https://ucj.org.ua
A. M. Karych, R. E. Khoma, S. V. Vodzinskii, V. S. Kovtun UCJ № 1/ Vol. 92
I (0.12) pβ - - -3.89 -4.94 -7.30 -
Δpβ - - 0.57 0.16 0.24 -
II (0.14) pβ - - -20.26 -20.68 -23.99 -
Δpβ - - 0.94 0.11 0.49 -
III (0.17) pβ - - -12.48 -12.55 -14.25 -
Δpβ - - 0.75 0.52 0.21 -
IV (0.18) pβ - - -36.34 -36.45 -38.55 -
Δpβ - - 0.55 0.23 0.35 -
V (0.22) pβ - - -20.64 -20.49 -21.24 -
Δpβ - - 0.55 0.18 0.16 -
Table 4.
According to reactivity toward cation hyd
rolysis, sulfate salts vary in the series:
Fe2+ > Cu2+ > Zn2+ > Ni2+ > Co2+ > Mn2+.
The reactivity toward formation of com-
pounds I – V decreases in the series:
Fe2+ » Cu2+ > Ni2+ > Zn2+ > Co2+ » Mn2+ (I),
Cu2+ > Fe2+ > Ni2+ > Co2+ » Zn2+ > Mn2+ (ІI),
Cu2+ » Ni2+ » Fe2+ » Co2+ > Mn2+ > Zn2+ (III, V),
Cu2+ » Fe2+ » Co2+ » Ni2+ > Mn2+ > Zn2+ (IV).
The sequence of complex stability corre-
sponds to the Irving-Williams series (Zn2+ <
Cu2+ > Ni2+ > Co2+ > Fe2+ > Mn2+ [18] (with the
exception of Fe2+), which is a consequence of
the stabilizing influence of the Jahn-Teller ef-
fect for chelate octahedral compounds [19].
Similar behavior is characteristic of complex
compounds of glycine, taurine, and its de-
rivatives of composition I and III [8, 20–22].
The positioning of the relative stability of Fe2+
compounds outside the Irving-Williams series
is probably due to a different mode of ligand
coordination with this cation compared to the
rest of the studied M2+ ions.
CONCLUSIONS. Thus, based on direct
pH-, redox-, and conductometry data, the
formation of water-soluble complex com-
pounds of five compositions was detected
for the first time: M(NH2CH2SO3)]+, [M2(N-
H2CH2SO3)3]
+, [M(NH2CH2SO3)2], [M2(N-
H2CH2SO3)5]
- and [M(NH2CH2SO3)3]
-. The
data from these methods confirm and com-
plement each other. The concentration stabil-
ity constants of these complex compounds in
terms of pb values vary in the ranges: -7.43 ÷
-5.74 (I), -25.38 ÷ -21.93 (II), -15.47 ÷ -11.41
(III), -41.81 ÷ -35.80 (IV), -23.65 ÷ -17.19
(V) in the presence of sulfates; -3.89 ÷ -7.30
(I), -20.26 ÷ -23.99 (II), -12.48 ÷ -14.25 (III),
-38.55 ÷ -36.34 (IV), -21.24 ÷ -20.49 (V) in
the presence of chlorides. The obtained values
of stability constants of 3d-metal ion com-
plexes with AMSA correlate with similar val-
ues obtained earlier for taurine and its deriva-
tives. The studied ligand forms the most stable
complexes predominantly with Cu2+ ions. The
relative stability of the complex compounds
corresponds to the Irving-Williams series,
with the exception of Fe2+ compounds.
In the future, synthesis and investigation
58 ISSN 2708-129X. Укр. хім. журн., 2026
BEHAVIOR OF AMINOMETHANESULPHONIC ACID – 3D-METAL SALT – WATER SOLUTIONS.INORGANIC CHEMISTRY
of the structure, physicochemical properties,
and biological activity (particularly antibacte-
rial and antiviral properties) of these complex
compounds are planned for the development
of new pharmaceutical preparations.
DETAILED DESCRIPTION OF THE
AUTHORS’ CONTRIBUTION.
A.M. Karych – conducting experimental
research, initial processing of results. R.E.
Khoma – conceptualization and research idea
formulation, methodology development, writ-
ing the article. S.V. Vodzinskii – summarizing
results, preparation of the initial draft of the
manuscript. V.S. Kovtun – providing materials
and resources, processing results.
CONFLICT OF INTEREST. The authors de-
clare no conflict of interest.
ACKNOWLEDGEMENT. The work
was performed within the framework
of the state budget research theme “Sci-
entific foundations for creating bio
cidal chemosorption-filtering materials
with active indication and catalysts for
personal protective equipment,” state
registration number: 0125U001717.”
ПОВЕДІНКА РОЗЧИНІВ АМІНОМЕТАНСУЛЬФО
КИСЛОТА – СІЛЬ 3d-МЕТАЛІВ – ВОДА
А. М. Карич, Р. Є. Хома*,
С. В. Водзінський, В. С. Ковтун
Одеський національний університет імені
І. І. Мечникова,
вул. Всеволода Змієнка, 2, Одеса 65082,
Україна,
e-mail: rek@onu.edu.ua
На основі даних прямих рН-, редокс та
кондуктометрії встановлено особливос-
ті кислотно-основної та електрохімічної
поведінки у водних розчинах амінометан-
сульфокислоти (AMSA) із солями 3d- мета-
лів (сульфатами марганцю(II), заліза(II), ко-
бальту(II), нікелю (II), міді(II) та цинку(II), а
також хлоридами кобальту(II), нікелю (II) та
міді(II)). Поведінку водних розчинів AMSA –
солі 3d-металів досліджували методом на-
сичення за лігандом (зсуву рівноваги) при
CM
2+ = 0.025 моль/л; CAMSA/CM
2+ = 0.08 ¸ 4.00.
Про склад утворених комплексів судили
за положеннями екстремумів та зламів на
інтегральних рН-, редокс-метричних кри-
вих та екстремумів на відповідних їхніх
диференційних кривих, а також за зламами
на кондуктометричних кривих. У дослі-
джених розчинах реалізуються комплек-
сні сполуки складу [M(NH2CH2SO3)]+ (I),
[M2(NH2CH2SO3)3]
+ (II), [M(NH2CH2SO3)2]
(III), [M2(NH2CH2SO3)5]
- (IV),
[M(NH2CH2SO3)3]
- (V). Оскільки продукта
ми реакції іонів металів з AMSA, окрім
вказаних вище комплексних сполук, є іони
гідроксонію, які характеризуються підви-
щеною рухливістю, значення Dk (Dk = k3 -
k2 - k1, де k1, k2, k3 – питомі електропровідно-
сті водних розчинів МzAn2, AMSA та МzAn2
із AMSA відповідно) набувають додатних
значень. На основі розробленої фізико-хі-
мічної моделі, що враховує закон діючих
мас, матеріальний баланс за AMSA та мета-
лом, а також принцип електронейтрально-
сті, розраховано йон-молекулярний склад
59https://ucj.org.ua
A. M. Karych, R. E. Khoma, S. V. Vodzinskii, V. S. Kovtun UCJ № 1/ Vol. 92
вивчених розчинів та оцінено концентра-
ційні константи комплексоутворення. Зі
збільшенням співвідношення CAMSA/CM
2+
відносний вміст мольної частки цвіттеріо-
ну зростає, а незв’язаного Cu2+ та закомп-
лексованих форм AMSA – зменшуються.
Відносний вміст закомплексованих форм
міді (спочатку зростає, набуваючи мак-
симального значення при CAMSA/CM
2+ 1.0,
а потім спадає. Водночас відносний вміст
гідролізованої форми Cu2+ (основної солі –
гідроксиду-сульфату міді(ІІ)) та амінометан-
сульфонат аніону складають менше 0.01 %.
Виявлено кореляції між константами
утворення зазначених комплексів. Віднос-
ні стійкості комплексів іонів 3d-металів з
AMSA корелюють з літературними даними
щодо аналогічних значень для таурину та
його похідних. Найбільшою стійкістю ха-
рактеризуються переважно сполуки іонів
Cu2+ із досліджуваним лігандом.
Ключові слова: амінометансульфокис-
лота, катіони 3d-металів, комплексоутво-
рення, кислотно-основна взаємодія, кон-
станти комплексоутворення, стійкість.
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Стаття надійшла 23.03.2026.
|
| id | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-764 |
| institution | Ukrainian Chemistry Journal |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-07-23T01:14:11Z |
| publishDate | 2026 |
| publisher | V.I.Vernadsky Institute of General and Inorganic Chemistry |
| record_format | ojs |
| resource_txt_mv | ucjorgua/42/6ec2bcc5dc535614843bb6a1cc8ddf42.pdf |
| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-7642026-07-22T08:23:57Z BEHAVIOR OF AMINOMETHANESULPHONIC ACID – 3D-METAL SALT – WATER SOLUTIONS. Khoma, Ruslan Vodzinskii, Sergey Karych, Anastasiya Kovtun, Vasyl aminomethanesulfonic acid, 3d-metal cations, complexation, acid-base interactions, complexation constants, stability. Based on direct pH, redox and conductometry data, the features of the acid-base and electrochemical behavior of aqueous solutions of aminomethanesulfonic acid (AMSA) with 3d metal salts (manganese(II), iron(II), cobalt(II), nickel(II), copper(II) sulfates and cobalt(II), nickel(II), copper(II) chlorides) were established. The behavior of aqueous solutions of AMSA – 3d metal salts was studied by the ligand saturation method (equilibrium shift) at CM2+ = 0.025 mol/l; CAMSA/CM2+ = 0.08 ¸ 4.00. The composition of the formed complexes was judged by the positions of extrema and kinks in the integral pH, redox-metric curves, and extrema in the corresponding differential curves, as well as by kinks in the conductometric curves. In the studied solutions, complex compounds of the composition [M(NH2CH2SO3)]+ (I), [M2(NH2CH2SO3)3]+ (II), M(NH2CH2SO3)2 (III), [M2(NH2CH2SO3)5]- (IV), [M(NH2CH2SO3)3]- (V), are realized.&nbsp; So, as the products of the reaction of metal ions with AMSA, in addition to the above-mentioned complex compounds, including hydroxonium ions, which are characterized by increased movability, the value Dk (Dk = k3 - k2 - k1, where k1 - k2 - k3 – specific of the electrical conductivity of water solutions MzAn2, AMSA and MzAn2 from AMSA, respectively) acquire positive values. Based on a developed physicochemical model taking into account the law of mass action, the material balance of AMSA and the metal, and the principle of electroneutrality, the ion-molecular composition of the studied solutions was calculated, and the concentration constants of complexation were estimated. Correlations were found between the formation constants of these complexes. The relative stabilities of 3d-metal ion complexes with AMSA correlate with literature data on similar values for taurine and its derivatives. The highest stability is predominantly demonstrated by compounds of Cu2+ ions with the studied ligand. &nbsp; V.I.Vernadsky Institute of General and Inorganic Chemistry 2026-02-25 Article Article Inorganic Chemistry Неорганическая химия Неорганічна хімія application/pdf https://ucj.org.ua/index.php/journal/article/view/764 10.33609/2708-129X.92.1.2026.45-60 Ukrainian Chemistry Journal; Vol. 92 No. 1 (2026): Ukrainian Chemistry Journal; 45-60 Украинский химический журнал; ##issue.vol## 92 ##issue.no## 1 (2026): Ukrainian Chemistry Journal; 45-60 Український хімічний журнал; Том 92 № 1 (2026): Ukrainian Chemistry Journal; 45-60 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/764/398 Copyright (c) 2026 Ruslan Khoma, Sergey Vodzinskii, Anastasiya Karych, Vasyl Kovtun https://creativecommons.org/licenses/by-nc/4.0 |
| spellingShingle | Khoma, Ruslan Vodzinskii, Sergey Karych, Anastasiya Kovtun, Vasyl BEHAVIOR OF AMINOMETHANESULPHONIC ACID – 3D-METAL SALT – WATER SOLUTIONS. |
| title | BEHAVIOR OF AMINOMETHANESULPHONIC ACID – 3D-METAL SALT – WATER SOLUTIONS. |
| title_full | BEHAVIOR OF AMINOMETHANESULPHONIC ACID – 3D-METAL SALT – WATER SOLUTIONS. |
| title_fullStr | BEHAVIOR OF AMINOMETHANESULPHONIC ACID – 3D-METAL SALT – WATER SOLUTIONS. |
| title_full_unstemmed | BEHAVIOR OF AMINOMETHANESULPHONIC ACID – 3D-METAL SALT – WATER SOLUTIONS. |
| title_short | BEHAVIOR OF AMINOMETHANESULPHONIC ACID – 3D-METAL SALT – WATER SOLUTIONS. |
| title_sort | behavior of aminomethanesulphonic acid – 3d-metal salt – water solutions. |
| topic_facet | aminomethanesulfonic acid 3d-metal cations complexation acid-base interactions complexation constants stability. |
| url | https://ucj.org.ua/index.php/journal/article/view/764 |
| work_keys_str_mv | AT khomaruslan behaviorofaminomethanesulphonicacid3dmetalsaltwatersolutions AT vodzinskiisergey behaviorofaminomethanesulphonicacid3dmetalsaltwatersolutions AT karychanastasiya behaviorofaminomethanesulphonicacid3dmetalsaltwatersolutions AT kovtunvasyl behaviorofaminomethanesulphonicacid3dmetalsaltwatersolutions |