Onium Sulfates and Hydrogen Sulfates: Products of Reactions of Sulfur(IV) Oxide with Aqueous Solutions of Alkylamines and Aniline

Article abstract of DOI:10.1134/S0036023618050157

The reaction products formed in the SO₂–L–H₂O–O₂ systems (L is n-propylamine, n-butylamine, tert-butylamine, n-heptylamine, n-octylamine, aniline) were isolated and identified as “onium” salts [n-C₃H₇NH₃]₂SO₄, [n-C₄H₉NH₃]₂SO₄, [t-C₄H₉NH₃]₂SO₄, [n-C₇H₁₅NH₃]₃SO₄(HSO₄), [n-C₈H₁₇NH₃]₃SO₄(HSO₄), and [C₆H₅NH₃]₂SO₄. The products were characterized by elemental analysis, IR and Raman spectroscopy, mass spectrometry, and thermogravimetry.

Full text of DOI:10.1134/S0036023618050157

ISSN 0036-0236, Russian Journal of Inorganic Chemistry, 2018, Vol. 63, No. 5, pp. 655–660. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © R.E. Khoma, V.O. Gel’mbol’dt, A.A. Ennan, V.N. Baumer, I.M. Rakipov, R.M. Dlubovskii, 2018, published in Zhurnal Neorganicheskoi Khimii, 2018, Vol. 63,
No. 5, pp. 625–630.
PHYSICAL METHODS
OF INVESTIGATION
Onium Sulfates and Hydrogen Sulfates:
Products of Reactions of Sulfur(IV) Oxide
with Aqueous Solutions of Alkylamines and Aniline
R. E. Khomaa, b, *, V. O. Gel’mbol’dtc, A. A. Ennana, V. N. Baumerd,
I. M. Rakipove, and R. M. Dlubovskiia
aPhysical Chemical Institute for Environment and Human Protection, MES and NAS of Ukraine, Odessa, 65082 Ukraine
bOdessa Mechnikov National University, Odessa, 65082 Ukraine
cOdessa National Medical University, Odessa, 65082 Ukraine
dNTK Institute of Single Crystals, National Academy of Sciences of Ukraine, Kharkiv, 61001 Ukraine
eBogatsky Physico-Chemical Institute, National Academy of Sciences of Ukraine, Odessa, 65080 Ukraine
*e-mail: rek@onu.edu.ua
Received June 17, 2017
Abstract⎯The reaction products formed in the SO2–L–H2O–O2 systems (L is n-propylamine, n-butyl-
amine, tert-butylamine, n-heptylamine, n-octylamine, aniline) were isolated and identified as “onium” salts
[n-C3H7NH3]2SO4,
[n-C4H9NH3]2SO4,
[t-C4H9NH3]2SO4,
[n-C7H15NH3]3SO4(HSO4),
[n-C8H17NH3]3SO4(HSO4), and [C6H5NH3]2SO4. The products were characterized by elemental analysis,
IR and Raman spectroscopy, mass spectrometry, and thermogravimetry.
DOI: 10.1134/S0036023618050157
The non-catalyzed auto-oxidation reactions of sul-
furous compounds, most often, sulfur(IV) oxide, are
of obvious interest for the theory and practice of
chemical engineering processes [1–3]. For example,
scavenging of sulfur(IV) oxide from gas–air mixtures
by chemisorbents based on organic nitrogen bases in
the presence of O2 is accompanied by S(IV) → S(VI)
oxidation [4]. The reaction products thus formed
(depending on the chemisorption conditions) may
suppress the absorption capacity during sulfur(IV)
oxide sorption–desorption cycles and complicate the
thermal regeneration of the sorbents [5, 6]. The sulfur
oxidation can also considerably affect the ion
exchange efficiency [7].
Previously [8–10], we isolate onium sulfites from
the SO2–L–H2O–O2 reaction systems (L = ethanol-
amines, aminoguanidine); in the case of analogous
systems in which L is methylamine, tert-butylamine
(t-BA), benzylamines, tris(hydroxymethyl)amino-
methane (TRIS), or hexamethylenediamine, onium
sulfates are formed under similar conditions [11–14].
This paper presents a method of synthesis, spectral
characteristics, and thermal stability data for the prod-
ucts of reactions of SO2 with aqueous solutions of
n-propylamine, n-butylamine, t-BA, n-heptylamine,
n-octylamine, and aniline (compounds I–VI, respec-
tively) in the presence of air oxygen.
EXPERIMENTAL
n-Propylammonium sulfate (I). A solution of n-pro-
pylamine (0.10 mol) in 25 mL of water was poured into
a temperature-controlled cell, and at 0°C, gaseous SO2
was bubbled though the solution at a 50 mL min–1 rate
until pH < 1.0 was attained. The solution with the pre-
cipitate was subjected to isothermal evaporation at
room temperature in air until water was completely
removed. The isolated white-colored crystalline prod-
uct I (10.28 g, 95.0% yield based on n-propylamine)
was not additionally purified. FAB MS: [ML + H]+
(m/z 60, I, 100%); [ML – H]+ (m/z 58, I, 5%); m/z 43,
I, 13%; [ML – NH3]+ (m/z 42, I, 96%); [ML – NH3 + H]+
(m/z 41, I, 15%).
For C6H20N2O4S anal. calcd. (%): C, 33.32; H,
9.32; N, 12.95; S, 14.82. FW = 216.30.
Found (%): C, 33.89; H, 9.54; N, 12.42; S, 15.31.
n-Butylammonium sulfate (II). A similar sequence
of procedures with the use of an aqueous solution of
n-butylamine (0.1 mol of the amine in 25 mL of H2O)
afforded a gel-like pale yellow product II (11.95 g iso-
lated; 97.8% yield based on n-butylamine). FAB MS:
m/z 245, I, 27%; m/z 194, I, 7%; m/z 75, I, 7%; [ML +
H]+ (m/z 74, I, 100%); m/z 69, I, 6%; [ML – NH3 +
H]+ (m/z 57, I, 9%); m/z 55, I, 9%.
655

656
KHOMA et al.
Analysis for carbon, hydrogen, and nitrogen was
For C8H24N2O4S anal. calcd. (%): C, 39.32; H,
9.90; N, 11.46; S, 13.12. FW = 244.36.
carried out on an elemental CHN analyzer; sulfur was
quantified by the Sheniger method [15]. IR absorption
spectra were recorded on a Spectrum BX II FT-IR
System spectrophotometer (Perkin-Elmer) (4000–
350 cm–1 range; the samples were prepared as KBr
Found (%): C, 39.82; H, 9.38; N, 12.78; S, 12.80.
tert-Butylammonium sulfate (III) was synthesized
using analogous procedures [11]. EI MS: [SO3]+• (m/z
80, I, 32%); [SO2]+• or [S2]+• (m/z 64, I, 13%); [ML – pellets); Raman spectra were measured on a DFS-24
NH3 + 2H]+• (m/z 58, I, 100%); [SO]+ (m/z 48, I,
10%); m/z 43, I, 10%; m/z 41, I, 22%; m/z 40, I, 12%;
[S]+ (m/z 32, I, 10%). Raman lines in the spectrum of
laser spectrometer with a semiconductor laser exci-
tation (emission wavelength of 532 nm; interference
monochromator; a 90° illumination scheme was
used); EI mass spectra were run on an MX-1321
instrument (direct sample injection to the source; ion-
izing electron energy of 70 eV); FAB mass spectra were
recorded on a VG 7070 instrument (ion desorption
from the liquid matrix was accomplished by a beam of
argon atoms with an energy of 8 keV; m-nitrobenzyl
alcohol was used as the matrix).
The thermochemical transformations of com-
pounds were studied on a Q-1500 D Paulik-Paulik-
Erdey derivatograph in air (platinum crucibles, tempera-
ture range of 20–1000°C, heating rate of 10°C/min,
DTA and DTG sensitivity of 1/5 of the maximum, and
Al2O3 as the reference).
III (cm–1): 3230 w, 3159 m [ν(
[ν (CH ), ν(
as
+)]; 2988 s, 2900 m
NH3
+)]; 2885 m, 2775 w, 2745 w, 2650 w
NH3
3
[ν (CH ), ν(
+)]; 1316 w [ν(CN), ν(CC)]; 1220 w
NH3
[νs(CN)]; 1125 m [ν3 ≡ νas(SO)]; 1010 m, 975 s, 941 m
3
[r(CH ), r(
+), ν1 ≡ νs(SO)] (recording the spectra
NH3
3
below 700 cm–1 is impossible because of strong lumi-
nescence of the sample).
n-Heptylammonium sulfate-hydrogen sulfate (IV).
A similar sequence of procedures with the use of an
aqueous solution of n-heptylamine (0.05 mol of the
amine in 25 mL of H2O) gave a white-colored waxy
product IV (8.74 g isolated, 96.8% yield based on
n-heptylamine). FAB MS: [ML + H]+ (m/z 116, I,
79%); m/z 57, I, 38%; m/z 56, I, 8%; m/z 55, I, 49%;
m/z 53, I, 8%; m/z, 43, I, 16%; m/z 42, I, 100%; m/z 41,
I, 14%.
RESULTS AND DISCUSSION
The mass spectra of n-alkylammonium salts I, II,
IV, and V exhibit an intense peak of the [ML + H]+ ion
(the maximum intensity is observed for compound II).
The characteristics of t-BA fragmentation products in
the mass spectra of onium salt III are in good agree-
ment with those in the tabulated mass spectrum of
t-BA [16]; the same is true for aniline [17] and its
onium salt VI. The mass spectrum of VI shows the
fragmentation of [ML]+ ion [18] involving the expul-
sion of HCN and H2CN, which is typical of aryl-
amines.
Table 1 presents the results of analysis of the IR
spectra of compounds I–VI. The IR absorption bands
of sulfates I, II, and VI and mixed sulfates–hydrogen
sulfates IV and V were assigned using published data
[19–25]; the IR and Raman absorption bands (lines)
of salt III were assigned taking account of the known
experimental and theoretical data [20].
For C21H55N3O8S2 anal. calcd. (%): C, 46.55; H,
10.23; N, 7.76; S, 11.84. FW = 541.82.
Found (%): C, 45.74; H, 10.11; N, 7.68; S, 12.32.
n-Octylammonium sulfate-hydrogen sulfate (V).
A similar sequence of procedures with the use of an
aqueous solution of n-octylamine (0.05 mol of the
amine in 25 mL of H2O) gave a gray-yellow waxy
product V (9.47 g isolated, 97.3% yield based on n-hep-
tylamine). FAB MS: [ML + H]+ (m/z 130, I, 32%);
m/z 56, I, 16%; m/z 55, I, 36%; m/z 53, I, 8%; m/z 42,
I, 100%; m/z 41, I, 8%.
For C22H61N3O8S2 anal. calcd. (%): C, 49.37; H,
10.53, N 7.20; S, 10.98. FW = 583.89.
Found (%): C, 49.12; H, 10.68; N, 7.66; S, 11.78.
In the IR spectra of I–VI, the νas, s
(
+) stretching
NH3
Anilinium sulfate (VI). A similar sequence of proce-
dures with the use of an aqueous solution of aniline
(0.05 mol of the amine in 25 mL of H2O) gave a color-
less crystalline product V (6.65 g isolated, 93.6% yield
based on aniline). EI MS: [ML]+• (m/z 93, I, 100%);
modes occur at 3550–3400 and 3050–3020 cm–1,
respectively, and the δas,s
+) bending modes occur
(
NH3
at 1690–1500 cm–1. In the Raman spectra of salt III,
the ν(
+) modes mainly give rise to low-intensity
[SO3]+• m/z 80, I, 46%; [ML – HCN]+• (m/z 66, I,
16%); [ML – HCN–H]+• (m/z 65, I, 10%); [SO2]+•
NH3
lines at 3230–2775 cm–1; and the δ(
+) vibrations
NH3
(m/z 64, I, 15%); [SO]+• m/z 48, I, 24%; [S]+ m/z 32,
I, 10%.
show low activity in the Raman spectra and have not
been considered.
It is known [19] that the vibrational spectra of the
For C12H16N2O4S anal. calcd. (%): C, 50.69; H,
5.67; N, 9.85; S, 11.28. FW = 284.33.
T -symmetric isolated
2− anion exhibit four normal
SO4
d
modes at 983 cm–1 (ν1, Raman-active), 450 cm–1 (ν2,
Found (%): C, 51.27; H, 5.48, N, 9.27; S, 11.76.
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ONIUM SULFATES AND HYDROGEN SULFATES
657
Table 1. Wave numbers (cm–1) of the principal absorption peaks in the IR spectra of I–VI*
Compound
I
II
III
IV
V
VI
+
3433 m 3550–3400 m.br.
3180 sh
3020 m
3020 m
3421m.br.
3061 w
νas,s
(
)
NH3
3031vs
3020 vs
3050 s
+), ν(CH)
NH3
2981 m
2870 m
2775 w
2715 w
2580 w
2936 s
2877 s
2592 s
νas,s
(
+
1569 s
1504 s
1590 s
1505 s
1690m
1615sh
1565 sh
1510 m
1613 w
1531 m
1506 sh
1612 w
1525 s
1507 w
1608 m
1587 m
1572 sh
δas,s
(
)
NH3
ν ( 2− ) ≡ νs(SO)
SO4
954 m
–
965 sh
–
980 m
–
966 sh
1048 s
965 m
1046 s
972 sh
–
1
ν (
−) ≡ νs(SO)
HSO4
1
ν ( 2− ) ≡ δs(OSO)
SO4
448 m
440 w
510 w
455 m
425 w
490 w
477 w
444 w
2
442 w
441 w
−) ≡ γ(S-OH)
HSO4
–
–
–
–
ν (
2
ν ( 2− ) ≡ νas(SO)
1120 vs
1119 vs
1118 vs
1117 vs
1115 vs
1133 vs
1115 sh
1088 s
1058 s
SO4
3
−) ≡ νas(SO) + δ(OH)
–
–
–
1209 m
1197 sh
1210 m
1197 m
–
ν (
HSO4
3
ν ( 2− ) ≡ δas(OSO)
669 w
660 w
618 vs
683 w
671 w
618 s
690 sh
617 s
605 sh
683 w
671 w
617 s
683 w
671 w
618 s
617 m
606 sh
SO4
4
−) ≡ νs(SO) + γ(OH)
–
–
–
882 w
880 w
–
ν (
HSO4
4
* Types of vibrations: ν is stretching, δ is bending, γ is out-of-plane (libration).
Raman-active), 1105 cm–1 (ν3, IR- and Raman-
active), and 611 cm–1 (ν4, IR- and Raman-active). In
the IR spectra of I and II, all ν1–ν4 modes are active:
A similar trend can be followed in the spectra of
sulfates III and VI. In the IR spectrum of salt III, in
which the anion has C2 symmetry according to X-ray
diffraction data [22], the ν1 stretching vibrations are
the νas, s
(
2−) stretching vibrations (ν3, ν1) give rise to
SO4
manifested at 980 cm–1 (in the Raman spectrum, this
1120, 954 cm–1 and 1119, 965 cm–1 bands, respectively,
while the δas, s
vibration is active at 975 cm–1) and the ν3 vibrations
(
2−) bending vibrations (ν4, ν2) occur occur at 1118 cm–1 (IR) and 1125 cm–1 (Raman). The
SO4
as 669, 660, 618, 448 cm–1 and 683, 671, 618, 440 cm–1
bands, respectively. The observed differences in the
anion characteristics in the spectra of I and II and in
the tabulated spectrum [19] (in particular, the appear-
ance of the ν1 and ν2 modes) reflect the decrease in the
anion bending vibrations ν4 are manifested as a triplet
at 617 cm–1 (a strong band), 690, and 605 cm–1 (shoul-
ders). Generally, the number and positions of the
2−
identified modes of the
anion incorporated in
SO4
salts I, II, III, and VI attest to a decrease in the anion
symmetry as compared with the perfect Td structure;
this is in line with X-ray diffraction data [22].
SO24−
anion symmetry in salts I and II caused by per-
turbing effect of the NH⋅⋅⋅O hydrogen bonds.
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KHOMA et al.
Table 2. Results of thermogravimetric analysis of onium sulfates and sulfates–hydrogen sulfates
Temperature, °C
Decomposition
Compound
Mass loss, %
71.2
stage
Tons
Tend
Tmax
[C3H7NH3]2SO4 (I)
First (endo)
Second (endo)
Third (exo)
260
320
500
270
480
125
275
340
500
290
480
290
470
550
210
380
510
320
350
560
340
580
140
340
400
570
350
620
330
550
630
260
415
650
300
330
540
330
550
130
310
370
520
330
530
320
510
610
250
410
600
93.3
75.6
94.3
0
[C4H9NH3]2SO4 (II)
First (endo)
Second (exo)
[(CH3)3CNH3]2SO4 (III) First (endo)
Second (endo)
67.4
Third (endo)
Fourth (exo)
74.1
78.7
93.3
76.6
[C7H15NH3]3SO4(HSO4) (IV) First (endo)
Second (exo)
[C8H17NH3]3SO4(HSO4) (V) First (endo)
Second (exo)
96.7
Third (exo)
[C6H5NH3]2SO4 (VI)
First (endo)
Second (endo)
Third (exo)
65.3
95.0
(10.77 + 0.86) > n-C3H7NH3+ (10.60 + 0.48) >
In comparison with the sulfate anion, an isolated
hydrogen sulfate anion has an additional proton,
C6H5NH3+ (4.63 + 0.90).
2−
which is bound to one hydrogen; on going from
SO4
This sequence of onium cations (except for the tert-
butylammonium cation) correlates with the basicity
and lipophilicity function (the values in parentheses
are pKa + logPow [26, 27]). Note that previously, an
attempt was made to relate the solubility and melting
points of compounds to their lipophilicity (logPow)
and pKa [28].
to
−, the symmetry changes from Td to C3ν [19, 23,
HSO4
25]. In the mixed salts with the (SO4HSO4)3– anions
2−
[23, 25], two tetrahedral
groups are linked by a
strong hydrogen bond: in the case of symmetric
SO4
1 SO2−
H-bond, the ν
vibrations give rise to a singlet
absorption band, 4 whereas asymmetric H-bond
induces splitting of the ν1 mode into two components.
The doublet nature of the ν1 band in the IR spectra of
The endothermic effects observed for salts I, II,
and IV–VI (the first and second for sulfates I and VI
and the first for sulfate II and hydrogen disulfates IV
and V) correspond to elimination of [RNH3]HSO4
(and its decomposition products; 1 mol for sulfates
and 2 mol for hydrogen disulfates) to the gas phase,
which is typical of ammonium sulfate [29]. The exo-
thermic effects in the thermograms of salts I–VI cor-
respond to the oxidative destruction of 1 mol of the
amine (and its decomposition products). Thermolysis
of compound III is accompanied by a phase transition
(endotherm at 125–140°C without mass loss) [22] fol-
lowed by elimination of 1 mol of (CH3)3CNH2 (its
decomposition products), 1 mol of SO3, and 1 mol of
H2O (100% H2SO4 boils with decomposition at 275°C
[30]), and the products of t-BA oxidative destruction
(exotherm).
mixed salts IV and V (1048, 966 cm–1 and 1046, 965 cm–1;
the splitting is 82 and 81 cm–1, respectively) attests to
asymmetric H-bond in the salt crystals; by analogy
with [24, 25], the lower-wavelength component of ν1
corresponds to the hydrogen sulfate anion.
The results of thermogravimetric analysis of com-
pounds I–VI are presented in Table 2. According to
these data, the relative thermal stability of the sulfate
salts decreases in the following order, depending on
the nature of the onium cation:
n-C8H17NH3+ (10.65 + 3.09) ≈ n-C7H15NH3+ (10.67 +
2.57) > (CH3)3CNH3+ (10.68 + 0.40) > n-C4H9NH3+
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ONIUM SULFATES AND HYDROGEN SULFATES
659
As has already been noted, the reactions in SO2– organic bases L with the following basicity constants:
aniline (pKa = 4.63), ethanolamines [8, 9, 32] (7.76 ≤
pKa ≤ 9.85), benzylamines [13] (8.52 ≤ pKa ≤ 9.84),
alkylamines (10.60 ≤ pKa ≤ 10.77), aminoguanidine
[10] (pKa = 11.04). In view of the fact that the reactions
RNH2–H2O–O2 solutions (R
=
CH3 [14],
(HOCH2)3C [12], C6H5CH2 [13], C6H5C(CH3)H
[13], (CH3)3C [11], and C6H5) give the corresponding
onium sulfates, which are stabilized, according to
X-ray diffraction data, by NH⋅⋅⋅O type hydrogen bond with less basic 2,2′-bipyridine (pKa = 4.34) give van
systems [11–14, 21, 22]. Evidently, the onium sulfates
[n-C3H7NH3]2SO4 and [n-C4H9NH3]2SO4 character-
ized in this study have a similar structure.
der Waals clathrates [33], the value pKa = 4.63 can be
taken, in the first approximation, as the lower bound-
ary of the ligand basicity to provide the formation of
salts in these reaction systems.
Thus, the transformation in the given reaction sys-
tems can be generally represented by the scheme
2SO2 + 4RNH2 + 2H2O + O2 → 2(RNH3)2SO4, (1)
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(6)
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2(RNH3)2S2O5 + O2
(7)
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