THE IMPREGNATED FIBROUS CHEMISORBENTS FOR COLORIMETRIC DETECTION OF THE SULFUR DIOXIDE
The paper presents the research results on the colorimetric behavior of impregnated fibrous chemisorbents (IFCS-I) of acid gases with visual identification of the dynamic absorption capacity “response” moment during the absorption of sulfur dioxide. Chemisorbents were obtained by impregnation of fib...
Saved in:
| Date: | 2022 |
|---|---|
| Main Authors: | , , , , , |
| Format: | Article |
| Language: | English |
| Published: |
V.I.Vernadsky Institute of General and Inorganic Chemistry
2022
|
| Online Access: | https://ucj.org.ua/index.php/journal/article/view/399 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| Journal Title: | Ukrainian Chemistry Journal |
| Download file: |  |
Institution
Ukrainian Chemistry Journal| _version_ | 1871465795290136576 |
|---|---|
| author | Khoma, Ruslan Ennan, Alim Bienkovska, Tetyana Dlubovskii, Ruslan Vodzinskii, Sergey Mykhailova, Tetiana |
| author_facet | Khoma, Ruslan Ennan, Alim Bienkovska, Tetyana Dlubovskii, Ruslan Vodzinskii, Sergey Mykhailova, Tetiana |
| author_institution_txt_mv | [
{
"author": "Ruslan Khoma",
"institution": "Odessa I.I. Mechnikov National University"
},
{
"author": "Alim Ennan",
"institution": "Physico-Chemical Institute of Environment and Human Protection"
},
{
"author": "Tetyana Bienkovska",
"institution": "Physico-Chemical Institute of Environment and Human Protection"
},
{
"author": "Ruslan Dlubovskii",
"institution": "Physico-Chemical Institute of Environment and Human Protection"
},
{
"author": "Sergey Vodzinskii",
"institution": "Odessa I.I. Mechnikov National University"
},
{
"author": "Tetiana Mykhailova",
"institution": "A.V. Bogatsky Physico-chemical Institute of National Academy of Science of Ukraine"
}
] |
| author_sort | Khoma, Ruslan |
| baseUrl_str | https://ucj.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-22T08:23:48Z |
| description | The paper presents the research results on the colorimetric behavior of impregnated fibrous chemisorbents (IFCS-I) of acid gases with visual identification of the dynamic absorption capacity “response” moment during the absorption of sulfur dioxide. Chemisorbents were obtained by impregnation of fibrous carriers by N-containing organic bases aqueous solutions with adding acid-base indicators (Ind). IFCS-I based on hexamethylenetetramine (IFCS-HMTA-I) and polyethylenepolyamine (IFCS-PEPA-I), as well as IFCS-MEA-EDTA-I based on monoethanolamine (MEA) and the disodium salt of ethylenediaminetetraacetic acid (EDTA) were used. The change specificity of colorimetric functions of indicator impregnated fibrous chemisorbents during their absorption of SO2 is revealed. IFCS-I original samples color significantly depends not only on the structure of Ind, but also the nature of amines (MEA, HMTA and PEPA), which are part of them. The color of the “response” samples of IFCS-MEA-EDTA-I, IFCS-PEPA-I and IFCS-HMTA-I, differ from the same properties of Bronsted acids aqueous solutions. The color change of azo-indicators occurs due to redox reactions with sulfite compounds. PEPA molecules and their ammonium cations in the composition of IFCS-I stabilize azo-indicators to these redox transformations. |
| doi_str_mv | 10.33609/2708-129X.88.01.2022.35-48 |
| first_indexed | 2025-09-24T17:43:43Z |
| format | Article |
| fulltext |
35
УДК 54-43:544.723: 546.224-31 doi:10.33609/2708-129X.88.01.2022.35-48
THE IMPREGNATED FIBROUS CHEMISORBENTS FOR COLORIMETRIC
DETECTION OF THE SULFUR DIOXIDE
R. E. Khoma1,2*, A. A.-A. Ennan1, T. S. Bienkovska1, R. M. Dlubovskii1,
S. V. Vodzinskii1,2, T. V. Mykhailova1,3
1Physico-Chemical Institute of Environment and Human Protection of MES of Ukraine and NAS of
Ukraine; 3, Preobrazhenskaya str., 65082, Odessa, Ukraine
2 Odessa I. I. Mechnikov National University; Dvoryankaya str., 2, 65082, Odessa, Ukraine
3A.V. Bogatsky Physico-chemical Institute of National Academy of Science of Ukraine; Lustdorf-
skaya doroga 86, 65080, Odessa, Ukraine
*e-mail: rek@onu.edu.ua
The paper presents the research results on the colorimetric behavior of impregnated fi-
brous chemisorbents (IFCS-I) of acid gases with visual identification of the dynamic absorp-
tion capacity “response” moment during the absorption of sulfur dioxide. Chemisorbents
were obtained by impregnation of fibrous carriers by N-containing organic bases aqueous
solutions with adding acid-base indicators (Ind). IFCS-I based on hexamethylenetetramine
(IFCS-HMTA-I) and polyethylenepolyamine (IFCS-PEPA-I), as well as IFCS-MEA-EDTA-I
based on monoethanolamine (MEA) and the disodium salt of ethylenediaminetetraacetic
acid (EDTA) were used. The change specificity of colorimetric functions of indicator impreg-
nated fibrous chemisorbents during their absorption of SO2 is revealed. IFCS-I original sam-
ples color significantly depends not only on the structure of Ind, but also the nature of amines
(MEA, HMTA and PEPA), which are part of them. The color of the “response” samples of
IFCS-MEA-EDTA-I, IFCS-PEPA-I and IFCS-HMTA-I, differ from the same properties of
Bronsted acids aqueous solutions. The color change of azo-indicators occurs due to redox
reactions with sulfite compounds. PEPA molecules and their ammonium cations in the com-
position of IFCS-I stabilize azo-indicators to these redox transformations.
Key words: colorimetry, fibrous chemisorbents, sulfur dioxide, acid-base indicators.
INTRODUCTION. When using known
respirators, the moment of their “response” is
determined by the workers of labor protec-
tion departments on the basis of data on the
absorption capacity of gasfiltering elements
(GFEs). The difficulty of the work done by
the user into two ways: the results of instru-
mental measurements of the air pollution level
during the operation of the respirator by the
user, or by organoleptic method. In the former
case, a special equipment and trained person-
nel are required to obtain the necessary infor-
mation, and in the latter case, the moment of
“breakthrough” is determined subjectively and
can lead to the poisoning of the user. That is,
a significant disadvantage of known filtering
THE IMPREGNATED FIBROUS CHEMISORBENTS FOR COLORIMETRIC DETECTION OF THE SULFUR DIOXIDE
36 ISSN 2708-129X. Укр. хім. журн., 2022
PHISICAL CHEMISTRY
respirators, designed for protection against to
xic acid gases, is the impossibility to determine
in proper time the moment of dynamic absorp-
tion capacity “response” of the GFE, to note the
breakthrough of sorptive into the mask cavity.
The authors of [1,2] proposed granular in-
dicator chemisorbents - ionites, which change
their color during “response” to NH3, H2S,
SO2, HCl, etc, for fitting up gas filter boxes and
gas sample preparation filters in the manufac-
ture of gas analyzers. The ionite filter body is
made by casting from an optically transparent
shock-resistant polymer material (polycar-
bonate fluoroplastic), which makes it possible
to watch the condition of chemiosorbent dur-
ing the “response” of the filter.
Belarusian colleagues [3] proposed indica-
tor materials for SO2 capture, obtained by im-
pregnating a fibrous anionite containing in its
structure functional groups of tertiary amine
(dimethylaminopropylamine) with acid – base
indicators in a pH range of 7.0–8.5.
To make GFEs, with which light respirators
are fitted, the Physico-Chemical Institute of
Environment and Human Protection of MES
of Ukraine and NAS of Ukraine (Odesa) has
developed impregnated fibrous chemisorbents
of acid gases with visual identification of the
moment of dynamic absorption capacity “re-
sponse” (IFCS-I) [4–6], obtained by impreg-
nating fibrous carriers with aqueous solutions
of N-containing organic bases (Am: monoetha
nolamine (MEA), hexamethylenetetramine
(HMTA) and polyethylenepolyamine (PEPA)),
to which acid-base indicators (Ind) with wider
color transition range between pH 5.0 and 9.2
were added.
The “response” of the dynamic absorption
capacity of such chemisorbents during the ab-
sorption of an acid gases (sulfur dioxide) can
be visually determined from GFE color change
on the side facing the face during the “break-
through” of sorptive.
However, the visual indication of dyna
mic absorption capacity “response” has only a
qualitative characteristic. The analytical signal
obtained by the visual detection of the color
change of GFE samples (IFCS-I) allows only
to note the moment of “breakthrough” of toxic
chemisorptive (SO2). The comparison of indi-
cator systems by the intensity of color change to
choose ones that are more suitable for practical
use can be only made at the qualitative level.
Besides this, digital colorimetry in aqueous
solutions and on different surfaces is use in
addition to spectrophotometry to solve diffe
rent chemical and analytical problems [7–12].
However, there is no theoretical basis today for
the development of indicator chemisorbents
of acid gases such as sulfur dioxide. Therefore,
the aim of this work to determine the peculiari
ties of colorimetric behavior of IFCS-I during
“response” to SO2. In view of this, this paper
presents data on the colorimetric assessment
of IFCS-I’s based on hexamethylenetetramine
(IFCS-HMTA-I) [5] and polyethylenepoly
amine (IFCS-PEPA-I) [4], developed by us ear-
lier, as well as a new IFCS-MEA-EDTA-I based
on a chemisorbent with prolonged action [12],
which contains MEA and a disodium salt of
ethylenediaminetetraacetic acid (EDTA).
EXPERIMENT AND DISCUSSION OF
THE RESULTS. To carry out the research, we
used chemically pure MEA and EDTA “rea-
gent grade”, HMTA “pharmacopoeial”, PEPA
(CAS 23920-38-5) without pre-purification,
as well as Inds, whose characteristics are listed
in Table 1. As a fibrous carried (FC) we used a
thickness of 2.2 mm and a surface density of
390 g/m2, for filtration.
R. E. Khoma, A. A.-A. Ennan, T. S. Bienkovska, R. M. Dlubovskii, S. V. Vodzinskii, T. V. Mykhailova
37https://ucj.org.ua
UCJ № 1 / Vol. 88
IFCS-MEA-EDTA-I. 0,02 g of Ind was dis-
solved in 50 ml of an aqueous solution contain-
ing 0,30 mol/L MEA and 0,02 mol/L EDTA.
The FC was impregnated with the resulting
solution at the rate of 56.3 mL of solution per
10 g of carrier until full suction. The samples
were air dried at 20-25 C.
IFCS-PEPA-I, IFCS-HMTA-I. The impreg-
nation solutions were prepared according to
[5,6], and the FC was impregnated with them
similarly to IFCS-MEA-EDTA-I.
The research was carried out under dynamic
conditions by means of a special gas dynamic
installation, described in [14]. The concentra-
tion of SO2 in the gas-air mixture (GAM) was
determined by means of an electrochemical
gas analyzer 667 EKh 10 (Ukranalyt LLC).
IFCS-I was tested under the real use condition
of respirators: SO2 concentration in the GAM:
150 mg/m3 (MPC), relative humidity of the
GAM: 90-95%, GAM flow rate: 2.0 cm/s. The
breakthrough correspondent to the moment of
appearance of SO2 in the purified GAM behind
the layer of material at a level of 1–3 mg/m3
(MPC=10 mg/m3).
The color characteristics of IFCS-I samples
(initial and “responded” to SO2) were estimat-
ed by the method of chemical colorimetry [11]
by processing the data from the flatbed scan-
ner in an A4 black and white multifunction
device (HP Laser 13) using the True Color
mode (16.5 million color shades), optical reso-
lution 600 dpi (increasing the resolution to
1200 dpi gave no improvement of image char-
acteristics). The averaged values of the R, G, B
characteristics of samples under investigation
were determined using the on line program
IMGonline [15]. The following colorimetric
functions were used: X, Y, Z (color coordinates
in the system CIEXYZ), L, A, B (color coor-
dinates in the equal contrast system CIELAB),
color saturation (S), color tone (T), full color
difference (∆E76), yellowness (G), calculated
according to [6]; relative whiteness of samples
(W) and intensity of yellow hue (Ky) [12].
As analytical signals of “response” of IFCS-I
samples we also used effective absorption in
the red (AR), green (AG), and blue (AB) ranges,
whose values were calculated from formulas
similar to those in [16]:
AR = -lg(Rr/R0); (1)
AG = -lg(Gr/G0); (2)
AB = -lg(Br/B0), (3)
Where R0, G0, B0 are the color coordinates
of initials samples; Rr, Gr, Br are the color coor-
dinates of “responded” samples. The values of
total absorption (AT) and color ratio (CR) were
determined similarly to [16]:
AT = AR + AG + AB; (4)
CR = Rr/R0 + Gr/G0 + Br/B0
(5)
The color sang colorimetric RGB charac-
teristics for original IFCS-I samples and those
that “responded” to SO2 are listed in Tables 2
and 3.
Results and discussion
According to the data obtained (Tables 2,3),
the color of original IFCS-I samples depends
largely not only on the structure of Ind, but
also on the nature of Am, which are part of
them. The presence of Am in original IFCS-I
samples causes the basicity of their surface:
Am + H2O →← AmH+ + OH−, (6)
which causes coloring. However, the color
of samples based only PEPA (Ind = TrOO,
TrOOO, BCY, BCP, BXB, BPB, BPR and CrR)
THE IMPREGNATED FIBROUS CHEMISORBENTS FOR COLORIMETRIC DETECTION OF THE SULFUR DIOXIDE
38 ISSN 2708-129X. Укр. хім. журн., 2022
PHISICAL CHEMISTRY
and some MEAs (Ind = BXB) and HMTAs
(AL, BXB) is similar to that of aqueous alka-
line solutions (Table 1,2). The difference of the
color of the other samples from that of aqueous
alkaline solutions with the same Ind is appa
rently due to specific interactions between am-
monium cations and anionic forms of dyes.
IFCS-MEA-EDTA-I
The chemisorption of sulfur dioxide by IF-
CS-MEA-EDTA-I samples takes place only
in the presence of “free” water. In this case,
“ammonium” sulfites, hydrosulfites and pyro-
sulfites are formed as a result of acid – base in-
teraction [17,18]:
SO2 + nН2О →← SO2⋅H2O + (n-1)Н2О, (7)
SO2⋅H2O + 2HOCH2CH2NH2 →
[HOCH2CH2NH3]2SO3,
(8)
[HOCH2CH2NH3]2SO3 + SO2⋅H2O →←
2[HOCH2CH2NH3]НSO3,
(9)
2[HOCH2CH2NH3]HSO3 + (n-2)H2O
→
← [HOCH2CH2NH3]2S2O5 + (n-1)H2O. (10)
Comparison of the data presented in [13]
shows that the presence of EDTA in IFCS-I
samples determines the degree of “response” of
MEA to SO2 owing to the deeper transforma-
tion of the latter with increasing the fraction of
hydrosulfites and pyrosulfites similar to [18].
The colors of “responded” IFCS-MEA-EDTA-I
samples, like IFCS-PEPA-I and IFCS-HMTA-I,
differ from the same properties of aqueous
solutions of Brönsted acids (Tables 1,2)
Тable 1
Characteristics of acid-base indicators
Name
A
bb
re
vi
at
io
n
Structure pKa
Th
e
pH
ra
ng
e
of
th
e
co
lo
r t
ra
ns
i-
tio
n
[1
8]
C
ol
or
ch
an
ge
in
aq
ue
ou
s s
ol
u-
tio
ns
[1
8]
1 2 3 4 5 6
Azolitmine AZ
N
N
NH
O
6,4 [20] 4,5-8,3
Anthraquinone dye
Alizarin AL OH
OH
O
O
6,0; 12,5
[21]
5,5-6,8
10,1-12,1
yellow –
dark pink
dark pink –
purple
R. E. Khoma, A. A.-A. Ennan, T. S. Bienkovska, R. M. Dlubovskii, S. V. Vodzinskii, T. V. Mykhailova
39https://ucj.org.ua
UCJ № 1 / Vol. 88
1 2 3 4 5 6
Azine dye
Lacmoid LA
O
N
O
OH
OH
NH2
OH
OH
5,31 [19] 4,4-6,4
Azo dyes
Methyl Orange MO
N N N SO3Na
3,1-4,4 red –
orange-yel-
low
Methyl Red MR
N N N
OH
O
4,4-6,2 red – yellow
Tropaeolin O TrO
OH N N SO3Na
OH -0,8 (4’-SO3H)
0,5 (-N=N-)
6,5 (2-OH)
12,0 (4-OH) [21]
11,0-12,7 yellow – red
Tropaeolin OO TrOO
N
H
N N SO3Na
-0,6 (4’-SO3H)
0,8 (-N=N-)
2,0 (-NH-) [22]
1,3-3,2 red – yellow
Tropaeolin
OOO
TrOOO
OH N N SO3Na
‑0,7 (4’‑SO3H)
2,0 (-N=N-)
8,5 (2-OH) [23]
7,4-8,6
10,2-11,8
amber –
orange
orange –
red
Congo Red CoR
N N
N
NH2NaO3S
N
NH2 SO3Na
3,0
4,1
[22]
3,0-5,2 yellow blue-
red – purple
Тable 1
THE IMPREGNATED FIBROUS CHEMISORBENTS FOR COLORIMETRIC DETECTION OF THE SULFUR DIOXIDE
40 ISSN 2708-129X. Укр. хім. журн., 2022
PHISICAL CHEMISTRY
Table 1
1 2 3 4 5 6
Triphenylmethane dyes
Bromocresol
green
BCG Br
OH
Br
O
Br
Br
NaO3S
0,3 (=OH+)
4,6 (4-OH) [21]
3,8-5,4 yellow –
blue-green
Bromocresol
purple
BCP Br
OH O
Br
NaO3S
0,4 (=OH+)
6,5 (4-OH) [21]
5,2-6,8 yellow –
purple
Bromoxylenol
blue
BXB OH O
NaO3S
Br Br
-1,5 (=OH+) [23]
6,80 (4-OH) [24]
6,0-7,6 yellow –
blue
Bromophenol
blue
BPB Br
OH
Br
O
Br
Br
NaO3S
0,3 (=OH+)
4,0 (4-OH) [21]
3,0-4,6 yellow –
blue-violet
Bromophe-
nol red
BPR Br
OH
Br
O
Br
Br
NaO3S
0,5 (=OH+)
6,5 (4-OH)
[21]
5,2-6,8 yellow –
red
R. E. Khoma, A. A.-A. Ennan, T. S. Bienkovska, R. M. Dlubovskii, S. V. Vodzinskii, T. V. Mykhailova
41https://ucj.org.ua
UCJ № 1 / Vol. 88
1 2 3 4 5 6
Bromothy-
mol blue
BTB Br
OH O
Br
NaO3S
0,5 (=OH+)
6,9 (4-OH)
[21]
6,0-7,6 yellow –
blue
Cresol red CrR OH O
NaO3S
1,5 (=OH+)
8,1 (4-OH)
[21]
0,2-1,8
7,0-8,8
red – yel-
low
yellow
– red-
dish-pur-
ple
Xylenol or-
ange
XO
OH O
NaO3S
N
OH
O
OH O
N
OH O
OH
O -1,1 (=OH+)
6,4 (4-OH)
[21]
6,4-10,4 yellow –
orange-red
Xylenol blue XB OH O
NaO3S
1,5 (=OH+)
9,5 (4-OH)
[21]
1,2-2,8
8,0-9,6
red –
yellow
yellow –
blue
Phenol red PR OH O
NaO3S
1,2 (=OH+)
8,4 (4-OH)
[21]
6,8-8,4 yellow –
red
Тable 1
THE IMPREGNATED FIBROUS CHEMISORBENTS FOR COLORIMETRIC DETECTION OF THE SULFUR DIOXIDE
42 ISSN 2708-129X. Укр. хім. журн., 2022
PHISICAL CHEMISTRY
Table 2
Color of samples ІFCS-І
Initial “Responded”
Am
Ind
MEA PEPA HMTA MEA PEPA HMTA
Az - - - -
AL
- - - -
LA
MO - - - -
MR - - - -
TrO
TrOO - -
TrOOO
CoR
BCG - -
BCP - -
BXB
BPB - -
BPR - -
BTB - -
CrR - -
XO
XB - - - -
PR - - - -
The color version of the table can be viewed in the online version of the journal https://ucj.
org.ua/index.php/journal
Abbreviation Ind see Table 1
MEA – monoethanolamine; HMTA – hexamethylenetetramine; polyethylenepolyamine –
PEPA
R. E. Khoma, A. A.-A. Ennan, T. S. Bienkovska, R. M. Dlubovskii, S. V. Vodzinskii, T. V. Mykhailova
43https://ucj.org.ua
UCJ № 1 / Vol. 88
Ta
bl
e
3
C
ol
or
im
et
ri
c f
un
ct
io
ns
R
, G
, B
o
f t
he
in
iti
al
a
nd
u
se
d
ІF
C
S-
І s
am
pl
es
in
p
re
se
nc
e
of
S
O
2
In
iti
al
“R
es
po
nd
ed
”
A
m
M
EA
PE
PA
H
M
TA
M
EA
PE
PA
H
M
TA
M
EA
PE
PA
H
M
TA
M
EA
PE
PA
H
M
TA
M
EA
PE
PA
H
M
TA
M
EA
PE
PA
H
M
TA
In
d
R 0
G
0
B 0
R r
G
r
B r
A
z
98
-
14
1
-
-
15
9
-
-
16
8
-
-
16
7
-
-
15
7
-
-
A
l
11
5
-
94
59
-
90
11
5
-
15
5
12
8
-
14
7
63
-
11
6
10
0
-
13
5
L
75
1
11
9
85
17
3
17
3
95
25
4
17
7
10
5
17
8
19
5
11
7
22
8
19
8
11
8
18
3
19
1
M
O
25
2
-
-
98
-
-
3
-
-
25
0
-
-
12
9
-
-
27
-
-
M
R
25
2
-
-
12
3
-
-
1
-
-
23
4
-
-
19
6
-
-
15
6
-
-
Tr
O
23
7
25
5
23
4
12
2
25
4
22
1
4
1
78
24
5
23
3
20
2
16
7
24
0
21
2
7
21
4
17
9
Tr
O
O
24
2
25
4
-
76
9
-
5
47
-
24
5
22
9
-
88
22
9
-
7
18
7
-
Tr
O
O
O
22
1
25
4
20
8
8
58
69
36
86
95
20
9
24
0
21
2
10
8
23
2
20
9
99
19
1
17
2
C
oR
24
8
25
4
19
5
3
44
87
20
70
97
24
4
22
6
19
5
3
22
7
19
9
15
19
2
16
7
BC
G
17
1
-
11
2
16
9
-
18
9
13
1
-
79
20
6
-
15
2
23
9
-
18
3
16
6
-
BC
P
38
17
2
-
61
97
-
14
6
20
1
-
10
1
19
9
-
11
3
21
4
-
11
7
19
7
-
BX
B
14
1
30
84
72
95
16
3
19
3
16
5
12
2
13
7
15
2
16
1
20
7
17
8
10
6
76
11
0
BP
B
-
2
66
-
15
7
16
9
-
25
4
20
0
-
21
0
18
4
21
4
20
9
-
19
5
16
9
BP
R
54
25
4
-
37
11
4
-
13
2
21
5
-
76
25
4
-
10
2
11
4
-
14
1
21
5
-
BT
B
46
1
68
12
0
22
9
14
4
16
9
25
0
16
5
92
18
2
17
8
14
4
22
0
19
3
12
1
13
9
13
8
C
rR
12
1
10
0
90
38
68
87
10
2
20
2
11
6
22
6
20
2
18
2
11
3
97
17
3
24
13
6
14
8
XO
13
8
10
4
-
72
66
-
10
2
14
9
-
18
8
21
5
-
12
2
19
2
-
97
16
0
-
X
B
-
8
18
3
-
22
3
11
8
-
22
8
19
3
-
21
7
19
3
-
21
7
19
9
-
20
6
18
8
PR
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
A
bb
re
vi
at
io
n
In
d
se
e T
ab
le
1
M
EA
–
m
on
oe
th
an
ol
am
in
e;
H
M
TA
–
h
ex
am
et
hy
le
ne
te
tr
am
in
e;
p
ol
ye
th
yl
en
ep
ol
ya
m
in
e
–
PE
PA
THE IMPREGNATED FIBROUS CHEMISORBENTS FOR COLORIMETRIC DETECTION OF THE SULFUR DIOXIDE
44 ISSN 2708-129X. Укр. хім. журн., 2022
PHISICAL CHEMISTRY
For IFCS-MEA-EDTA-I samples with tri
phenylmetane dyes, the colorimetric charac
teristics Xr, Zr, ∆S and AR change symbately
with the pH values of the lower limit (pH1) of
Ind color transition:
Xr = -55,72 + 13,11⋅pH1; R
2 = 0,9304;
n = 6 (except BXB),
(11)
∆S = -18270 + 2952⋅pH1; R
2 = 0,9640;
n = 6 (except BCG),
(13)
AR = -1,663 + 0,2168⋅pH1; R
2 = 0,8957;
n = 6 (except BXB),
(14)
And Gr, ∆S and AR with pK4-OH values:
Gr = -486,7 + 77,06⋅pK4-OH; R2 = 0,9468;
n = 6 (except BPR),
(15)
∆S = -21290 + 2966⋅pK4-OH; R2 = 0,9696;
n = 6 (except BCG),
(16)
AR = -1,746 + 0,1969⋅pK4-OH; R2 = 0,8354;
n = 6 (except BXB).
(17)
The indicates that during the chemisorp-
tion of sulfur dioxide by the above IFCS-I
samples, the color change of their surface oc-
curs by the Brönsted mechanism in a weak
acid medium.
During the chemisorption of SO2 by IFCS-
MEA-EDTA-I samples based on azo indica-
tors, the color change of their surface occurs
apparently through acid-base interactions be-
tween sulfur (IV) oxyanions and azo dyes as
well similar to [25].
IFCS-PEPA-I
The above- described coloring of initial
IFCS-PEPA-I samples with azo dyes in accom-
panied by the following: yellow ness changes
antibately to and relative whiteness symbately
with the pH values of the upper limit (pH2) of
Ind color transition:
G0 = 266,7 – 12,81⋅pH2; R
2 = 0,9286;
n = 5,
(18)
W0 = 34,19 + 2,441⋅pH2; R
2 = 0,9584;
n = 5.
(19)
Taking into account the data presented in
[18], the chemisorption of sulfur dioxide by
the above samples under static and dynamic
condition (takes place in the presence of “free”
water too) stops at the stage of formation of
polyammonium sulfites:
2NH2(CH2CH2NH)nH + (n+1)SO2 + (n+1)Н2О
→ [NH2(CH2CH2NH2)nH]2(SO3)n+1.
(20)
In this case, the following relations are ob-
served:
Wr = 82,14 + 0,572⋅pH2; R
2 = 0,9381;
n = 5,
(21)
∆E76 = 101,3 – 1,524⋅pH2; R
2 = 0,8574;
n = 5,
(22)
∆W = 47,95 – 1,869⋅pH2; R
2 = 0,9312;
n = 5.
(23)
The aforesaid indicates the stabilization of
azo indicators by PEPA molecules and their
ammonium cations in terms of the occurrence
of redox reactions. The color change in this
case occurs by the Brönsted mechanism.
IFCS-HMTA-I
The chemisorption of sulfur dioxide by
IFCS-HMTA-I samples occurs through con-
densation (accompanied by the oxidation S(IV)
→ S(VI)), which involves the acid-catalyzed
hydrolysis of HMTA to form aminometha
nesulfonic acid (AMSA) [26]:
R. E. Khoma, A. A.-A. Ennan, T. S. Bienkovska, R. M. Dlubovskii, S. V. Vodzinskii, T. V. Mykhailova
45https://ucj.org.ua
UCJ № 1 / Vol. 88
In this case, the colorimetric characteris-
tics Gr and Kgr of “responded” IFCS-HMTA-I
samples (Ind = triphenylmethane dyes) change
antibately to pH1 values:
Gr = 290,7 – 40,74⋅pH1; R
2 = 0,9236;
n = 4 (except BPB)
(25)
Kgr = 250,5 – 36,061⋅pH1; R
2 = 0,9786;
n = 4 (except BPB)
(26)
This indicates the formation of ion associ-
ates between AMSA zwitterions and the ani-
onic forms of the above indicators.
With increase in the pH values of the color
transition limit of azo indicators for HM-
TA-based IFCS samples, ∆S decreased (unlike
IFCS-MEA-EDTA-I samples with triphenyl-
metane dyes):
∆S = -93,78 – 364,7⋅pH2; R
2 = 0,9976;
n = 4,
(27)
∆S = -812,5 – 347,5⋅pH1; R
2 = 0,9792;
n = 4.
(28)
CONCLUSION. During the “response” of
IFCS-I samples to SO2, their decoloration takes
place (Table 2,3) as indicated by the positive
values of W and negative values of AT. As the
analytical signal of the “response” of IFCS-I
samples we chose the amount of total absorp-
tion whose absolute value for IFCS-MEA-ED-
TA-I, IFCS-PEPA-I and IFCS-HMTA-I de-
creased in the orders of indicators:
MR > ТOOO > MO ≈ BXB > BCG > BPR >
BCP > ТOO > LA > XO > AZ > BTB > ТOO;
Т0 ≈ BCG > BPB > ТOO > BXB > BTB > XB
> CoR > ТOOO > XO > BCP > CrR > BPR;
BXB > TOOO > XO > CoR > BTB > BPB >
LA > TO > AL > PB.
respectively.
Thus, the specificity of change in the colo
rimetric function of indicator impregnated
fibrous chemisorbents during the absorption
of SO2 by then has been established. The color
change of IFCS-MEA-EDTA-I samples with
triphenylmethan dyes occurs by the Brönsted
mechanism and that of azo indicators through
redox reactions with sulfite compounds. The
PEPA molecules and their ammonium ca
tions in IFCS-I stabilize azo indicators up to
the above redox transformations. For deeper
conclusions, an additional study of behavior
in SO2-Am-Ind-H2O model system is need-
ed, which will be the subject of our future re-
search.
Acknowledgement. The work was
carried out with financial support
from the Ministry of Education and
Science of Ukraine.
NN
N
N
+ H2OSO2 H3N S
O
O
O
4 46+
.
(24)
THE IMPREGNATED FIBROUS CHEMISORBENTS FOR COLORIMETRIC DETECTION OF THE SULFUR DIOXIDE
46 ISSN 2708-129X. Укр. хім. журн., 2022
PHISICAL CHEMISTRY
ІМПРЕГНОВАНІ ВОЛОКНИСТІ ХЕМОСОРБЕНТИ
ДЛЯ КОЛОРИМЕТРИЧНОЇ ДЕТЕКЦІЇ
ДІОКСИДУ СІРКИ
Р. Є. Хома1,2 , А. А.-А. Еннан1,
Т. С. Бєньковська1, Р. М. Длубовський1,
С. В. Водзінський1,2, Т. В. Михайлова1,3
1Фізико-хімічний інститут захисту навко-
лишнього середовища і людини МОН Украї-
ни та НАН України;
вул. Преображенська 3, Одеса 65082, Україна;
e-mail: eskvar@ukr.net
2Одеський національний університет імені
І. І. Мечникова;
вул. Дворянська, 2, Одеса, Україна, 65082;
email: rek@onu.edu.ua
3Фізико-хімічний інститут ім. О. В. Богат-
ського НАН України;
Люстдорфська дорога, 86, Одеса, Одеська
область 65080, Україна
У роботі наведено результати досліджень
особливостей кольорометричної поведінки
імпрегнованих волокнистих хемосорбентів
(ІВХС) кислих газів із візуальною ідентифі-
кацією моменту «спрацьовування» дина-
мічної поглинальної ємності (ІВХС-І) при
поглинанні діоксиду сірки. Хемосорбенти
одержані шляхом просочування волокни-
стих носіїв водними розчинами N-вмісних
органічних основ (Am), до складу яких до-
давали кислотно-основні індикатори (Ind).
Як об’єкти досліджень використовували
ІВХС-І на основі гексаметилентетраміну
(ІВХС-HMTA-I) та поліетиленполіаміну
(ІВХС-PEPA-I), а також ІВХС-MEA-EDTA-І
на основі моноетаноламіну (MEA) та ди-
натрієвої солі етилендіамінтетроцтової
кислоти (EDTA). Як кислотно-основні ін-
дикатори було використано наступні: азо-
літмін, алізарин (AL), лакмоїд, метиловий
оранжевий, метиловий червоний, Тропе-
олін О, Тропеолін ОО (TrOO), Тропеолін
ООО (TrOOO), конго червоний, бромкре-
золовий зелений (BCG), бромкрезоловий
пурпуровий (BCP), броксиленоловий синій
(BXB), бромфеноловий синій (BPB), бром-
феноловий червоний (BPR), крезоловий
червоний (CrR), ксиленоловий оранжевий,
ксиленоловий синій та феноловий черво-
ний. Виявлено специфіку зміни кольоромет
ричних функцій ІВХС-І під час поглинання
ними SO2. Встановлено що забарвлення
вихідних зразків ІВХС-І суттєво залежить
не лише від будови Ind, а й природи Am,
що входять до їхнього складу. Забарвлення
зразків на основі лише PEPA (Ind = TrOO,
TrOOO, BCG, BCP, BXB, BPB, BPR та CrR) та
деяких MEA (Ind = BXB) і HMTA (Ind = AL,
BXB) подібне до забарвлення водних роз-
чинів лугів. Відмінність забарвлення реш-
ти зразків від забарвлення водних розчинів
лугів з одними й тими ж Ind спричинена
специфічними взаємодіями між амонійни-
ми катіонами та аніонними формами барв-
ників. Забарвлення «спрацьованих» зраз-
ків ІВХС-MEA-EDTA-I, як і ІВХС-PEPA-I та
ІВХС-HMTA-I, по SO2 відмінні від таких же
властивостей водних розчинів бренстедов-
ських кислот. Зміна забарвлення зразків
ІВХС-MEA-EDTA-I з трифенілметановими
барвниками протікає за бренстедівським
механізмом, азо-індикаторів – за рахунок
окисно-відновних реакцій із сульфітними
сполуками. Молекули PEPA та їхні амонієві
катіони у складі ІВХС-І стабілізують азо-ін-
дикатори до вказаних редокс-перетворень.
Ключові слова: кольорометрія, волок-
нисті хемосорбенти, діоксид сірки, кислот-
но-основні індикатори.
R. E. Khoma, A. A.-A. Ennan, T. S. Bienkovska, R. M. Dlubovskii, S. V. Vodzinskii, T. V. Mykhailova
47https://ucj.org.ua
UCJ № 1 / Vol. 88
REFERENCES
1. Kats B.M., Olontsev V.F., Vihlancev A.V. А.В.,
Artushin G.A., Lazarev M.Yu., Dlubovskii
R.M., Barinova N.V. Ion-exchange filtering
gas mask with visual indication of the degree
of depletion of the gas absorber. Occupational
hygiene and occupational diseases. 1983, (7):
55–56 (in Russian).
2. Kats B.M., Dlubovskii R.M., Shevchenko V.N.
Gas sensors indicating filters. Sensor Electro
nics and Microsystem Technologies. 2006, (3):
89–94 (in Russian).
3. Kosandrovich E.G., Soldatov V.S., Shachen
kova L.N. Indicator materials based on fibrous
ion exchangers for visualizing of the sorption
resource of the chemical air cleaning filters.
Proc. National Acad. Sci. Belarus. Chem. Ser.
2020, 56 (2): 143–149 (in Russian).
doi: 10.29235/1561-8331-2020-56-2-143-149
4. Ennan A.A.-A., Khoma R.E., Dlubovskii R.M.,
Abramova N.M., Naumchak V.A. Composi-
tion for impregnating filter material. Patent
UA94660, IPC В01D 39/00, no u201405985,
25.11.2014 (in Ukrainian).
5. Ennan A.A.-A., Khoma R.E., Dlubovskii R.M.,
Abramova N.M., Berezovska T.I. Composi-
tion for impregnating filter material. Patent
UA 100677, IPC В01D 39/00, no u201413733,
10.08.2015 (in Ukrainian).
6. Ennan A.A.-A., Khoma R.E., Dlubovskii R.M.,
Abramova N.M., Berezovska T.I. Composi-
tion for impregnating filter material. Patent
UA 112848, IPC В01D 39/00, no a201305812,
10.11.2016. (in Ukrainian).
7. Ivanov V.M., Kuznetsova O.V. Chemical chro-
maticity: potential of the method, application
areas and future prospects. Russ. Chem. Rev.
2001, 70(5): 357–372.
doi: 10.1070/RC2001v070n05ABEH000636
8. Dolomatov M.Yu., Jarmuhametova G.U., Do
lomatova L.A. The interaction of color and
physic-chemical properties of hydrocarbon
systems in colorimetric systems RGB and
XYZ. Applied Physics. 2008, (4): 43–48 (in Rus-
sian).
9. Monogarova O.V., Oskolok K.V., Apyari V.V.
Colorimetry in chemical analysis. J. Analyt.
Chem. 2018, 73(11): 1076–1084.
doi: 10.1038/166623a0
10. Chebotaryov A.N., Snigur D.V., Bevziuk K.V.,
Efimova I.S. The trends analysis of chemi-
cal chromaticity method evolution (review).
Methods Objects Chem. Anal. 2014; 9(1): 4-11.
doi: 10.17721/moca. 2014, 4–11 (in Russian).
11. Chernousova O.V., Rudakov O.B. Digital ima
ges in analytical chemistry for quantitative and
qualitative analysis. Chemistry, physics and me-
chanics of materials. 2019; (2): 55–125 (in Rus-
sian).
12. Pimenov S.D., Sizov A.I., Mzokov G.V., Stroi-
televa A.D. Method for determining the white
ness of cellulosic materials using a scanner.
Izvestia Sankt-Peterburgskoj lesotehniceskoj
akademii. 2020. N 232: 169–180 (in Russian).
13. Ennan A.A.-A., Khoma R.E., Dlubovskii R.M.,
Abramova N.M. The method of impregnation
of the filter material. Patent UA147596, IPC
В01D 39/00, no u20200634. 27.05.2021 (in
Ukrainian).
14. Ennan A.А., Dlubovskiy R.M., Abramova
N.N., Khoma R.E. Chemisorption of Sulfur
Dioxide by Polyethylenepolyamine Impreg-
nated Fibrous Materials. 2. The Study of Wa-
ter Vapor Influence on Preadsorbtion SO2
Chemisorption by Fibrous Materials. Vіsn.
Odes. nac. unіv., Hіm. 2014, 19(3): 20 (in Rus-
sian)
doi: 10.18524/2304-0947.2014.3(51).40356.
15. Processing of JPEG photos online. Available at
https://www.imgonline.com.ua
16. Schults E.V., Monogarova O.V., Oskolok K.V.
Digital colorimetry: analytical possibilities
and prospects of use. Moscow Univ. Chem.
Bull. 2019, 74(2): 55–62 (in Russian).
17. Ennan A.A.-A., Dlubovskii R.M., Khoma R.E.
Water role in the gases chemosorporation
processes by sorption-active materials. Vіsn.
THE IMPREGNATED FIBROUS CHEMISORBENTS FOR COLORIMETRIC DETECTION OF THE SULFUR DIOXIDE
48 ISSN 2708-129X. Укр. хім. журн., 2022
PHISICAL CHEMISTRY
Odes. nac. unіv., Hіm. 2021, 26(3): 6–28 (in
Ukrainian).
doi: 10.18524/2304‑0947.2021.3 (79).240717
18. Ennan A.A.-A., Khoma R.E., Dlubovskiy R.M.,
Zakharenko Y.S., Abramova N.N., Mikhay-
lova T.V., Barbalat D. O. Effect of Modifying
Additives on Chemosorption of Sulfur (IV)
Oxide by Fibrous Material Impregnated with
Polyethylenepolyamine. Vіsn. Odes. nac. unіv.,
Hіm. 2020, 25(4): 56–73 (in Russian).
doi: 10.18524/2304-0947.2020.4(76).216927
19. Sabnis R. W. Handbook of acid-base indica-
tors. Boca Raton: CRC Press, 2008. 416.
20. Zevackiy U.E., Samoylov D.V., Ruzanov D.О.
Assessment of application field of photoemis-
sive method for determination of pKa values
for organic compounds. Bull. Saint Petersburg
State Inst. Technol. 2010, (9): 54–59 (in Rus-
sian).
21. Snigur D.V. The use of tristimulus colorimetry
functions in the study of the acid-base equi-
libria in solutions of organic compounds. The-
sis of Ph.D dissertation, 25.00.02. Uzhgorod,
2017. 140 (in Ukrainian).
22. Naseem K., Farooqi Z.H., Begum R., Irfan A.
Removal of congo red dye from aqueous me-
dium by its catalytic reduction using sodium
borohydride in the presence of various inor-
ganic nano-catalysts: A review. J Clean Prod.
2018, 187: 296–307.
doi: 10.1016/j.jclepro.2018.03.209.
23. Aragoni M.C., Arca M., Crisponi G., Nurchi
V.M., Silvagni R. Characterization of the ioni-
zation and spectral properties of sulfonephtha-
lein indicators. Correlation with substituent
effects and structural features. Part II. Talanta.
1995; 42(8): 1157–1163. doi: 10.1016/0039-
9140(95)01559-t
24. Shokrollahi A., Gohari M., Ebrahimi F. De-
termination of Acidity Constants of p-Ro-
solic acid and Bromoxylenol Blue by Solu-
tion Scanometric Method. Analyt. Bionalyt.
Chem. Res. 2018; 5(1): 67-79. doi: 10.22036/
ABCR.2017.89026.1153
25. Liu W., Hu W., Liu J. Study on the photoreduc-
tive decolorization of azo dyes by sulfite aqua.
AIP Conf. Proc. 2017. 1794(1): 050006-1 –
050006-8.
doi: 10.1063/1.4971952
26. Khoma R.E., Shestaka A.A., Shishkin O.V.,
Baumer V.N., Brusilovskii Yu.E., Koroeva L.V.,
Ennan A.A., Gel’mbol’dt V.O. Features of in-
teraction in the sulfur(IV) oxide-hexamethyl-
enetetramine-water system: A first example of
identification of the product with a sulfur-car-
bon bond. Russ. J. Gen. Chem. 2011. 81(3):
620. doi: 10.1134/S1070363211030352
Cтаття надійшла 17.11.2021
|
| id | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-399 |
| institution | Ukrainian Chemistry Journal |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-07-23T01:07:42Z |
| publishDate | 2022 |
| publisher | V.I.Vernadsky Institute of General and Inorganic Chemistry |
| record_format | ojs |
| resource_txt_mv | ucjorgua/94/b728f97eea4a67024bbd7c5ed2b1ec94.pdf |
| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-3992026-07-22T08:23:48Z THE IMPREGNATED FIBROUS CHEMISORBENTS FOR COLORIMETRIC DETECTION OF THE SULFUR DIOXIDE Khoma, Ruslan Ennan, Alim Bienkovska, Tetyana Dlubovskii, Ruslan Vodzinskii, Sergey Mykhailova, Tetiana colorimetry, fibrous chemisorbents, sulfur dioxide, acid-base indicators. The paper presents the research results on the colorimetric behavior of impregnated fibrous chemisorbents (IFCS-I) of acid gases with visual identification of the dynamic absorption capacity “response” moment during the absorption of sulfur dioxide. Chemisorbents were obtained by impregnation of fibrous carriers by N-containing organic bases aqueous solutions with adding acid-base indicators (Ind). IFCS-I based on hexamethylenetetramine (IFCS-HMTA-I) and polyethylenepolyamine (IFCS-PEPA-I), as well as IFCS-MEA-EDTA-I based on monoethanolamine (MEA) and the disodium salt of ethylenediaminetetraacetic acid (EDTA) were used. The change specificity of colorimetric functions of indicator impregnated fibrous chemisorbents during their absorption of SO2 is revealed. IFCS-I original samples color significantly depends not only on the structure of Ind, but also the nature of amines (MEA, HMTA and PEPA), which are part of them. The color of the “response” samples of IFCS-MEA-EDTA-I, IFCS-PEPA-I and IFCS-HMTA-I, differ from the same properties of Bronsted acids aqueous solutions. The color change of azo-indicators occurs due to redox reactions with sulfite compounds. PEPA molecules and their ammonium cations in the composition of IFCS-I stabilize azo-indicators to these redox transformations. V.I.Vernadsky Institute of General and Inorganic Chemistry 2022-02-16 Article Article Physical chemistry Физическая xимия Фізична xімія application/pdf https://ucj.org.ua/index.php/journal/article/view/399 10.33609/2708-129X.88.01.2022.35-48 Ukrainian Chemistry Journal; Vol. 88 No. 1 (2022): Ukrainian Chemistry Journal; 35-48 Украинский химический журнал; ##issue.vol## 88 ##issue.no## 1 (2022): Ukrainian Chemistry Journal; 35-48 Український хімічний журнал; Том 88 № 1 (2022): Український хімічний журнал; 35-48 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/399/210 Copyright (c) 2022 Ruslan Khoma, Alim Ennan, Tetyana Bienkovska, Ruslan Dlubovskii, Sergey Vodzinskii, Tetiana Mykhailova https://creativecommons.org/licenses/by-nc/4.0 |
| spellingShingle | Khoma, Ruslan Ennan, Alim Bienkovska, Tetyana Dlubovskii, Ruslan Vodzinskii, Sergey Mykhailova, Tetiana THE IMPREGNATED FIBROUS CHEMISORBENTS FOR COLORIMETRIC DETECTION OF THE SULFUR DIOXIDE |
| title | THE IMPREGNATED FIBROUS CHEMISORBENTS FOR COLORIMETRIC DETECTION OF THE SULFUR DIOXIDE |
| title_full | THE IMPREGNATED FIBROUS CHEMISORBENTS FOR COLORIMETRIC DETECTION OF THE SULFUR DIOXIDE |
| title_fullStr | THE IMPREGNATED FIBROUS CHEMISORBENTS FOR COLORIMETRIC DETECTION OF THE SULFUR DIOXIDE |
| title_full_unstemmed | THE IMPREGNATED FIBROUS CHEMISORBENTS FOR COLORIMETRIC DETECTION OF THE SULFUR DIOXIDE |
| title_short | THE IMPREGNATED FIBROUS CHEMISORBENTS FOR COLORIMETRIC DETECTION OF THE SULFUR DIOXIDE |
| title_sort | impregnated fibrous chemisorbents for colorimetric detection of the sulfur dioxide |
| topic_facet | colorimetry fibrous chemisorbents sulfur dioxide acid-base indicators. |
| url | https://ucj.org.ua/index.php/journal/article/view/399 |
| work_keys_str_mv | AT khomaruslan theimpregnatedfibrouschemisorbentsforcolorimetricdetectionofthesulfurdioxide AT ennanalim theimpregnatedfibrouschemisorbentsforcolorimetricdetectionofthesulfurdioxide AT bienkovskatetyana theimpregnatedfibrouschemisorbentsforcolorimetricdetectionofthesulfurdioxide AT dlubovskiiruslan theimpregnatedfibrouschemisorbentsforcolorimetricdetectionofthesulfurdioxide AT vodzinskiisergey theimpregnatedfibrouschemisorbentsforcolorimetricdetectionofthesulfurdioxide AT mykhailovatetiana theimpregnatedfibrouschemisorbentsforcolorimetricdetectionofthesulfurdioxide AT khomaruslan impregnatedfibrouschemisorbentsforcolorimetricdetectionofthesulfurdioxide AT ennanalim impregnatedfibrouschemisorbentsforcolorimetricdetectionofthesulfurdioxide AT bienkovskatetyana impregnatedfibrouschemisorbentsforcolorimetricdetectionofthesulfurdioxide AT dlubovskiiruslan impregnatedfibrouschemisorbentsforcolorimetricdetectionofthesulfurdioxide AT vodzinskiisergey impregnatedfibrouschemisorbentsforcolorimetricdetectionofthesulfurdioxide AT mykhailovatetiana impregnatedfibrouschemisorbentsforcolorimetricdetectionofthesulfurdioxide |