The decomposition mechanism for TDO in aqueous solution within 25–95?°C temperature range

Article abstract of DOI:10.1016/j.cplett.2019.136603

In this paper, the decomposition mechanism of Thiourea dioxide (TDO) aqueous solution in 25–95 °C temperature range were studied in detail by electrode potential method, time-of-flight mass spectrometry (TOF-MS), Raman spectroscopy and quantum chemistry calculations. Oxidation-Reduction Potential (ORP) were used to reveal the effect of temperature on the reduction performance of TDO. TOF-MS and Raman spectroscopy were used to determine the chemical constituents of TDO solution at different temperatures. Quantum chemistry calculations were used to assign Raman spectra. This work provides solid theoretical and experimental evidences for the decomposition mechanism of TDO in moisture-hot condition.

Full text of DOI:10.1016/j.cplett.2019.136603

ChemicalPhysicsLetters731(2019)136603
Contents lists available at ScienceDirect
Chemical Physics Letters
journal homepage: www.elsevier.com/locate/cplett
Research paper
The decomposition mechanism for TDO in aqueous solution within 25–95 °C
temperature range
⁎
Jianzhong Shaoa, Xiaoyun Liua, Sergei V. Makarovc, Kemei Peia,b,
a Engineering Research Center for Eco-Dyeing and Finishing of Textiles, Ministry of Education, Zhejiang Sci-Tech University, Hangzhou 310018, China
b Department of Chemistry, Zhejiang Sci-Tech University, Hangzhou 310018, China
c Ivanovo State University of Chemistry and Technology, Sheremetevsky str.7, 153000 Ivanovo, Russia
H I G H L I G H T S
There are three stages for TDO decomposition in water within 25 °C–95 °C.
•
The reducing substance in the instantaneous system increases the reduction performance increases.
•
TDO decomposes from 55 °C, and H2SO2 can be oxidized into H2SO3 and H2SO4 within 55 °C–95 °C.
•
A B S T R A C T
In this paper, the decomposition mechanism of Thiourea dioxide (TDO) aqueous solution in 25–95 °C temperature range were studied in detail by electrode potential
method, time-of-flight mass spectrometry (TOF-MS), Raman spectroscopy and quantum chemistry calculations. Oxidation-Reduction Potential (ORP) were used to
reveal the effect of temperature on the reduction performance of TDO. TOF-MS and Raman spectroscopy were used to determine the chemical constituents of TDO
solution at different temperatures. Quantum chemistry calculations were used to assign Raman spectra. This work provides solid theoretical and experimental
evidences for the decomposition mechanism of TDO in moisture-hot condition.
1. Introduction
temperature [6,7]. Up to now, the reductive decomposition perfor-
mance of TDO at different pH values has been studied in detail, but it
has not received much attention under moisture-hot conditions [8–12].
Therefore, it is of great significance to study the decomposition process
of TDO in the moisture-hot environment.
Thiourea dioxide (TDO), as a substitute for sodium hyposulfite
(Na2S2O4), was known by strong reducibility, good thermal stability,
convenient storage and transportation properties. TDO has lots of ap-
plications, such as a reducing agent, a bleaching decolorizing agent, a
plastic stabilizer, an organic synthetic antioxidant, and a photosensitive
material activator et al. [1–3]. In the printing and dyeing industry, TDO
is potentially used as a reducing agent for polyester fabric discharge
printing because of its non-polluting during application. The polyester
fabric reducing agent discharge printing method is a reduction reaction
between the reducing substance produced by the decomposition of the
reducing agent under the moisture-hot condition and the polyester
coloring dye, thereby destroying the chromogenic group and achieving
the decolorizing effect [4,5]. The decomposition process of the reducing
agent under the moisture-hot condition affects its application process
on the polyester fabric directly. Shao et al found the wet grinding
process endowed TDO with smaller particle sizes and narrower size
distributions in the presence of dispersants, and TDO reduction per-
formance became stronger with increasing aqueous solution
In this work, the decomposition mechanism of TDO in aqueous so-
lution with different temperature was investigated by electrode po-
tential method, time-of-flight mass spectrometry (TOF-MS) and Raman
spectroscopy experimental techniques. In order to assign the TOF-MS
and Raman spectra effectively, quantum chemistry calculations have
been done in detail. This work will provide more theoretical and ex-
perimental supports for the friendly reducing agent TDO which has
been applied to polyester fabric discharge printing successfully, and
effective techniques to explore the decomposition mechanism.
2. Experiments and calculations
15 g TDO was added to 500 mL distilled water. The above solution
was placed in a SHA-C constant temperature oscillating water bath
which can be heated to a set temperature, and the redox potential of the
⁎ Corresponding author.
E-mail address: peikemei@zstu.edu.cn (K. Pei).
https://doi.org/10.1016/j.cplett.2019.136603
Received 1 March 2019; Received in revised form 11 July 2019; Accepted 11 July 2019
Availableonline12July2019
0009-2614/©2019PublishedbyElsevierB.V.

J. Shao, et al.
ChemicalPhysicsLetters731(2019)136603
solution was measured. A pHS-3C precision pH meter with type 501
ORP redox electrode and L-201-C pH composite electrode, was used to
determine the real-time temperature and redox potential of the TDO
solution. ESI-TOF-MS (Waters Xevo G2-S TOF) was used to get the
molecular weight information about the TDO water solution with 500
ug/ml concentration. The condition 130 °C source temperature and
250 °C desolvation temperature with positive mode was used in TOF-
MS measurements. Raman spectra of TDO water solution were mea-
sured in real time by a Raman microscope with 488 nm excitation
wavelength. In a temperature-controlled quartz cell, a saturated solu-
tion of TDO was prepared. Na2SO4, Na2SO3, Na2S2O3, NaHSO3,
(NH2)2CO, Na2CO3 saturated solution were prepared and the Raman
spectra were collected by Nicolet 960 Fourier transform Raman spec-
troscopy with 1064 nm excitation wavelength.
Quantum chemistry calculations were used to get those frequencies
to assign the Raman and TOF-MS spectra with B3LYP/cc-PVDZ level.
The initial models for calculations were constructed by Chemoffice
software. Once structure optimization completed, the harmonic fre-
quencies were examined to confirm that the point is the true minimum
Fig. 1. Effect of temperature on the redox potential of TDO in water.
85oC
8.0x106
*
4.0x106
*
*
0.0
8.0x106
65oC
*
*
*
4.0x106
0.0
8.0x106
55oC
*
4.0x106
*
*
*
0.0
8.0x106
25oC
*
4.0x106
*
0.0
0
200
400
600
800
1000
1200
1400
1600
1800
2000
m /z
Fig. 2. ESI+-TOF-MS spectra of TDO solution at four temperatures. Asterisks (*) label for the interfering ions.
2

J. Shao, et al.
ChemicalPhysicsLetters731(2019)136603
or not. All calculations were carried out with the GAUSSIAN 09 package
[13].
Table 1
Identification of ESI+-TOF-MS spectra for TDO solution at four temperatures,
and the important data have been highlighted in bold.
3. Results and discussion
m/z
Assignment
m/z
Assignment
25 °C
131
3.1. Effect of temperature on the TDO redox potential
[II + Na]+
[I3 + Na]+
[I5 + Na]+
[I7 + Na]+
[I9 + Na]+
[I11 + Na]+
[I13 + Na]+
[I15 + Na]+
[I17 + Na]+
239
[II2 + Na]+
[I4 + Na]+
[I6 + Na]+
[I8 + Na]+
[I10 + Na]+
[I12 + Na]+
[I14 + Na]+
[I16 + Na]+
347
455
Redox potential reflects the oxidation-reduction performance of the
chemical compounds. The effect of temperature on the TDO redox po-
tential will influence the application effect of TDO in discharge printing
of polyester. In this work, the redox potential of TDO under different
temperatures was measured. Fig. 1 shows that the oxidation-reduction
electrode potential of TDO water solution decreases with the tem-
perature increase, and these properties indicate that the reduction
performance will be stronger when the temperature increases. At the
55 °C, the oxidation-reduction electrode potential of TDO water solu-
tion shows a sharp decline and a decomposition reaction may occur.
The oxidation-reduction electrode potential of TDO water solution de-
clines slowly in the 65–80 °C range. When the temperature reach to
80 °C, a significant drop was found. Three decomposition reaction
stages for TDO in water within 25–95 °C temperature range was found
obviously. The first stage is in 25–55 °C; the second stage is in 55–80 °C
and the third stage is in 85–95 °C temperature ranges respectively.
Liu et al found that the decomposition rate of TDO at a certain
temperature can be determined by High Performance Liquid
Chromatography (HPLC) at different temperatures and found the de-
composition rate accelerated with the temperature increasing [7]. It is
apparent from the above redox potential results that as the temperature
increases, the reductive performance is enhanced. This is very ad-
vantageous for the application of TDO to polyester fabric discharge
printing, because the discharge printing usually uses short steaming.
Steaming time is generally 10–20 min, and it needs a high decomposi-
tion rate and a short-time decomposition of reducing substances to
react rapidly with the ground color dye to destroy the chromophores.
563
671
779
887
995
1103
1319
1537
1753
1211
1427
1645
1837
55 °C
131
[II + Na]+
[II + K]+
[I3 + Na]+
[I5 + Na]+
[I7 + Na]+
[I9 + Na]+
[I11 + H]+
[I12 + Na]+
[I17 + H]+
135
191
455
[II + NH4]+
[II + H2SO3 + H]+
[I4 + Na]+
147
347
563
671
[I6 + Na]+
779
887
[I8 + Na]+
995
1103
1211
1427
[I10 + Na]+
[I11 + Na]+
[I13 + Na]+
1189
1319
1837
65 °C
135
[II + NH4]+
147
[II + K]+
191
[II + H2SO3 + H]+
[II2 + 2H2O + Na]+
[I10 + Na]+
246
[3H2SO3 + H]+
[3H2SO4 + Na]+
[I11 + H]+
274
318
1103
1211
1319
1837
85 °C
187
1189
1297
1405
[I11 + Na]+
[I12 + H]+
[I12 + Na]+
[I13 + H]+
[I17 + H]+
[2H2SO3 + Na]+
295
[3H2SO4 + H]+
202
[2H2SO3 + K]+
the Raman spectral characteristics of TDO aqueous solution don’t
change obviously from 25 °C to 50 °C, which indicates that TDO solu-
tion remains relatively stable at this stage. From 55 °C, the Raman
spectrum of TDO solution has a new peak of 1055 cm−1, and the in-
tensity of the 601 cm−1 peak is significantly reduced. These phenomena
indicate that the TDO in water solution begins to decompose about
55 °C. Fig. 5 presents the Raman spectra of TDO solution at 55 °C, 65 °C,
and 75 °C. It’s obviously that the TDO solution undergoes a significant
3.2. TOF-MS analysis for the temperature effect on TDO
According to the effect of temperature on the TDO reduction po-
tential (Fig. 1), it can be clearly seen that the state of the solution
changes significantly at the four temperatures (25 °C, 55 °C, 65 °C, and
85 °C). Therefore, TOF-MS experiments were carried out under those
four temperatures. Fig. 2 is the positive ion mass spectra of TDO water
solution at 25 °C, 55 °C, 65 °C, 85 °C. Table 1 shows the detailed iden-
tification of the positive ion mass spectra at the four temperatures. The
results show that at 25 °C temperature, the state of TDO in aqueous
solution is the mixture of the self-polymerized clusters and the single
molecule. When the temperature rises to 55 °C, the TDO aqueous so-
lution begins to change, both the single molecule and the clusters de-
decomposition reaction from 55 °C to 75 °C. 601 cm−1, 804 cm−1
,
1425 cm−1 are greatly reduced, and 731 cm−1, 980 cm−1, 1055 cm−1
new peaks are appeared. The strong peak 1004 cm−1 is still strong from
25 °C to 75 °C. Fig. 6 shows that at the stage of 75 °C-85 °C, the char-
acteristic peaks of 601 cm−1, 804 cm−1, 1121 cm−1, and 1425 cm−1 at
25 °C are disappeared. 731 cm−1 and 980 cm−1 peaks are strong. All
the 1004 cm−1, 1040 cm−1, 1055 cm−1 and 1089 cm−1 peaks have
certain strength. When the solution was heated to 95 °C, there are only
two strong (731 cm−1, 980 cm−1) peaks and 1004 cm−1 weak peak in
the whole Raman spectrum.
+
compose, and NH4 ions or H2SO3 information appear in the solution.
As the temperature is further increased to 65 °C, the single molecule and
+
clusters continue to decompose. NH4 ions, H2SO3, H2SO4 appear in
the solution. When the solution is heated to 85 °C, all the single mole-
cule and clusters are almost completely decomposed. H2SO2, H2SO3 and
H2SO4 are found in the solution above 85 °C.
Hydrogen bonding is central to understanding microscopic struc-
tures and functions in many molecular and supermolecular systems
[14]. Based on the TOF-MS, Raman spectrum, and our previous work,
intermolecular hydrogen bonding interaction plays an important role to
form the clusters in TDO water solution [15]. According to our previous
research, the Raman spectrum at 25 °C was assigned in detail [15].
804 cm−1 comes from II single molecule (II = NH2NHSO2H).
1004 cm−1 and 1425 cm−1 come from In-cyc clusters (I = (NH2)2SO2).
601 cm−1 and 1121 cm−1 peaks are contributed by II molecule and In-
cyc clusters. However, from 25 °C to 75 °C, the strength of the
1004 cm−1 peak don’t decrease with the decomposition of the clusters.
At 85 °C, the clusters are decomposed completely, the 1004 cm−1peak
still maintains a certain strength. As Table 2 shows, 1004 cm−1 is also
the characteristic peak of urea. According to the literature [16], urea
will undergo hydrolysis reaction at 80 °C to produce ammonia and
3.3. Raman spectroscopy analysis for the temperature effect on TDO
According to the results of electrode potential, the decomposition
process of TDO solution from 25 °C to 95 °C can be roughly divided into
three stages: 25–55 °C, 55–75 °C, 75–95 °C. TDO water solution has
been real-time detected by Raman spectroscopy at a series of tem-
peratures, as Figs. 3–5 shown. Table 2 lists the experimental Raman and
B3LYP/cc-PVDZ calculated vibrational frequencies (500–2000 cm−1
region) for possible chemical components lying in TDO solution at
different temperatures. Fig. 4 shows the Raman spectra of TDO water
solution at 25 °C, 50 °C and 55 °C. It can be seen clearly from Fig. 4 that
3

J. Shao, et al.
ChemicalPhysicsLetters731(2019)136603
Fig. 3. The Raman spectra of TDO in aqueous solution at 25 °C, 50 °C, 55 °C. Asterisks (*) label for the laser interfering line.
carbon dioxide. Here, the change of the 1004 cm−1 peak with tem-
perature reflects in the process that TDO water solution will produce
urea during the heating process and urea will decompose at 80 °C. As
we noticed, 1089 cm−1 starts at 25 °C and disappears at 85 °C, which
may be derived from CO32–. Comparing the calculated and the experi-
mental Raman characteristic peaks of the possible sulfur-containing
compounds, it was found that only H2SO3 or NaHSO3 have the
731 cm−1 peak in the Raman spectra calculations. Herein, we consider
aqueous solution at 55 °C. The results of TOF-MS and Raman spectro-
scopy explain the significant change in the redox potential of the TDO
aqueous solution at 55 °C well.
From 55 °C to 65 °C, the 731 cm−1 (H2SO3), 980 cm−1 (SO42−),
1055 (HSO4−type II) peaks are found more strong in the solution.
601 cm−1 (In-cyc clusters and II), 1425 cm−1 (In-cyc clusters) are
weakened significantly, and the 804 cm−1 (II) peak almost completely
disappears, and 1004 cm−1 (In-cyc clusters or urea) is still strong from
25 °C to 75 °C. These facts show that, when the TDO aqueous solution is
heated to 65 °C the II single molecule is almost decomposed, and the
amount of In-cyc clusters is greatly reduced. However, there is still a
certain number of clusters presented in the solution, and the TDO
aqueous solution contains a large amount of H2SO3, SO42−. 1004 cm−1
is the bending vibration peak of NH2-C-NH2 in II, In-cyc and urea. The
reason why 1004 cm−1 is still strong from 25 °C to 75 °C can be ex-
plained as the urea produced during the decomposition of In-cyc and II,
so that the peak of 1004 cm−1 keeps relative strong between 25 °C and
75 °C. The results of TOF-MS also indicate that when the temperature is
further increased to 65 °C, II and In-cyc clusters continue to decompose,
and NH4+, H2SO2, H2SO3 and H2SO4 are produced. From 65 °C to 75 °C,
the Raman spectrum of the solution don’t not change significantly, in-
dicates that the properties of the TDO aqueous solution from 65 °C to
75 °C are essentially the same. Raman and TOF-MS results are con-
sistent with the fact that the redox potential maintains a smooth var-
iation over this temperature range.
that the 731 cm−1 peak is originated from H2SO3 or NaHSO3. HSO4
2−
aqueous solutions in different conditions have two hydrated forms of
type (I) and type (II), Type (I) has a Raman peak at 1040 cm−1 and
Type (II) has a Raman peak at 1055 cm−1 [17]. From 75 °C to 95 °C, the
1055 cm−1 peak shifts to 1040 cm−1, which can be explained as the
solution properties changed with the temperature, and the hydrated
form of HSO4 is changed from Type (II) to Type (I). 980 cm−1 fre-
−
2−
quency comes from SO4
.
3.4. Decomposition mechanism
Based on the results of electrode potential, TOF-MS and Raman,
when the TDO aqueous solution is heated from 25 °C to 95 °C, and there
are three major change stages. The first stage is that the TDO solution is
substantially stable from 25 °C to 55 °C. Starting from 55 °C, new peaks
of 731 cm−1 (H2SO3) and 1055 cm−1 (type II of HSO42−) began to
−
appear. The results show that H2SO3 and HSO4 are formed. The re-
From 75 °C to 85 °C, the Raman spectra of the TDO aqueous solution
sults of TOF-MS showed that H2SO3 information appeared in the TDO
4

J. Shao, et al.
ChemicalPhysicsLetters731(2019)136603
Fig. 4. The Raman spectra of TDO in aqueous solution at 55 °C, 65 °C, 75 °C. Asterisks (*) label for the laser interfering line.
2−
has undergone tremendous changes. The Raman peaks from In-cyc
clusters and II single molecule are all disappeared. 731 cm−1 (H2SO3)
and 980 cm−1q (SO42−) are greatly enhanced, and the 1055 cm−1
almost only H2SO3 and SO4
signals in the TDO aqueous solution.
In order to clarify the change in the TDO aqueous solution with
temperature, we measured that the pH value of 500 ug/ml TDO aqu-
eous solution in 25–95 °C, as Fig. 6 shown. The results show that the pH
value of the solution gradually decreases in the heating process, reaches
the lowest about 75–85 °C, and then increases gradually. The pH
changing results indicate that the acidity of the TDO aqueous solution
first increases and then weakens from 25 °C to 95 °C, which can be
explained by the hydrolysis of urea to produce ammonium carbonate
and decomposes to produce ammonia and CO2. The ammonia product
dissolved in water to consume H+ leads to in the pH value increased.
The pH conclusion confirmed the analysis results of TOF-MS and the
Raman spectra. In summary, the decomposition process of the TDO
aqueous solution between 25 °C and 95 °C temperature can be described
by the following four chemical equations:
−
−
(HSO4
)
peak split into 1040/1055 cm−1 (HSO4
) peaks. The
1004 cm−1 (NH2-C-NH2) peak intensity decreased sharply, and
1089 cm−1 (CO32–) has a certain intensity peak. The results show that a
2−
large amount of H2SO3 and SO4
ions exist, and In-cyc and II are
decomposed completely in the TDO aqueous solution at 85 °C.
According to the literature, HSO4 ions have a 1055/1040 cm−1
−
−
spectral pair in aqueous solution because HSO4 has two hydrated
forms in aqueous solution. 1055 cm−1 corresponds to HSO4−(type II),
and 1040 cm−1 corresponds to HSO4−.H2O (type I), and this change
may come from the pH value of the solution. The change of 1055/
1040 cm−1 spectral pair shows that from 75 °C to 95 °C the solution
changed significantly. 1004 cm−1 (NH2-C-NH2) peak sharply reduced
and 1089 cm−1 (CO32–) has a certain intensity peak because around
85 °C, In-cyc and II decomposition are completed and urea decomposite
from 80 °C to produce ammonium and carbonate. The TOF-MS results
show that when the solution was heated to 85 °C, the II single molecule
and the clusters are almost completely decomposed. Information about
H2SO3 and H2SO4 are found in TOF-MS spectrum. As the temperature
continues to rise to 95 °C, Raman spectroscopy shows that there are
NH2NHCSO2H + H2O = 2H2SO2 + 2(NH2)2CO (55 °C–80 °C)
3H2SO2 + 2O2 = 2H2SO3 + H2SO4 (55 °C–95 °C)
(NH2)2CO + H2O = (NH4)2CO3 (> 80 °C)
(1)
(2)
(3)
(4)
(NH4)2CO3 = 2NH3 + H2O + CO2 (> 80 °C)
5

J. Shao, et al.
ChemicalPhysicsLetters731(2019)136603
Fig. 5. The Raman spectra of TDO in aqueous solution at 75 °C, 85 °C, 95 °C. Asterisks (*) label for the laser interfering line.
Table 2
4.8
4.6
4.4
4.2
4.0
3.8
3.6
3.4
3.2
Experimental Raman and B3LYP/cc-PVDZ calculated vibrational frequencies
(500–2000 cm−1 region) for possible chemical components lying in TDO aqu-
eous (s:strong, w:weak).
500ug/ml
Compounds
Frequencies
Calculated
Experimental (in aqueous solution)
−
HSO2
542, 924, 986
H2SO3
SO2
733, 736, 1081, 1087, 1210
1111, 1280
2−
SO2
704, 708
H2SO2
689, 918, 1034, 1077, 1148
1191, 2673, 2691
H2S
Na2SO4
Na2SO3
Na2S2O3
NaHSO3
(NH2)2CO
Na2CO3
611, 980 s, 1110
933, 954 s, 973 s
1001 s, 1125w
737, 769, 832, 1054 s
1004 s
20
30
40
50
60
70
80
90
100
T(oC)
1091
Fig. 6. The pH value of TDO in aqueous solution with 500ug/ml concentration.
4. Conclusions
temperature rises, the rapid increase of the decomposition reaction rate
of TDO means that the reducing substance in the instantaneous system
and the reduction performance increase. (iii) TOF-MS, Raman spec-
troscopy and pH results indicate that the decomposition process of TDO
in aqueous solution between 25 °C and 95 °C temperature can be de-
scribed as following: The TDO single molecular and the clusters are
In this work, three important conclusions can be drawn as fol-
lowing: (i) The oxidation-reduction electrode potential of TDO water
solution shows there are three stages for TDO in water within 25–95 °C
temperature range: 25–55 °C; 55–80 °C; 85–95 °C. (ii) When the
6

J. Shao, et al.
ChemicalPhysicsLetters731(2019)136603
decomposed from 55 °C; urea is produced below 80 °C and begin to
decompose above 80 °C. This work provides solid theoretical and ex-
perimental supports for the friendly reducing agent TDO application,
and effective techniques to explore the decomposition mechanism.
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The authors declared that they have no conflicts of interest to this
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This work was supported in parts by National Natural Science
Foundation of China (No. 21673208), Zhejiang Provincial Natural
Science Foundation of China (No. LY16B070009), Zhejiang Provincial
Key Innovation Team project (No. 2012R10038-02), the Young
Researchers Foundation of Zhejiang Provincial Top Key Academic
Discipline of Chemical Engineering and Technology, Russian
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