Research Article

Received: 18 December 2009 Revised: 6 May 2010 Accepted: 6 May 2010 Published online in Wiley Online Library: 14 June 2010

(wileyonlinelibrary.com) DOI 10.1002/jctb.2446

Optimization of the production

of thiocarbohydrazide using the Taguchi
method
Jiancheng Zhou, Dongfang Wu∗ and Dongsheng Guo

Abstract
BACKGROUND: The Taguchi method, a powerful tool for the optimization of quality, was used to improve the yield of
thiocarbohydrazide in its synthetic process. An orthogonal array was selected to analyze the effects of the process factors, i.e.
reflux time, molar ratio of hydrazine to carbon disulfide and reflux temperature. Experiments were undertaken to confirm the
effectiveness of the Taguchi method.

RESULTS: Through this study, the main factors that affect the yield of thiocarbohydrazide were found, together with the optimal
factor levels. It was shown that the reflux temperature was the most significant factor affecting the yield of thiocarbohydrazide,
followed by the molar ratio of hydrazine to carbon disulfide. The optimum factor levels were a reflux time of 6 h, molar ratio
of hydrazine to carbon disulfide 3.0 and reflux temperature 70 ◦ C. A 92.3% yield of thiocarbohydrazide was obtained at these
optimal factor levels.

CONCLUSIONS: The yield of thiocarbohydrazide can be significantly improved by optimization of the synthetic process factors.
The Taguchi method provided a systematic and efficient methodology for this optimization, with far less effort than would be
required for most other optimization techniques.

c 2010 Society of Chemical Industry

Keywords: thiocarbohydrazide; yield; process factor; optimization; Taguchi method

INTRODUCTION addition of carbon disulfide to an aqueous solution of hydrazine,

Thiocarbohydrazide (TCH), one of the simplest hydrazine deriva-
tives of thiocarbonic acid, is an important chemical intermediate
in organic synthesis and is used in the industrial production of
insecticides, fungicides and various agricultural chemicals as well
as in chemical laboratories as a chemical reagent.1,2 It is a white
crystalline solid melting with decomposition at about 171 ◦ C and
may be recrystallized from water.1,3
There are several processes described in the open literature1 – 6
for the preparation of TCH. For example, TCH may be obtained
during the hydrazinolysis of thiophosgene in moderate yields
using ether or water as the reaction medium. TCH is also produced
by the hydrazinolysis of diethyl xanthate, dialkyl trithiocarbonate
or methyl dithiocarbazinate. The most common synthesis of TCH is,
however, the conversion of carbon disulfide with hydrazine. First,
carbon disulfide reacts with hydrazine to produce hydrazinium
dithiocarbazinate (HDTC), a water-soluble salt formed in nearly
quantitative yield at relatively low temperatures:
CS2 + 2H2 NNH2 → H2 NNHCSSH · NH2 NH2 (1)
This compound is then heated to form TCH with the elimination
of hydrogen sulfide:
H2 NNHCSSH · NH2 NH2 → H2 NNHCSNHNH2 + H2 S (2)
It is unnecessary to isolate HDTC in order to effect its conversion
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followed by direct heating of the resultant reaction mixture.1 – 6 It
has been shown that dilution of the reaction medium with water
causes a decrease in the yield of TCH. Further, use of a water-free
solvent for hydrazine, e.g. methyl, ethyl or propyl alcohol, does
not increase the TCH yield.1,5 However, the yield of TCH may
be increased to about 70%, if an excess of hydrazine exists at
the start of the reaction with carbon disulfide and the resulting
HDTC is then heated under reflux in solution in the presence of
residual hydrazine.1,2,4 It has also been reported that the addition
of a mercaptan used as catalyst, e.g. mercaptoethanol, thioglycolic
acid or ethane dithiol, in the reaction medium can suppress the
formation of unwanted by-products and hence increase the yield
of TCH. In this case, a yield of approximately 88% of theory
was obtained.5,6 Although some information is already at hand
concerning the synthesis of TCH, no real effort has been made to
optimize the process parameters to improve the yield of TCH. The
present work is therefore designed for this purpose.
To optimize process factors, an appropriate design of experi-
ment is required. In general, classical experimental design methods
∗ Correspondence to: Dongfang Wu, School of Chemistry and Chemical
Engineering, Southeast University, Jiangning District, Nanjing 211189, China.
E-mail: dfwu@seu.edu.cn

School of Chemistry and Chemical Engineering, Southeast University, Jiangning

into TCH. So the synthetic process can be performed by the District, Nanjing 211189, China

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c 2010 Society of Chemical Industry
Optimization of thiocarbohydrazide production using the Taguchi method www.soci.org

are too complex and not easy to use. Furthermore, a large number
Table 1. Factors and their levels under investigation
of experiments have to be carried out when the number of process
factors is large. To solve this problem, the Taguchi method was Level
proposed in the late 1960s.7 – 9 The method, which is one of the
fractional factorial designs allows one statistically and ideally to Symbol Factor 1 2 3
obtain similar information to a full-factorial experimental design, A Reflux time (h) 6 8 10
but with fewer experiments. It uses a special design of orthogo- B Molar ratio of N2 H4 to CS2 2.5 3.0 3.5
nal arrays to study the entire parameter space. The experimental C Reflux temperature (◦ C) 70 80 90
results are then transformed into a signal-to-noise (S/N) ratio.
Taguchi recommends the use of the S/N ratio to measure the
quality characteristics deviating from the desired values. Based
on analysis of the S/N ratio, the optimal levels of the process fac- Table 2. Experimental layout using an L9 (34 ) orthogonal array
tors are determined. Furthermore, a statistical analysis of variance
(ANOVA) is performed to see which process factors are statisti- Factor and level
cally significant. Finally, a confirmation experiment is conducted
to verify the optimal process factors obtained from the Taguchi Trial no. A B C Error
method. 1 1 1 1 1
The Taguchi method has been shown to be a great success 2 1 2 2 2
in industry for improving the quality of products and processes. 3 1 3 3 3
The rapid growth of interest in the Taguchi method has led 4 2 1 3 2
to numerous applications of the method in various fields in a 5 2 2 1 3
world-wide range of industries and nations.10 – 13 In this work, 6 2 3 2 1
the Taguchi method was used to optimize the synthetic process 7 3 1 2 3
factors to improve the yield of TCH. An L9 orthogonal array was 8 3 2 3 1
selected for the experimental layout. 9 3 3 1 2

EXPERIMENTAL
Synthesis of TCH
The chemical reagents used, carbon disulfide and hydrazine
hydrate (85% aqueous solution), were of AR grade and purchased
in China. They were used as received. The synthesis of TCH
was carried out in a 1000 mL four-necked round-bottom flask
equipped with a thermometer, a mechanical stirrer, a dropping
funnel and a reflux condenser connected to a caustic trap. The
whole apparatus was kept in a water bath to maintain the required
reaction temperatures.
A specified quantity of 85% aqueous hydrazine hydrate was
placed in the flask. The temperature was lowered to 10 ◦ C and
the stirring rate was controlled at 800 rpm. 30.15 mL of carbon
disulfide (0.5 moles) were added dropwise over about one hour,
while maintaining the temperature below 15 ◦ C. After addition
the reaction mixture continued to be agitated for 30 min at
room temperature. The resultant mixture was then heated to
the required temperature and refluxed at this temperature for a
desired length of time. The reaction mixture was thereafter cooled
to room temperature and the crystalline precipitate separated from
the liquid by filtration. After washing with a minimum amount of
cold water, the TCH crystals were dried at 110 ◦ C in air for 5 h.
Taguchi experimental design
Three process parameters, i.e. molar ratio of N2 H4 to CS2 , reflux
time and reflux temperature, were selected as controllable factors.
Their ranges were chosen based on the conditions often used
in industry and reported in the literature.1 – 6,14 For each process
factor, three levels were selected in this study, as shown in Table 1.
Three factors, each at three levels, were considered; therefore,
an L9 orthogonal array with four columns and nine rows was
employed. This array has eight degrees of freedom and can
handle three-level process factors. Each process factor is assigned
Therefore, only nine experiments are required to study the entire
parameter space. The experimental layout for the three factors
using the L9 orthogonal array is shown in Table 2. Since the L9
orthogonal array has four columns, one column of the array is left
empty for the error of experiments; orthogonality is not lost by
letting one column of the array remain empty.9
Determination of quality characteristics
A balance with a precision of 0.0001 g was used to measure the
weight of the TCH crystal sample obtained for each experiment,
according to which the yield of TCH based on carbon disulfide was
determined as the quality characteristic of the TCH syntheses in
the Taguchi method. In addition, the IR spectra of the TCH samples
obtained were recorded on a PerkinElmer (Fremont, CA, USA)
Specrum-1000 Fourier transform infrared (FTIR) spectrometer.
Samples were prepared as thin films on KBr plates. The melting
points of the TCH samples were measured by a capillary method
on a Barnstead (Dubuque, IA, USA) digital melting-point tester
that can accommodate three capillary tubes so that up to
three independent samples can be analyzed simultaneously. The
heating stand (metal block) was rapidly preheated to 160 ◦ C, and
then three capillaries containing three dried samples in powdered
form were inserted. After the temperature stabilized, a heating
ramp with a rate of 1 ◦ C min−1 was immediately applied. The
temperature at which a sample began to melt was recorded as the
sample melting point.
RESULTS AND DISCUSSION
All of the nine synthesized samples gave a similar FTIR spectrum,
as illustrated in Fig. 1 for sample 1. It is absolutely identical with the
standard IR spectrum of TCH in the spectral database for organic
compounds provided by National Institute of Advanced Industrial
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to a column, nine process factor combinations being available. Science and Technology of Japan.15 The characteristic peaks at

J Chem Technol Biotechnol 2010; 85: 1402–1406

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 www.soci.org JC Zhou, D Wu, D Guo

Table 4. S/N response table for the yield of TCH

Mean S/N ratio (dB)

Factor Level 1 Level 2 Level 3 Max–min

A −2.434 −2.835 −2.578 0.401

B −3.406 −2.186 −2.256 1.220
C −1.425 −2.163 −4.259 2.834

The total mean S/N ratio η = −2.616 dB.

characteristic deviating from the desired value.7 – 9 The S/N ratio,

η, is defined as
η = −10 · log(M.S.D.) (3)

where M.S.D. is the mean square deviation for the output

characteristic.
Figure 1. IR spectrum of sample 1. Usually, there are three categories of quality characteristics
in the analysis of the S/N ratio, i.e. the-lower-the-better, the-
higher-the-better, and the-nominal-the-better.7 – 9 The M.S.D. for
Table 3. Experimental results for the yield of TCH and corresponding the-higher-the-better quality characteristic can be expressed as
S/N ratio

1
1
Trial Reflux Molar ratio of Reflux Yield S/N ratio r
no. time (h) N2 H4 to CS2 temperature (◦ C) (%) (dB) M.S.D. = (4)
r y2
i=1 i
1 6 2.5 70 76.4 −2.338
2 6 3.0 80 85.3 −1.381
and for the-lower-the-better quality characteristic
3 6 3.5 90 66.2 −3.583
4 8 2.5 90 55.6 −5.099
1
2
r
5 8 3.0 70 88.3 −1.081 M.S.D. = yi (5)
6 8 3.5 80 76.5 −2.327 r
i=1
7 10 2.5 80 72.6 −2.781
8 10 3.0 90 62.4 −4.096
where yi is the quality characteristic, and r is the number of
9 10 3.5 70 90.6 −0.857
repetitions done for each experiment in the orthogonal array.
Clearly, the-higher-the-better quality characteristic for the yield
of TCH should be taken to obtain optimal TCH synthesis. So, the
1530 and 1490 cm−1 are assigned to the coupled modes consisting S/N ratios corresponding to the yield of TCH were computed using
principally of N–H wagging and C–N stretching vibrations.16 The Equations (3) and (4), where r is equal to unity in this case, and
C S stretching vibration contributes to the two peaks at 1290 and listed in the last column in Table 3.
933 cm−1 , which also contain contributions from other vibrations, Since the experimental design is orthogonal, it is then possible
in particular C–N stretching and C–N–N bending vibrations.16 The to separate out the effect of each process factor at different levels.
N–H and H–N–H stretching vibrations contribute to the three For example, the mean S/N ratio for the reflux time at levels 1,
peaks at 3280, 3270 and 3200 cm−1 , and the H–N–H bending 2 and 3 can be calculated by averaging the S/N ratios for the
and wagging vibrations to the two peaks at 1640 and 1140 cm−1 , experiments 1–3, 4–6, and 7–9, respectively. The mean S/N ratio
respectively. A more detailed spectrum analysis can be found in for each level of the other process factors can be computed in a
the literature.16 The samples are all white crystalline solids with similar manner. As a result, an S/N response table can be obtained,
observed melting points of 170–172 ◦ C. These results reveal that as shown in Table 4. In addition, the total mean S/N ratio, η, for the
the nine samples are all pure TCH crystals. nine experiments is also calculated and listed in Table 4. Figure 2
Table 3 presents the experimental results for the yield of TCH shows the corresponding S/N response graph.
based on carbon disulfide. It shows that the process factors have Regardless of the category of the quality characteristic, a
great effects on the yield of TCH; there is therefore a great greater S/N ratio corresponds to a smaller variance of the output
possibility of improving the yield of TCH with the optimization of characteristic around the desired value, and hence to a better
the process factors in the TCH synthesis. quality characteristic. Therefore, the optimal level of the process
factor is the level with the greatest S/N ratio.7 – 9 From Table 4 and
Analysis of the S/N ratio Fig. 2, it can be seen that the optimum factor levels for the yield of
In the Taguchi method, the term ‘signal’ represents the desirable TCH are reflux time at level 1, molar ratio of N2 H4 to CS2 at level 2,
value (mean) for the output characteristic and the term ‘noise’ and reflux temperature at level 1, denoted as A1B2C1. The relative
represents the undesirable value (SD) for the output characteristic. importance among the process factors for the quality characteristic
Therefore, the signal-to-noise (S/N) ratio is the ratio of the mean still needs to be known so that the optimal combination of process
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to the SD. Taguchi used the S/N ratio to measure the quality factor levels can be determined more accurately.

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Optimization of thiocarbohydrazide production using the Taguchi method www.soci.org

Table 5. Analysis of variance for the yield of TCH

Sum Degrees Pure sum Percentage
of of Mean of contribution
Factor squares freedom square F-test squares (%)

A 0.248 2 0.124◦ – – –
B 2.816 2 1.408 8.442 2.483 15.09
C 12.97 2 6.484 38.87 12.63 76.80
Error 0.419 2 0.210
(Error) (0.667) (4) (0.167) (1.334) (8.110)
Total 16.45 8 16.45 100

The variance of factor A (with open circle) is pooled into the error factor.

Table 6. Results of the confirmation experiment

Experiment Prediction

Optimal level Yield (%) S/N ratio (dB) Yield (%) S/N ratio (dB)
Figure 2. S/N graph for the yield of TCH.
A1B2C1 92.3 −0.696 91.1 −0.814

Analysis of variance
The purpose of the analysis of variance (ANOVA) is to determine
which process factors significantly affect the quality characteristic.
This is accomplished by separating the total variability of the S/N
ratio, which is measured by the sum of the squared deviation from
the total mean S/N ratio, into contributions by each process factor
and by the error.7 – 9 First, the total sum of squared deviation from
the total mean S/N ratio η, SST , can be calculated as


k
SST = (ηi − η)2 (6)
i=1
where k is the number of experiments in the orthogonal array and
ηi is the S/N ratio for the ith experiment. The total sum of squared
deviation is decomposed into the sum of squared deviation for
each factor, SSp , and the sum of squared error, SSe . The SSp for
factor p can be calculated as
Table 5 shows the results of ANOVA for the yield of TCH. It can
be seen that reflux temperature is the most significant process
factor affecting the yield of TCH, followed by the molar ratio of
N2 H4 to CS2 . The change of reflux time in the range examined has,
however, little effect on the yield of TCH.
Confirmation experiment
Once the optimal levels of the process factors have been selected,
the final step is to predict and verify the improvement in the quality
characteristic using the optimal levels of process factors.7 – 9 The
S/N ratio at the optimal levels of the process factors, ηopt , can be
estimated as

o
ηopt = η + (ηp,opt − η) (9)
p=1

q where η is the total mean S/N ratio, ηp,opt is the mean S/N ratio
SSp = t · (ηp,i − η)2 (7)
i=1
where t is the number of repetitions of each level of the factor in
the orthogonal array, q is the number of levels of the factor, and
ηp,i is the mean S/N ratio for the factor at level i.
There is a tool called an F-test7 – 9,17 to see which process factors
have a significant effect on the quality characteristic. In performing
the F-test, the mean of squared deviation due to each factor, MSp ,
needs to be calculated. The MSp is equal to the sum of squared
deviation, SSp , divided by the number of degrees of freedom
associated with the factor, dfp (number of levels minus one). Then,
factors having lower MSp are pooled to the error factor. The F-test
value for each factor is simply the ratio of the mean of squared
deviation, MSp , to the mean of squared pooled error, MSe . Process
factors with a large F-test value have a more significant effect on
the quality characteristic. In addition, for significant factors their
percentage contributions, ρp , can be determined from
SSp SSp − MSe · dfp
ρp = · 100% = · 100% (8)
SST SST
for factor p at its optimal level, and o is the number of main
process factors that affect the quality characteristic. Based on the
ηopt value, the quality characteristic for the optimal levels of the
process factors can be predicted using Equations (3) and (4).
Table 6 shows a comparison of the predicted yield of TCH
with the experimental result using the optimal process factors.
Good agreement is observed between the predicted and actual
experimental values. It can also be seen that the yield of TCH for the
optimal factor levels is higher than any of the yield data shown in
Table 3. For instance, the increase in S/N ratio from no. 4 (−5.099)
to the optimal actual data (−0.696) is 4.403 dB, which means that
the yield of TCH increases by about 1.66 times. All these results
confirm the prior design and analysis for optimizing the process
factors. The yield of TCH is greatly improved by optimization of the
process factors in the TCH synthesis through the Taguchi method.
It should be mentioned that the optimal levels obtained for the
reflux time and reflux temperature are both at the lowest levels
examined in this study, indicating that the yield of TCH might be
further increased if further optimization was carried out.
It is worth noting that no catalyst was used in this synthesis of
TCH and that the optimal yield of TCH was much higher than those
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where SSp is the pure sum of squared deviation due to each factor. reported in the literature (88% or 70% for cases with or without

J Chem Technol Biotechnol 2010; 85: 1402–1406

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 www.soci.org
a mercaptan as catalyst, respectively.4,5 . Thus it can be seen that
optimization of the process factors is a key step to improve the
TCH yield in the synthesis.
CONCLUSIONS
This paper has discussed an application of the Taguchi method for
improving the yield of TCH. As shown in this study, the Taguchi
method provides a systematic and efficient methodology for the
optimization of the process factors in TCH synthesis with far
less effort than would be required for most other optimization
techniques.
It has been shown that the yield of TCH can be improved
significantly by optimization of the process factors in the TCH
synthesis. The optimal factor levels are reflux time 6 h, molar ratio
of N2 H4 to CS2 3.0, and reflux temperature 70 ◦ C. It was also found
that the reflux temperature is the most significant process factor
affecting the yield of TCH, followed by the molar ratio of N2 H4 to
CS2 . The change of reflux time in the range examined had little
effect on the yield of TCH. Finally, a confirmation experiment was
also conducted to verify the validity of the Taguchi method.
ACKNOWLEDGEMENTS
Financial support from the Program for New Century Excellent
Talents in University under Grant No. NCET-07-0185, and the
Jiangsu Provincial Natural Science Foundation under Grant No.
BK2007119 are gratefully acknowledged.
REFERENCES
1 Audrieth LF, Scott ES and Kippur PS, Hydrazine derivatives of the
carbonic and thiocarbonic acids. I. The preparation and properties
of thiocarbohydrazide. J Org Chem 19:733–741 (1954).
1406
wileyonlinelibrary.com/jctb

c 2010 Society of Chemical Industry
JC Zhou, D Wu, D Guo
2 Audrieth LF and Kippur PR, Preparation of thiocarbohydrazide. US
Patent 2726263 (1955).
3 Kurzer F and Wilkinson M, The chemistry of carbohydrazide and
thiocarbohydrazide. Chem Rev 70:111–149 (1970).
4 Malone JR, Production of thiocarbohydrazide. US Patent
4172092 (1979).
5 Jackman DE, Combs GW and Westphal DB, Process for the production
of thiocarbohydrazide. US Patent 4940815 (1990).
6 Sun XH and Liu YF, Study on the synthesis of thiocarbohydrazide.
Chemistry (China) 62:46–48 (1999).
7 Taguchi G, Introduction to Quality Engineering. Asian Productivity
Organization, Tokyo (1990).
8 Ross PJ, Taguchi Techniques for Quality Engineering. McGraw-Hill, New
York (1988).
9 Montgomery DC, Design and Analysis of Experiments. Wiley, New York
(2001).
10 Bendell A, Disney J and Pridmore WA, Taguchi Methods: Applications
in World Industry. IFS Publications, UK (1989).
11 Matin KT, Bastani D and Kazemian H, Applying the Taguchi method
to develop an optimized synthesis procedure for nanocrystals of
T-type zeolite. Chem Eng Technol 32:1042–1048 (2009).
12 Yu XW, Li YQ and Wu D, Microencapsulation of tannase by chitosan-
alginate complex coacervate membrane: synthesis of antioxidant
propyl gallate in biphasic media. J Chem Technol Biotechnol
79:475–479 (2004).
13 Ata ON, Yesilyurt M, Colak S and Bese AV, Determination of the
optimum conditions for zinc extraction from ore containing
sphalerite by HCl solutions. Can J Chem Eng 80:753–763 (2002).
14 Sun XH and Liu YF, Study on the scale-up for new technology of
thiocarbohydrazide synthesis. Chem Eng (China) 27:41–43 (1999).
15 Spectral Database for Organic Compounds SDBS, http://riodb01.
ibase.aist.go.jp/sdbs/cgi-bin/cre index.cgi. National Institute of
Advanced Industrial Science and Technology (AIST), Japan.
16 Burns GR, Metal complexes of thiocarbohydrazide. Inorg Chem
7:277–283 (1968).
17 Fisher RA, Statistical Methods for Research Workers. Oliver and Boyd,
London (1925).
J Chem Technol Biotechnol 2010; 85: 1402–1406