Z Lebensm Unters Forsch (1994)198:8-10
a%Nee N
Original paper
Analysisof dithiocarbamatefungicides.
Reactionproductsof the thiuramdisulphidefungicidethiram(TMTD)
duringacid hydrolysis
Wolfgang Schwack, Steven Nyanzi
Institut fiir Lebensmittelchemieder UniversitfitKarlsruhe, Kaiserstrasse 12, D-76128Karlsruhe, Germany
Received July 5, 1993
Analytik der Dithiocarbamat-Fungicide.
Reaktionsprodukte des Thiuramdisulfid-
Fungicids Thiram (TMTD) w~ihrend der S~iurehydrolyse
Zusammenfassung. Mittels Derivativ-UV-Spektroskopie
wurden die Produkte der S/iurehydrolyse (CS2, COS und
H2S) des Fungicids Thiram (TMTD) nach Absorption in
einem methanolischen Aminreagens (Ethylendiamin, Pi-
peridin) ermittelt. Bei Hydrolysetemperaturen unter dem
Siedepunkt ist die Bildung der Nebenprodukte COS und
HzS auf Kosten von CS2 unvermeidlich. Erfolgt kein
sorgffiltiges Waschen der hydrolytisch freigesetzten Gase
mit einer Bleiacetatl6sung, so wird auch H2S im Amin-
reagens absorbiert, das wie COS eine UV-Absorption bei
230 nm verursacht und die COS-Bestimmung verffilscht.
Mit der Derivativspektroskopie konnte eindeutig gezeigt
werden, dab Thiram unter den Bedingungen der DFG-
Methode S 15 zu CS2 and COS im molaren Verh/iltnis
von 1,92 zu 0,06 (8 Messungen) hydrolysiert wird und
nicht, wie von anderen Autoren angenommen, im mola-
ren Verh/iltnis von 1,5 zu 0,5. Daher ist es, den gehegten
Hoffnungen entgegen, nicht m6glich, auf der Basis der
Verteilung der Hydrolyseprodukte Thiram von anderen
Dithiocarbamaten r/ickstandsanalytisch zu unterschei-
den.
Abstract. The acid hydrolysis products (CS2, COS, and
HzS) of thiram (tetramethylthiram disulphide, T M T D )
absorbed in a methanolic amine reagent (ethylenedi-
amine, piperidine) were investigated by second derivative
UV spectroscopy. When the hydrolysis temperatures are
below the boiling point the formation of the side products
COS and HzS at the expense of CS2 is unavoidable. Fail-
ure to carefully scrub the liberated gases with a lead ace-
tate solution leads to the absorption of H/S also in the
amine reagent and, like COS, causes an absorption at
230 nm that is erroneously attributed to COS. With the
second-derivative technique it has been undoubtedly
proved that, under the conditions of the Deutsche For-
Correspondence to: W. Schwack
Zeitschrift fQr
9 Springer-Verlag 1994
schungsgemeinschaft method S 15, thiram liberates CS2
and COS in a molar ratio of 1.92 to 0.06 (average of eight
determinations) but not in a molar ratio of 1.5 to 0.5, as
previously reported by some workers. Under these condi-
tions it is impossible, contrary to earlier claims, to differ-
entiate thiram from other dithiocarbamates based on the
ratio of the hydrolysis products in residue analysis.
Introduction
Controversy surrounds the nature and the amounts of
the sulphur-containing acid hydrolysis products of tetra-
methylthiuram disulphide (thiram, T M T D ) using the
SnC12/HC1 reagent under the Deutsche Forschungsge-
meinschaft (DFG) recommended conditions. The official
method of the D F G for the spectrophotometric determi-
nation of thiram and dithiocarbamate fungicides [1] re-
ported the liberation of approximately 2 tool CS2 (yields
in the range 92-103%)/mol thiram. Furthermore, the
evolution of H2S would appear to be suspected since the
hydrolysis products have to be first scrubbed through a
lead acetate solution.
Working under the same conditions, Schmitt and Nie-
bergall [2] observed the liberation of 1.5 mol CS 2 (yield
about 75%) and 0.5 mol COS. They not only attributed
the high yields of CS 2 of the D F G method to the inability
of the D F G copper-diethanolamine reagent to differenti-
ate between CS2 and COS, but they also showed that CS2
and COS build complexes with copper-diethanolamine,
both of which display maximum absorptions at 435 nm.
The authors were able to differentiate and quantify the
liberated CS2 and COS by substituting the copper-
diethanolamine with the piperidine reagent [2].
In his elucidation of the mechanism of thiram hydro-
lysis under D F G conditions, Schmitt [3] ruled out the
possibility of the formation of the H2S during the hydro-
lysis, did not scrub the hydrolysis products with the lead
acetate and sodium hydroxide solutions as required by
the D F G method and carried out all the experiments at
70 ~ C instead of the boiling temperatures recommended
by the D F G [1]. In a continuation of our previous work
[4], a highly sensitive and selective second derivative UV-
spectroscopic technique for the simultaneous trace analy-
sis of CS2 and COS has been reported [5]. Application of
this method should help to clear the controversy sur-
rounding the chemical behaviour of the thiram fungicide
under D F G acid hydrolysis conditions.
Materials and methods
Materials. The chemicals and reagents, apparatus and the CS2 and
COS calibration curves are presented in [5].
Procedure. The apparatus was set up as described by the DFG [1],
however, with modified absorption tubes [4]. The first and the sec-
ond absorption tubes were filled with 25 ml lead acetate and 10 ml
sodium hydroxide solutions, respectively. In the third absorption
tube, 25 ml of the 0.08mol ethylened!amine (or 0.052mol pi-
peridine) in methanol reagent was added. The condenser attached to
the decomposition flask was thermostatted at 40~ C. Thiram (10-
60 Ixg as a talc-thiram mixture or in a glass capsule after evaporation
of the CHC13 solvent on a heating block under a stream of N 2 or
dissolved in water) was introduced into the decomposition flask.
After addition of the SnC12/HC1reagent to the decomposition flask,
the apparatus was closed and N 2 pressure was applied and allowed
to sweep the system at an approximate rate of 50 ml/min. With the
help of a heating mantle, the contents of the decomposition flask
were then quickly heated to the boiling temperature and the diges-
tion continued for an additional 45 rain. The N 2 was turned off and
the contents of the third absorption tube were transferred to a 25-ml
volumetric flask. The second-derivative spectrum of the sample was
recorded against a 0.08mol ethylenediamine (or 0.052 tool pi-
peridine) reagent blank between 320 and 220 nm using the same in-
strumental parameters as described [5] for the CS2 and COS stan-
dards.
Note that when using the piperidine reagent, the third absorp-
tion tube and the blank have to be kept in an ice-water (0-4~ C) bath
during the distillation. In addition, the recording of the spectrum
has to be done 10-15 min after removing the samples from the ice-
water bath [4].
Results and discussion
Acid hydrolysis of the thiram fungicide
under DFG conditions
The mechanisms of acid hydrolysis of thiram under D F G
conditions as presented by Schmitt et al. [2] noted the for-
mation of CS2 and COS in a molar ratio of 3 : 1 per mole
of thiram and raised hopes of differentiating thiram from
other dithiocarbamates during residue analysis based on
these findings. After identifying the reagents and their
optimum conditions for the determination of both CS2
and COS [4, 5], the acid hydrolysis of thiram under D F G
conditions was subjected to closer scrutiny.
Effect of temperature of hydrolysis. Table 1 shows the ef-
fect of temperature of hydrolysis on the formation of
both CS2 and COS from an aqueous thiram solution.
Higher temperatures ( > 9 0 ~ C) of hydrolysis favour
higher yields of CSv Lower temperatures ( < 80 ~ C) not
only lead to low CS2 yields and require longer hydrolysis
Table 1. Effect of the temperature of hydrolysis of an aqueous thiram
solution on the molarratio of the liberated CS2and COS
Temperature (~C) For each mole of thiram
Moles of C S 2 Moles of COS
51.5 1.00 -"
66.5 1.34 -"
81.0 1.47 0.40
90.5 1.67 0.27
96.5 1.93 0.05
Results are the average of three measurements
" COS was below the detection limit
times but they also favour the formation of side products
(COS and HzS ) at the expense of CS2. The need to bring
the contents in the decomposition/distillation flask
quickly to the boiling temperatures, as recommended by
the official D F G method, leads generally to high CS2
yields ( > 93%).
Liberation of H2S during hydrolysis. In his elucidation of
the mechanism of decomposition o f thiram under DFG
conditions, Schmitt [3] ruled out the possibility of forma-
tion of HzS. The building of HzS , especially when the
temperatures of hydrolysis are below 80 ~ C, has been
confirmed by the formation of black spots in the lead ace-
tate scrubbing reagent. Substitution of the lead acetate
with zinc acetate solution followed by quantification of
HzS (as zinc sulphide) with the help of 4-aminodimeth-
ylaniline [6] facilitated the colorimetric quantification of
the liberated HzS at 665 nm. This way, amounts of H~S
exceeding 3 gg/50 ml could be quantified. It should be
noted, however, that lead acetate is more effective in the
removal of H2S than zinc acetate because lead sulphide
is stabilized by an acidic medium unlike the zinc sul-
phide.
When the contents of the decomposition flask were
quickly brought to the boiling temperature, no H2S could
be detected photometrically. This was additionally con-
firmed by the absence of the black lead sulphide spots in
the lead acetate scrubbing solution and the almost theo-
retically expected CS2 yields.
Molar ratio of the liberated CS 2 and COS. In the absence
of the lead acetate and sodium hydroxide scrubbing solu-
tions, in the hot acid hydrolysis of thiram, the absorbance
readings at 290 nm when using the ethylenediamine (or
piperidine) reagent can only be attributed to CS2. Under
the same conditions using normal UV spectroscopy, the
absorbance readings at 230 nm may be due to CS z, COS
and HzS. However, in the presence of the lead acetate
scrubbing solution during the hot acid hydrolysis of
thiram, it is reasonable to ascribe the absorbance mea-
surements at 230 nm to only COS (second derivative
method). Since Schmitt [3] did not include the lead ace-
tate and the NaOH solutions, as required by the D F G
method, but attributed the absorbance readings at
230 nm to only CS2 and COS (normal UV method), the
reported high amounts of COS may be understood. In-
10
A >
0.4
0.3
0.2
0.1
0 I I i
220 240 260 280 rl m
Fig. 1. Normal UV absorption spectrum of H2S (90.65 ~tmol/L) in
methanolic piperidine (52 mmol/L)
clusion of the lead acetate solution has confirmed the
evolution of H2S as one of the thiram hydrolysis prod-
ucts, especially when the decomposition flask contents
are slowly brought to the boiling temperature or when
the temperature of the decomposition flask is held below
80 ~ C.
In a separate study, H2S was allowed to react with the
piperidine reagent. Figure 1 shows that the H2S-pi-
peridine adduct also absorbs at 230 nm. In the concentra-
tion range of 25-200 gmol H2S/L in methanolic pi-
peridine (52 mmol/L) the molar absorptivity of the H2S-
piperidine adduct at 230 nm was found to be 3982 L/mol
9cm. This confirms that in the acid hydrolysis of thiram,
in the absence of the lead acetate and the sodium hy-
droxide scrubbing solutions, the absorbance readings at
230 n m may justifiably be attributed to COS and HzS.
Repeated hydrolyses of thiram (eight determinations),
under D F G conditions, using the ethylenediamine or pi-
peridine reagent have confirmed the liberation of an
average of 1.92 reel CSz and less than 0.06 mol COS
from each mole of thiram.
Under D F G conditions the mechanism of acid hydro-
lysis of thiram is believed to predominantly proceed
along route A as shown in Fig. 2. Route A is favoured by
the presence of Sn 2 + ions in dilute HC1, bringing con-
tents quickly to boiling temperature and the absence of
interfering substances that would promote the formation
of side products. On the other hand, Route B is likely to
predominate in the absence of enough Sn 2 + in dilute
HCI, slowly bringing the contents to boiling temperature
or keeping the temperature below 80 ~ C and in the pre-
Route A
2 (CH3)2NH + 2 CS 2
N--C--S~S--C--N
nY"3t
/ \
CH 3 CH 3
Route B
> 2 (CH3)2NH + CS 2 + COS
+ H2S
Fig. 2. Decomposition pathways of the thiram fungicide on acid hy-
drolysis
sence of interfering substances. The incomplete decom-
position of thiram, when the hydrolysis is carried for 1 h
at lower temperatures (less than 80 ~ C) has also been ob-
served.
Conclusion
Under the D F G recommended acid hydrolysis condi-
tions of thiram and dithiocarbamate fungicides, the hot
hydrolysis of thiram fungicide does not lead to the forma-
tion of CSz and COS in a molar ration of 3 : 1 per mole
of the fungicide, as previously reported by some workers,
but to almost the theoretically expected moles of CS2 (i.e.
2). The number of moles of the evolved COS is negligibly
small (i.e. less than 0.06). Under these conditions, it is im-
possible to differentiate thiram from other dithiocarba-
mates based on the molar ratio of the liberated CS2 and
COS for each mole of the fungicide.
Acknowledgement.The authors are grateful to the German Aca-
demic Exchange Service (DAAD) for a doctoral scholarship to
Steven Nyanzi.
References
1. Rfickstandsanalytik von Pflanzenschutzmittel, Mitteilung VI der
Senatskommission fiir Pflanzenschutz-, Pflanzenbehandlung-
und Vorratsschutzmittel der Deutschen Forschungsgemein-
schaft, Methodensammlung der Arbeitsgruppe ,Analytik"
(1985), 5. Lieferung: Methode S 15. Verlag Chemie, Weinheim
2. Schmitt A, Niebergall H (1988) Dtsch Lebensm-Rdsch 84:13-
16
3. Schmitt A (1987) Doctorate thesis, University of Karlsruhe
4. Schwack W, Nyanzi S (1993) Fresenius J Anal Chem 345:705-
711
5. Schwack W, Nyanzi S (1994) Z Lebensm Unters Forsch 198:3-7
6. Welcher FJ (1947) Organic Analytical Reagents, vol 2. Van Nos-
trand, New York, pp 252259