Journal of Thermal Analysis and Calorimetry, Vol.

75 (2004) 583–590

KINETIC AND THERMODYNAMIC PARAMETERS OF

THE THERMAL DECOMPOSITION OF ZINC(II)
DIALKYLDITHIOCARBAMATE COMPLEXES

Marta C. D. Silva1*, Marta M. Conceição1, Maria F. S. Trindade1,

A. G. Souza1, C. D. Pinheiro1, J. C. Machado2 and P. F. A. Filho3
1
Departamento de Química, CCEN, Universidade Federal da Paraíba, 58059-900 João Pessoa, Paraíba,
Brazil
2
Departamento de Química, ICEx, Universidade Federal de Minas Gerais, 31270-901 Belo Horizonte,
MG, Brazil
3
Departamento Ciências Básicas Sociais, Campus IV, Universidade Federal da Paraíba, Bananeiras,
PB, Brazil

Abstract
The thermodynamic and kinetic parameters of the thermal decomposition of Zn(S2CNR2)2 com-
plexes (R=CH3, C2H5 and n-C3H7) were determined with the dynamic thermogravimetric method.
Superimposed TG/DTG/DSC curves show that thermal decomposition reactions for chelates with
R=C 2H5 and n-C3H7 occur in the liquid phase, at temperatures far away from their melting points,
whereas for the complex with R=CH3 the thermal decomposition begins at a temperature closer to its
melting point, suggesting a rather complex decomposition mechanism.

Keywords: dithiocarbamates, thermal decomposition, zinc

Introduction
The thermal decomposition mechanism of solid dialkyldithiocarbamates [M(CS2CNR2)n;
M=metal] shows a particular behavior: differently from most solid metal complexes that
decompose in the solid phase, metal dialkyldithiocarbamates decompose in the liquid
phase at temperatures far away from their melting points [1–3].
In the present work the kinetic and thermodynamic parameters for the thermal
decomposition of Zn[S2CN(CH3)2]2, Zn[S2CN(C2H5)2]2 and Zn[S2CN(n-C3H7)2]2
were determined using a non-isothermal method.

* Author for correspondence: E–mail: martacelia@yahoo.com

1388–6150/2004/ $ 20.00 Akadémiai Kiadó, Budapest

© 2004 Akadémiai Kiadó, Budapest Kluwer Academic Publishers, Dordrecht
584 SILVA et al.: ZINC(II) DIALKYLDITHIOCARBAMATE COMPLEXES

Experimental
Zn(II) dialkyldithiocarbamate complexes were synthesized from direct reaction of
ZnCl2 with appropriated dialkylammonium compounds in acetone, as described in
more detail elsewhere [4–7].
After purification, the complexes were vacuum dried and characterized by dif-
ferent techniques, such as melting point determination, thermal analysis (TG, DTG
and DSC), infrared spectroscopy, mass spectroscopy and elemental analysis.
The melting points were obtained with a Microquimica equipment model
MQAPF 301 and a differential scanning calorimeter Shimadzu-model DSC-50. The
infrared spectra, in the 4000–400 cm–1 region, were obtained with a Bomem spec-
trometer, model MB-102; samples were mixed with KBr and pressed to form pellets.
Mass spectra were obtained with a Varian (model MAT 311) spectrometer, at ioniza-
tion energy of 70 eV. The elemental analysis for C, H and N were performed with a
Perkin Elmer CHN analyzer, model PE 2400.
The dynamic thermogravimetric curves were obtained in a Shimadzu Thermo-
balance model TGA-50, under nitrogen atmosphere, at 50 mL min–1 carrier gas flow
and initial sample masses 5.0±0.7 mg, in the range of 25–500°C, with heating rates of
5, 10 and 15°C min–1.

Results and discussion

Characterization of complexes
The melting temperature values obtained either by the conventional method or by
DSC determination were rather similar (Table 1).

Table 1 Melting points obtained by conventional and DSC measurements

Melting temperatures/°C
Complexes
Conventional method DSC
Zn[S2CN(CH3)2]2 252.7–253.0 253.4
Zn[S2CN(C2H5)2]2 178.8–180.6 180.6
Zn[S2CN(n-C3H7)2]2 113.5–115.5 114.5

As summarized in Table 2, infrared spectra show typical bands of a complex forma-

tion, particularly due to the presence of strong stretching ν(C–N) vibration bands in the
range 1480–1550 cm–1, similarly to those observed for a number of dithiocarbamate
complexes [8, 9]. In addition, the lower wavenumber for the ν(C–S) stretching band and
an isolated band near 1000 cm–1 indicate that the ligand is bidentately bound to the metal.

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Table 2 Principal absorption bands observed in the infrared spectra

Attribution
Complexes
C=N N–C=S =C–S C–S
Zn[S2CN(CH3)2]2 1522.6(s) 1242.8(s) 1050.4(w) 973.2(s)
Zn[S2CN(C2H5)2]2 1503.0(s) 1272.2(s) 1073.0(s) 994.0(s)
Zn[S2CN(n-C3H7)2]2 1498.0(s) 1241.1(s) 1088.6(m) 974.6(m)
s=strong; m=medium; w=weak

Table 3 Elemental analysis for the complexes

mass% (calculated) mass% (experimental)
Complexes
C H N C H N
Zn[S2CN(CH3)2]2 23.6 3.9 9.2 23.7 3.6 9.3
Zn[S2CN(C2H5)2]2 33.2 5.6 7.7 33.4 5.7 7.8
Zn[S2CN(n-C3H7)2]2 40.2 6.7 6.7 40.4 6.3 6.8

The elemental compositions (Table 3) are in agreement with expected data from
stoichiometric formulae of the complexes.
The mass spectra data for all complexes were obtained with sample insertion by
direct probe injection. The intensities of molecular ions [ML2]+ and the loss of ligand
molecules suggest the following order of stability:
Zn[S2CN(C2H5)2]2>Zn[S2CN(n-C3H7)2]2>Zn[S2CN(CH3)2]2

Thermal behavior
The superimposed TG/DTG curves presented similar shapes with a single step corre-
spondent to decomposition of ligand. The mass loss was calculated stoichiometrically
(Table 4). The superimposed TG/DTG/DSC curves of Zn[S2CN(C2H5)2]2 and
Zn[S2CN(n-C3H7)2]2 complexes suggested thermal decomposition beginning in the liq-
uid phase and for Zn[S2CN(CH3)2]2 complex suggested thermal decomposition begin-
ning in the solid phase, at a temperature close to the melting point, followed by an ex-
pressive amount of decomposition occurring in the liquid phase.
According to the beginning temperature of the decomposition of complexes the
following order of thermal stability may be proposed:
Zn[S2CN(C2H5)2]2<Zn[S2CN(CH3)2]2<Zn[S2CN(n-C3H7)2]2

Figure 1 shows the dynamic thermogravimetric curve for the complex

Zn[S2CN(C2H5)2]2. Figures 2 and 3 show TG/DTG/DSC typical superimposed curves
for Zn[S2CN(C2H5)2]2 and Zn[S2CN(CH3)2]2 complexes, respectively.
As it can be seen from Figs 2 and 3 (DSC curves) there is an endothermic peak
near 90°C, probably due to a loss of residual water molecules; in Fig. 3 the DSC

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586 SILVA et al.: ZINC(II) DIALKYLDITHIOCARBAMATE COMPLEXES

Table 4 Thermal stability of the zinc(II) complexes

Mass loss/ %
Complexes Temperature range/° C
Calculated Experimental
Zn[S2CN(CH3)2]2 236.2–353.5 92.9 94.1
Zn[S2CN(C2H5)2]2 231.9–368.0 97.0 97.0
Zn[S2CN(n-C3H7)2]2 238.8–367.4 96.1 96.2

curve shows two peaks which are attributed to the thermal decomposition of
Zn[S2CN(CH3)2]2, as discussed above.

Dynamic thermal decomposition kinetic

The kinetic parameters for the Zn[S2CN(R)2]2 complexes were calculated from the
non-isothermal TG curves, with heating rates of 5, 10 and 15°C min–1, according to
the well known expression proposed by Coats–Redfern [10]:

Fig. 1 Dynamic TG curve for Zn[S2CN(C2H5)2]2

Fig. 2 Superimposed TG/DTG/DSC curves for Zn[S2CN(C2H5)2]2

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Fig. 3 Superimposed TG/DTG/DSC curves for Zn[S2CN(CH3)2]2

g (α ) AR E
ln = ln – (1)
T 2
ΦE RT
where T accounts for absolute temperature, E – apparent activation energy, A – pre-
exponential factor, R – gas constant, Φ – heating rate and g(α) – kinetic model.
The kinetic model that best fitted the experimental curves was the one-dimen-
sional phase-boundary controlled model (R1), within the range of decomposed frac-
tion 0.95≥α≥0.15.

Table 5 Kinetic parameters according to the Coats–Redfern equation

Heating rates
Complexes Kinetic parameters –1
5°C min 10°C min–1 15°C min–1
n 0.39 0.38 0.47
Zn[S2CN(CH3)2]2 E/kJ mol–1 121.97 110.20 110.06
A/s–1 2.85E+07 1.87E+06 1.82E+06
r 0.9997 0.9997 0.9999
n 0.23 0.28 0.58
Zn[S2CN(C2H5)2]2 E/kJ mol–1 113.80 106.18 120.89
A/s–1 4.46E+06 6.91E+06 1.61E+07
r 0.9999 1.0 0.9999
n 0.44 0.49 0.47
Zn[S2CN(n-C3H7)2]2 E/kJ mol–1 123.76 116.89 118.03
A/s–1 2.57E+07 6.35E+06 5.82E+06
r 0.9993 0.9998 0.9998

The kinetic parameters (n – reaction order; E – apparent activation energy,

A – pre-exponential factor) were calculated according to the expressions proposed by
Coats–Redfern (CR) [10], Madhusudanan (MD) [11], Horowitz–Metzger (HM) [12]
and Van Krevelen (VK) [13]. The CR and MD integral methods gave similar results

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588 SILVA et al.: ZINC(II) DIALKYLDITHIOCARBAMATE COMPLEXES

with correlation coefficients equal or better than 0.999, while the HM and VK ap-
proach methods showed kinetic parameter values somewhat higher than those for CR
and MD methods, due to different mathematical treatment (Tables 5–8).

Table 6 Kinetic parameters according to the Madhusudanan equation

Heating rates
Complexes Kinetic parameters –1
5°C min 10°C min–1 15°C min–1
n 0.47 0.30 0.50
Zn[S2CN(CH3)2]2 E/kJ mol–1 126.48 106.76 111.76
A/s–1 8.45E+07 9.43E+05 2.84E+06
r 0.9996 0.9999 0.9999
n 0.26 0.31 0.59
Zn[S2CN(C2H5)2]2 E/kJ mol–1 115.37 107.76 121.70
A/s–1 6.85E+06 1.05E+06 2.05E+07
r 0.9998 0.9999 0.9999
n 0.34 0.43 0.44
Zn[S2CN(n-C3H7)2]2 E/kJ mol–1 118.98 114.07 116.77
A/s–1 9.51E+06 3.68E+06 4.80E+06
r 0.9995 0.9996 0.9997

Table 7 Kinetic parameters according to the Horowitz–Metzger equation

Heating rates
Complexes Kinetic parameters
5°C min –1
10°C min–1 15°C min–1
n 0.58 0.41 0.41
Zn[S2CN(CH3)2]2 E/kJ mol–1 147.86 128.14 131.12
A/s–1 8.42E+09 8.52E+07 1.14E+08
r 0.9994 0.9998 0.9998
n 0.27 0.36 0.69
Zn[S2CN(C2H5)2]2 E/kJ mol–1 133.32 126.53 142.12
A/s–1 2.01E+08 5.33E+07 1.40E+09
r 0.9995 0.9999 0.9998
n 0.53 0.56 0.60
Zn[S2CN(n-C3H7)2]2 E/kJ mol–1 145.17 135.49 140.48
A/s–1 2.42E+09 3.59E+08 6.43E+08
r 0.9996 0.9998 0.9997

Thermodynamic parameters
The thermodynamic activation parameters for the zinc(II) chelates (Table 9) were es-
timated according to the Coats–Redfern equation, applied in the determination of ki-
netic model, and the following expressions:
∆H # = E – RTs (2)

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Table 8 Kinetic parameters according to the Van Krevelen equation

Kinetic Heating rates

Complexes
parameters 5°C min–1 10°C min–1 15°C min–1
n 0.48 0.32 0.32
Zn[S2CN(CH3)2]2 E/kJ mol–1 140.09 114.05 115.37
A/s–1 5.05E+14 1.45E+12 1.93E+12
r 1.0 0.9943 0.9943
n 0.25 0.42 0.62
Zn[S2CN(C2H5)2]2 E/kJ mol–1 114.98 124.32 130.24
A/s–1 1.90E+12 1.20E+13 4.14E+13
r 0.9667 1.0 0.9991
n 0.48 0.49 0.54
Zn[S2CN(n-C3H7)2]2 E/kJ mol–1 133.79 123.77 130.30
A/s–1 7.64E+13 9.58E+12 2.77E+13
r 0.9989 0.9989 0.9999

 Ah 
∆S # =R  ln –1 (3)
 kTs 
∆G # =∆H # – Ts ∆S # (4)
where ∆H# – activation enthalpy, ∆S# – activation entropy, ∆G# – Gibbs activation free
energy, h – Planck constant, k – Boltzmann constant and Ts – observed peak temperature.

Table 9 Thermodynamic activation parameters for the Zn(S2CNR2)2 complexes

Complexes ∆S#/J mol–1 K ∆H#/kJ mol–1 ∆G#/kJ mol–1

Zn[S2CN(CH3)2]2 –106.48 110.60 175.36
Zn[S2CN(C2H5)2]2 –126.01 89.49 165.97
Zn[S2CN(n-C3H7)2]2 –106.24 112.35 176.70

The estimated thermodynamic activation parameters are indicative of an endo-

thermic process related to an irreversible thermal decomposition suggesting a better
molecular orientation in the activated state. Similar results were obtained by
Kurup et al. and Straszko et al. in studies on thermal decomposition of different
solid-state systems [14, 15].

Conclusions
The thermal decomposition of the complexes Zn[S2CN(CH3)2]2, Zn[S2CN(C2H5)2]2
and Zn[S2CN(n-C3H7)2]2 occurs in a single step, following the same phase boundary
reaction of the unidimensional R1 model, at temperatures far from their characteristic

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590 SILVA et al.: ZINC(II) DIALKYLDITHIOCARBAMATE COMPLEXES

melting points, except for the methyl compound that decomposes only partially in the
solid phase. The estimated thermodynamic activation parameters indicate the occur-
rence of an irreversible thermal decomposition through an endothermic process, and
a better molecular orientation in the activated state.
* * *
The authors acknowledge CAPES and CNPq Foundations (Brazil) for scholarships and financial
support.

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