THERMAL DEGRADATION AND KINETICS OF 0D COPPER (II) COMPLEX

J. D. Zdravković 1, D. D. Poleti 2, J. R. Rogan 2, P. J. Vulić 3, D. M. Minić 4

1 Innovation Centre - Faculty of Technology and Metallurgy, University of Belgrade, Serbia
2 Faculty of Technology and Metallurgy, University of Belgrade, Serbia
3 Faculty of Mining and Geology, University of Belgrade, Serbia
4 Faculty of Physical Chemistry, University of Belgrade, Serbia

Table 1. Thermodynamic (for β = 15 °C min–1) and overall

kinetic parameters (Ea and A) for [Cu2(bipy)2(pht)2]·4H2O .
Thermolysis of coordination
compounds as precursors can be used Process Dehydration Degradation
for production of metals, metal oxides, Temperature range
metal sulfides or other nanosized 30-100 100-420
(oC)
materials. Therefore we prepared
dimeric [Cu2(bipy)2(pht)2]·4H2O (bipy = DSC peak minimum 218.7
81.5
2,2’-bipyridine, pht = dianion of (oC) 233.7
phthalic acid), whose degradation Mass loss (%),
process is practically finished up to 8.6 (8.6) 59.2 (57.4)
(calc. (%) )
280°C. The mechanism of all CO2 + C8H4O3 + 2 CO
degradation steps has been analyzed Fragment loss 4H2O
+ C10H8N2 + C5H4N
under non-isothermal conditions in
H (kJmol-1) 133.3 52.4
nitrogen atmosphere at following
heating rates: 5, 10 and 15 ºC min–1. 151.5 ± 12.2; 151.6 ±
Ea (kJ mol–1), 84.0 ± 8.0;
The second and the third degradation 10.2
(Kissinger; Ozawa) 85.3 ± 8.0
steps are highly overlapped and were 101.7 ± 8.2; 104.4 ± 8.9
deconvoluted (Fig. 3) using Fraser- ln A (min–1), 29.4 ± 10.3; 37.3 ± 17.5; 37.4 ± 13.3
Suzuki function as recommended for (Kissinger; Ozawa) 29.4 ± 9.3 24.0 ± 11.1; 24.9 ± 9.0
Fig. 1. TG-DTG curves for [Cu2(bipy)2(pht)2]·4H2O. this type of processes. 27.0
∆S# (J mol–1 K–1) -4.4
-83.8

Fig. 2. XRPD pattern of residue obtained at 330 °C. Fig. 3. Deconvolution using Fraiser-Suzuki function Fig. 4. Ea versus α for individual degradation
at β = 10 °C min–1. steps using Ortega isoconversional method.

Fig. 5. Màlek curves y(α) and z(α) for individual degradation steps.

Table 2. The kinetic triplets of individual degradation steps.

Individual
Ea (kJ mol–1) ln A (min–1) f(α) = αm (1- α) n
step
Step 1 111.1 ± 4.6 26.4 ± 10.6 α0.52(1 - α)1.10
Step 2 127.6 ± 11.2 31.3 ± 13.1 α0.58(1 - α)0.94
Step 3 87.9 ± 6.8 20.2 ± 10.9 α0.42(1 - α)1.30