Authors:R. K. Verma, L. Verma, M. Chandra, and A. Bhushan
Summary A comparative study of the non-isothermal decomposition of the dl-lactate hydrates of magnesium, calcium and strontium has been made with that of the dl-lactate hydrates chromium(III), manganese(II), iron(II), cobalt(II), nickel(II), copper(II) and zinc(II) keeping dry air as the purge gas and the heating rate maintained at 10 K min-1. While the dl-lactates of manganese(II), cobalt(II) and copper(II) followed single step decomposition scheme suggesting that dehydration and decomposition steps overlapped, the dehydration steps of the other compounds were distinct. &-T plots of none of the dehydration steps showed any induction period, indicating no physical desorption, nucleation or branching. Neither the & max-values nor the onset temperatures of the dehydration steps did show any pattern. The TG data of the dehydration steps have also been analyzed using the Freeman-Carroll, Horowitz-Metzger, Coats-Redfern, Zsakó, Fuoss-Salyer-Wilson and Karkhanavala-Dharwadkar methods. Values of order of reaction, activation energy and Arrhenius factor have been approximated and compared. There are similarities in the activation energy values for the dehydration steps (< 60 kJ mol-1 in general). It is higher with group 2 metals and lower in transition metals (maximum in magnesium and lowest in chromium and iron lactates). In cases of overlapping of dehydration and decomposition steps, the activation energy values are on the lower side with the same trend (lower in cobalt and copper cases).
The kinetic parameters of dehydration were determined under non-isothermal conditions for different polystyrenedivinylbenzene
sulfonic acid type cationites (DVB) and their dependence on the degree of cross-linking granulation, porosity, specific surface,
content of SO3M groups (M=Li, Na, K, Rb), nature of the alkali metal in partially neutralized -SO3H groups and heating rate was investigated.
Authors:Dorina Chambré, Cornelia Idiţoiu, and E. Segal
The kinetic parameters (reaction order, n, activation energy, E, pre-exponential factor, A, constant rate, k) for the dehydration step due to elimination of osmotic water and hydrogen-bounded water with the carboxylic groups, and
for the anhydrifying step owing to the dehydration of two neighboring (-COOH) groups, were determined under non-isothermal
conditions for some carboxylic resins with acrylic-divinylbenzene (DVB) matrix. The kinetic parameters were evaluated by means
of isoconversional methods from (TG/DTG) thermal analysis data. The results show a dependence of the apparent kinetic parameters
on the cross-linking degree, granulation, gel/macroporous matrix nature, exchange capacity and heating rate.
Authors:P. Thomas, P. Šimon, A. Smallwood, and A. Ray
The dehydration of an opal specimen was investigated
by thermogravimetric analysis (TG) in powder and bulk forms. The change in
geometry resulted in a significant difference in the temperature range in
which dehydration occurred with peak temperatures in the differential TG (DTG)
curve for the hand ground opal at 203°C and for the bulk opal at 340°C.
This difference was attributed to time taken for diffusion of free water in
the bulk opal to the specimen surface prior to evolution as a registered mass
loss. A model was proposed to account for the diffusion of water and was used
to estimate the diffusion coefficient.
Authors:Ray Frost, Sara Palmer, János Kristóf, and Erzsébet Horváth
Three halotrichites namely halotrichite Fe2&SO4·Al2(SO4)3·22H2O, apjohnite Mn2&SO4·Al2(SO4)3·22H2O and dietrichite ZnSO4·Al2(SO4)3·22H2O, were analysed by both dynamic, controlled rate thermogravimetric and differential thermogravimetric analysis. Because of the time limitation in the controlled rate experiment of 900 min, two experiments were undertaken (a) from ambient to 430 °C and (b) from 430 to 980 °C. For halotrichite in the dynamic experiment mass losses due to dehydration were observed at 80, 102, 319 and 343 °C. Three higher temperature mass losses occurred at 621, 750 and 805 °C. In the controlled rate thermal analysis experiment two isothermal dehydration steps are observed at 82 and 97 °C followed by a non-isothermal dehydration step at 328 °C. For apjohnite in the dynamic experiment mass losses due to dehydration were observed at 99, 116, 256, 271 and 304 °C. Two higher temperature mass losses occurred at 781 and 922 °C. In the controlled rate thermal analysis experiment three isothermal dehydration steps are observed at 57, 77 and 183 °C followed by a non-isothermal dehydration step at 294 °C. For dietrichite in the dynamic experiment mass losses due to dehydration were observed at 115, 173, 251, 276 and 342 °C. One higher temperature mass loss occurred at 746 °C. In the controlled rate thermal analysis experiment two isothermal dehydration steps are observed at 78 and 102 °C followed by three non-isothermal dehydration steps at 228, 243 and 323 °C. In the CRTA experiment a long isothermal step at 636 °C attributed to de-sulphation is observed.
An improved version of the Coats-Redfern method of evaluating non-isothermal kinetic parameters is presented. The Coats-Redfern approximation of the temperature integral is replaced by a third-degree rational approximation, which is much more accurate. The kinetic parameters are evaluated iteratively by linear regression and, besides the correlation coefficient, the F test is suggested as a supplementary statistical criterion for selecting the most probable mechanism function. For applications, both non-isothermal data obtained by theoretical simulation and experimental data taken from the literature for the non-isothermal dehydration of Mg(OH)2 have been processed.
Thermoanalytical (TA) and hot-stage microscopic techniques were employed to investigate the complicated behaviour of the non-isothermal
dehydration of single crystals of α-NiSO4·6H2O. Non-isothermal dehydration to the tetrahydrate proceeds in two stages: (1) surface nucleation and growth of nuclei, followed
by advancement of reaction fronts inward; (2) random nucleation and growth near the reaction front as well as in the bulk.
Corresponding TA curves were interpreted to represent diffusional removal of evolved water vapour through the surface layer
created in stage (1). The dehydration process of the tetrahydrate to the monohydrate is explained on the basis of textural
structures produced in the previous step. Crack formation in the surface layer and rapid escape of the water vapour were observed
in this step.
Non-isothermal dehydration of copper chloride dihydrate and nickel chloride hexahydrate were studied by using TG, DTG, DTA
and DSC measurements. The copper chloride salt loses its two water molecules in one step while nickel chloride salt dehydrates
in three consecutive steps. The first two steps involve the loss of 4 water molecules in two overlapped steps while the third
step involves the dehydration of the dihydrate salt to give the anhydrous NiCl2.
Activation energies (ΔE) and the frequency factor (A) were calculated from DTG and DTA results. We have also calculated the different thermodynamic parameters, e.g. enthalpy
change (ΔH), heat capacity (Cp) and the entropy change (ΔS) from DSC measurements for both reactants.
The isothermal rehydration of the completely dehydrated salts was studied in air and under saturated vapour pressure of water.
Anhydrous nickel chloride was found to rehydrate in three consecutive steps while the copper salt rehydrated in one step.
Authors:Rakesh K. Singh, A. Yadav, A. Narayan, Amrendra K. Singh, L. Verma, and R. K. Verma
, Chandra , M , Bhushan , A . Non-isothermaldehydration and decomposition of dl-lactates of transition metals and alkaline earth metals: a comparative study . J Therm Anal Calorim . 2005 ; 80 : 351 – 354 . 10.1007/s10973