▪ Abstract The kinetics of solid state reactions generally cannot be assumed to follow simple rate laws that are applicable to gas-phase reactions. Nevertheless, a widely practiced method for extracting Arrhenius parameters from thermal analysis experiments involves force fitting of experimental data to simple reaction-order kinetic models. This method can produce significant errors in predicted rates outside the experimental range of temperatures, and it is of limited utility for drawing mechanistic conclusions about reactions. In this review, we discuss how an alternative “model-free” approach to kinetic analysis, which is based on the isoconversional method, can overcome some of these limitations.

Kinetics in solids

Three isomorphous compounds M(CHOO)3[NH2(CH3)2] (M = Mn(1·Mn), Co(2·Co), Ni(3·Ni)) have been synthesized in solvothermal conditions. Single-crystal X-ray diffraction shows that they are all crystallized in the trigonal space group R 3c with small differences in the lattice parameters. Bridged by the three-atom single-bridge CHOO-, M ions form a three-dimensional distorted perovskite-like structure with dimethylamine (DMA) cations located in the cages of the network. Based on the magnetic data, these three 3D compounds are weak ferromagnets with the critical temperature Tc = 8.5 K (1·Mn), 14.9 K (2·Co), and 35.6 K (3·Ni), and for 2·Co and 3·Ni, spin reorientation might take place at 13.1 and 14.3 K, respectively. At 1.8 K, hysteresis loops can be observed for all three compounds with the coercivity field ca. 90 Oe (1·Mn), 920 Oe (2·Co), and 320 Oe (3·Ni). The canting angles are estimated to be 0.08°, 0.5°, and 0.6° for 1·Mn, 2·Co, and 3·Ni, respectively. The magnetic coupling between MnII ions in 1·Mn was...

Perovskite-like Metal Formates with Weak Ferromagnetism and as Precursors to Amorphous Materials

Inorganic lanthanide compounds with complex anions.

An approach to the solution of the inverse kinetic problem in the case of complex processes

The thermal decomposition of oxalates. A review

Kinetics of the thermal dehydration of magnesium oxalate dihydrate in a flowing atmosphere of dry nitrogen

Kinetic study of the thermal dehydration of calcium oxalate monohydrate

Study on the boundary structures in a series of lanthanide hexacyanoferrate(III) n-hydrates

Thermal decompositions of formates. Part IV. Thermal dehydrations of Mg(II), Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) formate dihydrates

The effect of water vapour pressure on the kinetics of the thermal dehydration of zinc formate dihydrate

Yoshio Masuda

Papers

Kinetics of the thermal dehydration of magnesium oxalate dihydrate in a flowing atmosphere of dry nitrogen

Kinetic study of the thermal dehydration of calcium oxalate monohydrate

Study on the boundary structures in a series of lanthanide hexacyanoferrate(III) n-hydrates

Thermal decompositions of formates. Part IV. Thermal dehydrations of Mg(II), Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) formate dihydrates

The effect of water vapour pressure on the kinetics of the thermal dehydration of zinc formate dihydrate