A generalisation of the non-parametric, NPK (SVD) kinetic analysis method: Part 1. Isothermal experiments

The non-parametric method of kinetic analysis using singular value decomposition of a matrix of data values, as proposed by Nomen and Sempere, is applied to isothermal experiments. It is demonstrated that a correction has to be applied to obtain the value of the pre-exponential constant A. The differential analysis method is extended to integral analysis and, when tested using simulated data, shows very accurate retrieval of the starting values of activation energy and pre-exponential constants. A set of data for the decomposition of calcite under vacuum, treated isothermally was taken from the ICTAC study of kinetic methods. The results obtained agree reasonably with those reported from the study.

[1]  J. Šesták,et al.  The study of heterogeneous processes by thermal analysis , 1973 .

[2]  J. Sempere,et al.  The NPK method: An innovative approach for kinetic analysis of data from thermal analysis and calorimetry , 2002 .

[3]  B. Roduit.  Computational aspects of kinetic analysis.: Part E: The ICTAC Kinetics Project—numerical techniques and kinetics of solid state processes , 2000 .

[4]  S. Vyazovkin.  Computational aspects of kinetic analysis. Part C. The ICTAC Kinetics Project — the light at the end of the tunnel? , 2000 .

[5]  J. Málek,et al.  Advantages of Combined Kinetic Analysis of Experimental Data Obtained under Any Heating Profile , 2002 .

[6]  Joseph H. Flynn,et al.  The ‘Temperature Integral’ — Its use and abuse , 1997 .

[7]  J. Sempere,et al.  A new method for the kinetic study of thermoanalytical data : The non-parametric kinetics method , 1998 .

[8]  M. Maciejewski,et al.  Computational aspects of kinetic analysis. Part B: The ICTAC kinetics project : the decomposition kinetics of calcium carbonate revisited, or some tips on survival in the kinetic minefield , 2000 .

[9]  G. R. Heal,et al.  Solid–liquid diffusion controlled rate equations , 1999 .

[10]  M. E. Brown,et al.  “Model-free” kinetic analysis? , 2002 .

[11]  J. Sempere,et al.  The Non-Parametric Kinetics A New Method for the Kinetic Study of Thermoanalytical Data , 1998 .

[12]  Edmund R. Malinowski,et al.  Factor Analysis in Chemistry , 1980 .

[13]  Joseph H. Flynn,et al.  General Treatment of the Thermogravimetry of Polymers. , 1966, Journal of research of the National Bureau of Standards. Section A, Physics and chemistry.

[14]  R. Nomen,et al.  Progress in Non-parametric Kinetics , 1999 .

[15]  Alan K. Burnham,et al.  Computational aspects of kinetic analysis: Part A: The ICTAC kinetics project-data, methods and results , 2000 .

[16]  J. Málek,et al.  Nanocrystallization of anatase in amorphous TiO2 , 2004 .

[17]  Alan K. Burnham,et al.  Computational aspects of kinetic analysis.: Part D: The ICTAC kinetics project — multi-thermal–history model-fitting methods and their relation to isoconversional methods , 2000 .