Numerical Integration of Weight Loss Curves for Kinetic Analysis

Research abounds in the literature on kinetic analyses using thermogravimetric (TG) runs. Many of these studies use approximations of integral or derivative forms of the kinetic law and all of them use programmed temperatures. In the present work, a numerical integration procedure was discussed and applied to different examples. We focused on materials presenting a single decomposition curve as well as other materials with more complex processes. Different examples were explored, and the methodology was applied to a number of wastes such as coffee husks, polystyrene and polyethylene. In all cases, the actual temperature measured by thermocouples close to the sample is used, and several runs are fitted using the same kinetic parameters, giving robustness to the results.

Numerical Integration of Weight Loss Curves for Kinetic Analysis

Research abounds in the literature on kinetic analyses using thermogravimetric (TG) runs. Many of these studies use approximations of integral or derivative forms of the kinetic law and all of them use programmed temperature, not the actual temperature measured by thermocouples close to the sample. In addition, it is common to conduct a single run in order to perform the calculation. Nevertheless, many authors consider that numerical methods should be used to analyse the kinetics of decomposition. In such cases, the actual temperature is used and, generally, several runs are fitted using the same kinetic parameters, giving robustness to the results. In the present work, a numerical integration procedure was discussed and applied to different examples. We focused on materials presenting a single decomposition curve as well as other materials with more complex processes. Different examples were explored, and the methodology was applied to a number of wastes such as coffee husks, polystyrene and polyethylene.

The stability of uric acid in ammonium hydroxide.

We examined the stability of uric acid in dilute aqueous ammonium hydroxide solution by mass spectrometry. Uric acid decomposes in ammonium hydroxide even as dilute as 15 mmol/L when the mole ratio of ammonium hydroxide to uric acid is 50:1. There are at least four products of the decomposition, two of which have been identified as allantoin and urea. The slope of the decomposition curve indicates that uric acid is destroyed at an initial rate of 2-3% per hour. In ammonium hydroxide at a concentration of 1 mmol/L and a mole ratio of ammonium hydroxide to uric acid of less than or equal to 3.4, uric acid is not detectably decomposed. Evidently, any method for determination of uric acid that involves treating the analyte with ammonium hydroxide before analysis may destroy it. Therefore, a published method described as being "definitive" for uric acid (J Clin Chem Clin Biochem 1985; 23:129-35) could produce incorrect results because it involves storing the uric acid in 15 mmol/L ammonium hydroxide at a mole ratio of ammonium hydroxide to uric acid of greater than 120:1.

Thermal decomposition in the solid state

The foundation of solid state decomposition kinetics is based on the well known theory of nucleation and nucleus growth put forward by Jacobs and Tompkins. It has now been shown that all the kinetic equations thus derived can be represented by a general differential form: ������������������������� dα/dt = kα1-p(1-α)1-q in which α, t and k are respectively the fractional decomposition, time and rate constant; while p and q are parameters lying between zero and unity inclusively. A method has been suggested to find p and q experimentally, thereby enabling one to find the appropriate kinetic form for the chemical decomposition. The conventional method involves the testing of various existing equations to the decomposition data. Different equations are found to fit over different ranges of the decomposition curve so that it is difficult to decide which is the correct kinetic equation for a particular reaction. The present approach however eliminates this complication.