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Abstract  

Humic acids represent a complicated mixture of miscellaneous molecules formed as a product of mostly microbial degradation of dead plant tissues and animal bodies. In this work, lignite humic acids were enriched by model compounds and the model-free method suggested by Šimon was used to evaluate their stability over the whole range of conversions during the first thermooxidative degradation step. The kinetic parameters obtained were used to predict the stability at 20 and 180�C, respectively, which served for the recognition of processes induced by heat and those naturally occurring at lower temperatures. Comparison of the conversion times brought a partial insight into the kinetics and consequently into the role of individual compounds in the thermooxidative degradation/stability of the secondary structure of humic acids. It has been demonstrated that aromatic compounds added to humic acids, except pyridine, increased stability of humic acids and intermediate chars. The same conclusion can be drawn for acetic and palmitic acids. Addition of glucose or ethanol decreased the overall humic stability; however, the char of the former showed the highest stability after 40% of degradation.

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Journal of Thermal Analysis and Calorimetry
Authors:
J. Kučerík
,
J. Kislinger
,
P. Majzlík
, and
M. Pekař

Abstract  

Application of the Arrhenius equation as the temperature function in modeling of the degradation kinetics of humic substances brought a high positive Pearson correlation coefficient with the carbon content and a reasonable negative correlation with the oxygen content. Ratio C/H indicating the aromaticity degree of humic samples did not show any significant correlation. Relatively high value of correlation coefficients provided also O + N and ratios C/(O + N) and C/O, respectively. In contrast, H, N content and natural and heat generated free radical content and their ratio gave substantially lower correlation coefficients. The latter indicates that free radicals are probably not the main reason of the collapse of the secondary structure of humic substances leading to their degradation.

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Journal of Thermal Analysis and Calorimetry
Authors:
J. Kučerík
,
H. Čechlovská
,
P. Bursáková
, and
M. Pekař

Abstract  

The thermodynamic stability of lignite humic acids (sodium salt) aggregates was studied by high resolution ultrasonic spectroscopy within the temperature interval from 5 to 90°C. The changes in differential ultrasonic velocity (U12) showed strong differences among humic solutions within the concentration range from 0.005 to 10 g L−1. Measurement revealed several transitions which were attributed to the weakening of humic secondary structure. Concentration around 1 g L−1 seemed to be a limit under which the change of the prevalence and importance of hydration occurred. Above this concentration the difference in U12 decreased following the temperature increase which was explained as a dominance of hydrophilic hydration. In contrast, below this concentration, the temperature dependence of U12 resulted in increasing tendency which was attributed to the prevalence of hydrophobic hydration, i.e. uncovering of apolar groups towards surrounding water. Additional experiments in which the humic sample was modified by hydrochloric acid resulted in a slight structural stabilization which lead to the conclusion that humic micelle-like subaggregates form an open-layer assemblies easily accessible for interaction with an extraneous molecule. That was partly verified by addition of propionic acid which brought about even larger reconformation of humic aggregates and exhibition of polar groups towards hydration water. The reversible changes in humate solutions induced by elevated temperatures provided the evidence about the existence of significant physical interactions among humic molecules resulting in formation of various kinds of aggregates. The nature of aggregates, mainly the stability and conformation, strongly depends on the concentration. Evidently, the changes observed in this work cannot be simply explained as expansions or conformational changes of macromolecular coils.

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Abstract  

The thermal and thermooxidative behavior of sodium salt of hyaluronic acid (HA) and its n-hexyl, n-decyl, n-tetradecyl and n-hexadecyl ether derivatives having an equal degree of substitution have been studied by means of differential scanning calorimetry (DSC) and thermogravimetry (TG). Derivatives were prepared by a substitution of H atom at the OH bound to the sixth C of N-acetyl-D-glucosamin of HA unit by n-hexyl, n-decyl, n-tetradecyl and n-hexadecyl chains. Both thermal and thermooxidative degradation of HA and derivatives resulted in multistep process. The main interest of this work was focused on processes occurring in the course of the first decomposition step. Experimental DSC data showed lower stability of derivatives and, remarkably lower heat evolution in comparison with original HA. On the other hand, TG measurement recorded lower mass loss for derivates which indicated appearance of new types of crosslinking reactions. Oxidative stability was evaluated by means of DSC that provided the induction period and the protection factor determination. Derivates showed remarkably lower stability in comparison with original HA; comparing each other, the highest oxidation stability showed n-decyl and n-tetradecyl derivates.

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Abstract  

Simultaneous DTA/TG technique has been used to study the influence of various model compounds (aromatics, organic acids, alkanes, ketone, heterocyclic and sterole) on the thermo-oxidative behavior of lignite humic acids. As a measure of stability the shift of the onset temperature of the exothermic degradation peak has been used. Further, the ratio of mass loss recorded in the high and low temperature ranges (thermogravimetric index) was used to evaluate the role of added compounds on the recombination reactions occurring during the thermooxidative degradation of humic acids. It has been demonstrated that most of added compounds play a role during those processes at relatively low concentrations (1% mass/mass) and affect the humic acid stability as well as the value of thermogravimetric index (i.e. the degree of the apparent aromaticity). It has been clearly shown, that the latter parameter reflects more the ‘qualitative’ than the ‘quantitative’ relationship between biodegradable humified parts in the extracted pool of organic matter.

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