Effect of deuteration on the thermal dehydration of lithium sulfate monohydrate

Effects of deuteration on the thermal stability, enthalpy change and kinetic parameters for the thermal dehydration of Li₂SO₄·H₂O were examined by means of TG and DSC. The enthalpy change for the monohydrate was smaller by 1.63±0.75 kJ/mol than that for the monodeuterate. The rate constant for the monohydrate was a little larger than that for the monodeuterate. However, the thermal stability, activation energy and frequency factor were practically unaffected by deuteration of the hydrate. It is suggested that the activation entropy as well as the activation energy should be considered in explaining the kinetic deuterium isotope effect in the thermal dehydration of Li₂SO₄·H₂O.

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Zusammenfassung Die Wirkung der Deuterisierung auf die Thermostabilität, die Enthalpie-Änderungen und kinetischen Parameter der thermischen Dehydratisierung von Li₂SO₄·H₂O wurden durch TG und DSC untersucht. Die Enthalpie-Änderung für das Monohydrat wurde um 1.63±0.75 kJ/mol niedriger gefunden als für das Monodeuterat. Die Geschwindigkeitskonstante für das Monohydrat war etwas größer als für das Monodeuterat. Die Thermostabilität, die Aktivierungsenergie und der Frequenzfaktor wurden jedoch von der Deuterisierung des Hydrats praktisch nicht beeinflußt. Es wird vorgeschlagen, daß bei der Erklärung des kinetischen Deuterium-Isotop-Effekts bei der thermischen Dehydratisierung von Li₂SO₄·H₂O sowohl die Aktivierungsentropie als auch die Aktivierungsenergie berücksichtigt werden müssen.

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, Li₂SO₄·H₂O. 1.63+0.75 /. , . , , . , Li₂SO₄·H₂O.

     

Self-cooling effect on the kinetics of nonisothermal dehydration of lithium sulfate monohydrate

The effects of self cooling on the apparent kinetics of the nonisothermal dehydration of crushed crystals of lithium sulfate monohydrate were investigated using TG accompanied by DTA and power-compensation type DSC. Linearity of the sample heating rate on the TG-DSC system is much better than that on the TG-DTA. Kinetic obedience and Arrhenius parameters obtained from the TG-DTA deviate considerably from those obtained from the TG-DSC; the latter are the more accurate due to the better linearity of the sample heating rate.

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Zusammenfassung Mittels TG, ergänzt durch DTA und DSC mit Leistungskompensation wurde der Einfluß des Self-cooling-Effektes auf die scheinbare Kinetik der nichtisothermen Dehydratation von zerkleinerten Kristallen aus Lithiumsulfat-Monohydrat geschätzt. Die mittels TG-DTA erhaltene Kinetik und die Arrheniusschen Parameter weichen erheblich von denen ab, die mittels TG-DSC ermittelt wurden. DSC mit Leistungskompensation und TG-DSC haben gegenüber TG oder TG-DTA den großen Vorteil, das nichtisotherme kinetische Verhalten von Feststoffzersetzungen zu charakterisieren. Mittels Thermoanalyse nichtisotherm ermittelte kinetische Parameter sind ohne Anwendung von DSC eher unreell, besonders wenn sie bei größeren Aufheizgeschwindigkeiten und Probengrößen bestimmt wurden.

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We thank Dr. A. K. Galwey for reading the text and for valuable comments.     

Calculation of the kinetic parameters

The paper reports the calculation of kinetic parameters (activation energy, pre-exponent and reaction order) of thermodegradation of some phenol stabilizers. For this purpose, a software package for IBM-compatible personal computers is proposed. The first calculation of kinetic parameters (E, Z, n) was carried out for these compounds. The package can be applied for kinetic calculations on the thermodegradation of other substances.     

Calculation of kinetic parameters from TG curve on the base of dehydration process of hydrous titanium dioxide

A direct method of evaluating of kinetic equation parameters based on TG curve is proposed. The method was applied to calculate kinetic parameters of the process of dehydration of hydrous titanium dioxide.

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Zusammenfassung Es wird ein direktes Verfahren zur Bestimmung der Parameter der kinetischen Gleichung auf der Basis von TG-Kurven gegeben. Das Verfahren wurde zur Berechnung der kinetischen Parameter des Dehydratationsprozesses von wasserhaltigem Titandioxid benutzt.

     

Combined derivatographic and thermo-gas-titrimetric examination of the thermal decomposition of copper tetra-ammine sulphate monohydrate

The thermal decomposition of copper tetra-ammine sulphate monohydrate has been investigated by a combined derivatographic and thermo-gas-titrimetric method. It has been found that decomposition starts with splitting off of the water of crystallization and only after part of this water has departed does stepwise release of ammonia begin. First two moles, then one and finally again one mole of ammania (per mole of compound) are released. It has been established that a small amount of sulphur trioxide splits off during the last decomposition step, and that about 20 % of the last ammonia to be released is thermally decomposed.     

由热重数据计算动力学参数

热重法(TG)是一种动态测量技术,可在程序升温或降温情况下对给定物质或体系提供一个连续的,以温度或时间为函数的重量变化曲线,所以由它跟踪反应能给出反应动力学的有关信息。这种非等温法与早期使用的等温法相比,有快速、连续和需要较少实验数据等优点,近年来在动力学研究方面得到广泛应用,但还只限于研究下列几种类型的简单     

Thermal dehydration of some food products and kinetic parameters of this process

Metal poly(vinyl acetates) polymers were obtained by radical polymerization with azodiisobutyronitrile. The thermal stabilities of the metal polymers (M-PVAC) have been studied by thermogravimetry (TG) between 25 and 550°C under nitrogen flow. The decomposition temperature was obtained from the maximum of the first derivative from TG curve. The kinetic parameters of the thermal decomposition were determined by the Arrhenius equation. All these polymers degrade mainly in a single step with a very small second step, probably via a complex reaction. The kinetic data thus obtained show that the thermostabilities decrease in the order: Sb-PVA_c～Ge-PVA_c>Bi-PVA_c～Cd-PCA_c>Ag-PVA_c～PVA_c>Zn-PVA_c> Au-PVA_c>In-PVA_c>Sn-PVA_c>Ga-PVA_c>Pd-PVA_c. Again, the thermal stability is dependent upon the metal incorporated in the backbone polymer. They loose weight after 320°C. The order of reaction from the thermal decomposition of these metal polymers was found to be ?0.5 for the first step and 0 for the second. The pre-exponential factor, the reaction order and the activation energy of the decomposition for metal (PVA_c) have been determined in most of them.     

A numerical method of computing the kinetic parameters

A numerical method of computing the kinetic parameters (the activation energy (E), the preexponential constant (A) and the reaction order (n)) of exothermic decomposition of energetic materials via the exothermic rate equation is presented. The values ofE, A, andn are reported for the exothermic decomposition of six typical energetic materials, 1,6-diazido-2,5-dinitrazahexane (I), 1,5-diazido-3-nitrazapentane (II), 2,2,4,7,9,9-hexanitro-5-methyl-4,7-dinitrazadecane (III), 2,2,2-trinitroethyl-4,4,4-trinitrobutyrate (IV), 1,4-dinitro-2,3-dioxo-1,4-dinitrazacyclohexane (V) and 1,3,5-trianitro-1,3,5-triazafurazano[3,4-f]cycloheptane (VI).

     

Rigorous approach to kinetic parameters: polymerization of styrene with benzoyl peroxide in carbon tetrachloride

Both the rate constant of initiator dissociation, k_d, and the chain transfer constant, C_x, are determined by monitoring the rates of monomer and transfer agent conversions in a chain polymerization. Statistical analysis that takes into account the errors of experimental variables has been used to treat the kinetic data for the polymerization of styrene initiated by benzoyl peroxide (Bz₂O₂) in carbon tetrachloride at 60°C. Values of k_d and C_x produced by this error-in-variable method (EVM) are in accordance with those reported in literature. More important, the EVM algorithm always results in the smallest standard deviations of estimates, and hence, it is superior to the usual least-squares calculations. Other distinct features of the method are outlined. The initiator efficiency for Bz₂O₂ is estimated to be 0.72 under the present conditions.     

Thermal analysis of lithium peroxide prepared by various methods

Behavior of lithium peroxide samples at heating in air was studied by the methods of thermogravimetric analysis (TGA) and differential thermal analysis (DTA). In the temperature range from 32 to 82°C all the studied samples we found to react with water vapor forming lithium peroxide monohydrate as confirmed by the methods of chemical analysis and of qualitative X-ray phase analysis. It was found experimentally that in the temperature range from 340 to 348°C lithium peroxide began to decompose into lithium oxide and oxygen, the starting temperature depended on the method of preparation of lithium peroxide. For all the studied samples polymorphism in the temperature range from 25 to 340°C was not detected.     

A method of finding invariant values of kinetic parameters

A method of calculating the Arrhenius parameters has been proposed, based on an evaluation of the coordinates of intersection of greatly extended confidence regions determined in solving the inverse kinetic problem. The validity of this method is illustrated by comparison of the Arrhenius parameters found from non-isothermal and isothermal data reported by other investigators.     

Establishment and application of a new method for the determination of kinetic parameters by plug-plug kinetic capillary electrophoresis (ppKCE)

A novel plug-plug kinetic capillary electrophoresis method was established, which can be used to si-multaneously determine the kinetic parameters kon and koff in interaction systems. The method is comparatively simple and some restrictions in conventional ppKCE methods can be effectively avoided. The requirements for resolution and detection sensitivity in this method are much lower than those of conventional ppKCE. The successful determination of the kinetic parameters and the binding constant Kb between citalopram and BSA showed availability of this method. The results were confirmed by us-ing the time ratio method. The application field of kinetic capillary electrophoresis can be expanded with this new method.