Some specific features of the thermochemistry of epoxy-amine curing at the later stages of the reaction are considered. Possible
mechanism of cross-linking and the question about the driving force leading to the infinite network are discussed. The coupling
of the reaction kinetics and rearrangement of the chains crosslinked into the rigid supramolecular structure is the essential
feature of epoxy-amine vitrified system. It has been proposed that owing to the contribution from the side process, different
curing temperatures can result in the structures with different Tg. It was also established that reaction of epoxy ring opening alone is not responsible for the residual curing. The latter
is the result of the side processes. As compared with the reaction of epoxy ring opening the side processes are strongly dependent
on the geometrical aspects.
The reaction process of the thermal dehydration of dilithium tetraborate trihydrate, Li2B4O7
3H2O, was reinvestigated from a viewpoint of reaction kinetics. On the basis of the results of thermogravimetry, constant rate thermal analysis, powder X-ray diffractometry, infrared spectroscopy and scanning electron microscopy, it was confirmed that the reaction proceeds via three consecutive kinetic steps characterized by different activation energies. The first and second kinetic steps, accompanied by the destruction of the original crystal structure of the reactant, seem to be assigned to the surface and internal reactions, respectively. During the third kinetic step, the thermal dehydration of hydrated amorphous intermediate, produced at the second kinetic step, and crystallization of the final dehydration product, Li2B4O7, are likely to take place concurrently.
The reaction [Mn(NH3)2]Cl2+ 4NH3 ⇄ [Mn(NH3)6]Cl2, which is of potential use in chemical heat pumps, was studied by means of differential scanning calorimetry. The thermodynamic conditions, the enthalpy of the reaction, and the heat capacity values for MnCl2, [Mn(NH3)2Ch and [Mn(NH3)6Cl2 were measured. The influence of the reaction kinetics of the experimental procedure and some parameters such as sample temperature, ammonia pressure and scanning rate was examined.
Aspects of the theories that are conventionally and widely used for the kinetic analyses of thermal decompositions of solids,
crystolysis reactions, are discussed critically. Particular emphasis is placed on shortcomings which arise because reaction
models, originally developed for simple homogeneous reactions, have been extended, without adequate justification, to represent
heterogeneous breakdowns of crystalline reactants. A further difficulty in the mechanistic interpretation of kinetic data
obtained for solid-state reactions is that these rate measurements are often influenced by secondary controls. These include:
(i) variations of reactant properties (particle sizes, reactant imperfections, nucleation and growth steps, etc.), (ii) the effects of reaction reversibility, of self-cooling, etc. and (iii) complex reaction mechanisms (concurrent and/or consecutive reactions, melting, etc.). A consequence of the contributions
from these secondary rate controls is that the magnitudes of many reported kinetic parameters are empirical and results of
chemical significance are not necessarily obtained by the most frequently used methods of rate data interpretation. Insights
into the chemistry, controls and mechanisms of solid-state decompositions, in general, require more detailed and more extensive
kinetic observations than are usually made. The value of complementary investigations, including microscopy, diffraction,
etc., in interpreting measured rate data is also emphasized.
Three different approaches to the formulation of theory generally applicable to crystolysis reactions are distinguished in
the literature. These are: (i) acceptance that the concepts of homogeneous reaction kinetics are (approximately) applicable (assumed by many researchers),
(ii) detailed examination of all experimentally accessible aspects of reaction chemistry, but with reduced emphasis on reaction
kinetics (Boldyrev) and (iii) identification of rate control with a reactant vaporization step (L’vov). From the literature it appears that, while the
foundations of the widely used model (i) remain unsatisfactory, the alternatives, (ii) and (iii), have not yet found favour. Currently, there appears to be no interest in, or discernible effort being directed towards,
resolving this unsustainable situation in which three alternative theories remain available to account for the same phenomena.
Surely, this is an unacceptable and unsustainable situation in a scientific discipline and requires urgent resolution?
Authors:Shivani Suri, K. K. Bamzai, and Vishal Singh
Non-isothermal kinetic parameter of pure and cadmium-doped barium phosphate single crystal grown by room temperature solution technique have been investigated. Single crystal X-ray diffraction establishes grown crystal to be orthorhombic in nature. Scanning electron microscopy supplemented with energy dispersive X-ray analysis was used to study the surface features and to find the exact stoichiometric composition of the grown crystal. Fourier transform infrared spectroscopy studies confirm the presence of various functional groups. The effect of cadmium doping on pure barium phosphate single crystal was studied using thermogravimetry analysis. Thermogravimetry studies shows that the pure crystal was stable up to a temperature of 330 °C whereas doped crystal was stable up to a temperature of 240 °C, i.e., pure crystals were more stable than doped ones. Various solid-state reaction kinetics, i.e., activation energy (Ea), frequency factor (Z), and entropy (ΔS∗) was calculated out to find the mechanism of thermal decomposition at different stages for pure and cadmium doped barium phosphate.
A Mangelsdorf's approach to modeling the epoxy-amine cure kinetics has been developed. Analysis of the data by means of Mangelsdorf's
approach makes it possible not only to determine the reaction rate constant and the heat of epoxy ring opening, but also to
elucidate the reaction mechanism. However, to model the kinetic curves obtained by the calorimetric method for the complicated
reaction should be derived an equation expressing the rate of change of the heat with time, as a function of the reaction
rate and the extent of conversion. In a detailed examination the thermokinetic data, we found that glassy state transition
is kinetically feasible. Using data available in literature, the kinetic model for epoxy-amine cure reaction was developed.
Our treatment of glass formation is based on the picture of the reaction system as a miscible mixture of two structurally
different liquids. This approach is similar to that presented by Bendler and Shlesinger as a Two-Fluid model. In the application
of this model to reaction kinetics, we believe the explanation of glass structure formation lies in the splitting of the homogeneous
mixture into two liquid phases.
This article studies the thermokinetics and safety parameters of cumene hydroperoxide (CHP) manufactured in the first oxidation tower. Vent sizing package 2 (VSP2), an adiabatic calorimeter, was employed to determine reaction kinetics, the exothermic onset temperature (T0), reaction order (n), ignition runaway temperature (TC, I), etc. The n value and activation energy (Ea) of 15 mass% CHP were calculated to be 0.5 and 120.2 kJ mol−1, respectively. The heat generation rate (Qg) of 15 mass% CHP compared with hS (cooling rate) = 6.7 J min−1 K−1 of heat balance, the TS,E and the critical extinction temperature (TC, E) under 110 °C of ambient temperature (Ta) were calculated 111 and 207 °C, respectively. The Qg of 15 mass% CHP compared with hS = 0.3 J min−1 K−1 of heat balance was applied to determine the TC, I that was evaluated to be 116 °C. This article describes the best operating conditions when handling CHP, starting from the first oxidation tower.
Authors:H. Treutler, G. Just, M. Schubert, and H. Weiss
The groundwater at a former gasoline production site in Germany is heavily contaminated with aromatic hydrocarbons (mostly
benzene) and is currently being treated in bioreactors under anaerobic conditions. To determine the reaction kinetics it is
essential to know the mean residence time of the groundwater in these reactors. Most of the commonly used tracers (dyes and
salts) did not give reliable results because of their interaction with the mineral matrix in the reactors. In this study radon
(222Rn) dissolved in the groundwater is used as the tracer. The flow rate of groundwater through the reactors is 1 l/h. Over a
period of 8 hours the radon-spiked groundwater was injected into the natural groundwater which has a very low radon concentration.
The radon concentration of the discharged water is measured online at the reactor outlet. An increasing radon concentration
at the reactor exit indicates the shortest residence time of the water. The time-dependent progress of the radon concentration
provides detailed information about the flow behavior and residence times of water in the reactor.
Authors:A. S. Al-Hobaib, D. M. Al-Dhayan, K. M. Al-Sulaiman, and A. A. Al-Suhybani
Sand filters are used as a filter bed in many ground water treatment plants to remove the physical contaminants and oxidation
products. A build-up of radioactivity may take place on the granules, where iron and manganese oxides are deposited and form
thin films on the surface of sand filter. The oxides of iron and manganese play an important role in adsorbing radium from
ground water. The disposal of those granules makes a significant problem. A batch technique is used for solubilization of
radium from sand filters in the presence of some organic acids, which act as reducing agents. These acids are formic acid,
acetic acid, benzoic acid, succinic acid, oxalic acid, phthalic acid, and adipic acid. The data were obtained as a function
of acidity, temperature, contact time and liquid/solid ratio particle size and shaking speed. It was found that oxalic acid
was the best for radium removal. The effectiveness of these acids on radium removal was as follows: oxalic acid > phthalic
acid > adipic acid > succinic acid > formic acid > acetic acid. The maximum removal obtained was 69.9% at 1M oxalic acid at
8 ml/g ratio. Reaction kinetics and mechanism parameters of the dissolution process were studied and compared with other published
Hydrogen phosphate (HPO42−) or poly(acrylic acid) (PAA) stabilized cobalt(0) nanoclusters were in situ generated from the reduction of cobalt(II) chloride during the catalytic hydrolysis of sodium borohydride (NaBH4) in the presence of stabilizers, HPO42− or PAA. Cobalt(0) nanoclusters stabilized by HPO42− or PAA were characterized by using UV–Visible spectroscopy, TEM, XPS and FT-IR techniques. They were employed as catalysts in the hydrolysis of NaBH4 to examine the effect of stabilizer type on their catalytic activity and stability. Detailed reaction kinetics of the hydrolysis of NaBH4 in the presence of both catalysts was studied depending on catalyst concentration, substrate concentration and temperature. PAA stabilized cobalt(0) nanoclusters provided higher total turnover number (TTON = 6,600) than that of HPO42− stabilized cobalt(0) nanoclusters (1,285 turnovers). However, the HPO42− stabilized cobalt(0) nanoclusters provided a lower activation energy (Ea = 53 ± 2 kJ mol−1) than the PAA stabilized cobalt(0) nanoclusters (Ea = 58 ± 2 kJ mol−1) for the hydrolysis of NaBH4. The use of two types of stabilizers in the preparation of the same metal(0) nanoclusters following the same methodology enables us to compare the electrostatic and steric stabilization in terms of the catalytic activity and stability of metal(0) nanoclusters.