Search Results
Abstract
Reaction calorimetry strongly penetrated process development laboratories in the fine chemicals industry. Applications of calorimetry to different fields of process optimization, chemical reactions and physical unit operations were developed. Applications were first developed in the field of process safety. The thermal data of reaction obtained in the calorimeters allow us to check if a reaction will be controllable at full scale under normal operating conditions and in case of equipment failure. Further, the accurate temperature control and heat flow measurement opened the door to more engineering related data, in the fields of phase equilibria like vapour liquid, solubilities, crystallization and also in the mixing techniques. Some examples of developments in these different fields will be reviewed.
Abstract
Chemical polymerization of pyrrole (Py) was carried out in a reaction calorimeter by using FeCl3 or CuCl2 as an oxidant in an acetonitrile medium. The formation heat of polypyrrole (PPy), determined under a wide range of reactant concentrations and reaction temperatures, is directly related to the PPy yields and to the degree of polymerization. Due to the negative values of both the entropy and enthalpy of the reaction the gravimetric yield is inversely related to the temperature and directly to the Py concentration. The yields to the PPy and the related reaction heats, are close to zero when the 
ceiling temperatures
are reached (T
ceil=348 K for Fe-doped and T
ceil=313 K for Cu-doped PPys). It was observed that a ceiling concentration corresponds to each ceiling temperature and only light oligomers are formed if Py concentration is too low. The electric conductivity values of the products were also determined and a direct relationship to the yields was found as well. The highest electric conductivity value (C=0.6 S cm–1) was related to the PPy fresh synthesized from a 0.017 M Py solution.
Abstract
When chemical reactions are performed in semi-batch mode and the reaction rate is relatively low, the reactant added may be accumulated. The resulting thermal accumulation is of major concern regarding process safety, as a fault in the cooling system may lead to a run-away reaction. The feed rate in semi-batch processes is usually constant, but this paper discusses methods of optimizing the feed rate interactively, based on the measured heat flow and the calculated amount of compound that has actually reacted. The prerequisite of such procedures is to run the experiments in a reaction calorimeter in which the heat flows can be measured accurately and continuously. For this purpose a ChemiSens reaction calorimeter CPA202, which is calibration free and gives stable, flat ‘zero-line-type’ baselines, was employed.
The RC1 calorimeter revealed itself a suitable instrument to obtain information about safety and mechanisms involved in the reaction between cyclohexanecarboxylic acid (AEB) and oleum. A previous hypothesis about the existence of an unstable intermediate was confirmed and its heat of formation was calculated. The heat of sulphonation related to undesirable by-products production and the heat of protonation of AEB with H2SO4 were also evaluated. Therefore, it was possible to distinguish the reactions involved in the process and, through their thermal behaviour, to determine the limit conditions to avoid the by-products formation.
Abstract
Isothermal titration calorimetry (ITC) and reaction calorimetry (RC) have been used to construct the solid-liquid equilibrium line in ternary systems containing the solute to precipitate and an aqueous mixed solvent, and to study polymerization reactions under real process conditions, respectively. Phase diagrams have been established over the whole concentration range for some benzene substituted derivatives, including o-anisaldehyde, 1,3,5-trimethoxybenzene and vanillin, in {water + alcohol}mixtures at different temperatures. Acrylamide polymerization in aqueous solution using potassium permanganate/acid oxalic redox system as initiator was investigated on a homemade calorimeter, which works according to the isoperibolic mode. A Calvet type differential RC was used to illustrate the applicability of temperature oscillation calorimetry (TOC) for the evaluation of the heat transfer coefficient during the course of reaction.
Abstract
For a great number of European safety groups, reaction calorimetry is the key technique for analysis of the main reaction in the risk assessment of chemical processes. A comparison of calorimetric studies of model reactions, the N-oxidation of two substituted pyridines with hydrogen peroxide, made by several European groups, can open the door to standardization of the methodologies used. However, the intrinsic experimental complexity of the model reactions, which included dosing at high temperature, a multiphase system and evaporation, and the different evaluation criteria, produced a considerable dispersion between the results obtained by the various groups.
Abstract
Materials with high surface areas and small particle size (nanophases), metastable polymorphs, and hydrated oxides are increasingly important in both materials and environmental science. Using modifications of oxide melt solution calorimetry, we have developed techniques to study the energetics of such oxides and oxyhydroxides, and to separate the effects of polymorphism, chemical variation, high surface area, and hydration. Several generalizations begin to emerge from these studies. The energy differences among different polymorphs (e.g., various zeolite frameworks, the 
- and 
-alumina polymorphs, manganese and iron oxides and oxyhydroxides) tend to be small, often barely more than thermal energy under conditions of synthesis. Much larger contributions to the energetics come from oxidation-reduction reactions and charge-coupled substitutions involving the ions of basic oxides (e.g., K and Ba). The thermodynamics of hydration involve closely balanced negative enthalpies and negative entropies and are very dependent on the particular framework and cage or tunnel geometry.
The estimation of reaction enthalpy for complex molecules using Benson groups
Comparison of different strategies
Summary
Estimation methods developed over years by S. W. Benson and co-workers for calculation the thermodynamic properties of organic compounds in the gas phase are applied to a pharmaceutical real process with all type of non-idealities. The different strategies used to calculate the reaction enthalpy of a chemical process, in the absence of data for complex molecules, using the Benson group additivity method are presented and also compared with the experimental value of reaction enthalpy obtained using reaction calorimetry (Mettler-Toledo, RC1). We demonstrate that there are some strategies that can be followed to obtain a good estimation of the reaction enthalpy in order to begin the safety assessment of a chemical reaction. This work is part of an industrial project [1] in which the main objective was the risk assessment of chemical real and complex processes using the commonly available tools for the SMEs (with limited resources).
Abstract
A Grignard reaction of reactantA and phenyl magnesium chloride is used to make a pharmaceutical intermediate at the production scale. The elimination of protecting groups onA was proposed as a means to reduce synthesis costs. This new synthesis route, however, had process efficiency and safety issues associated with it: (1) build-up of unreactedA in the reactor, (2) influence ofA's particle size on the reaction rate, (3) the sensitivity of the reaction rate to the reaction temperature and to the (changing) solvent composition, and (4) the highly exothermic nature of the reaction.
The Mettler RC1 Reaction Calorimeter was used to quantify the influence of solvent composition, temperature, and particle size on the reaction rate. Results indicated a dramatic effect of solvent composition and reaction temperature on the reaction rate; for example, over a temperature range of just 30°C, the reaction time decreased from more than a day to just a few minutes. At such high reaction rates, the vessel jacket could not remove the reaction heat sufficiently and the internal temperature rose adiabatically.
These results were used to make process design and operation recommendations for safe and efficient plant operation with this modified Grignard reaction system.
Abstract
A simple method for the on-line calibration, in which both the heat transfer coefficient and the heat capacity of the reactor contents are determined, is described for laboratory scale heat transfer calorimeters. The calorimeter is operated in the isoperibolic mode for the calibration and a constant power is supplied to a resistor placed inside the reactor. The reactor heat balance differential equation is used to produce a set of linear simultaneous equations with each data acquisition cycle giving one equation. The heat transfer coefficient and the heat capacity are obtained from this set of equations by linear least squares. The application of the calibration procedure is illustrated by experiments in which the heat of reaction is determined on-line fora simulated reaction with first order kinetics and for the hydrolysis of acetic anhydride.
