Exothermicity, defined

The relative degree of crystallinity, Xt, was determined from the partial area under the DSC exotherm defined as follows ... 

It is accepted that, at normal pressures, mtile is the thermodynamically stable form of titanium dioxide at all temperatures. Calorimetric studies have demonstrated that mtile is more stable than anatase and that brookite and Ti02 (ii) have intermediate stabiHties, although the relative stabiHties of brookite and Ti02(ii) have not yet been defined. The transformation of anatase to mtile is exothermic, eg, 12.6 KJ/mol (9), although lower figures have also been reported (63). The rate of transformation is critically dependent on the detailed environment and may be either promoted or retarded by the presence of other substances. For example, phosphoms inhibits the transformation of anatase to mtile (64). 

The scale-up of exothermic processes is greatly enhanced through the use of the coefficient of thermal stability. Kafarov [2] defined this as the ratio of the slope (tan ttj) of the line representing the heat removal (due to the heat transfer medium and changes in enthalpy) to the slope (tan ttj) of the line representing heat generation (by the reaction) at the intersection of the two lines when plotted on the T versus Q coordinates. This is expressed as... 

Adiabatic Reaction Temperature (T ). The concept of adiabatic or theoretical reaction temperature (T j) plays an important role in the design of chemical reactors, gas furnaces, and other process equipment to handle highly exothermic reactions such as combustion. T is defined as the final temperature attained by the reaction mixture at the completion of a chemical reaction carried out under adiabatic conditions in a closed system at constant pressure. Theoretically, this is the maximum temperature achieved by the products when stoichiometric quantities of reactants are completely converted into products in an adiabatic reactor. In general, T is a function of the initial temperature (T) of the reactants and their relative amounts as well as the presence of any nonreactive (inert) materials. T is also dependent on the extent of completion of the reaction. In actual experiments, it is very unlikely that the theoretical maximum values of T can be realized, but the calculated results do provide an idealized basis for comparison of the thermal effects resulting from exothermic reactions. Lower feed temperatures (T), presence of inerts and excess reactants, and incomplete conversion tend to reduce the value of T. The term theoretical or adiabatic flame temperature (T,, ) is preferred over T in dealing exclusively with the combustion of fuels. 

A considerable amount of research has been conducted on the decomposition and deflagration of ammonium perchlorate with and without additives. The normal thermal decomposition of pure ammonium perchlorate involves, simultaneously, an endothermic dissociative sublimation of the mosaic crystals to gaseous perchloric acid and ammonia and an exothermic solid-phase decomposition of the intermosaic material. Although not much is presently known about the nature of the solid-phase reactions, investigations at subatmospheric and atmospheric pressures have provided some information on possible mechanisms. When ammonium perchlorate is heated, there are three competing reactions which can be defined (1) the low-temperature reaction, (2) the high-temperature reaction, and (3) sublimation (B9). 

Sulfonation of the common feedstocks proceeds with a highly exothermic instantaneous initial reaction, followed by a fast but not instant step that is also highly exothermic. The second reaction does not always proceed to completion (e.g., LAB, FAME) in the lower zone of a short residence time falling film reactor (FFR). For these organic feedstocks aging under well-defined conditions of temperature and reaction time is required. 

Heats of Reaction. Chemical reactions absorb or liberate energy, usually in the form of heat. The heat of reaction, h.Hn, is defined as the amount of energy absorbed or liberated if the reaction goes to completion at a fixed temperature and pressure. When > 0, energy is absorbed and the reaction is said to be endothermic. When /sHr < 0, energy is liberated and the reaction is said to be exothermic. The magnitude of Is.Hr depends on the temperature and pressure of the reaction and on the phases (e.g., gas, liquid, solid) of the various components. It also depends on an arbitrary constant multiplier in the stoichiometric equation. 

Many physical and process constraints limit the cycle time, where cycle time was defined as the time to the maximum exotherm temperature. The obvious solution was to wind and heat the mold as fast and as hot as possible and to use the polymer formulation that cures most rapidly. Process constraints resulted in a maximum wind time of 3.8 minutes where wind time was defined as the time to wind the part plus the delay before the press. Process experiments revealed that inferior parts were produced if the part gelled before being pressed. Early gelation plus the 3.8 minute wind time constrained the maximum mold temperature. The last constraint was based upon reaction wave polymerization theory where part stress during the cure is minimized if the reaction waves are symmetric or in this case intersect in the center of the part (8). The epoxide to amine formulation was based upon satisfying physical properties constraints. This formulation was an molar equivalent amine to epoxide (A/E) ratio of 1.05. 

For 2,3,4,6-tetrachlorophenol hardly any discoloration was detected above 200°C instead the sample vaporized rapidly. Its sodium salt reacted similarly to sodium pentachlorophenate except that its exothermic decomposition (Figure 4) is less clearly defined no crystallization occurred on cooling, and the yield of hexachlorodioxins was much lower, the remaining products being higher molecular weight materials. The hexachlorodioxins were identified by gas-liquid chromatography as two isomers in a ratio of 35 65. 

Worz et al. stress a gain in reaction selectivity as one main chemical benefits of micro-reactor operation [110] (see also [5]). They define criteria that allow one to select particularly suitable reactions for this - fast, exothermic (endothermic), complex and especially multi-phase. They even state that by reaching regimes so far not accessible, maximum selectivity can be obtained [110], Although not explicitly said, maximum refers to the intrinsic possibilities provided by the elemental reactions of a process under conditions defined as ideal this means exhibiting isothermicity and high mass transport. 

Define exothermic and endothermic reactions. What is the sign of AH for an exothermic reaction An endothermic reaction ... 

Formation of the mono- and dinitrosyl complexes is a thermodynamically favorable process, which distinctly depends on the electronic configuration of the metal center. The adsorption energy, defined as A=. Eaddukt - ( mzsm-5+ no)> is shown in the form of a histogram in Figure 2.16. Formation of mononitrosyl complexes is exothermic... 

It is found that this reaction, more properly called a hydrogenolysis than a hydrogenation, is only ca 5 kJ mol 1 exothermic for simple species such as 1,3-butadiene and its mono and dimethylated derivatives12,23,24. This is surprisingly close to thermoneutrality. Nonetheless, we have decided to define E2q by equation 20,... 

For the identification of the onset temperature of the exotherm, the steady-state temperature difference may be plotted against the sample temperature. After calibration, the evolved heat can be estimated. A typical plot of an isoperibolic measurement is illustrated in Figure 2.16. The sample is heated by step-wise adjustment of the jacket (or oven) temperature. The actual sample temperature results from the heat accumulation as net difference between the heat generated by the chemical reaction and the heat transferred to the jacket (or oven). The resulting mean temperature difference is relatively small and not easy to detect accurately. Thus, a range of step changes in temperature is used to define a curve, which enables a more accurate determination of the start of the exothermic event and of To to be made. 

Certain compounds, when held at moderate ambient temperatures for an extended period of time, may undergo an exothermic reaction that accelerates with increase in temperature. If the heat liberated by this reaction is not lost to the environment, the bulk material increases in temperature, which leads to an increase in the rate of decomposition. Unchecked, the temperature grows exponentially to a point at which the decomposition cannot be stopped or slowed. The minimum temperature at which this exponential growth occurs in a material packed in its largest standard shipping container is defined as the self-accelerating decomposition temperature. Self-accelerating decomposition temperature is a measure of the... 

In each case the reaction is exothermic and the reaction enthalpy AHR known thereby the defining the adiabatic temperature rise which is always greater than ATadiab > 50 K. Below 60°C the reaction becomes dormant and an undesirable accumulation of reactants is to be expected. Major reaction energy releases are to be anticipated if the reaction re-initiates. 

The coordination of styrene is expected to be strongly influenced by substituents that are neglected in the minimal QM model A. Thus, for sake of clarity, we do not present the styrene coordination results using model A. Depicted in Figure 8 are the three most stable styrene coordinated isomers, 8a-c. The coordination energies, which are also shown in Figure 8 in kcal/mol, reveal that the initial formation of the tt-complex is slow and reversible. In fact, only for isomer 8a is the styrene coordination exothermic and here it is only exothermic by 0.5 kcal/mol. Isomers 8a-c all have the olefinic bond of the styrene lying parallel to the plane defined by the P-Pd-Si atoms. No other sterically accessible isomers could be located where this bond lies parallel to this plane. Due to steric reasons, complexes with the olefinic bond perpendicular to this plane were found to be at least 8 kcal/mol less stable. 

To understand the dissolution of ionic solids in water, lattice energies must be considered. The lattice enthalpy, A Hh of a crystalline ionic solid is defined as the energy released when one mole of solid is formed from its constituent ions in the gas phase. The hydration enthalpy, A Hh, of an ion is the energy released when one mole of the gas phase ion is dissolved in water. Comparison of the two values allows one to determine the enthalpy of solution, AHs, and whether an ionic solid will dissolve endothermically or exothermically. Figure 1.4 shows a comparison of AH and A//h, demonstrating that AgF dissolves exothermically. 

---