Thermodynamics exothermic reactions

The fact that, thermodynamically, exothermic reactions are favored at low temperatures rather than high temperatures the conversion of fuel at equilibrium will therefore be less than at low temperatures. In practice, the conversion achieved in low temperature cells is kinetically determined and is less than in high temperature cells. 

The kinetics and thermodynamics of the reaction, and of possible side reactions, need to be understood. The explosive potential of chemicals liable to exothermic reaction should be carefully appraised. 

In the case of thermodynamics, the designer can investigate the nature of the reaction heat and whether the reaction is reversible. If these exothermic reactions are irreversible, attention may be focused on the influence of reactor design on conversion and with heat transfer control. An objective of reactor design is to determine the size and type of reactor and mode of operation for the required job. The choice... 

In addition to molecular geometry, the most important quantity to come out of molecular modeling is the energy. Energy can be used to reveal which of several isomers is most stable, to determine whether a particular chemical reaction will have a thermodynamic driving force (an exothermic reaction) or be thermodynamically uphill (an endothermic reaction), and to ascertain how fast a reaction is likely to proceed. Other molecular properties, such as the dipole moment, are also important, but the energy plays a special role. 

A negative AE indicates an exothermic (thermodynamically favorable) reaction, while a positive AE an endothermic (thermodynamically unfavorable) reaction. 

By thermodynamic convention, l Hp < 0 for exothermic reactions, so that a negative sign is attached to the heat-generation term. When there are multiple reactions, the heat-generation term refers to the net effect of all reactions. Thus, the term is an implicit summation over all M reactions that... 

Common reaction rate v. temperature characteristics for reactions are illustrated in Figure 6.5. To avoid runaway conditions (Fig. 6.5a) or an explosion (Figure 6.5c), it may be essential to control the rate of addition of reactants and the temperature. The kinetics and thermodynamics of the reaction, and of possible side reactions, need to be understood. The explosive potential of chemicals liable to exothermic reaction should be carefully appraised. 

When one considers the potential high-energy release on rupture of a carborane unit, together with the thermodynamic stability of combustion products, it is hardly surprising that there is a body of literature that reports on the use of carbo-ranes within propellant compositions. Their use in energetic applications is to be expected when the enthalpy of formation (AH/) data for the products of combustion for boron are compared to those of carbon. Thermodynamic data for the enthalpy of formation of o-carborane and of typical boron and carbon combustion products is shown in Table 4. Measurements of the standard enthalpy of combustion32 for crystalline samples of ortho-carborane show that complete combustion is a highly exothermic reaction, AH = — 8994 KJmol. ... 

A facile exothermic reaction, catalysed by traces of zinc chloride and iron(III) chloride (4 and 40 ppm, respectively) to produce isopropyl propionate and 2-chloropropane (b.p., 35°C) led to pressure build up and bursting of a closed galvanised drum after 24 h. Similar reactions are thermodynamically possible with other acid chlorides and ethers (particularly if secondary or tertiary alkyl ethers), so such mixtures should only be prepared immediately prior to use. 

The cyclotrimer products are liberated in subsequent, consecutive substitution steps with new butadiene, which is an exothermic reaction (AH) for expulsion of all-t-CDT by three /ran.v-butadienes along 8b —> l b. This process, however, is endergonic by 7 kcal mol-1 (AG) after entropic costs are taken into account. Therefore, 7b and 8b (stabilized by donors) are indicated to be likely candidates for isolable intermediates of the catalytic process, while the active catalyst l b, the intermediate species 2b, in particular, and other species will not be present in a sufficient concentration, since they are either too reactive or thermodynamically too unfavorable, for experimental characterization. Overall, the cyclotrimerization process is driven by a strong thermodynamic force with an exothermicity of —44.6 kcal mol-1 (AH for the process without a catalyst) for the fusion of three trans-butadiene to afford the favorable all-t-CDT. 

In Figure 2.4, data for the equilibrium constants of esterification/hydrolysis and transesterification/glycolysis from different publications [21-24] are compared. In addition, the equilibrium constant data for the reaction TPA + 2EG BHET + 2W, as calculated by a Gibbs reactor model included in the commercial process simulator Chemcad, are also shown. The equilibrium constants for the respective reactions show the same tendency, although the correspondence is not as good as required for a reliable rigorous modelling of the esterification process. The thermodynamic data, as well as the dependency of the equilibrium constants on temperature, indicate that the esterification reactions of the model compounds are moderately endothermic. The transesterification process is a moderately exothermic reaction. 

The first law of thermodynamics also tells you that if no work is done on or by the sample, that is, pressure and volume are held constant, any heat flow is counterbalanced by a change in internal energy. An exothermic reaction releasing heat to the surroundings, therefore, is accompanied by a decrease in internal energy, whereas an endothermic reaction has a concomitant increase in internal energy. 

A single catalytic packed bed reactor is to be designed to treat 100 mol/s of reactant A and produce product R. Feed gas enters at 2.49 MPa and 300 K, the maximum allowable temperature is 900 K unless otherwise noted, the product stream is wanted at 300 K, and the thermodynamics and kinetics of the exothermic reaction are given to us in Fig. 19.11. Prepare a sketch showing the details of the system you plan to use ... 

Each term in the preceding equations has units of energy/time. Note the signs on each term indicating that heat is removed or added to the reactor. We preserve the minus sign on A Hji because we are more interested in exothermic reactions for which A Hr < 0. The student can recognize each term on the right side from the steady-state enthalpy balance we derived in the previous section from the thermodynamics of a steady-state flow system. 

Thermodynamics tells us that if we wait long enough the amount of products in an exothermic reaction will be greater than the amount... 

Stripping of chlorine from hydroxides such as Cl2Sn(OH)2 could eventually lead to gas-phase SnO or Sn02. However, at the relatively low temperatures typical of tin oxide CVD ( 873-973 K), we do not expect these oxides to form, based on the equilibrium calculations described above. Thus, the formation of tin hydroxides is not only thermodynamically favored (i.e., based on minimization of the Gibbs free energy), but there are also exothermic reaction pathways that we expect to be kinetically favorable. The primary tin carrier in the CVD process could therefore be a tin hydroxide. Complete conversion to Sn02 would most likely occur via reactions on the surface. 

The isobutene oligomerization is a highly exothermic reaction, carried out via the carbenium ion mechanism, which is thermodynamically favoured at low temperature. The kind of products obtained as well as the conversion and stability at constant temperature and pressure will depend on the reaction GHSV, which determine the intermediate carbenio ion formed during the first steps. 

The above model has been further explored to account for reaction efficiencies in terms of a scheme where nucleophilicities and leaving group abilities can be rationalized by a structure-reactivity pattern. Pellerite and Brau-man (1980, 1983) have proposed that the central energy barrier for an exothermic reaction (see Fig. 3) can be analysed in terms of a thermodynamic driving force, due to the exothermicity of the reaction, and an intrinsic energy barrier. The separation between these two components has been carried out by extending to SN2 reactions the theory developed by Marcus for electron transfer reactions in solutions (Marcus, 1964). While the validity of the Marcus theory to atom and group transfer is open to criticism, the basic assumption of the proposed model is that the intrinsic barrier of reaction (38)... 

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