Processes exothermic

Let us consider the formation of sodium chloride from its elements. An energy (enthalpy) diagram (called a Born-Haber cycle) for the reaction of sodium and chlorine is given in Figure 3.7. (As in the energy diagram for the formation of hydrogen chloride, an upward arrow represents an endothermic process and a downward arrow an exothermic process.)... 

Metals in higher oxidation states form halides which are essentially covalent, for example AICI3, SnCl, FeClj when these compounds dissolve in water they do so by a strongly exothermic process. Indeed it is perhaps incorrect to think of this only as a dissolution process, since it is more like a chemical reaction—but to differentiate for a particular substance is not easy, as we shall see. The steps involved in the case of aluminium chloride can be represented as... 

This is an exothermic process, due largely to the large hydration enthalpy of the proton. However, unlike the metallic elements, non-metallic elements do not usually form hydrated cations when their compounds dissolve in water the process of hydrolysis occurs instead. The reason is probably to be found in the difference in ionisation energies. Compare boron and aluminium in Group III ... 

Adsorption is invariably an exothermic process, so that, provided equilibrium has been established, the amount adsorbed at a given relative pressure must diminish as the temperature increases. It not infrequently happens, however, that the isotherm at a given temperature Tj actually lies above the isotherm for a lower temperature Ti. Anomalous behaviour of this kind is characteristic of a system which is not in equilibrium, and represents the combined effects of temperature on the rate of approach to equilibrium and on the position of equilibrium itself. It points to a process which is activated in the reaction-kinetic sense and which therefore occurs more rapidly as temperature is increased. 

Acrolein a.s Dienophile. The participation of acrolein as the dienophile in Diels-Alder reactions is, in general, an exothermic process. Dienes such as cyclopentadiene and l-dieth5laniino-l,3-butadiene react rapidly with acrolein at room temperature. 

The nonbonding electron clouds of the attached fluorine atoms tend to repel the oncoming fluorine molecules as they approach the carbon skeleton. This reduces the number of effective coUisions, making it possible to increase the total number of coUisions and stiU not accelerate the reaction rate as the reaction proceeds toward completion. This protective sheath of fluorine atoms provides the inertness of Teflon and other fluorocarbons. It also explains the fact that greater success in direct fluorination processes has been reported when the hydrocarbon to be fluorinated had already been partiaUy fluorinated by some other process or was prechlorinated, ie, the protective sheath of halogens reduced the number of reactive coUisions and aUowed reactions to occur without excessive cleavage of carbon—carbon bonds or mnaway exothermic processes. 

In this representation the FeCl2 which takes part in the first step of the reaction is not a tme catalyst, but is continuously formed from HQ. and iron. This is a highly exothermic process with a heat of reaction of 546 kj /mol (130 kcal/mol) for the combined charging and reaction steps (50). Despite the complexity of the Bnchamp process, yields of 90—98% are often obtained. One of the major advantages of the Bnchamp process over catalytic hydrogenation is that it can be mn at atmospheric pressure. This eliminates the need for expensive high pressure equipment and makes it practical for use in small batch operations. The Bnchamp process can also be used in the laboratory for the synthesis of amines when catalytic hydrogenation caimot be used (51). 

Exothermic processes, with cooling through heat transfer surfaces or cold shots. In use are sheU-and-tube reactors with smaU-diameter tubes, or towers with internal recirculation of gases, or multiple stages with intercoohng. Chlorination of methane and other hydrocarbons results in a mixture of products whose relative amounts... 

The work of Thiele (1939) and Zeldovich (1939) called attention to the fact that reaction rates can be influenced by diffusion in the pores of particulate catalysts. For industrial, high-performance catalysts, where reaction rates are high, the pore diffusion limitation can reduce both productivity and selectivity. The latter problem emerges because 80% of the processes for the production of basic intermediates are oxidations and hydrogenations. In these processes the reactive intermediates are the valuable products, but because of their reactivity are subject to secondary degradations. In addition both oxidations and hydrogenation are exothermic processes and inside temperature gradients further complicate secondary processes inside the pores. 

Control of pollutants by oxidation is another exothermic process in which high conversion is the most important performance criterion. Interest in efficiency is limited to minimize byproduct formation the byproducts can be more damaging and more refractory than the original pollutants were. Commercially, most adiabatic reactors used for pollution control are of the least expensive construction. 

Products formed through an exothermic reaction have a lower energy content than the reactants from which they are formed. Alternatively, products formed via an exothermic process have a higher... 

Chemical reaction hazards must be considered in assessing whether a process can be operated safely on the manufacturing scale. Furthermore, the effect of scale-up is particularly important. A reaction, which is innocuous on the laboratory or pilot plant scale, can be disastrous in a full-scale manufacturing plant. For example, the heat release from a highly exothermic process, such as the reduction of an aromatic nitro compound, can be easily controlled in laboratory glassware. Flowever,... 

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... 

Fresh charcoal is a strong absorbent for gases, and this is an exothermic process. The heat generated can be enough to cause spontaneous ignition in some cases. Hence it is customaiy to age charcoal by exposure to air and thus cover the absorption sites with a layer of nitrogen gas. Larger molecules will desorb and replace smaller molecules, so the charcoal will still be effective as a decolorant or deodorizer. 

The addition of 2,4-pentanedione to liquid ammonia is a highly exothermic process. Also, ammonia vapor reacts with the /3-diketone to produce an insoluble ammonium salt, which tends to clog the tip of the addition funnel. Cooling the reaction mixture in dry ice-acetone reduces the vigor of the reaction and minimizes the dogging of the addition funnel. The 2,4-pentanedione should be added in spurts which fall on the surface of the reaction mixture rather than on the wall of the flask... 

Endothermic and exothermic processes. On the left the icicle melts as heat is absorbed by the ice, an endothermic process. On the right, steam rises from boiling water, an exothermic process. 

A plot of the solubility of a certain compound (g/100 g H20) against temperature (°C) is a straight line with a positive slope. Is dissolving that compound an exothermic process ... 

A general problem in open mixing machines is that the exothermic process... 

Radical additions lo double bonds are, in general, highly exothermic processes and rates increase with increasing temperature. The rcgiospccificity of addition to double bonds and the relative reactivity of various olefins towards radicals are also temperature dependent. Typically, specificity decreases with increasing temperature (the Reactivity-Selectivity Principle applies). However, a number of exceptions to this general rule have been reported. 8 63... 

There have been few attempts to classify decomposition reactions of solids. Gamer [64] made only the broad distinction between endothermic processes (which are often reversible and include dissociation of crystalline hydrates and carbonates) and exothermic processes (which are usually... 

A process that releases heat into the surroundings is called an exothermic process. Most common chemical reactions—and all combustions, such as those that power transport and heating—are exothermic (Fig. 6.8). Less familiar are chemical reactions that absorb heat from the surroundings. A process that absorbs heat is called an endothermic process (Fig. 6.9). A number of common physical processes are endothermic. For instance, vaporization is endothermic, because heat must be supplied to drive molecules of a liquid apart from one another. The dissolution of ammonium nitrate in water is endothermic in fact, this process is used in instant cold packs for sports injuries. 

The change in enthalpy of a system is equal to the heat supplied to the system at constant pressure. For an endothermic process, AH > 0 for an exothermic process, AH < 0. 

FIGURE 7.17 (a) In an exothermic process, heat escapes into the surroundings and increases their entropy, (b) In an endothermic process, the entropy of the surroundings decreases. The red arrows represent the transfer of heat between system and surroundings, and the green arrows indicate the entropy change of the surroundings. 

---