Also heat of reaction

The rate of energy transfer is important in determining the temperature distribution in reactors. Also, heats of reaction are significant in connection with equilibrium calculations. The following section deals with data and methods concerning heats of reaction, followed by a discussion of equilibrium conversion. 

If indirect heat transfer is used with a large temperature difference to promote high rates of cooling, then the cooling fluid (e.g., boiling water) is fixed by process requirements. In this case, the heat of reaction is not available at the temperature of the reactor effluent. Rather, the heat of reaction becomes available at the temperature of the quench fluid. Thus the feed stream to the reactor is a cold stream, the quench fluid is a hot stream, and the reactor effluent after the quench is also a hot stream. 

A similar analysis for fluorination of methane gives AH° = -426 kJ for its heat of reaction Fluori nation of methane is about four times as exothermic as chlorination A reaction this exothermic if it also occurs at a rapid rate can proceed with explosive violence... 

The reaction is very exothermic. The heat of reaction of propylene oxidation to acrolein is 340.8 kJ /mol (81.5 kcal/mol) the overall reactions generate approximately 837 kJ/mol (200 kcal/mol). The principal side reactions produce acryUc acid, acetaldehyde, acetic acid, carbon monoxide, and carbon dioxide. A variety of other aldehydes and acids are also formed in small amounts. Proprietary processes for acrolein manufacture have been described (25,26). 

Another concentration method involves passing an inert gas such as N2 or CO2 through the reaction medium (12). As the gas passes through, it becomes humidified and carries captured water with it. Most of the energy required for the gas humidification comes from the heat of reaction. An advantage is that expensive drying equipment is not needed. Also, the sulfuric acid mist formed in typical concentrators is minimized. Du Pont uses a similar process in its nitrobenzene production faciUty. 

Potassium superoxide is produced commercially by spraying molten potassium iato an air stream, which may be enriched with oxygen. Excess air is used to dissipate the heat of reaction and to maintain the temperature at ca 300°C. It can also be prepared ia a highly pure state by oxidizing potassium metal that is dissolved ia Hquid ammonia at —50° C. 

Eigure 3 is a flow diagram which gives an example of the commercial practice of the Dynamit Nobel process (73). -Xylene, air, and catalyst are fed continuously to the oxidation reactor where they are joined with recycle methyl -toluate. Typically, the catalyst is a cobalt salt, but cobalt and manganese are also used in combination. Titanium or other expensive metallurgy is not required because bromine and acetic acid are not used. The oxidation reactor is maintained at 140—180°C and 500—800 kPa (5—8 atm). The heat of reaction is removed by vaporization of water and excess -xylene these are condensed, water is separated, and -xylene is returned continuously (72,74). Cooling coils can also be used (70). 

Ha/ogenation. Heats of reaction are highly exothermic for halogens, particularly fluorine (qv), and chain reactions can result in explosions over broad concentration ranges. Halogens also present severely challenging corrosion problems (see Corrosion and corrosion control). 

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). 

Reaction and Heat-Transfer Solvents. Many industrial production processes use solvents as reaction media. Ethylene and propylene are polymerized in hydrocarbon solvents, which dissolves the gaseous reactant and also removes the heat of reaction. Because the polymer is not soluble in the hydrocarbon solvent, polymer recovery is a simple physical operation. Ethylene oxide production is exothermic and the catalyst-filled reaction tubes are surrounded by hydrocarbon heat-transfer duid. 

A carbonated slurry of cyanamide solution, solid calcium carbonate, and graphite is cooled to remove the heat of reaction. Part of the slurry is recycled to faciUtate temperature control whereas the remainder is filtered yielding cyanamide solution and a cake of calcium carbonate and graphite. The filtered solution is also recycled ia order to control the soHds content. The final concentration of cyanamide is normally maintained at 25%. 

EPM and EPDM mbbers are produced in continuous processes. Most widely used are solution processes, in which the polymer produced is in the dissolved state in a hydrocarbon solvent (eg, hexane). These processes can be grouped into those in which the reactor is completely filled with the Hquid phase, and those in which the reactor contents consist pardy of gas and pardy of a Hquid phase. In the first case the heat of reaction, ca 2500 kJ (598 kcal)/kg EPDM, is removed by means of cooling systems, either external cooling of the reactor wall or deep-cooling of the reactor feed. In the second case the evaporation heat from unreacted monomers also removes most of the heat of reaction. In other processes using Hquid propylene as a dispersing agent, the polymer is present in the reactor as a suspension. In this case the heat of polymerisation is removed mainly by monomer evaporation. 

The partial derivative of heat generation rate with respect to temperature is also needed. This we can get from the usual rate law multiplied by the heat of reaction ... 

Igniters. A pellet composed of 26.5% K. perchlorate, 16.6% Ba nitrate, 53,9% 50/50 Zr/Ni alloy, and 3.0% et cellulose can be used to ignite solid propint grains (Ref 25), A series of mixts of K perchlorate with powd metals and other oxidizable mat were examined as substitutes for BikPdr as a gun primer. Most of the mixts tested were found to be satisfactory and to be compatible with brass and other metals (Ref 9) Incendiary Compositions. Stoichiometric mixts of K perchlorate with metals and oxidizable mat have been proposed as incendiaries of the Thermit type and have heats of reaction as follows Al dust 2504, powd Mg 2429. red P 1477, powd S 705 and powd C (lampblack) 1118cal/g (Ref 4). A mixt of 12.5% K perchlorate, 75% powd Zr, and 12,5% of a 50/50 Al/Mg alloy is reported to be a readily-ignited incendiary (Ref 20). Mixts of powd Al and/or powd Fe with K perchlorate with 1.5—2% NC as a binder are also good incendiaries (Ref 35). 

Both sets of results may also be discussed in terms of inductive differences between hydrogen and deuterium (see Halevi, 1963). Brown et al. (1966) jDoint out that both the inductive and steric explanations qualitatively predict isotope effects in the same direction, but that an inductive effect would be expected to operate from the 3 and 4 positions nearly as effectively as from the 2 position . Furthermore, there is no observable isotope effect on the heat of reaction of 2,6-(dimethyl-de)-pyridine with the relatively small molecule diborane A AH = —20 18 cal mol ), but a significant effect is obtained with the larger molecule boron trifluoride AAH = 230 + 150 cal mol ). 

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