Dangerous reactions pressure effects

Fluorine, the most reactive element known, is a dangerous material but may be handled safely using proper precautions. In any situation where an operator may come into contact with low pressure fluorine, safety glasses, a neoprene coat, boots, and clean neoprene gloves should be worn to afford overall body protection. This protection is effective against both fluorine and the hydrofluoric acid which may form from reaction of moisture in the air. 

Two accidents of vastly differing severity have occurred at nuclear power plants. On 28 March 1979, an accident occurred in the nuclear power plant at Three Mile Island, Pennsylvania, USA. The radiation was contained and the small amount released had negligible effects on the health of individuals at the plant. On 26 April 1986 an accident occurred in the nuclear power plant 10 miles from the city of Chernobyl, then part of the Soviet Union. The chain reaction in the radioactive core of one of the four reactors became uncontrolled. Steam pressure rose to dangerous levels there were several explosions and a subsequent fire took several hours to extinguish. Large amounts of radioactive material were scattered over a wide area and into the atmosphere (later descending in a dilute form in rain all over the world). 

In microwave-assisted synthesis, a homogeneous mixture is preferred to obtain a uniform heating pattern. For this reason, silica gel is used for solvent-free (open-vessel) reactions or, in sealed containers, dipolar solvents of the DMSO type. Welton (1999), in a review, recommends ionic liquids as novel alternatives to the dipolar solvents. Ionic liquids are environmentally friendly and recyclable. They have excellent dielectric properties and absorb microwave irradiation in a very effective manner. They exhibit a very low vapor pressure that is not seriously enhanced during microwave heating. This makes the process not so dangerous as compared to conventional dipolar solvents. The polar participants of organic ion-radical reactions are perfectly soluble in polar ionic liquids. 

The usual experimental criterion for diffusion control involves an evaluation of the rate of reaction as a function of particle size. At a sufficiently small particle size, the measured rate of reaction will become independent of particle size. The reaction rate can then be safely assumed to be independent of intraparticle mass transfer effects. At the other extreme, if the observed rate is inversely proportional to particle size, the reaction is strongly influenced by intraparticle diffusion. For a reaction whose rate is inhibited by the presence of products, there is an attendant danger of misinterpreting experimental results obtained for different particle sizes when a differential reactor is used, because, under these conditions, the effectiveness factor is sensitive to changes in the partial pressure of product. 

The direct palladation procedure is limited to substitution with aryl and heterocyclic groups. The met-allation is an electrophilic process and therefore does not work well with deactivated aromatics. When possible, mixtures of isomers may be obtained. Since the palladium salts employed for the metallation are moderately strong oxidizing agents, the reaction cannot be used with easily oxidizable alkenes or aromatics. The only effective method for making this procedure catalytic is to reoxidize the palladium in situ with oxygen under pressure an inconvenient and potentially dangerous procedure. 

The first reaction is carried out exothermically at about 120°C (Brown, 2003) and is succeeded by a three-phase separation system and a second reactor whose function is to increase the conversion of reactants. For this part of the process, temperature and pressure conditions do not represent a dangerous situation, even so, the chemical activity makes it necessary to take security measures oriented to minimise the effects of a possible leak. 

The catalyst plays a crucial role in the technology. A typical modern catalyst consists of 0.15-1.5 wt% Pd, 0.2-1.5 wt% Au, 4-10 wt% KOAc on silica spherical particles of 5 mm [8]. The very fast reaction takes place inside a thin layer (egg-shell catalyst). Preferred conditions are temperatures around 150 to 160 °C and pressures 8 to 10 bar. Hot spots above 200 °C lead to permanent catalyst deactivation. The excess of ethylene to acetic acid is 2 1 to 3 1. Because of explosion danger, the oxygen concentration in the reaction mixture should be kept below 8%. Small amount of water in the initial mixture are necessary for catalyst activation. The dilution of the reaction mixture with inert gas is necessary because of high exothermic effect. Accordingly, the reactor is designed at low values of the per-pass conversions, namely 15 - 35% for the acetic acid and 8-10% for ethylene. The above elements formulate hard constraints both for design and for plantwide control. 

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