Rapid cooling

Even if the reactor temperature is controlled within acceptable limits, the reactor effluent may need to be cooled rapidly, or quenched, to stop the reaction quickly to prevent excessive byproduct formation. This quench can be accomplished by indirect heat transfer using conventional heat transfer equipment or by direct heat transfer by mixing with another fluid. A commonly encountered situation is... 

The insoluble residue of diphenylurea from the original filtration is chemically almost pure. It may be recrystallised from hot rectified spirit or ethanol, a process which will be necessary if the material contains fragments of porcelain. When using either of these solvents, however, the hot solution should be filtered at the pump using a small Buchner funnel and flask which again have been preheated by the filtration of some of the hot solvent, as the solution when cooled rapidly deposits the diphenylurea. iSym-Diphenylurea (or carbanilide) is thus obtained as fine colourless crystals, m.p. 237° yield, 1-1 5 S ... 

The acetamide often contains a minute amount of impurity having an odour resembling mice excrement this can be removed by washing with a small volume of a 10 per cent, solution of ethyl alcohol in ether or by recrystallLsation. Dissolve 5 g. of impure acetamide in a mixture of 5 ml. of benzene and 1 5 ml. of dry ethyl acetate warm on a water bath until all is dissolved and cool rapidly in ice or cold water. Filter oflF the crystals, press between Alter paper and dry in a desiccator. The unpleasant odour is absent and the pure acetamide melts at 81°. Beautiful large crystals may be obtained by dissolving the acetamide (5 g.) in warm methyl alcohol (4 ml.), adding ether (40 ml.) and allowing to stand. 

To obtain the free base, dissolve the crude hydrochloride in 150-200 ml. of water, filter, and cool rapidly to about 20°. Pour the solution with stirring into a mixture of 150 g. of crushed ice and 50 ml. of 10 per cent, sodium hydroxide solution contained in a htre beaker. Filter oflF the... 

Dissolve 10 g. of p-nitroaniline (Section IV,51) in a mixture of 21 ml. of concentrated hydrochloric acid and an equal volume of water, and cool rapidly to 0° in order to obtain the hydrochloride of the base in a fine state of division. Diazotise in the usual way (see Section IV,68) by the gradual addition of a solution of 6 0 g. of sodium nitrite in 12 ml. of water. Continue the stirring for a few minutes, filter the solution rapidly, and add it from a separatory funnel to an ice-cold solution of 41 g. of sodium sulphite (90 per cent. NajS03,7H20) in 100 ml. of water containing... 

Evidence from the viscosities, densities, refractive indices and measurements of the vapour pressure of these mixtures also supports the above conclusions. Acetyl nitrate has been prepared from a mixture of acetic anhydride and dinitrogen pentoxide, and characterised, showing that the equilibria discussed do lead to the formation of that compound. The initial reaction between nitric acid and acetic anhydride is rapid at room temperature nitric acid (0-05 mol 1 ) is reported to be converted into acetyl nitrate with a half-life of about i minute. This observation is consistent with the results of some preparative experiments, in which it was found that nitric acid could be precipitated quantitatively with urea from solutions of it in acetic anhydride at —10 °C, whereas similar solutions prepared at room temperature and cooled rapidly to — 10 °C yielded only a part of their nitric acid ( 5.3.2). The following equilibrium has been investigated in detail ... 

Certain features of the addition of acetyl nitrate to olefins in acetic anhydride may be relevant to the mechanism of aromatic nitration by this reagent. The rapid reaction results in predominantly cw-addition to yield a mixture of the y -nitro-acetate and y5-nitro-nitrate. The reaction was facilitated by the addition of sulphuric acid, in which case the 3rield of / -nitro-nitrate was reduced, whereas the addition of sodium nitrate favoured the formation of this compound over that of the acetate. As already mentioned ( 5.3. i), a solution of nitric acid (c. i 6 mol 1 ) in acetic anhydride prepared at — 10 °C would yield 95-97 % of the nitric acid by precipitation with urea, whereas from a similar solution prepared at 20-25 °C and cooled rapidly to —10 °C only 30% of the acid could be recovered. The difference between these values was attributed to the formation of acetyl nitrate. A solution prepared at room... 

Footnote 2 - The Methylamine solutions in all steps should be cooled rapidly to promote smaller crystal formation. 

Potassium acid antimonate, KH2Sb04—Q.IN boil 23 g of the salt with 950 mL of water for 5 minutes, cool rapidly and add 35 mL of 6N KOH allow to stand for one day, filter dilute filtrate to a liter. 

Because the time at high temperature is much less, austenite is produced, which is chemically inhomogeneous especially with undissolved carbides, and has a fine grain crystal size. The formation of the hard martensite requites more rapid cooling than for conventional hardening. Thus case hardening by heat treatment intrinsically requites that the surface region to be hardened be relatively thin and cooled rapidly. 

In contrast to most extmsion processes, extmsion coating involves a hot melt, ca 340°C. The thin web cools rapidly between the die and nip even at high linear rates. Both mechanical and chemical bonding to substrates are involved. Mechanical locking of resin around fibers contributes to the resin s adhesion to paper. Some oxidation of the melt takes place in the air gap, thereby providing sites for chemical bonding to aluminum foil. Excessive oxidation causes poor heat-sealing characteristics. 

Flame spraying is no longer the most widely used melt-spraying process. In the power-feed method, powders of relatively uniform size (<44 fim (325 mesh)) are fed at a controlled rate into the flame. The torch, which can be held by hand, is aimed a few cm from the surface. The particles remain in the flame envelope until impingement. Particle velocity is typically 46 m/s, and the particles become at least partially molten. Upon impingement, the particles cool rapidly and soHdify to form a relatively porous, but coherent, polycrystalline layer. In the rod-feed system, the flame impinges on the tip of a rod made of the material to be sprayed. As the rod becomes molten, droplets of material leave the rod with the flame. The rod is fed into the flame at a rate commensurate with melt removal. The torch is held at a distance of ca 8 cm from the object to be coated particle velocities are ca 185 m/s. 

The most widely used austenitic stainless steel is Type 304, known as 18—8. It has excellent corrosion resistance and, because of its austenitic stmcture, excellent ductihty. It may be deep-drawn or stretch formed. It can be readily welded, but carbide precipitation must be avoided in and near the weld by cooling rapidly enough after welding. Where carbide precipitation presents problems. Types 321, 347, or 304L may be used. The appHcations of Types 304 are wide and varied, including kitchen equipment and utensils, dairy installations, transportation equipment, and oil-, chemical-, paper- (qv), and food-processing (qv) machinery. 

To produce amorphous anhydrous borax, the molten borax is mn between two large water-cooled roUs, forming sheets about 1.6 mm thick, which ate then cmshed and screened to the desired particle size. Because the borax is cooled rapidly by the roUs, it remains largely amorphous, though it may contain some crystalline anhydrous borax. 

Nucleation tempering of the stiU molten fat is necessary because the cocoa butter, if left to itself, can soHdify in a number of different physical forms, ie, into an unstable form if cooled rapidly, or into an equally unacceptable super stable form if cooled too slowly, as commonly happens when a chocolate turns gray or white after being left in the sun. The coarse white fat crystals that can form in the slowly cooled center of a very thick piece of chocolate are similarly in a super stable form known in the industry as fat bloom. 

Fig. 5. Metastable Fe—Ni—Cr "temary"-pliase diagram where C content is 0.1 wt % and for alloys cooled rapidly from 1000°C showing the locations of austenitic, duplex, ferritic, and martensitic stainless steels with respect to the metastable-phase boundaries. For carbon contents higher than 0.1 wt %, martensite lines occur at lower ahoy contents (43). A is duplex stainless steel, eg. Type 329, 327 B, ferritic stainless steels, eg. Type 446 C, 5 ferrite + martensite D, martensitic stainless steels, eg. Type 410 E, ferrite + martensite F, ferrite + pearlite G, high nickel ahoys, eg, ahoy 800 H,...

Poly(phenylene sulfide) (PPS) is another semicrystalline polymer used in the composites industry. PPS-based composites are generally processed at 330°C and subsequently cooled rapidly in order to avoid excessive crystallisation and reduced toughness. The superior fire-retardant characteristics of PPS-based composites result in appHcations where fire resistance is an important design consideration. Laminated composites based on this material have shown poor resistance to transverse impact as a result of the poor adhesion of the fibers to the semicrystalline matrix. A PPS material more recently developed by Phillips Petroleum, AVTEL, has improved fiber—matrix interfacial properties, and promises, therefore, an enhanced resistance to transverse impact (see PoLYAffiRS containing sulfur). 

Stainless steel is susceptible to sensitization when it is heated to the range of 900 to 1550°F (480 to 850°C). Since any welding operation involving stainless steel will produce such temperatures in the metals being joined, it would appear that all welded stainless steel would sensitize. However, sensitization is a function of both time and temperature, occurring most rapidly at temperatures near 1250°F (675°C). Metals that cool rapidly through this temperature range will not sensitize. Consequently, thin metal sections, which cool rapidly, are less susceptible to sensitization than thick sections. 

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