Caustic mechanisms

A high yield chemical pulp, eg, 52—53% bleached yield from softwoods, can be obtained, but strength properties ate inferior to those obtained from the kraft process. If a protector, eg, potassium iodide, is added, an additional 2—3% yield is obtained, as is an improvement in all strength properties. The gas penetration problem can be minimized if ftbetization is accompHshed before treatment with oxygen. Oxygen treatment of virtually all types of semichemical and mechanical pulps has been explored (55). Caustic, sodium bicarbonate, and sodium carbonate have been used as the source of base (56,57). In all cases, the replacement of the kraft by these other processes has not been justified over the alternative of pollution abatement procedures. 

Physical properties of hexachloroethane are Hsted in Table 11. Hexachloroethane is thermally cracked in the gaseous phase at 400—500°C to give tetrachloroethylene, carbon tetrachloride, and chlorine (140). The thermal decomposition may occur by means of radical-chain mechanism involving -C,C1 -C1, or CCl radicals. The decomposition is inhibited by traces of nitric oxide. Powdered 2inc reacts violentiy with hexachloroethane in alcohoHc solutions to give the metal chloride and tetrachloroethylene aluminum gives a less violent reaction (141). Hexachloroethane is unreactive with aqueous alkali and acid at moderate temperatures. However, when heated with soHd caustic above 200°C or with alcohoHc alkaHs at 100°C, decomposition to oxaHc acid takes place. 

Corrosion also occurs as a result of the conjoint action of physical processes and chemical or electrochemical reactions (1 3). The specific manifestation of corrosion is deterrnined by the physical processes involved. Environmentally induced cracking (EIC) is the failure of a metal in a corrosive environment and under a mechanical stress. The observed cracking and subsequent failure would not occur from either the mechanical stress or the corrosive environment alone. Specific chemical agents cause particular metals to undergo EIC, and mechanical failure occurs below the normal strength (5aeld stress) of the metal. Examples are the failure of brasses in ammonia environments and stainless steels in chloride or caustic environments. 

Just as at low pH, concentration mechanisms substantially increase attack. The two principal mechanisms of concentration are evaporation and condensation. Evaporation increases solute concentrations of compounds with vapor pressures lower than water (such as caustic compounds). Condensation increases concentration of aggressive gases such as ammonia. 

Several approaches are available to eliminate this problem. If stresses cannot be sufficiently reduced, a metal possessing greater resistance to caustic SCC can be specified for replacement tubing. Alteration to the environment, such as eliminating alkalinity or increasing system pressure to prevent flashing (thereby minimizing the potential for concentration of caustic), would also prevent failure by this mechanism. 

Two classes of resol are generally distinguished, water-soluble resins prepared using caustic soda as catalyst, and spirit-soluble resins which are catalysed by addition of ammonia. The water-soluble resins are usually only partially dehydrated during manufacture to give an aqueous resin solution with a solids content of about 70%. The solution viscosity can critically affect the success in a given application. Water-soluble resols are used mainly for mechanical grade paper and cloth laminates and in decorative laminates. 

Alloy 400 has good mechanical properties and is easy to fabricate in all wrought forms and castings. K-500 is a modified version of this alloy and can be thermally treated and is suitable for items requiring strength, as well as corrosion resistance. Alloy 400 has immunity to stress corrosion cracking and pitting in chlorides and caustic alkali solutions. 

Selective removal of the less noble constituent has been demonstrated by chemical analysis in the case of nickel-rich alloys in fused caustic soda or fused fluorides ", and by etching effects and X-ray microanalysis for Fe-18Cr-8Ni steels in fused alkali chlorides. This type of excessive damage can occur with quite small total amounts of corrosion, and in this sense its effect on the mechanical properties of the alloy is comparable with the notorious effect of intercrystalline disintegration in the stainless steels. 

Where caustic deposits occur, the resultant corrosion of steel by caustic gouging or stress corrosion cracking (SCC) mechanisms produces particulate iron oxides of hematite and magnetite. It is common to see white rings of deposited sodium hydroxide around the area of iron oxide formation. 

In practice, the potential causes of boiler section corrosion are many and often commonplace. Initiators include oxygen, carbon dioxide, acid, caustic, copper plating, chelant, and even the water itself. In addition, mechanical problems may be an initiator of corrosion, which in turn may lead to boiler mechanical failure. 

The precise protocols necessary to achieve effective corrosion control will vary dependent on individual boiler design and operation. For example, control of alkalinity is fundamental in controlling corrosion mechanisms. In small to midsize, general-purpose and industrial boilers, it is common practice to obtain adequate BW alkalinity as part of any water treatment program that operates under a free-caustic regimen. This approach generally is perfectly acceptable, and such programs normally can be relied on to ensure a clean, scale- and corrosion-free boiler. 

For caustic gouging to take place, it is necessary to have the availability of free caustic (or an alkaline-producing salt) in the BW and for some form of concentrating mechanism to be present. Concentration may result, for example, by virtue of the presence of existing (porous)... 

The removal of organics by industrial detergent cleaners. These products employ several mechanisms, depending on the formulation, but tend to include dissolution (using nonaqueous solvents such as kerosene, petroleum spirits, and naphtha, saponification, by caustic, or emulsification by nonionic detergents. 

Perfhioroalko] (Teflon) (PFA) was introduced in 1972 and is a fully fluorinated polymer that is melt-processible with better melt flow and molding properties than the FEP. The PFA has excellent resistance to chemicals. It can withstand acids as well as caustic materials. PFA has better mechanical properties than FEP above 300°F (149°C) and can be used up to 500°F (260°C) for some applications. The low physical strength and high cost of this polymer limit use for some applications. 

To the acidic distillate in the 125-mL separatory funnel, add 5 mL of 50% sodium hydroxide and 15 mL of dichloromethane. Cap the separatory funnel tightly, and allow its contents to cool for 30 min. Heat created by the addition of caustic to the acidic distillate will cause some of the dichloromethane to volatilize, creating pressure in the funnel therefore, the cap must be secured tightly to the funnel. Escaping solvent will result in loss of analytes. Shake the funnel for 5 min on a mechanical shaker. Allow 15 min for phase separation after shaking the funnel. Drain the lower dichloromethane layer into a second 125-mL separatory funnel. Extract the aqueous layer a second time with 15 mL of dichloromethane. Following shaking of the funnel and phase separation, combine both dichloromethane layers in the same 125-mL separatory funnel. 

---