Alkalinity and Acidity

Unused and used petroleum products may contain acidic constituents that are present as additives or as degradation products formed during service, such as oxidation products (ASTM D-5770). The relative amount of these materials can be determined by titrating with bases. The acid number is used as a guide in the quality control of lubricating oil formulations. It is also sometimes used as a measure of lubricant degradation in service. Any condemning limits must be empirically established. 

Thus the acid number is a measure of this amount of acidic substance in the oil, always under the conditions of the test. Because a variety of oxidation products contribute to the acid number and the organic acids vary widely in corrosion properties, the test cannot be used to predict corrosiveness of an oil under service conditions. 

The add number is the quantity of base, expressed in milligrams of potassium hydroxide per gram of sample, that is required to titrate a sample in this solvent to a green/green-brown end point with p-naphtholbenzein indicator solution (ASTM D-974, IP 139). However, many higher-molecular-weight oil products (dark-colored oils) that cannot be analyzed for acidity because of obscurity of the color-indicator end point can be analyzed by an alternate test method (ASTM D-664). The quality of the mineral oil products renders them suitable for determination of the acid number. 

In a manner akin to the acid number, the base number (often referred to as the neutralization number) is a measure of the basic constituents in the oil under the conditions of the test. The base number is used as a guide in the quahty control of oil formulation and is also used as a measure of oil degradation in service. 

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Modestov A D, Zhou G-D, Ge FI-FI and Loo B FI 1995 A study by voltammetry and the photocurrent response method of copper electrode behavior in acidic and alkaline solutions containing chloride ions J. Electroanal. Chem. 380 63-8... 

The following redox potentials are given for the oxidation of manganese(II) to manganese(III) in acid and alkaline solution. 

Under conditions of extreme acidity or alkalinity, acryhc ester polymers can be made to hydroly2e to poly(acryhc acid) or an acid salt and the corresponding alcohol. However, acryhc polymers and copolymers have a greater resistance to both acidic and alkaline hydrolysis than competitive poly(vinyl acetate) and vinyl acetate copolymers. Even poly(methyl acrylate), the most readily hydroly2ed polymer of the series, is more resistant to alkah than poly(vinyl acetate) (57). Butyl acrylate copolymers are more hydrolytically stable than ethyl acrylate copolymers (58). 

Propane and light ends are rejected by touting a portion of the compressor discharge to the depropanizer column. The reactor effluent is treated prior to debutanization to remove residual esters by means of acid and alkaline water washes. The deisobutanizer is designed to provide a high purity isobutane stream for recycle to the reactor, a sidecut normal butane stream, and a low vapor pressure alkylate product. 

Silver sulfide is one of the most insoluble salts known. It is not solubilized by nonoxidizing mineral acids, but it is soluble in concentrated nitric acid, concentrated sulfuric acid, and alkaline cyanide solutions. 

Hydrolysis of dialkyl sulfites under acidic and alkaline conditions, which is followed by the use of OH2, proceeds by attack at sulfur to give S—O cleavage (72). The rate of hydrolysis is generally faster for cycHc and aryl sulfites than for dialkyl sulfites (73). Activation parameters of hydrolysis are known for some sulfites, and the increased rate for ethylene sulfite results from a reduced entropy of activation which results from a rigid ring stmcture (74). 

Alkylphenol ethoxylates are chemically stable and highly versatile surfactants that find appHcation in a large variety of industrial products including acid and alkaline metal cleaning formulations, hospital cleaners, herbicides (qv) and insecticides, oil-weU drilling fluids, synthetic latices, and many others (see Disinfectants AND antiseptics Elastop rs, synthetic Insect control technology Metal surface treati nts Pesticides Petroleum, drilling fluids). 

At room temperature, ca 60 wt % ethylene oxide is needed to solubilize the fatty acids. Surface activity of the ethoxylates is moderate and less than that of alcohol or alkylphenol ethoxylates (84). The ethoxylates are low foamers, a useful property in certain appHcations. Emulsification is the most important function. Its importance is reflected in the wide range of lipophilic solubiHties available in the commercial products. Like all organic esters, fatty acid ethoxylates are susceptible to acid and alkaline hydrolysis. 

In the field, cassiterite ore is usually recognized by its high density (7.04 g/cm ), low solubiUty in acid and alkaline solutions, and extreme hardness. Tin in solution is detected by the white precipitate formed with mercuric chloride. Stannous tin in solution gives a red precipitate with toluene-3,4-dithiol. 

Toxicology. Inorganic tin and its compounds are generally of a low order of toxicity, largely because of the poor absorption and rapid excretion from the tissues of the metal (42—49). The acidity and alkalinity of their solutions make assessment of their parenteral toxicity difficult. The oral LD q values for selected inorganic tin compounds are Hsted in Table 2. It is estimated that the average U.S. daily intake of tin, which is mostly from processed foods, is 4 mg (see Food processing). 

Neutralization usually follows equalization so that acidic and alkaline streams can be partially neutralized in the equalization basin. If the wastewater is always acidic, neutralization may occur at a stage prior to the stream reaching the equalization basin, so as to minimize corrosion in the equalization basin. 

Benzal chloride is hydrolyzed to benzaldehyde under both acid and alkaline conditions. Typical conditions include reaction with steam in the presence of ferric chloride or a zinc phosphate catalyst (22) and reaction at 100°C with water containing an organic amine (23). Cinnamic acid in low yield is formed by heating benzal chloride and potassium acetate with an amine as catalyst (24). 

Effluents from both dye works and dyehouses are treated both before leaving the plant, eg, neutrali2ation of acidic and alkaline Hquors and heavy metal removal, and in municipal sewage works. Various treatments are used (34). 

Pla.tinum, Platinum plating has found appHcation in the production of platinised titanium, niobium, or tantalum anodes which are used as insoluble anodes in many other plating solutions (see Metalanodes). Plating solutions were often based on platinum "P" salt, which is diamminedinitroplatiniim (IT). A dinitroplatinite sulfate—sulfuric acid bath has been used to plate direcdy onto titanium (129). This bath contains 5 g/L of the platinum salt, pH adjusted to 2.0 with sulfuric acid. The bath is operated at 40°C at 10—100 A/m. Other baths based on chloroplatinic acid have been used in both acid and alkaline formulations the acid bath uses 20 g/L of the platinum salt and 300 g/L hydrochloric acid at 65° C and 10—200 A/m. The alkaline bath uses 10 g/L of the platinum salt, 60 g/L of ammonium phosphate and ammonium hydroxide to give a pH of 2.5—9.0. The alkaline bath can be plated directly onto nickel-base alloys acid baths require a gold strike on most metals. 

Alloxan forms an oxime (1007) which is the same compound, violuric acid, as that formed by nitrosation of barbituric acid likewise, a hydrazone and semicarbazone. Reduction of alloxan gives first alloxantin, usually formulated as (1008), and then dialuric acid (1004 R = OH) the steps are reversible on oxidation. Vigorous oxidation with nitric acid and alkaline hydrolysis both give imidazole derivatives (parabanic acid and alloxanic acid, respectively) and thence aliphatic products. Alloxan and o-phenylenediamine give the benzopteridine, alloxazine (1009) (61MI21300). 

Amino groups a to nitrogen are hydrolyzed to the corresponding oxo compounds (as in the purines and pteridines) in bo h acid and alkaline conditions. Schiff bases are reduced to benzylamino derivatives with borohydride. 

Pitting is also promoted by low pH. Thus, acidic deposits contribute to attack on stainless steels. Amphoteric alloys such as aluminum are harmed by both acidic and alkaline deposits (Fig. 4.4). Other passive metals (those that form protective corrosion product layers spontaneously) are similarly affected. 

Titanium dioxide used for adhesive applications should contain an inorganic coating to control polarity, improve its ease of dispersion, and improve its weather resistance. The inorganic coating (zirconium dioxide, silica, alumina) is applied in the aqueous sluny by precipitation of one or more hydrated metal oxides and by neutralization of acidic and alkaline compounds. 

In the acidic and alkaline hydrolysis rates of the same ester, the steric and resonance effects. re the same. 

Figure 13.16 Oxidation state diagram for As, Sb and Bi in acid and alkaline solutions, together with selected data on N and P for comparison.

In addition to simple dissolution, ionic dissociation and solvolysis, two further classes of reaction are of pre-eminent importance in aqueous solution chemistry, namely acid-base reactions (p. 48) and oxidation-reduction reactions. In water, the oxygen atom is in its lowest oxidation state (—2). Standard reduction potentials (p. 435) of oxygen in acid and alkaline solution are listed in Table 14.10- and shown diagramatically in the scheme opposite. It is important to remember that if or OH appear in the electrode half-reaction, then the electrode potential will change markedly with the pH. Thus for the first reaction in Table 14.10 O2 -I-4H+ -I- 4e 2H2O, although E° = 1.229 V,... 

Hydrogen peroxide has a rich and varied chemistry which arises from (i) its ability to act either as an oxidizing or a reducing agent in both acid and alkaline solution, (ii) its ability to undergo proton acid/base reactions to form... 

H28 is readily soluble in both acidic and alkaline aqueous solutions. Pure water dissolves 4.65 volumes of the gas at 0° and 2.61 volumes at 20° in other units a saturated solution is 0.1 M at atmospheric pressure and 25°, i.e. 

The standard reduction potentials of the elements in acid and alkaline solutions are summarized in the schemes below.It is... 

Figure 17.18 Standard reduction potentials for Cl, Br and I species in acid and alkaline solutions. For At see...

The data in Fig. 17.18 are presented in graphical form in Fig. 17.19 which shows the volt-equivalent diagrams (p. 436) for acid and alkaline solutions. It is clear from these that CI2 and Br2 are much more stable towards disproportionation in acid solution (concave angle at X2) than in alkaline solutions (convex angle). In terms of... 

Poly(L-malate) decomposes spontaneously to L-ma-late by ester hydrolysis [2,4,5]. Hydrolytic degradation of the polymer sodium salt at pH 7.0 and 37°C results in a random cleavage of the polymer, the molecular mass decreasing by 50% after a period of 10 h [2]. The rate of hydrolysis is accelerated in acidic and alkaline solutions. This was first noted by changes in the activity of the polymer to inhibit DNA polymerase a of P. polycephalum [4]. The explanation of this phenomenon was that the degradation was slowest between pH 5-9 (Fig. 2) as would be expected if it were acid/base-catalyzed. In choosing a buffer, one should be aware of specific buffer catalysis. We found that the polymer was more stable in phosphate buffer than in Tris/HCl-buffer. 

Table 1.10 Thermodynamics of reactions of noble metals with acids and alkaline solutions containing oxygen = 1 atm)...

The numerous metals and alloys used in practice show such a wide variation in response to various anions in acid and alkaline solutions that common features are difficult to discern and a basis for predicting corrosion behaviour is not very apparent. 

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