Mineral-acid corrosion

Mineral acids. Corrosion by nitric acid can be reduced by the addition of sulphuric acid (up to 10%). 

M.A Maguire and T.L. Yau. 1986. Electrochemical properties of zirconium in mineral acids. Corrosion 86, Paper No. 265, Houston, TX NACE International. 

Uses. Propargyl alcohol is a component of oil-well acidizing compositions, inhibiting the attack of mineral acids on steel (see Corrosion and CORROSION control). It is also employed in the pickling and plating of metals. 

Cation exchangers are regenerated with mineral acids when used in the form. Sulfuric acid [8014-95-7] is preferred over hydrochloric acid [7647-01-0], HCl, in many countries because it is less expensive and less corrosive. However, the use of hydrochloric acid is the best method of overcoming precipitation problems in installations which deionize water with high concentrations of barium or calcium compared to other cations. A 4% acid concentration is common, although sulfuric acid regenerations may start as low as 0.8—1% to minimize calcium sulfate [7718-18-9] precipitation. 

The corrosion behavior of tantalum is weU-documented (46). Technically, the excellent corrosion resistance of the metal reflects the chemical properties of the thermal oxide always present on the surface of the metal. This very adherent oxide layer makes tantalum one of the most corrosion-resistant metals to many chemicals at temperatures below 150°C. Tantalum is not attacked by most mineral acids, including aqua regia, perchloric acid, nitric acid, and concentrated sulfuric acid below 175°C. Tantalum is inert to most organic compounds organic acids, alcohols, ketones, esters, and phenols do not attack tantalum. 

Mineral acids are used as catalysts, usually in a concentration of 20— 40 wt % and temperatures of 30—60°C. An efficient surfactant, preferably one that is soluble in the acid-phase upon completion of the reaction, is needed to emulsify the a-pinene and acid. The surfactant can then be recycled with the acid. Phosphoric acid is the acid commonly used in the pine oil process. Its mild corrosion characteristics and its moderate strength make it more manageable, especially because the acid concentration is constandy changing in the process by the consumption of water. Phosphoric acid is also mild enough to prevent any significant dehydration of the alcohols formed in the process. Optimization of a process usually involves considerations of acid type and concentration, temperature, surfactant type and amount, and reaction time. The optimum process usually gives a maximum of alcohols with the minimum amount of hydrocarbons and cineoles. 

Corrosion Resistance. Zirconium is resistant to corrosion by water and steam, mineral acids, strong alkaUes, organic acids, salt solutions, and molten salts (28) (see also Corrosion and corrosion control). This property is attributed to the presence of a dense adherent oxide film which forms at ambient temperatures. Any break in the film reforms instantly and spontaneously in most environments. 

The polymer-supported catalysts are thus important conceptually in linking catalysis in solutions and catalysis on supports. The acid—base chemistry is fundamentally the same whether the catalytic groups are present in a solution or anchored to the support. The polymer-supported catalysts have replaced acid solutions in numerous processes because they minimise the corrosion, separation, and disposal problems posed by mineral acids. 

Severe concentration cell corrosion involves segregation of aggressive anions beneath deposits. Concentrations of sulfate and chloride, in particular, are deleterious. Acid conditions may be established beneath deposits as aggressive anions segregate to these shielded regions. Mineral acids, such as hydrochloric and sulfuric, form by hydrolysis. The mechanism of acid formation is discussed in Chap. 2. 

It is possible to confuse corrosion by a strong mineral acid with damage by cavitation. Both can produce jagged, undercut, spongelike surface... 

Naphthenic acid is a collective name for organic acids present in some but not all crude oils. In addition to true naphthenic acids (naphthenic carboxylic acids represented by the formula X-COOH in which X is a cycloparaffin radical), the total acidity of a crude may include various amounts of other organic acids and sometimes mineral acids. Thus the total neutralization number of a stock, which is a measure of its total acidity, includes (but does not necessaiily represent) the level of naphthenic acids present. The neutralization number is the number of milligrams of potassium hydroxide required to neutralize one gram of stock as determined by titration using phenolphthalein as an indicator, or as determined by potentiometric titration. It may be as high as 10 mg KOH/gr. for some crudes. The neutralization number does not usually become important as a corrosion factor, however, unless it is at least 0.5 mg KOH/gm. 

Free mineral acidity H2SO4, HCl, and other acids, expressed as CaCOj. Causes rapid corrosion and deterioration of surfaces. 

Mild steels are rapidly corroded by mineral acids even when they are very dilute (pH less than 5). However, it is often more economical to use mild steel and include a considerable corrosion allowance on the thickness of the apparatus. Mild steel is not acceptable in situations in which metallic contamination of the product is not permissible. 

Free mineral acids HCI H, SO4 Corrosion Any process usnig alkalines to neurralizc... 

The elements of Group 5 are in many ways similar to their predecessors in Group 4. They react with most non-metals, giving products which are frequently interstitial and nonstoichiometric, but they require high temperatures to do so. Their general resistance to corrosion is largely due to the formation of surface films of oxides which are particularly effective in the case of tantalum. Unless heated, tantalum is appreciably attacked only by oleum, hydrofluoric acid or, more particularly, a hydrofluoric/nitric acid mixture. Fused alkalis will also attack it. In addition to these reagents, vanadium and niobium are attacked by other hot concentrated mineral acids but are resistant to fused alkali. 

Published work relating to bimetallic corrosion in sodium chloride solution is reported in Referencesin sea-water in Refer-ences " in fresh waters in Referencesin mineral acids in References in water/glycol mixtures in Reference ... 

Much of the information available on resistance of nickel-iron alloys to corrosion by mineral acids is summarised by Marsh. In general, corrosion rates decrease sharply as the nickel content is increased from 0 to 30-40%, with little further improvement above this level. The value of the nickel addition is most pronounced in conditions where hydrogen evolution is the major cathodic reaction, i.e. under conditions of low aeration and agitation. Results reported by Hatfield show that the rates of attack of Fe-25Ni alloy in sulphuric and hydrochloric acid solutions, although much lower than those of mild steel, are still appreciable (Tables 3.35 and 3.36). In solutions of nitric acid, nickel-iron alloys show very high rates of corrosion. 

Many organic liquids, including oils (essential, animal, vegetable or mineral), alcohols, fatty acids, chlorinated hydrocarbons and aliphatic esters, are without action. The absence of any catalytic action of tin on oxidative changes is helpful in this respect. When, however, mineral acidity can arise, as with the chlorinated hydrocarbons containing water, there may be some corrosion, especially at elevated temperature. 

Hydrochloric and sulphuric acids are not so aggressive. Phosphoric acid when pure is no more corrosive than other mineral acids. 

Nail sickness Nail sickness is chemical decay associated with corroded metals in marine situations. Chemical degradation of wood by the products of metal corrosion is brought about by bad workmanship or maintenance, or unsuitable (permeable) timber species, all of which permit electrolyte and oxygen access which promotes corrosion. Chemical decay of wood by alkali occurs in cathodic areas (metal exposed oxygen present). Softening and embrittlement of wood occurs in anodic areas (metal embedded oxygen absent) caused by mineral acid from hydrolysis of soluble iron corrosion products. 

In extreme cases irritant chemicals can have a corrosive action. Corrosive substances can attack and weaken materials of construction, as mentioned in Chapter 3. They can also attack living tissue (e.g. to cause skin ulceration and in severe cases chemical burns), kill cells and possibly predispose to secondary bacterial invasion. Thus while acute irritation is a local and reversible response, corrosion is irreversible destruction at the site of the contact. The outcome is influenced by the nature of the compound, the concentration, duration of exposure, the pH (see Figure 4.1) etc. Thus dilute mineral acids may be irritant whereas at higher concentrations they may cause corrosion. 

Chemicals which give strong acid reactions, often on interaction with water, e.g. mineral acids. Some organic acids can also be corrosive. Phenolics can result in local anaesthesia so that the pain will be absent for a time. 

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