Free from metal salts

According to a later patent of E. Merck,4 if quinoline is electrolyzed in dilute sulphuric acid containing for 1 equivalent of the base at least 4 equivalents of the acid, and free from metallic salts, a good yield of dihydroquinoline is obtained. 

The "freeing" of metals from metal salts by various reducing agents is a process which is as old as civilized man itself. In the past thirty years, several new approaches to reducing metal salts have appeared(l-13). In the past few years, several workers have shown that if care is taken regarding the reducing procedure, finely divided and highly reactive metal powders or slurries can be prepared( 16-60). 

Electrosynthesis of Metal-Free and Metal-Containing Phthalocyanines Starting from Metal Salts [9]... 

An aqueous solution of periodic add free from metals can be prepared from commercial potassium metaperiodate this salt can be converted in high yield to the slightly soluble barium dimesoperiodate, Baa Og, which through reaction with an equivalent amount of sulfuric add yields a solution of pure periodic add.34... 

Crude petroleum is a naturally occurring complex material composed mainly of the elements hydrogen, carbon, sulphur, phosphorous and nitrogen, as well as a host of organometallic and free inorganic metal salts or complexes in the crude composition as contamination from the earth s surrounding minerals. The crude oil is present as solid (asphalt), liquid (crude oil) and gas (natural gas). 

Extraction of Ca with Azo-azoxy BN. Add sufficient 5M NaOH to the sample solution to make the NaOH concentration 0.5-1 M. Shake the solution for 1 min with the solution of Azo-azoxy BN. Strip calcium from the extract with a small volume of 1M hydrochloric acid. Determination of Ca. The sample solution should contain not more than 30 pg of Ca, and be free from ammonium salts and Analytical Group I-III metals (to mask small amounts of these metals, add 10 mg each of KCN and Na2S. Neutralize the sample solution (to pH 7-8) with NaOH or HCl, and add 20 mg of Na2S04. Add 12 ml of the GBHA solution and 1 ml of 1 M NaOH, and dilute the solution with water to the mark in a 25-ml standard flask. After 10 min, measure the absorbance of the solution at 516 nm against a blank solution. 

In another patent, Alexander and Her (80) describe the isolation of particles formed in the above process by coagulating them with a metal ion such as calcium, washing the precipitate free from sodium salt, and then peptizing the product to a more concentrated silica sol by removing the calcium ions by ion exchange, for example. 

The isolation of an aliphatic acid from its aqueous solution, particularly in the presence of metallic salts, is a tedious operation (cf. p. 56), although a few such acids, e.g., succinic acid, can be extracted with ether. Since, however, a solution of an acid or one of Its salts is admirably suited for most of the tests in this series, the isolation of the free acid is rarely necessary except as a nieans of distinguishing (as in (i)) between aliphatic and aromatic members. 

The primary and secondary alcohol functionahties have different reactivities, as exemplified by the slower reaction rate for secondary hydroxyls in the formation of esters from acids and alcohols (8). 1,2-Propylene glycol undergoes most of the typical alcohol reactions, such as reaction with a free acid, acyl hahde, or acid anhydride to form an ester reaction with alkaU metal hydroxide to form metal salts and reaction with aldehydes or ketones to form acetals and ketals (9,10). The most important commercial appHcation of propylene glycol is in the manufacture of polyesters by reaction with a dibasic or polybasic acid. 

Chromium Chromate. Chromium chromate treatment baths are acidic and made up from sources of hexavalent chromium and complex fluoride, fluorosiHcate, fluorozirconate, fluorotitanate, and siHcofluorides. Optional additional components added to accelerate coating rate are free fluoride, ferricyanide, and other metal salts such as barium nitrate. Conversion coating on aluminum precedes by the following reactions (2,3,17) ... 

Another method for producing petoxycatboxyhc acids is by autoxidation of aldehydes (168). The reaction is a free-radical chain process, initiated by organic peroxides, uv irradiation, o2one, and various metal salts. It is terrninated by free-radical inhibitors (181,183). In certain cases, the petoxycatboxyhc acid forms an adduct with the aldehyde from which the petoxycatboxyhc acid can be hberated by heating or by acid hydrolysis. If the petoxycatboxyhc acid remains in contact with excess aldehyde, a redox disproportionation reaction occurs that forms a catboxyhc acid ... 

Metal phthalocyanines may also be prepared using alkaU metal salts or from metal-free phthalocyanine by boiling the latter in quinoline with metal... 

The analysis of penicillins by mass spectrometry (qv) has developed with the advent of novel techniques such as fast atom bombardment. The use of soft ionization techniques has enabled the analysis of thermally labile nonvolatile compounds. These techniques have proven extremely valuable in providing abundant molecular weight information from underivatized penicillins, both as free acids and as metal salts (15). 

Fast Color Salts. In order to simplify the work of the dyer, diazonium salts, in the form of stable dry powders, were introduced under the name of fast color salts. When dissolved in water they react like ordinary diazo compounds. These diazonium salts, derived from amines, free from solubilizing groups, are prepared by the usual method and are salted out from the solutions as the sulfates, the metallic double salts, or the aromatic sulfonates. The isolated diazonium salt is sold in admixture with anhydrous salts such as sodium sulfate or magnesium sulfate. 

Acylglycerols can be hydrolyzed by heating with acid or base or by treatment with lipases. Hydrolysis with alkali is called saponification and yields salts of free fatty acids and glycerol. This is how soap (a metal salt of an acid derived from fat) was made by our ancestors. One method used potassium hydroxide potash) leached from wood ashes to hydrolyze animal fat (mostly triacylglycerols). (The tendency of such soaps to be precipitated by Mg and Ca ions in hard water makes them less useful than modern detergents.) When the fatty acids esterified at the first and third carbons of glycerol are different, the sec-... 

Yttrium and lanthanum are both obtained from lanthanide minerals and the method of extraction depends on the particular mineral involved. Digestions with hydrochloric acid, sulfuric acid, or caustic soda are all used to extract the mixture of metal salts. Prior to the Second World War the separation of these mixtures was effected by fractional crystallizations, sometimes numbered in their thousands. However, during the period 1940-45 the main interest in separating these elements was in order to purify and characterize them more fully. The realization that they are also major constituents of the products of nuclear fission effected a dramatic sharpening of interest in the USA. As a result, ion-exchange techniques were developed and, together with selective complexation and solvent extraction, these have now completely supplanted the older methods of separation (p. 1228). In cases where the free metals are required, reduction of the trifluorides with metallic calcium can be used. 

Salz-farbe,/. metallic dye, dye salt, -fehler, m. salt error, -fleisch, n. salt meat, -fiuss, m.. saline flux salt rheum, eczema, salz-fdrmig, a. saliniform. -frei, a. free from salt, salt-free. 

The modern procedure to minimise corrosion losses on underground structures is to use protective coatings between the metal and soil and to apply cathodic protection to the metal structure (see Chapter 11). In this situation, soils influence the operation in a somewhat different manner than is the case with unprotected bare metal. A soil with moderately high salts content (low resistivity) is desirable for the location of the anodes. If the impressed potential is from a sacrificial metal, the effective potential and current available will depend upon soil properties such as pH, soluble salts and moisture present. When rectifiers are used as the source of the cathodic potential, soils of low electrical resistance are desirable for the location of the anode beds. A protective coating free from holidays and of uniformly high insulation value causes the electrical conducting properties of the soil to become of less significance in relation to corrosion rates (Section 15.8). 

Packaging materials Materials to be used in contact with metals should be as free as possible from corrosive salts or acid. BS 1133, Section 7 1967 gives limits for non-corrosive papers as follows chloride, 0-05% (as sodium chloride) sulphate, 0-25% (as sodium sulphate) and pH of water extract 5 -5-8 0. Where there is doubt, contact corrosion tests may be necessary in conditions simulating those in the package. 

However, they can also be prepared by metal exchange from alkali-metal phthalocyanines. If proton donors like hydrochloric acid, water or methanol are added to the reaction mixture of a freshly prepared alkali-metal phthalocyanine, metal-free phthalocyanines (PcH2) are formed (see Section 2.1.4.1,). If, on the other hand, the appropriate metal salt is added to a solution of an alkali-metal phthalocyanine, the product is the metalated compound (PcM) (see Section 2.1.6.). 

The yielded product can be converted to a surface-active compound if at least one ester group has been transformed to the free acid or an alkali metal salt thereof [160]. There are also many compounds from phosphinic acid derivatives claimed to be useful as sequestrants and builders to improve detergency, especially bisphosphonylmethylphosphinic acids and polyphosphinic acids [structures (9) and (10)], respectively ... 

Unsymmetrical as well as symmetrical anhydrides are often prepared by the treatment of an acyl halide with a carboxylic acid salt. The compound C0CI2 has been used as a catalyst. If a metallic salt is used, Na , K , or Ag are the most common cations, but more often pyridine or another tertiary amine is added to the free acid and the salt thus formed is treated with the acyl halide. Mixed formic anhydrides are prepared from sodium formate and an aryl halide, by use of a solid-phase copolymer of pyridine-l-oxide. Symmetrical anhydrides can be prepared by reaction of the acyl halide with aqueous NaOH or NaHCOa under phase-transfer conditions, or with sodium bicarbonate with ultrasound. 

In the case of molten salts, the functional electrolytes are generally oxides or halides. As examples of the use of oxides, mention may be made of the electrowinning processes for aluminum, tantalum, molybdenum, tungsten, and some of the rare earth metals. The appropriate oxides, dissolved in halide melts, act as the sources of the respective metals intended to be deposited cathodically. Halides are used as functional electrolytes for almost all other metals. In principle, all halides can be used, but in practice only fluorides and chlorides are used. Bromides and iodides are thermally unstable and are relatively expensive. Fluorides are ideally suited because of their stability and low volatility, their drawbacks pertain to the difficulty in obtaining them in forms free from oxygenated ions, and to their poor solubility in water. It is a truism that aqueous solubility makes the post-electrolysis separation of the electrodeposit from the electrolyte easy because the electrolyte can be leached away. The drawback associated with fluorides due to their poor solubility can, to a large extent, be overcome by using double fluorides instead of simple fluorides. Chlorides are widely used in electrodeposition because they are readily available in a pure form and... 

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