Perchlorate sodium

Data reported for the protolysis constant of water in sodium perchlorate media are listed in Table 5.24. The data are solely for a temperature of 25 C, although there have been a few data that have been reported at other temperatures. There are too few data at other temperatures to allow an assessment of these data and to determine temperature-dependent ion interaction coefficients. 

For sodium perchlorate media, water activity data are reported in Brown, 

On the basis of the individual ion interaction parameters already derived for (Na, OH ) (see Table 5.5), those for (H, CIO4 ) are 

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NaClO sodium hypochlorite NaC102 sodium chlorite NaClO sodium chlorate NaClO sodium perchlorate... 

Ammonium perchlorate is a colorless, crystalline compound having a density of 1.95 g/mL and a molecular weight of 117.5. It is prepared by a double displacement reaction between sodium perchlorate and ammonium chloride, and is crystallized from water as the anhydrous salt. 

In commercial manufactuie of ammonium peichloiate, sodium peichloiate can be the starting material. The ammonium ion can be contributed by such materials as ammonium chloride, sulfate, and nitrate, eg, the metathetical reaction of sodium perchlorate and ammonium chloride ... 

The alkah metal perchlorates are either white or colorless, and have increasing solubiUty in water in the order of Na > Li > NH4 > K> Rb > Cs. The high solubiUty of sodium perchlorate, NaClO, makes this material useful as an intermediate for production of all other perchlorates by double metathesis reactions and controlled crystallization. 

The perchloryl fluoride [7616-94-6] FCIO, the acyl fluoride of perchloric acid, is a stable compound. Normally a gas having a melting poiat of —147.7° C and a boiling poiat of —46.7°C, it can be prepared by electrolysis of a saturated solution of sodium perchlorate ia anhydrous hydrofluoric acid. Some of its uses are as an effective fluorinating agent, as an oxidant ia rocket fuels, and as a gaseous dielectric for transformers (69). 

Perchlorates. Historically, perchlorates have been produced by a three-step process (/) electrochemical production of sodium chlorate (2) electrochemical oxidation of sodium chlorate to sodium perchlorate and (4) metathesis of sodium perchlorate to other metal perchlorates. The advent of commercially produced pure perchloric acid directly from hypochlorous acid means that several metal perchlorates can be prepared by the reaction of perchloric acid and a corresponding metal oxide, hydroxide, or carbonate. 

Sodium Perchlorate. The electrochemical oxidation of sodium chlorate is carried out at the anode ia an undivided cell according to the following reaction ... 

Table 1. Sodium Perchlorate Cell Operating Information 92-101.

The electrolyte feed to the cells is pretreated to remove impurities, and/or additives are added to the feed to improve cell performance (94). The cell hquor leaving the cell is evaporated, crystallised, and centrifuged to remove soHd sodium perchlorate. The clarified cell Hquor can undergo reaction in a double metathesis reactor to produce NH CIO, KCIO or other desired perchlorates. 

Ammonium Perchlorate. The commercial AP product is manufactured by the double-exchange reaction of sodium perchlorate and ammonium chloride (102,103). 

Ammonia, hydrochloric acid, and sodium perchlorate are mixed and the reaction mixture crystallised in a vacuum-cooled crystalliser. Ammonium perchlorate crystals are centrifuged, reslurried, recentrifuged, and then dried and blended for shipment. Mother Hquor is evaporated to precipitate sodium chloride and the depleted mother Hquor is recycled to the reactor. The AP product made by this method is 99% pure and meets the specifications for propeUant-grade ammonium perchlorate. The impurities are ammonium chloride, sodium perchlorate, ammonium chlorate, and water insolubles. 

The U.S. domestic capacity of ammonium perchlorate is roughly estimated at 31,250 t/yr. The actual production varies, based on the requirements for soHd propellants. The 1994 production ran at about 11,200 t/yr, 36% of name plate capacity. Environmental effects of the decomposition products, which result from using soHd rocket motors based on ammonium perchlorate-containing propellants, are expected to keep increasing pubHc pressure until consumption is reduced and alternatives are developed. The 1995 price of ammonium perchlorate is in the range of 1.05/kg. Approximately 450 t/yr of NH ClO -equivalent cell Hquor is sold to produce magnesium and lithium perchlorate for use in the production of batteries (113). Total U.S. domestic sales and exports for sodium perchlorate are about 900 t/yr. In 1995, a solution containing 64% NaClO was priced at ca 1.00/kg dry product was also available at 1.21/kg. 

Potassium permanganate oxidizes succinic acid to a mixture of malic and tartaric acid [133-37-9]. 3-Hydroxypropionic acid [503-66-2] is obtained with sodium perchlorate. Cerium(IV) sulfate in sulfuric acid medium oxidizes succinic acid to oxaloacetic acid (71). 

Analogous to the oxidation of hydrazones to azo compounds, A-unsubstituted pyrazolidines are oxidized to A -pyrazolines. For example, the blcyclic pyrazolidine (415) when treated with silver oxide yields the pyrazoline (416) (65JA3023). Pyrazolidine (417) is transformed into the perchlorate of the pyrazolium salt (411) by reaction with mercury(II) acetate in ethanol followed by addition of sodium perchlorate (69JOU1480). 

The reseai ch has been carried out by the liquid chromatograph Perkin-Elmer (Series 200), which has tandem detectors the diode array (X=210 nm) and the refractometer. The temperature of a column was 30 C, speed of a mobile phase is 1.5 ml/ min. As a mobile phase, mixtures of solvents methanol - water and acetonitrile - water with addition of sodium perchlorate. The columns with the modified silica gel C8 and Cl8 (4.6x220 mm, 5 pm) were used for sepai ation of the AIST and FAS components. In order to make the identification of AIST and FAS components more reliable the ratio of the values of the above-mentioned detectors signals of each substance analyzed. 

Storage and use of sodium perchlorate and other similar strong oxidants... 

Spray solution II Dissolve 92 mg potassium hydrogen phthalate in 100 ml water and adjust the pH to 5.0 with sodium hydroxide solution (1 mol/l). Dissolve 5 g sodium perchlorate in this solution [9]. 

Potassium hydrogen phthalate Sodium perchlorate monohydrate Sodium hydroxide solution (1 mol/l)... 

The ionization eonstant should be a function of the intrinsic heterolytic ability (e.g., intrinsic acidity if the solute is an acid HX) and the ionizing power of the solvents, whereas the dissoeiation constant should be primarily determined by the dissociating power of the solvent. Therefore, Ad is expeeted to be under the eontrol of e, the dieleetrie eonstant. As a consequenee, ion pairs are not deteetable in high-e solvents like water, which is why the terms ionization constant and dissociation constant are often used interchangeably. In low-e solvents, however, dissociation constants are very small and ion pairs (and higher aggregates) become important species. For example, in ethylene chloride (e = 10.23), the dissociation constants of substituted phenyltrimethylammonium perchlorate salts are of the order 10 . Overall dissociation constants, expressed as pArx = — log Arx, for some substanees in aeetie acid (e = 6.19) are perchloric acid, 4.87 sulfuric acid, 7.24 sodium acetate, 6.68 sodium perchlorate, 5.48. Aeid-base equilibria in aeetie acid have been earefully studied beeause of the analytical importance of this solvent in titrimetry. 

Interaction of the latter with triphenylphosphine in the presence of sodium perchlorate leads to the cationic complex [(dppm)Au2(li-L)Pd(C Fj)(PPh3)]C10. Reactions of [L Au(p-L)AuL ] (L = bibenzimidazolate L = PPh, dppm)] with [Pd(0C103)(C Fj)(PPh3)2] do not lead to the tetranuclear products. Only the bibenzimidazolate (L) dinuclear product [(PPh3)(C F3)Pd(p-L)Pd(C, F3)(PPh3)] could be isolated in both cases. 

Freiman, L. 1. and Kolotyrkin, Ya. M., Pitting Corrosion of Aluminium in Solutions of Sodium Perchlorate and Perchloric Acid , Zashch. Melal, 2, 488 (1966) C.A., 65, 19674d Novakovskii, V. M. and Sorokina, A. N., Comparative Electrochemistry of Stress Corrosion and Pitting of Stainless Steels in Chloride Solutions , Zashch. Melal, 2, 416 (1966) C.A., 65, 18152g... 

Sodium perchlorate is produced by the electrolysis of sodium chlorate. If a current of 1.50 X 103 A passes through an electrolytic cell, how many kilograms of sodium perchlorate are produced in an eight-hour run ... 

Kinetics studies of acid-catalysed chlorination by hypochlorous acid in aqueous acetic acid have been carried out, and the mechanism of the reactions depends upon the strength of the acetic acid an<( the reactivity of the aromatic. Different groups of workers have also obtained different kinetic results. Stanley and Shorter207 studied the chlorination of anisic acid by hypochlorous acid in 70 % aqueous acetic acid at 20 °C, and found the reaction rate to be apparently independent of the hydrogen ion concentration because added perchloric acid and sodium perchlorate of similar molar concentration (below 0.05 M, however) both produced similar and small rate increases. The kinetics were complicated, initial rates being proportional to aromatic concentration up to 0.01 M, but less so thereafter, and described by... 

With 77 % aqueous acetic acid, the rates were found to be more affected by added perchloric acid than by sodium perchlorate (but only at higher concentrations than those used by Stanley and Shorter207, which accounts for the failure of these workers to observe acid catalysis, but their observation of kinetic orders in hypochlorous acid of less than one remains unaccounted for). The difference in the effect of the added electrolyte increased with concentration, and the rates of the acid-catalysed reaction reached a maximum in ca. 50 % aqueous acetic acid, passed through a minimum at ca. 90 % aqueous acetic acid and rose very rapidly thereafter. The faster chlorination in 50% acid than in water was, therefore, considered consistent with chlorination by AcOHCl+, which is subject to an increasing solvent effect in the direction of less aqueous media (hence the minimum in 90 % acid), and a third factor operates, viz. that in pure acetic acid the bulk source of chlorine ischlorineacetate rather than HOC1 and causes the rapid rise in rate towards the anhydrous medium. The relative rates of the acid-catalysed (acidity > 0.49 M) chlorination of some aromatics in 76 % aqueous acetic acid at 25 °C were found to be toluene, 69 benzene, 1 chlorobenzene, 0.097 benzoic acid, 0.004. Some of these kinetic observations were confirmed in a study of the chlorination of diphenylmethane in the presence of 0.030 M perchloric acid, second-order rate coefficients were obtained at 25 °C as follows209 0.161 (98 vol. % aqueous acetic acid) ca. 0.078 (75 vol. % acid), and, in the latter solvent in the presence of 0.50 M perchloric acid, diphenylmethane was approximately 30 times more reactive than benzene. 

The accelerating effect of sodium perchlorate on the rate of mercuration by mercuric acetate in acetic acid arises out of the equilibrium... 

From this equilibrium it follows that 0.1 M sodium perchlorate will produce 6x10"5 M perchloric acid, i.e. sufficient to produce a significant acceleration for mercuration with mercuric acetate in the absence of added perchloric acid, but not otherwise. The acceleration of the rate of mercuration with mercuric perchlorate in 97 % aqueous acetic acid (but not with acetic acid containing a concentration of water of 0.2 M) was attributed to the fact that in the former... 

In this reaction the effect of changing the ionic strength of the medium was also studied by addition of sodium perchlorate which caused the rate coefficient to decrease. However, this was shown to arise from the resultant change in pH of the solution, for when this was allowed for, the normal positive salt effect was observed. 

For these selected data the medium is assumed to be perchloric acid or sodium perchlorate. 

Perchloric acid, HC104, is prepared by the action of concentrated hydrochloric acid on sodium perchlorate, followed by distillation. It is a colorless liquid and the strongest of all common acids. Because chlorine has its highest oxidation number, +7, in these compounds, they are powerful oxidizing agents contact between perchloric acid and even a small amount of organic material can result in a dangerous explosion. 

A mixture of water/pyridine appears to be the solvent of choice to aid carbenium ion formation [246]. In the Hofer-Moest reaction the formation of alcohols is optimized by adding alkali bicarbonates, sulfates [39] or perchlorates. In methanol solution the presence of a small amount of sodium perchlorate shifts the decarboxylation totally to the carbenium ion pathway [31]. The structure of the carboxylate can also support non-Kolbe electrolysis. By comparing the products of the electrolysis of different carboxylates with the ionization potentials of the corresponding radicals one can draw the conclusion that alkyl radicals with gas phase ionization potentials smaller than 8 e V should be oxidized to carbenium ions [8 c] in the course of Kolbe electrolysis. This gives some indication in which cases preferential carbenium ion formation or radical dimerization is to be expected. Thus a-alkyl, cycloalkyl [, ... 

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