Perchloric acid composition

Pollution Prevention. Procedures haven been developed for recovery of composite ammonium perchlorate propellant from rocket motors, and the treatment of scrap and recovered propellant to reclaim ingredients. These include the use of high pressure water jets or compounds such as ammonia, which form fluids under pressure at elevated temperature, to remove the propellant from the motor, extraction of the ammonium perchlorate with solvents such as water or ammonia as a critical fluid, recrystalli2ation of the perchlorate and reuse in composite propellant or in slurry explosives or conversion to perchloric acid (166,167). 

Medium D Perchloric acid in acetic acid, medium composition not quoted687 rate coefficients obtained by extrapolation from values at other temperatures. 

The reaction between Fe(IlI) and Sn(Il) in dilute perchloric acid in the presence of chloride ions is first-order in Fe(lll) concentration . The order is maintained when bromide or iodide is present. The kinetic data seem to point to a fourth-order dependence on chloride ion. A minimum of three Cl ions in the activated complex seems necessary for the reaction to proceed at a measurable rate. Bromide and iodide show third-order dependences. The reaction is retarded by Sn(II) (first-order dependence) due to removal of halide ions from solution by complex formation. Estimates are given for the formation constants of the monochloro and monobromo Sn(II) complexes. In terms of catalytic power 1 > Br > Cl and this is also the order of decreasing ease of oxidation of the halide ion by Fe(IlI). However, the state of complexing of Sn(ll)and Fe(III)is given by Cl > Br > I". Apparently, electrostatic effects are not effective in deciding the rate. For the case of chloride ions, the chief activated complex is likely to have the composition (FeSnC ). The kinetic data cannot resolve the way in which the Cl ions are distributed between Fe(IlI) and Sn(ll). 

The reaction between Tl(III) and U(IV) is one of the few redox reactions which have been studied in a mixed solvent. Solutions were kept under nitrogen. There are striking differences between the rate in aqueous perchloric acid and methanol-aqueous perchloric acid solutions. In the latter media the order with respect to Tl(III), U(IV), and H alters as the solvent composition is changed (Table 29). For 25% methanol-75 % water solvent the kinetic orders of 1.0, 1.5 and —1.33 with respect to U(IV), Tl(III), and H, respectively, are consistent with the existence of two competing pathr whose net activation processes are... 

At more positive potentials, processes occur that depend on the composition of the electrolyte, such as the formation of H2S2Og and HS05 in sulphuric acid solutions, while the CIO radical is formed in perchloric acid solutions, decomposing to form C102 and 02. The formation of ozone has been observed at high current densities in solutions of rather concentrated acids. 

The burning mechanism of composite propellants differs from that described above. There is no exothermic reaction which can lead to a self-sustaining fizz zone. Instead, the first process appears to be the softening and breakdown of the organic binder/fuel which surrounds the ammonium perchlorate particles. Particles of propellant become detached and enter the flame. The binder is pyrolysed and the ammonium perchlorate broken down, initially to ammonia and perchloric acid. The main chemical reaction is thus in the gas phase, between the initial dissociation products. 

Emersion has been shown to result in the retention of the double layer structure i.e, the structure including the outer Helmholtz layer. Thus, the electric double layer is characterised by the electrode potential, the surface charge on the metal and the chemical composition of the double layer itself. Surface resistivity measurements have shown that the surface charge is retained on emersion. In addition, the potential of the emersed electrode, , can be determined in the form of its work function, , since and represent the same quantity the electrochemical potential of the electrons in the metal. Figure 2.116 is from the work of Kotz et al. (1986) and shows the work function of a gold electrode emersed at various potentials from a perchloric acid solution the work function was determined from UVPES measurements. The linear plot, and the unit slope, are clear evidence that the potential drop across the double layer is retained before and after emersion. The chemical composition of the double layer can also be determined, using AES, and is consistent with the expected solvent and electrolyte. In practice, the double layer collapses unless (i) potentiostatic control is maintained up to the instant of emersion and (ii) no faradaic processes, such as 02 reduction, are allowed to occur after emersion. 

These results indicate that in the polymerisation of styrene by perchloric acid the propagating species is not a carbonium ion (either free or paired), but a complex between acid and monomer. Our results indicate that this has the composition HC104, 4C8H8 and that it participates in the equilibrium... 

Smith, G. Fredrick, The Wet-Chemical Oxidation of Organic Compositions, Employing Perchloric Acid, G. F. Smith Chemical Co., Columbus, Ohio, 1965. 

When large spherical AP particles dg = 3 mm) are added, large flamelets are formed in the dark zone.Pl Close inspection of the AP particles at the burning surface reveals that a transparent bluish flame of low luminosity is formed above each AP particle. These are ammonia/perchloric acid flames, the products of which are oxidizer-rich, as are also observed for AP composite propellants at low pressures, as shown in Fig. 7.5. The bluish flame is generated a short distance from the AP particle and has a temperature of up to 1300 K. Surrounding the bluish flame, a yellowish luminous flame stream is formed. This yellowish flame is produced by in-terdiffusion of the gaseous decomposition products of the AP and the double-base matrix. Since the decomposition gas of the base matrix is fuel-rich and the temperature in the dark zone is about 1500 K, the interdiffusion of the products of the AP and the matrix shifts the relative amounts towards the stoichiometric ratio, resulting in increased reaction rate and flame temperature. The flame structure of an AP-CMDB propellant is illustrated in Fig. 8.1. 

The effect of fluoride ions on the electrochemical behaviour of a metal zirconium electrode was studied by Pihlar and Cencic in order to develop a sensor for the determination of zirconium ion. Because elemental zirconium is always covered by an oxide layer, the anodic characteristics of a Zr/Zr02 electrode are closely related to the composition of the electrolyte in contact with it. These authors found the fluoride concentration and anodic current density to be proportional in hydrochloric and perchloric acid solutions only. In other electrolytes, the fluoride ion-induced dissolution of elemental zirconium led to an increase in the ZrOj film thickness and hindered mass transport of fluoride through the oxide layer as a result. The... 

F. C. Mathers, and A. W. Kenney prepared perchloric acid by distilling a mixture of potassium perchlorate and sulphuric acid in a current of steam. H. H. Willard oxidized ammonium perchlorate with an excess of a mixture of nitric and hydrochloric acids. As a result, a mixture of perchloric, nitric, and hydrochloric acids is formed. The latter are expelled by heating the mixture on a hot plate until white fumes of perchloric acid begin to appear. No unoxidized ammonia should be present in the soln. An acid of a composition approximately HCIO4+2H2O, boiling at 203°, remains. 

Table I.—Percentage Composition of Solutions of Perchloric Acid of Specific Gravity between 1-00 and 1-67 at 15°.

Table II.—Composition or Liquid and Vapour Phases or Solutions or Perchloric Acid or DirrERENT Boiling Points.

Fid. 27. — Composition of Liquid and Vapour Phases of Solutions of Perchloric Acid of different Boiling Points. 

The composition and constitution of perchloric acid.—The composition of perchloric acid was established by F. von Stadion,80 and verified by J. L. Gay Lussac by the decomposition of potassium chlorate. 10 03 grams of perchloric acid were dissolved in water, and treated with a small excess of potassium carbonate. The soln. was evaporated to dryness with a slight excess of acetic acid, and washed with absolute alcohol to remove the potassium acetate. The residual potassium perchlorate was dried and weighed. The potassium perchlorate was ignited to drive off the oxygen. The results were ... 

Mixtures composed of the salts of perchloric acid and an elastomer or plastic polymer are now the most popular of the composite propellants. 

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