Removal of graphite by oxidation with perchloric acid plus periodic acid: Inapplicability to the spectrophotometric determination of manganese in steel

An attempt has been made to improve the Willard and Greathouse periodate method for the determination of manganese in high-carbon steel and cast iron by oxidizing the graphite with periodic acid in the presence of perchloric acid and phosphoric acid. Graphite is rapidly oxidized at 150° by this mixture but manganese is lost by volatilization as the heptoxide and decomposition of the latter on hot surfaces to manganese dioxide. No way was found for either the quantitative removal and recovery of manganese by volatilization or for quantitative return to the main solution. The spectrophotometric determination of manganese in the supernatant liquid after allowing graphite to settle yields imprecise but not wholly unacceptable results; for the highest accuracy, graphite should be removed along with silica following dehydration of the latter with perchloric acid.     

Titrimetric, coulometric and spectrophotometric determination of manganese following perchloric acid oxidation in the presence of pyrophosphate

Manganese is oxidized quantitatively to a violet, tervalent pyrophosphate in a boiling mixture of equal parts of perchloric acid and phosphoric add. This Mn(III) can be titrated potentiometrically or coulometrically with iron(II); it can also be measured spectrophotometrically. If the titrimetric method is carried out with titanium (III) or chromium(II), iron can also be titrated immediately after the manganese. The methods were applied to a new reference sample, ISU 600 Manganiferous Iron Ore, and to manganese ore, spiegeleisen, ferromanganese, and rail steel. Manganese(II) oxalate dihydrate has been reinvestigated as a primary standard and is highly recommended.     

The oxidation of organic compounds by tervalent manganese compounds-II The determination of mandelic acid with a tervalent manganese standard solution in perchloric acid medium

An indirect titrimetric determination of mandelic acid, based on its oxidation by a standard solution of hexa-aquomanganese(III) in perchloric acid medium, is described.     

Sensitive, selective spectrophotometric determination of phenols with periodic acid

A new spectrophotometric determination of phenols with periodic acid has been developed. The colored product of phenol periodic acid reaction has a λ_max 380 nm. The determination of phenol, pyrocatechol, α-naphthol, β-naphthol, quinol, p-cresol, m-cresol, 8-quinolinol, resorcinol, phloroglucinol, and gallic acid has been done. The effects of possible variables e.g., temperature, reagent, pH buffers have been studied. A study of interferences is made. Mechanism of the reaction is discussed.     

Preparation of iodic acid by direct oxidation of iodine with perchloric acid dihydrate

Iodine is quantitatively oxidised to iodic acid by boiling with 70% perchloric acid and the iodic acid is isolated by cooling, filtering off the precipitated crystals, and washing them with concentrated nitric acid. The over-all stoichiometry of the reaction is one molecule of perchloric acid per atom of iodine.     

Wet ashing of coal with perchloric acid mixed with periodic acid for the determination of sulphur and certain other constituents

A method is described for the determination of sulphur and some other inorganic constituents of coal. Organic matter is destroyed by wet combustion with perchloric acid and periodic acid. The method is rapid and efficient. Silica and sulphur are determined gravimetrically, iron, aluminium, vanadium, titanium, phosphorus, and arsenic spectrophotometrically, and calcium and magnesium volumetrically. No loss occurred by volatilisation. The complete analysis scheme devised was applied to a bituminous coal of Iowa origin.     

Mechanistic aspects for the oxidation of brilliant green dye by chloramine-T in the presence of perchloric acid: a spectrophotometric kinetic approach

The kinetics of a triarylmethane dye, brilliant green (BG), by sodium N-chloro-p-toluenesulfonamide or chloramine-T (CAT) was studied spectrophotometrically in HClO₄ media at 303 K. Under identical experimental conditions, the rate law was ?d [BG]/dt = k [BG] [H⁺]. Variations in ionic strength (μ) of the medium had no effect on the oxidation velocity. Addition of p-toluenesulfonamide, the reduction product of CAT and Cl^?, had no significant effect on the rate of reaction. The values of rate constants observed at five different temperatures (298, 303, 308, 313, and 318 K) were utilized to calculate the activation parameters. The observed results have been explained by a general mechanism and the related rate law has been obtained. The process demonstrated in this study is cost effective, which holds great promise in potential application for pollutant control.     

Kinetics and mechanism of the oxidation of acetaldehyde by chromic acid in perchloric acid

Summary The oxidation of MeCHO by chromium(VI) has been studied in HClO₄ medium over a wide range of experimental conditions and has been found to obey the rate law;v=k[MeCHO][HCrO ₄ ^– ][H⁺]. The calculated H and-S values for the reaction are 30±2kJ mol^–1 and 171±7J mol^–1deg^–1, respectively. The mechanism is discussed in terms of carbon-hydrogen bond cleavage.     

Atomic-absorption spectrophotometric determination of traces of manganese with thenoyltrifluoroacetone

An atomic-absorption spectrophotometric method for the determination of traces of manganese in solution with thenoyltrifluoroacetone (TTA) is described. Manganese(II) is extracted with 0.01M TTA in methyl isobutyl ketone (MIBK) at pH 9.5. The atomic-absorption of the organic phase at 279.5 nm is measured. Except for chromium, iron, hafnium, niobium, nickel, rhodium, tin, titanium and zirconium, microquantities of many other cations and anions do not interfere. Iron can be removed by MIBK extraction before the TTA extraction. The sensitivity of the method was 1.6 ng/ml for 1% absorption in aqueous solution. The method was successfully applied to the analysis of environmental waters. Manganese in the filtered fractions of water samples was reliably determined with relative standard deviations of 7% at the 5 mug/l. level and 1% at 50 mug/l.     

Potentiometric determination of urea with perchloric acid in acetic anhydride

A potentiometric method for the quantitative determination of urea is proposed. Urea is titrated with perchloric acid in acetic anhydride solvent. This method is rapid and less costly than the semi-micro Kjeldahl method. In addition, its accuracy is nearly identical with that of Kjeldahl's method. An analysis of a given sample is completed in about 30 min.     

催化光度法测定粮食中的痕量锰

研究了测定痕量锰的新催化光度法,方法基于氨三乙酸为活化剂,锰（Ⅱ）催化高碘酸钾氧化溴酚蓝的反应。测定锰的线性范围为0．4－10ng/mL,检出限为0．082ng/mL,对于4.0ng/mL Mn(Ⅱ）的测定,相对标准偏差为3．4％（n=9),其方法已用于粮食中锰的测定。     

Kinetics of oxidation of ethanol by potassium permanganate in perchloric acid medium

The oxidation of ethanol by permanganate has been found to obey the rate law v=k[MeCHO][MnO ₄ ^– ][H⁺]. The results are compared with those found for chromium (VI) oxidation of the same substrate.

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V=k[MeCHO][MnO ₄ ^– ][H⁺]. , (VI).

     

Rapid spectrophotometric determination of boron in steel

A rapid spectrophotometric method is presented for the determination of boron in steel by use of the fluoborate-Methylene Blue complex. The method is in principle similar to that of Rosotte, but modifications simplify the operation, obviate contamination and avoid problems with emulsion formation. Up to 20% Cr, 10% Ni, and 1% each of V, Mo and W present either individually or collectively do not interfere in the determination, making it applicable to alloy steels. The determination limit of the method has been lowered from 5 to 0.2 ppm boron. Samples are dissolved at room temperature in polythene bottles, solubilizing all forms of boron including boron nitride, and avoiding loss of relatively volatile boron compounds. The precision of the method is good. Six samples can be analysed in less than 2 hr.     

Reduction of indium after oxidation in fuming perchloric acid

Evidence is given in support of the theory that high results obtained for reduction titrations of iridium solutions which have been fumed with perchloric acid are due to retention in solution of volatile reduction products of the acid.     

Gravimetric determination of selenium from perchloric acid solution with hydrazine

The gravimetric determination of selenium, by reduction of selenious acid in perchloric acid solution with hydrazine hydrate, has been studied in detail. Elemental selenium is completely precipitated in 3.2-5.1M perchloric acid at room temperature or 100 degrees C. One mole of selenious acid reacts with one mole of hydrazine hydrate to give elemental selenium.     

The oxidation of organic substances by compounds of trivalent manganese: XIV. Oxidation of malonic acid by manganese(III) sulfate in sulfuric acid medium and with hexaquomanganese(III) ions in noncomplexing perchloric acid medium

The oxidation of malonic acid by manganese(III) sulfate in a medium of sulfuric acid and by hexaquomanganese(III) ions in a noncomplexing perchloric acid medium was studied.The reaction stoichiometry was found and the effect of the concentrations of H⁺, Mn²⁺, and HSO₄^? ions and of the initial reactant concentrations on the course and rate of the reaction was studied.The optimum conditions have been found for analytical use of the reaction, procedures have been proposed for the determination of malonic acid using the two reagents, and the accuracy and reproducibility of the determinations have been found.     

Extraction—spectrophotometric determination of manganese(II) with xanthates

Manganese(II) (0.04–2 μmol) is extracted into chloroform from an aqueous phase at pH 6.5–9.0, containing a large excess of (n-butyl) xanthate and measured spectrophotometrically at 457 nm. The apparent molar absorptivity is 5.5 × 10³ dm³ mol^-1 cm^-1. The extractability of the manganese complexes decreases in the order n-butyl = benzyl- ? n-propyl- ? ethyl- ? methyl-xanthate. Interfering ions can be removed by a preliminary extraction with ethylxanthate. Ni, Co, Zn, Cd, Pb, Hg(II), Fe(III), As(III), Ce(III), Se(IV), V(V), Mo(VI), and the alkali and alkaline earth metals do not interfere.