Analytical applications of ternary complexes-V Indirect spectrophotometric determination of cyanide

An indirect spectrophotometric method is proposed for the determination of cyanide down to 0.2 ppm. It is based on the fact that cyanide prevents the formation of the strongly absorbing ternary complex between silver(I), 1,10-phenanthroline and Bromopyrogallol Red in nearly neutral aqueous solution. Among 17 cations examined, only mercury(II) could not be tolerated. Zinc, cadmium and cobalt interfered only when present in large amounts. A 1000-fold molar excess (over cyanide) of 14 anions can also be tolerated. Bromide, iodide and thiocyanate interference is overcome by addition of lead nitrate, ammonium sulphate and barium nitrate, followed by centrifugation.     

An investigation of some experimental parameters in atomic fluorescence spectrophotometry

Atomic fluorescence in flames is measured by an adaptation of a commercially available flame spectrophotometer. A study is reported of the effect of background radiation and source scattering on 3 flames, air-propane, air-hydrogen and air-acetylene, and of the effects of variation of fuel gas pressure, zone of measurement in the flame, analysing monochromator slit-width and wavelength of measurement. The air-propane flame appears to offer several advantages. The atomic fluorescence of 10 metals is described; those of Co, Fe and Mn have not been previously reported. Excitation of spectra is achieved by means of an a.c. xenon arc lamp or individual discharge lamps.     

A selective extraction system for trace amounts of silver

Silver can be extracted from near-neutral aqueous solution into nitrobenzene as the ion-association system formed between its 1,10-phenanthroline complex and bromopyrogallol red. In the presence of EDTA, mercury(II) and bromide ions as masking agents, the extraction system is highly selective. Of 42 ions examined, only thiosulphate and large amounts of gold interfere. The colour system is very sensitive (ε = 32,000). Also, it can readily be applied to the indirect determination of concentrations of cyanide down to 0–026 ppm by determination of an added excess of silver.     

Determination of cadmium by atomic-fluorescence and atomic-absorption spectrophotometry

The adaptation of a conventional atomic-absorption/flameemission spectrophotometer to the measurement of atomic-fluorescence in an air-acetylene flame is described. The determination of cadmium on the same instrument by both atomic-fluorescence and absorption shows that, even with a rather simple and inefficient means of exciting and measuring fluorescence, results can be obtained which indicate that the fluorescence technique is considerably more sensitive than atomic-absorbance and is equally free from inter-element interference.     

Inorganic polarography in organic solvents-III Analytical applications of metal-acetylacetonate complexes in toluene

Indium and palladium are determined polarographically with a dropping mercury electrode in a toluene phase, following extraction as the acetylacetonates from aqueous solutions containing 2-10 ppm of the metals (or 0.1-0.5 ppm with a greater ratio of sample volume to solvent volume). Of 31 elements examined, only Co(III), Cr(III), Cu(II), Fe(III), In, Mo(VI), Pd and Ti(IV) gave extractable complexes with reduction waves in the available potential range. Specificity for palladium is obtained by extraction at pH 0.5, and for indium at pH 9 m the presence of cyanide and ascorbic acid as masking agents.     

Studies in atomic-fluorescence spectroscopy-VI The fluorescence characteristics and analytical determination of bismuth with an iodine electrodeless discharge tube as source

The atomic-fluorescence characteristics of bismuth atoms in cool nitrogen-hydrogen and argon-hydrogen diffusion flames burning in air are described. Excitation is obtained from the non-resonance iodine line at 2061.63 Å emitted by a microwave-excited electrodeless discharge tube operating at 2450 Mc/s. Fluorescence of the bismuth resonance line at 2061.70 Å is observed and also direct-line fluorescence at 2697 and 3025 A. In addition thirteen other much weaker lines were observed and two unidentified lines at 2880 and 2680 Å. The emissions at 2628 and 2938 Å appear to arise from “thermally assisted direct line fluorescence”. The most intense line at 3025 Å permits linear-dependence analytical atomic-fluorescence measurements to be made in the range 0.1–200 ppm with a detection limit of 0.05 ppm and with no problems of source scatter. No interference was observed from hundred-fold concentrations of fourteen ions. Matrix effects from aluminium and magnesium were overcome by raising the temperature of the cool diffusion flames. A bismuth microwave-excited electrodeless discharge tube was used as a source for atomic-absorption measurement in air-hydrogen and air-propane flames at 2231Å with a detection limit of 1 ppm and a linear-dependence analytical range of 10–100 ppm. With the iodine microwave-excited electrodeless discharge tube the detection limit for atomic absorption was 10 ppm at 2062 Å.     

Some optical studies with the air-acetylene flame

The application of Schlieren and shadow techniques for the study of flame processes is discussed in relation to analytically useful premixed flames. The information obtained, particularly with shadowgraphs, may be correlated with the measured signals and signal noise in atomic-absorption and flame-emission spectrometry.