Comparison of photometry and conductometry for the determination of total carbonate by gas permeation flow injection analysis

The experimental system involves the permeative preconcentration of CO(2) from an acidified sample through a tubular silicone rubber membrane into a suitable receptor. Procedures for measuring the CO(2) collected in the receptor by the absorbance change of an acid-base indicator incorporated in the receptor or by the conductance change of the receptor are compared. Previous theoretical considerations of the photometric system are augmented for numerical modeling and the theoretical behavior of the conductometric system is considered in detail. Experimental data generally conform to theoretical expectations. Based on either reproducibility or sensitivity, the conductometric measurement method using a solution of 1-10mM tris(hydroxymethylamino)methane as receptor is recommended. The interference from sulfite or sulfide can be eliminated by adding acidic permanganate to the sample; considerably more involved arrangements are necessary to eliminate interferences from cyanide.     

Preconcentration/preelution ion chromatography for the determination of perchlorate in complex samples

The determination of perchlorate in complex matrices by ion chromatography (IC) with an online preconcentration and preelution technique is discussed. The method was applied to different sample types containing large concentrations of matrix anions that would otherwise interfere with analysis via conventional IC. The present approach was highly effective in removing most of the matrix anions and was thus resistant to the interferences commonly encountered in a high ionic strength background. Method performance was evaluated by analyzing for low-level perchlorate in synthetic high ionic strength solutions, tissue extracts, and hydroponic nitrate fertilizer samples. Not only is it easier to practice the present method compared to USEPA Method 314.0, but for most of these samples the present approach provided equal to or better recovery of perchlorate than Method 314.0. With a sample of specific conductance 12,650 μS cm⁻¹, for example, the present method provided a perchlorate recovery of 101% at the 25 μg L⁻¹ level versus 89% by EPA Method 314.0. Method detection limits of perchlorate in hydroponic fertilizer samples with this method (130-190 μg kg⁻¹) are the lowest thus far reported.     

Spectrophotometric determination of trace aqueous sulfate using barium-beryllon II

Summary The dibarium salt of beryllon II, 2-(8-hydroxy-3,6-disulfo-1-naphthylazo)-1,8-dihydroxynaphthalene-3,6-disulfonic acid is the basis of a sensitive (LOD 0.14 ppm) convenient Spectrophotometric procedure for determining trace sulfate through liberation of the dye in a 80% 2-propanol medium at an apparent pH of 4.3. The interferences are negligible and good agreement with ion Chromatographie results are demonstrated for environmental samples.     

Tris(salicylhydroxamato)manganese(III)

Summary Hydroxamic acids show a degree of selectivity towards transition metal ions having symmetrical d-electron configuration, e.g. vanadium(V) (d⁰) and iron(III) (d⁶⁵). Hydroxamato complexes of metal ions having unsymmetrical d-electron distribution are rare. Thus for manganese(III) (d⁴) only some thiohydroxamato complexes⁽¹⁾ have been characterised so far. In this communication we report on the first synthesis of a salicylhydroxamato complex of manganese(III). Such investigations are of interest because these higher valent manganese complexes are potentially models for the water-splitting complex present in photosystem II⁽²).     

A ring oven method for the determination of sulfate at nanogram levels

Summary A ring oven method for the determination of sulfate at ng levels is described. Sulfate is bound as 2-perimidinyl ammonium sulfate by spotting the sample solution on a glass fiber filter impregnated with 2-perimidinyl ammonium bromide. The excess reagent is removed by frontal elution chromatography with methanol and the sample spot cut out and then exposed to nitric acid vapor where upon the organic amine, bound as sulfate, is converted to the highly colored 2-amino 4,6,9-trinitro perimidine. The excess acid is neutralized by exposure to ammonia vapor. The sample spot is finally placed on a filter paper positioned on a ring oven and the color is eluted to the ring zone by successive aliquots of acetone. The sensitivity of the method is 5 ng sulfate and the working range is 20 ng to 1 g. The method is free of significant interferences.

---

Zusammenfassung Für die Bestimmung von Nanogramm-Mengen Sulfat wurde eine Ringofenmethode angegeben. Das Sulfat wird auf einem mit 2-Perimidinammoniumbromid imprägnierten Glasfaser-Filter durch Auftropfen der Probe als Salz der genannten Base gebunden. Der Reagensüberschuß wird elutionschromatographisch mit Methanol entfernt, der Probefleck ausgeschnitten und Salpetersäure-Dämpfen ausgesetzt, wobei die organische Base, die als Sulfat gebunden war, in das stark gefärbte 2-Amino-4,6,9-trinitroperimidin übergeht. Die überschüssige Säure wird mit Ammoniakdämpfen gebunden. Schließlich wird der Probefleck auf einen Ringofen gebracht und mit Aceton in den Ring gewaschen. Die Empfindlichkeit der Methode beträgt 5 ng Sulfat, der geeignete Arbeitsbereich erstreckt sich von 20 ng bis 1 g. Die Methode unterliegt keinen Störungen.

     

Time resolved photofragmentation of Au n + and Ag n + clusters (n = 9, 21)

Gold and silver cluster ions were produced by laser vaporization and stored in a Penning trap. After mass selection the cluster sizes of interest were illuminated by a laser pulse and electronically excited. Photoabsorption cross sections and fragmentation patterns were measured for photon energies of 2.3 eV to 5.2 eV. Unimolecular dissociation was observed time resolved on a microsecond to millisecond scale. Dissociation energies were deduced from the measured life times.     

Microtitration of Sulfate with Beryllon II as indicator: Determination of sulfate in environmental samples

Summary A new indicator, 2-(8-hydroxy-3,6-disulfo-1-naphthylazo)-1,8-dihydroxynaphthalene-3,6-disulfonic acid (Beryllon II, DSNADNS) is proposed for microtitrimetric determination of sulfate with barium. This method is an order of magnitude more sensitive (LOD 0.25 ppm) and has less interference than the existing indicators. The color change is sharper and faster compared to Thorin. Titration is carried out in 80% 2-propanol at an apparent pH of 3.5. The superiority of the indicator is attributed to the lower solubility of the bariumdye salt. Results are presented for environmental samples and compared with values obtained by ion chromatography.

---

Mikrotitration von Sulfat mit Beryllon II als Indikator: Bestimmung von Sulfat in Umweltproben

Zusammenfassung Als neuer Indikator für die Bestimmung von Sulfat mit Barium wurde 2-(8-Hydroxy-3,6-disulfo-l-naphthylazo)-1,8-dihydroxynaphthalin-3,6-disulfonsäure (Beryllon II, DSNADNS) vorgeschlagen. Das Verfahren ist um eine Größenordnung empfindlicher und wird weniger gestört als bei Verwendung üblicher Indikatoren. Der Farbwechsel ist schärfer und rascher als mit Thorin. Die Titration erfolgt in 80% 2-Propanol bei pH 3,5. Die Überlegenheit des vorgeschlagenen Indikators dürfte der geringeren Löslichkeit seines Bariumsalzes zuzuschreiben sein. Ergebnisse für Umweltproben wurdenmit den Werten der Ionenchromatographie verglichen.

     

Decomposition kinetics ofbis(biguanide)silver(III) cation in acid perchlorate media

Summary In acid perchlorate media, the title complex undergoes intramolecular redox decomposition generating ultimately Ag⁺ ion and oxidation products of the ligand. The reaction follows a simple first-order process, and the observed pseudo-first-order rate constant is given by k_obs=k₀+kK_a/[H⁺] where K_a is the deprotonation constant of the parent complex; pK_a is approximately 5.9 at 30°. The values of 10⁵ k₀(s^–1) and 10⁷ kK_a (Ms^–1) at 30°, I=1.0 M, are 9.3±0.1 and 11.8±1.3; corresponding H (kJ/mol), S (JK^–1 M^–1) values are 105±0.5, 23±1 and 79±8,-96±5, respectively. The results are compared with those for similar reaction of (ethylenebisbiguanide)silver(III) and effect of change in ligand structure on kinetic behaviours of these complexes is discussed.     

Automated determination of total phosphorus in aqueous samples

The determination of total phosphorus in an automated microbatch analyzer system is described. The procedure combines persulfate digestion of the sample and colorimetric detection of orthophosphate by the ascorbic acid reduction of phosphomolybdate in a single processing chamber. Approximately 9 min are required per sample; approximately 1.7 ml of sample and 0.17 ml of total reagent are consumed. The limit of detection is < or =10 microg/1. phosphorus. The method is tolerant of variations in salinity of the sample. Good agreements with ASTM procedures are shown for a variety of test compounds, lake water, wastewater and urine samples.