The elimination of the distillation procedure in the Kjeldahl method

Summary The distillation process in the Kjeldahl method can be eliminated by applying the hypochlorite titration ofKolthoff andStenger. Mercury is used as catalyst; other catalysts which were tried interfered in the titration. Digestion and titration can be done in the same vessel on the micro scale, but a suitable vessel remains to be designed for this to be achieved on the semi-micro scale.The method is not applicable when pre-reduction is necessary, for all the reagents tested interfered with the subsequent titration.

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Zusammenfassung Durch Anwendung der Hypochlorittitration nachKolthoff undStenger läßt sich die Destillation bei der Stickstoffbestimmung nachKjeldahl umgehen. Quecksilber dient als Katalysator; andere Katalysatoren stören die Titration. Veraschung und Titration können im selben Gefäß im Mikromaßstab durchgeführt werden, aber bei der Analyse im Semimikromaßstab wird die zu titrierende Lösung besser in ein anderes Gefäß gebracht.Wenn eine vorhergehende Reduktion nötig ist, eignet sich die Methode nicht, da die hierzu nötigen Reagenzien die Titration stören.

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Résumé Il est possible d'éliminer la distillation que comporte la méthode deKjeldahl par application du titrage par l'hypochlorite deKolthoff etStenger. On emploie le mercure comme catalyseur; les autres catalyseurs qui ont été essayés gênent le titrage. Digestion et titrage peuvent être effectués dans le même récipient à l'échelle microanalytique mais il conviendrait de prévoir un récipient spécial pour permettre de réaliser cette condition à l'échelle semi-microanalytique.Cette méthode n'est pas applicable lorsqu'il est nécessaire d'effectuer une réduction préalable car les réactifs qui sont alors employés réagissent ultérieurement lors du titrage.

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We have great pleasure in dedicating this paper to our good friend Professor Dr.R. Strebinger on the occasion of his 70th birthday.

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Our thanks are due to Mr.E. Parry for carrying out check determinations.     

Barium oxalate as a selective solid reagent for the absorption of sulphur trioxide

Barium and calcium oxalate monohydrates have been shown to be more suitable absorbents for sulphur trioxide than either anhydrous or hydrated oxalic acid. All four compounds are selective absorbents for the trioxide and do not absorb sulphur dioxide. Similarly all are elective absorbents for sulphuric acid aerosol, although the calcium salt may be decarboxylated under these conditions. Lead oxalate and formate may be suitable for the absorption of SO(3) and H(2)S, and SO(3), H(2)S and SO(2) respectively.     

Mercurous nitrate as a reductimetric reagent : The determination of hydroxylamine and nitrates

Hydroxylamine can be determined indirectly using standard mercurous nitráte, by treating the test solution with an excess of standard ferric alum, and back titrating the excess.The same procedure cannot be recommended for the determination of hydrazine and hydroquinone. The results with hydrazine were irregular and generally low. With hydroquinone, the brown colour of the oxidation product masked the endpoint.An attempt was made to determine nitrate after reduction with ferrous ammonium sulphate, but the high acidity required is unfavourable for mercurous nitrate titration, and results are only accurate to about 1 per cent.     

Trivalent manganese as an oxidimetric reagent

A study of the use of trivalent manganese as an oxidimetric reagent has been made. The manganic ion was stabilised with pyrophosphate. The stability of this reagent over a period of six weeks was established. The reagent may be used in conjunction with barium diphenylamine sulphonate for the titration of ferrous iron even in the presence of 5N hydrochloric acid. It may also be used for the titration of vanadium, nitrite, oxalate, peroxide and arsenite, but the procedures for oxalate and peroxide are unsatisfactory. The redox potential of the reagent was 1.22 volt at 25° C, which was lower than that found for manganic sulphate (ca. 1.4 volt).     

Rapid determination of tritium and carbon-14 in urine samples using a combustion technique

Traditionally in bioassay monitoring, ³H determinations in urine have been performed using either direct counting (with or without sample decolourisation) or distillation whilst ¹⁴C has been determined on separate sub-samples following chemical isolation of the carbon from samples. Although these techniques are relatively straightforward they do not permit simultaneous determination of ³H/¹⁴C. For ³H, direct counting can be significantly affected by variations in sample composition/colour resulting in varying degrees of sample quench, does not distinguish between aqueous/organically-bound ³H and is limited to small sample sizes. This study describes the use of purpose built multi-tube combustion furnace for the simultaneous extraction and determination of ³H and ¹⁴C. The technique is insensitive to sample composition and can be adapted to measure Tritiated water (HTO) and organically bound tritium separately. The development of a multi-tube system with integrated cool-down facility permits rapid throughput of high sample numbers and has been proven effective in decommissioning waste characterisation. In addition, the furnace-based technique is capable of processing larger sample sizes, increasing analytical sensitivity and accuracy of dose assessment.     

The role of symmetry and optical selection rules in revealing the molecular structure of the lowest Rydberg and ionic states of the 1,4-diazabicyclo[2.2.2]octane-Arn (n = 1,2,3) van der Waals complexes

The 1,4-diazabicyclo[2.2.2]octane-Arn (n = 1,2,3) van der Waals complexes (DABCO-Arn) have been investigated using a combination of (1 + 1') resonance enhanced multiphoton ionization (REMPI) and zero electron kinetic energy (ZEKE) spectroscopy. The additivity of the spectral shifts observed in both REMPI and ZEKE spectra, taken together with analysis of vibrational structure, suggest that in both DABCO-Ar and DABCO-Ar2 the argon atoms bind in equivalent equatorial (face) locations between two adjacent (CH2)2 bridges. However, the cumulative evidence from both REMPI and ZEKE spectra, together with ab initio results, suggests that the DABCO-Ar3 complex does not revert to D3h symmetry, but rather adopts a C2v structure in which all three argon atoms bind to one side of the DABCO framework. The exceptionally low wave-number vibrational structure observed in the REMPI spectra suggest that the van der Waals interaction in the excited state is extremely weak. However, ionization necessarily increases the strength of the interaction by virtue of the introduction of charge-induced dipole forces, as revealed by a consistent increase in vibrational wave numbers of the modes observed in the resultant ZEKE spectra.     

Bacterial biosynthesis of cadmium sulfide nanocrystals

Semiconductor nanocrystals, which have unique optical and electronic properties, have potential for applications in the emerging field of nanoelectronics. To produce nanocrystals cheaply and efficiently, biological methods of synthesis are being explored. We found that E. coli, when incubated with cadmium chloride and sodium sulfide, have the capacity to synthesize intracellular cadmium sulfide (CdS) nanocrystals. The nanocrystals are composed of a wurtzite crystal phase with a size distribution of 2-5 nm. Nanocrystal biosynthesis increased about 20-fold in E. coli cells grown to stationary phase compared to late logarithmic phase. Our results highlight how different genetic and physiological parameters can enhance the formation of nanocrystals within bacterial cells.