Solution kinetics of the degradation of the chemiluminescent reagent bis(2,4-dinitrophenyl) oxalate in water/acetonitrile

Simultaenous ultraviolet absorbance measurements at 240 and 260 nm are used to quantify DNPO and its principle degradation product 2,4-dinitrophenol. The stability of DNPO was determined in various water acetonitrile mixtures (23±0.5°C). The decomposition follows (pseudo)- first-order kinetics in each system, and is third order in water concentration. An Arrhenius plot was used to obtain estimates for the activation energy, activation enthalphy, and activation entropy.     

Structure in metastable peaks arising from reactions in which[C3H3]+ ions are produced

The metastable peak resulting from the fragmentation of [C₇H₇]²⁺? ions fram a variety of sources shows structure due to the presence of two reactions releasing different amounts of translational energy. The translational energy differences has been measured as 0.52 ± 0.04eV and is thought to be due to the formation of product ions of different structure via competing reactions from a single transition state. The possible structures of these ions are discussed, and it is proposed that the effect observed is due to the formation of [C₃H₃]⁺ ions in two forms, cyclopropenyl and proparg1. The metastable singly charged ions which also lead to product ions of formula [C₃H, ₃]⁺.     

A mass spectrometric study of the pyrolysis of gibberellic acid

The behaviour of gibberellic acid (GA₃) under electron impact and chemical ionization conditions has been examined. The tendency of GA₃ to undergo pyrolysis by the loss of the elements of water and carbon dioxide has been identified. Two methods of sample introduction can be used to minimize the occurrence of this pyrolysis. Accurate mass measurement allows the composition of the pyrolysis product to be determined and metastable techniques confirm the structure of this product to be epi-allogibberic acid rather than its isomer allogibberic acid. This result corrects a misconception in the literature and illustrates the advantage of metastable methods compared with accurate mass measurements, for the determination of small structural differences within a molecule.     

Electro-optic scattering from nitrocellulose solutions

Measurements have been made of the light intensity scattered from dilute solutions of a sample of nitrocellulose ($\text{M}{}_{\mathrm{w}}\text{= 460,000}$) in acetone, both in the absence and presence of a.c. and d.c. electric fields. In an earlier study, owing to a mathematical slip and a false interpretation of an experimental parameter, other workers [5] interpreted similar measurements in terms of a freely rotating polar chain model. It is shown herein that this cannot be so and that the molecules of nitrocellulose of this order of molecular weight and in this type of solvent are better regarded as extremely stiff and extended.     

Elution order in gas chromatography

The retention behavior of a heterogeneous group of solutes has been examined on seven different stationary phases under isothermal and temperature-programmed conditions. Both ΔH_v (enthalpy of solute vaporization from the stationary phase) and ΔS_v (entropy of solute vaporization from the stationary phase) values were determined for each solute – stationary phase combination under isothermal conditions. Both program rate and carrier gas velocity were shown to affect solute elution order. Unless these and other experimental factors discussed are controlled, column equivalency studies based on solute elution order have dubious value.