The Role of Cations in Some Inorganic Hydrolysis Reactions

Cations which shift certain equilibria from left to right by forming a compound with one of the reaction products were investigated with respect to their kinetic role in the process. Silver ions have no influence on the rate of the hydrolysis of cyanogen iodide. Similarly, cations which form sparingly soluble carbonates do not influence the rate of hydration of carbon dioxide. On the other hand, the hydrolysis of chlorine is accelerated by Ag⁺ and, to a lesser extent, by Cd²⁺ and Fe(III). It is shown that the effect is not due simply to a bimolecular reaction between chlorine and the cation. In the case of Ag⁺, heterogeneous catalysis may play some role, in analogy with the solvolysis of organic halides. In the case of Cd²⁺, there is spectrophotometric evidence for compounds between Cl₂ and HOCl on the one hand, and the cation on the other. It is suggested that these compounds interconvert more rapidly than do the parent substances. A similar mechanism may be operative in the case of Fe(III), and, possibly, also in the case of Ag⁺.     

Composition of mixed octadecadienoates via ozonolysis,chromatography and computer solution of linear equations

An approach to the analysis of 55 possible nonconjugated positional isomers of octadecadienoic acid is described and tested with mixtures of individual synthetic methyl esters. In the first example, by ozonolysis a sevencomponent mixture consisting ofcis,cis 5,12-, 6,10-, 6,11-, 6,12-, 7,12-, 8,12-, and 9,12-octadecadienoates was converted to aldehydes, aldehyde-esters and dialdehydes. These fragments were separated on a 50 m×0.2 mm free fatty acid phase (FFAP) vitreous silica capillary column. Equations for an arbitrarily restricted 12×15 matrix of linear simultaneous equations and a computer solution of the matrix provided the composition of the initial methyl octadecadienoate mixture. The power and significance of this method became apparent with the observation that only two of the seven isomers in the known mixture were resolved as single peaks by state-of-the-art capillary gas chromatography, but all seven were identified and estimated with acceptable error by the ozonolysis-capillary gas chromatography-computer procedure. In a generalized approach to the analysis of the 55 possible nonconjugated isomers, a computer program selects the appropriate matrix of linear simultaneous equations based on the aldehyde data supplied by the analyst. Twenty of 21 combinations of seven isomeric esters taken five at a time have been analyzed to assess the efficiency of the method. To illustrate applicability at this stage of development, the method has been used to analyze the diene products of the hydrazine reduction of γ-linolenic acid and the diene products from the biological desaturation of isomeric monoenes. The possibility of distinguishing geometric and positional isomers of 18∶2 has been opened by the observed separation ofcis-andtrans-unsaturated aldehydes and aldehyde-esters. Presented in part at the 16th World Congress of the International Society for Fat Research, October 4–7, 1983, in Budapest, Hungary, and at the American Oil Chemists' Society Meeting, May 15, 1986, in Honolulu, Hawaii.     

On-line process control of a fluidized bed reactor with non-catalytic gas/solid reaction

In a bench-scale, stainless steel reactor, experiments were carried out to investigate fluidized bed behavior by means of on-line process control. The non-catalytic thermal decomposition of sodium hydrogen carbonate to sodium carbonate, carbon dioxide and water was used a model reaction. The experimental equipment was provided with control systems and reulating units which were connected to a PDP 11/40 computer by means of suitable analogue and digital input/output interfaces. The operating conditions are highly influenced by the chemical reaction as well as by the fluid-dynamical behavior of the reactor. Several experiments were carried out to evaluate the kinetics of the model reaction. The fluid-dynamics was investigated by means of on-line experiments with and without chemical reaction. Based on the experimental results, a model was developed to describe the whole process so that model simulations should yield information on the process itself. With this model, strategies are tested before they are applied to the process computer for on-line process control.     

Modification of leather properties by grafting. I. Effect of monomer chain on the physico‐mechanical properties of grafted leather

Although leather has a number of desirable properties such as thermal stability and fire retardancey, in addition to high toughness, it has a few drawbacks such as weight, high water absorption, poor soil and rot resistance, and nonuniformity. If these defects are overcome, leather's usefulness would be further enhanced and its competitive position with respect to synthetics would increase. This study reports the physical and mechanical properties of buffalo leather after chemical graft copolymerization with ethyl acrylate, butyl acrylate, and 2‐ethyl hexyl acrylate using benzoyl peroxide as an initiator. The optimum conditions for grafting (e.g., monomer and initiator concentrations, temperature and time of grafting, and solvent leather ratio) were extensively investigated. The study achieved outstanding properties for buffalo leather in reduction of water uptake after grafting, especially on using 2‐ethyl hexyl acrylate and butyl acrylate monomers. FT‐IR and solid ¹³C‐NMR for leather before and after grafting confirmed the grafting process.© 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1478–1483, 2003     

Permittivite complexe de solutions electrolytiques non aqueuses

The complex permittivity * = ′ — j″ of ethanolic solutions of electrolytes has been measured between wavelengths 90 and 3·2 cm, at 25°C. Methods of measurement are briefly described. The results are interpreted by separating the conductivity and the dielectric losses. For solutions of LiClO₄, Mg(ClO₄) ₂, LiCl and LiI, a dielectric relaxation analogous to that of the solvent is observed, ie the dielectric loss factor passes through a maximum at a wavelength of about 30 cm. The ‘static’ permittivity, defined in terms of the relaxation spectrum, undergoes an important fall with increase of concentration. Solutions of (n-Bu)₄NI give more complicated behaviour, characterized by the probable existence of a new relaxation domain at longer wavelengths. The results are discussed in relation to data in the literature on the intermolecular structure of alcohols and the dielectric properties of electrolyte solutions in other types of solvent.

Zusammenfassung

Man ermittelte bei 25°C die komplexe Permittivität * = ′ — j″ verschiedener Elektrolytlösungen in Äthanol bei Wellenlängen zwischen 3,2 und 90 cm. Die Messmethoden werden kurz beschrieben. Die Ergebnisse werden interpretiert, indem die Leitfähigkeitsverluste von den dielektrischen Verlusten getrennt werden. Bei en Lösungen LiClO₄, Mg(ClO₄)₂, LiCl und LiI stellt man eine dem Lösungsmittel analoge dielektrische Relaxation fest, m.a.W.: der dilektrische Verlustfaktor geht bei Wellenlängen in der Nähe von 30 cm durch ein Maximum. Die “statische Permittivität”, welche aud dem Relaxationsspektrum definiert werden kann, nimmt mit zunehmender Konzentration stark ab. Lösungen von (n-Bu)₄NI zeigen ein komplizierteres Verhalten, welches möglicherweise durch das Auftreten eines neuen Relaxationsgebietes bei längeren Wellenlängen gekennzeichnet ist. Man diskutiert die Ergebnisse mit Bezug auf die Literaturdaten der intermolekularen Struktur von Alkoholen, und das dielektrische Verhalten von Elektrolylösungen in anderen Lösungsmitteln.     

Alkaline fuel cells: contemporary advancement and limitations

ZeTek Power recently introduced mass manufacturable and cost effective alkaline fuel cells on the market. Today's research is focused on further improvement both in terms of performance increase and cost reduction. This research is classically performed using small (4 cm²) experimental electrodes in the half-cell configuration. This allows the primary electrochemical losses in an anode or cathode to be determined independently. Additional performance losses occur when one integrates large electrodes into a module of 24 cells and in a stack comprised of many modules. By comparing the performance of half-cell experiments to that of modules, these losses can be distinguished and addressed. The information thus obtained, both for the small electrodes and in up-scaling is vital if one is to identify the key areas in which improvement is possible and where to focus future research. Furthermore, the identification of the losses in a module and system allows us to predict the final performance from half-cell measurements of a new laboratory scale experimental electrode.     

Redox chemistry of H2S oxidation by the British gas Stretford process part V: Aspects of the process chemistry

Stretford processes use air to oxidize H₂S in process and natural gases to elemental sulphur, by absorption in aqueous solution at about pH 9 and reaction of the resulting HS^– ions with dissolved oxygen, in the presence of anthraquinone disulphonates (AQDS) and vanadium (v) species, which act as catalysts. Kinetic measurements of the reactions (AQ27DS + HS^– ions), (V(v) + HS^– ions) and (AQ27DSH^– + O₂), primarily used stopped flow spectrophotometry, as reported here, following papers on the electrochemical behaviour of the individual redox couples in Stretford Processes. The course of reaction (AQ27DS + HS^– ions) was also followed with a gold bead indicator electrode, the potential of which was determined essentially by the AQ27DS/AQ27DSH^– couple as the former species were reduced to the latter. Attempts to use⁵¹V NMR to characterize aqueous vanadium-sulphur complexes were inconclusive. A possible mechanism for Stretford Processes is postulated, involving polysulphide (S _n ^2–) ions as intermediates, which are oxidized to elemental sulphur by another intermediate, H₂O₂, formed by reaction of AQ27DSH^– ions and dissolved oxygen.     

A Viscosity-Temperature Relation for Glass

A theory for the viscosity and structure of glass as a function of temperature and composition had been advanced, proposing that at a few critical temperatures silicate glasses undergo structural transformations. Between these transformation temperatures, the activation energy and lattice coefficient are constant. A series of special glasses were melted and viscosity was measured to test this theory. The results indicate that the viscosity-temperature behavior of glass does not conform to the previously proposed model. The activation energy appears to vary continuously over the entire temperature range studied. However, a critical temperature does exist at which the temperature coefficient of the activation energy changes. This discovery represents a more subtle change than that previously envisaged.     

Oxidative thermal decomposition of poly(vinyl chloride) compositions

“Pure” poly(vinyl chloride) resin and four compositions containing poly(vinyl chloride) were subjected to oxidative thermal degradation in air at &400°C both in a quiescent and a flow system. The volatiles formed were identified and quantitatively determined on a gram-per-gram basis. Hydrogen chloride was the main product found. The nature and relative concentration of the produced organic chlorinated species appeared to be dependent not only on the poly(vinyl chloride) constituent but also on the other ingredients. All the compositions contained phthalate ester plasticizers. In the dynamic system, these distilled largely unchanged, whereas under static conditions transformation into phthalic anhydride occurred.