The behaviour of Sal'nikov's reaction, P --> A --> B, in a spherical batch reactor with the diffusion of heat and matter

The behaviour of a simple chemical reaction, occurring with the release of heat in a closed batch reactor, is considered for the situation when matter and heat are transported only by diffusive processes; thus, the reacting fluid has negligible velocity, so that heat transfer is by thermal conduction. The reaction is Sal'nikov's, which consists of two, consecutive first-order steps, producing a product B, from a precursor P, via an active intermediate A, in P --> A --> B. The first of these steps is assumed to be thermoneutral, with zero activation energy, whilst the second is exothermic, with an appreciable activation energy. These features make Sal'nikov's reaction the simplest to display thermokinetic oscillations that characterise many, more complex schemes, e.g. cool flames in hydrocarbon combustion. This study involves identifying the regions of parameter space, in which these oscillations in the temperature and the concentration of the intermediate A occur, by means of numerical simulation. These regions are compared with previous analytical stability analyses in one-dimensional systems. It was found that oscillations occur over a much larger range of conditions in the case considered here, i.e. a reactor with spherical symmetry, than in the simple 1-D case, previously studied by Gray and Scott (P. Gray and S. K. Scott, Chemical Oscillations and Instabilities, Clarendon Press, Oxford, 1990, pp. 264-291). In addition, approximate analytical solutions for the temperature and concentration of A are presented for two limiting cases of non-oscillatory behaviour. These analytical solutions have been verified by comparison with full numerical solutions of the governing equations.     

The Formation of Rosocyanin in the Presence of Water

Abstract

The reaction between curcumin and boric acid to form the 2:1 complex rosocyanin has hitherto been considered to require an almost water-free solution. It has now been shown that rosocyanin may be formed even if large amounts of water are present, provided that a suitable organic solvent is added. The theoretical conditions for such a solvent have been investigated. Procedures are given where the reaction takes place in a homogeneous solution or possibly at the organic interface. For analytical purposes the rosocyanin formed could either be measured in a homogeneous solution or extracted into an upper or lower organicphase. Methylisobutylketone seems to be the most suitable solvent which possesses convenient analytical properties.     

A microcalorimetric enzymatic method for trehalose determination in food

As trehalose is a glucose font and also an additive in food, a new reliable method for trehalose determination is proposed. The analytical method uses an isothermal microcalorimeter, directly relates the analyte concentration with the heat variation of the enzymatic decomposition of trehalose into two glucose molecules. The enzymatic reaction is performed inside the calorimeter in the presence of trehalase enzyme immobilized on amino activated glass beads. Through the calibration curve, the trehalose quantity in some food samples (mushrooms and honey) has been determined. The calorimetric procedure was compared to a previously identified methodology based on an amperometric biosensor.     

The pressure and temperature dependence of methane decomposition

Single-channel hindered Gorin model RRKM calculations were performed on reaction (1). (1) Good agreement between theory and experiment was obtained for the temperature and pressure dependence of reaction (1). Isotopic data for the reverse association reaction, (?1), reported previously, are consistent with the model. Rate constants were cast in the form of an analytical expression and appropriate parameters were tabulated.     

A simplified kinetic model for isothermal catalytic ignition

The ignition of catalytic combustion of the stoichiometric propane/air mixture on an isothermally heated platinum wire in different experimental conditions of total pressure and wire temperature is studied and discussed on the basis of a simplified kinetic model. The platinum wire is heated electrically with a specially designed power supply, which ensures a quasi-rectangular profile of its temperature. The ignition process is monitored by measuring the input power required to maintain a constant temperature of the wire during an exothermic catalytic reaction. The difference between the input powers recorded in air and in a fuel/air mixture, for the same wire temperature and gas total pressure, allows the elimination of the heat transferred to surroundings and conversion of the results into the catalytic reaction rate r _R versus time curves of S-shaped form, illustrating the transition from kinetic to diffusion regime. The curve can be used to evaluate the ignition delay, as reported previously and also to fit different models to the data. The quasi-exponential increase of the isothermal reaction rate during the early stages of the process can be rationalized on the basis of a simplified kinetic model implying the multiplication of the adsorbed active intermediates. The adopted hypotheses allow the derivation of an analytical solution for the catalytic reaction rate before and during the ignition process, without diffusion limitations.     

Inhibitory Effects by Antioxidants on the Oscillations of the Briggs‐Rauscher Reaction in Mixed EtOH/H2O Medium

The Briggs‐Rauscher (BR) oscillating reaction in mixed 20% EtOH/H₂O (v/v) medium is studied together with the inhibitory effects by the addition of hydroalcoholic solutions of antioxidants on its oscillatory regime. As in aqueous BR mixtures, the inhibitory effect consists of an immediate cessation of oscillations, an inhibitory time that linearly depends on the concentration of the antioxidant added, and subsequent regeneration of oscillations. The effects of several water‐insoluble and water‐soluble antioxidants were investigated: at a parity of concentration of antioxidant added, inhibition times in the mixed EtOH/H₂O medium are 2–3 times lower than those reported previously in aqueous solution. However, the mechanism of the BR reaction, as far as that of the inhibitory effect, seems to be the same in either aqueous or mixed medium. The findings reported and discussed here are an indication that the analytical procedure to assess the activity of free radical scavengers based on the BR reaction can be extended to lipophilic antioxidants.     

Mathematical modeling of cyclic voltammetry for EC reaction

The non-steady-state concentration for an EC reaction at planar electrode is derived. The analytical expression for the concentration for EC reaction is reported for small and large value of reaction rate. The asymptotic expression for the non-steady-state current for EC reaction is also derived. The analytical solutions for normalized current response were formulated using the method of Laplace transformation. The concentration and current are compared with available limiting case results, and are found to be in good agreement.     

Mathematical modeling of cyclic voltammetry for EC<Subscript>2</Subscript> reaction

The non-steady-state concentration for an EC reaction at planar electrode is derived. The analytical expression for the concentration for EC reaction is reported for small and large value of reaction rate. The asymptotic expression for the non-steady-state current for EC reaction is also derived. The analytical solutions for normalized current response were formulated using the method of Laplace transformation. The concentration and current are compared with available limiting case results, and are found to be in good agreement.     

Kinetic-spectrometric three-dimensional chemiluminescence as an effective analytical tool. Application to the determination of benzo(a)pyrene

Kinetic and spectroscopic methods were used in combination in this work to develop a new analytical tool for use in chemiluminescence detection processes. Specifically, time-resolved chemiluminescence was used jointly with a stopped-flow assembly in order to monitor the chemiluminescence produced in the oxidation of bis(2,4-dinitrophenyl)oxalate (DNPO) by hydrogen peroxide in the presence of a polycyclic aromatic hydrocarbon. Recording of successive two-dimensional spectra during the emission process and treating the acquired spectral data with dedicated software allows the obtainment of three-dimensional chemiluminescence spectra, a result of the joint use of two analytical techniques. Thus, using a flow cell specifically designed for direct coupling to the charge-coupled device (CCD) detector increases the emission intensity without the need for fibre optics. Also, using dedicated software to process the acquired two-dimensional spectra affords a comprehensive kinetic and spectroscopic characterization of the chemiluminescence signal via the three-dimensional spectrum previously obtained. The analytical potential of this new tool was assessed by application to the chemiluminescent reaction between a peroxyoxalate and an oxidant (hydrogen peroxide); the reaction is induced by benzo(a)pyrene, which was used to determine this polycyclic aromatic hydrocarbon in an organic solvent. A linear calibration graph was obtained between 0.5 and 20 mg L(-1). The limit of detection found to be 3.97 μg L(-1) and a relative standard error of 0.64% and a relative standard deviation of 1.87% were obtained. The results reached testify to the usefulness of the proposed analytical tool for simple determinations and its potential for the resolution of complex mixtures or determinations in complex matrices.     

Computational modelling of amperometric biosensors in the case of substrate and product inhibition

In this paper the response of an amperometric biosensor at mixed enzyme kinetics and diffusion limitations is modelled in the case of the substrate and the product inhibition. The model is based on non-stationary reaction–diffusion equations containing a non-linear term related to non-Michaelis–Menten kinetics of an enzymatic reaction. A numerical simulation was carried out using a finite difference technique. The complex enzyme kinetics produced different calibration curves for the response at the transition and the steady-state. The biosensor operation is analysed with a special emphasis to the conditions at which the biosensor response change shows a maximal value. The dependence of the biosensor sensitivity on the biosensor configuration is also investigated. Results of the simulation are compared with known analytical results and with previously conducted researches on the biosensors.     

On the anionic polymerization of cyanogen

The reaction of anionic initiators with cyanogen was investigated by ultraviolet, visible, and infrared spectroscopy. It is argued that the reaction proceeds via formation of an analog of the heterocyclic anion C₇N₇? previously known from the reaction of KCN with (CN)₂. The analytical results and spectra of the final black product were indicative of the possible formation of open-structured C₇N₇? dimers. A molecular model of the dimer suggests why the polymerization might terminate at the dimer stage. The pyrolysis of the cyclic acid HC₇N₇ was studied with the aim of determining the structure and mechanism of the formation of the resulting black product. It is suggested that this thermally induced polymerization reaction probably proceeds via formation of azomethine-type intermolecular crosslinks and may serve as a model for the investigation of the mechanism of nitrile polymerization in pyrolyzed acrylonitrile polymers.     

Stoichiometry and chemical metrology: Karl Fischer reaction

 Stoichiometry of analytical reactions is discussed as an important element of many primary methods (gravimetry, volumetry, spectrophotometry, etc.) and therefore, of chemical metrology as a whole. Variations in stoichiometry caused by non-equilibrium conditions, by changes in the reaction medium or by other factors can be a source of the dominant uncertainty component in the analytical measurement. Such a situation is illustrated with the Karl Fischer (KF) reaction which is widely used in aquametry. Two kinds of solvents used as a part of the reaction medium – alcohols and amides – are compared. The influence of the media on the stoichiometry of the reaction and, correspondingly, on the titre of the KF reagent is evaluated. Received: 4 November 1998 · Accepted: 22 December 1998     

The Dynamics of the Reaction of FeO+ and H2: A Model for Inorganic Oxidation

Extensive density functional theory (DFT) calculations using the B3LYP functional were used to explore the sextet and quartet energy potential energy surfaces (PESs) of the title reaction, and as a basis to fit global analytical reactive PESs. Surface-hopping dynamics on these PESs reproduce the experimentally observed reactivity and confirm that hydrogen activation rather than spin-state change is rate-limiting at low reaction energy, where the main products are Fe⁺ and H₂O. A change in spin state is inefficient in the product region so that excited-state ⁴Fe⁺ is the dominant product. At higher energies, spin-allowed hydrogen atom abstraction to form FeOH⁺ predominates. At intermediate energy, a previously unexpected rebound mechanism contributes significantly to the reactivity.     

Spectroelectrochemical determination of trace concentrations by diffusion layer imaging

An analytical technique based on a previously reported optical probe of the electrode/solution interface is described. A collimated laser beam passing parallel to a planar electrode in partially absorbed by an electrogenated species, and the absorbance may be related to the concentration of material in solution. By modulating the potential and synchronously demodulating the light intensity, detection limits in the 10⁻⁸M range may be achieved. The approach is shown to be significantly less sensitive to interference from non-absorbers than the previously reported diffraction approach. In addition, it is shown that either the refractive index or absorbance changes within the electrochemical diffusion layer may be monitored by changing the phase angle of the demodulation electronics.     

Novel route for the transformation of a pyrimidine ring using hydrazides

It has been shown from X-ray structural analytical data that the reaction of 2-ethoxycarbonylmethyl-1,4,6-trimethylpyrimidinium iodide with carboxylic acid hydrazides gives pyrazolo[1,5-a]pyrimidine derivatives and not the isomeric triazolo[4,3-a]pyridines previously reported. This novel and previously unreported rearrangement of 1,2-dialkylpyrimidinium salts occurs via recyclization of the pyrimidine ring with inclusion of a fragment of the nucleophilic reagent into the transformation product. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 262–275, February, 2006.     

5-Hydroxy-2H-pyrrol-2-ones and not 2-aminofurans are the cycloaddition products between alkyl isocyanides and benzyliden-1,3-diketones

New insights into the cycloaddition reaction between alkyl isocyanides and benzyliden-1,3-diketones are reported. 5-Hydroxy-N-substituted-2H-pyrrol-2-ones and not substituted furans, as previously reported, are formed. The proof of the structure relies on a thorough analytical investigation and X-ray crystallography.     

Analytical expression of the steady-state catalytic current of mediated bioelectrocatalysis and the application of He’s Homotopy perturbation method

A mathematical model of mediated bioelectrocatalysis is restudied in this paper. Here He’s Homotopy perturbation method is implemented to give approximate and analytical solutions of steady-state non-linear reaction diffusion equation containing a non-linear term related to Michaelis–Menten kinetics of the enzymatic reaction. Approximate analytical expressions for mediator concentration and current have been derived for all values of saturation parameter α and reaction diffusion parameter k for the various types of boundary conditions. The Homotopy perturbation method which produces the solutions in terms of convergent series, requiring no linearization or small perturbation. These analytical results are compared with numerical results (Matlab program) and are found to be in good agreement.     

Use of spectroscopic techniques for the chemical analysis of biomorphic silicon carbide ceramics

Biomorphic silicon carbide ceramics are a new class of materials prepared by several complex processing steps including pre-processing (shaping, drying, high-temperature pyrolysis in an inert atmosphere) and reaction with liquid silicon to obtain silicon-carbide. The results of industrial process of synthesis (measured by the SiC content) must be evaluated by means of fast analytical methods. In the present work, diverse samples of biomorphic ceramics derived from wood are studied for to evaluate the capability of the different analytical techniques (XPS, LIBS, FT-IR and also atomic spectroscopy applied to previously dissolved samples) for the analysis of these materials. XPS and LIBS gives information about the major components, whereas XPS and FT-IR can be used to evaluate the content of SiC. On the other hand, .the use of atomic techniques (as ICP-MS and ETA-AAS) is more adequate for the analysis of metal ions, specially at trace level. The properties of ceramics depend decisively of the content of chemical elements. Major components found were C, Si, Al, S, B and Na in all cases. Previous dissolution of the samples was optimised by acid attack in an oven under microwave irradiation.     

An analytical approximation for the number of states along the reaction coordinate

A variant of a new empirical method, enables one to express a collinear triatomic potential energy surface as a family of Morse curves along “natural” bond order coordinates orthogonal to the reaction coordinate. The procedure depends on a single adjustable parameter which is related to the barrier's height. Because an analytical expression for the number of vibrational states of a Morse oscillator is available, one has an analytical approximation for the number of states along the reaction coordinate. The extrema in the number of states are utilized in various versions of classical microcanonical variational transition state theory (among which is a new version, which is in better agreement with dynamical results), to estimate the probability of a collinear reactions, as a function of the total energy. The analytical expressions are also used to analyze the origins of the maximum and minima in the number of states.