Analytical applications of absorption spectroelectrochemistry at grazing incidence

Analytical applications of spectroelectrochemistry are limited by the short path-length, in the absorbing medium, that can be produced with most light-beam/electrode configurations. This disadvantage is overcome for grazing incidence. A cell fitted with glassy-carbon electrodes and used in a conventional spectrophotometer is described and applied to model systems illustrating the use of (a) homogeneous redox reactions, (b) homogeneous redox reaction followed by chemical reaction and (c) electro-deposition followed by stripping into a reagent solution. This last technique is the spectroelectrochemical analogue of anodic-stripping voltammetry.     

Application of chemometrics methods with kinetic constraints for estimation of rate constants of second order consecutive reactions.

To determine the rate constants for the second order consecutive reactions of the form U + V -(k1)--> W -(k2)--> P, a number of chemometrics and hard modeling-based methods are described. The absorption spectroscopic data from the reaction were utilized for performing the analysis. Concentrations and extinctions of components were comparable, and all of them were absorbing species. The number of steps in the reaction was less than the number of absorbing species, which resulted in a rank-deficient response matrix. This can cause difficulties for some of the methods described in the literature. The standard MATLAB functions were used for determining the solutions of the differential equations as well as for finding the optimal rate constants to describe the kinetic profiles. The available knowledge about the system determines the approaches described in this paper. The knowledge includes the spectra of reactants and products, the initial concentrations, and the exact kinetics. Some of this information is sometimes not available or is hard to estimate. Multiple linear regression for fitting the kinetic parameters to the obtained concentration profiles, rank augmentation using multiple batch runs, a mixed spectral approach which treats the reaction using a pseudo species concept, and principal components regression are the four groups of methods discussed in this study. In one of the simulated datasets the spectra are quite different, and in the other one the spectra of one reactant and of the product share a high degree of overlap. Instrumental noise, sampling error are the sources of error considered. Our aim was the investigation of the relative merits of each method.     

An investigation of the two electron chemical bond calculating energy expectation values from density matrix partitionings. II. The heteronuclear case HeH+

Bond energy contributions calculated from first and second order density matrix terms as partitioned by Ruedenberg's procedure have been obtained for HeH⁺ in the ground state and in the first excited 1Σ⁺. For the chemically bonded ground state the full partitioning is investigated for all internuclear distances R. The wavefunctions used for calculating the density matrices are obtained from an SCF calculation at near Hartree-Fock quality, using Slater orbitals with exponents which for each R are optimized simultaneously with the coefficients. For the excited state a limited CI has been performed. The results for promotional, charge transfer, and interference terms for kinetic and potential bond contributions are presented in the form of energy plots E(R). Starting from the promoted atoms and subsequently allowing for charge transfer the importance of the electron interaction is demonstrated by the unusually low quasiclassical electron repulsion curve due to electronic charge transfer, which makes an essential contribution to the decrease in energy during bond formation.     

Potential application of the reaction between hydroquinone and chromate with respect to the kinetic determination of iron

The analytical potential of the reaction between hydroquinone and chromate in acidic media is explored with respect to the kinetic determination of iron in water samples. The extent of the reaction is followed spectrophotometrically at 350 nm. The reaction occurs more quickly in the presence of the metal ion, but the values of absorbance at reaction initiation and completion are not altered. No other transitional metal ion affects the course of the reaction, regardless of its concentration. This fact represents the most eye-catching and analytically exploitable aspect of this indicator reaction. Three procedures used to obtain calibration graphs from the same kinetic data are discussed: slope, fixed and variable time techniques. The reaction follows a sequence of two consecutive steps, both of first-order with respect to the colored species. First-order kinetics is preserved in the presence of iron. Curve fitting is used to determine the corresponding rate coefficients. The slope method requires much data and uses plots of rate constants against analyte concentration for calibration purposes. In this case, the best detection limit (0.5 mg l^–1) is given by the faster stage. On the other hand, the rate-determining step enables more precise results. The fixed and variable time methods rely on similar principles: they register either the value of absorbance achieved at a predetermined reaction time (here, 50 s) or the time interval required for the absorbance to drop to a predetermined value (here, 0.15 absorbance at 350 nm). In both cases, ratios between the average value from the blind runs and all individual values are plotted against the analyte concentration. The best results (detection limit of 0.3 mg l^–1) are derived from the variable time procedure. Advantageously, neither of the techniques require the entire kinetic curve, and so sophisticated equipment is not needed.     

Multiple reaction scheme modelling

A simple procedure whereby the energies of activation and pre-exponential factors of the individual reactions, of any kinetic model, comprising a wide variety of multiple reaction sets, is described. The sets belong to one of three classes, such that the single extent of reaction—temperature curves diverge, converge or are equally spaced at one prescribed temperature. The method has been applied to sets of first order reactions, which yield effectiven ^th order reactions with the order ‘n’varying from ～0.6 to ～ 3.0. Variations in Friedman iso-conversional reaction kinetics analytical data are indicative of the designed reaction complexity.     

Extracting the mechanisms and kinetic models of complex reactions from atomistic simulation data

Determining reaction mechanisms and kinetic models, which can be used for chemical reaction engineering and design, from atomistic simulation is highly challenging. In this study, we develop a novel methodology to solve this problem. Our approach has three components: (1) a procedure for precisely identifying chemical species and elementary reactions and statistically calculating the reaction rate constants; (2) a reduction method to simplify the complex reaction network into a skeletal network which can be used directly for kinetic modeling; and (3) a deterministic method for validating the derived full and skeletal kinetic models. The methodology is demonstrated by analyzing simulation data of hydrogen combustion. The full reaction network comprises 69 species and 256 reactions, which is reduced into a skeletal network of 9 species and 30 reactions. The kinetic models of both the full and skeletal networks represent the simulation data well. In addition, the essential elementary reactions and their rate constants agree favorably with those obtained experimentally. © 2019 Wiley Periodicals, Inc.     

Estimation of the rate constants of second order reactions using mean centering of ratio spectra

A new application of the mean centering of ratio spectra method is proposed for estimation of the rate constants of second order reactions, using kinetic-spectrophotometric data. The method is based on the mean centering of the ratio spectra to obtain a kinetic profile of the product. Using computational fitting, the rate constant can be obtained without any ambiguity. An interesting feature of second-order reactions is that the number of steps in the reaction is less than the number of absorbing species, resulting in a rank-deficient response matrix. Through using row mean centering of ratio spectra, the pure response of the product of the reaction could be obtained, and thus an accurate estimation of rate constant would be possible. The applicability of the method was evaluated by using several model data. The reaction of 1,2-naphthoquinone-4-sulfonate sodium (NQS) and 3-nitroaniline (TNA) in ethanol as a real system was also studied applying the proposed method.     

Kinetic Investigation of the Reaction between Triphenylphosphine,Dialkyl Acetylenedicarboxylate,and Carbazole by the UV Spectrophotometry Technique

The major objectives of the work undertaken were to carry out kinetic studies of the reaction between triphenylphosphine and dialkyl acetylenedicarboxylate in the presence of strong NH-acids, such as carbazole. To determine the kinetic parameters of the reaction, it was monitored by the UV spectrophotometer technique. The values of the second order rate constant (k ₂ ) were automatically calculated using standard equations within the program when the second order fits of the mentioned reactions were automatically drawn by the software associated with a Cary UV spectrophotometer model Bio-300 at an appropriate wavelength. At the temperature range studied, the dependence of the second order rate constant (Ln k) on reciprocal temperature was in agreement with the Arrhenius equation. This provided the relevant plots to calculate the activation energy of all reactions. Furthermore, useful information was obtained from studies of the effect of solvent and different alkyl groups within the dialkyl acetylenedicarboxylates on the rate of reactions.     

Cyclic chronopotentiometry of nickel(II) at mercury electrodes in acidic perchlorate solutions: Case of higher order nonregenerative reactions following electron transfer

The reduction of Ni²⁺ ions at mercury electrodes in acidic perchlorate solutions, at perchlorate concentrations below 0.2 M, is characterized by absence of kinetic control in the preceding step, and by a complex reaction mechanism following the electron transfer. This reaction sequence is known to involve intermetallic compound formation between Ni and Hg and is best described, as shown here, by a parallel second and third order kinetic scheme. Apparent rate coefficients for this kinetic scheme were determined using cyclic chronopotentiometric data and fitting by digital simulation. A linearization test of computed kinetic rate coefficients versus the number of transitions permits quantitative tests of validity of assumptions made.     

Thermoanalytical study of the pesticide 3-amino-1,2,4-triazole

Thermoanalytical study of the pesticide 3-amino-1,2,4-triazole (ATA) has been carried out, using simultaneous DTA-TG in nitrogen flow, in order to know its thermal behaviour and stability. These techniques have been further complemented using evolved gas analysis and mass spectroscopy (EGA-MS). Two different stages of ATA decomposition were observed: after the first decomposition step, a mixture of compounds is obtained, according to MS data, being the principal component a compound of molecular weight 126. It is formed by a first order reaction mechanism, according to the kinetic study, withE _a=124±8 kJ·mol^?1. The second decomposition step takes place about 735°C, with evolution of HCN and NH₃, being the final weight loss 96%.     

A simulation of the mass‐transfer effects on the kinetics of solid–gas reactions

A theoretical analysis of the influence of mass‐transfer effect on the kinetic of solid–gas reactions has been carried out by assuming that the partial pressures of the gases generated in the reaction are proportional to the reaction rate. The influence of mass‐transfer phenomena on the apparent activation energy, calculated by the isoconversional methods of Friedman, and on the reaction model is discussed. In the present study, simulated nonisotherm, isotherm, and controlled rate thermal analysis (CRTA) data have been used. Master plots based on the differential forms of the kinetic equations describing solid‐state reactions have been employed by using the concept of the generalized time (θ), introduced by Ozawa; this permits the application of these master plots to the kinetic analysis of reactions whatever the type of temperature program used for recording the experimental data. It has been shown that when the simulated mass‐transfer effect is present the variable effective activation energy E remains nearly constant while the reaction model approaches zero order. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 217–222, 2008     

Electrochemical and spectral studies on the reductive nitrosylation of water-soluble iron porphyrin

The reaction of iron(III) (meso-tetrakis(N-methylpyridinium-4-yl)porphyrin (Fe(III)TMPyP) with nitric oxide (NO) was studied by electronic absorption spectroscopy, ESR, and electrochemical and spectroelectrochemical techniques in aqueous solutions with pH from 2.2 to 12.0. Fe(III)TMPyP has been found to undergo a reductive nitrosylation in all pHs, and the product of nitric oxide binding to the porphyrin has been determined as iron(II) porphyrin nitrosyl complex ([Fe(II)(NO)TMPyP]). The rate of the reductive nitrosylation exhibits a tendency to get faster with increase in pH. An intermediate species was observed around neutral pH by spectroelectrochemical technique and was proposed to be the iron(II) nitrosyl complex of the mu-oxo dimeric form of FeTMPyP, which is known to be a predominant in neutral solutions.     

Electrochemistry of conductive polymers. 34. Two-dimensional correlation analysis of real-time spectroelectrochemical data for aniline polymerization

Electrochemical polymerization of aniline has been studied using real-time spectroelectrochemical experiments conducted concurrently with potentiodynamic scans in a nitric acid electrolyte with its pH adjusted to 0.50. Two-dimensional correlation spectral analysis and subsequent extraction of pure component spectra as well as their relative concentration profiles from complex spectroelectrochemical data employing the alternating least-squares regression iteration-based self-modeling curve resolution method led to positive identification of intermediate species. A conclusion was reached on the polymerization reaction mechanism based on these intermediate species and how their concentrations increased or decreased during the potential scans. The mechanism thus concluded represents a summary of a current understanding of the aniline polymerization reaction.     

A new integral method for the kinetic analysis of thermogravimetric data

Methods for the calculation of activation energies, pre-exponential factors and reaction orders from thermogravimetric data are briefly reviewed. A new integral method is proposed for the determination of these kinetic parameters, using data from pairs of TG curves produced at different heating rates. Employing accurate values of the temperature integral of the Arrhenius equation, tabulated over a range ofE andT, and a simple graphical procedure, the method offers advantages of speed and accuracy over those previously reported. It is suggested that at least one of the kinetic parameters should be allowed to move freely in order to achieve the best possible fit between calculated and experimental traces.     

Fast second order electron transfer reactions coupled to redox protein electrochemistry: Experiment and digital simulation

Chemical modification of metal surfaces by chemisorption provides a versatile method for the production of electrode interfaces which can be selective for the direct electrochemistry of one redox protein over another. The electrochemistry of a mixture of horse heart cytochrome c and spinach plastocyanin has been investigated at gold surfaces made selective for first one and then the other protein. The resulting cyclic voltammetry is quite unusual, containing pre-shoulders to both reduction current and reoxidation current peaks. The results have been interpreted in terms of fast second order electron transfer reactions taking place between the two proteins in homogeneous solution. This rationalisation has been corroborated by an explicit digital simulation of the proposed reaction scheme, using second order RKI. There are three independently variable parameters to the simulation: forward kinetic parameter, reverse kinetic parameter, and concentration ratio of non-electrode-active species to electrode-active species. The simulation has been used to explore a number of interesting trends in these parameters. Five such sequences of simulated cyclic voltammograms are reported, together with peak current and potential data in most cases. Attention is drawn to the possibility for further interesting experimental mixed redox protein electrochemistry at selective surfaces.     

A novel approach to the explanation the effect of microwave heating on isothermal kinetic of crosslinking polymerization of acrylic acid

The effect of microwave heating (MWH) on the isothermal kinetic of crosslinking-polymerization of acrylic acid (CPAA) was investigated. The kinetic curves of CPAA were determined in the temperature range from 303 to 328 K. By applying the model-fitting method it was revealed that the isothermal kinetics of CPAA was described by the first order chemical reaction kinetics model under the MWH and by the second order chemical reaction rate model for the conventionally heated (CH) process. The values of the reaction rate constants of CPAA are about 40 times higher for the microwave heated system than for the conventional heating. The kinetic parameters (activation energy (E _a) and pre-exponential factor (lnA)) of the CPAA are significantly lower than the corresponding values for CH process. It was found that the increase in the reaction rate of CPAA for MWH was not a consequence of overheating neither the hot spots in the reaction system. Based on model of selective energy transfer between the reacting molecules and the heating bath a novel explanation of the established effects of MWH on the kinetics of CPAA is given. A quantized nature and value of activation energy was confirmed. The decrease in the value of activation energy of CPAA under microwave heating is explained by the increased value of energy of ground vibration level of resonant oscillator in the AA molecule (v = 1417 cm^?1) caused by the absorption of non-thermal energy of MW field.     

Involvement of light absorbing transients upon photoreduction of 4-benzoylpyridine and 4,4′-dipyridylketone via donor and acceptor radicals

The photochemical properties of 4-benzoylpyridine and 4,4′-dipyridylketone were studied in argon-saturated aqueous solution in the presence of donors, such as formate, amines, e.g. triethylamine, and several alcohols. Quenching of the triplet state by the donor and subsequent reaction of both acceptor and donor radicals leads to specific quinoid intermediates: light absorbing transients (LATs). The radicals of the donor and 4-benzoylpyridine are suggested to react to LATs with maximum at 370 nm which disproportionate on the ms-s time scale forming phenyl-4-pyridylmethanol as stable species. The LATs of 4,4′-dipyridylketone absorb up to 500 nm, have similar decay rate constants (k_L) and eventually form 4-dipyridylmethanol. The properties of donor and acceptor radicals involved, the relevant effects of donor concentration and the solvent, pH and temperature dependences of k_L are discussed. The disproportionation kinetics support a cross-coupling reaction mechanism for formation of LATs.     

A New Infrared Spectroelectrochemical Cell for the Detection of Species Generated by Platinum and Screen‐Printed Carbon Electrodes

In this paper, we describe a simple and effective infrared (IR) spectroelectrochemical cell for detecting species generated from an electrochemical system featuring low‐IR‐reflectivity electrodes. The IR detection mode of attenuated total reflection (ATR) was employed to construct the spectroelectrochemical cell. Two kinds of electrodes, platinum (Pt) and screen‐printed carbon (SPC), were used to examine the performance of this new cell in detection of electroactive species generated by cyclic voltammetry. Because data generated from highly reflective electrodes are available in the literature, Pt electrode was used to characterize the performances of the developed spectroelectrochemical cell. Results indicated that species generated electrochemically can be observed readily and their responses were comparable to those described in the literature. The cell volume could be lower than 300 μL, which suggests that this approach may be very useful to obtain chemical information during electrochemistry for biological fluids with limited sample volumes. By examining the electrochemical behavior of several amino acids using both Pt and SPC electrodes, the redox behaviors can be readily observed indicating a new spectroelectrochemical cell was successfully developed for the purpose of using of SPC electrode.     

A modified double pulse technique for the investigation of coupled homogeneous chemical reactions

A double pulse technique for the investigation of coupled homogeneous chemical reactions is described; during the first pulse a constant current is used to generate an intermediate and during the second pulse the intermediate remaining in solution is determined by monitoring the I—t response at a controlled potential. The theory is developed and it is shown that a few simple tests of the experimental data allow systems with no chemical reaction, a first order reaction, and a second order reaction to be distinguished.The method has the capabilities of other similar techniques, e.g. cyclic voltammetry, double potential step, rotating ring-disc electrodes, but has particular advantages when the reactive intermediate results from the oxidation or reduction of the base electrolyte or the solvent. The method is used to investigate some bromination reactions.     

Reactions of molybdenum(VI) with metal ion reductants

The reactions of aqueous H2MoO4 at low pH with titanium(II), titanium(III), europium(II), vanadium(II), and germanium(II), as monitored at 430 nm, give biphasic profiles featuring a sharp rise in absorbance followed by a marked decrease (Fig. 1). The final product is the dimeric Mo(V) cation, [Mo2O4]2+, and the strongly absorbing intermediate is taken as a monomeric Mo(V) species. The molar absorbances of the transients from different reductants are not the same, nor are the rate laws governing the fadings. None of the decay curves exhibits evidence of a second order dependence on the transient. The kinetic behaviors of these systems are consistent with the intervention of successor complexes of the type [Chemical structure: see text], (formed by inner sphere reductions of Mo(VI)), which decompose, via first-order processes, to a monomeric Mo(V) species. The latter then experiences rapid dimerization, which is kinetically silent. The possibility that Ge(II) bypasses the unstable tripositive state by reducing Mo(VI) to Mo(IV) (which then undergoes rapid Mo(VI)-Mo(IV) comproportionation) is considered.