Potential dependent chronoamperometry: experimental verification

Potential dependent chronoamperometry is examined for its utility in examining homogeneous chemical reactions following charge transfer. By carrying out single step chronoamperometry experiments at potentials in the region of E^o′, kinetic information may be derived from the resulting current vs. time response. Advantages of the technique include the sensitivity of the response to reaction mechanism, and the ability to extend the time frame of the experiment to values greatly exceeding the true reaction half life. The method is compared with conventional methods for determining the rate constant of the benzidine rearrangement. The strengths and limitions of the method are discussed.     

The mechanism of formation of polymer films from heptane in a low-temperature,low-pressure plasma

Calculations of the apparent activation energy for the growth of macromolecular entities in the form of cones on the surface of a growing film, as well as the apparent activation energy for the interaction of free radicals of the film with air oxygen after exposure of the film to the atmosphere, confirmed the existence of three steps of the formation of polymer films from heptane in a low-temperature, low-pressure plasma. It was found that the cones have a structure other than that of the film on which they are formed.     

Investigation of sorption properties of carbon treated with low-temperature plasma

Plasma based technology for producing active carbon is proposed.     

The interaction of a low-temperature oxidizing plasma with modified cellulose

The influence of a low-temperature low-frequency glow discharge air plasma on the surface and physicomechanical properties of wood cellulose I was studied. Cellulose was formed as a paper sheet treated with an organic surface-active substance on the basis of a disubstituted alkylaromatic acid. The total effective surface energy of the initial sample was 31 mJ/m². Treatment in an air plasma decreased the hydrophobic properties of the surface. The total effective surface energy substantially increased, largely because of an increase in its polar component by many times. Treatment was accompanied by a decrease in the content of hydrogen and hydroxyl groups, which caused the destruction of macromolecules and the formation of functional carbonyl (aldehyde and ketone) groups. In the near IR range, bonds most probably related to epoxide groups were observed. Macromolecules in a very thin surface layer experienced chemical modification, and this layer likely became amorphous. The high degree of sample crystallinity in the bulk did not change. The mechanical properties of samples worsened only under intense plasma actions.     

Kinetic and mechanism of alkene polymerization

Triphenylmethyl salts of the very weakly-coordinating borate anions [CN{B(C₆F₅)₃}₂]⁻ (1), [H₂N{(C₆F₅)₃}₂]⁻ and [M{CNB(C₆F₅)₃}₄]²⁻ (M = Ni, Pd) have been prepared in simple one-pot reactions. Mixtures of (SBI)ZrMe₂/1/AlBu ₃ ⁱ (SBI = rac-Me₂Si(Ind)₂) are 30–40 times more active in ethylene polymerizations at 60–100°C than (SBI)ZrCl₂/MAO. The quantification of anion effects on propene polymerization activity at 20°C gives the order [CN{B(C₆F₅)₃}₂]⁻ > [H₂N{(C₆F₅)₃}₂]⁻ ≈ B(C₆F₅) ₄ ⁻ ≫ [MeB(C₆F₅)₃]⁻. The highest productivities were of the order of ca. 3.0 × 10⁸ g PP (mol Zr)⁻¹ h⁻¹ [C₃H₆]⁻¹, about 1.3–1.5 times higher than with B(C₆F₅) ₄ ⁻ as the counter anion. The titanium system CGCTiMe₂/1/AlBu ₃ ⁱ gave activities that were very similar to the zirconocene catalyst. The concentration of active species [C*] as determined by quenched-flow kinetic techniques indicates typical values of around 10%, independent of the counter anion, for both the borate and MAO systems. Pulsed field-gradient spin echo and nuclear Overhauser effect NMR experiments on systems designed to be more realistic models for active species with longer polymeryl chains, (SBI)M(CH₂SiMe₃)(μ-Me)B(C₆F₅)₃ and [(SBI)MCH₂SiMe ₃ ⁺ ...B(C₆F₅) ₄ ⁻ ] (M = Zr, Hf), demonstrated the influence of bulky alkyl chains on the ion pair solution structures: while the MeB(C₆F₅)₃ compound exists as a simple inner-sphere ion-pair, the B(C₆F₅) ₄ ⁻ compound is an outer-sphere ion pair (OSIP), a consequence of the relegation of the anion into the second coordination sphere by the γ-agostic interaction with the alkyl ligand. The OSIP aggregates to ion hextuples (10 mM) or quadruples (2 mM). Implications for the polymerization mechanism are discussed; the process follows an associative interchange (I _a) pathway. The text was submitted by the authors in English.     

Experimental and Kinetic Modeling Study of Methanol Ignition and Oxidation at High Pressure

A detailed chemical kinetic model for oxidation of CH₃OH at high pressure and intermediate temperatures has been developed and validated experimentally. Ab initio calculations and Rice–Ramsperger–Kassel–Marcus/transition state theory (RRKM/TST) analysis were used to obtain rate coefficients for , , , and . The experiments, involving CH₃OH/O₂ mixtures diluted in N₂, were carried out in a high‐pressure flow reactor at 600–900 K and 20–100 bar, varying the reaction stoichiometry from very lean to fuel‐rich conditions. Under the conditions studied, the onset temperature for methanol oxidation was not dependent on the stoichiometry, whereas increasing pressure shifted the ignition temperature toward lower values. Model predictions of the present experimental results, as well as rapid compression machine data from the literature, were generally satisfactory. The governing reaction pathways have been outlined based on calculations with the kinetic model. Unlike what has been observed for unsaturated hydrocarbons, the oxidation pathways for CH₃OH under the investigated conditions were very similar to those prevailing at higher temperatures and lower pressures. At the high pressures, the modeling predictions for onset of reaction were particularly sensitive to the reaction.     

High efficiency liquid chromatography on conventional columns and instrumentation by using temperature as a variable. Kinetic plots and experimental verification

Theoretical aspects of temperature in liquid chromatography (LC) have mostly been studied to elucidate changes in retention behavior of small and large molecules in various solvents. That temperature also plays a significant role in chromatographic performance is less known. Kinetic plots are an established tool to predict chromatographic performance in terms of speed and efficiency that can be obtained with a certain particle size at the maximum attainable column pressure. In this paper, temperature effects on mobile phase viscosity and analyte diffusion are incorporated in these plots to prove that superior performances are within experimental reach for conventional LC columns and equipment. Verification of the modified kinetic plots with experimental data points is presented.     

Dialkylbenzene hydrogenation: Kinetic analysis of rollover mechanism

Kinetic analysis is presented for the so-called rollover mechanism in hydrogenation of dialkylbenzenes. The theory of complex reactions and graph theory are applied for discussing plausible mechanisms. It is demonstrated that mechanisms which involve either desorption-readsorption of some reaction intermediate or some kind of “rollover” of an adsorbed intermediate, result in similar kinetic equations if these steps are reversible.     

Model for alkanol + alkane mixtures: Extension and experimental verification

A recently developed model for 1-alkanol+alkane mixtures is extended to methanol mixtures and to the non-polar mixing partners tetrachloromethane and benzene. The model contains chemical and physical terms, which are combined in a thermodynamically consistent way. For our calculations on methanol mixtures, we have measured g ^E of methanol+ hexane via static vapor pressure measurements. In order to check the model predictions for systems with higher alkanols and alkanes, we have also determined g ^E of 1-octanol+tetradecane by measuring the melting curve. The reproduction of the excess properties of methanol+hexane, the agreement between predicted and measured values of g ^E for 1-octanol+ tetradecane, and the capability to deal also with other non-polar mixing partners demonstrate the power and reliability of the model.Communicated at the Festsymposium celebrating Dr. Henry V. Kehiaian's 60^th birthday, Clermont-Ferrand, France, 17–18 May 1990.     

Miniaturized integrated evanescent field IR-absorption sensor: Design and experimental verification with deteriorated lubrication oil

In industry, a vast variety of processes can be optimized by means of online measurement of chemical properties of fluids in order to reduce costs of maintenance or increase productivity as well as production quality. Since the absorption measurement in the mid-IR-region is a powerful method to determine the chemical composition of fluids, we propose a fully integrated absorption sensor based on IR-absorption in the evanescent field region of an integrated mono-mode waveguide utilizing thermally generated and detected IR-radiation. For the coupling, two grating couplers are employed, which couple broadband thermal IR-radiation into the waveguide and the attenuated IR-radiation towards a thermal IR-detector, respectively. To achieve a spectroscopic measurement, we utilize the dispersive feature of the grating coupler, which couples the IR-beams out of the waveguide at angles depending on the frequency. We report on the design of the fully integrated infrared absorption sensor, which is capable to determine chemical properties of, e.g., lubrication oil by investigating infrared absorption. Beside the theory related to an optimum design of the mono-mode waveguide, we discuss the applicability of the proposed concept to the monitoring of deterioration of lubrication oil.     

Esterification of butyric acid with n-butanol: Kinetic study using experimental data and modeling

Present study involves the investigation of the esterification kinetics between butyric acid and n-butanol. This reaction was conducted in a batch reactor, utilizing homogeneous methanesulfonic acid (MSA) catalyst. Response surface methodology (RSM) was conducted prior to the kinetic study using “Design Expert; version-11.0” for finding the causal factors influencing the conversion of butyric acid. Most important factors identified with their limits against conversions (during optimization of the process using RSM) were taken up to critically analyze the effect of them on butyric acid conversion. Concentration and activity-based model of the process were proposed assuming second order reversible reaction scheme using homogeneous MSA catalyst. During the study of non-ideal behavior of the system, UNIFAC model was adapted for assessing the activity coefficients of species present in equilibrated liquid phase. Experimental data were used to evaluate kinetic and thermodynamic parameters such as rate constants, activation energy, enthalpy, and entropy of the system. The endothermic nature of esterification was confirmed by positive value of enthalpy obtained. The effect of various levels of causal variables like temperature (60–90°C), catalyst concentration (0.5–1.5 wt.%), and molar ratio of n-butanol to butyric acid (1–3) on conversion kinetics of butyric acid was investigated during transient and equilibrium phase of the reaction. It has been observed that molar ratio of butanol to butyric acid has the highest influence on the conversion. The rate equation derived offered a kinetic and thermodynamic framework to the generated data. It also exhibits a notable degree of conformity of predicted data to the experimental ones and effectively characterizes the system across different reaction temperatures, reactant molar ratio, and catalyst concentration.     

Kinetic parameters for gas-phase reactions: experimental and theoretical challenges

This article aims to illustrate the added value provided to experimental kinetics investigations by complementary theoretical kinetics studies, using as examples (i) reactions of two major hydrocarbon flame radicals, HCCO and C(2)H, and (ii) reactions of several oxygenated organic compounds with hydroxyl radicals of interest to atmospheric chemistry. The first part, on HCCO and C(2)H kinetics, does not attempt to give an extensive literature review, but rather addresses some major experimental techniques, mainly specific ones, that have allowed a great part of the available reactivity databases on these two species to be established. For several key reactions, it is shown how potential energy surfaces and statistical rate predictions based thereon have provided insight into the molecular mechanisms and have allowed estimates of product distributions as well as reliable extrapolations of experimental rate coefficients and branching ratios to higher temperatures. The second part addresses current issues in atmospheric chemistry relating mainly to hydroxyl radical reactions with oxygenated organics, and focuses on the experimental characterization of the often unusual temperature dependence of their rate coefficients and on the theoretical rationalization thereof, through the formation of hydrogen-bonded pre-reactive complexes and resulting tunnelling-enhanced H-abstraction. Finally, the development of general structure-activity relationships for OH reactions with organics, H-abstractions as well as OH-additions for unsaturated compounds, is briefly discussed.     

Alkaline hydrolysis of ethiofencarb: Kinetic study and mechanism degradation

The present paper deals with the hydrolysis of ethiofencarb [2‐ethylthiomethyl(phenyl)‐N‐methylcarbamate] in alkaline solution. The reaction kinetics has been investigated using spectrophotometric and liquid chromatographic techniques. The rate constants were determined following a proposed first‐order kinetic model. The positive activation entropy Δ S^≠ = +100.07 J mol^?1 K^?1 and the absence of general basic catalysis indicated an E1cB hydrolytic mechanism, involving the formation of methyl isocyanate. This result was confirmed by the fact that ethiofencarb fits well into Brönsted and Hammett lines, obtained for a series of substituted N‐methylcarbamate whose decomposition in aqueous media was established to follow an E1cB mechanism. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 45: 118–124, 2013     

Principles of rapid polymerase chain reactions: mathematical modeling and experimental verification

Polymerase chain reaction (PCR) is an important diagnostic tool for the amplification of DNA. The PCR process can be treated as a problem in biochemical engineering. This study focuses on the development of a mathematical model of the polymerase chain reaction. The PCR process consists of three steps: denaturation of target DNA, annealing of sequence-specific oligonucleotide primers and the enzyme-catalyzed elongation of the annealed complex (primer:DNA:polymerase). The denaturation step separates the double strands of DNA; this model assumes denaturation is complete. The annealing step describes the formation of a primer-fragment complex followed by the attachment of the polymerase to form a ternary complex. This step is complicated by competitive annealing between primers and incomplete fragments including primer-primer reactions. The elongation step is modeled by a stochastic method. Species that compete during the elongation step are deoxynucleotide triphosphates dCTP, dATP, dTTP, dGTP, dUTP, and pyrophosphate. Thermal deamination of dCTP to form dUTP is included in the model. The probability for a species to arrive at the active site is based on its molar fraction. The number of random insertion events depends on the average processing speed of the polymerase and the elongation time of the simulation. The numerical stochastic experiment is repeated a sufficient number of times to construct a probability density distribution (PDF). The moment of the PDF and the annealing step products provide the product distribution at the end of the elongation step. The overall yield is compared to six experimental values of the yield. In all cases the comparisons are very good.     

Kinetic energy release of protonated methanol clusters using the low-temperature fast-atom bombardment: experiment and theory combined

Low-temperature fast-atom bombardment was found to be an excellent method for generating large protonated methanol clusters, (CH(3)OH)(n)H(+) (n = 2 to 15). Metastable dissociations of these clusters, involving elimination of one methanol molecule, were studied using mass-analyzed ion kinetic energy spectra (MIKES). From metastable peak profiles kinetic energy release (KER) distributions were obtained, even for clusters as large as (CH(3)OH)(15)H(+). The results were analyzed by a simple thermal model, by the finite heat bath theory (FHBT) and by the RRKM-based MassKinetics algorithm. The KER distribution was shown to correspond to a three-dimensional translational energy distribution, implying statistical energy partitioning in the transition state. The mean KER values and transition state temperatures were found to increase with cluster size, reaching 25 meV and approximately 210 K for large clusters (n = 10).     

Modification of ultra-high-molecular-weight polyethylene fibers and powders using low-temperature plasma

Literature data on the surface modification of ultra-high-molecular-weight polyethylene as fibers and powder under the influence of low-temperature plasma are analyzed. The change in polymer chemical composition and structure is described. The results of the studies, indicating a significant improvement in the contact and adhesion characteristics of the modified polymer and composite materials, are discussed.     

Temperature and velocity fields in a gas stream exiting a plasma torch. A mathematical model and its experimental verification

A mathematical model was developed to predict the velocity and temperature fields in a free plasma jet issuing from a D.C. plasma torch. It was assumed that the temperature and velocity at the torch nozzle were specified and the turbulent Navier-Stokes equations were solved in conjunction with a two-equation model of turbulence and the energy transport equation. The model was formulated in terms of the two-dimensional elliptic equations to facilitate its future extension to nonparabolic problems. The predictions of the model were compared with experimental measurements obtained from laser Doppler and spectroscopic techniques. Good overall agreement was found between the theoretical predictions and the experimental measurements for two sets of initial conditions corresponding to nitrogen/hydrogen and argon/hydrogen plasmas. Radiation was found to have a small effect on the overall heat transfer process, and it is suggested that the assumption of an optically thin radiation loss per unit volume is sufficiently accurate for most engineering applications. The significance of this work lies in the fact that, for the first time, it is possible to test the assumptions of the current model against a reliable set of experimental measurements.Notation C ₁,C ₂,C _D constants inK- turbulence model, Table III - C _P average specific heat of plasma at constant pressure - h ₁ length of integration region - h ₂ width of integration region - K turbulent kinetic energy per unit mass - P pressure - r radial coordinate - R ₀ internal radius of anode - S _K source term forK equation - S _R radiation loss per unit volume - S source term for equation - T ₀ temperature of plasma atz=0 - T temperature of plasma - T _a ambient temperature - u velocity inz direction - u ₀ velocity of plasma atz=0 - v radial velocity of plasma - z axial coordinate - dissipation rate of turbulence energy - , _eff, _t molecular, effective, and turbulent viscosities, respectively - density - _K, _T, Prandtl numbers forK, T, and, respectively