Kinetic determination of ascorbic acid by the 2,6-dichlorophenolindophenol reaction with a stopped-flow technique.

The reaction of ascorbic acid with 2.6-dichlorophenolindophenol is applied for the kinetic determination of ascorbic acid in 0.05M oxalic acid. Stopped-flow techniques are used; the concentrations of the reactants of the second-order reaction can be adjusted so that the transmittance signal remains nearly invariant for a wide range of voltage. Theoretical and experimental results are in very good agreement. Analytical working curves are presented for the determination of ascorbic acid in the ranges 5.0·10^-4–1.0·10^-2M and 5.0·10^-5–1.0-·10^-3M with errors of 1.0% and 2.2%. respectively. The method is simple, fast and sensitive.     

Comparative kinetic study for rate constant determination of the reaction of ascorbic acid with 2,6-dichlorophenolindophenol

The rate constant k of the reaction of ascorbic acid with 2,6-dichlorophenolindophenol (DCPI) in oxalic acid solutions is determined, by stopped-flow techniques. Four different methods are used to evaluate the results. The values and errors are compared statistically. The average of the rate constant is 56.5 x 10(3) l. mole(-1), sec(-1) and the overall standard deviation is 0.6 x 10(3) l. mole(-1), sec(-1) or 1.0% relative. The pH-dependence of the rate constant suggests that DCPI reacts with undissociated ascorbic acid.     

Kinetic and mechanistic study of the reaction of 2,6-dichlorophenol-indophenol and cysteine

In this work the reaction of cysteine (H(2)Q) with 2,6-dichlorophenolindophenol (D) is studied kinetically in the pH range 2.5-9.0. Taking into consideration the distribution diagrams for the species H(3)Q(+), H(2)Q, HQ(-), Q(2-) for cysteine and DH(+)(2), DH, D(-) for 2,6-dichlorophenolindophenol the reaction rate constants k(i) for all possible combinations of the reacting species were determined. The maximum reactivity appears at pH 6.88 with an overall reaction constant k = 306 1.mole(-1).sec(-1) at 22 degrees . The effect of the concentrations of the reagents and the ionic strength on the reaction rate is also given. From Arrhenius plots an activation energy E(a) = 8.1 kcal/mole was calculated. Working curves for the determination of cysteine in aqueous solutions are also presented applying the reaction rate method. Finally the paper includes important analytical information for the calculation of the errors due to interference of cysteine by the kinetic determination of ascorbic acid, using its reaction with 2,6-dichlorophenolindophenol.     

Simulating Nuclear subsystem rearrangement in the redox reaction between Fe2+ and Fe3+ ions

An approach that allows the numerical simulation of conformational rearrangements accompanying redox reactions in molecular systems is examined. The proposed method makes it possible on the basis of metadynamics to identify automatically the groups of atoms whose conformational motions give rise to changes in the redox properties of an investigated system. The method is used to simulate a classic model electron transfer reaction, i.e., the redox reaction between Fe²⁺ and Fe³⁺ ions in a solution. The effective activation energy of the reaction is reproduced quantitatively, and the reaction coordinate is determined. It is shown that this approach is promising for use in studying conformational changes that are associated with electron transport processes in complex molecular systems.     

Kinetic study of the reaction between iodide and N-chloramines

We carried out a kinetic study of the reaction between iodide ion and various primary N-chloramines and found it to be first-order in the latter. Experiments also showed the rate constant for the reaction to be directly proportional to the iodide and hydrogen ion concentrations. The influence of the buffer concentration reveals the presence of general acid catalysis processes. © 1996 John Wiley & Sons, Inc.     

Kinetic study of the reaction Ca+ + N2O from 188 to 1207 K

Ion-molecule reactions involving metallic species play a central role in the chemistry of planetary ionospheres and in many combustion processes. The kinetics of the Ca(+) + N(2)O --> CaO(+) + N(2) reaction was studied by the pulsed multiphoton dissociation at 193 nm of organo-calcium vapor in the presence of N(2)O, followed by time-resolved laser-induced fluorescence spectroscopy of Ca(+) at 393.37 nm (4(2)P(3/2) <-- 4(2)S(1/2)). This yielded k(188-1207 K) = 5.45 x 10(-11) (T/300 K)(0.53) exp(282 K/T) cm(3) molecule(-1) s(-1), with an estimated accuracy of +/-13% (188-600 K) and +/-27% (600-1207 K). The temperature dependence of this barrierless reaction, with a minimum in the rate coefficient between 400 and 600 K, appears to be explained by the role of N(2)O vibrational excitation. This is examined using a classical trajectory treatment on a potential energy surface calculated at the B3LYP/6-311+g(2d,p) level of theory.     

Tl^3^+─H2O2─Fe^2^+体系的反应动力学研究

本文用Tl(I)离子选择性电极测定了Tl^3^+-H2O2-Fe^2^+体系的反应参数, 据此计算了该体系的反应级数, 得到了反应速率方程式, 对该反应体系的反应机理进行了探讨, 并用稳态处理法对所提出机理进行验证, 其结论与实验所得速率方程完全符合。     

Experimental study of the asymmetric charge transfer reaction between Ar+ ions and Fe atoms

We investigate the Ar(+)-Fe asymmetric charge transfer (ACT) reaction using a combination of plasma diagnostics methods and a kinetic model of the afterglow plasma, which allow monitoring of the temporal evolution of the densities of different species. The iron vapor is created inside a discharge cell by cathode sputtering; its density is measured by atomic absorption spectroscopy. The rate coefficient of the reaction is evaluated from the emission intensity decay of Fe(+)? lines pumped by the ACT process in the He-Ar-Fe and Ar-Fe afterglow plasmas. The measurements yield a rate coefficient k = 7.6( ± 3.0) × 10(-9) cm(3) s(-1) at T = 300 K.     

A Monte Carlo simulation of free energy relationships for the electron transfer reaction between Fe+ and Fe2+ in water

A free energy barrier ΔF^≠ = 174.2 kJ/mol for the self-exchange electron transfer reaction model Fe⁺/Fe²⁺ in water has been calculated by combining Monte Carlo simulations and the statistical perturbation theory. We have shown that, even for those electron transfer reactions that present a very high free energy barrier of activation, the free energy curve behaves parabolically versus the reaction coordinate, which justifies the quadratic expression for the activation free energy done by Marcus.     

Kinetic study of the recombination reaction OD + NO2 + M → DNO3 + M

Rate constants for the recombination reaction OD + NO₂ + M → DNO₃ + M have been determined in the falloff region (5–500 torr) and at 297 ± 2 K, in the presence of He, N₂, and SF₆ as third bodies, by using a pulsed laser photolysis-resonance absorption technique. Values of k₀, k_x and the falloff parameter F_c have been estimated. Our rate constants were, within the experimental uncertainty, the same as those reported for the reaction of OH radicals with NO₂.     

The use of 2,6-dichlorophenolindophenol as indicator in acid-base titrations

2,6-Dichlorophenolindophenol shows acid-base indicator properties. Its colour is red in acidicmedia and blue in alkaline media. 'Ihe transitional pH value is 5.7 and the colour change is sharp and easy to observe. The use of the indicator in various acid-base titrations, as well as the effects of neutral salts, alcohol and temperatures, were checked. The absorption spectra of the acidic and basic forms of the indicator are presented.     

Thermoanalytical study of the solid state reaction between hydrated ZnO and Fe2O3

The hydrated oxides which are formed by the addition of ammonium bi-carbonate to a solution of Zn(NO₃)₂ and Fe(NO₃)₃, and drying the precipitates at 110° are zinc hydroxy carbonate(I) and iron(III) oxide gel(II), respectively. A new, derived derivative thermogravimetric curve along with conventional DTA and DTG methods have been used to study the reaction between (I) and (II) in two components system.A mixture of (I) and (II) subjected to grinding yields about 16% zinc ferrite precursor. In a sample prepared by coprecipitation from the mixed nitrate solution and drying at 110°, nearly 70% precursor is formed. The formation of zinc ferrite spinel reported to take place at low temperature in such cases appears to be related with the formation of the precursor, and reactivity and phase transformation temperature in Fe₂O₃.

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Zusammenfassung Die durch Zugabe von Ammoniumbicarbonat zu einer Lösung von Zn(NO₃)₂ und Fe(NO₃)₃ und Trocknung des Niederschlags bei 110° gebildeten hydratisierten Oxide sind Zinkhydroxycarbonat (I) bzw. Eisen(III)oxidgel (II). Eine neue derivierte derivative thermogravimetrische Kurve wurde gemeinsam mit den konventionellen DTA und DTG Methoden zum Studium der Reaktion zwischen (I) und (II) in Zweikomponentensystemen eingesetzt.Das Gemisch von (I) und (II) ergibt beim Mahlen etwa 16% Zinkferrit »Prekursor«. In einer durch Mitfällung der gemischten Nitrate und Trocknung bei 110° erhaltenen Probe wurde fast 70 % »Prekursor« gebildet. Die Bildung von Zinkferritspinell, über dessen Entstehung in solchen Fällen bei niedrigen Temperaturen berichtet wird, scheint mit der Bildung des »Prekursors« verbunden zu sein, sowie mit der Reaktivität und der Phasenübergangstemperatur in Fe₂O₃.

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Résumé Les oxydes hydratés formés lors de l'addition du bicarbonate d'ammonium à une solution de Zn(NO₃)₂ et de Fe(NO₃)₂ suivie du séchage du précipité à 110°, sont l'hydroxy-carbonate de zinc(I) et le gel de l'oxyde de fer(III) (II). On a utilisé une nouvelle technique de thermogravimétrie en dérivation, ainsi que les méthodes d'ATD et TGD conventionnelles, pour étudier la réaction entre (I) et (II) dans le système à deux composants.Un mélange de (I) et de (II), soumis au broyage, donne environ 16 p.c. de ferrite de zinc «précurseur», tandis qu'un échantillon préparé par coprécipitation à partir de la solution des nitrates mixtes et séchage à 110°, en donne environ 70 p.c.La formation du spinelle de ferrite de zinc décrite comme ayant lieu, dans des cas similaires, à des températures faibles, paraît être en rapport avec la formation du «précurseur» ainsi qu'avec la réactivité et la température de la transformation de phase de Fe₂O₃.

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Zn(NO₃)₂ Fe(NO₃)₃, , 110°, , , (I) (II). , , I II . I II, , 16% , . , 110°, 70% , . « » , Fe₂O₃.

     

Kinetic study of the ClOO + NO reaction using cavity ring-down spectroscopy

Cavity ring-down spectroscopy was used to study the reaction of ClOO with NO in 50-150 Torr total pressure of O2/N2 diluent at 205-243 K. A value of k(ClOO+NO) = (4.5 +/- 0.9) x 10(-11) cm3 molecule(-1) s(-1) at 213 K was determined (quoted uncertainties are two standard deviations). The yield of NO(2) in the ClOO + NO reaction was 0.18 +/- 0.02 at 213 K and 0.15 +/- 0.02 at 223 K. An upper limit of k(ClOO+Cl2) < 3.5 x 10(-14) cm3 molecule(-1) s(-1) was established at 213 K. Results are discussed with respect to the atmospheric chemistry of ClOO and other peroxy radicals.     

Kinetic study of the reaction OH + HI by laser photolysis-resonance fluorescence

The gas phase reaction of OH radicals with hydrogen iodide (HI) has been studied using a Laser Photolysis-Resonance Fluorescence (LP-RF) apparatus, recently developed in our group. The measured rate constant at 298 K was (2.7 ± 0.2) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹. This rate constant is compared with the ones of the reactions OH + HCl and OH + HBr. The role of the reaction OH + HI in marine tropospheric chemistry is discussed. In addition, the LP-RF apparatus was tested and validated by measuring the following rate constants (in cm³ molecule⁻¹ s⁻¹ units): 𝓀(OH + HNO₃) = (1.31 ± 0.06) × 10⁻¹³ at p = 27 and 50 Torr of argon and 𝓀(OH + C₃H₈) = (1.22 ± 0.08) × 10⁻¹². These rate constants are in very good agreement with the literature data.     

Kinetic analysis of the reaction between (V2O5)n=1,2+ and ethylene

A systematic experimental and theoretical investigation of the influence of reactant energy on the reactivity of (V(2)O(5))(n)=1,2(+) clusters with ethylene (Justes, D. R.; Mitri?, R.; Moore, N. A.; Bonaci?-Koutecky, V.; Castleman, A. W., Jr. J. Am. Chem. Soc., 2003, 125, 6289) provided evidence of the rate controlling steps in the reaction. Herein, we present further experimental and theoretical evidence for our recently proposed radical cation mechanism for oxygen atom transfer from (V(2)O(5))(n)=1,2(+) clusters to ethylene. In particular the results of ab initio molecular dynamics simulations are found to further support the radical cation mechanism. Experimental reaction cross sections at the zero pressure limit and rate coefficients show that the energy dependence of the reaction cross section is in accord with the Langevin formula. Evidence is presented that ion-molecule association is the rate determining step, whereas subsequent hydrogen transfer and formation of acetaldehyde proceed without significant barriers. We propose a kinetic model for the reaction cross section that fully accounts for the experimental findings. The model offers the prospect of elucidating the details of the general reaction mechanisms through a study of the energy dependence of the reaction cross sections.     

Kinetic study of the CN radical reaction with 2-methylfuran

The gas phase reaction of the ground state cyano-radical (CN (X²∑⁺)) with 2-methylfuran (2-MF) is investigated in a quasi-static reaction cell at pressures ranging from 2.2 to 7.6 Torr and temperatures ranging from 304 to 440 K. The CN radicals are generated in their ground electronic state by pulsed laser photolysis of gaseous cyanogen iodide (ICN) at 266 nm. Their concentration is monitored as a function of reaction time using laser-induced fluorescence at 387.3 nm on the B²∑⁺ (ν′ = 0) ← X²∑⁺ (ν″ = 0) vibronic band. The reaction rate coefficient is found to be rapid and independent of pressure and temperature. Over the investigated temperature and pressure ranges, the rate coefficient is measured to be 2.83 (± 0.18) × 10⁻¹⁰ cm³ molecules s⁻¹. The enthalpies of the stationary points and transition states on the CN + 2-MF potential energy surface are calculated using the CBS-QB3 computational method. The kinetic results suggest the lack of a prereactive complex on the reaction entrance channel with either a very small or nonexistent entrance energy barrier. In addition, the potential energy surface calculations reveal only submerged barriers along the minimum energy path. Based on comparisons between previous CN reactions with unsaturated hydrocarbons, the most likely reaction pathway is CN addition onto one of the unsaturated carbons followed by either H or methyl elimination. The implications for the transformation of biomass-derived fuels in nitrogen-rich flames is discussed.     

乳酸-丙酮-BrO3^——Mn^2^+-H2SO4化学振荡体系动力学研究

本文报道了与生命代谢过程密切相关的中间物参与的乳酸(以下简称LA)-丙酮(以下简称Act)-BrO3^--Mn^2^+-H2SO4新型化学振荡体系, 考察了振荡体系中诸反应物的初始浓度范围及影响因素, 获得诱导期、振荡周期、振荡寿命所对应的表观活化参数EIN, EP, EL分别为60.68kJ.mol^-^1, 61.03kJ.mol^-^1,135.80kJ.mol^-^1。分析了诱导期的新特征及可能的振荡反应机理。     

Kinetic study of the reaction of OH with CH2I2

Flash photolysis (FP) coupled to resonance fluorescence (RF) was used to measure the absolute rate coefficients (k(1)) for the reaction of OH(X(2)Π) radicals with diiodomethane (CH(2)I(2)) over the temperature range 295-374 K. The experiments involved time-resolved RF detection of the OH (A(2)Σ(+)→X(2)Π transition at λ = 308 nm) following FP of the H(2)O/CH(2)I(2)/He mixtures. The OH(X(2)Π) radicals were produced by FP of H(2)O in the vacuum-UV at wavelengths λ > 120 nm. Decays of OH radicals in the presence of CH(2)I(2) are observed to be exponential, and the decay rates are found to be linearly dependent on the CH(2)I(2) concentration. The results are described by the Arrhenius expression k(1)(T) = (4.2 ± 0.5) × 10(-11) exp[-(670 ± 20)K/T] cm(3) molecule(-1) s(-1). The implications of the reported kinetic results for understanding the atmospheric chemistry of CH(2)I(2) are discussed.     

On-column complexation capillary electrophoretic separation of Fe2+ and Fe3+ using 2,6-pyridinedicarboxylic acid coupled with large-volume sample stacking

On-column complexation of Fe2+ and Fe3+ with 2,6-pyridinedicarboxylic acid (2,6-PDCA) formed anionic complexes, which were then separated by capillary zone electrophoresis with direct UV detection at 214 nm. To achieve reasonable separation selectivity and on-column complexation, the conditions such as pH, the concentration of 2,6-PCDA and the EOF modifiers in the electrolyte were examined. The electrolyte contained 5.0 mM 2,6-PDCA, 0.25 mM tetradecyltrimethlammonium bromide (TTAB) and 5% (v/v) acetonitrile at pH 4.0 was optimised for on-column complexation and the separation of Fe[PCDA]2(2-) and Fe[PCDA]2(-). To enhance the detection sensitivity, large-volume sample stacking (LVSS) was used for the on-line preconcentration of Fe[PCDA]2(2-) and Fe[PCDA]2(-). Under the optimised conditions, satisfactory working ranges (0.5-50 microM), lower detection limits (less than 0.1 microM) and good repeatability of the peak areas (R.S.D.: 5.2-7.8%, n = 5) was achieved using LVSS (300 s). With LVSS, the detection sensitivity was enhanced more than 50-fold compared to conventional hydrodynamic injection. The proposed method was used successfully for the determination of Fe2+ and Fe3+ in water samples.