scholarly journals KINETICS OF OZONE REACTIONS WITH ADENINE AND CYTOSINE IN AQUEOUS SOLUTIONS

2020 ◽  
Vol 63 (10) ◽  
pp. 17-22
Author(s):  
Aigul A. Maksyutova ◽  
Elvina R. Khaynasova ◽  
Yuriy S. Zimin
Keyword(s):  
Aqueous Solutions ◽  
Rate Constants ◽  
Correlation Coefficients ◽  
Activation Parameters ◽  
Second Order ◽  
Order Kinetic ◽  
Temperature Dependences ◽  
Ozone Reactivity ◽  
Kinetics Of ◽  
Ozone Reactions

The ultraviolet spectroscopy method has been applied to study the kinetics of the ozone reactions with nitrogenous bases (NB), namely adenine and cytosine in aqueous solutions. At the first research stage, the range of NB working concentrations has been determined. It was found that linear dependences between optical densities and concentrations of nitrogenous bases aqueous solutions are quite reliable, with correlation coefficients r ≥ 0.998, are satisfied up to [NB] = 2.3 ∙ 10–4 mol/l. According to the Bouguer-Lambert-Beer law, adenine and cytosine extinction coefficients in aqueous solutions were determined and subsequently used to calculate their residual concentrations. At the next stage, the kinetics of nitrogenous bases ozonized oxidation was studied with equal initial concentrations of the starting substances ([NB]0 = [О3]0). The results revealed that the kinetic consumption curves of the starting reagents are fairly well linearized (r ≥ 0.996) in the second-order reaction equation coordinates. As found with the bubbling installation, 1 mol of the absorbed ozone falls on 1 mol of the used NB. Thus, the reactions of ozone with adenine and cytosine explicitly proceed according to the second-order kinetic laws (the first – according to О3 and the first – according to NB). The rate constants were calculated by the integral reaction equations, the values of which indicate a higher ozone reactivity in relation to nitrogen bases. The temperature dependences of the second-order rate constants was studied ranging 285-309 K, and the activation parameters (pre-exponential factors and activation energies) of the ozone reactions with adenine and cytosine in aqueous solutions were determined.

Kinetics of chloride substitution in [Pt(bpma)Cl]+ and [Pt(gly-met-S,N,N)Cl] complexes by thiourea, nitrites, and iodides

2014 ◽  
Vol 68 (1) ◽  
Author(s):  
Adrian Topolski ◽  
Živadin Bugarčić
Keyword(s):  
Aqueous Solutions ◽  
Rate Constants ◽  
Activation Parameters ◽  
Second Order ◽  
Order Rate ◽  
Kinetics Of

AbstractSubstitution of chloride in [PtCl(bpma)]+ and [PtCl(gly-met-S,N,N)], where bpma is bis(2-pyridylmethyl)amine and gly-met-S,N,N is glycyl-l-methionine, was studied as a function of the entering nucleophile concentration and temperature. Reactions between the platinum(II) complexes and thiourea (TU), iodides (I−), and nitrites(III) (NO2−) were carried out in aqueous solutions using conventional UV-VIS spectrophotometry. Suitable ionic conditions were reached by an addition of 0.1 M NaClO4 and 0.01 M NaCl (to suppress hydrolysis). The second-order rate constants, k 2, for the studied reactions with NO2− varied between 0.036–0.038 M−1 s−1, and for the reactions with TU between 0.095–1.06 M−1 s−1, respectively. The reaction between TU and the [PtCl(bpma)]+ ion is ten times faster than that of the [PtCl(gly-met-S,N,N)] complex. An analysis of the activation parameters, ΔH ≠ and ΔS ≠, for the selected reactions clearly shows their associative nature.

scholarly journals The mechanism of reduction of single-site redox proteins by ascorbic acid

1979 ◽  
Vol 177 (2) ◽  
pp. 641-648 ◽  
Author(s):  
A I Al-Ayash ◽  
M T Wilson
Keyword(s):  
Ascorbic Acid ◽  
Rate Constants ◽  
Activation Parameters ◽  
Outer Sphere ◽  
Reducing Agent ◽  
Second Order ◽  
Single Site ◽  
Redox Proteins ◽  
Order Rate ◽  
Temperature Dependences

The reduction of single-site haem and copper redox proteins by ascorbic acid was studied as a function of pH. Evidence is presented that indicates that the double-deprotonated ascorbate anion, ascorbate2-, is the reducing agent, and the pH-independent second-order rate constants for reduction by this species are given. Investigation of the temperature dependences of these rate constants have yielded the values of the activation parameters (delta H++ and delta S++) for reduction. These values, together with ligand-replacement studies, suggest that ascorbate2- acts as an outer-sphere reductant for these proteins. Reasons to account for the apparent inability of ascorbic acid to reduce the alkaline conformer of mammalian ferricytochrome c are suggested.

Kinetics of ozone reactions with 1-naphthalene, 1,5-naphthalene and 3-nitrobenzene sulphonic acids in aqueous solutions

2001 ◽  
Vol 44 (5) ◽  
pp. 7-13 ◽  
Author(s):  
V. Calderara ◽  
M. Jekel ◽  
C. Zaror
Keyword(s):  
Aqueous Solutions ◽  
Hydroxyl Radicals ◽  
Oxidation Kinetics ◽  
Order Kinetic ◽  
Rate Of Reaction ◽  
Direct Reactions ◽  
Kinetics Of ◽  
By Products ◽  
Ozone Reactions ◽  
Primary Oxidation

This paper describes the ozone oxidation kinetics of 1-naphthalene (1NS), 1,5-naphthalene (1,5NDS), and 3-nitrobenzene (3NBS) sulphonic acid. The presence of hydroxyl radicals and their effect on the overall rate of reaction was studied. Second order kinetic constants of direct reactions were estimated at around 252 M-1s-1, 41 M-1s-1 and 22 M-1s-1, for 1NS, 1,5NDS, and 3NBS sulphonic acids, respectively. At pH 3, the indirect reaction accounted for 2%, 15% and 4% of total primary oxidation of 1NS, 1,5NBS, and 3NBS sulphonic acids, respectively. At pH 9, indirect reaction contribution increased to 73%, 84% and 48%, respectively. C4 compounds (maleic and fumaric acids), C2 (oxalic), C1 (formic) and sulphate were identified as oxidation by-products in all cases. TOC slowly decreased throughout ozonation, reaching around 40-60% and 60-70% reduction over 90 minutes at pH 7 and 3, respectively.

Kinetik der Reaktion von Papain mit Bromacetamid / Kinetics of the reaction of papain with bromoacetamide

1971 ◽  
Vol 26 (1) ◽  
pp. 43-46 ◽  
Author(s):  
Hans-Gerhard Löffler ◽  
Friedhelm Schneider ◽  
Helmut Wenck
Keyword(s):  
Rate Constants ◽  
Turning Point ◽  
Ph Dependence ◽  
Activation Parameters ◽  
Second Order ◽  
Order Rate ◽  
Ph Range ◽  
Kinetics Of

The pH-dependence of the second order rate constants of the reaction of papain with bromoacetamide in the pH-range 5,5-8,5 is described by a curve with a turning point corresponding to a pK 7,3 ± 0,1 at 25°. This is the pK of a catalytically essential imidazole residue. The activation parameters of the reaction of papain with bromoacetamide were determined. The second order rate constants at pH 7 for the reaction is 200 times greater than for the reaction of bromoacetamide with simple SH-compounds.

scholarly journals Recombination of Poly(Acrylic Acid) Radicals in Acidic Aqueous Solutions: A Pulse Radiolysis Study

2021 ◽  
Vol 11 (21) ◽  
pp. 10142
Author(s):  
Małgorzata Matusiak ◽  
Sławomir Kadłubowski ◽  
Piotr Ulański
Keyword(s):  
Acrylic Acid ◽  
Aqueous Solutions ◽  
Ph Dependence ◽  
Polymer Concentration ◽  
Second Order ◽  
Order Kinetic ◽  
Initial Number ◽  
Linear Charge Density ◽  
Kinetics Of ◽  
Poly Acrylic Acid

Carbon-centered radicals have been randomly generated on the chains of poly(acrylic acid), PAA, the simplest synthetic anionic polyelectrolyte, by pulse-irradiating its dilute, oxygen-free aqueous solutions by 6 MeV electron beam. In some experiments, oligo(acrylic acid), OAA, and propionic acid, PA, were used as PAA models. Recombination kinetics of PAA radicals has been followed by fast spectrophotometry. A strong pH dependence of radical lifetime on pH, and thus on the linear charge density due to deprotonated carboxylate groups, has been confirmed, while a weaker amplitude of pH dependence was observed for OAA and PA. Decay kinetics of PAA radicals in the protonated state, at pH 2, have been studied in some detail. At moderate doses of ionizing radiation, resulting in a moderate average initial number of radicals per chain, ZR0, the decay can be satisfactorily described by a second-order kinetic model, but a somewhat better fit is obtained by using a dispersive kinetics approach. While for a constant polymer concentration the reciprocal half-lives are proportional to the initial radical concentrations, such a data series for different PAA concentrations do not overlap, indicating that the overall radical concentration is not the decisive factor controlling the kinetics. Arranging all data, in the form of second-order rate constants, as a function of the average initial number of radicals per chain allows one to obtain a common dependence. The latter seems to consist of two parts: a horizontal one at low ZR0 and another one of positive slope at higher ZR0. This is interpreted as two kinetic regimes where two distinct reactions dominate, intermolecular and intramolecular recombination, respectively. Comparison of the low ZR0 data with calculations based on the translational diffusion model indicate that the latter is not the rate-controlling process in intermolecular recombination of polymer radicals; segmental diffusion is the more likely candidate.

Kinetics of Environmental Averaging, and the Stereochemistry of (CH3)ClGe(C5H7O2)2. A Case of a Second Order Kinetic Process

1975 ◽  
Vol 53 (3) ◽  
pp. 448-454 ◽  
Author(s):  
Ken A. Hersh ◽  
Nick Serpone
Keyword(s):  
Activation Parameters ◽  
Second Order ◽  
Bond Rupture ◽  
Methyl Groups ◽  
Order Kinetic ◽  
Line Broadening ◽  
Ring Proton ◽  
Kinetics Of ◽  
Oxygen Bond ◽  
Proper Orientation

Dynamic n.m.r. studies on the stereochemistry of (CH3)ClGe(C5H7O2)2 (acac = C5H7O2−), indicate that the complex adopts the cis configuration in CDCl3–CCl4 solutions. Kinetics of environmental averaging of the acac ring proton (—CH=) and acac methyl groups between the respective nonequivalent sites in the C1 isomer have been investigated in the temperature range −31.0 to 23.1° by line-broadening techniques. Kinetics of the averaging process are second order in complex concentration. Activation parameters are: Ea = 6.0 ± 0.3 kcal/mol, ΔS≠ = −30 ± 1 e.u., and k25 = 1.6 × 102 M−1 S−1. Rearrangements are viewed as occurring via a germanium–oxygen bond rupture as a first step to yield a five-coordinate intermediate. The rate-determining sequence is thought to involve proper orientation of two five-coordinate species prior to formation of a bis-acac bridged dimer.

Synthesis and Characterization of Chitosan templated Mesoporous Silica: Efficient use of Mesoporous Silica in the removal of Cu(II) from Aqueous Solutions

2016 ◽  
Vol 4 (2) ◽  
pp. 105-112
Author(s):  
Lalchhing puii ◽  
◽  
Seung-Mok Lee ◽  
Diwakar Tiwari ◽  
◽  
...  
Keyword(s):  
Mesoporous Silica ◽  
Aqueous Solutions ◽  
Background Electrolyte ◽  
Second Order ◽  
Order Kinetic ◽  
Sorption Data ◽  
Column Reactor ◽  
Wide Ph Range ◽  
Freundlich Adsorption Isotherm ◽  
Pseudo Second Order

A mesoporous silica was synthesized by annealing (3-Aminopropyl) triethoxysilane grafted chitosan at 800˚C. The mesoporous silica was characterized by the XRD (X-ray diffraction) analysis. The BET specific surface area and pore size of silica was found to be 178.42 m2/g and 4.13 nm. The mesoporous silica was then employed for the efficient remediation of aqueous solutions contaminated with Cu(II) under batch and column reactor operations. The mesoporous silica showed extremely high per cent removal of Cu(II) at wide pH range i.e., pH ~2.0 to 7.0. Relatively a fast uptake of Cu(II) was occurred and high percentage removal was obtained at initial concentrations studied from 1.0 to 15.0 mg/L. The equilibrium state sorption data were utilized for the Langmuir and Freundlich adsorption isotherm studies. Moreover, the effect of an increase in background electrolyte concentrations from 0.0001 to 0.1 mol/L NaNO3 was assessed for the uptake of Cu(II) by mesoporous silica. The equilibrium sorption was achieved within 240 min of contact and the kinetic data is best fitted to the pseudo-second-order and fractal like pseudo-second-order kinetic models. In addition, the mesoporous silica was used for dynamic studies under column reactor operations. The breakthrough curve was then used for the non-linear fitting of the Thomas equation and the loading capacity of the column for Cu(II) was estimated.

Kinetics of the reaction between hexamethylenediisocyanate and 1-pentanol

1983 ◽  
Vol 48 (11) ◽  
pp. 3279-3286
Author(s):  
Slavko Hudeček ◽  
Miloslav Bohdanecký ◽  
Ivana Hudečková ◽  
Pavel Špaček ◽  
Pavel Čefelín
Keyword(s):  
Liquid Chromatography ◽  
Rate Constants ◽  
Reversed Phase ◽  
Order Reaction ◽  
Second Order ◽  
Second Order Reaction ◽  
Reversed Phase Liquid Chromatography ◽  
Consecutive Reactions ◽  
Phase Liquid ◽  
Kinetics Of

The reaction between hexamethylenediisocyanate and 1-pentanol in toluene was studied by means of reversed-phase liquid chromatography. By employing this method, it was possible to determine all components of the reaction mixture including both products, i.e. N-(6-isocyanate hexyl)pentylcarbamate and N,N'-bis(pentyloxycarbonyl)hexamethylenediamine. Relations for the calculation of kinetic constants were derived assuming a competitive consecutive second-order reaction. It was demonstrated that the reaction involved in this case is indeed a second-order reaction, and the rate constants of the first and second consecutive reactions were determined.

Determination of the Nucleophilicity of Tricarbonyliron Coordinated Cyclohepta-1,3,5-triene

1999 ◽  
Vol 64 (11) ◽  
pp. 1770-1779 ◽  
Author(s):  
Herbert Mayr ◽  
Karl-Heinz Müller
Keyword(s):  
Gibbs Energy ◽  
Ambient Temperature ◽  
Rate Constants ◽  
Second Order ◽  
Order Rate ◽  
Electrophilic Additions ◽  
Kinetics Of

The kinetics of the electrophilic additions of four diarylcarbenium ions (4a-4d) to tricarbonyl(η4-cyclohepta-1,3,5-triene)iron (1) have been studied photometrically. The second-order rate constants match the linear Gibbs energy relationship log k20 °C = s(E + N) and yield the nucleophilicity parameter N(1) = 3.69. It is concluded that electrophiles with E ≥ -9 will react with complex 1 at ambient temperature.

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