The mechanism of the homogeneous,unimolecular gas‐phase elimination kinetic of 1,1‐dimethoxycyclohexane: experimental and theoretical studies

The gas‐phase elimination of 1,1‐dimethoxycyclohexane yielded 1‐methoxy‐1‐cyclohexene and methanol. The kinetics were determined in a static system, with the vessels deactivated with allyl bromide, and in the presence of the free radical inhibitor cyclohexene. The working temperature was 310–360 °C and the pressure was 25–85 Torr. The reaction was found to be homogeneous, unimolecular, and follows a first‐order rate law. The temperature dependence of the rate coefficients is given by the following Arrhenius equation: log k(s^?1) = [(13.82 ± 0.07) – (193.9 ± 1.0)(kJ mol^?1)](2.303RT)^?1; r = 0.9995. Theoretical calculations were carried out using density functional theory (DFT) functionals B3LYP, MPW1PW91, and PBE with the basis set 6‐31G(d,p) and 6‐31G++(d,p). The calculated values for the energy of activation and enthalpy of activation are in reasonably good agreement with the experimental values using the PBE/6‐31G (d,p) level of theory. Both experimental results and theoretical calculations suggest a molecular mechanism involving a concerted polar four‐membered cyclic transition state. The transition state structure of methanol elimination from 1,1‐dimethoxycyclohexane is characterized by a significantly elongated C? O bond, while the C_β? H bond is stretched to a smaller extent, as compared to the reactant. The process can be described as moderately asynchronic with some charge separation in the TS. Copyright © 2010 John Wiley & Sons, Ltd.     

Catalysis by hydrogen chloride in the gas‐phase elimination kinetics of 2‐phenyl‐2‐propanol and 3‐methyl‐1‐buten‐3‐ol

A homogeneous, molecular, gas‐phase elimination kinetics of 2‐phenyl‐2‐propanol and 3‐methyl‐1‐ buten‐3‐ol catalyzed by hydrogen chloride in the temperature range 325–386 °C and pressure range 34–149 torr are described. The rate coefficients are given by the following Arrhenius equations: for 2‐phenyl‐2‐propanol log k₁ (s^?1) = (11.01 ± 0.31) ? (109.5 ± 2.8) kJ mol^?1 (2.303 RT)^?1 and for 3‐methyl‐1‐buten‐3‐ol log k₁ (s^?1) = (11.50 ± 0.18) ? (116.5 ± 1.4) kJ mol^?1 (2.303 RT)^?1. Electron delocalization of the CH₂?CH and C₆H₅ appears to be an important effect in the rate enhancement of acid catalyzed tertiary alcohols in the gas phase. A concerted six‐member cyclic transition state type of mechanism appears to be, as described before, a rational interpretation for the dehydration process of these substrates. Copyright © 2007 John Wiley & Sons, Ltd.     

Experimental and theoretical study of the mechanism for the kinetic of elimination of methyl carbazate in the gas phase

The elimination kinetic of methyl carbazate in the gas phase was determined in a static system over the temperature range of 340–390 °C and pressure range of 47–118 Torr. The reaction is homogeneous, unimolecular, and obeys a first order rate law. The decomposition products are methyl amine, nitrous acid, and CO gas. The variation of the rate coefficients with temperatures is given by the Arrhenius expression: log k₁ (s^?1) = (11.56 ± 0.34) ? (180.7 ± 4.1) kJ mol^?1(2.303 RT)^?1. The estimated kinetics and thermodynamics parameters are in good agreement to the experimental values using B3LYP/6‐31G (d,p), and MP2/6‐31G (d,p) levels of theory. These calculations imply a molecular mechanism involving a concerted non‐synchronous quasi three‐membered ring cyclic transition state to give an unstable intermediate, 1,2‐oxaziridin‐3‐one. Bond order analysis and natural charges implies that polarization of O (alkyl)? C (alkyl) bond of the ester is rate determining in this reaction. Copyright © 2008 John Wiley & Sons, Ltd.     

Joint theoretical and experimental study of the gas‐phase elimination kinetics of tert‐butyl ester of carbamic,N, N‐dimethylcarbamic,N‐hydroxycarbamic acids and 1‐(tert‐butoxycarbonyl)‐imidazole

The gas‐phase elimination kinetics of the title compounds were carried out in a static reaction system and seasoned with allyl bromide. The working temperature and pressure ranges were 200–280 °C and 22–201.5 Torr, respectively. The reactions are homogeneous, unimolecular, and follow a first‐order rate law. These substrates produce isobutene and corresponding carbamic acid in the rate‐determining step. The unstable carbamic acid intermediate rapidly decarboxylates through a four‐membered cyclic transition state (TS) to give the corresponding organic nitrogen compound. The temperature dependence of the rate coefficients is expressed by the following Arrhenius equations: for tert‐butyl carbamate logk₁ (s^?1) = (13.02 ± 0.46) – (161.6 ± 4.7) kJ/mol(2.303 RT)^?1, for tert‐butyl N‐hydroxycarbamate logk₁ (s^?1) = (12.52 ± 0.11) – (147.8 ± 1.1) kJ/mol(2.303 RT)^?1, and for 1‐(tert‐butoxycarbonyl)‐imidazole logk₁ (s^?1) = (11.63 ± 0.21)–(134.9 ± 2.0) kJ/mol(2.303 RT)^?1. Theoretical studies of these elimination were performed at Møller–Plesset MP2/6‐31G and DFT B3LYP/6‐31G(d), B3LYP/6‐31G(d,p) levels of theory. The calculated bond orders, NBO charges, and synchronicity (Sy) indicate that these reactions are concerted, slightly asynchronous, and proceed through a six‐membered cyclic TS type. Results for estimated kinetic and thermodynamic parameters are discussed in terms of the proposed reaction mechanism and TS structure. Copyright © 2007 John Wiley & Sons, Ltd.     

Combined experimental and theoretical studies of the elimination kinetic of 2‐methoxytetrahydropyran in the gas phase

The products formed in 2‐methoxytetrahydropyran elimination reaction in the gas phase are 3, 4‐dihydro‐2H‐pyran and methanol. The kinetic study was carried out in a static system, with the vessels deactivated with allyl bromide, and the presence of the free radical suppressor toluene. Temperature and pressure ranges were 400–450 °C and 25–83 Torr, respectively. The process is homogeneous, unimolecular, and follows a first‐order rate law. The observed rate coefficient is represented by the following equation: log k (s^?1) = (13.95 ± 0.15) ? (223.1 ± 2.1) (kJ mol^?1) (2.303RT)^?1. The reactant exists mainly in two low energy chair‐like conformations, with the 2‐methoxy group in axial or equatorial position. However, the transition state (TS) for the elimination of the two conformers is the same. Theoretical calculations of this reaction were carried for two possible mechanisms from these conformations by using DFT functionals B3LYP, MPW1PW91, and PBE with the basis set 6‐31G(d,p) and 6‐31G++(d,p). The calculation results demonstrate that 2‐methoxytetrahydropyran exists mainly in two conformations, with the 2‐methoy group in axial or equatorial position, that are thermal in equilibrium. The average thermodynamic and kinetic parameters, taking into account the populations of the conformers in the equilibrium, are in good agreement with experimental values at B3LYP/6‐31++(d,p) level of theory. Copyright © 2010 John Wiley & Sons, Ltd.     

Kinetics of the gas‐phase homogeneous unimolecular elimination of selected ethyl esters of 2‐oxo‐carboxylic acids

The gas‐phase elimination kinetics of selected ethyl esters of 2‐oxo‐carboxylic acid have been studied over the temperature range of 270–415 °C and pressures of 37–114 Torr. The reactions are homogeneous, unimolecular, and follow a first‐order rate law in a seasoned static reaction vessel, with an added free radical suppressor toluene. The observed overall and partial rate coefficients are expressed by the following Arrhenius equations:

• Ethyl oxalyl chloride
• log k_overall (s^?1) = (13.22 ± 0.45) ? (179.4 ± 4.9) kJ mol^?1 (2.303 RT)^?1
• Ethyl piperidineglyoxylate
• log k_(CO2) (s^?1) = (12.00 ± 0.30) ? (191.2 ± 3.9) kJ mol^?1 (2.303 RT)^?1
• log k_(CO) (s^?1) = (12.60 ± 0.09) ? (210.7 ± 1.2) kJ mol^?1 (2.303 RT)^?1
• log k_t(overall) (s^?1) = (12.22 ± 0.26) ? (193.4 ± 3.4) kJ mol^?1 (2.303 RT)^?1
• Ethyl benzoyl formate
• log k_(CO2) (s^?1) = (12.89 ± 0.72) ? (203.8 ± 9.0) kJ mol^?1 (2.303 RT)^?1
• log k_(CO) (s^?1) = (13.39 ± 0.31) ? (213.3 ± 3.9) kJ mol^?1 (2.303 RT)^?1
• log k_t(overall) (s^?1) = (13.24 ± 0.60) ? (205.8 ± 7.6) kJ mol^?1 (2.303 RT)^?1

The kinetic and thermodynamic parameters of these reactions, together with those reported in the literature, lead to consider three different mechanistic pathways of elimination. Copyright © 2010 John Wiley & Sons, Ltd.     

The kinetics and mechanism of the homogeneous,unimolecular gas‐phase elimination of 2‐(4‐substituted‐phenoxy)tetrahydro‐2H‐pyranes

The gas‐phase elimination kinetics of tetrahydropyranyl phenoxy ethers: 2‐phenoxytetrahydro‐2H‐pyran, 2‐(4‐methoxyphenoxy)tetrahydro‐2H‐pyran, and 2‐(4‐tert‐butylphenoxy)tetrahydro‐2H‐pyran were determined in a static system, with the vessels deactivated with allyl bromide, and in the presence of the free radical inhibitor toluene. The working temperature and pressure were 330 to 390°C and 25 to 89 Torr, respectively. The reactions yielded DHP and the corresponding 4‐substituted phenol. The eliminations are homogeneous, unimolecular, and satisfy a first‐order rate law. The Arrhenius equations for decompositions were found as follows:

• 2‐phenoxytetrahydro‐2H‐pyran
• log k₁ (s^?1) = (14.18 ± 0.21) ? (211.6 ± 0.4) kJ mol^?1 (2.303 RT)^?1
• 2‐(4‐methoxyphenoxy)tetrahydro‐2H‐pyran
• log k₁ (s^?1) = (14.11 ± 0.18) ? (203.6 ± 0.3) kJ mol^?1 (2.303 RT)^?1
• 2‐(4‐tert‐butylphenoxy)tetrahydro‐2H‐pyran
• log k₁ (s^?1) = (14.08 ± 0.08) ? (205.9 ± 1.0) kJ mol^?1 (2.303 RT)^?1

The analysis of kinetic and thermodynamic parameters for thermal elimination of 2‐(4‐substituted‐phenoxy)tetrahydro‐2H‐pyranes suggests that the reaction proceeds via 4‐member cyclic transition state. The results obtained confirm a slight increase of rate constant with increasing electron donating ability groups in the phenoxy ring. The pyran hydrogen abstraction by the oxygen of the phenoxy group appears to be the determinant factor in the reaction rate.     

Thermal Cross‐Linking of Poly(Vinyl Methyl Ether). III. Rheological Kinetics of Cross‐Linking Reaction

Abstract

The kinetics of the thermally activated cross‐linking reaction of poly(vinyl methyl ether) (PVME) were investigated rheologically by evaluating the viscoelastic material functions such as elastic storage modulus, G′, viscous loss modulus, G″ and complex dynamic viscosity, η*, during the curing process, both isothermally and nonisothermally. The isothermal kinetics reaction was described using a phenomenological equation based on the Malkin and Kulichikhin model, which was predicated originally for the isothermal curing kinetics of thermosetting polymers followed by differential scanning calorimetery (DSC) and was found to be applicable for rheokinetic reactions as well. An excellent representation of the data was obtained using this model; the rate of the reaction was found to be second order regardless of the temperature, which is in good agreement with literature data. The temperature dependence of the cross‐linking rate constant was described by an Arrhenius plot with an apparent activation energy equal to 60–62 kJ mol^?1, in reasonable agreement with the value obtained previously from the temperature dependence of gel time, t _gel. The nonisothermal kinetics reaction rate was described by a model that included the classical rate equation, the Arrhenius equation, and the time–temperature relationships. The apparent activation energy obtained nonisothermally was found to be frequency independent and equal to 72 kJ mol^?1, in very good agreement with the value obtained isothermally from the temperature dependence of t _gel in part II.     

The keto-enol equilibrium in substituted acetaldehydes: focal-point analysis and ab initio limit

High-level ab initio electronic structure calculations up to the CCSD(T) theory level, including extrapolations to the complete basis set (CBS) limit, resulted in high precision energetics of the tautomeric equilibrium in 2-substituted acetaldehydes (XH₂C-CHO). The CCSD(T)/CBS relative energies of the tautomers were estimated using CCSD(T)/aug-cc-pVTZ, MP3/aug-cc-pVQZ, and MP2/aug-cc-pV5Z calculations with MP2/aug-cc-pVTZ geometries. The relative enol (XHC?=?CHOH) stabilities (ΔE _{e,CCSD(T)/CBS}) were found to be 5.98?±?0.17, ?1.67?±?0.82, 7.64?±?0.21, 8.39?±?0.31, 2.82?±?0.52, 10.27?±?0.39, 9.12?±?0.18, 5.47?±?0.53, 7.50?±?0.43, 10.12?±?0.51, 8.49?±?0.33, and 6.19?±?0.18?kcal?mol^?1 for X?=?BeH, BH₂, CH₃, Cl, CN, F, H, NC, NH₂, OCH₃, OH, and SH, respectively. Inconsistencies between the results of complex/composite energy computations methods Gn/CBS (G2, G3, CBS-4M, and CBS-QB3) and high-level ab initio methods (CCSD(T)/CBS and MP2/CBS) were found. DFT/aug-cc-pVTZ results with B3LYP, PBE0 (PBE1PBE), TPSS, and BMK density functionals were close to the CCSD(T)/CBS levels (MAD?=?1.04?kcal?mol^?1).     

Gas‐phase oxidation of CH2 = C(CH3)CH2Cl initiated by OH radicals and Cl atoms: kinetics and fate of the alcoxy radical formed

Relative kinetics of the reactions of OH radicals and Cl atoms with 3‐chloro‐2‐methyl‐1‐propene has been studied for the first time at 298 K and 1 atm by GC‐FID. Rate coefficients are found to be (in cm³ molecule^?1 s^?1): k₁ (OH + CH₂ = C(CH₃)CH₂Cl) = (3.23 ± 0.35) × 10^?11, k₂ (Cl + CH₂ = C(CH₃)CH₂Cl) = (2.10 ± 0.78) × 10^?10 with uncertainties representing ± 2σ. Product identification under atmospheric conditions was performed by solid phase microextraction/GC‐MS for OH reaction. Chloropropanone was identified as the main degradation product in accordance with the decomposition of the 1,2‐hydroxy alcoxy radical formed. Additionally, reactivity trends and atmospheric implications are discussed. Copyright © 2015 John Wiley & Sons, Ltd.     

Phase transition and freezing of ionic disorder in CsNO2 and TINO2 crystals2

The heat capacities of CsNO₂ and TlNO₂ have been measured in the temperature region between 13 and 350 K. The phase transitions of CsNO₂ and TlNO₂ were found at (209.16 ± 0.10)K and (282.4 ± 0.1)K. The enthalpy and entropy of the phase transition were (3.45 ± 0.20) kJ mol^?1 and (17.2 ± 1.0) JK^?1 mol^?1 for the former, and (6.44 ± 0.31) kJ mol^?1 and (23.8 ± 1.1) JK^?1 mol^?1 for the latter. The glass transitions were found around 42 K in CsNO₂ and around 60 K for TlNO₂, respectively. The corresponding dielectric relaxations were observed between 58 and 130 K for CsNO₂ in the frequency range between 10² and 10⁵ Hz and between 80 and 180 K for TlNO₂ in the frequency range between 2 × 10² and 10⁵ Hz. The calorimetric and dielectric relaxation times yielded a straight line in the Arrhenius plot over a wide time scale ranging from 10^?6 to 10⁵ sec. The slope gave the activation enthalpy of 13.8 kJ mol^?1 and 19.5 kJ mol^?1 for CsNO₂ and TlNO₂, respectively. The transition entropy supplemented by a residual entropy R ln 3 for CsNO₂ and R ln 2 for TlNO₂ gave (26.3 ± 1.0) JK^?1 mol^?1 and (29.6 ± 1.1) JK^?1 mol^?1 for the orientational entropy of the NO₂^? ion in the high-temperature phase. Based on the packing and symmetry considerations, these entropies were interpreted by the model which included two different sets of orientations of the NO₂^? ions parallel to [110] and [111] in the CsCl type unit cell. The existence of the different sets of orientation was proved by the doublet (Δv ~ 10 cm^?1) of the Raman spectrum of the bending mode of the NO₂^? ion in the cubic phase of the CsNO₂ crystal. The band narrowed to an ordinary singlet with increasing temperature. This observation was accounted for as the motional narrowing in which the NO₂^? ion felt an averaged field of the two different sets owing to the increased rate of jumping as the temperature increased.     

Dynamics of [n.3]paracyclophanes (n = 2 – 4) as studied by NMR. Obtaining separate Arrhenius parameters for two dynamic processes in [4.3]paracyclophane

Extending our earlier findings for [3.3]paracyclophane, NMR line shape studies of the conformational dynamics in [3.2] and [4.3]paracyclophanes are reported, of which the former is conformationally homogeneous and the latter occurs in two enantiomeric forms. For [3.2]paracyclophane, the Arrhenius activation energy E_a = 11.6 ± 0.1 kcal/mol and preexponential factor log (A/s^?1) = 12.92 ± 0.07 were found. In [4.3]paracyclophane, the conformational dynamics are quite complicated because, apart from interconversions of each enantiomer into itself proceeding via inversion of the propano bridge with rate constant k₁, the enantiomers mutually rearrange with rate constant k₂ due to inversion of the butano bridge. The determination of Arrhenius parameters from dynamic ¹H spectra of the aromatic protons for these two conformational processes (E_a = 11.2 ± 0.5 kcal/mol and log (A/s^?1) = 13.6 ± 0.5 for the former, and E_a = 9.7 ± 0.4 kcal/mol and log (A/s^?1) = 13.2 ± 0.4 for the latter) is the highlight of this work. In the investigated temperature range, in [4.3]paracyclophane, the occurrence of other conformational processes beyond those mentioned above can be excluded, because they would produce different line shape patterns than those actually observed. Copyright © 2013 John Wiley & Sons, Ltd.     

The heat capacity of the layer compounds (CH3CH2CH2NH3)2MnCl4 and (CH3CH2CH2NH3)2CdCl4 from 10 K TO 300 K

The heat capacity of the layer compounds tetrachlorobis (n-propylammonium) manganese II and tetrachlorobis (n-propylammonium) cadmium II, (CH₃CH₂CH₂NH₃)₂MnCl₄ and (CH₃CH₂CH₂NH₃)₂CdCl₄ respectively, has been measured over the temperature range 10 K ?T ? 300 K.Two known structural phase transitions were observed for the Mn compound in this temperature region: at T = 112.8 ± 0.1 K (ΔH_t= 586 ± 2 J mol^?1; ΔS_t = 5.47 ± 0.02 J K^?1mol^?1) and at T =164.3 ± (ΔH_t = 496 ± 7 J mol^?1; ΔS_t =3.29 ± 0.05 J K^?1mol^?1). The lower transition is known to be from a monoclinic structure to a tetragonal structure, while the upper is from the tetragonal phase to an orthorhombic one. From comparison with the results for the corresponding methyl Mn compound it is deduced that the lower transition primarily involves changes in H-bonding while the upper transition involves motion in the propyl chain.A new structural phase transition was observed in the Cd compound at T= 105.5 ± 0.1 K (ΔH_t= 1472.3 ± 0.1 J mol^?1; ΔS_t = 13.956 ± 0.001 J K^?1mol^?1), in addition to two transitions that have been observed previously by other techniques. The higher of these transitions(T = 178.7 ± 0.3 K; ΔH_t = 982 ± 4 J mol^?1 ΔS_t = 6.16 ± 0.02 J K^? mol^?1) is known to be between two orthorhombic structures, while the structural changes at the lower transition (T= 156.8 ± 0.2 K; ΔH_t = 598 ± 5 J mol^?1, ΔS_t = 3.85 ± 0.03 J K^?1 mol^?1) and at the new transition are not known. It is proposed that these two transitions correspond respectively to the tetragonal to orthorhombic and monoclinic to tetragonal transitions in the propyl Mn compounds.In addition to the structural phase transitions (CH₃CH₂CH₂NH₃)₂MnCl₄ magnetically orders at t? 130 K. The magnetic contribution to the heat capacity is deduced from the heat capacity of the corresponding diamagnetic Cd compound and is of the form expected for a quasi 2-dimensional Heisenberg antiferromagnet.     

Nucleophilic reactivity of thiolate, hydroxide and phenolate ions towards a model O-arylated diazeniumdiolate prodrug in aqueous and cationic surfactant media

The kinetics of aromatic nucleophilic substitution of the nitric oxide‐generating diazeniumdiolate ion, DEA/NO, by thiols (L ‐glutathione, L ‐cysteine, DL ‐homocysteine, 1‐propanethiol, 2‐mercaptoethanol, and sodium thioglycolate) from the prodrug, DNP‐DEA/NO, has been examined in aqueous solution and in solutions of cationic DOTAP vesicles. Second‐order rate constants in buffered aqueous solutions (k_RS‐ = 3.48–30.9 M^?1 s^?1; 30 °C) gave a linear Brønsted plot (β_nuc = 0.414 ± 0.068) consistent with the rate‐limiting S_NAr nucleophilic attack by thiolate ions. Cationic DOTAP vesicles catalyze the thiolysis reactions with rate enhancements between 11 and 486‐fold in Tris‐HCl buffered solutions at pH 7.4. The maximum rate increase was obtained with thioglycolate ion. Thiolysis data are compared to data for nucleophilic displacement by phenolate (k_PhO‐ = 0.114 M^?1 s^?1) and hydroxide (k_OH‐ = 1.82 × 10^?2 M^?1 s^?1, 37 °C) ions. The base hydrolysis reaction is accelerated by CTAB micelles and DODAC vesicles, with the vesicles being ca 3‐fold more effective as catalysts. Analysis of the data using pseudo‐phase ion‐exchange (PIE) formalism implies that the rate enhancement of the thiolysis and base hydrolysis reactions is primarily due to reactant concentration in the surfactant pseudo‐phase. Copyright © 2009 John Wiley & Sons, Ltd.     

Kinetics and mechanism of the reactions of O‐aryl S‐(4‐nitrophenyl) dithiocarbonates with anilines in aqueous ethanol

The reactions of O‐(4‐methylphenyl) S‐(4‐nitrophenyl) dithiocarbonate and O‐(4‐chlorophenyl) S‐(4‐nitrophenyl) dithiocarbonate with a series of anilines are subjected to a kinetic investigation in 44 wt% ethanol–water, at 25.0 °C and an ionic strength of 0.2 M. The reactions are followed spectrophotometrically at 420 nm (appearance of 4‐nitrobenzenethiolate anion). Under excess amine, pseudo‐first‐order rate coefficients (k_obs) are found. For the reactions of both substrates with anilines, plots of k_obs versus free amine concentration at constant pH are nonlinear upwards, according to a second‐order polynomial equation. This kinetic behavior is in agreement with a stepwise mechanism consisting of two tetrahedral intermediates, one zwitterionic (T^±) and the other anionic (T^?), with a kinetically significant proton transfer from T^± to an aniline to yield T^?. The rate equation was derived from the proposed mechanism. By nonlinear least‐squares fitting of the rate equation to the experimental data, values of the rate micro‐coefficients involved in both steps were determined. Copyright © 2009 John Wiley & Sons, Ltd.     

The effect of NH<Subscript>4</Subscript>NO<Subscript>3</Subscript> towards the conductivity enhancement and electrical behavior in methyl cellulose-starch blend based ionic conductors

Solid polymer electrolytes based on methyl cellulose (MC)-potato starch (PS) blend doped with ammonium nitrate (NH₄NO₃) are prepared by solution cast technique. The interaction between the electrolyte’s materials is proven by Fourier transform infrared (FTIR) analysis. The thermal stability of the electrolytes is obtained from thermogravimetric analysis (TGA). The room temperature conductivity of undoped 60 wt.% MC-40 wt.% PS blend film is identified to be (1.04 ± 0.19) × 10^?11 S cm^?1. The addition of 30 wt.% NH₄NO₃ to the polymer blend has optimized the room temperature conductivity to (4.37 ± 0.16) × 10^?5 S cm^?1. Conductivity trend is verified by X-ray diffraction (XRD), differential scanning calorimetry (DSC) and dielectric analysis. Temperature-dependence of conductivity obeys Arrhenius rule. Conductivity is found to be influenced by the number density (n) and mobility (μ) of ions. From transference number measurements (TNM), ions are found to be the dominant charge carriers.     

Green electrolytes based on dextran-chitosan blend and the effect of NH<Subscript>4</Subscript>SCN as proton provider on the electrical response studies

Dextran-chitosan blend added with ammonium thiocyanate (NH₄SCN)-based solid polymer electrolytes are prepared by solution cast method. The interaction between the components of the electrolyte is verified by Fourier transform infrared (FTIR) analysis. The blend of 40 wt% dextran-60 wt% chitosan is found to be the most amorphous ratio. The room temperature conductivity of undoped 40 wt% dextran-60 wt% chitosan blend film is identified to be (3.84?±?0.97)?×?10^?10 S cm^?1. The inclusion of 40 wt.% NH₄SCN to the polymer blend has optimized the room temperature conductivity up (1.28?±?0.43)?×?10^?4 S cm^?1. Result from X-ray diffraction (XRD) and differential scanning calorimetry (DSC) analysis shows that the electrolyte with the highest conductivity value has the lowest degree of crystallinity (χ _c) and the glass transition temperature (T _g), respectively. Temperature-dependence of conductivity follows Arrhenius theory. From transport analysis, the conductivity is noticed to be influenced by the mobility (μ) and number density (n) of ions. Conductivity trend is further verified by field emission scanning electron microscopy (FESEM) and dielectric results.     

A study of the adsorption of oxygen on Ni(111) using auger electron spectroscopy: Chemical shifts and valence spectra

Auger electron spectra have been recorded when oxygen is adsorbed on a Ni(111) single crystal surface. For the coverage range θ < 1, an analysis of the plot of the peak to peak height (H) of the oxygen KVV (516 eV) transition versus the total number of molecules cm^2? impinging on the surface (molecular beam dosing) shows agreement with the kinetic mechanism proposed by Morgan and King [Surface Sci. 23 (1970) 259] for the adsorption of oxygen on polycrystalline nickel films. In this coverage range, no energy shifts of the nickel or oxygen Auger peaks were recorded.At coverages θ > 1 (standard dosing procedure) shifts in the valence spectra M_{2, 3}VV (61 eV) and L₃M_{2, 3}V (782 eV) of ?2.3 eV and ?1.8eV respectively are recorded at 1.4 × 10^?2 torr-sec. Up to these coverages no shift of the L₃VV transition (849 eV) is observed. A chemical shift of ?2.1 eV is recorded in the L₃M_{2, 3}M_{2, 3} Auger transition (716 eV) at 1.4 × 10^?2 torr-sec.In the coverage range θ > 1, shifts in the energy of the oxygen Auger peaks are observed. At 5.8 × 10^?3 torr-sec. the KVV (516 eV) and KL₁V (495.2 ± 0.3 eV) transitions show shifts of ?1.5 eV and ?(1.0 ±0.3) eV respectively. No shift up to this coverage is recorded in the KL₁L₁ (480.6 ± 0.3 eV) transition.     

Rate coefficients for the gas-phase reaction of OH radical with α-pinene: an experimental and computational study

The rate coefficient for the gas-phase reaction of OH radical with α-pinene was measured at 298 K using relative rate methods, with propylene as a reference compound. The ratio of the rate coefficient for the reaction of OH radicals with α-pinene to that of with OH radicals with propylene was measured to be 1.77 ± 0.21. Considering the absolute value of the rate coefficient of the reaction of OH radicals with propylene as (3.01 ± 0.42)×10^?11 cm³ molecule^?1 s^?1, the rate coefficient for the reaction of OH radicals with α-pinene was determined to be (5.33 ± 0.79)×10^?11 cm³ molecule^?1 s^?1. To gain a deeper insight into the reaction mechanism, theoretical calculations were also carried out on this reaction. The rate coefficient of OH radical with α-pinene was calculated using canonical variational transition state theory with small-curvature tunnelling. The kinetics data obtained over the temperature range of 200–400 K were used to derive the Arrhenius expression: k(T) = 3.8×10^?28 T^5.2 exp[2897/T] cm³ molecule^?1 s^?1. The OH-driven atmospheric lifetime (τ) and ozone formation potential of α-pinene were calculated and reported in this work.     

克里奇中间体CH2OO与CF3CF=CF2反应的动力学研究

本文使用OH激光诱导荧光方法研究了结构最简单的克里奇中间体CH₂OO和CF₃CF=CF₂的反应动力学. 在压强为10 Torr条件下，测量了温度在283，298，308和318 K的反应速率常数，分别为(1.45±0.14)×10^-13，(1.18±0.11)×10^-13，(1.11±0.08)×10^-13和(1.04±0.08)×10^-13 cm³·molecule^-1·s^-1. 根据阿伦尼乌斯方程，获得该反应的活化能为(-1.66±0.21) kcal/mol. 在6.3∽70 torr压力范围内，未观察到该反应的速率常数存在压力相关.