scholarly journals Microwave Dielectric Measurements of 4-Nitroacetanilide at Different Temperatures in Carbon Tetrachloride Solution

2018 ◽  
Vol 34 (6) ◽  
pp. 3123-3128
Author(s):  
Chitra Manro ◽  
Ritu Jain
Keyword(s):  
Relaxation Time ◽  
Carbon Tetrachloride ◽  
Relaxation Process ◽  
Activation Parameters ◽  
Flow Process ◽  
Dielectric Parameters ◽  
Microwave Dielectric ◽  
Different Temperatures ◽  
Intramolecular Rotation ◽  
Probable Relaxation Time

The dielectric properties of 4-Nitroacetanilide have been discussed at four different temperatures in the dilute solution of carbon tetrachloride at a fixed frequency of 9.27GHz. The values of dielectric constant (εʹ), dielectric loss (εʺ), permittivity at an optical frequency (ε∞) and permittivity at a static frequency (ε0) are measured at different temperatures and mole fractions. The values of these dielectric parameters are used to calculate the values of relaxation time for overall molecular rotation (τ1), relaxation time for intramolecular rotation (τ2), most probable relaxation time (τ0) and dipole moment (μ) at different temperatures. In the present investigation we have found higher values of τ2 which indicate the existence of more than one relaxation process in the solution. The values of energy activation parameters for dielectric relaxation process (∆Fε, ∆Hε and ∆Sε) and viscous flow process (∆Fη, ∆Hη and ∆Sη) are also determined and compared for 4-Nitroacetanilide with carbon tetrachloride at different temperatures. It is observed that we may treat both the process as a rate process.

scholarly journals Molecular Association of Tetramethylurea and Chlorobenzene Molecules in Microwave Frequency Range

2010 ◽  
Vol 65 (10) ◽  
pp. 854-858
Author(s):  
Vimal Sharma ◽  
Nagesh Thakur
Keyword(s):  
Relaxation Time ◽  
Dielectric Relaxation ◽  
Viscous Flow ◽  
Relaxation Process ◽  
Binary Mixtures ◽  
Variation Method ◽  
Dielectric Relaxation Time ◽  
Flow Process ◽  
Dielectric Relaxation Process ◽  
Energy Parameters

The dielectric constant ε´ and dielectric loss ε´´ of the binary mixtures of tetramethylurea (TMU) and chlorobenzene (CB) have been calculated at 9.883 GHz by using standard standing microwave techniques. Gopalakrishna’s single frequency concentration variation method has been used to calculate dipole moment μ and dielectric relaxation time τ for different mole fractions of TMU in the binary mixture at different temperatures of 25 °C, 30 °C, 35 °C, and 40 °C. The variation of dielectric relaxation time with the mole fraction of TMU in the whole concentration range of the binary mixtures was found to be non-monotonic. The solute-solute and solute-solvent type of molecular associations may be proposed based upon above observations. Using Eyring rate equations the energy parameters ΔH, ΔF, and ΔS for the dielectric relaxation process and the viscous flow process have been calculated at the given temperatures. It is found from the comparison of energy parameters that, just like the viscous flow process, the dielectric relaxation process can also be treated as a rate process.

scholarly journals Frequency and Temperature Effects on Dielectric Properties of PEDOT-VC Copolymer

2021 ◽  
Vol 229 ◽  
pp. 01054
Author(s):  
Ouafae Ninis ◽  
Mohammed Bouachrine ◽  
Mustapha Abarkan
Keyword(s):  
Raman Spectroscopy ◽  
Relaxation Time ◽  
Dielectric Properties ◽  
Relaxation Process ◽  
Temperature Effects ◽  
Dc Conductivity ◽  
Dielectric Analysis ◽  
Dielectric Parameters ◽  
Polymeric Compound ◽  
Ftir And Raman Spectroscopy

The copolymer based on Poly(3, 4-Ethylene dioxythiophen) and Poly(n-Vinylcarbazole) was characterized by FTIR and Raman spectroscopy. The temperature and frequency evolutions of dielectric parameters are also plotted and studied. The dependence of ε” on the temperature shows relaxation process for studied copolymer especially with frequencies about 1kHz for the temperatures: 90°C < T < 118°C. The values of ε’∞, ε’’MAX, relaxation time and DC conductivity corresponding to the copolymer are also determined with the aim to provide dielectric analysis involving vital information about this new polymeric compound.

Dielectric relaxation of some aliphatic ester molecules in solutions

1979 ◽  
Vol 57 (7) ◽  
pp. 1035-1038 ◽  
Author(s):  
M. P. Madan
Keyword(s):  
Relaxation Time ◽  
Dielectric Relaxation ◽  
Relaxation Times ◽  
Activation Parameters ◽  
Dielectric Absorption ◽  
Aliphatic Ketones ◽  
Dielectric Data ◽  
Aliphatic Ester ◽  
Aliphatic Esters ◽  
Intramolecular Rotation

The dielectric absorption of several aliphatic esters has been examined in the microwave region over a range of temperatures in n-heptane, cyclohexane, and benzene. The relaxation times and the thermodynamic parameters have been determined using the measured dielectric data. The values of the relaxation time for those solutions for which there are available known data agree well with other determinations. The relaxation times and the various molar activation parameters have been discussed in terms of dipole reorientation by molecular and intramolecular rotation. It would appear that the relaxation behavior of aliphatic esters is similar to that for other aliphatic molecules, such as aliphatic ketones studied previously.

Relaxation processes of some simple aliphatic molecules in dilute solutions

1977 ◽  
Vol 55 (4) ◽  
pp. 297-301 ◽  
Author(s):  
M. P. Madan
Keyword(s):  
Carbon Tetrachloride ◽  
Dielectric Relaxation ◽  
Thermodynamic Parameters ◽  
Relaxation Times ◽  
Relaxation Processes ◽  
Dilute Solutions ◽  
Microwave Region ◽  
Nonpolar Solvents ◽  
Dielectric Data ◽  
Intramolecular Rotation

The dielectric relaxation processes of acetone, cyclohexanone, 4-methyl-2-pentanone, and 4-heptanone in dilute nonpolar solvents, n-heptane, cyclohexane, benzene, and carbon tetrachloride have been studied in the microwave region over a temperature range 10 to 60 °C. The relaxation times and the thermodynamic parameters for the activated states have been determined using the measured dielectric data. The results have been discussed in terms of dipole reorientation by molecular and intramolecular rotation and compared, wherever possible, with other similar studies on aliphatic molecules.

scholarly journals Poly(N-isopropylacrylamide-co-methacrylic acid) microgel stabilized copper nanoparticles for catalytic reduction of nitrobenzene

2015 ◽  
Vol 33 (3) ◽  
pp. 627-634 ◽  
Author(s):  
Zahoor H. Farooqi ◽  
Zonarah Butt ◽  
Robina Begum ◽  
Shanza Rhauf Khan ◽  
Ahsan Sharif ◽  
...  
Keyword(s):  
Copper Nanoparticles ◽  
Methacrylic Acid ◽  
Catalytic Reduction ◽  
Aqueous Media ◽  
Activation Parameters ◽  
Reducing Agent ◽  
Different Temperatures ◽  
Entropy Of Activation ◽  
Micro Reactors

Abstract Poly(N-isopropylacrylamide-co-methacrylic acid) microgels [p(NIPAM-co-MAAc)] were synthesized by precipitation polymerization of N-isopropylacrylamide and methacrylic acid in aqueous medium. These microgels were characterized by dynamic light scattering and Fourier transform infrared spectroscopy. These microgels were used as micro-reactors for in situ synthesis of copper nanoparticles using sodium borohydride (NaBH4) as reducing agent. The hybrid microgels were used as catalysts for the reduction of nitrobenzene in aqueous media. The reaction was performed with different concentrations of cat­alyst and reducing agent. A linear relationship was found between apparent rate constant (kapp) and amount of catalyst. When the amount of catalyst was increased from 0.13 to 0.76 mg/mL then kapp was increased from 0.03 to 0.14 min-1. Activation parameters were also determined by performing reaction at two different temperatures. The catalytic process has been discussed in terms of energy of activation, enthalpy of activation and entropy of activation. The synthesized particles were found to be stable even after 14 weeks and showed catalytic activity for the reduction of nitrobenzene.

scholarly journals Mechanistic aspects of oxidation on L-tyrosine by diperiodatocuprate(III) complex in alkali media: a kinetic model

2009 ◽  
Vol 7 (4) ◽  
pp. 929-937 ◽  
Author(s):  
Nagaraj Shetti ◽  
Rajesh Hegde ◽  
Sharanappa. Nandibewoor
Keyword(s):  
Alkaline Medium ◽  
Activation Parameters ◽  
Spectral Studies ◽  
Slow Step ◽  
Isokinetic Temperature ◽  
Thermodynamic Quantities ◽  
Radical Intermediate ◽  
Different Temperatures ◽  
Reactive Oxidant ◽  
Reaction Constants

AbstractOxidation of an amino acid, L-tyrosine (L-Tyr) by diperiodatocuprate(III) (DPC) in alkaline medium at a constant ionic strength of 0.1 mol dm−3 was studied spectrophotometrically at different temperatures (288.1–313.1 K). The reaction between DPC and L-Tyr in alkaline medium exhibits 1:4 stoichiometry (L-Tyr:DPC). Intervention of free radicals was observed in the reaction. Based on the observed orders and experimental evidence, a mechanism involving monoperiodatocuprate(III) (MPC) as the reactive oxidant species has been proposed. A suitable mechanism is proposed through the formation of a complex and free radical intermediate. The products were identified by spot test and characterized by spectral studies. The reaction constants involved in the different steps of the mechanism were calculated. The activation parameters with respect to slow step of the mechanism were computed and are discussed. The thermodynamic quantities were determined for different equilibrium steps. Isokinetic temperature was also calculated and found to be 252.3 K.

Kinetics and Mechanism of Oxidation of Aliphatic Secondary Alcohols by Benzimidazolium Fluorochromate in Dimethyl Sulphoxide Solvent

2021 ◽  
Vol 37 (3) ◽  
pp. 626-633
Author(s):  
Bhawana Arora ◽  
Jitendra Ojha ◽  
Pallavi Mishra
Keyword(s):  
Activation Parameters ◽  
Sigmatropic Rearrangement ◽  
Dimethyl Sulphoxide ◽  
Secondary Alcohols ◽  
Hydrogen Ions ◽  
Reaction Conditions ◽  
First Order Kinetics ◽  
Aqueous Solvent ◽  
Ester Formation ◽  
Different Temperatures

Oxidation of secondary alcohols is an important part of synthetic organic chemistry. Various studies are carried out at different reaction conditions to determine the best mechanistic pathways. In our study, oxidation of different secondary alcohols was done by using Benzimidazolium Fluorochromate in Dimethyl Sulphoxide, which is a non-aqueous solvent. Oxidation resulted in the formation of ketonic compounds. The reaction showed first order kinetics both in BIFC and in the alcohols. Hydrogen ions were used to catalyze the reaction. We selected four different temperatures to carry out our study. The correlation within the activation parameters like enthalpies and entropies was in accordance with the Exnerʼs criterion. The deuterated benzhydrol (PhCDOHPh) oxidation exhibited an important primary kinetic isotopic effect (kH / kD = 5.76) at 298 K. The solvent effect was studied using the multiparametric equations of Taft and Swain. There was no effect of addition of acrylonitrile on the oxidation rate. The mechanism involved sigmatropic rearrangement with the transfer of hydrogen ion taking place from alcohol to the oxidant via a cyclic chromate ester formation.

The decomposition of aliphatic N-nitro amines in aqueous sulfuric acid. Bisulfate as a nucleophile

1996 ◽  
Vol 74 (10) ◽  
pp. 1774-1778 ◽  
Author(s):  
Robin A. Cox
Keyword(s):  
Sulfuric Acid ◽  
Water Molecule ◽  
Rate Constants ◽  
Activation Parameters ◽  
Standard State ◽  
Aqueous Sulfuric Acid ◽  
Alkyl Groups ◽  
Different Temperatures ◽  
State Rate ◽  
Acid Catalyzed

In aqueous sulfuric acid, aliphatic N-nitro amines decompose to N2O and alcohols. An excess acidity analysis of the observed rate constants for the reaction shows that free carbocations are not formed. The reaction is an acid-catalyzed SN2 displacement from the protonated aci-nitro tautomer, the nucleophile being a water molecule at acidities below 82–85% H2SO4, and a bisulfate ion at higher acidities. Bisulfate is the poorer nucleophile by a factor of about 1000. Twelve compounds were studied, of which results obtained for nine at several different temperatures enabled calculation of activation parameters for both nucleophiles. The reaction appears to be mainly enthalpy controlled. The intercept standard-state rate constants are well correlated by the σ* values for the alkyl groups; the slopes are negative, with a more negative value for the slower bisulfate reaction. Interestingly the m≠m* slopes also correlate with σ*, although the scatter is bad. Key words: N-nitro amines, excess acidity, bisulfate, nucleophiles, acid-catalyzed, kinetics.

scholarly journals A Study on the Kinetics and Mechanism of the One-Pot Formation of 3,4,5-Substituted Furan-2(5H)-Ones in the Presence of Lactic Acid: Effect of Different Substituents

2018 ◽  
Vol 43 (3-4) ◽  
pp. 286-299 ◽  
Author(s):  
Osman Asheri ◽  
Sayyed Mostafa Habibi-Khorassani ◽  
Mehdi Shahraki
Keyword(s):  
Lactic Acid ◽  
Activation Parameters ◽  
General Mechanism ◽  
Common Mechanism ◽  
Substituted Anilines ◽  
One Pot ◽  
Isokinetic Relationship ◽  
Zero Order Kinetics ◽  
Different Temperatures ◽  
The One

The kinetics of the reaction between para-substituted anilines and dimethyl acetylenedicarboxylate (DMAD) with derivatives of benzaldehyde for the one-pot formation of 3,4,5-substituted furan-2(5 H)-ones in the presence of lactic acid as a catalyst have been studied spectrophotometrically at different temperatures. A mechanism involving four steps was proposed for the reactions, all of which followed second-order kinetics. The partial orders with respect to substituted aniline and DMAD were one and one and the reactions revealed zero-order kinetics for benzaldehyde and its derivatives. Changing of substituents on benzaldehyde left rates of reaction unaffected. However, various substituents on aniline showed that para electron-withdrawing groups decreased the rate of reaction. According to investigation of an isokinetic relationship, a common mechanism exists for all studied substituents and a general mechanism can be formulated. Kinetic values ( k and Ea) and associated activation parameters (Δ G‡, Δ S‡ and Δ H‡) of the reactions were determined.

scholarly journals Thermodynamic Analysis of Relaxation Model for Non-Equilibrium Phase Behavior of Hydrocarbon Mixtures

2021 ◽  
Vol 2090 (1) ◽  
pp. 012138
Author(s):  
I M Indrupskiy ◽  
P A Chageeva
Keyword(s):  
Relaxation Time ◽  
Phase Behavior ◽  
Relaxation Process ◽  
Thermodynamic Analysis ◽  
Balance Equation ◽  
Equilibrium Phase ◽  
Characteristic Relaxation Time ◽  
Relaxation Model ◽  
Entropy Balance ◽  
Non Equilibrium

Abstract Mathematical models of phase behavior are widely used to describe multiphase oil and gas-condensate systems during hydrocarbon recovery from natural petroleum reservoirs. Previously a non-equilibrium phase behavior model was proposed as an extension over generally adopted equilibrium models. It is based on relaxation of component chemical potentials difference between phases and provides accurate calculations in some typical situations when non-instantaneous changing of phase fractions and compositions in response to variations of pressure or total composition is to be considered. In this paper we present a thermodynamic analysis of the relaxation model. General equations of non-equilibrium thermodynamics for multiphase flows in porous media are considered, and reduced entropy balance equation for the relaxation process is obtained. Isotropic relaxation process is simulated for a real multicomponent hydrocarbon system with different values of characteristic relaxation time using the non-equilibrium model implemented in the PVT Designer module of the RFD tNavigator simulation software. The results are processed with a special algorithm implemented in Matlab to calculate graphs of the total entropy time derivative and its constituents in the entropy balance equation. It is shown that the constituents have different signs, and the greatest influence on the entropy is associated with the interphase flow of the major component of the mixture and the change of the total system volume in the isotropic process. The characteristic relaxation time affects the rate at which the entropy is approaching its maximum value.

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