scholarly journals Catalytic influence of 16- s -16 gemini surfactants on the rate constant of histidine and ninhydrin

2020 ◽  
Vol 7 (2) ◽  
pp. 191648 ◽  
Author(s):  
Dileep Kumar ◽  
Malik Abdul Rub
Keyword(s):  
Critical Micelle Concentration ◽  
Rate Constant ◽  
Gemini Surfactants ◽  
Conductivity Measurement ◽  
Activation Parameters ◽  
Resultant Data ◽  
Different Temperatures ◽  
Eyring Equation ◽  
Constant Characteristics ◽  
Systematic Explanation

The present paper reports the catalytic influence of 16- s -16 (spacer ( s ) = 4, 5, 6) gemini surfactants on the rate constant of histidine and ninhydrin at 343 K and pH 5.0 using the spectrophotometric technique. The effect of varying amounts of geminis was made on the rate constant of histidine and ninhydrin keeping other constituents constant. Characteristics of the rate constant ( k ψ ) versus [gemini] depict the effect of surfactants on the rate constant. A systematic explanation about the effect of surfactants is revealed and discussed in the text. The influence of different parameters that includes [reactants], temperature and pH has also been performed on the study. In order to determine the critical micelle concentration (cmc) of pure surfactants and their solution mixtures, conductivity measurement was employed. By using the Eyring equation, activation parameters at different temperatures have been obtained. The resultant data of k ψ versus [gemini] plot were rationalized with the pseudo-phase model of micelles.

Temperature-dependence of electrochemical kinetic parameters: Electrode reaction of the Zn(Hg)/Zn(II) system

1982 ◽  
Vol 47 (5) ◽  
pp. 1433-1443 ◽  
Author(s):  
S. Kang ◽  
K. Matsuda ◽  
R. Tamamushi
Keyword(s):  
Aqueous Solutions ◽  
Temperature Dependence ◽  
Kinetic Parameters ◽  
Rate Constant ◽  
Activation Parameters ◽  
Electrode Reaction ◽  
Thermodynamic Quantities ◽  
Empirical Correlations ◽  
Square Wave ◽  
Different Temperatures

The electrochemical kinetic parameters of the D.M.E./Zn(II) electrode reaction in aqueous solutions containing perchlorate, nitrate, chloride and bromide ions were measured at different temperatures (5-50 °C) by the modified square-wave polarographic technique. The Arrhenius activation parameters and thermodynamic quantities of the electrode reaction were determined from the temperature dependence of the rate constant and conditional potential, respectively. Empirical correlations were observed between some pairs of kinetic and thermodynamic quantities.

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.

Surface Activity Research of Cationic Gemini Surfactants

2013 ◽  
Vol 690-693 ◽  
pp. 2076-2080
Author(s):  
Zhen Zhong Fan ◽  
Lan Lan Li ◽  
Li Feng Zhang ◽  
Qing Wang Liu
Keyword(s):  
Surface Tension ◽  
Critical Micelle Concentration ◽  
Surface Activity ◽  
Surfactant Concentration ◽  
Gemini Surfactant ◽  
Gemini Surfactants ◽  
Ph Value ◽  
Inorganic Salts ◽  
Cationic Gemini Surfactant ◽  
Cationic Gemini Surfactants

Cationic Gemini surfactant concentration, the inorganic salts added and the pH value of surface tension obtained cationic gemini surfactant critical micelle concentration is 0.4mmol / L;by adding three kinds of inorganic salts NaCl, MgCl2, and Na2SO4 ,which Na2SO4 has the greatest impact on surface tension, followed by MgCl2.The surface minimum tension of the pH ranged from 9 to 11 , indicating that the surface activity of cationic gemini surfactants achieved the highest.

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 Reactivity of Phenol and Aniline towards Quinolinium Chloro Chromate: A Comparative Oxidation Kinetic Study

2015 ◽  
Vol 59 ◽  
pp. 81-92
Author(s):  
Seplapatty Kalimuthu Periyasamy ◽  
H. Satham Hussain ◽  
R. Manikandan
Keyword(s):  
Oxidation Kinetic ◽  
Activation Parameters ◽  
Dipole Interaction ◽  
Reaction Rates ◽  
Hydrogen Ion ◽  
Aqueous Acetic Acid ◽  
Acetic Acid Medium ◽  
First Order ◽  
Different Temperatures ◽  
Kinetics Of

The kinetics of Oxidation of Phenol and aniline by quinolinium Chlorochromate (QCC) in aqueous acetic acid medium leads to the formation of quinone and azobenzene respectively. The reactions are first order with respect to both Phenol and aniline. The reaction is first order with respect to quinolinium chlorochromate (QCC) and is catalyzed by hydrogen ion. The hydrogen-ion dependence has the form: kobs = a+b [H+]. The rate of oxidation decreases with increasing dielectric constant of solvent, indicating the presence of an ion-dipole interaction. The reaction does not induced the polymerization of acrylonitrile. The retardation of the rate by the addition of Mn2+ ions confirms that a two electron transfer process is involved in the reaction. The reaction rates have been determined at different temperatures and the activation parameters have been calculated. From the above observations kinetic results a probable mechanism have been proposed.

Kinetic Studies on the Polymerization of Dicyclohexylmethylmethane-4,4'-Diisocyanate with Polyoxytetramethylene Diol

2013 ◽  
Vol 791-793 ◽  
pp. 32-35
Author(s):  
Jian Cheng Wang
Keyword(s):  
Rate Constant ◽  
Arrhenius Equation ◽  
Activation Enthalpy ◽  
Kinetic Studies ◽  
Activation Entropy ◽  
Dimethyl Acetamide ◽  
Different Temperatures ◽  
Ft Ir ◽  
Temperature Activation

Dicyclohexylmethylmethane-4,4'-diisocyanate is used to react with polyoxytetramethylene diol at different temperatures. N,N-Dimethyl acetamide is used as solvent.In situFT-IR is used to monitor the reaction to work out rate constant, Arrhenius equation and Eyring equation. The polymerization has been found to be a second order reaction, and the rate constant increases with the rise of temperature. Activation energy (Ea), activation enthalpy (ΔH) and activation entropy (ΔS) for the polymerization are respectively calculated out, which are very useful to reveal the reaction mechanism.

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