• Title/Summary/Keyword: Thermodynamic mechanism

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Kinetics of the Formation of Nickel-Phthalocyanine (Nickel-Phthalocyanine 생성의 반응속도론적 연구)

  • Bae, Kook-Jin;Hahn, Chi-Sun
    • Journal of the Korean Chemical Society
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    • v.16 no.2
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    • pp.84-92
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    • 1972
  • A mechanism for the ring formation of nickel phthalocyanine (Ni-Pc) has been proposed based on chemical kinetics. The effect of the catalyst on the rate was examined, and ammonium molybdate has been found to be the most effective. The reaction order of the ring formation was determined to be of the 1st order over all, with only the concentration of urea affecting the rate of the ring formation. All the results including thermodynamic parameters support a conclusion that the rate-determining step seems to be the enolization of the urea-catalyst transition complex, followed by fast decomposition of the tautomeric enolized urea into ammonia and isocyanic acid. These intermediates then reacted with the phthalic anhydride to form imino and diimino-phthalimide, which condense to form nickel phthalocyanine in the presence of the nickel cation.

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A Kinetic Study on the Oxidation of Indole by Peroxomonosulphate in Acetonitrile Solvent

  • Kavery, Muniyappan;Govindasamy, Chandramohan;Johnson, Stephen
    • Journal of the Korean Chemical Society
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    • v.57 no.2
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    • pp.210-215
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    • 2013
  • Kinetics of oxidation of indole by peroxomonosulphate (PMS) in aqueous acetonitrile medium has been investigated. The reaction follows a total second order, first order each with respect to [Indole] and [PMS]. The rate of the reaction was not affected by added [$H^+$]. Variation of ionic strength (${\mu}$) had no influence on the rate. Increase of percentage of acetonitrile decreased the rate. Absen ce of any polymerization indicated a nonradical pathway. Activation and thermodynamic parameters have bee n computed. A suitable kinetic scheme based on these observations is proposed. The reactivity of PMS towards Indole was found to be higher than that with peroxodisulphate.

Solvent Effect in Nucleophilic Reactions of Substituted Benzoyl Chlorides with p-Nitroaniline (치환염 벤조일과 파라니트로아닐린과의 친핵반응에 미치는 용매효과에 관한 연구)

  • Kim, Wang Gi
    • Journal of the Korean Chemical Society
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    • v.18 no.4
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    • pp.251-258
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    • 1974
  • The rate constants for the nucleophilic substitution reactions of substituted benzoyl chlorides with p-nitroaniline in such solvents as acetone, acetonitrile, methanol, ethanol, etc. were conductometrically determined, and the activation thermodynamic parameters were also evaluated. In result, the reaction rates were faster in protic solvents than in aprotic solvent; in the solvents of similar property, the reaction rate in the solvent of the large dielectric constant was faster than that in the solvent of the small dielectric constant. Hammett plots in individual solvents showed the straight lines with positive slope; and we concluded that the reaction occurred via the addition-elimination mechanism.

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Thermochemical Behaviour of Some Salicylaldehyde G-P Complexes of Fe(Ⅲ), Co(Ⅱ), Cu(Ⅱ) and Zn(Ⅱ)

  • Hafez, M.A.H.;Moussa, M.N.H.
    • Bulletin of the Korean Chemical Society
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    • v.13 no.3
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    • pp.334-336
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    • 1992
  • Through two different techniques TGA and DSC the thermal decomposition processes of salicyaldehyde G-P complexes having the general formula: $$[MCl_2(L)_2]^{2+}$2Cl^-$; where L = salicyaldehyde carbohydrazone pyridinum cation, and M= Fe(III), Co(II), Cu(II) and Zn(II), have been studied. From the obtained thermogravimetric curves the following parameters n, $E_{\alpha}$, A, ${\Delta}S^{\neq}$, ${\Delta}H^{\neq}$ and ${\Delta}G^{\neq}$ were evaluated. The effect of the nature of the metal ions present in the complexes studied upon the calculated thermodynamic parameters was reported. A suitable mechanism for the thermal decomposition process was suggested.

Effects of a naturally derived surfactant on hydrate anti-agglomeration using micromechanical force measurement

  • Li, Mingzhong;Dong, Sanbao;Li, Bofeng;Liu, Chenwei
    • Journal of Industrial and Engineering Chemistry
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    • v.67
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    • pp.140-147
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    • 2018
  • The performance of a hydrate anti-agglomerant (AA) on cyclopentane (CyC5) hydrate anti-agglomeration at various concentrations (0-1 wt%, based on the oil phase) using MMF apparatus has been investigated. At low AA concentrations up to 0.01 wt%, the AA reduces the cohesion force (capillary force) by reducing the CyC5-water interfacial tension. At concentrations higher than 0.1 wt%, hydrate hydrophobicity alternation and AA's thermodynamic inhibition effects are the main part of AA's mechanism. Additionally, a "temporary agglomeration" phenomenon caused by surface melting of the hydrate particles is also observed, which may indicate the AA's weak ability to produce stable water-CyC5 interface.

Arylamino Substituted Mercaptoimidazole Derivatives as New Corrosion Inhibitors for Carbon Steel in Acidic Media: Experimental and Computational Study

  • Duran, Berrin;Yurttas, Leyla;Duran, Murat
    • Journal of Electrochemical Science and Technology
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    • v.12 no.3
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    • pp.365-376
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    • 2021
  • Two arylamino substituted mercaptoimidazole derivatives namely 4,5-dimethyl-1-(phenylamino)-1H-imidazole-2(3H)-thione (I1) and 4,5- dimethyl-1-((p-chlorophenyl)amino)- 1H-imidazole-2(3H)-thione (I2) were synthesized and investigated as corrosion inhibitors for carbon steel in 0.5 M HCl solution by means of electrochemical impedance spectroscopy (EIS), potentiodynamic polarization, ATR-FTIR spectroscopy and SEM. The results showed that the investigated mercaptoimidazole derivatives act as mixed type inhibitors and inhibition efficiency follows the I2>I1 order. Adsorption of inhibitors on metal surface was found to obey the Langmuir adsorption isotherm. Thermodynamic parameters revealed that adsorption of the inhibitors has both physisorption and chemisorption adsorption mechanism. Electrochemical test results were supported by quantum chemical parameters obtained from DFT calculations.

Spectroscopic Studies on the Interaction of N-alkyl Phenothiazines with Bovine Serum Albumin

  • Seetharamappa, J.;Shaikh, S.M.T;Kamat, B.P.
    • Journal of Photoscience
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    • v.12 no.1
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    • pp.25-32
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    • 2005
  • Binding of N-Alkyl phenothiazines (NAP) to bovine serum albumin (BSA) was studied by spectroscopic methods.It was found that the phenothiazine ring common to all drugs makes major contribution to interaction. However, the nature of alkylamino group at position 10 influences the protein binding significantly. Stern-Volmer plots indicated the presence of static component in the quenching mechanism. The high magnitude of rate constant of quenching indicated that the process of energy transfer occurs by intermolecular interaction and thus the drug-binding site is in close proximity to tryptophan residues of BSA. Binding studies in presence of hydrophobic probe, 8-anilino-1-naphthalein-sulphonic acid showed that there is hydrophobic interaction between drug and the probe and they do not share common sites in BSA. Thermodynamic parameters obtained from data at different temperatures showed that the binding of NAP to BSA predominantly involve hydrophobic forces. The effects of some cations and anions common ions were investigated on NAP-BSA interactions. The CD spectrum of BSA in presence of drug showedthat binding of drug leads to change in the helicity of the protein.

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Gadolinium Deposition in the Brain: Current Updates

  • Jin Woo Choi;Won-Jin Moon
    • Korean Journal of Radiology
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    • v.20 no.1
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    • pp.134-147
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    • 2019
  • Gadolinium-based contrast agents (GBCAs) are commonly used for enhancement in MR imaging and have long been considered safe when administered at recommended doses. However, since the report that nephrogenic systemic fibrosis is linked to the use of GBCAs in subjects with severe renal diseases, accumulating evidence has suggested that GBCAs are not cleared entirely from our bodies; some GBCAs are deposited in our tissues, including the brain. GBCA deposition in the brain is mostly linked to the specific chelate structure of the GBCA: linear GBCAs were responsible for brain deposition in almost all reported studies. This review aimed to summarize the current knowledge about GBCA brain deposition and discuss its clinical implications.

A Thermodynamic Study on Freezing Characteristics of Weathered Tuff Soil- Freezing Point Depression with the Variation of Overburden Pressure - (응회암 풍화토의 동결특성에 관한 열역학적 연구-상재하중과 동결점 저하를 중심으로-)

  • 서상열
    • Journal of the Korean Geotechnical Society
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    • v.15 no.6
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    • pp.297-306
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    • 1999
  • In this research, the frost heave mechanism of the weathered tuff soil sampled from the area tying between Ulanbator and Beijing was studied. The frost heave tests were carried maintaining the constant temperature at both upper$(+5^{\circ}C)\; and\; lower(-5^{\circ}C)$ ends of the sample. Here, main emphasis is given on variation of the freezing point depression with the variation of applied overburden pressure. The expansion of ice lens and migration of the pore water towards freezing front were observed in the test. It was found that with the increase in overburden pressure there is decrease in heave rate and increase in the absolute value of a segregation-freezing temperature. Hence the equation between segregation-freezing temperature and overburden pressure could be suggested. Also the water content of the samples at the frozen side was shown to be higher than those at the unfrozen side. Similarly, the water at warmer part of the frozen tuff was found much higher than that of the cooler part.

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Removal of different anionic dyes from aqueous solution by anion exchange membrane

  • Khan, Muhammad Ali;Khan, Muhammad Imran;Zafar, Shagufta
    • Membrane and Water Treatment
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    • v.8 no.3
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    • pp.259-277
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    • 2017
  • Adsorption is a widely used technique for the removal of dyes from wastewaters by variety of adsorbents. In this work, the main focus is on the potential assessment of anion exchange membrane for the removal of different dyes using batch system and investigation of experimental data by applying various kinetic and thermodynamic models. The removal of anionic dyes i.e., Eosin-B, Eriochrome Black-T and Congo Red by anion exchange membrane BII from aqueous solution was carried out and effect of various parameters such as contact time, membrane dosage, temperature and ionic strength on the percentage removal of anionic dyes was studied. The experimental data was assessed by kinetic models namely pseudo-first-order, pseudo-second-order, Elovich liquid film diffusion, Bangham and the modified Freundlich models equation have been used to analyze the experimental data. These results indicate that the adsorption of these anionic dyes on BII follows pseudo-second-order kinetics with maximum values of regression coefficient (0.992-0.998) for all the systems. The adsorption of dyes was more suitable to be controlled by a liquid film diffusion mechanism. The adsorptive removal of dye Eosin-B and Eriochrome Black-T were decreased with temperature and thermodynamic parameters such as free energy (${\Delta}G^o$), enthalpy (${\Delta}H^o$) and entropy (${\Delta}S^o$) for adsorption of dyes on membrane BII were calculated at 298 K, 308 K and 318 K. The values of enthalpy and entropy were negative for EB and EBT representing that the adsorption of these dyes on BII is physiosorptive and exothermic in nature. Whereas the positive values of enthalpy and entropy for CR adsorption on BII, indicating that its adsorption is endothermic and spontaneous in nature. It is evident from this study that anion exchange membrane has shown good potential for the removal of dyes from aqueous solution and it can be used as adsorbent for dues removal on commercial levels.