• Title/Summary/Keyword: first-order kinetics

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The Effect of Anion Catalysts in Transesterification Reaction (에스테르 교환반응(交渙反應)에서 음(陰)이온 촉매(觸媒)의 영향(影響))

  • Park, Keun-Ho
    • Journal of the Korean Applied Science and Technology
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    • v.9 no.2
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    • pp.141-148
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    • 1992
  • Transesterification reactions (methyl methacrylate with diethanolamine, ethylene glycol with dimethylphthalate) were kinetically investigated in the presence of zinc compound catalysts at $120{\sim}170^{\circ}C$ The amount of reactants was measured by gas chromatography. and the reaction rates also measured from the amount of reaction products and reactants upon each catalyst. The transesterification reactions were carried out under the first order conditions respect to the concentration of reactants, respectively, The overall reaction order was 2nd. The apparent rate constant (k') was found to obey first kinetics with respect to the concentration of catalyst. It shows that according to an increase in basicity of anionic species the rate constant increase, and that a linear relationship exists between ln k and pKa in transesterification reaction of methyl methacrylate with diethanolamine.

A Study on the Catalytic Activity of Nontoxic Organometallic Compound in Esterification Reaction between Succinic Acid and 1,4-Butanediol (Succinic Acid과 1,4-butanediol의 에스테르화반응에서 무독성 유기금속 화합물의 촉매 활성에 관한 연구)

  • Park, Keun-Ho
    • Journal of the Korean Applied Science and Technology
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    • v.27 no.1
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    • pp.6-13
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    • 2010
  • Esterification reaction between succinic acid and 1,4-butanediol was kinetically investigated in the presence of nontoxic organometallic compound catalyst(ESCAT-100E) at $150-190^{\circ}C$. The reaction rates measured by the amount of distilled water from the reaction vessel. The Esterification reaction was carried out under the first order conditions respect to the concentration of reactants, respectively. The overall reaction order was 2nd. The linear relationship was shown between apparent reaction rate constant and reciprocal absolute temperature. By the Arrhenius plot the activation energy have been calculated as 376.13 kJ/mol under nontoxic organometallic compound catalyst and also apparent reaction rate constant, k' was found to obey first kinetics with respect to the concentration of catalyst.

Effect of Monobutyl Tinoxide Catalyst in Esterification Reaction between Succinic Acid and 1,4-butanediol (Succinic Acid과 1,4-butanediol간의 에스테르화반응에서 Monobutyl Tinoxide 촉매의 영향)

  • Park, Keun-Ho;Kim, Duck-Sool
    • Journal of the Korean Applied Science and Technology
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    • v.26 no.3
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    • pp.362-369
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    • 2009
  • Esterification reaction between succinic acid and 1,4-butanediol was kinetically investigated in the presence of monobutyl tinoxide catalysts at $150{\sim}190^{\circ}C$. The reaction rates measured by the amount of distilled water from the reaction vessel. The esterification reaction was carried out under the first order conditions with respect to the concentration of reactants, respectively. The overall reaction order was 2nd. The linear relationship was shown between apparent reaction rate constant and reciprocal absolute temperature. By the Arrhenius plot the activation energy have been calculated as 87.567 kJ/mol under monobutyl tinoxide catalyst and also apparent reaction rate constant, k' was found to obey first kinetics with respect to the concentration of catalyst.

Sonochemical Reaction Mechanism of a Polycyclic Aromatic Sulfur Hydrocarbon in Aqueous Phase

  • Kim, Il-Kyu;Jung, Oh-Jin
    • Bulletin of the Korean Chemical Society
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    • v.23 no.7
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    • pp.990-994
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    • 2002
  • Hydroxybenzothiophenes, dihydroxy-benzothiophenes, and benzothiophenedione were identified as inter-mediates of benzothiophene (BT) exposed to ultrasonic irradiation. It is proposed that benzothiophene is oxidized by OH radical to sequentially for m hydroxybenzothiophenes, dihydroxybenzothiophenes, and benzothiophenedione. Benzothiophene is decomposed rapidly following pseudo-first-order kinetics in a first-order manner by ultrasonic irradiation in aqueous solution. The toxicity of sonochemically treated solutions was checked by E. coli and a less inhibition in bacterial respiration was observed from the 120-min treated benzothiophene sample than from the untreated benzothiophene sample. Also evolution of carbon dioxide and sulfite was observed during ultrasonic reaction. A pathway for ultrasonic decomposition of benzothiophene in aqueous solution is proposed.

Unexpected Rate Retardation in the Formation of Phthalic Anhydride from N-Methylphthalamic Acid in Acidic H2O-CH3CN Medium

  • Ariffin, Azhar;Khan, M. Niyaz
    • Bulletin of the Korean Chemical Society
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    • v.26 no.7
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    • pp.1037-1043
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    • 2005
  • Kinetic study on the cleavage of N-methylphthalamic acid (NMPA) in mixed acidic aqueous-acetonitrile solvent reveals the formation of both phthalic anhydride (PAn) (through O-cyclization) and N-methylphthalimide (NMPT) (through N-cyclization). The formation of NMPT varies from $\sim$20% to $\sim$3% with the increase in the content of acetonitrile from 2 to 70% v/v. Pseudo first-order rate constants for the formation of PAn are more than 4-fold larger than those for the formation of NMPT at 2% v/v $CH_3CN$ in mixed aqueous solvents. Pseudo first-order rate constants for alkaline hydrolysis of NMPT reveal a nonlinear decrease with increase in the content of $CH_3CN$ in mixed aqueous solvents.

Kinetics and Mechanism of Substitution Reaction of $PPN^+(\eta^n-MeCp)Mn(CO)_2\;Cl^-$ with $PR_3$(R=Me, Et, OEt, $C_6H_5$)

  • Park, Yong Gwang;Lee, Yong Gu;Kim, Gyu Sik
    • Bulletin of the Korean Chemical Society
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    • v.17 no.2
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    • pp.138-142
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    • 1996
  • The transition metal carbonylate, PPN+(${\eta}^5-MeCp)Mn(CO)_2Cl^-$ undergoes a novel ligand substitution reaction with PR3 (R=Me, Et, OEt, $C_6H_5$ in THF at elevated temperatures (40 $^{\circ}C$ up to 60 $^{\circ}C)$ under the pseudo-first-order reaction conditions (usually 20-fold excess of PR3 with respect to metal carbonylate concentrations) where chloride is displaced by PR3. The reaction follows overall first order dependence on [(${\eta}^5-MeCp)Mn(CO)_2Cl^-$]; however, the negative entropy changes of activation (${\Delta}S^{\neq}$=-19.3 e.u. for $P(OEt)_3$; ${\Delta}S^{\neq}$=-16.4 e.u. for $PPh_3$) suggest the existence of the intermediate, ((η3-MeCp)Mn(CO)2(THF)Cl-, which eventually transforms to the product (${\eta}^5-MeCp)Mn(CO)_2(PR_3)$.

Effect of Phenobarbital on the Metabolite Kinetics of Diltiazem in Rats (랫트에 있어서 딜티아젬의 대사동태에 미치는 페노바르비탈의 효과)

  • Lee, Yong-Bok;Koh, Ik-Bae;Shim, Chang-Koo;Kim, Shin-Keun;Lee, Min-Hwa
    • Journal of Pharmaceutical Investigation
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    • v.22 no.4
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    • pp.301-306
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    • 1992
  • The influence of phenobarbital (PB) pretreatment (75 mg/kg/day, i.p. for 4 days) on the metabolite kinetics of diltiazem (DTZ) was studied in rats in order to elucidate the effect of esterase induced by PB on the formation of DTZ to desacetyldiltiazem (DAD), DAD was injected via portal vein (3 mg/kg) to the control and PB-pretreated rats, The intrinsic hepatic clearance of DAD was significantly increased by PB pretreatment and the absolute bioavailability of DAD was significantly decreased in the PB-pretreated rats. According to the hepatic biotransformation model of DTZ, the fraction of systemic clearance of DTZ which forms DAD $(G_{mi})$ was different from that of DTZ which furnishes the available DAD to the systemic circulation $(F_{mi})$ in control rats. This result shows that DTZ was suspected of the sequential hepatic first-pass metabolism. On the other hand, PB pretreatment enhanced the $G_{mi}$ value of DTZ by 44%. It may be concluded that the deacetylation of DTZ to DAD in rats is increased by the esterase induced by PB but the transfer rate of DAD immediately formed from DTZ into systemic circulation is not affected by PB due to the 27% decreased absolute bioavailability of DAD resulting from PB pretreatment.

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Kinetics and Statistics of Structural Changes in Polyacrylonitrile (폴리아크릴로니트릴의 構造變化에 있어서의 動力學的 및 統計學的 硏究)

  • Noh, Ick-Sam
    • Journal of the Korean Chemical Society
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    • v.10 no.1
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    • pp.25-31
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    • 1966
  • It is well known that the coloration and structural changes in thermal treatment of polyacrylonitrile are due to the formation of partly hydrogenated naphthylidine-type ring involving the pendant nitrile groups. Any quantitative study of the reaction, in the sense of kinetics and/or statistics, however, has never been reported. This paper presents that, at first, the disappearance of the nitrile groups follows the first order kinetics, which indicates clearly that nitrile groups do not disappear by a long chain reaction-the kinetic chain length is very short. This observation rules out the long intramolecular and intermolecular propagation chain through which most of the nitrile groups disappear. From the evidence that a similar reaction occurs in propylene carbonate solutions without gel formation, one may conclude that the coloration and structural changes are not necessarily intermolecular reaction. Secondly, a finite amount of nitrile groups remains unreacted at the extrem of reaction-not contributed to the formation of naphthylidine-type ring. The concentration of this unreacted nitrile groups is 19∼22% which is good agreement with the statistically calculated value of 19.2%.

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Studies on the Browning of Ixeris sonchifolia (고들빼기의 갈변에 관한 연구)

  • Park, Soo-Sun;Kim, An-Keun
    • Korean Journal of Pharmacognosy
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    • v.15 no.2
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    • pp.78-84
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    • 1984
  • Polyphenol oxidase was purified from acetone powder extract of the root of Ixeris sonchifolia. The enzyme obtained by ammonium sulfate fractionation and sephadex G-200 gelfiltration gave 51-fold purification over the crude extract. The purified enzyme showed activity toward chlorogenic acid, caffeic acid and pyrocatechol. The kinetics of thermal inactivation of the enzyme followed first-order reaction. Potassium cyanide and cysteine were potent inhibitors.

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Development of spherical crystallization technique and its application to pharmaceutical systems

  • Kawashima, Yoshiaki
    • Archives of Pharmacal Research
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    • v.7 no.2
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    • pp.145-151
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    • 1984
  • A novel agglomeration technique, termed "Spherical Crystallization Process", which can transform directly the fine crystals produced in the crystallization or the reaction process into a spherical shape was developed. By this technique, needle like crystals such as salicylic acid were transformed into free flowing and directly compressible agglomerates. Sphericaly agglomerated aminophyline crystals were obtained directly from the reaction system, which could reduce the preparation processes, e. g. synthesis, crystallization and agglomeration, into only one step. Sodium theophyline monohydrate agglomerates were prepared by salting out, the rate process of which was described by a first order kinetics. Agglomerated crystals of ndw complex of indo-methacin-mepirizole were prepare with this technique; an improved therapeutic effect of the resultant crystals was expected. expected.

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