• Title/Summary/Keyword: Chemical reaction kinetics

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Kinetic Study on Bromine-Exchange Reaction of Antimony Tribromide with t-Butyl Bromide in Nitrobenzene and in 1, 2, 4-Trichlorobenzene$^*$

  • Choi, Sang-Up;Pae, Young-Il
    • Bulletin of the Korean Chemical Society
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    • v.3 no.4
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    • pp.144-148
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    • 1982
  • The kinetic study on the bromine-exchange reaction of antimony tribromide with t-butyl bromide in nitrobenzene or 1,2,4-trichlorobenzene has been carried out, using Br-82 labelled antimony tribromide. The results show that the exchange reaction is first order with respect to t-butyl bromide and 1.5th order with respect to antimony tribromide. It is assumed that the 1.5th order indicates the coexistance of first- and second-order kinetics. Reaction mechanisms for the exchange reaction are proposed.

Spectrophotometric Investigation of Oxidation of Cefpodoxime Proxetil by Permanganate in Alkaline Medium: A Kinetic Study (알칼리성 용매에서 과망간에 의한 세프포독심 프록세틸의 산화의 분광광도법적 조사: 속도론적 연구)

  • Khan, Aftab Aslam Parwaz;Mohd, Ayaz;Bano, Shaista;Siddiqi, K. S.
    • Journal of the Korean Chemical Society
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    • v.53 no.6
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    • pp.709-716
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    • 2009
  • A Kinetics pathway of oxidation of Cefpodoxime Proxetil by permanganate in alkaline medium at a constant ionic strength has been studied spectrophotometrically. The reaction showed first order kinetics in permanganate ion concentration and an order less than unity in cefpodoxime acid and alkali concentrations. Increasing ionic strength of the medium increase the rate. The oxidation reaction proceeds via an alkali-permanganate species which forms a complex with cefpodoxime acid. The latter decomposes slowly, followed by a fast reaction between a free radical of cefpodoxime acid and another molecule of permanganate to give the products. Investigations of the reaction at different temperatures allowed the determination of activation parameters with respect to the slow step of proposed mechanism and fallows first order kinetics. The proposed mechanism and the derived rate laws are consistent with the observed kinetics.

Estimating Diffusion-Controlled Reaction Parameters in Photoinitiated Polymerization of Dimethacrylate Macromonomers

  • Choe, Youngson
    • Macromolecular Research
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    • v.11 no.5
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    • pp.311-316
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    • 2003
  • The kinetics of photoinitiated polymerization of dimethacrylate macromonomers have been studied to determine the diffusion-controlled reaction parameters using attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR). A predicted kinetic rate expression with a diffusion control factor was employed to estimate an effective rate constant and to define the reaction-controlled and diffusion-controlled regimes in the photopolymerization. An effective rate constant, k$_{e}$, can be obtained from the predicted kinetic rate expression. At the earlier stages of polymerization, the average values of kinetic rate constants do not vary during the reaction time. As the reaction conversion, $\alpha$, reaches the critical conversion, $\alpha$$_{c}$, in the predicted kinetic expression, the reaction becomes to be controlled by diffusion due to the restricted mobility of dimethacrylate macromonomers. A drop in value of effective rate constant causes a drastic decrease of reaction rate at the later stages of polymerization. By determining the effective rate constants, the reaction-controlled and diffusion-controlled regimes were properly defined even in the photopolymerization reaction system.m.m.

Kinetics of Catalytic Reactions Occurring in a Small Reaction Volume (작은 반응 매질에서 일어나는 촉매 반응 속도에 관한 연구)

  • Kim, Jung-Han;Sung, Jae-Young
    • Journal of the Korean Chemical Society
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    • v.52 no.3
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    • pp.217-222
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    • 2008
  • We investigate the kinetics of diffusion-influenced catalytic reactions occurring in small reaction volume. From a simple exact model study, we find that the reaction rate coefficient decreases with the size of reaction volume. The explicit expression for the average reaction rate constant is presented, which can be regarded as a generalization of well-known Collins-Kimball rate constant into the reactions occurring in a small reaction volume. It turns out that the traditional diffusion influenced reaction dynamics is followed by a single exponential relaxation phase with a rate constant dependent on the reaction volume for the catalytic reactions occurring in small reaction volumes.

Tetramethyl orthosilicate(TMOS) Synthesis by the Copper-Catalyzed Reaction of the Metallic Silicon with Methanol (II) - The Kinetics of the Copper-Catalyzed Reaction of Silicon with Methanol - (구리 촉매하에서 규소와 메탄올의 반응에 의한 Tetramethyl orthosilicate(TMOS) 합성(제2보) - 구리촉매하에서 규소와 메탄올과의 반응의 반응속도론 -)

  • Soh, Soon-Young;Won, Ho-Youn;Chun, Yong-Jin;Lee, Bum-Jae;Yang, Hyun-Soo
    • Applied Chemistry for Engineering
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    • v.10 no.2
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    • pp.259-262
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    • 1999
  • The copper-catalyzed reaction of silicon with methanol was carried out in a mixed bed reactor to obtain tetramethyl orthosilicate (TMOS). In order to determine the kinetics of the reaction per active site on the silicon surface, a flow rate transition technique was employed. A kinetic study showed the reaction was in Linear relationship with the amount of contact mass and independent on the concentration of methanol. This result indicated that the rate-determining step was not the chemical process involving methanol, but the formation of silicon intermediate on the contact mass. On the basis of optimum experimental conditions, the maximum TMOS formation rate per g-silicon is 0.030 (g/min) at $210^{\circ}C$, in which activation energy was 8.5 kcal/mol and reaction rate equation was $k=4.09{\times}10^4\;exp$ ($-4.73{\times}10^3/T$).

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Cure Reactions of Epoxy/Anhydride/(Polyamide Copolymer) Blends

  • Youngson Choe;Kim, Wonho
    • Macromolecular Research
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    • v.10 no.5
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    • pp.259-265
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    • 2002
  • The cure kinetics of blends of epoxy (DGEBA, diglycidyl ether of bisphenol A)/anhydride resin with polyamide copolymer, poly(dimmer acid-co-alkyl polyamine), were studied using differential scanning calorimetry (DSC) under isothermal condition. On increasing the amount of polyamide copolymer in the blends, the reaction rate was increased and the final cure conversion was decreased. Lower values of final cure conversions in the epoxy/(polyamide copolymer) blends indicate that polyamide hinders the cure reaction between the epoxy and the curing agent. The value of the reaction order, m, for the initial autocatalytic reaction was not affected by blending polyamide copolymer with epoxy resin, and the value was approximately 1.3, whereas the reaction order, n, for the general n-th order of reaction was increased by increasing the amount of polyamide copolymer in the blends, and the value increased from 1.6 to 4.0. A diffusion-controlled reaction was observed as the cure conversion increased and the rate equation was successfully analyzed by incorporating the diffusion control term for the epoxy/anhydride/(polyamide copolymer) blends. Complete miscibility was observed in the uncured blends of epoxy/(polyamide copolymer) up to 120 $^{\circ}C$, but phase separations occurred in the early stages of the curing process at higher temperatures than 120 "C. During the curing process, the cure reaction involving the functional group in polyamide copolymer was detected on a DSC thermogram.gram.