• Title/Summary/Keyword: dissociation rate constant

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Studies of the Organic Molecules Dissociative Surface Ionization in the Mass-Spectrometric Surface Ionization Method

  • Ilkhomjan Saydumarov;Dilshadbek Usmanov
    • Mass Spectrometry Letters
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    • v.15 no.1
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    • pp.54-61
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    • 2024
  • An improved voltage modulation method (VMM) was used to control the heat release and adsorption properties of the adsorbent. In this work, the voltage and flux modulation methods were considered under unified experimental conditions of dissociative surface ionization (SI) of polyatomic organic molecules, the criteria were found when under VMM conditions the current relaxation of SI carries information about the kinetic properties of thermal desorption of ionizable dissociation particles arriving on the surface of polyatomic molecules. Conditions were found under which the relaxation of the ionic current in the flux modulation method is determined by the kinetics of the heterogeneous dissociation reaction of the original polyatomic molecules. The values of the thermal desorption rate constant K+ and the activation energy E+ obtained with VMM for desorption of (CH3)2NCH+2 ions with m/z 58 by adsorption of imipramine and amitriptyline molecules agree well with each other and with the results for the desorption of the same ions by adsorption of other molecules. This confirms one of the basic conditions for the equilibrium process SI - the a degree (β coefficient) of the same particles SI on the same emitter surface is the same and does not depend on the way these particles are formed on the emitter surface.

Protein Adsorption on Ion Exchange Resin: Estimation of Equilibrium Isotherm Parameters from Batch Kinetic Data

  • Chu K.H.;Hashim M.A.
    • Biotechnology and Bioprocess Engineering:BBE
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    • v.11 no.1
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    • pp.61-66
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    • 2006
  • The simple Langmuir isotherm is frequently employed to describe the equilibrium behavior of protein adsorption on a wide variety of adsorbents. The two adjustable parameters of the Langmuir isotherm - the saturation capacity, or $q_m$, and the dissociation constant, $K_d$ - are usually estimated by fitting the isotherm equation to the equilibrium data acquired from batch equilibration experiments. In this study, we have evaluated the possibility of estimating $q_m$ and $K_d$ for the adsorption of bovine serum albumin to a cation exchanger using batch kinetic data. A rate model predicated on the kinetic form of the Langmuir isotherm, with three adjustable parameters ($q_m,\;K_d$, and a rate constant), was fitted to a single kinetic profile. The value of $q_m$ determined as the result of this approach was quantitatively consistent with the $q_m$ value derived from the traditional batch equilibrium data. However, the $K_d$ value could not be retrieved from the kinetic profile, as the model fit proved insensitive to this parameter. Sensitivity analysis provided significant insight into the identifiability of the three model parameters.

A Kinetic Study of Br Atom Reactions with Trimethylsilane by the VLPR (Very Low Pressure Reactor) Technique$^1$

  • Choo Kwang Yul;Choe Mu Hyun
    • Bulletin of the Korean Chemical Society
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    • v.6 no.4
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    • pp.196-202
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    • 1985
  • A Very Low Pressure Reactor (VLPR) is constructed for the kinetic study of atom-molecule bimolecular elementary reactions. The basic principles and the versatility of the method are described. By using the VLPR technique the forward (k1) and the reverse (k-1) rate constants for Br atom reaction with trimethylsilane are studied; Br + $(CH_3)_3$SiH k1 ${\leftrightarrow}$ k-1 HBr + $(CH_3)_3$Si. From the kinetic data and the entropy estimation the bond dissociation energy for Si-H bond in trimethylsilane is calculated to be 90.1 kcal/mole $({\pm}1.1$ kcal/mole). The Arrhenius parameters for k1 are found to be log A = 10.6 l/mole·sec, $E_a$ = 4.4 kcal/mole respectively. For the comparison purpose analogous reaction for carbon compound ; Br + $(CH_3)_3$CH ${\rightarrow}$ HBr + $(CH_3)_3$C was also studied. The corresponding rate constant and equilibrium constant at $25^{\circ}C$ are found to be 2.67 ${\times}$ $10^6l$/mole${\cdot}$sec and 160 respectively.

The fermentation kinetics of protease inhibitor production by streptomyces fradiae (Streptomyces fradiae에서 분리한 단백질 분해효소 저해물질 생성의 동력학적 특성)

  • 이병규;정영화;이계준
    • Korean Journal of Microbiology
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    • v.28 no.3
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    • pp.264-267
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    • 1990
  • The objectives of the current studies were to establish the optimal conditions for the production of extracellular protease inhibitor in a strain of Streptomyces fradiae. As results, it was found that cell specific growth rate was very critical for the production of protease inhibitor and the optimum specific growth rate was found to be 0.05 h$^{-1}$ . Dissolved oxygen tension and pH were also important to regulate the inhibitor production. The inhibitory mode of the purified inhibitor to .alpha.-chymotrypsin was found to be competitive (K$_{i}$=5.5*10$^{-7}$ M). One mole of inhibitor could bind two moles of .alpha.-chymotrypsin and the complex has very low dissociation constant.t.

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An Inspection of Stability for Annealing SiOCH Thin Flim (SiOCH 박막의 열처리에 대한 안정성 검토)

  • Park, Yong-Heon;Kim, Min-Seok;Hwang, Chang-Su;Kim, Hong-Bae
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.22 no.1
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    • pp.41-46
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    • 2009
  • The low dielectric SiOCH films were deposited on p-type Si(100) substrates through the dissociation of BTMSM $(((CH_3)_3Si)_2CH_2)$ precursors with oxygen gas by using PECVD method. BTMSM precursor was introduced with the flow rates from 42 to 60 sccm by 2 sccm step into reaction chamber but with the constant flow rate of 60 sccm $O_2$. SiOCH thin films were annealed at $450^{\circ}C$ for 30 minutes. The electrical property of SiOCH thin films was studied by MIS, Al/SiOCH/p-Si(100), structure. Annealed samples showed large reduction of the maximum capacitance yielding low dielectric constant owing to reductions of surface charge density. After exposure at room temperature and atmospheric pressure, dielectric constant of SiOCH films was totally increased. However, annealed SiOCH thin films were more stable than as-deposited SiOCH thin films for natural oxidation.

Energy- and Time-Dependent Branching to Competing Paths in Coupled Unimolecular Dissociations of Chlorotoluene Radical Cations

  • Seo, Jongcheol;Kim, Seung Joon;Shin, Seung Koo
    • Bulletin of the Korean Chemical Society
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    • v.35 no.3
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    • pp.833-838
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    • 2014
  • The energy- and time-dependent branching to the competing dissociation paths are studied by theory for coupled unimolecular dissociations of the o-, m-, and p-chlorotoluene radical cations to $C_7{H_7}^+$ (benzylium and tropylium). There are four different paths to $C_7{H_7}^+$, three to the benzylium ion and one to the tropylium ion, and all of them are coupled together. The branching to the multiple paths leads to the multiexponential decay of reactant with the branching ratio depending on both internal energy and time. To gain insights into the multipath branching, we study the detailed kinetics as a function of time and internal energy on the basis of ab inito/RRKM calculations. The number of reaction steps to $C_7{H_7}^+$ is counted for each path. Of the three isomers, the meta mostly goes through the coupling, whereas the para proceeds with little or no coupling. In the beginning, some reactants with high internal energy decay fast to the benzylium ion without any coupling and others rearrange to the other isomers. Later on all three isomers dissociate to the products via long-lived intermediates. Thus, the reactant shows a multiexponential decay and the branching ratio varies with time as the average internal energy decreases with time. The reciprocal of the effective lifetime is taken as the rate constant. The resulting rate-energy curves are in line with experiments. The present results suggest that the coupling between the stable isomers is thermodynamically controlled, whereas the branching to the product is kinetically controlled.

Electrical Properties of SiOCH Thin Films by Annealing (SiOCH 박막의 열처리에 따른 전기적인 특성)

  • Kim, Min-Seok;Hwang, Chang-Su;Kim, Hong-Bae
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.21 no.12
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    • pp.1090-1095
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    • 2008
  • The SiOCH films that low dielectric interlayer dielectric materials were deposited on p-type Si(100) substrates through the dissociation of BTMSM precursors with oxygen gas by using PECVD method. BTMSM precursor was introduced with the flow rates from 42 sccm to 60 sccm by 2 sccm step in the constant flow rate of 60 sccm $O_2$. SiOCH thin films were annealed at $450^{\circ}C$ for 30 minutes. The electrical property of SiOCH thin films was studied by MIS, Al/SiOCH/p-Si(100), structure. Annealed samples showed even greater reductions of the maximum capacitance and the dielectric constant of the SiOCH samples, owing to reductions of surface charge density. we confirmed this result with derivative of C-V characteristic, leakage current density. The maximum capacitance and leakage current density were respectively decreased about 4 pF, 60% after annealing. The average of low-k value is approximatly 2.07 after annealing.

Preparation of High Molecular Weight Atactic Poly(vinyl alcohol) by Photo-induced Bulk Polymerization of Vinyl Acetate

  • Lyoo, Won-Seok;Ha, Wan-Shik
    • Fibers and Polymers
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    • v.2 no.2
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    • pp.108-115
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    • 2001
  • Vinyl acetate was polymerized in ultraviolet-ray initiated bulk system at low temperatures using 2,2-azobis(2,4-dimethylvaleronitrile) (ADMVN) or 2,2-azobis(isobutyronitrile) (AIBN) as the photoinitiator, respectively. High molecular weight (HMW) poly(vinyl alcohol) (PVA) having number-average degree of polymerization ($P_n$) of 3,900-7,800 and syndiotactic diad (S-diad) content of 52.5-54.0% could be prepared by complete saponification of synthesized linear poly(vinyl acetate) (PVAc) having $P_n$ 5,900-9,400 obtained at conversion of below 30%. $P_n$ of PVA using ADMVN was larger than that of PVA using AIBN. On the other hand, conversion of the former was smaller than that of the latter, and it was found that the initiation rate of the ADMVN was lower than that of AIBN. This could be explained by a fact that the rate of photolysis of AIBN is faster than that of ADMVN due to the higher quantum yield or dissociation rate constant of AIBN than that of ADMVN. The $P_n$, syndiotacticity, and whiteness of PVA from PVAc polymerized at lower temperatures were superior to those of PVA from PVAc polymerized at higher temperatures.

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Stabilization of Bioluminescence of Immobilized Photobacterium phosphoreum and Monitoring of Environmental Pollutants

  • Britz, Margaret L.;Nina Simonov;Chun, Uck-Han
    • Journal of Microbiology and Biotechnology
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    • v.7 no.4
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    • pp.242-249
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    • 1997
  • Stability of bioluminescence was investigated with Photobacterium phosphoreum immobilized on the strontium alginate in order to develope continuous real time monitoring of pollutants. The stability of bioluminescence emission was improved by prolonged aging time. The aging time of ${\geq}40$ min and the cell concentration of ${\leq}0.6\;of\;OD_660$ were selected for the immobilization of P. phosphoreum to give linearity between cell concentrations and bioluminescence intensity. In sensitivity tests using phenol, it was found that this compound quenched bioluminescence proportional to the concentration without lowering of cell growth. The lower value for maximum quenching ($q_s$) and higher dissociation constant ($K_s$) were observed with strontium-alginate immobilized cells compared to free cells. The response of bioluminescence to toxicants was evaluated with the immobilized luminescent bacteria. The sensitivity of the immobilized cells was found to be good in response to toxicants, 4-nitrophenol, salicylate and cadmium, when evaluated with a specific rate of bioluminescence quenching.

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EFFECTS OF SUBSTRATE TEMPERATURE ON PROPERTIES OF FLUORINE CONTAINED SILICON OXIDE FILMS PREPARED BY MICROWAVE PLASMA- ENHANCED CVD

  • Sugimoto, Nobuhisa;Hozumi, Atsushi;Takai, Osamu
    • Journal of the Korean institute of surface engineering
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    • v.29 no.5
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    • pp.577-584
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    • 1996
  • Silicon oxide films with high hardness and water repellency were prepared by microwave plasma-enhanced CVD using four kind of organosilicon compound-fluoro-alkyl silane mixtures as source gases. An argon gas was used as a carrier gas for fluoro-alkyl silane. The substrate temperatures during deposition were controlled by resistant heating at a constant value between 50 and $300^{\circ}C$. The hardness of the films increased, but the deposition rate and the contact angle for a water drop decreased with increasing substrate temperature. The number of methoxy groups also affected the water repellency and hardness. The deposited films became more inorganic with increasing substrate temperature because of the thermal dissociation of reactants.

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