• Title/Summary/Keyword: Hydronium

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The Kinetics and Mechanism of the Hydrolysis of a 1,1-Dicyano-2-p-dimethylaminophenyl-2-chloroethylene (1,1-Dicyano-2-p-dimethylaminophenyl-2-chloroethylene의 가수분해 반응메카니즘과 그의 반응속도론적 연구)

  • Tae Rin Kim;Tae Seong Huh
    • Journal of the Korean Chemical Society
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    • v.18 no.6
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    • pp.430-436
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    • 1974
  • The rate constants of hydrolysis of 1,1-dicyano-2-p-dimethylaminophenyl-2-chloroethylene(DPC) were determined at various pH and the rate equation which can be applied over wide pH range is obtained. From the rate equation the mechanism of the hydrolysis of a DPC over wide pH range is fully explained; below pH 3 and above pH 7.5, the rate constant is proportional to the concentration of hydronium ion and hydroxide ion, respectively. However, in the range of pH 3 to 7.5, water, hydronium ion and hydroxide ion catalyze the hydrolysis of DPC.

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Surface Segregation of Hydroniums and Chlorides in a Thick Ice Film at Higher Temperatures

  • Lee, Du Hyeong;Bang, Jaehyeock;Kang, Heon
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.02a
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    • pp.263-263
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    • 2013
  • This work examines the dynamic properties of ice surfaces in vacuum for the temperature range of 140~180 K, which extends over the onset temperatures for ice sublimation and the phase transition from amorphous to crystallization ice. In particular, the study focuses on the transport processes of excess protons and chloride ions in ice and their segregative behavior to the ice surface. These phenomena were studied by conducting experiments with a relatively thick (~100 BL) ice film constructed with a bottom $H_2O$ layer and an upper $D_2O$ layer, with excess hydronium and chloride ions trapped at the $H_2O$/$D_2O$ interface as they were generated by the ionization of hydrogen chloride. The migration of protons, chloride ions, and water molecules to the ice film surface and their H/D exchange reactions were measured as a function of temperature using the methods of low energy sputtering (LES) and Cs+ reactive ion scattering (RIS). Temperature programmed desorption (TPD) experiments monitored the desorption of water and hydrogen chloride from the surface. Our observations indicated that both hydronium and chloride ions migrated from the interfacial layer to segregate to the surface at high temperature. Hydrogen chloride gas desorbs via recombination reaction of hydronium and chloride ions floating on the surface. Surface segregation of these species is driven by thermodynamic potential gradient present near the ice surface, whereas in the bulk, their transport is facilitated by thermal diffusion process. The finding suggests that chlorine activation reactions of hydrogen chloride for polar stratospheric ice particles occur at the surface of ice within a depth of at most a few molecular layers, rather than in the bulk phase.

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Zundel- and Eigen-like Surface Hydrated Protons on Pt(111)

  • Kim, Youngsoon;Park, Youngwook;Shin, Sunghwan;Kang, Heon
    • Proceedings of the Korean Vacuum Society Conference
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    • 2016.02a
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    • pp.167.1-167.1
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    • 2016
  • The interaction between adsorbed water and hydrogen on metallic surfaces is important for fundamental understanding of heterogeneous catalysis and electrode surface reactions in acidic environment. Here, we explore a long-standing question of whether hydronium ion can exist or not on a Pt surface coadsorbed with atomic hydrogen and water. Studies based on mass spectrometry and infrared spectroscopy show clear evidence that hydrogen atoms are converted into hydrated protons on a Pt(111) surface. The preferential structures of hydrated protons are identified as multiply hydrated $H_5O_2{^+}$ and $H_7O_3{^+}$ species rather than as hydronium ions. The multiply hydrated protons may be regarded as two dimensional zundel ($H_5O_2{^+}$) and Eigen cation ($H_7O_3{^+}$) in water-metal interface. These surface-bound hydrated protons may be key surface intermediates of the electrochemical interconversion between adsorbed hydrogen atoms and solvated protons.

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The Role of Excipients in Iontophoretic Drug Delivery: In vitro Iontophoresis of Isopropamide and Pyridostigmine through Rat Skin and Effect of Ion-pair Formation with Organic Anions

  • Shim, Chang-Koo
    • Journal of Pharmaceutical Investigation
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    • v.23 no.3
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    • pp.41-50
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    • 1993
  • The iontophoretic delivery across rat skin of quaternary ammonium salts (isopropamide: ISP, pyridostigmine: PS), which are positively charged over a wide pH range, was measured ill vitro. The study showed that: (a) iontophoresis significantly enhanced delivery of ISP and PS compared to respective passive transport; (b) delivery of ISP and PS was directly proportional to the applied continuous direct current density over the range of $0-0.69\;mA/cm^2;$ (c) delivery of ISP and PS was also proportional to the drug concentration in the donor compartment over the range of $0-2{\time}l0^{-2}M:$ (d) sodium ion in the donor compartment inhibited the drug transport possibly due to decreasing the electric transference number of the drug; (e) delivery of ISP and PS increased as the pH of the donor solution increased over the pH range 2-7 suggesting permselective nature of the epidermis, and inhibition of the transference number of the drugs by hydronium ion; (f) some organic anions such as taurodeoxycholate, salicylate and benzoate which form lipophilic ion-pair complexes with ISP inhibited the delivery of ISP. The degree of inhibition by the organic anions was linearly proportional to the extraction coefficient $(K_e)$ of ISP from the partition system with each counteranion between phosphate buffer (pH 7.4) and n-octanol. For PS, however, taurodeoxycholate, but not salicylate and benzoate inhibited the iontophoretic delivery. It suggests that not only sodium ion and hydronium ion but also the counteranions which form lipophilic ion-pairs with quaternary ammonium drugs are not favorable components in formulating the donor solution of the drugs to achieve an effective iontophoretic delivery.

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A study on the Physico-chemical Properties of CB-ph. a New Anti-cancer drug

  • Kim, Su-Yoen;Kim, Dae-Duk;Lee, Chi-Ho
    • Proceedings of the PSK Conference
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    • 2002.10a
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    • pp.413.1-413.1
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    • 2002
  • Purpose To investigate the physico-chemical properties of CB-ph [2-benzoyloxycinnamaldehyde], an anticancer drug obtained from Cinnamomum cassia using methylenechloride. and its stability in various aqueous solutions. Results CB-ph was rarely soluble in water but soluble in methanol and very soluble in ether. Kinetic salt effect on degradation of CB-ph in buffer solutions at pH 4.0 and 6$0^{\circ}C$ showed a linear relationship having a positive slope that means reactions between hydronium ions and protonated substrates. (omitted)

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Understand the Molecular Orbital Theory on the Hydrolytic Reactivity of Herbicide Flumioxazine (제초제 Flumioxazine의 가수분해 반응성에 관한 분자 궤도론적 이해)

  • Sung, Nack-Do;Jung, Hoon-Sung
    • The Korean Journal of Pesticide Science
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    • v.8 no.4
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    • pp.265-271
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    • 2004
  • Hydrolytic reactivities of N-phenylphthalimid herbicide flumioxazine (S) were disccused using molecular orbital (MO) theoretical method. It is revealed that below pH 5.0, the protonation $(SH^+)$ to carbonyl oxygens atom $(O_{21})$ of 1,2-dicarboximino group by general acid catalysis $(k_A)$ with hydronium ion $(H_3O^+)$ proceeds via charge controled reaction. Whereas, the specific base catalysis $(k_{OH})$ with hydroxide anion via orbital controled reaction occurs above pH 8.0. We may concluded that in the range of pH $5.0\sim8.0$, the hydrolysis proceeds through nucleophilic addition elimination $(Ad_{N-E})$ reaction, these two reactions occur competitively.

Thermal Stability of Photo-produced H3O+ in the Photolyzed Water-ice Film

  • Moon, Eui-Seong;Kang, Heon
    • Proceedings of the Korean Vacuum Society Conference
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    • 2011.08a
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    • pp.192-192
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    • 2011
  • Hyperthermal ion scattering experiments were conducted with low kinetic energy (<35 eV) cesium ion beams to analyze the UV-photolyzed water-ice films. Neutral molecules (X) on the surface were detected as cesium-molecule ion clusters ($CsX^+$) which were formed through a Reactive Ion Scattering (RIS) process. Ionic species on the surface were desorbed from the surface via a low energy sputtering (LES) process, and were analyzed [1]. Using these methods, the thermal stability of hydronium ion ($H_3O^+$) that was produced by UV light was examined. As the thermal stability of $H_3O^+$ is related with the reaction, $H_3O^+$ + OH + $e^-$ (or $OH^-$) ${\rightarrow}$ $2H_2O$, which is similar or same with the reverse reaction of the auto-ionization of water, the result from this work would be helpful to understand the auto-ionization of $H_2O$ in water-ice that has not been well-understood yet. However, as $H_3O^+$ was not detected through a LES method, the titration experiment of $H_3O^+$ with methylamine ($CH_3NH_2$, MA), MA + $H_3O^+\;{\rightarrow}\;MAH^+$ + $H_2O$, was conducted. In this case, the presence of $MAH^+$ indicates that of $H_3O^+$ in the ice. Thus the pristine ice was photolyzed with UV light for a few minutes and this photolyzed ice was remained at the certain temperature for minutes without UV light. Then MA was adsorbed on that surface so that the population of $H_3O^+$ was found. From the calibration experiments, the relation of $MAH^+$ and $H_3O^+$ was found, so that the thermal stability of $H_3O^+$ can be investigated [2].

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A Study on the Kinetics and Mechanism of the Hydrolysis of N-Benzylidenebenzenesulfonamide Derivatives (BBSA 유도체의 가수분해메카니즘과 반응속도론적 연구)

  • Suck-Woo Lee;Byung-Man Jang;Gwang Il Lee;Gi Chang Lee
    • Journal of the Korean Chemical Society
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    • v.36 no.6
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    • pp.919-924
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    • 1992
  • The kinetics of the hydrolysis of N-benzylidenebenzenesulfonamide derivatives have been investigated by ultraviolet spectrophotometry in $H_2O$ at $25^{\circ}C$. A rate equation which can be applied over a wide pH range was obtained. The substituent effect on the hydrolysis of N-benzylidenebenzenesulfonamide derivatives were studied and rate of hydrolysis is known to be accelerated by electron withdrowing group. Final product of the hydrolysis was benzenesulfonamide and benzaldehyde. Base on the rate equation, substituent effect, general base effect and final products, hydrolysis of N-benzylidenebenzenesulfonamide derivatives seemed to be initiated by the hydronium ion at the pH 0.2${\sim}$2.5 and proceeded by the neutral $H_2O$ molecule at pH 3.0${\sim}$8.0 but proceeded by the hydroxide ion at above pH 8.5.

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