• Title/Summary/Keyword: Slow Reaction

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Chemical Reactions in Surfactant Solutions (Ⅳ) : Micellar Rate Effect on Reactions of Hydroxide and o-Iodosobenzoate Ions with Organic Phosphinates (계면활성제 용액속에서의 화학반응 (제 4 보) : $OH^-$ 및 o-Iodosobenzoate 이온에 의한 유기 포스피네이트의 탈인산화 반응에 미치는 CTAX 미셀의 영향)

  • Hong, Yeong Seok;Kim, Hyeon Muk
    • Journal of the Korean Chemical Society
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    • v.38 no.10
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    • pp.753-762
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    • 1994
  • Dephosphorylation of diphenyl- or isopropylphenyl-4-nitrophenylphosphinate (DPNPIN or IPNPIN) mediated by $OH^-$ or o-iodosobenzoate ion ($IB^-$) are relatively slow in aqueous solution. The reactions in CTAX micellar solutions are, however, very accelerated, because CTAX micelles can accommodate both reactants in their Stern layer in which they can easily react, while hydrophilic $OH^-$(or $IB^-$) and hydrophobic phosphinates are not mixed in water. Even though the concentrations (> $10^{-3}$ M) of $OH^-$(or $IB^-$) in CTAX solutions are much larger amounts than those ($6{\times}10^{-6}$ M) of phosphinates, the rate constants of the dephosphorylations are largely influenced by change of the concentration of the ions, which means that the reactions are not followed by the pseudo first order kinetics. In comparison to effect of the counter ions of CTAX in the reactions, CTACl is more effective on the dephosphorylation of DPNPIN (or IPNPIN) than CTABr due to easier expelling of $Cl^-$ ion by $OH^-$(or $IB^-$) ion from the micelle, because of easier solvation $Cl^-$ ion by water molecules. The reactivity of IPNPIN with $OH^-$(or $IB^-$) is lower than that of DPNPIN. The reason seems that the 'bulky' isopropyl group of IPNPIN hinders the attack of the nucleophiles. The mechanism of reaction of IPNPIN with IB- ion concluded as 'nucleophilic' instead of 'general basic' by a trapping experiment and a measured kinetic isotope effect.

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Removal of Soluble Fe(II) using Reactive Media Coated with both Fe and Mn (철과 망간이 동시에 코팅된 반응성 매질을 이용한 용존 Fe(II) 제거)

  • Min, Sang-Yoon;Chang, Yoon-Young;Yang, Jae-Kyu
    • Journal of Korean Society of Environmental Engineers
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    • v.33 no.2
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    • pp.85-92
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    • 2011
  • Evaluation of the removal efficiencies of Fe(II) by reactive sand media coated with manganese (MCS), iron (ICS) and both of iron and manganese (IMCS) was investigated as functions of solution pH ranging from 2 to 9, reaction time and concentration of Fe(II) in a batch reactor using each reactive medium and additional oxidants such as $KMnO_4$ and NaOCl. When only Fe(II) was present in solution without any reactive medium, removal of Fe(II) was quite low below pH 5 due to a slow oxidation of Fe(II) and/or negligible precipitation but greatly increased above pH 5 due to a rapid oxidation of Fe(II) and subsequent precipitation of oxidized Fe species. ICS showed negligible efficiency on the removal of Fe(II) through adsorption. However, an efficient removal of Fe(II) was observed at low solution pH in the presence of IMCS or MCS through rapid oxidation and subsequent precipitation. Removal efficiency of Fe(II) by IMCS in the presence or absence of NaOCl was quite similar. Removal rate of Fe(II) by IMCS and additional oxidants gradually increased as the solution pH increased. From the kinetic experiments, removal pattern of Fe(II) was better described by pseudo-second-order equation than pseudo-first-order equation. A rapid removal of Fe(II) using IMCS in the presence of $KMnO_4$ was observed in the first 10 min. The initial removal rate of Fe(II) using $KMnO_4$ was 14,286 mg/kg hr. In case of using NaOCl, the removal of Fe(II) occurred rapidly in the first 6 hrs and then reached the near-equilibrium state. Removal of Fe(II) on IMCS was well expressed by Langmuir isotherm and the maximum removal capacity of Fe(II) was calculated as 1,088 mg/kg.

Jet Lag and Circadian Rhythms (비행시차와 일중리듬)

  • Kim, Leen
    • Sleep Medicine and Psychophysiology
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    • v.4 no.1
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    • pp.57-65
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    • 1997
  • As jet lag of modern travel continues to spread, there has been an exponential growth in popular explanations of jet lag and recommendations for curing it. Some of this attention are misdirected, and many of those suggested solutions are misinformed. The author reviewed the basic science of jet lag and its practical outcome. The jet lag symptoms stemed from several factors, including high-altitude flying, lag effect, and sleep loss before departure and on the aircraft, especially during night flight. Jet lag has three major components; including external de synchronization, internal desynchronization, and sleep loss. Although external de synchronization is the major culprit, it is not at all uncommon for travelers to experience difficulty falling asleep or remaining asleep because of gastrointestinal distress, uncooperative bladders, or nagging headaches. Such unwanted intrusions most likely to reflect the general influence of internal desynchronization. From the free-running subjects, the data has revealed that sleep tendency, sleepiness, the spontaneous duration of sleep, and REM sleep propensity, each varied markedly with the endogenous circadian phase of the temperature cycle, despite the facts that the average period of the sleep-wake cycle is different from that of the temperature cycle under these conditions. However, whereas the first ocurrence of slow wave sleep is usually associated with a fall in temperature, the amount of SWS is determined primarily by the length of prior wakefulness and not by circadian phase. Another factor to be considered for flight in either direction is the amount of prior sleep loss or time awake. An increase in sleep loss or time awake would be expected to reduce initial sleep latency and enhance the amount of SWS. By combining what we now know about the circadian characteristics of sleep and homeostatic process, many of the diverse findings about sleep after transmeridian flight can be explained. The severity of jet lag is directly related to two major variables that determine the reaction of the circadian system to any transmeridian flight, eg., the direction of flight, and the number of time zones crossed. Remaining factor is individual differences in resynchmization. After a long flight, the circadian timing system and homeostatic process can combine with each other to produce a considerable reduction in well-being. The author suggested that by being exposed to local zeit-gebers and by being awake sufficient to get sleep until the night, sleep improves rapidly with resynchronization following time zone change.

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