• Title/Summary/Keyword: water dissociation reaction

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Thermal and Photochemistry of Methyl Iodide on Ice Film Grown on Cu(111)

  • Sohn, Young-Ku;White, John M.
    • Bulletin of the Korean Chemical Society
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    • v.30 no.7
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    • pp.1470-1474
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    • 2009
  • Thermal and photochemistry of methyl iodide ($CH_3I)\;adsorbed\;on\;D_2O$ ice film on Cu(111) at 100 K were studied using temperature-programmed desorption (TPD) time-of-flight mass spectrometry (TOF-MS), X-ray and ultraviolet photoelectron spectroscopies. On the basis of TPD, multilayer and monolayer $CH_3I$ molecules desorb from $D_2O$ ice layer at 120 and 130 K, respectively. Photo-irradiation at 100 K exhibits dramatic changes in the TPD and I $3d_{5/2}\;XPS\;of\;CH_3I$ on ice film, due to a dramatic dissociation of $CH_3I$. The dissociation is likely activated by solvated electrons transferred from the metal substrate during photo-irradiation. No other photo-initiated reaction products were found within our instrumental detection limit. During photo-irradiation, the $CH_3I$, $CH_3$ and I could be trapped (or solvated) in ice film by rearrangement (and self-diffusion) of water molecules. A newly appeared parent molecular desorption peak at 145 K is attributed to trapped $CH_3I$. In addition, the $CH_3$ and I may diffuse through ice and chemisorb on Cu(111), indicated by TPD and I $d_{5/2}$ XPS taken with photo-irradiation time, respectively. No molecular ejection was found during photo-irradiation at 100 K. The work functions for $CH_3I/Cu(111),\;D_2O/Cu(111)\;and\;CH_3I/D_2$O/Cu(111) were all measured to be about 3.9 eV, 1.0 eV downward shift from that of clean Cu(111).

Variation of the CO2 Capture Reaction by Ammonia Solution with Temperature (온도에 따른 암모니아 용액에 의한 CO2 포집 반응의 변화 양상)

  • Kim, Soo-Yeon;Choi, Ye-Seul;Kim, Dong-Su
    • Journal of Korean Society on Water Environment
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    • v.27 no.6
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    • pp.896-904
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    • 2011
  • The features of the capture reaction of $CO_2$ by ammonia solution have been investigated along with the effect of temperature on the reaction based upon computer program-utilizing calculation and thermodynamic estimation. The stable region of $CO{_3}^{2-}$ was observed to increase with temperature and the change of the stable region of $CO{_3}^{2-}$ with temperature was greater than the temperature variation of the stable region of other carbonate species. The distribution diagram for $NH_4{^+}-NH_3$ system was constructed and the rise of temperature resulted in the decrease of the stability of $NH_4{^+}$ ion, which was thought to be due to the endothermic nature of its acidic dissociation. Considering the introduction of $Ca^{2+}$ ion in the carbon capture reaction by $NH_4{^+}$, the temperature was observed to be important in the determination of the order of reaction between carbonate ion and these cations. The removal process of $CO_2$ gas by ammonia solution was presumed to occur in open system and the temperature variations of the concentration of carbonate system species along with their total concentration were calculated for the proper control and design of the real process.

Redox Reaction Mechanisms of Thorium (IV) Complexes with Crown Ethers in Dimethylsulfoxide (디메틸술폭시드용매중에서 Thorium (IV)-Crown Ether 착물의 산화-환원 반응메카니즘)

  • Jung, Hak-Jin;Jung, Oh-Jin;Suh, Hyouck-Choon
    • Journal of the Korean Chemical Society
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    • v.31 no.3
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    • pp.250-257
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    • 1987
  • The electrical conductances for the thorium (IV) complexes with crown ethers have been measured in DMSO, and water solvents, and the oxidation-reduction reaction mechanisms, electron number and diffusion coefficients in the reversible reduction process have been examined by polarography and cyclic voltammography. The dissociation mole ratio of $Th^{4+}$ and nitrate ion are 1:1 and in aprotic solvent, and 1:4 in protic solvent like as water. The limiting molar conductances of all complexes in aprotic solvent have been found to be in the range of $92.2{\times}159$ $ohm^{-1}cm^2mol^{-1}$. In aprotic solvent, DMSO, the reduction of each complex is reversible by one electron reduction of one step, and the range of diffusion coefficients is obserbed to be $5.83\;10^{-6}{\sim}6.90{\times}10^{-6}$. The complexes which have reduction step were hydrolyzed above at 1.8volt with reference saturated calomel electrode, generating the hydrogen gas. The reaction mechanisms of thorium (IV)-crown ether complexes appear as follows. ${Th_m(IV)L_n(H_2O)_x(NO_3)_{4y}}_=^{DMSO} {\overline{{Th_m(IV)L_n(H_2O)_x(NO_3)_{4y-1}}}^+ + NO_3-$

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Preparation and Characterization of Polyurethane Bioadhesive from Hydroxyl-terminated Polylactide and Imidazole-blocked Isocyanate (말단 수산화기를 가진 폴리락타이드와 이미다졸로 블록된 이소시아네이트를 이용한 폴리우레탄 바이오접착제의 합성 및 물성 평가)

  • Shen, Tengfei;Sun, Yingjuan;Sun, Chunfeng;Lu, Mangeng
    • Polymer(Korea)
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    • v.37 no.2
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    • pp.232-239
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    • 2013
  • A series of novel imidazole-blocked diisocyanate bioadhesives (IBAs) were synthesized from reaction of toluene 2, 4-diisocyanate (TDI), isophorone diisocyanate (IPDI), hydroxyl-terminated polylactide (HO-PLA-OH), 1,1,1-trimethylolpropane (TMP), and imidazole. Synthesis of IBAs was confirmed by Fourier transform infrared spectroscopy (FTIR) and gel permeation chromatography (GPC). Differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA) revealed that the TDI-based IBA had lower thermal dissociation temperature and a faster deblocking rate than IBA based on IPDI. Hydroxyl-terminated polyurethane (HPU) was introduced to study the adhesive effect of the synthesized IBAs. Improvement on elastic modulus, tensile strength and water resistance of IBA-modified HPU in comparison with neat HPU suggested the good adhesive effect of IBA due to the strong chemical reaction between released NCO groups from IBA and hydroxyl groups from HPU.

Adsorption Behaviors of Metal Elements onto Illite and Halloysite (일라이트, 할로이사이트에 대한 중금속 원소의 흡착특성)

  • 추창오;김수진;정찬호;김천수
    • Journal of the Mineralogical Society of Korea
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    • v.11 no.1
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    • pp.20-31
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    • 1998
  • Adsorption of metal elements onto illite and halloysite was investigated at $25^{\circ}C$ using pollutant water collected from the gold-bearing metal mine. Incipient solution of pH 3.19 was reacted with clay minerals as a function of time: 10 minute, 30 minute, 1 hour, 12 hour, 24 hour, 1 day, 2 day, 1 week, and 2 week. Twenty-seven cations and six anions from solutions were analyzed by AAs (atomic absorption spectrometer), ICP(induced-coupled plasma), and IC (ion chromatography). Speciation and saturation index of solutions were calculated by WATEQ4F and MINTEQA2 codes, indicating that most of metal ions exist as free ions and that there is little difference in chemical species and relative abundances between initial solution and reacted solutions. The adsorption results showed that the adsorption extent of elements varies depending on mineral types and reaction time. As for illite, adsorption after 1 hour-reaction occurs in the order of As>Pb>Ge>Li>Co, Pb, Cr, Ba>Cs for trace elements and Fe>K>Na>Mn>Al>Ca>Si for major elements, respectively. As for halloysite, adsorption after 1 hour-reaction occurs in the order of Cu>Pb>Li>Ge>Cr>Zn>As>Ba>Ti>Cd>Co for trace elements and Fe>K>Mn>Ca>Al>Na>Si for major elements, respectively. After 2 week-reaction, the adsorption occurs in the order of Cu>As>Zn>Li>Ge>Co>Ti>Ba>Ni>Pb>Cr>Cd>Se for trace elements and Fe>K>Mn>Al, Mg>Ca>Na, Si for major elements, respectively. No significant adsorption as well as selectivity was found for anions. Although halloysite has a 1:1 layer structure, its capacity of adsorption is greater than that of illite with 2:1 structure, probably due to its peculiar mineralogical characteristics. According to FTIR (Fourier transform infrared spectroscopy) results, there was no shift in the OH-stretching bond for illite, but the ν1 bond at 3695 cm-1 for halloysite was found to be stronger. In the viewpoint of adsorption, illite is characterized by an inner-sphere complex, whereas halloysite by an outer-sphere complex, respectively. Initial ion activity and dissociation constant of metal elements are regarded as the main factors that control the adsorption behaviors in a natural system containing multicomponents at the acidic condition.

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Interactions between Water-Soluble Polyparacyclophanes and Drugs (III) -Complex Formation of Water-Soluble Polyparacyclophanes with Fluorescent Hydrophobic Naphthalene Derivatives in Aqueous Solution- (수용성 폴리파라시클로판류와 약물과의 상호작용(제 3보)-수용액 중 수용성 폴리파라시클로판류와 형광 소수 나프탈렌 유도체류와의 복합체 형성-)

  • Chun, In-Koo;Lee, Min-Hwa
    • Journal of Pharmaceutical Investigation
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    • v.19 no.2
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    • pp.71-79
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    • 1989
  • Complex formation of water-soluble polyparacyclophanes bearing two diphenylmethane or two diphenyl ether skeletons with l-anilinonaphthalene-8-sulfonate (ANS) and 2-p-toluidinylnaphthalene-6-sulfonate (TNS) was investigated quantitatively to develop useful host compounds comparing with ${\alpha}\;-\;and\;{\beta}-cyc1odextrins$$({\alpha}-\;and\;{\beta}-CyDs$) in aqueous solution. Benesi-Hildebrand type analysis of the fluorescent intensity showed that the dissociation constants (Kd) of paracyclophane-ANS complexes were $1.55\;{\times}\;10^{-4}M$ for 1,6,20,25-tetraaza[6.1.6.1]paracyclophane(CPM 44) and $1.23\;{\times}\;10^{-4}M$ for 1,7,21,27-tetraaza[7.1.7.1]paracyclophane (CPM 55), and those of paracyclophane-TNS complexes were $6.99\;{\times}\;10^{-6}M$ for CPM 44 and $6.23\;{\times}\;10^{-5}M$ for CPM 55, in 1:1 molar ratio. On the other hand, the Kd values of 1,7,21,27-tetraaza-14,34-dioxa[7.1.7.1]paracyclophane (CPE 55)-ANS, 1,8,22,29-tetraaza-15,36-dioxa[8.1.8.1]paracyclophane (CPE 66)-ANS, CPE 55-TNS, CPE 66-TNS complexes were $1.75\;{\times}\;10^{-3}M$, $3.07\;{\times}\;10^{-3}M$, $3.75\;{\times}\;10^{-3}M$ and $2.15\;{\times}\;10^{-3}M$, respectively. On the contrary, the Kd values of ${\alpha}-CyD-ANS$, ${\beta}-CyD-ANS$, ${\alpha}-CyD-TNS$ and ${\beta}-CyD-TNS$ complexes were found to be $3.98\;{\times}\;10^{-2}M$, $1.05\;{\times}\;10^{-2}M$, $1.38\;{\times}\;10^{-2}M$ and $3.52\;{\times}\;10^{-4}M$, respectively. These results mean that the complexation of CPMs with ANS or TNS is by 5.6-1,975 fold stronger than that for ${\alpha}-or\;{\beta}-CyDs$, and the complex formation of CPEs with ANS or TNS is nearly same as or somewhat stronger than that for ${\alpha}-or\;{\beta}-CyDs$. From the Kd values determined at different temperatures, thermodynamic parameters were calculated and the complexation was found to be a spontaneous exothermic reaction. The effects of pH on Kd values of CPM 44-ANS, and CPM 55-ANS complexes were negligible in the range of pH 1.2-1.8. However, the Kd values of these complexes increased significantly with increasing ionic strength.

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Influence of Alkyl Chain Length on Fragmentations and Ion-Molecule Reactions of Ionized c-C6H11-(CH2)nCO2H

  • Choi, Sung-Seen;So, Hun-Young
    • Bulletin of the Korean Chemical Society
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    • v.26 no.11
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    • pp.1711-1716
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    • 2005
  • Fragmentations and ion-molecule reactions of ionized cyclohexane propionic acid and cyclohexane butyric acid were studied using FTMS and theoretical calculations. The difference in bond dissociation depending on the aliphatic chain length was investigated and mechanisms for the possible rearrangements depending on the aliphatic carbon length were suggested. The most abundant fragment ion of the ionized cyclohexane propionic acid was c-$C_6H_{11}CH_2\;^+$ formed from the molecular ion by the direct C-C bond cleavage, while that of the ionized cyclohexane butyric acid was c-$C_6H_9C(OH)=OH^+$ formed by rearrangement of the molecular ion from the acid to diol form and loss of propyl radical. Stabilities of the radical and distonic ions of $C_nH_{2n}O^{+\bullet}$ formed from the molecular ion were compared. Protonated molecules were dissociated into smaller ions by losing one or two water molecules. The $[nM + H]^+$, $[nM + H - H_2O]^+$, and $[nM + H - 2H_2O]^+$ with n = 2 and 3 were generated by solvation with the neutral molecules in the ICR cell at long ion trapping time.

PERIAPICAL TISSUE REACTION AND ROOT RESORPTION FOLLOWING REPLANTATION WITH DIFFERENT CALCIUM HYDROXIDE PASTES IN RAT (치아재식술 시 근관충전재로 사용된 수산화칼슘 제재의 치근단 조직 반응 및 치근 흡수의 평가)

  • 송상채;이승종;정일영;이찬영;금기연
    • Restorative Dentistry and Endodontics
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    • v.26 no.2
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    • pp.111-120
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    • 2001
  • Calcium hydroxide pastes is widely used in conventional endodontics. Along with the expanded clinical use of calcium hydroxide, literatures suggest mixing calcium hydroxide with other substance. Among added substances the vehicle plays the most importance role in the overall process because it is directly related with the velocity of ionic dissociation of $Ca^{2+}$ and OH ion. In this study, we evalutated and compared periapical tissue response and root resorption after canal was filled with mixture of saline and calcium hydroxide(Junsei Chemical Co.. Japan) as a aqueous vehicle, Metapaste(Meta Co., Korea) as a viscous vehicle paste, Vitapex(Neo Dental, Japan) as a oily vehicle paste and IRM(Caulk Dentsply, USA) in replantation of rat molar. A total of 31 maxillary first molars of Sprague-Dawley female rats, 30 days old were used. The upper 1st molar was extracted and the mesiobuccal canal was filled with mixture of saline and calcium hydroxide, Metapaste, Vitapex. IRM and then replanted. Rats were sacrificed 3 weeks after replantation. the maxillae were removed. section of 4 micron were cut and stained with hematoxylin-eosin, Apical tissue response were observed under light microscope. The results were as follows: 1. Saline mixing group and Metapaste group were significant different in fibrous capsule width compared to Vitapex group and IRM group(P<0.05). 2. Saline mixing group. Metapaste group. Vitapex group and IRM group did not prevent root resorption and there were no statistical difference. 3. In saline mixing group and Metapaste group. loss of pastes were observed in all samples. From the results of our study. we observed loss of pastes in saline mixing group and Metapaste group because of water soluble property and assumed it was related to inflammation in apical area and sealing ability of material. So, we should study and develop calcium hydroxide vehicle which is easily removed and more stable and because of only 3 weeks observation we need more evaluation in long period.

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Determination of Li generated from 10B(n·α)7Li reaction in Boric acid solution (붕산수용액에서 10B(n·α)7Li 핵반응에 의해 생성된 Li 정량)

  • Choi, Ke-Chon;Jung, Yongju;Yoon, Jei-Won;Kim, Won-Ho
    • Analytical Science and Technology
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    • v.16 no.6
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    • pp.443-449
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    • 2003
  • Thermal neutron irradiation experiment of boric acid solution was carried out using HANARO in following three conditions: (A) $^{10}B$ concentration = $203.0{\mu}g/mL$, irradiation time = 1 hr; (B) $^{10}B$ concentration = $381.4{\mu}g/mL$, irradiation time = 1 hr; (C) $^{10}B$ concentration = $381.4{\mu}g/mL$, irradiation time = 0.5 hr. The amount of lithium produced from $^{10}B(n{\cdot}{\alpha})^7Li$ reaction which was generated on neutron irradiation, was measured by flameless atomic absorption spectroscopy. The concentration of $^7Li$ measured in the three experiments was $0.18{\mu}g/mL$ (78.3% of theoretical value, $0.23{\mu}g/mL$) in (A), $0.31{\mu}g/mL$ (70.5% of theoretical value, $0.44{\mu}g/mL$) in (B) and $0.16{\mu}g/mL$ (71.6% of theoretical value, $0.22{\mu}g/mL$) in (C). The pH value of irradiated boric acid was shifted to considerably low. It is estimated that boric acid would be transformed into the polyborate fonn, by radiolysis products of water, which has high dissociation constant.

A Study on Deterioration of Stone Monuments by Acid Fog (산성안개에 의한 석조문화재 구성암석의 손상 연구)

  • Do, Jin Young;Kim, Sang Woo;Cho, Hyen Goo
    • Journal of the Mineralogical Society of Korea
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    • v.28 no.2
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    • pp.135-145
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    • 2015
  • In order to predict the deterioration of stone monument due to acid fog, an artificial fog test using pH4.0 and pH5.6 was applied to the Gyeongju Namsan granite, decite and marble. After the test had weathered Gyeongju Namsan granite a larger weight reduction due to acid fog than fresh one. Decite has shown the most significant changes among the tested rocks with about 0.005 % of weight reduction. Decite and weathered granite will have considerable weight reduction due to acid rain than the acid fog, whereas the marble was expected to show a weight reduction regardless of the phase of water. The porosity and water absorption rate of weathered granite had significantly increased. This result means that the weathered rock is predicted to be more susceptible to acid fog than the fresh rock. The absorption rate of the marble after the test had shown approximately 50 % increase. The color of the samples had slightly changed towards yellow, such tendency was greater shown in weathered rocks. The marble reacted with acid fog had an increased whiteness. A large amount of cation in the samples is caused mainly by the dissociation of minerals through the reaction with acid fog.