• Title/Summary/Keyword: reaction pH

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Mechanism of the Hydrolysis of 2-Phenyl-4H,5H,6H-3-methyl-3-thiazinium Perchlorate Derivatives

  • 김태린;이소영;변상용;김주창;한만소
    • Bulletin of the Korean Chemical Society
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    • v.20 no.10
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    • pp.1213-1217
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    • 1999
  • Hydrolysis reactions of 2-phenyl-4H,5H,6H-3-methyl-3-thiazinium perchlorate (PTP) and its derivatives at various pH have been investigated kinetically. The hydrolysis is quantitative, producing N-3-mercaptopropyl-N-methylbenzamide as the only product in the all pH ranges. The observed rate of hydrolysis of PTP was always of the first-order. For hydrolysis from PTP, Hammett ρvalues were 0.53, 0.84 and 1.13 for pH 5.0, 8.0, and 10.0, respectively. Bronsted βvalue was 0.53 for general base catalysis. This reaction is catalyzed by general w acetate concentration. However, as the amount of base becomes larger, the rate of hydrolysis reaction approaches the limiting values. The plot of log k vs. pH shows that the rate constants (kt) are two different regions in the profile; one part is directly proportional to hydroxide ion concentration and the other is not. On the bases of these result, the plausible hydrolysis mechanism and a reaction equation were proposed: Below pH 4.5, the hydrolysis was initiated by the addition of water to α-carbon. Above pH 9.0, the hydrolysis was proceeded by the addition of hydroxide ion to α-carbon. However, in the range of pH 4.5-8.0, these two reactions occured competitively.

The Effect of Initial pH on the Synthesis of Mesoporous Molecular Sieve, MCM-41 (MCM-41 분자체의 합성에 초기 pH가 미치는 영향)

  • Kim, Wha-Jung;Yoo, Jae-Churl
    • Applied Chemistry for Engineering
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    • v.8 no.3
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    • pp.463-472
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    • 1997
  • A mesoporous molecular sieve, MCM-41, was synthesized and the effent of various initial pH of reaction mixtures on the synthesis and physical properties of MCM-41 was investigated. Adjustment of initial pH for reaction mixtures was made before starting hydrothermal reaction rather than during the reaction. Highly crystalline MCM-41 which shows pore diameters of $30{\AA}$ to $40{\AA}$ and specific surface areas greater than $1000m^2/g$ has been successfully prepared through a single adjustment of initial pH. Results also suggest that the initial pH adjustment has a significant effect on the formation of MCM-41 with a long-range ordered hexagonal array and an excellent thermal stability. Finally, it is speculated that the adjustment of initial pH might accelerate the dissolution of stable polymeric sodium silicate to highly reactive monomeric sodium silicate resulting in well-ordered MCM-41.

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Effects of Reaction Conditions for Improvement of Caramelization Rate (Caramel화 반응속도 향상을 위한 반응조건의 영향)

  • Park, Cheon-Woo;Kang, Kun-Og;Kim, Woo-Jung
    • Korean Journal of Food Science and Technology
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    • v.30 no.4
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    • pp.983-987
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    • 1998
  • Effects of sugars, temperature, pH and some chemicals on caramelization were investigated for improving of its reaction rates. Among the sugars tested, fructose showed the fastest reaction rate, followed by sucrose, glucose, starch syrup and maltose. As the reaction temperature increased from 80 to $110^{\circ}C$, the rate greatly increased by the range of $150{\sim}8000$ folds depending on sugars. It was indicated that pH 10 resulted in the highest reaction rate in the range of $pH{\;}4{\sim}10$. When several chemicals, such as phosphates and organic acid salts, were added to starch syrup, the rate increased by more than 10 folds, in particular effects of $K_2HPO_4$ and sodium salts of citrate, oxalate and succinate were significant.

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Effect of Precipitation Temperature and Solution pH on the Precipitation of Ammonium Metavanadate (침전온도 및 수용액 pH가 암모늄메타바나데이트 침전반응에 미치는 영향)

  • Heo, Seo-Jin;Kim, Rina;Chung, Kyeong Woo;Jeon, Ho-Seok;Kim, Chul-Joo;Yoon, Ho-Sung
    • Resources Recycling
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    • v.30 no.6
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    • pp.3-11
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    • 2021
  • In this study, the effect of the solubility of ammonium metavanadate and the decomposition ratio of ammonium ions on a precipitation reaction-the precipitation of ammonium metavanadate by adding ammonium chloride to a sodium vanadate solution-was investigated. As the precipitation temperature and pH increased, the decomposition ratio of ammonium ions increased, and the decomposition ratio was greater than 81% at 45 ℃ and pH 9.3. This was approximately four times higher than that at pH 8. The result of the precipitation reaction, in view of these two factors that significantly influence the precipitation reaction, was that the precipitation yield increased as the temperature increased. However, the effect of temperature was not significant above 35 ℃. A kinetic study of the precipitation reaction revealed that the activation energy of the reaction was 42.3 kJ/mol. Therefore, considering the solubility of ammonium metavanadate, the lower the temperature, the better the vanadium recovery yield. Additionally, considering the decomposition of ammonium ions, the lower the pH of the aqueous solution, the more advantageous. However, at pH 8 or less, sodium polyvanadate is precipitated and the purity of vanadium oxide may reduce.

The pH Reduction of the Recycled Aggregate Originated from the Waste Concrete by the scCO2 Treatment (초임계 이산화탄소를 이용한 폐콘크리트 순환골재의 중성화)

  • Chung, Chul-woo;Lee, Minhee;Kim, Seon-ok;Kim, Jihyun
    • Economic and Environmental Geology
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    • v.50 no.4
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    • pp.257-266
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    • 2017
  • Batch experiments were performed to develop the method for the pH reduction of recycled aggregate by using $scCO_2$ (supercritical $CO_2$), maintaining the pH of extraction water below 9.8. Three different aggregate types from a domestic company were used for the $scCO_2$-water-recycled aggregate reaction to investigate the low pH maintenance of aggregate during the reaction. Thirty five gram of recycled aggregate sample was mixed with 70 mL of distilled water in a Teflon beaker, which was fixed in a high pressurized stainless steel cell (150 mL of capacity). The inside of the cell was pressurized to 100 bar and each cell was located in an oven at $50^{\circ}C$ for 50 days and the pH and ion concentrations of water in the cell were measured at a different reaction time interval. The XRD and SEM-EDS analyses for the aggregate before and after the reaction were performed to identify the mineralogical change during the reaction. The extraction experiment for the aggregate was also conducted to investigate the pH change of extracted water by the $scCO_2$ treatment. The pH of the recycled aggregate without the $scCO_2$ treatment maintained over 12, but its pH dramatically decreased to below 7 after 1 hour reaction and maintained below 8 for 50 day reaction. Concentration of $Ca^{2+}$, $Si^{4+}$, $Mg^{2+}$ and $Na^+$ increased in water due to the $scCO_2$-water-recycled aggregate reaction and lots of secondary precipitates such as calcite, amorphous silicate, and hydroxide minerals were found by XRD and SEM-EDS analyses. The pH of extracted water from the recycled aggregates without the $scCO_2$ treatment maintained over 12, but the pH of extracted water with the $scCO_2$ treatment kept below 9 of pH for both of 50 day and 1 day treatment, suggesting that the recycled aggregate with the $scCO_2$ treatment can be reused in real construction sites.

Quasiclassical Trajectory Calculations for the Reaction Ne + H2+ → NeH+ + H

  • Wang, Yuliang;Tian, Baoguo;Qu, Liangsheng;Chen, Juna;Li, Hui
    • Bulletin of the Korean Chemical Society
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    • v.32 no.12
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    • pp.4210-4214
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    • 2011
  • Quasiclassical trajectory (QCT) calculations of Ne + ${H_2}^+$ reaction have been carried out on the adiabatic potential energy surface of the ground state $1^2$ A'. The reaction probability of the title reaction for J = 0 has been calculated, and the QCT result is consistent with the previous quantum mechanical wave packet result. Quasiclassical trajectory calculations of the four polarization-dependent differential cross sections have been carried out in the center of mass (CM) frame. The P(${\theta}_r$), P(${\phi}_r$) and P(${\theta}_r$, ${\phi}_r$) distributions, the k-k'-j' correlation and the angular distribution of product rotational vectors are presented in the form of polar plots. Due to the well in $1^2$ A' PES, the reagent vibrational excitation has greater influence on the polarization of the product rotational angular momentum vectors j' than the collision energy.

Kinetics and Mechanism of Nucleophilic Addition of Sodium Thiophenoxide to $\alpha$-(n-Butyl)-N-Phenylnitrone Derivatives ($\alpha$-(n-Butyl)-N-Phenylnitrone 유도체에 대한 Sodium Thiophenoxide의 친핵성 첨가반응 메카니즘과 그의 반응 속도론적 연구)

  • Lee, Gwang Il;Lee, Seok U;Gwak, Cheon Geun;Kim, Yeong Ju;No, Seung Il;Lee, Gi Chang
    • Journal of the Korean Chemical Society
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    • v.38 no.6
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    • pp.442-448
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    • 1994
  • The rate constants of the nucleophilic reaction of ${\alpha}$-(n-butyl)-N-phenylnitrone and its derivatives have been determined by ultraviolet spectrophotometry at $25^{\circ}C$ and a rate equation which can be applied over a wide pH range was obtained. Final product of the addition reaction was $\alpha$-phenylthiobutylidene-aniline. Base on the rate equation, genernal base effect, substituent effect and final product, plausible mechanism of addition reaction have been proposed. Below pH 3.0 the reaction was inititated by the addition of thiophenol, and in the range of pH 3.0∼10.0, proceeded by the competitive addition of thiophenol and thiophenoxide anion. Above the pH 10.0, the reaction proceeded through the addition of a thiophenoxide anion.

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Wollastonite from and Its Dissolution Behaviors (수산 지역의 규회석과 그 용해 거동)

  • 김수진;현성필;이성근
    • Journal of the Mineralogical Society of Korea
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    • v.9 no.1
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    • pp.1-6
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    • 1996
  • Woolastonite from Susan occurs as intercalations in limestone beds of Lower Paleozoic Joseon Supergroup. It is a thermal metamorphic product of impure limestone. Electron microprobe analysis shows that it is considerably pure wollastonite. It has triclinic cell with a=7.932$\AA$, b=7.328$\AA$, c=7.069$\AA$, $\alpha$=89.995$^{\circ}$, $\beta$=$95.255^{\circ}$, and $ \Upsilon=103.367^{\circ}$.Dissolution behaviors of wollastonite have been studied conducting three different dissolution experiments; two different reactions with HC1 (one batch and one re-initialization experiment) and one traction with distilled water. In the batch type powder wollastonite-HCl reaction, pH of solution rapidly increases in the early stage and then its rate of increase slows down to reach plateau resulting in parabolic relationship with time. It is represented by the early rapid rise and fall in pH giving a sharp pH-edge and succeeding slow rise in the re-initialization experiment. The early rapid rise in pH is due to the rapid sorption of H- in solution to oxygens on the reactive surface of wollastonite and the fall in pH means that all reactive surface sites are occupied by H- ions and no more H- adsorption occurs. The slow rise in pH following the pH- edge is due to the dissolution of wollastonite as evidenced by the correlation of pH variation and cation concentration. Dissolution of powder wollastonite in HCl shows linear trend with time. Si is dissolved predominantly over Ca at a constant rate. Ca is dissolved predominantly in the very early stage. Dissolution rate of coarse-grained wollastonite fragments in distilled water is parabolic with times howing a rapid reaction in the early stage and a slow reaction in the advanced stage. The Ca/Si ratio in solution is high in the case of coarse-grained wollastonite fragment as compared with powder wollastonite. The coarse-grained wollastonite fragment-water (acid) reaction resulted in the solution with an elevated constant pH value (alkaline) giving an important significance on the environmental view point.

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Generation of Reactive Oxygen Species by Nonenzymatic Reaction of Menadione with Protein Thiols in Plasma (Menadione과 Plasma내의 Protein Thiol의 비효소적인 화학반응에 의한 활성산소 생성)

  • 정선화;이무열;이주영;장문정;정진호
    • Toxicological Research
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    • v.13 no.3
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    • pp.223-228
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    • 1997
  • Quinones have been reported to undergo nonenzymatic reaction with thiols to generate reactive oxygens. It is therefore possible that the nonenzymatic reaction of quinones with thiols in plasma could lead to potentJared cellular toxicity or disease. When 1 mM menadione was added in plasma under pH 11.2, 7.4 and 5.0, the increase in oxygen consumption rate was the order of pH 11.2 > pH 7.4 > pH 5.0. In addition, oxygen consumption rates under plasma anticoagulated with trisodium citrate solution (pH 7.85) was significantly higher than those with acid-citrate-dextrose solution (pH 6.87). SOD and catalase reduced the rate of oxygen consumption induced by menadione in plasma. Taken together, these results suggest that the menadione-induced increased oxygen consumption was due to nonenzymatic reaction of menadione with thiols in the plasma. The presence of plasma has an additive effect on the increased oxygen consumption rates induced by the menadione treatments on our model tissue, platelets, as compared between washed platelet (WP) and platelet rich plasma (PRP). Cytotoxicity, as determined by LDH release, are well correlated with the oxygen consumption rates observed in each system and strongly suggest that menadione-induced cytotoxicity can be increased with the presence of blood plasma.

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Improving the CO2 Sequestration Capability and Mechanical Properties of CO2 Reactive Cement Paste Using pH Swing Method (pH Swing법을 활용한 이산화탄소 반응경화형 시멘트 경화체의 CO2 고정화 성능 및 기계적 물성 개선)

  • Cho, Seong-Min;Kim, Gyeong-Ryul;Bae, Sung-Chul
    • Proceedings of the Korean Institute of Building Construction Conference
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    • 2023.05a
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    • pp.115-116
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    • 2023
  • This study aims to investigate and improve the carbon dioxide sequestration capability and the mechanical properties of non-hydraulic low calcium silicate cement especially designed for CO2 reaction and ordinary Portland cement subjected to the carbonation curing facilitating pH swing method. Nitric acid (HNO3) was utilized as an liquid for the mixing of cement paste to enhance the initial dissolution of Ca ions from the cements by promoting low pH environment and prevent the direct precipitation of Ca with the anion, owing to the high solubility of Ca(NO3)2 in water. The results presented that the higher the concentration of HNO3, the higher the compressive strength and CO2 sequestration (until 0.1 M). Ca dissolution caused by the harsh acid attack onto the anhydrous cement particle lead to the higher carbonation reaction degree, forming abundant CaCO3 crystals after the reaction. However, cement paste mixed with excessively high concentration of HNO3 presented deterioration due to the too harsh pH environment and abundant NO3- ions which are known to retard the reaction of cement.

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