• Title/Summary/Keyword: Bronsted acid

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Hydrogen-bonded clusters in transformed Lewis acid to new Brønsted acid over WOx/SiO2 catalyst

  • Boonpai, Sirawat;Wannakao, Sippakorn;Panpranot, Joongjai;Praserthdam, Supareak;Chirawatkul, Prae;Praserthdam, Piyasan
    • Advances in nano research
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    • v.12 no.3
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    • pp.291-300
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    • 2022
  • The behavior of hydrogen species on the surface of the catalyst during the Lewis acid transformation to form Brønsted acid sites over the spherical silica-supported WOx catalyst was investigated. To understand the structure-activity relationship of Lewis acid transformation and hydrogen bonding interactions, we explore the potential of using the in situ diffuse reflection infrared Fourier transform spectroscopy (DRIFTS) with adsorbed ammonia and hydrogen exposure. From the results of in situ DRIFTS measurements, Lewis acid sites on surface catalysts were transformed into new Brønsted acid sites upon hydrogen exposure. The adsorbed NH3 on Lewis acid sites migrated to Brønsted acid sites forming NH4+. The results show that the dissociated H atoms present on the catalyst surface formed new Si-OH hydroxyl species - the new Brønsted acid site. Besides, the isolated Si-O-W species is the key towards H-bond and Si-OH formation. Additionally, the H atoms adsorbed surrounding the Si-O-W species of mono-oxo O=WO4 and di-oxo (O=)2WO2 species, where the Si-O-W species are the main species presented on the Inc-SSP catalysts than that of the IWI-SSP catalysts.

Analysis of 'Ignorance' in Acid-base Models Contents of Chemistry I and Chemistry II Textbooks & Teacher's Guides in 2009 & 2015 Revised Curriculum (2009·2015 개정 교육과정 화학 I 및 화학 II 교과서 및 교사용 지도서에 제시된 산·염기 모델 내용에 대한 '이그노런스' 분석)

  • Lyu, Eun-Ju;Paik, Seoung-Hey
    • Journal of the Korean Chemical Society
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    • v.64 no.3
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    • pp.175-188
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    • 2020
  • The purpose of this study was to analyze chemistry textbooks and teachers' guidebooks from the perspective of 'Ignorance', one of the important features of model. This is because the emphasis is on developing modeling capabilities for students in the 2015 Revised Curriculum. For this, Arrhenius model and Brønsted-Lowry model were selected as acid and base models in neutralization reaction which are important contents in chemistry curriculum. The analysis criteria of this study were extracted by analyzing previous studies and four general chemistry textbooks dealing with 'Ignorance' related to acid and base neutralization reaction. Based on the analysis criteria, we analyzed nine chemistry I textbooks and teacher's guides and six chemistry II textbooks and teacher's guides of the 2015 revised curriculum. In addition, we analyzed contents of four chemistry I textbooks and teacher's guides and three chemistry II textbooks and teacher's guides in the 2009 revised curriculum for comparison according to revised curriculums. We analyzed the contents related to the concept of 'neutralization reaction', 'neutrality', 'quantitative relation of neutralization reaction', 'degree of ionization', and 'ionization constant'. Based on the results of this study, we proposed a way to present 'Ignorance' of the models in teachers' guidebooks that chemistry teachers can understand 'Ignorance' of model and teach modeling capabilities for students.

Analysis of Explanations and Examples of the Brønsted-Lowry Model Presented in Chemistry Textbooks Developed by 2009 Revised Curriculum (2009 개정교육과정의 화학교과서에 제시된 Brønsted-Lowry 모델에 관한 설명과 예시의 문제점 분석)

  • Choi, Hee;Park, Chul-Yong;Kim, Sungki;Paik, Seoung-Hey
    • Journal of the Korean Chemical Society
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    • v.62 no.4
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    • pp.279-287
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    • 2018
  • In this study, we analyzed the explanations and examples of Brønsted-Lowry model in Chemistry I and Chemistry II textbooks of the 2009 revised curriculum. In particular, the definition of the Brønsted-Lowry model, the examples, and the content of experiments were analyzed by the process perspective of chemical equilibrium, emergent process. The analyzed textbooks were 4 kinds of Chemistry I textbooks and 4 kinds of Chemistry II textbooks in 2009 revision curriculum. As a result, Chemical I textbooks did not adequately show the chemical equilibrium viewpoint when explaining the Brønsted-Lowry model. In the Chemistry II textbooks, the examples of Brønsted-Lowry model were not present emergent process viewpoint, and those were described as sequential viewpoint of Arrhenius model. In addition, examples of experiments to demonstrate the Brønsted-Lowry model of Chemistry II textbooks were insufficient. The experimental examples related to the definition of acid bases were at the level of classification by the color change of indicators. The experimental examples for explaining the strength of acid and base were to compare current intensity or amount of hydrogen gas generated from the reaction with metal. In addition, all textbooks presented the state of aqueous solution when describing the Brønsted-Lowry model, causing problems with differentiation from the Arrhenius model. Therefore, it is necessary to develop examples of experiments to help students understand Brønsted-Lowry model by presenting acid and base reaction in the non-aqueous solution state.

Bifunctional Perfluoroaryl Boranes as Cationic Initiators for Isobutylene Polymerization

  • Piers Warren E.;Chase Preston A.;Henderson Lee, D.;Sciarone Timo;Collins Scott;Chai, Jianfang;Parvez Masood
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.150-151
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    • 2006
  • Perfluoroaryl boranes are widely employed as co-catalysts in olefin polymerization processes. Perfluoroaryl diboranes, possessing borane centers in close proximity, are a subclass of this family of compounds that are in theory capable of chelating neutral and anionic bases. The resulting anions are exceptionally weakly coordinating. We have prepared examples of such compounds and studied their coordination behavior with neutral Lewis bases that have the capability to bridge Lewis acid sites in an effort to delineate the kinetic and thermodynamic factors that influence bonding mode. When protic Lewis bases such as alcohols or water are reacted with diboranes, strong Bronsted acids capable of initiating cationic polymerizations under unusual conditions result.

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The Simultaneous Hydrocracking and Hydrodesulfurization over CoPtMo/LaY Catalyst (CoPtMo/LaY 촉매상에서 동시적인 수소화분해반응 및 수소첨가탈황반응)

  • 김문찬;김경림
    • Journal of Korean Society for Atmospheric Environment
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    • v.11 no.2
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    • pp.171-178
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    • 1995
  • The hydrodesulfurization (HDS) of dibenzothiophene (DBT) were performed simultaneously over CoPtMo/LaY catalyst under high H$_{2}$ pressure. The structure and physical properties of this catalyst were characterized using XRD, IR and surface area analyzer. The origin of acid site was mainly Bronsted. The structures of impregnated molybdenum and platinum were deactivated by DBT to MoS$_{2}$ and PtS, respectively. The activities of the HDS and the hydrocracking increased with increasing temperature and pressure. They decreased with increasing the DBT mole ratio(DBT/n-heptane). They remained constant with increasing the H$_{2}$/H.C. mole ratio. With increasing pressure and DBT mole ratio, the products of secondary cracking increased. To perform simultaneous HDS and hydrocracking effectively, the optimum condition were 500.deg.C, 4MPa.

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Kinetics and Mechanism of the Addition of Benzylamines to Benzylidene Meldrum's Acids in Acetonitrile

  • Oh, Hyuck-Keun;Kim, Tae-Soo;Lee, Hai-Whang;Lee, Ik-Choon
    • Bulletin of the Korean Chemical Society
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    • v.24 no.2
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    • pp.193-196
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    • 2003
  • Nucleophilic addition reactions of benzylamines $(XC_6H_4CH_2NH_2)$ to benzylidene Meldrum's acids (BMA; $YC_6H_4CH=C(COO)_2C(CH_3)_2$) have been investigated in acetonitrile at 20.0 ℃. The rates of addition are greatly enhanced due to the abnormally high acidity of Meldrum's acid. The magnitudes of the Hammett $({\rho}_X\;and\;{\rho}_Y)$ and Bronsted $({\rho}_X$)$ coefficients are rather small suggesting an early transition state. The sign and magnitude of the cross-interaction constant, ${\rho}_{XY}$ (= -0.33), and kinetic isotope effects $(k_H/k_D\;{\stackrel}{~}{=}\;1.5-1.7)$ involving deuterated benzylamine nucleophilies $(XC_6H_4CH_2ND_2)$ are indicative of hydrogen-bonded cyclic transition state. The activation parameters, ${\Delta}H^{\neq}\;{\stackrel}{~}{=}\;4\;kcal\;mol^{-1}\;and\;{\Delta}S^{\neq}\;{\stackrel}{~}{=}\;-37\;e.u.$, are also in line with the proposed mechanism.

Preparation and Characterization of Chromium Oxide Supported on Zirconia

  • Sohn Jong Rack;Ryu, Sam Gon;Park Man Young;Pae Yeong Il
    • Bulletin of the Korean Chemical Society
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    • v.13 no.6
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    • pp.605-612
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    • 1992
  • Chromium oxide/zirconia catalysts were prepared by dry impregnation of powdered $Zr(OH)_4$ with ($NH_4$)$_2$CrO$_4$aqueous solution. The characterization of prepared catalysts was performed using FTIR, XPS, XRD and DTA methods, and by the measurement of surface area. The addition of chromium oxide to zirconia shifted the transitions of $ZrO_2$ from amorphous to tetragonal phase and from tetragonal to monoclinic phase to higher temperature due to the strong interaction between chromium oxide and zirconia, and the specific surface area of catalysts increased in proportion to the chromium oxide content. Since the $ZrO_2$ stabilizes supported chromium oxide, chromium oxide was well dispersed on the surface of zirconia, and ${\alpha}$-$Cr_2O_3$ was observed only at the calcination temperature above 1173 K. Upon the addition of only small amount of chromium oxide (1 wt% Cr) to $ZrO_2$, both the acidity and acid strength of catalyst increased remarkably, showing the presence of two kinds of acid sites on the surface of $CrO_x$/$ZrO_4$-Bronsted and Lewis.

A Study on NH3-SCR Vanadium-Based Catalysts according to Tungsten Content for Removing NOx Generated from Biogas Cogeneration (바이오가스 열병합 발전에서 발생하는 NOx 제거를 위한 텅스텐 함량에 따른 NH3-SCR 바나듐계 촉매 연구)

  • Jung, Min Gie;Hong, Sung Chang
    • Clean Technology
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    • v.27 no.4
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    • pp.315-324
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    • 2021
  • In this study, a vanadium catalyst study was conducted on the various characteristics of the exhaust gas in the Selective-Catalytic-Reduction (SCR) method in which nitrogen oxides emitted from cogeneration using biogas are removed by using ammonia as a reducing agent and a catalyst. V/W/TiO2, a commercial catalyst, was used as the catalyst in this study, and the effect was confirmed according to the tungsten content under various operating conditions. As a result of the NH3-SCR experiment, the denitrification performance was confirmed at 380 ~ 450 ℃ more than 95%, and durability to trace amounts of SO2 was confirmed through the SO2 durability experiment and TGA analysis. As a result of H2-TPR analysis, the higher the tungsten content, the better the redox properties. Accordingly, enhanced oxidizing properties were confirmed in the oxidation test for a trace amount of carbon monoxide emitted from the cogeneration. In NH3-DRIFTs analysis, it was confirmed that the higher the tungsten content, the higher both the Bronsted/Lewis acid sites and the better the thermal durability when tungsten is added to the catalyst. Based on the experiments under various operating conditions, it is considered that a catalyst with a high tungsten content is suitable to be applied to cogeneration using biogas.

CO2 Solubilities in Amide-based Brønsted Acidic Ionic Liquids

  • Palgunadi, Jelliarko;Im, Jin-Kyu;Kang, Je-Eun;Kim, Hoon-Sik;Cheong, Min-Serk
    • Bulletin of the Korean Chemical Society
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    • v.31 no.1
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    • pp.146-150
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    • 2010
  • A distinguished class of hydrophobic ionic liquids bearing a Br${\o}$nsted acidic character derived from amide-like compounds were prepared by a neutralization reaction of N,N-diethylformamide, N,N-dibutylformamide, 1-formylpiperidine, and $\varepsilon$-caprolactam with trifluoroacetic acid and physical absorptions of $CO_2$ in these ionic liquids were demonstrated and evaluated. $CO_2$ solubilities in these ionic liquids were influenced by the molecular structure of the cation and were apparently increased with the molar volume. Comparison based on a volume unit reveals that $CO_2$ solubilities in these liquids are relatively higher than those in imidazolium-based ionic liquids. Henry's coefficients calculated from low-pressure solubility tests at 313 to 333 K were used to derive the thermodynamics quantities. Enthalpy and entropy of solvation may share equal contributions in solubility.

Transesterification of Jatropha Oil over Ceria-Impregnated ZSM-5 for the Production of Bio-Diesel

  • Bhagiyalakshmi, Margandan;Vinoba, Mari;Grace, Andrews Nirmala
    • Bulletin of the Korean Chemical Society
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    • v.34 no.10
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    • pp.3059-3064
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    • 2013
  • In this study transesterification of Triglycerides (TG) from Jatropha curcas oil (JCO) with methanol for production of biodiesel was investigated over cerium impregnated ZSM-5 catalysts. NaZSM-5 was synthesized in an alkaline medium and impregnated with cerium oxide by wet method using cerium nitrate as a source for cerium. They were characterized by X-ray diffraction (XRD), Thermogravimeteric analysis (TGA), $CO_2$-temperature programmed desorption, and $N_2$ adsorption/desorption analysis. XRD analysis showed decrease in intensity of the patterns with the increase in the ceria loading but crystallization of ceria to larger size is an evident for 10 and 15% loading. The optimal yield of transesterification process was found to be 90% under the following conditions: oil to methanol molar ratio: 1:12; temperature: $60^{\circ}C$; time: 1 h; catalyst: 5 wt %. Here the yield of fatty acid methyl ester (FAME) was calculated through $^1H$ NMR analysis. The investigation on catalyst loading, temperature, time and reusability illustrated that these ceria impregnated NaZSM-5's were found to be selective, recyclable and could yield biodiesel at low temperature with low methanol to oil ratio due to the presence of both Lewis and Bronsted basicity. Hence, from the above study it is concluded that ceria impregnated ZSM-5 could be recognized as a potential catalysts for biodiesel production in industrial processes.