• Title/Summary/Keyword: Bronsted acid

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Oxidation of Propylene on Copper(Ⅱ)-Exchanged Zeolite. Active Site for the Formation of Acrolein (구리(Ⅱ)를 이온교환한 제올라이트 Y 에서 프로필렌의 산화반응. 아크롤레인 생성의 활성점)

  • Uh Young Sun;Chon Hakze
    • Journal of the Korean Chemical Society
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    • v.23 no.2
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    • pp.80-87
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    • 1979
  • The active site for the formation of acrolein in propylene oxidation reaction over copper(Ⅱ)-exchanged zeolite Y has been studied. At the early stage of the reaction, the formation of hydrocarbons was observed. The formation of hydrocarbons decreased gradually during the course of reaction, apparently due to the poisoning the Bronsted acid sites. The formation of acrolein was quite low when the formation of hydrocarbons was proceeding. The formation of acrolein was depend on the copper ion content and this can be related to the availability of the copper ions inside the supercage. It seems that it is the copper ion not the Bronsted acid site which is primarily responsible for the formation of acrolein.

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The Adsorption of Amines on Silicates. Distinction Protonic and Aprotonic Acids Sites (Silicate 上에서의 아민의 吸着. Protonic 酸 자리와 Aprotonic 酸 자리의 區別)

  • Kim Jong-Taik;Sohn Jong-Rack
    • Journal of the Korean Chemical Society
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    • v.20 no.6
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    • pp.441-447
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    • 1976
  • The infrared spectra obtained in the region of $4000∼1200 $cm^{-1}$ has been measured for pyridine, tertiary butylamine, and ethylenediamine adsorbed on various cation-exchanged silicates at various degassing temperature. It was possible to distinguish between protonic and aprotonic acid sites of all cation-exchanged silicates which exhibited both Bronsted and Lewis acidity. The sodium form appeared to be the least reactive towards adsorbates. The relative ratio of the band intensities of tertiary butylamine was directly related to the polarizing power of exchanged cations. Ethylenediamine was less easily desorbed from silicate surface than tertiary butylamine due to the additional amino group to react with surface active site, and probably to form ether hydrogen bond with surface oxgen by liberating migrating proton besides the coordination bond with Lewis acid site and the formation of$NH3^+$ species with Bronsted acid site.

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A Mechanistic Study for Aminolysis of p-Nitrophenyl Phenylacetate

  • 엄익환;Yeom, E. Suk;권혜진;권동숙
    • Bulletin of the Korean Chemical Society
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    • v.18 no.8
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    • pp.865-868
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    • 1997
  • Second-order rate constants have been measured spectrophotometrically for the reactions of p-nitrophenyl phenylacetate (1) and benzoate (2) with a series of alicyclic amines in H2O containing 20 mole % DMSO at 25.0 ℃. 1 appears to be more reactive than 2 toward all the amines studied, although phenylacetic acid is a weaker acid than benzoic acid. The higher reactivity of 1 can be attributed to resonance and/or steric effect, since the ground state of 2 can be stabilized by resonance and 1 would experience less steric hindrance due to the presence of CH2 group between phenyl and C=O group. The reactivity of the amines increases with increasing their basicity. The Bronsted-type plots for aminolysis of 1 and 2 show good linearity with βnuc values of 0.81 and 0.85, respectively, indicating that the TS structures of the aminolyses of 1 and 2 are similar. Besides, the linear Bronsted plots obtained in the present system clearly suggest that there is no mechanism change for the given series of the amines and the reactions of 1 and 2 proceed in a same mechanism.

Base Catalysed Hydrolysis of Aryl Phenylacetates (Aryl Phenylacetate류의 염기촉매 가수분해 반응)

  • Duk-Young Cheong;Soo-Dong Yoh;Jae-Hwan Choi;Kwang-Taik Shim
    • Journal of the Korean Chemical Society
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    • v.36 no.3
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    • pp.446-452
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    • 1992
  • The rates of hydrolysis of aryl phenylacetates have been measured in the presence of piperidine in 80% acetonitrile-20% water(v/v). For the electron withdrawing substituents of leaving group, the hydrolysis is catalyzed by a general base and the Hammett $\rho_{LG}$ and Bronsted value $\beta$ are 5.28 and -2.72 at $30^{\circ}C$, respectively. These high senstivities of Hammett and Bronsted values are $E1_{C}B$ mechanism. But in the electron donating ones, the hydrolysis is catalyzed by a specific base and $B_{AC}2 mechanism is predominated. $pK_{SH}'s of phenylacetic acid ester and rate constants of hydrolysis $k_1$, $k_{-1)$, $k_2$ were calculated.

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Acidity Effect on the Catalytic Properties for Phenol Isopropylation

  • Yu, Jeong Hwan;Lee, Cheol Wi;Wang, Bo;Park, Sang On
    • Bulletin of the Korean Chemical Society
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    • v.22 no.3
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    • pp.263-266
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    • 2001
  • Isopropylation of phenol with 2-propanol has been carried out over Na-exchanged ZSM-5 zeolites to determine the effect of catalyst acidity on phenol conversion and product selectivity. The acid type and strength of the catalyst such as Lewis, weak and strong Bronsted acid sites are measured by pyridine adsorbed XPS and the catalytic properties are interpreted in terms of the acid properties. The active site and mechanism for the reaction are suggested based on evidence of study from the reactant adsorbed FT-IR.

The Effect of Dealumination on the Structure and Acidity of SAPO-11 Molecular Sieve (탈알루미늄화가 SAPO-11 분자체의 구조 및 산성도에 미치는 영향)

  • Park, Jong Yul;Lee, Chi Hun;Kim, Soo Kyung
    • Journal of the Korean Chemical Society
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    • v.40 no.3
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    • pp.202-208
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    • 1996
  • SAPO-11 was synthesized hydrothermally and dealuminated with $H_4$EDTA. The framework structure of SAPO-11 was maintained safely by 24 hours' dealumination, but further dealumination for 48 hours caused SAPO-11 collapsed and to be changed to variscite($AIPO_4{\cdot}2H_2O$) and tridymite($SiO_2$). Dealuminated SAPO-11 showed two structural hydroxyl bands at 3607 $cm^{-1}$ and 3453 $cm^{-1}$ respectively. The intensities of these two bands increased according to the extent of dealumination, and disappeared by the adsorption of methylamine. Dealuminated SAPO-11 showed higher desorption temperatures and greater activation energies in desorption of water and methylamine compared to non-dealuminated SAPO-11. All the phenomena may be due to the stronger interactions of Bronsted acid sites of structural hydroxyl groups generated by dealumination with adsorbed water and methylamine molecules respectively.

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Acid and Base Properties of Chemical-Treated Natural Zeolite

  • Lee, Jae-Young;Shim, Mi-Ja;Kim, Sang-Woo
    • Korean Journal of Materials Research
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    • v.5 no.5
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    • pp.620-624
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    • 1995
  • To study the acid and base properties of chemical-treated natural zeolite, FT-IR analysis was performed by the adsorption of pyridne and pyrrole and thermo-gravimetric analysis was done by the adsorption of NH$_{3}$. These solid catalysts have two acid sites, which are related to the Bronsted and Lewis acid sites, respectively. HIC-treatment led to the increased acidity and the maintained basicity.Acidity of NaHO-treatment samples also increased with thr NaOH-treatment but basicity decreased. The p-xylene selectivity on the chemical-treatment zelite was higher than that on the untreated zeolite.

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The Hydrodesulfurization over NiPtMo Catalysts and Acidic Characterization of Supports (NiPtMo계 촉매 담체의 산특성 및 수소첨가 탈황반응)

  • 김문찬;이원묵;김경림
    • Journal of Korean Society for Atmospheric Environment
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    • v.10 no.4
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    • pp.281-288
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    • 1994
  • The hydrodesulfurization (DBT) were Peformed over NiPtMo catalysts supported on HZSM-5, LaY and ${\gamma}$- $Al_2$O$_3$under high H$_2$ pressure. And the acidities of these catalysts were characterized by using TGA and DSC. The result showed that the order of the acid strength for prepared supports was HZSM -5>LaY>${\gamma}$- A1$_2$O$_3$. For the acid amount we obtained the same result for the acid strength The acid strength and the acid amount mainly depended on the kinds of supports whose acid site were strong or not The activity of the hydrodesulfurization decreased for catalysts which had strong acid sites. The origin of acid site was Bronsted in NH50 and NY catalysts And it was Lewis in NA catalyst The order of desorption activation energy for Pyridine was NH50>NY>NA. And the result was the same for thiophene. The activity of the hydrodesulfurization decreased for catalysts which had strong acid sites. The conversion of DBT over NA catalyst was higher than NH and NY catalysts.

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Characterization of Zirconium Sulfate Supported on Zirconia and Activity for Acid Catalysis

  • Son, Jong Rak;Gwon, Tae Dong;Kim, Sang Bok
    • Bulletin of the Korean Chemical Society
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    • v.22 no.12
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    • pp.1309-1315
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    • 2001
  • Zirconium sulfate supported on zirconia catalysts were prepared by impregnation of powdered $Zr(OH)_4$ with zirconium sulfate aqueous solution followed by calcining in air at high temperature. The characterization of prepared catalysts was performed using Fourier transform infrared (FTIR), X-ray diffraction (XRD), differential scanning calorimetry (DSC), and by the measurement of surface area. The addition of zirconium sulfate to zirconia increased the phase transition temperature of $ZrO_2$ from amorphous to tetragonal due to the interaction between zirconium sulfate and zirconia, and the specific surface area and acidity of catalysts increased in proportion to the zirconium sulfate content up to 10 wt% of $Zr(SO_4)_2$. Infrared spectra of ammonia adsorbed on $Zr(SO_4)2}ZrO_2$ showed the presence of Bronsted and Lewis acid sites on the surface. $10-Zr(SO_4)_2}ZrO_2$ calcined at $600^{\circ}C$ exhibited maximum catalytic activities for 2-propanol dehydration and cumene dealkylation. The catalytic activities for both reactions were correlated with the acidity of catalysts measured by ammonia chemisorption method.

Strength and conversion characteristics of DeNOx catalysts with the addition of dispersion agent (분산제 첨가에 따른 탈질촉매의 강도세기 및 전환특성)

  • Lee, Hyun Hee;Park, Kwang Hee;Cha, Wang Seog
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.14 no.12
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    • pp.6575-6580
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    • 2013
  • Various modified SCR catalysts were prepared and tested to improve the strength of catalysts for use under severe conditions. The SCR catalysts were modified with a binder and dispersion agent, and tested at the fixed bed reactor. FT-IR and $H_2$-TPR were used to analyze the degree of hydrogen use and ammonia adsorption by the modified catalysts. In the case of the SCR catalysts coated with 2.3g of the binder, 4.7g of ethanol, and 0.1g of dispersion agent, the strength of catalyst was increased by approximately 12%. On the other hand, despite the enhancement of strength, the activities of the SCR catalysts were decreased by 2-10%. When the mixed solution composed of binder, dispersion agent and $SiO_2$ solution was precipitated on the catalyst, the $NO_x$ conversion of the catalyst was decreased slightly. The Bronsted acid site and Lewis acid site worked as the activators for the SCR reaction, and were decreased by $SiO_2$.