Pub Date : 2018-03-01DOI: 10.3184/146867818X15066862094905
Mohammad Niyaz Khan, I. I. Fagge
The aqueous surfactant (Surf) solution at [Surf] > cmc (critical micelle concentration) contains flexible micelles/nanoparticles. These particles form a pseudophase of different shapes and sizes where the medium polarity decreases as the distance increases from the exterior region of the interface of the Surf/H2O particle towards its furthest interior region. Flexible nanoparticles (FNs) catalyse a variety of chemical and biochemical reactions. FN catalysis involves both positive catalysis (i.e. rate increase) and negative catalysis (i.e. rate decrease). This article describes the mechanistic details of these catalyses at the molecular level, which reveals the molecular origin of these catalyses. Effects of inert counterionic salts (MX) on the rates of bimolecular reactions (with one of the reactants as reactive counterion) in the presence of ionic FNs/micelles may result in either positive or negative catalysis. The kinetics of cationic FN (Surf/MX/H2O)-catalysed bimolecular reactions (with nonionic and anionic reactants) provide kinetic parameters which can be used to determine an ion exchange constant or the ratio of the binding constants of counterions.
{"title":"Kinetics and Mechanism of Cationic Micelle/Flexible Nanoparticle Catalysis: A Review","authors":"Mohammad Niyaz Khan, I. I. Fagge","doi":"10.3184/146867818X15066862094905","DOIUrl":"https://doi.org/10.3184/146867818X15066862094905","url":null,"abstract":"The aqueous surfactant (Surf) solution at [Surf] > cmc (critical micelle concentration) contains flexible micelles/nanoparticles. These particles form a pseudophase of different shapes and sizes where the medium polarity decreases as the distance increases from the exterior region of the interface of the Surf/H2O particle towards its furthest interior region. Flexible nanoparticles (FNs) catalyse a variety of chemical and biochemical reactions. FN catalysis involves both positive catalysis (i.e. rate increase) and negative catalysis (i.e. rate decrease). This article describes the mechanistic details of these catalyses at the molecular level, which reveals the molecular origin of these catalyses. Effects of inert counterionic salts (MX) on the rates of bimolecular reactions (with one of the reactants as reactive counterion) in the presence of ionic FNs/micelles may result in either positive or negative catalysis. The kinetics of cationic FN (Surf/MX/H2O)-catalysed bimolecular reactions (with nonionic and anionic reactants) provide kinetic parameters which can be used to determine an ion exchange constant or the ratio of the binding constants of counterions.","PeriodicalId":20859,"journal":{"name":"Progress in Reaction Kinetics and Mechanism","volume":"163 1","pages":"1 - 20"},"PeriodicalIF":0.7,"publicationDate":"2018-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"91114846","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2018-03-01DOI: 10.3184/146867817X15066861009956
Yali Du, Yalin Feng, Chunlei Zou, Xu Wu, Wei Huang
The nitrate form of Ni–Al layered double hydroxide (denoted as Ni–Al–NO3-LDH) and the corresponding carbonate form (denoted as Ni–Al–CO3-LDH) were tunably fabricated by the hexamethylenetetramine hydrolysis method. A catalytic behaviour investigation proved Ni–Al–CO3-LDH to be an ineffective catalyst, while for Ni–Al–NO3-LDH excellent catalytic activity and reusability were obtained, in the acetalisation of furfural to furfural diethyl acetal. Characterisation and analysis revealed that the appearance of Lewis acid sites in Ni–Al–NO3-LDH was responsible for its excellent catalytic performance. The acquired kinetic parameters confirmed that this reaction was a first-order process and the apparent activation energy was 36.28 kJ mol−1, which is in reasonable agreement with the theoretical result of 38.57 kJ mol−1. Additionally, apart from the typical Brønsted acid catalytic mechanism, a possible Lewis acid catalytic mechanism was probed theoretically.
{"title":"Kinetics and Mechanism of Acetalisation of Furfural to Furfural Diethyl Acetal with Ni–Al Layered Double Hydroxides Containing Lewis Acid Sites","authors":"Yali Du, Yalin Feng, Chunlei Zou, Xu Wu, Wei Huang","doi":"10.3184/146867817X15066861009956","DOIUrl":"https://doi.org/10.3184/146867817X15066861009956","url":null,"abstract":"The nitrate form of Ni–Al layered double hydroxide (denoted as Ni–Al–NO3-LDH) and the corresponding carbonate form (denoted as Ni–Al–CO3-LDH) were tunably fabricated by the hexamethylenetetramine hydrolysis method. A catalytic behaviour investigation proved Ni–Al–CO3-LDH to be an ineffective catalyst, while for Ni–Al–NO3-LDH excellent catalytic activity and reusability were obtained, in the acetalisation of furfural to furfural diethyl acetal. Characterisation and analysis revealed that the appearance of Lewis acid sites in Ni–Al–NO3-LDH was responsible for its excellent catalytic performance. The acquired kinetic parameters confirmed that this reaction was a first-order process and the apparent activation energy was 36.28 kJ mol−1, which is in reasonable agreement with the theoretical result of 38.57 kJ mol−1. Additionally, apart from the typical Brønsted acid catalytic mechanism, a possible Lewis acid catalytic mechanism was probed theoretically.","PeriodicalId":20859,"journal":{"name":"Progress in Reaction Kinetics and Mechanism","volume":"1 1","pages":"21 - 29"},"PeriodicalIF":0.7,"publicationDate":"2018-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89646083","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2017-12-01DOI: 10.3184/146867817X14954764850397
M. Komasi, S. Fatemi, S. .. Mousavi
Pt–Sn/hierarchical SAPO-34 was synthesised and kinetically modelled as an efficient and selective catalyst for propylene production through propane dehydrogenation. The kinetics of the reaction network were studied in an integral fixed-bed reactor at three temperatures of 550, 600 and 650 °C and weight hourly space velocities of 4 and 8 h−1 with a feed containing hydrogen and propane with relative molar ratios of 0.2, 0.5 and 0.8, at normal pressure. The experiments were performed in accordance with the full factorial experimental design. The kinetic models were constructed on the basis of different mechanisms and various deactivation models. The kinetics and deactivation parameters were simultaneously predicted and optimised using genetic algorithm optimisation. It was further proven that the Langmuir–Hinshelwood model can well predict propane dehydrogenation kinetics through lumping together all the possible dehydrogenation steps and also by assuming the surface reaction as the rate-determining step. A coke formation kinetic model has also shown appropriate results, confirming the experimental data by equal consideration of both monolayer and multilayer coke deposition kinetic orders and an exponential deactivation model.
{"title":"Kinetic Modelling of Propane Dehydrogenation over a Pt–Sn/hierarchical SAPO-34 Zeolite Catalyst, Including Catalyst Deactivation","authors":"M. Komasi, S. Fatemi, S. .. Mousavi","doi":"10.3184/146867817X14954764850397","DOIUrl":"https://doi.org/10.3184/146867817X14954764850397","url":null,"abstract":"Pt–Sn/hierarchical SAPO-34 was synthesised and kinetically modelled as an efficient and selective catalyst for propylene production through propane dehydrogenation. The kinetics of the reaction network were studied in an integral fixed-bed reactor at three temperatures of 550, 600 and 650 °C and weight hourly space velocities of 4 and 8 h−1 with a feed containing hydrogen and propane with relative molar ratios of 0.2, 0.5 and 0.8, at normal pressure. The experiments were performed in accordance with the full factorial experimental design. The kinetic models were constructed on the basis of different mechanisms and various deactivation models. The kinetics and deactivation parameters were simultaneously predicted and optimised using genetic algorithm optimisation. It was further proven that the Langmuir–Hinshelwood model can well predict propane dehydrogenation kinetics through lumping together all the possible dehydrogenation steps and also by assuming the surface reaction as the rate-determining step. A coke formation kinetic model has also shown appropriate results, confirming the experimental data by equal consideration of both monolayer and multilayer coke deposition kinetic orders and an exponential deactivation model.","PeriodicalId":20859,"journal":{"name":"Progress in Reaction Kinetics and Mechanism","volume":"54 1","pages":"344 - 360"},"PeriodicalIF":0.7,"publicationDate":"2017-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84365093","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2017-12-01DOI: 10.3184/146867817X14954764850487
H. Fang
The ground-state triple proton transfer (GSTPT) reactions in HCOOH complexing with H2O, CH3OH, C2H5OH and mixed water–alcohol molecules were studied by quantum mechanical methods in the gas phase and in heptane. The triple proton transfer in HCOOH–S1–S2 (S1, S2 = H2O, CH3OH, C2H5OH) systems all occurred in an asynchronous but concerted protolysis mechanism. The formation pattern of the hydrogen-bonded chain was important to reduce the barrier height of the proton transfer process. When the hydrogen-bonded chain consisted of two identical CH3OH or C2H5OH molecules in the HCOOH–S1–S2 complexes, the GSTPT barrier height of HCOOH–S1–S2 decreased by more than 2 kcal mol−1 compared to that of HCOOH–H2O–H2O both in the gas phase and in heptane, because CH3OH and C2H5OH had larger proton-accepting abilities than had H2O. When the two solvent molecules in the hydrogen-bonded chain in the HCOOH–S1–S2 complexes were different, the barrier height of the proton transfer process varied depending on the proton-accepting ability (basicity) of the hydrogen-bonded chain. The bigger the proton-accepting ability (basicity) of the hydrogen-bonded chain, the lower the barrier height of the proton transfer process. Mixed bridging solvent molecules could accumulate their proton-accepting abilities and thus speeded up proton transfer. The solvent effect evidently decreased the zero point energy-corrected barrier heights of HCOOH clusters and increased the asynchronicity of the proton transfer, while the proton transfer mechanisms did not change in heptane.
{"title":"Ground-State Long-Range Proton Transfer Controlled by Proton-Accepting Ability of Hydrogen-Bonded Chains: A Theoretical Study","authors":"H. Fang","doi":"10.3184/146867817X14954764850487","DOIUrl":"https://doi.org/10.3184/146867817X14954764850487","url":null,"abstract":"The ground-state triple proton transfer (GSTPT) reactions in HCOOH complexing with H2O, CH3OH, C2H5OH and mixed water–alcohol molecules were studied by quantum mechanical methods in the gas phase and in heptane. The triple proton transfer in HCOOH–S1–S2 (S1, S2 = H2O, CH3OH, C2H5OH) systems all occurred in an asynchronous but concerted protolysis mechanism. The formation pattern of the hydrogen-bonded chain was important to reduce the barrier height of the proton transfer process. When the hydrogen-bonded chain consisted of two identical CH3OH or C2H5OH molecules in the HCOOH–S1–S2 complexes, the GSTPT barrier height of HCOOH–S1–S2 decreased by more than 2 kcal mol−1 compared to that of HCOOH–H2O–H2O both in the gas phase and in heptane, because CH3OH and C2H5OH had larger proton-accepting abilities than had H2O. When the two solvent molecules in the hydrogen-bonded chain in the HCOOH–S1–S2 complexes were different, the barrier height of the proton transfer process varied depending on the proton-accepting ability (basicity) of the hydrogen-bonded chain. The bigger the proton-accepting ability (basicity) of the hydrogen-bonded chain, the lower the barrier height of the proton transfer process. Mixed bridging solvent molecules could accumulate their proton-accepting abilities and thus speeded up proton transfer. The solvent effect evidently decreased the zero point energy-corrected barrier heights of HCOOH clusters and increased the asynchronicity of the proton transfer, while the proton transfer mechanisms did not change in heptane.","PeriodicalId":20859,"journal":{"name":"Progress in Reaction Kinetics and Mechanism","volume":"12 1","pages":"384 - 396"},"PeriodicalIF":0.7,"publicationDate":"2017-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"88981280","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2017-12-01DOI: 10.3184/146867817X14954764850496
M. L. Kremer
The effect of ethanol on the catalytic decomposition of H2O2 by Fe3+ was investigated. While expecting a simple competitive oxidation of C2H5OH, far more complex kinetics were encountered experimentally: already minute amounts of C2H5OH (1% of H2O2) had a powerful retardation effect on the disappearance of H2O2. This fact indicated the operation of an intricate mechanism. It excluded the possibility of OH• radicals being the active agents in the oxidation: OH• radicals generated by radiolysis react with C2H5OH with a very high rate constant. The interpretation of the experimental results was based on a mechanism involving iron in a +5 oxidation state (FeO3+) as the active intermediate and its binding in complex structures in which activity is reduced. The question of free radical versus non-radical mechanisms is discussed. The conclusions differ from generally accepted concepts in relation to the Fenton and related reactions.
{"title":"Strong Inhibition of the Fe3+ + H2O2 Reaction by Ethanol: Evidence against the Free Radical Theory","authors":"M. L. Kremer","doi":"10.3184/146867817X14954764850496","DOIUrl":"https://doi.org/10.3184/146867817X14954764850496","url":null,"abstract":"The effect of ethanol on the catalytic decomposition of H2O2 by Fe3+ was investigated. While expecting a simple competitive oxidation of C2H5OH, far more complex kinetics were encountered experimentally: already minute amounts of C2H5OH (1% of H2O2) had a powerful retardation effect on the disappearance of H2O2. This fact indicated the operation of an intricate mechanism. It excluded the possibility of OH• radicals being the active agents in the oxidation: OH• radicals generated by radiolysis react with C2H5OH with a very high rate constant. The interpretation of the experimental results was based on a mechanism involving iron in a +5 oxidation state (FeO3+) as the active intermediate and its binding in complex structures in which activity is reduced. The question of free radical versus non-radical mechanisms is discussed. The conclusions differ from generally accepted concepts in relation to the Fenton and related reactions.","PeriodicalId":20859,"journal":{"name":"Progress in Reaction Kinetics and Mechanism","volume":"8 1","pages":"397 - 413"},"PeriodicalIF":0.7,"publicationDate":"2017-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"91331208","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2017-12-01DOI: 10.3184/146867817X14954764850360
A. Mamantov
Photooxidation of tetrachloroethylene (PERC) and trichloroethylene (TCE) in simulated tropospheric smog chamber studies occurs with a time delay, accelerating simultaneous decreasing O3/chlorinated ethylene (CE) concentrations along with increasing CCl2O, which is attributed to CCl2 in the case of PERC and CCl2 or CHCl for TCE. The carbenes, chlorinated acetyl chlorides and CCl2O products may result from the rearrangement of the oxidised and/or excited oxidised CE, e.g. an epoxide. Analyses indicate scavenging experiments have not proved the existence of Cl atoms as being responsible for chlorinated acetyl chloride formation. Halocarbenes may form complexes with O3 which can undergo electron transfer (ET) and lead to dissociation of O3 to O2 and O and regeneration of carbene, resulting in a chain reaction. The direction of ET may be determined by the smallest differential HOMO–LUMO energy between the carbene and O3 which results in greater transition state stabilisation. Similarities in the reactions of O3 with carbenes and simple alkenes, nucleophilic carbenes with electron-poor alkenes and electrophilic carbene PhCCl with alkyl-substituted alkenes, i.e. (1) complex formation, (2) very low or negative activation energies and (3) the ability to undergo ET reactions with alkylalkenes are discussed. The possibility of the world-wide used perhalocarbons, e.g. perfluorinated carbons, hydroperhalocarbons, their halogenated replacements and starting materials degrading to halocarbenes which may degrade O3, is analysed.
{"title":"Halocarbenes May Deplete Atmospheric Ozone","authors":"A. Mamantov","doi":"10.3184/146867817X14954764850360","DOIUrl":"https://doi.org/10.3184/146867817X14954764850360","url":null,"abstract":"Photooxidation of tetrachloroethylene (PERC) and trichloroethylene (TCE) in simulated tropospheric smog chamber studies occurs with a time delay, accelerating simultaneous decreasing O3/chlorinated ethylene (CE) concentrations along with increasing CCl2O, which is attributed to CCl2 in the case of PERC and CCl2 or CHCl for TCE. The carbenes, chlorinated acetyl chlorides and CCl2O products may result from the rearrangement of the oxidised and/or excited oxidised CE, e.g. an epoxide. Analyses indicate scavenging experiments have not proved the existence of Cl atoms as being responsible for chlorinated acetyl chloride formation. Halocarbenes may form complexes with O3 which can undergo electron transfer (ET) and lead to dissociation of O3 to O2 and O and regeneration of carbene, resulting in a chain reaction. The direction of ET may be determined by the smallest differential HOMO–LUMO energy between the carbene and O3 which results in greater transition state stabilisation. Similarities in the reactions of O3 with carbenes and simple alkenes, nucleophilic carbenes with electron-poor alkenes and electrophilic carbene PhCCl with alkyl-substituted alkenes, i.e. (1) complex formation, (2) very low or negative activation energies and (3) the ability to undergo ET reactions with alkylalkenes are discussed. The possibility of the world-wide used perhalocarbons, e.g. perfluorinated carbons, hydroperhalocarbons, their halogenated replacements and starting materials degrading to halocarbenes which may degrade O3, is analysed.","PeriodicalId":20859,"journal":{"name":"Progress in Reaction Kinetics and Mechanism","volume":"106 2 1","pages":"307 - 333"},"PeriodicalIF":0.7,"publicationDate":"2017-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86529956","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2017-12-01DOI: 10.3184/146867817X14954764850342
H. Chemouri, S. Mekelleche
The mechanism, the regioselectivity, the stereoselectivity and the kinetics of Diels–Alder reactions of isoprene with acrylic acid and acrylonitrile have been studied, at the B3PW91/6-31G(d,p) level of theory, both in the gas phase and in the presence of organic [dichloromethane (DCM)] and ionic liquid [1-ethylpyridinium trifluoroacetate (EPTFA)] solvents. Intrinsic reaction coordinate calculations show that these reactions take place through an asynchronous concerted mechanism leading to the endo para cycloadducts as the major products in the gas phase and to the exo para cycloadducts as the major products both in organic and in ionic liquid solvents. The explicit solvation model involving the coordination of one molecule of the solvent with the dienophiles shows a considerable decrease of the activation energy when passing from DCM to EPTFA. The enhancement of these cycloaddition reactions can be explained by the strong hydrogen bonding created between the ion pair of the ionic liquid and the oxygen atom of the dienophile reagents. Moreover, density functional theory-based reactivity indices also show an increase of the reaction polarity and consequently of the reaction rate, when replacing DCM solvent by EPTFA solvent. The results obtained give evidence that the ionic liquid EPTFA is an excellent solvent for Diels–Alder reactions in comparison with conventional organic solvents.
{"title":"Theoretical Investigation of the Kinetic Effect of the 1-Ethylpyridinium Trifluoroacetate Ionic Liquid in the Acceleration of Diels–Alder Reactions of Isoprene with Acrylic Acid and Acrylonitrile","authors":"H. Chemouri, S. Mekelleche","doi":"10.3184/146867817X14954764850342","DOIUrl":"https://doi.org/10.3184/146867817X14954764850342","url":null,"abstract":"The mechanism, the regioselectivity, the stereoselectivity and the kinetics of Diels–Alder reactions of isoprene with acrylic acid and acrylonitrile have been studied, at the B3PW91/6-31G(d,p) level of theory, both in the gas phase and in the presence of organic [dichloromethane (DCM)] and ionic liquid [1-ethylpyridinium trifluoroacetate (EPTFA)] solvents. Intrinsic reaction coordinate calculations show that these reactions take place through an asynchronous concerted mechanism leading to the endo para cycloadducts as the major products in the gas phase and to the exo para cycloadducts as the major products both in organic and in ionic liquid solvents. The explicit solvation model involving the coordination of one molecule of the solvent with the dienophiles shows a considerable decrease of the activation energy when passing from DCM to EPTFA. The enhancement of these cycloaddition reactions can be explained by the strong hydrogen bonding created between the ion pair of the ionic liquid and the oxygen atom of the dienophile reagents. Moreover, density functional theory-based reactivity indices also show an increase of the reaction polarity and consequently of the reaction rate, when replacing DCM solvent by EPTFA solvent. The results obtained give evidence that the ionic liquid EPTFA is an excellent solvent for Diels–Alder reactions in comparison with conventional organic solvents.","PeriodicalId":20859,"journal":{"name":"Progress in Reaction Kinetics and Mechanism","volume":"22 1","pages":"361 - 371"},"PeriodicalIF":0.7,"publicationDate":"2017-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84291580","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2017-12-01DOI: 10.3184/146867817X14954764850469
Nazanin Noroozi-Shad, M. Gholizadeh, M. Izadyar, H. Eshghi
Frustrated Lewis pairs (FLPs) are the combination of Lewis acid and base motifs where steric hindrance prevents strong adduct formation. Accordingly, the ability of FLPs in small molecule activation and their capability in hydrogen cleavage led to their use in the hydrogenation of a wide range of unsaturated substrates. Here, we investigated theoretically the ability of three intramolecular phosphorus/boron FLPs as bifunctional catalysts in the metal-free hydrogenation of dimethylacetylene to cis-alkene. The mechanism of this hydrogenation reaction, based on the boron acceptor [including –OR substituents (B(OR)2), where R is an aliphatic or aromatic branch] and phosphorus donor, has been explored. Based on the results obtained, it was confirmed that the H2 splitting reaction and the formation of the phosphonium–borohydride motifs for these FLPs are endothermic. It has been shown that these FLPs have a moderate ability in H–H bond splitting. Also, the capability of the boron atom in FLPs on the hydrogenation reaction was investigated. The reduction steps of the mechanism showed an exothermic nature. This result revealed that the presence of the boron as a Lewis acid, with a very limited Lewis acidity, improves the catalytic hydrogenation reaction significantly. Finally, it was confirmed that the proposed FLPs in the cis-hydrogenation of alkynes will be effective.
{"title":"Theoretical Evaluation of the Efficiency of Novel Frustrated Lewis Pairs in the cis-Hydrogenation Reaction of Dimethylacetylene","authors":"Nazanin Noroozi-Shad, M. Gholizadeh, M. Izadyar, H. Eshghi","doi":"10.3184/146867817X14954764850469","DOIUrl":"https://doi.org/10.3184/146867817X14954764850469","url":null,"abstract":"Frustrated Lewis pairs (FLPs) are the combination of Lewis acid and base motifs where steric hindrance prevents strong adduct formation. Accordingly, the ability of FLPs in small molecule activation and their capability in hydrogen cleavage led to their use in the hydrogenation of a wide range of unsaturated substrates. Here, we investigated theoretically the ability of three intramolecular phosphorus/boron FLPs as bifunctional catalysts in the metal-free hydrogenation of dimethylacetylene to cis-alkene. The mechanism of this hydrogenation reaction, based on the boron acceptor [including –OR substituents (B(OR)2), where R is an aliphatic or aromatic branch] and phosphorus donor, has been explored. Based on the results obtained, it was confirmed that the H2 splitting reaction and the formation of the phosphonium–borohydride motifs for these FLPs are endothermic. It has been shown that these FLPs have a moderate ability in H–H bond splitting. Also, the capability of the boron atom in FLPs on the hydrogenation reaction was investigated. The reduction steps of the mechanism showed an exothermic nature. This result revealed that the presence of the boron as a Lewis acid, with a very limited Lewis acidity, improves the catalytic hydrogenation reaction significantly. Finally, it was confirmed that the proposed FLPs in the cis-hydrogenation of alkynes will be effective.","PeriodicalId":20859,"journal":{"name":"Progress in Reaction Kinetics and Mechanism","volume":"61 1","pages":"372 - 383"},"PeriodicalIF":0.7,"publicationDate":"2017-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89066182","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2017-12-01DOI: 10.3184/146867817X14954764850351
Jianguo Liu, Zhen-Tao An, Qian Zhang, Chao Wang
The thermal stability and kinetics of hydroxylamine nitrate (HAN) decomposition were studied by differential scanning calorimetry (DSC) and the thermal decomposition reaction mechanism was determined by density functional theory (DFT). With the help of parameter values from the non-isothermal DSC curves of HAN, the thermal decomposition activation energy and pre-exponential constant were obtained by the Kissinger and Ozawa methods. Then, the most probable mechanism function was calculated by the Šatava–Šesták method. Seven different paths for the thermal decomposition mechanism of HAN were formulated and DFT at the B3LYP/6-311++G(d,p) level was used to carry out the dynamics analysis. The calculated results show that the values of the activation energy calculated by the Kissinger and Ozawa methods are 67.892 and 70.412 kJ mol−1 respectively. The most probable mechanism function calculated by the Šatava–Šesták method is F ( α ) = ( 1 − α ) − 1 17 . The path being favoured energetically in the dynamics is in the order: Path6 > Path5 > Path4 > Path1 > Path2 > Path7 > Path3.
{"title":"Thermal Decomposition of Hydroxylamine Nitrate Studied by Differential Scanning Calorimetry Analysis and Density Functional Theory Calculations","authors":"Jianguo Liu, Zhen-Tao An, Qian Zhang, Chao Wang","doi":"10.3184/146867817X14954764850351","DOIUrl":"https://doi.org/10.3184/146867817X14954764850351","url":null,"abstract":"The thermal stability and kinetics of hydroxylamine nitrate (HAN) decomposition were studied by differential scanning calorimetry (DSC) and the thermal decomposition reaction mechanism was determined by density functional theory (DFT). With the help of parameter values from the non-isothermal DSC curves of HAN, the thermal decomposition activation energy and pre-exponential constant were obtained by the Kissinger and Ozawa methods. Then, the most probable mechanism function was calculated by the Šatava–Šesták method. Seven different paths for the thermal decomposition mechanism of HAN were formulated and DFT at the B3LYP/6-311++G(d,p) level was used to carry out the dynamics analysis. The calculated results show that the values of the activation energy calculated by the Kissinger and Ozawa methods are 67.892 and 70.412 kJ mol−1 respectively. The most probable mechanism function calculated by the Šatava–Šesták method is F ( α ) = ( 1 − α ) − 1 17 . The path being favoured energetically in the dynamics is in the order: Path6 > Path5 > Path4 > Path1 > Path2 > Path7 > Path3.","PeriodicalId":20859,"journal":{"name":"Progress in Reaction Kinetics and Mechanism","volume":"138 1 Suppl 1","pages":"334 - 343"},"PeriodicalIF":0.7,"publicationDate":"2017-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"91100675","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2017-09-01DOI: 10.3184/146867817X14806858831983
J. Zhang, W. Y. Wang, G. Wang, C. Kai, Hua Song, Lu Wang
A model natural gas consisting of hydrogen sulfide, nitrogen and oxygen mixture was used to simulate materials to test the performance of an amine-modified MCM-41 adsorbent prepared by the impregnation method. The adsorbent was characterised by X-ray diffraction analysis, Brunauer–Emmett–Teller analysis, Fourier-transform infrared spectroscopy, transmission electron microscopy and scanning electron microscopy. The results showed that more molecules are able to penetrate the pores following modification, resulting in rapid structural collapse, thus lowering the diffraction intensity. Although the capacity of amine-modified MCM-41 decreased the physical adsorption, chemisorption increased significantly. (3-Aminopropyl)trimethoxysilane/MCM-41 was found to exhibit a good performance for H2S desulfurisation. At 45 °C the breakthrough time was 186 min, the saturated sulfur capacity was 134.38 mg g−1 and the degree of desulfurisation was 54.19%. The adsorption isotherm and kinetics were investigated and the relevant parameters were obtained. The results showed that the adsorption isotherm could be well fitted by the Langmuir model and the maximum adsorption capacities increased with increase of temperature. The adsorption kinetics could be represented by the Bangham model, which suggested that chemical reaction seemed significant in the rate-controlling adsorption step. The adsorption process was spontaneous and exothermic.
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