Progress in Reaction Kinetics and Mechanism最新文献_第6页

Atmospheric reactions of glyoxal with NO2 and NH2 radicals: Hydrogen abstraction mechanism and natural bond orbital analysis 乙二醛与NO2和NH2自由基的大气反应:吸氢机理和自然键轨道分析

IF 0.7 4区化学

Progress in Reaction Kinetics and Mechanism Pub Date : 2019-05-14 DOI: 10.1177/1468678319848880

H. Saghafi, M. Vahedpour

{"title":"Atmospheric reactions of glyoxal with NO2 and NH2 radicals: Hydrogen abstraction mechanism and natural bond orbital analysis","authors":"H. Saghafi, M. Vahedpour","doi":"10.1177/1468678319848880","DOIUrl":"https://doi.org/10.1177/1468678319848880","url":null,"abstract":"Glyoxal can be important in atmospheric chemistry in terms of its ability to convert to secondary organic aerosols. In this study, the glyoxal-breaking reaction by two atmospheric active radicals, NO2 and NH2, has been investigated at the B3LYP and M06-2X levels in connection with 6-311++G(d,p) basis set. The formation of the most stable adducts from glyoxal with NO2/NH2 radical requires two hydrogen atom transfers. The accuracy of the predicted mechanisms in describing the hydrogen transfers was confirmed by atoms-in-molecules calculations and natural bond orbital analysis. The calculated results predict that hydrogen transfer process in both reactions at the M06-2X level is favourable from the kinetic and thermodynamic points of view. In the natural bond orbital analysis, the stabilization energy, E(2), delocalization corrections, at the B3LYP level is much higher than the same results at the M06-2X level (nearly twice). The activation thermodynamic parameters show that the first steps of the two reactions have lower barrier energy than the second steps. The Gibbs free energy values estimate that adducts of both the reactions at the mentioned method are spontaneous. The whole reaction of glyoxal + NH2 is more favourable than the whole reaction of glyoxal + NO2. The rate constants were calculated for the mentioned pathways using transition state theory for bimolecular steps and the fitted equations are reported.","PeriodicalId":20859,"journal":{"name":"Progress in Reaction Kinetics and Mechanism","volume":"11 1","pages":"187 - 209"},"PeriodicalIF":0.7,"publicationDate":"2019-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"82050022","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}

引用次数: 4

Understanding the mechanism of the 1,3-dipolar cycloaddition reaction between a thioformaldehyde S-oxide and cyclobutadiene: Competition between the stepwise and concerted routes 硫代甲醛s -氧化物与环丁二烯1,3-偶极环加成反应机理的研究:步进和协同反应途径的竞争

IF 0.7 4区化学

Progress in Reaction Kinetics and Mechanism Pub Date : 2019-05-12 DOI: 10.1177/1468678319845863

B. Mohtat, Seyyed Amir Siadati, M. Khalilzadeh

{"title":"Understanding the mechanism of the 1,3-dipolar cycloaddition reaction between a thioformaldehyde S-oxide and cyclobutadiene: Competition between the stepwise and concerted routes","authors":"B. Mohtat, Seyyed Amir Siadati, M. Khalilzadeh","doi":"10.1177/1468678319845863","DOIUrl":"https://doi.org/10.1177/1468678319845863","url":null,"abstract":"Changing the mechanism of the widely used 1,3-dipolar cycloaddition reaction from its usual asynchronous one-step pattern to the rarely observed stepwise form leads to the emergence of intermediates, side products, and other impurities. Thus, it is crucial to determine the nature of the mechanism of the 1,3-dipolar cycloaddition reaction between a special 1,3-dipole and a specified dipolarophile (by theoretical methods) before using them for synthesizing a desired product. In this study, therefore, we have investigated the possibility of some probable intermediates emergence in the 1,3-dipolar cycloaddition reaction between cyclobutadiene and thioformaldehyde S-oxide. The results showed that emergence of Int (B) (−52.1 kcal mol−1) via transition state (B-1) is favorable both thermodynamically and kinetically (in comparison with all other stepwise routes). That is, developing probable impurities should not be neglected at least in the cases of the reactions between some thioformaldehyde S-oxide and some dipolarophiles.","PeriodicalId":20859,"journal":{"name":"Progress in Reaction Kinetics and Mechanism","volume":"51 1","pages":"213 - 221"},"PeriodicalIF":0.7,"publicationDate":"2019-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"81549841","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}

引用次数: 3

[Cu-Ag2]O–C3N4 nanoframeworks for efficient photodegradation of wastewaters 高效光降解废水的[Cu-Ag2] O-C3N4纳米骨架

IF 0.7 4区化学

Progress in Reaction Kinetics and Mechanism Pub Date : 2019-05-09 DOI: 10.1177/1468678319825723

M. Padervand, Fatemeh Mesri Fasandouz, A. Beheshti

引用次数: 1

Ab initio study of mechanism of forming a Si-heterocyclic spiro-Sn-heterocyclic ring compound by cycloaddition reaction of Me2Si=Sn: and ethene Me2Si=Sn:与乙烯的环加成反应生成si - spro -Sn-杂环化合物机理的从头算研究

IF 0.7 4区化学

Progress in Reaction Kinetics and Mechanism Pub Date : 2019-05-01 DOI: 10.1177/1468678319825898

Xiaojun Tan, Xiuhui Lu

{"title":"Ab initio study of mechanism of forming a Si-heterocyclic spiro-Sn-heterocyclic ring compound by cycloaddition reaction of Me2Si=Sn: and ethene","authors":"Xiaojun Tan, Xiuhui Lu","doi":"10.1177/1468678319825898","DOIUrl":"https://doi.org/10.1177/1468678319825898","url":null,"abstract":"X2Si=Sn: (X = H, Me, F, Cl, Br, Ph, Ar, etc.) are a new chemical species. The cycloaddition reactions of X2Si=Sn: are a new field of stannylene chemistry. The mechanism of the cycloaddition reaction between singlet state Me2Si=Sn: and ethene has been investigated for the first time here using second-order Møller-Plesset perturbation theory together with the 6-311++G** basis set for C, H and Si atoms and the LanL2dz basis set for Sn atoms. From the potential energy profile, it could be predicted that the reaction has one dominant reaction channel. The reaction process presented is that the 5p unoccupied orbital of Sn in Me2Si=Sn: and the π orbital of ethene form a π → p donor–acceptor bond resulting in the formation of an intermediate. The instability of this intermediate makes it isomerize to a four-membered Si-heterocyclic ring stannylene. Because the 5p unoccupied orbital of the Sn atom in the four-membered Si-heterocyclic ring stannylene and the π orbital of ethene form a π → p donor–acceptor bond, the four-membered Si-heterocyclic ring stannylene further combines with ethene to form another intermediate. Because the Sn atom in this intermediate assumes sp3 hybridization after the transition state, the intermediate isomerizes to a Si-heterocyclic spiro-Sn-heterocyclic ring compound. This result indicates the modes of cycloaddition reactions between X2Si=Sn: and symmetric π-bonded compounds, i.e. this study opens up a new field for stannylene chemistry.","PeriodicalId":20859,"journal":{"name":"Progress in Reaction Kinetics and Mechanism","volume":"7 1","pages":"114 - 121"},"PeriodicalIF":0.7,"publicationDate":"2019-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78878810","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}

引用次数: 0

A density functional theory study of the oxygen reduction reaction on the (111) and (100) surfaces of cobalt(II) oxide 氧化钴(II)(111)和(100)表面氧还原反应的密度泛函理论研究

IF 0.7 4区化学

Progress in Reaction Kinetics and Mechanism Pub Date : 2019-04-24 DOI: 10.1177/1468678319825727

B. Qin, Yang Tian, Pengxiang Zhang, Zuoyin Yang, Guoxin Zhang, Zhao Cai, Yaping Li

{"title":"A density functional theory study of the oxygen reduction reaction on the (111) and (100) surfaces of cobalt(II) oxide","authors":"B. Qin, Yang Tian, Pengxiang Zhang, Zuoyin Yang, Guoxin Zhang, Zhao Cai, Yaping Li","doi":"10.1177/1468678319825727","DOIUrl":"https://doi.org/10.1177/1468678319825727","url":null,"abstract":"Density functional theory calculations were employed to investigate the electrochemical oxygen reduction reaction on the (111) and (100) surfaces of cobalt(II) oxide. Different mechanisms were applied to evaluate the oxygen reduction reaction performance of cobalt(II) oxide structures in terms of the Gibbs free energy and density of states. A variety of intermediate structures based on associative and dissociative mechanisms were constructed and optimized. As a result, we estimated the catalytic activity by calculating the free energy of the intermediates and constructing free energy diagrams, which suggested that the oxygen reduction reaction Gibbs free energy on cobalt(II) oxide (111) and (100) surfaces based on the associative mechanism is smaller than that based on the dissociative mechanism, demonstrating that the associative mechanism should be more likely to be the oxygen reduction reaction pathway. Moreover, the theoretical oxygen reduction reaction activity on the cobalt(II) oxide (111) surface was found to be higher than that on the cobalt(II) oxide (100) surface. These results shed light on the rational design of high-performance cobalt(II) oxide oxygen reduction reaction catalysts.","PeriodicalId":20859,"journal":{"name":"Progress in Reaction Kinetics and Mechanism","volume":"47 1","pages":"122 - 131"},"PeriodicalIF":0.7,"publicationDate":"2019-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"75035827","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}

引用次数: 4

Pyrolysis and gasification of macroalgae Enteromorpha prolifera under a CO2 atmosphere using the thermogravimetry–Fourier transform infrared spectroscopy technique 利用热重-傅里叶变换红外光谱技术研究了大型藻浒苔在CO2气氛下的热解气化过程

IF 0.7 4区化学

Progress in Reaction Kinetics and Mechanism Pub Date : 2019-04-24 DOI: 10.1177/1468678319825735

Junrui Cao, Yuhui Ma

{"title":"Pyrolysis and gasification of macroalgae Enteromorpha prolifera under a CO2 atmosphere using the thermogravimetry–Fourier transform infrared spectroscopy technique","authors":"Junrui Cao, Yuhui Ma","doi":"10.1177/1468678319825735","DOIUrl":"https://doi.org/10.1177/1468678319825735","url":null,"abstract":"Non-isothermal pyrolysis and gasification of Enteromorpha prolifera (also known as Ulva prolifera) under a CO2 atmosphere were investigated by thermogravimetry analysis. The gaseous products were measured online with Fourier transform infrared spectroscopy coupled with thermogravimetry. The kinetic parameters of pyrolysis and gasification reactions were obtained using the Coats–Redfern method. The experimental results showed that Enteromorpha prolifera had two derivative thermogravimetry peaks centered at 240 and 800°C, indicating the pyrolysis of organics and gasification of char, respectively. Carboxylic acids, ethers, and alcohols were the dominating condensable products generated from pyrolysis between 230 and 300°C. H2O, CH4, and aliphatic hydrocarbons were also formed in this temperature range, and they were also continuously released at higher temperatures, indicating further polymerization of the freshly generated pyrolytic char. CO was mainly produced between 700 and 900°C, and its yield was much higher than that of the pyrolytic gaseous products. The Ginstling equation (the D4 model) proved to be the most probable mechanism function for both the pyrolysis and gasification stages, with activation energies of 138.30 and 93.43 kJ mol−1, respectively.","PeriodicalId":20859,"journal":{"name":"Progress in Reaction Kinetics and Mechanism","volume":"93 1","pages":"132 - 142"},"PeriodicalIF":0.7,"publicationDate":"2019-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83889899","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}

引用次数: 8

Study on the reactions between dichlorido[2,2′:6′,2″-terpyridine] zinc(II) and biologically relevant nucleophiles in aqueous solution 二氯[2,2 ':6 '，2″-三吡啶]锌(II)与生物相关亲核试剂在水溶液中的反应研究

IF 0.7 4区化学

Progress in Reaction Kinetics and Mechanism Pub Date : 2019-04-22 DOI: 10.1177/1468678319825724

Enisa Selimović, T. Soldatović

引用次数: 1

Mechanistic and energetic studies of superparamagnetic iron oxide nanoparticles as a cyclophosphamide anticancer drug nanocarrier: A quantum mechanical approach 超顺磁性氧化铁纳米颗粒作为环磷酰胺抗癌药物纳米载体的机理和能量研究:量子力学方法

IF 0.7 4区化学

Progress in Reaction Kinetics and Mechanism Pub Date : 2019-04-10 DOI: 10.1177/1468678319825689

N. Mozayyeni, A. Morsali, M. Bozorgmehr, S. Beyramabadi

{"title":"Mechanistic and energetic studies of superparamagnetic iron oxide nanoparticles as a cyclophosphamide anticancer drug nanocarrier: A quantum mechanical approach","authors":"N. Mozayyeni, A. Morsali, M. Bozorgmehr, S. Beyramabadi","doi":"10.1177/1468678319825689","DOIUrl":"https://doi.org/10.1177/1468678319825689","url":null,"abstract":"Using Fe6(OH)18(H2O)6 as a ring cluster model for superparamagnetic iron oxide nanoparticles, noncovalent configurations and three mechanisms of covalent functionalization of superparamagnetic iron oxide nanoparticles with cyclophosphamide an anticancer drug were studied. Quantum molecular descriptors, solvation, and binding energies of noncovalent interactions were investigated the in gas and solution phases at the B3LYP and M06-2X density functional levels. In the vicinity of superparamagnetic iron oxide nanoparticles, the reactivity of the drug increases, showing cyclophosphamide can probably bind to superparamagnetic iron oxide nanoparticles through Cl (k1 mechanism), P=O (k2 mechanism), and NH in a six-membered ring (k3 mechanism) groups. The activation parameters of all pathways were calculated, indicating the high barriers related to the k1 and k2 mechanisms are higher the barrier related to the k3 mechanism. The k3 mechanism is also spontaneous and exothermic and is therefore the preferred mechanism for covalent functionalization.","PeriodicalId":20859,"journal":{"name":"Progress in Reaction Kinetics and Mechanism","volume":"66 1","pages":"101 - 92"},"PeriodicalIF":0.7,"publicationDate":"2019-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86890386","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}

引用次数: 0

The effect of neodymium and yttrium on benzofuran hydrodeoxygenation performance over a bulk Ni2P catalyst 钕钇对Ni2P催化剂上苯并呋喃加氢脱氧性能的影响

IF 0.7 4区化学

Progress in Reaction Kinetics and Mechanism Pub Date : 2019-04-10 DOI: 10.1177/1468678319830488

Hua Song, Xueyan Dai, N. Jiang, Zijin Yan, Tianhan Zhu, Feng Li

引用次数: 1

Effect of Ti on dibenzothiophene hydrodesulfurization performance over bulk Ni2P 钛对二苯并噻吩在Ni2P上加氢脱硫性能的影响

IF 0.7 4区化学

Progress in Reaction Kinetics and Mechanism Pub Date : 2019-04-10 DOI: 10.1177/1468678319825693

C. Han, Hua Song, N. Jiang, Yanguang Chen, Feng Li, Tianzhen Hao

引用次数: 0