{"title":"Mechanism of Nanostructured Fluorapatite Formation from CaO, CaF2 and P2O5 Precursors by Mechanochemical Synthesis","authors":"R. N. Mofrad, S. Sadrnezhaad, J. V. Khaki","doi":"10.3184/146867818X15233705894419","DOIUrl":"https://doi.org/10.3184/146867818X15233705894419","url":null,"abstract":"We determined the mechanism of mechanochemical synthesis of fluorapatite from CaO, CaF2 and P2O5 by characterisation of the intermediate compounds. We used atomic absorption spectroscopy, X-ray diffraction, field emission scanning electron microscopy, FTIR spectroscopy and transmission electron microscopy to find the transitional compounds. Investigation of the binary and ternary powder mixtures revealed the appearance of H3PO4, Ca(OH)2, Ca2P2O7 and CaCO3 as the intermediate compounds. At early stages of the milling, conversions of P2O5 to H3PO4 and CaO to Ca(OH)2 occurred in the wet atmosphere. Later, a combination of Ca(OH)2 and H3PO4 formed C a2P2O7 while the unreacted CaO was converted to CaCO3 by CO2 of the ambient atmosphere. Spherical crystalline Ca10 (PO4)6F2 particles formed after 48 hours of milling due to the reaction between Ca2P2O7, CaCO3 and CaF2.","PeriodicalId":20859,"journal":{"name":"Progress in Reaction Kinetics and Mechanism","volume":"76 1","pages":"201 - 210"},"PeriodicalIF":0.7,"publicationDate":"2018-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"85781061","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}
{"title":"Impact of Chloride Concentration on Ligand Substitution Reactions of Zinc(II) Complexes with Biologically Relevant Nitrogen Nucleophiles","authors":"Enisa Selimović, T. Soldatović","doi":"10.3184/146867818X15319903829164","DOIUrl":"https://doi.org/10.3184/146867818X15319903829164","url":null,"abstract":"The mole-ratio method was used to determine the metal–ligand stoichiometry between [ZnCl2(en)] and [ZnCl2(terpy)] (where en = 1,2-diaminoethane or ethylenediamine and terpy = 2,2′:6′,2″-terpyridine) and imidazole at pH 7.2 in the presence of different chloride concentrations. The results indicated step-wise formation of 1:1 and 1:2 complexes in the presence of 0.010 M NaCl and 1:1 complexes in the presence of 0.001 M NaCl for the [ZnCl2(en)] complex. These results are correlated with additional coordination of chlorides in the first coordination sphere and with changes in coordination geometry. In the presence of 0.001 M NaCl the five-coordinate complex anion [ZnCl3(en)]- is formed initially and then a substitution reaction with imidazole occurs. In the presence of 0.010 M NaCl the octahedral complex anion [ZnCl4(en)]2- is formed. Additional coordination of chloride in the [ZnCl2(terpy)] complex is not found and the metal–ligand stoichiometry is 1:2. The kinetics of ligand substitution reactions of zinc(II) complexes and biologically relevant nitrogen nucleophiles such as imidazole, 1,2,3-triazole and L-histidine were investigated at pH 7.2 as a function of nucleophile concentration in the presence of 0.001 M and 0.010 M NaCl. The reactions were followed under pseudo first-order conditions by UV-Vis spectrophotometry. The substitution reactions included two steps of consecutive displacement of chlorido ligands with changes only in the coordination geometry of the [ZnCl2(en)] complex. The order of reactivity of the investigated nucleophiles for the first reaction step towards both complexes was L-histidine > 1,2,3-triazole > imidazole, while in the presence of 0.010 M NaCl the most reactive ligand was 1,2,3-triazole towards the [ZnCl2(en)] complex.","PeriodicalId":20859,"journal":{"name":"Progress in Reaction Kinetics and Mechanism","volume":"1 1","pages":"244 - 253"},"PeriodicalIF":0.7,"publicationDate":"2018-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84329255","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}
{"title":"Application of Evolutionary Algorithms for Modelling and Optimisation of Ultrasound-Related Parameters on Synthesised SAPO-34 Catalysts: Crystallinity and Particle Size","authors":"M. Azarhoosh, R. Halladj, S. Askari","doi":"10.3184/146867818X15233705894446","DOIUrl":"https://doi.org/10.3184/146867818X15233705894446","url":null,"abstract":"First, the effects of ultrasound-related variables on the crystallinity and particle size of synthesised SAPO-34 catalysts were modelled using a genetic programming (GP) method. The results confirm that GP has good predictive power. Secondly, optimisation of the ultrasound parameters was considered using a genetic algorithm (GA) to obtain SAPO-34 catalysts with high crystallinity and minimum particle size for the best performance in the methanol to light olefins process. The GP models were used as the fitness functions inside the GA. Finally, the optimum solution was validated experimentally and the results indicate that there is a good agreement between experimental and predicted values.","PeriodicalId":20859,"journal":{"name":"Progress in Reaction Kinetics and Mechanism","volume":"3 1","pages":"236 - 243"},"PeriodicalIF":0.7,"publicationDate":"2018-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89974767","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}
{"title":"A Study on the Kinetics and Mechanism of the One-Pot Formation of 3,4,5-Substituted Furan-2(5H)-Ones in the Presence of Lactic Acid: Effect of Different Substituents","authors":"Osman Asheri, S. Habibi‐Khorassani, M. Shahraki","doi":"10.3184/146867818X15319903829218","DOIUrl":"https://doi.org/10.3184/146867818X15319903829218","url":null,"abstract":"The kinetics of the reaction between para-substituted anilines and dimethyl acetylenedicarboxylate (DMAD) with derivatives of benzaldehyde for the one-pot formation of 3,4,5-substituted furan-2(5H)-ones in the presence of lactic acid as a catalyst have been studied spectrophotometrically at different temperatures. A mechanism involving four steps was proposed for the reactions, all of which followed second-order kinetics. The partial orders with respect to substituted aniline and DMAD were one and one and the reactions revealed zero-order kinetics for benzaldehyde and its derivatives. Changing of substituents on benzaldehyde left rates of reaction unaffected. However, various substituents on aniline showed that para electron-withdrawing groups decreased the rate of reaction. According to investigation of an isokinetic relationship, a common mechanism exists for all studied substituents and a general mechanism can be formulated. Kinetic values (k and Ea) and associated activation parameters (ΔG‡, ΔS‡ and ΔH‡) of the reactions were determined.","PeriodicalId":20859,"journal":{"name":"Progress in Reaction Kinetics and Mechanism","volume":"48 1","pages":"286 - 299"},"PeriodicalIF":0.7,"publicationDate":"2018-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86854019","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}
{"title":"Nanopowder-Supported Ultra-Low Content Co–Rh Bimetallic Catalysts for Hydroformylation of Monoformyltricyclodecenes to Value-Added Fine Chemicals","authors":"Chengyang Li, Libo Zhang, Yubo Ma, Tianfu Wang","doi":"10.3184/146867818X15319903829173","DOIUrl":"https://doi.org/10.3184/146867818X15319903829173","url":null,"abstract":"The hydroformylation of monoformyltricyclodecenes (MFTD) to diformyltricyclodecanes (DFTD) was studied systematically. A series of 0.006 wt% Rh–0.006 wt% Co catalysts supported on commercially available nanopowders such as Al2O3, ZnO, TiO2 and CeO2 was prepared by the incipient wetness method and used to catalyse the hydroformylation of MFTD to DFTD. The 0.006 wt% Rh–0.006 wt% Co/ZnO catalyst showed the highest catalytic performance among the catalysts investigated, thus 41.8% DFTD yield with 100% DFTD selectivity could be achieved. This suggested that there may be a key role of the carrier on the catalytic performance in MFTD hydroformylation. Furthermore, the kinetic profiles for MFTD hydroformylation over the 0.006 wt% Rh–0.030 wt% Co/ZnO catalyst have been examined systematically to explore the effect of reaction temperature on the catalytic performance. These results collectively suggested that a particular reaction temperature might benefit MFTD hydroformylation. There may be some agglomeration of the active sites at higher reaction temperatures.","PeriodicalId":20859,"journal":{"name":"Progress in Reaction Kinetics and Mechanism","volume":"52 1","pages":"254 - 261"},"PeriodicalIF":0.7,"publicationDate":"2018-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"88967977","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}
Animesh Chattopadhyay, A. Dey, P. Karmakar, S. Ray, D. Nandi, Roshni Sarkar(Sain), A. K. Ghosh
{"title":"Mechanistic Aspects of Ligand Substitution on the Cis-Diaqua-Chloro-Tris(Dimethyl Sulfoxide)Ruthenium(II) Complex by Some Sulfur-Containing Bioactive Ligands in Aqueous Medium","authors":"Animesh Chattopadhyay, A. Dey, P. Karmakar, S. Ray, D. Nandi, Roshni Sarkar(Sain), A. K. Ghosh","doi":"10.3184/146867818X15319903829191","DOIUrl":"https://doi.org/10.3184/146867818X15319903829191","url":null,"abstract":"The synthesis and interactions of the cis-diaqua-chloro-tris(dimethyl sulfoxide)ruthenium(II) complex with selected sulfur-containing ligands such as 2-thiouracil, glutathione and L-cysteine have been studied by UV-Vis spectrophotometry in aqueous medium at pH 4.5. From experimental data it is clear that all three reactions proceed via two steps: the first one being a rate-limiting ligand-dependent replacement of one water molecule, followed by a ligand-independent ring closure step with the expulsion of the second water molecule. The substituted products have been characterised by Job's method, FTIR spectroscopy and electrospray ionisation mass spectrometry. Activation parameters (ΔH≠ and ΔS≠) and thermodynamic parameters (ΔH0 and ΔS0, from the temperature dependence of the outer-sphere association equilibrium constant) are presented. Consistent with the experimental findings, an associative interchange mechanism is proposed.","PeriodicalId":20859,"journal":{"name":"Progress in Reaction Kinetics and Mechanism","volume":"23 1","pages":"274 - 285"},"PeriodicalIF":0.7,"publicationDate":"2018-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"85219114","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}
{"title":"A Density Functional Theory Study of NH3 and NO Adsorption on the β-MnO2 (110) Surface","authors":"Hao Meng, Xuanwei Wu, Chao Ci, Qian Zhang, Zhe Li","doi":"10.3184/146867818X15233705894428","DOIUrl":"https://doi.org/10.3184/146867818X15233705894428","url":null,"abstract":"The adsorption of NH3 and NO on the β-MnO2 (1 1 0) surface has been investigated by density functional theory using periodic models. The energetically favourable sites of adsorption of the gases on the β-MnO2 surface are 4-fold coordinate Mn (Mn4-top) and 5-fold coordinate Mn (Mn5-top). The relative adsorption energies (Eads) of these gases on the Mn4-top site and Mn5-top site are in the orders NH3 (Eads = −1.02 eV) > NO (Eads = −0.96 eV) and NH3 (Eads = −0.63 eV) > NO (Eads = −0.49 eV). The N-H and N–O bond lengths, Mulliken charges and the densities of states of the NH3 and NO molecules are discussed after adsorption. The calculated results indicate that the coordination number of surface Mn ions has a significant influence on the adsorption capacity. Furthermore, the analysis of the results of the density of states determinations shows that when NH3 and NO are adsorbed with the NH3-Mn and NO-Mn configurations, the bonding mechanism is mainly from the interaction between the NH3 or NO molecule and the Mn d orbital, which is the major reason for the strong chemical adsorption of NH3 and NO.","PeriodicalId":20859,"journal":{"name":"Progress in Reaction Kinetics and Mechanism","volume":"28 1","pages":"219 - 228"},"PeriodicalIF":0.7,"publicationDate":"2018-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"81306526","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}
{"title":"Reactivity of β-Substituted Phosphoenol Pyruvates towards Alkoxides: A Theoretical and Experimental Study","authors":"Djilali Bassou, A. Ghomri, A. Atmani","doi":"10.3184/146867818X15161889114466","DOIUrl":"https://doi.org/10.3184/146867818X15161889114466","url":null,"abstract":"A new, practical, synthesis of pyruvic orthoesters relying on the conversion of β-substituted phosphoenol pyruvates by the action of alkoxides is described. Our study of the reaction mechanism was done experimentally and also theoretically. Density functional theory calculations were used to explain the major reaction products found experimentally. Geometry optimisations and atomic charges obtained using different population analyses and the global and local reactivity indices, namely global electrophilicity and the Parr function, were obtained at the B3LYP/6-311G(d) level of theory. The experimental reactivity was correctly reproduced using the Parr function.","PeriodicalId":20859,"journal":{"name":"Progress in Reaction Kinetics and Mechanism","volume":"70 1","pages":"211 - 218"},"PeriodicalIF":0.7,"publicationDate":"2018-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"82125283","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}
{"title":"Adsorption of P-Nitrophenol Onto Partially Reduced Graphene Oxide: An Experimental and Theoretical Study","authors":"Mengzhi Yang, Meiling Wang","doi":"10.3184/146867818X15233705894374","DOIUrl":"https://doi.org/10.3184/146867818X15233705894374","url":null,"abstract":"This study investigated the adsorption process of p-nitrophenol (p-NP) onto partially reduced graphene oxide (prGO) using both experiment and theoretical calculations. The maximum adsorption capacity of prGO at pH 6.0 and 293 K for p-NP was 29.94 mg g−1 which was significantly higher than previously reported using a metal-doped reduced graphene oxide composite. Systematic, comparative theoretical calculations were used to investigate the adsorption mechanism of p-NP onto graphene oxide, prGO and graphene nanosheet (GN). Calculations revealed three types of adsorption site and indicated that the adsorption force and sites were significantly affected by the quantity and type of oxygen-containing functional groups on the GN. The adsorption affinity was mainly derived from hydrogen bonds and π-π stacking which was further demonstrated by FTIR analysis. Due to its excellent adsorption performance, good recyclability and easy separation, prGO can be a promising adsorbent for the efficient elimination of p-NP from wastewater in the future.","PeriodicalId":20859,"journal":{"name":"Progress in Reaction Kinetics and Mechanism","volume":"1 1","pages":"189 - 200"},"PeriodicalIF":0.7,"publicationDate":"2018-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89639535","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}
{"title":"Quantifying Enhancement of Metal-Supported Zeolites Due to Hydrogen Spillover","authors":"Shrivanand M. Pai, B. L. Newalkar, P. Parikh","doi":"10.3184/146867818X15233705894347","DOIUrl":"https://doi.org/10.3184/146867818X15233705894347","url":null,"abstract":"As bifunctional catalysts, metal-supported zeolites play an important role in refining and petrochemical processes, e.g. isomerisation, alkylation, etc. Reduction in acidity and acid strength of zeolites upon their impregnation with metals have been widely reported. Also hydrogen spillover vis-a-vis the closeness of two catalyst functions (acid and metal) has been discussed at length. Hydrogen spillover has been claimed to give rise to formation of additional acid sites on supports. Here quantification of acid sites for two zeolites, zeolite Y and ZSM-5, impregnated with different metals in various proportions after exposing them to hydrogen, has been attempted using ammonia temperature programmed desorption. The observed acidity values have been explained on the basis of metal cluster size.","PeriodicalId":20859,"journal":{"name":"Progress in Reaction Kinetics and Mechanism","volume":"20 1","pages":"157 - 165"},"PeriodicalIF":0.7,"publicationDate":"2018-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84535822","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}