A comprehensive molecular dynamics study of a single polystyrene chain in a good solvent

In this study, molecular characteristics of polystyrene (PS) was calculated measuring its dilute-solution properties in toluene at 288.15 K via molecular dynamics (MD) simulations. The solution models consisted of PS chains with different number of repeating units all of which were in a dilute regime. In order to investigate the compatibility between the polymer and the solvent molecules, interaction energy and Flory-Huggins (FH) interaction parameter were estimated. The simulation results indicate that increasing the chain repeating units enhanced the interaction between the solute and the solvent. Additionally, the chain dimensions were evaluated calculating the radius of gyration (R_g) and end-to-end distance, r0. To determine the dynamic behavior of the chains in the solutions, mean square displacement (MSD) and diffusivity coefficient were calculated. The simulation results indicated that the chain rigidity at low molecular weight and chain flexibility with increasing the molecular weight influenced chains dynamic behavior and diffusivity. Moreover, radial distribution function (RDF) illustrated the effect of steric hindrance of the chains in dilute solution on capturing the solvent molecules. In addition, solution viscosity was calculated by performing non-equilibrium molecular dynamics simulation (NEMD). The obtained results of chain characteristics and viscosity showed a good agreement with experimental results published previously. This agreement confirms the accuracy of the applied simulation method to characterize the dilute solutions and the chains characteristics.     

A shock tube study of the auto-ignition of toluene/air mixtures at high pressures

The auto-ignition of toluene/air mixtures was studied in a shock tube at temperatures of 1021-1400 K, pressures of 10-61 atm, and equivalence ratios of Φ = 1.0, 0.5, and 0.25. Ignition times were measured using endwall OH∗ emission and sidewall piezoelectric pressure measurements. The measured pressure time-histories do not show significant pre-ignition energy release, in agreement with the rapid compression machine study of Mittal and Sung [G. Mittal, C.-J. Sung, Combust. Flame 150 (2007) 355-368] and disagreement with the shock tube study of Davidson et al. [D.F. Davidson, B.M. Gauthier, R.K. Hanson, Proc. Combust. Inst. 30 (2005) 1175-1182]. Kinetic modeling predictions from three detailed mechanisms are compared. Sensitivity analysis indicates that the reaction of toluene (C₆H₅CH₃) and the benzyl radical (C₆H₅CH₂) with molecular oxygen are important and examination of the rate coefficients for these reactions suggests that improved rate parameters for the multi-channel C₆H₅CH₂ + O₂ reaction may improve model predictions.     

Kinetic modeling of the benzyl + HO2 reaction

Benzyl is a resonantly stabilized radical that commonly occurs as an intermediate in the combustion of aromatic compounds. The bimolecular reaction of benzyl with HO₂ is important in the oxidation of toluene, especially at low to moderate temperatures, where unimolecular decomposition of the benzyl radical is slow. We show that the addition of HO₂ to the methylene site in benzyl produces a vibrationally excited benzylhydroperoxide adduct, with over 60 kcal mol⁻¹ (251 kJ mol⁻¹) of excess energy above the ground state. RRKM simulations are performed on the benzyl + HO₂ reaction, using thermochemical and kinetic parameters obtained from ab initio calculations, with variational transition state theory (VTST) for treatment of barrierless radical + radical reaction kinetics. Our results reveal that the benzyl + HO₂ reaction proceeds predominantly to the benzoxyl radical + OH at temperatures of around 800 K and above, with the production of stabilized benzylhydroperoxide molecules dominating at lower temperatures. The heat of formation of the benzyl radical is calculated as 52.5 kcal mol⁻¹ (219.7 kJ mol⁻¹) at the G3B3 level of theory, in relative agreement with other recent determinations of this value.     

Oxidative Methylation of Toluene with Methane over K-exchanged Y Type Zeolite Catalyst Promoted with Alkali Metal Bromide and Alkali Metal Oxide

IntroductionManyresearchgroupsareconductingextensiveresearchtoreplacecrudeoil-basedchemicalswithnaturalgasandcoal-basedchemicals.Itisknownthatstyreneisoneofthemostimportantindustrialmonomers.Currently,styreneisproducedbycatalyticalkylationofbenzenewithethyleneoverA1Cl,-HClcata-lyst,followedbyoxidativedehydrogenationoftheresultantethylbenzeneoverpotassium-promotedironoxidecatalystsL'l.However,thisprocessinvolvestheutilizationofbenzeneandethylene,obtainedfromcrudeoilandpetroleumgas,whichareexp…     

气相色谱法测定空气中苯、甲苯和邻二甲苯

使用3500有机挥发物监控器收集空气中的苯、甲苯和邻二甲苯。建立了气相色谱测定法。方法简单,快速,苯、甲苯和邻二甲苯的检出限小于OSHA允许限量的1／30,回收率为90．8％～99．7％,相对标准偏差为0．40％～0．63％。     

分光光度法测定香菇中硒的研究

在ＨＣｌ介质中３,３’－二氨基联 胺与硒反应生成黄色络合物,λｍａｘ＝４２０ｎｍ,ε＝４＊１０＾４Ｌ．ｍｏｌ＾－１．ｃｍ＾－１,硒含量在０．５－５０μｇ／２５ｍＬ范围内符合比耳定律,本方法用于香菇样品中硒的测定,结果令人满意。     

食品微晶蜡中苯及甲苯残留的顶空气相色谱法测定

应用带有顶空进样器气相色谱仪, 采用外标法定量, 分析食品微晶蜡中苯及甲苯残留量 ; 选择以食品用白油为母液制备一系列标准样品, 在选择的色谱条件下分析, 苯和甲苯含量分别在 10× 10-9～ 2 000× 10-9(w)间与峰面积呈现良好的线性关系, 检出限 (S/N=2)为 5× 10-9(w).     

气相质谱法对小鼠体内甲苯二异氰酸酯代谢产物的鉴定分析

应用气相质谱测定小鼠体内甲苯二异氰酸酯(TDI)的代谢产物,并鉴别了其在机体中的代谢途径。TDI色谱条件为Supelco PTETM-5色谱柱(30 mm×0.25 mm×0.25 μm),起始柱温90 ℃保持30 min,以40 ℃·min-1升至280 ℃,保持5.25 min;汽化室温度250 ℃;载气为氦气,流速为1.0μL·min-1。TDI体内代谢产物色谱条件为30+2mX0.25+0.02mm 94%甲基、4%乙烯基键合相弹性石英毛细柱,起始温度30 ℃保持5 min,以8 ℃·min-1升至280 ℃,保持5 min。汽化室温度250 ℃;载气为氦气,流速1.0μL·min-1。质谱条件为电离方式EI,电离能量70eV,连接管温度280 ℃,扫描范围35～350μ;进样量1.0μL。结果表明2,4甲苯二异氰酸酯在血液、尿液、粪便中都被代谢成为2,4甲苯二胺。GC-MS法可有效分离并鉴定TDI体内代谢产物。     

碱性X分子筛催化甲苯与甲醇侧链烷基化自由基机理研究

苯乙烯是重要的工业原料,年消耗量约3000万吨。传统工艺中,苯乙烯由乙苯催化脱氢得到。由于传统工艺高能耗,高污染,甲苯与甲醇侧链烷基化合成苯乙烯引起了人们广泛关注,但是目前该路线进入工业化还有很多问题需要解决,甚至催化机理仍不明确。本文对甲苯侧链烷基化机理及提高反应选择性等方面进行了研究。采用离子交换法制备CsX分子筛,在固定床反应器上进行甲苯与氘代甲醇的同位素示踪实验和硝基甲苯的侧链烷基化实验,结合量子计算明确反应机理。采用IGA-002系统测定甲醇在CsX, KX和NaX上的等温吸附线,考察甲醇在分子筛不同笼结构中的吸附情况。将氘代甲苯与甲苯在CsX, KX和活性炭催化下进行氢氘交换实验,检验自由基在不同催化剂上的稳定性。以CO2为载气进行甲苯与甲醇侧链烷基化实验,考察CO2对反应的影响。甲苯与氘代甲醇进行侧链烷基化反应时,大多数氘出现在甲苯上,仅少数氘存在于苯乙烯及乙苯上,表明甲苯氢与甲醇的甲基氘进行了氢氘交换。量子化学计算表明,甲苯与甲醇的氢氘交换沿自由基路径的能垒远小于沿离子路径的。氘代实验和量子计算结果表明,甲苯侧链烷基化过程中存在自由基,但并不能证明侧链烷基化是自由基反应。为了验证甲苯侧链烷基化反应是否为自由基机理,以4-硝基甲苯(NO2-Ph-CH3)代替甲苯与甲醇进行侧链烷基化反应。硝基是强吸电子基团,能稳定苄基负离子,如果甲苯侧链烷基化是离子反应,硝基甲苯侧链烷基化产物收率会升高。另外,硝基又能与活泼自由基生成稳定自由基,若反应为自由基机理,则硝基甲苯不发生侧链烷基化反应。分析结果表明,反应液中不存在侧链烷基化产物,确定了甲苯侧链烷基化反应为自由基机理,而不是离子机理。热力学上甲醇更容易进行生成CO和H2等的副反应,从而减少CH3?与H?碰撞甲醇的几率。甲醇等温吸附线显示甲醇在NaX和KX上的吸附容量相近且远大于CsX上的,表明Cs+阻碍了甲醇进入X分子筛的β-笼。由于甲苯不能进入β-笼, NaX和KX的β-笼内甲醇与甲基自由基接触发生副反应。 CsX催化时Cs+阻碍甲醇进入β-笼而抑制了副反应的发生,提高了甲醇利用率。甲苯与氘代甲苯在CsX, KX和活性炭上进行氢氘交换,反应物用GC-MS分析。结果表明,在CsX上氢氘交换进行得更彻底,在活性炭上几乎没有氢氘交换。 X分子筛活化甲苯为自由基的效果优于活性炭,这可能是推拉效应造成的。当甲苯进入分子筛后, Lewis酸性阳离子与苯环络合并吸引电子,催化剂阴离子骨架与甲苯的甲基作用并供给电子,推电子与吸电子共同作用使甲苯更容易生成苄基自由基,并使其更稳定。 CsX对甲苯的活化作用强于KX,表明CsX的酸碱搭配更有助于甲苯生成自由基。这也是CsX催化甲苯与甲醇侧链烷基化效果优于KX的原因。以CO2替代N2作为载气能显著提高苯乙烯的选择性,这是由于CO2的存在降低了H?和CH3?的浓度,提高了?CH2OH的浓度。?CH2OH与甲苯生成苯乙烯, H?的减少降低了苯乙烯加氢生成乙苯。