Methodik und Ergebnisse von Tracerexperimenten über katalytische Reaktionen von Kohlenwasserstoffen

Tracermethoden können wichtige Beiträge zur Aufklärung katalytischer Kohlenwasserstoffreaktionen liefern. In dieser Arbeit werden einige Ergebnisse mehrjähriger Untersuchungen mit ¹⁴C-markierten Verbindungen zusammenfassend dargestellt. Es wird speziell auf Benzenbildungsreaktionen bei der Leichtbenzin-Reformierung und auf Reaktionsmechanismen bei der Isomerísierung von C₈-Aromaten eingegangen.     

Divergent reaction pathways for one-pot,three-component synthesis of novel 4H-pyrano[3,2-h]quinolines under ultrasound irradiation

The present paper deal with the multi-component condensation of 8-hydroxy quinoline, aromatic aldehydes, and sulfone derivatives catalyzed by p-toluenesulfonic acid for the synthesis of a series of 4H-pyrano[3,2-h]quinoline derivatives in ethanol under ultrasonic irradiations. We provide a series of quinoline derivatives containing sulfone moiety interesting for biological screening tests. The reactions were carried out under both conventional and ultrasonic irradiation conditions. In general, improvement in rates and yields were observed when reactions were carried out under sonication compared with classical silent conditions. Also, also, sonochemical reaction give different reaction pathway other than silent reaction. These remarkable effects appeared in sonicated reactions can be reasonably interpreted in terms of acoustic cavitation phenomenon. Structures of the products were established on analytical and spectral data.     

Rates of diffusion controlled reactions for one-dimensionally-moving species in 3D space

ABSTRACT

The asymmetry in diffusion dimensionality between self-interstitial atom (SIA) clusters and vacancies is a fundamental feature of irradiation damage in crystals, leading to a defect buildup imbalance that manifests itself as measurable dimensional and mechanical property changes. It is well known that, while vacancies and mobile vacancy clusters diffuse in a three-dimensional (3D) fashion, SIA clusters perform one-dimensional motion along mostly rectilinear trajectories. Despite this, a complete set of kinetic coefficients, including coagulation reaction rates and sink strengths, does not exist for 1D-moving objects. In this paper, we derive analytical expressions for these coefficients from continuum diffusion theory particularised to 1D motion. Moreover, we carry out kinetic Monte Carlo simulations of numerical replicas of the geometry of diffusing particles and sinks to validate the proposed solutions. Our simulations, which are conducted entirely independently from the analytical derivations, reveal excellent agreement with the proposed expressions, adding confidence to their validity. We compare the 1D and 3D cases and discuss their relevance for kinetic codes for damage accumulation calculations.     

活性靶技术熔合截面测量极限研究

天体环境中丰中子核素熔合反应率对研究中子星表面超级暴现象的点火机制有重要意义。由于次级束流强过低,无法使用传统固体靶实验技术测量垒下熔合反应截面。活性靶技术的发展为垒下丰中子核素熔合反应截面的测量提供了可行的途径。基于Geant4模拟详细地分析了多重采样电离室（MUSIC）与时间投影室（TPC）两种活性靶探测器中熔合反应与弹性散射的运动学性质,给出了4种熔合反应鉴别判据,并且计算了由这些判据误判引起的熔合截面系统误差。在E_cm=13.6 MeV时,MUSIC与TPC的弹性散射误判截面分别为0.5 mb和2.9×10-3 mb,都远小于此时熔合截面（877 mb）。在垒下,MSUIC的熔合截面系统误差已经超出实验测量要求,而TPC能够进行实验测量的能量可以降低至E_cm=4.7 MeV。Reaction rates of fusion reactions among neutron-rich nuclei in the astrophysical environment are of great significance to understand the ignition of superbursts on neutron stars. Since beam intensity is rather low for radioactive ion beams, it is extremely difficult to operate a direct measurement for cross sections of such fusion reactions below the Coulomb barrier using thick target technique. In this case, a novel technique, active target technique, has been developed recently. To study the energy limit for measurement below Coulomb barrier, the kinematics of elastic scattering and fusion reaction in MUSIC and TPC are discussed with Geant4 simulation. Four identification methods are used and uncertainties of cross sections resulted from misjudgments are calculated. With E_cm=13.6 MeV, the uncertainties of cross sections for MUSIC and TPC are 0.5 mb and 2.9×10-3 mb, respectively. The uncertainties for MUSIC become far beyond measurement when below coulomb barrier, while TPC remains to be a suitable detector for measuring fusion cross sections until E_cm=4.7 MeV.     

Hamilton–Jacobi equation,reaction action surface and the emergence of the force concept in chemical reaction dynamics

A combination of Hamilton–Jacobi equation and fast marching algorithm can be used to study reaction dynamics by converting the potential energy surface to a reaction action surface. The reaction action surface has been found to be an important tool in theoretical chemistry, allowing us to provide a different force-based perspective of chemical reactions. Several properties such as reaction force, reaction force surface, reaction path force and reaction path force constant have been defined and calculated by using the reaction action surface. This paper investigates these newly defined properties in order to understand the role they play in chemical reaction with reference to a model 4-well potential energy surface.     

气相爆轰波在分叉管中传播现象的数值研究

数值研究气相爆轰波在分叉管中的传播现象.用二阶附加半隐龙格-库塔法和5阶WENO格式求解二维欧拉方程,用基元反应描述爆轰化学反应过程,得到了密度、压力、温度、典型组元质量分数场及数值胞格结构和爆轰波平均速度.结果表明:气相爆轰波在分叉管中传播,分叉口左尖点的稀疏波导致诱导激波后压力、温度急剧下降,诱导激波和化学反应区分离,爆轰波衰减为爆燃波(即爆轰熄灭).分离后的诱导激波在垂直支管右壁面反射,并导致二次起爆.畸变的诱导激波在水平和垂直支管中均发生马赫反射.分叉口上游均匀胞格区和分叉口附近大胞格区的边界不是直线,其起点通常位于分叉口左尖点上游或恰在左尖点.水平支管中马赫反射三波点迹线始于右尖点下游.分叉口左尖点附近的流场中出现了复杂的旋涡结构、未反应区及激波与旋涡作用.旋涡加速了未反应区的化学反应速率.反射激波与旋涡作用并使旋涡破碎.反射激波与未反应区作用,加速其反应消耗,并形成一个内嵌的射流.数值计算得到的波系演变和胞格结构与实验定性一致.     

DME/LPG混合燃料HCCI燃烧模拟

根据碳氢燃料化学反应系统具有层次结构的特性,本文通过分析二甲醚(DME)与液化石油气(LPG)的详细化学反应机理,构建了反映DME／LPG混合燃料均质压燃(HCCI)燃烧的详细化学反应机理．采用该机理应用单区燃烧模型对DME／LPG混合燃料HCCI燃烧的化学反应动力学过程进行了数值计算．计算结果与试验结果对比表明,所构建的DME／LPG混合燃料氧化的详细化学反应机理能够准确预测DME／LPG混合燃料的两阶段放热特性,对低温和高温着火始点的预测很好;但高温反应过程预测欠佳,高温反应机理需要改进．     

量子相干控制化学反应的进展和机遇

1995年 ,人们曾预言“量子控制多体动力学将成为化学物理的主流”(引自第 2 0届Ｓｏｌｖａｙ化学会议上ＳｔｕａｒｔＡ .Ｒｉｃｅ的主旨演说 .Ｓｏｌｖａｙ会议是研讨未来科学的高级会议 .这一届会议的主题是“光化学 :化学反应及其飞秒尺度上的控制”) .现在 ,我们看到了这股潮流正源源而来 ,每年都不断地在Ｎａｔｕｒｅ、Ｓｃｉｅｎｃｅ等杂志上刻下了里程碑 .人们一直希望控制化学反应的方向和历程 .早期的控制是被动的控制 ,即通过把握反应的宏观条件 (如温度、压力等 )或者选择适当的催化剂去实现 .自从分子反应动力学发展之后 ,人们在…     

能量修正的Glauber模型对中能反应总截面的影响

叙述了对Glauber模型中的透射系数进行半经验的能量修正,并利用该修正模型计算了^12—14C,⁶Li,⁷Be,⁸B+¹²C和⁶Li,⁷Be,⁸B+⁹Be以及²⁰Ne+¹²C,¹²C+²⁷Al等系统的激发函数(能区范围10—1000MeV/u),经与实验值比较,能量修正的Glauber理论计算值能够很好地描述中能条件下的反应总截面实验测量值.