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中国高分子科学卷。
31日，第12号，（2013），1623-1631 中国高分子科学卷中国化学会中国科学院化学研究所施普林格出版社柏林海德堡2013聚（苯乙烯-丁二烯-苯乙烯共聚物）和聚（硫脲- 偶氮萘基）共混物的机械稳定与热稳定Ayesha Kausar* 和Syed Tajammul Hussain纳米科学和催化司，国家大剧院物理，奎德- 真纳大学校园，44000伊斯兰堡，巴基斯坦摘要：一种新的芳香族偶氮聚合物，聚（脲- 偶氮 - 萘基）（PTAN），已经被用来合成（5-1二萘基偶氮）硫脲和2,6- 二氨基吡啶重氮盐溶液。
PTAN在极性溶剂中易于加工，并且具有高摩尔质量57×103克/摩尔。
通过溶液共混技术制备得聚（苯乙烯- 丁二烯 - 苯乙烯）（SBS）三嵌段共聚物和PTAN的橡胶共混物，具有导电性，机械稳定性和热稳定性。
SBS/PTAN共混物的扫描电镜结果表明导电填料有着良好的粘附性纳米级分散在矩阵和PTAN之间。
通过观察偶氮含量对于共混物的电导率的显著影响，PTAN质量含量从10%加到60％，电导率从1.24秒/厘米加至1.66秒/厘米。
研究PTAN的质量与物质的热稳定性的关系表明随着PTAN含量的增加，10％重量损失从484℃增加至500℃，而玻璃化转变从119℃增加到126℃。
相对于纯弹性体，热稳定性和共混物的数据显示结果更好，但是对于填料而言却相反。
同样，SBS/PTAN的拉伸强度（57.35-62.33兆帕）提高了，与SBS的状况相似。
特性新材料呈现出来的良好的平衡比在大多数应用中使用的弹性体共混物要好。
关键词：聚（脲- 偶氮 - 萘基）；SBS；电气导通；热稳定性；拉伸强度前言：最近，由分散的内部的所述导电填料绝缘聚合物基质建立的导电聚合物系统已经建立并作为一种制造聚合共混物的方法。
这些高性能材料具有良好的机械性能，基体的热稳定性和矩阵连同电气的加工导电组分的性质[1-3]。
Chapter 3 Inorganic Chemistry (28)3.1 The Atomic Nature of Matter (28)3.2 Electronic Structure of Atoms (30)3.3 Periodicity of Atomic Properties (32)3.5 Molecular Geometry and Bonding Theories......................................................... 错误！未定义书签。
3.6 Chemical Reactions................................................................................................. 错误！未定义书签。
3.7 The Behavior of Gases ............................................................................................ 错误！未定义书签。
3.8 Aqueous Reactions and Solution Stoichiometry................................................... 错误！未定义书签。
3.9 Chemical Equilibrium ............................................................................................ 错误！未定义书签。
3.10 Thermochemistry.................................................................................................. 错误！未定义书签。
以硝基苯基为配体的有机铋化合物的研究进展陈静【摘要】Application of many organobimuth compounds in catalysis, biological medicine and functional materials were rapid developed since these compounds of low toxicity and low radioactive characteristics. Three kinds of synthetic methods for organobismuth compounds bearing nitrophenyl ligand and comparison of these synthetic routes were introduced. The use of metal -halogen reaction of Grignard reagent method was emphatically described, which had a simple and practical advantages synthetic route. Furthermore, the synthetic products had good application propects in curing catalysis.%由于铋类化合物具有低毒性和低放射性等诸多优良特性，在催化剂、生物医药、功能性材料等多方面的应用研究发展迅速。
本文主要介绍了以硝基苯基为配体的有机铋化合物的三种合成方法并进行了比较。
着重叙述了采用金属-卤素交换反应的格氏试剂法，该方法具有合成路线简单，实用性强等优点。
另外，合成产物的在固化催化方面有良好的应用前景。
【期刊名称】《广州化工》【年(卷),期】2014(000)021【总页数】3页(P52-53,140)【关键词】硝基;有机铋化合物;合成;催化剂【作者】陈静【作者单位】黔南民族师范学院化学与化工系，贵州都匀 558000【正文语种】中文【中图分类】O625.61铋是第15 族中金属性最强的元素，具有特殊的理化性质。
![[自然科学]原子轨道与分子结构的轨道理论关系](https://img.taocdn.com/s1/m/da73009ed1d233d4b14e852458fb770bf78a3baf.png)
Linear Trigonal Tetrahedral TrigonalOctahedralBipyramidallinear LinearTrigonal planar Trigonal planar(AB3)Bent(AB E)TetrahedralBent (AB 2E 2)Tetrahedral (AB )Pyramidal (AB E)Trigonal BipyramidalTrigonal Bipyramidal(AB 5)Unsymmetrical Tetrahedron (AB 4E)T-shaped (AB 3E 2)Linear (AB 2E 3)Square planar(AB4E 2 )Octahedral(AB6)Squarepyramidal(AB5E)1.Determine the Lewis structure2.Determine the number of electron pairs (orclouds) around the CENTRAL ATOM –multiple bonds count as ONE CLOUD (seenext slide).3.Find out the appropriate VSEPR geometryfor the specified number of electron pairs,both bonding and lone pairs.e the positions of atoms to establishthe resulting molecular geometry.Multiple Bonds and Molecular GeometryMultiple bonds count as one -e.g. 4 bonding pairs aroundC, but trigonal planarinstead of tetrahedral.cysteineHF electron rich regionelectron poorregionGG10.2Cl2CONH3H2OThese types of molecules, where C = central atom and T = terminal atoms of the same type, are never polar.End to end overlap = sigma (109.5 o Lewis Structure Electron pairsaround CFig. 10.7Fig. 10.8BF3-trigonal planar according to VSEPR Theory (incomplete octet exception)Isolated S atom(upgraded –more will be added)1. Hybrid orbitals get 1 electron for a V-bond, 2 electrons for a lone pair.2. Remaining electrons go into unhybridized orbitals= S bondsDOUBLE BONDS: Ethylene, CH2CH2 Lewis Structure:sp2hybridization on each C atom -sp2hybrids and unhybridized p-orbitalV bond = end-to-end overlap of the sp 2hybridized orbitals••••••••••1 electron from the sp 2hybrid on C, the other from the hydrogen 1s orbital••S bond = side-by-side overlap of theunhybridized p-orbitalsElectron from the unhybridizedp-orbital on the C atomSigma (V) Bonding in EthylenePi (S) Bonding in EthyleneDOUBLE BONDS : Formaldehyde, CH 2O Lewis Structure:Apply VSEPR Theory and Determine HybridizationHC = O H ••••sp2 120 osp2hybridization on C -sp 2hybridization on O -Sigma (V ) Bonding in Formaldehyde••••••••••••sp hybrids and unhybridized p-orbitalsSigma (V) Bonding in AcetyleneUnhybridized p-orbitalsPi (S) Bonding in AcetyleneExplain the Bonding Using Valence Bond Theory CO2Sigma Bonding in CO2Pi Bonding in CO2Molecular Orbitals-Preliminary Ideas Don’t forget that electrons behave like WAVES, and there are WAVE FUNCTIONS (\)that describe the electron position in space = ATOMIC ORBITALS (\2)e'Waves (electrons) can interfere with each other, either CONSTRUCTIVELY or DESTRUCTIVELYSigma bond formation involving p-orbitalsV*2pV2pPi bond formation involving p-orbitalsS2pS*2pS2pPrinciples of Molecular Orbital Theory1. The total number of molecular orbitals= total number of atomic orbitals contributed by the bonding atoms2. Bonding MO’s are lower in energy (more stable) than antibonding MO’s3. Electrons occupy molecular orbitals following the Pauli Exclusion Principle (spins pair up) and Hund’s Rule (remain unpaired as long as an empty orbital isavailable of the same energy)Energy Levels of Molecular Orbitals for Homonuclear Diatomics -H 2, O 2, etcMolecular orbitalsAtomic orbitals Atomicorbitals 2p 2p 2s 2s1s1s V 1s V *1sV 2sV *2sS 2p V 2pS *2p V *2pMolecular Orbital Electron Configurations e.g. O 2Bond OrderOrder = ½[# electrons bonding MO’s -# electrons antibonding MO’s]1. The greater the bond order, the more stable the molecule2. A high bond order means higher bond energies and shorter bond lengths.3. Fractional bond orders are possibleV 1s V *1s1s 1sH 2+V 1sV *1s 1s 1s H 2Bond order =Bond order =sp2hybridization of theterminal oxygens-Sigma Bonding in O3Explain using Valence Bond TheoryPi Bonding in O 3Combine 3 p-orbitals = 3 molecular orbitalsPi Bonding in O 3Antibonding S orbital Nonbonding S orbital••••Bonding S orbitalBenzene -C6H6orbitals into molecular orbitals.。
Unit 5 Basic Chemicals基本化学品我们将化学工业部门分成两类，生产量较大的部门和产量较低的部门。
在产量高的部门中，各种化学品的年产量达上万吨至几十万吨。
结果这样所用的工厂专门生产某一个单个产品。
这些工厂的连续方式进行操作，自动化程度高（计算机控制）归类于产量高的部门有硫酸，含磷化合物，含氮化合物，氯碱及其相关化合物，加上石油化学品和商品聚合物（如聚乙烯）（生产部门）。
除商品聚合物外，其它的均为重要的中间体，或基本化学品。
这些基本化学品是其他许多化学品的生产原料，其他许多基本化学品的需求量很大。
相反，产量低的部门主要从事精细化学品的生产。
单个化学品的年产量只有几十吨到几千吨。
然而，与高产量的产品相比，这些产品单位重量具有很高的价值。
通常，精细化斜坡的生产与间歇方式操作在工厂中，而且这些工厂常进行多种产品的生产。
低产量生产部门生产农用化学品，染料，药品和特种聚合物（如聚醚醚酮）。
基础化学品在化学工业中得不到支持，它们不那么引人注意（如药品），有时候利润不很高。
其利润来自于经济盛衰时难以预测的周期。
这些基本化学品不被公众注意到和直接使用，因此其重要性常得不到理解。
即使在化学工业中，其重要性也得不到足够的重视。
然而，如果没有这些基本化学品，其他工业就不复存在。
基本化学品处于原料（及那些从地下通过采矿、开采或用泵抽出来的物质）和最终产品的中间位置。
基本化学品的一个显著的特征就是它们的生产规模，每一种（基本化学品）的生产规模都相当大。
图2-1 表示在 1993年美国市场上的 25中化学品。
（为了使我们了解化学品的分类与生产量有关。
）通常，基本化学品生产于那些年产量上万吨的工厂。
年产量 10万吨的工厂每小时要生产 1.25 吨。
基本化学品的另一显著重要的特征是其价格。
大多数价格相当便宜。
基本化学品工业所作的工作（或任务）是找到经济的途径将原来转变为有用的中间体。
生产厂家要对它们的产品收取较高的价格几乎没有余地，因此，那些最低费用生产产品的厂家可能获得的利润最高。
Chapter 10: Chemical Bonding II – Molecular Geometry & Intermolecular Forces 10.1: Molecular GeometryMolecular Structure: - the three-dimensional arrangement of atoms in a molecule.Valence Shell Electron-Pair Repulsion (VSEPR) Model:- the best structure for a molecule is one that minimizes electrons lone pairs repulsion.- most often used to predict molecular structures involving non-metals.Example: For molecules with a total of 4 e− pairs, the bond angles decreases from 109.5° as more lone pairs added. (Repulsion of Lone Pair(s) with bond electrons pushed the angle down.) Effective Electron Pairs: - sometimes refer to as substituents.-the number of lone pairs on the central atom of a molecule and the number of connectionsbetween the central atom with the outer atom(s). Each set of Multiple Bond (like double and triple bonds) count as one connection or one effective electron pair.Summary of Geometrical Shape of Covalent MoleculesCopyrighted by Gabriel Tang B.Ed., B.Sc. Page 123.Page 124. Copyrighted by Gabriel Tang B.Ed., B.Sc.Example 1: From Example 2 of Sections 9.7 & 9.8, determine the geometrical shape of SO32−. What is theCopyrighted by Gabriel Tang B.Ed., B.Sc. Page 125.Page 126. Copyrighted by Gabriel Tang B.Ed., B.Sc.Molecular Geometry of More than One Central Atom : - describe the geometry for each central atom.Example 2: Determine the geometrical shape of ethanol around each central atom. What are the possible10.2: Dipole MomentsDipole Moments (Dipolar): - the direction of the charge distribution of a polar molecule.- the length of the vector indicates the strength of the relative bond polarity, whereas the arrow head indicates the direction of the higher electronegative atom (negatively shifted).Example 1: Draw the molecular structures. Determine the dipole moments (if any) and their overallpolarity of the following molecules.b.Positive Pole (Less Electronegative) Negative Pole (More Electronegative)Copyrighted by Gabriel Tang B.Ed., B.Sc. Page 127.12.2: Intermolecular ForcesIntermolecular Forces : - attraction forces between molecules in a compound- the strengths of the intermolecular forces explain the physical properties of compounds (solubility, boiling and freezing points).a. van der Waals Forces : - Johannes van der Waals studied real gases and molecular interactions.- there are two kinds of van der Waals forces.- they are Dispersion Forces and Dipole-Dipole Interactions .i. Dispersion Forces : - also known as London Dispersion Forces (named after Fritz London who firstproposed how this force works).- on average, the non-polar molecules do not have any permanent dipoles like polar moleculesPage 128. Copyrighted by Gabriel Tang B.Ed., B.Sc.- the “dispersion ” is the temporary dipole that forms within the molecules even in non-polarmolecules due the constant motions of electrons. In one instance, they can move to one side of the molecule making it temporary polar. In another instance, electrons will move and the direction of this temporary dipole will switch.- This constant “sloshing around” of electrons causes non-polar molecules to have these temporary dipoles . These temporary “induced ” dipoles are what cause the attractions between non-polar molecules.- even monoatomic element like Helium has London Forces. (Check out animation at http://www.super-tech.ro/teoretic.html )- in general, the higher the molar mass or the more electrons there are in a molecule , thestronger the London Dispersion Force (attraction between molecules – intermolecular force). This causes an increase in melting and boiling points of the chemical .- N ote: All molecules have electrons. Hence, ALL molecules have London Dispersion Force.Example 1: Explain the boiling points and the melting points of the noble gases.Noble Gases# of e − Molar Mass (g/mol) Melting Point Boiling PointHe 2 4.00 −272°C (1 K) −269°C (4 K) Ne 10 20.18 −249°C (24 K) −246° C (27 K) Ar 18 39.95 −189°C (84 K) −186° C (87 K) Kr 36 83.80 −157° C (116 K) −153°C (120 K) Xe 54 131.29 −112°C (161 K) −108° C (165 K) Rn 86 222.00 −71°C (202 K) −62° C (211 K)δ +δ −δ +δ−“Electrons sloshing ”causes Temporary dipolesAll atoms of noble gases are monoatomic non-polar . The only intermolecular force that governs the melting and boiling points is the London Dispersion Force . As the number of electrons in the noble gases increase , London dispersion force makes the attraction between the atoms greater. This in turn has an effect of increasing the boiling and melting point of the noble gas as one goes down the column.HHδ + δ −HHδ +δ −HHδ +δ −HHδ +δ −Hδ −δ + H Hδ −+Hδ −+H Hδ −+Dispersion Forces Dispersion Forces Dispersion Forcesii.Dipole-Dipole Interaction: - also known as simply Dipole Interaction or Dipole-Dipole Force- intermolecular forces resulted from polar molecules.Example 2: Order the boiling points from the least to greatest for the following compounds with similar molar mass. PH 3 (34.00 g/mol), CH3F (34.04 g/mol), and SiH4 (32.13 g/mol)OClCl 3.23.23.4forOCl2δ +δ +δ−2δ−Since PH3, CH3F and SiH4 have similar molar mass; any differences in boiling points cannot be due to London Dispersion forces. Since dipole-dipole interactions exist in polar molecules, wehave to examine the molecular geometry and structure of each compound.PHHH2.22.22.22.2OofPH3δ +HHH2.234.0SiHHH2.6HCopyrighted by Gabriel Tang B.Ed., B.Sc. Page 129.Page 130. Copyrighted by Gabriel Tang B.Ed., B.Sc.b. Hydrogen Bonds : - are intermolecular bonds that involve hydrogen atom with veryelectronegative atom that also consists of lone pairs .- these include O −H, N −H, and H −Cl and H −F bonds .- the resulting molecule is always polar. Therefore, all hydrogen bonding molecules also have dipole interactions .- hydrogen bond is the STRONGEST of the intermolecular bonds amongst molecular compounds .(Check out the Hydrogen Bond Animation at/biology/Biology1111/animations/hydrogenbonds.html )Example 3: Account for the differences in the boiling points of the compounds listed below.Molecule Molar Mass (g/mol) London Dispersion Forces DipoleInteractionsHydrogen BondsBoiling Point OF 254.0099U−145°C (128 K)Ne20.18 9UU−246°C (27 K) HF 20.01 9 9 9 19°C (292 K) H 2O 18.02 9 9 9 100°C (373 K) NH 3 17.04 9 9 9 −33°C (240 K) CH 416.05 9UU−161°C (112 K)H H N Hδ+ δ+ δ+3δ− Hydrogen BondingExample 4: Given the graph below on the boiling points of hydrogen compounds with different group series, explain the following using the concepts of chemical bonding.a.The hydrogen compounds in the Group (VIA) series have higher boiling points than hydrogencompounds in the other series.b.The first hydrogen compounds in Groups (VA), (VIA) and (VIIA), namely NH3, H2O and HF,have higher boiling points than most other hydrogen compounds in their respective series. Onthe other hand CH4 has a lowest boiling point in its own Group (IVA) series.a. All hydrogen compounds in the Group (VIA) series are very polar and most have hydrogenbonds.The V-shape molecules characterized in Group (VIA) create a greater dipole moment than other series (Group (VA) with its trigonal pyramid shape and Group (VIIA) with itslinear form). On the other hand, all hydrogen compounds in the Group (IVA) series are non-polar and only have London dispersion forces. Since hydrogen bonds are strongerintermolecular forces than London dispersion forces,the hydrogen compounds in the Group (IVA) series have the lowest boiling points than the counterparts in the other series.b. NH3,HF and H2O have stronger hydrogen bonds than most other hydrogen compounds intheir series. The difference between the electronegativities with H is the greatest in row 2(Electronegativities increase from left to right and from bottom to top of the Table). This huge difference in electronegativities in NH3, HF and H2O is what causes their boiling points tobuckle the trend. After NH3, HF and H2O the rest of the hydrogen compounds in the respective series follow the effect of London dispersion forces, the higher the molar mass, the stronger the dispersion forces, and the increase in boiling points is the result.CH4 in the Group (IVA) series do not buckle the trend because the entire series are non-polar.The only intermolecular force at work is the London dispersion force.Hence, CH4 has a lower boiling point than SiH4.Copyrighted by Gabriel Tang B.Ed., B.Sc. Page 131.Page 132. Copyrighted by Gabriel Tang B.Ed., B.Sc.c. Ion-Dipole Force : - when ionic compounds dissolve in water, the cation and anion componentsseparate from one another. These ions are then attracted by the polar water molecules.- ion-dipole force is the STRONGEST of all intermolecular forces.Example : Sodium Chloride (Salt)NaCl (s ) ⎯⎯→⎯OH 2 Na + (aq ) + Cl − (aq )1. Intermolecular Bonds involve in a compound explain its physical properties such as solubility(“like dissolves like ”), boiling and melting points (energy involved in physical phase change).2. van der Waals Forces consist of London Dispersion forces (apply to all molecules) and DipoleInteractions (apply to polar molecules).3. Hydrogen Bond is the STRONGEST of the intermolecular bonds amongst molecular compounds4. Ion-Dipole Force is the strongest of all intermolecular bonds.Summary of Intermolecular ForcesHonour Chemistry Unit 3: Quantum Theory, Periodicity and Chemical Bonding Copyrighted by Gabriel Tang B.Ed., B.Sc. Page 133. Properties of Covalent Crystalline Solids (Metalloid Network Covalent)1. Metalloids : - consists of elements near the “staircase ” of the Table (Examples are carbon in a form ofdiamond and silicon dioxide in a form of quartz crystal).2. Three-Dimensional Network Solids as they form giant molecules by directional covalent bonding (contains no discrete molecular units where an array or network of atoms are held together by conventional covelent bonds, which are directional with dipoles of neighboring atoms .3. Covalent Compounds are Hard and have High Melting Points. This is due to a more organized crystalline structure and covalent bonds are strong intramolecular bonds.4. Covalent Compounds are Relatively Poor Heat and Electric Conductors (or Good Heat or Electric Insulators). Covalent compounds do not have any charge particles like ions. Therefore, they cannot conduct heat and electricity well. An exception is silicon elements . (Silicon has smaller networks than diamonds, allowing some electrons to pass through. Hence, silicon is called a semiconductor .)Example : Alloptropes of CarbonProperties of Molecular Crystalline Solids1. Molecular Compounds tend to have much Lower Boiling and Melting Points than ionic compounds. This is because solid molecular compounds use weak intermolecular forces to form their lattice structures , which does not take much energy to break them. Their boiling points are lower than ionic compounds because there are no ion interactions in liquid state, only intermolecular forces .2. Molecular Compounds are Soft. Again, molecular compounds have a weak lattice structure made of intermolecular bondsthat makes them soft.Carbon as Graphite has weak layered with delocalized bonding network (only some carbon atoms are connected – for each layer is 2sp 2 hybridized which explains its hardness and brittleness). The layers are connected by weak van der Waal forces and hence, graphite can be slippery to the touch. For this reason, we can use it as a lubricant. Carbon as Diamond has strong tetrahedral network (2sp 3) where all four bonding sites of each carbon atoms are connected. Hence, diamond is the hardest material known, and it has an extremely highmelting point (3550°C). Carbon Network as C 60, Buckminsterfullerene , was discovered in 1985. Fullerenes are a family of carbon allotropes, molecules composed entirely of carbon, in the form of a hollow sphere, ellipsoid, tube, or plane.Unit 3: Quantum Theory, Periodicity and Chemical Bonding Honour ChemistryPage 134. Copyrighted by Gabriel Tang B.Ed., B.Sc.3. Some Molecular Compounds and Elements tend to be More Flammable than ionic compound. This is due to the some non-metals like sucrose and sulfur, which combine readily with oxygen in combustion reactions .4. Most Molecular Compounds are Insoluble in Water. Because water is very polar, and it has lots of hydrogen bonds, it can only dissolve molecular compounds that are polar as well “Like Dissolves Like ”. Since most molecular compounds are fairly non-polar , they do not dissolve in polar water well.5. Molecular Compounds do NOT Conduct Electricity in their Solid States due to a lack of delocalized electrons.6. Soluble Molecular Compounds do NOT Conduct Electricity in Water. This is simply due to the fact that molecular compounds do not dissociate into ions or electrolytes like soluble ioniccompounds do.Due to the hydrogen bonds in water, it forms a honeycomb shape and expands in volumewhen it crystallizes into ice. Even though no two snowflakes are alike, all of themhave a basic hexagonal shape as dictated by the bentshape of water molecule and its hydrogen bonds. Dry Ice, CO 2 (s ), is a covalent compoundthat has a crystalline structure. Even a halogen like I 2 (s )has a crystalline structure. Phosphorus, P 4 (s ) can form crystalline structure.。
