Chemical bonding molecule shapes

Many of the important topics in chemistry, such as chemical bonding, the shape of molecules, and so on, are based on where the electrons in an atom are located. Simply saying that the electrons are located outside the nucleus isn t good enough chemists need to have a much better idea of their location, so this section helps you figure out where you can find those pesky electrons. 

Clusters are intennediates bridging the properties of the atoms and the bulk. They can be viewed as novel molecules, but different from ordinary molecules, in that they can have various compositions and multiple shapes. Bare clusters are usually quite reactive and unstable against aggregation and have to be studied in vacuum or inert matrices. Interest in clusters comes from a wide range of fields. Clusters are used as models to investigate surface and bulk properties [2]. Since most catalysts are dispersed metal particles [3], isolated clusters provide ideal systems to understand catalytic mechanisms. The versatility of their shapes and compositions make clusters novel molecular systems to extend our concept of chemical bonding, stmcture and dynamics. Stable clusters or passivated clusters can be used as building blocks for new materials or new electronic devices [4] and this aspect has now led to a whole new direction of research into nanoparticles and quantum dots (see chapter C2.17). As the size of electronic devices approaches ever smaller dimensions [5], the new chemical and physical properties of clusters will be relevant to the future of the electronics industry. 

What Are the Key Ideas The central ideas of this chapter are, first, that electrostatic repulsions between electron pairs determine molecular shapes and, second, that chemical bonds can be discussed in terms of two quantum mechanical theories that describe the distribution of electrons in molecules. 

We have to refine our atomic and molecular model of matter to see how bulk properties can be interpreted in terms of the properties of individual molecules, such as their size, shape, and polarity. We begin by exploring intermolecular forces, the forces between molecules, as distinct from the forces responsible for the formation of chemical bonds between atoms. Then we consider how intermolecular forces determine the physical properties of liquids and the structures and physical properties of solids. 

The Lewis stmcture of a molecule shows how its valence electrons are distributed. These stmctures present simple, yet information-filled views of the bonding in chemical species, hi the remaining sections of this chapter, we build on Lewis stmctures to predict the shapes and some of the properties of molecules. In Chapter 10. we use Lewis stmctures as the starting point to develop orbital overlap models of chemical bonding. 

The most stable shape for any molecule maximizes electron-nuclear attractive interactions while minimizing nuclear-nuclear and electron-electron repulsions. The distribution of electron density in each chemical bond is the result of attractions between the electrons and the nuclei. The distribution of chemical bonds relative to one another, on the other hand, is dictated by electrical repulsion between electrons in different bonds. The spatial arrangement of bonds must minimize electron-electron repulsion. This is accomplished by keeping chemical bonds as far apart as possible. The principle of minimizing electron-electron repulsion is called valence shell electron pair repulsion, usually abbreviated VSEPR. 

The characteristic times on which catalytic events occur vary more or less in parallel with the different length scales discussed above. The activation and breaking of a chemical bond inside a molecule occurs in the picosecond regime, completion of an entire reaction cycle from complexation between catalyst and reactants through separation from the product may take anywhere between microseconds for the fastest enzymatic reactions to minutes for complicated reactions on surfaces. On the mesoscopic level, diffusion in and outside pores, and through shaped catalyst particles may take between seconds and minutes, and the residence times of molecules inside entire reactors may be from seconds to, effectively, infinity if the reactants end up in unwanted byproducts such as coke, which stay on the catalyst. 

The nature of intermolecular force is essentially no different from that which participates in the chemical bond or chemical reaction. The factor which determines the stable shape of a molecule, the influence on the reaction of an atom or group which does not take any direct part in the reaction, and various other sterically controlling factors might also be comprehended by a consideration based on the same theoretical foundation. 

A thermoplastic polymer can be repeatedly softened by heating, molded to a new shape, and then cooled to harden it. Thermoplastic polymers consist of chains that have no permanent chemical bonds to their neighbors. When we heat them, their molecules take on the properties of a viscous liquid that flows when we apply pressure. When we cool them, they solidify to take on a shape that remains constant until they are once again subjected to heat and pressure. We can dissolve thermoplastic polymers in solvents without destroying any chemical bonds. 

Another approach to explain tubule formation was taken by Lubensky and Prost as part of a general theoretical study of the relationship between orientational order and vesicle shape.173 These authors note that a membrane in an Lp/ phase has orientational order within the membrane which is lacking in the La phase. The clearest source of orientational order is the tilt of the molecules with respect to the local membrane normal The molecules select a particular tilt direction, and hence the local elastic properties of the membrane become anisotropic. A membrane might also have other types of orientational order. For example, if it is in a hexatic phase, it has order in the orientations of the intermolecular bonds (not chemical bonds but lines indicating the directions from one molecule to its nearest neighbors in the membrane). 

Hybridization occurs during the formation of a chemical bond. It is not possible to occur in an individual atom. Hybrid orbitals play an important role in determining the geometric shape of a molecule. 

In this chapter, you will review and extend your understanding of chemical bonding. You will discover how and why each molecule has a characteristic shape, and how molecular shape is linked to the properties of substances. You will also consider the importance of molecular shape to the development of materials with specific applications in the world around you. 

In this section, you have used Lewis structures to represent bonding in ionic and covalent compounds, and have applied the quantum mechanical theory of the atom to enhance your understanding of bonding. All chemical bonds—whether their predominant character is ionic, covalent, or between the two—result from the atomic structure and properties of the bonding atoms. In the next section, you will learn how the positions of atoms in a compound, and the arrangement of the bonding and lone pairs of electrons, produce molecules with characteristic shapes. These shapes, and the forces that arise from them, are intimately linked to the physical properties of substances, as you will see in the final section of the chapter. 

In relating properties of molecules to their structure, three-dimensional shape is frequently of great importance. Three-dimensional shape is a function of many variables the nature and number of atoms composing the molecule and the nature of the chemical bonding pattern— which atoms are connected to which—are obvious factors. However, the situation can be more subtle than that. Even in cases in which the atomic composition of two molecules is the same and in which the chemical bonding pattern is the same, key differences in three-dimensional shape can arise. 

Space filling van der Waals models (A3) are useful for illustrating the actual shape and size of molecules. These models represent atoms as truncated balls. Their effective extent is determined by what is known as the van der Waals radius. This is calculated from the energetically most favorable distance between atoms that are not chemically bonded to one another. 

Double helix—The shape of DNA molecules, discovered by James Watson and Francis Crick. The double helix is made up of two chains of DNA bound to each other by weak chemical bonds between pairs of complementary bases. This base pairing allows the DNA to be copied precisely when the strands separate as cells divide. 

Fig. 3. Oxygen transport by perfluorocarbons versus hemoglobin (Hb) (a) In the case of PFCs, O2 dissolution is characterized by loose, nondirectional van der Waals interactions. Oxygen solubility follows Henry s law, that is, is directly proportional to the gas s partial pressure (curve c). (b) In the case of Hb, a strong, localized chemical bond is established with the iron atom of a heme. Successive binding of four O2 molecules to the four hemes of Hb is cooperative, and saturation occurs when all four iron atoms are bound. Hence, the sigmoid shape of the O2 uptake curve, which levels off when the partial pressure of O2 on earth is attained (curve d) [20].

The concept of conformational isomerism is central to any consideration of molecular shape. Molecules that are flexible may exist in many different shapes or conformers. Conformational isomerism is the process whereby a single molecule undergoes transitions from one shape to another the physical properties of the molecule have not changed, merely the shape. Conformational isomerism is demonstrated by compounds in which the free rotation of atoms around chemical bonds is not significantly hindered. The energy barrier to the transition between different conformations is usually very low... 

Throughout the book, theoretical concepts and experimental evidence are integrated An introductory chapter summarizes the principles on which the Periodic Table is established and describes the periodicity of various atomic properties which are relevant to chemical bonding. Symmetry and group theory are introduced to serve as the basis of all molecular orbital treatments of molecules. This basis is then applied to a variety of covalent molecules with discussions of bond lengths and angles and hence molecular shapes. Extensive comparisons of valence bond theory and VSEPR theory with molecular orbital theory are included Metallic bonding is related to electrical conduction and semi-conduction. 

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