Ionic and Covalent Bonds The Octet Rule

We have seen that attraction between negatively and positively charged particles is a basis for bonding. How does this concept work in real molecules Two extreme types of bonding explain the interactions between atoms in organic molecules  

We shall see that many atoms bind to carbon in a way that is intermediate between these extremes Some ionic bonds have covalent character and some covalent bonds are partly ionic (polarized). 

What are the factors that account for the two types of bonds To answer this question, let us return to the atoms and their compositions. We start by looking at the periodic table and at how the electronic makeup of the elements changes as the atomic number increases. 

The partial periodic table depicted in Table 1-1 includes those elements most widely found in organic molecules carbon (C), hydrogen (H), oxygen (O), nitrogen (N), sulfur (S), chlorine (Cl), bromine (Br), and iodine (I). Certain reagents, indispensable for synthesis and commonly used, contain elements such as lithium (Li), magnesium (Mg), boron (B), and phosphorus (P). (If you are not familiar with these elements, refer to Table 1-1 or the periodic table on the inside cover.) 

1 Note The superscripts indicate the number of electrons in each principal shell of the atom.  

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Ionic and Covalent Bonds The Octet Rule CHAPTER 1... 

In Chap. 3 the elementary structure of the atom was introduced. The facts that protons, neutrons, and electrons are present in the atom and that electrons are arranged in shells allowed us to explain isotopes (Chap. 3), the octet rule for main group elements (Chap. 5), ionic and covalent bonding (Chap. 5), and much more. However, we still have not been able to deduce why the transition metal groups and inner transition metal groups arise, why many of the transition metals have ions of different charges, how the shapes of molecules are determined, and much more. In this chapter we introduce a more detailed description of the electronic structure of the atom which begins to answer some of these more difficult questions. 

You have used Lewis structures to demonstrate how ionic and covalent bonds form between atoms. When given two elements, you determined how many atoms of each element bond together to form a compound, according to the octet rule. For example, you used the periodic table and your understanding of the octet rule to determine how calcium and bromine bond to form an ionic compound. Using a Lewis structure, you determined that calcium and bromine form a compound that contains two bromine atoms for every calcium atom, as shown in Figure 3.39. 

Although the title has an almost magical sound to it, the nature of the chemical bond was truly the domain Pauling began to explore. He formulated the concept of hybridization to explain how localized atomic orbitals best overlap to form two-electron bonds. The Kossel-Lewis-Langmuir picture explained ionic and covalent bonding in terms of the octet rule. An interesting question was... 

When ionic bonds form, the atoms of one element lose electrons and the atoms of the second element gain them until both types of atoms have reached a noble-gas configuration. The same idea can be extended to covalent bonds. However, when a covalent bond forms, atoms share electrons until they reach a noble-gas configuration. Lewis called this principle the octet rule ... 

There are also molecules that are exceptions to the octet rule because one of the atoms has fewer, rather than more than, eight electrons in its valence shell in the Lewis structure (Figure 1.19). These molecules are formed by the elements on the left-hand side of the periodic table that have only one, two, or three electrons in their valence shells and cannot therefore attain an octet by using each of their electrons to form a covalent bond. The molecules LiF, BeCl2, BF3, and AIC13 would be examples. However, as we have seen and as we will discuss in detail in Chapters 8 and 9, these molecules are predominately ionic. In terms of a fully ionic model, each atom has a completed shell, and the anions obey the octet rule. Only if they are regarded as covalent can they be considered to be exceptions to the octet rule. Covalent descriptions of the bonding in BF3 and related molecules have therefore... 

Lewis and many other chemists had recognized the shortcomings of the ionic bond. When diatomic molecules, such as or Cl, were considered, there was no reason why one atom should lose an electron and an identical atom should gain an electron. There had to be another explanation for how diatomic molecules formed. We have seen how the octet rule applies to the formation of ionic compounds by the transfer of electrons. This rule also helps explain the formation of covalent bonds when molecules (covalent compounds) form. Covalent bonds result when atoms share electrons. Using fluorine, F, as a representative halogen, we can see how the octet rule applies to the formation of the molecule. Each fluorine atom has seven valence electrons and needs one more electron to achieve the stable octet valence configuration. If two fluorines share a pair of electrons, then the stable octet configuration is achieved ... 

The primary difference between covalent and ionic bonding is that with covalent bonding, we must invoke quantum mechanics. In molecular orbital (MO) theory, molecules are most stable when the bonding MOs or, at most, bonding plus nonbonding MOs, are each filled with two electrons (of opposite spin) and all the antibonding MOs are empty. This forms the quantum mechanical basis of the octet rule for compounds of the p-block elements and the 18-electron rule for d-block elements. Similarly, in the Heider-London (valence bond) treatment... 

Initially, hypervalent molecules like PCI5 and SFe were described in terms of sp d" hybrid orbitals, in an extension of the sp" orbital description used to characterize molecules that obey the octet rule. However, ab initio calculations have shown that d orbitals play only a minor role in the bonding of hypervalent molecules. An alternative approach proposed by Pauling invoked combinations of resonance stmctures involving four covalent bonds and one or more additional ionic bonds, as shown in Scheme 1 for PF5. 

Barker [18] additionally comments, that teachers put far too much emphasis on the Octet rule in order to determine formulas and bindings of chemical species. As a result, the students rely on this rule to deduce formulae. During the lesson unit on ionic bonding, teachers often use this rule, in order to show that some atoms fill their shells through electron transfer instead of sharing electrons in covalent bonding. She further points out, that students are not capable of understanding how ion lattices are formed solely based on this explanation [18]. 

The octet rule is so simple and useful in introducing the basic concepts of bonding that you might assume it is always obeyed. In Section 8.2, however, we noted its limitation in dealing with ionic compounds of the transition metals. The rule also fails in many situations involving covalent bonding. These exceptions to the octet rule are of three main types ... 

CHEMICAL BONDS, LEWIS SYMBOLS, AND THE OCTET RULE (INTRODUCTION AND SECTION 8.1) In this chapter we have focused on the interactions that lead to the formation of chemical bonds. We classify these bonds into three broad groups ionic bonds, which result from the electrostatic forces that exist between ions of opposite charge covalent bonds, which result from the sharing of electrons by two atoms and metallic bonds, which result from a delocalized sharing of electrons in metals. The formation of bonds involves interactions of the outermost electrons of atoms, their valence electrons. The valence electrons of an atom can be represented by electron-dot symbols, called Lewis symbols. The tendencies of atoms to gain, lose, or share their valence electrons often follow the octet rule, which says that the atoms in molecules or ions (usually) have eight valence electrons. 

Monatomic Ions with Noble-Gas Electron Configurations Ionic Bonds Covalent Bonds Polar and Nonpolar Covalent Bonds Multiple Bonds Atoms That Are Bonded to Two or More Other Atoms Exceptions to the Octet Rule Metallic Bonds... 

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