Basic Concepts of Chemical Bonding Outline PDF

Basic Concepts of Chemical Bonding outline: Chemical Bonds, Lewis Symbols, and the Octet Rule The properties of many materials can be understood in terms of their microscopic properties. Microscopic properties of molecules include: the connectivity between atoms and...

Basic Concepts of Chemical Bonding outline: Chemical Bonds, Lewis Symbols, and the Octet Rule The properties of many materials can be understood in terms of their microscopic properties. Microscopic properties of molecules include: the connectivity between atoms and the 3-D shape of the molecule. When atoms or ions are strongly attracted to one another, we say that there is a chemical bond between them. In chemical bonds, electrons are shared or transferred between atoms. Types of chemical bonds include: ionic bonds (electrostatic forces that hold ions together, e.g., NaCl); covalent bonds (result from sharing electrons between atoms, e.g., Cl2); metallic bonds (refers to metal nuclei floating in a sea of electrons, e.g., Na). Lewis Symbols  The electrons involved in bonding are called valence electrons. Valence electrons are found in the incomplete, outermost shell of an atom. As a pictorial understanding of where the electrons are in an atom, we represent the electrons as dots around the symbol for the element. The number of valence electrons available for bonding are indicated by unpaired dots. These symbols are called Lewis symbols, or Lewis electron-dot symbols. We generally place the electrons on four sides of a square around the element’s symbol. The Octet Rule Atoms tend to gain, lose, or share electrons until they are surrounded by eight valence electrons; this is known as the octet rule. An octet consists of full s and p subshells. We know that s2p6 is a noble gas configuration. We assume that an atom is stable when surrounded by eight electrons (four electron pairs). Electron Configuration of Ions of the Representative Elements These are derived from the electron configuration of elements with the required number of electrons added or removed from the most accessible orbital. Electron configuration of ions can predict stable ion formation: Na: [Ne]3s1 Na+: [Ne]  Cl: [Ne]3s23p5 Cl–: [Ne]3s23p6 = [Ar] Transition-Metal Ions Lattice energies compensate for the loss of up to three electrons. We often encounter cations with charges of 1+, 2+ or 3+ in ionic compounds. However, transition metals cannot attain a noble gas conformation (>3 electrons beyond a noble gas core). Transition metals tend to lose the valence shell electrons first and then as many d electrons as are required to reach the desired charge on the ion. Thus, electrons are removed from 4s before the 3d, etc.. Polyatomic Ions Polyatomic ions are formed when there is an overall charge on a compound containing covalent bonds. Examples are NH4+ and CO22–. In polyatomic ions, two or more atoms are bound together by predominantly covalent bonds. The stable grouping carries a charge. Covalent Bonding  The majority of chemical substances do not have characteristics of ionic compounds. We need a different model for bonding between atoms. A chemical bond formed by sharing a pair of electrons is called a covalent bond. Both atoms acquire noble-gas electronic configurations. This is the “glue” that binds atoms together. Lewis Structures Formation of covalent bonds can be represented using Lewis symbols. The structures are called Lewis structures. We usually show each electron pair shared between atoms as a line and show unshared electron pairs as dots. Each pair of shared electrons constitutes one chemical bond. Example: H + H H has electrons on a line connecting the two H nuclei (H−H). Multiple Bonds  It is possible for more than one pair of electrons to be shared between two atoms (e.g., multiple bonding). One shared pair of electrons is a single bond (e.g., H2). Two shared pairs of electrons form a double bond (e.g., O2). Three shared pairs of electrons form a triple bond (e.g., N2). Bond length is the distance between the nuclei of the atoms in a bond. Generally, bond distances decrease as we move from single through double to triple bonds. Bond Polarity and Electronegativity The electron pairs shared between two different atoms are usually unequally shared. Bond polarity describes the sharing of the electrons in a covalent bond. There are two extremes: In a nonpolar covalent bond the electrons are shared equally. An example is bonding between identical atoms (example: Cl2). In a polar covalent bond, one of the atoms exerts a greater attraction for bonding electrons than the other (example: HCl) If the difference is large enough, an ionic bond forms (example: NaCl). Electronegativity The ability of an atom in a molecule to attract electrons to itself is its electronegativity. The electronegativity of an element is related to its ionization energy and electron affinity. The Pauling electronegativity scale ranges from 0.7 (Cs) to 4.0 (F).  Electronegativity increases across a period and decreases down a group. Electronegativity and Bond Polarity Electronegativity differences close to zero result in nonpolar covalent bonds. The electrons are equally or almost equally shared. The greater the difference in electronegativity is between two atoms, the more polar the bond (polar covalent bonds) is. There is no sharp distinction between bonding types. Dipole Moments Molecules like HF have centers of positive and negative charge that do not coincide. These are polar molecules. We indicate the polarity of molecules in two ways: The positive end (or pole) in a polar bond may be represented with a “δ+” and the negative pole with a “δ−”. We can also place an arrow over the line representing the bond. The arrow points toward the more electronegative element and shows the shift in electron density toward that atom. We can quantify the polarity of the molecule. When charges are separated by a distance, a dipole is produced. The dipole moment is the quantitative measure of the magnitude of the dipole (μ)μ=Qr  The magnitude of the dipole moment is given in debyes (D). Drawing Lewis Structure Here are some simple guidelines for drawing Lewis structures: Add up all of the valence electrons on all atoms. For an anion, add electrons equal to the negative charge. For a cation, subtract electrons equal to the positive charge. Identify the central atom. When a central atom has other atoms bound to it, the central atom is usually written first. Example: In CO32– the central atom is carbon. Place the central atom in the center of the molecule and add all other atoms around it. Place one bond (two electrons) between each pair of atoms. Complete the octets for all atoms connected to the central atom (exception: hydrogen can only have two electrons). Complete the octet for the central atom; use multiple bonds if necessary. Formal Charge  Sometimes it is possible to draw more than one Lewis structure with the octet rule obeyed for all the atoms. To determine which structure is most reasonable, we use formal charge. The formal charge of an atom is the charge that an atom (in a molecule) would have if all of the atoms had the same electronegativity. To calculate formal charge, electrons are assigned as follows: All nonbonding (unshared) electrons are assigned to the atom on which they are found. Half of the bonding electrons are assigned to each atom in a bond. Formal charge is the number of valence electrons in the isolated atom, minus the number of electrons assigned to the atom in the Lewis structure. example: consider CN– (cyanide ion): For carbon: There are four valence electrons (from the periodic table). In the Lewis structure there are two nonbonding electrons and three electrons from the triple bond. There are five electrons from the Lewis structure. Formal charge: 4 − 5 = −1. For nitrogen: There are five valence electrons. In the Lewis structure there are two nonbonding electrons and three from the triple bond. There are five electrons from the Lewis structure. Formalcharge=5−5=0.  Use formal charge calculations to distinguish between alternative Lewis structures: the most stable structure has the smallest formal charge on each atom and the most negative formal charge on the most electronegative atoms. It is important to keep in mind that formal charges do NOT represent REAL charges on atoms! Resonance Structures Some molecules are not adequately described by a single Lewis structure. Typically, structures with multiple bonds can have similar structures with the multiple bonds between different pairs of atoms. Example: Experimentally, ozone has two identical bonds whereas the Lewis structure requires one single (longer) and one double bond (shorter). Resonance structures are attempts to represent a real structure that is a mix between several extreme possibilities. Resonance structures are Lewis structures that differ only with respect to placement of the electrons. The “true” arrangement is a blend or hybrid of the resonance structures. Example: In ozone the extreme possibilities have one double and one single bond. The resonance structure has two identical bonds of intermediate character. We use a double headed arrow () to indicate resonance. Common examples are O3, NO3–, SO3, NO2, and benzene. Resonance in Benzene  Benzene belongs to an important category of organic molecules called aromatic compounds. Benzene (C6H6) is a cyclic structure. It consists of six carbon atoms in a hexagon. Each carbon atom is attached to two other carbon atoms and one hydrogen atom. There are alternating double and single bonds between the carbon atoms. Experimentally, the C−C bonds in benzene are all the same length. Experimentally, benzene is planar. To emphasize the resonance between the two Lewis structures (hexagons with alternating single and double bonds), we often represent benzene as a hexagon with a circle in it. 8.7 Exceptions to the Octet Rule There are three classes of exceptions to the octet rule: molecules with an odd number of electrons, molecules in which one atom has less than an octet, and molecules in which one atom has more than an octet. Odd Number of Electrons Most molecules have an even number of electrons and complete pairing of electrons occurs although some molecules have an odd number of electrons. Examples are ClO2, NO, and NO2. Less than an Octet of Valence Electrons Molecules with less than an octet are also relatively rare. They are most often encountered in compounds containing boron or beryllium. A typical example is BF3. More than an Octet of Valence Electrons This is the largest class of exceptions. Atoms from the third period and beyond can accommodate more than an octet. Examples are PCl5, SF4, AsF6–, and ICl4–. Elements from the third period and beyond have unfilled d orbitals that can be used to accommodate the additional electrons. Size also plays a role. The larger the central atom, the larger the number of atoms that can surround it. The size of the surrounding atoms is also important. Expanded octets occur often when the atoms bound to the central atom are the smallest and most electronegative (e.g., F, Cl, O).