Chemical bonds form to lower the total energy of the system.

The change is energy is a result of movement of the valence shell electrons. Three types of bonds: Ionic energy lowest when electrons are completely transferred Covalent energy lowest when electrons are shared completely Metallic metal cations held together by a sea of electrons. These electrons come from the metal atoms

Ionic bonds
Ionic bonds Metallic atoms (s-block) form ions by losing electrons to form noble gas configuration. (Except for Lithium and Beryllium, which form a duplet, instead of an octet, since they go to Helium configuration) For p block elements: Those in period 3 or less lose electrons to form configuration of previous noble gas Those in period 4 or higher lose electrons to form configuration of previous noble gas surrounded by a complete subshell of d-shell electrons. This includes d-block elements. Non-metals rarely lose electrons due to their high ionization energy. However, they can gain electrons to form an octet, noble gas like configuration of the next noble gas.

Energetics of ionic bond formation The change in energy of forming an ionic bond is determined in three steps The cation must be ionized from a neutral atom (ionization energy positive) The electron from the cation is then added to the anion (electron affinity positive, but it signifies a release of energy, so in calculation the value is negated) Energy released when the two ions are brought close together (coulombic potential energy negative) Final change in energy is IE EA + P Usually, only metals have a low enough IE for the change to be energetically favorable, which is why few nonmetals form cations in ionic bonds.

Interactions between ions However, in an actually ionic lattice, all the anions and cations interact. Because of this, the actually net energy change is determined by the lattice energy. Higher lattice energy indicates a stronger interaction, so more tightly packed solid. The strong ionic interaction result in the properties of ionic compounds: Brittleness: Ionic solids are extremely brittle because when they are hit, like charges come close to each other and repel very strongly, which causes the solid to shatter. High melting: Ionic solids have high melting points because the strong attractions between opposite forces keep the ions close together. The potential energy for an ion in a line of charged particles is: with d = rcation + ranion This gives us an idea of lattice energy. In order to account for the repulsive effects in an entire system, the Born-Meyer equation is used: ( )with d* commonly taken as 34.5 pm

Minimum potential energy is reached when the magnitude of the charges are large and the distance is small, but still larger than d*.

Covalent bonds
Octet rule: In covalent bond formation, atoms go as far as possible toward completing their octets by sharing electron pairs. Generally, the valence of an electron is the number of bonds it can form. Fluorine atoms have lone pairs. In a F2 bond, there are 3 lone pairs on each fluorine atom, which create so much repulsion that it's nearly enough to overcome the attractions of bonding atoms. This repulsion is why fluorine gas is so reactive.

Lewis Structures for Polyatomic Species Bond order for a bond is the total number of number of bonds that link the pair of atoms. A terminal atom is one that's only linked to one atom. A central atom is one that's linked to at least two other atoms.

General rules of thumb: Choose as the central atom the atom with lowest ionization energy. (Atoms with lower ionization energy are more likely to share electrons) Arrange the atoms symmetrically around the central atom. A common exception is N2O, which is NNO, not NON. Typically, the central atom is written first. Acids are an exception because for acids the H is written first. Generally the same for polyatomic ions, except electrons are added and subtracted to account for the charge of the ion.

Resonance Resonance occurs when a particular molecule can have multiple valid structures. Instead of being in one of those structures, the molecule takes a blend of those structures, called a resonance hybrid. The electron that is shown in different positions of a resonance hybrid is said to be delocalized. It is shared among the several bonds. Resonance stabilizes the entire molecule by lowing the total energy. For a molecule with multiple Lewis structures of different energies, the different Lewis structures contribute differently to the resonance hybrid. Those with lower energies will contribute more than those with higher energies.

Formal Charge It is possible to determine which Lewis structure contributes more by looking at the formal charges of the atoms. Formal charge is defined as the number of electrons an atom would have if it were perfectly covalently bonded. F = V (L + B) The closer the formal charges are to 0, the more stable a structure is (lower energy arrangement) and the greater its contribution to the resonance hybrid. Formal charges and oxidation number both indicate the number of electrons around an atom, but they are often different. Formal charges exaggerate the covalent nature of bonds, treating them as perfectly covalent. Oxidation numbers exaggerate the ionic nature of bonds, treating them as ions.

Exception to the Octet Rule

Some atoms have an odd number of electrons and do not obey the octet rule.

Some atoms, such as Phosphorus, Chlorine, Sulfur, and other non-metals that are in period 3 or higher can have more than 8 valence.

Radicals and Biradicals Radicals are species with an atom that has a odd number of valence. They are highly reactive Examples are CH3 and NO. Biradicals are species that have two unpair electrons. These are usually on different atoms, but can also be on one atom. The oxygen atom is a special example.

Expanded Valence Shells Central atoms with an empty d-orbital (those of period 3 or higher) can use those orbitals to form expanded valence shells. These atoms should be relatively large (to fit more atoms around it) The electrons in the expanded valence shell can be lone pairs or used for bonding. Such compounds are called hypervalent compounds. Very commonly, the central atoms of these compounds show variable covalence. This means they can form different number of covalent bonds. Eg. PCl3 and PCl5.

The Unusual Structures of Some Group 13/III Compounds (Boron, etc) The central atom in these compounds form a incomplete octet. (Boron atom only has 3 valence, so it can only form 3 bonds) For BF3, Boron has 6 valence electrons. BF3 has two resonances structures, one with single bonds between B and F, and on with a double bond between one of the B and F (fluorine contributes both) The first structure contributes most to the resonance hybrid since fluorine is so unlikely to give electrons. Another way Boron can get an octet is by coordinate covalent bonding, in which an atom brings in two electrons to form a bond with boron. (like BF4-)

Ionic versus Covalent Bonds

Ionic and covalent bonds are the extremes of chemical bonding. Most bonding lies somewhere in between.

Correcting the Covalent Model: Electronegativity

No bonds are purely ionic or purely covalent. Instead, they can be viewed as a resonance hybrid between the ionic and covalent possibilities: ClCl Cl+Cl- Cl-Cl+

For diatomic molecules, the covalent Lewis structure dominates while the ionic ones contribute very little, so the resonance hybrid is basically covalent. Also, because the two ionic structures contribute equally, the bond is nonpolar. For HCl, this is not true, since the chlorine atom has a stronger attraction for electrons. Cl will have a partial negative charge, and the bond will be a polar covalent bond. The two atoms will form an electric dipole. The electric dipole is a vector that points from the positive to the negative partial charge. The magnitude is measured in debyes. A debye is defined so that a positive and negative charge separated by 100. pm has a dipole moment of 4.8 D. To determine whether a bond is polar, we use electronegativity. Electronegativity is the average of the electron affinity and the ionization enengy. ( )

If the difference in electronegativity for a bond is greater than 2, it has a mostly ionic character. If the difference is less than 1.5, it has a mostly covalent character.

Correcting the Ionic Model: Polarizability All ionic bonds have some covalent character. The covalent character arises due to an atom/ion's polarizability. In an ionic bond, a cation will exert an attractive force on an anion's electron cloud, causing the electron cloud to distort towards the cation. The readiness of an anion to have its electron cloud distorted is called it's polarizability. Larger anions will have larger polarizabilities. Cations, in turn, have a polarizing power. This is the cation's ability to distort an anion's electron cloud. The smaller, more charged a cation is, the larger the polarizing power, in general.

The Strengths and Lengths of Covalent Bonds

The characteristics of a covalent bond is determined only by the two atoms of the bond. That is, regardless of the molecule a particular covalent bond is found, properties like bond length and strength will be about the same, provided that the bond is between two of the same atoms and have the same bond order.

Bond Strengths The strength of a bond is the dissociation energy. (See graph at right). The deeper the potential energy well, the stronger the bond is and the greater the dissociation energy. Covalent bond breaking is hemolytic, which means that each atom keeps one of the electrons.

Variation in Bond Strength In general, triple bonds are stronger than double bonds, which are stronger than single bonds. However, double bonds are not twice as strong as single bonds, and triple bonds are nowhere near thrice as strong as single bonds. Resonance can affect bond length and strength (eg. benzene) Lone pairs on neighbor atoms can weaken bonds because of the electrostatic repulsion of the electrons. Trends in bond strength are correlated with trends in atomic radii. Covalent bonds between atoms with smaller radii will be generally stronger since the nucleus can get closer to the electrons.

Bond lengths A bond length is the internucleii distance of a covalent bond at the potential energy minimum. The bond length is similarly affected by things that affect bond strength, such as the atomic radii, bond order, resonance, etc. In a covalent bond, each atom makes an equal contribution to the total bond length, called the covalent radius. The sum of the covalent radii is the bond length. The trend for covalent radii is the same as the trend for atomic radii.