Basic Concepts of Chemical Bonding Ionic, Covalent, Metallic Bonding Polarity & Electronegativity Lewis Structures Three Types of Chemical Bonds Ionic Bond: electrostatic forces that exist between ions of opposite charge. Metals + nonmetals. Ex: NaCl Covalent Bond: sharing of electrons between two atoms. Nonmetals. Ex: CO2 Metallic Bond: metal ions in a “sea of valence electrons.” Ex: Cu Lewis Symbols Only valence electrons are involved in chemical bonding. We use Lewis electron-dot symbols (Lewis symbols)to show valence electrons. Lewis symbol = element symbol + dots representing electrons. Use all four sides around element symbol and no more than two electrons per side. Usually balance one dot on one side with dot on opposite side. Examples of Lewis Symbols The Octet Rule Octet Rule: Atoms tend to lose, gain, or share electrons until they are surrounded by eight valence electrons. Full s & p orbitals = stability Sodium Chloride Formation Na(s) + 1/2 Cl2(g) NaCl(s) There is a transfer of an electron from the Na atom to the Cl atom. Ionic Bonding: Formation of NaCl NaCl is composed of Na+ and Cl- ions that are arranged in a regular threedimensional array. Stability of Ionic Compouds Very neg. heats of formation of ionic compounds. Ions are drawn together, releasing energy as a solid lattice forms. Ionic compounds are very stable. Ionic compounds are hard & brittle with high melting points. Lattice Energy Lattice energy: the energy required to completely separate a mole of solid ionic compound into its gaseous ions. Note: This is an endothermic process. ***The higher the lattice energy, the stronger the ionic bond.*** NaCl(s) Na+(g) + Cl-(g) ∆H = +788 kJ/mol Lattice Energy, Cont. Lattice energy depends on: Eelectric = (Q1Q2)/d Where: Q1 and Q2 = ion charges; = constant; d = distance between center of ions Lattice energy increases as the charges on the ions increase and as their radii decrease. 1+; 1- 2+; 1- 2+; 2- 3+; 3- Magnitude of lattice energy depends mainly on ionic charge because radii do not vary greatly. Practice With Lattice Energy Arrange the following in order of increasing lattice energy: NaF, CsI, CaO CsI < NaF < CaO Which substance has the greatest lattice energy? Why? AgCl, CuO, CrN CrN, because of larger 3+/3- charges Born-Haber Cycle Lattice energies cannot be measured experimentally. Use Hess’s Law to construct a Born-Haber cycle. A Born-Haber cycle shows the formation of ionic solids from elements. The principles of Hess’s Law can be applied in the Born-Haber cycle to determine the lattice energy of NaCl. Covalent Bonding Covalent Bond: chemical bond formed by sharing of electrons to form noble gas configurations. Ex: H2 molecule Multiple Bonds Single bond: sharing of 2 electrons. Shown as H-H or H:H Double bond : sharing of 4 electrons. Shown as O::C::O or O=C=O Triple bond: sharing of 6 electrons. Shown as :N:::N: or :NN: Examples of Multiple Bonds Bond Lengths Average bond distance varies with number of bonds. Generally, as number of shared electron pairs increases, bond length decreases. N-N (1.47Å) N=N (1.24Å) NN (1.10Å) Note: A triple bond is NOT 3x stronger than a single bond. The first bond in a triple bond is stronger than a “normal” single bond. The “second” and “third” bonds in a triple bond are weaker than the “first” bond. Bond Polarity Bond polarity describes the sharing of electrons between atoms. Nonpolar covalent bond: electrons shared equally between atoms. Polar covalent bond: one of the atoms in a compound exerts a greater attraction for the bonding electrons than the other. If the difference is big enough, we get an ionic bond. Electronegativity Use electronegativity to estimate whether a bond will be nonpolar covalent, polar covalent, or ionic. Electronegativity: the ability of atoms in a molecule to attract electrons to itself. The greater the electronegativity, the greater its ability to attract electrons. High ionization energy & very negative electron affinity = high electronegativity. Electronegativity Scale Linus Pauling makes electronegativity scale. Values are unitless Scale: 0.7 (cesium) - 4.0 (fluorine) Metals are less electronegative; nonmetals are more electronegative. Electronegativity & Bond Polarity The greater the difference in electronegativity between two bonded atoms, the more polar the bond. Difference < 0.5 = nonpolar covalent Ex: F2 4.0 - 4.0 = 0 0.5 ≤ difference < 2.0 = polar covalent Ex: HF 4.0 - 2.1 = 1.9 Difference ≥ 2.00 = ionic bond Ex: LiF 4.0 - 1.0 = 3.0 Use + and - to show partial positive and negative charges on atoms. Nonpolar covalent bond + - Polar covalent bond + - Ionic bond Polarity Practice Tell which bond is more polar and indicate in each case which atom has the partial negative charge. B-Cl or C-Cl? B-Cl, with - on Cl P-F or P-Cl? P-F, with - on F Polar Molecules Entire molecules can be polar, not just bonds within the molecules. Ex: HF Polarity is important--it helps to determine many properties of a cmpd! Drawing Lewis Structures 1. Sum valence e-’s of all atoms. Add e-’s for anions. 2. Sum number of e-’s each atom needs for an octet. All atoms need 8 e-’s except for H that needs only 2 e-’s. 3. (e-’s needed-valence e-’s)/2 = minimum number of bonds in the molecule Note: bonds may be single or multiple. One double bond=two single bonds Lewis Structures, Cont. 4. Draw symbols, attaching bonds as needed. Note: H only takes a single bond. C takes 4 bonds, is often central. 5. Complete the octets of atoms bonded to central atom. Use dots for lone pairs of e-’s. 6. Place any leftover e-’s on central atom even if it has more than an octet. Draw Structure for PBr3 Which is your central atom? Determine number of valence e-’s. P has 5, Br has (3 x 7). 5 + 21 = 26 e-’s Determine number of e-’s needed for octets. P has (1 x 8), Br has (3 x 8). 4 x 8 = 32 e-’s (Needs - valence)/2 = minimum bonds needed (32-26)/2 = 3 bonds needed at minimum PBr3 Lewis Structure Note: bonds + lone pairs = number of valence e-’s. Exceptions to Octet Rule Odd number of electrons: Less than an octet: Exceptions, Cont. More than an octet: Formal Charge Sometimes multiple Lewis structures can be drawn for a molecule. Formal charge can help determine correct one. Formal charge: charge that an atom would have in a molecule if all atoms had the same electronegativity (bonding e-’s are shared equally). Calculating Formal Charge Electrons are assigned as follows: 1) All unshared (nonbonding) e-’s are assigned to the atom on which they are found. 2) Half of the bonding e-’s are assigned to each atom in the bond. Formal charge = # of valence e-’s - # of e-’s assigned in Lewis structure. Oxidation Number Formal Charge Polarity It is important to note that oxidation number overstates the importance of electronegativity and formal charge ignores the role of electronegativity completely. Formal Charge as the “Tie Breaker” As a general rule, when several Lewis structures are possible, the most stable (and favored) one will be the one in which… 1) the atoms bear formal charges closest to zero. 2) any negative charges reside on the more electronegative atoms. Formal Charge & NO2 Resonance Structures Sometimes molecules and ions cannot be described by a single Lewis structure. Resonance structure: atoms keep same arrangement but placement of e-’s changes. Look for changes in placement of double bonds. Resonance All of the resonance structures are taken together as a description of a molecule or ion. A molecule or ion does not switch among resonance structures, it is more of a blending. Not all resonance structures are equivalent. Formal charges can help to predict favored structures. Resonance Structures Resonance In Benzene Benzene (C6H6) is an important example of an aromatic organic molecule. It is the “poster child” for resonance. Bond Enthalpy Stability of a molecule = strengths of its covalent bonds. Bond Enthalpy: ∆H for the breaking of a particular bond in a mole of gaseous substance. Always endothermic. Greater bond enthalpy = stronger bond Stronger bonds = less reactivity