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Chapter 14: Phenomena Chapter 14: Phenomena Phenomena: Scientists knew that in order to form a bond, orbitals on two atoms must overlap. However, px, py, and pz orbitals are located 90˚ from each other and compounds like CH4 (which would form bonds using their p orbitals) do not have bond angles of 90˚. Therefore, scientists had to explain this discrepancy or go back and reevaluate quantum mechanics. Scientists realized that because electrons have wave properties they should mix with each other forming new differently shaped orbitals. To determine what these new orbitals looked like scientists used computers to combine the orbitals on different atoms generating as many combinations as possible. The three picture set on the left shows three different combinations of two unmixed orbitals (green). The picture set in the middle shows all possible combinations of mixing the two orbitals. The mixed orbitals are shown in purple. The black dots in the pictures represent the nuclei of the two atoms. What patterns do you notice when the orbitals mix? The picture set on the right shows all of the orbital mixing for NO and HF. What do you notice about the orbital diagrams for these compounds. nitrogen monoxide NO Initial Orbitals Mixed Orbitals nitrogen oxygen N O p p s s p s Chapter 14: Covalent Bonding: Orbitals Chapter 14 Covalent Big Idea: Bonding can be Bonding: described using two theories which take Orbitals into account quantum mechanics. In the Local Electron Model, o Local Electron Model bonds are formed (Valence-Band Theory) from the overlap of o Molecular Orbital Theory atomic orbitals. In Molecular Orbital Theory, electrons are redistributed throughout the molecule and placed into new orbitals called molecular orbitals. 2 Local Electron Model (Valence-Bond Theory) VSPPR (Lewis Model): Did not take into account quantum mechanic’s effects. Assumes bonds located directly between atoms, therefore, electrons did not have wavelike properties Local Electron Model (Valence-Bond Theory): Uses a quantum mechanical description of the distribution of electrons in bonds that provides a way of calculating the numerical values of bond angles and bond lengths 3 Chapter 14: Covalent Bonding: Orbitals Local Electron Model (Valence-Bond Theory) σ-bonds Overlap: The merging of orbitals belonging to different atoms of a molecule. Note: The greater the extent of orbital overlap, the stronger the bond. σ-bond: Two electrons in a cylindrically symmetrical cloud between two atoms. Note: σ-bonds contain no nodal planes along the internuclear axis. Nodal Plane: A plane on which electrons will not be found. 4 Chapter 14: Covalent Bonding: Orbitals Local Electron Model (Valence-Bond Theory) A σ–bond is formed in HF when electrons in 1푠- and 2pz- orbitals pair (where z is the direction along the internuclear axis). Notice that there is cylindrical symmetry and no nodal plane on the internuclear axis. 5 Chapter 14: Covalent Bonding: Orbitals Local Electron Model (Valence-Bond Theory) 흅-bond: A bond formed by the side-to- side overlap of two p- orbitals A σ-bond is formed by the pairing of electron spins in the two 2pz- orbitals 휋-bonds are formed when electrons in two other 2p-orbitals pair and overlap side by side. Note: 휋-bonds contain a single nodal plane along the internuclear axis 6 Chapter 14: Covalent Bonding: Orbitals Local Electron Model (Valence-Bond Theory) Student Question How many 휎 bond and 휋 bonds are there in CO2? Hint: Draw the Lewis structure. a) 1 휎 bond and 1 휋 bonds b) 0 휎 bond and 2 휋 bonds c) 2 휎 bond and 2 휋 bonds d) None of the Above 7 Chapter 14: Covalent Bonding: Orbitals Local Electron Model (Valence-Bond Theory) Promotion of an electron is possible if: There are empty p-orbitals The energy gained by forming additional bonds is greater than the energy needed to promote the electron to the p orbital Promotion Can Promotion Cannot Occur For Carbon Occur For Nitrogen 8 Chapter 14: Covalent Bonding: Orbitals Local Electron Model (Valence-Bond Theory) These are the bonding orbitals of C, therefore, what angles should be between each H in CH4? 9 Chapter 14: Covalent Bonding: Orbitals Local Electron Model (Valence-Bond Theory) These hybrid orbitals can be mathematically represented by linear combinations of the atomic orbitals (within one atom). h1 = ½(s + px + py + pz) h2 = ½(s - px - py + pz) h3 = ½(s - px + py - pz) h4 = ½(s + px - py - pz) Note: Since one s orbital and three p orbitals went in to forming the new hybrid orbitals, these hybrid orbital are referred to as sp3 hybridized orbitals. 10 Chapter 14: Covalent Bonding: Orbitals Local Electron Model (Valence-Bond Theory) Note: The number of atomic orbitals that go into the linear combinations are the same number of hybrid orbitals that form. The new molecular orbitals have energies that are at the same level. The hydride orbitals show that CH4 should be in a tetrahedral bonding configuration. 11 Chapter 14: Covalent Bonding: Orbitals Local Electron Model (Valence-Bond Theory) Hybrid orbitals can be formed from other combinations of atomic orbitals. h1 = s + 2py h = s + p 3 1 1 h2 = s + 2px - 2py h2 = s - p 3 1 h3 = s - 2 px - 2py 12 Chapter 14: Covalent Bonding: Orbitals Local Electron Model (Valence-Bond Theory) 13 Chapter 14: Covalent Bonding: Orbitals Local Electron Model (Valence-Bond Theory) Assigning Hybridization Step 1: Draw Lewis structure. Step 2: Count the number of bonds and lone pairs on the atom of interest. Note: All types of bonds (single, double, and triple) between two atoms count as 1 bond. Step 3: Assign hybridization sup to 1 pup to 3 dup to 5 Describe Bonding using the local electron (LE) model Step 1: Draw Lewis structure (if possible obey the octet rule). Step 2: Determine hybridization. Step 3: Describe bonding. 14 Chapter 14: Covalent Bonding: Orbitals Local Electron Model (Valence-Bond Theory) The bonding model that we looked at before for N2 was a little oversimplified. The sigma bonding should be looked at as taking place between two sp hybridized orbitals instead of between two pz orbitals. However, sp hybridized orbitals are very similar in shape to pz orbitals 15 Chapter 14: Covalent Bonding: Orbitals Local Electron Model (Valence-Bond Theory) 2- SO3 LE Description of Bonding Sulfur forms one 휎 bond to each oxygen atoms. The bonds are formed from the overlap of a sp3 hybridized orbitals on both the sulfur and oxygen atoms. All the loan pair electrons on both sulfur and oxygen atoms are located in sp3 hybridized orbitals. 16 Chapter 14: Covalent Bonding: Orbitals Local Electron Model (Valence-Bond Theory) 2- CO3 LE Description of Bonding The carbon atom forms one 휎 bond to each of the single bonded oxygen atoms. These bonds are formed from the overlap of sp2 hybridized orbitals on the carbon atom and sp3 hybridized orbitals on the single bonded oxygen atoms. A third 휎 bond is formed from the overlap of an sp2 hybridized orbital on the carbon atom and a sp2 hybridized orbital on the double bonded oxygen atom. The π bond between the double bonded oxygen atom and the carbon atom is formed from the overlap of the unhybridized p orbitals on both the carbon and oxygen atoms. The loan pair electrons on the double bonded carbon sit in sp2 hybridized orbitals and the loan pair electron on the single bonded oxygen atoms sit in sp3 hybridized orbitals. 17 Chapter 14: Covalent Bonding: Orbitals Local Electron Model (Valence-Bond Theory) Student Question Identify the hybrid orbitals used by the underlined atom in acetone, CH3COCH3. The O atom is double bonded to the central carbon atom. a) sp3d b) sp2 c) None; pure pz-orbitals are used in bonding. d) sp3 e) sp If you have extra time tell the person next to you the LE description of the molecule. 18 Chapter 14: Covalent Bonding: Orbitals Local Electron Model (Valence-Bond Theory) What atoms can form double and triple bonds? Atoms in period 2 (especially C, N, O) readily form double bonds with themselves and other period 2 atoms. However, atoms in period 3 and later have trouble forming multiple bonds with other large atoms due to the fact that the atoms are so large and bond lengths so great that it is difficult for their p-orbitals to take part in effective side-by-side bonding. O N C O N 19 Chapter 14: Covalent Bonding: Orbitals Local Electron Model (Valence-Bond Theory) Limits of Lewis Theory/VSEPR and LE Model 1. Cannot draw some structures that are known to exist. - Ex: B2H6 (12 valence e ) Not enough electrons to make all of the bonds 2. Does not explain resonance structures 3. Paramagnetic/Diamagnetic Problems 20 Chapter 14: Covalent Bonding: Orbitals Local Electron Model (Valence-Bond Theory) Paramagnetic: Having the tendency to be pulled into a magnetic field; a paramagnetic substance is composed of atoms or molecules with unpaired spin. Note: Laymen would call these materials magnetic. Diamagnetic: A substance that tends to be pushed out of a magnetic field; a diamagnetic substance is composed of atoms or molecules with no unpaired electrons. Note: Very weak response and is not observable in every day life. 21 Chapter 14: Covalent Bonding: Orbitals Local Electron Model (Valence-Bond Theory) 22 Chapter 14: Covalent Bonding: Orbitals Molecular Orbital Theory Molecular orbitals are formed by superimposing atomic orbitals of all the atoms in the molecule. Note: Superimposing just means adding together. Note: This is similar to Local Electron Model (valence band theory), however, the Local Electron Model only formed hybrid orbitals from σ bonds and lone pair electrons within one atom.
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