GENERAL CHEMISTRY LECTURE 10 1. Valence Shell Electron Pair Repulsion (VSEPR) Theory Determine the shape (electronic and molecular geometry) of the molecule 2. Polar Molecules: The Influence of Molecular Geometry Determine the polarity of the molecule 3. Valence Bond (VB) Theory Determine the hybrid orbitals used for bonding
SCOPE Electron group domains around the central atom are arranged as far apart as possible to minimize repulsions. There are five basic molecular shapes based on the number of regions of high electron density around the central atom.
VSPER Theory 1. Two electron group domains around the central atom.
2. Three electron group domains around the central atom.
VSPER Theory 3. Four electron group domains around the central atom.
4. Five electron group domains around the central atom.
VSPER Theory 5. Six electron group domain around the central atom.
VSPER Theory MOLECULAR STRUCTURE AND COVALENT BONDING GENERAL CHEMISTRY LECTURE 10 Electron-group repulsions and the five basic molecular shapes.
Electronic geometry based on the number of electron domains around the central atom Molecular geometry accounts the number of nonbonding electrons/lone pairs
The same electron-group arrangement can give rise to different molecular shapes.
VSPER Theory Lone pairs of electrons require more volume than shared electrons.
Criteria for the ordering of the repulsions: a) Lone pair to lone pair is the strongest repulsion. b) Lone pair to bonding pair is intermediate repulsion. c) Bonding pair to bonding pair is weakest repulsion. lp/lp > lp/bp > bp/bp
VSPER Theory The Different Types of Shapes according to Electron Domains Examples
CO 2
BF 3
NO 2 -
Total Electron Domains: 4 pairs Examples
CCl 4
NH 3
H 2 O
Total Electron Domains: 5 pairs Examples
PCl 5
SF 4
ClF 3
XeF 2
Total Electron Domains: 6 pairs Examples
SF 6
BrF 5
XeF 5
The Steps in Determining a Molecular Shape.
Example: Methane, CH 4
Electronic and molecular geometries are the same: tetrahedral. VSPER Theory Exercise No. 1 Predicting Molecular Shapes Give the molecular shape and predict the bond angles (relative to the ideal angles) of (a) PF 3 (b)
COCl 2 and (c) BrF 5 . SOLUTION: (a) For PF 3 N = 8 x 4 = 32 A = 5 + 7 x 3 = 26 S = 6 -> 3 bonds A-S = 20
P F F F 4 electron group domain The electronic geometry is tetrahedral arrangement. The F-P-F bond is <109.5 o
The final shape (molecular geometry) is trigonal pyramidal. P F F F (b) For COCl 2 , C has the lowest EN and will be the center atom. N = 8 x 4 = 32 A = 4 + 6 + (7 x 2) = 24 S = 8 -> 4 bonds A-S = 16 C Cl O Cl The Cl-C-Cl bond angle is < 120 o
due to the electron density of the C=O. C Cl O Cl Predicting Molecular Shapes SOLUTION: 3 electron group domain The electronic geometry is trigonal planar The final shape (molecular geometry) is trigonal planar Exercise No. 1 111 o
124.5 o
Predicting Molecular Shapes (b) For BrF 5 , N = 8 x 6 = 48 A = 7 x 6 = 42 S = 6 e -> 10 e -> 5 bonds A-S = 42-10 = 32 SOLUTION: Br F F F F F 6 electron group domain The electronic geometry is octahedral arrangement. The final shape (molecular geometry) is square pyramidal. Exercise No. 1 Predicting Molecular Shapes with More Than One Central Atom SOLUTION: Determine the shape around each of the central atoms in acetone, (CH 3 ) 2 C=O. C C C O H H H H H H tetrahedral tetrahedral trigonal planar C O H C HH H C H H Exercise No. 2 3. What is the shape of each of the indicated atoms in the molecule below? 1. Trigonal planar
2. Tetrahedral
3. Trigonal planar
4. Bent or angular
Predicting Molecular Shapes with More Than One Central Atom Exercise No. 3 Molecular geometry affects molecular polarity. The bond dipoles either cancel or reinforce each other. linear molecule nonpolar A B
A B A angular molecule A polar Polarity and Molecular Geometry Polar molecules must meet the following requirements: One polar bond or one lone pair of electrons on central atom. Bonds and lone pairs are not symmetrically arranged. Their polarities do NOT cancel. Net dipole moment is NOT equal to zero. Polarity and Molecular Geometry Bond Polarity, Bond Angle and Bond Dipole Moment 1. Covalent bonds are formed by the overlap of atomic orbitals. Valence Bond (VB) Theory 2. Atomic orbitals on the central atom can mix and exchange their character with other atoms in a molecule. - Hybridization of atomic orbitals
3. Hybrid orbitals have the same shapes as predicted by VSEPR.
Valence Bond (VB) Theory The number of hybrid orbitals obtained is equal to the number of atomic orbitals mixed. The type of hybrid orbitals obtained varies with the types of atomic orbitals mixed. sp sp 2
sp 3
sp 3 d sp 3 d 2
Types of Hybrid Orbitals Hybrid Orbitals The sp Hybrid Orbitals in Gaseous BeCl 2 The sp Hybrid Orbitals in Gaseous BeCl 2 Shape: Linear sp-p The sp 2 Hybrid Orbitals in BF 3 The sp 2 Hybridized Orbitals Shape: Trigonal planar sp 2 -p The sp 3 Hybrid Orbitals in CH 4 The sp 3 Hybridized Orbitals The sp 3 Hybridized Orbitals Shape: Tetrahedral sp 3 -p sp 3 -s The sp 3 Hybrid Orbitals in NH 3 and H 2 O The sp 3 d Hybrid Orbitals in PCl 5 The sp 3 d Hybridized Orbitals Shape: Trigonal bipyramidal sp 3 d-p The sp 3 d 2 Hybrid Orbitals in SF 6 The sp 3 d 2 Hybridized Orbitals
Shape: Octahedral sp 3 d 2 -p Summary: Hybridization Regions of High Electron Density Electronic Geometry Hybridization 2 Linear sp 3 Trigonal planar sp 2 4 Tetrahedral sp 3 5 Trigonal bipyramidal sp 3 d 6 Octahedral sp 3 d 2 Summary: Hybridization Molecule Lewis Structure Electron group domain Electronic geometry Hybrid Orbitals CO 2 PO 4 3- XeF 4 SbF 5 2 Linear sp 4 Tetrahedral Octahedral 6 sp 3 sp 3 d 2 5 Trigonal bipyramidal sp 3 d 4. What is the hybridization of each of the indicated atoms in the molecule below? 1. sp 2 2. sp 3 3. sp 2 4. sp 3 Exercise No. 4 Take home quiz Consider the following ACl n species: SCl 2 , OCl 2 , PCl 3 , SiCl 4 , SiCl 6 2-
1) Determine the EGG and MGG of each compound 2) Arrange the compounds in decreasing Cl-A-Cl bond angles 3) Are all the molecules polar? Give the list of all the polar compounds from the given 4) Identify the orbitals involved in the bond A-Cl