Lecture B2 VSEPR Theory
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1 Lecture B2 VSEPR Theory
2 Covalent Bond Theories 1. VSEPR (valence shell electron pair repulsion model). A set of empirical rules for predicting a molecular geometry using, as input, a correct Lewis Dot representation. 2. Valence Bond theory. A more advanced description of orbitals in molecules. We emphasize just one aspect of this theory: Hybrid atomic orbitals. Works especially well for organic molecules, which is the reason we don t scrap it entirely for MO theory. 3. Molecular Orbital theory. The most modern and powerful theory of bonding. Based upon QM.
3 Covalent Bond Theories 1. VSEPR (valence shell electron pair repulsion model). A set of empirical rules for predicting a molecular geometry using, as input, a correct Lewis Dot representation. 2. Valence Bond theory. A more advanced description of orbitals in molecules. We emphasize just one aspect of this theory: Hybrid atomic orbitals. Works especially well for organic molecules, which is the reason we don t scrap it entirely for MO theory. 3. Molecular Orbital theory. The most modern and powerful theory of bonding. Based upon QM.
4 G. N. Lewis tried to develop a geometrical model for atoms and chemical bonding -- but failed. G. N. Lewis
5 Gillespie and Nyholm devised a simple scheme for geometry based on the Lewis dot structure (VSEPR). Valence shell electron pair repulsion (VSEPR) theory is a model in chemistry used to predict the shape of individual molecules based upon the extent of electron-pair electrostatic repulsion. It is also named Gillespie-Nyholm* theory after its two main developers. The acronym "VSEPR" is pronounced "vesper" for ease of pronunciation. *Ronald J. Gillespie and Ronald S. Nyholm University College, London, Ronald J. Gillespie
6 Living in 3 Dimensions What role does geometry play in chemical structure?
7 Gillespie and Nyholm looked at the structures of molecules of the form AXn: AX2 CO2 16 electrons O=C=O O-C-O angle: 180 Linear Geometry
8 AX2 X-A-X angle: 180 Linear Geometry
9 AX3 X-A-X angle: 120 Trigonal Geometry
10 BF3 AX3 24 electrons F F B F F-B-F angle: 120 Trigonal Planar Geometry
11 AX4 X-A-X angle: 90 Square Planar Geometry?
12 CH4 AX4 8 electrons H H C H H H-C-H angle:? Tetrahedral Geometry
13 AX4 CH4 from SketchUp H-C-H angle: Tetrahedral Geometry
14 Green Triangle: = 2 Hypotenuse = 2 AX4 Gray Triangle: = 3 Hypotenuse = 3 Grey Angle = cos -1 ( 2/ 3) from SketchUp H-C-H angle: Blue Triangle: Blue Angle = x GA Tetrahedral Geometry
15 VSEPR in Solids: Diamond Structure Diamond Also ZnS C-C-C angle: From CrystalMaker Tetrahedral Site Symmetry
16 CH4 AX4 8 electrons H H C H H H-C-H angle: Tetrahedral Geometry
17 AX5 X-A-X angle: 72 Pentagonal Planar Geometry?
18 AX5 PCl5 40 electrons Cl-P-Cl angles: 90,120 Trigonal Bipyramidal Geometry
19 AX6 X-A-X angle: 60 Hexagonal Geometry?
20 AX6 SF6 48 electrons F-S-F angle: 90 Octahedral Geometry
21 VSEPR in Solids: Body Centered Cubic Structure AX6 From CrystalMaker C-C-C angle: 90 Octahedral Site Symmetry
22 Gillespie and Nyholm realized that the covalent bonds were arranged so as to minimize overlap:
23 They also realized that non-bonding electron pairs on the central atom ALSO needed to be included, and actually required MORE relief from overlap.
24 Thus, the electron pairs around each atom in a molecule tend to be arranged to minimize repulsion - it doesn t matter whether these electron pairs are in bonds, or are non-bonding lone pairs.
25 For example: AX3E0 NO3 - s = 3 n = 3 m = 0 s is the total number of bonds (n) and lone pairs (m). Trigonal Planar Geometry
26 AX2E1 s = 3 n = 2 m = 1 SO2 O S O 18 electrons
27 AX4E0 s = 4 n = 4 m = 0 CH4 Tetrahedral Geometry
28 AX3E1 s = 4 n = 3 m = 1 NH3 Trigonal Pyramidal Geometry
29 AX2E2 s = 4 n = 2 m = 2 H2O
30 AX5E0 s = 5 n = 5 m = 0 PCl5 Trigonal Bipyramidal Geometry
31 Two different positions. Where do the lone pairs go? This geometry is the strange one...
32 Two different positions. Where do the lone pairs go? Axial position: Three 90 angles and One 180 angle: Average = (3x )/4 Average = 112.5
33 Two different positions. Where do the lone pairs go? Axial position: Three 90 angles and One 180 angle: Average = (3x )/4 Average = Equatorial position: Two 90 angles and Two 120 angles: Average = (2x90 + 2x120)/4 Average = 105
34 Equatorial is observed even though its average angle is smaller!!! Axial position: Three 90 angles and One 180 angle: Average = (3x )/4 Average = Equatorial position: Two 90 angles and Two 120 angles: Average = (2x90 + 2x120)/4 Average = 105
35 Equatorial is observed even though its average angle is smaller!!! Conclusion: electron overlap is a nonlinear function of distance. Equatorial position: Two 90 angles and Two 120 angles: Average = (2x90 + 2x120)/4 Average = 105
36 AX4E1 s = 5 n = 4 m = 1 SF4 Seesaw Geometry
37 AX3E2 s = 5 n = 3 m = 2 BrF3 Tee-Shape Geometry
38 AX2E3 s = 5 n = 2 m = 3 I3 - Linear Geometry
39 AX6E0 s = 6 n = 6 m = 0 SF6 Octahedral Geometry
40 AX5E1 s = 6 n = 5 m = 1 ClF5 Square Pyramidal Geometry
41 AX4E2 s = 6 n = 4 m = 2 XeF4 Square Planar Geometry
42
43 AX2 Dipole Moments X-A-X angle: 180 Linear Geometry
44 Two examples: BeCl2 and CO2 Both of these are of the AX2E0 format - linear geometry. Note that single and double bonds both count as one for VSEPR geometries.
45 We can also predict the existence of a molecular dipole moment from the molecular geometry, and the electronegativities of each element:
46 We can also predict the existence of a molecular dipole moment from the molecular geometry, and the electronegativities of each element: the two bond dipoles in BeCl2 cancel (they are equal in magnitude, and opposite in direction) BeCl2 has no net molecular dipole. CO2 has no net molecular dipole as well.
47 What about the molecule: BeClBr?
48 What about the molecule: BeClBr?
49 What about the molecule: BeClBr? the two bond dipoles in BeClBr do not cancel. BeClBr has a small molecular dipole oriented along the molecular axis, and directed towards the Cl.
50 Another example: H2O The oxygen is surrounded by four electron pairs, two in sigma bonds and two in lone pairs.the VSEPR group is AX2E2 -- bent geometry. or
51 Does H2O have a dipole moment? o we perform this vector addition in our heads: resultant
52 H2O has a dipole moment of 1.85D o the tetrahedral electron group geometry requires that the molecular geometry is bent. The molecular dipole moment bisects the H-O-H bond and is directed towards the oxygen.
53 Both Electronegativity differences and Geometry determine the dipole moment of a molecule:
54 A second molecule with tetrahedral electron group symmetry about the central atom is NH3 (ammonia): o 1.47D VSEPR class: AX3E1. molecular geometry = trigonal pyramidal. The molecular dipole moment is coincident with the 3-fold axis of the molecule and is directed towards the N.
55 A third molecule with tetrahedral electron group symmetry about the central atom is CH4 (methane): o VSEPR group: AX4E0 molecular geometry = tetrahedral. methane is non-polar.
56 Lone pairs actually need more room, and cause bond angle compression in NH3 and H2O: CH4 NH3 H2O o o o a perfect tetrahedron 1 lone pair 2 lone pairs
57 Given the formula for a molecule, you should be able to: 1. Produce the best Lewis Dot representation for that molecule, include resonance structures. 2. Determine the formal charge on each atom of your structure(s). 3. Indicate its molecular geometry. 4. Determine whether it is polar or nonpolar. 5. Specify the direction of the dipole moment.
58 Dipole moments for trigonal bipyramidal geometries: VSEPR group: AX2E3 = trigonal bipyramidal molecular geometry = linear and no dipole moment example: XeF2
59 .. F.. F F VSEPR group: AX3E2 = trigonal bipyramidal molecular geometry = t-shaped example: IF3 Dipole bisects lone pair and is directed towards F.
60 what about a SINGLE single lone pair - does it choose an equatorial or axial position within a molecule having a trigonal bipyramidal electron group geometry? answer: equatorial dipole directed along lone-pair-a axis. VSEPR group: AX4E1 = trigonal bipyramidal molecular geometry = see-saw
61 And remember to include resonance structures! An example: ozone, O3 (18 electrons): O.. O.. O.. O.. O O.. two resonance structures
62 Ozone, O3 (18 electrons): VSEPR group: AX2E1 = trigonal molecular geometry = bent Bond angle = 116
63 Ozone, O3 (18 electrons): VSEPR group: AX2E1 = trigonal molecular geometry = bent Bond angle = 116 Small dipole moment (0.53D), because it's all oxygen.
64 Hydrocarbons methane
65 Hydrocarbons cyclohexane C6H12
66 Hydrocarbons axial and equatorial hydrogens
67 Hydrocarbons two conformations of cyclohexane chair boat
68 Hydrocarbons adamantane C10H16
69 Hydrocarbons cyclopentane C5H10
70 Hydrocarbons cyclobutane C4H8
71 Hydrocarbons cubane C8H8
72 Hydrocarbons cyclopropane C3H6
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