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Lecture 10: VSEPR Theory ( Ch 8)

Lecture 10: VSEPR Theory ( Ch 8). Dr. Harris 9 /20/12 HW: Ch 8: 19, 23, 29, 33. Introduction. To date, we have learned about the Lewis structures of covalent bonds

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Lecture 10: VSEPR Theory ( Ch 8)

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  1. Lecture 10: VSEPR Theory (Ch 8) Dr. Harris 9/20/12 HW: Ch 8: 19, 23, 29, 33

  2. Introduction • To date, we have learned about the Lewis structures of covalent bonds • Lewis structures give insight into how atoms are bonded within a molecule, but does NOT tell us about the shape(moleculargeometry), of the molecule • Molecular geometry plays a major role in the properties of a substance. This is particularly true with biochemical reactions.

  3. Importance of Molecular Shape and Structure • Thalidomide was a popular drug for the treatment of morning sickness. The chemical formula of Thalidomide is C13H10N2O4 • If the synthetic procedure is not properly controlled, either of the two optical isomers (mirror images) of the drug can form Relieves morning sickness Severe birth defects

  4. Considering Molecular Geometry • If we draw the Lewis structures of water withoutconsidering geometry, we would derive the following: δ- • The Lewis structure suggests that water is a linear (straight) molecule. • However, if this were true, then the dipoles moments would be in opposite directions, as described above, and water would be a nonpolarmolecule • If this were the case, life as we know it would be very different δ+ δ+ H H O

  5. Considering Molecular Geometry • The actual geometry of water is shown below: δ- + = O δ+ δ+ H H 104.5o • This is a bentgeometry. The angle between the atoms is 104.5o. In this geometry, the molecule has a net dipole moment directed upward, which is why water is polar. • How do we determine the geometry?

  6. VSEPR Theory • The images below show balloons tied together at their ends. • There is an optimum geometry for each number of balloons, and the balloons spontaneously attain the lowest-energy arrangement. • In other words, the balloons try to “get out of each other’s way” as best they can. These arrangements maximize the distance between the balloon centers. Electrons behave the same exact way.

  7. VSEPR • In the valence-shell electron-pair repulsion theory (VSEPR), the electron groups around a central atom: • are arranged as far apart from each other as possible • have the least amount of repulsion of the negatively charged electrons • have a geometry around the central atom that determines molecular shape

  8. Using VSEPR To Predict Geometry STEP 1 Figure out the Lewis dot structure of the molecule.

  9. Total Electron Domains Domain Geometry Around Central Atom MOLECULAR GEOMETRY Bonding Domains Lone Pair Domains 2 0 2 Linear Ex. CO2 A A A B B B B B B B Trigonal planar 0 3 3 Ex. BH3 •• Bent 104.5o 2 1 Ex. NO2-

  10. Just a note • Any molecule containing only two atoms must be linear. There is no other possible arrangement. Ex. H2, HCl, CO, etc.

  11. Examples • Give the chemical structures and geometries of the following: • SO3 • BeCl2 • HCN • SO2 • F2

  12. 4-Coordinate Molecules Have a Tetrahedral Arrangement • A tetrahedron is a shape consisting of 4 triangular faces. The vertices are separated by an angle of 109.5o, and each position is equivalent. • Another way to view a tetrahedron is to imagine a cube with atoms at opposite corners, with the central atom at the center of the cube.

  13. Total Electron Domains Domain Geometry Around Central Atom MOLECULAR GEOMETRY Bonding Domains Lone Pair Domains Tetrahedral 4 0 A A B B B B B B B B B A Ex. CH4 Trigonal Pyramidal 4 •• •• 3 1 Ex. NH3 Bent 104.5o •• 2 2 Ex. H2O

  14. Examples • Give the chemical structures and geometries of the following: • SO42- • PF3 • OF2

  15. Expanded Electron Domains • As stated in the previous lecture, central atoms with a principal quantum number of n>3 can accommodate more than 8 valence electrons. • In many instances, there will be 5 or 6 bonds around these central atoms • The regions occupied by the constituent atoms in a 5-coordinate structure are not equivalent. The constituent atoms may be either equatorialor axial.

  16. Five-Coordinate Molecules Z X Axial position (z axis) Equatorial position (x-y plane) Y • Five coordinate molecules assume some variation of the trigonalbipyramidalconfiguration shown to the left. • If you have a 5 coordinate molecule which contains a lone pair, like SF4, the lone pair will go in an equatorial position. Lone pair want to be as far away from other electron domains as possible

  17. Axial vs. Equatorial Lone Pair • In the top arrangement, we have placed the lone pair in an equatorial position. Here, the lone pair has two ‘nearbyneighbors’ that are 90o, and two ‘distantneighbors’ 120o away • In the bottom arrangement, the lone pair is in an axial position. The lone pair has three ‘nearby neighbors’ 90o away and one ‘distantneighbor‘ 180o away. • The top arrangement is preferred because the lone pair has less ‘nearby neighbors’ F F A F F F F F S S F E •• E •• E A

  18. Total Electron Domains Domain Geometry Around Central Atom MOLECULAR GEOMETRY Bonding Domains Lone Pair Domains Trigonal Bipyramidal 5 0 B B Ex. PCl5 •• A A A B B B B B B B B B B Seesaw 1 4 5 •• •• Ex. SF4 T-shaped 3 2 Ex. ClF3

  19. A Five-Coordinate molecule with 3 Lone pairs is LINEAR Symmetrical about the central atom. Ex. XeF2 Note: In this chapter, you will find that Xe is actually able to make chemical bonds.

  20. Examples • Give the chemical structures and geometries of the following: • PBr5 • PF4- • TeCl4

  21. Six-Coordinate Molecules Take on an Octahedral Geometry • Unlike a trigonalbipyramid, the equatorial and axial positions in an octahedralare equivalent. • When placing lone pairs in the structure, we must still maximize their distance. It is customary to first place lone pair in the axialpositions.

  22. Lone Pairs Migrate As Far Away From One Another As Possible If a second lone pair exists, it is placed the maximum distance (180o) from the 1st pair First electron pair is placed in an axial position

  23. Total Electron Domains Domain Geometry Around Central Atom MOLECULAR GEOMETRY Bonding Domains Lone Pair Domains Octahedral 6 0 B A A B B B B B B B B B B Ex. SF6 6 Square pyramidal 5 1 •• Ex. BrF5

  24. Total Electron Domains Domain Geometry Around Central Atom MOLECULAR GEOMETRY Bonding Domains Lone Pair Domains Square Planar A B B B B •• 2 4 6 •• Ex. XeF4

  25. Examples • Give the chemical structures and geometries of the following: • SeF6 • ICl5 • NiCl42-

  26. Determining Polarity • Now that we know the geometry of molecules, we can determine whether or not the molecule is polar (has an overall dipole moment) • A polar molecule • contains polar bonds, as determined from differences in electronegativity (lecture 14) • has a separation of positive and negative partial charges, called a dipole, indicated with + and – • has dipoles that do not cancel (not symmetrical)

  27. Polar Molecules Overall Dipole moment = + - + δ δ δ C S Cl H - - - Overall Dipole moment = δ δ δ O N + + + Overall Dipole moment = δ δ δ H H H

  28. Nonpolar Molecules • A nonpolar molecule • contains nonpolar bonds, as determined from differences in electronegativity • Or may be symmetrical • Or dipoles cancel O C O - δ Symmetrical Cl Cl H H + δ - - H + δ δ δ C + + + OVERALL DIPOLE = 0 δ δ δ H H H

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