Chapter 10: Chemical Bonding II: Molecular Shapes.

Valence Bond and Molecular Orbital Theories Page |1

Unit 2:
Chapter 10: Chemical Bonding II: Molecular Shapes; VSEPR, Valence Bond and Molecular Orbital Theories
Homework: Read Chapter 10: Work out sample/practice exercises. Complete Expt 10 in Chemistry 1A lab manual. Suggested Chapter 10 Problems: 33, 35, 41, 45, 47, 59, 63, 65, 67, 71, 77, 79, 81, 83, 87, 89, 93 Check for the MasteringChemistry.com assignment and complete before due date Limitations in Lewis Structures: Lewis theory generally predicts trends in properties, but does not give good numerical predictions of bond strength and bond length Lewis theory gives good first approximations of the bond angles in molecules, but usually cannot be used to get the actual angle Lewis theory cannot write one correct structure for many molecules where resonance is important Lewis theory often does not predict the correct magnetic behavior of molecules. Oxygen, O2, is paramagnetic, though the Lewis structure predicts it is diamagnetic Valence Shell Electron Pair Repulsion (VSEPR) Theory: Three-dimensional Electron groups (all negatively charged) around the central atom are most stable when they are as far apart as possible valence shell electron pair repulsion theory. Use all the information that has been gained in the Lewis Dot Structure and convert it to a three dimensional model to predict electronic and molecular shapes, angles, and polarity of the molecule. VSEPR Guidelines: Use all the information from a Lewis Dot Structure Three-Dimensional Identify Electronic and Molecular Shapes Bonds angles Polarity of whole substance (ionic, ion, nonpolar, polar molecule) Lone pair (nonbonding) electrons take up more space

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Electronic and Molecular Geometry: Count the electron regions. Electron regions will give an electronic shape while the number of bonded versus nonbonded regions will give the molecular shape.
# Electron regions Electronic geometry 2 3 4 5 6

Linear 180

trigonal planar 120

tetrahedral 109.5

trig. bipyramidal 90, 120, 180 trig.bipyramida, see saw, T-shaped, linear

octahedral 90, 180

molecular geometry

Linear

Trig planar, bent

Tetrahedral, Trigonal pyramidal, bent

octahedral, square pyramidal, square planar

Samples

Cool website to try: ChemEdDL.org Click on molecules 360. This website shows the 3D structure of many chemicals and allows you to rotate in three dimensions, showing bonding, bond length, dipole arrows, dipole moment, etc.

Valence Bond (VB) Theory: The Valence Bond theory is a quantum mechanical model that expands the previous two theories to describe the electronic nature of covalent bonds. Linus Pauling and others applied the principles of quantum mechanics to molecules They reasoned that bonds between atoms would occur when the orbitals on those atoms interacted to make a bond The kind of interaction depends on whether the orbitals align along the axis between the nuclei ( bonds), or outside the axis ( bonds)

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VB Guidelines: Use all the information from a Lewis Dot Structure Three-Dimensional Visualize orbital picture using atomic (s, p) and hybridized (sp, sp 2, sp3, sp3d, and sp3d2) orbitals Direct overlap orbitals, sigma ( ) bonds Indirect overlap orbitals, pi ( ) bonds All bonds have a bond, while double bonds have 1 and 1 and triple bonds have 1 and 2 bonds (Bubble) Pictures draw the orbitals in balloon type pictures Delocalized bonding occurs in substances with resonance

Chapter 10: Chemical Bonding II: Molecular Shapes. Valence Bond and Molecular Orbital Theories Page |4

Chapter 10: Chemical Bonding II: Molecular Shapes. Valence Bond and Molecular Orbital Theories Page |5

Double bond:

Triple bond:

Limitations in Valence Bond Theory: VB theory predicts many properties better than Lewis theory bonding schemes, bond strengths, bond lengths, bond rigidity However, there are still many properties of molecules it doesnt predict perfectly magnetic behavior of O2 VB theory presumes the electrons are localized in orbitals on the atoms in the molecule it doesnt account for delocalization

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Molecular Orbital (MO) Theory: The Molecular Orbital Theory is separate from the first three. This theory explains the paramagnetic behavior found in O2 gas molecules. In MO theory, Schrdingers wave equation is applied to the molecule to calculate a set of molecular orbitals Electrons and orbitals belong to the whole molecule Delocalization When the wave functions combine constructively, the resulting molecular orbital has less energy than the original atomic orbitals it is called a Bonding Molecular Orbital where most of the electron density is between the nuclei. Lower energy-stabilizing When the wave functions combine destructively, the resulting molecular orbital has more energy than the original atomic orbitals it is called an Antibonding* Molecular Orbital where most of the electron densityis outside the nuclei creating nodes between nuclei. Higher energy-unstable Sigma ( ) px molecular orbitals

Pi (

) py or pz molecular orbitals

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Sigma (

) s molecular orbitals

MO Guidelines: Use all electrons in atoms, not just the valence electrons For this class, limit discussion and examples to diatomic species such as: H2, O2, CN-1, HF. Sometimes gives a more accurate electronic structure than VB Combination of 2 atomic orbitals make a molecular orbital Bonding orbitals can be sigma or pi orbitals. Sigma orbitals directly overlap and pi orbitals indirectly overlap Antibonding* sigma or pi orbitals create a node between the atoms with no overlap Two atomic s orbitals combine to form a lower energy bonding and a higher energy * antibonding* orbital six atomic p orbitals combine to form lower energy bonding orbitals, and 2 degenerate orbitals and higher energy antibonding* orbitals, and 2 degenerate orbitals Predict paramagnetic or diamagnetic behavior Predict bond order Compare bond lengths and bond strengths For diatomic molecules with fewer than 15 total electrons like N2, energy increases as follows: s, 1s*, 2s, 2s*, 2p, 2p, 2p, 2p*, 2p*, 2p* For diatomic molecules with 15 or more total electrons like O2, energy increases as follows: s, 1s*, 2s, 2s*, 2p, 2p, 2p, 2p*, 2p*, 2p*

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Heteronuclear Diatomic Elements and Ions: The more electronegative an atom is, the lower in energy are its orbitals Lower energy atomic orbitals contribute more to the bonding MOs Higher energy atomic orbitals contribute more to the antibonding MOs Nonbonding MOs remain localized on the atom donating its atomic orbitals

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Polyatomic Molecular Orbitals: When many atoms are combined together, the atomic orbitals of all the atoms are combined to make a set of molecular orbitals, which are delocalized over the entire molecule Gives results that better match real molecule properties than either Lewis or valence bond theories

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Molecular Shapes, Handedness and Drugs: The shapes of molecules can dramatically change its characteristics. Mirror images have different biological properties due to the specific shapes of receptor sites in the body. For a molecule to exhibit handedness it needs 4 different groups attached to a carbon. Identify: Electronic and molecular geometries, angles, and VB hybridization of center atom.

a)

h)

b)

i)

c)

j)

d)

k)

e) f)

l)

g)

m)

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Fill in the following tables: First page follows octet and duet rules, second page has extended octets. #of electron number of electronic molecular bond angles rough an example regions and bonded geometry geometry 3-D molecule or ion VB hybrid atoms name name sketch H2 CO any 1 linear linear OO (180 ) HF N2 CN-1 CO2

120

3 sp2

bent or angular

109.5

trigonal pyramidal

H2O

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#of electron regions and VB hybrid

number of bonded atoms 5

electronic geometry name trigonal bipyramidal

molecular geometry name

bond angles

rough 3-D sketch

an example molecule or ion

see-saw

180 3 90 (120 )

5 sp3d

octahedral

BrF5

6 sp3d2

square Planar

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Examples:
1. The valence bond hybrid atomic orbitals sp3 are used by both C in CH4 and O in H2O. Yet, the bond angles between atoms in H2O are less than in CH4. Explain. 2. Describe completely the main features of each of the following and explain what useful information we gain from each. a) b) c) d) Lewis Structures Valence Shell Electron Pair Repulsion (VSEPR) theory Valence Bond (VB) theory Molecular Orbital (MO) theory

3. a) Draw all possible resonance Lewis structures for NO3-1. Include formal charges and the correct angles. b) Draw the "realistic" hybrid resonance structure with appropriate angles that takes and average of the Lewis structures in part a. Include formal charges (fractions) and bond orders (fractions). Include nonbonding electrons on central atom but not on terminal atoms. Sketch the valence bond (bubble) probability picture of one of the NO3-1 resonances. Identify and label the hybridized orbitals. Identify sigma and pi bonds.

c)

4. Draw and identify the cis and trans isomers for 1,2-dichloroethene, C2H2Cl2 5. For each of the following: B2, Ne2, O2 a) Give the molecular orbital (MO) energy diagram for each. b) Write the MO configurations for O2 1s)2 c) Give the bond order of each B2, Ne2, O2 d) List the species in decreasing order of bond energy and stability e) Identify each as diamagnetic or paramagnetic? f) Using the bond order information, which is least expected to exist. Explain why. g) Which would have the shortest bond length? Explain.

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6. Complete the following table for the indicated substances. Electronegativities: Na = 0.9, N = 3.0, O = 3.5, F = 4.0, Cl = 3.0, Br = 2.8, I = 2.5 substance SO2 C2H4O2 ICl5 NaBrO3 a) Draw the best Lewis structure(s), resonances, and structural isomers if any with octet b) Include formal charges if they are not zero c) Indicate polar bonds with dipole arrows toward the more electronegative name electronic geometry around central atom give hybrid orbital for center name molecular geometry around central atom show 3-D sketch with atoms & bonds in it give all bond angles how many sigma bonds? how many pi bonds? is it an ionic compound, polar or nonpolar molecule or an ion? Draw the VB hybrid resonance (bubble) picture

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7. Complete the following table for the indicated substances. substance SCN-1 I3-1 SF6
a)Draw the best Lewis structure(s), resonances, and structural isomers if any with octet b) Include formal charges if they are not zero c) Indicate polar bonds with dipole arrows toward the more electronegative name electronic geometry around central atom give hybrid orbital for center name molecular geometry around central atom show 3-D sketch with atoms & bonds in it give all bond angles how many sigma bonds? how many pi bonds? is it an ionic compound, polar or nonpolar molecule or an ion? Draw the VB hybrid resonance (bubble) picture

K2SO3

Answer questions below for SO3-2