1. Theories of Chemical Bonding
Theories of bonding: explanations for chemical bond, Lewis dot structures and the following.
Valance-bond (VB) theory
Hybridization of atomic orbitals
Multiple covalent bonds
Molecular orbital (MO) theory
Delocalized electrons
Bonding in metals
Practice mental reasoning and verbal explanation
Theories of chemical bonding

2. Energy of Interaction Between Two H Atoms
Energies of attraction and repulsion as functions of distance between two H atoms are shown here.
The minimum of the attraction force occur at H–H bond length of 74 pm, at which, the antibonding orbital is +346 kJ mole–1 above 0, energy when H atoms are far apart.
Potential energy
+346 kJ mol –1 antibonding
distance
–346 kJ mol –1 H – H bond
How does energy affect the two-atom system?
Theories of chemical bonding

3. The Valence-bond Method
Valence bond method considers the covalent bond as a result of overlap of atomic orbitals. Electrons stay in regions between the two atoms. Some bond examples
s-s s-p s-d p-p p-d d-d H-H H-C H-Pd C-C Se-F Fe-Fe (?) Li-H H-N in Pd P-P H-F hydride
But overlapping of simple atomic orbitals does not explain all the features. Thus, we have to take another look, or do something about atomic orbitals – hybridization.
How does valence-bond approach explain the formation of chemical bonds?
Theories of chemical bonding

4. Hybridization of Atomic Orbitals
The solutions of Schrodinger equation led to these atomic orbitals.
1s, 2s, 2p, 3s, 3p, 3d, 4s, 4p, 4d, 4f, etc.
However, overlap of these orbitals does not give a satisfactory explanation. In order to explain bonding, these orbitals are combined to form new set of orbitals – this method is called hybridization.
During the lecture, these hybridized orbitals will be explained: sp 2 sp hybrid orbitals from mixing of a s and a p orbital sp 2 3 sp2 hybrid orbitals from mixing of a s and 2 p orbital sp3 fill in you explanation please sp3d 5 sp3d hybrid orbitals from mixing of a s and 3 p and a d orbital sp3d 2 ____________
Provide a description for hybrid orbitals sp, sp2, sp3, sp3d, and sp3d2
Theories of chemical bonding

5. Theories of chemical bonding
The sp Hybrid Orbitals
The sp hybrid orbitals: formation of two sp hybrid orbitals =
+ – = hybridization of s and p orbitals = 2 sp hybrid orbitals
_ _ __ __
 __ __ __ Two sp hybrid orbitlas =>
Two states of Be
Theories of chemical bonding

6. Bonds with sp Hybrid Orbitals
Formations of bonds in these molecules are discussed during the lecture. Be prepared to do the same by yourself.
Cl–Be–Cl H–CC–H H–CN : O=C=O
Double and triple bonds involve pi p bonding, and the the application of valence bond method to p bonds will be discussed.
You are expected to be able to draw pictures to show the p bonding.
Theories of chemical bonding

7. Theories of chemical bonding
A p Bond
Sigma (s) bond is symmetric about axis.
Pi (p) electron distribution above and below axis with a nodal plane, on which probability of finding electron is zero; p bond is not as strong as sigma - less overlap.
Nodal plane
Overlap of 2 2p orbitals for the formation of p bond
C 2s 2p 2p 2p sp2 sp2 sp2 2p
Bonding of C2H4
Theories of chemical bonding
How are pi bonds formed?

8. Triple Bonds in H-CC-H
H-C-C-H: three s bonds due to overlapping of 1sH – spC; spC – spC; and spC – 1sH.
Two p bonds in HCCH and HCN triple bonds are due to overlapping of p orbitals results.
sp hybrid orbitals
py over lap
C 2s 2p 2p 2p sp sp 2p 2p
in p bond H H
px over lap
Two nodal planes of p bonds are perpendicular to each other.
in p bond
Draw and describe how atomic orbitals overlap to form all bonds in acetylene, H–CC–H
Theories of chemical bonding

9. Theories of chemical bonding
Two p Bonds in H–CC–H
A triple bond consists of a sigma and two pi bonds. Overlaps of two sets of p orbitals form of two p bonds.
Theories of chemical bonding

10. Bonding of CO2
For CO2, the C atom forms a s bond and a p bond with each of two O atoms. The two nodal planes of the two p bonds are also perpendicular.
During the lecture, I draw diagrams and explain the two s two p bonds in CO2. You are expected to be able to do the same, in a test.
Resonance structures
: O – C  O :
: O  C – O :
. .
py over lap in p bond
px over lap in p bond
Overlap p–p in s bonds
Discuss the bonding of allene H2C=C=CH2
See extra problems B17 in the handout
O=C=O or H2C=C=CH2
Theories of chemical bonding

11. Bonding in CO2 – another view
Compare with H2C=C=CH2
Theories of chemical bonding

12. Theories of chemical bonding
The sp2 Hybrid Orbitals
Ground state and excited state electronic configuration of B
_ _ _ __
 _ __ __
The hybridization of a s and two p orbitals led to 3 sp2 hybrid orbitals for bonding.
Compounds involving sp2 hybrid orbitals: BF3, CO32–, H2CO, H2C=CH2, NO3–, etc
Theories of chemical bonding
Nov. 25

13. An example of using sp2 hybrid orbitals
__ orbitals for bonding?
Dipole moment = ____?
Theories of chemical bonding

14. Bonding of H2C=CH2 molecules
Utilizing the sp2 hybrid orbitals, each C atom form two H–C s bonds for a total of 4 s H–C bonds. The C–C s bond is common to both C atoms.
A C–C p bond is formed due to overlap of p orbitals from each of the C atoms.
C 2s 2p 2p 2p sp2 sp2 sp2 2p
Hybrid orbitals (sp2) for H–C and C–C s bond
Overlap of p orbital for C–C p bond
Theories of chemical bonding

15. The sp3 Hybridized Orbitals
Ground state and excited state electronic configuration of C
_ _ _ _
 _ _ __
The hybridization of a s and three p orbitals led to 4 sp3 hybrid orbitals for bonding.
Compounds involving sp3 hybrid orbitals: CF4, CH4, : NH3, H2O::, SiO44–, SO42–, ClO4–, etc
Theories of chemical bonding

16. Theories of chemical bonding
C 2s 2p 2p 2p sp3 sp3 sp3 sp3
Theories of chemical bonding

17. The sp3d Hybrid Orbitals
Hybridization of one s, three p, and a d orbitals results in 5 sp3d hybrid orbitals. The arrangement of these orbitals is a trigonal pyramid. Some structures due to these type of orbitals are PClF4, TeCl4E, and BrF3E2.
How many unshared electron pairs are present in TeCl4 and BrF3?
What are their shapes?
Theories of chemical bonding

18. The sp3d2 Hybrid Orbitals
Hybridization of one s, three p, and two d orbitals results in 6 sp3d2 hybrid orbitals. The arrangement of these orbitals is an octahedron. Compounds using these type of orbitals are shown here.
AX6,   AX5E,   AX4E2   AX3E3   and   AX2E4 IOF5,   IF5E,   XeF4E2
No known compounds of AX3E3 and AX2E4 are known or recognized, because they are predicted to have a T shape and linear shape respectively when the lone pairs of electrons are ignored.
Theories of chemical bonding

19. Molecules with more than one central atom
Describe the structure of CH3NCO.
Draw the skeleton and add all valence electrons
H3C – N – C – O
Which Lewis dot structure is the most important (stable)?
N = C = O
Take a new look at slide 22 in Bonding Basics
180o
NC–O
H–C
N–CO
H–C
Which structure is more stable, and why?
109o
120o
H–C
H H
H H
H H
What hybridized orbitals are used for bonding in N and C? Why are the bond angles as indicated? No of s and p bonds = __, __? Give formal charges to all atoms in all structures.
Theories of chemical bonding

20. Why Molecular Orbital (MO) Theory
Lewis dot and valence bond theories do not always give satisfactory account for various properties of molecules.
For example, the dot and VB theory does not explain the fact that O2 is paramagnetic and has a double bond.
Dot and VB structures : O O : • O O • are unsatisfactory.
MO theory, different from VB in that MO theory considers the orbitals of the whole molecules. However the approach of linear-combination-of-atomic-orbitals (LCAO) is usually used.
There are other reasons, but it’s human nature to theorize. The theory is beautiful, and worth learning or teaching.
Theories of chemical bonding

21. The Molecular Orbital (MO) Theory
For a molecule, there are certain orbitals each of which accommodates two electrons of opposite spin.
The MO theory combines atomic orbitals (AO) to form MOs, & this method is called LCAO s*
The two atoms in the H2 molecule may be represented by A and B. Their s orbitals 1sA and 1sB respectively, are used for two MOs:
s* = 1sA – 1sB
s = 1sA + 1sB
The energy levels of these AO and MO are represented by the diagram here, with the math hidden.
1sA
1sB
s MO AO AO
Theories of chemical bonding

22. MO for H2–type molecules: H2+, H2, H2–, He2+
Generalize the technique of LCAO
Theories of chemical bonding

23. Electronic configuration, s2, for H2 molecules
Generalize the technique of LCAO
Theories of chemical bonding

24. Electronic Configuration of H2-type Molecules
From the previous theory, we can fill the M Os with electrons for the H2-type molecule:
Molecule e-configuration Bond order bondlength H2+ 1s (1s1) ½ 106 pm H2, He22+ 1s , ~75 H2–, He2+ 1s2 1s* ½ ~106, 108 H22–, He2 1s2 1s*2 0 not formed
Describe the relationships of bondlength & bondorder and e-configurations; learn to reason
Theories of chemical bonding

25. Sigma MOs Formed Using p AOs
Sigma MOs (s2p s2p* ) can be formed using p AOs, similar to VB theory. The gain in bonding orbital s2p (lower energy) is at the expense of the anti-bonding orbital s2p* (higher energy)
Theories of chemical bonding
Generalize the technique of LCAO

26. Theories of chemical bonding
Pi p MOs from p AOs
Generalize the technique of LCAO
Theories of chemical bonding

27. Theories of chemical bonding
MO Diagrams for O2 and F2
A full diagram of the energy level of molecular orbitals of O2 and F2 is shown here.
The relative (approximate) height of these energies will be explained verbally during the lecture, and you are suppose to be able to do the same.
Write the electronic configurations for O2, O2–, F2, F2– & Ne2.
Theories of chemical bonding

28. The O2+, O2, O2– , & F2+, F2, F2– Molecules
For O=O _ _
O=O
Paramagnetic , bond length indicates double bond, electronic configuration agrees
F–F
Electronic configuration agree with single bond.
See p. 457 for two MO energy-level diagrams
Theories of chemical bonding

29. MO Energy Level Diagram for Be2 – N2
Due to close energy levels of 2s and 2p, the MO energy level diagram for Be2 to N2 differs from those of O2 to F2. Reasons and explanation are given during the lecture. Hope you can do the same.
                                                            
Give electronic configurations for Be2+, Be2–, B2+, B2, B2–, C2+, C2, C2–, N2+, N2, N2–.
See p. 457 for two MO energy-level diagrams
Theories of chemical bonding

30. __ s*2p __ __ p*2p __ s2p __ __p2p __ s*2s __ s2s Molecular orbitals
A more realistic energy level diagram for Be2 – N2 involving sp mixing, not in text
_ _ _ 2p _ 2s Atomic orbital
__ s*2p __ __ p*2p __ s2p __ __p2p __ s*2s __ s2s Molecular orbitals
_ _ _ 2p _ 2s Atomic orbital
This diagram from my CaCt website accounts for the sp mixing of the AO for the bonding consideration. This sp mixing effect is more detailed than that required for freshman chemistry (not to be tested).
The sp mixing of AO gives stronger s2s bond and a weaker s*2s bond. Thus, the split from 2s is not even. Effects on other bonds are also shown, but qualitatively.
Theories of chemical bonding

31. Theories of chemical bonding
Benzene
The benzene structure has fascinated scientists for centuries. It’s bonding is particularly interesting. The C atom utilizes sp2 hybrid AO in the sigma bonds, and the remaining p AO overlap forming a ring of p bonds.
Sigma s bonds are represented by lines, and the p orbitals for the p bonds are shown by balloon-shape blobs. Note the + and – signs of the p orbitals. Thus, we represent it by + + + + + + – – – –
Theories of chemical bonding

32. Theories of chemical bonding
More About Benzene
Chem120 students may ignore this slide.
The p and p* of C6H6 are shown here; the symmetry is also interesting.
Theories of chemical bonding

33. Delocalized electrons in Benzene and Ozone
When p bonds are adjacent to each other or separated by on single C-C bonds, the p bonding electrons are delocalized. The delocalized electron path for benzene and ozone are shown here. These pictures represent p electron of the the structures formula contribute most to their structures.
CO32– & have delocalized electrons O
O O
Theories of chemical bonding

34. Joy on structure of benzene – a story
Kathleen Londsdale ( ) came from a very poor family in Kildare who moved to Essex when she was five. She studied physics, math and chemistry at school and went to college in London when she was 16, where she did extremely well. She was offered a place in the research team of William Bragg, so starting her life's work on X-ray crystallography.
In 1929 she showed, by her analysis of hexamethyl benzene, that the benzene ring was flat. Benzene has fascinated scientists, and its precise structure was a matter of controversy till then.
In 1945 she was elected the first ever woman Fellow of the Royal Society. She was also created a Dame Commander of the Order of the Brittish Empire in 1956.
Theories of chemical bonding

35. MO for Heteronuclear Diatomic Molecules
For heteronuclear diatomic molecules, the atomic orbitals are at different energy levels. Thus, the MO shifts are different from those of homonuclear diatomic molecules.
The interactions of AO for MO for HF, LiF are similar, and explained in lectures.
                                                     
Theories of chemical bonding
Chem120 students may ignore this slide.

36. Theories of chemical bonding
Review
Explain the bonding and anti-bonding orbitals, with a picture if possible
Describe a s and a p bond, picture may be used.
Give the electronic configurations and bond orders for N2, N2+, N22+, N2–, N22–, O2,
Draw the Lewis dot structure for ozone. Describe the molecular shape and justify for it. Explain the delocalized electrons of ozone.
Use the MO theory to explain the fact that O2 is paramagnetic, and has a double bond. A diagram of the MO energy levels will help. Give a few compounds that have the same number of electrons as O3.
Theories of chemical bonding