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Lecture 15 Announcements (02/25)

Experiment 3, Atomic Orbitals, is running this week. You do not


need your lab coat & goggles, USB disk is recommended.

Quiz 3, this week in lab, covers Chapter 2, HW sets 1 3.

Midterm 1 is on Friday March 6th, covers Fundamentals A F, and


Chapters 1 4.

Quiz 4, the week of 03/09 is over Chapter 3, HW sets 1 3.

Reading assignment: Chapter 4, sections 4.7 4.10.

New homework is assigned, Chapter 4, set 3: 51, 52, 53, 55, 57 (a),
59, 61, 63, 65, 67, 71, 72, 75.
hybridization orbitals showing the amplitude of a single
wavefunction.

2 -bonds 3 -bonds 4 -bonds


linear trigonal planar tetrahedral

How do we account of 5 -bonds in trigonal


bipyramidal or 6 -bonds in octahedral
compounds? 2
Trigonal bipyramidal have 5 e pairs, so
1 d-orbital along with the valence
s- and p-orbitals of the atom.

five sp3d hybrid orbitals


6 e pairs for octahedral; use 2 d-orbitals
in addition to the valence s- and p-
orbitals to form 6 hybrids.

six sp3d2 hybrid orbitals


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Assign a hybridization scheme for phosphorous in PCl5.

Draw the Lewis structure.


Determine the e
arrangement about
the central atom. Trigonal bipyramidal

Identify the molecular shape.


Select the same number of atomic
orbitals as there are hybrid orbitals.

Construct the hybrid orbitals, starting


with the s-orbital, then p- and d-orbitals.
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Assign a hybridization scheme for bromine in BrF4 ?

Draw the Lewis structure.

Determine the electron


arrangement about the
central atom. octahedral

Identify the molecular shape.

Select the same number of atomic


orbitals as there are hybrid orbitals. 6

Construct the hybrid orbitals,


starting with the s-orbital, then
p- and d-orbitals.
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Characteristics of Multiple Bonds
Atoms of the Period 2 elements C, N, and O readily form
double bonds (especially oxygen).

However, double bonds are rarely found between atoms of


elements in Period 3 and later periods, because the atoms
are so large and bond lengths consequently are so great
that it is difficult for their p-orbitals to take part in
effective side-by-side overlap.

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Characteristics of Multiple Bonds
Ethene, CH2=CH2 has a double bond.

All six atoms in ethene lie in the same plane, with bond
angles near 120.

This angle suggests a trigonal planar e arrangement and


sp2 hybridization for each C atom.

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Characteristics of Multiple Bonds
The unhybridized 2p-orbital, is
perpendicular to the C-C
plane.

The es in the 2 unhybridized 2p-orbitals form a -bond


through side-by-side overlap.

-bond spin-pairing
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Double bond properties

Double bonds prevent one part of a molecule from


rotating around another (also happens w/ triple bonds).

The -bonds of ethene, hold


the entire molecule flat.

Rotation around the C-C bond


is prohibited.

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Ethyne HCCH (acetylene) has sp
hybridized Cs.

Each C has 2 remaining p-orbitals,


each forms a -bond.

The 2 bonds built from p-


orbitals, form a cylindrical
symmetry.

The triple bond is weaker than


the sum of 3 CC single bonds.
10
Account for the structure of a formic acid molecule, HCOOH, in terms
of hybrid orbitals, bond angles, and - and -bonds.

Draw the Lewis structure. O has 4 groups or sp3


C has 3 groups or sp2

Use the VSEPR model to


identify the e
arrangements around the
central C and O atoms.

Identify the hybridization and bond


angles.

Form the bonds.


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Molecular Orbital Theory

Valence-bond theory explained e pairs in terms of spin-


pairing but it could not explain the properties of some
molecules.

Molecular orbital theory, based on quantum mechanics,


has proved to be the most successful theory of the
chemical bond and it overcomes all the deficiencies of
Lewiss theory.

12
Valence-bond theory, describes O2 as having all es paired.
However, oxygen is a paramagnetic with unpaired es.

A Gouy balance is used to observe


magnetic properties

13
Lewiss theory fails to account for the compound diborane,
B2H6, that bursts into flame on contact with air.

Diborane has only 12 valence es instead of the 14 it is


predicted to have.

Bridging Hydride

Unknown at the time


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Molecular Orbitals

In MO theory, es occupy orbitals called molecular


orbitals that spread throughout the entire molecule.

Lewis and valence-bond models of molecules localizes


the es on atoms or between pairs of atoms.

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Molecular Orbitals
In every case, molecular orbitals are built by adding
together -or superimposing- atomic orbitals belonging to
the valence shells of the atoms in the molecule.

For H2:

A is atom A
B is atom B
1s is the 1s-orbital for hydrogen

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Molecular Orbitals
A is atom A
B is atom B
1s-orbital for hydrogen

is called the linear combination of


atomic orbitals or LCAO.

The term LCAO-MO is a molecular orbital formed from a


linear combination of atomic orbitals (LCAO-AO).

Note: a MO is an overlap of wavefunctions (superimposing).

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Molecular Orbitals
bonding antibonding (*)
constructive interference deconstructive interference

LCAO-MOs

A note on good practice: the sign represents the reverse


phase of a + (so a peak becomes a trough and vice versa),
resulting in a node in the wavefunction. 18
The relative energies of the original atomic orbitals and the
bonding () and antibonding (*) molecular orbitals.
Atomic orbitals
that interfere
destructively, give
rise to
antibonding
molecular orbitals.

Bonding
Molecular orbitals
form when atomic
orbitals interfere
constructively.
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