Structural Effects on Physical and Chemical Properties

At the end of the course the student should be able to:

- Discuss the different types of intermolecular forces of attraction
- Correlate structure of organic compounds to their properties
- Demonstrate the effect of intermolecular forces of attraction on physical properties
- Relate structural effects to stabilities of organic compounds
- Explain acid-base properties of organic compounds
- Discuss the nature of aromatic compounds
- Discuss the importance of aromaticity and acid/base reactions in biological systems.

Ionic forces
Ionic are interactions between charged atoms or molecules (“ions”). Positively charged ions, such as
Na(+) , Li(+), and Ca(2+), are termed cations. Negatively charged ions, such as Cl(–), Br(–), HO(–) are
called anions (I always got this straight through remembering that the “N” in “Anion” stood for
“Negative”) The attractive forces between oppositely charged ions is described by Coulomb’s Law, in
which the force increases with charge and decreases as the distance between these ions is increased.
The highly polarized (charged) nature of ionic molecules is reflected in their high melting points (NaCl
has a melting point of 801 °C) as well as in their high water solubility (for the alkali metal salts, anyway;
metals that form multiple charges like to leave residues on your bathtub)

. Hydrogen bonding

Hydrogen bonding occurs in molecules containing the highly electronegative elements F, O, or N

directly bound to hydrogen. Since H has an electronegativity of 2.2 (compare to 0.9 for Na and 0.8 for
K) these bonds are not as polarized as purely ionic bonds and possess some covalent character.
However, the bond to hydrogen will still be polarized and possess a dipole.

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The dipole of one molecule can align with the dipole from another molecule, leading to an attractive
interaction that we call hydrogen bonding. Owing to rapid molecular motion in solution, these bonds
are transient (short-lived) but have significant bond strengths ranging from (9 kJ/mol (2 kcal/mol) (for
NH) to about 30 kJ/mol (7 kcal) and higher for HF. As you might expect, the strength of the bond
increases as the electronegativity of the group bound to hydrogen is increased.

So in a sense, HO, and NH are “sticky” – molecules containing these functional groups will tend to
have higher boiling points than you would expect based on their molecular weight.

3. Van Der Waals Dipole-Dipole Interactions

Other groups beside hydrogen can be involved in polar covalent bonding with strongly electronegative
atoms. For instance, each of these molecules contains a dipole.

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These dipoles can interact with each other in an attractive fashion, which will also increase the boiling
point. However since the electronegativity difference between carbon (electronegativity = 2.5) and
the electronegative atom (such as oxygen or nitrogen) is not as large as it is for hydrogen
(electronegativity = 2.2), the polar interaction is not as strong. So on average these forces tend to be
weaker than in hydrogen bonding.

4. Van der Waals Dispersion Forces (“London forces”)

The weakest intermolecular forces of all are called dispersion forces or London forces. These
represent the attraction between instantaneous dipoles in a molecule. Think about an atom like
argon. It’s an inert gas, right? But if you cool it to –186 °C, you can actually condense it into liquid
argon. The fact that it forms a liquid it means that something is holding it together. That “something”
is dispersion forces. Think about the electrons in the valence shell. On average, they’re evenly
dispersed. But at any given instant, there might be a mismatch between how many electrons are on
one side and how many are on the other, which can lead to an instantaneous difference in charge.

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The polarizability is the term we use to describe how readily atoms can form these instantaneous
dipoles. Polarizability increases with atomic size. That’s why the boiling point of argon (–186 °C) is so
much higher than the boiling point of helium (–272 °C). By the same analogy, the boiling point of
iodine, (I-I, 184 °C) is much higher than the boiling point of fluorine (F-F, –188°C).

For hydrocarbons and other non-polar molecules which lack strong dipoles, these dispersion forces
are really the only attractive forces between molecules. Since the dipoles are weak and transient, they
depend on contact between molecules – which means that the forces increase with surface area. A
small molecule like methane has very weak intermolecular forces, and has a low boiling point.
However, as molecular weight increases, boiling point also goes up. That’s because the surface over
which these forces can operate has increased. Therefore, dispersion forces increase with increasing
molecular weight. Individually, each interaction isn’t worth much, but if collectively, these forces can
be extremely significant. How can a gecko lizard walk on walls? Look at its feet.

dispersion-forces-are-a-surface-area-phenomenon-boiling-point-increases-with-molecular-weight-
methane-ethane-propane-butane-pentane-boiling-points

1. Boiling points are a measure of intermolecular forces.

2. The intermolecular forces increase with increasing polarization of bonds.
3. The strength of intermolecular forces (and therefore impact on boiling points) is ionic > hydrogen
bonding > dipole dipole > dispersion
4. Boiling point increases with molecular weight, and with surface area.

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Introduction to Organic Reactions
At the end of the course the student should be able to:
Classify different types of organic reactions
Discuss mechanisms of reactions using thermodynamic and kinetic concepts
Illustrate organic reactions using energy diagrams
Explain reaction rates using transition state theory and collision theory

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References:
1.Klein, D. Organic Chemistry. John Wiley & Sons. 2012.
2. Bruice, Paula Y., Organic Chemistry, 7th ed. New Jersey: Prentice Hall. 2014.
3. Fox, M.A.; Whitsell, J.K. Organic Chemistry, 2nd ed. Massachusetts: Jones and Barlett
Publisher, Inc. 1997.
4. Lim-Sylianco, C.Y. Principles of Organic Chemistry, 8th ed. Philippines: Philippine
graphic Arts, Inc. 1994.
5. Morrison, R.T; Boyd, R.N., Organic Chemistry. Boston:Allyn and Bacon, Inc. 1991.
6. Pine, S.H. Organic Chemistry, 5th ed. N.Y: McGraw -Hill. 1987.
7. Loudon, M. Organic Chemistry, 5th ed. Roberts and Company Publishers, Colorado,
USA.2009.
8. Carey, F. Organic Chemistry. 5th ed. McGraw Hill. 2003.
9. McMurry, J. Organic Chemistry, 5th ed. Brooks/Cole. 2000.

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References:
1.Klein, D. Organic Chemistry. John Wiley & Sons. 2012.
2. Bruice, Paula Y., Organic Chemistry, 7th ed. New Jersey: Prentice Hall. 2014.
3. Fox, M.A.; Whitsell, J.K. Organic Chemistry, 2nd ed. Massachusetts: Jones and Barlett
Publisher, Inc. 1997.
4. Lim-Sylianco, C.Y. Principles of Organic Chemistry, 8th ed. Philippines: Philippine
graphic Arts, Inc. 1994.
5. Morrison, R.T; Boyd, R.N., Organic Chemistry. Boston:Allyn and Bacon, Inc. 1991.
6. Pine, S.H. Organic Chemistry, 5th ed. N.Y: McGraw -Hill. 1987.
7. Loudon, M. Organic Chemistry, 5th ed. Roberts and Company Publishers, Colorado,
USA.2009.
8. Carey, F. Organic Chemistry. 5th ed. McGraw Hill. 2003.
9. McMurry, J. Organic Chemistry, 5th ed. Brooks/Cole. 2000.

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