Review of Basic Concepts

Part 3
Prepared by: Ms. Marilyn A. Miranda
 Polar Covalent Bonds
• Covalent bonds are either polar or nonpolar:
– Nonpolar covalent bonds: bonded atoms share electrons evenly
– Polar covalent bonds: one of the atoms attracts electrons more than the
other
• Electronegativity:
– How strongly an atom attracts shared electrons

Copyright 2012 John Wiley & Sons, Inc.

1-2 Klein, Organic Chemistry 1e
 Polar Covalent Bonds
• Electrons tend to shift away from lower
electronegativity atoms to higher electronegativity
atoms.

• The greater the difference in electronegativity, the more

polar the bond.

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1-3 Klein, Organic Chemistry 1e
 Molecular Polarity
• Electronegativity differences cause induction.
• Induction (shifting of electrons WITHIN their orbitals)
results in a dipole moment.
– Dipole moment = (the amount of partial charge) x (the
distance the δ+ and δ- are separated)
– Dipole moments are reported in units of debye (D)
• 1 debye = 10-18 esu ∙ cm
• An electrostatic unit of charge (esu) is a unit of charge. One electron
has a charge of 4.80 x 10-10 esu.
• Centimeters (cm) are included in the unit because the distance
between the centers of + and – charges affects the dipole.

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1-4 Klein, Organic Chemistry 1e
 Molecular Polarity
• Consider the dipole for CH3Cl
• Dipole moment (μ) = charge (e) x distance (d)
– Plug in the charge and distance
• μ = (1.056 x 10-10 esu) x (1.772 x 10-8 cm)
– Note that the amount of charge separation is less
than what it would be if it were a full charge
separation (4.80 x 10-10 esu).
• μ = 1.87 x 10-18 esu ∙ cm
– Convert to debye
• μ = 1.87 D

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1-5 Klein, Organic Chemistry 1e
 Molecular Polarity
• For molecules with multiple polar bonds, the dipole moment is the vector sum of all
of the individual bond dipoles.

• It is important to determine a molecule’s geometry FIRST before analyzing its

polarity.
– If you have not drawn a molecule with the proper geometry, you may not
assess the polarity correctly.

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1-6 Klein, Organic Chemistry 1e
 Molecular Polarity
• Electrostatic potential maps are often used to give a
visual depiction of polarity.

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1-7 Klein, Organic Chemistry 1e
 Molecular Polarity

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1-8 Klein, Organic Chemistry 1e
Polar Molecules: The Influence of Molecular
Geometry
• Molecular geometry affects molecular polarity.
– Due to the effect of the bond dipoles and how they
either cancel or reinforce each other.

• Polar Molecules must meet two

requirements:
1. One polar bond or one lone pair of electrons
on central atom.
2. Neither bonds nor lone pairs can be
symmetrically arranged that their polarities
cancel.
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 Intermolecular Forces
• Many properties such as solubility, boiling point,
density, state of matter, melting point, etc. are affected
by the attractions BETWEEN molecules.
• Neutral molecules (polar and nonpolar) are attracted to
one another through:
– Dipole–dipole interactions
– Hydrogen bonding
– Dispersion forces (a.k.a. London forces or fleeting dipole–
dipole forces)

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1-12 Klein, Organic Chemistry 1e
 Intermolecular Forces –
Dipole–dipole
• Dipole–dipole forces result when polar molecules line up their OPPOSITE charges.
• Note that acetone’s permanent dipole results from the difference in
electronegativity between C and O.
• The dipole–dipole attractions BETWEEN acetone molecules affects acetone’s
boiling point (BP) and melting point (MP).

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1-13 Klein, Organic Chemistry 1e
 Intermolecular Forces –
Hydrogen Bonding
• Hydrogen bonds (H-bonds) are an especially strong type of dipole–dipole attraction.
• Hydrogen bonds are strong because the partial + and – charges are relatively large.

• Only when a hydrogen shares electrons with a highly electronegative atom (O,
N, F, or Cl) will it carry a large partial positive charge.
– The large δ+ on the H atom can attract large δ– charges on other
molecules.
• Even with the large partial charges, H-bonds are still about 20 times weaker
than covalent bonds.
• Compounds with H atoms that are capable of forming H-bonds are called
PROTIC.

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1-14 Klein, Organic Chemistry 1e
 Intermolecular Forces –
Hydrogen Bonding
• Explain why the following isomers have different boiling
points.

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1-15 Klein, Organic Chemistry 1e
 Intermolecular Forces –
London Dispersion Forces
• Nonpolar molecules normally have their electrons (-) spread out evenly
around the nuclei (+), completely balancing the charge.
• However, the electrons are in constant random motion within their MOs.
• The constant random motion of the electrons in the molecule will sometimes
produce an electron distribution that is NOT evenly balanced with the positive
charge of the nuclei.
• Such uneven distribution produces a temporary dipole, which can induce a
temporary dipole in a neighboring molecule.

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1-16 Klein, Organic Chemistry 1e
 Intermolecular Forces –
London Dispersion Forces
• The greater the surface area of a molecule, the more temporary dipole
attractions are possible.

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1-17 Klein, Organic Chemistry 1e
 Solubility
• We use the principle that like dissolves like.
• Polar compounds GENERALLY mix well with other polar
compounds:
– If the compounds mixing are all capable of H-bonding and/or
strong dipole–dipole interactions, then there is no reason why
they shouldn’t mix.
• Nonpolar compounds GENERALLY mix well with other
nonpolar compounds:
– If none of the compounds are capable of forming strong
attractions, then no strong attractions would have to be broken
to allow them to mix.
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1-18 Klein, Organic Chemistry 1e
 Solubility
• We know it is difficult to get a polar compound (like water) to mix with a
nonpolar compound (like oil):
– We can’t use just water to wash oil off our dirty cloths.
• To remove nonpolar oils, grease, and dirt, we need soap.

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