A Molecular comparison of gases, liquids, and solids.

state of substance depends on balance between the kinetic energies of the particles and
interparticle energies of attraction
kinetic energies depends on temperature and tend to keep particles apart and moving
interparticle attractions draw particles together
condensed phases liquids and solids because particles are close together compared
to gases
increase temperature forces molecules to be closer together increase in strength of
intermolecular forces

Gases
o average kinetic energy of the molecules is larger than average energy of
attractions between molecules
o lack of strong attractive forces allows gases to expand
Liquids
o denser than gases
o have a definite volume
o attractive forces not strong enough to keep molecules from moving allowing
liquids to hold shape of container
solids
o intermolecular forces hold molecules together and keep them from moving
o not very compressible
o crystalline solids with highly ordered structures

Intermolecular Forces

intermolecular forces weaker than ionic or covalent bonds

many properties of liquids reflect strengths of intermolecular forces
three types of intermolecular forces: dipole-dipole forces, London dispersion forces, and
hydrogen-bonding forces
o also called van der Waals forces
o less than 15% as strong as covalent or ionic bonds
o electrostatic in nature, involves attractions between positive and negative species

1. Ion Dipole Forces

Ion-Dipole Force exists between an ion and partial charge at one end of a polar
molecule
Polar molecules are dipoles
magnitude of attraction increases as either the charge of ion or magnitude of dipole
moment increases
2. Dipole-Dipole Forces
dipole-dipole force exists between neutral polar molecules
 effective only when polar molecules are very close together
weaker than ion-dipole forces
for molecules of approximately equal mass and size, the strengths of intermolecular
attractions increase with increasing polarity
increase dipole moment increase boiling point
3. Londen Dispersion Forces
interparticle forces that exist between nonpolar atoms or molecules
motion of electrons can create an instantaneous dipole moment
molecules have to be very close together
polarizability ease in which the charge distribution in a molecule can be distorted
greater polarizability more easily electron cloud can be distorted to give
momentary dipole
larger molecules have greater polarizability
London dispersion forces increase with increasing molecular size
Dispersion forces increase in strength with increasing molecular weight
Molecular shape affects intermolecular attractions
greater surface contact greater boiling point and London dispersion forces
dispersion forces operate between all molecules
comparing relative strengths of intermolecular attractions:
1) comparable molecular weights and shapes = equal dispersion forces
differences in magnitudes of attractive forces due to differences in strengths of
dipole-dipole attractions
most polar molecule has strongest attractions
2) differing molecular weights = dispersion forces tend to be the decisive ones
differences in magnitudes of attractive forces associated with differences in
molecular weights
most massive molecular has strongest attractions
4. Hydrogen Bonding
hydrogen bonding special type of intermolecular attraction that exists between the
hydrogen atom in a polar bond and an unshared electron pair on a nearby
electronegative ion or atom
hydrogen bond with F, N, and O is polar
density of ice is lower than that of liquid water
when water freezes the molecules assume the ordered open arrangement makes
ice less dense than water
a given mass of ice has a greater volume than the same mass of water
structure of ice allows the maximum number of hydrogen bonding interactions to
exist
 Solution Intermolecular Forces

The dissolving process involves a consideration of the relative strength of three intermolecular
attractive forces. The type of forces between solute-solute molecules and solvent-solvent molecules
must be considered. These intermolecular attractions must be broken before new solute-solvent
attractive forces can become effective. Perhaps the bond breaking and bond forming processes take
place simultaneously. A solute will dissolve in a solvent if the solute-solvent forces of attraction are
great enough to overcome the solute-solute and solvent-solvent forces of attraction. A solute will
not dissolve if the solute-solvent forces of attraction are weaker than individual solute and solvent
intermolecular attractions. Generally, if all three of the intermolecular forces of attraction are
roughly equal, the substances will be soluble in each other.

Solubility rule and summary:

Likes dissolves likes
This means that ionic or polar solutes dissolve in polar solvents. Non-polar solutes dissolve in
non-polar solvents. Polar and ionic solutes DO NOT dissolve in non-polar solvents and vice versa.
Remember that when applying the solubility rule: "Likes Dissolve Likes", that there are no
absolutes and there are exceptions with a small amount of solubility possible. The rule is most
useful when making comparisons between a series of compounds

Kinds of solution intermolecular forces:

1. Ionic solute Polar solvent
When an ionic crystal such as NaCl is placed in water, a dissolving reaction will occur. Initially, the
positive and negative ion are only attracted to each other. The water molecules are hydrogen
bonded to each other. If the crystal is to dissolve, these bonds must be broken.
Negative chloride ions on the surface are attracted by neighboring positive sodium ions and by the
partially positive hydrogen atom in the polar water molecule (See the graphic on the right).
Similarly, the positive sodium ions are attracted by both chloride ions and the partially negative
oxygen atom in the polar water molecule. (See the graphic on the right).
A "tug-of-war" occurs for the positive and negative ions between the other ions in the crystal and
the water molecules. Whether the crystal dissolves is determined by which attractive force is
stronger. If the internal ionic forces in the crystal are the strongest, the crystal does not dissolve.
This is the situation in reactions where precipitates form. If the attractions for the ions by the polar.
water molecules are the strongest, the crystal will dissolve. This is the situation in sodium chloride.
Once the ions are released from the crystals, the ions are completely surrounded by water
molecules. Note that the proper atom in the water molecule must "point" toward the correct ion.
The charge principle and the partial charges in the polar molecule determine the correct orientation.

2. Polar solute Polar solvent

Polar ammonia molecules dissolve in polar water molecules. These molecules mix readily because
both types of molecules engage in hydrogen bonding. Since the intermolecular attractions are
roughly equal, the molecules can break away from each other and form new solute (NH3), solvent
(H2O) hydrogen bonds.
A wide variety of solutions are in this category such as sugar in water, alcohol in water, acetic and
hydrochloric acids.

3. Non polar solute Non polar solvent

 In all types of non-polar compounds, about the only intermolecular attractions are the very weak
induced dipole forces. The weak attractive forces formed by the solute-solvent molecules
compensate for breaking those weak bonds in the two pure non-polar substances. An example is
solid iodine (I2) dissolved in liquid bromine (Br2).
In addition to diatomic molecules with identical atoms, the most common type of non-polar
compounds are the hydrocarbons. Many C-C and C-H non-polar bonds are present. Hydrocarbons
are present in oils, grease, fats, dry cleaning solvents, turpentine, gasoline, etc
.
4. Non polar solute Polar solvent
Non-polar Iodine is not very soluble in water. An intermolecular bond between an induced dipole
(I2) and a polar bond in water is not very strong compared to the hydrogen bonds in water. The
water molecules would rather remain hydrogen bonded to each other, then to allow an iodine
molecule come between them. The water molecules effectively "squeeze" out the non-polar iodine.
The intermolecular forces are not roughly equal, therefore, the "unlike" substances are not soluble
in each other.
Various gases such as O2, N2, H2, CO2 are not very soluble because the gases are essentially non-
polar. Of course you may say that oxygen must be dissolved in water to sustain fish life -- true, but
the solubility is very low. Carbon dioxide is soluble in water such as carbonated beverages -- again
this is true but why does it fizz when opened or lose the bubbles on standing? Carbon dioxide is not
very soluble in water.