Solutions and their

properties
Part I:
What’s a solution: The process of dissolving
Factors affecting solubility
Ways of expressing concentration
Part II:
Colligative properties
 Learning objectives
• Describe a solution
• Describe factors influencing solubility
• Predict solubility based on molecular properties
• Describe effect of temperature on solubility
• Predict solubility of gases using Henry’s law
• Perform concentration calculations using
molarity, molality, mole fraction and percent by
mass and volume
 Mixtures are a fact of life
• We learn about matter by studying pure
substances
• In nature, most things are mixtures –
nothing is “pure”:
– Air
– Water
– Soil
– Living systems
 Solution or colloid?
• Both contain a solid dispersed in a liquid
• In a solution, the particle size is on the molecular
scale (< 1 nm)
• In a colloid, the particles are larger (2 – 500 nm)
• Colloids scatter light – milk, fog
 Why do solutions form?
• Things tend to get mixed up (entropy)
• Without any interactions between molecules, gases always mix
• Intermolecular forces complicate matters
– May improve mixing if forces in mixture are stronger
– May oppose mixing if forces in pure substances are stroner
• Three intermolecular forces:
– Solvent – solvent
– Solute – solute
– Solvent – solute
• Like dissolves like:
– Polar solvents dissolve polar solutes
– Nonpolar solvents dissolve nonpolar solutes
 Review of intermolecular forces
Name of force Origin Strength

Ion-dipole Between ions and molecules Quite strong (10 – 50 kJ/mol)

Dipole-dipole Between permanent dipoles Weak (3 – 4 kJ/mol)

Hydrogen bonds Polar bonds with H and (O,N) Quite strong (10 – 40 kJ/mol)

London dispersion forces Fluctuating dipoles in non-polar Weak (1 – 10 kJ/mol)

bonds
 Ion - dipole
• Characteristic of interactions in solutions
of ionic compounds in polar solvents
– Negative ion with the positive dipole end
– Positive ion with the negative dipole end
 Dipole - dipole
• Important attractive force in polar
substances
• Strength of the order of 3 – 4 kJ/mol
(compared with 200 – 400 kJ/mol for
covalent bonds)
 Dipole force manifested in
boiling points:

• Nonpolar substances have much lower boiling

points
– Acetone (polar) 56ºC butane (nonpolar) -0.5ºC
• Boiling point increases with dipole strength
 London calling

• Even molecules with no net dipole moment attract each other.

• Electrons are not static but mobile:
– Fluctuation creates dipole in one molecule which induces dipole in another molecule
• Effect increases with atomic number – as atom becomes more polarizable
– Boiling increases with molar mass
• For small molecules, dispersion forces are weaker than other inter-molecular
forces. For large molecules this is not true. Large molecules are solids because
of dispersion forces
 Solute – solvent interactions
• The stronger the interactions between
solute and solvent, the greater the
solubility
– Dispersion forces, dipolar interactions and
liquids
– Ion-dipole interactions and ionic compounds
in water
 Dissolving an ionic compound
• Attractive forces between solute and
solvent compensate attractive forces
between solute – solute and solvent -
solvent
 Solution on the atomic scale

• The ions held tightly in the crystal lattice

become solvated by water molecules
• Ion-ion interactions are replaced by ion-
dipole interactions in the solution
 Profits and losses
• Energy costs
– Solvent – solvent interactions
– Solute – solute interactions (lattice energy)
• High lattice energy → low solubility
• Energy gain
– Solvent – solute interactions
• Small, more highly charged ions have stronger interactions
 Solutions, disorder and entropy
• Substances dissolve with either gain or loss of
enthalpy
• Dissolving usually results in an increase in
entropy
• Exothermic processes tend to occur
spontaneously
• Processes that result in increased entropy tend
to occur spontaneously
 Strong interactions complicate
predictions about solubility
• Weak interactions:
– Gases mix completely over all compositions
• Moderate interactions:
– Liquids exhibit limits on range of miscibility
• Strong interactions:
– Solubility of ionic compounds varies
– Some ionic compounds are completely
insoluble
 Super-saturate me
• Saturated solution is in equilibrium with
undissolved solute and cannot contain any
more solute
Supersaturation: a state of the solution
where it contains more solute than allowed
by saturation. Non-equilibrium condition
• Crystallization and rainfall depend on
supersaturation
 Temperature and solubility
• Solubility is amount of solute present in solution
at saturation point
• Solubility varies widely from compound to
compound
• Solubility varies with T
– Most substances increase with T (KNO3) although the
dependence can vary
– Some are unaffected by T (NaCl)
– A few decrease with T (Na2SO4)
• Results can be explained by sign of ΔH solution
and Le Chatelier’s principle (later)
Gases always decrease solubility
with temperature
• Solubility of gases always decreases as
temperature increases
 Solubility and pressure
• For solutions of solids in liquids and liquids in
liquids, pressure has almost no effect.
• For gases in liquids:
• Henry’s Law operates
Solubility = k P
• Solubility of gas depends on partial pressure
above solution
• k is function of gas for given solvent
 Henry’s law and equilibrium
• Amount of gas in solution is in equilibrium with
gas above solution
• When P is increased, density of molecules
above solution increases
• More molecules enter solution to restore
equilibrium
 Concentration: ways of
expressing it
• Molarity
• Mole fraction
• Mass percent/volume percent
• Molality
 Molarity (M)
Molarity (M) =
Moles solute (mol)
Vol solution (L)
• Stoichiometry calculations are easy
• Amounts of solution required are volumetric
• Concentration varies with T
• Amount of solvent requires knowledge of
density
 Mole Fraction (X)
Mole fraction (X) = Moles solute (mol)
Moles solution (mol)
• Dimensionless
• Independent of temperature
• Used for gas mixtures and solid solutions
 Mass percent (mass %)
Mass percent = Mass solute (g)
x 100%
Mass solution (g)
• For very dilute solutions:
Parts per million (ppm) = Mass solute (g)
6
x 10
Mass solution (g)
• Independent of temperature
• Need to work with masses rather than volumes
 Molality (m)
Molality (m) = Moles solute (mol)
Mass solvent (kg)
• Used in calculations of colligative properties
• Independent of temperature
• Need to know mass of solution
• Need to know density to convert to molarity