PROPERTIES OF SOLUTIONS
Solution Process
A solution is a homogeneous mixture of solute and solvent
Solutions may be gases, liquids or solids
Solvent is the component present in the largest quantity
Solutes are the other components
Consider NaCl dissolving in water
o Water molecules orient themselves on NaCl crystals
o H-bonds between water molecules have to be broken
o NaCl dissociates into Na+ and Clo Ion-dipole forces form between Na+ and the negative
end of the water dipole
o Similar forces form between CL- and the positive end
o This interaction is called solvation
Energy Changes
3 steps involving energy in solvation
o Separation of solute molecules ( H1 )
o Separation of solvent molecules ( H2 )
o Formation of solute-solvent interactions (H3 )
o Enthalpy change for the solution process is the sum of
all three
Solution enthalpy can be positive or negative depending on
the intermolecular forces
o Breaking intermolecular forces is always
endothermic(separation of solute and solvent)H is
positive
o Forming intermolecular forces is always exothermicH is negative
o Magnesium sulfate added to water has a H= 91.2kJ/mol
o Ammonium Nitrate added to water has a H=
+26.4kJ/mol
Predicting
o If H is negative a solution forms
o If H is to positive a solution will not form
Saturated solutions
o If crystallization and dissolution are in equilibrium
with undissolved solute present, the solution is
saturated
o Solubility is the amount of solute required to form a
saturated solution
Factors affecting solubility
Nature of the solute
Nature of the solvent
Temperature
Pressure
Solute-Solvent interactions
Liquids that mix are miscible
Intermolecular forces dictate solubility
o Polar dissolves polar
o Favorable dipole/dipole forces
Consider alcohol in water
o Water and ethanol are miscible. Not all alcohols are
o The longer the Carbon chain the lower the solubility
o More OH groups increase solubility
o Polarity determines solubility
o Network solids do not dissolve due strong inter
molecular forces
Pressure Effects
Solubility of a gas in a liquid is a function of pressure
Solubilities of liquids and solids are not affected by pressure
The solubility of a gas is directly proportional to the partial
pressure of the gas above the solution
Henry’s Law: Cg = k Pg where C is the solubility of the gas ,
P is the partial pressure and k is the Henry Law constant.
The constant differs with each solute/solvent pair and
temperature
Application: Carbonated beverages are bottled under P>1
atm. As the bottle is opened P is decreased and the solubility
of carbon dioxide decreases. Therefore, bubbles escape
from the solution
Temperature Effects
As temperature increases solids become more soluble and
gases become less soluble
Mass Percentage
Mass % of component= Mass of component in solution /
total mass of solution X 100
Mole Fraction
Mole fraction of component= moles of component / total
moles of all components
Molarity
M = moles of solute / liters of solution. Molarity will change
with temperature
Molality
m = moles of solute / kilograms of solvent convert between
molarity and molality using density
Colligative Properties
Vapor Pressure lowering( Raoult’s Law)
Boiling point elevation
Freezing point depression
Osmotic pressure
Vapor Pressure
Non-volatile solutes reduce the vapor pressure of the solvent
Vapor pressure of a solution is equal to the mole fraction of
the solvent times the vapor pressure of the pure solvent
Boiling Point Elevation
A nonvolatile solute lowers the vapor pressure of a solution
At the normal boiling point of the pure solvent, the solution
has a vapor pressure less than one atm.
Therefore, a higher temperature is required to reach a
vapor pressure of 1 atm
The molal boiling-point-elevation constant, K , expresses
how much T boiling changes with molality
Tb = Kb m
Freezing Point Depression
When a solution freezes, crystals of pure solvent form first
Solute molecules are usually not soluble in the solid phase of
the solvent
Therefore the triple point occurs at a lower temperature
because of the decreased vapor pressure of the solution
The freezing point is a vertical line from the triple point.
The decrease is directly proportional to molality
Tf = kf m
Osmosis
Semipermeable membranes permit the passage of some
molecules
Typically water moves through but not larger molecules or
ions
Osmosis is the net movement of a solvent from an area of
low solute concentration to an area of high solute
concentration.
Osmotic pressure, , is the pressure required to prevent
osmosis
Osmotic pressure obeys a law similar to the ideal gas law.
For n moles, V=volume, M=molarity, R= ideal gas constant
and absolute temperature, T, : V= nRT then =(n/v)RT
and then = MRT
If 2 solutions have the same , they are isotonic
Hypotonic solutions have a lower relative to a more
concentrated solution
Hypertonic solutions have a higher relative to a more
dilute solution
Colligative Properties of Electrolyte Solutions
Colligative properties of solutions depend on the total
concentration of particles in solution
In a .10M solution of NaCl the total concentration of
particles is .2 M
The expected freezing point depression is .2 m x 1.86 C/m
=.372 C. The actual depression is .348 C.
Ions in solution form ion pairs ( the oppositely charged ions
associate with each other for a short period) which reduces
the number of independent particles
The van’t Hoff factor (i) is a measure of the extent of
dissociation of electrolytes in solution
i = Tf (measured) / Tf (calculated for non-electrolyte