General Chemistry

Course # 111, two credits

Second Semester 2009

King Saud bin Abdulaziz University for Health Science

Textbook: Principles of Modern Chemistry

by David W. Oxtoby, H. Pat Gillis, and Alan Campion (6 edition; 2007)

Dr. Rabih O. Al-Kaysi

Ext: 47247
Email: kaysir@ksau-hs.edu.sa
 Lecture 12
Properties of Solutions

The Solution
• A solution is a homogeneous mixture of solute (present in
smallest amount) and solvent (present in largest amount).
• Solution may be gas, liquid, or solids
• Each substance present is a component of the solution.
• Solvent is the substances used to dissolve the solute.
• In the process of making solutions with condensed phases,
intermolecular forces become rearranged.
• Intermolecular forces hold the solute particle and the solvent
that surrounds it together.
• Solutions form when the attractive forces between solute and
solvent can overcome the attractive forces with in the solute or
solvent particles.
Types of Solutions
 Formation of a Solution
• Consider NaCl (solute) dissolving in water (solvent):
• The water H-bonds have to be interrupted,
• NaCl dissociates into Na+ and Cl-,
• Ion-dipole forces form: Na+ … δ -OH2 and Cl-… δ +H2O.
• Such interaction between solute and solvent are called
solvation.
– If water is the solvent, we say the ions are hydrated.
Enthalpic Contributions

• Breaking attractive intermolecular

forces is always endothermic.
• Forming attractive intermolecular
forces is always exothermic.

We define the enthalpy change in

the solution process as
∆ Hsoln = ∆ H1 + ∆ H2 + ∆ H3.
 Enthalpy Properties of a Solution
• To determine whether ∆ Hsoln is positive or negative, we
consider the strengths of all solute-solute and solute-
solvent interactions:
∀ ∆ H1 and ∆ H2 are both positive.
∀ ∆ H3 is always negative.
• Solutions will not form under certain conditions.
• “like substances dissolve like substance”.
 The Solution Process
• “Rule”: polar solvents dissolve polar solutes. Non-polar
solvents dissolve non-polar solutes. Why?
• If ∆ Hsoln is too endothermic a solution will not form.
• NaCl in gasoline: the ion-dipole forces are weak because
gasoline is non-polar. Therefore, the ion-dipole forces do
not compensate for the separation of ions.
• Water in octane: water has strong H-bonds. There are no
attractive forces between water and octane to compensate
for the H-bonds.
 The Solution Process
• Solution can either be endothermic or exothermic:
• For example:
– NaOH added to water has ∆ Hsoln = -44.48 kJ/mol.
– NH4NO3 added to water has ∆ Hsoln = + 26.4 kJ/mol.
• Endothermic meaning heat has been gained by the
system.
• This is represented by a ∆ Hsoln > 0.
• Exothermic meaning heat has been released (or lost) from
the system.
• This is represented by a ∆ Hsoln < 0.


Ways of Expressing Concentration

Mass Percentage, ppm, and ppb
• All methods involve quantifying amount of solute per
amount of solvent (or solution).
• Generally amounts or measures are masses, moles or
liters.
• Qualitatively solutions are dilute or concentrated.
• Definitions:
mass of component in solution
mass % of component = × 100
total mass of solution


Ways of Expressing Concentration

Mass Percentage, ppm, and ppb
mass of component in solution
ppm of component = × 106
total mass of solution
• Parts per million (ppm) can be expressed as 1 mg of
solute per kilogram of solution.
– If the density of the solution is 1g/mL, then 1 ppm = 1 mg
solute per liter of solution.
• Parts per billion (ppb) are 1 µ g of solute per kilogram of
solution.


Ways of Expressing Concentration

Mass Percentage, ppm, and ppb
mass of component in solution
ppb of component = × 109
total mass of solution
Mole Fraction, Molarity, and Molality
• Recall mass can be converted to moles using the molar
mass.
moles of component in solution
Mole fraction of component =
total moles of solution
moles solute
Molarity =
liters of solution


Ways of Expressing Concentration

Mole Fraction, Molarity, and Molality
• We define
moles solute
Molality, m =
kg of solvent
• Converting between molarity (M) and molality (m)
requires density.
 Class Guided Practice Problems
1) A solution containing equal masses of glycerol,
C3H8O3, and water has a density of 1.10g/mL.
Calculate the: (a) Molarity, (b) Mole Fraction of
glycerol, (c) Molality of the solution.

2) Calculate the percent by mass of CaCl2 in a

solution containing 5.2g CaCl2 in 450g of water.

3) Calculate the ppm, by mass, of CaCl2 in a

solution containing 0.149 moles of CaCl2 in 443g
of water.


Saturated Solutions and Solubility

• Dissolve: solute + solvent → solution. Dynamic
equilibrium
• Crystallization: solution → solute + solvent.
• Saturation: crystallization and dissolution are in equilibrium.
• Solubility: amount of solute required to form a saturated
solution.
• Example, only 35.7g of NaCl will dissolve at 0 oC in 100 mL of
H2O.
• Dissolving less solute than needed to saturate is called an
unsaturated solution.
• Supersaturated: a solution formed when more solute is
dissolved than in a saturated solution.


Factors Affecting Solubility

Solute-Solvent Interaction
• Polar liquids tend to dissolve in polar solvents.
• Miscible liquids: mix in any proportions.
• Immiscible liquids: do not mix.
• Intermolecular forces are important: water and ethanol
are miscible because the broken hydrogen bonds in both
pure liquids are re-established in the mixture.
• The number of carbon atoms in a chain affect solubility:
the more C atoms the less soluble in water.


Factors Affecting Solubility Cont.

Solute-Solvent Interaction
• The number of -OH groups within a molecule increases
solubility in water.
• Remember, as a generalization: “like dissolves like”.
• The more polar bonds contained in the molecule, the
better it dissolves in a polar solvent.
• The less polar the molecule the less it dissolves in a polar
solvent and the better is dissolves in a non-polar solvent.
• The magnitude of ∆ H3 must be comparable in magnitude to
∆ H1+ ∆ H2 before the solute will dissolve in the solvent.
Factors Affecting Solubility Cont.
Solute-Solvent Interaction
Fat and Water Soluble Vitamins
Solute-Solvent Interaction


Pressure Effects on Solubility

• Solubility of a gas in a liquid is directly related to the pressure of the
gas.


Solubility of a Gas
Pressure Effects
• The higher the pressure, the more molecules of gas are
close to the solvent and the greater the chance of a gas
molecule striking the surface and entering the solution.
– Therefore, the higher the pressure, the greater the solubility.
– The lower the pressure, the fewer molecules of gas are close to
the solvent and the lower the solubility.


Compression of CO2
Pressure Effects
• Carbonated beverages are bottled with a partial pressure
of CO2 > 1 atm.
• As the bottle is opened, the partial pressure of CO2
decreases and the solubility of CO2 decreases.
• Therefore, bubbles of CO2 escape from solution.


Temperature Effects on Solubility

• Experience tells us that sugar dissolves better in warm
water than cold.
• As temperature increases, solubility of solids generally
increases.
• Sometimes, solubility decreases as temperature increases
(e.g. Ce2(SO4)3, Cerous Sulfate).
• See Table 13.15
 

Temperature Solubility


Colligative Properties
• Colligative properties depend on quantity of solute
molecules. (E.g. freezing point depression and melting
point elevation.)
Lowering Vapor Pressure
• Non-volatile solutes reduce the ability of the surface
solvent molecules to escape the liquid.
• Therefore, vapor pressure is lowered.
• The amount of vapor pressure lowering depends on the
amount of solute present.
Colligative Properties
Lowering Vapor Pressure


Boiling-Point Elevation
• At the normal boiling point of pure liquid, the vapor
pressure the solution will be < 1atm . Therefore, a higher
temperature is required to attain a vapor pressure of 1 atm
for the solution (∆ Tb).
• Molal boiling-point-elevation constant, Kb, expresses
how much ∆ Tb changes with molality, m:
∆Tb = Kb m

• Kb is dependent only on the solvent used in the making of

the solution.


Freezing Point Depression

• Lower vapor pressure also affects the freezing point of
the solution.
• The freezing point is the temperature at which the first
crystal forms.
• When a solution freezes, almost pure solvent is formed
first.
• Therefore, the sublimation curve for the pure solvent is the
same as for the solution.
• Therefore, the triple point occurs at a lower temperature
because of the lower vapor pressure for the solution.


Freezing Point Depression Cont.

• The change in freezing point can be defined by

∆T f = K f m

• Decrease in freezing point (∆ Tf) is directly proportional

to molality (Kf is the molal freezing-point-depression
constant):
• Lowering of freezing points by added solute explains the
use of antifreeze in cars and the use of calcium chloride
to melt ice.


Osmosis
• Osmosis: the movement of a solvent from low solute
concentration to high solute concentration.
• Semipermeable membrane: permits passage of some
components of a solution. Example: cell membranes
• There is movement in both directions across a
semipermeable membrane.
• As solvent moves across the membrane, the fluid levels
becomes uneven.
 Osmotic Pressure
• Osmotic pressure, π , is the pressure required to stop osmosis:
πV = nRT
 n
π =   RT
V 
= MRT
• Isotonic solutions: two solutions with the same π separated by a
semipermeable membrane.
• Hypotonic solutions: a solution of lower π with respects to the
more concentrated solution.
• The osmotic process is spontaneous.

Colloids
• Colloids are suspensions in which the suspended particles
are larger than molecules but too small to drop out of the
suspension due to gravity.
• Tyndall effect: ability of a Colloid to scatter light. The
beam of light can be seen through the colloid.
• Particle size: 10 to 2000 Å.
• There are several types of colloid:
• aerosol (gas + liquid or solid, e.g. fog and smoke),
• foam (liquid + gas, e.g. whipped cream),
• emulsion (liquid + liquid, e.g. milk),
• sol (liquid + solid, e.g. paint),


Hydrophilic and Hydrophobic Colloids

• Types of colloids dispersed in water:
• “Water loving” colloids: hydrophilic.
• “Water hating” colloids: hydrophobic.
• Molecules arrange themselves so that hydrophobic
portions are oriented towards each other.
• If a large hydrophobic macromolecule (giant molecule)
needs to exist in water (e.g. in a cell), hydrophobic
molecules embed themselves into the macromolecule
leaving the hydrophilic ends to interact with water.
 Colloids Removal of Colloidal Particles

• Colloid particles are too small to be separated by physical

means (e.g. filtration).
• Colloid particles are coagulated (enlarged) until they can
be removed by filtration.
• Methods of coagulation:
• heating (colloid particles move and are attracted to each other
when they collide);
• adding an electrolyte (neutralize the surface charges on the
colloid particles).