Chapter 12

Solutions

8–1

John A. Chapter 12-1

 Overview

• Solution formation
– Types of solution
– Solubility and the solution process
– Effect of temperature and pressure on solubility
• Colligative properties
– Ways of expressing concentration
– Vapor pressure of a solution
– Boiling-point elevation and freezing point depression.
– Osmosis
– Colligative properties of ionic solutions
• Colloid Formation
8–2
– Colloids

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 Types of Solution

• Solution – homogeneous mixture of two or more

substances of ions or molecules. E.g. NaCl (aq)
– Solvent = component which is the component in greater
amount.
– Solute = component which is present in the smaller amount.
– Gaseous = gases are completely miscible in each other.
– Liquid = gas, liquid or solid solute dissolved in solute.
– Solid = mixture of two solids that are miscible in each other
to form a single phase.
• Colloid – appears to be a homogeneous mixture, but
particles are much bigger, but not filterable. E.g. Fog,
smoke, whipped cream, mayonnaise, etc.
• Suspension: larger particle sizes, filterable. E.g. mud, 8–3
freshly squeezed orange juice.

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 Solubility and the Solution Process

• The solid dissolves rapidly at first

but as the solution approaches
saturation the net rate of
dissolution decreases since the
process is in dynamic equilibrium.

• When the solution has reached

equilibrium the amount of solute
does not change with time;
• At equilibrium: the rate of
dissolution = rate of solution

Fig. 12.2 Solubility Equilibrium

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 Solubility and the Solution Process II

• Saturated solution: maximum amount of solute is

dissolved in solvent. Trying to dissolve more results in
undissolved solute in container.
• Solubility: Amount of solute that dissolves in a
solvent to produce a saturated solution. (Solubility
often expressed in g/100 mL.)
E.g. 0.30 g of I2 dissolved in 1000 g of H2O.
• Unsaturated solution: less than max. amount of
solute is dissolved in solvent.
E.g. 0.20 g of I2 dissolved in 1000 g of H2O.
• Supersaturation = more solute in solution than
normally allowed; we call this a supersaturated 8–5

solution.

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 Factors Affecting Solubility

• “like dissolves like” = substances with similar molecular

structure are usually soluble in each other.
• Gases = generally completely soluble in each other because of
entropy (Ch. 19, tendency towards maximum randomness).
• Molecules in gas phase are far apart from each other and not
interacting strongly with each other in solution.

8–6
Fig. 12.5 Mixing of Gas Molecules

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Energy Changes and the Solution Process
• Intermolecular forces are also important in determining the
solubility of a substance.
– “like” intermolecular forces for solute and solvent will make the
solute soluble in the solvent.
 Hsoln is sometimes negative and sometimes positive.
– Solvent – solvent interactions: energy required to break weak bonds
between solvent molecules.
– Solute – solute interactions: energy required to break intermolecular
bonds between the solute molecules.
– Solute – solvent interactions: H is negative since bonds are formed
between them.

Solvent Solute Solution

+ 8–7

Solvent – solvent Solute – solute Solute – solvent

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 Molecular Solutions

• Molecular compounds with similar chemical structures and

polarities tend to be miscible.
• Homologous alcohol series have polar and non-polar ends.

8–8

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 Ionic Solutions

• Solubility affected by:

– Energy of attraction (due Ion-dipole force) affects the solubility. Also
called hydration energy,
– Lattice energy (energy holding the ions together in the lattice.
Related
• to the charge on ions; larger charge means higher lattice energy.
• Inversely proportional to the size of the ion; large ions mean
smaller lattice energy.
• Solubility increases with increasing ion size, due to decreasing
lattice energy; Mg(OH)2(least soluble), Ca(OH)2, Sr(OH)2,
Ba(OH)2(most soluble) (lattice energy changes dominant).
• Energy of hydration increases with for smaller ions than bigger
ones; thus ion size. MgSO4(most soluble),... BaSO4 (least
soluble.) Hydration energy dominant. 8–9

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 Solubility: Temperature Dependence

• All solubilities are temperature dependent; must report temperatures

with solubilities.
• Most solids are more soluble at higher temperatures. Exceptions exist.

• All gases are less soluble at higher temperatures.

• Temperature related to sign of Hsoln;
– negative means less soluble at high temperatures
– positive means more soluble (Le Chatelier’s principle).
• E.g. Predict the temperature dependence of the solubility of Li2SO4,
Na2SO4 and K2SO4 if their Hsoln are 29.8 kJ/mol, 2.4 kJ/mol and
+23.8 kJ/mol, respectively.

8–10

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 Solubility: Pressure Dependence

• Pressure has little effect on the solubility of a

liquid or solid, but has dramatic effect on gas
solubility in a liquid.
• Henry’s law S = kHP. Allows us to predict the
solubility of a gas at any pressure.
E.g. At 25C P(O2 in air) = 0.21 atm. Its solubility in
water is 3.2x104M. Determine its solubility when
pressure of O2 = 1.00 atm.

8–11

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 Units of Concentration

• Physical properties of solutions are often

related to the concentration of the solute moles of solute
in the solution.Molarity Molarity 
liter of solution
• Mole fraction: The same quantity we
have used in fractional abundances as mol of A
X
well as with gases (Dalton’s law). A mol A  mol B
unitless number.
Weight (mass) Percent (wt%) – similar wt%  mass of solute x10 2
to mole fraction except use mass of each. mass of solution
• E.g. determine the wt% of a solution
prepared by dissolving 1.44 g of NaCl in
100.0 mL of water. Assume that the
density of water is 1.00 g/mL
• Other units: parts per million (ppm) and ppm  mass of solute x10 6
parts per billion (ppb) for small mass of solution
concentrations. mass of solute 8–12
ppb  x10 9
mass of solution

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 Units of Concentration2

• Molality(m): defined as the mol of solute per kg of

solvent. Unlike Molarity this unit is temperature
independent.
mol solute
Molality (m) 
mass of solvent (kg)

E.g. determine the molality of a solution prepared by dissolving

1.44 g NaCl into exactly 100.0 mL of water. Assume the
density of water is 1.00 g/mL.
E.g.2 Determine mass % of solution made from dissolving 30.0
g H2O2 with 70.0 g H2O.
E.g.3 Determine molality of 30% H2O2(aq)
E.g.4 Determine the mole fraction of the compound in E.g. 3
E.g.5 Concentrated ammonia is 14.8 M and has a density of 8–13
0.900 g/mL. What is the molar volume and the molality?

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 Physical Behavior of Solutions: Colligative
Properties

• Compared with the pure solvent the solution’s:

– Vapor pressure is lower
– Boiling point is elevated
– Freezing point is lower
– Osmosis occurs from solvent to solution when separated by
a membrane.

8–14

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 Vapor-Pressure Lowering of Solutions:
Raoult’s Law

• Raoult’s Law: Psoln = PsolvxXsolv

• Non–volatile solute: vapor pressure decreases upon addition
of solute.
• Linear for dilute solutions
• Vapor pressure lowering : P = Po  P = Po(1Xsolv)
E.g. Determine vapor pressure lowering when 5.00 g of sucrose
added to 100.0 g of H2O. FM(sucrose) = 342.3 g/mol. The
vapor pressure of water at 25°C is 23.8 mmHg.
E.g. 2 Determine the mass of sucrose dissolved in 100.0 g of
water if the vapor pressure was 20.0 mmHg.

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 Vapor-Pressure Lowering of Solutions: Volatile
Solute
• In ideal solutions each substance in the solution
obeys Raoult’s law. Thus,
• PA = XAP°o and Ptotal = PA + PB.
• Combining gives: .

Ptotal  X A PAo  X BPBo  X A PAo  (1  X A )PBo

 PBo  X A (PAo  PBo )

• Notice the equation predicts the linear variation in
total vapor pressure with variations in the mole
fraction of one of the components in the liquid phase.

E.g. Predict VP of ethylene (C 2H4Br2) and propylene

bromides (C3H6Br2) above solution that is 60.0 mass
% in C2H4Br2. Also, predict X of each in gas phase.
Given pressure pure C2H4Br2: P = 173 torr and of
pure C3H6Br2 is P = 127 torr.
• Determine:
– moles and then X of each (solution).
– VP of each above solution.
– Mole fraction in gas from ideal gas law.
• Fractional Distillation: differences between gas
and liquid phases leads to separation of complex 8–16
mixtures.

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 BP Elevation and FP Depression of Solutions

The magnitude of the change in FP and BP is directly proportional to the

concentration of the solute (molality) – expressed in terms of the total number
of particles in the solution.
• BP Elevation The magnitude of the BP increase is given by the equation:
Tb  K b  m

where Kb has units of °Ckg/mol or °C/m

• FP Depression: linear variation with composition and given by:
Tf  K f  m
where the units for this constant are the same as for Kb

E.g. Determine freezing point depression when 5.00 g of sucrose is added to

100.0 g of H2O. FM(sucrose) = 342.3 g/mol. Kf = 1.86°C/m.

E.g. Determine the BP elevation for the sucrose solution in the previous
example. Kb = 0.521 C/m. 8–17

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 Osmosis and Osmotic Pressure

Osmosis: the passage of solvent through a membrane from the less concentrated side
to the more concentrated side.
• Osmotic pressure: the amount of pressure necessary to stop Osmosis.
• Small molecules such as water can move through certain types of materials
(membranes).
• The tendency for this to occur is related to the molarity of the solution, is also a
function of the temperature and is measured with a device called a Thistle tube.
  MRT
where M = is molarity of solute particles
E.g. Determine osmotic pressure of a solution containing 0.100 g of hemoglobin
(molecular mass = 6.41x104 amu) in 0.0100 L at 1.00C.
E.g. Osmotic pressure of a solution containing 50.0 mg of a compound in 10.0 mL
of water was 4.80 torr at 5.00C. Determine FM of the compound.

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 Reverse Osmosis

• Application of a pressure to the

solution (that is equal to or greater
than the Osmotic pressure) and the
solvent flows from the more
concentrated side to the other one.
• This process is used to obtain pure
water from salt water.

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 Colligative Properties of Ionic Solutions

• Colligative properties of solutions depends upon the total

concentration of particles.
• Each equation describing colligative properties must be
modified to account for this with ionic solutions since each
ionic compound gives more than one mole of ions for every
mole of compound.
– BP elevation: Tb  K b  m  i
– Freezing point depression: Tf  K f  m  i
– Osmotic pressure:
  iMR  T
Where i = van’t Hoff factor.
• van’t Hoff factor can be something other than integer under
certain circumstances, but for completely ionic solutions is
equal to the number of ions/ionic compound to be found in
solution:
E.g. NaCl: i = 2; Na2SO4: i = 3; 8–20

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