Aqueous solubility of several salts as a function of temperature

The concentration of saturated solution is called solubility of the solute in the given
solvent. The solubility varies with temperature.

Solubilities can be expressed in

many ways: here it is given as
grams of solute per 100 g H2O.

For each solubility curve (as shown

here), points on the curve (S)
represent saturated solutions.

Regions above the curve (1)

correspond to supersaturated
solutions and below the curve (2),
to unsaturated solutions.
 13-5 Solubility of Gases
Effect of Temperature on the solubility

Most gases are less soluble in water as

temperature increases.
Solubilities of most gases in water decrease
with increasing temperature.
In organic solvents the reverse is often true.

Effect of temperature on the

solubilities of gases

In the figure: Dissolved air (as bubbles) is released as water is heated, even at
temperatures well below the boiling point.
 Effect of Pressure on the solubility
Pressure affects the solubility of a gas in a liquid much more than does temperature.
William Henry found that the solubility of a gas increases with increasing pressure.

C = k Pgas
Evaluation of the Henry’s law constant k,
For example, the aqueous solubility of N2(g) at 0o C and 1.00 atm is 23.54 mL N2 per liter.

C 23.54 mL
k= = = 23.54 mL N2/atm
Pgas 1.00 atm

If we want to increase the aqueous solubility of N2(g) to 100.0 mL N2 per liter, we must
increase the pressure above the solution.

C 100 mL
Pgas = = = 4.25 atm
k 23.54 mL N2/ 1.00 atm
 Rationale of effect of pressure on the solubility of a gas (Henry’s law)

In a saturated solution, the rate of evaporation of gas molecules from solution and the rate
of condensation of gas molecules into the solution is equal. Both rates depends on the
number of molecules per unit volume.

With increasing pressure on the system, the number of molecules in the gaseous state
increases (higher density of dots above the solution) and the number of molecules per
unit volume must also increase (darker blue color of the solution).

Henry’s law applies only to the equilibrium between molecules of a gas and the same
molecules in solution.
The unopened bottle of soda water is under a high pressure of CO2.

When a similar bottle is opened, the pressure quickly drops and some of the CO2
is released from solution (shown as bubbles).
 Physical behavior of solutions: Colligative properties
The behavior of solutions is qualitatively similar to pure solvent but it is
quantitatively different.

Pure water freezes at 0.0 oC and boils at 100.0 oC.

A 1.00 molal solution of NaCl in water freezes at -3.7 oC boils at 101.0 oC.

The higher boiling point and lower freezing point observed for a solution
compared to a pure solvent are examples of colligative properties – properties
that depends on the amount of dissolved solute but not its chemical identity.
 13-6 Vapor Pressures of Solutions
Raoult, 1880s, found that a dissolved solute lowers vapor pressure of solvent.
The partial pressure exerted by solvent vapor above an ideal solution is
the mole fraction of solvent (csolv ) * the vapor pressure of the pure solvent ( Psolv )

Psoln = csolv * Psolv

Take a solution of 1.00 mol glucose in 15.0 mol of water. The vapor pressure of pure
water is 23.76 mmHg at 25 oC.

Psolution = (15.0 / 1.00 + 15.0 ) * 23.76 mmHg = 22.3 mmHg

DPsoln = 23.76 mmHg - 22.3. mmHg = 1.5 mmHg, vapor pressure lowering

Take a solution of 1.00 mol NaCl (ionic substance) in 15.0 mol of water.

Psolution = (15.0 / 1.00 Na+ + 1.00 Cl- + 15.0 ) * 23.76 mmHg = 21.0 mmHg

DPsoln = 23.76 mmHg - 21.0 mmHg = 2.8 mmHg, vapor pressure lowering
Liquid-Vapor Equilibrium: Ideal Solutions
Liquid-vapor equilibrium for benzene-toluene mixtures at 25°C

The red line shows how the vapor

Psoln = csolv * Psolv pressure of benzene varies with the
solution composition. Because benzene
in benzene–toluene solutions obeys
Raoult’s law, the red line has the
equation Pbenz = xbenzPbenz°.

The blue line shows how the vapor

pressure of toluene varies with
solution composition and indicates that
toluene also obeys Raoult’s law.

The dashed black line shows how the

total vapor pressure varies with the
solution composition.

The line joining points 3 (xbenz: 0.50 in

solution) and 4 (xbenz: 0.77 in vapor)
is called a tie line.
 Fractional Distillation
Separating (purification) compounds from each other is an important task in chemistry. If
the compounds are volatile liquids, this separation is achieved by fractional distillation.
Instead of plotting vapor pressures as a function of the solution and vapor compositions,
let’s plot normal boiling temperature as a function of the solutions. the graph starts at a
high temperature —110.6°C, the boiling point of toluene—and ends at a lower temperature—
80.0°C, the boiling point of benzene.
Liquid-vapor equilibrium for benzene-toluene mixtures at 1 atm

At xbenz : 0.30, the benzene/toluene solution

boils at 98.6 oC and is in equilibrium with a vapor
0.51 in which xbenz : 0.51.

0.30 0.71 At this stage, extracting vapor and cooling the

solution to the point where it condenses to a
liquid, xbenz : 0.71.
 cooling
H2O

Fractional distillation is used in many

Fractional distillation industrial processes.