Objectives for Lecture #18 of 26

By the end of today, you will be able to:

• Explain the general idea of several colligative
properties
 13.4
Solubility of Gases in Liquids
Pressure strongly affects the solubility of gases in liquids

Low pressure: lower High pressure: higher

amount of dissolved gas amount of dissolved gas

Henry’s law: equilibrium concentration of a gas in a liquid

is directly proportional to the partial pressure of this gas
C [mol L-1] = kH [mol L-1 atm-1]  P [atm]
kH = Henry’s constant
2
 13.4
Solubility of Gases in Liquids
Gases are more soluble in liquids at lower temperatures

Killer Lake (Lake Nyos, West Africa)

In 8/21/1986 a giant CO2 bubble was released by
the lake (from supersaturation at the colder
bottom) causing 1700 casualties
3
 13.4
Solubility of Gases in Liquids
A 375 mL soft drink in a can at 25 oC contains CO2 gas at a pressure
of 5.0 atm. What is the concentration of CO2 before and (a long time)
after opening the can? How much CO2 will be released?

Atmospheric partial pressure of CO2, 4.0  10-4 atm

Henry’s law constant for CO2, kH = 3.1  10-2 mol/(Latm)

Before opening: C = kH  P = 3.1  10-2 mol/(Latm)  5.0 atm

= 0.16 mol/L (M)

After opening: C = kH  P = 3.1  10-2 mol/(Latm)  4.0 x 10-4 atm

= 1.2  10-5 mol/L

massCO2 = (0.16 mol/L – 1.2  10-5 mol/L)  0.375 L  44.0 g/mol =

= 2.6 g 4
 13.6
Colligative Properties
Colligative properties are properties that depend only
on the total number of solute particles in solution and
not on the chemical nature of the solute particles.

0
Vapor-Pressure Lowering P1 = X1 P 1

Boiling-Point Elevation DTb = Kb m

Freezing-Point Depression DTf = Kf m

Osmotic Pressure (p) p = CRT

5
 13.6
Vapor Pressure Lowering
Nonvolatile solutes lower the vapor pressure of volatile
solvent molecules.

Example: saturated solution of NaCl lowers the vapor

pressure of H2O above it by 25%! 6
 13.6
Vapor Pressure Lowering
The vapor pressure increases with
the mole fraction of the solvent

Psoln = Xsolvent P0solvent Raoult’s law

observed mole fraction vapor pressure of

pressure solvent pure solvent

Because Xsolvent = (1 – Xsolute) we can write,

Psoln = (1 – Xsolute)P0solvent

Psoln = P0solvent – Xsolute P0solvent

Psoln – P0solvent = DP = –Xsolute P0solvent

The decrease in pressure is directly proportional to the

mole fraction of solute(s) if Raoult’s law is obeyed 7
 13.6
Vapor Pressure Lowering
Calculate the vapor pressure of a 100 g/L solution of sorbitol (C6H14O6,
182.17 g/mol) in water at 37 °C. The density of the solution is 1.04 g/mL.
The vapor pressure of water at 37 °C is 47.1 mmHg. What is the vapor-
pressure lowering?
The pressure is found by using Raoult’s law: P1 = X1P10
Assume 1 L of solution, and so it has 100 g dissolved sorbitol, and therefore,
masssolvent = masssolution – masssolute = (1000 mL  1.04 g/mL) – 100 g = 940 g
mass of water 940 g
n1 = = = 51.65 mol H2O
molar mass 18.02 g/mol
mass of sorbitol 100 g
n2 = = = 0.549 mol C6H14O6
molar mass 182.17 g/mol
n1 51.65 mol
X1 = X1 = = 0.989
n1 + n 2 51.65 + 0.549 mol
8
P1 = 0.989 x 47.1 mmHg = 46.6 mmHg
Pressure lowering is 0.5 mmHg
 13.6
Ideal Mixture of Volatile Liquids
A modified form of Raoult’s law applies in case of
both solvent and solute are volatile:

A = toluene
Ideal Mixture
B = benzene
T = total

PA = XA P A0
PB = XB P B0
PT = PA + PB
PT = XA P A0 + XB P 0B
9
 13.6
Sample Problem
What is the total vapor pressure at 25 °C of a mixture of equal masses of benzene
and toluene? The vapor pressures of pure benzene (MW: 78.112 g·mol-1) and pure
toluene (MW: 92.139 g·mol-1) are 94.6 Torr and 29.1 Torr, respectively.

We need to solve for P = Pbenzene + Ptoluene , and for this we need to find
Pbenzene and Ptoluene , using Raoult's law.

For equal masses, we can choose 1.00 g each of 78.112 g·mol-1 C6H6
(benzene) and 92.139 g·mol-1 C6H5CH3 (toluene). Let us calculate the
corresponding molar amounts:

1.00 g
nbenzene = = 0.0128mol of benzene
78.112 g / mol
1.00 g
ntoluene = = 0.0109mol of toluene
92.139 g / mol
10
 13.6
And then calculate the molar fractions in the liquid:

nbenzene 0.0128 X toluene = 1 − X benzene = 0.460

X benzene = = = 0.540
nbenzene + ntoluene 0.0128 + 0.0109

Now, we will apply the Raoult's law to each of the components:

Pbenzene = X benzene  Ppure benzene = 0.540  94.6Torr = 51.1Torr

Ptoluene = X toluene  Ppure toluene = 0.460  29.1Torr = 13.4Torr

Finally, we can calculate the total pressure above the solution as the
sum of the partial pressures

Ptotal = Pbenzene + Ptoluene = 51.1Torr + 13.4Torr = 64.5Torr

11
 13.6
Deviations from Raoult’s Law
PT is greater than PT is less than
predicted by Raoult’s law predicted by Raoult’s law in
in a mixture of A and B: a mixture of A and B:

Force Force Force Force Force Force

A-B
< A-A & B-B A-B
> A-A & B-B
12
 13.6
Sample Problem
The liquids ethanol and hexane are mixed. Predict which
diagram reflects the vapor pressure of the solution.

Interactions among ethanol–hexane are weaker than

interactions among ethanol–ethanol and hexane–hexane 13
 FYI: Fractional Distillation
Vapor is enriched with the Repeated evaporation–condensation
lower-volatility compound separates the lower volatility compound

BLUE CURVE
– boiling point
of mixture vs
composition of
mixture

ORANGE
CURVE –
composition of
vapor that is in
equilibrium with
the mixture at
this boiling point

14
FYI: Fractional Distillation

15
 FYI: Fractional Distillation
Small scale distillation in Batch distillation
the lab (Wikipedia image) in a factory

Oil
distillation

16
 13.6
Freezing-Point Depression
DTf = T 0f – Tf
0
T f is the freezing point of
the pure solvent
Tf is the freezing point of
the solution

T 0f > Tf DTf > 0

DTf = Kf m
m is the molality of the solution
Kf is the molal freezing-point
depression constant (0C/m)
for a given solvent
17
 13.6
Boiling-Point Elevation
DTb = Tb – T b0
T b0 is the boiling point of
the pure solvent
T b is the boiling point of
the solution

Tb > T b0 DTb > 0

DTb = Kb m
m is the molality of the solution
Kb is the molal boiling-point
elevation constant (0C/m)
for a given solvent
18
 13.6
Sample Problem
Based on the data provided here, which solvent will have the
largest and the smallest change in the boiling point upon
dissolving 0.01 mol of solute in 1 kg of solvent? By how many C
will the boiling point change? Will it increase or decrease?

m = 0.01 mol/kg = 0.01 m… the change in temp is (0.01 x ki)

19
 13.6
Sample Problem
What is the freezing point of a solution containing 478 g of
ethylene glycol (antifreeze) in 3202 g of water? The molar mass
of ethylene glycol is 62.01 g/mol.

20
 13.6
Osmotic Pressure (p)
Osmosis is the selective passage of solvent molecules through a porous
membrane from a dilute solution to a more concentrated one.
A semipermeable membrane allows the passage of solvent molecules but
blocks the passage of (selected) solute molecules.
Osmotic pressure (p) is the pressure required to stop osmosis from
happening.

more H2O more

dilute concentrated

C is the molarity of the solution

p = CRT R is the gas constant
T is the temperature (in K) 21
 13.6
Reverse Osmosis

Reverse osmosis water treatment is one of the ways

water can be purified on a large scale. Pressure above the
osmotic pressure is applied to contaminated water and
pure water diffuses back through the membrane.
22
 13.6
Dialysis
Dialysis is used to remove waste products from blood

23
 Updates and Reminders
• Writing HW assignment is due this Sunday
• Midterm Exam #2 is Monday in one week
• It will be “harder” than Midterm Exam #1 so
please study a lot and come to office hours
and review sessions this week.
– Your success is dictated by how much you care,
and our combined Team efforts. Go Team!