Chapter 10

Properties of Solutions

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17.1 Solution Composition

17.2 The Thermodynamics of Solution Formation (skip)
17.3 Factors Affecting Solubility
17.4 The Vapor Pressures of Solutions
17.5 Boiling-Point Elevation and Freezing-Point Depression
17.6 Osmotic Pressure
17.7 Colligative Properties of Electrolyte Solutions
17.8 Colloids
GAS

Melting
Freezing

LIQUID

Colligative Properties of Solutions

For Colligative properties, the difference

between a pure solvent and dilute solution
depends only on the number of solute
particles present and not on their
chemical identity.
Examples

Vapor Pressure Depression

Boiling Point Elevation
Melting Point Depression
Osmotic Pressure

Lowering of Vapor Pressure

Vapor Pressure of a solvent above a dilute solution
is always less than the vapor pressure above the
pure solvent.
Elevation of Boiling Point
The boiling point of a solution of a non-volatile
solute in a volatile solvent always exceeds the
boiling point of a pure solvent
Boiling

liquid in equilibrium with its vapor at the external pressure.

Boiling Point

Vapor press = external pressure

Normal boiling point

Vap press. = 1 atm

Elevation of Boiling
Point & Vapor
Pressure Depression

T = K m
b solute
Tistheboilingpointelevation
Kbismolalboiling pointelevationconstant
m
isthemolalityofthesoluteinsolution
solute

Phase diagrams for pure water (red

lines)
and for an aqueous solution
containing a nonvolatile
solution (blue lines).

Solution Composition

The solute and solvent can be any

combination of solid (s), liquid (l), and
gaseous (g) phases.

Dissolution: Two (or more) substances mix at the level of

individual atoms, molecules, or ions.
Solution: A homogeneous mixture (mixed at level of atoms
molecules or ions
Solvent: The major component
Solute: The minor component

Solution Composition
Mass Fraction, Mole Fraction, Molality and
Molarity
Mass percentage (weight percentage):
mass percentage of the component =
mass of component
total mass of mixture

X 100%

Mole fraction: The amount of a given component (in moles)

divided by the total amount (in moles)

X1 = n1/(n1 + n2) for a two component system

X2 = n2/(n1 + n2) = 1 X1 or X1+X2=1

Molality
msolute =
moles solute per kilogram solvent
= moles per kg or (mol kg-1)

Molarity (biochemists pay attention)

csolute =
moles solute per volume solution
= moles per liter of solution (mol L-1)

Factors Affecting Solubility

1. Molecular Interactions
Review chapter 4
Polar molecules, water soluble, hydrophilic (water
loving)

E.g., Vitamins B and C; water-soluble

Non-polar molecules, soluble in non-polar

molecules, hydrophobic (water fearing)

E.g., Vitamins A, D, K and E; fat-soluble

Factors Affecting Solubility of Gases

1. Structure Effects
2. Pressure Effects

Henrys Law (for dilute solutions)

The mole fraction of volatile solute is proportional

to the vapor pressure of the solute.

P = kH X
kH = Henrys Law constant, X = mole fraction.
Increasing the partial pressure of a gas over a liquid
increases the amount of gas disolved in the liquid.
kH depends on temperature.

When the partial pressure of nitrogen over a sample of water at

19.4C is 9.20 atm, the concentration of nitrogen in the water is
5.76 x 10-3 mol L-1. Compute Henrys law constant for nitrogen in
water at this temperature.

Given
PN = 9.20atm
2

c N = [N 2 ] = 5.76x10 3 mol/L
2

Henry'sLaw
PN = k N X N
2

XN =
2

nN

nN + nH
2

2
2O

nN
nH

2O

When the partial pressure of nitrogen over a sample of water at

19.4C is 9.20 atm, then the concentration of nitrogen in the
water is 5.76 x 10-3 mol L-1. Compute Henrys law constant for
nitrogen in water at this temperature.

PN k N X N

Given
PN 9.20 atm

c N [N 2 ] 5.76x10 3 mol/l
2

Henry' s Law
PN k N X N
2

XN
2

nN

nN nH
2

O
2

nN
nH

rearrange
PN
Given
2
kN

XN
Find
2
2

O
2

Next assume 1 Liter

When the partial pressure of nitrogen over a sample

of water at 19.4C is 9.20 atm, then the
concentration of nitrogen in the water is 5.76 x 10-3
mol L-1. Compute Henrys law constant for nitrogen
PN
in water at this temperature.
Given
2
kN

XN

kN

nN
nH

2O

XN

Find

5.76x10 3 mol/l

1000g/l

18g/mol

1.0378 x 10 4
PN
Given
9.20 atm
2

XN
Find
1.0378x10 4
2

8.86 x 10 4 atm

Factors Affecting Solubility

1. Structure Effects
2. Pressure Effects
3. Temperature Effects for Aqueous Solutions
The solubility of some
solids as a function of
temperature.
The aqueous solubilities of most solids
increase with increasing temperature,
some decrease with temp.
Endothermic heat is absorbed by the
system (think evaporation of water, or
melting of ice)
Exothermic heat is evolved by the system
(think fire, or freezing of water).

Factors Affecting Solubility

1. Structure Effects
2. Pressure Effects
3. Temperature Effects for Aqueous Solutions
The solubility of some gases in
water as a function of
temperature at a constant
pressure of 1 atm.

The greatest gas solubility for a gas in

solution is predicted under what
conditions?
1)
2)
3)
4)
5)

low T, low P
low T, high P
high T, low P
high T, high P
solubility of gases does not depend
upon temperature

The greatest gas solubility for a gas in

solution is predicted under what
conditions?
1)
2)
3)
4)
5)

low T, low P
low T, high P
high T, low P
high T, high P
solubility of gases does not depend
upon temperature

According to Henry's Law, the solubility

of a gas in a liquid
1)
2)
3)
4)

depends on the polarity of the liquid

depends on the liquid's density
remains the same at all temperatures
increases as the gas pressure above the
solution increases

5)

decreases as the gas pressure above the

solution increases

According to Henry's Law, the solubility of a

gas in a liquid
1)
2)
3)
4)

depends on the polarity of the liquid

depends on the liquid's density
remains the same at all temperatures
increases as the gas pressure above
the solution increases

5)

decreases as the gas pressure above the

solution increases

The Person Behind the Science

Francois-Marie Raoult (1830-1901)

Highlights
1886 Raoult's law , the partial pressure
of a solvent vapor in equilibrium with a
solution is proportional to the ratio of the
number of solvent molecules to nonvolatile solute molecules.
allows molecular weights to be
determined, and provides the
explanation for freezing point depression
and boiling point elevation.

Moments in a Life

Psoln = XsolventPsolvent

Raoult was a prominent member of the

group which created physical chemistry,
including Arrhenius, Nernst, van t'Hoff,
Planck.

For ideal
solutions

Raoults Law, non-volatile solute

Consider a non-volatile solute (component 2)

dissolved in a volatile solvent (component 1).
X1 = the mole fraction of solvent
Raoults Law

P1=X1 P1
P1 = the vapor
pressure of pure
component 1

Raoults Law, volatile solute

Volatile solute (component 1)

Volatile solvent (component 2)

P1 = X1 P1
P2 = X2 P2
Ptot = P1+ P2

Vapor pressure for a solution of two volatile liquids.

Positive deviation
= solute-solvent attractions < solvent-solvent attractions
For non-ideal Solutions

Negative deviation
= solute-solvent attractions > solvent-solvent attractions

boilingpoint : T = K m
b solute
freezingpoint : T = K m
f solute

Osmotic Pressure

PV = nRT

Fourth Colligative Property

Important for transport of
molecules across cell
membranes, called
semipermeable membranes
Osmotic Pressure =
= M RT
V = n RT
Molarity (M) = moles/L or n/V

Osmotic Pressure
The normal flow of solvent into the solution
(osmosis) can be prevented by applying an
external pressure to the solution.
Osmotic Pressure useful for
Determining the Molar Mass of
protein and other macromolecules
small concentrations cause
large osmotic pressures
Can prevent transfer of all solute
particles
Dialysis at the wall of most
plant and animal cells

Dialysis: Representation of the functioning

of an artificial kidney
A cellophane (polymeric)
tube acts as the semipermeable membrane
Purifies blood by
washing impurities
(solutes) into the
dialyzing solution.

A dilute aqueous solution of a non-dissociating compound

contains 1.19 g of the compound per liter of solution and
has an osmotic pressure of 0.0288 atm at a temperature of
37C. Compute the molar mass of the compound.

Strategy
1)use = MRTtofindM(mol/L)
mass
2)Recallthat# ofmoles =
mwt
g
g
L
3)Rearrangemwt =
=
mole mole

1.19
=
M

A dilute aqueous solution of a non-dissociating

compound contains 1.19 g of the compound per liter
of solution and has an osmotic pressure of 0.0288 atm
at a temperature of 37C. Compute the molar mass of
the compound
Solution

RT

0.0288atm
c=
=
RT
(0.0820Latmmol1K 1 )(37 + 273.15K)

1)use = MRTorM =

M = 1.132x10 3 mol/L
g

2)RearrangeM =

M =

1.19 g L

g
L
=
mole
mole

1.132x10 3 mol/L

= 1.05x10 3 g/mol

The Person Behind the Science

J.H. vant Hoff (1852-1901)

Highlights
Discovery of the laws of chemical
dynamics and osmotic pressure in
solutions

Mathematical laws that closely

resemble the laws describing the
behavior of gases.
his work led to Arrhenius's theory of
electrolytic dissociation or
ionization
Studies in molecular structure laid
the foundation of stereochemistry.

Moments in a Life
1901 awarded first Noble Prize in
Chemistry

vant Hoff Factor (i)

moles of particles in solution

moles of solute dissolved

T = i m K

Colligative Properties of Electrolyte Solutions

Elevation of Boiling Point
Tb = m Kb
Where m = molality
(Molality is moles of solute per kilogram of solvent)

The Effect of Dissociation

Tb = i m Kb
i = the number of particles released into the
solution per formula unit of solute

e.g., NaCl dissociates into i = 2

e.g., Na2SO4 dissociates into i = 3
(2 Na+ + 1 SO4-2)
e.g., acetic acid (a weak acid and weak
electrolyte) does not dissociate i = 1

also
Depression of
Freezing Point

Tf = m Kf
Tf = i m Kf

Which aqueous solution would be expected to have

the highest boiling point?

1) 0.100 m NaCl
2) 0.100 m CaCl2
3) 0.080 m Fe(NO3)3
4) 0.080 m Fe(NO3)2
5) 0.080 m Co(SO4)

Which aqueous solution would be expected to have the

highest boiling point?

Tb = (2)(0.100) Kb = 0.200 Kb

1)

0.100 m NaCl

2)

0.100 m CaCl2

3)

0.080 m Fe(NO3)3 Tb = (4)(0.080) Kb = 0.320 Kb

4)

0.080 m Fe(NO3)2 Tb = (3)(0.080) Kb = 0.240 Kb

5)

0.080 m Co(SO4)

Tb = (3)(0.100) Kb = 0.300 Kb

Tb = (2)(0.080) Kb = 0.160 Kb

Elevation of Boiling Point

The Effect of Dissociation
Tb = i m Kb

Colloids: Colloidal Dispersions

Colloids are large particles dispersed in
solution
1nm to 1000 nm in size
E.g., Globular proteins 500 nm

Examples

Opal (water in solid SiO2)

Aerosols (liquids in Gas)
Smoke (solids in Air)
Milk (fat droplets & solids in water)
Mayonnaise (water droplets in oil)
Paint (solid pigments in liquid)
Biological fluids (proteins & fats in water)

Characteristics
Large particle size colloids: translucent, cloudy,
milky)
Small particle size colloids: can be clear

Colloidal Dispersions
Tyndall Effect
Light Scattering