Jeffrey Mack

California State University,

Sacramento
Chapter 14

Solutions and Their
Behavior
A solution is a homogeneous mixture of two or more
substances in a single phase.
By convention, the component present in largest amount is
identified as the solvent and the other component(s) as the
solute(s)
Solutions
Solutions can be classified as saturated or
unsaturated.
A saturated solution contains the maximum
quantity of solute that dissolves at that
temperature.
Solutions
An unsaturated solution can still take on more
solute at a given temperature.
SUPERSATURATED SOLUTIONS contain
more than is possible and are unstable.
Solutions
M =
moles solute
L of solution
Molarity (M)
Concentration Units
%

=
mass solute
Total mass of solution
Weight (mass) %
100
Concentration Units
% by mass =
x 100%
mass of solute
mass of solute + mass of solvent
X
i
=
moles solute (i)
Total moles in solution
Mole Fraction (X)
Concentration Units
Mole Fraction (X)
Where i is the moles of one component of the
solute.
Total moles are all species:
mols solute (i) + mols solvent.
The sum of all of the mole fractions for each
component are 1 exactly.
i
X 1 =

Concentration Units
Concentration Units
M =
moles of solute
liters of solution
m =
moles of solute
mass of solvent (kg)
Molarity (M)
Molality (m)
m =
mg solute
kg solution
Parts Per Million (ppm)
Concentration Units
Parts per million (ppm): grams of solute/grams
of solution (then multiplied by 10
6
or 1 million)
11
Molarity: moles of solute/liter of solution
Percent by mass: grams of solute/grams of solution (then multiplied
by 100%)
Percent by volume: milliliters of solute/milliliters of solution (then
multiplied by 100%)
Mass/volume percent: grams of solute/milliliters of solution (then
multiplied by 100%)
Most concentration
units are expressed
as:
Solution Concentration
Amount of solvent or
solution
Amount of solute
Problem:
62.1 g (1.00 mol) of ethylene glycol is dissolved in
250. g of water.
Calculate mol fraction, molality, and weight % of the
solution.
Calculating Concentrations
2 6 2
2 6 2 2 6 2
2
2 2
1 mol C H O
62.1 g C H O 1.00 mol C H O
62.1 g
1 mol H O
250. g H O 13.9 mol H O
18.02 g
=
=
Calculating Concentrations
Problem:
62.1 g (1.00 mol) of ethylene glycol is dissolved in
250. g of water.
Mole Fraction:
Problem:
62.1 g (1.00 mol) of ethylene glycol is dissolved in
250. g of water.
Mole Fraction:
2 6 2
2 6 2
2 6 2 2 6 2
2
2 2
C H O
1 mol C H O
62.1 g C H O 1.00 mol C H O
62.1 g
1 mol H O
250. g H O 13.9 mol H O
18.02 g
1.00 mol
X 0.0671
1.00 mol 13.9 mol
=
=
= =
+
Calculating Concentrations
2 6 2
2 6 2
2 6 2
C H O
2
3
1 mol C H O
62.1 g C H O
62.1 g
m 4.00 mol / kg
1 kg
250. g H O
10 g

= =

Problem:
62.1 g (1.00 mol) of ethylene glycol is dissolved in
250. g of water.
Molality:
Calculating Concentrations
( )
2 6 2
2 6 2
2 6 2 2
62.1 g C H O
% C H O 100 19.9%
62.1 g C H O 250. g H O
= =
+
Calculating Concentrations
Problem:
62.1 g (1.00 mol) of ethylene glycol is dissolved in
250. g of water.
Wt. %:
17
What is the molality of a 5.86 M ethanol (C
2
H
5
OH) solution whose density is
0.927 g/mL?
m =
moles of solute
mass of solvent (kg)
M =
moles of solute
liters of solution
Assume 1 L of solution:
5.86 moles ethanol = 270 g ethanol
927 g of solution (1000 mL x 0.927 g/mL)
mass of solvent = mass of solution mass of solute
= 927 g 270 g = 657 g = 0.657 kg
m =
moles of solute
mass of solvent (kg)
=
5.86 moles C
2
H
5
OH
0.657 kg solvent
= 8.92 m
Solutes dissolve in solvents by a process
called solvation.
Polar solvent dissolve polar solutes, non-
polar solvents dissolve non-polar solutes.
(aka: like dissolves like.
If two liquids mix to an appreciable extent to
form a solution, they are said to be miscible.
In contrast, immiscible liquids do not mix to
form a solution; they exist in contact with
each other as separate layers.
The Solution Process
The Solution Process
When a cation exists in solution, it is surrounded by
the negative dipole ends of water molecules.
When as anion exists in solution, it is surrounded by
the positive dipole ends of water molecules.
+
Solvation of Ions
Energy must be supplied to separate the ions from
their attractive forces. (an endothermic process)
A
lattice
H
Energetics of the Solution Process:
A
solution
H
Energetics of the Solution Process:
A
solution
H
Energy must be supplied to separate the ions from
their attractive forces. (an endothermic process)
A
lattice
H

Energy is evolved when the individual ions dissolve in
water where each ion is stabilized by solvation.
Energetics of the Solution Process:
A
solution
H
Energy must be supplied to separate the ions from
their attractive forces. (an endothermic process)
A
lattice
H

Energy is evolved when the individual ions dissolve in
water where each ion is stabilized by solvation.

This process, referred to as the Energy of Hydration
when water is the solvent, is strongly exothermic.

We can therefore represent the process of dissolving
KF in terms of these chemical equations:

Step 1: KF(s) K
+
(g) + F

(g) = A
lattice
H
Step 2: K
+
(g) + F

(g) K
+
(aq) +F

(aq) =A
hydration
H
Energetics of the Solution Process:
A
solution
H
The overall reaction is the sum of these two steps.
The enthalpy of the overall reaction, called the
enthalpy of solution (A
soln
H), is the sum of the two
enthalpies.

Overall:
KF(s) K
+
(aq) + F

(aq)

A
soln
H = A
lattice
H + A
hydration
H
Energetics of the Solution Process:
A
solution
H
Energetics of the Solution Process:
A
solution
H
If the enthalpy of
formation of the
solution is more
negative than that of
the solvent and
solute, the enthalpy
of solution is
negative.
The solution process
is exothermic!
Energetics of the Solution Process
One application of
a supersaturated
solution is the
sodium acetate
heat pack.
The enthalpy of
solution for sodium
acetate is
ENDOthermic.
Supersaturated Sodium Acetate
Sodium acetate has an ENDOthermic
heat of solution.
NaCH
3
CO
2
(s) + heat |
Na
+
(aq) + CH
3
CO
2
-
(aq)
Therefore, formation of solid sodium acetate from its
ions is EXOTHERMIC.
Na
+
(aq) + CH
3
CO
2
-
(aq) |
NaCH
3
CO
2
(s) + heat
Supersaturated Sodium Acetate
30
Temperature and Solubility
Solid solubility and temperature
solubility increases with
increasing temperature
solubility decreases with
increasing temperature
Gas solubility (mol/L)
S
g
=K
H
P
g
Factors Affecting: Solubility Pressure &
Temperature Henrys Law
32
Temperature and Solubility
O
2
gas solubility and temperature
solubility usually
decreases with
increasing temperature

Do you like your coke
hot or cold? Why?
33
Chemistry In Action: The Killer Lake
Lake Nyos, West Africa
8/21/86
CO
2
Cloud Released
1700 Casualties
Trigger?
earthquake
landslide
strong Winds
Relative to a pure solvent, a solution has:
Lower vapor pressure
Higher boiling point
Lower freezing point
A higher osmotic pressure
Example:
Pure water: b.p.=100C f.p.= 0C
1.00 m NaCl (aq) b.p.= 101C f.p. = -3.7 C
Colligative Properties
Upon adding a solute to a solvent, the properties of
the solvent are affected:
Vapor pressure decreases
Melting point decreases
Boiling point increases
Osmosis is possible (osmotic pressure)
Collectively these changes are called COLLIGATIVE
PROPERTIES.
They depend only on the NUMBER of solute particles
relative to solvent particles, not on the KIND of solute
particles.
Colligative properties
To understand colligative properties, one must
consider the LIQUID-VAPOR EQUILIBRIUM for a
solution.
Understanding Colligative
Properties
LIQUID-VAPOR EQUILIBRIUM
Understanding Colligative
Properties
Vapor pressure: pressure exerted by the
vapor when a liquid in a closed container is at
equilibrium with the vapor.
Vapor pressure of solution is decreased by
the presence of a solute.
More solute particles, lower vapor pressure of
solution.
Changes in Vapor Pressure:
Raoults Law
P
solution
= X
solvent
P
o

P
solution
= the vapor pressure of a mixture of solute
and solvent
P
o
= the vapor pressure of the pure solvent
X
solvent
= the mole fraction of the solvent.

The expression can also be written in the form:




A =
o
solvent solute
P X P
AP is the change to the vapor pressure of the pure solvent.
Raoults Law
40
P
A
= X
A
P
A

0
P
B
= X
B
P
B

0
P
T
= P
A
+ P
B

P
T
= X
A
P
A

0
+ X
B
P
B

0
Ideal Solution
Special case of 2 Liquids
41
P
T
is greater than
predicted by Raoultss law
P
T
is less than
predicted by Raoultss law
Force
A-B
Force
A-A
Force
B-B < &
Force
A-B
Force
A-A
Force
B-B > &
Vapor Pressure Lowering of
Benzene + non volatile solute
Problem:
Pure iodine (105 g) is dissolved in 325 g of CCl
4
at
65 C. Given that the vapor pressure of CCl
4
at this
temperature is 531 mm Hg, what is the vapor
pressure of the CCl
4
I
2
solution at 65 C? (Assume
that I
2
does not contribute to the vapor pressure.)
Raoults Law
2
2 2
4
4 4
1 mol I
105g I = 0.414 mol I
253.8 g
1mol CCl
325g CCl = 2.11 mol CCl
153.8 g

Raoults Law
Problem:
Pure iodine (105 g) is dissolved in 325 g of CCl
4
at
65 C. Given that the vapor pressure of CCl
4
at this
temperature is 531 mm Hg, what is the vapor
pressure of the CCl
4
I
2
solution at 65 C? (Assume
that I
2
does not contribute to the vapor pressure.)
4
4 4 4
2.11
0.836
2.11 0.414
0.836 531 444
CCl
CCl CCl CCl
mol
X
mol mol
P X P mm Hg mm Hg
= =
+
= = =
Raoults Law
Problem:
Pure iodine (105 g) is dissolved in 325 g of CCl
4
at
65 C. Given that the vapor pressure of CCl
4
at this
temperature is 531 mm Hg, what is the vapor
pressure of the CCl
4
I
2
solution at 65 C? (Assume
that I
2
does not contribute to the vapor pressure.)
The temperature of the normal boiling point of a
solution is increased by:

The temperature of the normal freezing point of a
solution is decreased by:

Where the Ks are the respective boiling and freezing
point constants and m
solute
is the molality of the
solution.
A =
b b solute
T K m
f f solute
T K m A =
Molecular Compounds
Boiling Point Elevation & Freezing
Point Depression
b b solute
T K m A =
f f solute
T K m A =
For boiling point elevation: K
b
> 0 (positive)
For freezing point depression: K
f
< 0 (negative)
Boiling Point Elevation & Freezing
Point Depression
Molecular Compounds
Boiling Point Elevation & Freezing
Point Depression
Boiling and Freezing point effects involving ions:
When solutions containing ions are involved, the total
concentration of solute particles must be considered.
The change in b.p. or f.p. is given by the equation:








solute
T K m i A =
Where m is the calculated molaity based on formula wt.
i = the number of ions (vant Hoff factor)
compound Type i
CH
3
OH molecular 1
NaCl strong electrolyte 2
Ba(NO
3
)
2
strong electrolyte 3
HNO
2
weak electrolyte 1 - 2
vant Hoff Factor
The Boiling Point of a Solution is
Higher Than That of a Pure Solvent
The freezing point of a solution is LOWER than
that of the pure solvent.
Pure water Water solution
Change in Freezing Point
Water with and without antifreeze

When a solution freezes, the solid phase is pure
water. The solution becomes more concentrated.
Lowering the Freezing Point
Problem:
If 52.5 g of LiF is dissolved in 306 g of water, what is
the expected freezing point of the solution? (Assume
the vant Hoff factor, i, for LiF is 2.)
Freezing Point Depression
solute
T K m i A =
2
3
1
52.5 LiF
25.94
6.61
1
306
10
LiF
mol LiF
g
g
m m
kg
g H O
g

= =

Freezing Point Depression

Problem:
If 52.5 g of LiF is dissolved in 306 g of water, what is
the expected freezing point of the solution? (Assume
the vant Hoff factor, i, for LiF is 2.)
1.86 C
6.61 m (2)
24.6 C
0 C ( 24.6 C) 24.6 C

A =
A =
= + =
fp
fp
fp
T
m
T
T
Freezing Point Depression
solute
T K m i A =
Problem:
If 52.5 g of LiF is dissolved in 306 g of water, what is
the expected freezing point of the solution? (Assume
the vant Hoff factor, i, for LiF is 2.)
Problem:
Benzyl acetate is one of the active components of oil of
jasmine. If 0.125 g of the compound is added to 25.0 g of
chloroform (CHCl
3
), the boiling point of the solution is 61.82
C. What is the molar mass of benzyl acetate?
Molar Mass By Boiling Point
Elevation
1. Solution: The molality of the solution can be found from the
freezing point depression.
2. Knowing molality and mass of solvent, one can find the
moles of solute.
3. Knowing mass and moles of solute, the molar mass of the
compound can be determined.
Molar Mass By Boiling Point
Elevation
Problem:
Benzyl acetate is one of the active components of oil of
jasmine. If 0.125 g of the compound is added to 25.0 g of
chloroform (CHCl
3
), the boiling point of the solution is 61.82
C. What is the molar mass of benzyl acetate?
f f solute
f
solute
f
T K m
T
m
K
A =
A
=
Molar Mass By Boiling Point
Elevation
Problem:
Benzyl acetate is one of the active components of oil of
jasmine. If 0.125 g of the compound is added to 25.0 g of
chloroform (CHCl
3
), the boiling point of the solution is 61.82
C. What is the molar mass of benzyl acetate?

61.82 C 61.70 C 0.12 C
0.12 C
0.033
3.63 C
A = =
A

= = =

bp
bp
benzyl acetate
bp
T
T
m m
K
m
Molar Mass By Boiling Point
Elevation
Problem:
Benzyl acetate is one of the active components of oil of
jasmine. If 0.125 g of the compound is added to 25.0 g of
chloroform (CHCl
3
), the boiling point of the solution is 61.82
C. What is the molar mass of benzyl acetate?
4
3
3
3
4
0.033 mol benzyl acetate 1 kg
25.0 g CHCl 8.3 10 mol
1 kg CHCl 10 g
0.125 g benzyl acetate
150 g/mol
8.3 10 mol benzyl acetate
=
=

Molar Mass By Boiling Point

Elevation
Problem:
Benzyl acetate is one of the active components of oil of
jasmine. If 0.125 g of the compound is added to 25.0 g of
chloroform (CHCl
3
), the boiling point of the solution is 61.82
C. What is the molar mass of benzyl acetate?
Dissolving the shell in vinegar Egg in corn syrup Egg in pure water
Osmosis
Solvent Solution
Semipermeable membrane
A semipermeable membrane allows only the
movement of solvent molecules.
Solvent molecules move from pure solvent to
solution in an attempt to make both have the
same concentration of solute.
Osmosis
Osmosis of solvent
from one solution to
another will occur as
they try to equalize
one anothers
concentration.
At the point where they
have equal osmotic
pressures, they are
said to be Isotonic.
Osmosis
Osmosis at the Particulate Level
Process of Osmosis
Equilibrium is reached when the
internal pressure of the apparatus
equals the external pressure of the
open tube.
Since the internal pressure, P
int
is
greater then the atmospheric
pressure, a column of liquid rises:
P
atm
+P
col
= P
int

Recall that:
P
col
= g d h
Osmotic Pressure, H
Osmotic
pressure
P
col
is referred to as the Osmotic Pressure,
.
= cRT
c = concentration of solute (mols/L)
T = the absolute temperature (K)
L atm
R 0.08206
mol K

H is in units of atm.
Osmotic Pressure, H
Osmosis & Living Cells
Water desalination plant
Reverse Osmosis: Water
Desalination
70
Colligative Properties of Nonelectrolyte Solutions
Colligative properties are properties that depend only on the number of solute
particles in solution and not on the nature of the solute particles.
Vapor-Pressure Lowering
P
1
= X
1
P
1

0
Boiling-Point Elevation AT
b
= K
b
m
Freezing-Point Depression AT
f
= K
f
m
Osmotic Pressure (t)
t = CRT
Boiling-Point Elevation AT
b
= i K
b
m
Freezing-Point Depression AT
f
= i K
f
m
Osmotic Pressure (t)
t = iCRT
Electrolyte Solutions
Colloids
In a solution, dispersed particles are molecules, atoms, or ions
(roughly 0.1 nm in size). Solute particles do not settle out of
solution.

In a suspension (e.g., sand in water) the dispersed particles
are relatively large, and will settle from suspension.

In a colloid, the dispersed particles are on the order of 1
1000 nm in size.

Although they are larger than molecules/atoms/ions, colloidal
particles are small enough to remain dispersed indefinitely.
A colloid is a dispersion of particles of one substance
throughout a dispersing medium of another substance.
Colloidal dispersions scatter light, a phenomenon
known as the The Tyndall effect
Colloids
A hydrophobic
colloid is stabilized
by positive ions
absorbed onto each
particle and a
secondary layer of
negative ions.
Because the
particles bear similar
charges, they repel
one another, and
precipitation is
prevented.
Hydrophobic Colloids
Soap molecules interact with water through the charged,
hydrophilic end of the molecule.
The long, hydrophobic end of the molecule binds through
dispersion forces with nonpolar hydrocarbons and other
non polar substances.
Soap
An emulsifier (also known as an emulgent) is a
substance which stabilizes an emulsion by increasing
its kinetic stability.
One class of emulsifiers is known as surface active
substances, or surfactants.
Examples of food emulsifiers are egg yolk (where the
main emulsifying agent is lecithin) and honey.
In some cases, particles can stabilize emulsions as well
through a mechanism called Pickering stabilization.
Both mayonnaise and Hollandaise sauce are oil-in-
water emulsions that are stabilized with egg yolk lecithin
or other types of food additives such as Sodium stearoyl
lactylate.
Emulsifiers & Surfactants