GENERAL CHEMISTRY

Solutions and Their

Physical Properties
LECTURE
15
Solutions and Their Physical
Properties

CONTENTS
15-1 Types of Solutions: Some
Terminology
15-2 Solution Concentration
15-3 Intermolecular Forces and
the Solution Process
15-4 Solubility of Gases
15-5 Vapor Pressures of
Solutions
15-6 Osmotic Pressure
15-7 Freezing-Point Depression
and Boiling-Point Elevation
of Nonelectrolyte Solutions
15-8 Solutions of Electrolytes
15-1 Types of Solution: Some
Terminology
Solutions are homogeneous mixtures and are uniform
throughout.
Solvent
Determines the state of matter in which the solution
exists.
Is the largest component.
Solutes
Other solution components said to be dissolved in the
solution.
15-2 Solution Concentration
Mass Percent (m
solute
/m
solution
)
Volume Percent (v
solute
/v
solution
)
Mass/Volume percent (m
solute
/v
solution
)

Example: Isotonic saline is prepared by
dissolving 0.9 g of NaCl in 100 mL of water.
The solution is said to be:
0.9% NaCl (mass/volume)
- quantity of solute in a given amount of solvent (or
solution)
Mole Fraction and Mole Percent
_
i
=
Amount of component i (in moles)
Total amount of all components (in moles)
_
1
+ _
2
+ _
3
+ _
n
= 1
Mole % i = _
i
100%
_
1
=
n
1

n
1
+ n
2
+ n
3
+...
=
n
1

n
total

Molarity and Molality
Molarity (M) =
Amount of solute (in moles)
Volume of solution (in liters)
Molality (m) =
Amount of solute (in moles)
Mass of solvent (in kilograms)
SAMPLE PROBLEM 15.1 Calculating Molality
SOLUTION:
What is the molality of a solution prepared by dissolving 32.0 g
of CaCl
2
(MW = 110.98 amu) in 271 g of water?
molality =
= 0.288 mol CaCl
2

271 g H
2
O
0.288 mol CaCl
2

kg
10
3
g
x
= 1.06 m CaCl
2

32.0 g CaCl
2

mol CaCl
2

110.98 g CaCl
2

x
moles of CaCl
2
kg of water
molality =
SAMPLE PROBLEM 15.2 Calculating Molality
What mass of BaCl
2
(MW = 208.23 amu) is needed to prepare
250 mL of 0.680 m BaCl
2
aqueous solution? (Assume the density
of the solution is 1.00 g/mL)
Mole Fraction
A sample of rubbing alcohol contains 142 g of isopropyl alcohol,
C
3
H
7
OH (MW =60.09 amu) and 58.0 g of water (MW =18.02 amu).
What are the mole fractions of isopropyl alcohol and water in
rubbing alcohol?
mol isopropyl alcohol = 142 g x
mol
60.09 g
= 2.36 mol C
3
H
7
OH
mol water = 58.0 g x
mol
18.02 g
= 3.22 mol H
2
O
2.36 mol C
3
H
7
OH
2.36 mol C
3
H
7
OH + 3.22 mol H
2
O
3.22 mol H
2
O
2.36 mol C
3
H
7
OH + 3.22 mol H
2
O
_ C
3
H
7
OH =
SOLUTION:
= 0.423
_ H
2
O =
= 0.577
SAMPLE PROBLEM 15.3
Expressing a Solution Concentration in
Various Units
SOLUTION:
An ethanol-water solution is prepared by dissolving 10.00 mL of
ethanol, C
2
H
5
OH (d =0.789 g/mL) in a sufficient volume of water to
produce 100.0 mL solution with a density of 0.982 g/mL. What is the
concentration of the solution, expressed as (a) volume percent; (b)
mass percent , (c) mass/volume percent
(a) Volume percent ethanol
= 10.00% x 100 %
10.00 mL ethanol
100.0 mL soln
volume percent ethanol =
SAMPLE PROBLEM 15.4
An ethanol water solution is prepared by dissolving 10.00 mL of
ethanol, C
2
H
5
OH (d =0.789 g/mL) in a sufficient volume of water to
produce 100.0 mL solution with a density of 0.982 g/mL.
(b) Mass percent ethanol
= 7.89 g
10.0 mL ethanol x
0.789 g ethanol
1 mL ethanol
mass ethanol =
= 98.2 g
100.0 mL solution x
0.982 g ethanol
1 mL ethanol
mass solution =
= 8.03 %
x 100 %
0.789 g ethanol
0.982 g solution
mass % ethanol =
SOLUTION:
Expressing a Solution Concentration in
Various Units
SAMPLE PROBLEM 15.4
An ethanol water solution is prepared by dissolving 10.00 mL of
ethanol, C
2
H
5
OH (d =0.789 g/mL) in a sufficient volume of water to
produce 100.0 mL solution with a density of 0.982 g/mL.
(c) Mass/volume percent ethanol
= 7.89 g 10.0 mL ethanol x
0.789 g ethanol
1 mL ethanol
mass ethanol =
= 7.89 %
x 100 %
0.789 g ethanol
100 mL solution
mass/volume percent =
SOLUTION:
Expressing a Solution Concentration in
Various Units
SAMPLE PROBLEM 15.4
Converting Concentration Terms
SOLUTION:
Hydrogen peroxide is a powerful oxidizing agent used in concentrated
solution in rocket fuels and in dilute solution as a hair bleach. An
aqueous solution of H
2
O
2
is 30.0% by mass and has a density of 1.11
g/mL. Molar mass of H
2
O
2
is 34.02 amu. Calculate its:
(a) Molality (b) Mole fraction of H
2
O
2
(c) Molarity
(a) g of H
2
O = 100.0 g solution - 30.0 g H
2
O
2
= 70.0 g H
2
O
molality =
70.0 g H
2
O x
kg H
2
O
10
3
g
= 12.6 m H
2
O
2

30.0 g H
2
O
2
x
34.02 g H
2
O
2

mol H
2
O
2

moles of H
2
O
2
=
= 0.882 mol H
2
O
2
0.882 mol H
2
O
2
SAMPLE PROBLEM 15.5
Converting Concentration Terms
0.882 mol H
2
O
2

70.0 g H
2
O x
mol H
2
O
18.02 g H
2
O
= 3.88 mol H
2
O
0.882 mol H
2
O
2
+ 3.88 mol H
2
O
= 0.185 _ of H
2
O
2

(b) Mole fraction of H
2
O
2

Hydrogen peroxide is a powerful oxidizing agent used in concentrated
solution in rocket fuels and in dilute solution as a hair bleach. An
aqueous solution of H
2
O
2
is 30.0% by mass and has a density of 1.11
g/mL. Molar mass of H
2
O
2
is 34.02 amu. Calculate the:
30.0 g H
2
O
2
x
34.02 g H
2
O
2

mol H
2
O
2

moles of H
2
O
2
=
= 0.882 mol H
2
O
2
moles of H
2
O

=
SAMPLE PROBLEM 15.5
Converting Concentration Terms
100.0 g solution x
mL
1.11 g
= 90.1 mL solution
0.882 mol H
2
O
2

90.1 mL solution x
L
10
3
mL
= 9.79 M H
2
O
2

(c) Molarity
Hydrogen peroxide is a powerful oxidizing agent used in concentrated
solution in rocket fuels and in dilute solution as a hair bleach. An
aqueous solution of H
2
O
2
is 30.0% by mass and has a density of 1.11
g/mL. Molar mass of H
2
O
2
is 34.02 amu. Calculate the:
30.0 g H
2
O
2
x
34.02 g H
2
O
2

mol H
2
O
2

moles of H
2
O
2
=
= 0.882 mol H
2
O
2
molarity =
SAMPLE PROBLEM 15.5
Pure solvent separated solvent molecules AH
solvent
> 0
AH
soln
= AH
solute
+ AH
solvent
+ AH
mix

Pure solute separated solute molecules AH
solute
> 0
separated solute solution AH
mix
< 0
and solvent molecules
Pure solute + pure solvent solution AH
soln


(a)
(b)
(c)
15-3 Intermolecular Forces and the
Solution Process
Enthalpy diagram for solution formation
Magnitude of H
solute
,
H
solvent
, and H
mix
depends
on intermolecular forces.
Examples
Predict the AH
soln
of the following sets of
solutions
Acetone and CO
2
Methanol and water
Hexane and pentane

Concept Check
Explain why water and oil (a long chain
hydrocarbon) do not mix. In your explanation, be
sure to address how H plays a role.
The Energy Terms for Various Types of
Solutes and Solvents
AH
1
AH
2
AH
3
AH
soln
Outcome
Polar solute, polar
solvent
Large Large Large,
negative
Small Solution
forms
Nonpolar solute, polar
solvent
Small Large Small Large,
positive
No solution
forms
Nonpolar solute,
nonpolar solvent
Small Small Small Small Solution
forms
Polar solute, nonpolar
solvent
Large Small Small Large,
positive
No solution
forms
In General
Processes that require large amounts of energy tend
not to occur.
Overall, remember that like dissolves like.
(c) Ethanol. Diethyl ether can interact through dipole-dipole and
dispersion forces. Ethanol can provide both while water would like to
H bond.
(b) Water. Hexane has no dipoles to interact with the -OH groups in
ethylene glycol. Water can H bond to the ethylene glycol.
Predicting Relative Solubilities of Substances
SOLUTION:
Predict which solvent will dissolve more of the given solute:
(a) Sodium chloride in methanol (CH
3
OH) or in 1-propanol (CH
3
CH
2
CH
2
OH)
(b) Ethylene glycol (HOCH
2
CH
2
OH) in hexane (CH
3
CH
2
CH
2
CH
2
CH
2
CH
3
)
or in water.
(c) Diethyl ether (CH
3
CH
2
OCH
2
CH
3
) in water or in ethanol (CH
3
CH
2
OH)
(a) Methanol. NaCl is ionic and will form ion-dipoles with the -OH
groups of both methanol and 1-propanol. However, 1-propanol is
subject to the dispersion forces to a greater extent.
SAMPLE PROBLEM 15.6
15-4 Solution Formation and
Equilibrium
Formation of a saturated solution
solute (undissolved) solute (dissolved)
Equilibrium in a saturated solution
Supersaturated
Recrystallization of
KNO
3

Aqueous solubility of several
salts as a function of temperature
Unsaturated
Sodium acetate crystallizing from a
supersaturated solution.
Effect of Temperature on Solubility
( )
( ) ( )
kJ/mol 8 . 48 Br Li LiBr
- +
s
+ +
aq aq
( )
( ) ( ) aq aq
-
4
+
s
4
MnO K kJ/mol 6 . 43 KMnO + +
Upon dissolution, will the solution feel cold or warm?
What will happen to the solubility of LiBr if the
solution is warmed?
Upon dissolution, will the solution feel cold or warm?
What will happen to the solubility of KMnO
4
if the
solution is warmed?
Warm
Cold
Solubility decreases
Solubility increases
15-5 Solubility of Gases
Effect of temperature on
the solubilities of gases
Effect of Temperature
Most gases are less soluble
in water as temperature
increases.

Effect of Pressure
William Henry found that the solubility of a gas increases with
increasing pressure.
C = kP
gas

Effect of pressure on the solubility of a gas
15-6 Vapor Pressures of Solutions
Raoults Law
Dissolved solute lowers vapor pressure of solvent.
The effect of a solute on the vapor pressure of a solution.
15-6 Vapor Pressures of Solutions
solvent
P
solvent
= _
solvent

P
P
solvent
= partial pressure exerted by solvent vapor
above the ideal solution
_
solvent
= mole fraction of solvent in the solution
P
solvent
= vapor pressure of solvent at a given
temperature.
Using Raoults Law to Find the Vapor
Pressure Lowering
Calculate the vapor pressure at 25 C of a solution containing
165 g of the nonvolatile solute, glucose, C
6
H
12
O
6
(MW=180 amu)
in 685 g H
2
O. The vapor pressure of water at 25 C is 23.8 mmHg
SOLUTION:
165 g C
6
H
12
O
6
x
mol C
6
H
12
O
6

180 g C
6
H
12
O
6

= 0.917 mol C
3
H
8
O
3

685 g H
2
O x
mol H
2
O
18.02 g H
2
O
= 38.01 mol H
2
O
P =
38.01 mol H
2
O
38.01 mol H
2
O + 0.917 mol C
3
H
8
O
3


23.8 mmHg x = 23.24 mmHg
P
solvent
= X
solvent
x P
o
solvent

SAMPLE PROBLEM 15.7
For liquid-liquid solutions, where both
components are volatile:
P
total
= _
A

P
A
+ _
B

P
B

Calculating the vapor pressure of a
solution containing two liquids
A solution is prepared by mixing 5.81 g acetone (MW =58.1 amu)
and 11.9 g chloroform (Mw= 119.4 amu). At 35 C, the vapor
pressure of pure acetone and pure chloroform are 345 torr and
293 torr, respectively. Assuming it is an ideal solution, what is the
vapor pressure exerted by the solution at 35 C?
SAMPLE PROBLEM 15.8
Answer: P
Total
= 319 torr
Vapor-pressure lowering by a nonvolatile solute
15-7 Freezing-Point Depression
and Boiling Point Elevation of
Solutions
Vapor pressure is lowered when a solute is
present.
This results in boiling point elevation.
Freezing point is also effected and is lowered.

T
f
= K
f
m T
b
= K
b
m
T
f
= T
f,

solvent
T
f,

solution
15-7 Freezing-Point Depression
and Boiling Point Elevation of
Nonelectrolyte Solutions
T
b
= T
b, solution
T
b, solvent
m

= molality

K
f
and K
b
= constants that depends on the solvent

Practical Applications
Determining the Boiling Point Elevation and
Freezing Point Depression of a Solution
You add 1.00 kg of ethylene glycol (Mw of C
2
H
6
O
2
= 62.07 amu)
antifreeze to your car radiator, which contains 4450 g of water.
What are the boiling and freezing points of the solution?
SOLUTION:
1.00 x 10
3
g C
2
H
6
O
2
x
mol C
2
H
6
O
2

62.07 g C
2
H
6
O
2

= 16.1 mol C
2
H
6
O
2

AT
bp
= 0.512
o
C/m
16.1 mol C
2
H
6
O
2

4.450 kg H
2
O
= 3.62 m C
2
H
6
O
2

3.62 m x = 1.85
o
C bp = 100.00
o
C + 1.85
o
C = 101.85
o
C
fp = 0.00
o
C - 6.73
o
C = -6.73
o
C
AT
fp
=
1.86
o
C/m 3.62 m = 6.73
o
C x
T
f
= K
f
m T
b
= K
b
m
SAMPLE PROBLEM 15.9
A 37.0 g sample of a new covalent compound, a nonelectrolyte, was
dissolved in 2.00 x 10
2
g of water. The resulting solution froze at -
5.58
o
C. What is the molecular weight of the compound?
Determining the Boiling Point Elevation and
Freezing Point Depression of a Solution
m =
5.58 C
1.86 C/m
= 3.0 m
T
f

K
f

m =
T
f
= K
f
m
mol solute
kg solvent
=
3.0 m X 0.2 kg Mol of compound =
= 0.60 mol
Molar mass =
37.0 g
0.600 mol
= 61.7 g/mol
SOLUTION:
SAMPLE PROBLEM 15.10

15-8 Osmotic Pressure
Osmotic Pressure
V = nRT
= RT
n
V
= MRT
= Osmotic pressure
M = Molarity of solution
R = Ideal gas law constant (0.0821 L-atm/mol-K)
T = Temperature in K
Determining Molar Mass from Osmotic
Pressure
Biochemists have discovered more than 400 mutant varieties of
hemoglobin, the blood protein that carries oxygen throughout the body.
A physician studying a variety associated with a fatal disease first finds its
molar mass. She dissolves 21.5 mg of the protein in water at 5.0
o
C to
make 1.50 mL of solution and measures an osmotic pressure of 3.61 torr.
What is the molar mass of this variety of hemoglobin?
SOLUTION:
M =
H
RT
=
3.61 torr x
atm
760 torr
(0.0821 Latm/molK)(273.15 K + 5.0)
= 2.08 x 10
-4
M
2.08 x 10
-4
mol
L
x 1.50 mL x
10
3
mL
L
= 3.12 x 10
-7
mol
21.5 mg x
g
10
3
mg
1
3.12 x 10
-7
mol
= 6.89 x 10
4
g/mol
x
SAMPLE PROBLEM 15.11
Colligative Properties
Vapor Pressure Lowering
P
solvent
= X
solvent
x P
o
solvent

P
total
= X
A
P
o
A
+ X
B
P
o
B

Boiling Point Elevation and Freezing Point Depression
AT
b
= K
b
m AT
f
= K
f
m
Osmotic Pressure
H = M R T
15-9 Solutions of Electrolytes
Svante Arrhenius
Nobel Prize 1903.
Ions form when electrolytes
dissolve in solution.
Explained anomalous colligative
properties.
T
f
= -K
f
m = -1.86C m
-1
0.0100 m = -0.0186C
Compare 0.0100 m aqueous urea to 0.0100 m NaCl (aq)
Freezing point depression for NaCl is -0.0361C.
Vant Hoff
T
f
= i K
f
m
i = = = 1.98
measured T
f

T
b
= i K
b
m
expected T
f

0.0361C
0.0186C
= i M RT
i = 1 (nonelectrolyte solute)
i = # of ions in solution (electrolyte solute in ideal solution)
Depicting a Solution to Find Its Colligative
Properties
A 0.952-g sample of magnesium chloride is dissolved in 100. g of water.
(b) Assuming the solution is ideal, what is its freezing point (at 1 atm)?
(a) Which scene depicts the solution best?
SOLUTION:
(a) MgCl
2
(s) Mg (aq) + 2Cl- (aq)
The correct depiction must be A with a ratio of 2 Cl
-
/ 1 Mg
2+
.
SAMPLE PROBLEM 15.12
(b)
molality (m) =
0.0100 mol MgCl
2

100. g x
10
3
g
1 kg
= 0.100 m MgCl
2

Assuming this is an IDEAL solution, the vant Hoff factor, i, should be 3.
AT
f
= i (K
f
m)
= 3(1.86
o
C/m x 0.100 m) = 0.558
o
C
T
f
= 0.000
o
C - 0.558
o
C = - 0.558
o
C
SOLUTION:
A 0.952-g sample of magnesium chloride is dissolved in 100. g of water.
(b) Assuming the solution is ideal, what is its freezing point (at 1 atm)?
AT
f
= i (K
f
m)
Depicting a Solution to Find Its Colligative
Properties
SAMPLE PROBLEM 15.12
Additional Exercises
1. Which has a higher concentration of lithium cations, 0.05 M
Lithium phosphate or 0.07 M lithium sulfate? (2 pts)
2. Identify which of the following vitamins are water soluble
and fat soluble. (2 pts)



3. Calculate the molality and the molarity of an aqueous solution
that is 10.0% (m/m) glucose, C
6
H
12
O
6
. The density of the
solution is 1.04 g/mL. 1 mol C
6
H
12
O
6
= 180 g (8pts)


1. Which has a higher concentration of lithium cations,
0.05 M lithium phosphate or 0.07 M lithium sulfate?
* 0.05 M Li
3
PO
4
(2 pts)

Li
3
PO
4
(s) 3Li
+
(aq) + PO
4
3-
(aq)

0.05 M

Li
2
SO
4
(s) 2Li
+
(aq) + SO
4
2-
(aq)

0.07M

Answer
3(0.05M) 0.05M
2(0.07M) 0.07M
2. Identify which of the following vitamins are water
soluble and fat soluble. (2 pts)

Water soluble Vitamin C
Fat Soluble- Vitamin A and D




3. Calculate the molality and the molarity of an aqueous
solution that is 10.0% glucose, C
6
H
12
O
6
. The density of the
solution is 1.04 g/mL. (1 mol C
6
H
12
O
6
= 180 g)
. molality in ion concentrat the is This
O H C 617 . 0
O H C g 180
O H C mol 1
O H kg 1
O H g 1000
O H g 90.0
O H C g 0 . 10
O H kg
O H C mol
6 12 6
6 12 6
6 12 6
2
2
2
6 12 6
2
6 12 6
m
m
=
=
=
3. Calculate the molality and the molarity of an aqueous
solution that is 10.0% glucose, C
6
H
12
O
6
. The density of
the solution is 1.04 g/mL. (1 mol C
6
H
12
O
6
= 180 g)
12 6
6 12 6
6 12 6 6 12 6
6 12 6
H C 578 . 0
O H C g 180
O H C mol 1
L 1
mL 1000
n sol' mL
n sol' g 04 . 1
n sol' g 100.0
O H C g 0 . 10
n sol' L
O H C mol
M
M
=
=
=