Chapter 3

Solutions
Solutions are homogeneous mixtures of two or more substances.
Dissolving medium is called the solvent.
Dissolved species are called the solute.
Concentration and solubility
Ways of Expressing Concentration
Solution Concentration:
The amount of solute dissolved in a given amount of solvent or
dissolved in a given amount of solution is called the concentration of
the solution. Dilute solutions have relatively low concentrations;
concentrated solutions have relatively high concentrations. A
solution that contains as much solute as can be dissolved is called a
saturated solution; solutions with lower concentration are called
unsaturated solutions.
Methods for expressing the solution concentration:-
a) Weight to weight expression.
b) Weight to volume expression.
a) Weight to weight expression;
1) Weight percent (wt%)
Weight percent is defined as: Number of grams of solute
which present in 100 gram of solution.
weight of solute
mass% x 100
total weight of solution
weight of solute
weight fraction
N.B total weight of solution
e.g. 10% by weight glucose means:
10 gm glucose + 90 gm H2O = 100 gm solution.
 % Solute = (10/100) x 100 = 10 %.
% Solvent = (90/100) x 100 = 90 %

2) Mole fraction (X):

The ratio of the number of moles of one component to the total number of
moles of all components in the mixture solution
Mole fraction is essentially self-defined. In equation form the mole
fraction (usually symbolized by X) is

3) Molality
Molality is similar to but not the same as molarity. Molality, m, is
defined by,

( )

N.B
W solution = W solute + W solvent
W solvent = W solution - W solute
W solvent =dV solution - W solute
Where d = density of the solution
V = Volume of the solution
Example 1: What is the molality of 12.5 % solution of glucose
C6H12O6, in water? M.wt. of glucose is 180.0

Solution: 1) in 12.5 % solution 12.5 gm C6H12O6 is dissolved in l00

gm solution.
W solvent = 100 - 12.5 = 87.5 g H2O
2) no. of moles glucose = 12.5/180
Physical Chemistry First Year First semester Page 31
Example 2: What are the mole fractions of solute and solvent in a
1.0m aqueous solution?

Solution: The molecular weight of H2O is 18.0 we find the number of

moles of water in 1000 gm of H2O.
1000
no of moles of H2O 55.6 mol H2O
18
A 1.0 m aqueous solution contains
n solute =1.0 mol
n H2O 55.6

n total 56.6
The mole fractions are
n solute 1.0 mol
X solute 0.018
n total 56.6 mol
n H2O 55.6
X water = 0.982
n total 56.6
b) Weight to volume expression:
Molarity (M):
h d d ion.

/ w /V

(Molarity is mol of solute per Liter of solution, not per liter of solvent.
Molarity is defined so that we can always know how many mols of
solute there are in any given amount of solution.)
In dilute aqueous solution the molarity and molality are about the
same. However, in concentrated water solutions and in solutions

Physical Chemistry First Year First semester Page 32

where the solvent is not water the molarity and molality are very
different.

Example 3: a) How many grams of concentrated nitric acid solution

should be used to prepare 250 ml of 2.0M HNO 3? The
concentrated acid is 70.0 %
b) If the density of the concentrated nitric acid solution
is 1.42 g/ml. What volume should be used? M.wt.
(HNO3) =63
Solution: a) 70 gm HNO3 l00 gm solution
W 1000 W 1000
M x 2 x
M.Wt 250 63 250
2 x 63 x 250
Mass of pure HNO3
1000
31.5 x 100
mass of HNO3 solution = 45.0 gm
70
b) ml cone. NHO3 = (45/1.42) = 31.7 ml cone. HNO3

Example 4: An aqueous solution of acetic acid was prepared by

dissolving 164.2 gm of acetic acid in 800 ml of the solution. If the
density of the solution was 1.026 gm/ml. M. wt of acetic acid = 60
Calculate:
a) The molar concentration of the solution
b) The molality
c) The mole fraction of both the solute and the solvent
d) The mole % e) The weight %.

Solution:
W 1000 164.2 x 1000
M x 3.4
a) M.Wt solute Vml 60 x 800
b) d = 1.026g/ml V = 800 ml
W solution = V x d = 800 x 1.026 = 820.8 gm
W slvent = 820.8 - 164.2 = 656.6 gm

Physical Chemistry First Year First semester Page 33

 mass 1000 164.2 x 1000
m (Solute) x 4.17 m
M.Wt W(Solvent) 60 x 656.6
c) no. of acetic acid moles = 164.2 / 60 = 2.737 mole
no. of H2O moles = 656.6 / 18 = 36.44 mole
2.737
Mole fraction of acetic acid = 0.0699
2.737 36.44
36.44
Mole fraction of H2O = 0.9299
2.737 36.44
d) mole % acetic acid = 0.0699 x 100 = 6.99 %
mole % of H2O = 0.9299 x 100 = 92.99 %
164.2 x 100
e) percentage weight of acetic acid = 20 %
820.8
656.6 x 100
percentage weight of H2O= 80 %
820.8

Principles of Solubility
Factors Affecting Solubility
The extent to which a solute dissolves in solvent depends
1. The nature of the solute.
2. The nature of the solvent.
3. The temperature.
4. The pressure (for gases).

In this section we will consider in turn the effect of each of these factors
upon solubility.

I. Solute-Solvent Interactions:
1. Intermolecular forces are an important factor in determining
solubility of a solute in a solvent. The stronger the attraction
between solute and solvent molecules, the greater the
solubility. For example, polar liquids tend to dissolve in polar
solvents. Favorable dipole-dipole interactions exist (solute-
solute, solvent-solvent, and solute-solvent).

Physical Chemistry First Year First semester Page 34

 2. Pairs of liquids that mix in any proportions are said to be
miscible. Example: Ethanol and water are miscible liquids. In
contrast, immiscible liquids do not mix significantly. Example:
Gasoline and water are immiscible.
3. Consider the solubility of alcohols in water. Water and ethanol
are miscible because the broken hydrogen bonds in both pure
liquids are re-established in the mixture. However, not all
alcohols are miscible with water. Why? The number of
carbon atoms in a chain affects solubility. The greater the
number of carbons in the chain, the more the molecule
behaves like a hydrocarbon. Thus, the more C atoms in the
alcohol, the lower its solubility in water. Increasing the
number of OH groups within a molecule increases its
solubility in water. The greater the number of OH groups
along the chain, the more solute-water H-bonding is possible.
4. Generalization: Like dissolves like. Substances with
similar intermolecular attractive forces tend to be soluble in
one another. The more polar bonds in the molecule, the better
it dissolves in a polar solvent. The less polar the molecule the
less likely it is to dissolve in a polar solvent and the more likely
it is to dissolve in a nonpolar solvent..

Example: Most nonpolar substances have very small water

solubilities. Petroleum, a mixture of hydrocarbons, spreads out in a thin
film on the surface of a body of water rather than dissolving. The mole
fraction of pentane, C5H12 in a saturated water solution is only
0.00003. Few organic compounds that dissolve readily in water, most
contain - OH groups. Three familiar examples are methyl alcohol,
ethyl alcohol, and ethylene glycol, all of which are soluble in water in
all proportions.

Physical Chemistry First Year First semester Page 35

 H H H H H

H C OH H C C OH H C C H

H H H OH OH

methyl alcohol ethyl alcohol ethylene glycol

II. Solubility and Temperatune

As temperature increases, solubility of solids generally
increases. Sometimes solubility decreases as temperature
increases (e.g., Ce2(SO4)3).
Gases are less soluble at higher temperatures. An
environmental application of this is thermal pollution.
Since solubility is an equilibrium concentration, we can apply Le
Chateher"s principle in order to find out what happens when the
temperature of a saturated solution is changed. It is important to
know whether the dissolving process is

exothermic
+ +h
endothermic
+ +h

The heat of solution is defined as H for the dissolving process, and so is

equal to H solution - (H solute + H solvent). Therefore, for the exothermic case, H
solution is negative, and for the endothermic, positive.
Consider now a saturated aqueous solution of potassium iodide with excess
KI(s) present. For KI, H solution = 21 kJ mol -1, so we know that KI dissolves
in water with the absorption of heat and can write the saturation equilibrium
equation as
21 kJ + KI(s) K+ + I-

Physical Chemistry First Year First semester Page 36

If we raise the temperature
of the saturated KI solution,
we predict according to Le
Chatelier's principle that the
above equilibrium will shift to
the right (1) using up some of
the added heat (and some
of the excess solid KI) and
(2) increasing the
concentration of K and I-
+

ions in solution. After

equilibrium has been
reestablished at a higher
temperature, the
concentration of dissolved KI
has become higher, that is,
the solubility of KI increases with increasing temperature.
An example of an exothermic process is the dissolving of lithium
iodide (Lil) in water for which H solution 71 kJ mol-1. We can write the
saturation equilibrium equation as
LiI (s) Li+ + I- + 71 KJ

If we raise the temperature of a

saturated solution of LiI, the
equilibrium shifts to the left (1)
using up some of the added
heat (and I- and Li+ ions in
solution) and , (2) forming more
solid Lil. (We observe the
precipitation of some Lil out of
solution.)

After equilibrium has been

reestablished at a higher
temperature, the concentration of
Physical Chemistry First Year First semester Page 37
dissolved Lil is lower, so we can say that the solubility of lithium iodide
decreases with an increase in temperature. Dissolving solids or liquids in
liquids can be either positive or negative. For aqueous solutions it is
more frequently positive; so the majority of substances have solubilities
which increase with temperature. (This should not be used as a rule,
however; there are too many exceptions.)
When gases dissolve in liquids, H is usually negative; that is, heat is
liberated. (The solvation energy usually exceeds the energy necessary
to separate the molecules in the liquid.)Thus in the majority of cases the
solubility of gas decreases with temperature. This nearly always is true in
water. Boiled water, for example, tastes "flat," in part because dissolved
air (and chlorine) is less soluble at the boiling point and is removed from the
water.

III. Effect of Pressure on Solubility (solubility of gas in liquid)

Pressure changes have little or no effect on solubility of liquids and
solids in liquids.
Liquids and solids are not compressible.
Pressure changes have large effects on the solubility of gases in
liquids.
Sudden pressure change is why carbonated drinks fizz when
opened.
Solubility of a gas in a liquid is a function of the pressure of the gas.
The higher the pressure, the greater the solubility.

Henrys Law The solubility of a gas increases in direct

proportion to its partial pressure above the solution.

Cg kPg
Cg - solubility of gas
Pg - the partial pressure of the gas
k-H w

Physical Chemistry First Year First semester Page 38

An application of Henry's law: preparation of carbonated soda.
Carbonated beverages are bottled under PCO2> 1 atm. As the
bottle is opened, PCO2 decreases and the solubility of CO2
decreases. Therefore, bubbles of CO2 escape from solution.

Problem: At 740 torr and 20C, nitrogen has solubility in H2O of 0.018
g /I. At 620 torr and 20C its solubility is 0.015 g/l.
Do these data show that nitrogen obey Henry's law or not?

Example 5: At 25C oxygen gas collected over water at a total

pressure of 101 kPa is soluble to the extent of
0.0393 g dm-3. What would its solubility be if its
partial pressure over water were 107 kPa? The
vapor pressure of water is 3.0 kPa at 25C.

Solution: P total = PH2O + PO2

PO2 = P total - PH2O = 101-3 = 98 kPa

Physical Chemistry First Year First semester Page 39

Solution of liquids in liquids

1- Completely miscible liquids

2- Completely immiscible liquids H2O and aniline, H2O and
chlorobenzene
3- Partially immiscible liquids, H2O and phenol, H2O and ether

Completely miscible liquids of binary solution

a) Ideal solution
b) Non - ideal solution

a) Ideal Solution:-
e.g: (n - heptane / n - hexane) (chlorobenzene / brombenzene)

1) The force of attraction between all molecules are identical i.e.

the attraction force is not affected by addition of other
components A - A = B-B = A - B.
2) h d b b dd H
Zero
3) The volume of solution is the sum of volumes of the two liquids.
4) The solution obeys
RaouLt's law.

At constant temperature
the partial vapor pressure
of liquid component in
ideal solution is
proportional to the mole
fraction of this constituent
in solution (Figure 1).

Physical Chemistry First Year First semester Page 40

 At constant T

Where and = vapor pressure of pure liquids A and B

PA and PB = partial vapor pressure of liquids A and B in solution.
PA = (1) PB = (2)
Pt = PA + PB Pt = + (3)
nA nB
Where XA = mole fraction of A = XB = mole fraction of B=
nt nt
XA + XB = 1 XA = 1 XB
By substituting in (1)
Pt = + ( ) (4)
Or Pt = ( - ) (5)
N.B Composition of solution % XA and % XB.
% A= XA x 100 % B = XB x 100

Example 6: Heptane (C7H16) and octane (C8H18) form ideal solutions

What is the vapor pressure at 40C of a solution that
contains 3.0 mol of heptane and 5 mol of octane? At 40C,
the vapor pressure of heptane is 0.121 atm and the vapor
pressure of octane is 0.041 atm.
Solution: The total number of moles is 8.0. therefore
X heptane = 3.0/8.0 = 0.375
X octane = 5.0/8.0 = 0.625
Total = X heptane . Po heptane + X octane. Po octane
= 0.375 x 0.12 +0.625 x 0.04
= 0.045 atm + 0.026 atm.
= 0.071 atm.

Physical Chemistry First Year First semester Page 41

Example 7 : Assuming ideality, calculate the vapor pressure of 1.0
m solution of a non - volatile, on dissociating solute in
water at 50C. The vapor pressure of water 50C is 0.122
atm.

Solution : From example 2 the mole fraction of water in 1.0m

solution is 0.982.
PH2O = XH2O PH2O = 0.982 x 0.122 = 0.120 atm.

Example 8: A solution is prepared by mixing 5.81 g acetone C3H6O,

(M. wt = 58.1 g/mole) 11.9 g chloroform (CHCI3 M.wt
119.4 g/mole). At 35C this solution has a total vapor
pressure of 260 torr. Is this an ideal solution? Comment?
The vapor pressure of pure acetone and pure CHCI3 at
35C are 345 and 293 torr, respectively.

Solution: n acetone = W 5.81

0.1 mole
M.Wt 58.1

n CHCl3= 11.9 0.1mole

119
nt = 0.1 + 0.1 = 0.2 mole

Xacetone = n acetone 0.1mol 0.5 XCHCl3 = 0.5

n total 0.2 mol

Pt = + = 345 x 0.5 + 293 x 0.5 = 319 torr.

The observed value = 260 torr

h h w h h d
h b d 6 h h d h
is a negative deviation from Roault's law.
a) In liquid region (apply Rault's law).
b) Non- ideal solutions (Solutions deviate from ideal behavior).

Physical Chemistry First Year First semester Page 42

 Negative deviation
1- The force of attraction
increase by mixing
A - A, B-B < A-B
2- The vapor pressure will be
lower than that given by Roault's
law
3- H solution :- Ve
(exothermic)
4- Temperature change when
solution is formed: increase
5- Example: Acetone-water
Positive deviation
The force of attraction
decrease by mixing A-A , B-B
> A-B
The vapor pressure will be
higher than that given by
Raoult's law.
H solution: + Ve
(endothermic)
Temperature change when
solution is formed: decrease.
Ethanol-hexane

Fig.2: Vapour pressure of non- Fig.3: Vapour pressure of

ideal solution (-ve deviation) non-ideal solution (+ve
deviation)

Colligative Properties of Solutions

(Solution of solid in liquids)

Colligative properties depend on number of solute particles.

Colligative properties do not depend on the kinds of particles
dissolved
There are four colligative properties to consider:
Vapor pressure lowering (Raoult's Law).

Physical Chemistry First Year First semester Page 43

 Boiling point elevation.
Freezing point depression.
Osmotic pressure.
Vapor pressure lowering is the key to all four of the colligative
properties.

1. Lowering of Vapor Pressure:

Addition of a nonvolatile solute to a solution lowers the vapor

pressure of the solution.
The effect is simply due to fewer solvent molecules at
h
The solute molecules occupy some of the spaces that
would normally be occupied by solvent.
R L w d h ideal solutions.
Ideal solution: one that obeys Raoult w
Real solutions show approximately ideal behavior when:
The solute concentration is low.
The solute and solvent have similarly sized molecules.
The solute and solvent have similar types of intermolecular
attractions.
R wb d w when the solvent-solvent and solute-
solute intermolecular forces are much greater or weaker than
solute-solvent intermolecular forces.
Raoults Law The equilibrium vapor pressure of the solvent
over the solution is directly proportional to the mole fraction of
the solvent in the solution
Psolvent X solventPsolvent
0

where Psolvent vapor pressureof solvent insolution

0
Psolvent vapor pressureof pure solvent
X solvent mole fraction of solvent insolution

Physical Chemistry First Year First semester Page 44

Lowering of vapor pressure, DPsolvent, is defined a

Psolvent Psolvent
0
Psolvent
Psolvent
0 0
- ( X solvent )(Psolvent )
(1 X solvent )Psolvent
0

Remember that the sum of the mole fractions must equal 1.

Thus Xsolvent + Xsolute = 1, which we can substitute into our
expression.

X solute 1 - X solvent
Psolvent X solute Psolvent
0

which is Raoult's Law

h h h w h w h h db
h h wh h R w

Examples 9
The vapor pressure of water is 17.5 torr at 20C. Imagine holding the
temperature constant while adding glucose, C6H12O6, to the water so
that the resulting solution has XH2O = 0.80 and XGlu = 0.20.
What is, the vapor pressure of water over the solution

PA X APA0 0.80 X17.5torr 14torr

Physical Chemistry First Year First semester Page 45

 2. Boiling point elevation

Addition of a nonvolatile solute to a solution raises the boiling point

of the solution above that of the pure solvent
h b h w d
described by Raoults law.
The amount that the temperature is elevated is determined by the
number of moles of solute dissolved in the solution.
Boiling point elevation relationship is

Tb K b m
where : Tb boilingpoint elevation
m molal concentration of solution
K b molalboilingpoint elevation constant
for the solvent
Example 10
What is the normal boiling point of a 2.50 m glucose, C6H12O6,
solution?
Tb K b m
Tb (0.512 0 C/m )( 2.50m )
Tb 1.280 C
BoilingPoint of the solution= 100.00 C + 1.280 C = 101.280 C

The addition of a nonvolatile solute lowers the vapor pressure of the

solution. At any given temperature, the vapor pressure of the
solution is lower than that of the pure liquid

Physical Chemistry First Year First semester Page 46

 The increase in boiling point relative to that of the pure solvent,
b, is directly proportional to the number of solute particles per
mole of solvent molecules.
Molality expresses the number of moles of solute per 1000 g of
solvent, which represents a fixed number of moles of solvent

Example 11
Automotive antifreeze consists of ethylene glycol, C2H6O2, a
nonvolatile nonelectrolyte. Calculate the boiling point of a 25.0 mass
percent solution of ethylene glycol in water.
Solution:
b +

( )( )( )

Tb = Kbm = (0.52o C/m)(5.38 m) = 2.8 oC

= 100.0 oC + 2.8 oC = 102.8 oC

Physical Chemistry First Year First semester Page 47

 3. Freezing Point Depression

Addition of a nonvolatile solute to a solution lowers the

freezing point of the solution relative to the pure solvent.
See previous table for a compilation of boiling point and
freezing point elevation constants.
Relationship for freezing point depression is:

Tf K f m
where : Tf freezing point depressionof solvent
m molal concentration of soltuion
K f freezing point depressionconstant for solvent

Notice the similarity of the two relationships for freezing point

depression and boiling point elevation.

Tf K f m vs.Tb K b m

Fundamentally, freezing point depression and boiling point

elevation are the same phenomenon.
The only differences are the size of the effect which is
reflected in the sizes of the constants, Kf & Kb.
This is easily seen on a phase diagram for a solution.

Example 12: Calculate the freezing point of a 2.50 m aqueous

glucose solution.
Tf K f m
Tf (1.860 C/m )(2.50m)
Tf 4.650 C
Freezing Point of solution = 0.000 C - 4.650 C = - 4.650 C

Physical Chemistry First Year First semester Page 48

 The size of the freezing point depression depends on two
things:
1. The size of the Kf for a given solvent, which are well
known.
2. And the molal concentration of the solution which depends
on the number of moles of solute and the kg of solvent.
If Kf and kg of solvent are known, as is often the case in an
experiment, then we can determine # of moles of solute and
use it to determine the molecular weight.

Example 13: A 37.0 g sample of a new covalent compound, a

nonelectrolyte, was dissolved in 2.00 x 102 g of water. The resulting
solution froze at -5.58oC. What is the molecular weight of the
compound?
Tf K f m thus the
Tf 5.58 0 C
m 3.00m
Kf 1.86 0 C
In this problem there are
200 mL 0.200 kg of water.
? mol compoundin 0.200 kg H2 O = 3.00 m 0.200 kg
0.600 mol compound
37 g
Thus the molar massis 61.7 g/mol
0.600 mol

Physical Chemistry First Year First semester Page 49

 4. Osmotic Pressure

Osmosis is the net flow of a solvent between two solutions

separated by a semipermeable membrane.
The solvent passes from the lower concentration
solution into the higher concentration solution.
Examples of semipermeable membranes include:
cellophane and saran wrap
skin
cell membranes
Osmosis is a rate controlled phenomenon.
The solvent is passing from the dilute solution into the
concentrated solution at a faster rate than in opposite
direction, i.e. establishing an equilibrium.

The osmotic pressure is the pressure exerted by a column of

the solvent in an osmosis experiment.

MRT
where : = osmotic pressurein atm
n
M = molar concentration of solution
V
L atm
R = 0.0821
mol K
T = absolute temperature
Physical Chemistry First Year First semester Page 50
 For very dilute aqueous solutions, molarity and molality are
nearly equal.

m RT for dilute aqueous solutions only M m

Osmotic pressures can be very large.

For example, a 1 M sugar solution has an osmotic
pressure of 22.4 atm or 330 p.s.i.
Since this is a large effect, the osmotic pressure
measurements can be used to determine the molar
masses of very large molecules such as:
Polymers
Biomolecules like
proteins
Ribonucleotides
Osmosis plays an important role in plant and animal
physiological processes; the passage of substances through the
semipermeable walls of a living cell, the action of the kidneys,
and the rising of sap in trees are examples.

Example 14: A 1.00 g sample of a biological material was dissolved

in enough water to give 1.00 x 102 mL of solution. The osmotic
pressure of the solution was 2.80 torr at 25oC. Calculate the molarity
and approximate molecular weight of the material.

MRT M
RT
1 atm
? atm = 2.80 torr 0.00368 atm =
760 torr
0.00368 atm
M= 1.50 10 4 M
0.0821mol K 298 K
L atm

?g 1.00 g 1L
6.67 10 4 g mol
mol 0.100 L 1.50 10 4 M
typical of smallproteins

Physical Chemistry First Year First semester Page 51

 Application of osmosis

1) Revesse osmosis: When an external pressure is applied over

the solution, the solvent is forced in a direction contrary to that
normally observed. This process called reverse osmosis is used
to secure pure water from salt water. This is used in desalination
of seawater to be suitable for drinking.
2) Isotonic solution: In the living cells, the osmotic pressure of
solution is equal to the osmotic pressure of the cell.
e.g: NaCI (0.9%) has the same osmotic pressure as
blood.
3) Hypertonic solution: A solution of higher osmotic pressure. In
this solution red blood cells shrink. The cells are called
plasmolysed.
4) Hypotonic solution: A solution of lower osmotic pressure. In this
solution red blood cells swells up and burst. The cell is said to be
haemolysed

Physical Chemistry First Year First semester Page 52