Ca2+(aq) + 2Cl–(aq) + 2Na+(aq) + CO2–

3
(aq) → CaCO3(s) + 2Na+(aq) + 2Cl–(aq)

The resulting equation is:

Ca2+(aq) + CO2–
3
(aq) → CaCO3(s)

This net ionic equation, is without spectator ions and the reaction that actually occurs at an
ionic level is between calcium ions and carbonate ions which form solid calcium carbonate.

Activity 1.11

Form a group and discuss the following:

1. How are sodium carbonate and calcium hydroxide found in water solution? Write
dissociation reaction for each of them.
2. Write the ionic equation for the reaction between sodium carbonate and calcium
hydroxide. Are the products formed soluble in water?
3. Write the soluble product in ionic form. Are there the same ions in the reactant and
product side?
4. Write the net ionic equation.

Exercise 1.13
For each of the following molecular equations, write ionic equation, write a net ionic
equation, and identify the spectator ions:
a 2AgNO 3 (aq) + Na 2 CrO 4 (aq) → Ag 2CrO 4 (s) + 2NaNO 3 (aq)
b 2HClO4 (aq) + Ca(OH)2 (aq) → Ca(ClO4 )2 (aq) + 2H2 O (l)
c 2HNO 3 (aq) + Mg(OH) 2 (s) → 2H 2O(l) + Mg(NO3 ) 2 (aq)
d Pb(NO3 ) 2 (aq) + Na 2SO 4 (aq) → PbSO 4 (s) + 2NaNO3 (aq)

1.9 COLLIGATIVE PROPERTIES OF SOLUTION

At the end of this section, you should be able to:
• define colligative properties:
• list the important properties of solvents that are affected by the formation of a solution;
• state Raoult’s law;

46
 • explain the change in the colligative properties of solvent when a certain solute is
added;
• describe the Van’t Hoff’s factor;
• calculate the vapour pressure, boiling point, and freezing point of a solvent after a
given amount of solute is dissolved in it;
• define osmosis and osmotic pressure of a solution;
• calculate the osmotic pressure of a solution; and
• compare and contrast change in colligative properties of electrolytic and non
electrolytic solution.
What is meant by colligative? Why does the addition of ethylene glycol lower the
freezing point and raise the boiling point of water? Discuss this question with
your classmates.
Certain physical properties of solutions differ in important ways from those of pure solvents.
For example, pure water at 1 atm pressure freezes at 0°C, while an aqueous solutions at 1
atm pressure freezes at a lower temperature. Ethylene glycol is added to water in radiators of
cars as antifreeze to lower the freezing point of the solution. This also raises the boiling point
of the solution above that of pure water, permitting operation of engines at higher temperatures.
The lowering of the freezing point and the raising of the boiling point are examples of the
physical properties of solutions that depend on the quantity (concentration) of the solute but
not on the kind of solute particle. Properties that depend on the number of particles or
concentration of the solute in the given amount of solvent and not on their nature are called
colligative properties. (Colligative is a Latin word that means “depending on the collection”.)
There are four important properties of a solution that are affected by the addition of a non-
volatile solute to a solvent. These are:
1. Vapour pressure lowering
2. Boiling point elevation
3. Freezing point depression
4. Osmotic pressure

1.9.1 Vapour Pressure Lowering

How do non-volatile solutes affect the vapour pressure of the solvent?
If a solute is non-volatile i.e., it does not have a measurable vapour pressure, the vapour
pressure of its solution is always less than that of the pure solvent. Vapour pressure lowering
47
is the lowering of the vapour pressure of the solvents that results when a non-volatile solute
is added to form a solution. The solute prevents (blanket) the tendency of the solvent to
escape and it also lowers the vapour pressure of the solvent (Figure 1.14). Thus, the
relationship between solution vapour pressure and solvent vapour pressure depends on
the concentration of the solute in the solution.

Solute particles

Solvent Solution

Figure 1.14 shows the lowering of the rate of vaporization of a solvent when a non-
volatile solute is added.

The relationship between solution vapour pressure and solvent vapour pressure is expressed
by Raoult’s law. This law states that “the partial pressure of a solvent over a solution,
P1, is given by the vapour pressure of the pure solvent, times the mole fraction of the
solvent in the solution, x1 , at constant temperature”.
P1 = x1P°1
DP = P°1 – P1
where DP = Change in vapour pressure (vapour pressure lowering)
P° = Vapour pressure of pure solvent
P 1 = Vapour pressure of solvent in solution
Note that the vapour pressure of a solvent is not a colligative property. Only the change in
vapour pressure, ∆P, which occurs when a solute is added to the solvent, is a colligative
property. It can be defined as the difference between the vapour pressure of the pure
solvent and the vapour pressure of solvent in the solution.
In a solution containing only one solute, x1 = 1 – x2, where x2 is the mole fraction of the
solute. Inserting this into the Raoult’s-law equation gives:
P1 = (1 – x2) P°1
P1 = P°1 – P°1 x2

48
 P°1 – P1= P°1 x2
∆P = P°1 x2

Example 1.18
Calculate the vapour pressure of water at 90 °C in a solution containing 5.0 g of
glucose (C6H12O6) in 100 g of water. The vapour pressure of pure water at
90 °C is 525.8 Pa.
Solution:
Given:
Mass of C6H12O6 = 5.0 g
Mass of water = 100 g
Vapour pressure of pure water at 90oC = 525.8 Pa
Required:
Vapour pressure of water in a solution P1 = ?
First, we find mole fractions of both solute and solvent. To do this, we must find
the number of moles of glucose and water.
Mass of C 6 H12 O 6 5.0 g
Number of moles of C6H12O6 = =
Molar mass of C 6 H12 O 6 180 g mol
= 0.028 mol
100 g
Number of moles of H2O = = 5.56 mol
18 g mol
0.028 mol
x C6 H12 O6 = = 0.005
0.028 mol + 5.56 mol

5.56 mol
x H2 O = = 0.995
5.56 mol + 0.028 mol

P1 = xH 2O P1°

= 0.995 × 525.8 Pa = 523.17 Pa

DP = P° – P
= 525.8 Pa – 523.17 Pa = 2.63 Pa

49
 Example 1.19
Calculate the vapour pressure of a solution made by dissolving 218 g of glucose in
460 mL of water at 30 °C. What is the vapour pressure lowering? (Assume that
the density of water is 1.00 g/mL). Vapour pressure of water at 30 °C is
31.82 torr.
Solution:
Given: Required:
Mass of solute (C6H12O6) = 218 g P1 (vapour pressure of solution) = ?
Volume of water = 460 mL = 0.46 L DP (lowering in vapour pressure) = ?
From Raoult’s law
P1 = x1 P°1
To determine the number of moles of H2O, its density is used.
460 mL × 1 g
1 mL → 1 g = 460 g
1 mL
460 mL Æ?
460 g
Number of moles of H2O = = 25.56 mol
18 g mol

218 g
Number of mole of C6H12O6 = = 1.21 mol
180 g mol

25.56 mol
xH 2O = = 0.955
25.56 mol + 1.21 mol
1.2 mol
xC6 H12O6 = = 0.045
1.21 mol + 25.56 mol
P1 = x1 P°1
P°1 is the vapour pressure of water at 30°C, which is equal to 31.82 torr.
P1 = 0.955 × 31.82 torr
= 30.4 torr
DP = P° – P
= 31.82 torr – 30.4 torr
= 1.42 torr

50
 Exercise 1.14
1. Why is the vapour pressure of a solution less than that of the pure solvent?
2. The vapour pressure of pure water at 110°C is 1070 torr. A solution of ethylene
glycol in water has a vapour pressure of 1.00 atm at 110°C. Assuming that Raoult’s
law is obeyed, what is the mole fraction of ethylene glycol in water?
3. Calculate the vapour pressure lowering, DP, when 10.0 mL of glycerol (C3H8O3)
is added to 500.0 mL of water at 50°C. At this temperature, the vapour pressure
of pure water is 92.5 torr and its density is 0.988 g/mol. The density of glycerol is
1.26 g/mL.

Solutions that obey Raoult’s law are said to be ideal solutions. If both components of a
solution are volatile, i.e., have measurable vapour pressure, the vapour pressure of the
solution is the sum of the individual partial vapour pressures. Thus, for two volatile
components, A and B, the vapour pressure of each component above the solution is
proportional to its mole fraction in the solution.
PA = xA P°A
PB = xB P°B
According to Dalton’s law of partial pressure, at constant temperature, the pressure of a
mixture of gases is equal to the sum of the partial pressures of all of the constituent gases.
The total pressure, is:

PT = PA + PB = x A PA° + xB PB°
This can be shown graphically as in Figure 1.15, assuming that A is more volatile than B.

Figure 1.15 Vapour pressure versus mole fraction for an ideal solution.

51
Ideal solutions are characterized by the following properties:

i) The volume of an ideal solution is the sum of the volumes of its pure components.
i.e., there is no expansion or contraction on mixing.
ii) The heat of a solution is zero. i.e., mixing is neither exothermic nor endothermic.
Intermolecular forces between solute-solute and solute-solvent molecules are equal,
as are those between solvent-solvent molecules and solute-solvent molecules.
iii) The vapour pressure above the solution is equal to the sum of the individual partial
vapour pressures.
iv) The components have similarity in their chemical structures.
v) The solutions obey Raoult’s law.

Can you give examples of an ideal solution?

Many solutions do not behave ideally. They deviate from Raoult’s law and are said to be
non-ideal. Here, we can consider the following two cases.

Case 1: If the intermolecular forces between A and B molecules are weaker than those
between A and A molecules and those between B and B molecules, then there is
a greater tendency for A-B molecules to leave the solution, compared to the case
of an ideal solution. Consequently, the vapour pressure of the solution is greater
than the sum of the vapour pressures that would be predicted by Raoult’s law for
the same concentration.

This behaviour exemplifies the positive deviation from Raoult’s law (Figure
1.16 a). In this case, the heat of mixing is an endothermic process.

Case 2: If A molecules attract B molecules more strongly than they do their own kind,
then the escaping tendency decreases and the vapour pressure of the solution is
less than the sum of the vapour pressures as predicted by Raoult’s law.

Here, we have a negative deviation from Raoult’s law, and mixing is an exothermic
process (Figure 1.16 b).

52
 a) Positive deviation b) Negative deviation
T = constant T = constant

Non-ideal solution
Ideal solution
PT
Vapour Pressure

Vapour Pressure
PT

PT
PT
PA Ideal solution
PA PA
PA
PB Non-ideal solution
PB
PB
PB

XA = 0 XA = 1 XA = 0 XA = 1
XB = 1 XB = 0 XB = 1 XB = 0
(Dotted lines show the expected values and the solid lines show the observed values).
Figure 1.16 Vapour pressure versus mole fraction for real solutions.

1.9.2 Boiling Point Elevation

Which do you think has a higher boiling point, a pure solvent or a solution
containing a non-volatile solute? Why?
The boiling point of a liquid is the temperature at which its vapour pressure equals the
atmospheric pressure. If a non-volatile solute is added to a solvent, the solution’s boiling
point will be increased. This is due to the fact that the vapour pressure of a solvent at a
given temperature is lowered by the presence of a non-volatile solute in it, because less
number of solvent molecules are available on the surface exposed to atmosphere in presence
of solute molecules, as shown in Figure 1.14. Therefore, such a solution must be heated to
a higher temperature than the pure solvent in order for its vapour pressure to be equal to
the atmospheric pressure.
The boiling-point elevation (DTb) is defined as the boiling point of the solution (Tb) minus
the boiling point of the pure solvent (Tb°).
DTb = Tb – Tb°
The elevation in boiling point (DTb) is directly proportional to the molality of the solution.
That is:
DTb a m
DTb = Kbm

53
where m is the molality of the solution, and Kb is the molal boiling point elevation constant
for the solvent.
Table 1.2 Boiling points, molal boiling point elevation constants, freezing points and
molal freezing point depression constants of some solvents at 1 atm pressure.
Solvent Boiling Kb (°C/m) Freezing Kf (°C/m)
point (°C) point (°C)
Acetic acid (C2H4O2) 118.10 3.07 16.60 3.90
Benzene (C6H6) 80.10 2.53 5.50 5.12
Camphor (C10H16O) 208.00 5.95 179.00 39.70
Carbon disulfide (CS2) 46.30 2.34 – 111.50 3.83
Chloroform (CHCl3) 61.26 3.63 – 63.50 4.70
Cyclohexane (C6H12) 80.70 2.79 6.60 20.00
Nitrobenzene (C6H5NO2) 210.88 5.24 5.70 7.00
Phenol (C6H5OH) 182.00 3.56 43.00 7.40
Water (H2O) 100.00 0.51 0.00 1.86

Example 1.20
Calculate the boiling point of a 0.33 m solution of a solute in benzene.
(Kb = 2.53°C /m).
Solution:
Given: Required:
Molality = 0.33 m Boiling point of the solution?
Kb = 2.53°C /m
DTb = Kbm,
DTb = 2.53°C /m × 0.33 m = 0.83°C
Therefore, the boiling point of the solution is determined from the boiling point of
the pure solvent benzene (Table 1.2) and the change, in boiling point, DTb.
Boiling point of the solution = 80.1°C + 0.83°C
= 80.93°C

Example 1.21
Calculate the boiling point of a solution that contains 200 g of sucrose, C12H22O11,
in 500 g of water.

54
 Solution:
From the given masses of solute and solvent, we can find the molality of the solution.
Mass of sucrose
Molality (m) =
Molar mass of sucrose × Mass of H2O in kg
200 g
= 342 g / mol × 0.5 kg = 1.17 m

DTb = Kbm, from Table 1.2, Kb for H2O is 0.512°C /m

Therefore, DTb = 0.512°C/m × 1.17 m = 0.6°C
Since the normal boiling point of water is 100°C, the boiling point of the solution
will be equal to 100°C + 0.6°C = 100.6°C.

Exercise 1.15
1. What is the boiling point of 1.93 m solution of a non-volatile solute in nitrobenzene?
2. Automotive antifreeze consists of ethylene glycol, C2H6O2, a non-volatile
non-electrolyte solute. Calculate the boiling point of a 25.0 mass percent solution
of ethylene glycol in water.

1.9.3 Freezing Point Depression

Activity 1.12

Discuss in group and account for the following processes. Report your idea to the class.
1. In countries with extremely cold conditions, anti-freezing substances like ethylene
glycol (C2H6O2) are used in the cooling system of the automobiles.
2. Salts such as NaCl or CaCl2 can be used to prepare ice cream or to de-ice the roads.

When a solution begins to freeze, the component that crystalize out first is almost pure.
Pure ice, for example, crystallizes out of a solution of salt and water. Solute particles,
because of their different size and shape, do not fit into the crystal lattice of the frozen
solvent. They tend to concentrate in the remaining liquid, and they interfere with the freezing
process by getting in the way of solvent molecules looking for lattice sites. This interference
causes the solution to freeze at lower temperature than the pure solvent. The greater the
concentration of the solution, the greater the interference and therefore, the lower the
freezing point of the solution.

55
The freezing point depression (DTf) is defined as the freezing point of the pure solvent (T)
minus the freezing point of the solution (Tf).
DTf = T – Tf
The freezing point depression (DTf) of solutions of nonelectrolytes has been found to be
equal to the molality of the solution times a proportionality constant. This constant is the
molal freezing point depression constant, Kf , of the solvent.
DTf = Kf m

Example 1.22
The freezing point of pure camphor (C10H16O), T°f, is 179.0°C, and its Kf is
39.70°C kg/mol. Find the freezing point of a solution containing 1.50 g of a
compound of molecular mass 125, dissolved in 35 g camphor (solvent).
Solution:
First we find number of moles of the compound
1.5 g
Number of moles = = 0.012 mol
125 g mol

Number of moles of solute 0.012 mol

Molality = = = 0.343 mol kg
Weight (kg) of solvent 0.035 kg

DTf = Kf m = 39.7°C kg/mol × 0.343 mol/kg

= 13.6°C
The normal freezing point of camphor is lowered by 13.6°C. Therefore, the freezing
point of the solution, Tf, will be:

DTf = T– Tf = 179.0°C – 13.6°C = 165.4°C

Exercise 1.16
1. Calculate the freezing point of a solution that contains 60.0 g of urea, N2H4CO, in
500.0 g of water.

2. Calculate the molecular mass of sulphur if 35.5 g of sulphur dissolves in 100.0 g of

CS2 to produce a solution that has a boiling point of 49.48°C.

56
 1.9.3 Osmosis and Osmotic Pressure
How do you calculate osmotic pressure?
Osmosis is the selective passage of solvent molecules through a porous (semi- permeable)
membrane from a dilute to a more concentrated solution or from the solvent side into the
solution side.
Figure 1.17 shows two solutions on equal level, separated by a semi-permeable membrane.
Solvent molecules move through the membrane from left to right. As a result, the liquid
levels in the two arms become uneven. Eventually, the pressure difference resulting from
the unequal heights of the liquid in the two arms becomes so large that the net flow of
solvent ceases. Alternatively, we may apply pressure to the right arm of the apparatus, as
shown in Figure 1.17 b, to stop the net flow of solvent either way.
The pressure required to prevent osmosis is known as the osmotic pressure, p, of the
solution.

Figure 1.17 Apparatus for measuring osmotic pressure.

Jacobus Henricus Van’t Hoff found that the osmotic pressure obeys a law similar to the
ideal gas law, PV = nRT,

where V is the volume of the solution, n is the number of moles of solute, R is the ideal gas
constant, and T is the temperature on the Kelvin scale. From the equation, we can write:
 
p = P =  n  RT = MRT
V
where M is the molarity of the solution.

Like other colligative properties, osmotic pressure can be used to determine the molar
mass of solute. Especially osmotic pressure is used in biological laboratories to determine
molecular masses of huge molecules like proteins and nucleic acids.

57
 Example 1.23
What is the osmotic pressure at 17°C of 150 mL aqueous solution containing
1.75 g of sucrose (C12H22O11) per 150 mL of solution?

Solution:
First we calculate the molarity (M) of the solution
Number of moles of solute
Molarity (M) =
Volume (L) of solution

=
1.75 g ( 342 g mol ) = 0.034 mol L
0.150 L
p = MRT
 Latm 
= 0.0851mol /L 0.0821 (290K)=0.812 atm
 mol K 


Example 1.24
In an experiment to measure the molar mass of polyethylene, 2.20 g of polyethylene
plastic was dissolved in enough toluene to produce a 100 mL solution. Its osmotic
pressure at 25°C was measured as 1.10 × 10–2 atm. Calculate the molar mass of
polyethylene.

Solution:
π
From the equation, π = MRT ⇒ M =
RT

1.10 × 10 –2 atm
M= = 4.5 × 10 –4 mol L
 L.atm 
 0.0821  ( 298 K )
 mol.K 

That is, 1 L solution contains 4.5 × 10–4 mole of polyethylene. The amount of
polyethylene in 100 mL of the solution is therefore
1 L Æ 4.5 × 10–4 mol
0.10 L Æ ?

58
 0.10 L × 4.5 × 10 –4 mol
Amount of polyethylene (mol) =
1L
= 4.5 × 10–5 mol
2.20 g
Molar mass of polyethylene ( g mol ) =
4.5 × 10 –5 mol
= 4.89 × 104 g / mol

Activity 1.13
Take 5%,10% and 20% solutions of sucrose in water.
Take 3 potatoes of almost equal size and make one cubic hole in each potato of equal
dimensions.
Fill the holes with water and keep these potatoes in different solutions of sucrose.
Observe the change in the water level at different time intervals.
Discuss your observations with your teacher as well as classmates.

Exercise 1.17
1. A sample of 2.05 g of polystyrene plastic was dissolved in enough toluene to form
100 mL of solution. The osmotic pressure of this solution was found to be 1.21
kPa at 25°C. Calculate the molar mass of polystyrene.
2. What is the osmotic pressure, in atm, of a 0.30 M solution of glucose in water that
is used for intravenous infusion at body temperature, 37°C?

1.9.4 Colligative Properties of Electrolytic Solutions

Activity 1.14

Form groups and discuss the following. Present the result of your discussion to the class as
a report.
1. What is the difference between electrolytes and non-electrolytes?
2. How do the effects of the presence of electrolyte solute on the properties of pure
solvent differ from the effect of the presence of non-electrolyte solvent? Justify your
answer by giving example.

59
The effective number of moles of ions produced by one mole of a solute is expressed in
terms of the Van’t Hoff factor (i).

Measured value for electrolyte solution

i=
Expected value for nonelectrolyte solution

Thus, i is 1 for all solutions of nonelectrolytes, but is greater than 1 for solutions of electrolytes.
Therefore, the colligative-property relationship should be modified to account for dissociation
of electrolyte solutes. Consequently,
DP = i x2P°1
DTb = i Kbm
DTf = i Kf m
p = i MRT
Table 1.3 Experimental values of the Van’t Hoff factor for some substances.
Compound 0.100 m 0.001 m
HCl 1.9 2.0
NaCl 1.87 1.97
MgSO4 1.21 1.82
K2SO4 2.32 2.84
KBr 1.88 1.97

As can be seen in Table 1.3 the experimental Van’t Hoff factors are less than the theoretical
prediction. This is mainly due to the cation-anion interaction in the solution of the electrolytes
that prevents complete dissociation.

Example 1.25
If a 0.10 m MgSO4 solution causes an elevation of 0.062°C in the boiling point of
water, what is:
a the Van’t Hoff Factor (i)?
b the boiling point of this solution?
Solution:
a First, we find i by applying the modified colligative-property relationship for
DTb.
DTb = i Kbm

60
 Given:
DTb = 0.062°C

Kb, H2O = 0.512°C/m

m = 0.1 m
0.062°C = i × 0.512°C /m × 0.1 m
i = 1.21. What does this indicate?
b Recall that DTb = Tb – T°b
0.062°C = Tb – 100°C
Tb = 100°C + 0.062°C = 100.062°C

Exercise 1.18
A 0.0622 m solution of iron (III) chloride, FeCl3, in water freezes at –0.412°C.
Determine the Van’t Hoff’s factor of FeCl3 in this solution.

Unit Summary
• Solutions are homogeneous mixtures of two or more substances.
• Solubility depends on the relative magnitude of solute-solute, solute-solvent,
and solvent-solvent attractive forces.
• The relative amounts of solute and solvent in a solution can be described
quantitatively in terms of mass percentage, parts per million, parts per billion,
mole fraction, molarity, molality and normality.
• Increasing the temperature usually increases the solubility of solids in water
and liquids in water while it decreases the solubility of gases in water.
• Raoult’s law states that the partial vapour pressure of substance A over a
solution is equal to the mole fraction of A, XA, times the vapour pressure of
pure solvent. An ideal solution obeys Raoult’s law over the entire range of
concentration. Non ideal solutions show positive or negative deviation from
Raoult’s law.
• Some physical properties of solutions are colligative, that is, they depend on
the concentration of the solute particles that are present in a given amount

61