Solution and colligative properties

In chemistry, a solution is a homogeneous mixture composed of only

one phase. In such a mixture, a solute is dissolved in another
substance, known as a solvent.

The ability of one compound to

dissolve in another compound is
called solubility.
 Dissolution of ionic compounds in water
To dissolve an ionic compound, the water molecules must be able to
stabilize the ions that result from breaking the ionic bond. This is done
by hydrating the ions of ionic compound. Water is a polar molecule. It
has a permanent dipole. The O atom has a partial negative charge, and
the H atoms have a partial positive charge. When an ionic substance is
placed in water, the water molecules attract the positive and negative
ions from the crystal. The particles are
then free to move around within the
solution. The positive ions have several
water molecules around them, all with
their O atoms close to the positive ion.
The negative ions have several water
molecules around them, all with their H
atoms close to the negative ion.
The "shell" of water molecules reduces
the attractions between the ions. The ions
are hydrated.
Water is a polar solvents. An ionic substance, when placed in water furnishes
cations (+) and anions (–). These ions are surrounded by solvent (H2O)
molecules with their oppositely charged ends directed towards the ion. The
ion enveloped by a layer of the solvent molecules in this manner, is called a
Solvated ion or Hydrated ion in case water is the solvent For example,
sodium chloride dissolves in water to give Na+ and Cl– ions. The Na+ ion is
hydrated by a layer of water molecules so that their negative ends are directed
towards it. The Cl– ion, on the other hand, attracts positive ends of water
molecules which envelop and the hydrated sodium and chloride ions are
represented as Na+ (aq) and Cl– (aq).
The mechanism of solution of sodium crystal in water could be explained as
follows. The polar water molecules try to pull out the Na+ and Cl– ions from
the crystal by hydration. This becomes possible since the forces operating
between the ion (Na+ or Cl–) and water molecules are strong enough to
overcome the force binding the ion in the crystal. The ions detached from the
crystal are now surrounded by cluster of water molecules. The layer of water
molecules enveloping the ions effectively shields them and prevents them
from coming in contact with each other.
PHENOL–WATER SYSTEM
The curve in Fig. represents the miscibility of
phenol and water. The left hand side of the
parabolic curve represents one of the two
conjugate solutions which depicts the
percentage of phenol dissolved in water at
various temperatures. The solubility of phenol
increases with temperature. The right hand side
of the curve represents the other conjugate
solution layer that gives the percentage of water
in phenol.
The solubility of water in phenol also increase with increase of
temperature. The two solution curves meet at the maxima on the
temperature-composition curve of the system. This point here
corresponds to temperature 66°C and composition of phenol as 33%.
Thus at a certain maximum temperature the two conjugate solutions
merge, become identical and only one layer results.
The temperature at which the two conjugate solutions (or layers) merge
into one another to from one layer, is called the Critical Solution
Temperature (CST) or Upper Consolate Temperature. At any
temperature above the critical solution temperature, phenol and water
are miscible in all proportions. Outside the curve there is complete
homogeneity of the system, i.e., one layer only exists; and under the
curve there may be complete miscibility but it depends upon the
composition of the mixture.It is clear from Fig. (a) that at a
temperature below 50°C a mixture of 90% phenol and 10% water or 5%
phenol and 95% water, will be completely miscible since the
corresponding points do not lie under the curve. Two layers will always
separate out below the curve and the curve gives compositions of the
conjugate solutions constituting the two layers. At 50°C a mixture of
equal proportion of phenol and water (50% each) will form two layers
whose compositions are given by A and B. The line joining the points
(M and N) corresponding to the compositions A and B is called the tie
line. This line helps in calculating the relative amounts of the two
layers, which is here given by the ratio MN/ML.
 Triethylamine and water
The temperature-composition curve of mutual
solubilities of triethylamine and water is given in
Fig. 14.3 (b). The left hand side of the curve
indicates the solubility curve of triethylamine in
water and the right hand side of that of water in
triethylamine. Unlike phenol-water system, the
solubilities decrease with the increase in
temperature in this system. The two conjugate
solutions mix up completely at or below 18.5°C.
This temperature is also called the critical solution temperature or the
lower consolate temperature. As in the above case, any point above the
horizontal line corresponds to heterogeneity of the system (two layers)
while below it is complete homogeneity (one layer). Thus an equi-
component mixture (50–50) will be completely miscible at 10°C but at
50°C there will be separating out two layers having compositions
corresponding to the points C and D.
 Raoult’s Law
The partial pressure of solvent, PA, over a solution equals the vapor
pressure of the pure solvent, 𝑃𝐴𝑜 , times the mole fraction of solvent, XA ,
in the solution. Consider a solution of volatile solvent, A, and
nonelectrolyte solute, B, which may be volatile or nonvolatile.
PA = 𝑃𝐴𝑜 XA
If the solute is nonvolatile, PA is the total vapor pressure of the solution.

Colligative properties

Colligative properties of solutions are properties that depend on the

concentration of solute molecules or ions in solution but not on the
chemical identity of the solute
 Raoult’s Law for lowering of vapour pressure:
The vapour pressure of a pure solvent is decreased when a non-
volatile solute is dissolved in it. the relative lowering of the vapour
pressure of a dilute solution is equal to the mole fraction of the
solute present in dilute solution.
If p0 is the vapour pressure of the solvent and p that of the solution,
the lowering of vapour pressure is (p0 – p) and relative lowering of
vapour pressure is (p0 – p)/p0. According to Raoult’s law
p0 – p n2
=
p0 n1+ n2 = X2
Where, n1 and n2 are the number of moles of solvent and solutes and
X2 is the mole fraction of solute in the solution.
Lowering of vapour pressure of a dilute solution is a colligative property
The vapour pressure of the pure solvent is caused by the number of
molecules evaporating from its surface. When a nonvolatile solute is
dissolved in solution, the presence of solute molecules in the surface
blocks a fraction of the surface where no evaporation can take place.
This causes the lowering of the vapour pressure.
According to Raoult’s Law of partial pressure of solution
Psolvent = Pºsolvent Xsolvent
Psolute = Pºsolute Xsolute
Now since, the solute used in non volatile only pressure from solvent
can be considered. Hence,
Psolution = Pºsolvent Xsolvent or P = Pº X1 ….. (1)
We knew, X1 + X2 = 1 or X1 = 1- X2 X1= mole fraction of solvent
X2= mole fraction of solute
P = Pº X1= Pº (1- X2)
Pº-P = Pº X2 The relative vapor pressure lowering depends only on the
Pº−P mole fraction of the solute, X2. Therefore, the relative
= X2
Pº vapor pressure lowering is a colligative property.
 Molecular mass determination from the Raoult’s Law
According to Raoult’s law, we have
Since for very dilute solution, the
Pº−P number of moles (molecules) of
= X2 ....... (1)
Pº solute (w2/M2), is very small, it
Where, P and Pº are the vapor
can be neglected in the
pressure of solution and pure
denominator. The equation (2) can
solvent, respectively. X2 is the
now be written as
mole fraction of solute.
If the number of moles of solvent 𝑤2
Pº−P 𝑀2 𝑤2 𝑀1
and solution are n1 and n2, and that = = ….(3)
Pº 𝑤1
𝑀1
𝑤1 𝑀2
of molecular mass are M1 and M2,
respectively. If we consider w1 and
Knowing the experimental value
w2 gram of solvent and solute are Pº−P
present in the solution, then from of , and the molecular mass
Pº
equation (1), we get of the solvent (M1), the molecular
𝑤2 weight of solute (M2) can be
Pº−P n 𝑀2
= X2 = 2 = ….(2) calculated from (3).
Pº n1+n2 𝑤1 𝑤2
+
𝑀1 𝑀2
 Ostwald and Walker’s dynamic method:
This method is used to determine the relative lowering of vapor
pressure directly. The figure below shows the experimental setup
consisting of two sets of bulbs (i) Set A containing the solution, (ii)
Set B containing the solvent. Each set is weighed individually. A
known volume of dry air is first blown through the solution and then
solvent. During the passing, air is made to be saturated by the vapor
of solution and solvent. The loss in mass of solution and solvent
occurs due to saturation air gives the lowering of vapor pressure of
solution.
Consider, the air bubbles through set A is saturated up to the vapor
pressure P of the solution and then up to vapor pressure P0 of solvent in
set B. Thus, the amount of solvent taken up in set A is proportional to P
and the amount taken up in set B is proportional to (Pº -P). If w1 and w2
be the loss of weight in set A and B, respectively.
w1 ∝Pº………………(1)

w2 ∝ Pº - P …………..(2)

Adding (1) and (2)

w1 + w2 ∝ Pº -P + P = Pº ...(3)

Dividing (2) by (3)

Pº−P 𝑤
∝ 2 …… 4
Pº 𝑤1 + 𝑤2

Knowing the loss of mass in set (w2) and the total mass in the two
sets (𝑤1 + 𝑤2 ), relative lower of vapor pressure could be estimated.
 Relation between Elevation of Boiling Point and
Lowering of Vapour-pressure
When a liquid is heated, its vapour pressure rises and when it equals the
atmospheric pressure, the liquid boils. The addition of a non volatile
solute lowers the vapour pressure and consequently elevates the boiling
point as the solution has to be heated to a higher temperature to make its
vapour pressure become equal to atmospheric pressure. If Tb is the
boiling point of the solvent and T is the boiling point of the solution, the
difference in the boiling points (ΔT) is called the elevation of boiling
point. 𝑝0
T–Tb = ΔTb
The vapour pressure curves of the pure
solvent, and solutions (1) and (2) with
𝑝0
different concentrations of solute are
shown in Fig right. For dilute solutions,
the curves BD and CE are parallel and
straight lines approximately. Therefore for
similar triangles ACE and ABD, we have
 𝑝0
𝐴𝐵 𝐴𝐷 𝑇1 − 𝑇𝑏 − 𝑝1 𝑝0
= => = 0
𝐴𝐶 𝐴𝐸 𝑇2 − 𝑇𝑏 𝑝 − 𝑝2
Where, p – p1 and p – p2 are 𝑝0

lowering of vapour pressure for

solution 1 and solution 2
respectively. Hence the elevation of
boiling point is directly
proportional to the lowering of
vapour pressure. According to Raoult’s law for
dilute solution, we get
 ΔTb ∝ 𝑝0 − 𝑝 ……….. (1) Pº−P 𝑤2 𝑀1
= … … (3)
Pº 𝑤1 𝑀2
Since 𝑝0 is constant for the same
Since, M1 (the molar mass of the
solvent at a fixed temperature, from
solvent) is constant.
(1) we can write
Pº−P 𝑤2
𝑝0 −𝑝 ∝ … … (4)
ΔTb ∝ ……….. (2) Pº 𝑤1 𝑀2
𝑝0
 From equation (2) and (4), we have
𝑤2
ΔTb ∝
𝑤1 𝑀2
𝑤2 1 1
∝ . = 𝐾𝑏𝑛2. = 𝐾𝑏 . 𝑚2
𝑀2 𝑤1 𝑤1
=> ΔTb = 𝐾𝑏 × Molality of solute …(5)
Here, 𝐾𝑏 is called a boiling point constant or molal elevation constant.
If 𝑛2 = 1, w1 = 1, then, Kb =ΔTb; thus
Molal elevation constant may be defined as the boiling-point elevation
produced when 1 mole of solute is dissolved in one kg (1000 g) of the solvent.
If the mass of the solvent (w1) is given in grams, it has to be converted
into kilograms. Thus the expression (5) assumes the form
1 𝑤2 1
ΔTb = 𝐾𝑏𝑛2. = 𝐾𝑏 .
𝑤1 𝑀2 𝑤1 /1000
1000 ×𝐾𝑏× 𝑤2
M ………….(6)
=> 2 = 𝑤1 ×ΔTb

Where, ΔTb = elevation of boiling point; Kb = molal elevation

constant; w2 = mass of solute in grams; M2 = mol mass of solute; and
w1 = mass of solvent in grams.
Landsberger-Walker Method.
The apparatus used in this method is
consists of : (i) An inner tube with a hole in
its side and graduated in ml; (ii) A boiling
flask which sends solvent vapour in to
the graduated tube through a ‘rosehead’ (a
bulb with several holes)’ (iii) An outer tube
which receives hot solvent vapour issuing
from the side-hole of the inner tube; (iv) A
thermometer reading to 0.01 K, dipping in
solvent or solution in the inner tube.
Procedure. Pure solvent is placed in the
graduated tube and vapour of the same
solvent boiling in a separate flask is passed
into it. The vapour causes the solvent in the
tube to boil by its latent heat of
condensation.
 When the solvent starts boiling and temperature
becomes constant, its boiling point is recorded.
Now the supply of vapour is temporarily cut off
and a weighed pellet of the solute is dropped into
the solvent in the inner tube. The solvent vapour
is again passed through until the boiling point of
the solution is reached and this is recorded. The
solvent vapour is then cut off, thermometer and
rosehead raised out of the solution, and the
volume of the solution read.
From a difference in the boiling points of solvent
and solution, molecular weight
of the solute could be find out by
1000 ×𝐾𝑏× 𝑤2
M2 =
𝑤1 ×ΔTb
where w1 = weight of solute taken, w2 = weight of solvent which is
given by the volume of solvent (or solution) measured in ml
multiplied by the density of the solvent at its boiling point.
Relation between Depression of Freezing-point and
Lowering of Vapour-pressure
has shown by the curve ABC, in Fig. There is a sharp break at B, which
corresponds to the freezing point of pure solvent, Tf. The vapour pressure
curve of a solution (solution 1) of a nonvolatile solute in the same
solvent is also shown in the Figure. It meets the freezing point curve at
F, indicating that T1 is the freezing point of the solution. Thus, the
depression of freezing point (ΔTf ) is ΔTf = Tf–T1

When more of the solute is added to

the solution 1, we get a more
concentrated solution (solution 2). The
vapour pressure of solution 2 meets
the freezing-point at C, indicating a
further lowering of freezing point to
T2.
For dilute solutions FD and CE are
approximately parallel straight lines and
BC is also a straight line. Since the 𝑝0
triangles BDF and BEC are similar,
𝐷𝐹 𝐵𝐷 𝑇𝑓 − 𝑇1 𝑝0 − 𝑝1
= => = 0
𝐸𝐶 𝐵𝐸 𝑇𝑓 − 𝑇2 𝑝 − 𝑝2
Where, p1 and p2 are vapour pressure of
solution 1 and solution 2, respectively.
Hence, depression of freezing point is
directly proportional to the lowering of
vapour pressure.
 ΔTf ∝ 𝑝0 − 𝑝 ……….. (1)

Since 𝑝0 is constant for the same solvent at a fixed temperature, from

(1) we can write
𝑝0 −𝑝
ΔTf ∝ ……..(2)
𝑝0
 According to Raoult’s law for Molal depression constant may be
dilute solution, we get defined as the freezing-point
depression produced when 1 mole of
Pº−P 𝑤2 𝑀1 solute is dissolved in one kg (1000 g)
= … … (3)
Pº 𝑤1 𝑀2 of the solvent.
Since, M1 (the molar mass of the If the mass of the solvent (w1) is
solvent) is constant. given in grams, it has to be
Pº−P 𝑤2 converted into kilograms. Thus the
∝ … … (4)
Pº 𝑤1 𝑀2 expression (5) assumes the form
1 𝑤2 1
From equation (2) and (4), we have ΔTf = 𝐾𝑓𝑛2. 𝑤 = 𝐾𝑓 𝑀 . 𝑤 /1000
1 2 1
𝑤2 1000 ×𝐾𝑓× 𝑤2
ΔTf ∝ => M2 = ………….(6)
𝑤1 𝑀2 𝑤1 ×ΔTf
𝑤 1 1
∝ 2 . = 𝐾𝑓𝑛2. = 𝐾𝑓 . 𝑚2 Where, ΔTf = elevation of boiling
𝑀2 𝑤1 𝑤1
=> ΔTf = 𝐾𝑓 × Molality of solute …(5) point; Kf = molal elevation
Here, 𝐾𝑏 is called a freezing-point constant; w2 = mass of solute in
constant or molal depression grams; M2 = mol mass of solute;
constant. If 𝑛 = 1, w = 1, then, K and w1 = mass of solvent in grams.
2 1 f
=ΔTf; thus
Beckmann’s Method for measuring
depression of Freezing point:
Apparatus used to measure depression of
freezing point consists of (i) A freezing
tube with a side-arm to contain the solvent or
solution, while the solute can be introduced
through the side-arm; (ii) An outer larger tube
into which the freezing tube is fixed , the space
in between providing an air jacket which
ensures a slower and more uniform rate of
cooling; (iii) A large jar containing a freezing
mixture e.g., ice and salt, and having a stirrer.
Procedure. 15 to 20 g of the solvent is taken in the freezing point of the
solvent by directly coding the freezing point tube and the apparatus set
up as shown in Fig. so that the bulb of the thermometer is completely
immersed in the solvent. First etermine the approximate freezing point
of the solvent by directly cooling the freezing point tube in the cooling
bath.
When this has been done, melt the solvent and place the freezing-
point tube again in the freezing bath and allow the temperature to fall.
When it has come down to within about a degree of the approximate
freezing point determined above, dry the tube and place it cautiously
in the air jacket. Let the temperature fall slowly and when it has come
down again to about 0.5° below the freezing point, stir vigorously.
This will cause the solid to separate and the temperature will rise
owing to the latent heat set free. Note the highest temperature reached
and repeat the process to get concordant value of freezing point.
The freezing point of the solvent having been accurately determined,
the solvent is remelted by removing the tube from the bath, and a
weighed amount (0.1–0.2 g) of the solute is introduced through the
side tube. Now the freezing point of the solution is determined in the
same way as that of the solvent. Knowing the depression of the
freezing point, the molecular weight of the solute can be determined
by using the expression
1000 ×𝐾𝑓× 𝑤2
M2 =
𝑤1 ×ΔTf
 Osmosis
Osmosis is the phenomenon of solvent flow through a semipermeable
membrane to equalize the solute concentrations on both sides of the
membrane.
Osmotic pressure of a solution equal to the external pressure that,
when applied to the solution, just stops osmosis.

Van’t Hoff equation for osmotic pressure

Van’t Hoff reasoned that
(a)The osmotic pressure (π) of a solution at a given temperature is
directly proportional to its molar concentration (M).
i.e. π ∝ CM ........ (1) , where, T is constant.
(b) The osmotic pressure (π) of a solution of a given concentration is
directly proportional to the absolute temperature (T) .
i.e. π ∝ T ..........(2) , when, M is constant.
Now combining the equation (1) and (2), we get
π ∝ CMT
=> Π = RTCM ........(3)
Where, R is called real gas constant. Now if n moles of solute is
dissoved in a volume of V. Then,
𝑛
𝐶𝑀 = .......(4)
𝑉
𝑛
Hence, π= RT
𝑉
 πV= 𝑛 RT………(5) This is called Van’t Hoff equation for osmotic
pressure.

Determination of Molar mass from osmotic pressure

From Vant’t Hoff equation we have,

𝑤
πV= 𝑛 RT = RT
𝑀
𝑊𝑅𝑇
=> M = … … … (6)
𝜋𝑉
Berkeley and Hartley Method: This technique apply external pressure
on the solution to prevent osmosis. The osmometer used by them is
illustrated in Fig. A porcelain tube with copper ferrocyanide membrane
deposited in its walls is enclosed in a metallic jacket. The tube is fitted
with a reservoir of pure solvent at one end and a capillary tube at the
other. Mechanical pressure can be applied on the solution with a piston
connected to a pressure gauge.
Procedure. The inner porcelain tube is
filled with pure solvent and the jacket
with the solution whose osmotic
pressure is to be determined. The level
of the solvent meniscus in the capillary
tube will tend to move down as solvent
flows into the solution across the membrane.
Pressure is then applied through the piston so that the meniscus becomes
stationary. It indicates that osmosis has been stopped and now the
pressure recorded by the pressure gauge gives the osmotic pressure of the
solution.
 Henry’s Law
At constant temperature, the solubility of a gas or concentration of the
gas that dissolves in the solvent is directly proportional to the partial
pressure of the gas above the solution.
C∝P
 C = k HP

Where, C is the concentration of the gas, P is the partial pressure and kH

is Henry’s law constant for the gas for a particular liquid at a given
temperature
Limitations of Henry’s Law
It applies closely to gases with nearly ideal behaviour.
(1) at moderate temperature and pressure.
(2) if the solubility of the gas in the solvent is low.
(3) the gas does not react with the solvent to form a new species. Thus
ammonia (or HCl) which react with water do not obey Henry’s Law.
NH3+H2O = NH4++OH–
(4) the gas does not associate or dissociate on dissolving in the solvent.
Math1: Camphor is a white solid that melts at 179.5 C and its freezing-point-depression
constant (40 C/m. a. A 1.07-mg sample of a compound was dissolved in 78.1 mg of camphor.
The solution melted at 176.0 C. What is the molecular mass of the compound? b. If the
empirical formula of the compound is CH, what is the molecular formula?
Math1: Calculate the osmotic pressure at 20 C of an aqueous solution containing 5.0 g of
sucrose, C12H22O11, in 100.0 mL of solution.