CHM 222: PHYSICAL CHEMISTRY II

Credit load: 2 units

By
Engr. Dr. J. C. Igwe
B.Sc., M.Sc., DCHE, M. Eng., PhD
Physical Chemist/Environmental Engineer
Email: [email protected]

MODULE 4
MOLECULAR WEIGHT DETERMINATIONS
4.1. Systems
A system is defined as that space or region where a specific reaction or
activity is taking place and it is excluded from other external influence, e.g. if a
substance is reacting in a test tube, the substance inside the test tube can be
classified as a system because the walls of the test tube has excluded the
reagents which are not in the test tube.

Types of Systems
We have
(i) Open System; where the reactants are influenced by external
conditions or external bodies, e.g. of external condition is
atmospheric pressure.
(ii) Close system: They are not affected by external bodies/conditions
e.g. destructive distillation of wood
There are three types of properties of a system:
a. Additive or Extensive Properties: These properties are such that for a
given system it is the sum of the corresponding component properties of that
system e.g. masses of two objects.
b. Constitutive Properties (Intensive): A constitutive property depends
primarily on the-arrangement of the atoms in molecules and to a lesser extent on
their nature, mass number and physical properties (e.g. boiling point, melting
point, density, etc.)

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c. Colligative properties: This is the property of a system or substance e.g. a
solution; which depends only on the concentration of the particles, molecules or
ions or number of molecules present and not upon nature e.g. the pressure of a
gas depends on the number of molecules of the gas present.
With respect to dilute solution we shall be concerned with non-volatile
solids in volatile solutions. For such dilute solutions the known Colligative
properties includes;
(i) Lowering of vapor pressure
(ii) Depression of freezing point
(iii) Elevation of boiling point and
(iv) The Osmotic pressure
They are very useful in the determination of relative molecular mass.

4.2 LOWERING OF VAPOUR PRESSURE

Let us indicate that the saturation vapor pressure of solvent is P°. If we
dissolve a non-volatile solute/solid in the solvent, we discover that the P° is
lowered, that is, dissolving a non-volatile solute, the V.P. about the solution is
less than the V.P. above the solvent, that is P < P°; where P° is V.P. of pure
solvent and P is V.P. of the solution.
Von Babo discovered that lowering of vapor pressure is proportional to
the vapor pressure of pure solvent; that is:
P° - P P (4.1)
Therefore, P° - P = KP°; K = a constant
Hence he affirmed that at any temperature the lowering of vapor pressure is
equal to a certain constant multiplied by the vapor pressure of the pure solvent
at that temperature, Raoult’s concluded that;
P°- P = X2 (4.2)
0
P
Where, X2 =mole fraction of the solute and P°-P/P0 = relative lowering of V.P.

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Hence, Raoult’s law states that the vapor pressure of a solution is equal to the
product of the V.P of solvent and mole fraction of solvent OR relative lowering
of V.P. is equal to mole fraction of solute.
Therefore, it is possible to prove these two statements of Raoult’s law:
Proof: 1f n1 = number of moles of solvent;
n2 = number of moles of solute;
X1 = mole fraction of solvent;
X2 = mole fraction of solute
Then, from Raoult's law the expression below is valid
P° - P = X2 = n2
P° (n1 + n2)
But we know that X1 + X2 =1.
But, X1=n2/ (n1 + n2) and X2 = n2 / (n1 + n2)
X1 + X2= (n1 + n2) / (n1 + n2) = 1.
P° - P = 1- X1
Po
P° - P = 1- X1
P° P°
= 1 - P =X1
Po
P= X1
P0
P = PoX1
Raoult’s law is therefore proved.

Use of Raoult’s Law in calculating Relative Molecular Mass

We recall that;
P° - P = X2 = n2 /(n1 + n2) (4.3)
0
P
If the solution is dilute, we can say or assume that n1>> n2
This implies that; n1 + n2≈ n1
Thus, when n2 = W2/M2 and n1 = W1/M1
Then,

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 P0 – P= n2 = W2/W2
P n1 M1/M1
= W2 x M1
M2 W1
For very dilute solutions
P° - P = W2 x M1 (4.4)
0
P W1 M2
Where W1 = Weight of the solvent
M = Molecular mass (weight) of solvent
W2 = Weight of the solute and
M2 = Molecular mass (weight) of solute
The above relationship is for non-volatile solute dissolved in a volatile solvent.
This is not a very popular method of determining molecular masses
because the lowering of V.P. in general is very small and therefore, cannot be
very accurately measured.

Example: 4.1
The vapor pressure of water at 50 0C is 12333 Nm-2. At this temperature a
solution of 9.14 g of carbamide (urea) in 150.0 g of water has a vapor pressure
of 12106 Nm-2. Find the relative molecular mass of carbamide.
Solution
P0 = 12333
P = 12106
M1 = Molecular mass of H2O = 18
M2 = Molecular mass of carbamide =?
W1 = Weight of water = 150.0g
W2 = Weight of carbamide = 9.14g

Substituting in the equation;

P° - P = W2 x M1
P0 M2 W1
We have;
12333 - 12106 = 9.14 x 18
12333 M2 150.0
12333 X 9.14 X 18 = (12333 -12106) x M2 x 150.0
M2= 59.6

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4.3 ELEVATION OF BOILING POINTS BY DISSOLVED SOLUTES
In any given liquid that is in equilibrium with its vapor, on addition of
non-volatile solute, the vapor pressure is lowered, consequently, there should be
elevation of Boiling point. As the dissolved solute lowers the vapor pressure, we
have to heat our solution to a higher temperature before its vapor pressure can
equal the atmospheric pressure so that the solution can boil.
The difference between the boiling point of the solution and the pure
solvent at any given constant pressure is referred to as the boiling point
elevation of the solution. The boiling point elevation of a solution depends on:
(i) The nature of solvent and
(ii) The concentration of the solute,

Generally, ∆T = KX2 (let K= Ke)

:. ∆T =Ke X2 (4.5)
Remember that for dilute solutions;
X2 =W2 x M1
M2 W1
Considering different weights of solute dissolved in the same solvent then
the elevation of boiling point is proportional to the weight of the solute
dissolved in a given solvent i.e. ΔT W2. Considering also different number of
moles of different solutes in a given weight of given solvent than the elevation
of boiling point for the two will be equal. Let the elevation of boiling point
when we dissolved 1 mole of solute in 1000 grams of solvent, let the constant
be Ke, then the formula below is generally accepted;
∆T =1000 KeW2 (4.6)
M2W1
Where, ∆T = Elevation of Boiling point
Ke = Ebullioscopic constant

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Ebullioscopic Definition
It is defined as the elevation of boiling point when we dissolve 1 mole of
solute in 1000 grams of solvent. Van't Hoff, defined Ke from a thermodynamic
function, he gave Ke, to be theoretically equal to,
RT02 (4.7)
1000L
Where, T0 = boiling pt. Of solvent
L = Latent heat of vaporization of solvent
R = molar gas constant
Hence, Ke varies for different solvents.

Values of Ke for some solvents

Solvent Calculated Value of Ke Observed Value of Ke
Water 0.52 0.52
Ethanol 1.19 1.20
Benzene 2.60 2.70
Chloroform 3.85 3.70

There are methods of determining the relative molecular masses of solutes using
elevation of boiling points. All these methods must ensure the accurate
measurement of ΔT; avoid fluctuations in the temperature readings and avoid
superheating of the apparatus.

There are about three methods available in finding ∆T, they are:
 Beckman's method,
 Landsbergers method and
 Cottrells method.
Limitations of the Boiling Point Method
The boiling point method for finding relative molecular masses has the
limitation that it cannot be applied when solute and solvent reacts together
chemically; when ionic dissociation occurs or when solutions are concentrated.
Also the dissolved substance must be nonvolatile, sothat vapor is evolved from
solvent only when the solution is boiling.
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Example 4.2:
Solution containing 103.8g of sucrose (C12H22O11) dissolved in 1000g of water is
to have a density of 1.038g/cm3at 20oC. Assuming the density to be independent
of temperature. Calculate (i) The vapor pressure of the solution at 100 oC. (ii)
The boiling point of the solution. (Take vapor pressure of pure solvent (H 2O) to
be 760 mmHg at 100OC; R=8.314 Jmol-1K-1, Latent heat of vaporization =
2260Jg-1,Ke=0.52).

Solution
Ke = RTo2
1000L
Where, Ke = Ebullioscopic constant
R = Molar gas constant
To = Boiling point = 100oC = 273 +100 = 373K
L = Latent heat of vaporization
Ke = 8.31 x (373)2
1000 x 2260
= 0.512 = 0.51(Compare to given value)
Using Raoult’s Law

P0 – P = n2 n2 (for dilute solutions)

P0 n1 + n2 n1

So,
n2 = W2 x M1
n1 M2 W1

P0 – P = W2 x M1
0
P M2 W1
P = V.P of the solute
P0 = V.P of pure solvent
W2 = Weight of solute dissolved
M2 = Molecular weight of solute
M1 = Molecular weight of solvent
W1 = Weight of solvent
Substituting we have;
760- P = 103.8 x 18
760 342 1000

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 760- P = 1868.4
342000
P = 756mmHg
(ii) T1 - T0 = ΔT = 1000KeW2
M2W1
ΔT = 1000 x 0.52 x 103.8
342 x 1000
ΔT = 0.156
Then, T1 - T100 = ΔT = 0.156
The boiling point of solution is
T1 = ΔT + T100
= 0.156t + 100
= 100.156oC
Example 4.3
In an experiment 10g of a solute were dissolved in 100g of benzene. The
boiling point of the resultant solution was found to rise from 80. 10 oc to
80.90oC. What is the relative molar mass of the solute? Take Ke = 1.64.

Solution
Data given:
W2 = 10g = mass of solute
W1 = 100g = mass of benzene
M2 = relative molar mass of solute
The boiling point elevation ΔT = 80.9 – 80.1 = 0.8K
The ebullioscopic constant Ke = 1.64
Using the relation: ΔT = 1000 KeW2
M2W1
M2 = 1000 KeW2
ΔT W1
Substituting we have;
M2 = 1000 x 1.64 x 10
0.8 x 100 = 205g/mole

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4.4 DEPRESSION OF FREEZING POINT
Freezing is a change of state from liquid to solid. Freezing takes place at
constant temperature and this temperature is called the freezing point for any
given substance under a given pressure. The freezing point normally quoted is
that for standard atmospheric pressure. It is a common observation that when a
solute is dissolved in a solvent, that the temperature of the solution is less than
that of original solvent. It is also observed that the freezing point of a solution is
below that of the solvent. This principle is used in making anti-freeze
substances e.g. ethanol and ethylene glycol, the two substances may be added to
water in cooling system of cars, thus making the freezing point of the solution
to be less than 0oC. As a result, water in the cooling system of cars does not
freeze overnight.
The above fact can also be applied to the freezing substances e.g. mixture
of salt and water. It must be understood that at this point we can say that the
melting point of a solid is equal to the freezing point of a liquid. Therefore, at
this point the vapor pressure of solid is equal to the vapor pressure of the liquid.
However, if a liquid is frozen to a point, some of the solid might separate out.
This implies that this solid is in equilibrium in the solution (mixture of solids
and liquids).
The solid that separates out is the pure solid solvent. Therefore we can
say that the vapor pressure of pure solid solvent is equal to the vapor pressure of
solution at freezing point.
Generally we know that ΔT/X2 = Constant
ΔT = KX2 (4.8)
If the solution is sufficiently dilute;
Then,
X2 =
W2 x M1 (4.9)
M2 W1
:. ΔT = K W2 x M1 (Putting equation (4.9) into (4.8))
M2 W1

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For a given solvent with variable solute, M2, M1, and W1 are constant
ΔT = KW2 (where W2 is the weight of the solute)
ΔT W2
Where in this case T is depression of freezing point of the solvent, that is T o –
Tn and W2 = weight of solute).
If we consider one mole of solute dissolved in 1000g of solvent W 1 and
depression of freezing point T produced is equal to K 1 where K1 is molal
depression constant. This implies that;
ΔT = Kf = k x 1 x M1
1000
ΔT = 1000kf = K x 1 x M1
KM1 = 1000kf = ΔT
K = 1000kf
M1
Putting the value of K above into equation (1)
ΔT = 1000kf x X2
M1

= 1000kf x W2 xM1
M1 M2 W1

:. ΔT = 1000kfW2 (4.10)
M2W1
(kf is called the Cryoscopic constant)
Kf is defined in terms of qualities characteristic of the solvent only and does not
depend on either the concentration or nature of the solvent. It is the freezing
point elevation constant Ke of solute only. Thus, like the vapor pressure
lowering and boiling point elevation kf is a colligative property.

Eutectic Mixture
A solid solution of two or more substances having the lowest freezing
point of all the possible mixtures of the component. This is taken advantage of
in boils of low melting points which are generally Eutectic mixtures.

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Eutectic Point
Two or more substances capable of forming solid solutions with each
other have the property of lowering each other’s freezing points, the minimum
freezing point attainable; corresponding to the Eutectic mixture is termed the
Eutectic point.

Determination of Molecular Mass using Freezing Point Depression

This method is preferred to the method of elevation of boiling point. This
is because we can measure freezing point more accurately than boiling point.
The following conditions are necessary for accurate results:
 There should be no association or dissociation of solute in the solvent.
 The solution must be dilute
 There should be no reaction between solute and solvent
 Only a small solid solvent should separate out at the freezing point of the
solution, otherwise the solution would no longer be dilute.
The methods available includes
1. Beckman’s method
2. Rast’s method

Example 4.4
Two solutions containing respectively 7.5g of urea (CO[NH 2]2) and 42.75g of a
substance X each in 1000g of water freeze at the same temperature. Calculate
the molecular mass of X
(C =12, O=16, N=14, H=1)

Solution: Using the equation:

ΔT = 1000kfW2
M2W1
Where,
Kf = Cryoscopic constant
W2 = Weight of solute
M2 = Molecular mass of solute
W1 = Weight of solvent

Since the two solutions freeze at the same temperature then T for the first
solution is equal to T for the second solution,
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 ΔT(1) = 1000kfW2 = 1000kfW2 = ΔT(2)
M2W1 M2W1
st
For the 1 solution, 7.5g = W2 = Weight of urea, molecular mass of
urea(CO[NH2]2) = M2 = 60g
ΔT(1) = 1000kf7.5 (1)
60 x W1
nd
For the 2 solution,
42.75g = W2 = Weight of X
M2 = Molecular mass of X
ΔT(2) = 1000kf 42.75 (2)
M2 x W1
Equating (1) to (2)
1000kf7.5 = 1000kf 42. 75
60 x W1 M2 x W1

=> 7.5 =42.75

60 M2
M2 = 342g

4.5 OSMOTIC PRESSURE

Certain membranes allow the passage of pure solvent molecules but do
not allow solute molecules or ions to pass. These are called semi-permeable
membrane. They may be found in living systems and an aqueous solution of
sugar or salt, etc, as shown in the figure below, the phenomenon of osmosis
occurs.

Figure 4.1: A diagram of solvent-solution separated by semi-permeable

membrane
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 After sometime, analysis of water in the beaker will show that no sugar or
salt solution is in it, but water has passed through the membranes into the
solution. That is solvent diffusion into the solution and the height of the solution
rises upwards. The membrane is called a semi-permeable membrane and it
allows solvent instead of solute to pass through it into a region of higher
molecular concentration. When a semi-permeable membrane separates two
solutions of the same substance in the same solvent, solvent flows from one
concentrated solution to one of more concentration. This flow of solvent, which
is an attempt to equalize the concentration of the two solutions, is Called
osmosis.
However, if we exert sufficient pressure on the solution (i.e. hydrostatic
pressure), we can stop or even reverse the flow of solvent from less
concentrated solution. The process of osmosis continues until the hydrostatic
pressure due to the extra height of the solution prevents further osmosis. Also
because the solvent, which has passed through the membrane, dilutes the
solution, the concentration of the solution after osmosis is not equal to the
original concentration.
Thus, we can now define osmotic pressure as follows:
1. That hydrostatic pressure which is just sufficient enough to prevent the flow
of solvent from pure solvent into a solution through a semi-permeable
membrane.
2. The pressure which must be applied above the solution to prevent passage of
solvent through a semi-permeable membrane into the solution. This means that
osmotic pressure is the pressure required to prevent osmosis from occurring.
Osmotic pressure is found to be proportional to the concentration of a
solute in a particular solvent or in general proportional to the molar
concentration of any solute in a given solvent. Equimolar concentration of any
solute in a given solvent has the same osmotic pressure. Thus, the measurement
of osmotic pressure can also be used for the determination of molecular
weights. Osmotic pressure can be extremely high, of the order 200 atmospheres
and this is a relatively sensitive way of measuring molecular weights. It is
particularly useful in the determination of the molecular weight of substances
with very large molecules.

Osmotic Pressure and Boyle’s law

According to Boyle’s law for gases
PV = K or P = K x 1
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 V
Where P = Pressure and V =Volume
That is, the pressure of a gas is proportional to its concentration. As an
illustration, the value for the osmotic pressure of solution for a given solute
considering the solution of cane sugar at 0oC is given below.

Concentration Osmotic Volume (dm3) π x V (dm3atm)

(g/dm3) Pressure containing 1
(atm) (π) Mole of solute
2.02 0.134 169.3 22.7
10.00 0.66 34.2 22.6
20.00 1.32 17.1 22.6
45.00 2.97 7.60 22.6
93.75 6.18 3.65 22.6

1. From the chart above, it can be seen that the concentration is always
proportional to the osmotic pressure (π).
2. When we multiply the volume (V) containing 1 mole of solute by
osmotic pressure (π), we get a constant.

Deductions
1. The osmotic pressure of a given dilute solution at a given temperature is
proportional to the concentration of the solute.
2. The product of osmotic pressure and the volume containing 1 mole of the
solute is always constant.

Osmotic Pressure and Charles’s Law

The osmotic pressure for a solution of cane sugar is given below:
Temp. (T) (K) Osmotic Pressure(π) π/T
273 7.085atm 0.02594
283 7.334 atm 0.2591
293 7.605 atm 0.2595
298 7.729 atm 0.2594

From the table above, one can conclude that osmotic pressure is directly
proportional to the absolute temperature (this is analogous to Charles law).
However, this does not conform accurately which cane sugar beyond 25oC.

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 The osmotic pressure of a solution is independent of the nature of
dissolved substance. The osmotic pressure of a dilute solution is equal to the gas
pressure which the dissolved substance would exert if it were gas at the same
temperature and occupying the same volume as that of the solution provided
that the solution is so dilute that the volume occupied by the solute is negligible
when compared to the volume occupied by the solvent.

Osmotic Pressure and the Ideal Gas Equation

By combining the above laws, similar to Boyle’s, Charles and
Avagadro’s, we can have an equation in the form
πV = nRT (4.11)
This is identical to ideal gas equation. Van’t Hoff summarized this law by
showing that R for osmotic pressure above, agrees very closely with the gas
constant.,
Therefore, we have that,
πV = nRT = πV = w/mRT (4.12)
Where
π = Osmotic pressure
V = Volume
R = Gas constant
T = Temperature in Kelvin
W = Weight of substance
M = Molar mass of substance
Thus, we can calculate the molecular mass of a given solute.

Some Units of osmotic Pressure

1Nm-2 = 1 Pascal
1 atm = 101325Nm-2
1 atm = 760mmHg = 76cmHg
1 torr = 1mmHg

Example 4.5
An aqueous solution of sucrose containing 19.15g of the sugar per dm -3 has an
osmotic pressure of 136300 Pa at 20oC. Find the relative molecular mass of
sucrose.

Solution

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 Imagine the sugar to be a gas in the volume occupied by the solution.
1dm of gas at 20oC and 136300 Pa pressure has a volume at S.T.P. of;
-2

1x 273 x 136300dm-3
293 101300
= 1.254 dm-3
At S.T.P. 1.254dm-3 of gas contain 19.15g of sucrose
:. 22.4dm-3 at S.T.P. contain 1915 x 22.4 g
1.254
= 342.3g
Example 4.6
What is the molecular mass of a given substance containing 2.4g of
substance in 120cm3 of water and the solution gave an osmotic pressure (π) of
998mmHg at 16oC.

Solution
Considering 1M of gas at s.t.p. and this values hold,

T = 273, V = 22400 cm3 and P = 760 mmHg

We know that PV = nRT, but n = 1 mole
PV = 1 x RT
760 x 22400 = 1 x 273 x R
R = 760 x 22400
273
= 623589
Also πV = nRT = w/mRT
=> M = wRT = 2.4 x 62359 x 289
πV 998 x 120
= 361.2g
Two methods are readily employed to measure osmotic pressure. These
are Pfeffer’s method and Berkeley and Hartley’s method. As a result of the
difficulties in measuring osmotic pressure accurately, we do not usually use this
method in calculating molecular mass. Other methods such as freezing point
depression are preferred. However, when we consider solutes of higher
molecular masses, it is preferable to use the osmotic pressure method because
the dilute solution of the substances can give an appreciable value of osmotic

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pressure. Such solutions that can produce high appreciable value of osmotic
pressure include; protein, amino acid, hemoglobin found in blood cells.

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