Christ Jyoti Hr. Sec.

School

Colligative Properties
and
Molecular Mass

Year: 2022-2023

CHEMISTRY PROJECT

SUBMITTED BY: SUBMITTED TO:

Aditya Vijay Dwivedi Mrs. SUJA
12th Rose ABRAHAM
 INDEX
S Description Page
No. No.

1. Certificate 3
2. Acknowledgement 4
3. Introduction 5
4. Boiling point elevation 7

5. Freezing point Depression 19

6. Osmotic pressure 21
7. Molecular Mass 27

8. Molecular Mass Calculation 30

 CERTIFICATE

This is to certify that Chemistry project on colligative

properties is developed by Aditya Vijay Dwivedi of class
12th under my supervision in the chemistry lab of Christ
Jyoti Hr. sec. School in the session 2022-2023. The work
done by them is original.

Aditya Vijay Dwivedi

MRS. SUJA
ABRAHAM

Signature:
 ACKNOWLEDGEMENT

I would like to express my sincere gratitude to my

Chemistry teacher SUJA ABRAHAM for her vital
support, guidance and encouragement without
which this project would not come forth from my
side. Who helped me completing the project by
giving ideas, thoughts and made this project easy
and accurate.
I wish to thank my parents for their undivided
support and interest who inspired me and
encouraged me to go my own way, without which I
would be unable to complete my project.
Colligative Properties
Introduction
Properties of solutions that depend on the
number of molecules present and not on the
kind of molecules are called colligative
properties.

These properties include boiling point

elevation, freezing point depression, and
osmotic pressure. Historically, colligative
properties have been one means for
determining the molecular weight of
unknown compounds.

In this chapter we discuss using colligative

properties to measure the
molecular weight of polymers. Because
colligative properties depend on the number of
molecules, we expect, and will show, that
colligative property experiments give a
number average molecular weight.
Boiling Point Elevation

Figure 5.1 shows the vapor pressure of a liquid

for pure liquid and for a solution with that
liquid as the solvent
. In an ideal solution, the vapor pressure of the
solvent, PA, is reduced from the vapor pressure
of a pure liquid,
where XAis the mole fraction of liquid A. This
reduction is reflected in a shift to the right of
the vapor-pressure curves in Fig. 5.1.
By definition, boiling point is the temperature
at which the vapor pressure of the liquid
reaches 1 atm.
Thus, the right-shift caused by the dissolution
of component B in solvent A causes the boiling
point to increase. This increase, ∆Tb, is the
boiling point elevation effect.
A well known result from introductory
chemistry is that the boiling point elevation is
proportional to the molar concentration of
solute particles

∆Tb = Kbm

(5.1)
where m is the molality of solute molecules
and Kb is the boiling point elevation
coefficient that is a function of only the
solvent. Molality is the number of moles of
component B per 1000 grams of solvent. If we
prepare a solution of an unknown compound
of molecular weight B at a concentration

Pure Solvent
1 atm

Solution

∆T

Temperature Tb

Figure 5.1: Boiling point elevation effect is a

consequence of the effect of solute
molecules on the vapor pressure of the
solvent.

c in g/cm3, then
(5.
2)
where ρ is the density of the solvent (in
g/cm3). Substituting into the expression for
∆Tb gives
(5
.3
)
or
(5.4)
For a given solvent (e.g., water where Kb =

0.52 and ρ = 1.00) and concentration (c), all

terms in Eq. (5.4) are known except

for MB. Thus, measuring ∆Tb can be used to

determine the molecular weight MB.

 We can also express boiling point elevation
in terms of mole fraction.
Mole fraction is
(5.5
)
where V is total volume and MA is
molecular weight of the solvent. The boiling
point elevation becomes

(5.
6)
To apply boiling point elevation to
polymers, we begin by using solution
thermodynamics to derive an
expression for ∆Tb. At equilibrium, the chemical
potential of the vapor is equal to the chemical
potential of the liquid
µvapA= µliqA = µ◦ A + RT lnXA or

(5.7)
 BOILING POINT ELEVATION

where we have assumed an ideal solution.

Differentiating both sides gives

(5.
8)
which is used to get
(5.
9)
where is the heat of vaporization of
the solvent or ∆Hvap.
Now consider the process of forming a

solution. As the polymer is added, the mole

fraction of A will go from 1 at the start to XA
which is the mole fraction of
the final solution. During the process, the
boiling point will go from Tb to T where Tb
is the boiling point of the pure liquid and
T is the boiling point of the solution.
Integrating over this process gives

(5.10)
The integrals are easily evaluated if we
assume that ∆Hvapis independent of
temperature over the small temperature
range from Tb to T. The result is

(
5
.
1
1
)
We can simplify this result using ∆Tb = T
−Tb, TTb ≈ Tb2, and lnXA = ln(1−XB) ≈ −XB.
These simplifications apply when XBis small
(which occurs when the solution is dilute) and
when ∆Tb is small. In general,
dilute. The previous equation simplifies to

(5.
12
)
or
(5.
13
)
Comparison of this result to Eq. (5.6)
gives a theoretical expression of Kb:
(
5
.
1
4
)
The result is often derived in physical
chemistry books.
In applying boiling point elevation to
polymer solutions, we should realize that
polymer solutions are really solutions of many
property, we can write the boiling point
elevation of a polymer solution as a sum over
the mole fractions of each molecular weight
component:

(5.15
)
where Xiis the mole fraction of polymer
with molecular weight Mi. We more
conveniently rewrite Xiin terms of
concentration:

(
5
.
1
6
)
where ci is the concentration in
weight/unit volume (e.g., g/cm3) of polymer
with molecular weight i. The approximation in
the total number of moles of polymer.
Summing the mole fractions, Xi, results in

(5.17)
where
c = Xci (5.18)
i
The final expression for the
boiling point elevation
becomes
(5.19)
It is common to express the boiling point
elevation in terms of the latent heat of
vaporization, lvap,
defined as energy or vaporization
per unit weight or
∆HvapJ/mole (5.20)
lvap = = = heat of
vaporization in J/g
MA g/mole
The boiling point elevation
becomes
(
5
.
2
1
)
Except for incorporation of
polydispersity, there is nothing new
about the boiling point elevation
expression for polymer solutions vs. the
comparable expression for small molecule
solutions. In polymers, however, the solution is
more likely to be non-ideal. For this equation to
apply we will probably need to use very low
concentrations or techniques to extrapolate to
very low concentrations.
For an example, let’s consider a solution of
polystyrene in benzene. For benzene ρ =
and lvap = 104 cal/g. We assume a
relatively concentrated solution of c = 1 g/cm3

of a polymer with molecular weight MN=

20,000. The change in the boiling point
elevation for this solution is ∆Tb = 1.4 × 10−3 ◦ C.
This boiling point elevation is very small. It is
probably beyond the accuracy of most
temperature measuring equipment. The small
change arises despite relatively ideal conditions
of a fairly concentrated solution and a low
molecular weight polymer. More dilute
solutions or higher molecular weight polymers
would give
an even smaller ∆Tb. The problem with
polymer solutions is that for a given weight of
material, the polymer solution will

FREEZING POINT DEPRESSION

have many less molecules than the comparable
small molecule solution. When there are a
small number of molecules, the change in
boiling point (a colligative property) is small.
The problem with the boiling point elevation
method applied to polymer solutions is that it is
not sensitive enough. It has found some use
with polymers but it is limited to polymers with
relatively low molecular
weights. (e.g., MNless than 20,000 g/mol).

5.3Freezing Point Depression

A similar analysis (but with sign changes)
can be applied to the freezing point
depression of a polymer solution. The final
result is

(
5
.
2
2
)
where Tf is the freezing point of the
solvent and lf is the latent heat of fusion. We
consider the same example of
polystyrene in benzene with Tf = 5.5◦ C, lf
= 30.45 cal/g for the freezing point
20,000, the change in the freezing point
of the solution is ∆Tf = 2.9×10−3 ◦ C. Like the
boiling point elevation effect, the freezing
point depression effect is too small. The
technique is insensitive and only useful

for low molecular weight polymer (e.g.,

MNless than 20,000 g/mol).

Osmotic Pressure
Another colligative property is osmotic
pressure. Figure 5.2 illustrates the osmotic
pressure effect. Imagine a pure solvent and a
solution separated by a semipermeable
membrane. An ideal
semipermeable membrane will allow the
solvent molecules to pass but prevent the
solute molecules (polymer molecules) from
passing. The different concentrations on the
two sides of the membrane will cause an
initial difference in chemical potential. At
equilibrium, this difference in potential will
be counteracted by an effective pressure
across the membrane. As shown in Fig. 5.2, it
can be imagined that solvent molecules pass
from the pure solvent side to the solution
side.
The excess height in the column of liquid above
the solution side is related to the
osmotic pressure by π = ρgh. Here π is the
osmotic pressure, ρ is the density of the
solution, g is the acceleration of gravity (9.81
m/sec2) and h is the height of the column of
liquid.
We begin with a thermodynamic analysis of
osmotic pressure. At equilibrium the
chemical potential in the solution will be
equal to the chemical potential in the pure
solvent:

µsolventA = µsolutionA (5.23)

=
µ◦ A + RT lnaA

where µsolventAis the chemical

potential of the pure liquid or
A
µsolvent
A = µ◦ (5.24)
 π = ρgh

Membrane

Solvent Solution

Figure 5.2: A schematic view of

osmotic pressure across a
semipermeable membrane.

The only way the chemical potentials will be

equal will be if the activity of component A in
the solution is equal to
1. The activity can be raised to 1 by
applying pressure. That is, activity is a
pressure dependent quantity. By applying
the correct pressure, the osmotic
pressure, the activity in the solution can
be changed to 1. The
osmotic pressure that gets applied occurs
naturally by the tendency to approach
equilibrium.
To get the pressure dependence of activity,
we consider the pressure dependence of the
chemical potential
(5.
25)
Rearranging and integrating the left

hand side from the original activity aA to

the final activity 1 and the right hand side

from the initial pressure 0 to the final pressure

— the osmotic pressure π — results in:

(5.26)
which
integrates to
 (5.27)
Now, in an ideal solution
−lnaA = −lnXA ≈ XB. (5.28)
This last approximation follows because ln(1
− x) ≈ −x for small x. Finally, as in the analysis
of boiling point elevation, we replace XBby Pi Xi
which was derived in Eq. (5.17) to be
(5.2
9)
giving
(5.3
0)
MOLECULAR MASS
Molecular mass is a number equal to the sum of
the atomic masses of the atoms in a molecule.
The molecular mass gives the mass of
a molecule relative to that of the 12C atom,
which is taken to have a mass of 12. Molecular
mass is a dimensionless quantity, but it is given
the unit Dalton or atomic mass unit as a means
of indicating the mass is relative to 1/12th the
mass of a single atom of carbon-12.

Molecular mass is also called molecular

weight. Because the mass is relative to carbon-
12, it's more correct to call the value "relative
molecular mass".
A related term is molar mass, which is the mass
of 1 mol of a sample. Molar mass is given in
units of grams.
Calculation
Molecular masses are calculated from the atomic
masses of each nuclide present in the molecule,
while relative molecular masses are calculated from
the standard atomic weights[3] of each element. The
standard atomic weight takes into account
the isotopic distribution of the element in a given
sample (usually assumed to be "normal"). For
example, water has a relative molecular mass of
18.0153(3), but individual water molecules have
molecular masses which range between
18.010 564 6863(15) Da (1H216O) and
22.027 7364(9) Da (2H218O). Atomic and molecular
masses are usually reported in Daltons which is
defined relative to the mass of the isotope 12C
(carbon 12). Relative atomic and molecular mass
values as defined are dimensionless. However, the
"unit" Dalton is still used in common practice. For
example, the relative molecular mass and molecular
mass of methane, whose molecular formula is CH4,
are calculated respectively as follows:
The uncertainty in molecular mass reflects variance (error) in
measurement not the natural variance in isotopic abundances
across the globe. In high-resolution mass spectrometry the
mass isotopomers 12C1H4 and 13C1H4 are observed as distinct
molecules, with molecular masses of approximately 16.031
Da and 17.035 Da, respectively. The intensity of the mass-
spectrometry peaks is proportional to the isotopic abundances
in the molecular species. 12C 2H 1H3 can also be observed with
molecular mass of 17 Da.
Molecular Mass
Calculation
Molecular mass may be calculated by taking the
atomic mass of each element present and
multiplying it by the number of atoms of that
element in the molecular formula. Then, the
number of atoms of each element is added
together.
For example. to find the molecular mass of
methane, CH4, the first step is to look up the
atomic masses of carbon C and hydrogen H using
a periodic table:
carbon atomic mass = 12.011
hydrogen atomic mass = 1.00794
Mass
spectrometry
In mass spectrometry, the molecular mass of a small
molecule is usually reported as the monoisotopic mass,
that is, the mass of the molecule containing only the most
common isotope of each element. Note that this also
differs subtly from the molecular mass in that the choice
of isotopes is defined and thus is a single specific
molecular mass of the many possibilities. The masses
used to compute the monoisotopic molecular mass are
found on a table of isotopic masses and are not found on
a typical periodic table. The average molecular mass is
often used for larger molecules since molecules with
many atoms are unlikely to be composed exclusively of
the most abundant isotope of each element. A theoretical
average molecular mass can be calculated using
the standard atomic weights found on a typical periodic
table, since there is likely to be a statistical distribution of
atoms representing the isotopes throughout the molecule.
The average molecular mass of a sample, however,
usually differs substantially from this since a single
sample average is not the same as the average of many
geographically distributed samples.
Mass photometry
Mass photometry (MP) is a rapid, in-solution,
label-free method of obtaining the molecular
mass of proteins, lipids, sugars & nucleic
acids at the single-molecule level. The
technique is based on interferometric
scattered light microscopy.[4] Contrast from
scattered light by a single binding event at the
interface between the protein solution and
glass slide is detected and is linearly
proportional to the mass of the molecule. This
technique is also capable of measuring sample
homogeneity,[5] detecting
protein oligomerization state, characterization
of complex macromolecular assemblies
(ribosomes, GroEL, AAV) and protein
interactions such as protein-protein
interactions.[6] Mass photometry can measure
molecular mass to an accurate degree over a
wide range of molecular masses (40kDa –
5MDa).
Hydrodynamic methods

To a first approximation, the basis for

determination of molecular mass according
to Mark–Houwink relations[7] is the fact that
the intrinsic viscosity of solutions (or suspensions)
of macromolecules depends on volumetric
proportion of the dispersed particles in a
particular solvent. Specifically, the hydrodynamic
size as related to molecular mass depends on a
conversion factor, describing the shape of a
particular molecule. This allows the apparent
molecular mass to be described from a range of
techniques sensitive to hydrodynamic effects,
including DLS, SEC (also known as GPC when
the eluent is an organic solvent), viscometry, and
diffusion ordered nuclear magnetic resonance
spectroscopy (DOSY). The
apparent hydrodynamic size can then be used to
approximate molecular mass using a series of
macromolecule-specific standards. As this
requires calibration, it's frequently described as a
"relative" molecular mass determination method.
Static light scattering

It is also possible to determine absolute

molecular mass directly from light
scattering, traditionally using the Zimm
method. This can be accomplished either
via classical static light scattering or
via multi-angle light scattering detectors.
Molecular masses determined by this
method do not require calibration, hence
the term "absolute". The only external
measurement required is refractive index
increment, which describes the change in
refractive index with concentration.