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GMR Institute of Technology

Rajam, Andhra Pradesh


(An Autonomous Institution Affiliated to JNTUK, AP)

Department of Chemical Engineering


rd
Class 3 Sem. - B. Tech. (Chemical Engineering)
Course Chemical Process Calculations Course Code CHEM-2403
Prepared by Mr. P. Satya Sagar, Sr. Assistant Professor
Lecture Topic Raoults law, Non-volatile solutes
Course Outcome CCHEM203.2 Program Outcome PO1,PO13
Duration 50 min Lecture 9 of 45 Unit I
REMEMBER UNDERSTAND APPLY ANALYSE EVALUATE CREATE
Learning Level
(Tick whichever is applicable)

1. Objectives
To familiarize Raoults law of Ideal solutions
a. Impart knowledge on calculation of vapor pressure of Non-volatile solutes
2. Topic Learning Outcomes: After the completion of the class the students will able to:
a. Utilise Raoults law of Ideal solutions for engineering calculations
b. Calculate vapor pressure of Non-volatile solutes
3. Teaching Methodology
a. Chalk & Talk/PPT Mode
4. Applications
a. Distillation
b. Evaporation
c. drying
d. condensation
e. air conditioning
f. air separation
g. humidification
h. dehumidification

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5. Evocation

6. Discussion

Solutions: The surface of a homogeneous solution contains molecules of all its components,
each of which has an opportunity to enter the vapor state. However, the number of molecules of
any one component per unit area of surface will be less than that component exposed the same
area of surface in the pure liquid state. For this reason the rate of vaporization of a substance will
be less per unit area of surface when in solution than when present as a pure liquid. However, a
molecule from a homogeneous solution which is in the vapor state may strike the surface of the
solution at any point and will be absorbed by it, reentering the liquid state. Thus, although the
opportunity for vaporization of any one component is diminished by the presence of the others,
the opportunity for the condensation of its vapor molecules is unaffected. For this reason, the
equilibrium vapor pressure which is exerted by a component in a solution will be, in general, less
than that of the pure substance.

This solution is entirely different from that of a non-homogeneous mixture. In a non-


homogeneous mixture the rate of vaporization of either component, per unit area of total surface,
in diminished because the effective surface exposed is reduced by the presence of the other
component. However, condensation of a component can take place only at the restricted areas
where the vapor molecules impinge upon its own molecules. Thus , both the rate of vaporization
and the rate of condensation are reduced in the same proportion, and the equilibrium vapor

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pressure of each component is unaffected by the presence of the others.

Raoults Law:

The generalization known as Raoults law states that the equilibrium vapor pressure that is
exerted by a component in a solution is proportional to the mole fraction of that component.
Thus,

nA
pA PA N A PA
nA nB nC ......

Where pA = vapor pressure of component A in solution with components B, C,

PA = vapor pressure of A in the pure state.

nA, nB, nC..= moles of components A,B,C

NA = mole fraction of A.

From the kinetic theory of equilibrium vapor pressures it would be expected that this
generalization would be correct. When the following conditions exists:

1. No chemical combination or molecular association between unlike molecules takes place


in the formation of the solution.

2. The sizes of the component molecules are approximately equal.

3. The attractive forces between like and unlike molecules are approximately equal.

4. The component molecules are non-polar, and no component is concentrated at the surface
of the solution.

Few combinations of liquids would be expected to fulfill all the conditions, and it is not
surprising that Raoults law represents only a more or less rough approximation to actual
conditions. Where the conditions are fulfilled, a solution will be formed from its components
with out thermal change, and with out change in total volume. A solution that exhibits these
properties is termed an ideal or perfect solution. Solutions that approximate the ideal are formed
only by liquids of closely related natures such as the homologs of a series of non-polar organic
compounds. For example, Paraffin hydrocarbons of not too widely separated characteristics form
almost ideal solutions in each other. The behavior of the ideal solution is useful as a criterion by

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which to judge solutions and also as a means of approximately predicting quantitative data for
solutions that would not be expected to deviate widely from ideal behavior. For the accuracy
required in the majority of industrial problems, a great many solutions of chemically similar
materials may be included in this class.

Nonvolatile solutes: If one component of a binary solution has a negligible vapor pressure, its
presence will have no effect on the composition of the vapor in equilibrium with the solution.
The vapor will consist entirely of the volatile component, but its equilibrium pressure will be less
than that of the pure liquid at the same temperature. Thus, a nonvolatile solute produces a vapor
pressure lowering or a boiling point elevation in its solvent. If the components possess closely
related characteristics, the system may approach ideal behavior. Then the total vapor pressure
will be the product of the vapor pressure and the mole fraction of the solvent. With ionizing or
associating solutes the effective mole fraction of the solutes is dependent on the degree of
ionization or association. For these reasons, the theories of ideal behavior are not valid in the
estimation of vapor pressure data for such solutions, which include those in which water is the
solvent.

Limitations on Raoult's Law

Raoult's Law only works for ideal solutions. An ideal solution is defined as one which obeys
Raoult's Law.

Features of an ideal solution

In practice, there's no such thing! However, very dilute solutions obey Raoult's Law to a
reasonable approximation. The solution in the last diagram wouldn't actually obey Raoult's Law -
it is far too concentrated. I had to draw it that concentrated to make the point more clearly.

In an ideal solution, it takes exactly the same amount of energy for a solvent molecule to break
away from the surface of the solution as it did in the pure solvent. The forces of attraction
between solvent and solute are exactly the same as between the original solvent molecules - not a
very likely event!

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Suppose that in the pure solvent, 1 in 1000 molecules had enough energy to overcome the
intermolecular forces and break away from the surface in any given time. In an ideal solution,
that would still be exactly the same proportion.

Fewer would, of course, break away because there are now fewer solvent molecules on the
surface - but of those that are on the surface, the same proportion still break away.

If there were strong solvent-solute attractions, this proportion may be reduced to 1 in 2000, or 1
in 5000 or whatever.

In any real solution of, say, a salt in water, there are strong attractions between the water
molecules and the ions. That would tend to slow down the loss of water molecules from the
surface. However, if the solution is sufficiently dilute, there will be good-sized regions on the
surface where you still have water molecules on their own. The solution will then approach ideal
behaviour.

The nature of the solute

There is another thing that you have to be careful of if you are going to do any calculations on
Raoult's Law (beyond the scope of this site). You may have noticed in the little calculation about
mole fraction further up the page, that I used sugar as a solute rather than salt. There was a good
reason for that!

What matters isn't actually the number of moles of substance that you put into the solution, but
the number of moles of particles formed. For each mole of sodium chloride dissolved, you get 1

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mole of sodium ions and 1 mole of chloride ions - in other words, you get twice the number of
moles of particles as of original salt.

So, if you added 0.1 moles of sodium chloride, there would actually be 0.2 moles of particles in
the solution - and that's the figure you would have to use in the mole fraction calculation.

Unless you think carefully about it, Raoult's Law only works for solutes which don't change their
nature when they dissolve. For example, they mustn't ionise or associate (in other words, if you
put in substance A, it mustn't form A2 in solution).

If it does either of these things, you have to treat Raoult's law with great care.

Department of Chemical Engineering


Class 3rd Sem. - B. Tech. (Chemical Engineering)
Course Chemical Process Calculations
Prepared by Mr. P. Satya Sagar, Sr. Assistant Professor

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7. Mind Map:

8. Readings:

1. Hougen, Olaf A., and Kenneth M. Watson. "Chemical Process Principles-Part 1: Material
and Energy Blances." (1948)
2. Himmelblau, David Mautner, and James B. Riggs. Basic principles and calculations in
chemical engineering. FT Press, 2012
3. Bhatt, B. I., and S. M. Vora. Stoichiometry:(si units). Tata McGraw-Hill Pub. Co., 1996
4. http://www.chemguide.co.uk/physical/phaseeqia/raoultnonvol.html#top
9. Questions:
Remember:
1. State Raoult's Law for a non-volatile solute in a single volatile solvent.
Understand:

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1. Raoult's Law only really works for ideal solutions. An ideal solution is defined as one
which obeys Raoult's Law. How do the following affect how ideal a solution is? a) The
concentration of the solution. b) The forces between the particles in the solution. c)
Changes to the solute molecules when they dissolve.
Apply:
1. A mixture of acetone vapor and nitrogen contains 14.8% acetone by volume. Calculate
the relative saturation and percentage saturation of the mixture at a temperature of
200C, and the pressure of 745 mm Hg. Vapour pressure of acetone at 200C is 184.8
mm Hg.
10. Key Words:
Ideal solutions
Homogeneous solution
Kinetic theory
Equilibrium vapor pressures
Non-polar
No chemical combination
Molecular association
Attractive forces

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