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NationalInstituteofTechnology,
Rourkela
Department of Metallurgy and Materials
Engineering

PROCESS METALLURGY LAB

EXPERIMENT – 2

GUIDED BY
Prof. Archana Mallik

SUBMITTED BY
Avvaru Sai Bharadwaja
120MM0764
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TITLE: Determination of deviation from ideality in the formation DATE: 03/02/2022

of binary solutions.

1) AIM: To determine the deviation from ideality in the formation of binary solutions.

2) Theory:
BINARY SOLUTION
 change in volume in binary solutions formed by mixing water and methanol or ethanol in
different proportions
 Deviation from ideality
There are three cases as follows:
 Case-1: When ΔV=0, ideal solution is formed.
 Case-2: When ΔV>0, positive deviation from ideality occurs.
 Case-3: When ΔV<0, negative deviation from ideality occurs.
A binary solution is a homogeneous mixture of two or more than two substances whose
composition can change within a certain limits. An ideal solution of two liquids and obeys
Raoult's law, which states that the partial vapor pressure of each component is proportional to
its mole fraction: and , where and are the vapor pressures of the pure components at a given
temperature (very often 25 °C). The total vapor pressure above the solution is then given by ,
assuming Dalton's law. Ideal solutions are fairly uncommon but serve as a convenient reference
system to describe nonideal solutions. Pairs of liquids that are well approximated by Raoult's
law usually contain molecules of similar size, shape, and chemical structure. Some well-known
examples are benzene and toluene, chlorobenzene and bromobenzene, and carbon
tetrachloride and silicon tetrachloride.

The above diagram shows the positive and negative deviations from Raoult’s law
Ideal solutions are such that 2εAB=εAA+εBB, i.e. their intermolecular forces are exactly the
same. Nonideal solutions can either have positive or negative deviation away from ideal mixed
volumes. For ideal binary mixtures, let us suppose both components are at least somewhat
volatile liquids. When two liquids A and B combine, there is a competition between AA or BB
interactions, and AB interactions:
 Liquid A may prefer to interact more with liquid B than with liquid A (negative deviation).
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 Liquid A may prefer to interact with liquid A more than with liquid B (positive deviation).
 There may be no preference of A or B to interact with either A or B over the other (ideal
solution). We can examine this relationship by considering the energies ε of AA, BB, and AB
interactions.
 NEGATIVE DEVIATION LEADS TO VOLUME CONTRACTION
With negative deviation:
2εAB<εAA+Εbb

You can see the vapor pressure vs. mole fraction curve dip below the ideal/Raoult's Law lines,
hence negative deviation.
Here, A prefers to interact with B and B prefers to interact with A because the AB interactions
are less repulsive. So, liquid A mixes favorably with liquid B.
Therefore, after mixing, the most likely average distance of molecule A from
molecule B is closer together than it would be from molecule A. This means the volume of the
solution contracts after mixing, relative to the ideal solution.
That means A and B are difficult to make vaporize overall because the molecules A and B are
well-attracted together.

POSITIVE DEVIATION LEADS TO VOLUME EXPANSION

On the other hand, with positive deviation:
2εAB>εAA+εBB
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You can see the vapor pressure vs. mole fraction curve bulge above the ideal/Raoult's Law lines,
hence positive deviation.
Here, A prefers to interact with A and B prefers to interact with B because the AB interactions
are more repulsive. So, liquid A mixes poorly with liquid B.
Therefore, after mixing, the most likely average distance of molecule A from
molecule B is farther away than it would be from molecule A. This means the volume of the
solution expands after mixing, relative to the ideal solution.
That means A and B interact unfavorably, and are easy to make vaporize overall because the
molecules A and B are poorly-attracted together

3) APPARATUS AND MATERIAL REQUIRED:

 Apparatus used are
1. Beaker
2. Pipette
3. Glass rod
4. Thermometer
5. Stopwatch
 Materials used are
1. Water
2. Methanol
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BEAKER PIPETTE THERMOMETER

STOPWATCH GLASSROD

4) PROCEDURE:
 Take a mixture of water and methanol in different ratio as given below such that the
mixture volume should be 50ml
90% of methanol + 10% of water = 45 ml of methanol + 5 ml of water
70% of methanol + 30% of water = 35 ml of methanol + 15 ml of water
50% of methanol + 50% of water = 25 ml of methanol + 25 ml of water
30% of methanol + 70% of water = 15 ml of methanol + 35 ml of water
10% of methanol + 90% of water = 45 ml of methanol + 5 ml of water
 All these solutions are taken in different glass beakers, thoroughly mixed and then allowed
to settle to final fixed volume.
 They should be given sufficient time(20-25 min) also to bring back the solutions to room
temperature.
 Now, volume of each of these solutions is taken and difference between the final volume of
each of the solutions and initial volume taken is determined and reported as deviation.
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5)OSERVATION TABLE:

S.N Methanol: Volume of Volume Initial Final Initial Final ΔV Deviation

O water methanol of temperat tempe Volum volume
Ratio (ml) water ure rature e
(ml)
1 90:10 45 5 23 22 50 48 -2 Negative

2 70:30 35 15 25 22 50 45 -5 Negative
3 50:50 25 25 26 22 50 46 -4 Negative
4 30:70 15 35 25 22 50 46 -4 Negative
5 10:90 5 45 24 22 50 47 -3 Negative

GRAPH :

7) CONCLUSION:
The deviation will be either positive or negative from ideal behavior and this should be
discussed for methanol and ethanol both. This is related to heat evolved during mixing. Graphs
between % methanol vs deviation and % ethanol vs deviation should be plotted and reported.

PRECAUTIONS:
 We need to wear gloves while doing the experiment
 We should not do the experiment without concerning teacher

REFERENCES:
 https://en.wikipedia.org/wiki/Raoult%27s_law
 https://socratic.org/questions/592c8b087c01495cbd66490e