Ideal and Non-Ideal solutions

Non-ideal solutions
Ideal solutions Positive deviation from Raoult's law Negative deviation from
Raoult's law

1.Obey Raoult's law at every range of 1. Do not obey Raoult's law. 1.Do not obey Raoult's law.
concentration.

2. Hmix = 0; neither heat is 2. Hmix > 0. Endothermic dissolution; 2. Hmix < 0. Exothermic
evolved nor absorbed during heat is absorbed. dissolution; heat is evolved.
dissolution.

3. Vmix = 0; total volume of 3. Hmix > 0. Volume is increased after 3. Hmix < 0. Volume is
solution is equal to sum of volumes of dissolution. decreased during dissolution.
the components.

4. P = pA + pB = poAXA +poBXB i.e., 4. pA > poAXA; pB >poBXB 4. pA < poAXA; pB <poBXB

pA = poAXA : pB = poBXB .
. . p A + pB > poAXA +poBXB ... pA + pB < poAXA +poBXB

5. A-A, A-B, B-B interactions should
be same, i.e., 'A' and 'B' are identical
in shape, size and character.
5. A-B attractive force should be weaker
than A-A and B-B attractive forces. 'A' and
'B' have different shape, size and
character.
5. A-B attractive force should be
greater than A-A and B-
B attractive forces. 'A' and 'B'
have different shape, size and
character.

6. Escaping tendency of 'A' and 'B' 6. 'A' and 'B' escape easily showing 6. Escaping tendency of both
should be same in pure liquids and in higher vapor pressure than the expected components 'A' and 'B' is
the solution. value. lowered showing lower vapor
pressure than expected ideally

Examples: Examples:
Examples: Acetone +ethanol Acetone + aniline;
acetone + CS2: acetone + chloroform;
Dilute solutions; water + methanol; CH3OH + CH3COOH ;
water + ethanol; H2O + HNO3
benzene + toluene: CCl4 + toluene; chloroform + diethyl ether;
CCl4 + CHCl3 ; water + HCl;
n-hexane + n-heptane; acetone + benzene; acetic acid + pyridine;
CCl4 + CH3OH; chloroform + benzene
chlorobenzene + bromobenzene; cyclohexane + ethanol

ethyl bromide + ethyl iodide;

n-butyl chloride + n-butyl bromide

Graphical representation of ideal and non-ideal solutions