CHM 301

IDEAL SOLUTIONS
An ideal solution is a solution for which the chemical potential of each component is given by:
μi = μi * + RT lnXi (1)

where μi * is the chemical potential of pure component i, Xi is the mole fraction of component i
in the solution.

An ideal solution is also defined as a solution which obeys Raoult’s law over the full range of
composition:
Pi = XiPi* (2)

where Pi * is the vapour pressure (v.p.) of pure component i.

An ideal solution can be proved to obey Raoult’s law as follows:

Consider a solution of two components, where the mole fraction of component i is Xi. The
chemical potential (c.p) of component i must be the same in the solution as in the vapour in
equilibrium with the solution i.e.,

μil = μig (3)

but the solution is ideal, so

μil = μ*il + RT lnXi (4)

Also, the vapour of an ideal gas can be approximated, hence:

μig = μ0ig + RT ln Pi (5)

1atm

where Pi is the v.p (or partial pressure) of component i above the solution.
Combining equations 3, 4, and 5 gives:

μ*il + RT lnXi = μoig + RT ln Pi (6)

1atm

For the pure component i, Xi = 1; also the pressure of component i vapour in equilibrium with
the liquid is just the v.p of the pure liquid, P*il.
Hence,

μ*il = μoig + RTln Pi* (7)

1atm

Subtracting eqn. (7) from eqn. (6) gives:

RT1nXi = RT lnPi – RT lnP*i (8)

1atm 1atm

It is concluded from eqn. (8) that:

ln Xi = ln Pi (9a)
*
Pi
or Xi = Pi (9b)
Pi*

or Pi = XiPi* (9c) (Raoult’s law)

Example
Consider a mixture of benzene (b) and toluene (t) at 600C. The vapour pressures (v.p.s) of pure
benzene and pure toluene at 600C are 385 torr and 139 torr, respectively.
(1) What are the v.p.s of benzene and toluene in a mixture with Xb = 0.400, and Xt =
0.600?
(2) What is the composition of the vapour in equilibrium with this solution?

Note: Benzene is more volatile than toluene.

Solution
(1) Use eqn. (9c) to find the v.p.s of the two species.
Pb = XbPb* = 0.400 x 385 torr = 154 torr

Pt = XtPt* = 0.600 x 139 torr = 83.4 torr

The total pressure is Pb + Pt = 154 + 83.3 = 237.4 torr
(2) The composition of the vapour phase is obtained from the v.p.s and Dalton’s law of
partial pressures:
Xb = Pb/Ptotal = 154 torr/237.4 torr = 0.649
Xt = Pt/Ptotal = 83.4 torr/237.4 torr = 0.351
 Properties of ideal solutions
A number of properties of ideal solutions can be calculated from the chemical potentials of the
components of an ideal solution. E.g., the Gibbs free energy of mixing is calculated as follows:
ΔGmix = Gmixed – Gunmixed (1a)
= nlμ1 + n2μ2 + ……- nlμl* - n2μ2*…………… (1b)
= nl (μl* + RT lnXl) + n2 (μ2* + RT lnX2) + …… – nlμl* - n2μ2* - ………. (1c)
= RT (nl lnXl + n2 lnX2 + ……………..) (1d)

To bring eqn (1d) into the usual form, multiply and divide by the total number of moles, n, and
bring the 1/n inside the parentheses to covert the number of moles of each component into a
mole fraction.
ΔGmix = nRT (Xl lnXl + X2 lnX2 + …….) (2)
ΔGmix is negative for a spontaneous process at constant temperature and pressure.
Other properties of mixing ideal solutions can also be calculated.
The entropy of mixing is:

ΔSmix = - ∂ΔGmix (3)

∂T Pi ni

= - nR (X1 lnX1 + X2 lnX2 + ……..) (4)

The volume change on mixing can be found from:
Δ Vmix = - ∂ΔGmix = 0, (5)
∂P Tnl
So that the volumes are additive for an ideal solution. i.e., if 1L of benzene is mixed with 1L of
toluene, the final volume of the solution would be 1 + 1 = 2 L.
The enthalpy change (heat change) on mixing is:
ΔHmix = ΔGmix + T ΔSmix (6)
= nRT (X1 lnX1 + X2 lnX2 + ……..) + T(-nR) (X1 lnX1 + X2 lnX2……..) (7a)
ΔHmix = O (7b)
i.e., there is no heat change involved in the mixing of ideal solutions. If several components are
mixed and the mixture becomes hot or cold, then it is certain that the solution formed was not
ideal.
 Non-ideal solutions

For solutions that are not ideal, the vapour pressure of the solute depends linearly on the amount
of solute present at low solution concentrations only. However, the vapour pressure of such a
solute deviates from the Raoult’s law at high concentrations.

It, therefore, follows that for a non-ideal solution, the vapour pressure of the solute does obey the
Henry’s law, which is given by equation (1) below:
PB = XBKB (1)
Where XB is the mole fraction of the solute, and KB is the Henry’s constant.

Example
Evaluate the solubility of methane in water at 30 0C and 180 mmHg, if the Henry’s constant is
4.5 x 106 mmHg.

Solution
X (CH4) = n (CH4) / {(n CH4)} + {n (H2O)} = n (CH4) / nH2O)
Because n (CH4) << n (H2O)
From Henry’s Law, X = P/K = n (CH4) / n (CH4)
n (CH4) = P (CH4) x n(H2O) = 180 x 1000/18
K (CH4) 4.5 x 106

= 180 x 55.5mol kg-1 ; Note: 1000g kg-1 = 55.5 mol kg-1

4.5 x 106 18g mole-1

= 2.22 x 10-3 mol kg-1

Real Solutions

Real solutions are solutions obtained from liquid in which the A – A, A – B, and B – B
interactions are different. For ideal solutions, these interactions are not zero but are virtually the
same. However, in ideal gases, there are no interactions between the molecules. An enthalpy
change is involved in the disruption of A – A and B – B interactions and their replacement by
A – B interactions.
The change in the Gibb’s function when two liquids are mixed is given by equation (1) below:

ΔG = nRT (XA lnXA) + (XB lnXB)} (1)

The activity of a solvent is given by equation (2):
αA = PA/ PA* (2)
Where PA is the vapour pressure of the liquid in the mixture, and PA* is the vapour pressure of
the pure liquid.

All solvents obey Raoult’s law increasingly closely as they approach purity; therefore, the
activity of the solvent, αs, becomes equal to its mole fraction, Xs; as Xs turns to 1.
The activity coefficient ‘r, is defined by equation (3):
αs = ɤ sxs or ɤs = αs/Xs (3)
As α s turn to 1 (pure solvent), so does ɤs.

Example

In a particular experiment, the following set of data were obtained:

(1) (2) (3) (4) (5)
m(sucrose), mol/kg: 0.000, 0.200, 0.400, 1.000, 1.350

P(water), mmHg : 23.75, 23.50, 23.41, 22.95, 22.18

*
P (pure)
Determine the activity, and the activity coefficient of the solvent.

Solution ; X = (n (H2O) / {n (H2O) + m (sucrose)}

α = P/P*; = (1000g/18g)/{(1000g/18g) + m(sucrose)}
ɤ = α/X ; = 55.5/55.5 + m (sucrose)
 m: 0.000, 0.200, 0.400, 1.000, 1.350
 X(H2O) = 1.000, 0.9964, 0.9928, 0.9823, 0.9763
 α (H2O) = 1.000, 0.989, 0.986, 0.966, 0.934
 ɤ(H2O) = 1.000, 0.993, 0.993, 0.983, 0.957