CHEMICAL THEORY OF SOLUTIONS

A solution is a homogenous mixture of substances with

variable composition. The substance present in the major
proportion is called the solvent, whereas the substance
present in the minor proportion is called the solute.

A solution in thermodynamics refers to a system with more

than one chemical component that is mixed
homogeneously at the molecular level.
Solutions are not limited to liquids

For example air, a mixture of predominantly N2 and O2, forms

a vapor solution. Solid solutions such as the solid phase in the
Si-Ge system are also common.
Also known as NERNST DISTRIBUTION LAW, OR PARTITION LAW

DISTRIBUTION LAW
If we take two immiscible solvents A and B in a beaker, they form separate layers.

When a solute X which is soluble in both solvents is added, it gets distributed or

partitioned between them.

Molecules of X pass from solvent A to B and from solvent B to A.

Finally a dynamic equilibrium

is set up.

At equilibrium, the rate, at

which molecules of X pass
from one solvent to the other
is balanced
Nobel prize Walther Hermann Nernst, (1864 –1941) was a German chemist who is known for
contributions on chemical affinity, the third law of thermodynamics, physical chemistry,
electrochemistry, thermodynamics , solid state physics and for developing the Nernst equation.

Nernst in 1891 studied the distribution of several solutes

between different appropriate pairs of solvents.

 He gave a generalization which governs the distribution

of a solute between two non-miscible solvents.

Nernst’s 𝑪𝟏
Distribution law 𝑲𝑫 =
𝑪𝟐
at constant temperature.

• C1 is the concentration of the solute in solvent A or phase 1

• C2 is the concentration of the solute in solvent B or phase 2
• KD constant (or simply K) is called the Distribution coefficient or Partition
coefficient or Distribution ratio.
LIMITATIONS OF DISTRIBUTION LAW

1. Constant temperature.
2. Same molecular state. The molecular state of the solute is the
same in the two solvents. The law does not hold if there is
association or dissociation of the solute in one of the solvents.
3. Equilibrium concentrations.
4. Dilute solutions. The concentration of the solute in the two
solvents is low.
5. Non-miscibility of solvents.

𝛼
𝐶1 𝛼 𝜌𝛼 𝑋1
Nernst’s Law can be expressed also as: 𝐾𝐷 = 𝛽
= 𝛽
𝐶1 𝜌𝛽 𝑋1
Where
α and β represent the phases 1 and 2 respectively.
ρ represents the molar density of the pure solvent for small molar fractions X1
 Deviations in Nernst’s Law may occur while
experimenting with different solutions and
equilibrium systems. Sometimes one of the
liquid phases may not obbey ideal dilute
solutions models: this is due to chemical
behaviour effects.
Insights: Monomers and Polymers

DIMERIZATION
If we think of a chain, it’s easier to comprehend how monomers interact and
form other structures

Monomer: a molecule that is able to bond in long chains.

Polymer and Polymerization: a polymer means many

monomers. Polymers are also known as macromolecules
or large-sized molecules.
Usually, polymers are organic (but not necessarily).
This linking up of monomers is called polymerization.

Dimer and Dimerization: Di means two. So we bond two

monomers together to form a dimer.
 SUBSTANCES’ INFORMATION
BENZOIC ACID
• Weak acid
• Acts as the monomer in this
experiment
• Appearance: White colorless crystals
or powder.
• Effects on short-term exposure: Eyes,
skin and respiratory tract irritation
and serious damage . The substance
may cause a non-allergic rash on
contact.
• Acute toxicity if swallowed.
• Benzoic acid is a fungistatic
compound that is widely used as a
food preservative O
C OH
BENZENE
• It’s an aprotic solvent
• Appearance: clear, colorless, highly
flammable and volatile, liquid
aromatic hydrocarbon with a
gasoline-like odor.
• Highly Flammable liquid and vapor
• Effects on short-term exposure:
Causes serious eye and skin
irritation.
• May be fatal if swallowed. May
cause cancer and central nervous
system damage
• Used as an industrial solvent in
paints, etc, and in the production of
polyestyrene.
REACTION AND ITS MECHANISM
 BENZOIC ACID, WATER AND BENZENE DISTRIBUTION

BENZENE (APROTIC SOLVENT)

*HIDROGEN BONDING*
O

COH
1 O O
C C
O O

BENZOIC ACID (HBz)

DIMER

O
O
COH
C O
3

𝐻+

BENZOIC ACID BENZOATE ION

WATER (PROTIC SOLVENT)

BENZOIC ACID, WATER AND BENZENE DISTRIBUTION

The equilibrium constant in the benzene phase KD (dimerization constant) can be

1
described as:
2 HBz (HBz)2
Thus: [(𝐻𝐵𝑧)2 ]𝐵
𝐾𝐷 =
[𝐻𝐵𝑧]𝐵 𝟐
Where:
[HBz]B represents the molar concentration of the monomer in Benzene.
[(HBz)2]B represents the molar concentrarion of the dimer in Benzene.

The equilibrium constant Kmin the water-benzene interphase can be described as:
2
[HBz]W [HBz]B
Thus:
[𝐻𝐵𝑧]𝐵
𝐾𝑀 =
[𝐻𝐵𝑧]𝑊
Where:
[HBz]B represents the molar concentration of the HBz in Benze.
[HBz]W represents the molar concentrarion of the HBz in Water.
BENZOIC ACID, WATER AND BENZENE DISTRIBUTION.- CONCENTRATIONS

Titration is necessary to obtain the total concentration of

HBz in water (Cw) and benzene (CB). Concentration is
defined as it follows:

𝐶𝑊 = [HBz]W + [𝐵𝑧 − ]𝑤

𝐶𝐵 = [HBz]B + [(𝐻𝐵𝑧)2 ]𝐵
Considering that [HBz]B = CW ( 1- α ) and the following equations:

[(𝐻𝐵𝑧)2 ]𝐵
𝐾𝐷 =
[𝐻𝐵𝑧]𝐵 𝟐

[𝐻𝐵𝑧]𝐵
𝐾𝑀 =
[𝐻𝐵𝑧]𝑊

𝐶𝐵 = [HBz]B + [(𝐻𝐵𝑧)2 ]𝐵

We can rewrite these equations as:

𝑐𝐵
= 𝐾𝑀 + 2 𝐾𝐷 𝐾𝑀 2 𝐶𝑤 1 − 𝛼
𝐶𝑤 1−𝛼
 𝑐𝐵
= 𝐾𝑀 + 2 𝐾𝐷 𝐾𝑀 2 𝐶𝑤 1 − 𝛼
𝐶𝑤 1−𝛼

If we let:

𝑐𝐵
= 𝑦 𝐾𝑀 = b
𝐶𝑤 1−𝛼

2 𝐾𝐷 𝐾𝑀 2 = 𝑚 𝐶𝑤 1 − 𝛼 = x

And ploting y vs x, we obtain the linear expression:

y = mx + b
To obtain the values of α :
𝜶𝟐 𝑪 𝑾 𝒎𝒐𝒍
Ka = 6.3 𝒙𝟏𝟎−𝟓 = (𝟏−𝜶)
=
𝑳

It can be rewrited as:

𝜶𝟐 𝑪𝑾 + 𝟔. 𝟑𝒙𝟏𝟎−𝟓 𝜶 − 𝟔. 𝟑𝒙𝟏𝟎−𝟓 = 𝟎

Titration gives us the molar concentration of Cw and CB in each phase according to:

𝑽𝑾 𝑵𝒂𝑶𝑯 ∗ 𝑵 𝑽𝑩 𝑵𝒂𝑶𝑯 ∗ 𝑵
𝑪𝑾 = 𝑪𝑩 =
𝑽𝑨𝑳𝑰𝑸𝑼𝑶𝑻 𝑽𝑨𝑳𝑰𝑸𝑼𝑶𝑻

Where:
VxNaOH is the NaOH volume consumed in titration
N is the concentration of NaOH