Solute solvent Interactions

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 Solute solvent Interactions
Solubility depends on
1. Chemical,
2. Electrical and
3. Structural effects which lead to mutual interactions between the
solute and the solvent.
 Like dissolves Like
Polar materials dissolve in Polar solvents and vice versa.
Eg: Salt dissolves in water; Naphthalene dissolves in Benzene.

Miscible liquids mix in any proportions.

More number of Carbon atoms in a molecule Less is the solubility.
More number of –OH groups in a molecule High is the solubility.
 Solute solvent Interactions
If the solvent is A and the solute is B, and the forces of attraction are represented by A-
A, B-B and A-B, one of the following conditions will occur:

1. If A-A >> A-B The solvent molecules will be attracted to each other &
the solute will be excluded.
Example: Benzene & water, where benzene molecules are unable to penetrate the
closely bound water aggregates.

2. If B-B >> A-A The solvent will not be able to break the binding forces
between solute molecules.
Example: NaCl in benzene, where the NaCl crystal is held by strong electrovalent forces
which cannot be broken by benzene.

3. If A-B >> A-A or B-B, or the three forces are equal the solute will
disperse and form a solution. Example: NaCl in water.
 Solute solvent Interactions Mechanism
Solute Solvent

Solute-Solute attractions must be Solvent-Solvent attractions must be

broken to free solute molecules to broken to create room for solutes to
interact with solvent enter and interact with solvent

Strong solute solvent attractions must

develop and must be stronger to have
dissolution possible
 Solute solvent Interactions Mechanism
• 1st step: The ions or molecules of solute must break the attractive forces between
them so that they can free up themselves to interact with the solvent.

• 2nd step: The ions or molecules of solvent must break the attractive forces
between them so that they can make room to allow the solute ions or molecules
to interact with the solvent.

• 3rd step: The ions or molecules of solute must strongly attract the ions or
molecules of solvent.

When will a solute dissolve in a solvent?

• A solute will dissolve in a solvent when the 3rd step generates enough energy to
drive the 1st and 2nd steps.
 Step 1 Cleavage of solvent-solvent bonds and formation of cavities
between solvent entities
ΔH1

Step 1: Separation of solvent molecules

Step 2 Cleavage of solute-solute bonds and formation of cavities

between solute entities
ΔH2

Step 2: Separation of solute molecules

Step 3
ΔH3

Step 3: Movement of solute into solvent cavities and formation of solute solvent bonds
 Solute solvent Interactions Mechanism
• Why’s energy necessary to drive the 1st and 2nd steps?
• To form a solution,
• 1st step: The ions or molecules of solute must absorb energy to break
the attractive forces between them. As you can tell, the stronger the
attractive forces, the more energy you will require to overcome these
forces.
• 2nd step: The ions or molecules of solvent must absorb energy to break
the attractive forces between them. Similarly, the stronger the
attractive forces, the more energy you will require to overcome these
forces.
• 3rd step: The ions or molecules of solute must strongly attract the ions
or molecules of solvent. The stronger the attraction, the more energy is
released into the dissolving process.
 Solute solvent Interactions Mechanism Contd.
Now, if we represent the change in energy for the
• 1st step as ΔEstep1,
• 2nd step as ΔEstep2, and
• 3rd step as ΔEstep3,
• then we can say that the total energy change when a solute
dissolve in a solvent is the sum of the three steps
ΔE total = ΔEstep 1 + ΔEstep 2 + ΔEstep 3
 Solute solvent Interactions Mechanism
• Since step 1 and 2 absorb energy, we can say that the change in energy for these
steps is positive.
• Since step 3 releases energy, we can say that the change in energy for step 3 is
negative.

• Now, if the amount of energy released in step 3 is larger than the amount of
energy absorbed in step 1 and 2, then the solute will dissolve in the solvent. This
happens because step 3 generates enough surplus energy to drive step 1 and 2.
• Thus, chemists will say, if ΔE total < 0, the solute will dissolve in the solvent.
• On the other hand, if the amount of energy released in step 3 is smaller than the
amount of energy absorbed in step 1 and 2, then the solute will not dissolve.
• This happens because step 3 generates an energy loss.
• Thus, chemists will say, if ΔE total > 0, the solute may not dissolve in the solvent.
• So some solutes dissolve in solvents when we heat the solute-solvent mixture.
General rule to determine whether a solute will dissolve in a solvent

The general rule is often summarized as “like dissolves like.”

• Polar solutes will dissolve best in polar solvents
• Non-polar solutes will dissolve best in non-polar solvents
• This rule make sense because when the solute and solvent have similar
polarities they are more likely to generate surplus energy to drive step 1
and 2 forward.
 Types of Solute solvent Interactions
Introduction
Now that you understand how chemists classify solvents, it's time to
consider a similar classification system for the compounds that dissolve in
them, i.e. for solutes. At the risk of oversimplifying, we will divide solutes
into 3 groups:

ionic
polar covalent
non-polar covalent
 Types of Solute solvent Interactions
We will use the adage "like dissolves like" as our guide to understanding
the forces that enable a solute to dissolve in a solvent.
Remember that this adage is really a variation on the statement of
Coulomb's Law that says "opposite charges attract".
The force of attraction depends upon the nature of the solvent and the
nature of the solute. We will look at four types of interactions:

• charge-dipole
• dipole-dipole
• dipole-induced dipole
• induced dipole-induced dipole
 Polarity of molecules

Intermolecular forces

Van der Hydrogen

Waal’s forces bonding

Very Weak when compared with covalent bonds between atoms in molecule
 3 Types of
dipoles

Permanent Instantaneous
Induce dipole
dipole dipole
 Permanent Dipole
Permanent dipole exists in all “Polar molecules” as a result of differences
in electro negativity of bonded atoms

Permanent Dipole

δ+ δ-
 Instantaneous Dipole
Instantaneous dipole is a temporary dipole that exists as a result of
fluctuation in the electron cloud Instantaneous dipole

δ+ δ-
Fluctuation of
Non-polar diatomic electron cloud
molecule H H

A higher concentration of
electron cloud

Non-polar monoatomic Instantaneous dipole

molecule
Fluctuation of
δ+ δ-
electron cloud He
He

A higher concentration of
electron cloud
 Induced dipole
Induced dipole is a temporary dipole that is created due to the influence
of neighboring dipole (which may be a permanent or instantaneous
dipole)

Permanent Dipole
Induced dipole
δ+ δ-
δ+ δ-

He
 Van der Waal’s forces

Van der Waal’s

forces

Instantaneous
Dipole dipole Dipole induced
dipole induced
interaction dipole interaction
dipole Interaction
 Dipole-dipole interaction
Polar molecules have permanent dipole moments.
They tend to orient themselves in such a way that the attractive forces
between molecules are maximised while repulsive forces are minimised.

δ+ δ- δ+ δ-
} Permanent dipole in
polar molecule
 Dipole-induced dipole interaction
When “Non-polar molecule” approaches a “Polar molecule (with a
permanent dipole)”, a dipole will be induced in the non-polar molecule.

The dipole induced will be in opposite orientation to that of the polar

molecule

} Induced dipole in
non-polar molecule

δ+
} δ-

Permanent dipole in polar molecule

Instantaneous dipole-induced dipole interaction
The instantaneous dipole will induce a dipole moment in the neighbouring
atom by attracting opposite charges.

If the +ve end of the dipole is pointing towards a neighbouring atom, the
induced dipole will then have its –ve end pointing towards the +ve pole of
the dipole.
Instantaneous dipole-induced dipole
interaction

δ+ δ- δ+ δ-

Fluctuation of the electron cloud leads to the Induced dipole in the neighbouring
formation of an instantaneous dipole monoatomic molecule
 Charge-Dipole Interactions
The Ion (charge)–dipole interactions are fundamental attractive forces,
akin to hydrogen bonds and Van der Waals interactions, that are formed
between ions or charged molecules and dipolar groups with partial
charges.

- ……….. δ+ δ-
Anion Polar Molecule

+ ……….. δ- δ+

Cation Polar Molecule

 Dipole-Dipole Interactions
Dipole-dipole forces are attractive forces between the positive end of one
polar molecule and the negative end of another polar molecule.

Dipole-dipole forces have strengths that range from 5 kJ to 20 kJ per mole.

They are much weaker than ionic or covalent bonds and have a significant
effect only when the molecules involved are close together (touching or
almost touching).

Polar molecules have a partial negative end and a partial positive end.

A dashed line is used to represent an intermolecular attraction between

molecules because these forces are NOT as strong as chemical bonds.
 Dipole-Dipole Interactions Contd.
Because the opposite charges that are attracting each other are only partial
charges, dipole-dipole interactions are inherently weaker than charge-dipole
interactions.
The partially positive end of a polar molecule is attracted to the partially
negative end of another.
In a HCl molecule the more electronegative chlorine atom bears the partial
negative charge; the less electronegative Hydrogen atom bears the partial
positive charge.
The partially positive Hydrogen end of one HCl molecule is attracted to the
partially negative chlorine end of another HCl molecule.
When one of the bonds involved in a dipole-dipole interaction is an O-H bond,
the interaction is given the special, but common, designation hydrogen
bonding.
Dipole-Dipole Interactions

δ+ δ- δ+ δ-
H Cl H Cl
 Dipole-Induced Dipole Interactions
When a non-polar molecule approaches a polar molecule (with a permanent
dipole), a dipole will be induced in the non-polar molecule.

The dipole induced will be in the opposite direction to that of the polar
molecule

However, when a molecule with a permanent bond dipole comes close to one
with no bond dipole, the electric field associated with the permanent dipole
can temporarily distort the electron distribution in the non-polar molecule,
thereby inducing a temporary bond dipole.
 Dipole-Induced Dipole Interactions Contd.
Dipole-induced dipole interactions are invoked when a non-polar
molecule dissolves in a polar or a dipolar solvent.
The assumption is that the solute dissolves because the forces of
attraction between the solvent and the solute are stronger than
the intermolecular forces holding the non-polar solute molecule
together.
The interactions between non-polar molecules are the weakest
secondary bonding forces we will consider.
They are called induced dipole-induced dipole interactions or
London forces.
Dipole-Induced Dipole Interactions or London
Dispersion forces

Spherical atom
with no dipole

Upon approach of a molecule with dipole

δ+ δ- ……….. δ+ δ-

Development of dipole after the electrons in the atom respond to

influence of approached molecule with dipole
 Induced Dipole-Induced Dipole Interactions
Furthermore, the induced dipole in one molecule influences the electron
distribution in other, nearby molecules. This is called an induced dipole-
induced dipole interaction.
These are temporary attractive force that cause non-polar substances to
condense to liquids and to freeze into solids when the temperature is
lowered sufficiently.
Because of the constant motion of the electrons, an atom or molecule can
develop a temporary (instantaneous) dipole when its electrons are
distributed unsymmetrically about the nucleus.
A second atom or molecule, in turn, can be distorted by the appearance of
the dipole in the first atom or molecule (because electrons repel one
another) which leads to an electrostatic attraction between the two atoms or
molecules.
Induced Dipole-Induced Dipole Interactions Contd.

δ+ δ- ……….. δ+ δ-………..δ+ δ-

Since these induced dipoles are transient, the intermolecular

interactions between them, the London forces, are very weak.

Chemists invoke these very weak forces to rationalize the

interactions between non-polar molecules.

We'll see an example of that when we discuss the relationship

between intermolecular interactions and boiling points.