Solvation, Association and Dissociation

Solvation and Association
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Difference between solute and solvent
BASIS FOR COMPARISON SOLUTE SOLVENT

Meaning The substance that gets The substance that dissolves the
dissolved in the solvent in a solute in a solution is called as
solution is called as the solute; the solvent; the solvent is
the solute is present in the lesser present in the higher amount
amount than the solvent. than the solvent.
Boiling point The boiling point is higher than It is lower than that of solute.
solvent.
Physical state Found in solid, liquid or gaseous Mainly in the liquid state, but
state. can be gaseous as well.
Dependability Solubility depends on the Solubility depends on the
properties of the solute. properties of the solvent.
The main thumb rule of the solubility is “like dissolve like“.
Solvation
Molecule Liberation
Solute
Exothermic
Solvation (release of
energy)
Solvent Void creation

Solution
Endothermic (Absorption of energy)

Solvation is commonly known as disolution
• Solvation is the process of attracting and associating the molecules
of a solvent with molecules of a solute.
• When solute or ions dissolve in solvent the solute get surrounded
with molecules or ions of solute.
• This process is called Solvation Complex and energy required to
form this complex is called as solvation energy.
• If solvation energy is a positive number the dissolution is
endothermic if not exothermic.
• There are two conceptual steps to form a solution, each corresponding to
one of the two opposing forces that dictate solubility.
• The first conceptual step is dissolution, which corresponds to the force of
the solvent -solvent and solute -solute intramolecular attractions that
needs to be broken down.
• The second conceptual step is solvation, which corresponds to the force of
the solute-solvent intermolecular attraction that needs to be formed in
order to form a solution.
• Many intermolecular forces can contribute to solvation, including
hydrogen bonding, dipole -dipole forces, Van Der Waals forces, and ion -
dipole interactions.
Key Terms
Intermolecular forces: attractive and repulsive forces between molecules
• Solvation describes the interaction of solvent with dissolved molecules.
• In the process of solvation, ions are surrounded by a concentric shell of solvent.
• Solvation is the process of reorganizing solvent and solute molecules into
solvation complexes.
• Solvation involves bond formation, hydrogen bonding, and van der Waals forces.
Solvation of a solute by water is called hydration
• Which of these forces are at play depends on the molecular structure and
properties of the solvent and solute.
• The similarity or complementary character of these properties between solvent
and solute determines how well a solute can be solvated by a particular solvent.
A sodium ion solvated by water molecules

•Solvation or dissolution is a kinetic process (movement of solute from
core of solute to bulk of solvent) and is quantified by its rate(per time).
•Solubility quantifies the dynamic equilibrium state achieved when the
rate of dissolution equals the rate of precipitation.
•The consideration of the units makes the distinction clearer. The
typical unit for dissolution rate is mol/s.
•The units for solubility express a concentration: mass per volume
(mg/mL), molarity (mol/L).
• Solvent polarity is the most important factor in determining how well it
solvates a particular solute.
• Polar solvents have molecular dipoles, meaning that part of the solvent
molecule has more electron density than another part of the molecule.
• The part with more electron density will experience a partial negative charge
while the part with less electron density will experience a partial positive
charge.
• Polar solvent molecules can solvate polar solutes and ions because they can
orient the appropriate partially charged portion of the molecule towards the
solute through electrostatic attraction.
• This stabilizes the system and creates a solvation shell (or hydration shell in
the case of water) around each particle of solute.
• The solvent molecules in the immediate vicinity of a solute particle
often have a much different ordering than the rest of the solvent, and
this area of differently ordered solvent molecules is called the
cybotactic region.
• Water is the most common and well-studied polar solvent, but others
exist, such as ethanol, methanol, acetone, acetonitrile, and dimethyl
sulfoxide. Polar solvents are often found to have a high dielectric
constant.
• Polar solvents can be used to dissolve inorganic or ionic compounds
such as salts.
• The conductivity of a solution depends on the solvation of its ions.
• Nonpolar solvents cannot solvate ions, and ions will be found as ion
pairs.
• Water is the most common and well-studied polar solvent, but others
exist, such as ethanol, methanol, acetone, acetonitrile, and dimethyl
sulfoxide. Polar solvents are often found to have a high dielectric
constant.
• Polar solvents can be used to dissolve inorganic or ionic compounds
such as salts.
• The conductivity of a solution depends on the solvation of its ions.
• Nonpolar solvents cannot solvate ions, and ions will be found as ion
pairs.
• Hydrogen bonding among solvent and solute molecules depends on the
ability of each to accept H-bonds, donate H-bonds, or both.
• Solvents that can donate H-bonds are referred to as protic, while solvents
that do not contain a polarized bond to a hydrogen atom and cannot
donate a hydrogen bond are called aprotic.
• H-bond donor ability is classified on a scale (α).
• Protic solvents can solvate solutes that can accept hydrogen bonds.
• Similarly, solvents that can accept a hydrogen bond can solvate H-bond-
donating solutes.
• The hydrogen bond acceptor ability of a solvent is classified on a scale
(β).
• Solvents such as water can both donate and accept hydrogen bonds,
making them excellent at solvating solutes that can donate or accept (or
both) H-bonds.
Association
• Association of ions is a chemical reaction in which the opposite electric charge ions
come together in solution and form distinct chemical entity.
• The extent of the ionic association depends on the dielectric constant of the solvent.
• The opposite charged ions are naturally attracted by another electrostatic force.
• This is described by Coulomb’s Law C1 C2
F=q1q2/εr2 + +
+++
F F
-- -
- - -
• Where F is force of attraction ++ ----
• q1 and q2 are the magnitudes of the electric charges, r

• ϵ is the dielectric constant of the medium (solvent)
• and r is the distance between the ions C1, C2 are points of Charges
F is force acting between the charges
Ion association will increase if r is distance between the two charges
1. The magnitude of the electrical charge q1 and q2 increase
2. The size of the ions decreases so that the distance r between cation and anion decreases
3. The magnitude of the dielectric constant ϵ decreases
Key Points
• Entropy can be thought of as the randomness or spread-outedness of a group
of molecules. Increasing randomness is favourable.
• There is an entropy change associated with the formation of a solution, an
increase in entropy (randomness) that thermodynamically favours the solution
over the two original states.
• If the other energetics of dissolution are favourable, this increase in entropy
means that the conditions for solubility will always be met.
• Even if the energetics are slightly endothermic the entropy effect can still allow
the solution to form.
• Entropy: A thermodynamic property that is the measure of a system’s thermal
energy per unit temperature that is unavailable for doing useful work.

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Solvation and Association

BASIS FOR COMPARISON SOLUTE SOLVENT

Solvent Void creation

Endothermic (Absorption of energy)

A sodium ion solvated by water molecules

• q1 and q2 are the magnitudes of the electric charges, r

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