7.

14

TOPIC: 7.14 FREE ENERGY OF DISSOLUTION

ENDURING UNDERSTANDING:
SPQ-5 The dissolution of a salt is a reversible process that can be influenced by environmental factors such as pH or
other dissolved ions.
LEARNING OBJECTIVE:
SPQ-5.D Explain the relationship between the solubility of a salt and changes in the enthalpy and entropy that occur in
the dissolution process.
ESSENTIAL KNOWLEDGE:
SPQ-5.D.1 The free energy change (ΔG°) for dissolution of a substance reflects a number of factors: the breaking of the
intermolecular interactions that hold the solid together, the reorganization of the solvent around the dissolved
species, and the interaction of the dissolved species with the solvent. It is possible to estimate the sign and
relative magnitude of the enthalpic and entropic contributions to each of these factors. However, making
predictions for the total change in free energy of dissolution can be challenging due to the cancellations among
the free energies associated with the three factors cited.
EQUATION(S):
N/A

NOTES:
There are two driving forces that determine the spontaneity of a reaction. Spontaneity is another way of
describing if a reaction will take place, it doesn’t mean that the reaction will take place quickly, it just states that
the reaction will happen without any external forces.

The first driving force is enthalpy. Exothermic reactions are favored. Some dissolution reactions are enthalpically
favorable but others are not.

The second driving force is called entropy. Entropy is often described as a measure of the disorder or randomness
of the energy in a system, but another way to describe it is to think of the probability of the particles or energy
being distributed into microstates, essentially all the tiny places within a container.

Entropy is given the designation, S, with positive values meaning that the system is increasing in entropy and
negative values mean that the system is decreasing in entropy. The universe moves towards greater disorder;
positive entropy is favored.

Consider a solution at 298 K, the particles are moving within the container and have kinetic energy. If that same
solution were heated the particles would be moving more rapidly with greater kinetic energy and would therefore
have greater entropy. Likewise, mixing two substances (or dissolving a solid) will generally increase the entropy
of the system because volume increase leads to more available microstates, thus the probability of the particles
(and their energies) occupying the different microstates increases. This means that solution formation is usually
entropically favorable.

The two driving forces, ΔS and ΔH, are linked together through Gibb’s Free Energy, ΔG. There are several ways to
calculate Gibb’s Free Energy, one way is: ΔG° = ΔH° – TΔS°, this will be discussed in more detail in unit 9. The
larger the negative value for Gibb’s free energy the more the reaction will favor the products.

• If the enthalpy and entropy are both favorable, the reaction will proceed all the time.
• If the enthalpy is unfavorable, then the reaction will only proceed at high temperatures.
• If the entropy is unfavorable, then the reaction will only proceed at low temperatures.
• If the enthalpy and entropy are both unfavorable, the reaction will not proceed under any circumstances.

1
 7.14

There are three processes that occur when a solution is formed.

ΔH ΔS
• The intermolecular forces between solvent particles are overcome. + +
• The intermolecular forces between solute particles are overcome. + +
• The intermolecular forces between solvent and solute particles must reform. - -

I DO:
Which solution would have greater entropy with all other factors remaining equal? Justify your answer
A) A saturated solution of cobalt hydroxide (Co(OH)2 KSP=5.92x10-15)
B) A saturated solution of beryllium hydroxide (Be(OH)2 KSP=6.92x10-22)
A) The cobalt (II) hydroxide solution because a greater number of ions will be dissociate due to the higher
KSP value, this means that there are more possible configurations within the system, thus the
entropy increases more.

WE DO:
The dissolution of calcium chloride, CaCl2, is exothermic. Draw a model of the following:
A) Water B) CaCl2(s) C) CaCl2(aq)

YOU DO:
1) For each of the following choose the variable that will be more favorable in solution formation.
s
A) Weak or Strong Solvent intermolecular forces

B) Weak or Strong Solute intermolecular forces h

C) Weak or Strong Solvent-Solute intermolecular force s

D) Increase or Decrease in Entropy h

E) Increase or Decrease in Enthalpy s

2) Two ionic solids are placed into 1.00 L of distilled water.

KSP ΔH ΔS
AB(s)⇌ A2+(aq) + B2-(aq) 5 x10-4 <0 >0
CB(s)⇌ C2+(aq) + B2-(aq) 2 x 10-3 <0 >0
Draw a particle diagram that could represent the two solutions (if a solution will form).

Less products favored lower entropy More products favored would lead ot
Lower concentration of products compared to higher entropy making
CB

AB CB