Entropy How far?

Revision
The second law of thermodynamics states that spontaneous changes result in disorder or entropy. This dictates whether or not the reaction will take place (spontaneity) at a particular temperatures and the position of equilibrium. It is split into entropy of system and entropy of surroundings, so

Stotal = Ssurroundings + S system

If s-total is positive, the change is thermodynamically spontaneous. The value of s-total can be altered if you change the temperature. S-total also determines the extent of the reaction. The more positive the value, the more the position of equilibrium will lie to the right.

Entropy change of the system

This is affected by the reaction equation. Entropy of a solid has the lowest entropy, and gases have the highest.

e.g.

This side has 5 moles of gas

This side has 0 moles of gas

P 4(s)

5O 2(g)

P 4 O 10(s)

The right hand side has more solids, which have lower entropy compared to the 5 moles of gas on the left hand side, so the entropy of the system decreases, the S system is negative. Each component in the reaction has a standard entropy value, so a numerical value for the S system can be calculated by the following equation:

S system = nS(products) - nS(reactants) n = stoichiometric numbers in the chemical equation

Entropy change of the surroundings
This is affected by the environment of the surroundings. Heating the surroundings increases its entropy. Ssurroundings is negative for all endothermic reactions (as endothermic reactions take in heat from the environment) and positive for all exothermic reactions(as exothermic reactions release heat into the surroundings).

Ssurroundings

= -

If the temperature increases for an exothermic reaction, Ssurroundings becomes less positive, this in turn will make Stotal less positive. If temperature increases for endothermic reactions, Ssurroundings becomes less negative; this in turn will make Stotal less negative.

If the surroundings are hot, the entropy increase is small because the molecules all have high entropy and are already in chaotic motion.

Solubility
Ionic Compounds
As it dissolves, the lattice structure of an ionic solid breaks down and the ions are separated. This is very endothermic, so you might expect this not to be feasilble. However, due to the highly exothermic nature of hydration (when strong ion-dipole forces form between the cations and the oxygens and between the anions and the + hydrogens). The enthalpy of solution therefore depends on the enthalpies of lattice and hydration, demonstrated by the Hesss law cycle below:

Hsolution NaCl(s) Na+(aq) + Cl-(aq)

-Hlatt(NaCl) Na+(g) + Cl-(g)

Hhyd(Na++ Cl-)

Hsolution = Hhyd(Na++ Cl-) + -Hlatt(NaCl)

So, the more endothermic the lattice energy, the less exothermic the enthalpy of solution, and the more exothermic the sum of the hydration enthalpies, the more exothermic the enthalpy of solution. The sign of the enthalpy of solution is determined by the difference in magnitude between the lattice energy and the sum of the hydration energies.

Factors affecting lattice energy

The product of the charges on the ions increases the magnitude of the lattice energy (as the charges are greater, so is the attraction, and therefore the bonds are harder to break.) As sum of the radii of the cation and the anion increases, the magnitude decreases ( as the sum of the radii increases, the ions get farther away from one another in the lattice, so decreasing the strength of the attractions and making the bonds easier to break) As the extent of covalency increases, magnitude increases

Factors affecting hydration enthalpy

Magnitude of the charge on the ion increases the hydration enthalpy As the radius of the ion decrease, the enthalpy increases.