2.2.

7 Entropy
There are two thermodynamic concepts that are considered in chemical reactions; enthalpy and entropy. Entropy is often described as a measure of disorder. All substances possess some degree of disorder because particles are always moving, so S is always a __________ __________. Entropy (S)

Nature tends to move from order to disorder in isolated systems e.g. gas molecules spread out over time to fill a space, increasing their entropy. Entropy explains why some things happen naturally:

Entropy increases during the changes in state that give more randomness:

Entropy increases when a solid lattice dissolves Entropy increases in a reaction where a gas is evolved

Entropy Change in Chemical Reactions, S Entropy calculations using standard entropy values use the following equation:

For Example: Formation of ammonia from nitrogen and hydrogen

Key Definitions Standard entropy change of reaction -

Gibbs Free Energy Change in Chemical Reactions, G A combination of two factors, enthalpy and entropy, govern the feasibility of reactions. Exothermic processes tend to happen quite often but, equally endothermic processes which lead to an increase in entropy also happen quite often. The sometimes conflicting demands of enthalpy and entropy are brought together in the relationship:

This combines the influence of both enthalpy change and entropy change. With H negative (exothermic) and S positive (increase in entropy) then G will be ___________ If G for a reaction is negative (or zero) then the reaction is feasible; if it is positive then the reaction is not feasible. Note 1: If H is positive (endothermic) then, providing TS is __________ positive then the reaction will be feasible. Note 2: The term TS is temperature dependent meaning that some reactions may be feasible at one temperature but not at another. Note 3: A reaction with G negative means it can go. It does not necessarily mean that it will go. There is the kinetics of a reaction to take into account as well as the thermodynamics. For example, a feasible reaction ( thermodynamically unstable) may have a very high _________ preventing it from proceeding to any significant extent (kinetically stable). Example: Calculate the standard free-energy change for the combustion of graphite at 298K. C(s) + O2(g) CO2(g) (H = -394 kJ mol-1 S = +3.3 J K-1 mol-1) Answer:

Note: Because S is so small, G will not vary much with temperature, though in practice the reaction is extremely slow at 298K due to high activation energy. Example: Calculate the standard free-energy change for the rusting of iron at 298K 2Fe(s) + 1.5O2(g) Fe2O3(s) (H = -825 kJ mol-1 S = -272 J K-1 mol-1) Answer:

Note: G is very negative so the rusting of iron is highly feasible at room temperature even though S is negative. The reaction would become less feasible at higher temperatures as TS gets closer in value to H. Example: Calculate the standard free-energy change for the decomposition of 1 mol sodium hydrogencarbonate at 298K. 2NaHCO3(s) Na2CO3(s) + H2O(g) + CO2(g) (H = +130 kJ mol-1 S = +335 J K-1 mol-1) Answer:

Note: At 298K G is positive so the reaction is not feasible. However, G is not very positive so raising the temperature will make TS more positive and at a certain temperature the reaction will become feasible. Effect of Temperature on Feasibility Reaction H negative (exothermic) S positive (entropy gain) Feasible at all T S negative (entropy loss)

H positive (endothermic)

Not feasible at any T.

Calculating the Temperature at which a reaction becomes Feasible A reaction that is not feasible at one temperature may become feasible if the temperature is changed. The temperature at which feasibility is just achieved is the temperature at which there is no tendency for the reaction to go one way or the other. At this temperature G = 0 so:

Example: Calculate the temperature at which the thermal decomposition of sodium hydrogencarbonate becomes feasible. 2NaHCO3(s) Na2CO3(s) + H2O(g) + CO2(g) (H = +130 kJ mol-1 S = +335 J K-1 mol-1) Answer:

Note: The feasibility temperature gives the break-even point for the reaction. That is the temperature at which the concentrations of reactants and products become roughly equal. In this example, the reaction becomes more feasible as the temperature is increased above this point and product formation will be increasingly favoured. Example: Calculate the temperature above which limestone will spontaneously decompose to quicklime and carbon dioxide. CaCO3(s) CaO(s) + CO2(g) (H = +178 kJ mol-1 S = +161 J K-1 mol-1) Answer:

Entropy in Physical Changes In many physical changes there is an increase or decrease in disorder (and hence entropy). 1. Melting (Fusion) At 00C (273K) and 100 kPa a mixture of ice and water has no spontaneous tendency to either solidify or liquefy. The mixture is at equilibrium and G = 0 H2O(s) = H2O(l) H = +6 kJ mol-1 The entropy change S for melting of ice at 273K can be determined as follows:

2..Freezing (Solidification) H2O(l) = H2O(s) H = -6 kJ mol-1 The entropy change S for freezing of water at 273K can be determined as follows:

3. Boiling (Vaporisation) H2O(l) = H2O(g) H = +44 kJ mol-1 The entropy change S for boiling of water at 373K can be determined as follows: