ENTROPY: The basics

Predicting spontaneity2 methods

Method 1. S(total) = S(system) + S(surroundings)

- spontaneous when S > 0

System and surroundings?

The system is the part of the universe of interest to us, the chemical reaction the test tube or beaker the REACTION system. The surroundings is everything else. The surroundings of most reactions are the bench upon which they are sitting and air.
The entropy change of the SURROUNDINGS results from the enthalpy change of the reaction exothermic
reactions increase the entropy of the surroundings and vice versa.
The entropy change of the SYSTEM results from the state/number of particles etc of the system eg if more
gas particles are produced the entropy of the system increases
An EXOTHERMIC reaction (+ S(surroundings)) with an INCREASE in ENTROPY (+ S(system)) will be spontaneous AS S(total) >0
An ENDOTHERMIC reaction (- S(surroundings)) with a DECREASE in ENTROPY (- S(system)) will NOT be
spontaneous (S(total) <0)
An EXOTHERMIC reaction (+ S(surroundings)) with a DECREASE in ENTROPY (- S(system)) will be spontaneous at LOW TEMP (S(total) >0)
An ENDOTHERMIC reaction (- S(surroundings)) with an INCREASE in ENTROPY (+ S(system)) will be spontaneous at HIGH TEMP (S(total) >0)

Method 2. G = H(system) - TS(system) - spontaneous when G is NEGATIVE

H

-TS

Spontaneity

Non-spontaneous

Spontaneous

+ or -

+ or -

Low temp: Spontaneous

High temp: Nonspontaneous
Low temp: Nonspontaneous
High temp: Spontaneous

Remember to explain the following for ANY question using EITHER method (without the last/messy bit):
Nature is LAZY: exothermic reactions that release energy are favoured, lower energy products are more stable
Nature is MESSY: reactions where disorder/randomness increase are favoured

Practice questions
NCEA 2014

NCEA 2013

NZIC 2013

Some endothermic reactions are spontaneous. For example, at 25 C the standard enthalpy change
for the dissolving of sodium chloride in water is +387 kJ mol1, but sodium chloride still dissolves at
this temperature.
Elaborate on why it is not possible to predict the spontaneity of a reaction from enthalpy change
alone.