Finals Lesson 5: Spontaneous and Non-Spontaneous Process and Entropy

LEARNING COMPETENCY:

 Predict the spontaneity of a process based on entropy. (STEM_GC11CTIVa-b-140)

OBJECTIVES: At the end of the module, learners will be able to

1. define spontaneity of a process; and
2. determine the spontaneity of a process and whether entropy increases or decreases if its factors
are changed.

CONTENT:

The spontaneity of a process refers how it occurs on its own without the help of any external
factors. The reverse of any spontaneous process is non-spontaneous.

Various spontaneous processes happen every day. Water always flows from the faucet down up
of to the sink, and not the other way around. A hot cup of coffee will eventually turn cold left on a table
will never become hot by itself. The spontaneous redox reaction in a battery produces electrical energy;
spent battery does not recharge without an external output.

Spontaneity only tells whether a reaction will occur or not. It does not predict the rate of a
process (i.e. how fast or slow it occurs). The combustion of alcohol is fast, while the rusting of iron is
slow, but both processes occur spontaneously.

According to the Thomsen-Berrhelot principle, almost all exothermic chemical processes are
spontaneous. This principle was proposed independently by Danish chemist Julius Thomsen (1826-1909)
and French chemist Pierre-Eugene-Marcellin Berthelot (1827-1907). Combustion reactions, for example,
produce heat as reflected in their thermochemical equations.

However, some spontaneous processes do not follow this generalization. Ice melts
spontaneously into liquid water as it absorbs heat. Similarly, volatile liquids such as acetone and alcohol
evaporate in a spontaneous endothermic process.

Randomness also influences spontaneity. Spontaneous processes occur from an ordered state to
a more random arrangement. The melting of ice occurs spontaneously as the water molecules break
away from the more ordered crystalline structure to the mobile liquid phase. The transition from the
liquid phase to the more random gas phase is also a spontaneous process; although in these cases,
randomness is not the only factor that determines spontaneity. Melting and evaporation are
spontaneous only above the melting and boiling points, respectively. The effusion and diffusion of gases
are also examples of naturally random process.

Entropy is a measure of molecular randomness or disorder. A solid with rigid structure has low
entropy. Gases whose molecules are in constant motion in various directions are described to has a very
high entropy.
Factors that influence Entropy

1. Temperature
A change in temperature can result in change in entropy. Raising the temperature of a
system increases the average kinetic energy and the freedom of motion of particles in the
system; thus increasing the entropy of the system. Conversely, lowering the temperature of the
system will lead to a decrease in entropy. This implies that if the temperature is reduced
indefinitely, a system will reach a condition with zero entropy. This is what the third law of
thermodynamics states – that a perfectly ordered pure crystalline solid at zero Kelvin will have
zero entropy.

2. Number of particles
Chemical reactions that produce higher number of product particles than that of
reactant particles are usually spontaneous. The increase in the number of particles consequently
lead to more disorder in the system and thus it increases entropy.
Consider the spontaneous decomposition of calcium carbonate (CaCO 3). For every mole
of CaCO3 used, two moles of products are produced.

1 mol 1 mol + 1 mol = 2 mol

Chemical reactions with fewer product particles than the reactants are described to
have negative entropy and are thus non- spontaneous. Such is the case for ammonia (NH 3)
production.

1 mol + 3 mol 2 mol

= 4 mol

References:

1. Bayquen, A. et al (2016). General Chemistry 2 (First Ed.). Phoenix Publishing Corp. Quezon City,
Phils.