A Matter of Spontaneity
Chapter 5
Lesson 5.1 Spontaneous and Non-Spontaneous
Processes
Spontaneous Process – is a process which occurs without any external input to
the system. A spontaneous process is one that occurs naturally without the help
of any external factors.
Non-Spontaneous Process – is a process that will not take place unless it is
“driven” by the continual input of energy from an external source.
A process that is spontaneous in one direction under a particular set of
conditions is nonspontaneous in the reverse direction. At room temperature and
typical atmospheric pressure, for example, ice will spontaneously melt, but
water will not spontaneously freeze.
Lesson 5.1 Spontaneous and Non-Spontaneous
Processes
The spontaneity of a process is not correlated to the speed of the process. A
spontaneous change may be so rapid that it is essentially instantaneous or so
slow that it cannot be observed over any practical period of time.
Thomsen-Berthelot principle – states that almost all exothermic chemical
processes are spontaneous.
However, some spontaneous processes do not follow this generalization. Some
endothermic reactions also occur spontaneously.
Lesson 5.1 Spontaneous and Non-Spontaneous
Processes
Identify whether each process is spontaneous or non-spontaneous:
1. Water decomposes into hydrogen and oxygen gases with application of
electricity.
2. Wood burns to ash after being set on fire.
3. Silverware tarnish when exposed to air.
Lesson 5.2 Entropy
Entropy (S) – is a measure of molecular randomness. A solid with a rigid
structure has low entropy. Gases whose molecules are in constant random
motion in various directions are described to have a very high entropy.
ΔS = Sfinal – Sinitial
A positive ΔS indicates an increase in randomness of a system; a negative ΔS
indicates a decrease in randomness.
Lesson 5.2 Entropy
Factors that Influence Entropy
1. A change in temperature can result in change in entropy. Raising the
temperature of a system increases its entropy and vice versa.
2. The increase in the number of particles consequently lead to more disorder in
the system and thus increase in entropy (spontaneous process). Chemical
reactions with fewer product particles than the reactants are described to have
negative entropy and are thus non-spontaneous.
Lesson 5.2 Entropy
Examples:
Predict the sign of the change in entropy for the following processes.
1. Formation of nitrosyl chloride (NOCl) from nitric oxide and chlorine gases
2NO + Cl2 → 2NOCl
2. Freezing of water
3. Hearing liquid water to its boiling point
Lesson 5.2 Entropy
Standard Molar Entropy
Standard Molar Entropy (S˚) – is the entropy of one mole of a substance at the
standard conditions (1atm and 25˚C). Note that standard molar entropy of
substance in their elemental form is not zero; those of pure substances are
always positives values (S˚ ).
As a state function, ΔS˚ can be calculated from the difference between the
standard molar entropies of the products and the reactants involve in the
reaction.
ΔS˚ = ΣS˚(products) – ΣS˚(reactants)
Lesson 5.2 Entropy
Example:
Compute the change in standard molar entropy (ΔS˚) from the following
reactions:
1. CaCO3 → CaO + CO2
S˚(CaCO3) = 92.9 J/mol.K
S˚(CaCO) = 39.8 J/mol.K
S˚(CO2) = 213.6 J/mol.K
Lesson 5.2 Entropy
Example:
Compute the change in standard molar entropy (ΔS˚) from the following
reactions:
2. N2 + 3H2 → 2NH3
S˚(N2) = 191.5 J/mol.K
S˚(H2) = 130.6 J/mol.K
S˚(NH3) = 192.3 J/mol.K
Short Quiz
Predict the sign of the change in entropy for the following processes.
1. Decomposition of carbonic acid (H2CO3) into water and carbon dioxide
2. Sublimation of naphthalene (mothballs)
3. Melting of lead metal at room temperature
4. Formation of nitrogen tetroxide (N2O4) from nitrogen dioxide:
2NO2 → N2O4
5. Combustion of ethane (C2H6) gas:
2C H + 7O → 4CO + 6H O
Short Quiz
Compute the change in standard molar entropy (ΔS˚) from the following
reactions:
1. 2H2 + O2 → 2H2O
Substance H2 O2 H2O
So(J/mol.K) 130.6 205.0 188.7
2. Ca3(PO4)2 → 3Ca2+ + 2PO43-
Substance Ca3(PO4)2 Ca2+ PO43-
So(J/mol.K) 241.0 -53.1 -222.0
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