A Matter of Spontaneity

Wednesday, February 9, 2022 10:35 AM

Spontaneous and Nonspontaneous Reactions

• The spontaneity of a process refers to how it occurs naturally without the help of any external factors.
• A reaction is said to occur naturally when there is a decrease in the enthalpy and an increase in the entropy of a
system.

Non-spontaneous
• The reverse of any spontaneous process

Spontaneity
• only tells whether a reaction will occur or not.
• Spontaneity only tells whether a reaction will occur or not.

Thomsen-Berthelot principle
According to it, almost all exothermic chemical processes are spontaneous.
• Example:
During the combustion of wood in a bonfire, an exothermic reaction, there is a decrease in the energy of the
system as energy is released to the surroundings. At the same time, the entropy of the system increases.
• The combination of these processes dictate that combustion reactions are spontaneous reactions.

However, some spontaneous processes do not follow the generalization

• Example: When the ice melts spontaneously into liquid water as it absorbs heat from the system (endothermic
reaction).

Randomness also influences spontaneity

• Spontaneous processes occur from an ordered state to a more random arrangement.
• Example:
A deck of cards that has been taken out of its box for the first time and is arranged from lowest to highest and
according to suit.
• Shuffling the cards will make the cards arranged randomly.
• It is unnatural for a random set of cards to be shuffled into a well-ordered arrangement.

Some spontaneous reactions occur in a faster rate

• once started like the combustion of alcohol.

Others would have a slower rate of reaction

• like the formation of rust.
• The effusion and diffusion of gases are also example of naturally random processes

ENTROPY

• Entropy 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 very high
entropy.

Like enthalpy, entropy is a state function; it only depends on the initial and final states of a system. It does not take int o
consideration how the final state was attained.

∆S = Sfinal – Sinitial
• A positive ∆S indicates an increase in randomness of a system; a negative ∆S indicates a decrease in randomness.

FACTORS THAT INFLUENCE ENTROPY

Change in Temperature
• Increasing the temperature, increases the entropy of the system
• Conversely, lowering the temperature 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.

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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.

Chemical reactions that produce high number of product particles than that of reactant particles are usually
spontaneous.
• The increase in the number of particles would also lead to more disorder in the system and increases entropy.

A steady increase in entropy as the temperature is raised for a particular phase, then an abrupt increase once the
temperature for a phase changed is reached:
• However, the change of entropy is not only affected by temperature and the number of particles. The graph of
entropy versus temperature shows a general trend for all substances

Standard Molar Entropy

Standard molar entropy (S°)

• SME of a substance is the entropy of one mole of a substance at the standard conditions (1 atm and 25°C).
• Unlike enthalpy, the standard molar entropy of substances in their elemental form is not zero; those of pure
substances are always positive values (S°>0).

As a state function, the standard molar entropy of a reaction (∆S°) can be calculated from the difference between the
standard molar entropies of the products and the reactants involved in the reaction.

∆S° = ∑ S°(products) - ∑ S°(reactants)

For a general reaction
aA + bB → cC + dD
where a, b, c, d are the coefficients of the substances in the balanced equation, the standard entropy of the reaction is
calculated as
∆ °=∑ °( ) −∑ °( )

∆ °=[ °( )+ ° ( )] − [ °( )+ ° ( )]

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 SECOND LAW OF THERMODYNAMICS

• The second law of thermodynamics states that for any spontaneous process, there is a net increase in the total
entropy of the system and its surroundings.
• This net entropy change of the process is represented as ∆Suniv.
∆Suniv = [ ∆Ssys + ∆Ssurr] > 0
• even if ∆Ssys is negative, the process can be spontaneous if ∆Ssurr is positive and has a greater magnitude than ∆Ssys.
• If the system is a chemical reaction, ∆Ssys is simply the ∆S° of the reaction calculated from the S° values of the
reactants and products.
• Calculating the ∆Ssurr however, requires recalling the first law of thermodynamics, which states that energy is
exchanged between the system and its surroundings in the form of heat and work
• The entropy change in the surroundings is directly proportional to the enthalpy change of the reaction and
inversely proportional to the absolute temperature (in Kelvin) of the surroundings

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 GIBBS FREE ENERGY AND SPONTANEITY

• Gibbs free energy (G) determines the spontaneity of a reaction.

• It is named after the American mathematician and physicist Josiah Willard Gibbs.
• Free energy is a portion of the total energy of a system that is available to do useful work.

Free energy is a portion of the total energy of a system that is available to do useful work.
G = H – TS
• Gibbs free energy is also a state function like enthalpy and entropy.
The equation above can be modified to give the Gibbs Helmholtz equation expressed
∆G = ∆H – T∆S
• The value of ∆G determines the spontaneity of a chemical reaction at constant pressure and temperature.
• A reaction is spontaneous if ∆G is negative; it is non-spontaneous if ∆G is positive.

This follows that for a reaction to be spontaneous, either of these two conditions must be met

• ∆H must be negative while ∆S is positive

• If ∆H is positive, ∆S must be large, or T must be high enough so that ∆G will be negative.
• Under standard conditions of 1 atm and 25°C, the standard free energy change (∆G°) of a chemical reaction can be
obtained from the standard enthalpy change (∆H°) and standard entropy change (∆S°).
• The Gibbs-Helmholtz equation then becomes
∆ °=∆ °− ∆ °
The standard free energy change of a reaction can also be calculated from the standard free energy formation ( ∆ °)
of the reactants and products.
∆ ° = ∑∆ °( ) − ∑∆ °( )
Like enthalpy, the ∆ ° of elements is zero.

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Like enthalpy, the ∆ ° of elements is zero.

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