Lesson 12

Spontaneous Processes & The Law of Thermodynamics

Objectives:
The learners shall be able to:
1. predict the spontaneity of a process based on entropy
2. determine whether entropy increases or decreases if the following are changed:
temperature, phase, number of particles
3. explain the second law of thermodynamics and its significance
4. use Gibbs’ free energy to determine the direction of a reaction

Concepts in a Box

Spontaneous and Non-Spontaneous Process:

The spontaneity of a process refers to 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 to
the sink, and not vice versa. A hot cup of coffee will eventually turn cold, but a cold coffee left on
a table will never become hot by itself. The spontaneous redox reaction in a battery produces
electrical energy; a spent battery does not recharge without an external input.

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

𝐶𝐻4(𝑔) + 2𝑂2(𝑔) → 𝐶𝑂2(𝑔) + 2𝐻2 𝑂2(𝑔) 𝛥𝐻 = −890.4 𝐾𝐽

2𝐻2(𝑔) + 𝑂2(𝑔) → 2𝐻2 𝑂2(𝑔) 𝛥𝐻 = −571.6 𝐾𝐽

2𝑀𝑔(𝑠) + 𝑂2(𝑔) → 2𝑀𝑔𝑂(𝑔) 𝛥𝐻 = −1 203.4 𝐾𝐽

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
alcohols evaporate in a spontaneous endothermic process.

Randomness also influences spontaneity. Spontaneous processes occur from an ordered state
to a more random arrangement. For example, a deck of cards that has been taken out of its box for
the first time is arranged from lowest to highest and according to suit. Shuffling the cards will make
them randomly arranged. It is unnatural for a random set of cards to be shuffled into a well-ordered
arrangement of numbers and suits.

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 actor that determines spontaneity. Melting and evaporation are spontaneous only above the
melting and boiling points, respectively.

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.

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

𝛥𝑆 = 𝑆𝑓𝑖𝑛𝑎𝑙 − 𝑆𝑖𝑛𝑖𝑡𝑖𝑎𝑙

A positive AS indicates an increase in randomness of a system; a negative AS indicates a

decrease in randomness.

Factors That Influence Entropy

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 the 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.

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 its increased entropy.

Consider the spontaneous decomposition of calcium carbonate (𝐶𝑎𝐶𝑂3). For every mole of
𝐶𝑎𝐶𝑂3 used, two moles of products are produced.

𝐶𝑎𝐶𝑂3(𝑠) → 𝐶𝑎𝑂(𝑠) + 𝐶𝑂2(𝑔) (𝑠𝑝𝑜𝑛𝑡𝑎𝑛𝑒𝑜𝑢𝑠)

1 𝑚𝑜𝑙𝑒 1 𝑚𝑜𝑙𝑒 1 𝑚𝑜𝑙𝑒

2 𝑚𝑜𝑙𝑒𝑠

Chemical reaction with fewer product particles that the reactants are described to have
negative entropy and are thus non-spontaneous. Such is the case for ammonia (𝑁𝐻3) production.

𝑁2(𝑔) + 3𝐻2(𝑔) → 2𝑁𝐻3(𝑔) (𝑛𝑜𝑛 − 𝑠𝑝𝑜𝑛𝑡𝑎𝑛𝑒𝑜𝑢𝑠)

1 𝑚𝑜𝑙𝑒 3 𝑚𝑜𝑙𝑒 2 𝑚𝑜𝑙𝑒

4 𝑚𝑜𝑙𝑒𝑠

` The change in entropy, however, is affected not

only by temperature and number of particles. The graph
of entropy versus temperature in the figure shows a slow
and steady increase in entropy of a solid substance.

At this solid phase range, the vibrational energy of

the particles steadily increases. Once the melting point of
the substance is reached, its entropy suddenly shoots up.

At this condition, the liquid particles are freer to

move than in the solid phase. Aside from vibrational
motion, the liquid particles can have rotational and
translational (i.e., different directions) movements at this stage.

When all solid particles are liquefied, the entropy of the system returns to a steadily
increasing pattern. Once the boiling point of the substance is reached, entropy abruptly increases.
At this state, the gas particles are much freer to move.

This generals trend is observed for all substances: a steady increase in entropy as the
temperature is raised for a particular phase, the abrupt increased once the temperature for a phase
change is reach.
Sample Problem:

Predict the sign of the change in entropy for the following processes:

1. Formation of nitrosyl chloride (NOCI) from nitric oxide and chlorine gases

2𝑁𝑂(𝑔) + 𝐶𝑙2(𝑔) → 2𝑁𝑂𝐶𝐼(𝑔)

2. Freezing of water
3. Heating liquid water to its boiling point

Solution:
1. There will be more reactant particles than the product particles. Thus, entropy change will
be negative.
2. Particles in ice are more orderly arranged than those of liquid. Entropy change will be negative
3. Particles will become more energetic at higher temperature. Entropy change will be positive

Entropy of the System

Spontaneous reactions are associated with an increase in entropy, or the disorderliness of a

system and its surroundings. Here, the increase should refer to the total or net entropy, wherein the
sum should be positive. The entropy of the universe tends to always increase. This increase in entropy
is the essence of the second law of thermodynamics.

Usually, entropy increases if the reaction yields gases; the reaction can then be classified as
spontaneous. On the other hand, if the reaction involves the conversion of a gas to a solid or liquid,
the entropy tends to decrease.

The entropy of a substance depends on the temperature and on its physical phase. Entropy
changes are based on a change in volume and on a change in heat, as given by

𝛥𝑆 = 𝑆𝑓𝑖𝑛𝑎𝑙 − 𝑆𝑖𝑛𝑖𝑡𝑖𝑎𝑙

For an ideal gas that is undergoing a reversible compression from 𝑉1 to 𝑉2 ,

𝑉
𝛥𝑆 = 𝑛𝑅 ln (𝑉2 )
1

𝑃
𝛥𝑆 = 𝑛𝑅 ln (𝑃2 )
1

For isothermal expansion-compression of ideal gas, change in entropy can be calculated using

𝑞𝑟𝑒𝑣
𝛥𝑆 = 𝑇

Sample Problem:

A 200.0-g sample of N2 gas undergoes compression from pressure of 101 325 Pa to 607 950 Pa
at 300K. Assuming that nitrogen is an ideal gas, calculate ΔS.
Dependence of Entropy on Temperature

The change in entropy for a given change in temperature can be calculated using the following
formulas.

At constant pressure,

𝑇
𝛥𝑆 = 𝑛𝐶𝑝 ln 𝑇2
1

At constant volume,

𝑇
𝛥𝑆 = 𝑛𝐶𝑣 ln 𝑇2
1

Calculating Entropy Change Associated with Phase Change

Melting is a reversible process. The change in entropy associated with a phase change can be
calculated using

𝛥𝐻𝑓𝑢𝑠𝑖𝑜𝑛
𝛥𝑆 = 𝑇

As shown, 𝑞𝑟𝑒𝑣 = 𝛥𝐻𝑓𝑢𝑠𝑖𝑜𝑛 . Similarly, for the boiling process, the change in entropy can be
determined by using

𝛥𝐻𝑣𝑎𝑝𝑜𝑟𝑖𝑧𝑎𝑡𝑖𝑜𝑛
𝛥𝑆 = 𝑇

Sample Problem:

To what extent does entropy change when 1.00 mole of water is heated from 353 K (80°C) to
403 K (130°C) at a pressure of 101 325 Pa? Given are the following constants:

• enthalpy of vaporization of water = 4.07 × 104 𝐽/𝑚𝑜𝑙 𝑎𝑡 373 𝐾 (100°𝐶)

• molar heat capacity of liquid water = 75.3 𝐽/𝐾 · 𝑚𝑜𝑙
• molar heat capacity of gaseous water = 36.4 𝐽/𝐾 · 𝑚𝑜𝑙

Standard Molar Entropy

The standard molar entropy (S°) of a substance is the entropy of one mole of a substance at
the standard conditions (1 atm and 25°C). Note that 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 entropy of reaction (ΔS°) can be calculated from the
difference between the standard molar entropies of the products and the reactants involved in the
reaction.

𝜟𝑺° = ∑ 𝑺° (𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔) − ∑ 𝑺° (𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔)

 For a general reaction

𝒂𝑨 + 𝒃𝑩 → 𝒄𝑪 + 𝒅𝑫

… 𝑎, 𝑏, 𝑐, and 𝑑 are the coefficient of the substances in the balanced equation, the balanced
entropy of the reaction is calculated as

𝛥𝑆 ° = ∑ 𝑆 ° (𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠) − ∑ 𝑆 ° (𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠)

= [𝑐𝑆 ° (𝐶 ) + 𝑑𝑆 ° (𝐷 )] − [𝑎𝑆 ° (𝐴) + 𝑏𝑆 ° (𝐵)]

Consider the decomposition of calcium carbonate, the mineral found in the limestone.

𝐶𝑎𝐶𝑂3(𝑠) → 𝐶𝑎𝑂(𝑠) + 𝐶𝑂2(𝑔)

Molar Entropy (𝑆°):

𝐶𝑎𝐶𝑂3(𝑠) = 92.9 𝐽/𝑚𝑜𝑙 · 𝐾

𝐶𝑎𝑂(𝑠) = 39.8 𝐽/𝑚𝑜𝑙 · 𝐾

𝐶𝑂2(𝑔) = 213.6 𝐽/𝑚𝑜𝑙 · 𝐾

The 𝛥𝑆° is then obtained from the 𝑆° values of the reactants and the products

𝛥𝑆° = [𝑆 ° (𝐶𝑎𝑂) + 𝑆 ° (𝐶𝑂2 )] − [𝑆 ° (𝐶𝑎𝐶𝑂3 )]

= [(1 𝑚𝑜𝑙𝑒)(39.8 𝐽/𝑚𝑜𝑙 · 𝐾 ) + (1 𝑚𝑜𝑙𝑒)(213.6 𝐽/𝑚𝑜𝑙 · 𝐾 )] − [(1 𝑚𝑜𝑙𝑒)(92.9 𝐽/𝑚𝑜𝑙 · 𝐾 )]
= 160.5 𝐽/𝐾

The decomposition of 𝐶𝑎𝐶𝑂3 , gives a positive 𝛥𝑆° which means that the system is in a more
randomstate under standard conditions than when 𝐶𝑎𝐶𝑂3 , is formed (reverse reaction). This is mainly
becausethe 𝐶𝑂2 gas produced has higher entropy than the reactant and the other product 𝐶𝑎𝑂.

This quantitative result is also consistent with the earlier qualitative discussion on the number
of particles as a factor that influences entropy. As a rule, a reaction that produces a greater number
of moles of gas results in an increase in its entropy. Conversely, a reaction that produces a smaller
number of moles of gas will result in a decrease in entropy.

The Haber process for the industrial synthesis of ammonia is another process that involves
gaseous species.

𝑁2(𝑔) + 3𝐻2(𝑔) → 2𝑁𝐻3(𝑔)

Molar Entropy (𝑆°):

𝑁2(𝑔) = 191.5 𝐽/𝑚𝑜𝑙 · 𝐾

𝐻2(𝑔) = 130.6 𝐽/𝑚𝑜𝑙 · 𝐾

𝑁𝐻3(𝑔) = 192.3 𝐽/𝑚𝑜𝑙 · 𝐾

 The 𝛥𝑆° is then obtained using the following equation.

𝛥𝑆° = [2𝑆 ° (𝑁𝐻3 )] − [𝑆 ° (𝑁2 ) + 3𝑆 ° (𝐻2 )]

= [(2 𝑚𝑜𝑙𝑒)(192.3 𝐽/𝑚𝑜𝑙 · 𝐾 )] − [(1 𝑚𝑜𝑙𝑒)(191.5 𝐽/𝑚𝑜𝑙 · 𝐾 ) + (3 𝑚𝑜𝑙𝑒)(130.6 𝐽/𝑚𝑜𝑙 · 𝐾 )]
= −198.7 𝐽/𝐾

Consistent with the earlier discussion, the negative 𝛥𝑆° value results from the decrease in the
number of moles of gas (from 4 mol reactant to 2 mol product). The system is described to have
achieved a state of less randomness (or more order).

Sample Problem

Calculate the 𝛥𝑆° for each given reaction.

1. 2𝐻2(𝑔) + 𝑂2(𝑔) → 2𝐻2 𝑂(𝑔)

Molar Entropy (𝑆°):
𝑂2(𝑔) = 205.0 𝐽/𝑚𝑜𝑙 · 𝐾
𝐻2(𝑔) = 130.6 𝐽/𝑚𝑜𝑙 · 𝐾
𝐻2 𝑂(𝑔) = 188.7 𝐽/𝑚𝑜𝑙 · 𝐾

2. 𝐶𝑎2 (𝑃𝑂4 )2(𝑠) → 3𝐶𝑎2+(𝑎𝑞) + 2𝑃𝑂4 3−(𝑎𝑞)

Molar Entropy (𝑆°):

𝐶𝑎2 (𝑃𝑂4 )2(𝑠) = 241.0 𝐽/𝑚𝑜𝑙 · 𝐾
𝐶𝑎2+ = −53.1 𝐽/𝑚𝑜𝑙 · 𝐾
𝑃𝑂4 3− = 222.0 𝐽/𝑚𝑜𝑙 · 𝐾

Second Law of Thermodynamics

The second law of thermodynamics explains the relationship between entropy change and
spontaneity of a process. It stares that for any spontaneous process, there is a net increase in the
total entropy the system and its surroundings. This net entropy change of the process is represented

𝜟𝑺𝒖𝒏𝒊𝒗 = [𝜟𝑺°𝒔𝒚𝒔 + 𝜟𝑺°𝒔𝒖𝒓𝒓 ] > 𝟎

Thus, even if 𝛥𝑆𝑠𝑦𝑠 is negative, the process can be spontaneous as long as 𝛥𝑆𝑠𝑢𝑟𝑟 is positive
and has greater magnitude than 𝛥𝑆𝑠𝑦𝑠 . If the system is a chemical reaction, 𝛥𝑆𝑠𝑦𝑠 is simply the 𝛥𝑆°
of the reaction calculated from the 𝑆° values of the reactants and products.

Calculating 𝛥𝑆𝑠𝑢𝑟𝑟 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. In a
mathematical expression,

𝜟𝑯𝒓𝒙𝒏
𝜟𝑺𝒔𝒖𝒓𝒓 =
𝑻
Sample Problems

1. Compute the total entropy change (𝛥𝑆𝑢𝑛𝑖𝑣 ) in the oxidation of metallic iron into ferric oxide
(Fe2O3) under standard conditions. Determine the spontaneity of the process at these
conditions.

4𝐹𝑒(𝑠) + 3𝑂2(𝑔) → 2𝐹𝑒2 𝑂3(𝑠)

Molar Entropy (𝑆°):

𝐹𝑒(𝑠) = 27.3 𝐽/𝑚𝑜𝑙 · 𝐾
𝑂2(𝑔) = 205.0 𝐽/𝑚𝑜𝑙 · 𝐾
𝐹𝑒2 𝑂3(𝑔) = 87.4 𝐽/𝑚𝑜𝑙 · 𝐾
Specific Heat of Formation (𝛥𝐻𝑓𝑜 ):
𝐹𝑒(𝑠) = 0 𝐾𝐽/𝑚𝑜𝑙
𝑂2(𝑔) = 0 𝐾𝐽/𝑚𝑜𝑙
𝐹𝑒2 𝑂3(𝑔) = −824.2 𝐾𝐽/𝑚𝑜𝑙

2. Calculate the total entropy change for the decomposition of hydrogen peroxide (H 2O2). Is the
reaction spontaneous or not?
2𝐻2 𝑂2(𝑙) → 2𝐻2 𝑂(𝑙) + 𝑂2(𝑔)
Molar Entropy (𝑆°):
𝐻2 𝑂2 = 109.6 𝐽/𝑚𝑜𝑙 · 𝐾
𝐻2 𝑂 = 69.9 𝐽/𝑚𝑜𝑙 · 𝐾
𝑂2 = 205.0 𝐽/𝑚𝑜𝑙 · 𝐾
Specific Heat of Formation (𝛥𝐻𝑓𝑜 ):
𝐻2 𝑂2 = −187.8 𝐾𝐽/𝑚𝑜𝑙
𝐻2 𝑂 = −285.8 𝐾𝐽/𝑚𝑜𝑙
𝑂2 = 0 𝐾𝐽/𝑚𝑜𝑙

Gibbs Free Energy and Spontaneity

From earlier discussions, the spontaneity of a process depends on two thermodynamic

quantities: enthalpy and entropy. Combining these two into a single equation introduces a third
thermodynamic quantity that ultimately determines spontaneity. This quantity is referred to as the
Gibbs free energy (G), 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.
The three thermodynamic quantities are related by the equation

𝑮 = 𝑯 − 𝑻𝑺

Like enthalpy and entropy, Gibbs free energy is also a state function. As such, considering the
final and initial states involved in a process, the equation above can be modified to give the Gibbs-
Helmholtz equation expressed as
 𝜟𝑮 = 𝜟𝑯 − 𝑻𝜟𝑺

The value of 𝛥𝐺 determines the spontaneity of a chemical reaction at constant pressure and
temperature. A reaction is spontaneous if 𝛥𝐺 is negative; it is non-spontaneous if 𝛥𝐺 is positive. This
follows that for a reaction to be spontaneous, either of these two conditions must be met:

• 𝛥𝐻 must be negative, while 𝛥𝑆 is positive.

• If 𝛥𝐻 is positive, 𝛥𝑆 must be large or T must be high enough so that 𝛥𝐺 will be negative.

Under standard conditions of 1 atm and 25°C, the standard free energy change (𝛥𝐺 𝑜 ) of a
chemical reaction can be obtained from the standard enthalpy change (𝛥𝐻 𝑜 ) and standard entropy
change (𝛥𝑆 𝑜 ) The Gibbs-Helmholtz equation then becomes,

𝜟𝑮𝒐 = 𝜟𝑯𝒐 − 𝑻𝜟𝑺𝒐

The standard free energy change of a reaction can also be calculated from the standard free
energy of formation 𝛥𝐺𝑓𝑜 of the reactants and products.

𝜟𝑮𝒐 = ∑ 𝛥𝐺𝑜𝑓 (𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠) − ∑ 𝛥𝐺𝑜𝑓 (𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠)

Similar to enthalpy, the 𝛥𝐺𝑓𝑜 of elements is zero.

Consider the dissolution of silver chloride (AgCl)

𝐴𝑔𝐶𝑙(𝑠) → 𝐴𝑔+ (𝑎𝑞) + 𝐶𝑙− (𝑎𝑞)

The 𝛥𝐺 𝑜 of the reaction can be calculated from the standard molar free energies of formation
of the substances.

Given: Gibb’s Energy of Formation (𝛥𝐺𝑓𝑜 ):

𝐴𝑔𝐶𝑙 = −109.8 𝐾𝐽/𝑚𝑜𝑙
𝐴𝑔+ = 77.1 𝐾𝐽/𝑚𝑜𝑙
𝐶𝑙 − = −131.3 𝐾𝐽/𝑚𝑜𝑙

𝛥𝐺 𝑜 = [𝛥𝐺𝑓𝑜 (𝐴𝑔+) + [𝛥𝐺𝑓𝑜 (𝐶𝑙1 )] − [𝛥𝐺𝑓𝑜 (𝐴𝑔𝐶𝑙 )

𝐾𝐽 𝐾𝐽 𝐾𝐽
= [(1 𝑚𝑜𝑙𝑒) (77.1 𝑚𝑜𝑙) + (1 𝑚𝑜𝑙 ) (131.3 𝑚𝑜𝑙 )] − [(1 𝑚𝑜𝑙𝑒) (−109.8 𝑚𝑜𝑙)]

= 55.7 𝐾𝐽

The positive value of 𝛥𝐺 𝑜 indicates that the reaction is non-spontaneous at 25°C. This means
that the reverse reaction is more spontaneous. In other words, the formation of the precipitate is
favored over dissolution, validating the insolubility of AgCl in water. Recall that for thermodynamic
processes, if a reaction is spontaneous, its reverse is non-spontaneous and vice versa.
Sample Problem #1

Determine the spontaneity of the dissociation of ammonium nitrate (NH4NO3), the compound
used in cold packs. Interpret the values obtained from the calculations.

𝑁𝐻4 𝑁𝑂3(𝑠) → 𝑁𝐻4 + (𝑎𝑞) + 𝑁𝑂3 − (𝑎𝑞)

Molar Entropy (𝑆°):
𝑁𝐻4 𝑁𝑂3 = 151.1 𝐽/𝑚𝑜𝑙 · 𝐾
𝐻𝑁4 + = 113.0 𝐽/𝑚𝑜𝑙 · 𝐾
𝑁𝑂3 − = 146.4 𝐽/𝑚𝑜𝑙 · 𝐾
Specific Heat of Formation (𝛥𝐻𝑓𝑜 ):
𝑁𝐻4 𝑁𝑂3 = −365.6 𝐾𝐽/𝑚𝑜𝑙
𝐻𝑁4 + = −132.5 𝐾𝐽/𝑚𝑜𝑙
𝑁𝑂3 − = −207.4 𝐾𝐽/𝑚𝑜𝑙