Module 1

Spontaneity and Entropy

Consider the following examples: a waterfall flows downhill, but never up, heat flows from
a warmer object to a cooler one, but the reverse never happens spontaneously. Iron exposed to
water and oxygen forms rust, but rust does not spontaneously change back into iron. Chemical
processes can be spontaneous as well. An example is spontaneous combustion, wherein a
flammable substance burns by itself even without direct application of spark or flame. The
spontaneous reaction between magnesium ribbon and hydrochloric acid wherein the magnesium
metal instantly disappears with the evolution of heat and gas is irreversible. This type of process
does not need the application of energy to take place is said to be spontaneous process.

Conversely, a nonspontaneous process cannot proceed unless there is a driving force or

outside help that acts on the system. For example, a ball cannot be brought uphill unless someone
pushes it. Spontaneity of a process can be determined from the change in entropy and change in
free energy of a system.

The driving force for a spontaneous process is an increase in the entropy of the universe.
Entropy, S, can be viewed as a measure of randomness, or disorder. Nature spontaneously
proceeds toward the states that have the most “spread out energy”, or the highest probabilities
of existing. In other words, towards an arrangement where energy can be contained in the
greatest number of ways. Everyone will agree that a person usually spends more time and effort
in arranging or organizing things as compared to creating a mess. An orderly room becomes
messy with time. Neatly arranged items on a shelf do not stay orderly for long. They tend to
become disordered as time passes by. This is inevitable, because creating a mess is a more
natural and spontaneous process. Hence, if we will compare the entropies of 1 mole of a substance
in the three physical states based on the kinetic molecular theory theory, molar entropy of the
gaseous state will be highest, molar entropy of the liquid state will be intermediate, and molar
entropy of the solid state will be the lowest. The change in entropy, ΔS, depends only on the
entropies of the final and initial states of the system.
ΔS = Sfinal -Sinitial
A positive value of ΔS (ΔS>0), indicates that the final state is more random or disordered
than the initial state. A negative ΔS value (ΔS<0), indicates that the final state is more ordered
than the initial state. Spontaneity of a process is not solely determined by the tendency of a
system to proceed to a state of lower energy. It is also dependent on the state of disorder. The
direction in which a chemical reaction proceeds is governed by the tendency to attain a state that
is statistically more probable. In other words, an increase in disorder or entropy is
thermodynamically favorable for a reaction to proceed spontaneously. This is simply implies that
entropy change is the factor that can account for the spontaneity of endothermic processes.
There are several factors that influence the amount of entropy present in a system at a particular
state. These factors are the following:

1. Change in Phase. Solid particles are confined to fixed positions or compactly arranged so
that they can hardly move, thus, entropy is relatively low. In liquids, the particles are
slightly far from each other, allowing limited movement, which results in higher entropy as
compared to solids. Whereas in gases, the particles are very far apart, hence, there is a
great freedom of movement and increase kinetic energy, giving rise to greater entropy as
compared to liquids. On the other hand, conversion of gas to liquid, and from liquid to solid,
result in a decrease in entropy.
2. Change in Temperature. Rising the temperature increases the average kinetic energy of
molecules. With an increase in temperature, solid particles vibrate more energetically,
while liquid and gas particles move about more rapidly. Hence, increasing the temperature
increases the entropy of a system while a decrease in temperature results in lowering of
entropy.
3. Number of particles. The phrase “ the more the merrier” can certainly be applied to
entropy. It is definitely “merrier” when there are more people in gathering. When a lot of
people are present, there will be more movement, more noise, more wastes, and definitely
greater disorder.

Consider a chemical system presented by the following equation,

A2B 2A + B
At the left arrow, only one particle is present as reactant, but at the right side, a total of
two particles are produced from the reaction. Since there are more particles in products as
compared to the reactants, there is a corresponding increase in disorder. Generally, an increase
in the number of particles, increase the entropy.

Example. Predict whether the entropy increases or decreases, and consider the degree of
disorder, from initial to final state or form.

1. Sublimation of solid carbon dioxide (dry ice):

CO2(s) CO2(g)
 Solution: Entropy increases and ΔS is > 0, because once the solid is converted to gas, the
particles are more scattered and are no longer confined to a limited volume of space, thus leading
to greater disorder.

A numerical value for entropy can be possibly determined for any substance under a given
set of conditions. The change in entropy is related to heat transferred during the process. The
relationship of ΔS and the heat transferred under constant pressure. For processes occurring at
constant temperature and pressure, the change entropy can be calculated using the equation, ΔS
= qrev/T where: is change in entropy in J/K ( it is negative if heat is released by the system and
positive if heat is absorbed by the system), q= heat transferred at a particular temperature, in J
and T= temperature in Kelvin, (K). However, this equation applies only to processes that are almost
reversible. Any process that can go back to its original state due to a very slight change in
condition is reversible. A typical example is the melting and freezing.

Example: Calculate the entropy change, ΔSvap, when 1 mole water in liquid state is converted to 1
mole stam at 1 atm pressure?

Given: q= heat of vaporization, ΔHvap (amount of heat transferred to the system), equal to
+ 40.7kJ/mol
T= temperature at which the process occurs is the boiling point (1000C or 373 K)

ΔSvap= ΔHvap/ T
= (1mol)(40.7kJ/mol)(1000J/kJ
373K
= +109 J/K

Note that the change in entropy is positive, thus indicating that water molecules in gaseous state
are more disordered than the liquid state. It is also possible to calculate entropy change for
various processes that occur under standard conditions using standard entropy values of
substances. Standard molar entropy or standard entropy, S0, is defined as the entropy of one
mole of a substance at standard condition, 250C and 1 atm pressure. The entropy of a substance
can be obtained from the tabulated values of standard molar entropies, and entropy change can
be calculated using this equation,
ΔSo = ΣySo products - ΣzSo reactants
 The superscript o in the symbol indicates standard conditions (25oC and 1 atm pressure)
while letters y and z, represent the number of moles.
 This table shows molar entropies for the standard conditions of 298.15 K (25°C) and 101.3
kPa. Such conditions need to be specified, since entropy is proportional to substance amount, and
dependent on temperature, pressure. Entropy is also dependent upon volume, but since the
amount, n, temperature, and pressure are given, volume is implicitly defined. This table is taken
from Core Chem: Standard Molar Entropies and is also used on Core Chem: Dependence of S on
Molecular Structure as well as CoreChem: Some Trends In Entropy Values.
Example:

Calculate the entropy change when graphite burns in sufficient supply of oxygen as shown
in the equation below,
C graphite (s) + O2 (g) CO2 (g)
Solution:
Given: So of C graphite (s) =5.7 J/mol-K
So O2 (g) = 205J/mol-K
So CO2 (g) = 213 J/mol-K
ΔSo = ΣySo products - ΣzSo reactants
= [ So of CO2 (g) ]- [So of C graphite (s) + So O2 (g) ]
= [ ( 1mol)(213.6J/mol-K) ]-( 1mol)(5.7J/mol-K)+(1 mol)(205J/mol-K) ]
= +2.97 J/K

Since the entropy change is positive, there is an increase in entropy from reactants to
products.

What is Second Law of Thermodynamics and Its Significance?

The second law of thermodynamics expresses the relationship between spontaneity of a

process. It states that the natural processes proceed in the direction that maintains or increases
the total entropy of the universe, and in any spontaneous change, there is a net increase in
entropy. In principle, the second law can be used in predicting the spontaneity of a process. This
law is one of the most powerful tools that helps explain everything in the physical world. It enables
us to understand why things work as they do, why gasoline makes the engine run, why hot pans
cool down, or why our bodies stay warm even when it is cold. In industry or engineering, the
second law can help to determine which reaction will favor the formation of desired products to
obtain better economic yield. It is important to note that spontaneity is also affected by changes
in temperature and concentrations.
 In predicting the spontaneity of a process, the enthalpy factor is considered in conjunction
with the entropy factor. The balance between these two quantities is given by another state
function called free energy or Gibbs free energy, represented by G, named after the proponent,
William Gibbs. This is a more convenient method to assess spontaneity is to use a single
thermodynamic function that serves the same purpose, a function that is associated with the
system only. Therefore, there is no need to assess surroundings. This state function where both
enthalpy and entropy factors are taken into consideration, is called Gibbs free energy, G, is defined
mathematically as
G = H − TS

Where H is enthalpy, T is temperature in Kelvin, and S is entropy. Gibbs free energy is

represented using the symbol G and typically has a unit of KJ/mol- reaction. Free energy, G, is a
portion of energy change in spontaneous reactions that is available to do useful work. It is the
maximum amount of work that can be done by the system on its surroundings at constant
temperature and pressure. In nonspontaneous process, free energy is a measure of the minimum
amount of work that must be done on the system in order to drive the reaction. In this equation,
G,H, and S, all refer to the system. Every substance possesses free energy, but the actual amount
is seldom known, hence, what will be considered is the change free energy, of a system. For a
process occurring at constant temperature, the change in free energy of the system is given by
the expression
AG = ΔH - TΔS

This equation is valid in all conditions. If both temperature and pressure are constant, the
relationship between the sign of AG and spontaneity of a reaction is as follows:

AG < 0, reaction is spontaneous in the forward direction

AG > 0, nonspontaneous in the forward direction, work must be supplied to make it occur
AG = 0, reaction is at equilibrium
If application is limited to standard condition, 25oC and 1 atm pressure, the new equation
will be in the form:
AGo = ΔHo - TΔSo
Standard state means that solid and liquid substance are pure, gaseous substance is at 1
atm pressure, and for substances in solution, concentration is normally 1M. AGo can readily be
calculated from the tabulated values of ΔHfo and So at 25oC.
Sample Problem.
A drying agent has the chemical composition CaSO4. Calculate the AGo at 25oC, for the
following reaction, which has ΔSo value of -139.7 J/K.
CaSO4(s) Ca-2 (aq) + SO4-2 (aq) ΔHo = -18.0 KJ
Solution:
Given: ΔHo = -18.0 KJ
ΔSo = -139.7 J/K
Required: AGo for the reaction

Strategy: Convert J to KJ and 25oC to K

ΔSo = (-139.7 J/K) (1Kj/1000J)
= -0.1397 kJ/K

K = OC + 273 K
= 25 + 273 = 298K

Substitute the given values into the equation,

AGo = ΔHo - TΔSo
= -18.0 kJ- (298K)(-0.1397 kJ/K
= 18.0 kJ - (-41.6 kJ)
= -59.63 kJ

Since AGo > 0 or positive, the reaction is not spontaneous at 25oC. In other words, at this
temperature, CaSO4, does not dissolve in water to produce a 1M solution. The table below shows
the relationship between temperature, AGo, and spontaneity.
ΔH ΔS ΔG =ΔH-TAS Characteristic of reaction
- + Always - Spontaneous at all temperatures
+ - Always + Nonspontaneous at all temperatures
+ + -at high T Spontaneous at high temperature
+ + + at low T Nonspontaneous at low temperature
- - -at low T Spontaneous a low temperature
- - + at high T Nonspontaneous at high temperature