22/11/2017 Entropy and the 2nd & 3rd Laws of Thermodynamics

Entropy and the 2nd & 3rd Laws of Thermodynamics

Entropy and the 2nd & 3rd Laws of Thermodynamics

Spontaneous Entropy as a
Entropy and the Second
Chemical Measure of
Law of Thermodynamics
Reactions Disorder
Standard-State Enthalpy of Reaction vs.
The Third Law of
Entropies of Entropy of Reaction
Thermodynamics
Reaction Calculations

Spontaneous Chemical Reactions

The first law of thermodynamics suggests that we can't get something for nothing. It allows us to
build an apparatus that does work, but it places important restrictions on that apparatus. It says
that we have to be willing to pay a price in terms of a loss of either heat or internal energy for any
work we ask the system to do. It also puts a limit on the amount of work we can get for a given
investment of either heat or internal energy.

The first law allows us to convert heat into work, or work into heat. It also allows us to change the
internal energy of a system by transferring either heat or work between the system and its
surroundings. But it doesn't tell us whether one of these changes is more easy to achieve than
another. Our experiences, however, tell us that there is a preferred direction to many natural
processes. We aren't surprised when a cup of coffee gradually loses heat to its surroundings as it
cools, for example, or when the ice in a glass of lemonade absorbs heat as it melts. But we would
be surprised if a cup of coffee suddenly grew hotter until it boiled or the water in a glass of
lemonade froze on a hot summer day, even though neither process violates the first law of
thermodynamics.

Similarly, we aren't surprised to see a piece of zinc metal dissolve in a strong acid to give bubbles
of hydrogen gas.

Zn(s) + 2 H+(aq) Zn2+(aq) + H2(g)

But if we saw a film in which H2 bubbles formed on the surface of a solution and then sank through

the solution until they disappeared, while a strip of zinc metal formed in the middle of the solution,
we would conclude that the film was being run backward.

Many chemical and physical processes are reversible and yet tend to proceed in a direction in
which they are said to be spontaneous. This raises an obvious question: What makes a reaction
spontaneous? What drives the reaction in one direction and not the other?

So many spontaneous reactions are exothermic that it is tempting to assume that one of the
driving forces that determines whether a reaction is spontaneous is a tendency to give off energy.

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The following are all examples of spontaneous chemical reactions that are exothermic.

2 Al(s) + 3 Br2(l) 2 AlBr3(s) Ho = -511 kJ/mol AlBr3

2 H2(g) + O2(g) 2 H2O(g) Ho = -241.82 kJ/mol H2O

P4(s) + 5 O2(g) P4O10(s) Ho = -2984 kJ/mol P4O10

There are also spontaneous reactions, however, that absorb energy from their surroundings. At

100oC, water boils spontaneously even though the reaction is endothermic.

H2O(l) H2O(g) Ho = 40.88 kJ/mol

Ammonium nitrate dissolves spontaneously in water, even though energy is absorbed when this
reaction takes place.

H2O

NH4NO3(s) NH4+(aq) + NO3-(aq) Ho = 28.05 kJ/mol

Thus, the tendency of a spontaneous reaction to give off energy can't be the only driving force
behind a chemical reaction. There must be another factor that helps determine whether a reaction
is spontaneous. This factor, known as entropy, is a measure of the disorder of the system.

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Entropy as a Measure of Disorder

Perhaps the best way to understand entropy as a driving force in nature is to conduct a simple
experiment with a new deck of cards. Open the deck, remove the jokers, and then turn the deck
so that you can read the cards. The top card will be the ace of spades, followed by the two, three,
and four of spades, and so on. Now divide the cards in half, shuffle the deck, and note that the
deck becomes more disordered. The more often the deck is shuffled, the more disordered it
becomes.What makes a deck of cards become more disordered when shuffled?

In 1877 Ludwig Boltzmann provided a basis for answering this question when he introduced the
concept of the entropy of a system as a measure of the amount of disorder in the system. A deck
of cards fresh from the manufacturer is perfectly ordered and the entropy of this system is zero.
When the deck is shuffled, the entropy of the system increases as the deck becomes more
disordered.

There are 8.066 x 1067 different ways of organizing a deck of cards. The probability of obtaining

any particular sequence of cards when the deck is shuffled is therefore 1 part in 8.066 x 1067. In
theory, it is possible to shuffle a deck of cards until the cards fall into perfect order. But it isn't very
likely!

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Boltzmann proposed the following equation to describe the relationship between entropy and the
amount of disorder in a system.

S = k ln W

In this equation, S is the entropy of the system, k is a proportionality constant equal to the ideal
gas constant divided by Avogadro's constant, ln represents a logarithm to the base e, and W is the
number of equivalent ways of describing the state of the system. According to this equation, the
entropy of a system increases as the number of equivalent ways of describing the state of the
system increases.

The relationship between the number of equivalent ways of describing a system and the amount of
disorder in the system can be demonstrated with another analogy based on a deck of cards. There
are 2,598,960 different hands that could be dealt in a game of five-card poker. More than half of
these hands are essentially worthless. Winning hands are much rarer. Only 3,744 combinations
correspond to a "full house," for example. The table below gives the number of equivalent
combinations of cards for each category of poker hand, which is the value of W for this category.
As the hand becomes more disordered, the value of W increases, and the hand becomes
intrinsically less valuable.

Number of Equivalent Combinations for Various Types of Poker Hands

Hand W ln W

Royal flush (AKQJ10 in one suit) 4 1.39

Straight flush (five cards in sequence in one suit) 36 3.58

Four of a kind 624 6.44

Full house (three of a kind plus a pair) 3,744 8.23

Flush (five cards in the same suit) 5,108 8.54

Straight (five cards in sequence) 10,200 9.23

Three of a kind 54,912 10.91

Two pairs 123,552 11.72

One pair 1,098,240 13.91

No pairs 1,302,540 14.08

Total 2,598,960

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Entropy and the Second Law of Thermodynamics

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The second law of thermodynamics describes the relationship between entropy and the
spontaneity of natural processes.

Second Law: In an isolated system, natural processes are spontaneous when

they lead to an increase in disorder, or entropy.

This statement is restricted to isolated systems to avoid having to worry about whether the
reaction is exothermic or endothermic. By definition, neither heat nor work can be transferred
between an isolated system and its surroundings.

We can apply the second law of thermodynamics to chemical reactions by noting that the entropy
of a system is a state function that is directly proportional to the disorder of the system.

Ssys > 0 implies that the system becomes more

disordered during the reaction.

Ssys < 0 implies that the system becomes less

disordered during the reaction.

For an isolated system, any process that leads to an increase in the disorder of the system will be
spontaneous. The following generalizations can help us decide when a chemical reaction leads to
an increase in the disorder of the system.

Solids have a much more regular structure than liquids. Liquids are
therefore more disordered than solids.

The particles in a gas are in a state of constant, random motion.

Gases are therefore more disordered than the corresponding liquids.

Any process that increases the number of particles in the system

increases the amount of disorder.

Practice Problem 2:

Which of the following processes will lead to an increase in the entropy of the system?

(a) N2(g) + 3H2 (g) 2 NH3(g)

(b) H2O(l) H2O(g)

(c) CaCO3(s) CaO(s) + CO2(g)

(d) NH4NO3(s) + H2O(l) NH4+ (aq) + NO3- (aq)

Click here to check your answer to Practice Problem 2.

The sign of H for a chemical reaction affects the direction in which the reaction occurs.

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Spontaneous reactions often, but not always, give off energy.

The sign of S for a reaction can also determine the direction of the reaction.

In an isolated system, chemical reactions occur in the direction that leads to

an increase in the disorder of the system.

In order to decide whether a reaction is spontaneous, it is therefore important to consider the

effect of changes in both enthalpy and entropy that occur during the reaction.

Practice Problem 3:

Use the Lewis structures of NO2 and N2O4 and the stoichiometry of the following reaction to

decide whether H and S favor the reactants or products of this reaction:

2 NO2(g) N2O4(g)

Click here to check your answer to Practice Problem 3.

Click here to see a solution to Practice Problem 3.

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The Third Law of Thermodynamics

The third law of thermodynamics defines absolute zero on the entropy scale.

Third law: The entropy of a perfect crystal is zero when the temperature of
the crystal is equal to absolute zero (0 K).

The crystal must be perfect, or else there will be some inherent disorder. It also must be at 0 K;
otherwise there will be thermal motion within the crystal, which leads to disorder.

As the crystal warms to temperatures above 0 K, the particles in the crystal start to move,
generating some disorder. The entropy of the crystal gradually increases with temperature as the
average kinetic energy of the particles increases. At the melting point, the entropy of the system
increases abruptly as the compound is transformed into a liquid, which is not as well ordered as
the solid. The entropy of the liquid gradually increases as the liquid becomes warmer because of
the increase in the vibrational, rotational, and translational motion of the particles. At the boiling
point, there is another abrupt increase in the entropy of the substance as it is transformed into a
random, chaotic gas.

The table below provides an example of the difference between the entropy of a substance in the
solid, liquid, and gaseous phases.

The Entropy of Solid, Liquid, and Gaseous Forms of Sulfur Trioxide

Compound So (J/mol-K)
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SO3(s) 70.7

SO3(l) 113.8

SO3(g) 256.76

Note that the units of entropy are joules per mole kelvin (J/mol-K). A plot of the entropy of this
system versus temperature is shown in the figure below.

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Standard-State Entropies of Reaction

Because entropy is a state function, the change in the entropy of the system that accompanies any
process can be calculated by subtracting the initial value of the entropy of the system from the
final value.

S = Sf - Si

S for a chemical reaction is therefore equal to the difference between the sum of the entropies of
the reactants and the products of the reaction.

S = S(products) - S(reactants)

When this difference is measured under standard-state conditions, the result is the standard-

state entropy of reaction, So.

So = So(products) - So(reactants)

By convention, the standard state for thermodynamic measurements is characterized by the

following conditions.

Standard-state conditions:

All solutions have concentrations of 1 M.

All gases have partial pressures of 0.1 MPa (0.9869 atm)

Although standard-state entropies can be measured at any temperature, they are often measured

at 25oC.

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Practice Problem 4:

Calculate the standard-state entropy of reaction for the following reactions and explain the sign
of S for each reaction.

(a) Hg(l) Hg(g)

(b) 2NO2(g) N2O4(g)

(c) N2(g) + O2(g) 2NO(g)

Click here to check your answer to Practice Problem 4.

Click here to see a solution to Practice Problem 4.

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The Difference Between Enthalpy of Reaction and Entropy of Reaction

Calculations

At first glance, tables of thermodynamic data seem inconsistent. Consider the data in the table
below, for example.

Thermodynamic Data for Aluminum and Its Compounds

Substance HFo(kJ/mol) So (J/mol-K)

Al(s) 0 28.33

Al(g) 326.4 164.54

Al2O3(s) -1675.7 50.92

AlCl3(s) -704.2 110.67

The enthalpy data in this table are given in terms of the standard-state enthalpy of formation of

each substance, Hfo. This quantity is the heat given off or absorbed when the substance is made

from its elements in their most thermodynamically stable state at 0.1 MPa. The enthalpy of
formation of AlCl3, for example, is the heat given off in the following reaction.

2 Al(s) + 3 Cl2(g) 2 AlCl3(s) Hfo = -704.2

kJ/mol

The enthalpy data in this table are therefore relative numbers, which compare each compound
with its elements.

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Enthalpy data are listed as relative measurements because there is no absolute zero on the
enthalpy scale. All we can measure is the heat given off or absorbed by a reaction. Thus, all we
can determine is the difference between the enthalpies of the reactants and the products of a
reaction. We therefore define the enthalpy of formation of the elements in their most
thermodynamically stable states as zero and report all compounds as either more or less stable
than their elements.

Entropy data are different. The third law defines absolute zero on the entropy scale. As a result,
the absolute entropy of any element or compound can be measured by comparing it with a perfect

crystal at absolute zero. The entropy data are therefore given as absolute numbers, So, not

entropies of formation, Sof.

AlCl3(s) So = 110.67 J/mol-K

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