Larry Brown

Tom Holme

www.cengage.com/chemistry/brown

Chapter 10
Entropy and the Second Law of
Thermodynamics

Jacqueline Bennett • SUNY Oneonta

Chapter Objectives

•Explain the concept of entropy in your own words.

•Deduce the sign of S for many chemical reactions by

examining the physical state of the reactants and products.

•State the second law of thermodynamics in words and

equations and use it to predict spontaneity.

•State the third law of thermodynamics.

2
Chapter Objectives
• Use tabulated data to calculate the entropy change in a chemical
reaction.

• Derive the relationship between the free energy change of a system

and the entropy change of the universe.

• Use tabulated data to calculate the free energy change in a

chemical reaction.

• Explain the role of temperature in determining whether a reaction is

spontaneous.

• Use tabulated data to determine the temperature range for which a

reaction will be spontaneous.

3
Recycling of Plastics
• Standard plastic soft drink bottles are made from
poly(ethylene terephthalate) or PET/PETE.
• PET is manufactured in a two step process starting with
ethylene glycol and dimethyl terephthalate.

4
Recycling of Plastics
• Soft drink bottles manufactured from PET can be recycled.

• The PET plastic bottles are separated from other plastic

types and crushed.

• The crushed PET is washed, dried, and cut into small

flakes.

• The PET flakes are melted and extruded into spaghetti-like

strands that are cut into smaller pellets, which are sold to
manufacturers to make items such as fiberfill for sleeping
bags and coats, fleece fabrics for outdoor wear, carpeting,
and industrial strapping.

5
Recycling of Plastics
• Recycled PET is not used in the manufacture of new soda bottles for
economic and legal restrictions.

• Cheaper to manufacture virgin PET than to use recycled PET.

• Recycled PET not allowed into food and beverage containers due
to possible contamination fears.

• During the recycling process, PET polymer degrades.

• The length of the polymer chain decreases.

• If PET were recycled into soda bottles, the resulting bottles would
be thicker and heavier than bottles manufactured from virgin PET.

6
Spontaneity: Natures Arrow
• Some processes or reactions proceed in only one direction.
• Gasoline reacts spontaneously with oxygen to form carbon
dioxide and water, but water and carbon dioxide never
spontaneously react to reform gasoline.

• A spontaneous process takes place without continuous

intervention, according to thermodynamics.
• Spontaneous processes are not necessarily rapid
processes.
• The combustion of diamond is thermodynamically
spontaneous, but diamonds are considered to last forever.

7
Spontaneous Processes
• Some spontaneous reactions only occur once they are
initiated.

• The combustion of gasoline is a spontaneous reaction but

only occurs when the reaction is initiated with a spark.

• Nonspontaneous reactions only occur with a continual input of

energy.

8
Spontaneous Processes

• Once initiated, the spontaneous reaction between methyl

methacrylate monomer to produce poly(methyl methacrylate),
PMMA, polymer occurs rapidly.
• The reverse reaction, production of methyl methacrylate
monomer, only occurs with a continual input of heat energy.
9
Enthalpy and Spontaneity
• Exothermic reactions are generally preferred over
endothermic reactions.

• Melting ice is an endothermic process but occurs

spontaneously.

• Enthalpy is not the exclusive determinant of spontaneity.

10
Entropy
• Entropy is a state function and was first introduced in
considering the efficiency of steam engines.

• The Carnot cycle uses a combination of adiabatic

processes (no heat is exchanged) and isothermal
processes (temperature is constant).

11
Entropy

• For the Carnot cycle, the

sum of q/T around the
closed path is equal to zero
and therefore defines the
state function.

• The state function is

entropy.

12
Probability and Spontaneous Change

• Probability has important uses in

chemistry.

• The fundamentals of probability

explained using the rolling of dice.

• The probability of rolling a 4 for one

die is 1 in 6.

13
Probability and Spontaneous Change

• As the number of dice increases, the probabilities of a set of

fours increases.
N
 1
Probability =  
 6

• N is the number of dice being thrown.

• The chance of a highly specified arrangement in a collection

of molecules with ~1023 particles is phenomenally small.

14
Definition of Entropy
• Entropy can be tentatively defined as a measurement of the
randomness, or disorder, of a system.

• For large numbers of particles, probability favors random

arrangements.

• Statistical mechanics or statistical thermodynamics

provides a quantitative basis and molecular perspective to
entropy using probability.

15
Definition of Entropy
• For entropy, the probability for the number of ways in which
particles can achieve the same energy is used.

• The way by which a collection of particles can assume a

given energy is a microstate.

• The number of possible microstates is designated by .

• The number of microstates increases as the “randomness”

of the system increases.

16
Defining Entropy

• The Maxwell-Boltzmann
distribution indicates the
overall collection of
molecular speeds but not
the speed of individual
particles.

• Energy is exchanged during

molecular collisions, without
disrupting the overall
distribution of speeds.

17
Definition of Entropy
• As the number of microstates for a system increases, the
entropy of the system increases. This relationship is defined
by the equation:

S  kb ln
• S is entropy

• kb is the Boltzmann constant.

•  is the number of microstates.

18
Judging Entropy Changes in Processes

• Certain types of changes will result in increased entropy.

• Certain phase changes.

• An increase in the number of particles present.

• An increase in the temperature of a substance.

19
Judging Entropy Changes in Processes

• When a solid melts to form a liquid, entropy increases.

• In solids, the particles are held in place rigidly, limiting the

number of ways a specific energy can be obtained.

• In liquids, the particles move past each other, increasing

the number of ways a specific energy can be obtained.

• The number of microstates increases during melting.

20
Judging Entropy Changes in Processes

• A chemical reaction that generates two moles of gas when only one
mole of gas was initially present will increase the entropy of a sample.

• The number of possible microstates increases as the number of

particles increases.

• When a sample is heated, the temperature of the sample increases.

• As temperature increases, the number of possible velocities

increases.

• The number of ways to distribute the kinetic energy of the sample

increases, resulting in an increase in the number of microstates.

21
The Second Law of Thermodynamics

• Whenever energy is converted from one form to another,

some energy is “lost” or “wasted”.

• Not all of the energy available is directed into the desired

process.

• Entropy provides the key to understanding that “loss” of

useful energy is inevitable.

22
The Second Law
• The second law of thermodynamics: in any spontaneous
process, the total entropy of the universe is positive
• (Su > 0).

Su  Ssys  Ssurr

• Su = entropy of the universe
• Ssys = entropy of the system
• Ssurr = entropy of the surroundings

• It is impossible to convert heat completely to work, since

work is a process that involves moving random motions into
more ordered ones.
23
Implications and Applications

• The formation of poly(methyl methacrylate), PMMA, is a

spontaneous process.
• The formation of PMMA is exothermic, which favors
spontaneity.
• The entropy change for the formation of PMMA is negative,
which does not favor spontaneity.
24
Implications and Applications
• The entropy change for the surroundings can be calculated
from the heat flow from the system, which is equal to –H.

H
Ssurr 
T

• For an exothermic reaction, the entropy of the

surroundings increases.

25
Implications and Applications
• For the formation of PMMA, Su is greater than zero only if
the Ssurr is greater than the absolute value of Ssys.

Su  S  Ssurr  0
• Above some temperature T, the Su is less than zero, and
the formation of PMMA becomes nonspontaneous.

• The reverse reaction, the thermolysis of PMMA back

into monomer, will be spontaneous.

• The thermolysis of PMMA is one method to recycle

PMMA.

26
The Third Law of Thermodynamics

• The third law of thermodynamics states that the entropy of a

perfect crystal of any pure substance approaches zero as the
temperature approaches absolute zero.

• The entropy of one mole of a chemical substance under

standard conditions is the standard molar entropy, So.

• The entropy change for a reaction can be calculated from the

standard molar entropies of the reactants and products. This
law allows for the quantification of entropy.

S = vi S (products)i   v j S (reactants) j
o o o

i j
27
The Third Law of Thermodynamics

• Standard molar entropies for selected substances.

28
The Third Law of Thermodynamics

• Entropy is a state function, so the value of S must be

independent of the path taken from reactants to products.
29
Example Problem 10.1
• Use data from Table 10.1 to calculate S for this reaction.

2C2 H 4 (g)  H 2 (g)  C 4 H10 (g)

30
Gibbs Free Energy
• The Gibbs free energy function, G, is defined as:

G  H  TS
• Changes in this function can predict whether or not a process
is spontaneous under conditions of constant pressure and
temperature.

G  H  T S

G  T Su
31
Free Energy and Spontaneous Change

• For a spontaneous reaction, the Gibbs free energy change

must be negative.

G  H  T S
• For a negative H and a positive S, the G will always be
negative and the reaction spontaneous.

• For a positive H and a negative S, the G will always be

positive and the reaction nonspontaneous.

32
Free Energy and Spontaneous Change

• For a positive H and a positive S, the value for G depends

on the temperature.

• For a negative H and a negative S, the value for G

depends on the temperature.

• The temperature at which a reaction changes from

spontaneous to nonspontaneous can be calculated.

H
T
S

33
Free Energy and Spontaneous Change

• The four possible combinations for the signs of H and S

used to determine spontaneity for a chemical reaction.

34
Free Energy and Spontaneous Change

• For a spontaneous reaction with a negative H and a

negative S, the reaction only occurs at low temperature.
• These reactions are referred to as enthalpy driven
because the negative value for the enthalpy is responsible
for the negative value of the Gibbs free energy change.

• For a spontaneous reaction with a positive H and a positive

S, the reaction only occurs at high temperature.
• These reactions are referred to as entropy driven because
the product of the positive entropy change and the
absolute temperature is responsible for the negative value
of the Gibbs free energy change.

35
Example Problem 10.2
• Use the signs of H and S to explain why ice spontaneously
melts at room temperature but not outside on a freezing
winter day.

36
Example Problem 10.3
• The heat of fusion of polyethylene is approximately 7.7
kJ/mol, and the corresponding entropy is 19 J/mol K. Use
these data to estimate the melting point of polyethylene.

37
Free Energy and Work
• It can be shown that the Gibbs free energy change is equal to
the maximum useful work done by the system.

G  wmax

• Work is not a state function.

• Maximum work realized only if the reaction or process is

carried out along a very specific path.

38
Free Energy and Work
• A reversible path is the specific path required for maximum
useful work.

• For systems with a reversible path, the system is near

equilibrium and a small incremental change in a variable
will bring the system back to its initial state.

• In an irreversible change, a small incremental change in any

variable does not restore the initial state.

• The amount of work available is always less than

maximum for an irreversible change.

39
Free Energy and Work
• The Gibbs free energy change establishes the upper bound to
the amount of work obtained from a given process.

• Actual work produced in any real application may be

considerably less.

• Reactant mixtures are generally very far from equilibrium.

• Systems that are far from equilibrium often change rapidly,

and rapid changes tend to be irreversible.

40
Free Energy and Chemical Reactions

• The standard Gibbs free energy change, Go, can be

calculated from Gibbs free energies of formation, Gfo.

• Gfo = 0 for elements in their free standard state.

G o   vi Gfo (products)i   v j Gfo (reactants) j

i j

• This equation provides an alternative method to calculate

G, without entropy or enthalpy.

41
Free Energy and Chemical Reactions

• Values of the free energy change of formation, Gfo, for

selected compounds.
42
Example Problem 10.4
• Confirm that the reaction below would be spontaneous by
calculating the standard free energy change using values
from Table 10.3.

2C2 H 4 (g)  H 2 (g)  C 4 H10 (g)

43
Implications of ∆Go for a Reaction

• Gibbs free energy changes indicate the spontaneity of a

chemical reaction.

• For the formation of PMMA at 298 K, Ho = –56 kJ and

So = –117 J/K.

• Go = –21 kJ at 298K for the formation of PMMA.

• The negative value indicates that the formation of

PMMA is spontaneous at 298 K.

44
Implications of ∆Go for a Reaction

• The reverse reaction, the thermolysis of PMMA to form

methyl methacrylate monomer, has a Go = +21 kJ at
298 K.
• The positive value indicates that the thermolysis of
PMMA is nonspontaneous at 298 K.
• The temperature at which the thermolysis of PMMA
becomes spontaneous is 480 K.
• The thermolysis of PMMA above 480 K is an
entropy driven process.

H 56 kJ
T  1
 480 K
S 0.117 kJ K
45
The Economics of Recycling
• Almost 50% of all aluminum cans were recycled in 2001
compared to 22% of all PET bottles.

• The difference in recycling rates is based in economics.

• When an aluminum can is recycled, the paint and other

coatings are removed and the aluminum can melted down to
make new cans.

• The energy required to recycle 4 aluminum cans equals

the energy required to produce 1 can from aluminum ore.

46
The Economics of Recycling
• When plastic bottles are recycled, the different types of plastic
must be hand sorted.

• Hand sorting increases the cost of recycling plastics.

• The recycling process leads to a degraded polymer.

• Recycled plastics have shorter polymer chain lengths than

virgin materials and different physical properties.

• Recycled aluminum has the same physical properties as

aluminum extracted from ore.

47
The Economics of Recycling
• The cost of producing virgin plastics is lower than costs
associated with recycled plastics.

• Recycling of plastics are economically favored when the cost

of producing virgin plastics increases, the cost of recycling
plastics decreases, or both.

48
The Economics of Recycling

• Symbols, structures, sources, and uses for various recycled

plastics. 49
The Economics of Recycling

50