Chapter 19.

1 Spontaneous Process
 First Law of Thermodynamics
 Energy cannot be created nor destroyed.
 Therefore, the total energy of the universe is
a constant.
 Energy can, however, be converted from one
form to another or transferred from a system
to the surroundings or vice versa.
 Chapter 19.1 Spontaneous Process
 Spontaneous Processes

 Spontaneous processes
are those that proceed
on its own without any
outside assistance.
 The gas in vessel B will
spontaneously effuse into
vessel A, but once the
gas is in both vessels, it
will not spontaneously
return to vessel B.
 Chapter 19.1 Spontaneous Process
 Spontaneous Processes

 The rusting process

is spontaneous,
whereas the reverse
process is
nonspontaneous.
 Processes that are
spontaneous in one
direction are
nonspontaneous in
the reverse direction.
 Chapter 19.1 Spontaneous Process
 Spontaneous Processes
 Processes that are spontaneous at one temperature may
be nonspontaneous at other temperatures.
 Above 0 °C it is spontaneous for ice to melt.
 Below 0 °C the reverse process is spontaneous.
 At 0 °C, the solid and liquid phases are in equilibrium.
 Thermodynamics can tell us the direction and extent of a
reaction but tells us nothing about the speed of the reaction.

© 2009, Prentice-Hall, Inc.

Sample Exercise 19.1 Identifying Spontaneous Processes

Predict whether the following processes are spontaneous as

described, spontaneous in the reverse direction, or in equilibrium:
(a) When a piece of metal heated to 150 °C is added to water at 40 °C,
the water gets hotter.
(b) Water at room temperature decomposes into H2(g) and O2(g),
(c) Benzene vapor, C6H6(g), at a pressure of 1 atm condenses to
liquid benzene at the normal boiling point of benzene, 80.1 °C.

Solution
(a) This process is spontaneous.

(b) Experience tells us that this process is not spontaneous.

(c) This is an equilibrium situation.

 Chapter 19.1 Spontaneous Process
 Seeking a Criterion for Spontaneity
 What makes a process spontaneous?
 “the direction of spontaneous changes in chemical
systems is also determined by the loss of energy
(exothermic).” – Marcellin Bertholet –
• The melting of ice at room temperature
(endothermic)
• The dissolving of NH4NO3 (endothermic)
 One of the keys to understanding spontaneity is
distinguishing between reversible and irreversible
paths between states.
 Chapter 19.1 Spontaneous Process
 Reversible Processes

 In a reversible process,
the system changes in
such a way that the
system and
surroundings can be put
back in their original
states by exactly
reversing the process.

Figure 19.4 Reversible flow of heat.

 Chapter 19.1 Spontaneous Process
 Irreversible Processes

 Irreversible processes cannot be undone by exactly

reversing the change to the system.
 Spontaneous processes are irreversible.
• Compressing the gas back to the original state
requires that the surroundings do work on the system
 Chapter 19.2 Entropy and the Second Law of Thermodynamics
 Entropy
 Entropy (S) is a term coined by Rudolph
Clausius in the 19th century.
 Clausius was convinced of the significance of
the ratio of heat delivered and the temperature
q
at which it is delivered, .
T
 Entropy can be thought of as a measure of the
randomness of a system.
 It is related to the various modes of motion in
molecules.
 Chapter 19.2 Entropy and the Second Law of Thermodynamics
 Entropy

 Like total energy, E, and enthalpy, H, entropy

is a state function.
 Therefore,
∆S = Sfinal − Sinitial

 For a process occurring at constant temperature

(an isothermal process), the change in entropy is
equal to the heat that would be transferred if the
process were reversible divided by the temperature:
qrev
∆S =
T
Sample Exercise 19.2 Calculating ΔS for a Phase Change
The element mercury, Hg, is a silvery liquid at room temperature. The
normal freezing point of mercury is –38.9 ゜C, and its molar enthalpy of
fusion is ΔHfusion = 2.29 kJ/mol. What is the entropy change of the
system when 50.0 g of Hg(l) freezes at the normal freezing point?
MW of Hg is 200.59 g
Solution
qrev
∆S =
T
 Chapter 19.2 Entropy and the Second Law of Thermodynamics

 Second Law of Thermodynamics

 The entropy of the universe increases for
spontaneous processes, and the entropy of the
universe does not change for reversible
processes.
For reversible processes:
∆Suniv = ∆Ssystem + ∆Ssurroundings = 0
For irreversible processes:
∆Suniv = ∆Ssystem + ∆Ssurroundings > 0
 These last truths mean that as a result of all
spontaneous processes the entropy of the
universe increases.
 Chapter 19.3 The Molecular Interpretation of Entropy

 Expansion of gas at the molecular level

 The probability that all the molecules are in the left
flask at the same time is (1/2)N
 The gas spontaneously expands to fill both flasks,
and it does not spontaneously all go back in the
left flask: the probability is too small

Figure 19.6 Possible arrangements of two gas molecules in two flasks.

 Chapter 19.3 The Molecular Interpretation of Entropy

 Entropy on the Molecular Scale

 Ludwig Boltzmann described the concept of
entropy on the molecular level.
 Microstate
• A particular microscopic arrangement of the
atoms or molecules of the system that
corresponds to the given
state of the system
• Expressed by positions
and kinetic energies
 Chapter 19.3 The Molecular Interpretation of Entropy

 Molecular motions and entropy

 Molecules exhibit three types of motion:
• Translational: Movement of the entire molecule
from one place to another.
• Vibrational: Periodic motion of atoms within a
molecule.
• Rotational: Rotation of the molecule on about an
axis or rotation about σ bonds.

Figure 19.8 Vibrational and rotational motions in a water molecule.

 Chapter 19.3 The Molecular Interpretation of Entropy

 Entropy on the Molecular Scale

 Boltzmann envisioned the motions of a sample of
molecules at a particular instant in time.
• This would be akin to taking a snapshot of all the
molecules.
 He referred to this sampling as a microstate of the
thermodynamic system.

Figure 19.8 Vibrational and rotational motions in a water molecule.

 Chapter 19.3 The Molecular Interpretation of Entropy

 Entropy on the Molecular Scale

 Each thermodynamic state (at P, V, and T) has a
specific number of microstates, W, associated with it.
 Entropy is
S = k lnW
where k is the Boltzmann constant, 1.38 × 10−23 J/K.
 Thus, entropy is a measure of how many
microstates are associated with a particular
macroscopic state
 Chapter 19.3 The Molecular Interpretation of Entropy

 Entropy on the Molecular Scale

 The change in entropy for a process,

then, is
∆S = k lnWfinal − k lnWinitial

Wfinal
∆S = k ln
Winitial

 Entropy increases with the number of

microstates in the system.
 Chapter 19.3 The Molecular Interpretation of Entropy

 Entropy on the Molecular Scale

 The number of microstates and,

therefore, the entropy tends to increase
with increases in
• Temperature.
• Volume.
• The number of independently moving
molecules.
 Chapter 19.3 The Molecular Interpretation of Entropy

 Entropy and Physical States

 Entropy increases with the freedom of motion of
molecules. Therefore, S(g) > S(l) > S(s).
 Chapter 19.3 The Molecular Interpretation of Entropy

 Entropy and Solution

 Generally, when a solid
is dissolved in a solvent,
entropy increases.
• The ionic solid becomes
more disordered and
water becomes more
ordered
• The disordering process
is dominant
Figure 19.10 Entropy changes when
an ionic solid dissolves in water.
 Chapter 19.3 The Molecular Interpretation of Entropy

 Entropy Changes
 In general, entropy
increases when
• Gases are formed from
liquids and solids;
• Liquids or solutions are
formed from solids;
• The number of gas
molecules increases;
• The number of moles
increases.
Figure 19.11 Entropy decreases when
NO(g) is oxidized by O2(g) to NO2(g).
 Chapter 19.3 The Molecular Interpretation of Entropy

CHEMISTRY AND LIFE

 Entropy and human society
 Our life is full of well-
ordered materials and
getting more ordered
 Does this mean that our
existence is a violation of
the second law?
 Humans are, in effect,
using up our storehouse
of energy-rich materials
to create order and Figure 19.12 Fighting the second law.
advance technology.
Sample Exercise 19.3 Predicting the Sign of ΔS
Predict whether ΔS is positive or negative for each of the following processes,
assuming each occurs at constant temperature:

Solution
(a) Positive
(b) Negative
(c) Negative
(d) Close to zero

Practice Exercise
Indicate whether each of the following processes produces an
increase or decrease in the entropy of the system:

Answer: (a) increase, (b) decrease, (c) decrease, (d) decrease

Sample Exercise 19.4 Predicting Which Sample of Matter Has the Higher Entropy
Choose the sample of matter that has greater entropy in each pair, and explain
your choice: (a) 1 mol of NaCl(s) or 1 mol of HCl(g) at 25 ﾟC, (b) 2 mol of HCl(g)
or 1 mol of HCl(g) at 25 ﾟC, (c) 1 mol of HCl(g) or 1 mol of Ar(g) at 298 K.

Solution

(a) Gaseous HCl has the higher entropy because gases have more
available motions than solids.

(b) The sample containing 2 mol of HCl has twice the number of molecules
as the sample containing 1 mol. Thus, the 2-mol sample has twice the
number of microstates and twice the entropy when they are at the same
pressure.

(c) The HCl sample has the higher entropy because the HCl molecule is
capable of storing energy in more ways than is Ar. HCl molecules can rotate
and vibrate; Ar atoms cannot.
 Chapter 19.3 The Molecular Interpretation of Entropy

 Third Law of Thermodynamics

 The entropy of a pure crystalline substance at
absolute zero is 0.

S = k ln W = k ln 1 = 0
 Chapter 19.3 The Molecular Interpretation of Entropy

 Entropy as a Function of T

 Entropy generally
increases with
increasing T
 The entropies of the
phases of a given
substance follow the
order

Figure 19.13 Entropy increases with

increasing temperature.
 Chapter 19.4 Entropy Changes in Chemical Reactions

 Standard Molar Entropies

19.13
 Chapter 19.4 Entropy Changes in Chemical Reactions

 Standard Molar Entropies

 Chapter 19.4 Entropy Changes in Chemical Reactions

 Entropy changes for a reaction

 Entropy changes for a reaction can be estimated in a
manner analogous to that by which ∆H is estimated:
∆S° = ΣnS°(products) — ΣmS°(reactants)
where n and m are the coefficients in the balanced
chemical equation.

Sample Exercise 19.5 Calculating ΔS from Tabulated Entropies

Calculate ΔSﾟﾟ for the synthesis of ammonia from N2(g) and H2(g) at 298 K:
N2(g) + 3 H2(g) → 2 NH3(g)

ΔSﾟﾟ = 2Sﾟﾟ(NH3) - [Sﾟﾟ(N2) + 3Sﾟﾟ(H2)]

ΔSﾟﾟ = (2)(192.5) J/K - [(1)(191.5) + (3)(130.6)] J/K
= -198.3 J/K (Note the negative value)
 Chapter 19.4 Entropy Changes in Chemical Reactions

 Entropy Changes in Surroundings

 Heat that flows into or out of the system
changes the entropy of the surroundings.
 For an isothermal process:
−qsys
∆Ssurr =
T

 At constant pressure, qsys is simply ∆H°

for the system.
 Chapter 19.4 Entropy Changes in Chemical Reactions

 Entropy Changes in the Universe

Note ∆Suniverse > 0 for a spontaneous reaction.

 Chapter 19.5 Gibbs Free Energy
 Gibbs free energy
G = H − TS, ∆G = ∆H − T∆S [Eq. 19.11]
−qsystem
• Since ∆Ssurroundings =
T
and qsystem = ∆Hsystem
This becomes:
−∆Hsystem
∆Suniverse = ∆Ssystem +
T
Multiplying both sides by −T, we get
−T∆Suniverse = ∆Hsystem − T∆Ssystem
−T∆Suniverse = ∆G by comparing with Eq 19.11
 Chapter 19.5 Gibbs Free Energy

 Gibbs free energy

 At constant T & P and with

a proper catalyst,
• From H2 and N2, NH3 is
formed spontaneously.
• From NH3, NH3 is
decomposed, and
H2 and N2 are formed
spontaneously
to reach equilibrium.
Sample Exercise 19.6 Calculating Free-Energy Change from ΔH°, T, ΔS°

Calculate the standard free energy change for the formation of NO(g) from
N2(g) and O2(g) at 298 K:
N2(g) + O2(g) → 2 NO(g)

given that ΔH˚ = 180.7 kJ and ΔS˚ = 24.7 J/K. Is the reaction spontaneous
under these circumstances?

Solution

Because ΔG° is positive, the reaction is not spontaneous under standard

conditions at 298 K.
 Chapter 19.5 Gibbs Free Energy

 Standard Free Energy Changes

 Analogous to standard enthalpies of

formation are standard free energies of
formation, ∆G°f .

∆G° = ∑n∆G°f (products) − ∑m∆G°f (reactants)

Where n and m are the stoichiometric

coefficients.
Sample Exercise 19.7 Calculating Standard Free-Energy Change from
Free Energies of Formation

(a) Use data from Appendix C to calculate the standard free-energy change
for the following reaction at 298 K:
P4(g) + 6 Cl2(g) → 4 PCl3(g)

(b) What is ΔG° for the reverse of the above reaction?

4 PCl3(g) → P4(g) + 6 Cl2(g) ΔG° = +1102.8 kJ

Sample Exercise 19.8 Estimating and Calculating ΔG°
In Section 5.7 we used Hess’s law to calculate ΔH˚ for the combustion of
propane gas at 298 K:
C3H8(g) + 5 O2(g) → 3 CO2(g) + 4 H2O(l) ΔH˚ = –2220 kJ

(a) Without using data from Appendix C, predict whether ΔG˚ for this reaction is
more negative or less negative than ΔH˚. (b) Use data from Appendix C to
calculate the standard free-energy change for the reaction at 298 K. Is your
prediction from part (a) correct?
(a) ΔG˚ is less negative than ΔH˚.

(b)

Hess’s law states that the energy change for any chemical or physical process is independent of the
pathway or number of steps required to complete the process provided that the final and initial reaction
conditions are the same. In other words, an energy change is path independent, only the initial and final
states being of importance. This path independence is true for all state functions
 Chapter 19.6 Free Energy and Temperature

 Free Energy and Temperature

At temperatures other than 25 ˚C,

∆G° = ∆H° − T∆S°

How does ∆G° change with temperature?

 Chapter 19.6 Free Energy and Temperature

 Free Energy and Temperature

 There are two parts to the free energy equation:
∆H° : the enthalpy term
– T∆S° : the entropy term
 The temperature dependence of free energy,
then mainly comes from the entropy term.
 Consider the melting of ice to liquid water
H2O (s) → H2O (l) ∆H > 0, ∆S > 0.
∆G = ∆H - T∆S
When T < 0 ˚C, ∆G > 0, nonspontaneous
When T > 0 ˚C, ∆G < 0, spontaneous
 Chapter 19.6 Free Energy and Temperature
 Free Energy and Temperature

∆G = ∆H - T∆S
Sample Exercise 19.9 Determining the Effect of Temperature on Spontaneity
The Haber process for the production of ammonia involves the equilibrium

Assume that ΔH˚ and ΔS˚ for this reaction do not change with temperature. (a)
Predict the direction in which ΔG˚ for this reaction changes with increasing
temperature. (b) Calculate ΔG˚ at 25 ˚C and 500 ˚C.

Solution
(a) ΔG˚ increases with increasing temperature. The equilibrium moves to the
reverse direction with increasing temperature.
(b) From the previous examples, ΔH˚ = –92.38 kJ and ΔS˚ = –198.3 J/K.
At T = 298 K we have:
 Chapter 19.7 Free Energy and the Equilibrium Constant

 Free Energy and Equilibrium

Under any conditions, standard or
nonstandard, the free energy change can be
found this way:

∆G = ∆G° + RT lnQ

(Under standard conditions, all concentrations are 1

M, so Q = 1 and lnQ = 0; the last term drops out.)
Sample Exercise 19.11 Calculating the Free-Energy Change under
Nonstandard Conditions
We will continue to explore the Haber process for the synthesis of ammonia:

Calculate ΔG at 298 K for a reaction mixture that consists of 1.0 atm N2, 3.0 atm H2,
and 0.50 atm NH3.

Solution

From Ex 19.9, ΔG゜ = -33.3 kJ/mol.

 Chapter 19.7 Free Energy and the Equilibrium Constant

 Free Energy and the Equilibrium Constant

 At equilibrium, Q = K, and ∆G = 0.
 The equation becomes
0 = ∆G° + RT lnK
 Rearranging, this becomes
∆G° = −RT lnK
or,
-∆G°
K = e RT
Sample Exercise 19.12 Calculating an Equilibrium Constant for ΔG°
Use standard free energies of formation to calculate the equilibrium constant,
K, at 25 ˚C for the reaction involved in the Haber process:

The standard free-energy change for this reaction was calculated in Sample
Exercise 19.9:
ΔG˚ = –33.3 kJ/mol = –33,300 J/mol.

Solution
-∆G°
K= e RT
Sample Integrative Exercise Putting Concepts Together

Consider the simple salts NaCl(s) and AgCl(s). We will examine the equilibria in
which these salts dissolve in water to form aqueous solutions of ions:

(a) Calculate the value of ΔG˚ at 298 K for each of the preceding reactions.
ΔGﾟsoln (NaCl) = ΔGﾟf (Na+, aq) + ΔGﾟf (Cl- , aq) - ΔGﾟf (NaCl, s)

(b) The two values from part (a) are very different. Is this difference primarily due
to the enthalpy term or the entropy term of the standard free-energy change?
The difference in the values of ΔG°soln is dominated by the difference in
the values of ΔH°soln
Sample Integrative Exercise Putting Concepts Together

Consider the simple salts NaCl(s) and AgCl(s). We will examine the equilibria in
which these salts dissolve in water to form aqueous solutions of ions:

(c) Use the values of ΔG˚ to calculate the Ksp values for the two salts at 298 K.

(d) Sodium chloride is considered a soluble salt, whereas silver chloride is

considered insoluble. Are these descriptions consistent with the answers to part (c)?

Yes.
Sample Integrative Exercise Putting Concepts Together

Consider the simple salts NaCl(s) and AgCl(s). We will examine the equilibria in
which these salts dissolve in water to form aqueous solutions of ions:

(e) How will ΔG˚ for the solution process of these salts change with increasing T?
What effect should this change have on the solubility of the salts?

For the solution process, ΔS > 0 for both salts. So –T ΔSﾟsoln is negative.
Therefore, ΔGﾟsoln increases with increasing temperature.
 Many desirable chemical reactions are
nonspontaneous
 Consider the extraction of copper metal from
the mineral chalcocite

 We can find some way to make this reaction

spontaneous by coupling the reaction with
another one Chalcocite
 Biological systems employ the same principle of
using spontaneous reactions to drive
nonspontaneous ones