THE SKYLINE OF HONG KONG The construction

of our human environment entails the use of

enormous amounts of energy to create complex
ordered structures, such as modern skyscrapers.

THERMODYNAMICS:
THE SECOND AND THIRD LAWS
Spontaneous Processes
Spontaneity can depend on temperature. At T > 0oC, ice melts
spontaneously to liquid water. At T < 0oC, , the reverse process, water
freezing to ice, is spontaneous. At T = 0oC the two states are in equilibrium.
Spontaneous Processes
Reversible and Irreversible Processes

A reversible process is a specific way in which a system changes its

state. In a reversible process, the change occurs in such a way that the
system and surroundings can be restored to their original states by
exactly reversing the change.

An irreversible process is one that cannot simply be reversed to

restore the system and its surroundings to their original states.
Spontaneous Processes

Reversible flow of heat.

Spontaneous Processes
“isothermal process”

An irreversible process

Any spontaneous process is irreversible.

Entropy
Entropy (S) is often described as a measure of how spread out or
dispersed the energy of a system is among the different possible ways
that system can contain energy.

Microstates and Entropy

The eleven possible ways of

distributing the molecules are
called microscopic states or
microstates and each set of
similar microstates is called a
distribution
The probability of occurrence of
a particular distribution (state)
depends on the number of ways
(microstates) in which the
distribution can be achieved.
Entropy
k is called the Boltzmann constant (1.38  10-23 J/K)

The entropy change for the process, S, is

Entropy
Changes in Entropy
• A system with fewer microstates (smaller W) among which to spread its
energy (small dispersal) has a lower entropy.
• A system with more microstates (larger W) among which to spread its
energy (large dispersal) has a higher entropy.

melting: Sliquid > Ssolid

vaporization: Svapor > Sliquid;

Entropy

Dissolving:
Ssoln > Ssolute + Ssolvent

Heating: ST2 > ST1

Entropy
Example : When an ionic solid such as NaCl dissolves in water

There are two contributions to entropy increase: the solution process

(mixing of solute with solvent) and the dissociation of the compound
into ions.
There is also a process decreases entropy: hydration, which causes
water molecules to become more ordered around the ions.
Heating also increases the entropy of a system.

vibrational motions rotational motions

Entropy
Standard Entropy

Standard entropy is the absolute

entropy of a substance at 1 atm and
25°C.

It is possible to determine the absolute

value of entropy of a substance, called
absolute entropy, something we
cannot do for energy or enthalpy.

Units of entropy: J/K or J/K  mol

Entropy
Example: Predict whether the entropy change is greater or less
than zero for each of the following processes: (a) freezing ethanol, (b)
evaporating a beaker of liquid bromine at room temperature, (c)
dissolving glucose in water, (d) cooling nitrogen gas from 80°C to
20°C.
Solution: (a) Upon freezing, the ethanol molecules are held rigid in
position. This phase transition reduces the number of microstates and
therefore the entropy decreases; that is, ΔS < 0.
(b) Evaporating bromine increases the number of microstates because
the Br 2 molecules can occupy many more positions in nearly empty
space. Therefore, ΔS > 0.
(c) Glucose is a nonelectrolyte. The solution process leads to a greater
dispersal of matter due to the mixing of glucose and water molecules so
we expect ΔS > 0.
(d) The cooling process decreases various molecular motions. This
leads to a decrease in microstates and so ΔS < 0.
The Second Law of Thermodynamics
The second law of thermodynamics: The entropy of the
universe increases in a spontaneous process and remains unchanged
in an equilibrium process.

Mathematically, we can express the second law of thermodynamics

as follows :

ΔSuniv: the entropy change in the universe

ΔSsys: the entropy changes in system
ΔSsurr: the entropy change in the surroundings
The Second Law of Thermodynamics
Entropy Changes in the System
Suppose that the system is represented by the following reaction:

(ΔS°rxn: standard entropy of reaction )

The Second Law of Thermodynamics
Example: From the standard entropy values, calculate the standard
entropy changes for the following reactions at 25°C.
(a) CaCO3(s)  CaO(s) + CO2(g)
(b) N2(g) + 3H2(g)  2NH3(g)
(c) H2(g) + Cl2(g)  2HCl(g)

Solution
ΔS°rxn = [S°(CaO) + S°(CO2)] – [S°(CaCO3)]
= [(39.8 J/Kmol) + (213.6 J/Kmol)] － (92.9 J/Kmol)
= 160.5 J/Kmol
Thus, when 1 mole of CaCO3 decomposes to form 1 mole of
CaO and 1 mole of gaseous CO 2 , there is an increase in
entropy equal to 160.5 J/Kmol.
The Second Law of Thermodynamics

(b) ΔS°rxn = [2S°(NH3)] – [S°(N2) + 3S°(H2)]

= (2)(193 J/Kmol) – [(192 J/Kmol) + (3)(131 J/Kmol)]
= -199 J/Kmol
this result shows that when 1 mole of gaseous nitrogen reacts
with 3 moles of gaseous hydrogen to form 2 moles of gaseous
ammonia, there is a decrease in entropy equal to -199 J/Kmol.
(c) ΔS°rxn = [2S°(HCl)] – [S°(H2) + S°(Cl2)]
= (2)(187 J/Kmol) – [(131 J/Kmol) + (223 J/Kmol)]
= 20 J/Kmol
Thus, the formation of 2 moles of gaseous HCl from 1 mole of
gaseous H2 and 1 mole of gaseous Cl2 results in a small increase
in entropy equal to 20 J/Kmol.
The Second Law of Thermodynamics

The general rules:

• If a reaction produces more gas molecules than it consumes
[above Example (a)], ΔS° is positive.
• If the total number of gas molecules diminishes [above
Example (b)], ΔS° is negative.
• If there is no net change in the total number of gas molecules
[above Example (c)], then ΔS° may be positive or negative,
but will be relatively small numerically.
The Second Law of Thermodynamics
Example : Predict whether the entropy change of the system in each
of the following reactions is positive or negative.
(a) 2H2(g) + O2(g)  2H2O(l)
(b) NH4Cl(s)  NH3(g) + HCl(g)
(c) H2(g) + Br2(g)  2HBr(g)

Solution (a) Two reactant molecules combine to form one product molecule.
Even though H2O is a more complex molecule than either H2 and O2, the fact
that there is a net decrease of one molecule and gases are converted to liquid
ensures that the number of microstates will be diminished and hence ΔS° is
negative.
(b) A solid is converted to two gaseous products. Therefore, ΔS° is positive.
(c) The same number of molecules is involved in the reactants as in the product.
Furthermore, all molecules are diatomic and therefore of similar complexity. As a
result, we cannot predict the sign of ΔS°, but we know that the change must be
quite small in magnitude.
The Second Law of Thermodynamics
Entropy Changes in the Surroundings

An exothermic process An endothermic process

For constant-pressure processes:

The Second Law of Thermodynamics
The change in entropy for a given amount of heat absorbed also depends
on the temperature.

Example: Whether the reaction of synthesis of ammonia is spontaneous at

25°C

Because Suniv is positive, we predict that the reaction is spontaneous at 25°C.

The Second Law of Thermodynamics
The Third Law of Thermodynamics and Absolute
Entropy
Consider a perfect crystalline substance at absolute zero (0 K):

The third law of

thermodynamics, the
entropy of a perfect crystalline
substance is zero at the
absolute zero of temperature.

“absolute entropy”
Gibbs Free Energy
For a spontaneous process, we have

ΔSuniv = ΔSsys + ΔSsurr > 0

Substituting -ΔHsys/T for ΔSsurr, we write

Hsys
Suniv = Ssys - >0
T

TSuniv = -Hsys + TSsys > 0

Now we have a criterion for a spontaneous reaction:
Gibbs Free Energy
In order to express the spontaneity of a reaction more directly, we
introduce another thermodynamic function called Gibbs free energy
(G), or simply free energy :

Free energy is the energy available to do

work.

We can now summarize the conditions for spontaneity and equilibrium at

constant temperature and pressure in terms of ΔG as follows:
✪ ΔG < 0 The reaction is spontaneous in the forward direction.
✪ ΔG > 0 The reaction is nonspontaneous. The reaction is spontaneous in
the opposite direction.
✪ ΔG = 0 The system is at equilibrium. There is no net change.
Gibbs Free Energy
Standard Free-Energy Changes
The standard free-energy of reaction (ΔG°rxn) is the free-energy
change for a reaction when it occurs under standard-state conditions,
when reactants in their standard states are converted to products in
their standard states.
To calculate ΔG°rxn we start with the equation
Gibbs Free Energy
The term ΔG°f is the standard free-energy of formation of a
compound, that is, the free-energy change that occurs when 1 mole
of the compound is synthesized from its elements in their standard
states.

For the combustion of graphite:

The standard free-energy change is

We define the standard free-energy of formation of any element in its stable

allotropic form at 1 atm and 25°C as zero. Thus,
Gibbs Free Energy
Example: Calculate the standard free-energy changes for the following
reactions at 25°C.
(a) CH4(g) + 2O2(g)  CO2(g) + 2H2O(l)
(b) 2MgO(s)  2Mg(s) + O2(g)
Solution (a) we write
ΔGorxn = [ΔGof(CO2) + 2ΔGof(H2O)] – [ΔGof(CH4) + 2ΔGof(O2)]
= [(-394.4 kJ/mol) + (2)(-237.2 kJ/mol)]
– [(-50.8 kJ/mol) + (2)(0 kJ/mol)]
= -818.0 kJ/mol

(b) The equation is

ΔGorxn = [2ΔGof(Mg) + ΔGof(O2)] – [2ΔGof(MgO)]
= [(2)(0 kJ/mol) + (0 kJ/mol)] – [(2)(-569.6 kJ/mol)]
= 1139 kJ/mol
Gibbs Free Energy
Applications of Equation ΔG = ΔH - TΔS

v If both ΔH and ΔS are positive, then ΔG will be negative only when

the TΔS term is greater in magnitude than ΔH. This condition is
met when T is large.

v If ΔH is positive and ΔS is negative, ΔG will always be positive,

regardless of temperature.

v If ΔH is negative and ΔS is positive, then ΔG will always be

negative regardless of temperature.

v If ΔH is negative and ΔS is negative, then ΔG will be negative only

when TΔS is smaller in magnitude than ΔH. This condition is met
when T is small.
Gibbs Free Energy

Factors Affecting the Sign of G in the Relationship G = H - TS

H S G Example
+ + Reaction proceeds spontaneously at high 2HgO(s) ® 2Hg(l) +
temperatures. At low temperatures, reaction O2(g)
is spontaneous in the reverse direction
+ − G is always positive. Reaction is 3O2(g) ® 2O3(g)
spontaneous in the reverse direction at all
temperature.
− + G is always negative. Reaction proceeds 2H2O(aq) ® 2H2O(l) +
spontaneously at all temperatures. O2(g)
− − Reaction proceeds spontaneously at low NH3(g) + HCl(g) ®
temperatures. At high temperature, the NH4Cl(s)
reverse reaction becomes spontaneous.
Gibbs Free Energy
Temperature and Chemical Reactions
In order to make ΔG° negative, we first have to find the temperature at
which ΔG° is zero; that is,

At a temperature higher than 835°C, ΔG° becomes negative,

indicating that the reaction now favors the formation of CaO and CO2.
Gibbs Free Energy
Phase Transitions
At the temperature at which a phase transition occurs (that is, at the melting
point or boiling point) the system is at equilibrium (ΔG = 0), so

Considering the ice-water equilibrium

 Gibbs Free Energy
Example: The molar heats of fusion and vaporization of benzene are 10.9
kJ/mol and 31.0 kJ/mol, respectively. Calculate the entropy changes for the solid
S liquid and liquid S vapor transitions for benzene. At 1 atm pressure, benzene
melts at 5.5°C and boils at 80.1°C.

Solution Hfus
The entropy change for Sfus =
Tf
melting 1 mole of benzene
at 5.5°C is (10.9 kJ/mol)(1000J/1kJ)
=
(5.5 + 273) K
= 39.1 J/Kmol
Similarly, the entropy Hvap
change for boiling 1
Svap =
Tbp
mole of benzene at
80.1°C is (31.0 kJ/mol)(1000J/1kJ)
=
(80.1 + 273) K
= 87.8 J/Kmol
Free Energy and Chemical Equilibrium

(where R is the gas constant (8.314 J/K  mol), T is the absolute temperature
of the reaction, and Q is the reaction quotient .)

At equilibrium, by definition, ΔG = 0 and Q = K, where K is the equilibrium

constant. Thus

(In this equation, KP is used for gases and Kc for reactions in solution.)

It is the sign of ΔG and not that of ΔG° that determines the direction
of reaction spontaneity. The sign of ΔG° only tells us the relative
amounts of products and reactants when equilibrium is reached, not
the direction of the net reaction.
Free Energy and Chemical Equilibrium

ΔG < 0. At
equilibrium,
there is a
significant
conversion
of reactants
to products.
Free Energy and Chemical Equilibrium

ΔG > 0. At
equilibrium,
reactants are
favored over
products.
Free Energy and Chemical Equilibrium
Relation Between G° and K as Predicted by the
Equation G° = -RTlnK

For example, the formation of nitric oxide from molecular nitrogen and
molecular oxygen:
Free Energy and Chemical Equilibrium
Example : Calculate the equilibrium constant (KP) for the following
reaction at 25°C:
2H2O(l) 2H2(g) + O2(g)
Solution:
Free Energy and Chemical Equilibrium
Example: The equilibrium constant (KP) for the reaction
N2O4(g) 2NO2(g)
is 0.113 at 298 K, which corresponds to a standard free-energy change of
5.40 kJ/mol. In a certain experiment, the initial pressures are PNO2 = 0.122
atm and PN2O4 = 0.453 atm. Calculate G for the reaction at these pressures
and predict the direction of the net reaction toward equilibrium.
Solution

Because G < 0, the net reaction proceeds from left to right to reach equilibrium.
Thermodynamics in Living Systems
The principle of coupled reactions (偶联反应) is based on a
simple concept: We can use a thermodynamically favorable reaction
to drive an unfavorable one.

Extracting zinc from the ore sphalerite 闪锌矿(ZnS):

Thermodynamics in Living Systems
Glucose (C6H12O6), are converted to carbon dioxide and water during
metabolism with a substantial release of free energy:
Thermodynamics in Living Systems
Consider the formation of the dipeptide (二肽） (a two-amino-acid unit)
alanylglycine(丙氨酰甘氨酸) from alanine （丙氨酸）and glycine （甘氨酸）.

Schematic
representation
of ATP
synthesis and
coupled
reactions in
living systems.