Chapter 17

Spontaneity, Entropy, and Free Energy

The goal of this chapter is to answer a
basic question: will a given reaction occur
by itself at a particular temperature and
pressure, without the exertion of any
outside force?

Thermodynamics
The science that deals with heat and energy
effects.
First Law of thermodynamics / The Law of
Conservation of Energy:
Energy can be neither created nor destroyed
by a process, it is only transformed from one
form to another.
Any energy lost by a system must be gained by
the surroundings and vice versa
CH4+2O2(g) CO2(g)+ 2H2O(g) + energy
Here potential energy has been converted to
thermal energy.

Figure 16.1 Methane and Oxygen React

Spontaneous Processes
A process is said to be spontaneous if it
occurs without outside intervention.
Thermodynamics lets us predict whether
a process will occur or not.
Spontaneous processes may be fast or
slow.
Thermodynamics can tell the direction in
which a process will occur but can say
nothing about the speed of the process.

Figure 16.2 Rate of Reaction

Entropy
What common characteristic cause the
processes to be spontaneous?
The driving force for the spontaneous process is
an increase in the Entropy (denoted by s) of the
universe

What is Entropy?
Entropy is a measure of randomness or disorder
State property depends upon the state of a
system
Thermodynamic function that describe the
number of arrangements

S = Sfinal - Sinitial

Microstate
Each configuration that gives a particular
arrangement is called a microstate.
Which arrangement is most likely to
occur?
One with greatest number of microstate.

Positional probability (microstates) which

depends on the number of configurations
in space.
Positional probability increases (entropy
increases) in going from solid to liquid to gas.
Ssolid < Sliquid << Sgas

Figure 16.3 The Expansion of an Ideal Gas into an Evacuated Bulb

Figure 16.4 Three Possible Arrangements (states) of Four Molecules in a Two-Bulbed Flask

Examples
Choose the compound with the greatest
positional entropy in each case.
a. 1 mol H2 (at STP) or 1 mol H2 (at 100 oC, 0.5
atm) H2 at 100 oC and 0.5 atm; higher
temperature and lower pressure means greater
volume and hence, greater positional entropy.
b. 1 mol N2 (at STP) or 1 mol H2 (at 100 K, 2.0
atm) N2 at STP has the greater volume.
c. 1 mol H2O(s) (at 0 oC) or 1 mol H2O(l) (at 20 oC)
H2O(l) is more disordered than H2O(s)

Second Law of Thermodynamics

In any spontaneous process there is
always an increase in the entropy of the
universe.
Universe
System: Portion of the universe in
which we are interested
Surroundings: everything else in the
universe besides the system.

Change in entropy of the universe

Suniv = Ssys+ Ssur
Where Ssys and Ssurr represent the
changes in entropy
Suniv - positive the process is
spontaneous in the direction written.
Suniv - negative the process is
spontaneous in the opposite direction.
Suniv - zero the system is at
equilibrium.

The Effect of Temperature on Spontaneity

Consider, H2O(l) H2O(g)
1 mole, 18 grams, 18 mL 1 mole, 18 grams,
31 litters (1 atm, 100 oC)
Positional probability increases entropy of the
system increases, Ssys Positive
The sign of Ssurr depends on the direction of
the heat flow
The magnitude of Ssurr depends on the
temperature
Ssurr depends directly on the quantity of heat
transferred and inversely on temperature.

Continued....

Exothermic process: Ssurr = + quantity of

heat (J) / temperature (K)
Endothermic process: Ssurr = - quantity of
heat (J) / temperature (K)
Heat flow (constant P) = Change in enthalpy
= H
Endothermic H positive and exothermic H
negative
Ssurr = - H/T (at constant temp. and
pressure)

Example
Calculate Ssurr for the following reactions at
25 oC and 1 atm.
C3H8(g) + 5O2(g) 3CO2(g) + 4H2O(l) Ho
= -2221kJ
Ssurr = - H/T = -(-2221 kJ) / (25+273)K =
7.45 kJ/K = 7.45 X 103 J/K
2NO2(g) 2NO(g) + O2(g) H = 112 kJ
Ssurr = - H/T = -112 kJ/298 K = -0.376 kJ/K
= -376 J/K

Free Energy
Free energy is a thermodynamic function
related to spontaneity and is useful in
dealing with temperature dependence of
spontaneity, defined by the relationship:
G = H TS where, G is free energy, H is
enthalpy, T is Kelvin temperature, S is
entropy
For a process that occurs at constant
temperature, the changes in free energy
(G) is given by the equation,
G = H TS

G = H TS
Lets see how this equation relates to
spontaneity,
-G/T = - H/T TS/-(T) [Divide both
side by T]
-G/T = - H/T + S = Ssurr+ S = Suniv
[Recall, Ssurr = - H/T]
Suniv = - G/T at constant T and P
G negative process is spontaneous
at constant T and P

Example
Example: The boiling point of chloroform
(CHCl3) is 61.7 oC. The enthalpy of
vaporization is 31.4 kJ/mol. Calculate the
entropy of vaporization.
G = H - TS
At the boiling point, G = 0, so TS = H
S = H/ T = 31.4 kJ/mol (273.2+61.7)K
=9.38 X 10-2 kJ/K.mol = 93.8 J/K.mol

 Example: For mercury, the enthalpy of

vaporization is 58.51 kJ/mole and the
entropy of vaporization is 92.92 J/K.mole.
What is the normal boiling point of
mercury?
At the boiling point , G = 0, so H = TS
T=H/S=58.51X103J/mol92.92 J/K.mol
= 629.7 K

 Example: For ammonia (NH3), the enthalpy of

fusion is 5.65 kJ/mol and the entropy of fusion is
28.9 J/K.mol
a. Will NH3(s) spontaneously melt at 200 K?
b. What is the approximate melting point of
ammonia?
a. NH3(s) NH3(l)
G = H - TS = 5650 J/mol 200 K.(28.9
J/K.mol)
= 5650 J/mol - 5780 J/mol = - 130 J/mol
Yes, NH3 will melt since G < 0 (negative) at this
temperature
b. At the melting point G = 0
H = TS
T = H / S = 5650 J/mol 28.9 J/K.mol
= 196 K

Entropy Changes in Chemical Reactions

The entropy changes in the system (the
reactants and the products of the
reaction) are determined by positional
probability. eg. In the ammonia synthesis
reaction
N2(g) + 3H2(g) 2NH3(g)
Four reactant molecules becomes two
product molecules.
Fewer molecules mean fewer possible
configuration.

Entropy Changes in Chemical Reactions

Does positional entropy increases or
decreases for the following reaction
4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g)
9 gaseous molecule 10 gaseous
molecule Positional entropy increases
If the number of molecules of the
gaseous products is greater than the
number of molecules of the gaseous
reactants, positional entropy increases,
and S will be positive for the reaction.

Figure 16.5 Entropy

Predicting the Sign of So

Predict the sign of So for each of the following changes
a. AgCl(s) Ag+(aq) + Cl-(aq)
Increase in disorder; So (+)
b. 2H2(g) + O2(g) 2H2O(l)
Decrease in disorder; n < 0; So (-)
c. H2O(l) H2O(g)
Increase in disorder; n > 0; So (+)
d. Na(s) + 1/2Cl2(g) NaCl(s)
Decrease in disorder; n < 0; So (-)
e. 2SO2(g) + O2(g) 2SO3(g)
Decrease in disorder; n < 0; So (-)

Third Law of Thermodynamics

The entropy of a perfect crystal at 0 K is
zero
Entropy is a state function of the system
Entropy change for a given chemical
reaction can be calculated by taking the
difference between the standard entropy
values of products and those of the
reactants:
Soreaction = npSoproducts- nrSoreactants
Entropy is an extensive property
(depends on amount)

Example
Calculate So at 25oC for the reaction
2NiS(s) + 3O2(g) 2SO2(g) + 2NiO(s)
Soreaction = npSoproducts- nrSoreactants
= 2SoSO2(g) + 2SoNiO(s) (2SoNiS(s) + 3SoO2(g))
= 2 mol(248 J/K.mol) + 2mol(38 J/K.mol) 2mol(53 J/K.mol) - 3mol(205 J/K.mol)
= 496 J/K + 76 J/K - 106 J/K - 615 J/K
= -149 J/K
We would expect So to be negative because
the number of gaseous molecules decreases.

Free Energy and chemical Reactions

Go, the change in free energy that will
occur if the reactants in their standard
states are converted to the products in
their standard states.
N2(g) + 3H2(g) 2NH3(g) Go = -33.3 KJ
Go = Ho - TSo

 Example:

C(s) + O2(g) CO2(g)

The values of Ho and So are -393.5 KJ

and 3.05 J/K, calculate Go at 298 K.
Go = H - TSo
= -3.935 x 105J (298)(3.05 J/K)
= -3.944 x 105J = -394.4 KJ
(per mol of CO2)

Free Energy Change and

Chemical Reactions
Go = standard free energy change that
accompanies the formation of 1 mole of
that substance from its constituent
elements with all reactants and products
in their standard states.
Go = npGof (products)
nrGof (reactants)
The standard free energy of formation of
an element in its standard state is zero.

Free Energy and Pressure

G = Go + RTln(P) where,
Go = the free energy of the gas at a pressure of 1 atm
G = the free energy of the gas at a pressure of P atm
R = the universal gas constant
T = the Kelvin temperature
G = npG products nrG reactants

Where, Gproducts = Go products + RTln(Pproducts)

Greactants= Go reactants + RTln(Preactants)
G = Go + RTln(Q) where,
Q = reaction quotient from the law of mass action

Free Energy and Equilibrium

G = Go + RTln(Q)
At equilibrium,
G = 0 (Gproducts = Greactants)
and Q = K (equilibrium constant)
So, G = 0 = Go + RTln(K)
Go = -RTln(K)

Figure 16.8 The Dependence of Free Energy on Partial Pressure

Continued.

Case 1: Go = 0, the system is at equilibrium when

the pressures of all reactants and products are 1
atm, which means that K = 1
Case 2: Go < 0 , in this case Go products < Go reactants.
The system will adjust to the right to reach
equilibrium, K will be greater than 1, since the
pressure of the products at equilibrium will be greater
than 1 atm and the pressure of the reactants will be
less than 1 atm.
Case 3: Go > O, in this case Go reactants < Go products. The
system will adjust to the left to reach equilibrium. The
value of K will be less than 1.

Temperature Dependence of K
Go = -RTln(K) = Ho - TSo
ln(K) = - Ho/RT + So/R
ln(K) = -[Ho/R][1/T] + So/R
This is a linear equation of the form
y = mx + b
where, y = ln(K), m = -Ho/R = slope,
x = 1/T, and b = So/R = intercept
(Ho and So independent of temperature
over a small temperature range)

Summary
First law of thermodynamics
Spontaneous process
Entropy
S = Sfinal Sinitial
Microstate
Second law of thermodynamics
Effect of temperature
System
Surroundings

Summary
Suniv = Ssys + Ssurr
Free energy G = H TS
Entropy change in chemical reactions
Soreaction = npSoproducts- nrSoreactants
Go = npGof(products) = nrGof(reactants)
Go = Go + RTln(p) = Go + RTln(Q)
Go = -RTln(K)
ln(K) = -[Ho/R][1/T] + So/R