Chapter 16 2022

Sulaiman Al-Isaee
College of Applied Sciences-Suhar

Department of Engineering
©2017
Thermodynamics vs. Kinetics
• Domain of Kinetics
 Rate of a reaction depends
on the pathway from
reactants to products.
• Thermodynamics tells us
whether a reaction is
spontaneous based only on the
properties of reactants and
products.
16.1 Spontaneous Processes and Entropy
System and Surroundings
• Suppose we have a box containing some substances.

System and Surroundings
• System- is the part of the universe that is of interest, including the

substances involved in a chemical reaction
• Surroundings- everything outside the system in contact with the
system.
• Universe- everything in existence.
Spontaneous Processes
• Chemical thermodynamics is concerned

with energy relationships in chemical
reactions.
 let’s consider enthalpy H
 We also consider entropy in the reaction S.
• Thermodynamics lets us predict whether a
process will occur, but gives no
information about the amount of time
required for the process.
• A spontaneous or “thermodynamically favored” process is one that

occurs without outside intervention.
• EX; A ball rolls down a hill but never spontaneously rolls back up
the hill.
Spontaneous processes can release energy (a ball rolling downhill),

require energy (ice melting at temperatures above 0oC), or involve
no energy change at all (two gases mixing) .
Spontaneity is independent of the speed or rate of a reaction. A

spontaneous process may proceed very slowly.
Entropy
• What common characteristic causes the processes listed above to

be spontaneous in one direction only?
 Scientists have concluded that the characteristic common to all
spontaneous processes is an increase in a property called entropy,
denoted by the symbol S.
 Entropy, S, is a measure of randomness or disorder. The natural
tendency of things is to tend toward greater disorder. This is
because there are many ways (or positions) that lead to disorder,
but very few that lead to an ordered state.
• Entropy is a state function just as enthalpy
• S = Sfinal  Sinitial
Entropy
The Expansion of An Ideal Gas Into an Evacuated Bulb
Trends in Entropy
• Entropy for gas phase is greater than that of liquid or

solid of same substance
– I2 (g) has greater entropy than I2 (s)
• More complex structures have greater entropy
– C2H6 (g) has greater entropy than CH4 (g)
• Allotropes - more ordered forms have lower entropy
– Diamond has lower entropy than graphite
Entropy Changes in a System Qualitative
• Ssolid < Sliquid

• Sliquid < Svapor

• Spure < Saqueous

Slower temp < Shigher temp

• Sfewer moles < Smore moles

Determine the sign of S for the following

(qualitatively)
1. Liquid nitrogen evaporates
2. Two clear liquids are mixed and a
solid yellow precipitate forms
3. Liquid water is heated from 22.5 C to 55.8 C
16.2 Entropy and the 2nd low of Thermodynamics
Second Law of Thermodynamics

• In any spontaneous process there is always an
increase in the entropy of the universe.
• The entropy of the universe is increasing.
• The total energy of the universe is constant, but the
entropy is increasing.
Δ Suniverse = ΔSsystem + ΔSsurroundings

16.2 Entropy and the 2nd low of Thermodynamics
Second Law of Thermodynamics
DSuniv = DSsys + DSsurr
DSuniv > 0 The reaction is spontaneous.
DSuniv < 0 The reaction is spontaneous in the opposite direction.
DSuniv = 0 The reaction mixture is at equilibrium.

16.3 The Effect of Temperature on Spontaneity
• The sign of ΔSsurr depends on the direction of the

heat flow.
• The magnitude of ΔSsurr depends on the temperature.
DSsurr a  DH
DSsurr a 1
DSsurr =  DH
T
The impact of the transfer of a given quantity of energy as heat to
or from the surroundings will be greater at lower temperatures
16.3 The Effect of Temperature on Spontaneity
Interplay of Ssys and Ssurr in Determining the Sign of Suniv

16.4 Free Energy
Entropy, temperature and heat flow all play a

role in spontaneity.
A thermodynamic quantity, the Gibbs Free Energy
(G), combines these factors to predict the
spontaneity of a process.
ΔG = ΔH - TΔS
16.4 Free Energy
Spontaneity
ΔG = ΔH - TΔS
If a process releases heat (ΔH is negative) and

has an increase in entropy (ΔS is positive), it
will always be spontaneous.
The value of ΔG for spontaneous processes is
negative.
16.4 Free Energy
Spontaneity
ΔG = ΔH - TΔS
16.4 Free Energy
ΔG
Although ΔG can be used to predict in
which direction a reaction will proceed, it does
not predict the rate of the reaction.
For example, the conversion of diamond
to graphite has a ΔGo = -3 kJ, so diamonds
should spontaneously change to graphite at
standard conditions. However, kinetics shows
that the reaction is extremely slow.
16.5 Entropy Changes in Chemical reactions
Predicting the sign of ΔS o
For many chemical reactions or physical

changes, it is relatively easy to predict if the
entropy of the system is increasing or
decreasing.
If a substance goes from a more ordered phase
(solid) to a less ordered phase (liquid or gas),
its entropy increases.
Predicting the sign of ΔS o
For chemical reactions, it is sometimes

possible to compare the randomness of
products versus reactants.
2 KClO3(s)  2 KCl(s) + 3 O2(g)
The production of a gaseous product from a solid

reactant will have a positive value of ΔSo.
Calculating Entropy Changes

Since entropy is a measure of randomness, it is
possible to calculate absolute entropy values.
This is in contrast to enthalpy values, where
we can only calculate changes in enthalpy.

A perfect crystal at absolute zero has an entropy value (S) =0. All
other substances have positive values of entropy due to some
degree of disorder.
Thus a perfect crystal represents the lowest possible entropy; that is,
the entropy of a perfect crystal at 0 K is zero.
This is a statement of the third law of thermodynamics.

Fortunately, the entropy values of most
common elements and compounds have been
tabulated. Most thermodynamic tables,
including the appendix in the textbook, include
standard entropy values, So.
Entropy Values of Common Substances

Entropy Values
For comparable
structures, the
entropy increases
with increasing mass
Entropy Values
For molecules with similar masses, the more
complex molecule has greater entropy. The
molecule with more bonds has additional ways
to absorb energy, and thus greater entropy.

For any chemical reaction,
Δ Soreaction= Σnprod Soproducts- Σnreact Soreactants
The units of entropy are joules/K . mol.

16.6 Free Energy and Chemical reactions
For chemical reactions we are often interested in the standard
free energy change the change in free energy that will occur if
the reactants in their standard states are converted to the
products in their standard states.
It is important to recognize that the standard free energy change
for a reaction is not measured directly. For example, we can
measure heat flow in a calorimeter to determine ΔH°, but we
cannot measure ΔG° this way.
Why is it useful to know ΔG° for a reaction?
knowing the ΔG° values for several reactions allows us to compare
the relative tendency of these reactions to occur. The more negative
the value of ΔG° the further a reaction will go to the right to reach
equilibrium.
Calculation of ∆Go
∆Go, the standard free energy change, can be
calculated in several ways.
It can be calculated directly, using the standard

enthalpy change and entropy change for the process.
∆Go = ∆Ho - T ∆So

∆Ho is usually calculated by using standard

enthalpies of formation, ∆Hfo.
∆Horxn = Σnprod ∆Hoproducts- Σnreact ∆Horeactants

Once ∆Ho and ∆So have been calculated, the

value of ∆Go can be calculated, using the
temperature in Kelvins.
∆Go can also be calculated by combining the
free energy changes of related reactions. This
is the same method used in Hess’ Law to
calculate enthalpy changes. If the sum of the
reactions gives the reaction of interest, the sum
of the ∆Go values gives ∆Go for the reaction.
Lastly, ∆Go can be calculated using standard
free energies of formation, ∆Gfo. Some tables
of thermodynamic data, including the
appendix of your textbook, include values of
∆Gfo.
∆Gorxn = Σnprod ∆Gfo prod - Σnreact ∆Gfo react

When calculating ∆Go from standard free
energies of formation, keep in mind that ∆G fo
for any element in its standard state is zero.
As with enthalpies of formation, the
formation reaction is the reaction of
elements in their standard states to make
compounds (or allotropes).
Note the values of zero for nitrogen,

hydrogen and graphite.
Spontaneity Problem
• Consider the reaction:
CaCO3(s) ↔CaO(s) + CO2(g) at 25oC.
Calculate ∆Go using the tables in the appendix
of your textbook. Is the process spontaneous
at this temperature? Is it spontaneous at all
temperatures? If not, at what temperature does
it become spontaneous?
Spontaneity Problem
at this temperature?
Calculation of ∆Grxno will indicate spontaneity
at 25oC. It can be calculated using ∆G fo values
or from ∆Hfo and ∆So values.
CaCO3(s) ↔CaO(s) + CO2(g)

∆Grxno = Σnprod ∆Gfo prod - Σnreact ∆Gfo
react

∆Grxno =[(1 mol) (-604.0 kJ/mol) + (1
mol)(-394.4 kJ/mol)] –[1 mol(-

∆Grxno =[(1 mol) (-604.0 kJ/mol) + (1
mol)(-394.4 kJ/mol)] –[1 mol(-
Spontaneity Problem
at this temperature?
Since ∆Grxno =+130.4 kJ, the reaction is not
spontaneous at 25oC.
Spontaneity Problem
Is it spontaneous at all temperatures? If not, at
what temperature does it become spontaneous?
Inspection of the reaction shows that it involves
an increase in entropy due to production of a gas
from a solid.
Spontaneity Problem
Is it spontaneous at all temperatures? If not, at
what temperature does it become spontaneous?
We can calculate the entropy change and the
enthalpy change, and then determine the
temperature at which spontaneity will occur.

Since ∆Go = ∆Ho - T∆So, and there is an
increase in entropy, the reaction will become
spontaneous at higher temperatures.
To calculate ∆So, use the thermodynamic
tables in the appendix.
∆Srxno =[1mol(213.6J/K-mol)
+1mol(39.7J/K-mol)]

∆Go = ∆Ho - T∆So
Since we know the value of ∆Go (+130.4 kJ)

and ∆So (160.4 J/K), we can calculate the value
of ∆Ho at 25oC.
130.4 kJ = ∆Ho –(298K) (160.4 J/K)
∆Ho = 130.4 kJ + (298K) (.1604 kJ/K)
∆Ho = + 178.2 kJ

If we assume that the values of ∆H o and ∆So

don’t change much with temperature, we can
estimate the temperature at which the reaction
will become spontaneous.

∆Go is positive at lower temperatures, and will

be negative at higher temperatures. Set ∆G o
equal to zero, and solve for temperature.
0 = ∆Ho - T∆So
T = ∆Ho
∆So

0 = ∆Ho - T∆So
T = ∆Ho
∆So
T = (178.2 kJ)/(160.4 J/K)(10-3kJ/J)
=1111K or 838oC
The reaction will be spontaneous in the
forward direction at temperatures above
838oC.
16.7 The Dependence of Free Energy on Pressure
∆G for Non-Standard Conditions

The thermodynamic tables are for standard
conditions. This includes having all reactants
and products present initially at a temperature
of 25oC. All gases are at a pressure of 1 atm,
and all solutions are 1 M.
16.7 The Dependence of Free Energy on Pressure
∆G for Non-Standard Conditions

For non-standard temperature, concentrations
or gas pressures:
∆G = ∆Go + RTlnQ
Where R = 8.314 J/K-mol

T is temperature in Kelvins
Q is the reaction quotient

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Sulaiman Al-Isaee

College of Applied Sciences-Suhar

• Suppose we have a box containing some substances.

• System- is the part of the universe that is of interest, including the

• Chemical thermodynamics is concerned

• A spontaneous or “thermodynamically favored” process is one that

Spontaneous processes can release energy (a ball rolling downhill),

Spontaneity is independent of the speed or rate of a reaction. A

• What common characteristic causes the processes listed above to

• Entropy for gas phase is greater than that of liquid or

Entropy Changes in a System Qualitative

• Ssolid < Sliquid

Entropy Changes in a System Qualitative

• Sliquid < Svapor

Entropy Changes in a System Qualitative

• Spure < Saqueous

Entropy Changes in a System Qualitative

Slower temp < Shigher temp

Entropy Changes in a System Qualitative

• Sfewer moles < Smore moles

Entropy Changes in a System Qualitative

Determine the sign of S for the following

Second Law of Thermodynamics

Δ Suniverse = ΔSsystem + ΔSsurroundings

Second Law of Thermodynamics

DSuniv = DSsys + DSsurr

DSuniv > 0 The reaction is spontaneous.

DSuniv < 0 The reaction is spontaneous in the opposite direction.

DSuniv = 0 The reaction mixture is at equilibrium.

• The sign of ΔSsurr depends on the direction of the

Interplay of Ssys and Ssurr in Determining the Sign of Suniv

Entropy, temperature and heat flow all play a

If a process releases heat (ΔH is negative) and

Predicting the sign of ΔS o

For many chemical reactions or physical

For chemical reactions, it is sometimes

2 KClO3(s)  2 KCl(s) + 3 O2(g)

The production of a gaseous product from a solid

Calculating Entropy Changes

Calculating Entropy Changes

Calculating Entropy Changes

Entropy Values of Common Substances

Calculating Entropy Changes

Δ Soreaction= Σnprod Soproducts- Σnreact Soreactants

The units of entropy are joules/K . mol.

It can be calculated directly, using the standard

∆Go = ∆Ho - T ∆So

∆Ho is usually calculated by using standard

∆Horxn = Σnprod ∆Hoproducts- Σnreact ∆Horeactants

Once ∆Ho and ∆So have been calculated, the

∆Gorxn = Σnprod ∆Gfo prod - Σnreact ∆Gfo react

Note the values of zero for nitrogen,

CaCO3(s) ↔CaO(s) + CO2(g)

CaCO3(s) ↔CaO(s) + CO2(g)

CaCO3(s) ↔CaO(s) + CO2(g)

CaCO3(s) ↔CaO(s) + CO2(g)

CaCO3(s) ↔CaO(s) + CO2(g)

CaCO3(s) ↔CaO(s) + CO2(g)

Since we know the value of ∆Go (+130.4 kJ)

CaCO3(s) ↔CaO(s) + CO2(g)