Chemical Thermodynamics

Part II: Fundamentals and

Spontaneity
Louie Paolo D. Carpio

Instructor 3
Institute of Chemistry, UP Diliman

OBJECTIVES for today

1. Discuss the different laws of
thermodynamics
2. Define entropy
3. Define Gibbs free energy
4. Define spontaneity in terms of
thermodynamic parameters

SKILLS that you will need

1. Solving for G, S ,E and work of
processes.
2. Determine whether a chemical
reaction is spontaneous or not.

Thermodynamics

THERMODYNAMICS the study of

the energy transfers accompanying
physical and chemical changes

Laws of Thermodynamics

1. Zeroth law thermal equilibrium

2. 1st Law - energy
3. 2nd Law entropy
4. 3rd Law perfect crystal

1st Law of Thermodynamics

Law of Conservation of Energy
energy in the universe is constant

Esystem = (-) Esurroundings

1st Law of Thermodynamics

In any process, the total change in
the energy of a system (E) is equal
to the sum of the transferred heat
between the heat and the
surroundings

Esystem = q + w
w = work

q = heat

*work all types of energy except heat

Work and heat at constant pressure

w = - Pexternal(V)
V > 0, work is done by the
system since w < 0
V < 0, work is done on the
system since w > 0

qrxn = nLR(H0rxn)
Enthalpy of reaction

Conventions
Thermodynamic
variable

(+)

(-)

Work (w)

Work is done
on the system

Work is done
by the system

Heat (q)

Heat is
absorbed

Heat is
released

Change in
energy of the
system (Esys)

Energy of the
system
increased

Energy of the
system
decreased

Difference between H and E

Criteria

Heat

Heat at
constant
pressure

Instrument
used to
quantify

Coffee-cup
calorimeter

E
Heat at
constant
volume, w =
0
Bomb
Calorimeter

Relation between H and E

From E = q + w:

H = E + (PV)
H and E are expressed in joules
P is in Pascal (101325 Pa = 1 atm)
V is in m3 (0.001 m3 = 1 liter)
(PV) = (-) work

Conversion of conventional
chemistry units into joules
If P is in atm and V is in liters,
their product can be converted
into joules by multiplying the ratio
of the gas constant R.
J

8.314

mol K = joules
( Patm )( Vliters )
0.0821 L atm

mol K

*R = 8.314 Jmol-1K-1
(gas constant in terms of joules)

PV for reactions involving solids

and liquids only
Take note that the product of
pressure and volume for solids
and liquids can be ignored since
their molar volume is typically 0.1
% of that for a gas.
PV = very small
(for solids and liquids)

PV for reactions involving gases

(PV) = (ngas)RT
From the ideal gas equation
where
ngas = (ngaseous products) (ngaseous reactants)

Relation between H and E for

chemical reactions w/ gases

H = E + (PV)
since (PV) = (ngas)RT

H = E + (ngas)RT

Spontaneous Processes
definition a spontaneous process
is one that moves the reaction
system to equilibrium
Usually proceeds with a decrease
in energy
Proceed from more ordered to
more random states (greater
entropy)

ENTROPY
denoted by the symbol S
Measure of disorder
Change in entropy is a state
function
S = Sfinal Sinitial
Unit: J/K

ENTROPY
For reversible processes:

S =

qreversible process
T

*
reversible
processes
cause
infinitesimally small changes in
thermodynamic states P, V, T or n.
Example: adding 100 J of heat but the
temperature almost did not increase

ENTROPY
In general,
2. Sgas > Sliquid > Ssolids
3. Increasing the temperature of a
substance increases its entropy
* Entropy is hard to quantify. How do
we compute the entropies of
substances?

3rd Law of Thermodynamics

A
completely
ordered
pure
crystalline solid has an entropy of
zero at 0 K (absolute zero).
3rd law of thermodynamics is the
basis of the numerical scale of
entropy

3rd Law of Thermodynamics

Since S is a state function and
assume that the initial state of a
substance is a perfect crystalline
solid at 0 K:
S = Sfinal Sinitial
S = Sfinal Sperfect crystalline solid
S = Sfinal 0
S = So = standard molar entropy

Standard Molar Entropies

Entropy of a substance at 1 atm
and a given temperature (usually
25oC)
Denoted by the So
Units of joule per mole per Kelvin
(J/molK)

Standard Molar Entropies

In general, as molecules become
more complex in structure, there
are more ways for atoms to move
about with respect to one another,
leading to a higher entropy.
Ex. molecular oxygen vs ozone

0
O2

<S

0
O3

0
NO

<S

0
NO2

<S

0
N2O 4

Change in entropy of a chemical rxn

Change in entropy of a chemical
reaction (S)

Srxn = ni ( Sproducts ) i n j ( Sreactants ) j

i

Entropy is also a state function.

Example
Solve for the S of the reaction
below:
2 H2O2(l) 2 H2O(l) + O2(g)
So values:
H2O2(l)
H2O(l)
O2(g)

109.6 J/Kmol
69.91 J/Kmol
205.0 J/Kmol

ENTROPY and Spontaneity

The entropy change of the universe
(system
and
surroundings)
determines the spontaneity of a
chemical reaction.

In spontaneous changes, the

universe tends toward a state
of greater disorder.

2nd Law of Thermodynamics

A net increase in the entropy of the
universe results to a spontaneous
reaction

Suniverse > 0

(spontaneous)

Suniverse = Ssystem + Ssurroundings

Change in entropy of a chemical rxn

Entropy of a chemical reaction
increases if:
1. The number of product molecules
are greater than the reactant
molecules
2. reaction produces greater number
of gaseous products than gaseous
reactants
3. reaction involves mixing

Change in entropy of a chemical rxn

Entropy of
increases if:

chemical

reaction

4. the molar volume of the products is

greater than that of the reactants
5. the temperature of a reaction system
increased
6. The reaction produces gases or the
solid is diminished. Formation of
gases are favored since Sgas > Sliquids >
Ssolids.

Problem using entropy

The change in the entropy of the
universe is difficult to quantify,
hence it is difficult to predict
spontaneity based on entropy alone.
Free energy is a much better
thermodynamic parameter to use
when predicting spontaneity of
chemical reactions.

Gibbs Free Energy, G

It is the energy that a chemical
reaction use to do work.
Recall: (system is a chemical reaction)
w > 0,

work is done on the system

w < 0,

work is done by the system

w = 0,

no work is done

Change in Gibbs Free Energy, G

It is the energy that a chemical
reaction use to do work.
G is also a state function

Grxn = ni ( Gproducts ) i n j ( Greactants ) j

i

Recall: (system is a chemical reaction)

G > 0, work is done on the reaction
G < 0, work is done by the reaction
G = 0, no work is done by the reaction

Change in Gibbs Free Energy, G

A chemical reaction that does work
is spontaneous!

Grxn = ni ( Gproducts ) i n j ( Greactants ) j

i

Recall: (system is a chemical reaction)

G > 0,

non-spontaneous

G < 0,

spontaneous

G = 0,

equilibrium

SPONTANEITY OF REACTIONS

A reaction can be spontaneous if:

1. Suniverse > 0
2. Greaction < 0

Standard Free Energy Change, Go

Standard free energy change at 1 atm
and 25oC.
Gfo is the standard energy of
formation or free energy content of
substances similar to Hfo.
G

o
rxn

= ni G
i

o
f,products

) n ( G
i

o
f,reactants j

Example
Solve for the Go of the reaction
below:
2 H2O2(l) 2 H2O(l) + O2(g)
Gfo values:
H2O2(l)
H2O(l)
O2(g)

- 120.4 kJ/mol
- 228.6 kJ/mol
0 kJ/mol

Gibbs-Helmholtz Equation
Provides the relationship between
G, H and S at a given temperature
in K:

Grxn = Hrxn - TSrxn

If the reaction is in standard
conditions
Go = Ho TSo

Gibbs Free energy and spontaneity

For a spontaneous reaction, G < 0

G = H - TS
A chemical reaction would always be
spontaneous if:
2. Hreaction < 0
3. Sreaction > 0

Gibbs Free energy and spontaneity

In general, spontaneous
reactions involve:

chemical

1. Release of heat or exothermic (H < 0)

2. Increase in entropy (S > 0)
Both H and S must be considered to be
able to predict the spontaneity of a reaction.
Some
endothermic
reactions
are
spontaneous. Some reactions involving a
decrease in entropy can be spontaneous. G
must be computed to accurately predict the
spontaneity of a chemical reaction.

Example
Solve for the Go of the reaction below:

2 C8H18(l) + 25 O2(g) 18 H2O(l) + 16 CO2(g)

Substance Hfo (kJ/mol)

So (J/Kmol)

C8H18(l)

- 249.9

358

O2(g)

205.14

H2O(l)

- 285.83

69.91

CO2(g)

- 393.51

213.74

Example
Solve for the So of the reaction below:
Express your answer in J/Kmol.
OF2(g) + H2O(g) O2(g) + 2 HF(g)
Ho = - 323.2 kJ/mol
Go = - 358.4 kJ/mol

Change in Gibbs Free Energy, G

Grxn = ni ( Gproducts ) i n j ( Greactants ) j
i

Recall: (system is a chemical reaction)

G > 0,

non-spontaneous

G < 0,

spontaneous

G = 0,

equilibrium

Gibbs Free energy and equilibrium

For a reaction in equilibrium, G = 0

G = H TS = 0
A chemical reaction is in equilibrium
if the reaction is reversible and both
reversible reactions occur at the
same rate.

Reactants Products

Equilibrium reactions
For a reaction in equilibrium, G = 0

Reactants Products
The rate of formation of products is
equal to the rate of degradation of
reactants at equilibrium.
Phase changes at their phase change
temperatures
are
equilibrium
reactions.

Phase changes and equilibrium

H2O(l) H2O(s) at 0oC
Phase changes at their phase change
temperatures are equilibrium reactions.
Hence, at 0oC, melting and freezing
occurs at the same rate. (G = 0)
Gfreezing = Gmelting = 0

(at 0oC)

Gibbs-Helmholtz & equilibrium

G = H TS = 0
H TS = 0
H = TS

H
T=
S

Gibbs-Helmholtz & equilibrium

Hreaction
T=
Sreaction
Significance of equation:
2. This is the minimum temperature at
which
a
reaction
would
be
spontaneous if Srxn > 0.
3. This T is the estimated phase
change temperature in Kelvin for a
phase change reaction.

Example
Estimate the boiling point of CH3OH
given the following thermodynamic
data below:
CH3OH(l) CH3OH(g)
substance

Hfo

So

CH3OH(l)

- 238.86 kJ/mol 126.8 J/Kmol

CH3OH(g)

- 200.66 kJ/mol 239.81 J/Kmol

Example
Estimate at which temperature in Kelvin
will the reaction below will become
spontaneous:
CaCl2(s) Ca(s) + Cl2(g)
substance

Hfo

So

Ca(s)

0 kJ/mol

41.42 J/Kmol

CaCl2(s)
Cl2(g)

- 795.8 kJ/mol 104.6 J/Kmol

0 kJ/mol

223.07 J/Kmol

END OF CLASS

Chapter covered: Chapter 15

Next meeting: Problem Set day!
Next topic: Electronic Structure of
Atoms
QUESTIONS????