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Chapter 19

Chemical Thermodynamics
Thermodynamics

The study of the relationships between


heat, work, and the energy of a
system.

First Law of
Thermodynamics

You will recall from Chapter 5


that 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.

Second Law of
Thermodynamics

The total Entropy of the universe


increases in any spontaneous,
irreversible process.

Entropy

Molecules have more entropy


(disorder) when:
1) Phase Changes from: S L
G
Example: Sublimation
CO2(s) CO2(g)
2) Dissolving occurs (solution
forms):
Example:
NaCl(s) Na+(aq) + Cl-(aq)

Entropy

3) Temperature increases
Example:
Fe(s) at 0 oC Fe(s) at 25 oC
4) For Gases ONLY, when
Volume increases or Pressure
decreases
Examples:

Entropy

2 Liters He(g) 4 Liters He(g)

Entropy can be thought of as a


measure of the randomness or
disorder of a system.

3 atm He(g) 1 atm He(g)

It is related to the various


modes of motion in molecules
(microstates).
Vibrational

Entropy

5) Rx results in more molecules/moles


of gas
Examples:
2NH3(g) N2(g) + 3H2(g)

Rotational
Translational

CaCO3(s) CaO(s) + CO2(g)

N2O4(g) 2 NO2(g)

Processes that are spontaneous


at one temperature may be
nonspontaneous at other
temperatures.

Above 0C it is spontaneous for


ice to melt.

Below 0C the reverse process


is spontaneous.

Spontaneous Processes

This one is difficult to predict:


N2(g) + O2(g) 2 NO(g)

Entropy

6) When there are more moles


Example:
1 mole H2O(g) 2 moles
H2O(g)
7) When there are more atoms per
molecule
Examples:
1 mole Ar(g) 1 mole HCl(g)
1 mole NO2(g) 1 mole N2O4(g)

Entropy

8) When an atom has a bigger atomic


number
1 mole He(g) 1 mole Ne (g)

Spontaneous Processes

Spontaneous processes are


those that can proceed without
any outside intervention.

The gas in vessel B will


spontaneously effuse into
vessel A, but once the gas is in
both vessels, it will not
spontaneously move to just one
vessel.
Spontaneous Processes

Processes that are spontaneous in one


direction are nonspontaneous in the
reverse direction.
Spontaneous processes are
irreversible.

Second Law of
Thermodynamics

A reversible process results in


no overall change in Entropy while an
irreversible, spontaneous process
results in an overall increase in
Entropy.

Third Law of
Thermodynamics

The Entropy of a pure crystalline


substance at absolute zero is zero.
why?

Third Law of
Thermodynamics

Standard Entropies

Standard Conditions:

298 K, 1 atm, 1 Molar

The values for Standard


Entropies (So) are expressed in
J/mol-K.

Note: Increase with increasing


molar mass.

There are two parts to the free


energy equation:

H the enthalpy term

TS the entropy term

Standard Entropies

Larger and more complex molecules


have greater entropies.

The temperature
dependence of free
energy comes from the
entropy term.

What causes a reaction to


be spontaneous?

DSo = S n Soproducts - S m Soreactants

Think Humpty Dumpty

Gibbs Free Energy

System tend to seek:

Gibbs Free Energy

Entropy Changes

Minimum Enthalpy
Exothermic Rx, DH = negative

1. If DG is negative
DG = maximum amt of energy
free to do
work by the reaction

Maximum Entropy
More disorder, DS = positive

Because: DGo = DHo TDSo

2. If G is positive
DG = minimum amt of work
needed
to make the reaction
happen

Gibbs Free Energy

Free Energy and


Temperature

At Equilibrium

DGo = zero
TDSo

In our tables, units are:

Or:

DGo = kJ/mol
DHo = kJ/mol
DSo = J/mol-K

Free Energy and Temperature

= (-)

(+)

Therefore: DHo =
DSo = DHo
T

Use this equation when asked to


calculate enthalpy of vaporization or
enthalpy of fusion.

Standard Free Energy


Changes

Be careful: Values for Gf are in


kJ/mol

Free Energy and Equilibrium

Remember from above:


If DG is 0, the system is at
equilibrium.

So DG must be related to the


equilibrium constant, K (chapter 15).
The standard free energy, DG, is
directly linked to Keq by:

Where R = 8.314 J/molK

DGo = - RT ln K

If the free energy change is a


negative value,

the reaction is spontaneous, ln


K must be a positive value, and
K will be a large number
meaning the equilibrium
mixture is mainly products.

If the free energy change is


zero,

ln K = zero and K = one.

Free Energy and Equilibrium

DGo = - RT ln K

Relationships

Under non-standard conditions, we


need to use DG instead of DG.