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Principles of General Chemistry, 2nd ed. By M. Silberberg Chemistry, 8th ed. by W. Whitten, R. Davis, R., M. L. Peck, and G. Stanley.

Chemical Thermodynamics:
Heat and Thermochemistry

Fundamental Laws
2nd Law of Thermodynamics
In spontaneous changes, the

universe tends towards a state of greater disorder.

Spontaneity of Physical and Chemical Changes

Spontaneous changes happen without any continuing outside influences. A spontaneous change has a natural direction.
Example: rusting of iron & melting of ice at room temperature occurs spontaneously.

Aspects of Spontaneity
1. An exothermic reaction (H) does not ensure spontaneity. 2. An increase in disorder (S) of the system also does not ensure spontaneity. A proper combination of exothermicity and disorder that determines spontaneity. (G)

Entropy, S
Entropy is a measure of the disorder or randomness of a system. Also a state function and follow the following sign conventions: S > 0 disorder increases (which generally favors spontaneity). S < 0 disorder decreases (generally does not favor spontaneity).

Entropy, S
From the Second Law of Thermodynamics, one condition for a spontaneous process to occur:

S universe

S system

S surroundings

In general for a substance in its three states of matter:

Sgas > Sliquid > Ssolid

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Entropy, S

Entropy & the 3rd of Thermodynamics

The 3rd Law of Thermodynamics states,

The entropy of a pure, perfect, crystalline solid at 0 K is zero.

This law permits us to measure the absolute values of the entropy for substances.

Entropy, S
Entropy changes for reactions can be determined similarly to H for reactions.

Entropy, S
Example: Calculate the entropy change for the following reaction at 25oC.

2 NO 2

N 2O 4 n So reactants
n

o 298 n

nS

o products n

nS

o reactants

So rxn
n

n So products So N 2O4(g)

2So NO2(g)

(304.2 J mol K ) 2(240.0 J mol K ) 175.8 J mol K or - 0.1758 kJ mol K

Entropy, S
The negative sign of S indicates that the system is more ordered. If the reaction is reversed the sign of S changes. For the reverse reaction: So298= +0.1758 kJ/K The (+) sign indicates the system is more disordered.

Entropy, S
Calculate the S for the reaction: O2(g) + 2 H2(g) 2 H2O(g) Given:
O2(g) H2(g) H2O(g) S = 205.0 J/mol-K S = 130.6 J/mol-K S = 188.7 J/mol-K

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More On The 2nd Law of Thermodynamics

In spontaneous changes the universe tends towards a state of greater disorder. Spontaneous processes require:
1. The free energy change of the system must be a negative quantity. 2. The entropy of universe must increase, i.e. fundamentally, the system must be capable of doing useful work on surroundings for a spontaneous process to occur.

Free Energy Change, G

In the mid 1800s J. Willard Gibbs determined the relationship of enthalpy, H, and entropy, S, that best describes the maximum useful energy obtainable in the form of work from a process at constant temperature and pressure. The relationship also describes the spontaneity of a system.

Free Energy Change, G

Changes in free energy obey the same type of relationship we have described for enthalpy, H, and entropy, S, changes.

Free Energy Change, G

Example: Calculate Go for the reaction.
C3H8 (g)
o Grxn

5 O2 (g) 4

3 CO 2 (g) [

4 H2O() 5 Go f O2(g) ] 5(0)]} kJmol

[3

Go f C O2(g)

Go f H2O( ) ]

Go f C3H8(g)

G0 298
n

n G0 products
n

n G0 reactants

{[3( 394 .4)

4( 237 .3)] [( 23 .49) 2108 .9 kJmol

Free Energy Change, G

Calculate the G for the reaction: 6 H2O(l) + 6 CO2(g) C6H12O6(s) + 6 O2(g)
Given: C6H12O6(s) CO2(g) H2O(l) O2(g) G = -916.0 kJ/mol G = -394.4 kJ/mol G = -237.2 kJ/mol G = 0.000 kJ/mol

Free Energy Change, G

The relationship of the new state function, G, the Gibbs Free Energy with enthalpy, H, and entropy, S.

G =

H-T S

(at constant T & P)

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Free Energy Change, G

Example: Calculate So for the following reaction. Note: Ho= -2219.9 kJ, and Go= -2108.5 kJ.

Free Energy Change, G, and Spontaneity

The change in the Gibbs Free Energy, G, is a reliable indicator of spontaneity of a physical process or chemical reaction. However, G does not tell us how quickly the process occurs.

CH
3

8(g)

5O G

2(g)

3 CO H
o

2(g) o

4H O
2 o

()

T S T S
o

H H
So So

G G

2108.5 kJ 298 K 0.374 kJ -374 J K K

T 2219.9

G > 0 reaction is non-spontaneous G = 0 system is at equilibrium G < 0 reaction is spontaneous

Free Energy Change, G, and Spontaneity

Go < 0, so the reaction is spontaneous at standard state conditions. If the reaction is reversed: Go > 0, and the reaction is nonspontaneous at standard state conditions.

Free Energy Change, G, and Equilibrium

Example: Use thermodynamic data to estimate the normal boiling point of water.
H 2O () H 2 O (g) 0.

Because this is an equlibrium process G H Thus H T S and T S

Free Energy Change, G, and Equilibrium

assume H@ BP Ho Ho H
o

Free Energy Change, G, and Equilibrium

S0 rxn
0 H 2O

Ho 298 Ho H 2O( l )
J K o

assume S @ BP S
0 rxn

Ho H 2 O (g)

0 H 2O

Estimate the boiling point of PCl3. Hf Liquid PCl3 Gaseous PCl3 -319.7 kJ/mol -287.0 kJ/mol Sf 217.1 J/mol-K 311.7 J/mol-K

2418 . ( 285.8) 44.0 kJ@25 C

S0 rxn S
0 rxn

188.7 69.91

118.8 J K or 0.1188 kJ K

T=

H S

Ho 44.0 kJ 370 K So 0.1188 kJ K

370 K-273 K=97o C

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The Temperature Dependence of Spontaneity

Free energy has the relationship G = H -T S. Because 0 H 0 and 0 S 0, there are four possibilities for G. H <0 <0 >0 >0 S >0 <0 >0 <0 G <0 T dependent T dependent >0 Forward reaction spontaneity Spontaneous at all Ts Spontaneous at low Ts Spontaneous at high Ts Nonspontaneous at all Ts

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