THE THIRD LAW OF

THERMODYNAMICS
The Nernst heat theorem:
“The entropy change accompanying any physical or chemical transformation
approaches zero as the temperature approaches zero: ∆S → 0 as T → 0 provided all
the substances involved are perfectly crystalline”
It follows from the Nernst theorem that, if we arbitrarily ascribe the value zero
to the entropies of elements in their perfect crystalline form at T = 0, then all perfect
crystalline compounds also have zero entropy at T = 0
This conclusion is summarized by the Third Law of thermodynamics:
“The entropy of all perfect crystalline substances is zero at T = 0”
COMPARISON OF DIFFERENT SUBSTANCES
Gases have highest values
Solids have the lowest values
STANDARD ENTROPY OF
REACTIONS o  S products
o
 S reactants
o

In the reaction N2O4 = 2NO2

S  2 S
o o
NO2 S o
N 2O4

Products have more particles than reactants

Predicting entropy change from chemical equation by counting
particles
EXAMPLE
To calculate the standard reaction entropy of H2(g) + ½ O2(g) → H2O(l) at 25°C, we use
the data in Table 2.7 of the Data Section to write
ΔrSo = Som(H2O,l) − {Som (H2,g) + ½ Som(O2, g)}
= 69.9 J K−1 mol−1 − {130.7 + ½ (205.0)} J K−1 mol−1
= −163.4 J K−1 mol−1
THREE RESULTS
S tot  S sys  S surr

Stotal > 0 the process is spontaneous

Stotal < 0 the process is nonspontaneous

Stotal = 0 the process is at equilibrium

SURROUNDINGS
Entropy change for the system is obtained from the entropies of the initial and final
states
What about the surroundings?
At constant pressure, the entropy change in the surroundings is related to the
enthalpy change for the system

S surr   H
T
ENTHALPY CHANGE OF SYSTEM DETERMINES ENTROPY
CHANGE OF SURROUNDINGS

Heat released by the system increases the disorder of the surroundings.

The effect of this is modulated by the temperature:
 At low temperature the effect is much more significant
 At high temperature, where there is already considerable disorder, the effect is muted – the difference
between tossing a rock into a calm pool (low T) and a storm-tossed ocean (high T)
THE HELMHOLTZ AND GIBBS ENERGIES

When a change in the system occurs and there is a transfer of energy as heat between
the system and the surroundings, the Clausius inequality

dq
dS  0
T

dU
The Absence of non-expasion work, dq dS  0
= dU
T
TdS  dU (V constant, no additional work)
At either constant internal energy (dU = 0) or (dS = 0)
dSU,V  0 dUS,V  0
When energy is transferred as heat at constant pressure, and there is no work other
than expansion work, dqp = dH and
TdS  dH (p constant, no additional work)
At either constant enthalpy or constant entropy this inequility becomes, respectively
dSH,P  0 dHS,P  0
Helmholtz energy
A = U – TS
Energy Gibbs
G = H- TS
When the state of the system change at constat temperature, the two properties
change as follow
dA = dU – Tds dG = dH –TdS
dAT,V  0 dGT,P  0
WORK FUNCTION
The change in the Helmholtz function is equal to the maximum work
accompanying a process:
dwmax = dA
When a macroscopic isothermal change take palce in the system
wmax = A
With
A = U - T S
LAND OF THE FREE... ENERGY
Since Stotal is obtained from the Ssystem and the ΔHsystem, everything can be written in
terms of the system:
Gibbs free energy
G  H  TS
 State function, depends only on initial and final states

G  H  TS
SIGNIFICANCE OF ΔG
Stot  S sys  S surr

But from before,

H sys
Stot  S sys 
T
TStot  TS sys  H sys
So…
TStot  G
ΔG IS INDICATOR OF
SPONTANEITY
G  TStot

1. ΔG < 0 reaction always spontaneous

2. ΔG > 0 reaction always nonspontaneous
3. ΔG = 0 reaction at equilibrium
The Gibbs Free Energy is a measure of the total entropy change
FOUR POSSIBLE CONDITIONS
ΔH ΔS ΔG Spontaneity Example
Spontaneous at all T 2NO2 = N2 + 2O2
- + -
- Or Spontaneous at low T, N2 + 3H2 = 2NH3
- - nonspontaneous at high T
+
Nonspontaneous at all T 3 O2 = 2 O3
+ - +
- Or Spontaneous at high T, 2HgO = Hg + O2
+ + nonspontaneous at low T
+
STANDARD FREE ENERGIES
Solids liquids and gases in pure form at 1atm pressure
Solution at 1 M concentration
Standard temperature usually 25°C
Standard free energy change:
ΔG°
Change in free energy that occurs when reactants in standard states
are converted to products in their standard states
ΔG° AS A PREDICTOR OF
REACTIONS
Consider the reaction
N 2 ( g )  3H 2 ( g )  2 NH 3 ( g )
We want to calculate ΔG°
Need ΔH° and ΔS°
ΔH° is equal to ΔH°(formation) for NH3
ΔS° comes from the S° values for the reactants and product
ΔH° = 2 x -46.1 kJ/mol = -92.2 kJ/mol
ΔS° = -198.7J/mol K
ΔG°(25°C) = -92.2 – 298x-198.7x.001 kJ/mol
= -33.0 kJ/mol
STANDARD FREE ENERGY OF
FORMATION
The free energy of formation of one mole of the substance in its standard state from
the most stable forms of the elements in their standard states
Thus the ΔG°f for NH3 is given by
-33.0/2 kJ/mol = -16.5 kJ/mol
 Elements in the standard state have ΔG°f = 0
STANDARD FREE ENERGY OF
FORMATION OF SOME COMMON
COMPOUNDS ΔG º/kJ/ ΔG º/kJ/
Substance Formula f Substance Formula f
mol mol
Nitrogen
Acetylene C2H2 209.2 dioxide NO2 51.3

Ammonia NH3 -16.5 Water H2O -237.2

Carbon
dioxide
CO2 -394.4 Diamond C 2.9

Ethylene C2H4 68.1 Graphite C 0

RELATIONSHIP BETWEEN ΔG Fº
AND K
ΔGº Ln K K Comment

Mainly products
<0 >0 >1
Mainly reactants
>0 <0 <1
Even ratio of reactants and
=0 =0 1 products
KERJA BUKAN PEMUAIAN
MAKSIMUM
Analog interpretasi kerja maksimum A, dan asal usul nama energi bebas gibbs dapat ditemukan
untuk G. dalam perubahan umum :
dH = dq + dw + d(pV)
Jika perubahannya reversible dq = TdS
dG = TdS + dw + d(pV) – TdS = dw + d(pV)
Kerja bukan pemuaian diberi notasi dwe.
Oleh karena itu, dengan d(pV) = pdV + Vdp
dG = -pdV + dwe + pdV + Vdp = dwe + Vdp
Jika perubahan terjad pada tekanan tetap dan T tetap, V dp hilang, sehingga dG = dwe. Sehingga
IdweI = IdGI (temperature dan tekanan tetap)
STANDART REACTION
ENERGY GIBBS
Standart entropies and enthalpies of reaction can be combined to obtain the standard
Gibbs energy of reaction
PRACTICE
Using the standard entropies in Appendix C, calculate the standard entropy change,
S0, for the following reaction at 298 K:
Calculate S0 for the synthesis of ammonia from N2(g) and H2(g) at 298 K:
N2(g) + 3 H 2(g) ----> 2 NH3(g)
The formation of ammonia from H2{g) and N2{g) at 298 K, qsys is the enthalpy change
for reaction under standard conditions, H0•
Thus at 298 K the formation of ammonia from H2{g) and N2{g) is exothermic.
Absorption of the heat given off by the system results in an increase in the entropy of
the surroundings:
Notice that the magnitude of the entropy gained by the surroundings is greater than
that lost by the system
Calculate the standard free energy change for the formation of NO(g) from N2{g) and
02{g) at 298 K:
N2{g) + O2{g) -----> 2 NO{g)
Given that H0 = 180.7 kj and S0 = 24.7 J/K. Is the reaction spontaneous under
these circumstances?