Thermodynamics

(Part 2)
Reminder:
Problem Set 1 (INDIVIDUAL):
• Coverage: ALL Concepts discussed in Stoichiometry and
Concepts of Thermodymanics/Thermochemistry
• Using ALEKS App in Blackboard (Kindly create NEW
account)
• Availability: Feb 13 to Mar 5 (Sun of 3rd Week before
the Module 1 Exam)
• Max. number of questions = 30
• Difficulty and type of questions: NO idea
 Thermochemical Equations
• a chemical equation with the ΔH for the
reaction included

Example
NH4NO3 (s) → NH4+ (aq) + NO3- (aq) ΔH = +28.1kJ

This means:

+28.1 kJ +28.1 kJ +28.1 kJ

or
1 mol NH4NO3(s) 1 mol NH4+(aq) 1 mol NO3-(aq)
Conventions for Thermochemical
Equations
1. The sign of ΔH indicates whether the reaction
is endothermic or exothermic
2. The coefficients of the thermochemical
equation represent the number of moles of
reactant and product
3. The phases of all reactant and product species
must be stated
4. The value of ΔH applies when products and reactants are
at the same temperature, usually 25 °C
EXAMPLE
The thermite reaction produces tremendous heat:
2 Al + Fe2O3 → Al2O3 + 2 Fe ΔrH° = – 851.5 kJ/mol
How much heat is released when 10.0 g of Al reacts with excess Fe2O3 at
constant P ? Answer: -158 kJ
 Rules of Thermochemistry
• ΔH is directly proportional to the amount of
reactant or product
– If a reaction is divided by 2, so is ΔH
– If a reaction is multiplied by 6, so is ΔH
• ΔH changes sign when the reaction is reversed
• ΔH has the same value regardless of the
number of steps
DIRECT METHOD

The standard enthalpy of reaction

is the enthalpy of a reaction carried out at 1 atm.

aA + bB → cC + dD ( ΔH )
0
rxn

ΔH 0
rxn =  nΔH 0
f ( products ) −  mΔH ( reactants ) 0
f

ΔH rxn
0
= cΔH f0 ( C ) + dΔH f0 ( D )  − aΔH f0 ( A ) + dΔH f0 ( B ) 
© McGraw-Hill Education. 6-8
EXAMPLE
Calculate the ΔH°rxn for the decomposition of calcium
carbonate to calcium oxide and carbon dioxide.
ΔH°f [CaCO3(s)] = -1206.9 kJ/mol; ΔH°f [CaO(s)] = -635.1
kJ/mol; ΔH°f [CO2(g)] = -393.5 kJ/mol
Answer: +178.3kJ/mol
CaCO3(s) → CaO(s) + CO2(g)
 INDIRECT METHOD - Hess’s Law

Hess’s Law: When reactants are converted to products, the

change in enthalpy is the same whether the reaction takes place
in one step or in a series of steps.

(Enthalpy is a state function. It doesn’t matter how you get there,

only where you start and end.)

© McGraw-Hill Education. 6-10

EXAMPLE
Use Hess's Law to calculate the enthalpy change for the reaction
WO3(s) + 3H2(g) → W(s) + 3H2O(g)
from the following data:
2W(s) + 3O2(g) → 2WO3(s) ΔH = -1685.4 kJ
2H2(g) + O2(g) → 2H2O(g) ΔH = -477.84 kJ
Answer: +125.9 kJ
Renewable Energy Sources

Wind Energy

Microbial Fuel Cells

Relationship of H and E
• At the start of the Chapter we defined
H = qP.
• Here we define H = E + PV.
• Remember E = q + w.
• We have also defined w = -PV .
• Thus E = q + w = q -PV
• Consequently, H = q- PV + PV = q
• At constant pressure H = qP.

13
Relationship of H and E
• For reactions in which the volume change is very small or equal to zero.
For small volume changes,
V  0 and PV  0.
Since H = E + PV then
H  E.
For no volume change,
H = E.
• Change in enthalpy, H, or heat of reaction is amount of heat absorbed
or released when a reaction occurs at constant pressure.
• The change in energy, E, is the amount of heat absorbed or released
when a reaction occurs at constant volume.
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Example
The Ho = -3523 kJ/mol for the combustion of one n-pentane, n-C5H12
when one mol of n-pentane at constant pressure releases 3523 kJ of heat.
What are the values of the work term and E for this reaction?
C5 H12(  ) + 8 O 2(g) → 5 CO2(g) + 6 H 2 O(  )
C5 H12(  ) + 8 O 2(g) → 5 CO 2(g) + 6 H 2 O (  )
  
8 mol gas 5 mol gas

Since H o = - 3523 kJ/mol, we know that T = 298 K.

w = - PV = - (n gas )RT
n gas = 5 − 8 mol = - 3 mol
w = -(-3 mol)(8.314 J mol K )(298 K) = 7433 J = 7.433 kJ

H = E + PV  E = H - PV
since w = - PV = 7.433 kJ
then PV = - 7.433 kJ
E = - 3523 kJ - (-7.433 kJ) = -3516 kJ
Spontaneity of Physical and Chemical
Changes
• Spontaneous changes happen without any continuing
outside influences.
• A spontaneous change has a natural direction.
• For example the rusting of iron occurs spontaneously.
• Have you ever seen rust turn into iron metal without man
made interference?
• The melting of ice at room temperature occurs
spontaneously.
• Will water spontaneously freeze at room temperature?

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The Two Aspects of Spontaneity
• An exothermic reaction does not ensure
spontaneity.
• For example, the freezing of water is exothermic but
spontaneous only below 0oC.
• An increase in disorder of the system also does not
insure spontaneity.
• It is a proper combination of exothermicity and
disorder that determines spontaneity.

17
The Second Law of Thermodynamics
• The second law of thermodynamics states, “In
spontaneous changes the universe tends towards
a state of greater disorder.”
• Spontaneous processes have two requirements:
1. The free energy change of the system must be
negative.
2. The entropy of universe must increase.
• Fundamentally, the system must be capable of doing useful
work on surroundings for a spontaneous process to occur.

18
 Entropy, S
• Entropy is a measure of the disorder or randomness of
a system.
• As with H, entropies have been measured and
tabulated in Appendix K as So298.
• When:
• S > 0 disorder increases (which favors spontaneity).
• S < 0 disorder decreases (does not favor spontaneity).

19
 Entropy, S
• From the Second Law of Thermodynamics, for a
spontaneous process to occur:

Suniverse = Ssystem + Ssurroundings  0

• In general for a substance in its three states of
matter:
Sgas > Sliquid > Ssolid

20
Entropy, S
• The Third 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.
• To get the actual value of S, cool a substance to 0 K, or as
close as possible, then measure the entropy increase as
the substance heats from 0 to higher temperatures.
• Notice that Appendix K has values of S not S.

21
Entropy, S
• Entropy changes for reactions can be determined
similarly to H for reactions.

S o
298 =  nS o
products −  nS o
reactants
n n

22
Example
• Calculate the entropy change for the following reaction
at 25oC. Use appendix for Standard Entropy values.

• 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.
Free Energy Change, G, and Spontaneity

• In the mid 1800’s 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.
• The relationship is a new state function, G, the
Gibbs Free Energy.

G = H - TS (at constant T & P)

24
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.
• G does not tell us how quickly the process occurs.
• Chemical kinetics indicate the rate of a reaction.
• Sign conventions for G.
• G > 0 reaction is nonspontaneous
• G = 0 system is at equilibrium
• G < 0 reaction is spontaneous

25
Free Energy Change, G,
and Spontaneity
• Changes in free energy obey the same type of
relationship we have described for enthalpy, H, and
entropy, S, changes.

G 0
298 =  nG 0
products −  nG 0
reactants
n n

26
Example
Calculate Go298 for the reaction using the appendix for
standard Gibb’s Energy change.

• Go298 < 0, so the reaction is spontaneous at standard

state conditions.
• If the reaction is reversed:
• Go298 > 0, and the reaction is nonspontaneous at standard
state conditions.
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 S G Forward reaction spontaneity
<0 >0 <0 Spontaneous at all T’s.
<0 <0 T dependent Spontaneous at low T’s.
>0 >0 T dependent Spontaneous at high T’s.
>0 <0 >0 Nonspontaneous at all T’s.
28
The Temperature Dependence of
Spontaneity

29
 Example
Calculate So298 for the following reaction.

Calculating the Ho298, we found that Ho298= -2219.9 kJ, and

from the previous Example, Go298= -2108.5 kJ

S o
=
− 2219.9 − (− 2108.5) kJ
298 K
So = −0.374 kJ = -374 J
K K
• So298 = -374 J/K which indicates that the disorder of the system decreases .
• For the reverse reaction,
3 CO2(g) + 4 H2O(g) → C3H8(g) + 5 O2(g)
• So298 = +374 J/K which indicates that the disorder of the system increases .
End of Part 2 Discussion