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2nd&3rdlaw

Lecture 8 covers the Second and Third Laws of Thermodynamics, detailing the concept of entropy and its implications for spontaneous processes. The Second Law states that the entropy of the universe increases in spontaneous processes, while the Third Law establishes that the entropy of a perfect crystal at absolute zero is zero. Examples illustrate how to calculate entropy changes for reactions and phase transitions, determining spontaneity based on entropy values.

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Mohsin Ehsan
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5 views15 pages

2nd&3rdlaw

Lecture 8 covers the Second and Third Laws of Thermodynamics, detailing the concept of entropy and its implications for spontaneous processes. The Second Law states that the entropy of the universe increases in spontaneous processes, while the Third Law establishes that the entropy of a perfect crystal at absolute zero is zero. Examples illustrate how to calculate entropy changes for reactions and phase transitions, determining spontaneity based on entropy values.

Uploaded by

Mohsin Ehsan
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PPT, PDF, TXT or read online on Scribd
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Lecure 8: The Second and Third

Laws of Thermodynamics
• Reading: Zumdahl 10.5, 10.6

• Outline
– Definition of the Second Law
– Determining S
– Definition of the Third Law
The Second Law
• The Second Law: In any spontaneous
process, there is always an increase in the
entropy of the universe.

• From our definitions of system and


surroundings:
Suniverse = Ssystem + Ssurroundings
The Second Law (cont.)
• Three possibilities:
– IfSuniv > 0…..process is spontaneous
– If Suniv < 0…..process is spontaneous in opposite direction.
– If Suniv = 0….equilibrium

• Here’s the catch: We need to know S for both


the system and surroundings to predict if a
reaction will be spontaneous!
The Second Law (cont.)
• Consider a reaction driven by heat flow
from the surroundings at constant P.
– Exothermic Process: Ssurr = heat/T
– Endothermic Process: Ssurr = -heat/T

• Heat transferred = qP,surr = - qP,system= -Hsys


ΔH sys
ΔSsurr =−
T
Example
• For the following reaction at 298 K:

Sb4O6(s) + 6C(s) 4Sb(s) + 6CO2(g) H = 778 kJ

What is Ssurr?

Ssurr = -H/T = -778 kJ/298K = -2.6 kJ/K


The Third Law
• Recall, in determining enthalpies we had standard
state values to use. Does the same thing exist for
entropy?

• The third law: The entropy of a perfect crystal at


0K is zero.

• The third law provides the reference state for use


in calculating absolute entropies.
What is a Perfect Crystal?

Perfect crystal at 0 K Crystal deforms at T > 0 K


Standard Entropies
• With reference to this state, standard
entropies have been tabulated (Appendix 4).

• Recall, entropy is a state function; therefore,


the entropy change for a chemical reaction
can be calculated as follows:
ΔS o
reaction = ∑S
o
prod . − ∑So
react .
Example
• Balance the following reaction and determine
S°rxn.
Fe(s) + H2O(g) Fe2O3(s) + H2(g)
2Fe(s) + 3H2O(g) Fe2O3(s) + 3H2(g)
S°rxn = (S°(Fe2O3(s)) + 3S°H2(g))
-(2S°Fe(s) + 3S°H2O(g))

S°rxn = -141.5 J/K


Big Example
• Is the following reaction spontaneous at 298
K? (Is S°univ > 0?)
2Fe(s) + 3H2O(g) Fe2O3(s) + 3H2(g)
S°rxn = S°system = -141.5 J/K
S°surr = -H°sys/T = -H°rxn/T

H°rxn= H°f(Fe2O3(s)) + 3H°f(H2(g))


- 2H°f(Fe (s)) - 3 H°f(H2O(g))
Big Example (cont.)
H°rxn= -100 kJ

S°surr = -H°sys/T = 348 J/K

S°univ = S°sys + S°surr


= -141.5 J/K + 348 J/K
= 207.5 J/K

S°univ > 0 ; therefore, reaction is spontaneous


Entropy and Phase Changes
• Phase Change: Reaction in which a substance goes
from one phase of state to another.

• Example:
H2O(l) H2O(g) @ 373 K

• Phase changes are equilibrium processes such that:


Suniv = 0
S and Phase Changes (cont.)
H2O(l) H2O(g) @ 373 K
• Now, S°rxn = S°(H2O(g)) - S°(H2O(l))
= 195.9 J/K - 86.6 J/K
= 109.1 J/K

• And, S°surr = -Hsys/T


= -40.7 kJ/373 K
= -109.1 J/K

• Therefore, Suniv = Ssys + Ssurr = 0


Example
• Determine the temperature at which liquid
bromine boils:
Br2(l) Br2(g)

• Now, S°rxn = S°(Br2 (g)) - S°(Br2(l))


= 245.38 J/K - 152.23 J/K
= 93.2 J/K
Example (cont.)
• Now, S°surr = - S°sys = -93.2 J/K = -sys/T

• Therefore, calculate Hsys and solve for T!


0
• Now, H°rxn = H°f(Br2(g)) - H°f(Br2(l))
= 30.91 kJ - 0 (standard state)
= 30.91 kJ
• Such that, -93.2 J/K = -kJ/T
Tboiling = 331.6 K

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