Introduction to Entropy

BY HARESH VANIYA
Entropy (S) = a measure of randomness or disorder
MATTER IS ENERGY.
ENERGY IS INFORMATION.
EVERYTHING IS INFORMATION.
PHYSICS SAYS THAT
STRUCTURES... BUILDINGS,
SOCIETIES, IDEOLOGIES...
WILL SEEK THEIR POINT OF
LEAST ENERGY.
THIS MEANS THAT
THINGS FALL.
THEY FALL FROM HEIGHTS
OF ENERGY AND STRUCTURED
INFORMATION INTO
MEANINGLESS, POWERLESS
DISORDER.
THIS IS CALLED
ENTROPY.
Entropy: Times Arrow
In any spontaneous process, the entropy of the
universe increases.
S
universe
> 0

Another version of the 2
nd
Law:
Energy spontaneously spreads out if it has no
outside resistance

Entropy measures the spontaneous dispersal of
energy as a function of temperature
How much energy is spread out
How widely spread out it becomes
Entropy change = energy dispersed/T
Second Law of Thermodynamics
occurs without outside intervention
+
Entropy of the Universe
S
universe
= S
system
+ S
surroundings
Positional disorder Energetic disorder
S
universe
> 0 spontaneous process
Both S
sys
and S
surr
positive
Both S
sys
and S
surr
negative
S
sys
negative, S
surr
positive
S
sys
positive, S
surr
negative
spontaneous process.
nonspontaneous process.
depends
depends
Entropy of the Surroundings
(Energetic Disorder)
System
Heat
Entropy
Surroundings
System
Heat
Entropy
Surroundings
T
H
S
sys
surr
=
Low T large entropy change (surroundings)
High T small entropy change (surroundings)
H
sys
< 0
H
sys
> 0
S
surr
> 0
S
surr
< 0
Positional Disorder and Probability
Probability of 1 particle in left bulb =
" 2 particles both in left bulb = ()() =
" 3 particles all in left bulb = ()()() =
1
/
8
" 4 " all " = ()()()() =
1
/
16
" 10 " all " = ()
10
=
1
/
1024
" 20 " all " = ()
20
=
1
/
1048576
" a mole of " all " = ()
6.0210
23

The arrangement with the greatest entropy is the one
with the highest probability (most spread out).
S
solid
< S
liquid
<< S
gas
Entropy of the System: Positional Disorder
Ludwig Boltzmann
Ordered
states
Disordered
states
Low probability
(few ways)
High probability
(many ways)
Low S
High S
S
system
Positional disorder
S increases with increasing # of possible positions
Ludwig Boltzmann
The Third Law:
The entropy of a perfect
crystal at 0 K is zero.

Everything in its place
No molecular motion
The Third Law of Thermodynamics
Entropy Curve
Solid Gas Liquid
S
(q
rev
/T)
(J/K)
Temperature (K)
0
0
fusion
vaporization
S (absolute entropy) can be calculated for any substance
Entropy Increases with...
Melting (fusion) S
liquid
> S
solid

H
fusion
/T
fusion
= S
fusion
Vaporization S
gas
> S
liquid
H
vaporization
/T
vaporization
= S
vaporization

Increasing n
gas
in a reaction
Heating S
T2
> S
T1
if T
2
> T
1

Dissolving (usually) S
solution
> (S
solvent
+ S
solute
)
Molecular complexity more bonds, more entropy
Atomic complexity more e
-
, protons, neutrons
Recap: Characteristics of Entropy
S is a state function
S is extensive (more stuff, more entropy)
At 0 K, S = 0 (we can know absolute entropy)
S > 0 for elements and compounds in their standard states
S
rxn
= EnS
products
- EnS
reactants

Raise T increase S
Increase n
gas
increase S
More complex systems larger S
Entropy and Gibbs Free Energy
by Mike Roller
Entropy (S) Review
S
universe
> 0 for spontaneous processes
S
universe
= S
system
+ S
surroundings
|
positional
|
energetic
We can know the absolute entropy value for a substance
S values for elements & compounds in their standard
states are tabulated (Appendix C, p. 1019)
For any chemical reaction, we can calculate S
rxn
:
S
rxn
= ES(products) - ES(reactants)
S
universe
and Chemical Reactions
S
universe
= S
system
+ S
surroundings
For a system of reactants and products,
S
universe
= S
rxn
H
rxn
/T
If S
universe
> 0, the reaction is spontaneous
If S
universe
< 0, the reaction is not spontaneous
The reverse reaction is spontaneous
If S
universe
= 0, the reaction is at equilibrium
Neither the forward nor the reverse reaction is favored
C
6
H
12
O
6(s)
+ 6 O
2(g)
6 CO
2(g)
+ 6 H
2
O
(g)
Compound
C
6
H
12
O
6(s)
O
2(g)
CO
2(g)
H
2
O
(g)
H
f
(kJ/mol)
-1275
0
-393.5
-242
S (J/mol K)
212
205
214
189
S
universe
= S
rxn
H
rxn
/T


S
rxn
= ES(products) - ES(reactants)
= [6 S(CO
2(g)
) + 6 S(H
2
O
(g)
)] [S(C
6
H
12
O
6(s)
) + 6 S(O
2(g)
)]
= [6(214) + 6(189)] [(212) + 6(205)] J/K
S
rxn
= 976 J/K

H
rxn
= EH
f
(products) - EH
f
(reactants)
= [6 H
f
(CO
2(g)
) + 6 H
f
(H
2
O
(g)
)] [H
f
(C
6
H
12
O
6(s)
) + 6 H
f
(O
2(g)
)]
= [6(-393.5) + 6(-242)] [(-1275) + 6(0)] kJ
H
rxn
= -2538 kJ
C
6
H
12
O
6(s)
+ 6 O
2(g)
6 CO
2(g)
+ 6 H
2
O
(g)
Compound
C
6
H
12
O
6(s)
O
2(g)
CO
2(g)
H
2
O
(g)
H
f
(kJ/mol)
-1275
0
-393.5
-242
S (J/mol K)
212
205
214
189
S
universe
= S
rxn
H
rxn
/T


S
rxn
= 976 J/K (per mole of glucose)
H
rxn
= -2538 kJ (per mole of glucose)

At 298 K,
S
universe
= 0.976 kJ/K (-2538 kJ/298 K)
S
universe
= 9.5 kJ/K
G means +S
univ
A process (at constant T, P) is
spontaneous if free energy decreases

Gibbs Free Energy (G)
Josiah Gibbs
G = H TS
At constant temperature,
G = H TS
(systems point of view)
G = H TS
Divide both sides by T
-G/T = -H/T + S
S
universe
= S H/T
G and Chemical Reactions
G = H TS

If G < 0, the reaction is spontaneous
If G > 0, the reaction is not spontaneous
The reverse reaction is spontaneous
If G = 0, the reaction is at equilibrium
Neither the forward nor the reverse reaction is favored
G is an extensive state function
Ba(OH)
2(s)
+ 2NH
4
Cl
(s)
BaCl
2(s)
+ 2NH
3(g)
+ 2 H
2
O
(l)
H
rxn
= 50.0 kJ (per mole Ba(OH)
2
)

S
rxn
= 328 J/K (per mole Ba(OH)
2
)

G = H - TS
G = 50.0 kJ 298 K(0.328 kJ/K)
G = 47.7 kJ Spontaneous
At what T does the reaction stop being spontaneous?
The T where G = 0.
G = 0 = 50.0 kJ T(0.328 J/K)
50.0 kJ = T(0.328 J/K)
T = 152 K
not spontaneous below 152 K
Effect of H and S on Spontaneity
H

+

+
S
+
+


Spontaneous?
Spontaneous at all temps

Spontaneous at high temps
Reverse reaction spontaneous at low temps
Spontaneous at low temps
Reverse reaction spontaneous at high temps
Not spontaneous at any temp
G = H TS
G negative spontaneous reaction
1. G = EG
f
(products) - EG
f
(reactants)
G
f
= free energy change when forming 1 mole of
compound from elements in their standard states
2. G = H - TS
3. G can be calculated by combining G
values for several reactions
Just like with H and Hesss Law
Ways to Calculate G
rxn
2H
2(g)
+ O
2(g)
2 H
2
O
(g)
1. G = EG
f
(products) - EG
f
(reactants)
G
f
(O
2(g)
) = 0
G
f
(H
2(g)
) = 0
G
f
(H
2
O
(g)
) = -229 kJ/mol
G = (2(-229 kJ) 2(0) 0) kJ = -458 kJ

2. G = H - TS
H = -484 kJ
S = -89 J/K
G = -484 kJ 298 K(-0.089 kJ/K) = -457 kJ
2H
2(g)
+ O
2(g)
2 H
2
O
(g)
3. G = combination of G from other reactions
(like Hesss Law)
2H
2
O
(l)
2H
2(g)
+ O
2(g)
G
1
= 475 kJ
H
2
O
(l)
H
2
O
(g)
G
2
= 8 kJ
G = - G
1
+ 2(G
2
)
G = -475 kJ + 16 kJ = -459 kJ
Method 1: -458 kJ
Method 2: -457 kJ
Method 3: -459 kJ
What is Free Energy, Really?
NOT just another form of energy
Free Energy is the energy available to do useful work
If G is negative, the system can do work (w
max
=
G)
If G is positive, then G is the work required to
make the process happen
Example: Photosynthesis
6 CO
2
+ 6 H
2
O C
6
H
12
O
6
+ 6 O
2
G = 2870 kJ/mol of glucose at 25C
2870 kJ of work is required to photosynthesize 1 mole of
glucose