Chapter 17 2-4 Entropy 2nd Law

Laws of Thermodynamics
http://en.wikipedia.org/wiki/Laws_of_thermodynamics
Chapter 6
Chapter 17
Fourth law of thermodynamics: Emergent complexity?

1
Chapter 6 Review
2
Reaction Enthalpy
Direct Reaction
C (graphite) + O2 (g) CO2 (g)
Multistep Reaction
C (graphite) + 1/2O2 (g) CO (g)
CO (g) + 1/2O2 (g) CO2 (g)
C (graphite) + O2 (g) CO2 (g)
3
The First Law of Thermodynamics
 Exothermic reactions
generate specific
amounts of heat Q
and have a negative
enthalpy change:
H = –Q
 This is because the
potential energies of
the products are
lower than the
potential energies of
the reactants.
4
Chapter 6 Review
Enthalpy (H) is used to quantify the heat flow into or out of
a system in a process that occurs at constant pressure.
DHrxn = Hproducts – Hreactants
Hproducts < Hreactants Hproducts > Hreactants
DH < 0 DH > 0
Exothermic Endothermic
Enthalpically favorable Enthalpically unfavorable
If we mix reactants and products together

will the reaction occur?
Not enough information. We need to know the change in
entropy to predict if a reaction will spontaneously occur.
5
Chapter 17
7
Chapter 17
8
Chapter 17
9
Spontaneity
Does something happen?
• Spontaneity- the tendency for a process to advance to
equilibrium without external influence
• Something that happens naturally is spontaneous
• Any process will be spontaneous in one direction
• The reverse is nonspontaneous
• If work needs to be done, it is not spontaneous
Spontaneous: process that does occur under a specific set of

conditions
Nonspontaneous: process that does not occur under a specific
set of conditions
Spontaneity
• A waterfall runs downhill
• A lump of sugar dissolves in a cup of coffee
spontaneous • Smell diffusing in a room
• Heat flows from a hotter object to a colder
object
• Iron exposed to oxygen and water forms
rust
• A ball rolling down hill
Processes that are spontaneous in one

nonspontaneous direction are nonspontaneous in the
reverse direction.
Spontaneity
spontaneous
nonspontaneous
Spontaneity
• Processes that are spontaneous at one

temperature may be nonspontaneous at
other temperatures.
• Above 0C it is spontaneous for ice to melt.
• Below 0C the reverse process is
spontaneous.
Spontaneity and Speed
• The speed of a reaction is not an indicator of its spontaneity.
• Spontaneity is determined by the relative positions of the initial
and final states (thermodynamic state functions)
• Additionally spontaneity does not tell you how fast a reaction is.
Fast spontaneous process Slow spontaneous process Very slow
spontaneous process
• Speed is determined by the pathway (kinetics)

• Two independent regimes (thermodynamics vs kinetics)
Spontaneity and Exo/Endothermicity
Spontaneous: process that does occur under a specific set of
conditions.
Nonspontaneous: process that does not occur under a specific
set of conditions.
Often spontaneous processes are exothermic, but not always….
CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (l) DH0 = -890.4 kJ/mol
exothermic
H+ (aq) + OH- (aq) H2O (l) DH0 = -56.2 kJ/mol
H2O (s) H2O (l) DH0 = 6.01 kJ/mol

endothermic
H2O
NH4NO3 (s) NH4+(aq) + NO3- (aq) DH0 = 25 kJ/mol
Spontaneity
If we mix reactants and products together
will the reaction occur?
CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (l) DH0 = -890.4 kJ/mol
H+ (aq) + OH- (aq) H2O (l) DH0 = -56.2 kJ/mol
H2O (s) H2O (l) DH0 = 6.01 kJ/mol

H2O
NH4NO3 (s) NH4+(aq) + NO3- (aq) DH0 = 25 kJ/mol
Not enough information. We need to know the change enthalpy

and in entropy to predict if a reaction will spontaneously occur.
Chapter 17
17
Entropy
Entropy (S): Can be thought of as a measure of the randomness
or disorder of a system.
order S disorder S
- A measure of the loss of information in a transmitted message
(Computer science/information theory).
- A thermodynamic quantity representing the unavailability of a
system's thermal energy for conversion into mechanical work.
- A measure of how spread out or dispersed the energy of a
system is among the different possible ways a system can contain
energy.
- Is a measure of the number of specific ways (microstates) in
which a thermodynamic system may be arranged.
Microstates
Microstates- The detailed microscopic configuration of a system.
How many different ways can a system be arranged.
Red, blue, green and yellow spheres in a two compartment container.
Microstates
Microstates- The detailed microscopic configuration of a system.
How many different ways can a system be arranged.
Red, blue, green and yellow spheres in a two compartment container.
Total microstates = 22
4 and 0 = 2 microstates
Microstates and Entropy
More order, Less entropy
Less order, more entropy
• Configurations (macrostates) associated with large numbers of

microstates are said to be more disordered than those with fewer
microstates.
• The equilibrium state of a system is the most disordered
configuration (largest no. of microstates) available.
• The number of microstates is called the multiplicity (W) of the
configuration.
The Austrian physicist Ludwig Boltzmann introduced a model
to relate the total number of microstates (the multiplicity, W)
to entropy (S).
Boltzmann constant (k)
S = k ln W k = 1.38 x 1023J/K
R Gas constant
units on S is J/K
k
NA Avogadro constant
Boltzmann was the founding father of statistical mechanics,

a completely new way of thinking about theoretical physics.
His work was ridiculed by his fellow professors.
S = k ln W k = 1.38 x 1023J/K
4 and 0 = 2 microstates S = 9.6 x 10-25 J/K


has > than 3 times as much entropy as

Entropy and Cards
Ordered Deck
W=1
Unordered Deck
W = (52!) - 1
W = 80658175170943878571660636856403766975289505440883277823999999999999
Entropy and Cards
High card Flush
Full house Royal Flush
A pair Three of a kind
Poker: The game that

rewards lowest entropy!
Entropy and Cards
Hand W ln W S (J/K)
Royal flush (AKQJ10 in one suit) 4 1.39 1.92 x 10-23
Straight flush (sequence in one suit) 36 3.58 4.94 x 10-23
Four of a kind 624 6.44 8.89 x 10-23
Full house (three of a kind plus a pair) 3,744 8.23 1.14 x 10-22
Flush (five cards in the same suit) 5,108 8.54 1.18 x 10-22
Straight (five cards in sequence) 10,200 9.23 1.27 x 10-22
Three of a kind 54,912 10.91 1.51 x 10-22
Two pairs 123,552 11.72 1.62 x 10-22
One pair 1,098,240 13.91 1.92 x 10-22
No pairs 1,302,540 14.08 1.94 x 10-22
Total 2,598,960
Poker: The game that rewards the player with the hand that has the least entropy.
Table does not account for high card (the equivalent of enthalpy?).
Entropy and Reactions
“All” chemical and physical changes involve a
change in entropy (DS) for the system.
A+B C+D DS = Sf - Si
Sinitial Sfinal
If the change from initial to final results in an

increase in randomness and number of states. Sf > Si DS > 0
DS = Sf - Si
S = k ln W Wf > Wi then DS > 0
DS = k ln W f - k ln W i Wf < Wi then DS < 0
Wf
DS = k ln
Wi
“All” chemical and physical changes involve a
change in entropy (DS) for the system.
Sinitial Sfinal
General Molecular Trends:

1) Structure (gas vs solid, etc.)
less structure =more states = more entropy
2) Temperature
higher temp = more energy states = more entropy
3) Number of particles/atoms
more particles = more states = more entropy
1) Structure/Phase
Increasing disorder
Increasing entropy (S)
For any substance, the solid state is more ordered than the liquid
state and the liquid state is more ordered than gas state.
Ssolid < Sliquid << Sgas
When a gas expands into a vacuum, its entropy increases because

the increased volume allows for greater atomic or molecular
disorder.
29
Phase Change
I2(s) I2(g)
DH = 107 kJ/mol
DS > 0
Structure/Phase
Processes that lead to an increase in entropy (DS > 0)
Structure/Phase
The entropy change accompanying the dissolution of a salt
pure solid
MIX
pure liquid
solution
DS > 0
Structure/Phase
The small increase in entropy when ethanol and water mix
O O
H H H
MIX
Water Ethanol Solution of

ethanol and
water
DS > 0
“All” chemical and physical changes involve a change
in entropy (DS) for the system.
Sinitial Sfinal

1) Structure/Phase (gas vs solid, etc.)
2) Temperature
Entropy and Temperature
Entropy increases as temperature increases.
Slower temp < Shigher temp
Higher temperature allows the system to access more microstates.

35
• Molecules exhibit several types of motion:
– Translational: Movement of the entire molecule from one
place to another.
– Vibrational: Periodic motion of atoms within a molecule.
– Rotational: Rotation of the molecule on about an axis or
rotation about  bonds.
Higher temperature allows the system to access more

vibrational and rotational states (increases microstates).
Higher temperature allows the

system to access more
vibrational and rotational states
(increased # of microstates).
Low temp High temp

Temperature and Phase Change
S increases
slightly with T
S increases a large
amount with phase
changes
Sinitial Sfinal

2) Temperature
Number of Atoms/Particles
More particles leads to a greater number of microstates (greater S).
2 molecules 4 molecules
Sfewer moles < Smore moles

Larger and more complex molecules have greater entropies.
5 atoms 8 atoms 11 atoms
More atoms = more vibrational and rotational states
Sfewer atoms < Smore atoms

Sinitial Sfinal

2) Temperature
Example 17.1
Predict whether the entropy change is greater or less than zero
for each of the following processes:
(a) freezing ethanol
(b) evaporating a beaker of liquid bromine
(c) dissolving glucose in water
(d) cooling nitrogen gas from 80°C to 20°C
43
Example 17.1
EtOH(l)  EtOH(s) ΔS < 0
Br2(l)  Br2 (g) ΔS > 0

C₆H₁₂O₆(s)  C₆H₁₂O₆ (aq) ΔS > 0

ΔS < 0 44
Standard Entropy
• Difficult to count the number of

microstates directly.
• Measured by calorimetery.
• Standard entropy (S) absolute entropy
of a substance at 1 atm (typically at 25C)
• Units of J K-1 mol-1
• All positive values.
• Absolute values (unlike DH which is
relative)
46
Standard Entropy
• Entropy for gas phase is greater than
that of liquid or solid of same substance
– I2 (g) > I2 (s)
• More complex structures have greater

entropy
– C2H6 (g) > CH4 (g)
• Allotropes - more ordered forms have

lower entropy
– Diamond > graphite
Can be used to calculate DSrxn and DSsys.
47
Chapter 17
48
Entropy
Entropy (S): Can be thought of as a measure of the randomness
or disorder of a system.
order S disorder S
- A measure of the loss of information in a transmitted message
(Computer science/information theory).
- A thermodynamic quantity representing the unavailability of a
system's thermal energy for conversion into mechanical work.
- A measure of how spread out or dispersed the energy of a
system is among the different possible ways a system can contain
energy.
- Is a measure of the number of specific ways (microstates) in
which a thermodynamic system may be arranged.
• Configurations (macrostates) associated with large numbers of

microstates are said to be more disordered than those with fewer
microstates.
• The equilibrium state of a system is the most disordered
configuration (largest no. of microstates) available.
• The number of microstates is called the multiplicity (W) of the
configuration.
The Austrian physicist Ludwig Boltzmann introduced a model
to relate the total number of microstates (the multiplicity, W)
to entropy (S).
Boltzmann constant (k)
S = k ln W k = 1.38 x 1023J/K
R Gas constant
units on S is J/K
k
NA Avogadro constant
Boltzmann was the founding father of statistical mechanics,

a completely new way of thinking about theoretical physics.
His work was ridiculed by his fellow professors.
S = k ln W k = 1.38 x 1023J/K


has > than 3 times as much entropy as

Entropy and Cards
Hand W ln W S (J/K)
Royal flush (AKQJ10 in one suit) 4 1.39 1.92 x 10-23
Straight flush (sequence in one suit) 36 3.58 4.94 x 10-23
Four of a kind 624 6.44 8.89 x 10-23
Full house (three of a kind plus a pair) 3,744 8.23 1.14 x 10-22
Flush (five cards in the same suit) 5,108 8.54 1.18 x 10-22
Straight (five cards in sequence) 10,200 9.23 1.27 x 10-22
Three of a kind 54,912 10.91 1.51 x 10-22
Two pairs 123,552 11.72 1.62 x 10-22
One pair 1,098,240 13.91 1.92 x 10-22
No pairs 1,302,540 14.08 1.94 x 10-22
Total 2,598,960
Poker: The game that rewards the player with the hand that has the least entropy.
Table does not account for high card (the equivalent of enthalpy?).
Sinitial Sfinal

2) Temperature
1) Structure/Phase
Increasing disorder
Increasing entropy (S)
For any substance, the solid state is more ordered than the liquid
state and the liquid state is more ordered than gas state.
Ssolid < Sliquid << Sgas
When a gas expands into a vacuum, its entropy increases because

the increased volume allows for greater atomic or molecular
disorder.
55
Higher temperature allows the

system to access more
vibrational and rotational states
(increased # of microstates).
Low temp High temp

Temperature and Phase Change
S increases
slightly with T
S increases a large
amount with phase
changes
2 molecules 4 molecules
Sfewer moles < Smore moles
More atoms = more vibrational and rotational states

Sfewer atoms < Smore atoms
Example 17.1
EtOH(l)  EtOH(s) ΔS < 0
Br2(l)  Br2 (g) ΔS > 0

C₆H₁₂O₆(s)  C₆H₁₂O₆ (aq) ΔS > 0

ΔS < 0 59
Standard Entropy
• Difficult to count the number of

microstates directly.
• Measured by calorimetery.
• Standard entropy (S) absolute entropy
of a substance at 1 atm (typically at 25C)
• Units of J K-1 mol-1
• All positive values.
• Absolute values (unlike DH which is
relative)
Can be used to calculate DSrxn and DSsys. 60
Chapter 17
61
Thermodynamics
First Law of Thermodynamics
Energy can be converted from one form to another but energy
cannot be created or destroyed.
Second Law of Thermodynamics

The entropy of the universe increases in a spontaneous process
and remains unchanged in an equilibrium process.
DSuniv = DSsys + DSsurr
g
din
un
Equilibrium : DSuniv = 0
r ro
m
su
ste
DSuniv > 0
sy
Spontaneous process:
If something happens the total entropy of the universe increases.

Side Note: Entropy and Time
Entropy is the only quantity in the physical sciences (apart from
certain rare interactions in particle physics) that requires a particular
direction for time, sometimes called an arrow of time.
Lower Higher
Entropy Entropy
As one goes "forward" in time, the second law of

thermodynamics says, the entropy of an isolated system
can increase, but not decrease.
Thermodynamics

DSuniv = DSsys + DSsurr
g
din
un
Equilibrium : DSuniv = 0
r ro
m
su
ste
DSuniv > 0
sy
Spontaneous process:
If something happens the total entropy of the universe increases.

Thermodynamics
For chemical reactions our system is the reaction and
DSsys is DS0rxn
g
din
The standard entropy of reaction (DS0rxn) is the
un
entropy change for a reaction carried out at 1 atm
r ro
m
su
ste
and 250C.
sy
aA + bB cC + dD
Standard Entropy of Reaction (DS0rxn)- The difference between the

sum of the entropies of the products and the sum of the entropies
of the reactants:
DS0rxn = S nS0(products) - S mS0(reactants)
DSrxn
0
= [ cS0(C) + dS0(D) ] - [ aS0(A) + bS0(B) ]
Example 17.3
Predict whether the Standard Entropy of Reaction (DS0rxn)of the
system in each of the following reactions is positive or negative.
DS0rxn = S nS0(products) - S mS0(reactants)
(a) 2H2(g) + O2(g) 2H2O(l)

DSorxn < 0
(b) NH4Cl(s) NH3(g) + HCl(g)
DSorxn > 0
(c) H2(g) + Br2(g) 2HBr(g)
DSorxn = ?
66
Calculating Entropy for a Reaction
aA + bB cC + dD
DSrxn
0
= [ cS0(C) + dS0(D) ]
- [ aS0(A) + bS0(B) ]
What is the DS0rxn for:

2H2(g) + O2(g)  2H2O (l)
First, qualitatively predict the

entropy change:
Increase, decrease or none
Entropy for a Reaction
From appendix 3:
H2(g) S = 131.0 J/Kmol
2H2(g) + O2(g)  2H2O (l) O2(g) S = 205.0 J/Kmol
H2O(l) S = 69.9 J/Kmol
Srxn = nSproducts  mSreactants
Srxn = [(2)(69.9 J/K·mol)] - [(2)(131.0 J/K·mol) + (1)(205.0 J/K·mol)]
From appendix 3:
H2(g) S = 131.0 J/Kmol
2H2(g) + 1O2(g)  2H2O (l) O2(g) S = 205.0 J/Kmol
H2O(l) S = 69.9 J/Kmol
Srxn = nSproducts  mSreactants
Srxn = -327.2 J/K·mol Entropy Decreases!

2H2(g) + O2(g)  2H2O (l) Srxn = -327.2 J/K·mol
2H2(g) + O2(g)  2H2O (g) Srxn = ?
Greater than or less than - 327.2 J/K·mol ?

Srxn = -89.6 J/K·mol
Entropy Decreases!
From appendix 3:
but by less: H2(g) S = 131.0 J/Kmol
2H2O (l)  2H2O (g) O2(g) S = 205.0 J/Kmol
H2O(l) S = 69.9 J/Kmol
Srxn = 237.6 J/K·mol H2O(g) S = 188.7 J/Kmol
Example 17.2
From the standard entropy values in Appendix 3, calculate the
standard entropy changes for the following reactions at 25°C.
(a) CaCO3(s) CaO(s) + CO2(g)
(b) N2(g) + 3H2(g) 2NH3(g)
(c) H2(g) + Cl2(g) 2HCl(g)
71
Example 17.2
From the standard entropy values in Appendix 3, calculate the
standard entropy changes for the following reactions at 25°C.
(a) CaCO3(s) CaO(s) + CO2(g)
ΔS°rxn = [S°(CaO) + S°(CO2)] - [S°(CaCO3)]
= [(39.8 J/K·mol) + (213.6 J/K·mol)] - (92.9 /K·mol)
= 160.5 J/K·mol
(b) N2(g) + 3H2(g) 2NH3(g)

ΔS°rxn = [2S°(NH3)] - [S°(N2) + 3S°(H2)]
= (2)(193 J/K·mol) - [(192 J/K·mol) + (3)(131 J/K·mol)]
= -199 J/K·mol
(c) H2(g) + Cl2(g) 2HCl(g)
ΔS°rxn = [2S°(HCl)] - [S°(H2) + S°(Cl2)]
= (2)(187 J/K·mol) - [(131 J/K·mol) + (223 J/K·mol)]
= 20 J/K·mol 72
3 Laws of Thermodynamics

Third Law of Thermodynamics

The entropy of a pure crystalline substance at absolute zero is 0.
3rd Law of Thermodynamics
Third Law of Thermodynamics
The entropy of a pure crystalline substance at absolute zero is 0.
Only 1 possible microstate!
This is the why we have an absolute entropy scale for substances.

Real Crystals
Experimentally we “can’t” get

down to 0 K (absolute zero).
Absolute zero cannot be reached using

only thermodynamic means, as the In September 2014, scientists in the
temperature of the substance being CUORE collaboration cooled a copper
cooled approaches the temperature of vessel with a volume of one cubic meter
the cooling agent asymptotically. to 0.006 Kelvins (−273.144 °C;
−459.659 °F) for 15 days.
S = k ln W
W=1
S=0
76
Chapter 17
77

Chapter 17 2-4 Entropy 2nd Law

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Laws of Thermodynamics

Fourth law of thermodynamics: Emergent complexity?

If we mix reactants and products together

Spontaneous: process that does occur under a specific set of

Processes that are spontaneous in one

• Processes that are spontaneous at one

• Speed is determined by the pathway (kinetics)

H2O (s) H2O (l) DH0 = 6.01 kJ/mol

H+ (aq) + OH- (aq) H2O (l) DH0 = -56.2 kJ/mol

H2O (s) H2O (l) DH0 = 6.01 kJ/mol

Not enough information. We need to know the change enthalpy

• Configurations (macrostates) associated with large numbers of

Boltzmann constant (k)

Boltzmann was the founding father of statistical mechanics,

4 and 0 = 2 microstates S = 9.6 x 10-25 J/K

3 and 1 = 8 microstates S = 2.9 x 10-24 J/K

2 and 2 = 12 microstates S = 3.4 x 10-24 J/K

has > than 3 times as much entropy as

High card Flush

Full house Royal Flush

A pair Three of a kind

Poker: The game that

If the change from initial to final results in an

General Molecular Trends:

Ssolid < Sliquid << Sgas

When a gas expands into a vacuum, its entropy increases because

Water Ethanol Solution of

General Molecular Trends:

Higher temperature allows the system to access more microstates.

Higher temperature allows the system to access more

Higher temperature allows the

Low temp High temp

General Molecular Trends:

Sfewer moles < Smore moles

5 atoms 8 atoms 11 atoms

More atoms = more vibrational and rotational states

Sfewer atoms < Smore atoms

General Molecular Trends:

(b) evaporating a beaker of liquid bromine

(c) dissolving glucose in water

(d) cooling nitrogen gas from 80°C to 20°C

EtOH(l)  EtOH(s) ΔS < 0

(b) evaporating a beaker of liquid bromine

Br2(l)  Br2 (g) ΔS > 0

C₆H₁₂O₆(s)  C₆H₁₂O₆ (aq) ΔS > 0

• Difficult to count the number of

• More complex structures have greater

• Allotropes - more ordered forms have

Can be used to calculate DSrxn and DSsys.

• Configurations (macrostates) associated with large numbers of

Boltzmann constant (k)

Boltzmann was the founding father of statistical mechanics,

4 and 0 = 2 microstates S = 9.6 x 10-25 J/K

3 and 1 = 8 microstates S = 2.9 x 10-24 J/K

2 and 2 = 12 microstates S = 3.4 x 10-24 J/K

has > than 3 times as much entropy as

General Molecular Trends:

Ssolid < Sliquid << Sgas

When a gas expands into a vacuum, its entropy increases because