Second Law of Thermodynamics:

∆SUNIV = ∆SSYS + ∆SSURR ≥ 0

The
The net
net entropy
entropy will
will increase
increase or
or stay
stay the
the
same.
same. It
It will
will never
never decrease.
decrease.

q
∆SSURR > 0 ∆SSURR ≥
T
∆SSYS < 0 q

∆SUNIV = 0 only for a reversible process

∆SUNIV > 0 for all other processes

Atkins:
Atkins: The
The entropy
entropy of
of the
the universe
universe tends
tends to
to increase.
increase.
∆Suniv is pathway dependent:

Irreversibleexpansion
Irreversible expansion ∆∆SSsys == 13.8
13.8JJKK-1-1
sys

M w = - P2 ∆V = -1.42 kJ ∆∆SSsurr ==-4.8 JJKK-1-1

surr -4.8
q = -w = 1.42 kJ
P1 = 15 atm
∆∆SSuniv ==99JJKK-1-1
univ
V1 = 1 L
T = 298 K P1 = 15 atm, V1 = 1 L
P2 = 1 atm

Pressure
V2 = 15 L
T = 298 K
M P2 = 1 atm, V2 = 15 L
Reversibleexpansion
Reversible expansion
Volume
V2
w = - nRT ln ( ) = -4.12 kJ
V1
∆∆SSsys == 13.8
13.8JJKK-1-1
qrev = -wrev = 4.12 kJ sys
∆∆SSuniv ==00JJKK-1-1
∆∆SSsurr ==-13.8
-13.8JJKK-1-1 univ
surr
Isothermal compression is pathway dependent:

∆∆SSsys ==-13.8
-13.8JJKK-1-1
sys
Irreversiblecompression
Irreversible compression
w = - P1 ∆V = 21.3 kJ ∆∆SSsurr ==71.4
71.4JJKK-1-1
M surr

q = -w = -21.3 kJ ∆∆SSuniv ==57.6

57.6JJKK-1-1
univ
P1 = 15 atm
V1 = 1 L P1 = 15 atm, V1 = 1 L
T = 298 K
P2 = 1 atm

Pressure
V2 = 15 L
T = 298 K
M P2 = 1 atm,
V2 = 15 L
Reversiblecompression
Reversible compression
Volume
V1
w = - nRT ln ( ) = 4.12 kJ
V2
∆∆SSsys ==-13.8
-13.8JJKK-1-1
qrev = -wrev = -4.12 kJ sys
∆∆SSuniv ==00JJKK-1-1
∆∆SSsurr ==13.8
13.8JJKK-1-1 univ
surr
 Corollary: For an isolated system ∆SSYS ≥ 0

A gas will not spontaneously compress. number of

molecules
Spontaneous ∆S=27.7 k
×10-13
WLeft = (0.25)20 = 9.09×

WRight = (1)20 = 1
Will not happen
in a truly macroscopic system N ≈ 1023
∆S=-27.7 k

Heat will not flow spontaneously from a cooler to a warmer object.

q -q
∆S1 = ∆S2 =
T1 T2 T1 T2
q? q -q T2 - T1
∆SSYS = ∆S1 + ∆S2 = T + T = q T T < 0
1 2 1 2

T1 > T2
∆∆SSSYS <<00violating
violatingthe
thesecond
secondlaw
law
q small ⇒ T1, T2 ≈ constant SYS
∴∴ititwill
willnot
nothappen
happen
Second Law of Thermodynamics:

“The second law of thermodynamics has as much truth as

saying that, if you poured a glass of water into the
ocean, it would not be possible to get the same glass of
water back again”
James Clerk Maxwell (1831-1879)
In a constant pressure process (most of real life):

∆H = qp ∴ ∆S = ∆H
T

Consider the entropy change associated with the melting of an ice

cube at T = 273.15.
∅
n ∆fusH
∆S =
T
∅
∆S = ∆fusH = 6.01 kJ mol-1
∆S = 22.0 J K-1 mol-1
n T 273.15 K

What if the temperature changes during an expansion, reaction or

phase transition?
T2 C
dS = dH
T
dH = dqp = Cp dT ∴ ∆S = ∫T1 pdT
T
Sample
SampleProblem:
Problem:

B: 35.0 g H2O
T = 25.0 oC 1. Calculate the final temperature assuming
adiabatic mixing (i.e. no heat transfer to or
from surroundings).
A: 160 g H2O
T = 86.0 oC 2. Calculate the entropy change for A, B and
the whole system.
Cp = 75.3 J K-1 mol-1

Sample
SampleProblem:
Problem:
The heat capacity of chlorine gas is given by:

Cp = (31.0 + 0.008 T ) J K-1 mol-1

Calculate ∆S when 2.00 moles of Cl2 (g) are heated from 300K to 400K at
constant pressure.
Spontaneity:
When will a chemical reaction occur spontaneously?
Endothermic, exothermic and energy neutral processes
all may occur spontaneously. ∴ ∆HSYS and ∆USYS do not
control spontaneity.
a reaction is
Second
Law ∆SUNIV = ∆SSYS + ∆SSURR ≥ 0 spontaneous if
∆SUNIV > 0

heat absorbed from or

∆SSYS = ∆ rS
released to the surroundings

∆SSURR = qp = -∆
∆ rH
T T A reaction is spontaneous
if and only if:
∆∆SSUNIV = ∆ S- ∆ H ≥ 0
UNIV = ∆rrS - ∆rrH ≥ 0 ∆ rS > ∆ rH
TT T
Enthalpy Entropy Exothermic? Spontaneous?

∆rS < 0
Endothermic NO
∆rH > 0 ∆SUNIV < 0
“heat required”

Exothermic YES
∆rH < 0 ∆rS > 0 ∆SUNIV > 0
“heat released”

Endothermic IF ∆rS > ∆rH

∆rH > 0 ∆rS > 0 “heat required” T
Entropy Driven
Exothermic IF −∆rH > -∆
∆rS
∆rH < 0 ∆rS < 0 T
“heat released” Enthalpy Driven

Energy
Energy must
must be
be conserved
conserved First Law

But ...

Entropy
Entropy Rules!
Rules! Second Law
Standard Entropy of Reaction:

∆RS = ∑ S - ∑ S (React.)

∅
∅
(Prod.)

Sample
SampleProblem:
Problem:

Calculate the change in entropy and change in enthalpy for the combustion
of ten grams of table sugar (sucrose) at 298 K. How does this compare with
the information on the label?

Sample
SampleProblem:
Problem:

Consider the following reaction: 3/2 O2(g) + 2 Fe (s) → Fe2O3 (s)

Calculate ∆SSYS, ∆ SSURR, and ∆ SUNIV.