20.110J / 2.772J / 5.

601J
Thermodynamics of Biomolecular Systems
Instructors: Linda G. Griffith, Kimberly Hamad-Schifferli, Moungi G. Bawendi, Robert W. Field

20.110/5.60 Fall 2005

Lecture #6

page

The Second Law

First Law
U = q + w ,

showed the equivalence of work and heat

dU = 0 for cyclic process q = w

Suggests engine can run in a cycle and convert heat into useful work.

Second Law

Puts restrictions on useful conversion of q to w

Follows from observation of a directionality to natural

or spontaneous processes

Provides a set of principles for

- determining the direction of spontaneous change
- determining equilibrium state of system

Need a definition:

Heat reservoir

Definition: A very large system of uniform

T, which does not change regardless of the
amount of heat added or withdrawn.
Also called a heat bath. Real systems can come close to this
idealization.
Two classical statements of the Second Law:
Kelvin
Clausius
and a Mathematical statement

20.110J / 2.772J / 5.601J

Thermodynamics of Biomolecular Systems
Instructors: Linda G. Griffith, Kimberly Hamad-Schifferli, Moungi G. Bawendi, Robert W. Field

20.110/5.60 Fall 2005

Lecture #6

page

I. Kelvin: It is impossible for any system to operate in a cycle that

takes heat from a hot reservoir and converts it to work in the
surroundings without at the same time transferring some heat to a
colder reservoir.
q> 0
w< 0
-w= q

T1 (hot)
q

T1 (hot)
q1

-w

q 1> 0
w< 0
q 2< 0
-w q 1= -w-q 2

-q 2

IMPOSSIBLE!!

T2 (cold)

OK!!

II. Clausius:
It is impossible for any system to operate in a cycle
that takes heat from a cold reservoir and transfers it to a hot
reservoir without at the same time converting some work into heat.
q 2> 0 T1 (hot)
q 1< 0
-q 1
-q 1= q 2

T1 (hot)

q2

q2

IMPOSSIBLE!! T2 (c old)

Alternative Clausius statement:

-q 1

T2 (c old)

q 2> 0
w> 0
q 1< 0
w -q 1= w+ q 2

OK!!

All spontaneous processes are

irreversible.
(e.g. heat flows from hot to cold spontaneously and irreversibly)

20.110J / 2.772J / 5.601J

Thermodynamics of Biomolecular Systems
Instructors: Linda G. Griffith, Kimberly Hamad-Schifferli, Moungi G. Bawendi, Robert W. Field

20.110/5.60 Fall 2005

Lecture #6

qrev
T

qrev = 0

Mathematical statement:

page

is a state function = dS

and
dS =

qirrev < 0

qrev
T

S ENTROPY

dS

=0

S = S2 S1 =

2 qirrev
qrev
>
1
T
T

irrev
rev
for cycle [1]
[2]
[1]

1 qrev
q irrev
q
+
= irrev < 0
2 T
T
T
2 qirrev
qirrev
S < 0 S >
1
T
T

Kelvin and Clausius statements are specialized to heat engines.

Mathematical statement is very abstract.

Lets Link them through analytical treatment of a heat engine.

The Carnot Cycle

a typical heat engine

All paths are reversible

T1 (hot)

q1

isotherm (T1)

adiabat

adiabat

4
isotherm (T2)

q2
T2 (cold)

20.110J / 2.772J / 5.601J

Thermodynamics of Biomolecular Systems
Instructors: Linda G. Griffith, Kimberly Hamad-Schifferli, Moungi G. Bawendi, Robert W. Field

20.110/5.60 Fall 2005

Lecture #6

page

12

isothermal expansion at T1 (hot)

23

adiabatic expansion (q = 0)

34

isothermal expansion at T2 (cold) U = q2 + w 2

41

Kelvin:

U = w1

adiabatic compression (q = 0)

Efficiency =

1st Law

U = q1 + w 1

U = w 2

work output to surroundings (w 1 + w1 + w 2 + w 2 )

=
heat in at T1 (hot)
q

v dU

= 0 q1 + q2 = (w1 + w1 + w 2 + w 2 )

Efficiency =

q1 + q2
q
=1+ 2
q1
q1

q2 < 0 Efficiency < 1 (< 100%)

-w = q1 = work output

Note: if the cycle were run in reverse, then q1 < 0, q2 > 0, w > 0.
Its a refrigerator!
Carnot cycle for an ideal gas
12
23

U = 0; q1 = w1 = 1 pdV = RT1 ln 2
V

q = 0; w1 = CV (T2 T1 )
Rev. adiabat

T2 V2
=
T1 V3

V4

V3

U = 0; q2 = w2 = 3 pdV = RT2 ln

41

q = 0; w2 = CV (T1 T2 )

34

Rev. adiabat

T1 V4
=
T2 V1

20.110J / 2.772J / 5.601J

Thermodynamics of Biomolecular Systems
Instructors: Linda G. Griffith, Kimberly Hamad-Schifferli, Moungi G. Bawendi, Robert W. Field

20.110/5.60 Fall 2005

Lecture #6

page

q2 T2 ln (V4 V3 )
=
q1 T1 ln (V2 V1 )
1

V1

V4

T V
= 2= 2
T1 V3

or

q1 q2
+
=0
T1 T2

V4 V1
=
V3 V2

qrev
T

q2
T
= 2
q1
T1

=0

this illustrates the link between heat engines to the

mathematical statement of the second law
Efficiency

=1+

q2
T
=1 2
q1
T1

For a heat engine (Kelvin):

100% as T2 0 K

q1 > 0, w < 0, T2 < T1

T T2
q1

Total work out = w = q1 = 1

T1

For a refrigerator (Clausius):

q2 > 0, w > 0, T2 < T1

( w ) < q1

Note: In the limit T2 0 K, (-w) q1, and 100% conversion of

heat into work. 3rd law will state that we cant reach this limit!

Total work in
But

q1
q
= 2
T1
T2

T T
= w = 2 1 q1
T1
T T
w = 1 2 q2
T2

Note: In the limit T2 0 K, w . This means it takes an infinite

amount of work to extract heat from a reservoir at 0 K 0 K
cannot be reached (3rd law).

20.110J / 2.772J / 5.601J

Thermodynamics of Biomolecular Systems
Instructors: Linda G. Griffith, Kimberly Hamad-Schifferli, Moungi G. Bawendi, Robert W. Field

20.110/5.60 Fall 2005

Lecture #6

page

The efficiency of any reversible engine has to be the same as the

Carnot cycle, this can be shown by running the reversible engine
as a refrigerator, using the work output of a Carnot engine to
drive it so that the total work out is zero, and showing that, if
the efficiency of the reversible engine is higher, then the second
law is broken.

Additionally:

We can approach arbitrarily closely to any cyclic process using a

series of only adiabats and isotherms.

So, for any reversible cycle

This is consistent with the mathematical statement of the second

law, which defines Entropy, a function of state, with
dS =

Note:

qrev
T

S = S2 S1 =

qrev
T

=0

qrev
T

Entropy is a state function, but to calculate S from q

requires a reversible path.

An irreversible Carnot (or any other) cycle is less efficient than a

reversible one.
p

irreversible
isotherm with p ext = p 2

adiabat

adiabat
isotherm (rev.)

12
( w )irrev < ( w )rev wirrev > w rev
U = qirrev + wirrev = qrev + w rev

qirrev < qrev

20.110J / 2.772J / 5.601J

Thermodynamics of Biomolecular Systems
Instructors: Linda G. Griffith, Kimberly Hamad-Schifferli, Moungi G. Bawendi, Robert W. Field

20.110/5.60 Fall 2005

**

Lecture #6

page

An irreversible isothermal expansion requires less heat **

than a reversible one.
irrev = 1 +

also

q2rev
q2rev
<
1
+
= rev
q1irrev
q1rev

qirrev qrev
T

<

(q2 < 0)

qirrev

<0

This leads to the Clausius inequality

v T

qrev
v T = 0
contains
qirrev < 0
v T

Important corollary: The entropy of an isolated system never

decreases
(A): The system is isolated and
irreversibly (spontaneously) changes
from [1] to [2]

(A) irreversible

2
(B) reversible

(B): The system is brought into contact with a heat

reservoir and reversibly brought back from [2] to [1]

qirrev = 0

Path (A):
Clausius

v T

(isolated)

qirrev
T

=0 !

qrev
T

20.110J / 2.772J / 5.601J

Thermodynamics of Biomolecular Systems
Instructors: Linda G. Griffith, Kimberly Hamad-Schifferli, Moungi G. Bawendi, Robert W. Field

20.110/5.60 Fall 2005

Lecture #6

qrev
T

page

= S1 S2 = S 0
S = S2 S1 0

This gives the direction of spontaneous change!

For isolated systems

2
But!

Ssurroundings

S > 0

Spontaneous, irreversible process

S = 0

Reversible process

S < 0

Impossible

S = S2 S1

independent of path

depends on whether the process is

reversible or irreversible
(a)

Irreversible:

Consider the universe as an isolated system

containing our initial system and its
surroundings.

Suniverse = Ssystem + Ssurroundings > 0

(b)

Ssurr > Ssys

Reversible:
=0
Suniv = Ssys + Ssurr

= Ssys
Ssurr

Suniverse 0 for any change in state (> 0 if irreversible, = 0 if reversible)