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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Definition: A very large system of uniform T, which does not change regardless of the amount of heat added or withdrawn.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.
T 1 (hot) q -w -q 2 q> 0 w< 0 -w= q T 1 (hot) q1 q 1> 0 w< 0 q 2< 0 -w q 1= -w-q 2

IMPOS S IBLE!!

T 2 (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.
1 (hot) q 2> 0 T q 1< 0 -q 1 -q 1= q 2

T 1 (hot) -q 1

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

q2

q2 T 2 (c old)

IMPOS S IBLE!! T 2 (c old)

OK!!

All spontaneous processes are irreversible. (e.g. heat flows from hot to cold spontaneously and irreversibly)

Alternative Clausius 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

Mathematical statement:

qrev = 0

and
dS =

qirrev < 0

qrev
T

is a state function = dS

qrev

S ENTROPY

dS

=0

S = S2 S1 =

2 qirrev qrev > 1 T T

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

1 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


p

T 1 (hot) 1
adiabat isotherm (T 1)

q1 w q2 T 2 (cold)

2
adiabat

4
isotherm (T 2)

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 23 34 41

isothermal expansion at T1 (hot) adiabatic expansion (q = 0) adiabatic compression (q = 0)

U = q1 + w 1

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


U = w 2

U = w1

Efficiency =

work output to surroundings (w 1 + w1 + w 2 + w 2 ) = heat in at T1 (hot) q

1st Law

dU v

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

Efficiency =

q1 + q2 q =1+ 2 q1 q1

Kelvin:

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

V
1

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

T2 V2 = T1 V3

34 41

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

q = 0; w2 = CV (T1 T2 )
Rev. adiabat
T1 V4 = T2 V1

V4 V3

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 )
V1 V4 or
1

T V = 2= 2 T1 V3

V4 V1 = V3 V2 =0

q2 T = 2 q1 T1

q1 q2 + =0 T1 T2

qrev
T

this illustrates the link between heat engines to the mathematical statement of the second law Efficiency
=1+ q2 T =1 2 q1 T1

100% as T2 0 K

For a heat engine (Kelvin): Total work out = w = q1 = 1 T1

q1 > 0, w < 0, T2 < T1

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! For a refrigerator (Clausius): Total work in But
q1 q = 2 T1 T2
T T = w = 2 1 q1 T1 T T w = 1 2 q2 T2

T T2 q1

( w ) < q1

q2 > 0, w > 0, T2 < T1

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

qrev
T

=0

This is consistent with the mathematical statement of the second law, which defines Entropy, a function of state, with
dS =

qrev
T

S = S2 S1 =

qrev
T

Note:

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

1
adiabat

irreversible isotherm with p ext = p 2

12 ( w )irrev < ( w )rev wirrev > w rev


U = qirrev + wirrev = qrev + w rev

2 4
adiabat isotherm (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 +

q2rev q2rev < 1 + = rev q1irrev q1rev


<

(q2 < 0)

also

qirrev qrev
T T

qirrev
T

<0

This leads to the Clausius inequality

v T

qrev T =0 v contains qirrev < 0 T v

Important corollary: The entropy of an isolated system never decreases


(A) irreversible

1
(B) reversible

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

(B): The system is brought into contact with a heat reservoir and reversibly brought back from [2] to [1] Path (A): Clausius

qirrev = 0

(isolated)

v T

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

page

qrev
T

= S1 S2 = S 0 S = S2 S1 0

This gives the direction of spontaneous change!


S > 0 Spontaneous, irreversible process Reversible process Impossible

For isolated systems

S = 0 S < 0

1
But!

2
Ssurroundings

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 Ssurr > Ssys

(b)

Reversible:
=0 Suniv = Ssys + Ssurr = Ssys Ssurr

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