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5.60 Thermodynamics & Kinetics

Spring 2008

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5.60 Spring 2008

Lecture #9

page 1

Entropy

For a reversible ideal gas Carnot cycle: Efficiency

=
w

qrev

q2rev T = 1 + rev = 1 2
q1 T1

q1 q2 + =0 T1 T2

qrev
T

=0

The efficiency of any reversible engine has to be the same as the Carnot cycle:
T1 (hot) q1 w w q2 T2 (cold) q2 Carnot cycle
=

( w )
q1

( w )
q1

Some reversible engine

Assume > (left engine less efficient than Carnot cycle)

Since the engine is reversible, we can run it backwards. Use the work (-w) out of the Carnot engine as work input (w) to run the left engine backwards. Total work out = 0 (-w = w > 0) But ' >
w w > q1 q1

w w w > = q1 q1 q1

q1 < q1 since q1 < 0, q1 > 0

(q1 + q1 ) > 0

This contradicts the 2nd law (Clausius). This says that we have a net flow of heat into the hot reservoir, but no work is being done! The efficiency of any reversible engine is = 1
T2 T1

5.60 Spring 2008

Lecture #9

page 2

We can approach arbitrarily closely to any cyclic process using a series of only adiabats and isotherms. For any reversible cycle

qrev
T

=0

This defines Entropy, a function of state

dS =

qrev
T

S = S2 S1 =

qrev
T

Note:

Entropy is a state function, but to calculate S requires a reversible path.

An irreversible Carnot (or any other) cycle is less efficient than a reversible one.
p

1
adiabat

irreversible isotherm with pext = p2

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

U = qirrev + wirrev = qrev + w rev

2 4
adiabat isotherm (rev.)

qirrev < qrev

**

An irreversible isothermal expansion requires less heat ** than a reversible one.

irrev

q2rev q2rev = 1 + irrev < 1 + rev = rev q1 q1

(q2 < 0)

also

qirrev qrev <

T T

qirrev
T

<0

5.60 Spring 2008

Lecture #9

page 3

Leads to Clausius inequality

v T

The entropy of an isolated system never decreases

(A) irreversible

qrev T =0 v contains qirrev < 0 T

v

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

0
1

qirrev
T

=0 !

qrev
T

qrev
T

= S1 S2 = S 0 S = S2 S1 0

This gives the direction of spontaneous change!

S > 0 S = 0 S < 0
Spontaneous, irreversible process Reversible process Impossible

For isolated systems

1
But!

2
Ssurroundings

S = S2 S1

independent of path

depends on whether the process is

reversible or irreversible

5.60 Spring 2008

Lecture #9

page 4

(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

Examples of a spontaneous process

T1

T2

Connect two metal blocks thermally in an isolated system (U = 0)

Initially

T1 T2

dS = dS1 + dS2 =

q1
T1

q2
T2

= q1

(T2 T1 )
TT 1 2

( q1 = q2 )

dS > 0 for spontaneous process

if T2 >T1
T2 <T1

q1 > 0 q1 < 0

in both cases heat flows from hot to cold as expected

gas V

vac. V

Joule expansion with an ideal gas

5.60 Spring 2008

adiabatic

Lecture #9

page 5

1 mol gas (V,T)

U = 0
S = Sbackwards

q=0

1 mol gas (2V,T)

w=0

Compress back isothermally and reversibly 1 mol gas (2V,T) = 1 mol gas (V,T)
qrev 0

Sbackwards =

qrev
T

w
T

V
2

RdV 1 = R ln V 2

S = R ln2 > 0

spontaneous

Note that to calculate S for the irreversible process, we needed to q find a reversible path so we could determine qrev and rev .
T