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 #7

page 1

Entropy, Reversible and Irreversible Processes and

Disorder
Examples of spontaneous processes

T1

Connect two metal blocks thermally in

an isolated system (U = 0)

T2

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

gas
V

vac.
V

q1 > 0
q1 < 0

in both cases heat flows

from hot to cold as expected

Joule expansion with an ideal gas

1 mol gas (V,T)

U = 0

adiabatic

q=0

1 mol gas (2V,T)

w=0

Need a reversible path to compute S from q! Close the cycle and go

back to the initial state reversibly and isothermally
S = Sbackwards

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 #7

page 2

qrev 0

1 mol gas (2V,T) = 1 mol gas (V,T)

Sbackwards =

qrev

w
T

V
2

RdV
1
= R ln
V
2

spontaneous

S = R ln2 > 0

IMPORTANT!! To calculate S for the irreversible process, we

needed to find a reversible path so we could determine

qrev and

qrev
T

Mixing of ideal gases at constant T and p

nA A (g, VA, T) + nB A (g, VB, T) = n (A + B) (g, V, T)

nA
VA

nB
VB

spontaneous
mixing

n = nA + nB
V = VA + VB

To calculate Smix , we need to find a reversible path between

the two states.
constant T

A+ B
piston
permeable
to A only

piston
permeable
to B only

Sdemix = Smix

back to initial state

function of state

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 #7

page 3

For demixing process

U = 0

qrev = w rev = pAdVA + pB dVB

work of compression of each gas

Sdemix =

VA p dV
VB p dV
V
dqrev
V
= A A + B B = nAR ln A + nB R ln B
V
V
T
T
T
V
V

Put in terms of mole fractions

Ideal gas

XA =

VA
V

XB =

XA =

nA
n

XB =

nB
n

VB
V

Sdemix = nR [XA ln X A +XB ln XB ]

Smix = nR [XA ln XA +XB ln XB ]

Since XA , XB < 1

Smix > 0

mixing is always spontaneous

The mixed state is more disordered or random than the

demixed state.
Smixed > Sdemixed

This is a general result:

Entropy is a measure of the disorder of a system

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 #7

page 4

For an isolated system (or the universe)

S > 0
S = 0
S < 0

Spontaneous, increased randomness

Reversible, no change in disorder
Impossible, order cannot happen in isolation

There is an inexorable drive for the universe to go to a

maximally disordered state.

Microscopic understanding: Boltzmann Equation of Entropy:

S = k ln
Where k is Boltzmanns constant (k=R/NA).
And is the number of equally probable microscopic
arrangements for the system.
This can also be used to calculate S
In the case of the Joule expansion of an ideal gas in volume V
expanding to a volume 2V (as on the first page of these notes):
if we divide the initial volume V into m small cubes, each with
volume v, so that mv=V, the number of ways of placing the N
molecules of ideal gas into these small cubes initially is mN.
After the expansion the number of ways of placing the n
molecules of ideal gas into the now 2m small cubes is (2m)N.

The number of probably microscopic arrangements initially is:

N
N
( m ) , or = C ( m ) (C is a constant)

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 #7

page 5

After the expansion it is:

N

(2m ) , or = C (2m )

So using Boltzmanns equation to calculate S for the

expansion:
N
S = k ln (2m ) k ln m N = kN ln 2 = R ln 2

As we had found above!

More examples of S calculations

In all cases, we must find a reversible path to calculate
(a)

qrev
T

Mixing of ideal gases at constant T and p

nA A (g, VA, T) + nB A (g, VB, T) = n (A + B) (g, V = VA + VB, T)

Smix = nR [X A ln X A +XB ln XB ]

(b) Heating (or cooling) at constant V

A ( T1 , V) = A ( T2 , V )
S =

qrev
T

T2

CV dT
T

if CV is

T -independent

T
CV ln 2
T1

[Note S > 0 if T2 >T1 ]

(c) Reversible phase change at constant T and p
e.g. H2O (l, 100C, 1 bar) = H2O (g, 100C, 1 bar)

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 #7

page 6

q p = Hvap
Svap (100C ) =

(d)

q pvap
Tb

H vap

(Tb = boiling Temp at 1 bar)

Tb

Irreversible phase change at constant T and p

e.g. H2O (l, -10C, 1 bar) = H2O (s, -10C, 1 bar)

This is spontaneous and irreversible.
\

We need to find a reversible path between the two states

to calculate S.
irreversible

H2O (l, -10C, 1 bar)

H2O (s, -10C, 1 bar)

qrev = C p ( A )dT

H2O (l, 0C, 1 bar)

qrev = C p ( s ) dT
reversible

rev
p

H2O (s, 0C, 1 bar)

= Hfus

Note: Hfus is for the process going from the solid state to the
liquid state, the opposite of what we have above, same for Sfus.
S = Sheating Sfus + Scooling
=

Tfus

S =

Hfus

C p ( A ) dT Hfus
T C p ( s ) dT
+
+
Tfus
T
Tfus
T

S =

Hfus

Tfus

T1

Tfus
T1

+ C p ( A ) C p ( s ) ln

dT

C p ( A ) C p ( s )
T

if Cp values are T-independent