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 #4 page 1

EXPANSIONS, THERMODYNAMIC CYCLES

Reversible Adiabatic Expansion (or compression) of an Ideal Gas

1 mole gas (V1,T1) = 1 mole gas (V2,T2)

adiabatic q = 0 Reversible w = -pd V

Ideal gas dU = Cv d T

From 1st Law dU = -pd V CvdT = -pdV along path

dT dV
CV dT = pdV CV = R
p =RT T V
V
Cp
R CV 1
T2 dT V dV T2 V1 C p CV =R for i.g. T2 V1 CV
CV = R
2
= =
T1 T V V 1
T1 V2 T1 V2

1
Cp T2 V1
Define =
CV T1 V2

3
CV = R
2 5
For monatomic ideal gas: = ( > 1 generally)
5 3
Cp = R
2

[More generally the heat capacity for a molecular species has a

temperature dependence that can be approximated as
C p (T ) = a + bT + cT 2 with a, b, and c tabulated.]

In an adiabatic expansion (V2 > V1), the gas cools (T2 > T1).
And in an adiabatic compression (V2 < V1), the gas heats up.
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 #4 page 2

pV p2 V1
For an ideal gas (one mole) T = = pV
1 1 = pV

R p1 V2
2 2

pV is constant along a reversible adiabat

Recall, for an isothermal process T = constant pV = constant

p
p1 isotherm V2adiabat < V2isotherm
pV=constant because the gas
cools during reversible
pV=const.
p2 adiabatic expansion
adiabat

V1 V2ad V2iso

Irreversible Adiabatic Expansion of an ideal gas against a constant

external pressure

1 mol gas (p1,T1) = 1 mol gas (p2,T2) (pext=p2)

adiabatic q = 0
Constant pext = p2 w = -p2d V
Ideal gas dU = Cv d T
1st Law dU = -p2 dV

Cv d T = - p 2 dV

Integrating: Cv ( T2 - T 1 ) = - p 2 ( V2 - V1 )

p2
Using pV = RT T2 (CV + R ) =T1 CV + R
p1
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 #4 page 3

Note p2 < p1 T2 < T1 Again, expansion cools

Note also (-wrev) > (-wirrev) as expected, less work is

recovered through an
irreversible process

Thermodynamic Cycles

Reversible Ideal Gas processes:

Find U , H , q , w

(I) (II)
p p
(T1) (T1) D (const. p ) (T3)
p1 p1
A (isotherm)
B (T1) A E (const. V)
p2 p2
p3 (rev. C (const. V) (isotherm) (T1)
adiabat) (T2)

V1 V2 V1 V2

For (I)

A
1gas(p1,V1,T1) 1gas(p2,V2,T1)
B
C
1gas(p3,V2,T2)

There are two paths from initial to final states (A) and (B+C). As far
as functions of states (e.g. U, H) are concerned it doesnt matter
which path is taken.
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 #4 page 4

const. T
[A] 1 mol gas (p1,V1,T1) = 1 mol gas (p2,V2,T1)

Ideal gas isotherm: UA = 0 HA = 0

V V
wA = RT1 ln 2 qA = RT1 ln 2
V1 V1

rev.adiabat
[B] 1 mol gas (p1,V1,T1) = 1 mol gas (p3,V3,T2)

Adiabat: qB = 0

UB = CV (T2 T1 )
Ideal gas:
HB = C p (T2 T1 )

1st Law: w B = CV (T2 T1 )

reversible
[C] 1 mol gas (p3,V2,T2) = 1 mol gas (p2,V2,T1)
const. V

UC = CV (T1 T2 )
Constant V: wC = 0 Ideal gas:
HC = C p (T1 T2 )
1st Law: qC = CV (T1 T2 )
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 #4 page 5

[A] vs. [B] + [C]

UA = 0 UB + UC = 0 = UA
HA = 0 HB + HC = 0 = HA

V
qA = RT1 ln 2 qB + qC = CV (T1 T2 ) qA
V1
V
w A = RT1 ln 2 wB + w C = CV (T2 T1 ) w A
V1

UD = CV (T3 T1 )
[D] qD = C p (T3 T1 ) wD = R (T3 T1 )
HD = C p (T3 T1 )

UE = CV (T1 T3 )
[E] wE = 0 qE = CV (T1 T3 )
HE = C p (T1 T3 )

[A] vs. [D] + [E]

UA = 0 UD + UE = UA
HA = 0 HD + HE = HA

V
qA = RT1 ln 2 qD + qE = R (T3 T1 ) qA
V1
V
w A = RT1 ln 2 wD + w E = R (T3 T1 ) w A
V1