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5.60 Thermodynamics & Kinetics

Spring 2008

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5.60 Spring 2008

Lecture #5

page 1

Reversible Adiabatic Expansion (or compression) of an Ideal Gas 1 mole gas (V1,T1) = 1 mole gas (V2,T2) adiabatic q = 0 Ideal gas Reversible dU = Cv d T w = -pd V

From 1st Law

dU = -pd V
CV dT dV = R T V
T2 V1 = T1 V2
R CV

CvdT = -pdV along path

CV dT = pdV

p =RT V
2

CV

T2

T1

V dV dT = R V V T
1

C p CV =R for i.g.

T2 V1 CV = T1 V2

Cp

Define

Cp CV

T2 V1 =
T1 V2

For monatomic ideal gas:

5 ( > 1 generally)
= 5 3
Cp = R 2

CV = R 2

In an adiabatic expansion (V2 > V1), the gas cools (T2 > T1). And in an adiabatic compression (V2 < V1), the gas heats up. For an ideal gas (one mole)
pV
pV T = R
p2 V1 = p1 V2
pV 1 1 = pV 2 2

is constant along a reversible adiabat

For an isothermal process

T = constant

pV = constant

5.60 Spring 2008

Lecture #5

page 2

p p1 V2adiabat < V2isotherm because the gas cools during reversible adiabatic expansion V2ad V2iso

p2 V1

Irreversible Adiabatic Expansion of an ideal gas against a constant external pressure

1 mol gas (p1,T1) = 1 mol gas (p2,T2) adiabatic Constant pext = p2 Ideal gas 1st Law (pext=p2)

q = 0
w = -p2dV
dU = CvdT
dU = -p2dV

Integrating: Using pV = RT Note

Cv d T = - p2 dV Cv ( T2 - T 1 ) = - p2 ( V2 - V1 )
T2 (CV + R ) =T1 CV +

p2
R p1

p2 < p1

T2 < T1

Again, expansion cools

Note also (-wrev) > (-wirrev)

Less work is recovered through an irreversible process

5.60 Spring 2008

Lecture #5

page 3

Some Thermodynamic Cycles

Reversible Ideal Gas processes: Find U , H , q , w ,

p p1 p2 p3

(I)
(T 1)

p p1 p2
(T 1)

(II) D (const. p ) A
(isotherm) (T 3)

A (isotherm) B
(rev. adiabat) (T 1) (T 2)

E (const. V)
(T 1)

C (const. V)

V1

V2

const. T

V1

V2

[A]

1 mol gas (p1,V1,T1)

1 mol gas (p2,V2,T1)

Ideal gas isotherm:

V wA = RT1 ln 2 V1

UA = 0
V qA = RT1 ln 2 V1
rev.adiabat

H A = 0

=R ln

V2 V1

[B]

1 mol gas (p1,V1,T1)

qB = 0

1 mol gas (p3,V3,T2)

Adiabat: Ideal gas:

UB = CV (T2 T1 )
HB = C p (T2 T1 )
w B = CV (T2 T1 )

1st Law:

qB

=0

5.60 Spring 2008

Lecture #5
reversible const. V

page 4

[C]

1 mol gas (p3,V2,T2)

wC = 0

1 mol gas (p2,V2,T1) Ideal gas:

Constant V: 1st Law:

UC = CV (T1 T2 ) HC = C p (T1 T2 )

qC = CV (T1 T2 )
T = CV ln 1 T2

qC

[A]

vs.

[B] + [C]

UA = 0 HA = 0
V qA = RT1 ln 2 V1 V w A = RT1 ln 2 V1

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

qB + qC = CV (T1 T2 ) qA wB + w C = CV (T2 T1 ) w A

qA

= R ln

V2 V1

qB

qC
T

V q = R ln 2 = A T V1

q This result suggests that rev is a state function! T

[D]

UD = CV (T3 T1 ) HD = C p (T3 T1 )

qD = C p (T3 T1 )

wD = R (T3 T1 )

qD

T = C p ln 3 T1

5.60 Spring 2008

Lecture #5

page 5

[E]

UE = CV (T1 T3 ) HE = C p (T1 T3 )

wE = 0

qE = CV (T1 T3 )

T
[A] vs.

qE

T = CV ln 1 T3

[D] + [E]

UA = 0 HA = 0
V qA = RT1 ln 2 V1 V w A = RT1 ln 2 V1

UD + UE = UA HD + HE = HA
qD + qE = R (T3 T1 ) qA wD + w E = R (T3 T1 ) w A

qA

= R ln

V2 V1

qD

qE
T

V q = R ln 2 = A T V1

q Here again rev looks like a state function! T