MIT OpenCourseWare

http://ocw.mit.edu

5.60 Thermodynamics & Kinetics

Spring 2008

For information about citing these materials or our Terms of Use, visit: http://ocw.mit.edu/terms.
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 ⇒ đq = 0 Reversible ⇒ đw = -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 ⎠

γ −1

Cp ⎛T2 ⎞ ⎛V1 ⎞
Define γ ≡ ⇒ ⎜ ⎟ =
⎜ ⎟
CV ⎝T1 ⎠ ⎝V2 ⎠

3 ⎫

CV = R ⎪
2 ⎪ 5
For monatomic ideal gas: ⎬ γ = ( > 1 generally)

5 ⎪ 3

Cp = R
2 ⎪⎭

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

γ
pV ⎛ p2 ⎞ ⎛V1 ⎞
For an ideal gas (one mole) T = ⇒ ⎜ ⎟=⎜ ⎟ ⇒ pV
1 1 = pV
γ γ

R ⎝ p1 ⎠ ⎝V2 ⎠
2 2

pV γ 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
p2 adiabatic expansion

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 ⇒ đq = 0

Constant pext = p2 ⇒ đw = -p2dV

Ideal gas ⇒ dU = CvdT

1st Law ⇒ dU = -p2dV

∴ Cv d T = - p2 dV

Integrating: Cv ( T2 - T 1 ) = - p2 ( V2 - V1 )

⎛ p2 ⎞

Using pV = RT T2 (CV + R ) =T1 ⎜ CV + R⎟

⎝ p1 ⎠

Note 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

đq
• Reversible Ideal Gas processes: Find ∆U , ∆H , q , w , ∫T

(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

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

Ideal gas isotherm: ∆UA = 0 ∆H A = 0

V V đq V2
wA = −RT1 ln 2 qA = RT1 ln 2 ∫T =R ln
V1 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 )

đqB
1st Law: w B = CV (T2 −T1 ) ∫T =0
5.60 Spring 2008 Lecture #5 page 4

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 )

đqC ⎛T ⎞
∫T = CV ln ⎜ 1 ⎟
⎝T2 ⎠

[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
đqA V2 đqB đqC ⎛V ⎞ đq
∫T = R ln ∫T +∫ = R ln ⎜ 2 ⎟ = ∫ A
V1 T ⎝V1 ⎠ T

⎛ đq ⎞
This result suggests that ⎜ ∫ rev ⎟ is a state function!
⎝ T ⎠

∆UD = CV (T3 −T1 )

[D] qD = C p (T3 −T1 )
∆HD = C p (T3 −T1 )

đqD ⎛T ⎞
wD = −R (T3 −T1 ) ∫T = C p ln ⎜ 3 ⎟
⎝T1 ⎠
5.60 Spring 2008 Lecture #5 page 5

∆UE = CV (T1 −T3 )

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

đqE ⎛T ⎞
∫T = CV ln ⎜ 1 ⎟
⎝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

đqA V2 đqD đqE ⎛V ⎞ đq

∫T = R ln ∫T +∫ = R ln ⎜ 2 ⎟ = ∫ A
V1 T ⎝V1 ⎠ T

⎛ đq ⎞
Here again ⎜ ∫ rev ⎟ looks like a state function!
⎝ T ⎠