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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:

−w q2rev T
Efficiency ε= = 1 + rev = 1 − 2

qrev q1 T1

q1 q2 đqrev
⇒ +
T1 T2
=0 ⇒ v∫ T
=0

• The efficiency of any reversible engine has to be the same as

the Carnot cycle:

T1 (hot) ( −w ) ( −w ′ )
ε= ε′ =
q1 q1 q1′

w w
Assume ε ′ > ε (left
Some
reversible q2 q2 Carnot engine less efficient
engine T2 (cold) cycle 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)

−w ′ −w w −w w
But ε ' > ε ⇒ > ⇒ > = ⇒ q1 < −q1′ since q1 < 0, q1′ > 0
q1′ q1 q1′ q1 −q1
⇒ − (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!

T2
∴ The efficiency of any reversible engine is ε = 1 −
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.

đqrev
∴ For any reversible cycle v∫ =0
T

• This defines Entropy, a function of state

đqrev 2 đqrev
dS = ⇒ ΔS = S2 − S1 = ∫
T 1 T

Note: Entropy is a state function, but to calculate ΔS requires a

reversible path.

• An irreversible Carnot (or any other) cycle is less efficient

than a reversible one.

p
1→2
1 irreversible
isotherm with pext = p2
( −w )irrev < ( −w )rev ⇒ wirrev > wrev
adiabat 2 ΔU = qirrev + wirrev = qrev + w rev
adiabat
4
isotherm (rev.) 3 ∴ qirrev < qrev

** An irreversible isothermal expansion requires less heat **

than a reversible one.

q2rev q2rev
ε irrev = 1 + irrev < 1 + rev = ε rev (q2 < 0)
q1 q1

đqirrev đqrev đqirrev

also < ⇒ v∫ <0
T T T
5.60 Spring 2008 Lecture #9 page 3

⎧ đqrev
đq ⎪⎪ v∫ T = 0
• Leads to Clausius inequality v∫ T ≤0 contains ⎨
⎪ đqirrev < 0
⎪⎩ v∫ T

The entropy of an isolated system never decreases

(A) irreversible
(A): The system is isolated and
1 2 irreversibly (spontaneously) changes
(B) reversible 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): qirrev = 0 (isolated)

đq
=0 !
2 đqirrev 1 đqrev
Clausius v∫ T ≤0 ⇒ ∫ +∫ ≤0
1 T 2 T

1 đqrev
⇒ ∫ = S1 − S2 = −ΔS ≤ 0
2 T

∴ ΔS = S2 − S1 ≥ 0

This gives the direction of spontaneous change!

ΔS > 0 Spontaneous, irreversible process

For isolated systems ΔS = 0 Reversible process
ΔS < 0 Impossible

1 2 ΔS = S2 − S1 independent of path

But! ΔSsurroundings 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.

ΔSuniverse = ΔSsystem + ΔSsurroundings > 0

∴ ΔSsurr > −ΔSsys

(b) Reversible:

ΔSuniv = ΔSsys + ΔSsurr

′ =0
∴ ΔSsurr
′ = −ΔSsys

Examples of a spontaneous process

T1 T2 Connect two metal blocks thermally in

an isolated system (ΔU = 0)

Initially T1 ≠T2

dS = dS1 + dS2 =
đq1 đq2 (T2 −T1 )
T1
−
T2
= đq1
TT
( đq1 = −đq2 )
1 2

dS > 0 for spontaneous process

⇒ if T2 >T1 ⇒ đq1 > 0 in both cases heat flows

T2 <T1 ⇒ đq1 < 0 from hot to cold as expected

Joule expansion with an ideal gas

gas vac.
V V
5.60 Spring 2008 Lecture #9 page 5

adiabatic
1 mol gas (V,T) =
1 mol gas (2V,T)
ΔU = 0 q=0 w=0

ΔS = − ΔSbackwards Compress back isothermally and reversibly

qrev ≠ 0
1 mol gas (2V,T) = 1 mol gas (V,T)

đqrev đw V RdV 1
ΔSbackwards = ∫ = −∫ = ∫V = R ln
T T 2 V 2

∴ ΔS = R ln2 > 0 spontaneous

Note that to calculate ΔS for the irreversible process, we needed to

đq
find a reversible path so we could determine đqrev and ∫ rev .
T