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3-Entropy As A State Function

Entropy is a state function whose change for a cyclic process is zero. The Carnot cycle is a four stage reversible cycle consisting of two isothermal and two adiabatic processes. For the Carnot cycle, the total entropy change is zero since the heat absorbed from the high temperature reservoir equals the heat rejected to the low temperature reservoir. The efficiency of a heat engine depends only on the temperatures of the reservoirs and not on the details of the engine design according to Carnot's theorem.

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381 views2 pages

3-Entropy As A State Function

Entropy is a state function whose change for a cyclic process is zero. The Carnot cycle is a four stage reversible cycle consisting of two isothermal and two adiabatic processes. For the Carnot cycle, the total entropy change is zero since the heat absorbed from the high temperature reservoir equals the heat rejected to the low temperature reservoir. The efficiency of a heat engine depends only on the temperatures of the reservoirs and not on the details of the engine design according to Carnot's theorem.

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Ariel Raye Rica
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© © All Rights Reserved
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Entropy as a State Function

Chem 153: Physical Chemistry I (Santiago)


Believe the power of statistics.

 Entropy as a State Function. Entropy is a state function. For a cyclic process,


dS = ∫ dqrev/T = 0
 Carnot Cycle. Carnot cycle, named after Sadi Carnot, is a reversible four stage cycle: (1)
Reversible Isothermal Expansion from A to B at T1, (2) Reversible Adiabatic Expansion
from B to C, T falls from T1 to T2, (3) Reversible Isothermal Compression from C to D at
T2, and (4) Reversible Adiabatic Compression from D to A, T rises from T2 to T1.

 Reversible Isothermal Expansion from A to B at T1. The entropy is equal to q1/T1,


where q1 is the heat supplied by the reservoir. For perfect gases, q1 = -w = nRT ln V2/V1, as
shown from the previous discussions.
 Reversible Adiabatic Expansion from B to C, T falls from T1 to T2. For adiabatic
processes, ∆S = 0. The temperature falls from T1 to T2.
 Reversible Isothermal Compression from C to D at T2. The entropy is equal to q2/T2,
where q2 is the heat released to the sink. For perfect gases, q2 = -w = nRT ln V1/V2, as
shown from the previous discussions.
 Reversible Adiabatic Expansion from B to C, T rises from T2 to T1. For adiabatic
processes, ∆S = 0. The temperature rises from T2 to T1.
 Total ∆S. The total entropy change is the sum of the entropy changes of each stage. The
total entropy change is equal to
∆S = (q1/T1) + (q2/T2)
And for a perfect gas
(q1/T1) = -(q2/T2)
And ∆S can be calculated equal to 0.
 Efficiency. The efficiency of a heat engine, η, is defined by Carnot using the following
similar expressions
η = |w|/|q1| = (|q1| - |q2|)/|q1| = 1 – (|q1|/|q2|) = 1 – (T1/T2)
This shows that all reversible engines have the same efficiency regardless of their
construction.

1
 Thermodynamic Temperature. Rearranging the equation for efficiency we can express the
temperature of the cold sink T2 as
T2 = (1 – η)T1
The temperature T2 is the basis of the construction of a thermodynamic temperature scale. With a
known temperature of the reservoir, the temperature can be obtained. Kelvin scale is a
specialized thermodynamic temperature scale where boiling water is the temperature of the
heat source.
 Clausius Inequality. Clausius inequality states that
dS = dqrev/T > dq/T
This is a direct consequence of the relation that more work is done for a reversible change
than an irreversible change.
For an isolated system, dq = 0, which suggests that for a spontaneous irreversible process
dS > 0

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