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thermodynamics

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Things to learn

We define the concept of entropy and understand the 2nd law of thermodynamics (Entropy never decreases) We will understand engines and refrigerators as devices interconverting heat and work.

20-2 Irreversible Processes and Entropy Irreversible process Inverse process is improbable ! Fig 20-1 free expansion [entropy is increasing] Entropy : multiplicity of a system Reversible process Inverse process happens [entropy is invariant] .

20-3 Change in Entropy Irreversible process .

Reversible process .

Entropy calculation .

SP 20-1 .

.CP 1 Water is heated on a stove. Find the entropy changes of the water as its temperature rises.

CP 2 Find the entropy changes of the two processes of an ideal gas. .

SP 20-2 .

Entropy as a state function Entropy change is independent of the path. we know the Entropy change. Once we know i and f states. .

SP 20-1 Once again free expansion Gas was the only system (closed). Entropy of the closed system has been increased! Æ irreversible process Corresponding Reversible process Gas + Reservoir was the closed system Entropy of the closed system has been unchanged Æ reversible process Reservoir gave the same dQ to gas at the same T .

20-4 The 2nd Law of Thermodynamics The entropy of a closed system never decreases Reversible process : constant Irreversible process : increasing .

Problem 18 .

(gasoline explosion) Through the expansion of gas. (outside the engine) . (rotate the crank) Partial heat (QL) is lost to the colder reservoir.20-5 The entropy in the real world Heat Engine Heat (QH) is supplied from the hotter reservoir. work W is performed.

= the most efficient engine. .The Carnot Engine = ideal engine (reversible). No energy loss due to friction and turbulence.

The Carnot Engine (Work) Work = Heat in – Heat out .

The Carnot Engine (Entropy) .

The Carnot Engine (Efficiency) Perfect engine impossible .

SP 20-4 .

Input : Work (compressor) Output : QL (heat lost by the cold reservoir) .20-6 Refrigerator Refrigerator is cooling a cold reservoir cooler.

Perfect Refrigerator Æ impossible Perfect Refrigerator is cooling without input Work . Æ violates the 2nd law of Thermodynamics Æ impossible .

If εX > εC. couple X to Carnot refrigerator: Violate the 2nd law of thermodynamics .20-7 The efficiencies of real engines No real engine has efficiency greater than εC.

20-8 A statistical view of entropy Macroscopic definition • dS=dQ/T Microscopic definition • S=k ln W k=Boltzmann constant W=multiplicity W=1 for each microscopic configuration .

Multiplicity calculation S=k ln W Count the number of ways to distribute balls in the two partitions .

Multiplicity calculation As n Æ ∞. system tends to make a transition into a state with more multiplicity. Æ Second law of thermodynamics . the peak value of the W becomes sharper and sharper at n1=n2=n/2 Entropy (log multiplicity) becomes maximum at this point For a system with a large number of particles (order of mol). which has a larger entropy.

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