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Describe The 2nd law of Thermodynamics

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thermodynamics

Introduce heat engines, which are cycle processes that

convert heat into work.

Show various forms of the second law of thermodynamics

and prove their equivalence, in particular showing that

no engine can be more efficient than a Carnot engine.

Prove Clausius’ theorem.

Show the concept of entropy.

Derive the important equation dU = TdS-pdV, which

combines the first and second laws of thermodynamics.

Introduce the Joule expansion.

**The second law of thermodynamics was develop by three
**

different statements from Carnot, Clausius and Kelvin.

Clausius’s statement of the second law of thermodynamics

“No process is possible whose sole result is the transfer of

heat from a colder to a hotter body”

Example 1:

Pick up a brick of mass, m, and carry it up

to the top of building of height, h, and then

let it fall back to ground level by dropping it

off the top.

All the work done that carrying the brick to

the top of the building will be dissipated in

heat as the brick hits the ground (plus a

small amount of sound).

Work done = mgh

**Kelvin’s statement of the second law of thermodynamics
**

“No process is possible whose sole result is the complete

conversion heat into work”

**These two statements of the second law of
**

thermodynamics do not seem to be obviously connected.

The equivalence of these two statements will be discuss

later.

**The Carnot engine
**

**Kelvin’s statement of the second law of thermodynamics says
**

that you can’t completely convert heat into work.

The Carnot engine will show a conversion from heat to work is

possible.

**A Carnot cycle consists of two reversible
**

adiabats (BC and DA) and two reversible

isotherms (AB and CD).

As shown in the figure, it is operated in

the direction of ABCDA, i.e.,

clockwise around the solid curve.

Heat Q2 enters in the isotherm AB and

heat Q1 leaves in the isotherm CD.

Process: a b c d a

Example 2: Carnot engine

**The Carnot cycle consists of two reversible adiabats and two reversible isotherms
**

for an ideal gas. The engine operates between two heat reservoirs, one at a

higher temperature, Th and one at a lower temperature, Tc. Heat enters and

leaves only during the reversible isotherms (because no heat can enter and leave

during an adiabat). Heat Q2 enters during the expansion AB and heat Q1 leaves

during the compression CD.

**Because the Carnot process is cyclic, the change of internal
**

energy (as state function) in going round the cycle is zero.

Thus, the work done (output) by the engine, W is given by:

W Q2 Q1

**The Carnot engine is drawn as a machine with
**

heat input Q1 from a reservoir at temperature T1,

and two outputs, one of work, W and the other

of heat, Q, which passes into the reservoir at

temperature T2.

The efficiency of an engine is important to

characterize engines.

The efficiency, of an engine is defined as the

ratio of the work out to the heat in,

HOT

Carnot

W

Q1

**Note that since the work out cannot be greater than the heat in (i.e. W Q1)
**

we must have that 1. The efficiency must be below 100 %.

COLD

T1 T2

Example 4:

For the Carnot engine, determine the efficiency in terms of the temperatures

T2 and T1.

Carnot

Q Q1

Q

T

W

2

1 1 1 1

Q1

Q2

Q2

T2

** How does this efficiency compare to that of a real engine? It turns
**

out that real engines are much less efficient than Carnot engines.

Example 5:

A power station steam turbine operates between T1 ~ 800 K and T2 ~ 300 K. If

it were a Carnot engine, it could achieve an efficiency of Carnot,

Carnot 1

300 K

60 %

800 K

**but in fact real power stations do not achieve the maximum efficiency and
**

figures closer to 40 % are typical.

Carnot’s theorem

Of all the heat engines working between two given temperature,

none is more efficient than a Carnot engine.

Reversible engines

Q2’

Q2

E

Q1’

W

T2

Carnot

Carnot

Q1

Q1

T2

Q2’

Q2

W

R

Q1’

T1

T1

E Carnot

R Carnot

** All reversible engines working between two temperatures have
**

the same efficiency, Carnot .

T2 T1

Carnot

T2

**Equivalence of Clausius’ and Kelvin’s statements
**

If a system violates Kelvin’s

statement of the second law of

thermodynamics, one could connect

it to a Carnot engine as shown in (a).

Q2’

(a)

Q2

Kelvin

violator

W

**If a system violates Clausius’
**

statement of the second law of

thermodynamics, one could connect

it to a Carnot engine as shown in (b).

T2

Carnot

Q1

(b)

Clausius

R

violator

Q1

Q1

T2

Q2

Q1

T1

**The first law implies:
**

Q2' W

Q2 W Q1

**The heat dumped in the reservoir at
**

temperature, T2:

Q2 Q2' W

Kelvin violator does not exist

W

T1

**The first law implies:
**

Q2 Q1 W

Clausius violator does not exist

Clausius’ theorem

**In a one Carnot cycle, heat Q2 enters and heat
**

Q1 leaves. Heat is therefore not a conserved

quantity of the cycle.

Q2 T2

Q1

T1

**For heat entering the system at each point,
**

Qrev

Q1 0,

Q

2

T

T2

T1

cycle

dQrev

0

For Carnot cycle,

T

For general cycle, heat dQi enters at a particular

part of the cycle. At this point the system is

connected to a reservoir, which is at

temperature Ti. The total work extracted from

the cycle is W, given by:

W

dQ ,

i

cycle

from the first law of thermodynamics.

**(a) A general cycle in which heat dQi
**

enters in part of the cycle from a

reservoir at temperature Ti. (b) The heat

entering the reservoir at Ti from a

reservoir at temperature T via a Carnot

engine.

**For the heat at each point is supplied via a
**

Carnot engine, each Carnot engine produces

work, dWi, and,

heat to reservoir at Ti

heat to reservoir at T

Ti

T

Thus,

T

dWi dQi 1

Ti

dQi

dQi dWi

Ti

T

Total work produced per cycle =

W+

dW

i

0

cycle

dQi +

cycle

T

T

dQi 1 0

Ti

cycle

dQi

0

T

i

cycle

Clausius’theorem:

For any closed system,

dQi

0,

Ti

Where equality necessarily holds for a reversible cycle (T0).

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