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the hot region and the cold region is the measure of the

available energy.

However, the second law states that, in an isolated

system heat must flow from a hot region to a cold.

With time, therefore, this temperature difference must

decrease, for as the heat flows in the only direction it can

flow, the hot region cools down and the cold region

warms up.

Consequently, the available energy decreases with

time. Since the total energy remains constant, the

unavailable energy must increase as the available

energy decreases.

If an ideal frictionless reversible engine removes

Q

h

from some substance at T

h

, does some work,

and delivers Q

c

to some other substance at T

c

, then

Q

h

/Q

c

= T

h

/ T

c

or

Q

h

/ T

h

= Q

c

/ T

c

.

Clausius used the last expression to introduce

entropy, S.

Entropy

Definition: Consider any infinitesimal process in

which a system changes from one equilibrium state

to another. If dQ

r

is the amount of energy transferred

by heat when the system follows the reversible path

between the states, then the change in entropy dS is

equal to this amount of energy for the reversible

process divided by the absolute temperature of the

system, T:

dS = dQ

r

/T

The temperature is assumed constant because the

process is infinitesimal.

Entropy has units of Joules per Kelvin [J/K]

Entropy

Calculating entropy always use temperature in

Kelvin!

Consider a system in two different conditions, for

example 1 kg of ice at 0

o

C, which melts and turns into

1 kg of water at 0

o

C. We associate the entropy with

each condition.

The entropy of any substance is a function of the

condition of the substance.

For an ideal gas it is a function of its temperature and

volume, and for a solid and liquid it is a function of its

temperature and internal structure.

Entropy

The entropy is independent of the past history of the

substance. The entropy of the 1 kg of water at 0

o

C is the

same if we obtained the water from ice, or if we cooled the

water from room temperature down to 0

o

C.

Entropy is a state function (as temperature and internal

energy) because the change in entropy does not depend on

the path followed.

Sign:

When the energy is absorbed by the system, change in the

heat is positive and the entropy of the system increases.

When energy is expelled by the system, dQr is negative, and

the entropy of the system decreases.

Entropy

To calculate the change in entropy for a

finite process we need to integrate the energy

transferred by heat divided by the temperature

(which is not constant) along a reversible

path:

S =

=

f

i

f

i

T

dQr

dS

In Carno-engine, the entropy of the substance at T

h

decreases by Q

h

/ T

h

and the entropy of the

substance at T

c

increases by the same amount.

There is no net change in entropy, if we consider

the entire system.

But a real engine always delivers more heat at T

c

than a reversible engine. For a real engine Q

c

/ T

c

is always greater than Q

h

/ T

h

.

The entropy of the substance at T

h

decreases, but

the entropy of the substance at T

c

increases by a

larger amount. The entropy of the whole system

increases.

The total entropy of an isolated system is always

increasing is another way of stating the second law

of thermodynamics.

A closed system is a system that does not interact in

any way with its surroundings. In practice there are

really no closed isolated systems except, perhaps,

the universe as a whole.

Therefore we state the second law in the following

way: The total entropy of the universe is always

increasing.

Entropy

Entropy in thermal processes measures the extent to which

energy of a system is available for conversion to work.

If a system undergoing an infinitesimal reversible change takes

in a quantity of heat dQ at absolute temperature T, its entropy is

increased by:

dS = dQ

r

/T

The area under the absolute temperature-entropy graph for a

reversible process represents the heat transferred in the process.

S

T

Q

For an adiabatic process, there is no heat transfer and the

temperature-entropy graph is a straight line, the entropy remaining

constant through the process.

The first law of thermodynamics says that the total quantity of energy in

the universe remains constant. This is the principle of the conservation of

energy.

The second law of thermodynamics states that the quality of this energy

is degraded irreversibly. This is the principle of the degradation of

energy.

The first principle establishes the equivalence of the different forms of

energy (radiant, chemical, physical, electrical, and thermal), the possibility

of transformation from one form to another and the laws that govern these

transformations.

Physical, chemical, and electrical energy can be completely changed into

heat. But the reverse (heat into physical energy, for example) cannot be

fully accomplished without outside help or without an inevitable loss of

energy in the form of irretrievable heat.

This does not mean that the energy is destroyed; it means that it

becomes unavailable for producing work.

More About Change in Entropy

dQ

r

is measured along a reversible path,

even if the system may have followed an

irreversible path

The meaningful quantity is the change in

entropy and not the entropy itself

For a finite process,

Change in Entropy

The change in entropy of a system

going from one state to another has the

same value for all paths connecting the

two states

The finite change in entropy depends only

on the properties of the initial and final

equilibrium states

S for a Reversible Cycle

S = 0 for any reversible cycle

In general,

This integral symbol indicates the integral is

over a closed path

S for a Quasi-Static, Reversible Process

Assume an ideal gas undergoes a quasi-

static, reversible process

Its initial state has T

i

and V

i

Its final state has T

f

and V

f

The change in entropy is

This demonstrates that S depends on only

the initial and final states and not the path

between the states

Entropy and Heat

The change in entropy depends only on the

endpoints and is independent of the path

followed

The entropy change for an irreversible

process can be determined by calculating

the change in entropy for a reversible

process that connects the same initial and

final points

Entropy Changes in Irreversible Processes

To calculate the change in entropy in a real

system, remember that entropy depends

only on the state of the system

Do not use Q, the actual energy transfer in

the process

Distinguish this from Q

r

, the amount of energy

that would have been transferred by heat along a

reversible path

Q

r

is the correct value to use for S

In general, the total entropy and therefore

the total disorder always increases in an

irreversible process

The total entropy of an isolated system

undergoes a change that cannot decrease

This is another statement of the second law of

thermodynamics

Entropy Changes in Irreversible Processes

If the process is irreversible, then the total

entropy of an isolated system always

increases

In a reversible process, the total entropy of an

isolated system remains constant

The change in entropy of the Universe

must be greater than zero for an

irreversible process and equal to zero for a

reversible process

Entropy Changes in Irreversible Processes

Heat Death of the Universe

Ultimately, the entropy of the Universe should

reach a maximum value

At this value, the Universe will be in a state of

uniform temperature and density

All physical, chemical, and biological processes

will cease

The state of perfect disorder implies that no energy is

available for doing work

This state is called the heat death of the Universe

S in Thermal Conduction

The cold reservoir absorbs Q and its entropy

increases by Q/T

c

At the same time, the hot reservoir loses Q and

its entropy decreases by -Q/T

h

Since T

h

> T

c

, the increase in entropy in the cold

reservoir is greater than the decrease in entropy

in the hot reservoir

Therefore, S

U

> 0

For the system and the Universe

Adiabatic Free Expansion

This is an example of adiabatic

free expansion

The process is adiabatic because

it takes place in an insulated

container

Because the gas expands into a

vacuum, it does not apply a force

on a piston and W = 0

Since Q = 0 and W = 0, E

int

= 0

and the initial and final states are

the same

No change in temperature is

expected

S in a Free Expansion

Consider an adiabatic free expansion

Q = 0 but cannot be used since that is for

an irreversible process

S in Free Expansion

For an isothermal process, this becomes

?S = nRln(V

f

/V

i

)

Since V

f

> V

i

, S is positive

This indicates that both the entropy and

the disorder of the gas increase as a result

of the irreversible adiabatic expansion

S in Calorimetric Processes

The process is irreversible because the system

goes through a series of nonequilibrium states

Assuming the specific heats remain constant

and no mixing takes place:

If mixing takes place, this result applies only to

identical substances

S will be positive and the entropy of the Universe

increases

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