Entropy

Change in Entropy
Reversible Isobaric Process
Ideal Gas in a Reversible Process
Free Expansion of an Ideal Gas
Microscopic Interpretation of Entropy
Entropy and the Second Law of Thermodynamics
Homework

Change in Entropy
The second law of thermodynamics states that when irreversible (real) processes occur, the disorder in the system plus the surroundings increases
The measure of disorder in a system is called entropy




The change in entropy

equilibrium states is

of a system as it moves through an infinitesimal process between two








where

is the heat transferred in a reversible process between the same two states


of a system as it goes from an initial state to a final state

The change in entropy

is







Entropy is a state variable like internal energy and temperature





The change in entropy for an irreversible process can be determined by calculating the change in
entropy for a reversible process with the same initial and final states

Example 1


Calculate the change in entropy when 0.235 kg of ice melts at 0 C.

Change in Entropy for a Reversible Isobaric Process











 





Change in Entropy for a Reversible Process with an Ideal Gas

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&


& 

&

Note that it is clear from this result that the change in entropy depends only on the properties of the
initial state ( and ) and the properties of the final state ( and )

Free Expansion of an Ideal Gas

Consider the example of free expansion shown below in which gas that is confined in the left half
of an insulated container is allowed to expand into a larger volume
The process is irreversible - it does not occur in reverse with the gas spontaneously collecting
itself in the left half of the container








%



&

The walls are rigid, so

The container is insulated, so

"#

, so

!

From the first law of thermo we have

Free Expansion of an Ideal Gas (contd)

To calculate the change in entropy for free expansion, we need to consider a reversible process
that connects the same initial and final states
We can use the isothermal expansion of an ideal gas


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&


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&







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&
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*
+


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Example 2: One mole of nitrogen undergoes free expansion to double its volume. What is the
change in entropy of the gas?

Microscopic Interpretation of Entropy

Consider the free expansion of an ideal gas
&

If we assume that each molecule occupies a volume

and that each location of a molecule is
equally probable, then the total number of possible locations, or microstates, in the initial volume
is
,

&

&

&

.


1
0 -

molecules in the initial volume is

The number of possible microstates for

0
&

&
,

2
0



-

molecules in the final volume is

Similarly, the number of possible microstates for

0
&
,
3

& 
2

The probability of a given macrostate is proportional to the number of microstates corresponding to the macrostate, and thus the ratio of the probabilities of given initial and final macrostates
occurring is
0
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0

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& 


7


4 
5


0
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96

Taking the natural log and multiplying by Boltzmanns constant we have



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=

 

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& 








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Microscopic Interpretation of Entropy (contd)

Earlier we found that the change in entropy for free expansion of an ideal gas in terms of the
macroscopic thermodynamic variables is
& 





 



(

&



Comparison of the previous two expressions yields the following connection between entropy and
the number of microstates associated with a given macrostate


 ;

>

This is the famous Boltzmanns entropy equation, and is engraved on his tombstone
Example 3: One mole of nitrogen undergoes free expansion to double its volume. Use the microscopic interpretation of entropy to find the change in entropy of the gas?

Entropy and The Second Law of Thermodynamics

The second law of thermo can be stated in terms of entropy as: The entropy of an isolated system
never decreases. It can only stay the same or increase.

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3

If the system is not isolated, then the change in entropy of the system plus the change in entropy
of the environment must be greater than or equal to zero







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Only (idealized) reversible, cyclic processes have

The total entropy of any system plus that of its environment increases as a result of any natural
process

Homework Set 9 - Due Fri. Jan. 30

Read Sections 18.6 - 18.8
Answer Questions 18.8 & 18.11
Do Problems 18.22, 18.23, 18.26, 18.28 & 18.33