CHAPTER 5 - THE 2ND LAW OF THERMODYNAMICS

Why do we need the 2

nd
Law? What is wrong with the 1
st
Law?
Not every process that is consistent with the law of conservation of energy can
occur. We know from experience that there is a definite direction for a
spontaneous process.
Examples: - cooling of a cup of coffee
- unrestrained expansion of a gas
- rocks falling from a cliff
- drop of ink diffusing in a glass of water
See Fig 5.1 (overhead)
Intuitively, we know that the reverse process cannot happen spontaneously, even
though they would not violate the 1
st
law. So, an energy balance alone is not
sufficient to tell if a process can occur. We conclude that the first law is
insensitive to the direction of the process.
It has been observed that processes which transfer energy from organized states
to more microscopically disordered states can proceed spontaneously.
An Alternate View: Note that in each case, work must be done to reverse the
process. A spontaneous processes will tend to proceed in the direction that
represents a lost opportunity to do work.
Entropy
How can we define the randomness of energy? The property Entropy can be
defined, which is a measure of the disorder of a system. It is a state property that
can be measured and tabulated in the same way as internal energy or enthalpy.
S =>Entropy (kJ/K)
s => Specific Entropy (kJ/kgK) The reasons for these units will be explained
later in the course (Chapter 6).
Entropy Statement of the 2
nd
Law
Any process that results in an increase in the entropy of an isolated system can
proceed spontaneously
or, stated in a negative way,
Any spontaneous process that results in a decrease in entropy of an isolated
system is impossible.
The entropy of a non-isolated system may increase or decrease, but the entropy
of the system and surroundings must always increase (or at the very best stay the
same). Can you think of some everyday examples?
Mathematically, for any process:
A Reversible Process
Only in an ideal process can . This is called a reversible
process.
Examples of theoretical reversible processes:
stretching or compressing a perfectly elastic spring
oscillating of a pendulum in a perfect vacuum with a frictionless pivot.
In the real world, no process is perfectly reversible. But, sometimes we can come
close.
A Reversible Process is an important concept, which we will revisit later.
Other Statements of the 2
nd
Law of Thermodynamics
There are other statements of the 2nd law, which can be shown to be equivalent.
Clausius Statement: It is impossible for any system to operate in such a way
that the sole result would be energy transfer by heat from a cooler body to a
hotter body.
Of course, it is possible to
transfer heat from a cold body
to hot body, such as with a
refrigerator. But work input
is required.
Implies that it is impossible
to build a refrigerator that
operates without work input.
Kelvin-Planck Statement: It is impossible for any system to operate in a
thermodynamic cycle and deliver a net amount of work to the surroundings,
while receiving energy from a single thermal reservoir.
implies that heat cannot
be converted 100% to work
in a cycle.
Note that the Clausius and Kelvin-Planck statements can be shown to be
equivalent. To do this suppose we had a refrigerator that required no work (i.e.,
that violated the Clausius statement). We can use this machine to create a
machine that violates the K-P statement. See Fig. 5.2
You have to be careful when interpreting the K-P statement. For example,
considered a piston/cylinder containing a gas. If heat is added (from a single
reservoir), the gas will produce net work as it expands.
Does this process violate the K-P statement of the second law?
Note that the Kelvin Planck statement does not rule out the possibility of net
work to the system over a cycle. It just cannot be positive. The best you can do
when exchanging heat with a single reservoir is get zero work out of the cycle.
So, mathematically, the Kelvin-Planck statement is:
(for single reservoir)
The less than and equal to in the above equation corresponds to the presence
or absence of irreversibilities within the cycle.
W
cycle
= 0 for a reversible cycle (single reservoir)
W
cycle
< 0 for a irreversible cycle (single reservoir)
Note that the Kelvin-Planck statement places limits on the maximum possible
efficiency of a cycle. This can be shown as follows:
Recall, that the thermal efficiency of a power producing cycle is :
But Q
C
cannot be zero. (This would violate the K-P statement.) Therefore the
maximum possible efficiency must be less than 1, even under the most ideal
conditions.
This is a surprising result. Usually, one would expected ideal conditions to yield
100% efficiency. But this is not the case.
So, what is for a heat engine? This will be one of the most important
results, which we will derive later in Chapter 5.
In all real systems, irreversibilities are present. Of course, irreversibilities reduce
the thermal efficiency of real cycles.
IRREVERSIBILITIES
Definition: Irreversible Processes
A process is called irreversible if the system and surroundings cannot be exactly
restored to their initial states, after the process has taken place.
Some factors that cause a process to be irreversible:
- friction
- heat transfer across a finite temperature difference
- magnetic hysteresis
- unrestrained expansion of a gas
- inelastic deformation
- mixing of matter with difference compositions
Definition : Reversible Process
A reversible process is one where the system and surroundings can be exactly
restored to their initial states, after the process has taken place.
i.e. (No increase in overall disorder)
More Examples of Reversible Processes:
- a perfectly elastic ball, bouncing in a vacuum.
- adiabatic compression of a gas in a frictionless
piston/cylinder.
- heat transfer across an infinitely small
temperature difference. (Why infinitely small?)
Engineers are interested in reversible processes because work-producing devices
(like engines and gas turbines) deliver the most work when they are reversible.
Also, work-consuming devices (like pumps and fans) consume the least work
when they operate reversibly.
A demonstration that reversible processes deliver the most work and consume
the least work:
Consider the worked needed to return the sliding wall to its initial position.
Very slow process: W
expansion
=W
compression
Fast Process: W
compression
>W
expansion

In the same way, fast expansion of a gas in a piston/cylinder arrangement (such as
the exploding combustion gases in your cars pistons), renders the process
irreversible and some potential work is lost.
It is clear that a reversible process is an idealization. No real world process is
completely reversible.
Irreversibilities reduce the amount of work that can be done by a cycle. This
leads to the Carnot Corollaries. French engineer, Nicolas Carnot, stated the
2nd law in 1824.
The Carnot Corollaries (Nicolas Carnot, 1796-1832)
1. The thermal efficiency of an irreversible power cycle is always less than the
thermal efficiency of a reversible power cycle, when each operates between the
same two thermal reservoirs.
2. All reversible power cycles operating between the same thermal reservoirs
have the same efficiency.
A reversible cycle is a theoretical ideal cycle in which all the processes are
internally reversible.
i.e. no friction, heat transfer across a infinitely small
temperature difference, etc.
The first corollary is perhaps, an expected result since irreversibilities can be
expected to exact a penalty on performance.
The second corollary implies that all reversible cycles must have the same
thermal efficiency, regardless of choice of working fluid and the specific series
of processes in the cycle.
Proof
Defining the Kelvin Temperature Scale
From Carnots second corollary we know that all reversible power cycles
operating between the same reservoirs have the same thermal efficiency,
regardless of the substance used for the cycle.
Since the only distinguishing feature of the reservoirs is their temperature, then: