Entropy, Gibbs Energy, The

Second Law of Thermodynamics

Basic concepts
Lesson 5
The second law of thermodynamics:The entropy of the universe is always

increasing Éva or

No cyclic process can convert heat into work with 100% ef ciency

Heat cannot ow back out of cold reverse (Heat ows from hot to cold)
Entropy (rudolf Clausius)

Entropy was developed by him , it was known that the engines of the day
converted only small portions of their heat into useful work and the rest is lost .

Clausius goal was to account for this loss”the portion of energy in a heat engine
that is lost as waste heat and cannot be converted back into usable work.

-While converting any energy from one form to another form there are always
some losses associated with that conversion. Most of the cases friction is a major
loss which in turn dissipates in to heat.
So,

work to heat
-whenever we want to convert **work to heat** even the losses like friction will
also dissipates as Heat. So, there must be no losses because even losses are
converting to heat energy.
-But, this will not happens while converting **heat to work.** Because losses are
also dissipated as Heat. Means some heat energy is lost during this process. So, we
can't convert heat completely in to work.

nt to work
Sadi Carnot Digram explained:
“Heat engines use heat to produce work(**steam locomotives** heat-steam -work
it absorbed heat from coal furnaces to generate stem which would move piston
connect to trains wheel system ”

the only way to achieve 100% efficiency would be if every process in the engine
were reversible

The Carnot diagram serves as a standard to measure the efficiency of real

engines and illustrates fundamental thermodynamic principles
A few years later he coined the term entropy. Clausius
himself said he took the Greek word trope meaning
“transformation” and put it in a form intended to resemble
the word energy. So, from trope and energy he got entropy.
The change in entropy as the result of a process is defined as
The change in ΔS = Q/T 8
where S is the entropy and Q is the heat irreversibly lost to
the surroundings at absolute temperature T. Notice that the
units on entropy are energy units divided by temperature
units, for example, joules per degree celsius.
If a process or transformation involves passing the heat
through a working body (for example, a heat engine) so that
the heat is passing from a place at temperature T1 to a place
at temperature T2, then the entropy change is defined as
ΔS = Q (1/T2 - 1/T1)
2
PROBLEM
If the heat engine transfers heat from a body at
350 K to a body at 300 K, what is the entropy
change for this process?
SOLUTION
From prev. Prob. the amount of heat lost is 397 J.
The entropy change in going from 350 K to 300 K
is then:

ΔS =(397 J) (1/300K – 1/ 350K) = 0.189 J/K

DS a 9 1 1 7
Problem. heat engine takes 400 J of heat and converts it into
3 J of work. Assuming that reversing the process will convert
all of the work back into heat, how much of the original heat
is not compensated for by reversing the process? What is the
entropy change for this process at a temperature of 298 K?
SOLUTION
The amount of heat not compensated for by reversing the
process is Still
Uncompensated heat = original heat - work back into heat
The original heat is 400 J. Assuming reversing the process
converts all the work back into heat, the heat compensated
for by converting the work back into heat is 3 J. Therefore the
uncompensated heat is
Uncompensated heat = 400 J - 3 J = 397 J step
The entropy change, by definition, is
ΔS=Q/T = 397 J / 298 K = 1.33 J/K 82
5
Entropy is actually a measure of disorder in a system
order and disorder relate directly to the number of different ways of
accomplishing one particular thing.
The more ways there are for a system to do one particular thing , the more
disorder and entropy the system has.
For example, when there are only a few ways for the molecules of a system to
arrange themselves to achieve a particular temperature, system is highly ordered.
But when there are many different ways , then we say that the system is
disordered.

The probability of obtaining the specific arrangement of all heads (HHH) is

1/8 or 0.125. This means that, on average, you would need to shake the tray eight
times

As you increase the number of coins, the total number of possible

arrangements increases exponentially. For 10 coins, there are

210=1024 arrangements, making the probability of all heads

(HHHHHHHHHH)

1/1024,which is approximately 0.0009766, or about 0.001. Thus, the more coins you
have, the less likely you are to return to the all-heads arrangement after shaking
the tray.
Gibbs energy
This idea that it is impossible to convert all of the energy into work without some
loss gave rise to the second law of thermodynamics.
**The free energy as Gibbs** defined it is It is as
G= H - TS. where H is enthalpy, T is the absolute temperature, and S is the entropy.
that Gibbs energy is what remains of the enthalpy after subtracting out the energy
loss due to entropy. Get high test scores

Gibbs energy and spontaneity of a process

The Gibbs energy change for process is defined as :

Gibbs energy of the final state is always less than that of the initial state. That is,

for a process that happens spontaneously (i.e., on its own, with no outside push),
Gibbs energy always decreases; G is negative.

Gibbs found it. Just as the force of gravity causes a ball to roll down hill, so too,
for any process that takes a system from state A to state B, if state B has less
Gibbs energy than state A, then the process will proceed spontaneously, rolling
down the Gibbs energy hill from A to B.
\
Second law of thermodynamics

- The universe is winding down. like more disorder

meaning
- Heat spontaneously flows from a place of higher temperature to a place of lower
temperature. And not in the reverse direction
- When converting energy into work, some of the energy is always lost to heat.
- In any process, the entropy of a closed system will either increase or remain
constant.
- In any process, the entropy of the open system and its surroundings, taken
together, will either increase or remain constant.
- In any process, a system taken together with its surroundings will always go
from a more ordered state to a less ordered state.
- It is possible to convert one form of energy into another
- It is not possible to convert back heat completely into work

The second law of thermodynamics states that in an isolated system, entropy

tends to increase, leading to greater disorder. While living organisms can locally
decrease entropy by organizing themselves, they do so by consuming energy and
matter from their environment, which ultimately increases the overall entropy of
the universe. Thus, although life creates order locally, it does not violate the
second law, as the total disorder, when considering the entire system, still
increases.
The Gibbs function as driver of biophysical processes

We can see from the Gibbs function that there are three things that contribute to
negative 4G and thus to rolling down the Gibbs energy hill and to driving a
process forward.

1. Releasing energy. When a system goes from a higher-energy state to a lower

energy state, it releases energy; its enthalpy decreases. AH is negative, and a
negative 4H contributes toward a decrease in Gibbs energy.
2. Increasing disorder. When a system goes from more ordered to less ordered, its
entropy increases, AS is positive, and so, all else being equal, its Gibbs energy
decreases.
3. Changing temperature. Note that the effect of temperature depends on whether
the entropy change is positive or negative. For a positive entropy change,
increasing temperature contributes to a favorable Gibbs energy change.

In such a case if the process is driven forward primarily by releasing energy,

then the process is said to be **enthalpy driven**.

On the other hand if the process is driven forward primarily by increasing

disorder, then the process is said to be **entropy driven.**
 Entropy
The idea of entropy was developed by Rudolf
Clausius in the mid-1800s. It was well known at the
time that heat engines of the day converted only a
small portion of their heat into useful work. Typically
only about 1% of the heat was transformed. The rest of
the heat was lost, dissipated, merely warming up the
surroundings.
Clausius’s goal was to account quantitatively for this loss.
He originally called this lost energy the “equivalence
value of all uncompensated transformations,” meaning
that it was equivalent to the portion of the original heat
that could not be compensated for by transforming the
resulting work back into heat.
Although Clausius explained how he came up with
the term entropy, he never indicated why he chose
the letter [S] for entropy. Some have speculated that
it was in honor of another famous early researcher of
thermodynamics, Sadi Carnot. Figure shows a
diagram by Sadi Carnot illustrating the flow of heat
and work in a heat engine.

Hot Cold

Diagram of heat engine by Sadi Carnot from the year 1824

 Entropy Is Related to the Number of
Ways of Doing Something
It is worth mentioning here that entropy is related to order
and disorder. You may have already heard this concept.
Although Clausius originally defined entropy as a simple
thermodynamic property (related to energy and work),
research over the years has shown that entropy is actually a
measure of disorder in a system. But what do we mean by
disorder? For now, let’s just say that order and disorder in
physics are not, as common sense might imply, a matter of
neat versus messy. Rather, order and disorder relate directly
to the number of different ways of accomplishing one
particular thing.
The more ways there are for a system to do one
particular thing or to be in one particular state,
the more disorder and the more entropy the
system has. For example, when there are only a
few ways for the molecules of a system to
arrange themselves to achieve a particular
temperature, then we say that the system is
highly ordered. But when there are many
different ways for the same molecules to achieve
a given temperature, then we say that the
system is disordered.
 The ordering of
three coins
Coin Coin Coin
1 2 3 As an example, consider three coins arranged heads up on
H H H a tray. We will consider this an ordered arrangement.
Suppose that we now shake the tray so that each coin has
H H T
an equal chance of landing on the tray with either head or
H T H tail up. The possible arrangements of coins that we may
T H H obtain are shown in table. Note that there are eight
H T T possible outcomes of tossing the three coins. Of these, only
T H T one yields the original ordered arrangement of three heads
(H,H,H). Because the probabilities of obtaining any one of
T T H
the coin arrangements in Table 1. are given. The
T T T
probability of obtaining the three-head arrangement after shaking
the tray once is 1/8, or 0.125; that is, on the average, we must
toss the coins eight times before we can expect to see the three-
head arrangement again. As the number of coins in the
experiment is increased, the probability of returning to the
ordered arrangement of all heads decreases. With 10 coins on the
tray, the probability of obtaining all heads after shaking the tray is 0.001.
 Gibbs Energy
About 10 years after Clausius coined the term
entropy, Josiah Willard Gibbs used Clausius’s
concept of entropy to define available energy,
energy available to do useful work. Later Gibbs
renamed it free energy, meaning the energy that is
free to do useful work as compared with energy
that is bound to be lost through dissipation as
entropy. This latter way of thinking reflected the
increasing realization that some heat energy is
inevitably lost and simply can never be converted into
work no matter how hard one tries.
This idea that it is impossible to convert all of
the energy into work without some loss gave
rise to the second law of thermodynamics. The
free energy as Gibbs defined it is now called
Gibbs free energy, or simply Gibbs energy, or
the Gibbs function. It is defined as G = H - TS
where H is enthalpy, T is the absolute temperature,
and S is the entropy. You can see clearly from this
definition that Gibbs energy is what remains of the
enthalpy after subtracting out the energy loss due
to entropy.
Gibbs Energy Tells Us Something about
the Spontaneity of a Process
The Gibbs energy change for a process is defined as
ΔG = Δ H - T ΔS

It didn’t take long for scientists to realize that if we

measure the Gibbs energy change for a process that
happens spontaneously, then the Gibbs energy of the final
state is always less than that of the initial state. That is,
for a process that happens spontaneously (i.e., on its own,
with no outside push), Gibbs energy always decreases;
ΔG is negative.
This was in fact what Gibbs was striving for when he
proposed a way to measure the available energy. Gibbs
knew well, from the branch of physics called mechanics,
that a force is what moves a physical object. He also knew
that there is a simple mathematical relation between force
and movement (F = ma). Physical chemists at that time
were looking for a property analogous to force which could
be measured and which could be shown to be the force
that drives chemical reactions. Gibbs found it. Just as the
force of gravity causes a ball to roll down hill, so too, for
any process that takes a system from state A to state B, if
state B has less Gibbs energy than state A, then the process
will proceed spontaneously, rolling down the Gibbs energy
hill from A to B.
Second Law of Thermodynamics

There are many imaginable phenomena that are not forbidden

by the First Law of Thermodynamics but still do not occur. For
example, when an object falls from a table to the ground, its
potential energy is first converted into kinetic energy; then, as
the object comes to rest on the ground, the kinetic energy is
converted into heat. The First Law of Thermodynamics does
not forbid the reverse process, whereby the heat from the floor
would enter the object and be
converted into kinetic energy, causing the object to jump back
on the table. Yet this event does not occur. Experience has
shown that certain types of events are irreversible. Broken
objects do not mend by themselves. Spilled water does not
collect itself back into a container. The irreversibility of these
types of events is intimately connected with the probabilistic
behavior of systems comprised of a large ensemble of
The Second Law of Thermodynamics
No review of thermodynamics would be complete
without some discussion of the second law of
thermodynamics. In all likelihood you’ve heard of the
second law and learned something about it. And you
probably know that it has something to do with
entropy increasing. Perhaps you even know there
are many ways to state the second law of
thermodynamics, and as different as they all may
sound, they are all various views of the same thing.
For example:
• The universe is winding down.
• Heat spontaneously flows from a place of higher
temperature to a place of lower temperature.
• When converting energy into work, some of the
energy is always lost to heat.
• In any process, the entropy of a closed system will
either increase or remain constant.
• In any process, the entropy of the open system and
its surroundings, taken together, will either increase
or remain constant.
• In any process, a system taken together with its
surroundings will always go from a more ordered
state to a less ordered state.
Some statements of the second law are very
precise. Others, such as “The universe is winding
down,” can be ambiguous. Care must be taken not
to misinterpret their meaning. For example, it is not
scientifically correct to make statements like “His dorm
room is proof of the second law of thermodynamics.”
When a living thing develops from an undifferentiated
mass of cells to a fully grown plant or animal, it is clear
that it has gone from a less ordered state to a more
ordered state. Because of this fact and the fact that living
things continue to propagate their order by having
offspring, scientists have speculated that living things
may somehow violate the second law.
 Or, at least, they considered it a possibility there are
physical laws we have yet to discover that are apparent
only in the case of living matter. But living things are
open systems. When taken together with their
surroundings, the impact of the living is to increase the
disorder of the environment to a greater extent than
they increase their own order. Overall the result is an
increase in disorder and the second law of
thermodynamics is not violated.
 The Gibbs Function as the Driver of Biophysical
Processes
For the most part (and this may strike you as odd)
biophysics is not concerned with the second law of
thermodynamics, at least not as stated. What
concerns us more is the Gibbs function. The Gibbs
function effectively has the second law of
thermodynamics built into it, so by focusing on the
Gibbs function alone, everything is taken care of.
In this context we can make the following statement,
which is akin to other statements of the second law:
All else being equal, in any process, an increase
in entropy makes a favorable contribution to the
Gibbs energy change, whereas a decrease in
entropy makes an unfavorable contribution to
the Gibbs energy change. By favorable and
unfavorable we mean whether or not the process
is driven forward. So forget about the second law of
thermodynamics. Well, don’t actually forget about it,
but focus on biophysical processes in terms of the
Gibbs function being the force that drives the
process.
ΔG = ΔH - T ΔS
 ΔG = ΔH - T ΔS
We can see from the Gibbs function that there are three things that
contribute to negative ΔG and thus to rolling down the Gibbs energy hill
and to driving a process forward.
1. Releasing energy. When a system goes from a higher-energy state to
a lower energy state, it releases energy; its enthalpy decreases. ΔH is
negative, and a negative ΔH contributes toward a decrease in Gibbs
energy.

2. Increasing disorder. When a system goes from more ordered to less

ordered, its entropy increases, ΔS is positive, and so, all else being
equal, its Gibbs energy decreases.

3. Changing temperature. Note that the effect of temperature depends on

whether the entropy change is positive or negative. For a positive
entropy change, increasing temperature contributes to a favorable Gibbs
energy change.
Some processes are driven forward by simultaneously
releasing energy and increasing disorder. For other
processes it may be the case that either the enthalpy
change or the entropy change are unfavorable, yet the
process is still driven forward because the overall Gibbs
energy change is favorable. In such a case if the process
is driven forward primarily by releasing energy, then the
process is said to be enthalpy driven. On the other hand
if the process is driven forward primarily by increasing
disorder, then the process is said to be entropy driven.
 Introduction of the Second Law of
thermodynamics
1. While the first law establishes the equivalence between heat and
work, it imposes no condition on their mutual convertibility. In other
words, it never tells us under what circumstances and to what extent
it is possible to convert one form of energy into another.
2. First law tells us that the amount of heat lost by the hot body must be
equivalent to that gained by the cold body but there is nothing in the
first law which tells us that the heat has to flow spontaneously from
the hotter to the colder body and not in the reverse direction.
3. When we examine the relationship between heat and work, we notice
that whereas different forms of energy can be readily and completely
converted into heat, it is not possible to convert back heat completely
into work.
• Hence there must be some other law besides the first law, which
governs the direction of flow of heat and the extent of its convertibility
into work. This limitation forms the basis of the second law of
thermodynamics.