The ENTROPY demon distilled into 10 simple concepts

A Level chemistry lecture notes (by Asish George)

Commented [AG1]: To understand what you mean by
CONCEPT #1 THE BIG PICTURE predicting the future in chemistry and the two conditions
which determine this
Entropy is the key to predicting the future in chemistry it is the central clue in a puzzle
which tells you whether a chemical reaction is possible or not (it is times arrow)

2 Conditions have to be met for a reaction to occur/to be absolutely sure that a

certain reaction WILL occur (to know the future w.r.t chemistry)
o Spontaneity is the first condition
o Spontaneity determines whether or not a reaction CAN occur/proceed by
itself possibility (It is TIMES ARROW); It makes no indication as to whether
or not the reaction WILL occur
o (We will learn how to determine the spontaneity of any process by the end
of this lecture that is the final concept!)
o Chemical kinetics is the second condition
o Chemical kinetics determines what stands in the way and how fast a
reaction proceeds (if at all it is possible) (It is TIMES VARIABLE CLOCK); It
makes no indication whether or not a particular reaction is possible
o (We have already learnt how to determine the chemical kinetics of any
process/reaction: from activation barrier Ea and rate of reaction!)

Let us take 2 examples to analyse these statements:

Gasoline/Air
Diamond/Carbon
Chemical kinetics (activation energies and rates) restrain times arrow in the taut bow of
thermodynamics for milliseconds or millennia

Commented [AG2]: To conclude that there are 2 factors

CONCEPT #2 UNDERSTANDING SPONTANEITY which influence spontaneity
To mention the term entropy
First lets define what a spontaneous and non-spontaneous process/reaction is: To tell entropy determines spontaneity somehow
o Spontaneous reaction: a process that, once it is initiated, proceeds on its
own without any external influence (under the original conditions)
o In more of a chemistry sense*, a spontaneous reaction is a reaction that
favors the formation of products at the conditions under which the reaction
is occurring.
 o Non-spontaneous reaction: a process that takes place only in the presence of
continuous external influence
Now, think about few examples of spontaneous reactions that you know:
o Decompressing a spring
o Rolling a ball downhill
o Combustion of gasoline/nitroglycerine/explosive
o (Note* that spontaneous does not necessarily mean instantaneous; In fact
some spontaneous processes proceed extremely slowly)
o Transition of diamond to graphite
Now, think about few examples of non-spontaneous reactions that you know:
o A spring getting compressed by itself, once you start it off
o Rolling a ball uphill
o Electrolysis of water
o (Note* that the reverse of any spontaneous reaction will be a non-
spontaneous one under the same conditions)
o Transition of graphite to diamond
What is the recurring principle that you find here?
o Processes/reactions that decrease the potential energy (elastic,
gravitational or chemical) of a system, tend to occur spontaneously and
those that increase the energy of a system, tends to occur non-spontaneously
(the increase and decrease is due to heat transfer between system and
surroundings)
o OR In other words,
o Exothermic reactions (which release heat because the chemical potential
energy of the products is lower than that of the reactants) tend to occur
spontaneously
o Example: Combustion of methane {CH4 + 2 O2 -> CO2 + 2 H2O + 890 kJ}
o Endothermic reactions (which absorb heat because the chemical potential
energy of the products is greater than that of the reactants) tend to be non-
spontaneous
o Example: Electrolysis of water {2 H2O(l) + 286 kJ 2 H2 (g) + O2 (g)}
With this concept in mind, it would be interesting to look at the following examples:
o 1st Example: Crystallization of ammonium nitrate from aqueous solution
o NH4+(aq) + NO3(aq) -> NH4NO3(s) + 25.7 kJ
o This reaction is not spontaneous!
o 2nd Example: Reaction between barium hydroxide and ammonium chloride
o Ba(OH)2(s) + 2 NH4Cl (s) + 63.6 kJ -> BaCl2(s) + 2 NH3(aq) + 2 H2O(l)
o This reaction is spontaneous! (CHEMICAL ICE PACKS is another example)
How can this be??
o This brings us to conclude that there must be a second factor, other than the
change of chemical potential energy (H), which must influence spontaneity
o And that guess is true.
o This second factor is called as entropy!
 o So, together, (the total change in chemical potential energy) AND (the total
change in entropy) of a process is what determines Spontaneity!
o Well talk about entropy and change in entropy in detail in a minute, but
before that well need to take a slight detour to another linked concept.
Commented [AG3]: Understand microstate as a
CONCEPT #3 INTRODUCING THE MICROSTATE configuration for energy
That the distribution of energy is actually continually
The words, macro and micro are not exactly big and small in thermodynamics. changing into different configurations/microstate because of
molecular motions and because there are different
Instead, they are two very different ways of looking at a system. accessible energy levels + particles
Macrostate always has to involve an amount of matter large enough for us to
measure its P, V, T, H and number of moles, i.e. in bulk. Thus, a macrostate is the
same as long as its observable properties do not change.
Microstate is a microscopic, detailed look at the energy of each of the constituent
molecules or other particles in the system possess at a particular moment.
SELF-SHUFFLING RUBICS CUBE analogy for microstate and macrostate
TOTAL ENERGY AND ITS DISTRIBUTION IN AN IDEAL GAS translating the same
analogy to a chemical system
In a system, its energy is constantly being redistributed among its particles. The
particles themselves are constantly redistributing the quanta (the individual
amount of energy that each molecule has) due to their incessantly colliding,
bouncing off each other with (usually) a different amount of energy for each
molecule after the collision.
{*One important thing to keep in mind is to recall that just like quantum mechanics
restricts the energy levels possible for an electron, energies associated with
molecules (their translational, rotational and vibrational motional energy) is also
quantized and not allowed to vary continuously as in classical mechanics.}
A microstate is one of the huge number of different accessible arrangements
(CONFIGURATIONS) in which the total motional energy* of a collection of
molecules can be distributed for a particular macrostate. (Motional energy
includes the translational, rotational, and vibrational modes of molecular motion.)
One microstate then is something like a theoretical "absolutely instantaneous
freeze-photo" of the location and momentum of each molecule and atom in the
whole macrostate. (This is talking in classical mechanics language where molecules
are assumed to have location and momentum. In quantum mechanics the
behaviour of molecules is only described in terms of their energies on particular
energy levels.)
Every microstate for a particular system has exactly the total energy of the
macrostate because a microstate is just an instantaneous quantum energy-photo
of the whole system.
Every instant, a system the macrostate rapidly and successively changes to be
in a gigantic number of different microstates out of the gazillions of accessible
microstates.
 Commented [AG4]: Weve found out 2 things:
CONCEPT #4 ENERGY DISPERAL CONNECTING ALL 3 CONCEPTS 1.What the condition for a reaction to be spontaneous is
energy dispersal/increase in the number of ways of
OF SPONTANEITY, MICROSTATE AND ENERGY DISPERSAL energy distribution/increase in the number of microstates
2.And why this condition has to be met probability for a
Lets analyse some more common examples of spontaneous reactions: systems energy to be localized to a few microstates is
1. A hot pan spontaneously disperses some of its energy to the cooler air of a room. extremely miniscule when compared to the probability for
it to be dispersed across all the possible/accessible
(That means that the faster vibrating iron atoms in the pan transfer some of their microstates
motional energy to the slower moving nitrogen and oxygen molecules that strike the
pan and thereby spread the thermal energy within the pan-room system)
Conversely, even a cool room would disperse a portion of its energy to colder ice
cubes placed in it.
2. When a container of nitroglycerine explodes, its chemical bonds break to form
gaseous products wherein some of its bond energy is transferred in enormously
increasing the vigorous motions of those product molecules and this energy then
spreads throughout the system/atmosphere.
3. At a high pressure in a car tire, the compressed air tends to blow out (because then
that localized energy of the air molecules can be far more spread out among the air
molecules in the lower pressure normal atmosphere).
4. Batteries, small or large, lose their charge (i.e., spontaneously react to decrease
the amount of the reactants) and thereby disperse their chemical potential energy
in heat if even a slightly conductive path is present between the two poles.

What is common in all these examples?

Energy distribution within a closed system always tends to disperse.
So naturally, processes which allows (a net) dispersion of the energy distribution
will be spontaneous.
Though youve been able to relate to dispersion of energy distribution in these
examples, let me make the phrase, clearer.
From our definition of microstate, we know that, each microstate is a single
arrangement of energy distribution. Increasing the number of ways in which energy
quanta can be arranged in the system i.e. greater ways of energy distribution is
called dispersion.
So, spontaneous processes are those processes in which there is energy
dispersion/increase in the number of ways of energy distribution/increase in the
number of microstates.

But WHY?
Energy distribution always changes from being localized to becoming dispersed or
spread out, unless stopped from doing so.
This process happens spontaneously because of two things:
due to an increased probability of those dispersed/disordered arrangements
(many) over localized/orderly arrangements (few) {Explain with picture}
AND
Obviously because of the motional energy of molecules (which lets it form those
arrangements)

CONCEPT #5 WHAT IS ENTROPY REALLY?
You already now know what entropy is!
Entropy change is just a formal term for the measure of Energy dispersal or
the change in number of ways of energy distribution in a system (microstates)
Commented [AG5]:
Understand that terms entropy and entropy change and the
two ways in which they can be influenced
SYLLABUS OBJECTIVE:
a) explain that entropy is a measure of the disorder of a
system, and that a system becomes more stable when its
energy is spread out in a more disordered state

If Energy dispersal is happening, it means that the number of microstates is

increasing and entropy is increasing (or change in entropy is positive)

Since processes in which energy dispersal is happening, is spontaneous, we can

rightfully say that in all spontaneous processes, entropy change is positive

If Energy dispersal in a process is the entropy change of the process, then what is
Entropy of a substance in a particular state?

It is the total increase in the energy dispersal up to that current state from the
state when it was completely localized (at 0K)

Entropy is a measure of the disorder of a system.

This overall process of energy dispersal is measured quantitatively as

thermodynamic entropy. Entropy and entropy change are concerned with the
energy dispersed in a system. Entropy is a measure of the number of accessible
microstates, in any one of which the system's total energy might be at one
instant and hence, energy distribution within a system. And, entropy change is
the difference in energy distribution within a system after a process has taken
place.

Entropy of a system increases in 2 ways:

o If the existing motional energy disperses more within a closed system (1)
o If heat is introduced into a closed system (2)
 Commented [AG6]: Understand what you mean by
CONCEPT #6 STANDARD MOLAR ENTROPY (of substances) standard molar entropy of a substance

Total entropy content of 1 mole of a substance under standard conditions.

When heat energy is input into a system, it introduces some level of entropy.
Entropy of a substance at 0K = 0 (negligible).
For a substance at 0K to be brought to standard conditions 273K, heat energy has
to be introduced: heat capacity of solid (0K->M.P.), latent heat of fusion (S->L),
heat capacity of liquid (M.P->B.P), latent heat of vaporization (L->G), heat
capacity of gas (B.P->std. state)
At each of these stages of heat introduction, some amount of entropy is also
introduced.
The total amount of entropy that 1 mole of a substance gains as it is brought
from 0K to the standard conditions is known as Standard molar entropy.
Its units are J/(Kmol)
Standard molar entropies of reactants and products can be used to calculate the
change in entropy of a chemical reaction, pretty much the same way we used
Standard Molar Enthalpies.

CONCEPT #7 WHAT FACTORS DETERMINE ENTROPY OF A

Commented [AG7]: What are the factors which
SUBSTANCE? determine the entropy of a substance/system and why?

Previously we came to an idea that no of microstates is directly related to SYLLABUS OBJECTIVES:

b) explain the entropy changes that occur:
entropy. Any fact or which increases the number of microstates, will increase (i) during a change in state e.g. (s) (I); (I) (g); (s) (aq)
entropy: (ii) during a temperature change
(iii) during a reaction in which there is a change in the
o STATE OF MATTER constraints increase from gases-liquids-solids, the number of gaseous molecules
modes of energy distribution (translational, rotational, vibratory) also
decrease, hence lesser number of microstates
o TEMPERATURE (a higher temperature implies higher total internal
energy of the molecules and so they can occupy higher energy levels
Boltzmann distribution for different T, becomes more spread out for
higher T) increases the number of accessible energy levels -> increases the
no. of possible arrangements
o NUMBER OF PARTICLES more ways of arranging, more microstates
o VOLUME and Mr increases the density of energy levels/makes it more
closely spaced (quantum mechanics)

CONCEPT #7a PREDICTING THE FUTURE 1.0 AN EDUCATED GUESS Commented [AG8]: SYLLABUS OBJECTIVES:
c) predict whether the entropy change for a given process is
Using the factors which determine entropy as the rough yardsticks positive or negative

CONCEPT #7b PREDICTING THE FUTURE 2.0 A MUCH REFINED GUESS WORK Commented [AG9]: SYLLABUS OBJECTIVES:
d) calculate the entropy change for a reaction, S, given the
standard entropies, S, of the reactants and products
Using actual standard entropy values to find the change in entropy for the system
 Commented [AG10]: To understand that there is also
CONCEPT #8 INTRODUCING AN OLD FRIEND Mr. H entropy change occurring in the surroundings as a result of
heat transfer and to learn the formula to calculate it
How do you calculate the change in entropy for the surroundings?
Refer to Concept #5 (The two ways in which entropy changes)
The first way is applicable for the entropy change in the system (because there is
a chemical change and energy is getting distributed within the system)
The second way is applicable for the entropy change in the surrounding (because
heat is liberated into or gained from the surrounding)
If heat energy is liberated into the surroundings, it will increase the entropy of the
surroundings.
How much?
S = q/T
Analogy - The effect of the same shouting in a market and in a library
H is defined as the q which is gained from the surrounding
So the q which the surrounding gets will always be -(H)
So the change in entropy of the surrounding will be -H/T

CONCEPT #8a PREDICTING THE FUTURE 3.0 THE OTHER HALF OF THE COIN

Using H values to find the change in entropy for the surroundings

CONCEPT #9 PREDICTING THE FUTURE 4.0 THE ULTIMATE

JUSTICE LEAGUE AND THE SECOND LAW OF
Commented [AG11]: To understand that the total
THERMODYNAMICS entropy change is what determines spontaneity and to
mathematically represent it using a formula
Now since you know that ultimately for a reaction to be spontaneous, the total
entropy change has to be positive (system + surroundings), we will need to merge
the two (Concept 7 and 8)
And we get,
Stotal = Ssystem + Ssurroundings
Stotal = Ssystem - H/Tsurroundings
This is a useful form of the second law of thermodynamics
CONCEPT #10 THE GIBBS FREE ENERGY THE CRYSTAL BALL
Commented [AG12]:
OF CHEMISTRY To understand the implications of T in the equation and to
find the usefulness of the concept of G
Discussion on the implications of the T factor in the equation (How certain ordinarily
SYLLABUS OBJECTIVES:
non-spontaneous reactions can become spontaneous at higher temperatures)
a) define standard Gibbs free energy change of reaction by
So Stotal i.e, the term (Ssystem H/Tsurroundings) is the useful bit means of the equation G = H TS
We can make those useful terms into a slightly neater format, with some playing b) calculate G for a reaction using the equation G = H
TS
around with the equation: c) state whether a reaction or process will be spontaneous
Stotal = Ssystem - H/Tsurroundings by using the sign of G
d) predict the effect of temperature change on the
- Stotal = - Ssystem + H/Tsurroundings spontaneity of a reaction, given standard enthalpy and
- TStotal = - TSsystem + H entropy changes

- TStotal = H - TSsystem
Now the term (H - TSsystem) is neat!
And we are going to call this term the Gibbs Free Energy
If Stotal is negative then the reaction is spontaneous
Since, Gibbs free energy is basically - TStotal, it is implied that G should be negative
for a reaction to be spontaneous.
So thats it; the final distilled answer, the crystal ball of chemistry - If at all you
want to know whether some ridiculous chemical reaction is possible, all you
need to do is:
FIND WHETHER ITS G IS NEGATIVE OR NOT! (It is as simple as that)

An alternative way to find G for a chemical reaction is to use standard G values

for the reactants/products and apply the ideas learnt in Hesss law
Just to wrap up, what all does G tell you?
o G of a reaction - Feasibility of a reaction
o G = 0 (for equilibrium state)
o G of formation of a compound Stability of the compound (A whole
system (system + surroundings) becomes more stable, in 2 ways: when
the total entropy decreases (when its energy is spread out in more
number of arrangements than few ordered states) and when its total
potential energy decreases (as we saw in the beginning)

SUMMARY OF KEY POINTS:

2 Conditions have to be met for a reaction to occur/to be absolutely sure that a
certain reaction WILL occur: Its Spontaneity and Reaction Kinetics

Spontaneity of a process is determined by (the change in chemical potential

energy) AND (the change in entropy)
 A system becomes more stable, in 2 ways: when the its entropy decreases (when
its energy is spread out in more number of arrangements than few ordered states)
and when its potential energy decreases (as we saw in the beginning)

In a spontaneous reaction, there is dispersal of energy/increase in the number of

arrangements for energy distribution (increase in the number of microstates)

Entropy is a measure of dispersal of the energy of a system: How much energy is

spread out in a process, or how widely spread out it becomes at a specific
temperature.

{How much, of course, means the input of energy to a system as in the examples of
phase change or heating a system. How widely includes those processes in which
the initial energy in a system is unchanged but it becomes more spread out:
expansion of an ideal gas or mixing of all types ideal gases or liquids or solutes in
liquids. The combination of both how much and how widely applies to a wide
variety of chemical rebactions in which not only are bonds broken and formed in
reactants and products (energy is transferred between system/surroundings) but the
products have more molecules or undergo phase change or become mixed with
reactants. (energy is distributed within)}

To put it in different words, Entropy of a system increases in 2 ways:

If the existing motional energy disperses more within a system (1) {due to phase
change, number of particles, volume increases number of microstates}

If heat is either taken from or introduced into the surroundings (2) {increased
number of higher accessible energy levels increases number of microstates}

In a chemical reaction, both (1) and (2) will be happening. How?

(1), due to changes in state, volume, molecular mass, number of particles in the
system as a result of the chemical change etc.

(2), due to heat transfer to/from the surroundings (due to bonds forming/breaking
within the system)

To calculate entropy change in the system due to (1) well use the entropy values
of reactants/products and find the change in a reaction. This is why we built the
neat table of standard entropy values.

To calculate entropy change in the surroundings due to (2), we have a formula S =

q/T

When we combine both, to get the total entropy change, we get a form of the
second law of thermodynamics
Gibbs free energy is a useful term within the formula, which we use to find the
spontaneity of a particular process/reaction