This is written for you quickly to understand the second

law and entropy. All but a few general chemistry texts have
discarded entropy is disorder and adopted my approach.
However, if your text and instructor describe things
differently, dont argue with or correct her/him! Just
memorize what you read in the text and hear in class so
that you can give the expected answers on exams. Grades are
important at this time in your life :-( but the
understanding that you will get here will last a lifetime.

A Students Approach to the Second Law and

Entropy
The Second Law of Thermodynamics

Many texts define the second law as the entropy of the

universe increases during any spontaneous process and then
throw qrev/T or free energy = G and S at you.
Thats too complex too fast. Well see that the second law
and entropy are simple, at the level of first-year university
chem.
The second law is based on human experience. It doesnt
come from complicated theory and equations. So, think of
these experiences that you have had: A rock will fall if you lift it
up and then let go. Hot frying pans cool down when taken off
the stove. Iron rusts (oxidizes) in the air. Air in a highpressure tire shoots out from even a small hole in its side to the
lower pressure atmosphere. Ice cubes melt in a warm room.
Whats happening in each of those processes? Energy of
some kind is changing from being localized ("concentrated" in
the rock or the pan, etc.) to becoming more spread out. Look at
those examples again to see how that statement fits them all.
OK? Thats it a simple way of stating fundamental science
behind the second law:
Energy spontaneously disperses from being localized
to becoming spread out if it is not hindered from doing
so.

But what about entropy and universe that is in so many

textbooks and may be in yours? Well see what entropy is in a
minute. But the universe just means the system youre
looking at PLUS its surroundings, i.e., everything thats close
around it. System plus surroundings. If that system plus
surroundings bothers you, or if you want details of three of the
processes mentioned above, read the next paragraphs.
If not, skip down to What Is Entropy, REALLY?
1. The rock has potential energy localized in it when you lift it
up above the ground. Drop it and that PE changes to
kinetic energy (energy of movement), pushing air aside as
it falls (therefore spreading out the rocks KE a bit) before
it hits the ground, dispersing a tiny bit of sound energy
(compressed air) and causing a little heating of the ground
it hits and the rock itself. The rock is unchanged (after a
minute when it disperses to the air the small amount of
heat it got from hitting the ground). But the potential
energy that your muscles localized in by lifting it up is now
totally spread out and dispersed all over in a little air
movement and a little heating of the air and ground.
[System: rock above ground, then on ground.
Surroundings: air plus ground.]
2. The iron atoms in a hot frying pan are vibrating very
rapidly (like dancing in place fast) and therefore the
motional energy in the hot pan is localized. That motional
energy will spread out if it can. Whenever the less
rapidly moving molecules in the cooler air of the room hit
the hot pan, the fast-vibrating iron atoms transfer some of
their energy to the air molecules. The pans localized
energy thus becomes dispersed, spread out more widely to
molecules in the room air. [System: pan. Surroundings:
room air.]
3. Iron in nails or other objects doesnt have to be hot (i.e.,
with very fast moving atoms or molecules) to have
localized energy within it in a chemical sense: Iron atoms
plus oxygen molecules of the air have more energy
localized within their BONDS than does iron rust (iron

oxide). (Thats why iron reacts with oxygen to release

energy from their higher energy bonds and form the lower
energy bonds in iron oxide, with all that difference in
energy being dispersed to the surroundings as heat i.e.,
the reaction is exothermic and makes molecules in the
surroundings move faster . But don't forget that even
substances with lots of energy in their bonds are hindered
extremely! from immediately spreading out that
energy. It takes much energy to break the bonds just
before or as they react, even though far more energy may
be then given out as the result of the reaction as the new
bonds form.) Therefore, even in moist air that speeds up
the process, iron spontaneously (but not very rapidly)
reacts with oxygen and each spreads out some of its bond
energy to the surroundings when the iron and oxygen form
iron oxide. [System: iron and oxygen, iron oxide.
Surroundings: the nearby air and any moisture or salt in
the air plus any object in contact with the rusting iron.]
What Is Entropy, REALLY?

Entropy measures the spontaneous dispersal of

energy: how much energy is spread out in a process, or
how widely spread out it becomes at a specific
temperature. (Sometimes, its a simple equation, Entropy
change = energy dispersed/T, or qreversible/T , as in phase
changes like melting or vaporization where S = Hfusion /T or
Hvaporization /T, respectively.)
(In chemistry the energy that entropy measures as dispersing
is motional energy, the translational and vibrational and
rotational
energy
of
molecules
[Figure
1
of http://2ndlaw.oxy.edu/entropy.html ] and the H of phase
change energy both motional or phase change energy being
designated either as "q" or H in many equations. Bond
energy, the potential energy associated with chemical bonds
that we talked about in the iron oxidation example, is only
measured by entropy change in connection with a chemical
reaction in G = H - T S

Is that description of an entropy change complicated?

Entropy is a sophisticated kind of "before and after" yardstick
measuring how MUCH energy is spread out/T as a result of a
process, or how WIDELY spread out is the energy after
something happens than before (at a constant
temperature). Maybe entropy seems confusing and abstract
when the first entropy equation is thrown at you in your text,
about a change in entropy in a reversible process: S = qrev /
T. Lets look at it by using a how MUCH practical example: ice
spontaneously melting in a warm room. (Phase change S, an
increase in entropy)
Phase Change a how much energy is dispersed example

From your experience remember, thats the basis of the

second law what direction do you think the energy of
molecules would go from those faster moving air molecules in
the warm room to the slower moving water molecules in the
cold ice ... or would the slower moving molecules in the ice give
up some of their energy to the warm air? Sure. From the
hotter to the colder! Always. [If you need a math proof, it is
given in the middle of http://secondlaw.oxy.edu/six.html] The
greater motional energy of the warmer air molecules spreads
out some energy to the cold ice and this breaks (or alters)
intermolecular hydrogen bonds between the water molecules in
the ice. Liquid water forms at the tiniest temperature above the
melting point of 0oC (273 K) and, reversibly, solid ice forms at
the tiniest temperature below 0oC.
As the warmer air molecules transfer some of their motional
energy to be dispersed in the ice, it breaks many hydrogen
bonds in the ice. This allows the molecules to move with the
same amount of energy that they had when just "dancing in
place" in the ice but now form new bonds with other water
molecules, and actually move a little bit, but thats a lot
compared to being in one place in a solid. (Their speed is not
increased, and thus the resulting liquid's total motional energy
is unchanged, and the temperature doesn't rise above 273 K
when ice melts to water.) Even though there is an increase only
in the potential energy of the liquid water at 273 K compared to
ice, no longer are all the molecules held in the very rigid
framework of ice. They still are hydrogen bonded in the liquid

but constantly move through space by forming new bonds after

breaking others.

How MUCH energy is dispersed in melting ice, breaking

those original H-bonds and allowing the molecules to move
relatively freely? The enthalpy of fusion, Hfusion , of
course! Thats why your text says the entropy increase in
melting is S = qrev /T = H/T.
Standard Entropy a how much energy is dispersed example

Then, many texts go on to talk about standard entropies,

S 298 , of all kinds of elements and compounds. Actually,
standard entropies should be called standard
entropy changes for substances. This is because the entropy
values of So298 that are listed in Tables come from the total
amount of energy (qrev ) that has had to be reversibly spread
out (at each incremental fraction of temperature, i.e., qrev/T) in
any substance as it was very slowly heated up from 0 K to 298
K a big change from 0 entropy at 0 K to So at 298 K.
o

Texts usually urge you to look at So298 values to see the

differences between the standard entropies of different types of
molecules monatomic gases vs. polyatomic, gases vs liquids
of the same element, graphite vs. diamond vs. metals vs
iodine. However, some texts fail to tell you that these
So298 numbers
show
a
rough comparative amount
of
motional energy (plus any phase change energy given to the
substance from 0 K) that each particular substance must have
to exist at 298 K substances that are capable of more free
motion need to have more energy spread out in them or they
just
could
not be at
298
K.
Specifically, monatomic gases dont require any energy to
rotate, but polyatomic gases do and the more different kinds
of turning and wiggling in large molecules, the greater the
energy required and the larger is the So value. Graphite has a
relatively loose structure, a less rigidly bonded solid than
diamond; therefore, graphite requires more energy for the
normal slight movement in its crystals than does diamond with
its lesser possible movement. Iodine molecules are much less
strongly bound by intermolecular attractions to other
I2 molecules that are metal atoms kept in place in their sea of
electrons; thus iodine has a higher So value because it requires

more energy for its molecules to vibrate a bit at 298 K than do

held in place iron or copper or gold atoms.

Volume Increase: Gas expansion, gases mixing, liquids mixing how

widely examples

Most texts show before and after illustrations of a gas

spontaneously expanding into an evacuated bulb. When that
happens, theres no energy change, no temperature change.
Thus, the total motional energy of the initial gas in one bulb is
spread out to be half that amount of energy (and half the
molecules of gas) in in each of the two bulbs finally. WHY should
a gas behave this way?
Your text may use that kind of illustration and then talk
about calculating the probability of the gas all being in one bulb
versus being in two with little red dots for energetically
colliding molecules and tables for calculations. (But those texts
dont emphasize the energy of those little molecules that are
racing around and hitting each other!) If your text does that
kind of calculation, go along with it; memorize it; youre going
to have it on an exam. But "probabilities" are just half the
reason for the gas expanding; they are the math for
the results (that would not have occurred if motionally energetic
molecules hadnt been part of the system. Marbles or dice or
playing cards dont move to other places no matter what their
probability arrangement might be!!).
YOU know the simplified explanation for a gas to move into
an evacuated bulbthe second law of thermodynamics as
does any energy, the motional energy of the molecules
(translation and rotation) spreads out as widely as it can, if it is
not hindered. (It certainly wasnt hindered from spreading out
just as soon as that stopcock between the two bulbs was
opened!) More fundamentally, if there are particles with
motional energy AND there is an increased space that
probability shows could be occupied, those particles will spread

out widely and the entropy of the gas will increase. Wider
energy dispersal = entropy increase.
How to calculate the entropy increase in the spontaneous
expansion process is not obvious, because (1) there isn't any
change in the energy of the gas that expands (q = 0), (2) even
if there was a change in energy, you couldn 't use the simple
equation with qrev/T because it is anirreversible process unlike
the reversible melting of ice at 273 K! It isnt a how much
energy is dispersed situation, its a question of howmore
widely spread out in two bulbs is the gas than it was in
one. (Of course, from the definition of entropy as a
spontaneous increase in energy dispersal, there is an entropy
increase in the expansion because the energy of the gas has
obviously spread out more.) In your text probably this entropy
increase is calculated from the energy required to reversibly
compress the gas back to the volume of one bulb, i.e., RT ln
(V2/V1) and thus S = R ln (V2/V1)
Gases spontaneously mix a how widely energy is dispersed
example;

If you put two different gases in that same two-bulb

apparatus we talked about just now but both at the same
atmospheric pressure when you opened the stopcock, they
would slowly spontaneously mix. Why? Just the second law, of
course!
The molecules of each gas are rapidly moving and
colliding; they have motional energy. So, as the second law
predicts, the motional energy in those molecules will cause them
to spread out if it is not hindered. Sure enough, when you open
the stopcock, you are letting the motional energy of each gas
spread out more widely into the larger volume of two bulbs
rather than staying in one. Is the probability that there are
more positions in two bulbs for the molecules than there are in
one important? Yes. Even though our simple predictions based
on energy dispersal always works, technically and
fundamentally, entropy change requires both the presence of
molecules that have motional energy and also calculations that

show that it is more probable for such particles to be in two

rather than one volume.
Liquids spontaneously mix (if they are like each other) a how
widely example

When liquid water and alcohol are added to one another,

they spontaneously mix as do any like (similar to each other
in chemical structure) liquids. This is true regardless of volume
change because the mere presence of two substances in the
same total volume involves a dispersal of the energy of each in
that whole mixture and increased dispersal and greater
entropy change as the relative quantities of each liquid in the
mixture increases toward a 50:50 mole ratio. This is one of
several cases in which the simple view of energy becoming more
dispersed when substances are mixed works i.e., predicts the
correct result of spontaneity and of entropy increase. However,
the fundamental calculations are relatively complex and involve
statistical mechanics in which the solution is considered to be in
many cells with each cell a different combination of molecules
in the ratio of the quantities of the two liquids present. The
equation for the entropy increase in the mixture uses the
relative molar quantities of liquids that were mixed.
A small amount of solute is added to a solvent a how widely
example

When even a small amount of solid solute is added to a

solvent, just as in the mixtures of liquids above, the motional
energy of the individual solvent molecules (and the solute
molecules) in the new solution is each more separated from its
own type of molecule than before, and thus each individual
molecules energy is more spread out or dispersed. The entropy
of the solvent and the solute each increases in the solution.
(The more fundamental reasoning and resulting equations from
statistical mechanics are the same as described above for liquid
mixtures.) If we realize that a solvents energy is more
dispersed in a solution than when it is a pure solvent, we can
see why a solvent in a solution should be increased in entropy
compared to its entropy as a pure solvent. Then also, it is

obvous that the entropy will be larger depending on how many

molecules of solute are added to the solvent. That increased
entropy of the solvent in a solution is the cause of the
"colligative effects" that we study: (1) osmotic pressure, (2)
boiling point elevation, and (3) freezing point depression.
Now, if the solvent tends to stay in a solution (because its
energy is more dispersed there), rather than being with only
with its own kind of molecules in pure solvent, it will stay in that
solution if it has a choice! That means (1) if there is a
membrane placed between a pure solvent and a solution
containing it (and that membrane allows solvent molecules from
pure solvent to go through it from the other side but not the
solute molecules), pure solvent will go through the membrane
to get to the solution because its energy is more spread out
there. Thats osmosis, a very important phenomenon in
biochemistry; (2) solvent molecules in a solution will not leave
that solution to become vapor molecules in the atmosphere
above a solution as readily as at the normal boiling point of the
pure solvent; a higher temperature will be necessary to cause
enough molecules to leave the solution to be in equilibrium with
the atmospheric pressure and boil; (3) solvent molecules in a
solution will not be in equilibrium with the solid phase
(composed of pure solvent molecules) at the normal freezing
point; a lower temperature is necessary to reduce the motional
energy of the solvent molecules so that they can make
intermolecular bonds to form a solid; i.e., be in equilibrium with
their molecules in the solid phase), All of these colligative
effects increase as the amount of solute in the solvent is
increased because the entropy (i.e., energy dispersal) of the
solvent increases in the solution with a greater concentration of
solute.
Heating a substance a how much energy is dispersed example

Textbooks that do not use calculus omit this example, but it

can easily be described qualitatively because we know the basic
idea energy spontaneously spreads out if it is not hindered.
Motional energy from hot surroundings is spontaneously spread
out in cooler systems/substances, never the other way

around. The entropy of the cooler system always increases

more as it is heated than the hot surroundings decrease in
entropy. (Calculations are available
at http://entropysite.oxy.edu/entropy_isnot_disorder.html#m3
)
Chemical reactions how much and "how widely energy is
dispersed

Spontaneous exothermic reactions are usually due to the

chemical bonds in the reactants being relatively weaker than the
bonds in the products. (What you actually calculate in the H
change of a reaction is the enthalpy ["heat"] of formation of
products minus the enthalpy of formation of reactants.
Enthalpies of formation are closely related to bond
strengths/energies) That how much energy difference of H
in a chemical reaction is spread out as old bonds are being
broken and new ones formed by the product molecules (and any
unreacted molecules of reactant) in moving much more rapidly
than the reactant molecules did at the original T. Then, this
motional energy of the products is dispersed to the surroundings
and the temperature of the system returns to T.
Now, consider the entropy change in a reaction. It is the
reactants motional energy (plus any phase change energy in
them) that determines the value/magnitude of the entropy state
of each reactant at T. Then, because the entropy values of
possible products at T are usually different than those of the
reactants, the S in the reaction is easily calculated from
Sproducts Sreactants . That difference is a combination of how
much and how widely is energy dispersed in the reaction
process whether heat is evolved or absorbed and whether the
volume changes or more mixtures are formed. (Thus, the S
change alone can be responsible for a spontaneous reaction
even though most often it either simply adds to or subtracts
from the usually larger H change.)
Both kinds of energy difference (i.e., how much and how
widely) are combined in the S change you calculate, but
often you can estimate whether the S change in a reaction is

greater or lesser simply by estimating the how widely factor

of energy spreading out in the products as compared to the
reactants. This is the scientific reason for the textbook rules of
entropy increase in reactions: (1) if more molecules are
produced, this involves how widely (motional energy is more
widely spread out if there are more molecules among which it
is dispersed); (2) if a phase change from a solid to a liquid
occurs (a phase change involves how much, an increase in
potential energy from that in solids to liquids, and how widely,
less restricted locations in space in a liquid allow energy to be
more spread out); (3) if a gas is produced from a solid or liquid
(as stated in (2), the process involves a phase change in which
both how much and how widely energy is more dispersed.)

Spontaneous endothermic reactions are due to the greater

motional energy in the hotter surroundings that can be
transferred to reactants in a system. As you know from the
Gibbs equation, G = H TS, a high temperature makes the
TS function dominate. Thus, entropy change is causal in
endothermic reactions.
In the Gibbs equation, G = H TS, each term describes
an aspect of the energy that is dispersed because of a chemical
reaction occurring in a system:
G is the total energy that is spread out in the universe
(system plus surroundings) due to the reaction that has taken
place in the system.
H is the energy from the reaction that is
dispersed from the system to the surroundings.
TS is the energy that is dispersed in the system in the
products of the reaction as compared to the reactants.
If each term is divided by T, the Gibbs can be seen as
an all entropy equation.
The Gibbs works because it corresponds to the second law
as we would state it, Energy spontaneously disperses, if it is
not hindered. When it does so, entropy increases in the
combination of system plus surroundings.

This is what the conventional statement means when it says

more succinctly but more obscurely, The entropy of the
universe increases during any spontaneous process.