Foundations to Chemistry - adapted from "Chemistry, Matter and the Universe"
13. How To Measure Disorder Online Multimedia Links
INTRODUCTION
The U.S. Army Corps of Engineers had an extravagant slogan during
World War II: "The difficult we do at once; the impossible takes a little
longer."
This time division into the easy, the difficult, and the impossible also
applies to chemical reactions. Some chemical reactions are very fast;
others will take place eventually if you have the patience to wait. Yet a
third class of chemical reactions will never go in a desired direction
without outside help, even if you wait forever.
If you want a particular reaction to occur, it is obviously of interest to be
able to predict into which category the reaction falls. In the next two
chapters we will see what governs how fast a reaction will go. In this
chapter we are concerned with the simpler question of predicting
whether a given reaction will ever occur by itself, given unlimited time.
The key step will be learning how to measure the order or disorder that
is produced when molecules interact, or the entropy of a reaction.
Whether a reaction ever will proceed by itself depends on two quantities
that sometimes co-operate but more often conflict: heat or energy, and
disorder or entropy.
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The central theme of this chapter is that a lowering
of energy, and an increase in disorder, both are
changes that tend to occur spontaneously.
In the melting of the icicle, water can lose heat and
go to a state of lower energy by freezing, but at a
cost of increasing its order in the ice crystal.
Conversely, a frozen icicle can go to a more
disordered state by melting, but only if enough heat
is supplied to break the hydrogen bonds in the ice
crystal. The energy factors say "freeze," and the
entropy factors say "melt". For reasons that we will
explore in this chapter, energy is more important at
low temperatures, and entropy, or disorder,
dominates at higher temperatures. The temperature
at which these two conflicting tendencies balance is
the melting point of ice.
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13. How To Measure Disorder
SPONTANEOUS REACTIONS
Spontaneous reactions are those that will take place by themselves, given
enough time. They do not have to be rapid; speed is not a factor in the definition
of spontaneity. Explosions and many other spontaneous reactions are rapid, but
other spontaneous processes, such as the precipitation of calcium carbonate in
the stalactites of Mammoth Cave, require thousands of years.
We recognize the irrelevance of time to the idea of spontaneity when we use the
term "spontaneous combustion" for the slow smouldering of paint-soaked rags.
The oxidation of newsprint is spontaneous, although we do not worry about our
morning paper bursting into flames as we read it. At 25° C, the reaction of
newsprint with oxygen is exceedingly slow, but the gradual browning of old
newspapers in library files shows us that the process is spontaneous
nevertheless.
In contrast, the same reaction at the temperature of a lighted match is both
spontaneous and rapid. By raising the temperature we have hastened the
achievement of a chemical reaction, but the tendency for the reaction to take
place was already there, even at room temperature. It is this tendency to react
that we mean when we talk about spontaneity, and it is this tendency toward
reaction that we would like to be able to predict.
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Online Multimedia Links
One good reason for wanting to predict spontaneity is
that, if a reaction is genuinely spontaneous but slow, we
may be able to speed it up by changing the experimental
conditions.
Changing the temperature is one way that is particularly
effective for oxidations. Finding a suitable catalyst is
another.
If a reaction is spontaneous, a catalyst will accelerate it.
If the reaction is not spontaneous to begin with, then
looking for a catalyst is a waste of time.
This chapter is focused on one fundamental question:
How can we tell in advance whether a reaction that has
not been tried will be spontaneous?
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ENERGY AND SPONTENEITY

If we let a ball loose on a slope, it will roll spontaneously downhill (right).

If we give one object a positive charge, it will be attracted spontaneously toward

a second object with a negative charge.

If we bring the north pole of a bar magnet near a compass needle, the needle
will rotate to point its south pole toward the magnet.

All three of these spontaneous processes are in the direction of lower energy -
lower gravitational energy for the ball on a slope, lower electrostatic energy for
the two charged objects, and lower magnetic energy for the compass and
magnet.

Common sense seems to tell us that spontaneous processes are those that lead
to a decrease in some form of energy. We would be surprised indeed to see
boulders roll up a mountainside by themselves. There is a duck hunter's joke
about a hardy breed of bird that always flies past the blind upside down, so that
when they are hit, they fall up. We find this ridiculous because common sense
tells us that things always happen spontaneously in the direction of lower, not
higher, energy. But in predicting chemical reactions, common sense often is
wrong.

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ENERGY AND SPONTANEITY

It is true that in most spontaneous chemical reactions, energy or enthalpy falls.
The energy that the chemical substances lose during reaction is given off as
heat.

Another way of expressing the situation is to say that most spontaneous

chemical processes are exothermic.

The combustion of gasoline, like all combustions, liberates heat, because the
carbon dioxide and water molecules produced have lower energy than the
gasoline and oxygen molecules from which they came.

Is it valid to state as a general law that all spontaneous reactions go in the

direction of lower energy, or that all spontaneous reactions are exothermic?

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ENERGY AND SPONTANEITY

The difficulty with general laws is that they are so hard to prove but so easy to
disprove.

If you are testing the proposition that "all Irishmen have red hair," then ten million
red-haired Irishmen will not prove the law beyond challenge; they merely will
make it more probable. But a single blond Irishman will wipe out the proposition Crystalline N205 is unstable and will explode
completely. (All is not necessarily lost, however. If you look into the reasons for spontaneously:
the yellow hair you may learn something about people.)

The analogy is not facetious. Any number of spontaneous, heat emitting

reactions will not rigorously prove the statement "all spontaneous reactions tend
to minimize energy," yet one lone, spontaneous but heat-absorbing process will
scuttle it. If we look more closely at why some heat-absorbing reactions are
spontaneous, we will discover a new fundamental principle about chemical
reactions.
The remarkable aspect is that when N205 decomposes it
absorbs 26 kcal of heat per mole. Here is a spontaneous
and rapid reaction that clearly goes to a state of higher
energy.

Exceptions to the principle that all spontaneous reactions emit heat are not hard
to find. N205 is the oxide of nitrogen with its highest oxidation number, +5. The
solid dissolves in water to form HNO3:

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ENERGY AND SPONTANEITY

Another example is the cooling effect when a salt such as ammonium chloride is Ammonium Chloride Crystals dissolved in
dissolved in water (right). The reaction: Water

absorbs enough heat to chill its surroundings, yet we do not expect an

ammonium chloride solution to separate spontaneously into salt crystals and
pure water just because in this direction the reaction gives off heat.

An even simpler example is the vaporization of water. The heat of vaporization at

room temperature is ∆H0= +10.5 kcal mole-1. Heats of vaporization for all liquids
are positive because energy is required to break the attractive forces between
molecules in the liquid and create a gas. Yet evaporation frequently is
spontaneous. If only heat-yielding processes were spontaneous, then all gases
in the universe would condense to liquids, all liquids would freeze to crystalline
Ammonium Chloride crytals dropped into water absorb heat
solids, and the world would be nothing but rock and ice. This obviously is not so,
from the surroundings as they dissolve. The tumbler feels
and energy obviously cannot be the only factor in making chemical reactions cold to the touch.
spontaneous.

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ENERGY AND SPONTANEITY

What is the missing factor? What do the N20, NH4Cl, and evaporation processes Disorder increases from ice to liquid to vapour, as
have in common with most exothermic reactions that X makes them take place more Hydrogen bonds are broken and as water
spontaneously, even though these reactions are endothermic? molecules begin to move past one another.

The answer is that all of these reactions create disorder NO2 and O2 gas
molecules are more disordered than crystals of N206. Hydrated ammonium and
chloride ions in solution are more disordered than the regular array of NH4Cl
ions in a crystal. H20 molecules moving about freely as water vapor are more
disordered than the closely packed molecules of the liquid, or the frozen
molecules of the solid .

Most explosions are destructive precisely because they convert solids or liquids
into gases that push out against their surroundings. (The expansion of the gases
when they are heated by the reaction is another destructive factor.) A decrease
in energy or enthalpy certainly is an important component in determining
spontaneity, but the other aspect is the production of disorder.

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DISORDER AND SPONTANEITY

How do we measure disorder? The means of doing this came originally from It is easy to change coordinated motion into random
physics, not chemistry. During the middle of the last century, physicists were motion but impossible to turn uncoordinated motion
interested in the nature of heat and its manipulation, an understandable bias in completely back into uniform motion. When we heat a
an era of steam power. James Joule, Julius Mayer, and others concluded after can of soup, all the molecules begin moving faster but in
careful experimental measurements that heat, work, and energy all were merely a random manner. What is the probablility that, purely by
different aspects of the same thing. chance, all the molecules in the soup will begin to move
faster in the same direction, taking the pan and the
William Thomson (later Lord Kelvin, of the Kelvin or absolute temperature scale) kitchen wall with them.
and Rudolf Clausius were struck by the fact that the interconversion of heat and
work is a one-way street. It is easy to convert the energy of work completely into
heat, but the reverse transformation is never complete. Thomson's version of the
second law of thermodynamics states that it is impossible by any cyclic,
repeatable process to take heat and convert it entirely into work without losing
some of this heat to a reservoir at a lower temperature. There can be no steam
engines without condensing cylinders, and part of the available heat always is
lost to the condenser instead of being converted to useful work. The second law
in any of its forms makes heat look like the lowest or most degraded form of
energy: easy to obtain but hard to reconvert.

We know what Thomson and Clausius a century ago did not. On a molecular
level, kinetic energy is the coordinated motion of all of the molecules in a solid in
the same direction (right). Heat in a solid is the disunited motion of individual
moleculed about their equilibrium positions. Kinetic energy is organised,
coherent motion and heat is random incoherent motion.

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DISORDER AND SPONTANEITY

As any good statistical physicist or cook can tell you, the chance of this
happening is effectively zero. If every one of n molecules has an equal chance of
moving up or down in the soup, or a 50% chance of being found moving upward,
the probability that at some instant all n molecules will move upward in unison is
given by the expression (½)n. For the n = 1.7 x 1025 molecules in a half litre of
soup, this is an unimaginably small number.
It is true that, given enough time, the most unlikely events
could happen by chance. Order could come from
molecular disorder spontaneously, and an array of
monkeys could type all the books in the British Museum.
Neither is worth waiting for in the real world.

Arthur Eddington expressed these probabilities vividly in 1928 in his book The
Nature of the Physical World. Speaking of the mathematically identical problem
of the probability of finding all of the molecules of a gas in one half of a container
at the same time, he said:

"The reason why we ignore this chance may be seen by a rather classical
illustration. If I let my fingers wander idly over the keys of a typewriter it might
happen that my screed made an intelligible sentence. If an army of monkeys
were strumming on typewriters they might write all the books in the British
Museum. The chance of their doing so is decidedly more favourable than the
chance of the molecules all moving to one half of the vessel."

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