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Mass, Energy, and Freedom - The Coins of Thermodynamics
Gary L. Bertrand, Department of Chemistry
University of Missouri-Rolla (now Missouri S&T)
Basics
The universe is made up of bits of matter, and the bits of matter
have mass and energy.
Neither mass nor energy may be created or destroyed, but in some special
cases interconversions between mass and energy may occur.
The things that happen in nature occur because matter is trying to gather to
itself as much mass as it can (gravity) and to release as much of its energy
as it can (the Sun, for example).
This gathering of mass and loss of energy requires a price to be paid - the
price of freedom.
It seems that mass, energy, and freedom are the coins of the universe.
Mass and energy must be conserved: if one part of the universe gathers
more "wealth" as mass or energy, those must come from somewhere else in
the universe, so there is always competition in the trading of these
commodities.
Freedom, on the other hand, is not conserved. However, there are some
strange restraints on freedom.
The freedom of the universe can take many forms, and appears to be able to
increase without limit.
However, the total freedom of the universe is not allowed to decrease.
The energy or the mass of a part of the universe may increase or decrease,
but only if there is a corresponding decrease or increase somewhere else in
the universe.
The freedom in that part of the universe may increase with no change in the
freedom of the rest of the universe. There might be decreases in freedom in
the rest of the universe, but the sum of the increase and decrease must
result in a net increase.
There can be a decrease in the freedom in one part of the universe,
but ONLY if there is an equal or greater increase in the rest of the
universe.
Most of us have a general idea of what mass and energy are, and we may
have a fair understanding of how we can quantify them, or to say how much
of them we have.

Freedom is a more complicated concept. The freedom within a part of the

universe may take two major forms: the freedom of the mass and
the freedom of the energy.
The amount of freedom is related to the number of different ways the mass
or the energy in that part of the universe may be arranged while not gaining
or losing any mass or energy.
We will concentrate on a specific part of the universe, perhaps within a
closed container.
If the mass within the container is distributed into a lot of tiny little balls
(atoms) flying blindly about, running into each other and anything else (like
walls) that may be in their way, there is a huge number of different ways the
atoms could be arranged at any one time.
Each atom could at different times occupy any place within the container
that was not already occupied by another atom, but on average the atoms
will be uniformly distributed throughout the container.
If we can mathematically estimate the number of different ways the atoms
may be arranged, we can quantify the freedom of the mass.
If somehow we increase the size of the container, each atom can move
around in a greater amount of space, and the number of ways the mass may
be arranged will increase.
Now let us turn to the freedom of the energy within the container.
If the mass is in the form of atoms flying around, energy is only in the form of
the kinetic energy of these atoms, and the energy of the electrons in the
atoms moving around their nucleus (and sometimes we have to consider the
neutrons, protons, and other stuff moving around in the nucleus).
An atom's kinetic energy is related to its mass and its velocity.
The energy in the container is the sum of the kinetic energies of all of the
atoms, but the velocity is not the same for each atom, and the atoms are
continually exchanging this energy through collisions with each other and
through collisions with the walls.
In the same way that the mass may have freedom in the number of ways the
atoms may be arranged in space, the energy may have freedom in the
number of ways that the velocities and directions of the atoms may be
arranged.
The velocities of the molecules are closely related to the temperature.
The energy and freedom of gaseous atoms appear only in velocities and
directions, and is called translational energy and translational freedom.
In the case of molecules (a molecule is a group of two or more atoms held
together by chemical bonds) there are additional freedoms and additional
forms of energy.

Bonds between atoms act as springs allowing the atoms to vibrate

within the molecule, so that the molecules may contain different
levels of vibrational energy and vibrational freedom.
Additionally, the entire molecule may rotate on different axes,
allowing different levels of rotational energy and rotational
freedom.
While the freedom of mass is related to the volume in which the
mass is distributed, the freedom of energy is related to the
temperature.
An increase in the temperature of a gas leads directly to an increase
in energy, and this can only occur if there is a decrease in energy
somewhere else in the universe.
We say that energy is transferred to the gas and the container (we will call
that the "system")) from somewhere in the remainder of the universe (we
will call that the "surroundings").
The increase in energy is accompanied by an increase in the
energetic freedom of the system.
The thermodynamic term for quantifying freedom is entropy, and it is given
the symbol S.
Like freedom, the entropy of a system increases with the temperature and
with volume.
The effect of volume is more easily seem in terms of concentration,
especially in the case of mixtures.
For a certain number of atoms or molecules, an increase in volume
results in a decrease in concentration.
Therefore, the entropy of a system increases as the concentrations of the
components decrease.
The part of entropy which is determined by energetic freedom is
called thermal entropy, and the part that is determined by concentration is
called configurational entropy.
The units of entropy are the same as those of heat capacity and of the gas
law constant.
The product of entropy (or a change in entropy) and the absolute
temperature has the same units as energy (or a change in energy).
The First Law of Thermodynamics states that the energy of the
universe is constant.
The Second Law of Thermodynamics states that the entropy of the
universe cannot decrease.
If the temperature of a gas is increased while the volume remains
constant, the energy of the gas is increased and there is an increase in

energetic freedom or thermal entropy. There is no change in

concentration, and no change in configurational entropy.
Increase in Temperature
Increase in Energy
Increase in Thermal Entropy
-->
No Change in Volume or
Concentration
No Change in Configurational Entropy
If the volume of the gas is increased while the temperature remains
constant, the energy of the gas does not change and there is no change in
thermal entropy. The increase in volume lowers the concentration and
there is an increase in configurational entropy.

No Change in
Temperature;
No Change in
Energy;
No Change in
Thermal Entropy.
-->
Increase in Volume;
Decrease in
Concentration;
Increase in
Configurational
Entropy
The opening paragraph stated that matter tends to draw more matter to
itself and tries to reduce its energy. There is also the tendency to increase
its freedom and thus its entropy. There is a natural conflict between these
tendencies to lower energy and increase entropy, since a reduction in energy
is usually accompanied by a reduction in freedom and entropy. For changes
in which the initial and final temperatures are the same, these are combined
into a net tendency for a system to change, in which the symbol U is used for
energy and T is the absolute temperature.
U - TS

in which U and S represent the changes in energy and entropy that would
be measured for the change IF it occurred. If this net quantity is positive,
the change cannotoccur without some additional help. If this quantity
is negative, the change might occur but there is no guarantee that
it will occur. However, when the quantity is negative,
the reverse change cannot occur without additional help. Changes that
actually occur when this quantity is less than zero are said to
be spontaneous or irreversible.
If the quantity is equal to zero, the change will not occur, but it could be
pushed either forward or backward with very little additional help. This
condition is described asequilibrium, and the change is said to
be reversible.

Physical States
Crystal: A crystalline solid has very little movement and it is in a very low
energy state. Movement of the atoms or molecules is limited to vibrations
around a fixed point, so there is very little thermal entropy. The
atoms/molecules are very close together (high concentration) and they are
arranged in a very specific configuration (the crystal structure) which is
repeated over and over within the crystal. There is very little freedom in the
ways that the mass can be arranged, so the crystalline state has very little
configurational entropy.

Liquid: When a solid melts, the atoms/molecules begin to move around,

and perhaps also rotating and vibrating. The liquid has considerably more
energy than the solid and thus has more thermal entropy. The volume does
not change appreciably when a solid melts. Normally there is a small
increase in volume on melting (the solid sinks in the liquid), but a few
materials (water is one of them) show a decrease in volume on melting (the
solid floats in the liquid). Normally there is a small increase in
configurational entropy, but for materials like water there is a small
decrease. Overall, there is an increase in both energy and entropy when a
solid melts.

Gas: When a liquid vaporizes, the atoms/molecules receive a huge increase

in energy - so large that it seems like they are no longer subject to gravity.
There is a large increase in volume and the concentration becomes very
small. There is a correspondingly large increase in freedom, so that both the
thermal entropy and the configurational entropy are greatly increased.

Transitions
Melting (fusion): Both energy and entropy increase on melting,
so U and S are positive for fusion. At low temperatures (below the
melting point) the positive Ucontributes more than TS so the quantity
U - TS
is positive, and melting cannot occur. As the temperature is raised however,
both U and S increase but TS increases much more rapidly than U.
The quantity above will eventually become equal to zero at some
temperature (the melting point) and the solid will spontaneously melt at
any higher temperature.
The opposite of melting is freezing.
Boiling (vaporization): Both U and S are large and positive for
vaporization. The configurational entropy of the gas is related to the
concentration of the gas molecules, so S is greater for smaller
concentrations of molecules in the vapor. This allows a balance
between U and TS at low temperatures, providing the concentration of
gas molecules (and the vapor pressure) is sufficiently low. As the
temperature is raised, this balance is maintained by an increase in the
concentration of the gas molecules (and an increase in vapor pressure).
This results in a wide range of temperatures for a liquid and its vapor to be in
equilibrium, with the vapor pressure increasing as the temperature is raised.

The temperature at which the vapor pressure is exactly 1 atmosphere is

defined as the normal boiling point of the liquid.
The opposite of vaporization is condensation.
Sublimation:
In the same way that U and TS can balance for a liquid with its vapor at
very low temperature, a similar balance can occur for a solid and
its vapor below the melting point. For most solids, the vapor pressure is so
low that we aren't concerned about it. However, we can see the effect in
snow disappearing from a rooftop on a cold day without ever melting. This
process is called sublimation. For a few solids (carbon dioxide or "dry ice"
is one) the vapor pressure reaches 1 atmosphere at a temperature below the
melting point, so that we never see the liquid at atmospheric pressure. The
liquid state can be observed, however, at higher pressures and pressurized
cylinders of carbon dioxide usually contain a mixture of the liquid and the
gas.
The opposite of sublimation is deposition.

Solutions
When pure materials in some physical state are mixed to form a solution
in the same physical state at the same temperature and pressure, the
process is called mixing. The energy change on mixing may be either
positive or negative, but the entropy change is always positive. The entropy
change is due mainly to the decrease in the concentrations of the individual
components in the change from a limited volume in the pure state to a much
larger volume in the mixed state.

No Change in Temperature
Small Change in Energy
Small Change in Thermal Entropy
-->
Small Change in Volume
Decrease in Concentration of Red Molecules
Decrease in Concentration of Blue Molecules
Increase in Configurational Entropy
When the mixed components are roughly equal in concentration, they are
usually just called components (component A and component B, or

components 1 & 2). For these solutions, concentrations are usually

expressed in mole fractions, and occasionally in mass
fractions or volume fractions.
When the concentration of one component in a liquid solution is much
greater than the others, it is usually called the solvent, and the lessconcentrated components are calledsolutes. For these solutions,
the concentration of the solute may be expressed as mole
fraction, molality (moles of solute per kilogram of solvent),
or molarity (moles of solute per liter of solution). If needed, the
concentration of solvent is usually expressed as mole fraction.
Solubility of Solutes: Before mixing, the pure solute may have been
a gas, a liquid, or a solid. The first bit of solute that dissolves will have an
extremely lowconcentration, so the change in configurational entropy for
that dissolution will be very large if the pure solute is a liquid or a solid. If
the pure solute is a gas, the change in configurational entropy will
depend on the concentration of the gas. In all cases, the change
in thermal entropy may be positive or negative, but the configurational
entropy usually dominates at very low concentrations.
We can get a "feel" for the energy change as something dissolves. If the
solution becomes colder as the solute dissolves, the energy change is
positive since energy will have to be transferred to the solution in order to
bring it back to the original temperature. If the solution becomes hotter as
the solute dissolves, the energy change is negative since energy will have
to be removed from the solution in order to return to the initial temperature.
If the energy change is positive and unfavorable the positive entropy
change may allow a small amount of the solute to dissolve. However, as
more of the solute dissolves the concentration increases and the entropy
change decreases until the energy change is exactly balanced by TS and
no more of the solute will dissolve. The concentrationat this point
determines the solubility of the solute in the solvent at this temperature.
When there is a positive energy change for dissolution, an increase in
temperatureincreases the effect of the positive entropy change and
the solubility of the solute increases.
In the case of gases dissolving in liquids, the solubility of the gas depends on
the concentration of the gas molecules. As the concentration in the gas
phase increases, the concentration in the liquid phase increases. At low
concentrations there is a direct proportionality between the concentrations in
the two phases. This relationship is generally known as Henry's Law. Its
most common form is for the concentration in the vapor phase to be
represented by the partial pressure of the solute and for the concentration in
the liquid phase to be represented by the mole fraction of the solute.

Henry's Law is normally associated with the solute in dilute solutions, but
it also applies to the solvent in these dilute solutions. The application to
the solvent is a special case of Henry's Law, called Raoult's Law. Raoult's
Law states that the vapor pressure (or partial pressure) of the solvent
becomes equal to the mole fraction of the solvent multiplied by the vapor
pressure of the pure solvent when the solutes become very dilute.
Colligative Properties (Solvent): Colligative properties of solutions
are properties which depend only on the concentration of the solvent,
and are independent of what the solute might be. Raoult's Law is the most
basic example of a colligative property, because the vapor pressure (or
partial pressure) of the solvent is determined only by the mole fraction of the
solvent in a sufficiently dilute solution. This is usually stated as vapor
pressure lowering by a non-volatile solute: The difference between the
vapor pressure of the solution and that of the pure solvent is proportional to
the mole fraction of solute.
All colligative properties are based on the fact that the concentration of the
solvent is greatest when the solvent is pure, and the concentration of the
solvent decreases as solute is added. When applied
to freezing and melting, the entropy change is greater for the frozen pure
solvent to melt when a solute is present than when the liquid phase is pure,
and the solvent can melt at a lower temperature. This freezing point
depression depends only on the concentration of the solvent and not on the
nature of the solute, and is therefore a colligative property.
In a similar fashion, when a solution containing a solvent and a non-volatile
solute is heated to near its boiling point at 1 atmosphere pressure, the
entropy of the solvent in the solution is greater than in the pure liquid. This
makes the entropy change for vaporization from the solution less than from
the pure liquid, and the solvent will not boiluntil the temperature
is higher than the normal boiling point. This boiling point elevation is
also a colligative property.
In some cases, a solvent may be separated from a solution containing a
solute by a semi-permeable membrane. The solvent can move through
the pores in this membrane, but the solute is unable to move through the
pores because of its size or perhaps its charge or polarity. This movement
of the solvent is called osmosis. Since the concentration of the solvent is
lower in the solution than in the pure liquid, the solvent molecules have
greater entropy in the solution, and there is a tendency for the molecules to
move through the membrane. As the solvent molecules move, the liquid
level of the solution becomes higher than that of the pure liquid, and
eventually the pressure becomes sufficient to prevent any more solvent
molecules from crossing the membrane. This pressure difference between

the solution and the pure solvent is called the osmotic pressure. Osmotic
pressure is a colligative property.

ORDER and DISORDER

This discussion has carefully avoided
associating entropy with order and disorder. Instead, the focus has been
on different types of freedom. Many textbooks use the order/disorder
interpretation, and refer to examples such as the entropy of a shuffled deck
of cards, or the entropy of a messy desk (or room) in comparison to a neat
one. While these are strong images, the concept is basically incorrect.
The example with a deck of cards assumes that there is some order of the
cards which represents perfect order. This simply happens to be the order
given to a sealed deck by the manufacturer, namely each suit increasing
from the Ace sequentially to the King, with alternating colors of the suits.
That is no more orderly than starting with the 2and increasing through the
King to the Ace, or the reverse order. The deck could be arranged with all
four Aces in some order of suits, followed by the four 2's in the same order
of suits, etc. - that is also ordered. A new manufacturer may decide to
package the decks in some order that has significance only to that
manufacturer. Does that arrangement then become the perfect order for
his product? Perhaps we should also be concerned with whether the cards
are all facing the same direction.
The point is that there are many possible arrangements of the cards in a
deck. When the cards are randomly and thoroughly shuffled, each of these
arrangements has equal probability of occurring. When an arrangement is
established, there is no freedom for the deck to acquire any other
arrangement unless someone shuffles it or rearranges it in some manner.
Since there is no freedom for that arrangement, there is no entropy
associated with a single arrangement.
On the other hand, if a very large number of decks of cards are thoroughly
and randomly shuffled, there are many possibilities for the arrangements of
the cards within the different decks. When this idea of different
arrangements of the cards is applied
to atoms and molecules in solids and liquids, the number of possible
arrangements createfreedom of arrangement, a type of configurational

entropy - not for any specific deck, but for the group of decks - or
the ensemble (technically, the ensemble is the huge imaginary group of all
of these decks arranged in all of the possible arrangements) of decks. The
number of possible arrangements of the 52 cards in a deck is 52! (fifty-two
factorial) which is equal to 52 x 51 x 50 x 49 x...x 3 x 2 x 1 , an
astronomical number. If these cards were atoms or molecules, the entropy
due to this incredible amount of freedom would be related to the number of
randomized decks multiplied by the natural logarithm of 52!. We can
calculate the entropy per deck by dividing the entropy of the group of
decks by the number of decks, but it is important to differentiate between
the entropy per deck (which is a property of the group) and
the entropyof a single deck (which really has no meaning in chemical
systems).