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Mass, Energy, and Freedom Mass, Energy, and Freedom Mass, Energy, and Freedom Mass, Energy, and Freedom - -- - The Coins of Thermodynamics The Coins of Thermodynamics The Coins of Thermodynamics The Coins of Thermodynamics
Gary L. Bertrand, Department of Chemistry
University of Missouri-Rolla (now Missouri S&T)

Basics Basics Basics Basics
The universe is made up of bits of matter, and the bits of matter
have mass mass mass mass and energy energy energy energy.
Neither mass nor energy may be created or destroyed, but in some special cases some special cases some special cases some special cases
interconversions between mass and energy may occur. interconversions between mass and energy may occur. interconversions between mass and energy may occur. 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 freedom freedom 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 can be a decrease in the freedom in one part of the universe, but ONLY if There can be a decrease in the freedom in one part of the universe, but ONLY if 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. there is an equal or greater increase in the rest of the universe. there is an equal or greater increase in the rest of the universe. 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 m freedom of the m freedom of the m freedom of the mass ass ass ass and the freedom freedom freedom freedom
of the energy of the energy of the energy 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 Bonds between atoms act as springs allowing the atoms to vibrate within the Bonds between atoms act as springs allowing the atoms to vibrate within the Bonds between atoms act as springs allowing the atoms to vibrate within the
molecule, so that the molecules may contain different levels of vibrational molecule, so that the molecules may contain different levels of vibrational molecule, so that the molecules may contain different levels of vibrational molecule, so that the molecules may contain different levels of vibrational
energ energ energ energy and vibrational freedom. y and vibrational freedom. y and vibrational freedom. y and vibrational freedom.
Additionally, the entire molecule may rotate on different axes, allowing Additionally, the entire molecule may rotate on different axes, allowing Additionally, the entire molecule may rotate on different axes, allowing Additionally, the entire molecule may rotate on different axes, allowing
different levels of rotational energy and rotational freedom. different levels of rotational energy and rotational freedom. different levels of rotational energy and rotational freedom. different levels of rotational energy and rotational freedom.
While the freedom of mass is related to the volume in which the mass is While the freedom of mass is related to the volume in which the mass is While the freedom of mass is related to the volume in which the mass is While the freedom of mass is related to the volume in which the mass is
distributed, distributed, distributed, distributed, the fre the fre the fre the freedom of energy is related to the temperature edom of energy is related to the temperature edom of energy is related to the temperature edom of energy is related to the temperature.
An increase in the temperature of a gas leads directly to an increase in energy, An increase in the temperature of a gas leads directly to an increase in energy, An increase in the temperature of a gas leads directly to an increase in energy, 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 and this can only occur if there is a decrease in energy somewhere else in the and this can only occur if there is a decrease in energy somewhere else in the and this can only occur if there is a decrease in energy somewhere else in the
universe. universe. universe. 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 The increase in energy is accompanied by an increase in the energetic freedom The increase in energy is accompanied by an increase in the energetic freedom The increase in energy is accompanied by an increase in the energetic freedom
of the system. of the system. of the system. of the system.
The thermodynamic term for quantifying freedom is entropy entropy entropy entropy, and it is given
the symbol S SS 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 For a certain number of atoms or molecules, an increase in volume results in a For a certain number of atoms or molecules, an increase in volume results in a For a certain number of atoms or molecules, an increase in volume results in a
decrease in concentration. decrease in concentration. decrease in concentration. decrease in concentration.
Therefore, the entropy entropy entropy entropy of a system increases as the concentrations concentrations concentrations concentrations of the
components decrease.
The part of entropy which is determined by energetic freedom is called thermal thermal thermal thermal
entropy entropy entropy entropy, and the part that is determined by concentration is
called configurational entropy configurational entropy configurational entropy configurational entropy.
The units units units units of entropy are the same as those of heat capacity heat capacity heat capacity heat capacity and of the gas law gas law gas law gas law
constant constant constant constant.
The product product product product of entropy entropy entropy entropy (or a change in entropy) and the absolute temperature absolute temperature absolute temperature absolute temperature
has the same units as energy energy energy energy (or a change in energy).

The First Law of Thermodynamics states that the energy of the The First Law of Thermodynamics states that the energy of the The First Law of Thermodynamics states that the energy of the The First Law of Thermodynamics states that the energy of the universe is universe is universe is universe is
constant. constant. constant. constant.
The Second Law of Thermodynamics states that the entropy of the universe The Second Law of Thermodynamics states that the entropy of the universe The Second Law of Thermodynamics states that the entropy of the universe The Second Law of Thermodynamics states that the entropy of the universe
cannot decrease. cannot decrease. cannot decrease. cannot decrease.

If the temperature temperature temperature temperature of a gas is increased increased increased increased while the volume remains constant,
the energy energy energy energy of the gas is increased and there is an increase in energetic freedom
or thermal entropy thermal entropy thermal entropy thermal entropy. There is no change in concentration, and no change in
configurational entropy.




Increase in Temperature Increase in Temperature Increase in Temperature Increase in Temperature
Increase in Energy Increase in Energy Increase in Energy Increase in Energy
Increase in Thermal Entropy Increase in Thermal Entropy Increase in Thermal Entropy Increase in Thermal Entropy
-- -- -- --> >> >
No Change in Volume or No Change in Volume or No Change in Volume or No Change in Volume or
Concentration Concentration Concentration Concentration
No Change in No Change in No Change in No Change in Configurational Configurational Configurational Configurational
Entropy Entropy Entropy 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 increase in volume increase in volume increase in volume lowers the concentration and there is
an in in in increase crease crease crease in configurational entropy configurational entropy configurational entropy configurational entropy.




No Change in No Change in No Change in No Change in
Temperature Temperature Temperature Temperature; ;; ;
No Change in Energy No Change in Energy No Change in Energy No Change in Energy; ;; ;
No Change in No Change in No Change in No Change in
Thermal Entropy Thermal Entropy Thermal Entropy Thermal Entropy. .. .
-- -- -- --> >> >
Increase in Volume Increase in Volume Increase in Volume Increase in Volume; ;; ;
Decrease in Decrease in Decrease in Decrease in
Concentration Concentration Concentration Concentration; ;; ;
Increase in Increase in Increase in Increase in
Configurational Configurational Configurational Configurational
Entropy Entropy Entropy 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 UU U is used for energy
and T TT T is the absolute temperature temperature temperature temperature.
U U U U - -- - TS TS TS TS
in which U U U U and S S S S represent the changes in energy and entropy that would be
measured for the change IF IF IF IF it occurred. If this net quantity is positive positive positive positive, the
change cannot cannot cannot cannotoccur without some additional help. If this quantity is negative negative negative negative,
the change might might might might occur but there is no guarantee that it will will will will occur. However,
when the quantity is negative negative negative negative, the reverse reverse reverse reverse change cannot cannot cannot cannot occur without
additional help. Changes that actually occur when this quantity is less than
zero are said to be spontaneous spontaneous spontaneous spontaneous or irreversible irreversible irreversible irreversible.
If the quantity is equal equal equal equal to zero, the change will not occur, but it could be could be could be could be
pushed pushed pushed pushed either forward or backward with very little additional help. This
condition is described asequilibrium equilibrium equilibrium equilibrium, and the change is said to be reversible reversible reversible reversible.




Physical States Physical States Physical States Physical States
Crystal: Crystal: Crystal: 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: Liquid: Liquid: 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: Gas: Gas: 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 Transitions Transitions Transitions
Melting (fusion): Melting (fusion): Melting (fusion): Melting (fusion): Both energy and entropy increase on melting,
so U U U U and S S S S are positive positive positive positive for fusion. At low temperatures (below the melting
point) the positive U U U Ucontributes more than TS TS TS TS so the quantity
U U U U - -- - TS TS TS TS
is positive, and melting cannot occur. As the temperature is raised however,
both U U U U and S S S S increase but TS TS TS TS increases much more rapidly than U U U U. The
quantity above will eventually become equal to zero at some temperature (the the the the
melting point melting point melting point melting point) and the solid will spontaneously melt at any higher temperature.
The opposite of melting melting melting melting is freezing freezing freezing freezing.

Boiling (vaporization): Boiling (vaporization): Boiling (vaporization): Boiling (vaporization): Both U U U U and S S S S are large and positive for
vaporization. The configurational entropy of the gas is related to the
concentration of the gas molecules, so S S S S is greater for smaller concentrations
of molecules in the vapor. This allows a balance between U U U U and TS TS TS 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 vapor pressure vapor pressure vapor pressure is exactly 1 atmosphere 1 atmosphere 1 atmosphere 1 atmosphere is
defined as the normal boiling point normal boiling point normal boiling point normal boiling point of the liquid.
The opposite of vaporization vaporization vaporization vaporization is condensation condensation condensation condensation.

Sublimation: Sublimation: Sublimation: Sublimation:
In the same way that U U U U and TS TS TS TS can balance for a liquid with its vapor at very
low temperature, a similar balance can occur for a solid solid solid solid and its vapor vapor vapor 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 sublimation sublimation 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 subli subli subli sublimation mation mation mation is deposition deposition deposition deposition.


Solutions Solutions Solutions 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 mixing mixing 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 No Change in Temperature No Change in Temperature No Change in Temperature
Small Change in Energy Small Change in Energy Small Change in Energy Small Change in Energy
Small Change in Thermal Entropy Small Change in Thermal Entropy Small Change in Thermal Entropy Small Change in Thermal Entropy
-- -- -- --> >> >
Small Change in Volume Small Change in Volume Small Change in Volume Small Change in Volume
Decrease in Concentration of Red Decrease in Concentration of Red Decrease in Concentration of Red Decrease in Concentration of Red
Molecules Molecules Molecules Molecules
Decrease in Concentration of Blue Decrease in Concentration of Blue Decrease in Concentration of Blue Decrease in Concentration of Blue
Molecules Molecules Molecules Molecules
Increase in Configurational Entropy Increase in Configurational Entropy Increase in Configurational Entropy Increase in Configurational Entropy


When the mixed components are roughly equal in concentration, they are
usually just called components components components components (component A AA A and component B BB B, or
components 1 11 1 & 2 22 2). For these solutions, concentrations oncentrations oncentrations oncentrations are usually expressed
in mole fractions mole fractions mole fractions mole fractions, and occasionally in mass mass mass mass fractions fractions fractions fractions or volume fractions volume fractions volume fractions volume fractions.
When the concentration of one component in a liquid solution is much greater
than the others, it is usually called the solvent solvent solvent solvent, and the less-concentrated
components are calledsolutes solutes solutes solutes. For these solutions, the concentration concentration concentration concentration of
the solute solute solute solute may be expressed as mole fraction mole fraction mole fraction mole fraction, molality molality molality molality (moles of solute per
kilogram of solvent), or molarity molarity molarity molarity (moles of solute per liter of solution). If
needed, the concentration of solvent solvent solvent solvent is usually expressed as mole fraction mole fraction mole fraction mole fraction.
Solubility of Solutes: Solubility of Solutes: Solubility of Solutes: Solubility of Solutes: Before mixing, the pure solute pure solute pure solute pure solute may have been a gas gas gas gas,
a liquid liquid liquid liquid, or a solid solid solid solid. The first bit of solute that dissolves will have an
extremely low low low lowconcentration, so the change in configurational entropy configurational entropy configurational entropy configurational entropy for that
dissolution will be very large large large large if the pure solute is a liquid or a solid. If the pure
solute is a gas gas gas gas, the change in configurational entropy configurational entropy configurational entropy configurational entropy will depend on
the concentration concentration concentration concentration of the gas. In all cases, the change in thermal entropy thermal entropy thermal entropy thermal entropy may
be positive positive positive positive or negative negative negative 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 colder colder colder as the solute dissolves, the energy change is energy change is energy change is energy change is
positive positive positive 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 hotter hotter hotter as the
solute dissolves, the energy change is negative energy change is negative energy change is negative 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 p pp positive ositive ositive ositive and unfavorable unfavorable unfavorable 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 T T T TS SS S and no more of the solute
will dissolve. The concentration concentration concentration concentrationat this point determines the solubility solubility solubility solubility of the
solute in the solvent at this temperature temperature temperature temperature. When there is a positive positive positive positive energy
change for dissolution, an increase in temperature increase in temperature increase in temperature increase in temperatureincreases the effect of the
positive entropy change and the solubility solubility solubility solubility of the solute increases increases increases 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 Henry's Law Henry's Law 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 Henry's Law Henry's Law Henry's Law is normally associated with the solute solute solute solute in dilute solutions, but it
also applies to the solvent solvent solvent solvent in these dilute solutions. The application to
the solvent solvent solvent solvent is a special case of Henry's Law, called Raoult's Law Raoult's Law Raoult's Law 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 (Solvent): Colligative Properties (Solvent): Colligative Properties (Solvent): Colligative Colligative Colligative Colligative properties properties properties properties of solutions are
properties which depend only on the concentration of the solvent concentration of the solvent concentration of the solvent concentration of the solvent, and are
independent of what the solute might be. Raoult's Law Raoult's Law Raoult's Law 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 vapor pressure vapor pressure vapor pressure
lowering lowering lowering 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 freezing freezing freezing and melting melting melting 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 melt melt melt at
a lower lower lower lower temperature. This freezing point depression freezing point depression freezing point depression freezing point depression depends only on the
concentration of the solvent and not on the nature of the solute, and is
therefore a colligat colligat colligat colligative property ive property ive property ive property.
In a similar fashion, when a solution containing a solvent and a non non non non- -- -volatile volatile volatile volatile
solute solute solute 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 boil boil boil boiluntil the temperature is higher higher higher higher than the
normal boiling point. This boiling point elevation boiling point elevation boiling point elevation 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 semi semi semi- -- -permeable membrane permeable membrane permeable membrane 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 size size size or perhaps its charge charge charge charge or polarity. This movement of the solvent is
called osmosis osmosis osmosis 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 osmotic pressure osmotic pressure. Osmotic pressure is a colligative property.




ORDER and DISORDER ORDER and DISORDER ORDER and DISORDER ORDER and DISORDER
This discussion has carefully avoided
associating entropy entropy entropy entropy with order order order order and disorder disorder disorder disorder. Instead, the focus has been on
different types of freedom freedom freedom 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 perfect order perfect order perfect order. This simply happens to be the order given to a
sealed deck by the manufacturer, namely each suit increasing from
the Ace Ace Ace Ace sequentially to the King King King King, with alternating colors of the suits. That is no
more orderly than starting with the 2 22 2and increasing through the King to
the Ace, Ace, Ace, Ace, or the reverse order. The deck could be arranged with all four Aces Aces Aces Aces in
some order of suits, followed by the four 2 22 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 perfect order perfect order 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 each each each of these
arrangements has equal probability equal probability equal probability 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 very large number very large number 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 atoms atoms atoms and molecules molecules molecules molecules in solids solids solids solids and liquids liquids liquids liquids, the number of
possible arrangements createfreedom of arrangement freedom of arrangement freedom of arrangement freedom of arrangement, a type of configurational configurational configurational configurational
entropy entropy entropy entropy - not for any specific deck, but for the group of decks group of decks group of decks group of decks - or
the ensemble ensemble ensemble ensemble (technically, the ensemble ensemble ensemble 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! 52! 52! 52! (fifty-two factorial)
which is equal to 52 x 51 x 50 x 49 x...x 3 x 2 x 1 52 x 51 x 50 x 49 x...x 3 x 2 x 1 52 x 51 x 50 x 49 x...x 3 x 2 x 1 52 x 51 x 50 x 49 x...x 3 x 2 x 1 , an astronomical number. If
these cards were atoms atoms atoms atoms or molecules molecules molecules 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! 52! 52! 52!. We can calculate the entropy per deck entropy per deck entropy per deck 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 entropy entropy entropy per per per per deck deck deck deck (which is a property of the group group group group)
and the entropyof entropyof entropyof entropyof a a a a single deck single deck single deck single deck (which really has no meaning in chemical
systems).