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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.
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.
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.
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
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.
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).