The Laws of Thermodynamics

1st Law of Thermodynamics - Energy cannot be created or destroyed.

 
2nd Law of Thermodynamics - For a spontaneous process, the entropy of the
universe increases.
 
3rd Law of Thermodynamics - A perfect crystal at zero Kelvin has zero entropy.

The First Law of Thermodynamics

The First Law of Thermodynamics states that energy cannot be created or
destroyed.  Alternatively, some sum it up as "the conservation of energy." 
Ultimately, the First Law of Thermodynamics is a statement that energy can be
transferred between the system and the surroundings through the transfer of heat (q)
or by the performance of mechanical work (w).
 
ΔE = q + w
 
Energy doesn't simply materialize or disappear.  Any gain in energy by the system
will correspond to a loss in energy by the surroundings, or any loss in energy by the
system will correspond to a gain in energy by the surroundings.

The Second Law of Thermodynamics

The Second Law of Thermodynamics can be stated in any of three synonymous ways:
 
For a spontaneous process, the entropy of the universe increases.
 
For a spontaneous process,  ΔSuniverse > 0.
 
For a spontaneous process, ΔSsystem + ΔSsurroundings > 0
 
Ultimately, for any spontaneous process the entropy, which is related to randomness
or disorder, of the universe increases.  Entropy is covered in much greater detail in the
next lesson (18.2 Entropy) but that it correlates with disorder will suffice for now.
 
The last statement of the Second Law of Thermodynamics divides the universe into
two parts: the system (what you're investigating) and the surroundings (everything in
the universe besides the system).  In chemistry the system is often a chemical reaction
under investigation.  To be clear the Second Law does NOT mean that ΔSreaction must
be positive as ΔSreaction is just the ΔSsystem which can be either positive or negative.  But
if ΔSreaction for a spontaneous reaction is negative, then the Second Law does mean that
ΔSsurroundings must be positive and of greater magnitude in this example so that ΔSsystem +
ΔSsurroundings > 0.
 
In one sense you can view the Second Law of Thermodynamics as being the most
important of the three; in the sense that it is the one most commonly tested upon in
this chapter and students should recognize it in any of the three forms presented
above.

The Third Law of Thermodynamics

The Third Law of Thermodynamics states that a perfect crystal at zero Kelvin
(absolute zero) has zero entropy.  First, a perfect crystal means that there are no
impurities, has achieved thermodynamic equilibrium, and that it is in a crystalline
state where all the atoms/ion/molecules are in well-defined positions in a highly-
ordered crystalline lattice.  This would exclude amorphous solids like glass that don't
have an ordered, crystalline structure and have not achieved thermodynamic
equilibrium.
 
The Third Law is not intuitive but was derived empirically as a system's entropy
always approached the same minimum value as the absolute temperature was lowered
and approached zero.  From the standpoint of statistical mechanics the Third Law
implies that a perfect crystal at absolute zero must exist in a single microstate as we'll
see in the next lesson on Entropy.
 
The Third Law also provides us with a reference point, which combined with the fact
that entropy is a state function allows us to determine the absolute entropy of a
substance at any temperature which is very useful for calculating ΔSreaction as we'll see
later in the chapter (18.4 Delta G, Delta H, Delta S and Formation Reactions).  We'll
also learn that such a reference point is not available for Gibbs Free Energy or
Enthalpy leading to the use of formation reactions in calculating ΔGreaction and ΔHreaction.