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The 1st Law of Thermodyamics simply states that energy can be neither
created nor destroyed (conservation of energy). Thus power generation
processes and energy sources actually involve conversion of energy from
one form to another, rather than creation of energy from nothing. For
example:
As you can see conversion between chemical energy and other forms of
energy are extremely important, whether you are veterinarian or a
mechanical engineer. That is what we will focus on for the remainder of
this chapter.
The 1st Law of Thermodynamics tells us that energy is neither created nor
destroyed, thus the energy of the universe is a constant. However, energy
can certainly be transferred from one part of the universe to another. To
work out thermodynamic problems we will need to isolate a certain portion
of the universe (the system) from the remainder of the universe (the
surroundings).
For example consider the pendulum example given in the last section. In
real life there is friction and the pendulum will gradually slow down until it
comes to rest. We can define the pendulum as the system and everything
else as the surroundings. Due to friction there is a small but steady
transfer of heat energy from the system (pendulum) to the surroundings
(the air and the bearing upon which the pendulum swings). Due to the 1 st
law of thermodynamics the energy of the system must decrease to
compensate for the energy lost as heat until the pendulum comes to rest.
[Remember though the total energy of the universe remains constant as
required by the 1st Law.]
When it comes time to work homework, quiz and exam problems (not to
mention to design a power plant or computer chip) the 1 st Law of
Thermodynamics will be much more useful if we can express it as an
equation.
This reformulation of the 1st Law tells us that once we define a system
(remember we can define the system in any way that is convenient) the
energy of the system will remain constant unless there heat added or
taken away from the system, or some work takes place.
Internal Energy
We have already discussed work and heat extensively, but a few
comments are in order regarding internal energy. The internal energy
encompasses many different things, including:
E = E(final) – E(initial) = q + w
Sign Convention
Example
Solution A
System � You
Surroundings � Ice + the rest of the universe
q < 0 � Heat flows out of the system (you) into the ice.
Solution B
System � Ice
Surroundings � You + the rest of the universe
q > 0 � Heat flows into the system (ice) from you.
You can see that the answer changes depending upon how you define the
system, but the physical reality is exactly the same, but both solutions A
and B are correct. It doesn’t matter how you define the system as long as
you are consistent.
Example
Solution A
System � The sweat
Surroundings � Your body + the rest of the universe
q > 0 � Heat flows into the system (sweat) from you in order to
raise the kinetic energy of the sweat molecules enough to allow
them to go from the liquid phase to the gas phase.
Solution B
System � You
Surroundings � The sweat + the rest of the universe
q < 0 � Heat flows out of the system (you) into the sweat.
Since heat leaves your body this cools you down. That’s why we sweat
after all.
Example
Exothermic Reactions
q<0
reaction releases heat (heat leaves the system)
heat is a product of the reaction (i.e. explosions, combustions, etc.)
Endothermic Reactions
q>0
reaction absorbs heat (heat enters the system)
heat is a reactant in the reaction
P-V Work
Most chemical reactions either give off or absorb heat, but not all
chemical reactions do a significant amount of work. By far the most
common types of work associated with chemical reactions are:
At this point in the course we will not concern ourselves with electrical
work (until chapter 20). Therefore, we only have to worry about work
when a gaseous product or reactant is involved (for example the previous
example of the reaction that takes place in the automobile cylinder).
Let us return to 1st Law equation with the restriction that the only type
of work we will consider is done by the expansion/ contraction of a gas
(think of the cylinder example).
E = q + w = q - (F � d) = q - Fh
where F is the force opposing the upward push of the cylinder, and h is
the distance we move the cylinder upwards against this force. The
negative sign in front of the second term comes from the sign convention
for work. If the gas expands then h will be positive and the system will
do work on the surroundings (the piston), and when that happens work
must be negative. Now we use the relationship:
P = F/A � F = PA
E = q - PAh
but the cross sectional area of the cyliner (piston) multiplied times h is
simply the change in the volume of the cylinder:
E = q - PV
E = H - PV
H = H(final) – H(initial) = qp
At first you might think that constant pressure reactions are a special
case, so that enthalpy isn’t a terribly useful concept. As it turns out any
reaction which is carried out in an open container (such as a beaker or a
test tube) is a constant pressure reaction. Therefore, as you will soon see
enthalpy is a concept that we will use over and over again.
State Functions
Example
Lets say I move two bricks from the sidewalk outside McPherson Hall to
the roof of the building so that the change in elevation of both bricks is
exactly the same. However, lets say I don’t take the same route to get to
the roof in each case.
Brick B � I first carry this brick over to high street because I have to
stop by the bank. Then having some money I stop into BW-3 to get a pint
of beer. Then I wander over to my office in Newman and Wolfrom to
check my e-mail. Finally I go back outside and then take the stairs up to
the roof of McPherson.
Example
Consider two beakers of water. I raise the temperature of beaker A to
80� C using a bunsen burner. I attempt to raise the temperature of
beaker B in the same manner, but accidentally heat up to 90� C instead.
At this point I turn the burner off to let the water cool. I unexpectedly
get called away and when I return the temperature of beaker B is now
50� C, so I have to heat it again to get to 80� C.
You can see that while the temperature is a state function (a sample at
80� C is at 80� C regardless of what temperature it was 2 hours ago),
while the amount of heat transferred into or out of a system is very
dependent upon the history of the system, so that heat is not a state
function.
When you exercise, some of the food energy gets converted into muscle work, but most of
it gets converted to what we engineers call low-grade thermal energy. That's why you get
all hot and sweaty. In fact, more than 60% of the food energy is converted to body-
warming sweat-making thermal energy during metabolism of food energy. That leaves only
40% to do useful work in the cells. If you also figure in the energy required to digest the
food and to pump it around in blood to all the cells, the final number can be significantly
less than 40%. That's about the same as many of our human-made engines.
And, as with human-made machines and devices, all of the mechanical work done by the
cells also ends up as low-grade heat (thermal energy), lost to us forever. The total amount
of energy hasn't changed (1st law), but we can't use it anymore (2nd Law)
For anything to happen, energy has to move or flow or change. Energy will keep flowing or
changing from a higher concentration to a lower concentration until the concentrations are
equal (not necessarily more disordered). We call that condition, cleverly enough,
equilibrium.
So that's one part of the Second Law of Thermodynamics. Energy will flow to a more
"spread out" or "less concentrated" condition. It stops flowing when there is no longer a
difference in concentration levels - when things have reached the great state of
equilibrium.
We can slow it down, or even stop it by blocking the more concentrated energy from
reaching or connecting with the less concentrated energy. But the potential is still there. If
we close the switch, open the valve, start the chemical reaction, or break the levee, look
out.
Zeroth law of thermodynamics: If two systems are both in thermal equilibrium with a
third system then they are in thermal equilibrium with each other. This law helps define
the notion of temperature.
First law of thermodynamics: Heat and work are forms of energy transfer. Energy is
invariably conserved however the internal energy of a closed system may change as heat
is transferred into or out of the system or work is done on or by the system. In real
systems work does not always leave the system. For example, changes in molecular
energy (potential energy), are generally considered to remain within the system.
Similarly, the rotational and vibrational energies of polyatomic molecules remain within
the system.
From the above, all the energy associated with a system must be accounted for as heat,
work, chemical energy etc., thus perpetual motion machines of the first kind, which
would do work without using the energy resources of a system, are impossible.