Thermodynamics Principles of Inorganic Chemistry

Kettering College of Medical Arts Document #16

Prepared by: Richard E. Bleil, Ph.D. 1
The Kettering College of Medical Arts

Thermodynamics

Prepared By: Richard E. Bleil, Ph.D.

Introduction:

Thermodynamics gets a bad rap. If I were to tell you how my best friend refers to
it, you would be offended, and I would lose my job! Admittedly, thermodynamics can be
a very difficult, abstract and mathematically intensive subject. Then again, on the other
hand, if we stick to the basics, it is not so difficult and, as we will see, not even so
abstract. Before we discuss the details of thermodynamics, however, lets decide what
thermodynamics is.
Thermodynamics is the study of energy changes in chemical processes. Well,
THATS exciting. So whats the point? Well, with thermodynamics, we can predict
several things. We can predict if a reaction will be exothermic (get hot) or endothermic
(get cold). In fact, we can even predict exactly how much heat a reaction will give off or
absorb. More importantly, however, we can predict if a reaction will even occur and
under what conditions!
Do you own any diamonds? Diamonds are very VERY poor investments. This is
because there is a reaction that converts diamonds into graphite.

C (Diamond) --> C (Graphite)

Thermodynamics tells us that this reaction is occuring (at the temperature and pressure of
the surface of the earth) naturally. In other words, once this reaction is complete, all those
diamonds you own will be nothing more than graphite, pencil lead! So, take a good close
hard look at your diamonds. Remember how sparkly they were when you first got them?
Now, as you look, do you notice changes in color, or black flacks imbedded in them? No?
Well, just wait, you will. Yep, in a few billion years, well start to be able to notice the
discoloration.
See, thermodynamics will tell us if a reaction will occur or not, but
thermodynamics will not tell us how quickly this reaction will occur. The speed with
which reactions occur falls under the heading kinetics, a fascinating field in and of itself,
but unfortunately, beyond the scope of this document.
Well, lets get to thermodynamics.

Foundations: Enthalpy

There are two primary driving forces that set chemical reactions in motion, namely,
enthalpy and entropy. We shall discuss enthalpy here.
Thermodynamics Principles of Inorganic Chemistry
Kettering College of Medical Arts Document #16
Prepared by: Richard E. Bleil, Ph.D. 2
Enthalpy can be thought of as heat energy. Everything tends to minimize its
energy. As a ball rolls down a hill, it is going to lower potential energy. Even we tend to
do this. After all, would you rather carry four bags of groceries one mile uphill, or one
mile downhill? No, we would want energy on our side, we want to minimize our energy.
Chemical reactions are the same. They want to minimize their energy. To do this,
they have to lose some of the energy they have. This excess energy is given off as heat.
When a reaction minimizes its reaction, it gives off heat, so the surroundings become
hotter, and we say the reaction is exothermic. The converse is true as well. If a reacion
is exothermic, then its energy is being minimized. Since processes tend to want their
energy to be minimized, we say that the enthalpy is favorable when it is exothermic.
Following is an energy diagram for an exothermic reaction.



Notice three things about this diagram. First, it is an exothermic reaction because
the energy of the products is lower than the energy of the reactants. The difference in
energy between these two states is exactly how much energy that will be released.
Second, notice that the change in enthalpy does not include the activation energy. The
activation energy is how much energy we must supply to get the reaction to begin, but any
energy absorbed initially (as we start up the energy barrier or hill) will be released as the
reaction proceeds (go back down on the opposite side). The heat released will only be the
difference between the initial and final states. Finally, notice that if we trace the reaction
backwards, from products to reactants, the amount of energy that will be absorbed will be
exactly identical to the amount of energy released in the forward reaction.
Still, though, we know of examples that are not exothermic. When I got my scuba
license, I bought a small first aid kit, and within this kit is a cold pack, a plastic bag filled
with a chemical that, when agitated, becomes very cold. Well, if the bag gets cold, that
means that heat is being absorbed, and the energy of the chemicals within that bag are
Thermodynamics Principles of Inorganic Chemistry
Kettering College of Medical Arts Document #16
Prepared by: Richard E. Bleil, Ph.D. 3
going to a higher energy. We say that such a process is endothermic. Following is an
energy diagram for such an endothermic reaction:



Here, notice that the activation energy is larger than the change in enthalpy. The
products have a higher energy than the reactants, so the change in enthalpy is the amount
of energy that will be absorbed. Again, the reverse reaction would be exothermic, and the
change in enthalpy is only a function of the inital and final energies.
But what is the source of all of this energy? Bonds. Yep, chemical or
intermolecular. Intermolecular forces are those forces that hold atoms and molecules
together to form a liquid or solid, while a chemical bond is the force that holds atoms
together to form molecules. Chemical bonds are much stronger than intermolecular
forces.
Chemicals form bonds because their energy is always lower with the bond than
they are without these bonds. If this were not the case, then chemical bonds would not
ever form. Therefore, bond formation is always exothermic. If forming a bond is
exothermic, then breaking a bond must be endothermic. In other words, it always requires
energy to break a bond, and there is always energy released when we break a bond.
For a chemical reaction to occur, two things must happen. First, the bonds holding
the reactants together must be broken. This always requires energy to be put into the
system. Sometimes there is enough energy just in the initial conditions to cause the
reaction to proceed, but sometimes it takes a little more energy. The Hindenberg flew
across an entire ocean with the deadly mixture of hydrogen and oxygen, but there was not
enough energy to break the hydrogen-hydrogen and oxygen-oxygen bonds to get the
reaction started until a spark here in the US began the deadly reaction.
Once the bonds of the reactants have been broken, then new bonds will form as we
make the products. As these new bonds are formed, energy is released. So how can we
Thermodynamics Principles of Inorganic Chemistry
Kettering College of Medical Arts Document #16
Prepared by: Richard E. Bleil, Ph.D. 4
tell if a reaction is endothermic or exothermic? Simple. If more energy is released when
the new bonds were formed than the energy absorbed when the old bonds were broken,
then the reaction will be exothermic. If more energy is required to break the old bonds
than the energy we get out by the formation of the new bonds, then the reaction will be
endothermic.



Enthalpy Calculations Using Bond Energy:

So can we calculate enthalpy changes? Would I ask if we could not? Enthalpy is
designated with a capital H, so change in enthalpy is designated ? H. Change between
what and what? Well, the change between reactants and products.
The first thing we must understand is that, by convention, as with any changes we
calculate in chemistry, when we talk about changes in enthalpy, we mean the enthalpy of
the products minus the enthalpy of the reactants.

? H=H
products
-H
reactants


Changes are always products minus reactants.
Well, since the primary source of enthalpy changes occurs in the changes of the
bonds, you might have already guessed that if we had a table of bond energies, we could
calculate enthalpy changes. This is very true, and it works to some extent, but its not a
great method. This is because there are often exceptions to these bond energies, things
happening electronically that makes these energies poor estimates. In addition, we are
forced to stay with gas-phase reactions. We are forced to this realm so that the
intermolecular forces that will affect enthalpy are negligible in the gas phase only. Still,
though, as a first attempt, its not a bad place to start. Lets do an example or two.

Thermodynamics Principles of Inorganic Chemistry
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Example 1: Calculation of Enthalpy using Bond Energies

In appendix I, you will find a table of bond energies. Lets calculate the change in
enthalpy for the reaction of hydrogen with oxygen, the reaction that caused the
Hindenberg to explode:

2 H
2
(g) + O
2
(g) --> 2 H
2
O (g)

First, lets see which bonds we are breaking or forming. We have to break two
hydrogen-hydrogen bonds (one bond per H
2
molecule, and 2 molecules in the reaction)
and one oxygen-oxygen double bond. Notice that the energy of the oxygen-oxygen
double bond is not simply twice the bond of an oxygen-oxygen single bond. The nature of
the second bond is different from the first bond, so it will require different amounts of
energy to break the second bond than the first.
Anyway, we are forming hydrogen-oxygen bonds, but how many of them? Well,
we are forming two such bonds per water molecule, and we are forming two water
molecules, so we are forming a total of four hydrogen-oxygen bonds. Our formula, then,
is

? H=(4*H
H-O
) - (2*H
H-H
+ H
O=O
)

Now lets go to the table and substitute in the appropriate values. We see that H
H-O
= -111
kcal/mol, H
H-H
= -104 kcal/mol and H
O=O
= -119 kcal/mol. So

? H=[4*(-111 kcal/mol)] - {[2*(-104 kcal/mol)]+(-119 kcal/mol)}
? H=-117 kcal/mol

Example 2: Formation of benzene from its elements. Benzene, C
6
H
6
, is a well known
organic solvent. It has been the source of fear lately because of its carcinogenic nature,
and yet, it is certainly not one of the worst carcinogenic substances known. There was a
time when organic chemists would wash their hands in benzene every night before going
home.
Anyway, benzene has the structure of a 6-member ring with alternating single and
double bonds:

Thermodynamics Principles of Inorganic Chemistry
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The chemical reaction for the formation of this from its elements might be

3 H
2
(g) + 6 C (g) --> C
6
H
6
(g)

In the reactants, we see that we have no bonds to break in carbon, and only three
hydrogen-hydrogen bonds. If we study the figure above, we see that we form six carbon-
hydrogen bonds, three carbon-carbon single bonds and three carbon-carbon double bonds.
So

? H=(6*H
C-H
+ 3*H
C-C
+ 3*H
C=C
) - (3*H
H-H
)

From the table in appendix I, H
C-H
= -99.2kcal/mol, H
C-C
= -82.2 kcal/mol and H
C=C
= -147
kcal/mol, and H
H-H
= -104 kcal/mol. Substituting, we find

? H={[6*(-99.2kcal/mol)]+[3*(-82.2kcal/mol)]+[3*(-147kcal/mol)]}-[3*(-104kcal/mol)]
? H=-970.8 kcal/mol.

The whole problem with this approach, aside from the fact that we are forced to stick with
gas-phase reactions, is that it is relatively inaccurate. Using more accurate methods of
calculation (which we will learn now), we see that the true value for the formation of
benzene is closer to -1006.8 kcal/mol. The 36 kcal/mol difference comes about because of
an electronic phenomena called resonance, which occurs because of the alternating
positive and negative bonds. This alternation creates the additional resonance stabilization
force that we would not have considered unless we had prior knowledge.
For this reason, there has been created a better way to calculate enthalpy changes.

Enthalpy Calculations Using Enthalpies of Formation:

Well, seems to me that we could experimentally measure enthalpies using
calorimetry (which we learned already). And this is what they do. They are called
enthalpy of formation, which is exactly what it is. If we were to measure the enthalpy to
Thermodynamics Principles of Inorganic Chemistry
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Prepared by: Richard E. Bleil, Ph.D. 7
make the compound in question experimentally from its elements, then we would end up
with a table where all wed have to do is find the enthapy for the reactancts and the
enthalpy for the products and subtract.
Oy, not real coherent today, am I? Well, OK, first of all, note that the convention
is still the same; change in enthalpy is the enthalpy of the products minus the enthalpy of
the reactants.

? H=H
products
- H
reactants


just like before. Last time we had to go and look up the energy of every bond. This time,
we go to the table in appendix II and look up the enthalpy for each compound or element
in the reaction. Before we do, however, there are two final issues that must be addressed.
First, notice that we have to pay attention to states here. One of the great benefits
of this approach is that we are not stuck in gas phase as we were before. Enthalpy of
formation takes into account not only chemical bonds, but intermolecular forces as well.
So, we can deal with any state. We must be cautious, however, because often the same
chemical will be listed in these tables in two or three different states, so watch those
carefully and be sure the value you are using is for the correct conditions.
Second, a comment on relativity is in order. See, the problem is that it is really
really really difficult to measure absolute enthalpy. So we dont bother. The enthalpies
listed are all relative. Its like altitude. Altitudes are all measured relative to sea level,
the average altitude of the oceans. We may not know exactly how high above the center
of the earth this is (although, actually, now we do know), but it really doesnt matter. Its
a reference point. So if I am at 1,200 feet above see level, and my friend Doug is at 200
feet below sea level, then we can measure our exact difference in altitude, 1,200-(-
200)=1,400 feet. It does not matter our exact distance from the center of the earth. The
relative distance is sufficient, because any errors that might occur cancel out.
These enthalpies of formation are the same. The reference point is always the
most stable elemental state, which is set to 0 kcal/mol. For instance, oxygen in its
elemental state is a diatomic gas, so even without looking at the table, I know the H(O
2

gas) = 0. kcal/mol. Similarly, mercurys elemental state is liquid, so H (Hg) = 0 kcal/mol.
Any element in its natural state will be zero.
Lets do a few examples:

Example 1: Benzene

Now you know how I calculated the benzene problem. We are forming benzene
from its elements (carbon and hydrogen), but all in gas phase. Lets calculate the enthalpy
of the formation of benzene from its elements:

6 C (g) + 3 H
2
(g) --> C
6
H
6
(g)

Hydrogen is in its elemental state, so its value for H is zero. Carbon is not. The elemental
state for carbon is solid graphite. Therefore, we need to find the value for the enthalpy of
Thermodynamics Principles of Inorganic Chemistry
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formation of carbon gas (H=171.1 kcal/mol) , as well as for benzene gas (H=19.80
kcal/mol). Now we can plug in these values.

? H=(19.80 kcal/mol) - {(3*0. kcal/mol ) + [6*( 171.1 kcal/mol)]}
? H=-1006.8 kcal/mol

Notice in this example that I did account for the stoichiometric coefficients.

Example 2: How much heat is released when hydrogen reacts with oxygen?

Equation: 2 H
2
(g) + O
2
(g) --> 2 H
2
O (g)

Molar Enthalpy (H) 0 kcal/mol 0 kca/lmol -57.75 kcal/mol

? H=[2*(-57.75)] - 0
? H = -115.5 kcal/mol

Example 3: There has been a lot of talk lately of the use of methanol as fuel for cars.
How much heat is released when we burn methanol?

2 CH
3
OH (l) + 3 O
2
(g) --> 2 CO
2
(g) + 4H
2
O(g)

H -57.00 kcal/mol 0 kcal/mol -93.97 kcal/mol -57.75 kcal/mol

? H = {[2*(-93.97)]+[4*(-57.75)]}-{[4*(-57.75)]+[2*(-57.00)+3*0.]}
? H=-304.9 kcal/mol

Foundations: Entropy

If energy changes were the only driving force in chemical reaction, endothermic
reactions would not be possible. In such a world, life itself would not be possible since so
many of our bodily chemical processes are endothermic. Indeed, any reaction that is
exothermic in one direction, will be endothermic in the reverse reaction as we have seen.
Therefore, any chemical cycle would be impossible. There must be a second driving force
for chemical reactions, and that second driving force is entropy.
So what is entropy? The best definition Id ever heard of entropy comes from
Websters dictionary. Although Im paraphrasing here, the definition of entropy states
that entropy is that portion in the total energy of a reaction that is used internally and
therefore not available to do work. When we calculated enthalpy above, we calculated the
total energy of the reaction, but this energy is in part heat that is released and therefore
available to do work, plus heat used internally for the rearrangement of matter.
OK, its a little odd stated this way. The more common way to state entropy is to
say that it is a measure of disorder. Well, this isnt bad. If we start comparing, say,
different states, we could see where a gas is more disordered than a condensed phase,
liquid or solid. After all, as a gas, all particles are free to move throughout the entire
Thermodynamics Principles of Inorganic Chemistry
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Prepared by: Richard E. Bleil, Ph.D. 9
space defined by its container. Since it can move anywhere in a larger volume, we might
think that the state is more disordered.
This is a decent way to think of entropy. If we think about the implications, this
says basically that gases have higher entropy than liquids, liquids have higher entropy than
solids, and solutions have higher entropy than liquids or solids (but lower than gases).
Mixtures have higher entropy than pure compounds. Its not bad. But, its not great
either. The problem is, how do we quantify disorder?
We all have different definitions of disorder. Have children? Know anybody who
does? Have you yourself ever been a child? Ask a child if his or her room is neat or not.
Then ask her or his parents. Chances are the child will see the room as clean and ordered,
and the parents will see it as disordered. We cannot quantify disorder. Oddly enough,
however, we can quantify information.
Stick with me on this one for a minute, were about to get abstract. The
microscopic world is quantized. If it were within our computational capabilities, we could
determine exactly every possible energy level of a system, including electronic energy,
bending energy, stretching energy, and translation energy. What this means is that there
are only a finite number of electronic configurations for a molecule, and a finite number of
ways it can bend, a finite number of ways it can stretch and a finite number of speeds it
can have. The higher the entropy, the more quantum states that are possible, and the less
we can know about the system.
Think of it this way. Suppose we have $100. If we have available to us only $20
bills, then we know that we have five twenty dollar bills. Entropy is zero because we
know exactly how we have the $100. Now, suppose we have available to us both $20
bills as well as $10 bills. Then we may have five $20 bills, or ten $10 bills, or we may
have one $20 and eight $10 bills, two $20 and six $10 bills, three $20 and four $10 bills,
or four $20 and two $10 bills. We can split up the $100 six different ways. We still know
we have $100, but we do not know how it is distributed. Our information of the system is
lower, so the entropy is higher. If we include now $5 bills, the entropy will behigher still.
So, the higher the entropy, the less information we have about the system. This example
also demonstrates that the reason we have less information is because there is more
disorder.
Any given system will want to maximize its entropy. That is, it wants to reach
maximum disorder, or, better still, it wants us to have as little information about it as
possible. This is the second driving force, but we have to be careful about how we
describe the system.

Entropy: Systems versus the Universe!

Entropy is possibly the most misquoted principle in science. Well, this makes
sense. It is a very difficult concept. The second law of Thermodynamics tells us that the
entropy for the universe must always increase (or remain the same). Often you will hear
this as entropy is always increasing, and the universe is dropped from the statement.
However, it is easy to prove that for an isolated system, we can indeed decrease the
entropy.
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Here are a few examples. If entropy is always increasing, how do we explain
water forming ice in our freezers? Liquids have higher entropy than solids, therefore, we
have decreased entropy by freezing water. How about a deck of cards? We can shuffle
them, increasing the entropy in the system, true. However, we can also sort the cards
back out again, thereby decreasing the entropy of the system. If entropy is always
increasing, how are these processes possible?
They are possible because the second law of thermodynamics applies to the
universe, not an isolated system. In our freezer, heat is removed (via freon) from inside
the freezer to the outside, thereby heating up the room the freezer is in, and, by extension,
the rest of the universe. By heating up the room, the gases in the room are moving faster.
Since they are moving faster, it is harder to track them down, and entropy is increasing.
By decreasing the entropy within the freezer, we increase the entropy in the room. The
net change for the universe in entropy is the amount that the entropy increases in the room
minus the amount the entropy decreases in the refrigerator. The second law of
thermodynamics tells us that this difference will either be zero, or we will find the entropy
increases more in the room than it decreases in the freezer. We will never have a process
where the total entropy of the universe decreases.
What about the cards? Well, we are increasing the order in the cards, true, but in
putting in the work, in shuffling the cards, the friction in the cards is causing an increase in
the entropy of the molecules making the cards and the air they are in contact with. In
addition, in putting in this work we are burning sugar and converting it into carbon
dioxide to fuel the muscles that are causing this process. Going from sugar in solution to
gaseous carbon dioxide is a huge increase in entropy. The entropy increase created by the
work we put in to arrange the cards is much greater than the decrease in entropy by
having an organized deck.
So, in any argument, be very very careful to define the system. In a chemical
reaction, the reaction itself is the system. If we see the entropy decrease for such a
system, know that the entropy of the universe is somehow increasing as a result.

Entropy Calculations:

Determination of entropy for physical and chemical changes is much more
challenging to determine experimentally than the determination of enthalpy. However,
they, whoever they are, have been kind enough to put this work in for us and provide us
with tables of entropy just as we have tables of enthalpy. Entropy is designated by
convention by a capital S, and just like enthalpy, change in entropy ? S, is the entropy of
the products minus the entropy of the reactants.

? S=S
products
-S
reactants


Once again, well have to take stoichiometric coefficients into account, but still, its a
straightforward calculation. A table of several experimentally determined entropy values
are presented in appendix III. For entropy calculations, we do the same thing we did for
enthalpy, but lets take a moment to look at this table before we move on.
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Kettering College of Medical Arts Document #16
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First of all, notice that for elements, the entropy is not zero. For enthalpy we were
always measuring the enthalpy relative to the elemental state. Entropy, however, is always
non-zero and positive. Second, notice that for any given element or compound, the
entropy of the gas is always greater than the liquid, and the entropy of the liquid is always
greater than the solid. This is as expected. We decided early on that entropy would
increase as we go to liquid and gas states. Third, notice that all entropies are positive.
This is to be expected. A perfect crystal at absolute zero would have zero entropy,
however, there are no perfect crystals, and it is impossible to reach absolute zero.
Therefore, all entropies must be greater than that ideal case. Finally, notice that there are
a few compounds for which the entropy is not available. Entropy, as you might imagine,
is a rather more difficult experiment to perform than enthalpy determination. Although
most entropies are available, there are still those for which the experiment has not been
performed.
So, lets do some calculations:

Example 1: What is the entropy change as we burn coal (graphite)?

C (s) + O
2
(g) --> CO
2
(g)

Entropy S 0.0014 kcal/mol
.
K 0.0490 kcal/mol
.
K 0.0510 kcal/mol
.
K

As always, it is products minus reactants, so

? S=0.0510 kcal/mol
.
K - (0.0014 kcal/mol
.
K + 0.0490 kcal/mol
.
K)
? S=6.0x10
-4
kcal/mol
.
K

You may notice that entropy changes are much much smaller than enthalpy changes. This
is true, but notice that they are also a function of temperature (in kelvin). Well see how
this comes into play in the next section. Two more examples first, though.

Example 2: What is the entropy change for water as it evaporates? Well, evaporation is
the process of going from a liquid to a gas below the boiling point, so our equation is

H
2
O (l) --> H
2
O (g)

Entropy S 0.0167 kcal/mol
.
K 0.0451 kcal/mol
.
K

So

? S=0.0451 kcal/mol
.
K - 0.0167 kcal/mol
.
K
? S=0.0284 kcal/mol
.
K

In both of these examples, entropy ended up being positive. This is, if you recall,
favorable, since all things in the univers strive to maximize their entropy. There will be
times, however, that entropy is negative. This does not mean that such a process is
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impossible (consider, for instance, the freezing of water, or the condensation of water
vapor to liquid). However, it takes work to overcome this negative entropy to force the
process to occur, and that work requires energy, or, enthalpy.

Example 3: What is the entropy change associated with converting carbon monoxide into
carbon dioxide in an automobiles catalytic converter?

2 CO (g) + O
2
(g) --> 2 CO
2
(g)

Entropy (S) 0.0472 kcal/mol
.
K 0.0490 kcal/mol
.
K 0.0510 kcal/mol
.
K

? S = (2)(0.0510 kcal/mol
.
K) - [(2)(0.0472 kcal/mol
.
K) + 0.0490 kcal/mol
.
K]
? S=0.102 kcal/mol
.
K - 0.143 kcal/mol
.
K
? S=-0.0410 kcal/mol
.
K

Ah, haaa...this is a negtive entropy change. First, notice that I took the stoiciometric
coefficients into account. The fact that this is a negative entropy implies that the entropy
is decreasing. Well, this is to be expected since we have three moles of gas as reactants
and only two moles as product. Since entropy is decreasing, however, this must mean that
the enthalpy is also decreasing, and moreso, in fact, than the entropy. How do I know
this?

Bringing it Together: Gibbs Free Energy

So now we understand the two central driving forces in chemistry (and the
universe, in fact)...the strive to minimize enthalpy and maximize entropy. For any
chemical process where entropy is maximized and enthalpy is minimized, we know the
process will occur, because both driving forces are cooperating. But what happens when
both entropy and enthalpy are being minimized, or both are being maximized? Surely
there must be a way to bring to two together to figure out which force will win.
There is. We call it Gibbs Free Energy. Free energy refers to the energy in a
chemical system that is available to do work, the total energy output. The formula is
actually surprisingly simple;

? G=? H-T? S

where ? G is the change in the Gibbs free energy, ? H is change in enthalpy, ? S is change
in entropy and T is absolute temperature. Since we know how to calculate changes in
enthalpy and changes in entropy, we could use this equation blindly and come up with a
number for a given chemical reaction, but what will this number tell us? Amount of
energy available for work? Sure. But it can tell us more.
Consider this. Processes want to minimize their enthalpy and maximize their
entropy. Well, if we minimize enthalpy, then that means the the enthalpy of the products
will be less than the reactants, and ? H will therefore be negative. Meanwhile, we want to
maximize entropy, so ? S will be positive. For such a process, since we multiply entropy
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by a positive temperature (since the temperature is absolute it must be positive), we can
see that for such a process, ? G must be negative. (Prove it!) We also know that since
both enthalpy and entropy are favorable, this reaction must occur.
What about a reaction that cannot occur? If enthalpy is maximized and entropy is
minimized, then neither is favorable and there is no driving force for the reaction to
proceed. This is a reaction that cannot proceed. So, enthalpy increasing implies ? H is
positive, while minimizing entropy forces ? S to be negative. In this case, ? G must be
positive.
What this tells us is that the sign of ? G will tell us if a reaction will occur (is
spontaneous) or not (is non-spontaneous);

? G < 0 ; spontaneous (exergonic)
? G > 0 ; non-spontaneous (endergonic)

Notice the terms exergonic and endergonic. An erg is a unit of work. So, just as a
change of heat can be exothermic (heat released) or endothermic (heat absorbed), a
reaction can be exergonic (able to do work) or endergonic (meaning it is necessary to do
work to force the reaction to occur).
Before we do some calculations, notice that to calculate the Gibbs free energy we
need to specify the temperature of the reaction. However, this temperature only affects
the entropy term. When a reaction does not occur on its own, what do we tend to do?
We add heat. We put it on a hot plate, or under a bunsen burner, or on a stove top (if we
are in the kitchen). What we are doing is increasing the temperature, and thereby
increasing the entropy term in Gibbs free energy. Eventually, the entropy will increase to
the point where it becomes the dominant factor in the reaction and the reaction proceeds.
However, this trick will not work for any reaction where the entropy is decreasing. This
makes sense, if we think about it. Would we heat up water to get ice?

Gibbs Free Energy: Calculations

OK...lets get on with the sample calculations.

Example 1: Is the conversion of diamond to graphite spontaneous at room temperature
(about 18
o
C)? (What, do you think I was liing?)

C (diamond) --> C (graphite)

Enthalpy H 0.4530 kcal/mol 0 kcal/mol
Entropy S 0.0006 kcal/mol
.
K 0.0014 kcal/mol
.
K

? H=0. kcal/mol - 0.4530 kcal/mol
? H=-0.4530 kcal/mol

? S=0.0014 kcal/mol
.
K - 0.0006 kcal/mol
.
K
? S=8.0x10
-4
kcal/mol
.
K
Thermodynamics Principles of Inorganic Chemistry
Kettering College of Medical Arts Document #16
Prepared by: Richard E. Bleil, Ph.D. 14

Remember, we must use absolute temperature, so 18+273=281 K

Now plug -n- chug . ? G=-0.4530 kcal/mol - (281 K)(8.0x10
-4
kcal/mol
.
K)
? G=-0.7 kcal/mol

Both enthalpy and entropy favors the conversion of diamond to graphite. This means the
conversion of graphite into diamond is endergonic, but where does the energy come from
to force this reaction? The pressure in the mines. This is why such high pressure is
required.

Example 2: Can diamonds burn at 281 K?

Well...lets do the calculation.

C (diamond) + O
2
(g) --> CO
2
(g)

Enthalpy H 0.4530 kcal/mol 0 kcal/mol -93.97 kcal/mol
Entropy S 0.0006 kcal/mol
.
K 0.0490 kcal/mol
.
K 0.0510 kcal/mol
.
K

? H = -93.97 kcal/mol - ( 0.4530 kcal/mol + 0. kcal/mol)
? H = -94.42 kcal/mol

? S=0.0510 kcal/mol
.
K - (0.0006 kcal/mol
.
K + 0.0490 kcal/mol
.
K)
? S=0.0014

? G=-94.42 kcal/mol- (281 K)(0.0014 kcal/mol
.
K)
? G=-94.81 kcal/mol

Yep, sign of ? G is negative, so diamonds burn. Surprised?

Example 3: Will carbon vapor burn at 281 K? Well...we expect it will, but there is a
reason I want to do this problem.

C (g) + O
2
(g) --> CO
2
(g)

Enthalpy (H) 171.1 kcal/mol 0 kcal/mol -93.97 kcal/mol
Entropy (S) 0.0377 kcal/mol
.
K 0.0490 kcal/mol
.
K 0.0510 kcal/mol
.
K

? H=-93.97 kcal/mol - (171.1 kcal/mol + 0 kcal/mol)
? H=-265 kcal/mol

? S=0.0510 kcal/mol
.
K - ( 0.0377 kcal/mol
.
K + 0.0490 kcal/mol
.
K)
? S=-0.0357 kcal/mol
.
K

Thermodynamics Principles of Inorganic Chemistry
Kettering College of Medical Arts Document #16
Prepared by: Richard E. Bleil, Ph.D. 15
? G=-265 kcal/mol - (281K)(-0.0357 kcal/mol
.
K)
? G=-255 kcal/mol

Notice that for this reaction, entropy is decreasing. This is what we would call an
enthalpy driven reaction, because it is the enthalpy that is overwhelming the entropy to
force the reaction to proceed.

Example 4: At what temperature will the reaction in example 3 no longer be exergonic
(spontaneous)?

Now we know the change in enthalpy and the change in entropy. The reaction will
not be spontaneous when ? G=0, so lets find the temperature where ? G=0.

0=-265 kcal/mol - T (-0.0357 kcal/mol
.
K)
265 kcal/mol = 0.0357 kcal/mol
.
K * T
T=7,423 K

As long as our temperature is below 7,423 K, this reaction will proceed. It may seem odd
that something will burn at lower temperatures, but not at higher, but recall that it is
entropy at this point that takes over. The more gas particles, the higher the entropy.

Example 5: Assuming we can prevent the water from boiling, at what temperature can we
burn water?

2 H
2
O (l) + O
2
(g) --> H
2
O
2
(l)

Enthalpy (H) -68.26 kcal/mol 0 kcal/mol -44.85 kcal/mol
Entropy (S) 0.0167 kcal/mol
.
K 0.0490 kcal/mol
.
K 0.0263 kcal/mol
.
K

? H=-44.85 kcal/mol- [(2)(-68.26 kcal/mol)+0 kcal/mol]
? H=91.67 kcal/mol

? S=0.0263 kcal/mol
.
K - [(2)(0.0167 kcal/mol
.
K)+0.0490 kcal/mol
.
K]
? S=-0.0561 kcal/mol
.
K

Again, we solve for ? G=0

0.=91.67 kcal/mol - T (-0.0561 kcal/mol
.
K)
-91.67 kcal/mol = 0.0561 kcal/mol
.
K T
T=-1634 K

Well, theres a problem here. The temperature is negative, but since this is an absolute
temperature scale, it is impossible to get a negative temperature. Therefore, this reaction
will not be spontaneous at any temperature.
Thermodynamics Principles of Inorganic Chemistry
Kettering College of Medical Arts Document #16
Prepared by: Richard E. Bleil, Ph.D. 16
Actually, we could have skipped the last step to this calculation. After all,
enthalpy is positive and entropy is negative. Immediately this combination tells us that
under no condition will this reaction be spontaneous. Yep, I pulled a fast one...watch out
for these!

How about one more example?

Example 4: Can we convert red lead (I) oxide to yellow lead (I) oxide by heating the red
lead (I) oxide to 1,500 K?

PbO (s...red) --> PbO (s...yellow)

Enthalpy (H) -52.30 kcal/mol -51.89 kcal/mol
Entropy (S) 0.0159 kcal/mol
.
K 0.0164 kcal/mol
.
K

? H=-51.89 kcal/mol - (-52.30 kcal/mol)
? H=0.41 kcal/mol

? S=0.0164 kcal/mol
.
K - 0.0159 kcal/mol
.
K
? S=5.0x10
-4
kcal/mol
.
K

? G=0.41 kcal/mol - (1,500 K)(5.0x10
-4
kcal/mol
.
K)
? G=-0.34 kcal/mol

Here we have an example of an entropy driven reaction. Entropy driven reactions are
spontaneous at high temperatures, while enthalpy driven reactions are spontaneous at low
temperatures (think about it). Also notice that the temperature in an entropy driven
reaction tends to need to have an extremely high temperature to proceed spontaneously.
This is because of the generally small magnitude of entropy when compared with enthalpy.

Ready to try a few on your own?

Thermodynamics Principles of Inorganic Chemistry
Kettering College of Medical Arts Document #16
Prepared by: Richard E. Bleil, Ph.D. 17
Drill Problems:

-> Calculate the enthalpy change for the following reactions using bond energies. (HINT!
Calculate the enthalpies of products and reactants from their elements, then take the
difference as usual.)

1. 2 H
2
C
2
(g) + 5 O
2
(g) --> 4 CO
2
(g) + 2 H
2
O (g)

The carbon carbon bond is a triple bond here. This is the reaction used in an acetylene
torch (H
2
C
2
is acetylene).

2. 2 C
8
H
18
(g) + 25 O
2
(g) --> 16 CO
2
(g) + 18 H
2
O (g)

C
8
H
18
is octane, considered to be the perfect fuel for an automobile (hence the octane
rating, which is a number to relate how well the fuel were to burn compared to pure
octane, for instance, 89 octane fuel burns as well as a fuel with 89% octane). It contains 7
C-C single bonds and 18 C-H bonds. CO
2
contains two carbon oxygen double bonds.

3. CH
4
(g) + 2 O
2
(g) --> CO
2
(g) + 2 H
2
O (g)

Methane (CH
4
) has been suggested as a possible alternative source of fuel. The source of
methane? Flattulent cows!

4. C (g) + F
2
(g) + Cl
2
(g) --> CF
2
Cl
2
(g)

This product is a chloro-floro carbon (CFC).

->In each of the following problems, calculate the change in enthalpy (using the table of
enthalpy of formation), the change in entropy, and the Gibbs free energy for the reaction
at the temperature given. Decide if the reaction is spontaneous or non-spontaneous, and if
it is exothermic or endothermic, and exergonic or endergonic. Is the reaction entropically
driven, enthalpy driven, both or neither?

5. 4 Fe (s) + 6 H
2
O (l) + 3 O
2
(g) --> 4 Fe(OH)
3
(s) at 273 K.

(rusting iron)

6. CHCl
3
(l) --> CHCl
3
(g) at 250 K.

(One of the replacement gases to CFCs being considered is this one, CHCl
3
. 250 K is
below freezing, so the question is, can this be used as a refrigerant?)

7. SO
3
(g) + H
2
O (l) --> H
2
SO
4
(l) at 280 K.

(This is one of the principle reactions leading to acid rain.)
Thermodynamics Principles of Inorganic Chemistry
Kettering College of Medical Arts Document #16
Prepared by: Richard E. Bleil, Ph.D. 18

8. 3 O
2
(g) --> 2 O
3
(g) at 5,000 K.

(This is the reaction that makes ozone from oxygen. It occurs in electrical discharges such
as lightening strikes.)

9. N
2
(g) + 3 H
2
(g) --> 2 NH
3
(g) at 600 K.

10. Ca (s) + 2 H
2
O (l) --> Ca(OH)
2
(s) + H
2
(g)

(We know sodium metal will react with water to form hydrogen gas in an exothermic
reaction...will calcium?)

->For the following problems, determine the temperature where the reaction will become
spontaneous.

11. CaCO
3
(s) --> CaO (s) + CO
2
(g)

12. 16 Cu (s) + S
8
(s) --> 8 Cu
2
S (s)

13. 6 Fe
2
O
3
(s) --> 4 Fe
3
O
4
(s) + O
2
(g)

14. 4 Cr (s) + 3 O
2
(g) --> 2 Cr
2
O
3
(s)

(Rusting of a chrome bumper.)

15. CH
3
CH
2
OH (l) + O
2
(g) --> CH
3
COOH (l) + H
2
O (l)

(This is the reaction that converts alcohol into vinegar, thereby transforming expensive old
bottles of wine into expensive salad dressing if improperly stored. Can old wines be saved
by cooling them?)

Thermodynamics Principles of Inorganic Chemistry
Kettering College of Medical Arts Document #16
Prepared by: Richard E. Bleil, Ph.D. 19
Appendix I: Bond Energies (kcal/mol)

All data is for single bonds except where otherwise specified.

H C N O F S Cl Br I
H -104 -99.2 -93 -111 -88
C -82.2 single
-147 double
-194 triple
-70 single
-147 double
-213 triple
-84 single
-173 double
-105 -62 -78 -77 -57
N -38 single
-100 double
-226 triple
-42 -48
O -34 single
-119 double

F -38
S -64
Cl -58

Data taken from Ira N. Levine, Physical Chemistry, 2
nd
ed. (McGraw-Hill, Inc., New York, NY, 1983).

Thermodynamics Principles of Inorganic Chemistry
Kettering College of Medical Arts Document #16
Prepared by: Richard E. Bleil, Ph.D. 20
Appendix II: Enthalpies of Formation (kcal/mol) at 298 K

Substance H
f
(kcal/mol) Substance H
f
(kcal/mol)

Al (s) 0 Cr (s) 0
Al (g) 77.8 Cr (g) 94.80
Al
2
O
3
(s) -400.2 Cr
2
O
3
(s) -272.2
AlF
3
(s) -359.1 CrO
3
(s) -140.8
AlCl
3
(s) -168.2 Cu (s) 0
Al
2
S
3
(s) -173 Cu (g) 80.79
Al
2
(SO
4
)
3
(s)

-821.7

CuO (s) -37.5
Ba (s) 0 Cu
2
O (s) -40.4
Ba (g) 41.93 Cu
2
S (s) -19.0
BaO (s) -133.3 CuSO
4
(s) -184.2
BaCl
2
(s) -205.4 Cu(NO
3
)
2
(s) -72.4
BaSO
4
(s) -349.8 F
2
(g) 0
Br
2
(l) 0 HF (g) -64.71
Br
2
(g) 7.381 H
2
(g) 0
BrF
3
(g) -61.04 H
2
O (l) -68.26
HBr (g) -8.69 H
2
O (g) -57.75
Ca (s) 0 H
2
O
2
(l) -44.85
Ca (g) 45.99 I
2
(s) 0
CaO (s) -151.8 I
2
(g) 14.91
Ca(OH)
2
(s) -235.6 HI (g) 6.33
CaSO
4
(s) -342.1 Fe (s) 0
CaCO
3
(s) [calcite] -288.2 Fe (g) 99.34
C (s) [graphite] 0 Fe
2
O
3
(s) -196.8
C (s) [diamond] 0.4530 Fe
3
O
4
(s) -267.0
C (g) 171.1 FeO (s) -64.95
CO (g) -26.39 Fe(OH)
2
(s) -135.9
CO
2
(g) -93.97 Fe(OH)
3
(s) -196.5
CH
4
(g) -17.86 Pb (s) 0
CH
3
OH (l) -57.00 Pb (g) 46.57
CH
3
OH (g) -47.93 PbO (s) yellow -51.89
CCl
4
(g) -24.57 PbO (s) red -52.30
CHCl
3
(l) -32.12 Pb(OH)
2
(s) -123.2
CHCl
3
(g) -24.62 PbO
2
(s) -66.15
CH
3
COOH (l) -115.7 N
2
(g) 0
C
2
H
5
OH (l) -66.31 NH
3
(g) -11.01
C
2
H
5
OH (g) -56.14 O
2
(g) 0
C
6
H
6
(l) 11.71 O
3
(g) 34.15
C
6
H
6
(g) 19.80 S
8
(s) 0
Cl
2
(g) 0 S(g) 66.58
ClF (g) -13.01 SO
3
(g) -94.49
HCl (g) -22.04 H
2
SO
4
(l) -194.4
Thermodynamics Principles of Inorganic Chemistry
Kettering College of Medical Arts Document #16
Prepared by: Richard E. Bleil, Ph.D. 21
Appendix III: Entropies in kcal/mol
.
K at 298 K

Substance S
f
(kcal/mol
.
K) Substance S
f
(kcal/mol
.
K)

Al (s) 0.00676 Cr (s) 0.0057
Al (g) 0.0393 Cr (g) 0.0416
Al
2
O
3
(s) 0.0122 Cr
2
O
3
(s) 0.0194
AlF
3
(s) 0.0159 CrO
3
(s)
AlCl
3
(s) 0.0264 Cu (s) 0.0079
Al
2
S
3
(s) Cu (g) 0.0397
Al
2
(SO
4
)
3
(s)

0.0571

CuO (s) 0.0102
Ba (s) 0.0160 Cu
2
O (s) 0.0222
Ba (g) 0.04007 Cu
2
S (s) 0.0159
BaO (s) 0.0168 CuSO
4
(s) 0.0260
BaCl
2
(s) 0.00300 Cu(NO
3
)
2
(s) 0.0260
BaSO
4
(s) 0.0315 F
2
(g) 0.0484
Br
2
(l) 0.0364 HF (g) 0.0415
Br
2
(g) 0.0586 H
2
(g) 0.0312
BrF
3
(g) 0.0698 H
2
O (l) 0.0167
HBr (g) 0.0474 H
2
O (g) 0.0451
Ca (s) 0.0099 H
2
O
2
(l) 0.0263
Ca (g) 0.0370 I
2
(s) 0.0277
CaO (s) 0.0096 I
2
(g) 0.0622
Ca(OH)
2
(s) 0.0182 HI (g) 0.0493
CaSO
4
(s) 0.0256 Fe (s) 0.0065
CaCO
3
(s) [calcite] 0.0222 Fe (g) 0.0431
C (s) [graphite] 0.0014 Fe
2
O
3
(s) 0.0209
C (s) [diamond] 0.0006 Fe
3
O
4
(s) 0.0349
C (g) 0.0377 FeO (s)
CO (g) 0.0472 Fe(OH)
2
(s) 0.0210
CO
2
(g) 0.0510 Fe(OH)
3
(s) 0.0256
CH
4
(g) 0.0445 Pb (s) 0.0155
CH
3
OH (l) 0.0303 Pb (g) 0.419
CH
3
OH (g) 0.0572 PbO (s) yellow 0.0164
CCl
4
(g) 0.0740 PbO (s) red 0.0159
CHCl
3
(l) 0.0482 Pb(OH)
2
(s)
CHCl
3
(g) 0.0706 PbO
2
(s) 0.0164
CH
3
COOH (l) 0.0382 N
2
(g) 0.0457
C
2
H
5
OH (l) 0.0384 NH
3
(g) 0.0459
C
2
H
5
OH (g) 0.0675 O
2
(g) 0.0490
C
6
H
6
(l) 0.0413 O
3
(g) 0.0570
C
6
H
6
(g) 0.0643 S
8
(s) 0.0607
Cl
2
(g) 0.0532 S(g) 0.0401
ClF (g) 0.0520 SO
3
(g) 0.0613
HCl (g) 0.0446 H
2
SO
4
(l) 0.0375
Thermodynamics Principles of Inorganic Chemistry
Kettering College of Medical Arts Document #16
Prepared by: Richard E. Bleil, Ph.D. 22

Enthalpy and entropy data taken from Henry F. Holtzclaw, Jr., William R. Robinson and
Jerome D. Odom, General Chemistry with Qualitative Analysis, 9th ed. (D.C. Heath and
Co., Lexington, MA, 1991).