What is the significance of the different thermodynamic variables?

The Gibbs free energy (Grxn) tells us whether a reaction will take place. Grxn is
the Gibbs Free Energy of the right hand side of a reaction, minus the Gibbs Free
Energy of the left hand side. If Grxn < 0, the reaction will proceed to the right; if
it is > 0, the reaction will proceed to the left.

The enthalpy of reaction (Hrxn) tells us how much heat will flow in or out of the
system. If Hrxn < 0, the reaction is exothermic -- it releases heat. For example,
combustion of carbon based compounds (C + O 2 = CO2) gives off a lot of heat. If
Hrxn > 0, the reaction is endothermic -- it consumes heat. Melting ice [H2O
(ice) = H2O (water)] is endothermic and, consequently, cools our gin and tonics
in the summer.

The entropy of a reaction (Srxn) tells us whether the products or reactants are
more disordered. For example, the reaction of liquid water to steam (boiling) has
a large associated entropy. The steam molecules are more dispersed, are less
well bonded together, and have greater kinetic energy.

The volume of a reaction (Vrxn) tells us whether the products or the reactants
have greater volume. The reaction of graphite to diamond, both made entirely of
carbon, proceeds at high pressure because diamond is more dense (has smaller
volume) than graphite.

For any reaction under a given set of P-T conditions: If the Grxn < 0, the reaction proceeds to
the right. If the Grxn >0, the reaction proceeds to the left. The univariant reaction curve that
separates the two assemblages actually represents the locus of points where Grxn = 0

Introduction
Firstly, it is important to mention that a chemical reaction has kinetic and thermodynamic
aspects. The quantity related to kinetics is the rate constant k; this constant is associated
with the activation energy required for the reaction to move forward. The
thermodynamic quantity is the energy difference resulting from the free energy
(G) given off during a chemical reaction. While kinetics can tell us about the rates of
reactions and how fast equilibrium is reached, they don't tell us anything about
equilibrium conditions once the reaction equilibrates. In the same measure,
thermodynamics only gives us information regarding the equilibrium conditions of
products after the reaction takes place, but doesn't tell us the rate of reaction.

Kinetics Overview
The rate constant k shows how fast a chemical reaction reaches equilibrium, which means
the reactants were supplied with enough activation energy to enable the reaction to
proceed in the forward direction-- turning reactants into products. This need for input of
energy symbolizes the fact that the reaction is kinetically stable; meaning that the reaction
must have some sort of energy input before it can proceed, otherwise, the reactants
cannot reach the activation energy threshold and begin going in the downhill direction
towards becoming products. Essentially, the reaction will be activated by the energy
supplied to the reactants by different energy sources. The rate reaction k, and the kinetic
energy required for activation of reaction tell us how fast this reaction will reach
equilibrium-- reactants becoming fully converted to products. See Diagram #1.
Diagram #1: Depicted in the bottom graph are the main points talked about in the top
paragraph. The transition state represents a threshold the reactants must pass before the
reaction can proceed in the forward direction. The activation energy is the energy
required to reach the transition state threshold. Once this threshold is reached, the
reaction can begin to go downhill. It is important to remember that each reaction has a
different transition state threshold, requiring different amounts of activation energies, and
determined by the reactants reacting, and the conditions which the reaction is taking place
in. The value of rate constant k is affected by these two aspects, and can be increased in
the presence of a catalyst-- an enzyme, which speeds-up reactions, increasing their rate.
In chemical reactions, specifically, the catalyst will both provide more energy to the
reactants, and lower the transition state. The provider of activation energy can also be a
spark, heat, or anything else that gives-off kinetic energy. Regardless of what provides the
activation energy, a kinetic/nonspontaneous reaction is one in which the most stable state
is that of the reactants. The change in energy between the reactants and products, also
known as ?G, relates to thermodynamics and will be discussed shortly.
Diagram #1 link: http://www4.nau.edu/meteorite/Meteorite/Images/EnergyDiagram.jpg

Example #1: Gas in a Fuel Tank:

This example will be a lot easier to understand. Have you ever wondered how gas in a
fuel tank doesn't get "wasted" or burnt away while it's sitting in the parking lot? Fuel is
kinetically stable, meaning that the spark you create while turning on the engine is what
provides the activation energy to the reactants, beginning the process of fuel-burning-which eventually enables your car to function. For more information about the way by
which fuel-burning reactions are driven, visit 'outside link' number 1. For a video that
shows why two elements don't spontaneously combust (as fuel would, had it not needed
activation energy), go to 'outside link' number 5.
Thermodynamics Overview
One can think of thermodynamics as the energy stored within a reaction, a reactant, or a
product. Most often, we think of thermodynamics as the different forms of energy that are

converted every time a reaction excretes energy or uses energy to initiate itself. With
relation to free energy (?G), thermodynamics is either (1) the energy released during a
reaction, in which case ?G will be negative and the reaction exothermic/spontaneous, or
(2) the energy consumed during a reaction, in which case ?G will be positive and the
reaction endothermic/nonspontaneous. The thermodynamic reaction will favor the
products, resulting in a spontaneous reaction that occurs without the need to input any
sort of activation energy. This indicates that the reactions' most stable state is that of the
products.
Thus, going back to Diagram #1, thermodynamics is what describes the free energy
between the reactants and the products. Since thermodynamic values apply only after the
reactants have turned into products, we can say that it describes the equilibrium state.
The way by which free energy (aka, Gibbs free energy) is related to thermodynamics is
best expressed through the following equation:

Since "U" is the variable representing the internal energy of a system, we can indefinitely
conclude that free energy and thermodynamics are closely correlated. Furthermore, as the
equation shows, changes in internal energy will change the value of the free energy,
which, in turn, affect our general reaction in several ways (affecting the rate of reaction k,
whether the reaction is spontaneous, or nonspontaneous, and even whether or not
activation energy will be needed to initiate the reaction).

Example #2: Thermodynamic Systems

The best way to understand thermodynamics is by realizing that anything that transfers,
receives or contains heat can be described as a system. Heat can enter or leave a system,
which affects the amount of thermal energy it contains. You can think of a kettle sitting
on a stove. As you heat it up (and the water inside it), you are adding thermodynamic
(thermal) energy to the system (the kettle with the water). As you turn off the stove, the
kettle will cool down as the heat will diffuse back to the room and slowly equilibrate to
room temperature. This is an example of the system losing thermal energy. To view an
animated diagram of a thermodynamic system, click on 'Outside Link' number 2.

Thermodynamic Stability vs. Kinetic Stability

Now that the overviews introduced you to kinetics and thermodynamics, the difference
between their stabilities will be discussed.
As mentioned above, the most stable states of a kinetic reaction are those of the reactants,
in which an input of energy will be required to move the reaction from a state of stability,
to that of reacting and converting itself to products. On the other hand, the most stable
state of a thermodynamic reaction is that of being in the state of products, because the

reaction will happen spontaneously, without the need for energy to be added to make the
reaction go forward.
Therefore, something that is kinetically stable will desire to stay in the form of reactants,
which will require an input of energy to cause the reaction to go forward, converting
reactants into products. This is illustrated in example #3 below. Something that is
thermodynamically stable will not need an input of energy to be converted from reactants
to products, because its most stable and preferred state is that of being composed of
products. Instead, a thermodynamically-stable reaction will require energy to be
converted from products back to reactants. It's almost as if a kinetically-stable reaction is
stubborn and does not want to be converted into products-- it's too lazy. You have to
induce it to become products by giving it kinetic energy, which MOVES the reaction
forward (kinetics = movement). The same is for thermodynamically-stable reactions,
except you'd be inducing the reaction to go back into reactants from a state of products.

Example #3: ATP- Kinetically-Stable

Adenosine triphosphate, also known as ATP, is the energy our cells produce and require
in order to maintain metabolic pathways, DNA synthesis and repair, and any other
cellular function we need in order to survive. ATP itself is a high-energy molecule that
has three phosphate groups. As we learned in the chemistry series, molecules in life
desire to become as stable as possible, and do so by converting to states of lower
energies. Thus, ATP, a high-energy molecule, wants to give off a phosphate group and
become adenosine diphosphate, ADP. In order for this to happen, ATP needs to involve an
enzyme that will strip one phosphate group off ATP, making it the more stable molecule
ADP. This enzyme provides the energy of activation that enables ATP to become ADP,
proving that ATP is kinetically stable.

Example#4: Water + Sugar - Thermodynamically-Stable

Solvents and polarity: A simple situation, a spoonful of sugar is added to a cup of water.
If the two are left to be reacted, within a certain period of time the sugar will dissolve
inside the water, becoming the product of sugar+water. The natural charges and polarity
of water causes the sugar molecules to react with it, eventually dissolving within the
water. There was no needed input of energy, meaning that this reaction was
thermodynamically stable, and spontaneous. Clearly, the two reactants prefer to react and
maintain stability as products.
Note: although this is a thermodynamically-stable/spontaneous reaction and doesn't
require energy input, the use of kinetic energy will force this reaction to happen faster.
Think of what would happen if you distributed the sugar into the cup of water, and then
heated up the cup. The kinetic energy of the reactants will be increased by the thermal
energy of the heat, which will cause the molecules to react with one another at a much

faster rate had they been left alone at room temperature. This can give you an idea of how
thermodynamics and kinetics are closely related, yet, how their stabilities differ.