Margavio 1

Hannah Margavio

UHON 3580

Dr. Matt Matthews

11 November 2017

Gibbs Free Energy

In chemistry, the change in the quantity known as Gibbs free energy, denoted by , can

be used to predict the spontaneity of a reversible reaction, i.e., whether the reaction will occur

without added heat, temperature, or pressure in the forward direction. A reaction is considered

nonspontaneous in the forward direction if it is spontaneous in the reverse direction. Since Gibbs

free energy is a state function, or one that depends only on the initial and final states, and not

what happens in between, we calculate the change in Gibbs free energy giving an expression

representing the part of the energy content of a system that is available to do external work:

= . (1)

is the change in enthalpy of a reaction in joules; when a chemical process occurs at a

constant pressure, energy in the form of heat is either absorbed or released, this energy is referred

to the heat of reaction, or change in enthalpy. If > 0, then heat is absorbed in order for the

reaction to take place; a positive change in enthalpy is also referred to as an endothermic

reaction. If < 0, then heat is released from the reaction, also called an exothermic reaction.

T is simply the temperature in kelvins at which the reaction takes place.

is the change in entropy of the system, or the randomness of a system. This quantity is

not as straightforward as the previous two because it is more conceptual. Imagine you have a

balloon filled with helium gas, shown below in figure 1.

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Figure 1.

Gas molecules inherently want to be as far away from each other as possible due to

electron repulsion, and they move at extremely large velocities. So, we say the system of the gas-

filled balloon has a high entropy, as the gas molecules are moving around very quickly and very

randomly. Now consider a brick shown in figure 2.

Figure 2.

As you can imagine, the molecules that compose this brick are very tightly packed, not moving,

save for the molecular vibrations. The system of this brick and the molecules within are not very

random at all, for the most part, they are stable and stationary, so we say that the system of this

brick has low entropy.

Putting all this information together into equation (1), we see that the mathematical signs of

enthalpy and entropy are crucial to determining if the given reaction is spontaneous because they

will ultimately affect the sign of the change in Gibbs free energy which is the determining factor
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of spontaneity in this equation. A positive change in free energy will yield a nonspontaneous

reaction, and a negative change in free energy will yield a spontaneous reaction.

If, for a certain reaction 1, the change in enthalpy is positive, and the change in entropy is

positive, then the term will be negative, since we assume temperature to be a positive unit

of kelvin, and, thus, the change in Gibbs free energy is positive, yielding a nonspontaneous

reaction. For another reaction 2, if change in enthalpy is negative, and the change in entropy is

positive, then the term will also be positive, giving a negative change in free energy, which

will yield a spontaneous reaction.

For another reaction 3, the change in enthalpy is negative, and the change in entropy is

also negative, giving the term a negative value, then the change in free energy may be either

positive OR negative depending on the temperature at which the reaction is run. If reaction 3 is

run at a low temperature then the change in free energy will be negative, and the reaction is

spontaneous because all terms in the equation are negative since the value for T is low enough to

where it will not cancel with the negative change in enthalpy. However, if reaction 3 is run at a

high temperature, then the term will become a very large negative term and subtracting this

large negative term from a smaller negative term will yield a positive result, meaning the

reaction will be nonspontaneous.

Likewise, for another reaction 4, the change in enthalpy is positive, and the change in

entropy is also positive, then the reaction will be nonspontaneous at low temperatures, and

spontaneous at higher temperatures for the same reason as described above.

Reaction 2 is very important for chemists and our understanding of chemical

thermodynamics because if we know that a system is exothermic, meaning the change in

enthalpy is negative, and if the entropy of the system overall increases, meaning the change in
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entropy is positive, then we know that the reaction will proceed as written, so long as the

temperature is greater than absolute zero, or 0 Kelvin. This information tells us that reactions

tend to proceed in the direction that will decrease the amount of heat required to begin the

reaction and that will increase the randomness of a system; this is crucial information to

understand the second law of thermodynamics.

The information above can be summarized in table 1.

Table 1.

Reaction () Spontaneity
1 (+) (-) (+) (+) Non-
spontaneous
2 (-) (+) (-) (-) Spontaneous
3 (-) (-) (+) (+) or (-) Spontaneous
at low temps
Non-
spontaneous
at high temps
4 (+) (+) (-) (+) or (-) Non-
spontaneous
at low temps
Spontaneous
at high temps

At this point you may be wondering, how was this super helpful and fundamental

equation thought of? In 1873, American mathematical physicist Willard Gibbs developed

equation (1) initially in expanded form, eq. (2):

= + (2)

which shows enthalpy as a function of internal energy U and pressure volume work pV. In 1882,

Hermann von Helmholtz continued Gibbs work to form the conclusion that free energy is a

measure of the chemical affinity between the reactants, or the tendency for reactants to
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chemically attract one another, from which an affinity table could be formed. The first affinity

table was constructed by French chemist tienne Geoffroy in 1718, shown in figure 3.

Figure 3.

Two years later in 1884, Dutch physical chemistry Jacobus vant Hoff showed for a

reversible reaction

+ +

where a, b, c, and d are stoichiometric coefficients, and equilibrium constant can be calculated as

[] []
= [][] (3)

where [A], [B], are concentrations of the products and reactant at equilibrium. Based on this

constant, another expression can be derived for the free energy of a system, which was not done

by vant Hoff exactly, but with reference to the chemical thermodynamic studies of August

Horstmann:

= ln() . (4)
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Now, consider the reaction between acetic acid and sodium bicarbonate, otherwise

known as vinegar and baking soda:

3 () + 3 () 3 () + 2 () + 2 () (5)

+ + +

The change in standard enthalpy and entropy values for each compound are summarized in table

2, where the reactants are indicated in red and the products indicated in blue.

Table 2.

3 () 3 () 3 () 2 () 2 ()

-483.5 -950.9 -1604 -285.8 -393.5

( )

158.0 102.0 262.0 69.95 214.0

( )

Calculations
= = , ,
= {[(1604) + (285.5) + (393.5)] [(483.5) + (950.9)]}/
=-848.6 kJ/mol

=
= {[69.95 + 214.0] [158.0 + 102.0 + 262.0]}/

= 238.05 = 0.238/

So, now that we have gather the thermodynamic data for the compounds in the reaction

and have found the standard enthalpy of reaction and standard entropy of reaction, we are ready

to calculate the change in Gibbs free energy, if we assume T=298.15 K, or room temperature.

=

= 848.6 (298.15) (0.238 )


= 777.64

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The change in Gibbs free energy for the reaction between vinegar and baking soda is

-777.64 kJ/mol which indicates that the reaction is spontaneous, proceeding in the direction in

which it is written. Practically, we know this to be true! If youve ever cleaned your drains by

sprinkling baking soda down the drain, then pouring vinegar down it, you know that it will form

a white-ish paste, which is the sodium acetate and water mixture that give off carbon dioxide

bubbles, not the other way around.