Statistical Mechanics Gibbs Free Energy

MODULE 5
STATISTICAL MECHANICS
Gibbs Free Energy
Standard Free Energy Changes
The standard Gibbs Free Energy is calculated using the free energy of formation of
each component of a reaction at standard pressure.
LEARNING OBJECTIVES
Calculate the change in standard free energy for a particular reaction.

Key Points
 The standard free energy of a substance represents the free energy change
associated with the formation of the substance from the elements in their most
stable forms as they exist under standard conditions.
 Combine the standard enthalpy of formation and the standard entropy of a
substance to get its standard free energy of formation.
 ΔG∘(rxn)=ΣΔG∘f(products)−ΣΔG∘f(reactants)ΔG∘(rxn)=ΣΔGf∘(products)
−ΣΔGf∘(reactants) can be used to determine standard free energy change of a
reaction.
Key Terms
 enthalpy: In thermodynamics, a measure of the heat content of a chemical or

physical system.
 entropy: A thermodynamic property that is the measure of a system’s thermal
energy per unit temperature that is unavailable for doing useful work.
 free energy of formation: The change of free energy that accompanies the
formation of 1 mole of a substance in its standard state from its constituent
elements in their standard states.
Reviewing Standard States
The concept of standard states is especially important in the case of free energy, so
take a moment to review it. For most practical purposes, the following definitions of
standard states are acceptable:
 Gases: 1 atmosphere partial pressure.

 Pure liquids: the liquid under a total pressure of 1 atm.
 Solutes: an effective concentration of 1 Molar.
 Solids: the pure solid under 1 atm pressure.
Note also that there is actually no “standard temperature “, but because most
thermodynamics tables list values for 298.15 K (25° C), this temperature is usually
implied. These same definitions apply to standard enthalpies and internal energies.
Don’t confuse these thermodynamic standard states with the “standard temperature and
pressure” (STP) widely employed in gas law calculations.
Calculating Gibbs Free Energy
In order to make use of Gibbs energies to predict chemical changes, it is necessary to

know the free energies of the individual components of the reaction. To accomplish this,
combine the standard enthalpy and the standard entropy of a substance to get the
standard free energy of a reaction:
ΔG∘=ΔH∘−TΔS∘ΔG∘=ΔH∘−TΔS∘
Recall that the symbol ° refers to the standard state of a substance measured under the
conditions of 1 atm pressure or an effective concentration of 1 Molar and a temperature
of 298K. The other factor to keep in mind is that enthalpy values are normally given
in kJmolekJmole while entropy values are given in JK×moleJK×mole. The energy units
will need to be the same in order to solve the equation properly.
The standard Gibbs free energy of the reaction can also be determined according to:
ΔG∘(rxn)=ΣΔG∘f(products)−ΣΔG∘f(reactants)ΔG∘(rxn)=ΣΔGf∘(products)−ΣΔGf∘
(reactants)
As with standard heats of formation, the standard free energy of a substance represents
the free energy change associated with the formation of the substance from the
elements in their most stable forms as they exist under the standard conditions of 1 atm
pressure and 298K. Standard Gibbs free energies of formation are normally found
directly from tables. Once the values for all the reactants and products are known, the
standard Gibbs free energy change for the reaction can be found. Most tables of
thermodynamic values list ΔGf°’s for common substances. They can, of course, always
be found from values of ΔH∘fΔHf∘ and ΔS∘fΔSf∘.
Gibbs Energy of Formation: The standard Gibbs free energy of formation of a
compound is the change of Gibbs free energy that accompanies the formation of 1 mole
of that substance from its component elements, at their standard states.
Example Problem: Calculate the ΔG0rxn for the following equation using the values in
the table:
CO(g)+12O2(g)→CO2(g)CO(g)+12O2(g)→CO2(g)
ΔG∘(rxn)=ΣΔG∘f(products)−ΣΔG∘f(reactants)ΔG∘(rxn)=ΣΔGf∘(products)
−ΣΔGf∘(reactants)
*Remember that substances in elemental form (such as O 2) have ΔGof ΔGfo values

equal to zero. It is also important to remember that the table provides per mole values. If
the balanced equation calls for more than one mole the ΔGofΔGfo must be multiplied.
ΔG∘(rxn)=(−394.4 kJ)−(−137.2 kJ+0 kJ)
ΔG∘(rxn)=−257.2 kJ
Self –Assessment Questions :
1. Calculate the Gibbs free energy change (G) for the following chemical reaction: ATP
ADP + Pi The reaction occurs at 68 °F, the change in heat (H) = 19,070 cal, and the
change in entropy (S) = 90 cal/K. 68 °F = 293 K
2. Calculate the Gibbs free energy change (G) for the following chemical reaction:
glutamate + NH3 glutamine + H2O The reaction occurs at 68 °F, the change in heat
(H) = 4103 cal, and the change in entropy (S) = 2.4 cal/K. 68 °F = 293 K, therefore
the equation is set up in the following way: G = H – TS G = 4103 cal – 293 K (2.4
cal/ K) G = 3399.8 cal = 3.4 kcal 3. Would either of the reactions above occur
spontaneously?
3. Would either of the reactions above occur spontaneously? If so, which one(s) and
why? The reaction with ATP in #1.
4. Are either of the above reactions endergonic? If so, which one(s) and why? The
reaction with glutamate and NH3 in #2.
Answer to the Self- Assessment Questions:
1. therefore the equation is set up in the following way:

G = H – TS G = 19,070 cal – (293 K) (90 cal/K)
G = –7300 cal = –7.3 kcal
2. therefore the equation is set up in the following way:

G = H – TS G = 4103 cal – 293 K (2.4 cal/ K)
G = 3399.8 cal = 3.4 kcal
3. The change in Gibbs free energy (∆G) is negative for exothermic reactions
and can only be negative for spontaneous reactions. However, the
activation energy required would still cause this reaction to occur slowly.
4. The change in ∆G (free energy) is positive, meaning free energy is

absorbed, making this reaction endergonic.
References:
Paul Flowers (University of North Carolina - Pembroke), Klaus Theopold

(University of Delaware) and Richard Langley (Stephen F. Austin State
University) with contributing authors. Textbook content produced by OpenStax
College is licensed under a Creative Commons Attribution License
4.0 license. Download for free at http://cnx.org/contents/85abf193-
[email protected]).
Adelaide Clark, Oregon Institute of Technology
. www.citethisforme.com › topic-ideas › Reductant stren...

Gibbs free energy and spontaneity (article) | Khan Academy
www.khanacademy.org › ... › Gibbs free energy
Activity coefficients in electrolyte solutions

KS Pitzer - 2018 - books.google.com
First published 1991 by CRC Press Taylor & Francis Group 6000 Broken Sound
Parkway
NW, Suite 300 Boca Raton, FL 33487-2742 Reissued 2018 by CRC Press © 1991
By CRC
Press, Inc. CRC Press is an imprint of Taylor & Francis Group,
Abrams A, Baron C. Reversible attachment of adenosine triphosphatase to

streptococcal membranes and the effect of magnesium ions. Biochemistry. 1968
Feb;7(2):501–507. [PubMed]

Statistical Mechanics Gibbs Free Energy

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MODULE 5

Gibbs Free Energy

Standard Free Energy Changes

Calculate the change in standard free energy for a particular reaction.

 enthalpy: In thermodynamics, a measure of the heat content of a chemical or

Reviewing Standard States

 Gases: 1 atmosphere partial pressure.

Calculating Gibbs Free Energy

In order to make use of Gibbs energies to predict chemical changes, it is necessary to

*Remember that substances in elemental form (such as O 2) have ΔGof ΔGfo values

1. therefore the equation is set up in the following way:

2. therefore the equation is set up in the following way:

4. The change in ∆G (free energy) is positive, meaning free energy is

Paul Flowers (University of North Carolina - Pembroke), Klaus Theopold

Adelaide Clark, Oregon Institute of Technology

. www.citethisforme.com › topic-ideas › Reductant stren...

www.khanacademy.org › ... › Gibbs free energy

Activity coefficients in electrolyte solutions

Abrams A, Baron C. Reversible attachment of adenosine triphosphatase to

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