Gibbs (Free) Energy
Gibbs (Free) Energy
Gibbs (Free) Energy
Skills to Develop
To get an overview of Gibbs energy and its general uses in chemistry.
Understand how Gibbs energy pertains to reactions properties
Understand how Gibbs energy pertains to equilibria properties
Understand how Gibbs energy pertains to electrochemical properties
Gibbs free energy, denoted G, combines enthalpy and entropy into a single value. The change in free energy, ΔG, is equal
to the sum of the enthalpy plus the product of the temperature and entropy of the system. ΔG can predict the direction of
the chemical reaction under two conditions:
1. constant temperature and
2. constant pressure.
If ΔG is positive, then the reaction is nonspontaneous (i.e., an the input of external energy is necessary for the reaction to
occur) and if it is negative, then it is spontaneous (occurs without external energy input).
Introduction
Gibbs energy was developed in the 1870’s by Josiah Willard Gibbs. He originally termed this energy as the “available
energy” in a system. His paper published in 1873, “Graphical Methods in the Thermodynamics of Fluids,” outlined how
his equation could predict the behavior of systems when they are combined. This quantity is the energy associated with a
chemical reaction that can be used to do work, and is the sum of its enthalpy (H) and the product of the temperature and
the entropy (S) of the system. This quantity is defined as follows:
G = H −TS (1)
or more completely as
G = U +PV −TS (2)
where
U is internal energy (SI unit: joule)
P is pressure (SI unit: pascal)
Example 1.1
Calculate ∆G at 290 K for the following reaction:
2 NO(g) + O (g) → 2 NO (g) (4)
2 2
Given
∆H = -120 kJ
6/28/2020 1 https://chem.libretexts.org/link?1951
∆S = -150 JK -1
Solution
now all you have to do is plug in all the given numbers into the above equation that was introduced earlier. expect you
have to convert ΔS so the same unit was ΔH .
1 kJ
ΔS = −150 J /K ( ) = −0.15 kJ/K
1000 J
looks like:
= −120 kJ + 43 kJ
= −77 kJ
N +3 H ⇌ 2 NH (5)
2 2 3
Answer
−1
ΔG = −49.35 kJ mol
Since the changes of entropy of chemical reaction are not measured readily, thus, entropy is not typically used as a
criterion. To obviate this difficulty, we can use G. The sign of ΔG indicates the direction of a chemical reaction and
determine if a reaction is spontaneous or not.
ΔG < 0 : reaction is spontaneous in the direction written (i.e., the reaciton is exergonic)
ΔG = 0 : the system is at equilibrium and there is no net change either in forward or reverse direction.
ΔG > 0 : reaction is not spontaneous and the process proceeds spontaneously in the reserve direction. To drive such a
reaction, we need to have input of free energy (i.e., the reaction is endergonic)
The factors affect ΔGof a reaction (assume ΔH and ΔS are independent of temperature):
ΔH ΔS ΔG Example
Note:
1. ΔG depends only on the difference in free energy of products and reactants (or final state and initial state). ΔG is
independent of the path of the transformation and is unaffected by the mechanism of a reaction.
2. ΔG cannot tell us anything about the rate of a reaction.
The standard Gibbs energy change ΔG (at which reactants are converted to products at 1 bar) for:
o
aA + bB → cC + dD (6)
o o o o o
ΔrG = c Δf G (C ) + dΔf G (D) − aΔf G (A) − b Δf G (B) (7)
0 0 0
Δf G = ∑ vΔf G (products) − ∑ vΔf G (reactants) (8)
The standard-state free energy of reaction ( ΔG ) is defined as the free energy of reaction at standard state conditions:
o
o o o
ΔG = ΔH − T ΔS (9)
6/28/2020 2 https://chem.libretexts.org/link?1951
Note
If |ΔH | >> |T ΔS|: the reaction is enthalpy-driven
If ΔH << T ΔS : the reaction is entropy-driven
Example 1.2
Used the below information to determine if N H 4N O3(s) will dissolve in water at room temperature.
Compound ΔH
f
o
ΔS
f
o
+
NH
4(aq ) -132.51 113.4
−
NO
3(aq ) 205.0 146.4
SOLUTION
This question is essentially asking if the following reaction is spontaneous at room temperature.
H O
2
+ −
NH NO (s) ⟶ NH (aq) + NO (aq) (11)
4 3 4 3
This would normally only require calculating ΔG and evaluating its sign. However, the ΔG values are not
o o
tabulated, so they must be calculated manually from calculated ΔH and ΔS values for the reaction. o o
Calculate ΔH :o
o o o
ΔH = ∑ nΔH − ∑ mΔH (12)
fproducts frea cta nts
o
kJ −
kJ
ΔH = [(1 mol N H3 ) (−132.51 ) + (1 mol N O ) (−205.0 )] (13)
3
mol mol
kJ
− [(1 mol N H4 N O3 ) (−365.56 )] (14)
mol
o
ΔH = −337.51 kJ + 365.56 kJ = 28.05 kJ (15)
Calculate ΔS :o
o o o
ΔS = ∑ nΔS − ∑ SΔH (16)
f f
products rea cta nts
o
J −
J
ΔS = [(1 mol N H3 ) (113.4 ) + (1 mol N O ) (146.6 )] (17)
3
mol K mol K
J
− [(1 mol N H4 N O3 ) (151.08 )] (18)
mol K
o
ΔS = 259.8 J/K − 151.08 J/K = 108.7 J/K (19)
Calculate ΔG :o
6/28/2020 3 https://chem.libretexts.org/link?1951
1 kJ
o
ΔS = 108.7 J /K ( ) = 0.1087 kJ/K (21)
1000 J
o
ΔH = 28.05 kJ (22)
o o o
ΔG = ΔH + T ΔS (23)
o
ΔG = 28.05 kJ − (298.15 K )(0.1087 kJ/ K ) (24)
o
ΔG = 28.05 kJ − 32.41 kJ (25)
o
ΔG = −4.4 kJ (26)
Example 1.3
Calculate ΔG for the following reaction at 25 o
C . Will the reaction occur spontaneously?
ΔS = −284.8 J/K
Solution
calculate ΔG from the formula
ΔG = ΔH − T ΔS (27)
but first we need to convert the units for ΔS into kJ/K (or convert ΔH into J) and temperature into Kelvin
1 kJ
ΔS = −284.8 J /K ( ) = −0.284.8 kJ/K
1000 J
o
T = 273.15 K + 25 C = 298 K
ΔG = ΔH − T ΔS (28)
ΔG = −91.1 kJ (31)
The following equation relates the standard-state free energy of reaction with the free energy at any point in a given
reaction (not necessarily at standard-state conditions):
o
ΔG = ΔG + RT ln Q (33)
6/28/2020 4 https://chem.libretexts.org/link?1951
At equilibrium, ΔG = 0 and Q=K. Thus the equation can be arranged into:
[C ][D]
o
ΔG = ΔG + RT ln (34)
[A][B]
with
ΔG
o
= standard free energy change
R = gas constant = 1.98 * 10-3 kcal mol-1 deg-10
T = is usually room temperature = 298 K
[C ][D]
K =
[A][B]
The Gibbs free energy ΔG depends primarily on the reactants' nature and concentrations (expressed in the ΔG term and o
[C ][D]
o
ΔG = −RT ln (36)
[A][B]
When K eq is large, almost all reactants are converted to products. Substituting K eq into Equation 1.14, we have:
o
ΔG = −RT ln Keq (38)
or
o
ΔG = −2.303RT log10 Keq (39)
Rearrange,
o
−Δ G /(2.303RT )
Keq = 10 (40)
This equation is particularly interesting as it relates the free energy difference under standard conditions to the properties
of a system at equilibrium (which is rarely at standard conditions).
Table 1.1: Converting K ea to ΔG
Keq ΔGo (kcal/mole)
10
−5
6.82
10
−4
5.46
10
−3
4.09
10
−2
2.73
10
−1
1.36
1 0
10
1
-1.36
10
2
-2.73
10
3
-4.09
10
4
-5.46
10
5
-6.82
Example 1.4
What is ΔG for isomerization of dihydroxyacetone phosphate to glyceraldehyde 3-phosphate?
o
6/28/2020 5 https://chem.libretexts.org/link?1951
o −3
ΔG = −2.303 RT log10 Keq = (−2.303) ∗ (1.98 ∗ 10 ) ∗ 298 ∗ (log10 0.0475) = 1.8 kcal/mol (41)
Given:
The initial concentration of dihydroxyacetone phosphate = 2 × 10 −4
M
SOLUTION
From equation 2:
ΔG = 1.8 kcal/mol + 2.303 RT log10(3*10-6 M/2*10-4 M) = -0.7 kcal/mol
Note
Under non-standard conditions (which is essential all reactions), the spontaneity of reaction is determined by ΔG, not
′
ΔG .
o
with
E = cell potential in volts (joules per coulomb)
n = moles of electrons
F = Faraday's constant: 96,485 coulombs per mole of electrons
o
RT
E =E − ln Q (43)
nF
o
ΔG = ΔG + RT ln Q (47)
Therefore,
o o
ΔG = −nF E (49)
6/28/2020 6 https://chem.libretexts.org/link?1951
most important attributes of energy in that it is not conserved. Thus although the free energy always falls when a
gas expands or a chemical reaction takes place spontaneously, there need be no compensating increase in energy
anywhere else. Referring to G as an energy also reinforces the false but widespread notion that a fall in energy must
accompany any change. But if we accept that energy is conserved, it is apparent that the only necessary condition
for change (whether the dropping of a weight, expansion of a gas, or a chemical reaction) is the redistribution of
energy.The quantity –ΔG associated with a process represents the quantity of energy that is “shared and spread”,
which as we have already explained is the meaning of the increase in the entropy. The quotient –ΔG/T is in fact
identical with ΔStotal, the entropy change of the world, whose increase is the primary criterion for any kind of
change.
Free Energy is not even "real": G differs from the thermodynamic quantities H and S in another significant way:
it has no physical reality as a property of matter, whereas H and S can be related to the quantity and distribution of
energy in a collection of molecules (e.g., the third law of thermodynamics). The free energy is simply a useful
construct that serves as a criterion for change and makes calculations easier.
References
1. Chang, Raymond. Physical Chemistry for the Biosciences. Sansalito, CA: University Sciences, 2005.
2. Atkins, Peter and de Paula, Julio. Physical Chemistry for the Life Sciences. New York, NY: W. H. Freeman and
Company, 2006. Page 153-163, 286.
3. Stryer, Lubert. Biochemistry (Third Edition). New York, NY: W.H. Freeman and Company, 1988. Page 181-184.
Contributors
Cathy Doan (UC Davis), Han Le (UC Davis)
Stephen Lower, Professor Emeritus (Simon Fraser U.) Chem1 Virtual Textbook
6/28/2020 7 https://chem.libretexts.org/link?1951