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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)
V is volume (SI unit: m )
3
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
∆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 .
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1 kJ
ΔS = −150 J /K ( ) = −0.15 kJ /K
1000 J
looks like:
= −120 kJ + 43 kJ
= −77 kJ
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 ΔG of a reaction (assume ΔH and ΔS are independent of temperature):
ΔH ΔS ΔG Example
+ + at low temperature: + , at high temperature: - 2HgO(s) -> 2Hg (l) + O2 (g)
- - at low temperature: - , at high temperature: + NH3 (g) + HCl (g) -> NH4Cl (s)
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
Δr G = cΔf G (C) + dΔf G (D) − a Δf G (A) − bΔf 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)
Note
If |ΔH| >> |T ΔS | : the reaction is enthalpy-driven
If ΔH << T ΔS : the reaction is entropy-driven
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o o o
ΔG = ∑ ΔG − ∑ ΔG (10)
fprodu cts freactants
Example 1.2
Used the below information to determine if N H 4 N 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.
H2 O
+ −
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
o
ΔG
o
values are not 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)
fprodu cts freactants
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 − ∑ S ΔH (16)
fprodu cts freactants
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
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?
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N H3(g) + HC l(g) → N H4 C l(s)
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 = −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)
o
[C][D]
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
o
term and the
logarithmic term of Equation 1.11, respectively).
At equilibrium, ΔG = 0 : no driving force remains
′ [C][D]
o
0 = ΔG + RT ln (35)
[A][B]
[C][D]
o
ΔG = −RT ln (36)
[A][B]
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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
−ΔG /(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
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
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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)
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
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