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Gibbs Free Energy Gibbs Free Energy

For a constant temperature and constant pressure process:
DG = DH - TDS
-TDSuniv = DHsys - TDSsys
• If you know DG for reactants and products then you can
DG = DHsys - TDSsys calculate if a reaction is spontaneous.
Gibbs free energy (DG)- Can be used to predict spontaneity. • If you know DG for two reaction then you can calculate if the
sum is spontaneous.
DG < 0 The reaction is spontaneous in the forward direction. • If you know DS, DH and T then you can calculate spontaneity.
• Can predict the temperature when a reaction becomes
-DG = -T(+DSuniv) DSuniv > 0
spontaneous.
DG > 0 The reaction is nonspontaneous as written. The • If you have DHvap or DHfus and DS you can predict boiling and
reaction is spontaneous in the reverse direction. freezing points.
+DG = -T(-DSuniv) DS < 0 • If you have DHvap or DHfus and T you can predict the entropy
univ
DG = 0 The reaction is at equilibrium. change during a phase change.
DG = -T(DSuniv) = 0 • Can predict equilibrium shifts.
DSuniv = 0 1 2

Free Energy and Equilibrium Free Energy and Equilibrium

The standard free-energy of reaction (DG0rxn) is the free-energy
change for a reaction when it occurs under standard-state DG° = -R T lnK equilibrium constant
(Kp, Kc, Ka, Ksp, etc.)
conditions.
aA + bB cC + dD standard free-energy
(kJ/mol) temperature
gas constant
(K)
DGrxn
0
= S nDG0f (products) - S mDG0f (reactants) (8.314 J/Kmol)

• Arguably most important equation in chemical thermodynamics!

DG° < 0 favors products spontaneously
DG° > 0 favors reactants spontaneously • It allows us to calculate the extent of a chemical reaction if its
enthalpy and entropy changes are known.
Does not tell you it will go to completion! • The changes in enthalpy and entropy can be evaluated by
measuring the variation of the equilibrium constant with
DG° fwd temperature.
aA + bB cC + dD DG° fwd = -DG° rev
DG° rev • This relationship is only valid for the standard conditions, i.e. when
The value of DG° calculated under the standard conditions characterizes the the activities of all reactants and products are equal to 1.
“driving force” of the reaction towards equilibrium. 3 4

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Free Energy and Equilibrium Using DG° and K

DG° = -R T lnK Using the table of standard free energies, calculate the
R is constant so at a given temperature: equilibrium constant, KP, for the following reaction at 25 C.
DG0(kJ) K Significance 2HCl(g) H2(g) + Cl2(g)
200 9x10-36 Essentially no forward reaction;
reverse reaction goes to completion
DG0rxn = S nDG0 (products) - S mDG0f (reactants)
100 3x10-18 f

50 2x10-9 DG0rxn = [1(0) + 1(0)] - [2(-95.3 kJ/mol)]

FORWARD REACTION

REVERSE REACTION
10 2x10-2 Non-spontaneous!
DG0rxn = 190.6 kJ/mol
Favors reactants!
1 7x10-1
Forward and reverse reactions
0 1 proceed to same extent DG° = -R T ln K
-1 1.5
From literature :
-10 5x101
H2(g) DGf = 0 kJ/mol
-50 6x108
Cl2(s) DGf = 0 kJ/mol
Forward reaction goes to completion;
-100 3x1017
essentially no reverse reaction
HCl(g) DGf = -95.3 kJ/mol
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-200 1x1035

Example 17.6
Using DG° and K
Using data listed in Appendix 3, calculate the equilibrium
Using the table of standard free energies, calculate the constant (KP) for the following reaction at 25°C:
equilibrium constant, KP, for the following reaction at 25 C.
2H2O(l) 2H2(g) + O2(g)
2HCl(g) H2(g) + Cl2(g) ΔG°rxn = [2ΔG°f(H2) + ΔG°f(O2)] - [2ΔG°f(H2O)]
DG0 = S nDG0 (products) - S mDG0f (reactants) = [(2)(0 kJ/mol) + (0 kJ/mol)] - [(2)(-237.2 kJ/mol)]
rxn f
= 474.4 kJ/mol
DG0rxn = [1(0) + 1(0)] - [2(-95.3 kJ/mol)] o
ΔGrxn = -RTln K p
Non-spontaneous!
DG0rxn = 190.6 kJ/mol 474.4 kJ/mol ×
1000 J
= -(8.314J/K  mol)(298 K)lnK p
Favors reactants!
1 kJ
DG° = -R T ln K lnK p = -191.5

190.6 kJ/mol = - (8.314 J/K·mol)(25C) ln KP K p  e -191.5 = 7 × 10-84

correct units Bonus: What is the Kp for the reverse reaction?

2H2(g) + O2(g) 2H2O(l)
190.6 kJ/mol = - (8.314 x 10-3 kJ/K·mol)(298 K) ln KP
lnKp(fwd) = -lnKp(rev)
ΔG°rxn = -474.4 kJ/mol or 1/Kp(fwd) = Kp(rev)
KP = 3.98 x 10-34 Favors reactants! 7 8

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Example
Free Energy and Equilibrium
we discussed the solubility product of slightly soluble substances.
Using the solubility product of silver chloride at 25°C (1.6 x 10-10),
DG° = -R T lnK
calculate ΔG° for the process
DG°
AgCl(s) Ag+(aq) + Cl-(aq) Rearrange: ln K = -
RT
Ksp = [Ag+][Cl-] = 1.6 x 10-10
Substitution: ln K = - DH - TDS
DG° = -R T lnK DG = DH - TDS RT
ΔG° = -(8.314 J/K·mol) (298 K) ln (1.6 x 10-10)
= 5.6 x 104 J/mol Rearrange: ln K = - DH +
TDS
RT RT
= 56 kJ/mol

ln K = - DH DS
Favors reactants.
1
Not very soluble! ()
R T
+
R

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Free Energy and Equilibrium Free Energy and Equilibrium

DG° = -R T lnK Find the DS and DH of the following:

Measure equilibrium with kobs

DG° respect to temperature:
Rearrange: ln K = - kf
RT

Substitution: ln K = - DH - TDS A B
DG = DH - TDS RT rateAB = kobs [A]

rateBA = kf [B]
Rearrange: ln K = - DH TDS
+ At equilibrium:
RT RT
rateAB = rateBA
DH 1 DS
ln K = -
R T() +
R
kobs [A] = kf [B]

y = m•x + b kobs [B]

11 kf
=
[A]
= Ku
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Free Energy and Equilibrium DG° vs DG

Find the DS and DH of the following: You have already delta ΔG°, ΔS° and ΔH° in which the ° indicates that
kobs all components are in their standard states.
Definition of “standard”:
kf • Even if we start a reaction at standard
conditions (1 M) the reaction will
quickly deviate from standard.
DS DH° = 60 kJ/mol
R DS° = 200 J/Kmol
• DG° indicates whether reactants or
products are favored at equilibrium.
Slope = -7261.1 K
• DG at any give time is used to predict
the direction shift to reach equilibrium.
DH
-
R
• If a mixture is not at equilibrium, the
liberation of the excess Gibbs free
energy (DG) is the “driving force” for
the composition of the mixture to
*There is no "standard temperature", change until equilibrium is reached. 14
13
but we usually use 298.15 K (25° C).

Free Energy and Equilibrium Free Energy and Equilibrium

At equilibrium: DG° = -R T ln K DG = DG° + R T ln Q reaction quotient

At any time: DG = DG° + R T ln Q reaction quotient

standard free-energy temperature
non-standard free-energy (kJ/mol) gas constant (K)
(kJ/mol) (8.314 J/Kmol)
standard free-energy temperature
non-standard free-energy (kJ/mol) gas constant (K)
(kJ/mol) (8.314 J/Kmol)
If Q/K < 1, then ln Q/K < 0; the reaction proceeds to the right (DG < 0)

The sign of DG tells us that the reaction would have to shift to the left to If Q/K > 1, then ln Q/K > 0; the reaction proceeds to the left (DG > 0)
reach equilibrium.
If Q/K = 1, then ln Q/K = 0; the reaction is at equilibrium (DG = 0)
DG < 0, reaction will shift right
DG > 0, reaction will shift left
DG = 0, the reaction is at equilibrium
The magnitude of DG tells us how far it has to go to reach equilibrium.
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Another Example Another Example

For the following reaction at 298 K: For the following reaction at 298 K:
H2(g) + Cl2(g)  2 HCl(g) H2(g) + Cl2(g)  2 HCl(g)
Given: From appendix 3: Given: From appendix 3:
H2 = 0.25 atm H2 = 0.25 atm
H2(g) DGf = 0 kJ/mol H2(g) DGf = 0 kJ/mol
Cl2 = 0.45 atm Cl2(s) DGf = 0 kJ/mol
Cl2 = 0.45 atm Cl2(s) DGf = 0 kJ/mol
HCl = 0.30 atm HCl(g) DGf = -95.3 kJ/mol HCl = 0.30 atm HCl(g) DGf = -95.3 kJ/mol

Which way will the reaction shift to reach equilibrium? Which way will the reaction shift to reach equilibrium?
DG = DG° + R T ln Q DG = DG° + R T ln Q
constant calculate
(P )2 (0.30) 2
calculate given DG° = [2(-95.27 kJ/mol)] - [0 + 0] QP  HC l   0.80
(P ) (P ) (0.25) (0.45)
H Cl
= -190.54 kJ/mol 2 2

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Example
Another Example
The equilibrium constant (KP) for the reaction
For the following reaction at 298 K:
N2O4(g) 2NO2(g)
H2(g) + Cl2(g)  2 HCl(g) is 0.113 at 298 K, which corresponds to a standard free-energy change of
Given: From appendix 3: 5.40 kJ/mol. In a certain experiment, the initial pressures are PNO2 = 0.122
H2 = 0.25 atm atm and PN2O4 = 0.453 atm.
H2(g) DGf = 0 kJ/mol
Cl2 = 0.45 atm Cl2(s) DGf = 0 kJ/mol Calculate ΔG for the reaction at these pressures and predict the direction of
HCl = 0.30 atm HCl(g) DGf = -95.3 kJ/mol the net reaction toward equilibrium.

Which way will the reaction shift to reach equilibrium? ΔG = ΔG o + RTlnQp Because ΔG < 0, the net reaction proceeds
2
PNO from left to right to reach equilibrium.
DG = DG° + R T ln Q o
= ΔG + RTln 2

PN2O4
DG° = -190.54 kJ/mol Q = 0.80
constant
given 3 (0.122) 2
= 5.40 × 10 J/mol + (8.314J/K  mol)(298 K) × ln
0.453
DG = -190,540 J/mol + (8.314J/K·mol)(298 K) ln (0.80)
= 5.40 × 103 J/mol - 8.46 × 103 J/mol
DG = -191.09 kJ/mol = -3.06 × 103J/mol = - 3.06kJ / mol
Because ΔG < 0, the net reaction proceeds from left to right to reach equilibrium.
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Free Energy and Equilibrium “Uphill” Reactions

At equilibrium: DG° = -R T ln K
Synthesis of proteins: (first step)
At any time: DG = DG° + R T ln Q alanine + glycine  alanylglycine DG° = 29 kJ/mol

Because ΔG > 0, the reaction is non-spontaneous.

No reaction!

Need to couple two reactions!

DG0 < 0 DG0 > 0
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Coupled Reactions Coupled Reactions

Coupled Reactions- using a thermodynamically favorable (DG° < 0) Coupled Reactions- using a thermodynamically favorable (DG° < 0)
reaction (DG° < 0) to drive an unfavorable one (DG° > 0) . reaction (DG° < 0) to drive an unfavorable one (DG° > 0) .
Example: Industrial ore separation- Example: Industrial ore separation-

Unfavorable reaction (DG° > 0)

Zinc Metal
Major applications in the US
1) Galvanizing (55%)
Sphalerite ore 2) Alloys (21%)
3) Brass and bronze (16%)
95 % of Zinc is produced by this method
4) Miscellaneous (8%)
White pigment (ZnO)
Fire retardant (ZnCl2)
Vitamin supplement (Zn2+)
Reducing agent (Zn(s))

We need 2000 tones of the zinc metal per year!23 24

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Coupled Reactions in Biology Coupled Reactions in Biology

DG° < 0
Food
Structural motion and maintenance

DG° > 0

Fats and Carbohydrates Coupled reactions

ATP and NADPH

Chemical Batteries for the Body

glucose + Pi → glucose-6-phosphate Stored bond energy
ATP + H2O → ADP + Pi
glucose + ATP → glucose-6-phosphate + ADP 25 26

Coupled Reactions in Biology “Uphill” Reactions

Digestion/respiration:
Synthesis of proteins: (first step)

Generation of ATP:

alanine + glycine  alanylglycine DG° = 29 kJ/mol

ATP + H2O  ADP + H3PO4 DG° = -31 kJ/mol
alanine + glycine + ATP + H2O  alanylglycine + ADP + H3PO4 DG° = -2 kJ/mol
Burning
Glucose Spontaneous!

Low Energy Higher Energy

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Coupled Reactions in Biology Coupled reactions to drive the synthesis of:

Aminoacids
Ribose
Nucleic acids
Polypeptides
DNA This is why we eat!
Phospholipids …and why plants
absorb light.

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