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Gibbs Free Energy ( Gθ )
1. What is Gibbs free energy & why it is important?
The total entropy which includes the system & surrounding was used previously to
predict the feasibility of a reaction. In chemical thermodynamics it’s often
preferred to focus on the system than the surroundings. Free energy enables us to
do this for changes that occur at constant temperature and pressure. (Not
necessary at standard conditions).
Gibbs free energy refers to the amount of energy of the system available to do
work. This energy is referred to as the “FREE” energy as it is the remaining energy
of the system after it had used some of its energy for entropy. Since this was
discovered by [Link] Gibbs it is called as Gibbs Free Energy. Symbolized by ΔG.
Gibbs free energy is important to predict the feasibility of a reaction where
feasibility cannot be predicted when enthalpy & entropy is considered together.
Eg: Reaction which is feasible with respect to enthalpy but not entropy
(exothermic reaction with negative entropy) or Feasible with respect to entropy
but not enthalpy. (Endothermic reaction with positive entropy)
2. Define Standard Gibbs free energy change, ΔGθ
Gibbs free energy / Gibbs function is the combination of entropy and enthalpy. The
change in the Gibbs free energy of the system that occurs during a reaction is
therefore equal to the change in the enthalpy of the system minus the change in
the product of the temperature times the entropy of the system. And can be
defined by the following equation:
ΔGθ = ΔHθ - TΔSθ
Where, ΔHθ is the standard enthalpy change of the reaction. (298K, 1atm)
T is the temperature in Kelvin
ΔSθ is the standard entropy change of the system.
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ΔGθ is the standard Gibbs free energy. Remember that the superscript θ on
ΔGθindicates that the numerical value of Gibbs free energy is based on the
reaction at standard conditions and it refers to 1M concentrated solution & 1 atm
pressure. Temperature is NOT a part of standard conditions for ΔGθ.
3. Derive the Gibbs free energy equation from total entropy equation. Gibbs free energy
change is given by the equation ΔG = - TΔStotal
4. Define the term Standard molar Gibbs free energy of formation.
Standard molar Gibbs free energy of formation is the free energy change
which accompanies the formation of one mole of a compound from its
elements in their standard state.
Symbolized by ΔGѲf and units are kJmol-1
5. Explain how ΔG determines the direction & extent of a chemical change hence
spontaneity.
Thus negative ΔG indicates that the reaction is spontaneous, a positive ΔG
indicates a non-spontaneous reaction and if ΔG is zero the reaction is at
equilibrium. ΔGѲf is a measure of the stability of the compound. Greater the
negative value greater the stability thus difficult to decompose and vice versa.
The ΔGѲf of an element under standard condition is zero.
(Eg:H2,O2,Br2,C,Mg,Na)
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6. Discuss the effect of temperature on spontaneity of a reaction
As ΔG = ΔH - TΔS , ΔG changes with temperature.
ΔH could be negative (an exothermic reaction) or positive (an endothermic
reaction). Similarly ΔS could be either positive or negative. Thus there are
four possible combinations of the signs of ΔH and ΔS
a. ΔH is negative and ΔS is positive:
As both ΔH and -TΔS terms are negative irrespective of the temperature,
ΔG is also will to be negative. The reaction will be spontaneous at all
temperatures.
b. ΔH is positive and ΔS is negative :
As both ΔH and -TΔS terms are positive irrespective of the temperature,
ΔG is also will be positive. The reaction will not be spontaneous at any
temperature.
c. ΔH is positive and ΔS is positive :
ΔH is positive. -TΔS is negative.
Increasing the temperature will result -TΔS will become more negative, and
will eventually outweigh ΔH thus the reaction will be spontaneous.
But at low temperatures, ΔG becomes positive thus the reaction will be non
spontaneous. Eg : Decomposition of CaCO3
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d. ΔH is negative and ΔS is negative :
ΔH is negative. -TΔS is positive.
As temperature increases, -TΔS will become more positive, and will
eventually outweigh the effect of ΔH thus reaction will be non spontaneous.
But at low temperatures ΔG will be negative thus be spontaneous.
7. State the factors which is to be considered when Calculating ΔG° hence explain how ΔG of
a reaction is calculated.
ΔG° and ΔH° are both measured in kJmol-1 whereas the entropy change is
calculated in JK-1mol-1, Thus one must change the entropy change value into
kJ before when calculating ΔG°.
Similar to enthalpies and entropies the standard Gibbs free energy of a
reaction can be calculated as to the below equation:
ΔG° = n ΔG°(products) - n ΔG°(reactants) n = [Link] moles
8. Calculate the ΔG° in below examples hence comment on the feasibility of the reaction.
I. C(graphite) + O2(g) CO2(g)
Calculate ΔGº for CO2 at 298 K. ΔH°(CO2) = −393 KJ/mol, S° (O2) = 205 J/mol.K ,
S°(C) = 6 J/mol.K, S° (CO2) = 213 J/mol.K
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II. C(graphite) + O2(g) 2CO(g)
Calculate ΔGº for CO at 298 K. ΔHf ° (CO) = −110 KJ/mol, S°(O2) = 205 J/mol.K, S°(C) = 6
J/mol.K, S°(CO) = 198 J/mol.K
III. 2Na(s) + O2(g) Na2O2(s)
Calculate ΔGº for the reaction at 298 K. ΔH = −510 KJ/mol, S°(Na) = 51.2 J/mol.K, S°(
Na2O2) = 95.0 J/mol.K, S°(O2) = 205.0 J/mol.K
9. Calculate ΔGº for the following Reactions, Given that;
ΔGºf (SO2, g) = −300 kJ/mol ΔGºf (SO3, g) = −371 kJ/mol
ΔGºf (H2SO4, l) = −690 kJ/mol º
ΔG f (H2SO4, aq) = −742 kJ/mol
ΔGºf (H2O, l) = −237 kJ/mol ΔGºf (H2S, g) = −34 kJ/mol
a) S(s) + O2(g) SO2(g)
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b) 2SO2(g) + O2(g) 2SO3(g)
c) SO3(g) + H2O(l) H2SO4(l)
d) 2H2S(g) + 3O2(g) 2SO2(g) + 2H2O(l)
10. Calculate the temperature above at which the following non spontaneous reaction
becomes spontaneous. (Assume that ΔH° and ΔS° does not change much with temperature)
Fe2O3 + 3CO 2Fe + 3CO2 ΔH° = +465 kJ/mol
ΔS° = +552 J/molK
ΔG° = +301 kJ/mol (at 298 K)
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11. With the help of a Gibbs free energy cycle calculate ΔGѲf for the below
decomposition, hence comment on the feasibility.
2NaHCO3(s) Na2CO3(s) + CO2(g) + H2O(l)
The relevant ΔGѲf values are :
ΔGѲf[NaHCO3(s)] = -850 kJmol-1 ΔGѲf[H2O(l)] = -235. kJmol-1
ΔGѲf[CO2g)] = -390 kJmol-1, ΔGѲf[Na2CO3(s)] = -1045 kJmol-1
Chembase - School of Chemistry I All Rights Reserved I [Link]
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