AP Chemistry Spontaneity: Entropy and Free Energy: What Drives A Reaction To Be Spontaneous? Enthalpy (Entropy (
AP Chemistry Spontaneity: Entropy and Free Energy: What Drives A Reaction To Be Spontaneous? Enthalpy (Entropy (
(1) ENTHALPY (ΔH) – heat content (exothermic reactions are generally favored)
(2) ENTROPY (ΔS) – disorder of a system (more disorder is favored) Nature tends toward
chaos! Think about your room at the end of the week! Your mom will love this law.
Spontaneous reactions are those that occur without outside intervention. They may occur
fast OR slow (that is kinetics). Some reactions are very fast (like combustion of hydrogen)
other reactions are very slow (like graphite turning to diamond)
ENTROPY:
The second law of thermodynamics: the universe is constantly increasing disorder. Rudolph
Clausius (you=ll hear lots about him later when we study vapor pressures) Adiscovered@ it and gave it its
symbol.)
1) The greater the disorder or randomness in a system, the larger the entropy.
2) The entropy of a substance always increases as it changes from solid to liquid to gas.
3) When a pure solid or liquid dissolves in a solvent, the entropy of the substance increases
(carbonates are an exception!--they interact with water and actually bring MORE order to the
system)
4) When a gas molecule escapes from a solvent, the entropy increases
5) Entropy generally increases with increasing molecular complexity (crystal structure: KCl vs
CaCl2) since there are more MOVING electrons!
*AP is a registered trademark of the College Board, which was not involved in the production of, and does not endorse, this product.
© 2008 by René McCormick. All rights reserved
6) Reactions increasing the number of moles of particles often increase entropy.
K In general, the greater the number of arrangements, the higher the entropy of the system!
Calculating Entropy from tables of standard values: (Just the same as calculating the enthalpy
earlier)
Sample Problem A:
Which of the following has the largest increase in entropy?
a) CO2(s) Æ CO2(g)
b) H2(g) + Cl2(g) Æ 2 HCl(g)
c) KNO3(s) Æ KNO3(l)
d) C(diamond) Æ C(graphite)
Sample Problem B:
Calculate the entropy change at 25°C, in J/K for:
2 SO2(g) + O2(g) Æ 2 SO3(g)
! ΔS = heat transferred = q
temperature at which change occurs T
**where the heat supplied (endothermic) (q > 0) or evolved (exothermic) (q < 0) is divided by the
temperature in Kelvins
** It is important here to note if the reaction is endothermic or exothermic. The actual significance of
this is really dependent on the temperature at which the process occurs.
(i.e., If you gave a millionaire $100 it would not make much difference in his happiness; if you gave a
poor college student $100 it would create a totally different expression of happiness!)
• Taking favored conditions into consideration, the equation above rearranges into:
ΔS = - ΔH
T
! Give signs to ΔH following exo/endo guidelines! (If reaction is exo.; entropy of system increases—
makes sense!)
• Whether a reaction will occur spontaneously may be determined by looking at the ΔS of the universe.
ΔS system + ΔS surroundings = ΔS universe
IF ΔS universe is +, then reaction is spontaneous
IF ΔS universe is -, then reaction is NONspontaneous
Consider
2 H2 (g) + O2 (g) 6 H2O (g) ignite & rxn is fast!
ΔSsystem = -88.9J/K
entropy declines (due mainly to 362 moles of gas!)
. . . to confirm we need to know entropy of surroundings
First law of thermodynamics demands that this energy is transferred from the system to the surroundings so...
-ΔHsystem = ΔHsurroundings OR
- (-483.6 kJ) = +483.6 kJ
Even though the entropy of the system declines, the entropy change for the surroundings is SOOO large that
the overall change for the universe is positive.
Bottom line: A process is spontaneous in spite of a negative entropy change as long as it is extremely
exothermic. Sufficient exothermicity offsets system ordering.
FREE ENERGY
Calculation of Gibb’s free energy is what ultimately decides whether a reaction is spontaneous or not.
NEGATIVE ΔG’s are spontaneous. ΔG can be calculated one of several ways:
(a) Big Mamma,verse 3: ΔGErxn = Σ ΔGE (products) - Σ ΔGE (reactants)
This works the same way as enthalpy and entropy from tables of standard values! Standard molar free
energy of formation--same song, 3rd verse. ΔGEf = 0 for elements in standard state
(b) GRAND Daddy: ΔG = ΔH - TΔS
This puts together all information thus far! By far, one of the most beneficial equations to
learn for AP exam!
(c) Hess’s law summation
Works same as Hess’s in the enthalpy section—sum up equations using the guidelines as
carried out at 25°C and 1 atm. Calculate ∆H°, ∆S°, and ∆G° using the following data:
∆H° = -198 kJ
∆S° = -187 J/K
∆G° = -142 kJ
ΔG = ΔGE + RT ln (Q)
One method for synthesizing methanol (CH3OH) involves reacting carbon monoxide and hydrogen gases:
CO(g)+2H2(g)→CH3OH(l)
Calculate ∆G at 25°C for this reaction where carbon monoxide gas at 5.0 atm and hydrogen gas at 3.0 atm are
converted to liquid methanol.
K = 10261
Sample Problem:
Find the thermodynamic boiling point of H2O(l) Æ H2O(g)
Given the following information:
Hvap = +44 kJ Svap = 118.8 J/K
Answer: 370K
Relationship to K and E :
ΔG K E
0 at equilibrium; K = 1 0
negative >1, products favored positive
positive <1, reactants favored negative