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Spontaneity, Entropy
and Free Energy
DE Chemistry
Dr. Walker
Laws Of Thermodynamics
• The first law of thermodynamics is a
statement of the law of conservation of
energy:
– Energy can be neither created nor destroyed. In
other words, the energy of the universe is
constant.
Energy in Chemical Reactions
A+B C + D + Energy
• Exothermic process
– Ssurr = positive, exothermic = more disorder in
surroundings
• Endothermic process
– Ssurr = negative, endothermic = less disorder in
surroudings
– ssystem must increease to obey 2nd Law of
Thermodynamics
More on Entropy
• 1st reaction
• H = -125 kJ, 25 oC + 273 = 298 K
• Ssurr = -125 kJ/298 K = 419 J/K
• Remember 125 kJ = 125000 J
• ssurr is positive, calculation refers
to system!
Example
• 2nd reaction
• H = 778 kJ, 25 oC + 273 = 298 K
• S = 778 kJ/298 K = -2.61 kJ/K
• Remember 778 kJ = 778000 J
Free Energy, G
G = H - TS
• Typically defined as the energy available to
perform work
• G determines whether a process is spontaneous
or not (G = negative = spontaneous)
– Takes into account enthalpy, entropy, and
temperature
– Symbol honors Josiah Gibbs (sometimes called Gibbs
Free Energy or Gibbs energy), a physics professor at
Yale during the late 1800’s who was important in
developing much of modern thermodynamics
Energy Diagrams
• As a result
G < 0 The reaction is spontaneous.
G = H - TS
G = H TS
S 0
reaction n S0
p products nr So
reactants
S 0
reaction n S0
p products nr S
o
reactants
• 2 (28 J/Kmol) + 3 (189 J/Kmol) – 51 J/K mole – 3
(131 J/Kmol) = 179 J/K
• System gained entropy – water more complex
than hydrogen!
Second Example
• Evaluate the entropy change for the reaction:
CO + 3 H2 -> CH4 + H2O
in which all reactants and products are gaseous.
So values: CO 198 J/Kmol
H2 131 J/Kmol
CH4 186 J/Kmol
H2O 189 J/Kmol
Second Example
• Evaluate the entropy change for the reaction:
CO + 3 H2 -> CH4 + H2O
in which all reactants and products are gaseous.
So values: CO 198 J/Kmol
H2 131 J/Kmol
CH4 186 J/Kmol
H2O 189 J/Kmol
G np G
0 0
f (products) nr G 0
f (reactants)
G = Go + RTln(Q)
G = -33.3 kJ/mole + (8.314 J/K mol)(298 K) ln( [0.02 atm]2 )
___________________
Go = - RTln(K)
• Go = -RTln(K)
• -5.40 kJ/mole = -(8.31 J/K mol)(298 K)ln K
• 2.18 = ln K
• 8.85 = K
Free Energy and Work
• The maximum possible useful work obtainable
from a process at constant temperature and
pressure is equal to the change in free energy
• The amount of work obtained is always less the
maximum
– Work is changed to heat in surroudings – You lose
efficiency, but the Ssurr increases (favorable!)
• Henry’s Bent’s First Two Laws of Thermodynamics
– 1st Law: You can’t win, you can only break even
– 2nd Law: You can’t break even