CHEM 1001 Chapter Notes - Chapter 19: Thermodynamic Equilibrium, Standard Molar Entropy, Gibbs Free Energy

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CHAPTER 19: Spontaneous Change: Entropy & Gibbs Energy
19.1 Spontaneity: Meaning of Spontaneous Change
Spontaneous process: occurs in system left to itself; once started no
external action is necessary for process to continue. Doesn’t determine rate
though.
Nonspontaneous process: doesn’t occur unless some external action is
continuously applied.
19.2 Concept of Entropy
Entropy (S): thermodynamic property describing how energy of a system is
distributed among available energy levels. More # of arrangements of
particles = more entropy. Function of state like U and H and G (doesn’t
depend on path)
S = klnW where k is Boltzmann constant (R/Na) and W is # of microstates.
ΔS = q(rev) / T and unit is J/K or ΔS = ΔH / T
4 situations increase entropy: Solids  liquid, solid/liquid  gas, # of gas
molecules increasing, and temperature of substance increases b/c more
energy levels accessible.
19.3 Evaluating Entropy & Entropy Changes
3rd Law of Thermodynamics: entropy of a pure perfect crystal at 0 K is
zero.
Standard molar entropy (at 25ºC): ΔS = [(sum of n*products) – (sum of
n*reactants)]
More complex molecules (ones with more atoms) have greater molar entropy.
Trouton’s Rule: standard entropy of vaporization at normal B.P is 87 J/molK
19.4 Criteria for Spontaneous Change: 2nd Law of Thermodynamics
2nd Law of Thermodynamics: all spontaneous processes increase entropy
of universe. So if reaction creates positive ΔS in system & surroundings, it’s
spontaneous.
Since for surroundings, ΔS = -ΔH / T..
Gibbs energy (G): ΔG = ΔH - T ΔS and ΔG = - T ΔSuniverse (make sure
units match)
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Document Summary

Chapter 19: spontaneous change: entropy & gibbs energy. Spontaneous process: occurs in system left to itself; once started no external action is necessary for process to continue. Nonspontaneous process: doesn"t occur unless some external action is continuously applied. Entropy (s): thermodynamic property describing how energy of a system is distributed among available energy levels. More # of arrangements of particles = more entropy. Function of state like u and h and g (doesn"t depend on path) S = klnw where k is boltzmann constant (r/na) and w is # of microstates. S = q(rev) / t and unit is j/k or s = h / t. 4 situations increase entropy: solids liquid, solid/liquid gas, # of gas molecules increasing, and temperature of substance increases b/c more energy levels accessible. 3rd law of thermodynamics: entropy of a pure perfect crystal at 0 k is zero. Standard molar entropy (at 25 c): s = [(sum of n*products) (sum of n*reactants)]

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