17.

1 Spontaneous Processes
• 메탄가스가 연소 된다.
CH4(g) + 2 O2(g) → CO2(g) + 2H2O(1)

Chapter 17 • 상온에서 얼음이 녹는다.

H2O(s) → H2O(1) (at 25°C)

Spontaneity of Reaction
• 공기 중에 노출된 철은 녹슨다.

2Fe(s) + 2/3O2(g)+3H2O(l) →2Fe(OH)3(s)

Copyright® 2005 연세대학교 이학계열 일반화학 및 실험(2) 강의노트

Factors affecting on Spontaneity 17.2 Entropy, S

Energy factor:
factor at 25°C, 1 atm, exothermic reactions are ordinarily
spontaneous (∆H < 0). ∆S : randomness factor can be treated quantitatively in terms of
a function called entropy

Calculation of ∆S°
Η
H2O(s) → H2O(1) (at 25°C) ∆H = +6.0kJ ?? Reactions

Randomness factor:
factor other things being equal, system tends to move
from a more ordered to a more random state. (high probability)
Entropy, S : “degree of dispersal or disorder” △S
∆S = Sproducts – Sreactants; measure of change in order

S(J/mol.K)
• Phase transition: solid → liquid :
liquid → gas :

처음의 분자가 모두 왼쪽 플라스크에 존재할 확률 • Increased Temperature, increases entropy Τ(Κ)

6개의 분자 :
1몰의 분자 :
•∆S is usually positive for a reaction in which the number of moles
of gas increases.
엔트로피 : 무질서도에 대한 정량적 표시 2SO3(g) → 2SO2(g) + O2(g);
(확률적으로 유리한 상태, 무질서한 상태의 S 가 크다) N2(g) + 3H2(g) → 2NH3(g);

Standard Molar Entropies: S° Standard Molar Entropies: S°

Unit : J/mol· K (1atm, at a given T) S° gas S° liquid S°solid

• Third law of thermodynamics:
“A completely ordered pure crystalline solid has an entropy of zero • higher the molar mass, higher the S°
at 0 K” – CH4 S° = 186.2 kJ/mol · k
– CH3CH3 S° = 229.5 kJ/mol · k
• pure substances (elements, compounds) : S° >0 – CH3CH2CH3 S° = 269.9 kJ/mol · k
• In water solution, S° Η+(aq) =0
∆S° for Reactions The Second Law of Thermodynamics
(∆S°, Standard Entropy Change ⇒ ∆S at 1 atm, 1 M)
Reactions for which ∆S° is positive tend to be spontaneous, at least
∆S = ∑Sproducts
o
− ∑Sreactants
o
at high temperatures

Fe2O3(s) + 3H2(g) → 2Fe(s) + 3H2O(g) H2O(s) → H2O(1) ∆S° > 0

H2O(l) → H2O(g) ∆S° > 0
∆S° = 2S° Fe(s) + 3S° H2O(g) – S° Fe2O3(s) – 3S° H2(g) Fe2O3(s) + 3H2(g) → 2Fe(s) + 3H2O(g) ∆S° > 0
= __(27.2 J/K) + __(188.7 J/K ) –__(90.0 J/K) – __(130.6 J/K)

All of these reactions are endothermic (∆H > 0). They become
Note that S° is a positive quantity for both compounds and elements. spontaneous at high temperatures.

The Second Law of Thermodynamics 17.3 Free Energy, G

• In a spontaneous process, there is a net increase in entropy, ∆G° = ∆H° – T∆S° : ∆G represents that portion of the total energy
taking into account both system and surroundings. change that is available at constant pressure and temperature

∆Suniverse= (∆Ssystem + ∆Ssurroundings) > 0 : spontaneous process Effect of ∆H°, ∆S° on spontaneity

ex) 2Fe(s) + 2/3O2(g) + 3H2O(l) → 2Fe(OH)3(s)

∆H = -571.6 kJ ; ∆Ssystem = -358.4J/K
Gibbs Free Energy Free Energy Change

• At constant Temperature & Pressure Calculation of ∆G° from ∆H° and ∆S°

G = H – TS ⇒ ∆G = ∆H – T∆S
Calculation of ∆G° at 25°C from ∆Gf°
(Gibbs- Helmholtz eqn)

• Sign of free energy change and spontaneity : (at constant T & P) Calculation of ∆G from ∆G°

∆G < 0, spontaneous process

∆G > 0, nonspontaneous process Relation between ∆G° and K
∆G = 0, at equilibrium

∆G = ∆H – T∆S : Spontaneity of the reaction 17.4 Standard Free Energy Change, ∆G°
• ∆H < 0 : exothermic reaction ∆G° = ∆H° – T∆S
: forms strong bonds at the expense of weak ones Standard condition : 1 atm partial pressure,
concentration 1M in solution

• ∆S > 0 : tendency for a reaction to be spontaneous if the products ex ① Fe2O3(s) + 3H2(g) → 3Fe(s) + 3H2O(g)
are less ordered than the reactant
∆H° = +96.8 kJ ; ∆S° = +138.7 J/K = +0.1387 kJ/K

• ∆G is a state property and depends on pressure, concentration, and

temperature
 Calculation of ∆G° (at 25°C) :
Calculation of ∆G° from ∆H° and ∆S° (cont.) Free Energy of Formation ∆Gf°

ex ② At what temperature does the reduction of Fe2O3 by ∆G° = Σ∆Gf° products – Σ∆Gf° reactants
hydrogen become spontaneous at 1 atm?

PbCl2(s) → Pb2+(aq) + 2Cl–(aq)

∆G° = ∆Gf° Pb2+ + 2∆Gf° Cl– – ∆Gf° PbCl2 = +27.3 kJ

1 atm, 1 M : ∆Gf° = ∆Hf° – T∆S°

Calculation of ∆G° at Other Temperatures 17.5 Effect of Temperature, Pressure, and

Concentration on Reaction Spontaneity

∆H°, ∆S° : weak temperature dependence •If ∆H° > 0, ∆S° < 0, ∆G° > 0 at all T, nonspontaneous
∆G° : strong temperature dependence
∆G° = ∆H° – T∆S° •If ∆H° < 0, ∆S° > 0, ∆G° < 0 at all T, spontaneous

•If ∆H° > 0, ∆S° > 0, ∆G° > 0 at low T, < 0 at high T, spontaneous
only at high T

•If ∆H° < 0, ∆S° < 0, ∆G° < 0 at low T, > at high T, spontaneous
only at low T
Pressure and Concentration 17.6 ∆G° and K

∆G = ∆G° + RT lnQ ∆G° = –RT1nK

If K > 1, ∆G° < 0, reaction spontaneous at standard conditions

ex ① PbCl2(s) → Pb2+ (0.0010 M) + 2Cl– (0.0010 M)
If K < 1, ∆G° > 0, reaction nonspontaneous at standard cond.
If K = 1, ∆G° = 0, reaction at equilibrium at standard cond.

H2O(1) → H+(aq) + OH–(aq)

ex ② NH4Cl(s) → NH3(g) + HCl(g) ∆Go = +13.0 kJ (300 °C )
∆G° = –(0.00831)(298) ln(1.0 × 10–14) = +79.8 kJ
PNH3 = PHCl = 0.1
Nonspontaneous at standard conditions (1 M H+, 1 M OH–)

17.7 Additivity of ∆G : Coupled Reaction ∆G° = ∆H° – T∆S°

Reaction 3 = Reaction 1 + Reaction 2
Note that ∆G, like ∆S, is dependent on pressure, concentration.
∆G3 = ∆G1 + ∆G2 Unlike ∆H° and ∆S°, ∆G° is strongly temperature dependent
because of T in equation.
Ex1) Fe2O3(s) → 2Fe(s) + 3/2 O2 (g) ∆Gº = +742.2 kJ
CO(g) + 1/2 O2 (g) → CO2 (g) ∆Gº = -257.1 kJ
If ∆G° < 0, reaction spontaneous at standard conditions (T, P)
Fe2O3(s) + 3 CO (g) →2Fe(s) +3CO2 (g)
If ∆G° > 0, reaction nonspontaneous at standard conditions
If ∆G° = 0, reaction at equilibrium at standard conditions
Ex2) (at 25 °C)
C6H12O6(aq) + 6 O2 (g) → CO2 (g) + H2O ∆Gº = -2870 kJ
38 (ADP (aq) + HPO42- + 2H+ → ATP (aq) + H2O) ∆Gº =38( +31) kJ