ENTROPY, S CHEMICAL CHEMICAL EQUILIBRIA:

2nd law: the entropy, S of an isolated THERMODYNAMICS REACTIONS

system tends to increase
∆𝑛𝑗 𝐺(𝑗)
GIBBS FREE ENERGY PHASE DIAGRAM ∆𝜀 = 𝜇𝑗 = 𝐺𝑚 𝑗 =
𝑞𝑟𝑒𝑣 𝑣𝑗 𝑛𝑗
∆𝑆 = ∆𝑆 = 𝑘 𝑙𝑛𝑊
𝑇 𝐺 = 𝐻 − 𝑇𝑆
The solid-liquid 𝑑𝑝 ∆𝑓𝑢𝑠 𝐻 𝑣𝐴 𝐴 𝑔 + 𝑣𝐵 𝐵 𝑔 → 𝑣𝐶 𝐶 𝑔 + 𝑣𝐷 𝐷 𝑔
Isothermal 𝑉𝑓 𝐺 = 𝑉∆𝑃 − 𝑇∆𝑆 =
boundary 𝑑𝑇 𝑇∆𝑓𝑢𝑠 𝑉
expansion, ∆𝑆 = 𝑛𝑅𝑙𝑛
perfect gas 𝑉𝑖 P constant T constant
∆𝑓𝑢𝑠 𝐻 𝑇𝑓
𝑇𝑓 ∆p = 𝑙𝑛
Heating ∆𝑆 = 𝐶𝑙𝑛 ∆𝑓𝑢𝑠 𝑉 𝑇𝑖
𝑇𝑖
∆𝐺
Phase transition
𝑑𝑙𝑛 𝑝 ∆𝑣𝑎𝑝 𝐻 ∆𝑟 𝐺 =
The liquid-vapour
= ∆𝜀
∆𝑡𝑟𝑠 𝑆 ∅ 𝑇𝑡𝑟𝑠 = ∆𝑡𝑟𝑠 𝐻∅ 𝑇𝑡𝑟𝑠 /𝑇𝑡𝑟𝑠 boundary 𝑑𝑇 𝑅𝑇 2
∆𝐺𝑚 = −𝑆𝑚 ∆𝑇 𝑃𝑓
∆𝐺𝑚 = 𝑅𝑇𝑙𝑛 ∆𝑟 𝐺 = 𝐶𝜇𝐶 + D𝜇𝐷 − (A𝜇𝐴 + B𝜇𝐵 )
Chemical reaction 𝑃𝑖
∆𝑣𝑎𝑝 𝐻 1 1 𝑣 𝑣
∆𝑟 𝑆 ∅ = ∅
𝑣 𝑆𝑚 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − ∅
𝑣 𝑆𝑚 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 ln 𝑝𝑓 = 𝑙𝑛𝑝𝑖 + − 𝑎𝐶𝑐 𝑎𝐷𝐷
𝑅 𝑇𝑖 𝑇𝑓 ∆𝑟 𝐺 = ∆𝑟 𝐺 ∅ + 𝑅𝑇𝑙𝑛 𝑣 𝑣
PHASE DIAGRAM 𝑎𝐴𝐴 𝑎𝐵𝐵
Reversible process
∆𝑆𝑡𝑜𝑡 = ∆𝑆𝑠𝑦𝑠 +∆𝑆𝑠𝑢𝑟 = 0 The solid-vapour 𝑑𝑝 ∆𝑠𝑢𝑏 𝐻
boundary = Reaction quotient, Q
𝑑𝑇 𝑇∆𝑠𝑢𝑏 𝑉
Irreversible process Spontaneous!
∆𝑟 𝐺 = ∆𝑟 𝐺 ∅ + 𝑅𝑇𝑙𝑛Q
∆𝑆𝑡𝑜𝑡 = ∆𝑆𝑠𝑦𝑠 + ∆𝑆𝑠𝑢𝑟𝑟 > 0 ∆𝑠𝑢𝑏 𝐻 = ∆𝑣𝑎𝑝 𝐻 + ∆𝑓𝑢𝑠 𝐻
Equilibrium constant,K
−𝑞 −∆𝐻
∆𝑆𝑠𝑢𝑟𝑟 = =
𝑇 𝑇
∆𝑟 𝐺 ∅ = −𝑅𝑇𝑙𝑛𝐾
Le Chatelier’s Principle
−∆𝐻 Perturbation of a system at equilibrium will
∆𝑆𝑡𝑜𝑡 = ∆𝑆𝑠𝑦𝑠 + cause the equilibrium position to change in
𝑇
such a way as to tend to remove the Van’t Hoff equation
Mixing process perturbation.
∆𝑚𝑖𝑥 𝑆 = −𝑛𝑅(𝑥𝐴 𝑙𝑛𝑥𝐴 + 𝑥𝐵 𝑙𝑛𝑥𝐵 ) ∆𝑟 𝐻 ∅ 1 1
Concentration 𝑙𝑛𝐾2 = ln𝐾1 + −
𝑅 𝑇1 𝑇2
Entropy,S < <
The Gibbs phase rule If the concentration of a reactant (solute or
gas) is increased, the equilibrium position Temperature
𝐹 = 𝐶−𝑃+2 shifts to use up the added reactants resulting
in more products.
If the temperature of an endothermic
equilibrium system is increased, the
equilibrium position shifts to use up the heat
F: Number of degrees of freedom Pressure by producing more products.
C: Number of components If the pressure of an equilibrium system is If the temperature of an exothermic
increased, then the equilibrium position shifts equilibrium system is increased, the
P: Number of phases to reduce the pressure. equilibrium position
3rd law: A perfect crystal at T=0 K has shifts to use up the heat by producing more
zero entropy reactants. Masniroszaime/2017

DETERMINATION OF THE ORDER OF THE REACTION
1 SINGLE REACTANT
𝐴 → 𝑃𝑟𝑜𝑑𝑢𝑐𝑡
2 MULTIPLE REACTANT
𝐴 + 𝐵 → 𝑃𝑟𝑜𝑑𝑢𝑐𝑡
ISOLATION METHOD
B is in excess, isolate A to
determine the order
𝑘′ = 𝑘 𝐵 0 𝑎𝐼
−𝑘 ′ 𝑇
𝐴 = 𝐴 0𝑒
3 3
MECHANISM
RATE DETERMINING STEP
Overall reaction rate = rate
of the slowest step
INTRODUCTORY CHEMICAL
KINETICS DETERMINATION OF THE RATE CONSTANT
1 ARRHENIUS EQUATION
𝑑𝐴
𝑟𝑎𝑡𝑒, 𝑣 = −
𝑑𝑡 𝑘 = 𝐴𝑒 −𝐸𝑎/𝑅𝑇
𝑚𝑜𝑙 𝑘 the rate constant (unit depends on the order
𝑚𝑜𝑙 of the reaction)
𝐿. 𝑠
𝐿
𝑛 𝐴 the pre-exponential factor (unit same as k)
𝑣=𝑘 𝐴
𝐸𝑎 the activation energy
Thermodynamically favorable but
kinetically unfavorable
• diamond convert into graphite
Ea 1
• hydrogen and oxygen - the reaction ln k  ln A 
won’t start unless ignited by a spark R T
INITIAL RATES METHOD 2 COLLISION THEORY
[A] [B] Initial rate, v
A rA strongly T- k = s c NA f p
𝑎 𝑏 𝑣 rB dependent
B f = exp(-Ea/ RT)
𝑏 𝑣𝐼 s= collision cross section (m2)
A= s c NA p
𝑎 𝑏 𝐼
𝑣 𝐼𝐼
c= average relative speed (m s-1)
Steric, p = fraction of collisions with correct c=(8kT / pm)1/2 nearly T-
𝑛 𝑚
𝑣=𝑘 𝐴 𝐵 independent
orientation to react
factor non-quantitative
𝐼 𝑛 𝐼 𝐼 𝑚 𝐼𝐼
𝑎 𝑣 𝑏 𝑣
= =
𝑎 𝑣 𝑏 𝑣
TRANSITION-STATE THEORY
k = k‡ K‡
• simple 'statistical' theory
• not limited to reactions of a particular
Eyring
RAPID PRE-EQUILIBRIUM order or phase
equation
Overall reaction rate = rate of k = k‡ exp (+DS‡ / R) exp(- DH‡ / RT)
the slowest step + equilibrium A = k‡ exp (+DS‡ / R) steric factor related to
constant, K entropy of activation
**see example exp(- DH‡ / RT)= em exp(- Ea / RT) Masniroszaime/2017
PARTIAL MOLAR QUANTITIES THERMODYNAMICS OF EQUILIBRIUM
SOLUTIONS AND MIXTURES ELECTROCHEMISTRY
𝑉 = 𝑉𝐴 𝑛𝐴 + 𝑉𝐵 𝑛𝐵
𝐺 = 𝜇𝐴 𝑛𝐴 + 𝜇𝐵 𝑛𝐵 MIXTURES Zn(s) I ZnSO4 (aq) II CuSo4 (aq) I Cu (s)

𝑛𝐵
IDEAL SOLUTION Molarity, M 𝑐𝐵 =
𝑉
𝑛𝐵
Molality 𝑏𝐵 =
Obeys Raoult’s Law 𝑚𝐴
𝑛𝐵
𝑝𝐴 = 𝑥𝐴 𝑝𝐴∗ Mole fraction 𝑥𝐵 =
Solvent, A
𝑛 Solute, B
𝑝𝑇 = 𝑥𝐴 𝑝𝐴∗ ∗ +𝑥𝐵 𝑝𝐵∗ Gibbs free
energy ∆𝑟 𝐺 = −𝑣𝑒𝑁𝐴 𝐸𝑐𝑒𝑙𝑙
𝜇𝐴 = 𝜇𝐴∗ + 𝑅𝑇𝑙𝑛𝑥𝐴
Nernst ∅ 𝑅𝑇
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − 𝑙𝑛𝑄
equation 𝑣𝐹

Cells at 𝑣𝐹𝐸𝑐𝑒𝑙𝑙
equilibrium ln 𝐾 =
𝑅𝑇
∅
Standard
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑅∅ − 𝐸𝐿∅ Standard reduction
Standard reduction potential potential for the
potentials for the reduction half oxidation half
reaction occuring at
reaction occurring at the the anode
cathode
COLLIGATIVE
NON-IDEAL PROPERTIES ∅
𝜕𝐸 ∅
Entropy ∆𝑟 𝑆 = 𝑣𝐹
SOLUTION 𝜕𝑇
Freezing point 𝑅𝑇 ∗2
∆𝑇𝑏 = 𝑥𝐵
𝑝𝐵 = 𝑥𝐵 𝐾𝐻′ depression ∆𝑣𝑎𝑝 𝐻 Enthalpy ∆𝑟 𝐻 = ∆𝑟 𝐺 − 𝑇∆𝑟 𝑆
= 𝐾𝑏 . 𝑏
𝑝𝑇 = 𝑥𝐴 𝑝𝐴∗ ∗ +𝑥𝐵 𝐾𝐻′
𝑅𝑇 ∗2
Boiling point ∆𝑇𝑓 = 𝑥𝐵
𝜇𝐵 = 𝜇𝐵∗ + 𝑅𝑇𝑙𝑛𝑎𝐵 ∆𝑓𝑢𝑠 𝐻
elevation
𝑝𝐵 = 𝐾𝑓 . 𝑏
𝑎𝐵 =
𝑝𝐵∗ 𝜋𝑉 = 𝑛𝐵 𝑅𝑇
Van’t Hoff
𝜋 = 𝐵 𝑅𝑇
𝑎𝐵 = 𝛾𝐵 𝑥𝐵 equation
Masniroszaime/2017