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Chapter 1: Thermodynamics
First Law of Thermodynamics
ΔU = q + w
Energy cannot be created or destroyed
Enthalpy (H)
H = U + PV
ΔH = ΔU + Δ(PV)
ΔH = ΔU + Δn_gRT
Heat Capacity
- Specific Heat (c): Heat for 1g by 1°C
- Molar Heat (C): Heat for 1 mole by 1°C
Hess's Law
Total enthalpy change independent of route.
Bond Energy
ΔH = Σ(BE_reactants) - Σ(BE_products)
Second Law
Entropy of universe always increases.
ΔS_universe = ΔS_system + ΔS_surroundings > 0
Gibbs Free Energy
ΔG = ΔH - TΔS
ΔG < 0: Spontaneous
ΔG > 0: Non-spontaneous
Chapter 2: Chemical Kinetics
Rate of Reaction
Rate = -d[Reactant]/dt = d[Product]/dt
Rate Law
Rate = k[A]^m[B]^n
k = rate constant, m,n = order
Order of Reaction
- Zero Order: Rate independent of concentration
- First Order: Rate proportional to [A]
- Second Order: Rate proportional to [A]²
Integrated Rate Equations
Zero: [A] = [A]₀ - kt
First: ln[A] = ln[A]₀ - kt
Second: 1/[A] = 1/[A]₀ + kt
Half-Life
t½ = 0.693/k (First order)
Activation Energy
ln(k₂/k₁) = E_a/R (1/T₁ - 1/T₂)
Chapter 3: Electrochemistry
Oxidation-Reduction
- Oxidation: Loss of electrons
- Reduction: Gain of electrons
- Oxidizing Agent: Gets reduced
- Reducing Agent: Gets oxidized
Electrochemical Cells
Galvanic (Voltaic)
Spontaneous redox reaction produces electricity.
Electrolytic
Electrical energy drives non-spontaneous reaction.
Standard Electrode Potential
E°_cell = E°_cathode - E°_anode
Nernst Equation
E = E° - (0.0591/n) log Q (25°C)
Faraday's Laws
m = (ItM)/nF
Where: I = current, t = time, M = molar mass, n = electrons, F = 96500 C
Chapter 4: Transition Elements
Characteristics
- Incomplete d-orbitals
- Variable oxidation states
- Colored compounds
- Magnetic properties
- Catalytic activity
First Row Transition Metals
- Sc (21) to Zn (30)
- Cu, Fe, Mn, Cr, Ni common
Oxidation States
- Mn: +2, +3, +4, +6, +7
- Fe: +2, +3
- Cu: +1, +2
Complex Ions
Central metal ion surrounded by ligands.
[Fe(CN)₆]⁴⁻, [Cu(H₂O)₆]²⁺
Coordination Number
Number of donor atoms bonded to metal ion. Common: 4, 6.
Chapter 5: Alkyl Halides
Classification
- Primary (1°): R-CH₂-X
- Secondary (2°): R₂CH-X
- Tertiary (3°): R₃C-X
Preparation
- Alcohol + HX → Alkyl halide
- Alcohol + PCl₅/SOCl₂ → Alkyl chloride
Reactions
Nucleophilic Substitution (SN)
- SN¹: Tertiary, carbocation intermediate
- SN²: Primary, back-side attack
Elimination (E)
Grignard Reagent
R-X + Mg → R-Mg-X (in dry ether)
Chapter 6: Alcohols and Phenols
Classification of Alcohols
- Primary: R-CH₂OH
- Secondary: R₂CHOH
- Tertiary: R₃COH
Preparation
- Hydration of alkenes
- Hydrolysis of alkyl halides
- Reduction of aldehydes/ketones
Reactions
- Oxidation: 1° → aldehyde → carboxylic acid
2° → ketone
- Esterification: R-OH + R'-COOH → R'-COOR + H₂O
- Dehydration: R-OH → alkene + H₂O
Phenols
Ar-OH. More acidic than alcohols.
Acidity Order
Carboxylic > Phenol > Water > Alcohol
Chapter 7: Aldehydes and Ketones
Carbonyl Group
C=O. Aldehyde: R-CHO, Ketone: R-CO-R
Nucleophilic Addition
With HCN
R-CHO + HCN → R-CH(OH)CN
With Grignard
R-CHO + R'-MgX → R-CH(OH)R'
With 2,4-DNP
Forms yellow/orange precipitate (test for carbonyl).
Oxidation
- Aldehydes → Carboxylic acids (oxidize easily)
- Ketones → Do not oxidize easily
Reduction
- LiAlH₄, NaBH₄ → Alcohols
- Zn(Hg)/HCl → Alkanes (Clemmensen)
Chapter 8: Carboxylic Acids and Derivatives
Acidity
R-COOH ⇌ R-COO⁻ + H⁺
More acidic than phenol and alcohol
Factors Affecting Acidity
- Electron withdrawing groups increase acidity
- Resonance stabilization of conjugate base
Reactions
- Salt formation: + NaOH → R-COONa + H₂O
- Esterification: + ROH → R-COOR' + H₂O
- Amide formation: + NH₃ → R-CONH₂
- Reduction: → Primary alcohol
Derivatives
- Acid Chlorides: R-COCl
- Anhydrides: R-CO-O-CO-R
- Esters: R-COOR'
- Amides: R-CONH₂
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