Introduction to Chemical Reactions
Chemical reactions are processes where substances (reactants) transform into different substances (products) through the breaking and forming of chemical bonds. Understanding reaction types and mechanisms is fundamental to chemistry and enables predictions about how substances interact. This cheatsheet provides a comprehensive reference for identifying, balancing, and applying common chemical reactions across organic and inorganic chemistry.
Fundamental Concepts
Components of a Chemical Reaction
- Reactants: Starting substances consumed in the reaction
- Products: New substances formed by the reaction
- Coefficients: Numbers preceding formulas that balance the equation
- Reaction Arrow: Indicates direction of reaction (→, ⇌, ⇄)
- Conditions: Temperature, pressure, catalysts, etc. (often shown above or below arrow)
Balancing Chemical Equations
- Identify all elements present in the reaction
- Balance elements one at a time (typically start with most complex molecules)
- Verify that atoms of each element are equal on both sides
- Use fractional coefficients for half-reactions if needed, then multiply to get whole numbers
Reaction Yield Calculations
- Theoretical Yield: Maximum amount of product possible based on limiting reactant
- Actual Yield: Amount of product actually obtained experimentally
- Percent Yield: (Actual Yield ÷ Theoretical Yield) × 100%
- Limiting Reactant: Reactant that determines the maximum amount of product
Types of Inorganic Reactions
Combination/Synthesis Reactions
General Form: A + B → AB
| Type | General Equation | Example |
|---|---|---|
| Metal + Nonmetal | M + X → MX | 2Na + Cl₂ → 2NaCl |
| Nonmetal + Nonmetal | X + Y → XY | H₂ + Cl₂ → 2HCl |
| Metal Oxide + Water | M₂O + H₂O → 2MOH | Na₂O + H₂O → 2NaOH |
| Nonmetal Oxide + Water | X₂O + H₂O → H₂XO₃ | CO₂ + H₂O → H₂CO₃ |
| Metal + Oxygen | 2M + O₂ → 2MO | 4Fe + 3O₂ → 2Fe₂O₃ |
| Nonmetal + Oxygen | 2X + O₂ → 2XO | S + O₂ → SO₂ |
Decomposition Reactions
General Form: AB → A + B
| Type | General Equation | Example |
|---|---|---|
| Metal Carbonates | MCO₃ → MO + CO₂ | CaCO₃ → CaO + CO₂ |
| Metal Hydroxides | M(OH)₂ → MO + H₂O | Cu(OH)₂ → CuO + H₂O |
| Metal Chlorates | 2MClO₃ → 2MCl + 3O₂ | 2KClO₃ → 2KCl + 3O₂ |
| Hydrogen Peroxide | 2H₂O₂ → 2H₂O + O₂ | 2H₂O₂ → 2H₂O + O₂ |
| Oxyacids | H₂SO₄ → H₂O + SO₃ | H₂CO₃ → H₂O + CO₂ |
| Metal Oxides | 2HgO → 2Hg + O₂ | 2HgO → 2Hg + O₂ |
Single Replacement/Displacement Reactions
General Form: A + BC → AC + B
| Type | General Equation | Example |
|---|---|---|
| Metal replacing metal | M₁ + M₂X → M₁X + M₂ | Zn + CuSO₄ → ZnSO₄ + Cu |
| Metal replacing hydrogen | M + H₂O → MOH + H₂ | 2Na + 2H₂O → 2NaOH + H₂ |
| Metal replacing hydrogen (acid) | M + 2HX → MX₂ + H₂ | Zn + 2HCl → ZnCl₂ + H₂ |
| Halogen replacing halogen | X₂ + 2MY → MX₂ + Y₂ | Cl₂ + 2NaBr → 2NaCl + Br₂ |
Activity Series of Metals (decreasing reactivity): Li > K > Ba > Sr > Ca > Na > Mg > Al > Mn > Zn > Cr > Fe > Cd > Co > Ni > Sn > Pb > H > Cu > Ag > Hg > Au
Activity Series of Halogens (decreasing reactivity): F₂ > Cl₂ > Br₂ > I₂
Double Replacement/Displacement Reactions
General Form: AB + CD → AD + CB
| Type | General Equation | Example |
|---|---|---|
| Precipitation | AX + BY → AY↓ + BX | AgNO₃ + NaCl → AgCl↓ + NaNO₃ |
| Gas Formation | AX + BY → AB + XY↑ | Na₂CO₃ + 2HCl → 2NaCl + H₂O + CO₂↑ |
| Neutralization | HA + BOH → BA + H₂O | HCl + NaOH → NaCl + H₂O |
| Water Formation | H⁺ + OH⁻ → H₂O | H₂SO₄ + 2KOH → K₂SO₄ + 2H₂O |
Combustion Reactions
General Form: Fuel + O₂ → CO₂ + H₂O (+ energy)
| Type | General Equation | Example |
|---|---|---|
| Hydrocarbon | C₍ₓ₎H₍ᵧ₎ + (x+y/4)O₂ → xCO₂ + (y/2)H₂O | CH₄ + 2O₂ → CO₂ + 2H₂O |
| Alcohol | C₍ₓ₎H₍ᵧ₎OH + O₂ → xCO₂ + (y+1)/2H₂O | C₂H₅OH + 3O₂ → 2CO₂ + 3H₂O |
| Carbohydrate | C₍ₓ₎(H₂O)₍ᵧ₎ + xO₂ → xCO₂ + yH₂O | C₆H₁₂O₆ + 6O₂ → 6CO₂ + 6H₂O |
Oxidation-Reduction (Redox) Reactions
Key Concepts:
- Oxidation: Loss of electrons (increase in oxidation number)
- Reduction: Gain of electrons (decrease in oxidation number)
- Oxidizing Agent: Gets reduced and causes oxidation of another substance
- Reducing Agent: Gets oxidized and causes reduction of another substance
Common Oxidizing Agents:
- KMnO₄ (potassium permanganate)
- K₂Cr₂O₇ (potassium dichromate)
- H₂O₂ (hydrogen peroxide)
- HNO₃ (nitric acid)
- O₂ (oxygen)
- F₂, Cl₂, Br₂, I₂ (halogens)
Common Reducing Agents:
- Metals (Na, Mg, Zn, Fe, Al)
- H₂ (hydrogen)
- CO (carbon monoxide)
- C (carbon)
- SO₂ (sulfur dioxide)
- Na₂S₂O₃ (sodium thiosulfate)
Balancing Redox Reactions in Acidic Solution:
- Write skeletal equation
- Split into half-reactions
- Balance elements other than O and H
- Balance O using H₂O
- Balance H using H⁺
- Balance charge using electrons
- Equalize electrons transferred in both half-reactions
- Add half-reactions
- Cancel identical species
Balancing Redox Reactions in Basic Solution:
- Follow steps 1-7 for acidic solution
- Add OH⁻ to both sides to neutralize H⁺ (for each H⁺, add one OH⁻)
- Form H₂O where H⁺ and OH⁻ appear on same side
- Cancel identical species
Acid-Base Reactions
Acid-Base Theories
| Theory | Definition of Acid | Definition of Base | Example |
|---|---|---|---|
| Arrhenius | H⁺ donor in water | OH⁻ donor in water | HCl + NaOH → NaCl + H₂O |
| Brønsted-Lowry | Proton (H⁺) donor | Proton (H⁺) acceptor | NH₃ + H₂O ⇌ NH₄⁺ + OH⁻ |
| Lewis | Electron pair acceptor | Electron pair donor | BF₃ + NH₃ → F₃B-NH₃ |
Conjugate Acid-Base Pairs
- Conjugate acid: Formed when a base gains a proton
- Conjugate base: Formed when an acid loses a proton
Examples:
- HCl (acid) → H⁺ + Cl⁻ (conjugate base)
- NH₃ (base) + H⁺ → NH₄⁺ (conjugate acid)
Acid-Base Strength
Relative Strength of Acids:
- Hydrohalic acids: HI > HBr > HCl > HF
- Oxoacids: Strength increases with:
- More oxygen atoms: HClO₄ > HClO₃ > HClO₂ > HClO
- More electronegative central atom: H₂SO₄ > H₂SeO₄
Relative Strength of Bases:
- Alkali metal hydroxides: LiOH < NaOH < KOH < RbOH < CsOH
- Organic amines: NH₃ < CH₃NH₂ < (CH₃)₂NH < (CH₃)₃N
Ka and Kb Values:
- Strong acids: Ka > 1 (HCl, HNO₃, H₂SO₄, HBr, HI, HClO₄)
- Weak acids: Ka < 1 (CH₃COOH, HF, H₂CO₃, HNO₂)
- Strong bases: Kb > 1 (NaOH, KOH, Ca(OH)₂, Ba(OH)₂)
- Weak bases: Kb < 1 (NH₃, organic amines)
Precipitation Reactions & Solubility Rules
General Solubility Rules
| Compound Type | Solubility | Exceptions |
|---|---|---|
| Alkali metal compounds | Soluble | Few exceptions |
| Ammonium compounds | Soluble | Few exceptions |
| Nitrates (NO₃⁻) | Soluble | No exceptions |
| Acetates (CH₃COO⁻) | Soluble | Few exceptions |
| Chlorides, bromides, iodides | Soluble | Ag⁺, Pb²⁺, Hg₂²⁺ |
| Sulfates (SO₄²⁻) | Soluble | Ca²⁺, Sr²⁺, Ba²⁺, Pb²⁺, Ag⁺ |
| Carbonates (CO₃²⁻) | Insoluble | Alkali metals, NH₄⁺ |
| Phosphates (PO₄³⁻) | Insoluble | Alkali metals, NH₄⁺ |
| Hydroxides (OH⁻) | Insoluble | Alkali metals, Sr²⁺, Ba²⁺, Ca²⁺ (slightly) |
| Sulfides (S²⁻) | Insoluble | Alkali metals, NH₄⁺, Be²⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺ |
| Oxides (O²⁻) | Insoluble | Most dissolve in acid; alkali metal oxides form hydroxides in water |
Common Ion Effect & Solubility Product (Ksp)
- Ksp: Product of concentrations of ions in a saturated solution
- Common Ion Effect: Decreases solubility when a common ion is added
Example:
- For AgCl ⇌ Ag⁺ + Cl⁻, Ksp = [Ag⁺][Cl⁻]
- Adding NaCl decreases AgCl solubility by increasing [Cl⁻]
Complexation Reactions
Formation of Complex Ions
- Ligands: Electron pair donors that bind to metal ions
- Coordination Number: Number of donor atoms bound to central metal ion
Common Ligands:
- Monodentate: H₂O, NH₃, CN⁻, Cl⁻, OH⁻
- Bidentate: C₂O₄²⁻ (oxalate), H₂NCH₂CH₂NH₂ (ethylenediamine)
- Polydentate: EDTA⁴⁻
Examples:
- Cu²⁺ + 4NH₃ → [Cu(NH₃)₄]²⁺ (tetraamminecopper(II))
- Fe³⁺ + 6CN⁻ → [Fe(CN)₆]³⁻ (hexacyanoferrate(III))
Complex Ion Equilibria
- Formation Constant (Kf): Measures stability of complex ion
- Higher Kf = more stable complex
Example:
- For Ag⁺ + 2NH₃ ⇌ [Ag(NH₃)₂]⁺, Kf = [[Ag(NH₃)₂]⁺]/([Ag⁺][NH₃]²)
Organic Reactions
Substitution Reactions
Nucleophilic Substitution (SN)
| Type | Mechanism | Rate Law | Stereochemistry | Example |
|---|---|---|---|---|
| SN1 | Two-step: leaving group departs first, then nucleophile attacks | Rate = k[R-LG] | Racemization | (CH₃)₃C-Br + H₂O → (CH₃)₃C-OH + HBr |
| SN2 | One-step: nucleophile attacks as leaving group departs | Rate = k[R-LG][Nu] | Inversion | CH₃CH₂Br + OH⁻ → CH₃CH₂OH + Br⁻ |
Electrophilic Aromatic Substitution (EAS)
| Reaction | Reagents | Example |
|---|---|---|
| Nitration | HNO₃, H₂SO₄ | C₆H₆ + HNO₃ + H₂SO₄ → C₆H₅NO₂ + H₂O |
| Sulfonation | SO₃, H₂SO₄ | C₆H₆ + SO₃ + H₂SO₄ → C₆H₅SO₃H |
| Halogenation | X₂, FeX₃ | C₆H₆ + Cl₂ + FeCl₃ → C₆H₅Cl + HCl |
| Friedel-Crafts Alkylation | R-X, AlCl₃ | C₆H₆ + CH₃Cl + AlCl₃ → C₆H₅CH₃ + HCl |
| Friedel-Crafts Acylation | RCOX, AlCl₃ | C₆H₆ + CH₃COCl + AlCl₃ → C₆H₅COCH₃ + HCl |
Effect of Substituents on EAS:
- Activating groups (increase reaction rate): -NH₂, -NHR, -NR₂, -OH, -OR, -R
- Deactivating groups (decrease reaction rate): -NO₂, -CN, -SO₃H, -COOH, -CHO, -COR, -COOR, -NH₃⁺
- Ortho/para directors: -NH₂, -NHR, -NR₂, -OH, -OR, -R, -X (halogens)
- Meta directors: -NO₂, -CN, -SO₃H, -COOH, -CHO, -COR, -COOR, -NH₃⁺
Addition Reactions
Addition to Alkenes
| Reaction | Reagents | Product | Example |
|---|---|---|---|
| Hydrogenation | H₂, Pt/Pd/Ni | Alkane | CH₂=CH₂ + H₂ → CH₃-CH₃ |
| Halogenation | X₂ (Cl₂, Br₂) | Dihaloalkane | CH₂=CH₂ + Br₂ → CH₂Br-CH₂Br |
| Hydrohalogenation | HX | Haloalkane | CH₂=CH₂ + HBr → CH₃-CH₂Br |
| Hydration | H₂O, H⁺ | Alcohol | CH₂=CH₂ + H₂O → CH₃-CH₂OH |
| Oxymercuration-demercuration | Hg(OAc)₂, H₂O, NaBH₄ | Alcohol | CH₂=CH₂ + Hg(OAc)₂ + H₂O → CH₃-CH₂OH |
| Hydroboration-oxidation | BH₃, H₂O₂, OH⁻ | Alcohol | CH₂=CH₂ + BH₃ → CH₃-CH₂OH |
| Epoxidation | RCOOOH or H₂O₂ | Epoxide | CH₂=CH₂ + RCOOOH → CH₂-CH₂(O) |
| Ozonolysis | O₃, then Zn/H₂O | Aldehydes/Ketones | CH₃CH=CHCH₃ + O₃ → 2CH₃CHO |
Markovnikov’s Rule: In addition of HX to alkene, H attaches to carbon with more hydrogen atoms, X to carbon with fewer hydrogen atoms
Anti-Markovnikov Addition: Occurs in hydroboration-oxidation (H attaches to carbon with fewer hydrogen atoms)
Elimination Reactions
| Type | Mechanism | Reagents | Example |
|---|---|---|---|
| E1 | Two-step: leaving group departs, then proton removed | H₂O, heat, acid | (CH₃)₃C-OH + H⁺ → (CH₃)₂C=CH₂ + H₂O + H⁺ |
| E2 | One-step: base removes proton as leaving group departs | Strong base | CH₃CH₂-CH(Br)-CH₃ + OH⁻ → CH₃CH=CH-CH₃ + Br⁻ + H₂O |
Zaitsev’s Rule: In elimination reactions, the major product is the more substituted alkene (more stable)
Condensation Reactions
| Reaction | Reagents | Product | Example |
|---|---|---|---|
| Aldol Condensation | Aldehyde/ketone, base | β-hydroxy aldehyde/ketone | 2CH₃CHO → CH₃CH(OH)CH₂CHO |
| Claisen Condensation | Esters, strong base | β-keto ester | 2CH₃COOCH₃ → CH₃COCH₂COOCH₃ + CH₃OH |
| Esterification | Carboxylic acid, alcohol, H⁺ | Ester | CH₃COOH + CH₃OH ⇌ CH₃COOCH₃ + H₂O |
| Amide Formation | Carboxylic acid, amine | Amide | CH₃COOH + NH₃ → CH₃CONH₂ + H₂O |
Redox Reactions in Organic Chemistry
| Reaction | Change | Reagents | Example |
|---|---|---|---|
| Oxidation of Alcohols | R-OH → R=O | CrO₃, H₂SO₄ or PCC | CH₃CH₂OH → CH₃CHO → CH₃COOH |
| Oxidation of Aldehydes | R-CHO → R-COOH | Ag₂O (Tollens’) or Cu²⁺ (Fehling’s) | CH₃CHO + Ag₂O → CH₃COOH + 2Ag |
| Reduction of Aldehydes/Ketones | C=O → C-OH | NaBH₄ or LiAlH₄ | CH₃CHO + NaBH₄ → CH₃CH₂OH |
| Reduction of Carboxylic Acids | RCOOH → RCH₂OH | LiAlH₄ | CH₃COOH + LiAlH₄ → CH₃CH₂OH |
Polymerization Reactions
Addition Polymerization
- Mechanism: Monomers with double bonds join end-to-end
- Examples:
- Ethylene → Polyethylene: n(CH₂=CH₂) → -(CH₂-CH₂)ₙ-
- Styrene → Polystyrene: n(CH₂=CH-C₆H₅) → -(CH₂-CH(C₆H₅))ₙ-
- Vinyl chloride → PVC: n(CH₂=CHCl) → -(CH₂-CHCl)ₙ-
Condensation Polymerization
- Mechanism: Monomers join with loss of small molecules (H₂O, HCl, etc.)
- Examples:
- Nylon 6,6: n(HOOC-(CH₂)₄-COOH) + n(H₂N-(CH₂)₆-NH₂) → -[OC-(CH₂)₄-CO-NH-(CH₂)₆-NH]ₙ- + 2nH₂O
- Polyester (PET): n(HOOC-C₆H₄-COOH) + n(HO-CH₂-CH₂-OH) → -[OC-C₆H₄-CO-O-CH₂-CH₂-O]ₙ- + 2nH₂O
Electrochemical Reactions
Galvanic/Voltaic Cells
- Anode: Oxidation occurs (electrons generated)
- Cathode: Reduction occurs (electrons consumed)
- Example: Zn|Zn²⁺||Cu²⁺|Cu
- Anode (oxidation): Zn → Zn²⁺ + 2e⁻
- Cathode (reduction): Cu²⁺ + 2e⁻ → Cu
Electrolytic Cells
- Anode: Oxidation occurs (electrons leave cell)
- Cathode: Reduction occurs (electrons enter cell)
- Example: Electrolysis of molten NaCl
- Anode (oxidation): 2Cl⁻ → Cl₂ + 2e⁻
- Cathode (reduction): 2Na⁺ + 2e⁻ → 2Na
Nernst Equation
- E = E° – (RT/nF)ln(Q)
- At 25°C: E = E° – (0.0592/n)log(Q)
- E° = standard cell potential
- n = number of electrons transferred
- Q = reaction quotient
Nuclear Reactions
Types of Nuclear Decay
| Decay Type | Particle Emitted | Change in Nucleus | Example |
|---|---|---|---|
| Alpha (α) | ₂⁴He nucleus | Z → Z-2, A → A-4 | ₂₃₈U → ₂₃₄Th + ₄He |
| Beta (β⁻) | Electron | Z → Z+1, A unchanged | ₁₄C → ₁₄N + ₀e |
| Positron (β⁺) | Positron | Z → Z-1, A unchanged | ₁₁C → ₁₁B + ₀e |
| Gamma (γ) | Photon | No change | ₆₀*Co → ₆₀Co + γ |
| Electron capture | None (absorbs e⁻) | Z → Z-1, A unchanged | ₇Be + ₀e → ₇Li |
| Neutron emission | Neutron | Z unchanged, A → A-1 | ₁⁷N → ₁₆N + ₁n |
Nuclear Equations
- Fission: ₂₃₅U + ₁n → ₁₄₁Ba + ₉₂Kr + 3₁n + energy
- Fusion: ₂H + ₃H → ₄He + ₁n + energy
Chemical Kinetics
Rate Laws
- First-Order: Rate = k[A], t₁/₂ = 0.693/k
- Second-Order: Rate = k[A]², t₁/₂ = 1/(k[A]₀)
- Zero-Order: Rate = k, t₁/₂ = [A]₀/2k
Determining Reaction Order
- Method of Initial Rates: Compare rates at different initial concentrations
- Integrated Rate Law Plots:
- First-Order: ln[A] vs t gives straight line
- Second-Order: 1/[A] vs t gives straight line
- Zero-Order: [A] vs t gives straight line
Factors Affecting Reaction Rate
- Temperature: Higher T → faster rate (Arrhenius equation)
- Catalysts: Lower activation energy → faster rate
- Concentration: Higher conc. → faster rate (except zero-order)
- Surface Area: More SA → faster rate
- Pressure: Higher P → faster rate (for gaseous reactions)
Reaction Mechanisms & Intermediates
Common Reaction Intermediates
| Intermediate | Structure | Example Reaction |
|---|---|---|
| Carbocation | R₃C⁺ | SN1, E1 reactions |
| Carbanion | R₃C⁻ | Nucleophilic addition |
| Free Radical | R₃C• | Halogenation of alkanes |
| Carbene | R₂C: | Cyclopropanation |
| Nitrene | R-N: | Aziridination |
Multi-Step Reaction Mechanisms
- Rate-Determining Step: Slowest step that determines overall rate
- Steady-State Approximation: Intermediates consumed as quickly as formed
Spectroscopic Analysis of Reactions
IR Spectroscopy Functional Group Identification
| Functional Group | Wavenumber (cm⁻¹) | Characteristic |
|---|---|---|
| Alkanes (C-H stretch) | 2850-2960 | Strong |
| Alkenes (C=C) | 1620-1680 | Medium |
| Alkynes (C≡C) | 2100-2260 | Medium to weak |
| Aromatics (C=C) | 1450-1600 | Medium, multiple bands |
| Alcohols (O-H) | 3200-3600 | Strong, broad |
| Carboxylic acids (O-H) | 2500-3300 | Strong, very broad |
| Carbonyls (C=O) | 1670-1820 | Strong |
| Amines (N-H) | 3300-3500 | Medium |
| Nitriles (C≡N) | 2210-2260 | Medium |
NMR Spectroscopy in Reaction Monitoring
- ¹H NMR: Tracks changes in proton environments
- ¹³C NMR: Monitors carbon skeleton changes
- Time-resolved NMR: Follows reaction kinetics in real-time
Green Chemistry & Sustainable Reactions
Principles of Green Chemistry
- Prevention: Better to prevent waste than treat it
- Atom Economy: Maximize incorporation of reactants into final product
- Safer Reagents: Use less hazardous chemical synthesis
- Design Safer Chemicals: Maintain efficacy while reducing toxicity
- Safer Solvents: Use safer solvents and auxiliaries
- Energy Efficiency: Minimize energy requirements
- Renewable Feedstocks: Use renewable raw materials
- Reduce Derivatives: Minimize or avoid derivatization
- Catalysis: Catalytic reagents superior to stoichiometric reagents
- Degradation: Design for degradation
- Real-time Analysis: Real-time monitoring for pollution prevention
- Accident Prevention: Minimize potential for accidents
Sustainable Reaction Examples
- Aqueous-phase reactions: Replaces organic solvents with water
- Solvent-free reactions: Eliminates solvent waste
- Catalytic reactions: Reduces energy requirements and waste
- Microbial transformations: Environmentally friendly alternatives
- Electrochemical reactions: Avoids chemical oxidants/reductants
- Photochemical reactions: Uses light energy instead of reagents
Resources for Further Learning
Chemical Reaction Databases
- NIST Chemical Kinetics Database
- Chemical Reactivity Database (CRD)
- Organic Reactions Database
- Reaxys
- SciFinder
Important Reference Books
- March’s Advanced Organic Chemistry
- Organic Chemistry by Clayden, Greeves, Warren
- Inorganic Chemistry by Shriver & Atkins
- Physical Chemistry by Atkins & de Paula
- Comprehensive Organic Transformations by Larock
This cheatsheet provides a structured reference for chemical reactions across various disciplines. For specific reaction details, always consult appropriate reference texts or databases for the most accurate and up-to-date information.
