Topic 1: Atoms, Molecules, Stoichiometry and Redox Reactions 1. Relative atomic mass: Average mass of one atom (an isotope in its relative abundance) in an element relative to 1/12 the mass of a 12-Carbon 2. Relative isotopic mass: Mass of one atom of an isotope of an element relative to 1/12 the mass of a 12-Carbon 3. Relative molecular mass: Average mass of one molecule of a substance relative to 1/12 the mass of a 12-Carbon 4. Relative formula mass: Average mass of one formula unit of a substance relative to 1/12 the mass of a 12-Carbon 5. Isotopic Abundance: The abundance of each isotope in a mixture 6. One mole of a substance contains the same number of particles as there are in 12g of the 12-Carbon isotope 7. Avogadro’s Constant: L= 6.02 x 1023mol-1 8. Molar mass: The mass of one mole of a substance 9. Stoichiometry: The study of quantitative aspects of chemical formulae and reactions. It involves both the determination of chemical formulae as well as calculations using balanced chemical equations based on the central idea of the mole 10. Empirical Formula: Simplest formula showing the ration of the atoms of the different elements in the compound 11. Avogadro’s Law: Equal volume of gases, under the same temperature and pressure, contain the same number of molecules 12. Redox reaction: A reaction that involves Reduction and Oxidation simultaneously 13. Reduction: A process whereby a substance gains electrons, resulting in a decrease in oxidation number 14. Oxidation: A process whereby a substance loses electrons, resulting in an increase in oxidation number 15. A redox reaction is a reaction in which the same reactant is both oxidised and reduced 16. Disproportionation: A redox reaction in which the same reactant is both oxidised and reduced 17. Aqueous metathesis: Double displacement reaction 18. Eocell = EoR - EoO Common Oxidising Agents Oxidant MnO4- (purple) Cr2O72- (orange) I2 (brown in aq solution) H2O2 (colourless) Reaction Medium Acidic Alkaline Acidic Neutral Acidic Product Mn2+ (colourless) MnO2 (brown solid/ppt) Cr3+ (green) I- (colourless) H2O Common Reducing Agents Reductant Fe2+ (pale green) I- (colourless) S2O32- (colourless) H2O2 (colourless) C2O42- (colourless) Reaction Medium Acidic Acidic/Alkaline/Neutral Neutral Acidic Acidic Product Fe3+ (yellow) I2 (brown in aq solution) S4O62- (colourless) O2 CO2 Topic 2: Atomic Structure and Physical Properties 1. Angle of deflection ∝ ๐๐๐๐๐๐ ๐๐๐๐ 2. Atomic number (Z): The number of protons in the nucleus of each atom of an element 3. Mass number (A): Total number of neutrons and protons present in the nucleus if an atom of an element 4. Isotopes: Elements of the same atomic number but different number of neutrons. They have the same electronic configuration and chemical properties but different relative isotopic masses and physical properties 5. Isoelectronic: Same number of electrons 6. Isotonic: Same number of neutrons 7. Isotopic: Same number of protons 8. Principal Quantum Number: describes the main energy level of an electron and the size of an atomic orbital 9. Subshells: subdivision of each principal quantum shell 10. Atomic Orbital: region of space with ≥90% probability of finding an electron 11. Aufban’s Principle: Electrons in their ground states occupy orbitals in order of energy levels. The orbital with the lowest energy is always filled first 12. Hund’s Rule of Multiplicity: When filling subshells that contain more than one orbital with the same energy level, each orbital must be singly occupied before electrons are paired 13. Pauli’s Exclusion Principle: An orbital cannot hold more than two electrons and the two electrons sharing the same orbital must have opposite spins 14. Effective nuclear charge: Zeff is the net nuclear charge experienced by an outer electron (Zeff ≈ Z - S) 15. Shielding effect: Partial offsetting of the charge of the nucleus by inner-shell electrons 16. Electronegativity: The relative ability of an atom in a molecule to attract the shared electrons in a covalent bond 17. 1st Ionisation Energy: The energy required to remove 1 mole of electrons from 1 mole of gaseous atoms to form 1 mole of unipositively charged gaseous ions Topic 3: Chemical Bonding 1. Ionic Bond: The electrostatic forces of attraction between oppositely charged ions in an ionic compound 2. Lattice Energy: The result of electrostatic interactions between the oppositely charged ions in an ionic compound/ The energy released when 1 mole of a pure ionic solid is formed from its constituent gaseous ions ๐+ ๐− 3. Lattice Energy ∝ |r+ +r−| 4. Metallic Bond: The electrostatic forces of attraction between metal cations and a sea of delocalised electrons in a metal 5. Covalent Bond: The electrostatic forces of attraction between the nuclei of atoms and their shared pair of electrons 6. Bond Length (Covalent Bond): The distance between the nuclei of the 2 bonded atoms when their atomic orbitals overlap to form molecular orbitals 7. Bond Energy: The energy required to break a particular bond in one mole of a gaseous substance 8. Sigma (σ) Bond: “Head-on” overlap of two atomic orbitals 9. Pi (π) Bond: “Side-on” overlap of two atomic orbitals 10. Valence Shell Electron Pair Repulsion (VSEPR) Theory states: a. Electron groups around a central atom locate themselves as far away from each other as possible to minimise electron repulsion b. LP-LP repulsion > LP-BP repulsion > BP-BP repulsion (as electron density of LP resides closer to the atom as compared to electron density of BP) c. Repulsion between EPs depend on the relative electronegativity of central and bonding atoms 11. Pure Ionic Bond: Complete transfer of electrons, resulting from a large difference in electronegativity between the 2 atoms 12. Ionic Bond with covalent character: due to the distortion of the electron cloud by cation of high charge density 13. Polar covalent Bond: Unequal sharing of electrons due to some electronegativity difference between 2 atoms 14. Covalent Bond: Equal sharing of electrons due to no difference in electronegativity between 2 atoms 15. Fajan’s Rules: Bonding tends to be ionic if a. cation is large and anion is small b. charges on both cation and anion are small 16. Bond polarity: separation of positive and negative charges 17. Non-polar Bond: bonding electrons shared equally due to no differences in electronegativity 18. Polar Bond: unequal sharing of electrons due to difference n electronegativity of bonding atoms 19. Dispersion Forces (London forces or instantaneous dipole-induced dipole interactions): caused by temporary fluctuations in the electron density of an atom or non-polar molecule 20. Permanent dipole-permanent dipole interactions: electrostatic forces of attraction between polar molecules 21. Hydrogen bonding: occurs between molecules with a H atom bonded to a small, highly electronegative atom with LP (F, O and N only) 22. Ionic solute – Polar solvent (Ion-dipole interactions) 23. Polar solute – Polar solvent (H bonding and pd-pd interactions) 24. Non-polar solute – non-polar solvent (dispersion forces) 25. Non-polar solute – Polar solvent (immiscible) Topic 4: The Gaseous State 1 1. Boyle’s Law: V ∝ ๐ (Ceteris paribus) 2. Charles’ Law: V ∝ T (Ceteris paribus) 3. Avogadro’s Law: V ∝ n (Ceteris paribus) 4. Ideal gas equations: pV = nRT 5. Ideal gas: a hypothetical gas whose pressure-volume-temperature behaviour can be completely accounted for by the ideal gas equation pV = nRT 6. R: the proportionality constant/molar gas constant = 8.31 JK-1mol-1 7. Combined gas equation: ๐1 ๐1 ๐1 = ๐2 ๐2 ๐2 8. Partial Pressure: Pressure exerted by a particular gas on the sides of a container in a mixture of gases 9. Dalton’s Law of partial pressure: The total pressure of a mixture of gases is the sum of the partial pressures of the constituent gases (pTotal = pA + pB +pC) 10. Kinetic Theory of Gases (assumptions applied to an ideal gas): a. The gas particles occupy negligible volume as compared to the volume of its container b. The forces of attraction and repulsion between gas particles are negligible ie. There are negligible intermolecular forces c. Gas particles collide elastically ie. There is no loss in kinetic energy after collisions d. Gas particles are in constant random motion e. The average kinetic energy of the gas particles is directly proportional to the absolute temperature 11. At high pressure: a. There are many gas particles per unit volume; the volume of particles cannot be considered negligible b. The molecules are close together, thus intermolecular forces are significant 12. At low temperature: the gas particles have low speeds and average kinetic energy and are less able to overcome intermolecular forces, which are thus significant 13. Real gases behave most ideally at low pressures and high temperatures 14. Potential deviants: a. Large molecules – large electron cloud result in stronger intermolecular forces b. Polar molecules – stronger intermolecular forces of attraction such as pd-pd interactions or H bonding 15. Maxwell-Boltmann Distribution Curve: As the temperature of the gas increases, the average speed and kinetic energy of the gas molecules increases Topic 5: Chemical Energetics and Thermodynamics 1. Activation Energy: The minimum energy which the reacting particles must possess in order to overcome the energy barrier before the formation of products 2. Enthalpy change of reaction (ΔHrัณ): Enthalpy change when molar quantities of reactants as specified by the chemical equation react to form products at 1 atm and 298K 3. Enthalpy change of combustion (ΔHcัณ): Heat evolved when 1 mole of a substance is completely burnt in excess oxygen at 1 atm and 298K 4. Heat capacity (C): The amount of heat required to raise an object’s temperature by 1K 5. Specific eat capacity (c): The amount of heat required to raise the temperature of 1g of the substance by 1K 6. c of water is 4.18 Jg-1K-1 7. q = mcΔT 8. Hess’s Law of Constant Heat Summation: The enthalpy change of a particular reaction is determined only by the initial and final states of the system regardless of the pathway taken 9. Enthalpy change of formation (ΔHfัณ): Enthalpy change when 1 mole of a substance is formed from its constituent elements in their standard states at 1 atm and 298K 10. Enthalpy change of neutralisation (ΔHneutัณ): Heat evolved when 1 mole of H2O is formed in the neutralisation reaction between an acid and a base at 1 atm and 298K 11. Enthalpy change of atomization (ΔHatomัณ): Energy required when 1 mole of gaseous atoms are formed the element at 1 atm and 298K 12. Enthalpy change of hydration (ΔHhydัณ): Heat evolved when 1 mole of free gaseous ions is surrounded by water molecules at 1 atm and 298K 13. Enthalpy change of solution (ΔHsolัณ): Enthalpy change when 1 mole of solute is completely dissolved in a solvent to form an infinitely dilute solution at 1 atm and 298K 14. Lattice Energy: Heat evolved when 1 mole of pure solid is formed from its constituent gaseous ions 15. LE = ΔHhyd - ΔHsol 16. ΔHrัณ = ∑ ๐๐ซ๐๐ ัณ (๐๐๐๐๐๐๐๐๐) − ∑ ๐๐ซ๐๐ ัณ (๐๐๐๐ ๐๐๐๐) 17. ΔHrัณ = ∑ ๐๐ซ๐๐ ัณ (๐ฉ๐ซ๐จ๐๐ฎ๐๐ญ๐ฌ) − ∑ ๐๐ซ๐๐ ัณ (๐๐๐๐๐๐๐๐๐) 18. Bond dissociation energy: The energy required to break 1 mole of a specified covalent bond in a specified compound in the gaseous state 19. Bond energy: Average energy required to break 1 mole of covalent bond in the gaseous state 20. Factors affecting bond energy: a. Bond order b. Effectiveness of bond overlap c. Bond polarity 21. 1st Electron Affinity: The enthalpy change when 1 mole of electrons is added to 1 mole of gaseous atoms to form 1 mole of singly charged gaseous anions 22. Bond Haber Cycle: An extension of Hess’s Law to ionic compounds. It can be used to determine the LE of ionic compounds 23. Entropy: S is a thermodynamic quantity related to the number of ways the energy of a system can be dispersed through the motions of its particles 24. 2nd Law of Thermodynamics: The total entropy of the universe always tends to increase 25. ΔS>0: greater disorder/more no. of ways energy can be dispersed in a system 26. ΔS<0: more ordered state/less no. of ways energy can be dispersed in a system 27. Factors affecting entropy of a system: a. Change in temperature b. Change in phase c. Mixing of particles d. Expansion of a gas e. Change in number of particles f. Dissolution of an ionic solution 28. Gibbs free energy: ΔG = ΔH – TΔS 29. ΔG<0: Reaction is feasible and can take place spontaneously (reaction is exergonic) 30. ΔG=0: Reaction is at equilibrium. There is no net change (during melting and boiling) 31. ΔG>0: Reaction is not feasible and cannot take place spontaneously (reaction is endergonic, and spontaneous if in reverse direction) ΔH<0 ΔS<0 ΔS>0 Feasible at low Feasible at all temperatures temperatures ΔH>0 Not feasible Feasible at high temperatures Topic 6: Reaction Kinetics 1. Collision Theory: For effective collisions to occur, reactant molecules must: a. Collide with each other b. Collide with a certain minimum energy called activation energy, Ea c. Collide with the correct orientation 2. Activation Energy, Ea: The minimum energy which the reacting particles must possess in order to overcome the energy barrier before the formation of products 3. Transition State/ Activated Complex: the arrangement of atomic nuclei and bonding electrons at the maximum potential energy 4. Rate of reaction: Change in concentration of reactant or product per unit time 5. Rate = − 6. For any reaction: aA + bB → cC +dD, Rate = − ๐ 7. Average rate of reaction = − 8. Instantaneous rate of reaction: the reaction rate at a specified time = gradient of the ๐ [๐๐๐๐๐๐๐๐] ๐ ๐ ๐๐ ๐ [๐๐๐๐ ๐๐๐] ๐ ๐ 1 ๐[๐ด] = − 1 ๐[๐ต] ๐๐ก ๐ ๐๐ก ๐๐๐๐๐ [๐๐๐๐๐๐๐๐]− ๐๐๐๐๐๐๐ [๐๐๐๐๐๐๐๐] = 1 ๐[๐ถ] ๐ ๐๐ก = 1 ๐[๐ท] ๐ ๐๐ก โ๐ tangent of a concentration-time graph at the specified time 9. Initial rate of reaction: the reaction rate at the start of a reaction when an infinitesimally small amount of the reactant has reacted = gradient of the tangent of a concentrationtime graph at t=0 10. Rate equation: An experimentally determined equation that relates the rate of reaction to the concentration of the reactants raised to appropriate powers. 11. Rate = k[A]m[B]n 12. Overall order of reaction = order of reaction wrt A + order of reaction wrt B 13. Rate constant: affected by temperature and presence of catalyst only (k = Ae -Ea/RT) 14. Order of reaction: the power of the concentration terms in the experimentally determined rate equation 15. Half-life of a reaction: the time taken for the concentration of a reactant to decrease to half of its initial value 16. Zero-order Reactions: Rate = k[A]0 = k, t½ = [๐ด]0 2๐ 17. First-order Reactions: Rate = k[A]1 = k[A], t½ = ๐๐2 ๐ 1 18. Second-order Reactions: Rate = k[A]2, t½ = ๐[๐ด]๐ 19. Pseudo-zero order Reactions: A particular reactant is present in large excess with respect to other reactants, thus its concentration with not change significantly during the reaction, causing the rate to appear to be independent of this reactant concentration 20. A reaction mechanism: A sequence of steps through which reactants react to form products 21. Reaction intermediate: a chemical species that is produced in an elementary step and consumed in another 22. Elementary step: a step which cannot be broken down into simpler steps 23. Molecularity: the number of reactant particles taking part in the reaction in that elementary step 24. Molecularity of an elementary step = overall order of reaction 25. The slowest step is the rate-determining step