Chemistry

Introduction to Solutions & Solubility

Solution  Homogeneous mixture of 2 or more substances
 Types
o Saturated
 contains maximum amount of dissolved solute at a given temperature in the presence of undissolved
solute
o Unsaturated
 contains less than the maximum amount of dissolved solute
 able to dissolve more solute
o Supersaturated
 Contains more than the equilibrium amount of dissolved solute
 Unstable solution
 Solution crystalize immediately when seed crystal is added & forms saturated solution
Solvent  Dissolving medium (most abundant)
 Gaseous, liquid, solid
Solute  Substance(s) that dissolves
Miscible  Substances (liquid) that are soluble in each other in any proportion
Solubility, S  Maximum amount of solute that dissolves completely in a given amount of solvent at a particular temperature
Dissolution  Process of dissolving a solute in a solvent to give a homogeneous solution

Factors Affecting Solubility

Solute-Solvent Interaction
Temperature
Pressure (Gases)
 Stronger attraction between solute and solvent  stronger solubility
o Solute will dissolve in the solvent if the IMF of solutes is comparable to IMF of solvent
o Example
NaCl + H2O NaCl + Benzene
NaCl - Ionic Bond NaCl - Ionic Bond
H2O - Hydrogen Bond Benzene - LDF
Both bonds are comparable LDF is weaker than Ionic Bond  cannot
Thus, it can dissolve compensate to the strong force of solute
Thus, it cannot dissolve
 Number of Carbon atoms
o If length of carbon chain ↑, OH group becomes a smaller part of the group (C > 5, non-soluble)
o The molecule become more hydrocarbon, Solubility ↓
o If number of OH group ↑, solute-water hydrogen bonding ↑, Solubility ↑
 Example: Glucose (C > 5 but OH ↑)
 Strength of LDF
o Increase in molar mass leads to increase in LDF, Solubility ↑
o Size ↑, easier to distort electron, instantaneous dipole moment occurs, LDF ↑
 Temperature ↑, solubility of solid ↑
 Temperature ↑, solubility of gases ↓
o KE of gases ↑, easier for the gases to escape
 Pressure ↑ (at constant T), frequency of collision of gas molecules with the surface of the solvent ↑, solubility ↑
 Gas dissolves when gas molecules strike the surface of the solution (and are surrounded & dispersed by solvent)
 Pressure does not affect solubility of solids & liquids
 Dynamic Equilibrium
o Rate of gas molecules enters the solution = rate of solute
molecules enters the gas phase (constant concentration)
o If piston is pushed down, pressure ↑, volume of gas ↓
o More gas dissolves until equilibrium is reached
 Gas-Liquid Solutions  For gases that do not react with solvent  Henry’s Law (only true at low concentrations & pressure)
 𝑺(𝒈) = 𝒌𝑯 𝑷(𝒈) , 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕 𝑻
𝑺𝟏 𝑺𝟐
 =
𝑷𝟏 𝑷𝟐
Liquid-Liquid Solutions  Formation of liquid-liquid solution requires overcoming the attractive forces between the molecules of 2 pure liquids
 Substances that form layers upon the addition of one another is IMMISCIBLE
 Example: Ethanol + H2O (Dissolves)
 Benzene + H2O (Does not Dissolve)
Solid-Liquid Solutions  SOLVATION - solute molecule surrounded by solvent molecules
 HYDRATION - solutes become surrounded by water
 Solution does not form when IMF within solute & solvent are significantly different
 Ksp – solubility product
o 𝑴𝒂 𝑿𝒃 ⇌ 𝒂𝑴𝒄+ (𝒂𝒒) + 𝒃𝑿𝒅− (𝒂𝒒)
o 𝑲𝒔𝒑 = [𝑴𝒄+ ]𝒂 [𝑿𝒅− ]𝒃
 Relationship between Ksp & Solubility
o Molar Solubility (s)
 molar concentration in its saturated solution
 used to calculate Ksp, assuming all salt that dissolves dissociate 100% into ions
 Common Ion Effect
o Ionic salt less soluble in the presence of a common ion (in the salt)
o Example
 PbCl2(s)  Pb2+(aq) + 2Cl– (aq)
 Ksp= [Pb2+] [Cl–]2
 Addition of Pb(NO3)2 to saturated solution of PbCl2 increases Pb2+, thus, Qsp ↑
 Qsp > Ksp, PbCl2 is precipitated
 Prediction of Precipitation
o Qsp > Ksp - precipitate forms
 Qsp < Ksp - precipitate will not form

Expressing Concentration
Mole Fraction, X  Number of moles of a particular component ÷ Total number of moles of material in the solution
𝒏𝒂
 𝑿𝒂 =
𝒏𝒂 +𝒏𝒃+𝒏𝒄
 Sum of mole fraction = 1
 Temperature independent
Mole Percentage 𝑴𝒐𝒍𝒆 𝒐𝒇 𝒄𝒐𝒎𝒑𝒐𝒏𝒆𝒏𝒕 𝒊𝒏 𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏 × 𝟏𝟎𝟎
 𝐌𝐨𝐥𝐞 % =
𝑻𝒐𝒕𝒂𝒍 𝒎𝒐𝒍𝒆 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏
Parts per Million, ppm 𝑴𝒂𝒔𝒔 𝒐𝒇 𝒄𝒐𝒎𝒑𝒐𝒏𝒆𝒏𝒕 𝒊𝒏 𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏 × 𝟏𝟎𝟔
 𝐏𝐏𝐌 =
𝑻𝒐𝒕𝒂𝒍 𝒎𝒂𝒔𝒔 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏
 mg/kg = ppt wt
 µl/L = ppm vol
Parts per Billion, ppb  1 ppb = 1g of solute per billion grams of solution / 1µg of solute per litre of solution
𝑴𝒂𝒔𝒔 𝒐𝒇 𝒄𝒐𝒎𝒑𝒐𝒏𝒆𝒏𝒕 𝒊𝒏 𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏 × 𝟏𝟎𝟗
 𝐏𝐏𝐁 =
𝑻𝒐𝒕𝒂𝒍 𝒎𝒂𝒔𝒔 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏
 1ppb = 1µg/L
Molarity, M  Amount of substance in a particular volume of solution
𝑴𝒐𝒍𝒆𝒔 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒆
 𝐌=
𝑽𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏 (𝑳)
 Solutions increase in volume with increasing temperature
 Thus, M changes with temperature
Molality, m  Number of moles per kilogram of solvent
𝑴𝒐𝒍𝒆𝒔 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒆
 𝐦=
𝑲𝒊𝒍𝒐𝒈𝒓𝒂𝒎𝒔 𝒐𝒇 𝒔𝒐𝒍𝒗𝒆𝒏𝒕
 Preferred when expressing solution composition when involving colligative properties
 Temperature independent
Colligative Properties of Solutions
Colligative Properties
Vapor Pressure Lowering
Boiling Point Elevation &
Freezing Point Depression
Osmotic Pressure, π
 Depends on number of dissolved particles in solution & not on their identity
 Example
o Adding Ethylene Glycol to water in car radiator
o Lowers freezing point of solution
o Raises boiling point of solution (to operate at high temperature)
 Affects
o Vapor Pressure Lowering
o Boiling Point Elevation
o Freezing Point Depression
o Osmotic Pressure
 BP of a solution containing a non-volatile solute is higher than that of the pure solvent
 BP of solvent is the temperature at which the vapor pressure of the solvent is equal to the atmospheric pressure
 Vapor pressure of solvent above solution is expressed as
o 𝑷𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏 = 𝒙𝒔𝒐𝒍𝒗𝒆𝒏𝒕 𝑷∗ 𝒔𝒐𝒍𝒗𝒆𝒏𝒕
o For simple 2 component system
o Solution is sufficiently dilute
 Amount of solute vs Magnitude of vapor pressure lowering
o 𝑷𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏 = 𝒙𝒔𝒐𝒍𝒗𝒆𝒏𝒕 𝑷∗ 𝒔𝒐𝒍𝒗𝒆𝒏𝒕
o 𝒙𝒔𝒐𝒍𝒗𝒆𝒏𝒕 = 𝟏 − 𝒙𝒔𝒐𝒍𝒖𝒕𝒆
o 𝑷𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏 = (𝟏 − 𝒙𝒔𝒐𝒍𝒖𝒕𝒆 )𝑷∗ 𝒔𝒐𝒍𝒗𝒆𝒏𝒕
o 𝑷𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏 = 𝑷∗ 𝒔𝒐𝒍𝒗𝒆𝒏𝒕 − 𝒙𝒔𝒐𝒍𝒖𝒕𝒆 𝑷∗ 𝒔𝒐𝒍𝒗𝒆𝒏𝒕
o 𝜟𝑷 = 𝒙𝒔𝒐𝒍𝒖𝒕𝒆 𝑷∗ 𝒔𝒐𝒍𝒗𝒆𝒏𝒕
o 𝜟𝑷 = 𝑷∗ 𝒔𝒐𝒍𝒗𝒆𝒏𝒕 − 𝑷𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏
 Raoult’s Law (Ideal Solution)
o Dilute solution & have small interactions between their constituent molecules
o Solutions containing more than 1 volatile component
 A : 𝒑𝒂 = 𝑿𝒂 𝒑∗ 𝒂
 B : 𝒑𝒃 = 𝑿𝒃 𝒑∗ 𝒃
 Total : 𝒑𝒕𝒐𝒕𝒂𝒍 = 𝑿𝒂 𝒑∗ 𝒂 + 𝑿𝒃 𝒑∗ 𝒃
 BPE 𝜟𝑻𝒃 = 𝑲𝒃 𝒃
 FPD 𝜟𝑻𝒇 = 𝑲𝒇 𝒃
 Osmosis – movement of solvent from low solute concentration to high solute concentration through semipermeable
membrane (or high to low)
 As solvent moves across membrane the fluid level becomes uneven
 Pressure difference between the arms stops osmosis
 Osmotic pressure is the pressure required to stop osmosis
o 𝝅 = 𝒄𝑹𝑻
𝒏
o 𝒄=
𝒗
o 𝝅𝑽 = 𝒏𝑹𝑻
Reaction Rate Expression
Rate of Reaction
Reaction Rates &
Stoichiometry
Factors Affecting Reaction Rate
Principal Factors
Rate Laws
Rate Laws
 Change in concentration of reactant/products per unit time
 Speed which reactants disappear & products form
o +ve Values
o Unit mol L-1 s-1
𝜟[ ]
 𝑨𝒗𝒆𝒓𝒂𝒈𝒆 𝑹𝒂𝒕𝒆 =
𝜟𝒕
 INSTANTANEOUS RATE - slope of a line tangent to the curve at a point
 INITIAL RATE - instantaneous rate when reactants are mixed
 AVERAGE RATE - slope of line joining any 2 points
 1-1 Relationship - rate of reactant consumed = rate of product formed
 Not 1-1 Relationship - rate of reactant consumed ≠ rete of product formed
 aA + bB  cC + dD
𝟏 𝜟[𝑨] 𝟏 𝜟[𝑩] 𝟏 𝜟[𝑪] 𝟏 𝜟[𝑫]
o 𝑹𝒂𝒕𝒆 = − =− = =
𝒂 𝜟𝒕 𝒃 𝜟𝒕 𝒄 𝜟𝒕 𝒅 𝜟𝒕
 Chemical nature of reactants
o Bonds break & form during reaction
o Some reactions are fast/slow
 Ability of reactant to come in contact with each other (Surface Area)
o Collision between particles must occur for reaction to occur
o Surface Area ↑, Collision Freq.↑, Rate ↑
 Concentration of reactant
o Concentration ↑, Collision Freq. ↑, Rate ↑
 Temperature
o Temperature ↑, Collision Energy ↑, Rate ↑
 Availability of catalyst
o Catalyst increase rate of reaction without being used up
o + Catalyst  EA ↓, Effective Collision ↑, Rate ↑
 Equation where the rate is given as a function of reactant concentration
 Differential rate law - rate as a function of concentration
𝒅[𝑨]
o 𝑹𝒂𝒕𝒆 = − = 𝒌[𝑨]𝒏 …
𝒅𝒕
o 𝑘 = 𝑟𝑎𝑡𝑒 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 (depends on reaction studied & temperature)
o 𝑛 = 𝑜𝑟𝑑𝑒𝑟 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 (+ve/-ve/integer/fraction)
o Example
Experiment Initial Conc. [A] Initial Conc. [B] Initial Rate of Formation of C
1 0.1 0.1 0.2
2 0.2 0.1 0.4
3 0.3 0.1 0.6
4 0.3 0.2 2.4
5 0.3 0.3 5.4
o EXP. 1 – EXP. 3 - A affects rate
𝑟𝑎𝑡𝑒𝑒𝑥𝑝2 0.4
 = =2
𝑟𝑎𝑡𝑒𝑒𝑥𝑝1 0.2
[𝐴]𝑒𝑥𝑝2 0.2
 [𝐴]𝑒𝑥𝑝1
= =2
0.1
 2 = 2𝑚
 𝑚=1
o EXP. 3 – EXP. 5 - B affects rate
𝑟𝑎𝑡𝑒𝑒𝑥𝑝4 2.4
 = =4
𝑟𝑎𝑡𝑒𝑒𝑥𝑝3 0.6
[𝐵]𝑒𝑥𝑝4 0.2
 [𝐵]𝑒𝑥𝑝3
= =2
0.1
 4 = 2𝑛
 𝑛=2
 Integrated rate law - concentration as a function of time
[𝑨]𝟎
o 1st Order 𝒍𝒏
[𝑨]𝒕
= 𝒌𝒕 𝒐𝒓 [𝑨]𝒕 = [𝑨]𝟎 𝒆−𝒌𝒕
 Graph Plot (SL, slope = -k)
𝟏 𝟏
o 2nd Order = 𝒌𝒕 +
[𝑩]𝒕 [𝑩]𝟎
 Graph Plot (SL, slope = +k)
o 0 Order [𝑪]𝒕 = −𝒌𝒕 + [𝑪]𝟎
 Graph Plot (SL, slope = -k)
 Half Life  Time required for half of a reactant to disappear, t1/2
o Half-life of first order is not affected by the initial
concentration
𝟏
 𝒂𝒕 𝒕 = 𝒕𝟏 , [𝑨]𝒕 = [𝑨]𝟎
𝟐
𝟐
[𝑨]𝟎 𝒍𝒏 𝟐
 𝒍𝒏 𝟏 = 𝒌𝒕𝟏/𝟐 𝒐𝒓 𝒕𝟏/𝟐 =
[𝑨]𝟎 𝒌
𝟐
o Half-life of second order depends on the initial
concentration
𝟏
 𝒂𝒕 𝒕 = 𝒕𝟏 , [𝑩]𝒕 = [𝑩]𝟎
𝟐 𝟐
𝟏 𝟏 𝟏
 𝟏 − = 𝒌𝒕𝟏/𝟐 𝒐𝒓 𝒕𝟏/𝟐 =
[𝑩]𝟎 [𝑩]𝟎 𝒌[𝑩]𝟎
𝟐

Theory of Chemical Kinetics

Activation Energy  Minimum energy required for a reaction to occur
 Determines the rate of reaction
 At a given temperature, certain fraction of the collisions possesses
enough energy to be effective & form products
 Transition State Theory – activated complex is unstable species &
what exist is neither reactant nor product but a translational
species with partial bonds
 𝒌 = 𝑨𝒆−𝑬𝒂 /𝑹𝑻
 Can also be obtained from 2 rate components measured at
different temperatures
𝒌 −𝑬 𝟏 𝟏
o 𝒍𝒏 𝟐 = 𝒂 [ − ]
𝒌𝟏 𝑹 𝑻𝟐 𝑻𝟏

Reaction Mechanisms
Reaction Mechanisms
 Net overall reaction is the result of a series of simple reactions (elementary reaction)
 Entire set of elementary processes is the reaction mechanisms
 The overall rate law derived from the mechanism must agree with the observed rate law for the overall reaction
 The rate law for the rate-determining step is directly related to the rate law for the overall reaction

Catalysts
Catalyst  Substance that changes the rate of a chemical reaction without being used up
 Provides path to the products that has rate-determining step with a lower Ea
o +ve catalyst – speeds up reaction
o -ve catalyst – slow reactions down
 Homogeneous Catalyst
o Same phase as reactants
 Heterogeneous Catalyst
o Different phase as the reactants
o Promote a reaction on its surface
Thermochemistry
Energy  Forms of Energy & The Interconversion
o All changes in matter accompanied by changes in the energy/heat content of the matter
o Energy (Potential & Kinetic) – convertible from one another
o An object has U from its position & K from its motion
o U + K = Internal Energy, E
o 𝜟𝑬 = 𝑬𝒇 − 𝑬𝒊 = 𝑬𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔 − 𝑬𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔
o Reacting systems change its E by transfer of E to surroundings
(vice versa)
 losing energy to surroundings 𝑬𝒇 < 𝑬𝒊
 gaining energy from surroundings 𝑬𝒇 > 𝑬𝒊
 System & Surroundings
o System – part of universe whose change to be
observed
o Surroundings – everything relevant to the change of the system
 Forms of Energy Transfer
o Heat (Thermal Energy), q
 Energy transfer between system & surrounding
 Result of difference in temperature between system & surrounding
o Work, w
 Energy transfer when a force moves an object
o Total change in system’s E, 𝜟𝑬 = 𝒒 + 𝒘
 System gain energy  +ve
 System lose energy  -ve
 First Law of Thermodynamics (Law of Conservation of Energy)
o Law – total energy of the universe is constant
 𝜟𝑬𝒖𝒏𝒊𝒗𝒆𝒓𝒔𝒆 = 𝜟𝑬𝒔𝒚𝒔𝒕𝒆𝒎 + 𝜟𝑬𝒔𝒖𝒓𝒓𝒐𝒖𝒏𝒅𝒊𝒏𝒈𝒔 = 𝟎
o Energy
 Can be converted from one to another
 Cannot be appear/disappear
 Cannot be created/destroyed
 State Functions & The Path Independence of Energy Change
o System’s E – state of function
 Property determined by the current state of the system
 Not dependent on the path the system took to reach the state
 Changes in state function depend on the initial & final state of the system
o q & w – not state of function
 Values are dependent on the path the system takes in undergoing the energy change
Enthalpy  Enthalpy change of reaction is also called heat of reaction ΔHrxn
(state of function) o 𝜟𝑯 = 𝑯𝒇 − 𝑯𝒊 = 𝑯𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔 − 𝑯𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔
 Thermodynamic property of a system
o 𝑯 = 𝑬 + 𝑷𝑽
o 𝜟𝑯 = 𝜟𝑬 + 𝑷𝜟𝑽 𝜟𝑬 = 𝒒𝒑 + 𝒘
o 𝜟𝑯 = 𝒒𝒑 + 𝒘 + 𝑷𝜟𝑽 𝒘 = −𝑷𝜟𝑽
o 𝜟𝑯 = 𝒒𝒑
 ΔH equals/close to ΔE in three cases
o Reactions that do not involve gases
 Liquids & Solids undergo very small volume of changes
 ΔV ≈ 0, PΔV ≈ 0, ΔH ≈ ΔE
o Reactions where the amount of moles of gas do not change
 Amount of gaseous reactants = Amount of gaseous products
 ΔV = 0, PΔV = 0, ΔH = ΔE
o Reaction where the amount of moles of gas change
 𝜟𝑯 = 𝒒𝒑 = 𝜟𝑬 + 𝑷𝜟𝑽
 𝜟𝑯 = 𝒒𝒑 − 𝑷𝜟𝑽 = 𝜟𝑬
 ΔE ≈ qp ≈ ΔH, ΔE ≈ ΔH
 Exothermic Process
o Process releases heat
o Results in a decrease in enthalpy
o 𝑯𝒇 < 𝑯𝒊 𝜟𝑯 < 𝟎
 Endothermic Process
o Process absorbs heat
o Results in an increase in enthalpy
o 𝑯𝒇 > 𝑯𝒊 𝜟𝑯 > 𝟎
 Important Types of Enthalpy Change
o Heat of Combustion ΔH = ΔHcomb
 1 mol of a substance react with O2 in a combustion reaction
o Heat of Formation ΔH = ΔHf
 1 mol of a compound is produced from its element
o Heat of Fusion ΔH = ΔHfus
 1 mol of substance melts
o Heat of Vaporization ΔH = ΔHf
 1 mol of substance vaporize
 Calorimetry  Enthalpy cannot be measures, change in enthalpy can be measured
 Heat Capacity
o Heat required to change the temperature of a substance by 1K
𝒒
o 𝑪=
𝜟𝑻
 Specific Heat Capacity
o Heat required to change the temperature of 1g of a substance by 1K
𝒒
o 𝒄=
𝒎𝜟𝑻
 Practice of Calorimetry
o Calorimeter – equipment used to measure the heat released/absorbed by a physical/chemical process
o Constant-Pressure Calorimetry
 Determine the c of a solid (do not react/dissolve in water) using Styrofoam-cup
 −𝒒𝒔𝒐𝒍𝒊𝒅 = 𝒒𝒘𝒂𝒕𝒆𝒓
 −(𝒎𝒂𝒔𝒔𝒔 × 𝒄𝒔 × 𝜟𝑻𝒔 ) = 𝒎𝒂𝒔𝒔𝒘 × 𝒄𝒘 × 𝜟𝑻𝒘
o Constant-Volume Colorimetry
 Determine the heat released in combustion
Stoichiometry of  Thermochemical Equations – Balanced equation that states the ΔHrxn
Thermochemical Reactions  Aspects of ΔH
o Sign of ΔH depends on the reaction of the change (endothermic/exothermic)
o Magnitude of ΔH is proportional to the amount o substances in the reaction
Hess’ Law of Heat  The enthalpy change of an overall process is the sum of the enthalpy changes of its individual steps
Summation  Hess Law – the difference between the enthalpies of the reactant & the product has the same value even though the
reaction takes place differently
 Calculating Unknown Enthalpy
o Identify target equation, no. of moles of reactant & products
o Manipulate equation of known ΔH
o Add manipulated equation to obtain target equation (unknown ΔH)
 Standard Heats of Reaction (ΔH°rxn)
o Measured with all substances in standard states
o Standard States are used to compare heats or reaction & other thermodynamic data
 Gas Standard (1 atm), Aqueous Solution Standard (1M), Pure Substance Standard (1 atm, 25°C)
 Formation Equations & Their Standard Enthalpy
o 1 mol of compound forms from its element
o Standard heat of formation (ΔH°f) – enthalpy change accompanying the formation equation
 Determining ΔH°rxn from ΔH°f values of Reactants & Products
o 𝜟𝑯𝟎𝒓𝒙𝒏 = ∑ 𝒎 𝜟𝑯𝟎𝒇 (𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔) − ∑ 𝒎 𝜟𝑯𝟎𝒇 (𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔)

Chemical Thermodynamics
Chemical Thermodynamics  Limitations of 1st Law of Thermodynamics
o Tells only the amount of heat released/absorbed & work done by system
o Sign of enthalpy is not enough to predict whether the reaction will proceed
o Enthalpy is not the only factor governed
 Reactants/Product favoured  change in randomness or disorder in reaction is considered
Spontaneous Process  Chemical/Physical change occurs by itself
o Occurs without any outside intervention
 Affected by Temperature
Entropy, S  Measure of randomness/disorder of a system
(state of function)  Dependent on pressure & temperature
 Randomness/Disorder of System
o Solid – regular structure than liquids
 Liquids > disordered than Solids
o Gas – particles in random motion
 Gas > disordered than Liquids
o No. of Particles ↑, Disorder ↑
 Entropy Change 𝜟𝑺 = 𝑺𝒇 − 𝑺𝒊
o ΔS > 0, system more disordered
o ΔS < 0, system less disordered
Molecular Interpretation  Structure & behaviour of molecules affect entropy of the system
of Entropy  Reaction leads to decrease in number of gaseous particles generally, decreases entropy
o 2A + B  2C
o ΔS = -ve, 3 mol of gas forms 2 mol of gas
 Formation of new bonds decreases the degree of freedom/forms of motion (atoms are less free to move randomly)
o No. of freedom of system ↑, S↑
 3 Types of Motion (Freedom of Motion)
o Translational
o Vibrational
o Rotational
 Temperature ↑, S↑
o Ssolid < Sliquid < Sgas
o S↑ when
 Liquids/solutions are formed from solids
 Gases are formed from either solids/liquids
 No of molecules of gas increases in a reaction
Calculation of ΔS  𝜟𝑺𝟎 = ∑ 𝒎𝑺𝟎 (𝑷𝒓𝒐𝒅𝒖𝒄𝒕𝒔) − ∑ 𝒏𝑺𝟎 (𝑹𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔)
Second Law of  Law – Total energy of a system & its surroundings always increases for a spontaneous process
Thermodynamics o Energy - cannot be created/destroyed
o Entropy - created during spontaneous/natural process
𝒒
 𝜟𝑺 = 𝒆𝒏𝒕𝒓𝒐𝒑𝒚 𝒄𝒓𝒆𝒂𝒕𝒆𝒅 +
𝑻
o ΔS > q/T – spontaneous process
 Law* – for a spontaneous process at a given temperature, change in entropy of the system is greater than the heat divided
by the absolute temperature, q/T
ΔS for Phase Transition  Under equilibrium conditions, no significant amount of entropy is created
o ΔS results only from absorption of heat
𝒒
o 𝜟𝑺 =
𝑻
o E.g. Vaporization of Liquid, Fusion of Solid
Gibbs Free Energy  𝑮 = 𝑯 − 𝑻𝑺
 𝜟𝑮 = 𝜟𝑯 − 𝑻𝜟𝑺 – at constant T
 If T & P are constant
o ΔG = -ve - Reaction is spontaneous in forward reaction
o ΔG = +ve - Reaction in the forward reaction is non-spontaneous, work must be supplied
- Reverse reaction is spontaneous
 Standard Free Energy Change
o Quantity of ΔG0 shows whether mixture of reactants & products:
 Spontaneously react in forward direction to produce more products (ΔG0 < 0)
 Spontaneously react in reverse direction to form more reactants (ΔG0 > 0)
Free Energy &  From 𝜟𝑮 = 𝜟𝑯 − 𝑻𝜟𝑺 , ΔH & ΔS change very little with T, but T affects the magnitude of -TΔS
Temperature o As T ↑, -TΔS ↑
Free Energy & the  Uses:
Equilibrium Constant o To calculate value of ΔG under non-standard conditions using ΔG0
o Directly relate the ΔG0 for a reaction to the value of the equilibrium constant for the reaction
 Most chemical reaction occur at non-standard conditions
o 𝜟𝑮 = 𝜟𝑮𝟎 − 𝑹𝑻 𝐥𝐧 𝑸
o Q = reaction quotient that corresponds to the particular reaction mixture of interest
 aA + bB ⇋ pP + qQ
[𝑷]𝒑 [𝑸]𝒒
o 𝒆𝒒𝒖𝒊𝒍𝒊𝒃𝒓𝒊𝒖𝒎 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕, 𝑲 =
[𝑨]𝒂 [𝑩]𝒃
o At Equilibrium
 ΔG = 0, Q = K
 ΔG = ΔG0 + RT lnQ
 0 = ΔG0 + RT lnK
 ΔG0 = - RT lnK
−𝜟𝑮𝟎
 𝑲=𝒆 𝑹𝑻
Electrochemistry – Relationship Between Electricity & Chemical Reactions
Oxidation & Reduction
Oxidation & Reduction
(REDOX)
OIL – Oxidation Lose
Electron
RIG – Reduction Gain
Electron
Balancing Net Ionic Equations for REDOX Reaction in Acidic Solution
Balancing
Electrochemical Cell
Electrochemical Cell
Shorthand Notation
Shorthand Notation
Cell EMF
Cell EMF
 Transfer of electrons during redox reaction produces energy in the form of electricity
 Determine Redox Reaction
o Oxidation Number
 Oxidation Number ↑, Oxidation Substance: Reducing Agent
 Oxidation Number ↓, Reduction Substance: Oxidizing Agent
Rules
State Oxidation Number
Atom in Elemental Form 0
Monoatomic Ion Equals to Charge of Ion
Group 1a, Group 2a, Group 3a +1, +2, +3 Respectively
Oxygen (Molecular & Ionic) -2
Peroxides -1
Hydrogen (Bonded to Metals) -1
Hydrogen (Bonded to Non-Metals) +1
Fluoride Ions -1
Halides (Binary Compounds) -1
Halides (Oxyanions) + Values
Neutral Compound 0
Polyatomic Ion Equals to Charge of Ions
 Oxidation & Reduction are divided into half-reactions
o Balance charge & number of each type of atom
o Add electrons to the side that is more positive/less negative
o Combine to form balanced net ionic equation
 Consists of 2 electrodes & an electrolyte
 2 types:
o Voltaic Cell - produces electricity as a result of spontaneous reaction
Zn + CuSO4  ZnSO4 + Cu
Zn  Zn2+ + 2e Cu2+ + 2e  Cu
Zn Oxidised (Lose e) Cu Reduced (Gain e)
[Zn] ↓ [Zn2+] ↑ [Cu2+] ↓ [Cu] ↑
Anode Cathode
 Salt Bridge/Porous Barrier used for neutralising charge
o Electrolytic Cell - non-spontaneous reaction is driven by an external source of no current
 To describe components of an electrochemical cell
o Example: Zn|Zn2+||Cu2+|Cu|
o LHS – Oxidation (Anode) RHS – Reduction (Cathode)
 Electron flows through the external circuit due to:
o Difference in potential difference
o Potential energy of e is higher at the anode
o Electron flows from high potential energy to low potential energy
𝑼
 𝑬𝒄𝒆𝒍𝒍 = 𝑽 =
𝒒
o Ecell depends on:
 Specific reactions occur at cathode-anode
 Concentration of reactants & products
 Temperature
 Under standard conditions, EMF is stated as E0cell
Standard Reduction Potential
Standard Reduction
Potential
EMF & Free Energy Change
EMF & Free Energy Change
Electrochemical Decomposition
Electrolysis  Electricity passed through a molten ionic compound/electrolytic solution
 Cell Potential
o 𝑬𝟎𝒄𝒆𝒍𝒍 = 𝑬𝟎𝒓𝒆𝒅 (𝒄𝒂𝒕𝒉𝒐𝒅𝒆) − 𝑬𝟎𝒓𝒆𝒅 (𝒂𝒏𝒐𝒅𝒆)
 Reference half-reaction is the reduction of H+ to H2 under standard conditions (Standard Hydrogen Electrode SHE)
o E0red = 0V
 Oxidation of Zn & Reduction of H+ Changing the stoichiometry coefficient does
o Zn|Zn2+ (anode) & SHE (cathode) not affect the standard reduction potential
o Cell voltage = 0.76V
o 0
E red of H + = 0V
o E0cell = E0red (cathode) - E0red (anode)
o E0red (anode) = -0.76V
 E0red provides a measure of driving force for a reduction to occur
o More +ve E0red, driving force for reduction ↑
o Spontaneous operation – cathode must have more +ve E0red
than the anode
 E0cell is the difference between the standard reduction potential of the
cathode reaction & anode reaction
o Voltaic Cell – Cathode reaction will be the higher on the
scale
 The more +ve the value for half-reaction, the greater the tendency for the reactant of the half-reaction to be reduced
 Li+ is the hardest to reduce (poor oxidising agent), easy to oxidise (good reducing agent)
o E0red = +ve Easy to Reduce (Strong Oxidising Agent)
o E0red = -ve Easy to Oxidise (Strong Reducing Agent)
 𝜟𝑮 = −𝒏𝑭𝑬
o Positive E gives Negative ΔG
o +E, -ΔG indicates spontaneous reaction
o DC source act as an ‘electron pump’, pulling e from one electrode & pushing it through external wiring to the
other electrode
o Positive electrode becomes the anode, Negative electrode becomes the cathode
 Electrolytic Cell vs Galvanic Cell
o Electrode
 EC: Cathode (-), Anode (+) GC: Cathode (+), Anode (-)
o Electrolysis in Aqueous Solution
 Consider oxidation & reduction of solute as well as oxidation & reduction of water
o Stoichiometry of Electrochemical Reactions
 Amount of chemical change that occurs during electrolysis is directly proportional to the amount of
electric charge that is passed through an electrolysis cell
𝑰𝒕
 Calculated using Faraday’s Law 𝑨𝒎𝒐𝒖𝒏𝒕 𝒐𝒇 𝑷𝒓𝒐𝒅𝒖𝒄𝒕 =
𝒏𝑭
Functional Groups
Functional Group  Atom / group of atoms with characteristic chemical & physical properties (reactive part of the molecule)
Determines:  Most organic compound have C – C & C – H bonds
 Bonding & shape  Structural Features – determine molecular geometry, physical properties, reactivity and include functional group
 Type & strength of o Heteroatoms
IMF  Atoms other than C & H
 Physical properties  Have lone-pairs
 Nomenclature  Create electron-deficient sites on carbon
 Chemical Reactivity o π Bonds
 Most occur in C – C & C – O double bonds
 Easily broken in chemical reactions
 Makes a compound a base & nucleophile
 Ethane
o Only C – C & C – H bonds (no functional group)
o No polar bonds, lone pairs & π bonds
 Ethanol
o Has OH group (hydroxyl group) attached
o Has lone pairs, polar bonds which makes it reactive
Hydrocarbon  Alkane
 Alkene
 Alkyne
 Aromatic Compound
o Has strong characteristic odour
o E.g. Benzene
o Benzene group + Attached group  phenyl
group

C – Z σ Group

C = O Group  Carbonyl Group

o Polar C – O bond makes the carbonyl carbon an electrophile
o Lone pairs on O allow reaction as a nucleophile & base
o Contains π bonds > easily broken than C – O σ bond
Physical Properties of  Boiling Point
Organic Compounds o Temperature at which liquid molecules are converted to gas
o Energy needed to overcome IMF in liquid state (IMF ↑, B.P ↑)
o Same Molecular Weight:
 Van Der Waals’ < Dipole-Dipole < Hydrogen Bonding
o Same Functional Group:
 Surface Area ↑, B.P ↑
 Polarizability ↑, B.P ↑
 Melting Point
o Temperature at which solid is converted to liquid
o Energy neede to overcome IMF in solid state (IMF ↑, M.P ↑)
o Same Functional Group:
 Symmetry ↑, M.P ↑
o Ionic Compounds have high M.P due to strong interactions
o Covalent Compounds depends on identity of functional group
 Same Molecular Weight:
 Van Der Waals’ < Dipole-Dipole < Hydrogen Bonding
 Solubility (Most ionic compound are soluble in water & not in organic solvents)
o Organic compound are water soluble when one polar functional group capable of HB with solvent for every 5 C
atoms it contains

o Size (C ≤ 5) of organic compound with a polar functional group determines its water solubility

Influence of Functional  Functional groups contain a heteroatom, π bond which creates electrophillic sites & nucleophillic sites
Groups on Reactivity

electronegative heteroatom makes C electrophillic

lone pair on heteroatom makes it basic & nucleophillic

π bonds create nucleophillic sites & are easily broken than σ bonds
 Electrophillic C reacts with Nucleophile (:Nu-)

 Nucleophillic C reacts with Electrophile (E+)

Acids & Bases
Brownsted-Lowry Acid &  Brownsted-Lowry Acid = proton donor
Bases  Brownsted-Lowry Base = proton acceptor
(proton = H+) o Donates electron pair to a proton
 Brownsted-Lowry Acid Base reaction results in
the transfer of a proton from acid to a base
o One bond is broken, another is formed
o Electron pair of the base B – forms a new
bonds to the proton of acid
o Acid H – A loses a proton, leaving the
electron pair on A

Lewis Acids & Bases  Lewis Acid = electron pair acceptor

o Accepts electron pair due to unfilled valence shells

o
 Lewis Base = electron pair donor
o Donates electron pair to electrophile

o
 All Brownsted-Lowry Acid are Lewis acid but the reverse is not always true
o Species that are electrophilic & capable of accepting electron pair are Lewis acid
Structure & Bonding
Bonding  Joining of 2 atoms in a stable arrangement
 Atoms attain complete outer shell of valence electrons & stable noble gas configuration
 Ionic bonds - transfer of electrons from 1 element to another
 Covalent bonds - sharing of electrons between 2 nuclei
Lewis Structure  Electron representations for molecules
o Draw valence electron
o Give second row element octet configuration
o Give H 2 electrons
Formal Charge  Charge assigned to individual atoms in a lewis structure
 𝒇𝒐𝒓𝒎𝒂𝒍 𝒄𝒉𝒂𝒓𝒈𝒆 = 𝒏𝒐. 𝒐𝒇 𝒗𝒂𝒍𝒆𝒏𝒄𝒆 𝒆𝒍𝒆𝒄𝒕𝒓𝒐𝒏𝒔 − 𝒏𝒐. 𝒐𝒇 𝒆𝒍𝒆𝒄𝒕𝒓𝒐𝒏𝒔 ′𝒐𝒘𝒏𝒆𝒅′

Isomers  Different molecules having the same molecular formula

Resonance  2 Lewis structure having the same placement of atoms but a different
arrangement of electrons
 True resonance is a composite of both resonance forms (resonance
hybrid)
o Allows certain electron pairs to be delocalized over several atoms
 adds stability
o Molecule with ≥2 resonance forrms is called resonance stabilized
 Basic Principles
o Individual resonance does not accurately represent structure of ion/molecule (Hybrid does)
o Resonance structures are not in equilibrium with each other (no movement from one form to another)
o Resonance structures are not isomers
Drawing Resonance  2 resonance structure differ in position of multiple bonds & non-bonded electrons, placement of atoms & single bonds
Structures always stays the same
 2 resonance structures have the same number of unpaired electrons
 Resonance structures must be valid Lewis structure
 Curved arrow notation
o Shows how electron position differs between 2 resonance forms
o Shows movement of electron pair
Drawing 3D Structures  Line
o Solid – bond in the plane of the paper
o Wedge – bond in front of the plane
o Dashed – bond behind the plane

Condensed Structures  All atoms are drawn but two-electron bond lines are omitted
 Atoms are drawn next to the atoms to which they are
bonded
 () are used around similar groups bonded to the same atom
 Lone pairs are omitted

Skeletal Structures  Assume C atom at junction of 2 lines or at the end of any

line
 Assume there are enough H around C to make tetravalent
 Draw all heteroatoms & H directly bonded to them
Alkanes
Alkanes  Aliphatic hydrocarbons having C – C & C – H σ bond (categorised as acyclic/cyclic)
 Acyclic
o CnH2n+2
o Only linear & branched chains of C
o Saturated Hydrocarbons – having maximum number of H per C
 Cycloalkanes
o CnH2n
o C joined in one/more rings
o Fewer H atoms for the same no. of C
o NAMING : cyclo-name

o
 C atoms in alkane are surrounded by 4 groups & all bond angles are 109.5°

o
Nomenclature  3 Parts
o Parent Name - No. of C in the longest continuous chain
o Suffix - Functional group
o Prefix - Identity, location & no. of substituents attached to the main chain
 Alkyl Group
o C subtituents bonded to a long C chain
o Formed by removing 1 H from an alkene
o NAMING: name-yl
 NAMING ALKANE
o Longest chain (add suffix) with more subtituents;
o Lowest number for 1st substituent, if same distance;
o Lowest number for 2nd substituent, if same distance;
o Assign name alphabetically to 1st substituent;
o Name & number substituents
o (No., Alphabet)Substituent – Parent – Suffix
 NAMING CYCLOALKANE
o Parent cycloalkane
o Name & number substituents (no number needed for 1 substituent)
 If more than 1 substituent, number at one substituent & proceed around (2nd substituent lowest number)
 Assign lower number substituent alphabetically
 NAMING COMPOUND WITH RING & LONG CHAIN
o Proceed with higher no. of C
o Name & number substituents (no number needed for 1 substituent)
 If ≥ 1 substituent, number one substituent & proceed around (2nd substituent lowest number)
 Assign lower number substituent alphabetically
Physical Properties of  Boiling Point
Alkanes o Lower BP compared to more polar compounds of similar molecular weight (Lower IMF)
o No. of C ↑, Surface Area ↑, BP↑
Oxidation of Alkanes  Oxidation
o Increases C – Z bonds
o Decreases C – H bonds
 Reduction
o Decreases C – Z bonds
o Increases C – H bonds

Combustion of Alkanes  Alkanes + O2  CO2 + H2O

Isomers
Isomers
- different compounds,
same molecular formula
Stereochemistry
Chiral – mirror but not
identical
Achiral – mirror & identical
Enantiomers –
stereoisomers that are
non-superimposable
(mirror of each other)
Diastereomers –
stereoisomers that are not
enantiomers
(not mirror of each other)
 Constituitional Isomers
o Different IUPAC name, same/different functioanl group, different physical & chemical properties
 Stereoisomers
o Differ only in atom arrangement, same IUPAC name (except for prefix), same functional group
 3D structure of molecule
o Minor differences in 3D structure results in different properties
 Chiral Molecules – molecules that is not superimposable on its mirror image
o 1 Stereogenic centre (≥2 may/may not be chiral)
o A & B are stereoisomers (enantiomers)
o
 Achiral Molecules – molecules that is superimposable on its mirror image
o Contain plane of symmetry
o
 Stereogenic Centre
o C atom with 4 different groups in a tetrahedral
o Larger organic molecules can have ≥2 stereogenic centre
o
o Max stereoisomers is 2n, n = stereogenic centre
 Designation of R & S on Enantiomers (Precede IUPAC Name of Molecule)
o Priority to group bonded to stereogenic centre based on atom of highest atomic number, if 2 same atoms;
o Priority given to atom of highest number bonded to atoms bonded to stereogenic centre
 Atom of Multiple Bond
 Treat multiple bonded atoms as equivalent single bonded atoms
o Orient lowest prioritygroup on back
o Trace circle from higher priority to lower priority
 Clockwise - R isomer
 Anticlockwise - S isomer
 Meso Compounds – compounds with plane of symmetry (achiral)
o
  Physical Properties of Stereoisomers
o Enantiomers
 Chemical & physical properties are the same except when interacting with chiral substances
 Identical physical properties except when interacting with plane-polarized light
 Plane Polarized Light - Light with electric vector that oscillates in a single plane
o Achiral Compounds
 Light exits tha sample tube remains unchanged
 Compound that does not change the plane of polarized light is optically inactive


o Chiral Compounds
 Plane of polarized light rotates at an angle α (observed rotation)
 Compound that rotates polarized light is optically active
 Rotation can be clockwise/anti-clockwise
 2 enantiomers rotate plane-polarized light at an equal angle but opposite directions

Understanding Chemistry Organic Reactions

Writing Equations for  Reagent, chemical substance with which organic
Organic Reactions compounds react is sometimes drawn on the left
side of the equation with other reactants &
sometimes reagent is drawn above the arrow
 Solvent & temperature are added above/below
the arrow
 ‘hv’ & Δ are used for reactions that require light &
heat respectively

 2 sequential reaction carried without

intermediate compound are numbered

Types of Organic Reactions  Subtitutions

o reaction where atom(s) is replaced by other atom(s)
o Y replaces Z on C atom
o 1 σ bond breaks another forms at the same C

 Elimination
o Reaction where elements of starting material are ‘lost’ & π
bonds are formed
o X & Y are removed from starting material
o 2 σ bonds breaks & π bond forms

 Addition
o Reaction where elements are added to the starting material
o X & Y are added to starting material
o π bond breaks & 2 σ bonds are formed

 Reaction Mechanisms
o Detailed description of how bonds are broken & formed as starting material converted to product
o Concerted Reaction (One-Step Reaction)
 starting material directly converts to product
o Stepwise Reaction (> 1 Step Reaction)
 starting material is converted to reactive intermediate & then to product
Bond Breaking  2 ways to break bond
o Homolysis/Homolytic Cleavage : Electrons in bond divided equally between 2 atoms
o Heterolysis/Heterolytic Cleavage : Electrons in bond divided unequally between 2 atoms
 Homolysis & Heterolysis require energy
o Homolysis generates uncharged reactive intermediates with unpaired electrons
 Generates 2 uncharged species with unpaired electron
 Reactive intermediate with unpaired electrons is called a radical
o Heterolysis generates charged intermediates
 Generates carbocation/carbonion
 Carbocation contains C surrounded by 6 electrons
 Carbonion has C with negative charge

o
o Radical & Carbocations are electrophiles, Carbonions are nucleophile
Bond Making  2 ways to form bond
o 2 radicals donate 1 electron to form two electron-bond
o 2 ions with unlike charges come together with negatively charged ion donating both electrons forming 2 electron-
bond
 Bond Formation releases energy

o
Arrows

Energy Diagrams  A – B + C:-  A:- + B – C

 Ea ↑, rate ↓
Alkyl Halides & Nucleophilic Substitution
Alkyl Halides
- halogen denoted as ‘X’
Nomenclature
Physical Properties
Nucleophilic Substitution
Reaction
 Components
o Alkyl Group
o Nucleophile
o Leaving Group
 Classified based on no.of carbon bonded to halogen
o Primary (1°)
o Secondary (2°)
o Tertiary (3°)
 Naming of Alkyl Halide
o Name longest C chain with Halogen as substituent (more subtituents)
o Lowest number for 1st substituent, if same distance;
o Lowest number for 2nd substituent, if same distance;
o Name & number substituents
o Assign name alphabetically to substituent;
 Boilng Point & Melting Point
o Higher BP & MP than alkanes with same no. of C
o Size of R ↑, Surface Area ↑, BP & MP ↑
o Size of X ↑, Polarizability ↑, BP & MP ↑
 Solubility
o Soluble in organic solvents
o Insoluble in water
 Polar Carbon-Halogen Bond
o Alkyl halides undergo substitution reactions with nucleophile

o Alkyl halides undergo elimination reactions with Bronsted-Lowry Bases

 Negative charged Nu are used as salts with Li/Na/K to balance charge
o
 Sub product bears a +ve charge as neutral necleophile is used
o
 Initially formed sub product readily loses electron in Bronsted Lowry reaction forming a neutral product when sub product
bearing a +ve charge & contain a proton bonded to O/N
o
 Drawing Nucleophilic Sub Product
o Find sp3 hybridized C with leaving group
o Identifu nucleophile/species with lone pair/species with π bond
o Sub nucleophile for leaving group
o Assign charges to atom(s) involved in bond breaking/formation
 Leaving Group
o C – X bond undergo heterolysis cleavage forming X:- (more stable X:-, better accepting electron pair)
o
o The better leaving group is the weaker base
o Periodic Trends in Leaving Group Ability
 LR, Basicity ↓, Leaving Group Ability ↑
 UD, Basicity ↓, Leaving Group Ability ↑
  The Nucleophile
o Structurally similar with bases (both have lone pair/π bond)
o Bases attack proton, Nucleophiles attack electrophiles

o
 Mechanisms for Nucleophilic Substitution
o Bond breaking/formation occur at the same time (2nd Order)


o Bond Breaking before Bond Formation, Carbocation as intermediate (1st Order)


o Bond Formation before Bond Breaking
Types of Mechanisms for  Substitution Nucleophilic Bimolecular (SN2)
Nucleophilic Substitution o Rate of reaction is dependent on concentration of both reactants
o No. of R ↑, Leaving Group ↑, Crowding ↑, Rate ↓

o
o SN2 reactions proceed with backside attack of the nucleophile  inversion of configuration at stereogenic centre

o
 Substituition Nucleophilic Unimolecular (SN1)
o Rate of reaction is dependent on concentration of alkyl halide
o No. of R ↑, Leaving Group ↑, Rate ↑

o Heterolysis forms carbocation intermediate

o Nucleophile attacks carbocation

o Energy Diagram
Carbocation Stability  Classified based on no. of R groups bonded to charged C
o R↑, Carbocation Stability ↑

Predicting Likely
Mechanisms of
Substitution Reaction

Products of SN2
Alkyl Halides & Elimination Reaction
General Features of
Elimination Reaction
Alkenes – Products of
Elimination
 Elimination Reaction  involve loss of elements from starting material to form π bond
o Removal of HX is called dehydrohalogenation (β elimination)
o Common Bases used in Dehydrohalogenation
 Sodium Hydroxide
 Potassium Hydroxide
 Sodium Methoxide
 Sodium Ethoxide
 Potassium Tert-butoxide
o Drawing Product of Dehydrohalogenation
 Find α C (with Halogen)
 Find β C (with Hydrogen)
 Remove H & X
 Form π Bond
 Alkenes are classified based on no. of R atoms bonded to C with double bond
 Due to restricted rotation, 2 stereoisomers of 2-butene are possible (diastereomers)
 2 diastereomers are possible when there are 2 different groups on each end of C=C
 Trans alkenes are more stable than cis alkenes  groups bonded to C=C are further apart reducing steric interactions
 No. of R bonded to C=C ↑, Stability of Alkenes ↑
o Percent of S-character ↑, more readily an atom accepts electron density
o sp2 C more able to accept electron density
o sp3 C more able to donate electron density
o no. of electron donating groups on C able to accept electron density ↑, stability of alkene ↑
Types of Mechanisms  Bimolecular Elimination (E2) – most common for dehydrohalogenation
o 2nd Order Reaction
Regioselective - reaction o Reaction is concerted – bond breaking/formation occur at the same time
that yields predominantly
1 constitutional isomer
when more than 1 is
possible

Stereoselective – reaction o Energy Diagram (CH3)2CBr + -OH  (CH3)2C=CH2 + H2O + Br-

that forms predominantly
1 stereoisomer when more
than 1 is possible

o Strength of Base ↑, Rate of E2 Reaction ↑

o Leaving Group Ability ↑, Rate of E2 Reaction ↑
 Polar aprotic solvents increase rate of E2 reactions

o No. of R groups ↑, Stability of Alkenes ↑, Rate of E2 Reaction ↑

o Zaitsev Rule
 Major product in β elimination has more substituted double bond

 In mixture of steroisomers in dehydrohalogenation, mojor product becomes the more stable isomer
Regioselective - reaction
that yields predominantly
1 constitutional isomer
when more than 1 is
possible
Zaitsev’s Rule applies
o 1st Order Reaction
o Two-step mechanisms
 Bond to leaving group breaks first, π bond forms later
o No. of R Groups on C with leaving group ↑, Stability of Carbocation ↑, Rate of E1 ↑
o Strength of Base ↓, Rate of E1 ↑
o Steps

 Heterolysis of C-I bond forms carbocation

 Base removes a proton from C adjacent to Carbocation, Electron

pair in C-H bond forms π bond
o Energy Diagram

 Comparison

Alkyne Synthesis  Single elimination reaction produces π bond of an alkene

 2 consecutive elimination reactions produce 2 π bonds of alkyne (2 consecutive Dehydrohalognation)

 2 elimination are needed to remove 2 moles of HX from a dihalide substrate

o 2 different starting materials can be used (vicinal dhalide/geminal dihalide)

o Stronger bases are needed to synthesise alkynes by dehydrohalogenation

Alcohols & Ethers
Alcohol  Contains hydroxy group (OH) bonded to sp3 hybridized carbon

 Bent with bond angle at 109.5°

 Naming
o Name longest chain with OH (suffix -ol)
o Number C chain with OH as lowest number
o Name & Number other substituents
o Compounds with > 1 hydroxy group
 2 OH – diols/glycols
 3 OH – triols
 Physical Properties
o Exhibits dipole-dipole interaction
o Capable of Hydrogen Bonding (more polar)
o R ↑, steric hindrance ↑, ability to hydrogen bond ↓
o IMF ↑, BP/MP ↑
o Ability to hydrogen bond ↑, BP/MP ↑
o C ≥ 5, solubility in water ↓
o Soluble in organic solvents
 Interesting Alcohols

Ethers  Contains 2 alkyl group bonded to O

 Bent with bond angle at 111°

 Naming
o Name simpler R as alkoxy substituent
o Name other R as an alkane
 Physical Properties
o Exhibits dipole-dipole interaction
o C ≥ 5, solubility in water ↓
o Soluble in organic solvents
Preparation of Alcohol &  Alcohols & Ethers are common products of nucleophillic substitution
Ethers  Steps
o Alkoxide salt is needed to make ether
o Alkoxide can be prepared from alcohols by Bronsted-Lowry Acid-Base reaction
Reactions of Alcohols
Reactions  Nucleophilic Substitution
o OH (poor leaving group) must be converted to H2O by using strong acid

 Dehydration (using strong acids/POCl3 in amine base)

o Β elimination reaction of OH & H from α C & β C respectively

o R ↑, dehydration ↑
o Dehydration is regioslective & follow Zaitsev’s Rule when involving 2/3 β C
 More substituted alkane is the major product

o 2° & 3° prefer E1 mechanism

o 1° prefer E2 mechanism

Conversion of Alcohol to Alkyl Halide with HX

Conversion  Substitution reaction does not occur unless OH is coverted to a good leaving group
 R ↑, rate with HX ↑

 Steps

 Acidity ↑, Reactivity of HX ↑
Alkenes
Structure & Bonding  Contains C=C bond
o Terminal alkenes have double bond at the end of the C chain
CnH2n o Internal alkenes have at least one C atom bonded to each end of double bond
o Cycloalkene contains double bond in a ring

 Properties
o Restricted rotation around C=C
 Rotation only occurs if π bond breaks then reforms (unfavourable)
o Stereoisomerism
 2 diastereomers are possible when groups on each end of C=C are different

o Stability
 Trans alkenes are more stable
 R ↑, stability ↑
 Unsaturation
o Alkenes are unsaturated because they have fewer than the maximum number of H per C
o Each π bond/ring removes 2 H from a molecule  one deree of unsaturation
Nomenclature  Steps
o Name longest chain with both C in double bond, C=C (suffix -ene)
o Number C chain with double bond as lowest number
 #1 for cycloalkene, continue to next C bond to double bond as #2
o Name & Number other substituents
Physical Properties  Exhibits only Van der Waals’ forces (comparable to alkanes)
 C↑, Surface Area ↑, BP/MP ↑
 Soluble in organic solvents, insoluble in water
 C-C bond between alkyl group and double bond C is slightly polar
o Cis-alkenes are slightly polar, higher BP/BP (soluble in polar solvents)
o Trans-alkenes are non-polar, lower BP/MP
Preparation of Alkene  Prepared from alkyl halides & alcohol via elimination reactions

 Elimination reactions are stereoselctive & regioselective  more stable alkene is formed as major product
 Alkene Reaction  π bond of alkene is broken, 2 σ bonds are formed
 Alkenes are nucleophilic  does not react with nucleophiles/bases, reacts with electrophiles
 C of alkenes are both trigonal planar, added elements can be added from the same side or opposite

Hydrohalogenation
(electrophilic addition)

2 Successive Lewis Acid-

Base Reaction
 HX is electrophilic
 Steps
o Addition of electrophile H+ to π bond

o Nucleophilic attack of Br—

o Markovnikov’s Rule
 For unsymmetrical alkene, electrophillic H+ is added to double bond C with more H

Alkynes
Structure & Bonding  Contains C≡C bond (2π bond & 1 σ bond)
o Terminal alkynes have triple bond at the end of C chain
CnH2n-2 o Internal alkynes have C bonded to triple bond C
 Introduces 2 degree of unsaturation (4 fewer H)

Nomenclature  Steps
o Name longest chain with both C in triple bond, C≡C (suffix-yne)
o Number C chain with triple bond as lowest number
o Name & Number other substituents
Physical Properties  C ↑, surface area ↑, BP/MP ↑
 Soluble in organic solvents, insoluble in water
Preparation of Alkynes  Prepared by elimination reaction
o Using strong base which removes 2 equivalents of HX from vicinal/geminal dihalide thorugh 2 successive E2 reaction

Alkyne Reactions  2 sequential reactions takes place

o Addition of 1 equivalent of reagent forms alkene
o Addition of 2nd equivalent of reagent froms product with four new bonds
 4 Reactions of Alkyne
Hydrohalogenation  2 equivalents of HX are used
(electrophilic addition) o Addition of 1 mole of HX forms vinyl halide
o Addition of 2nd mole of HX forms geminal dihalide

 From addition of 2 equivalent HX, both H bond to the same C

Halogenation  Addition of X2 to alkynes

o Addition of 1 mole of X2 forms trans dihalide (anti addition)
o Addition of 2nd mole of X2 forms tetrahalide
Oxidation & Reduction Reactions of Organic Compounds
REDOX Reactions  Oxidation : increase in number of C-Z bonds (usually C-O bonds) or decrease in C-H bonds
 Reduction : decrease in number of C-Z bonds (usually C-O bonds) or increase in C-H bonds

 For redox reactions involving 2 C, the net change in number of C-H/C-Z at both atoms must be taken into account
o Conversionof alkyne  alkene invloves reduction reaction due to the addition of C-H bonds

Reducing Agents  3 types of reduction differing in how H2 is added

o Addition of H2 (carried out with metal catalyst)
o Addition of 2 protons & 2 electrons to a substrate (dissolving metal reductions)
 H2 = 2H+ + 2e
 Carried out using alkali metal as a source of electrons & Ammonia(l) as source of protons
o Addition of hydride(H-) & proton (H+)
 Hydride reducing agents deliver H- to substrate, proton is added from H2O/alcohol
Catalytic Hydrogenation  Addition of H2 occurs in the presence of metal catalyst

 Catalyst used are metals (Pt, Pd, Ni) absorbed onto finely divided inert solid (charcoal)

o H2 adds in syn addition

 ΔH° of hydrogenation  used to measure the relative stability of 2 different alkenes that are hydrogenated to same alkene
o Hydrogenation of 2 alkenes giving the same alkene, the more stable alkene has the smaller ΔH°

 3 ways H2 can be added to triple bond

Reduction of Alkyne   Alkane formation
Alkane

 Palladium is too reactive to allow hydrogenation of alkyne to stop after one equivalent H2 adds
o A less active Pd catalyst is used (Pd absorbed onto CaCO3 with added Lead (iii) acetate & quinoline)
o One equivalent H2 adds to an alkyne to form cis product

 Reduction of Alkyne  trans Alkene

o Dissolving metal reduction (Na/NH3), the elements of H2 are added in an anti fashion to form a trans alkene

 Summary

Oxidation of Alkenes  Oxidative cleavage of an alkene breaks π & σ bonds of the double bond to form carbonyl compounds

Oxidation of Alkynes  Oxidative cleavage of internal alkyne forms carboxylic acid

 Oxidative cleavage of terminal alkyne forms carboxylic acid & CO2

Oxidation of Alcohols  Oxidation of alcohol forms various carbonyl compounds

o 1° alcohols are oxidised to form aldehydes/carboxylic acids by replacing one/two C-H bonds with C-O

o 2° alcohols are oxidised to form ketone by replacing one C-H with C-O

o 3° alcohols are not easily oxidised due to lack of H on C with OH

Radical Reaction
Radical  Reactive intermediate with single unpaired electron
 Formed by homolysis of covalent bond

 Classification

 R ↑, Stability ↑

General Features  Formed from covalent bonds by adding heat

 Some reactions are carried out in the presence of a radical initiator
o Radical initiator contain weak bond which serves as a source of radicals
 Common radicals : Peroxides
o Heating peroxide causes homolysis of O-O forming 2 RO. radicals
 Radicals react with σ bond & add to π bonds
 Reaction of Radical X. with C-H bond
o Radical X. abstracts H from C-H σ bond to form H-X & carbon radical

 Reaction of Radical X. with C=C bond

o Radical X. adds to π bond of C=C

 Reaction of 2 Radical x.
o 2 radicals react to form σ bond

o Reaction of radical with O

Halogenation of Alkenes  In presence of heat/light, alkanes react with halogens to form alkyl halides
 Mixture of alkyl halides may result from alkane with more than one type of hydrogen

 Monohalogenation occurs when single H on a C has been replaced by halogen

o More than 1 H on a single C with halogen is replaced when excess halogen is used

 Radical halogenation has 3 parts

o 2 radicals are formed by homolysis of a σ bond
o Radical reacts with another reactant to form new σ bond & another radical
o 2 radicals combine forming stable bond
o Removing radicals from the reaction mixture wihout generating new radicals stops the reaction

o Radical halogenation involving ≥2 repeating steps  chain mechanisms

o Steps that lead to product formation  propogation steps
Mechanism  Steps
o Reaction begins with homolysis of weakest bond using light/heat

o 1 radical reacts & forms another radical

o 2 radicals react forming σ bond

Chlorination vs  Chlorination is faster, unselective, yields mixture of products

Bromination  Bromination is slower, selective, yields one major product

Polymers & Polymerization  Radical Polymerization

o C radical is formed by 2-step process
o Chain initiation begins with homolysis of weak O-O bond of peroxide to form RO which then adds to a molecule of
monomer to form a C radical

o C radical formed during initiation adds to another alkene forming new C-C bond & another C radical

o More substituted radical adds to the less substituted end of the monomer (head-to-tail polymerization)