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2013 A Levels H2 Chemistry 9647

Loh Zheng Yi 12S74


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CONTENTS PAGE
1-8. Physical Chemistry (42%) Page

1. Atoms, Molecules & Stoichiometry 2


2. Atomic Structure & Physical Periodicity 6
3. Chemical Bonding 11
4. The Gaseous State 21
5. Energetics & Thermodynamics 24
6. Electrochemistry 28
7A. Chemical Equilibrium 36
7B. Ionic Equilibrium 40
7C. Solubility Equilibrium 48
8. Reaction Kinetics 51
9. Inorganic Chemistry (16%)

9.1 The Periodic Table – Chemical Periodicity 61


9.2 Group II 68
9.3 Group VII 72
9.4 An Introduction to the Chemistry of Transition Elements 74
10. Organic Chemistry (42%)

10.1 Introduction to Organic Chemistry 85


10.2.1 Hydrocarbons – Alkanes 94
10.2.2 Hydrocarbons – Alkenes 98
10.2.3 Hydrocarbons – Arenes 105
10.3 Halogen Derivatives 116
10.4 Hydroxyl Compounds 124
10.5 Carbonyl Compounds 136
10.6 Carboxylic Acids & Derivatives 142
10.7 Nitrogen Compounds 152

**Note: Annexes are not in the syllabus

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1. ATOMS, MOLECULES AND STOICHIOMETRY


1.1 RELATIVE MASSES OF ATOMS AND MOLCULES

Average mass of one atom of an element


 Relative Atomic Mass, Ar = 1
×Mass(12 C) atom
12
Average mass of one atom of an isotope of an element
 Relative Isotopic Mass= 1
×Mass(12 C) atom
12
Average mass of one fomula unit of a substance
 Relative Molecular Mass Mr = 1
×Mass(12 C) atom
12

1.2 MOLE AND AVAGADRO CONSTANT

 One mole of a substance is the amount of substance that contains the same number of particles as there
are atoms in 12g of the carbon-12 isotope
 One mole = 6.02 x 1023 particles (Avogadro's constant, L)
 Molar Mass - Mass of one mole of substance
 Molar gas volume - The volume occupied by one mole of gas at a specified temperature and pressure.
 Molarity - Concentration of a solution/ M

1.3 STOICHIOMETRY

 Empirical formula - The simplest formula of a compound which shows the ratio of the atoms of the
different elements in the compound
 Molecular formula - A compound formula which shows the actual number of atoms of each element in
one molecule of the compound
 Avogadro's law - Equal volumes of all gases under the same temperature and pressure contain the same
number of molecules. V ∝ n

1.4 STOICHIOMETRIC FORMULAS

Units What to find Formula


Particles N(X) = n(x) × NA
dm3 Vol(x) (Gas) = n(x)×24
dm3 Vol (x) (Aq) = n(x) ÷ M
n(x) ÷ [X]
mol/ dm3 [X] or M = n(x)÷Vol(solution)
g/ dm3 [X] = Mass(x)÷Vol(solution)
M×Mr (x)
g Mass(x) = n(x)×M𝑟 (x)
[X]×Vol(solution)
mol n(x) = Vol(x) ÷ 24 @ RTP (22.4 @STP)
Mass(x)
M𝑟 (x)
M×Vol(solution)
N(x)
NA

Finding Mass(X) in a compound C

 n(C) × N(x in C) ×M𝑟 (x)

Finding N(X) in a Y mol of compound C

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 n(C) × N𝐴 ×N(x in C)

Percentage composition of X in a compound C

N(x in C)×A𝑟 (X)



M𝑟 (C)

Percentage composition of Water of crystallization in a compound C

N(H2 O in C)×M𝑟 (H2 O)



M𝑟 (C)

Finding molecular formula

X1 X2 Xn
Mass/100g
No. of mol
Mass(x)
n(x)=
M𝑟 (x)

Mol Ratio
(Mol divided by smallest
number of mol)
Multiplication (If
necessary to make mol
ratio integral)

M𝑟 (C)𝑛
Finding molecular formula  n=
M𝑟 (C)

n(x)
Stoichiometric Ratio  n(Known)

Experimental no. of mols


Percentage Yield  × 100%
n(Theoretical mass)

Mass (Pure Substance present)


Percentage purity  × 100%
Mass(Impure substance)

Percentage purity of acid in a 1.00dm3 solution when concentration of acid is known


Mass (Acid)
 Mass(Impure acid added) × 100%

1.5 TITRATION

 Technique where a solution is added from the burette to the aliquot (solution in the conical flask,
measured with a pipette) until the reactants in the two solutions have reacted completely.
 One of the solutions used will be of a known concentration (standard solution)
 Equivalence point - Occurs when the reactants in the two solutions react according to the stoichiometry of
the reaction. The volume of solution added from the burette is the titre volume
 End point - The point where the indicator changes colour.
 Back titration

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 Known excess of reagent A is allowed to react with an unknown amount of B. The amount of
unreacted A is then determined by titration with reagent C of know concentration.
 Precautions
 Iodine solution should be titrated as soon as it is prepared as iodine is volatile at room temperature
and can readily escape into the air.
 Starch is only added near the end point of thiosulfate-iodine titrations as some iodine may remain
trapped in starch even at end point
 Atmospheric oxidation of iodide ions back to iodine causes the blue-colour to return after titration is
carried out

1.6 REDOX

 Oxidation number of an element in any particular molecule or ion is defined as the electrical charge it
appears to have as determined by a set of arbitrary rules.
 Note that atoms of the same element can have different oxidation numbers in the same compound.
E.g. in thiosulfate, the central sulfur has an ON of +4 and the other sulfur 0.
 Oxidation
 A process whereby a molecule loses electron, resulting in an increase in oxidation number
 Oxidizer  Takes away electrons from a chemical = Itself gets reduced (Causes the oxidation number
of a reactant to increase)
 Oxidized  Loses electrons (Gain in ON)
 Reduction
 A process whereby a molecule gains electron, resulting in an decrease in oxidation number
 Reducer  Loses electrons to another chemical = itself gets oxidized (Causes the oxidation number of
a reactant to decrease)
 Reduced  Gains electrons (Decrease in ON)
 How to calculate ON
 ON(XY)  ON(X) + ON(Y) = 0,  a + b = 0
 Redox reactions
 As the oxidation number of (Element e.g. Iron) (decreased/increased) from (ON) in (Element
Compound) to (resultant ON) in (Resultant element compound), (Element) is (oxidized/reduced).
 E.g. As the oxidation number of Iron increased from +2 in FeCl2 to +3 in FeCl3, Iron is oxidized. (Solids
 Do not split ions up)
 Disproportionation
 A redox reaction in which the same reactant is both oxidized and reduced.
 How to get ionic equations (half cell equations) of redox reactions
 1. Determine the 2 half cell equations
 2. Arrange both half equations in the order the reaction is taking place
 3. Check that electrons appear on alternate sites of the 2 half equations
 4. Multiply by the LCM to balance the electrons so they cancel out when both equations are added
together
 5. Combine the equations
 Oxidizing agents
 Acidified Potassium Dichromate (K2Cr2O7) (thus there are H+ ions present)
 Cr2O72- + 14H+ + 6e-  2Cr3+ + 7H2O
 Orange  Green
 Add Acidified potassium dichromate solution to the unknown solution. If the solution changes
from orange to green, the unknown is a reducing agent.
 Acidified Potassium Permanganate (KMnO4)

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 MnO4- + 8H+ + 5e-  Mn2+ + 4H2O


 Purple  Colourless
 Add acidified potassium manganate (VII) solution to the unknown solution. If the potassium
permanganate solution turns from purple to colourless, the unknown is a reducing agent.
 Reducing agent
 Potassium Iodide (KI)
 2I-  I2 + 2e
 Colourless  Brown/formation of black precipitate
 Add potassium iodide solution to the unknown solution. If the potassium iodide solution changes
from colourless to brown, the unknown is an oxidizing agent.
 Thiosulfate (S2O32-)
 S2O32-  S4O62- + 2e-
 Commonly used in conjunction with Iodine (I2) as a back titration technique
 During the titration, the thiosulfate ions are added from the burette to the flask and reduce
iodine into colourless iodide ions. The solution fades to pale yellow.
 Starch is then added into the flask, causing the solution to turn dark blue.
 Colour change at endpoint is from blue-black to colourless

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2. ATOMIC STRUCTURE & PHYSICAL PERIODICITY


 An element if a pure substance that cannot be split up into two or more simple substances by chemical
processes

2.1 ATOMIC STRUCTURE

 Nucleus is formed by protons and neutrons.


 Z = Proton Number/Atomic Number (number of protons in the nucleus of each atom of an element)
 A = Atomic mass/Nucleon Number (total number of neutrons and protons present in the atom of an
element)
 Atoms of a same element always have the same atomic number
 Isotopes are atoms of the same element with different number of neutrons in the nucleus (Isotopes may be
unstable)
 Relative atomic mass is the ratio of the weighted average mass of an element compared to 1/12 of the
mass of 1 mol of carbon-12 atom.
 Eg. Hydrogen-0, Hydrogen-1, Hydrogen-2
 Isoelectronic refers to atoms/ions or groups of atoms having the same total number of electrons
 Isotonic = Same number of neutrons
 Isotopic = Same number of protons
 Calculating relative abundance
 The relative atomic mass will be given
 Let proportion of first isotope be x, let proportion of 2 nd isotope be (1-x)
 Relative atomic mass = nucleon number1(x) + nucleon number2(1-x)
 X = Relative abundance of isotope1
 Relative atomic mass => (Frequency of occurrence*mass number1) + (Frequency of occurrence*mass
number2)
 Isotopes of an element will display the same chemical behavior
 Electric fields
Charge
 For a charged particle, Angle of Deflection ∝
Mass
 This technique is commonly used to separate isotopes or ions of different charges.

2.2 – ELECTRON SHELLS

 Electrons are particles that move in orbits called quantum shells


 Orbitals are the region of space where you can find electrons 90% of the time
 Principal Quantum Number (n)
 1 to ∞
 Determinant of the main energy level of the electron
 Determines the probability of locating the electron with the distance from the nucleus
 Maximum number of electrons that can occupy each principal quantum shell is 2n 2
 Subshells
 Number of subshells same as that of the principal quantum number (n)
 S,p,d,f,g,h
 Subshells within a given quantum shell differ slightly in energy, with the energy of the subshell
increasing according to the order given above
 Sub-orbitals
 Describes the sub orbitals

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 In alphabets – x,y,z

Orbital Number of sub orbitals


S 1
P 3
D 5
F 7

N= Orbital Number of sub orbitals Max number of electrons (2n2)


1 1s 1 2
2 2s,2p 1+3 8
3 3s,3p,3d 1+3+5 18
4 4s,4p,4d,4h 1+3+5+7 32

 s – Orbital
 Spherical in Shape with no nodal plane (region of zero electron density
 Only one S orbital per S subshell
 p – Orbital
 Each p subshell has 3 p orbitals. No p orbitals in the first quantum shell
 P orbital is dumbbell in shape
 Each p orbital is identical in size and shape but differ in their spatial orientation
 All 3 p-orbitals are degenerate (at identical energy levels)
 d – orbital
 Each d subshell has five d orbitals
 All 5 d orbitals degenerate
 Drawing orbitals (remember to label axis)

1s 2s 2px 2py 2pz

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 Electrons in box diagram (Chromium has 24 electrons)

Chromium:

1s 2s 3p 3s 3p 3d 4s

 Rules
 AUFBAU Principle – Electrons in their ground states will occupy orbitals in the order of their energy
levels. The lowest energy levels are ALWAYS FILLED FIRST.
 4s always filled before 3d
 Pauli Exclusion Principle – A sub-orbital cannot contain more than 2 electrons and the two electrons
sharing the same orbital must have opposite spins.
 Hund’s rule of maximum spin multiplicity – Orbitals in a sub-shell must be occupied singly and with
parallel spins before they can be occupied in pairs.
 Complete orbital is prioritized over incomplete orbitals
 Complete orbital means each sub-orbital has at least 1 electron
 Having only 1 electron in each sub-orbital is more stable than 2 electron shells
 Empty sub-orbital boxes must be drawn
 Electronic configuration (shows the distribution of electrons in various orbitals in an atom)
 Eg. K: 1s2 2s2 2p6 3s2 3p6 4s1
 Of ions
 Write out the electronic configuration
 Add/Subtract the electrons from the outermost shell (means 4s before 3d as 4s orbital, once
occupied by electrons, is repelled to a higher energy level than 3d)

2.3 PHYSICAL PERIODICITY

 Fundamental Considerations
 Electronic configuration
 Effective nuclear charge (Zeff = Z – S); Z = Total nuclear charge, S = shielding effect
 Shielding effect is negligible for electrons in the same outer quantum shell
 Atomic Radii
 Atomic Radii decreases across the period
 As the nuclear charge increases as the number of protons increases, the shielding effect remains
approximately constant as valence electrons are added to the same principal quantum number,
hence the effective nuclear charge increases across the period as the nucleus exerts a greater
attraction for the valence electrons, hence the atomic radii decreases across the period.
 Atomic Radii increases down the group
 Down the group, the number of quantum shell increases, thus the nucleus exerts a smaller
attraction for the valence electrons, hence the atomic radii increases.
 Ionic Radii
 Ionic Radii decreases from group 1 to group 3
 Group 1 to Group 3 elements are electropositive metals which form ions by losing their valence
electrons. The nuclear charge increases from group 1 to group 3 due to an increase in protons,
but since the shielding effect remains approximately constant as all the ions have the same
number of electrons, the effective nuclear charge increases from group 1 to group 3 and the
nucleus exerts a greater attraction on the valence electrons, hence the ionic radii decreases from
group 1 to group 3.
 Ionic Radii decreases from group 5 to group 7

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 Group 5 to group 7 elements are electronegative elements that form ions by gaining electrons to
attain a noble gas electronic configuration. The nuclear charge increases from group 5 to group 7
due to an increase in protons, but the shielding effect remains approximately constant as all the
ions have the same number of electrons, hence the effective nuclear charge increases from group
5 to group 7 and the nucleus exerts a greater attraction on the valence electrons, hence the ionic
radii decreases from group 5 to 7.
 Ionic Radii increases from the group containing groups I, II, III to the group containing groups V, VI, VII
 The anions have one more quantum shell than the cations, thus the anions’ nucleus exerts a
smaller attraction for the valence electrons, hence the ionic radii increases.

2.4 – IONISATION ENERGY

 Ionization energy of an element is the energy required to remove 1 mole of electrons from 1 mole of
gaseous atoms to form 1 mole of unipositively charged gaseous ions.
 X(g)  X(g)+ + e
 X(n-1) (g)  X(g)n+ + e
 Factors affecting ionization energy of an atom
 Nuclear Charge Z
 The larger the nuclear charge, the stronger the attractive forces between the nucleus and the
electrons to be removed, thus the greater the ionization energy.
 Size of atoms
 The smaller the atom, the stronger the attractive forces between the nucleus and the electrons
to be removed, thus the greater the ionization energy.
 Successive IE
 Gradual increase as electrons are removed from the same electron subshell
 Increases due to an increasingly charged positive ion as number of protons get increasingly more
than the number of electrons. More energy is required to remove another electron from the
increasingly positively charged ion, thus resulting in a higher ionization energy.
 Massive increase once electrons are removed from the next inner shell
 Due to the ion being much smaller than the previous ion as a quantum shell is removed, resulting
in an increase in attractive forces between the nucleus and electrons to be removed, thus the
large jump in IE
 Slightly steeper increase from an electron subshell at a higher energy level to an electron subshell at a
lower energy level
 The electrons from the electron subshell at a lower energy level are closer to the nucleus than
the electrons from the electron subshell at a higher energy level, thus the nucleus exerts a
stronger attraction on them, which leads to a higher ionization energy.

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 Trends in the first IE of successive elements


 IE decreases down the group
 Down the group, the atomic radii increases due to an increase in the number of quantum shells.
Therefore, the electrostatic forces of attraction between the nucleus and outermost electron are
weaker and less energy is required to remove this electron.
 Across the period, IE increases
 As the nuclear charge increases as the number of protons increases, the shielding effect remains
approximately constant as valence electrons are added to the same principal quantum number,
hence the effective nuclear charge increases across the period as the nucleus exerts a greater
attraction for the valence electrons, hence causing the increase in first ionization energy across
the period.
 Abnormalities
 DIP FROM GRP II TO GRP III (BERYLLIUM TO BORON)
 Be:

1s 2s
 B:

1s 2s 2p
 As the 2p shell has a higher energy than 2s, and since there are weaker electrostatic forces of
attraction between the nucleus and the outermost electron, less energy is needed to remove the
electron in the 2p shell than in 2s shell
 DIP IN IE OF NITROGEN TO OXYGEN (GRP V TO GRP VI)
 N:

1s 2s 2p
 O:

1s 2s 2p

 Oxygen has an extra electron in the P shell which is paired.


 This causes inter-electronic repulsion within that 3p orbital hence less energy is required to
remove the paired electron from the 3p subshell in the atom in group VI. Hence lower first
ionization energy is required.

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3. CHEMICAL BONDING
 The purpose of bonding
 Achieve a noble gas electronic configuration
 Valence electrons of atoms involved in bonding
 Types of bonds
 Ionic bonds
 Covalent bonds
 Metallic bonding
 Ion-Dipole Interactions
 Van Derr Waals forces of intermolecular attraction
 Induced temporary dipole-dipole forces (London Dispersion force)
 Permanent dipole-dipole forces
 Hydrogen Bonding
 Diagrams
 Dot-Cross for Covalent & Ionic
 Lewis for covalent (lone pairs represented by dots)

3.1 – IONIC BONDS

 Ionic bonds (transfer of valence electrons)


 Def: Electrostatic forces of attraction between oppositely charged ions in an ionic compound
 Exist as a ionic compound in the solid state
 Formed between an electropositive element (metals with low ionization energies) and an
electronegative element (atoms with high electron affinity)
 Non-directional bonding  Ions in crystal lattice attracted equally to surrounding ions of the opposite
charge
 It may not include more than two oppositely charged ions
 Ionic compound has already achieved its noble gas electronic equation and is unlikely to bond to
another ion
 Having another ion will cause it to lose its noble gas electronic configuration, which is not desirable
 Strength of an ionic bond
 Lattice Energy – The amount of energy given off when 1 mole of a pure ionic solid is formed from its
constituent gaseous ions
𝑞+ ×𝑞−
 𝐿𝐸 ∝
𝑟+ +𝑟−
 Hence it is dependent on the charge of the ions and the radius of the ions
 Radius of the ions becomes larger further down the group
 Ionic compounds
 Def: Giant ionic lattice consisting of positive ions and negative ions arranged alternately that are held
in a fixed, regular position with strong electrostatic forces of attraction between the positive cations
and negative anions
 High melting point
 Large amounts of energy required to be supplied to overcome the lattice energy to break the
giant ionic lattice to form free ions.
 Ionic compounds solid at room temperature
 Usually soluble (dependent on lattice energy of ionic compound)

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 Due to Ion dipole attraction (Water is a polar molecule), resulting in hydration which releases
energy to break down the ionic crystal lattice and dissolve the ionic compound
 Conducts electricity ONLY in AQUEOUS or LIQUID/MOLTEN form due to the presence of mobile ions
which act as charge carriers.
 Conduction of electricity is done by the ions themselves
 Ionic compounds in their solid state have immobile ions and cannot respond to an electric field.
 Hard and rigid
 Ions held in specific positions throughout the crystal by strong attractive forces, which are not
easily overcome, allowing the salt to resist bending and denting.
 Brittle
 High pressure can cause ions to be displaced, bring ions of like charge next to each other,
resulting in repulsive forces that crack the salt.
 Additional Notes
 Sodium Oxide and Calcium oxide reacts with water to form their respective hydroxides
 Ionic bonds are formed with atoms that have a electronegativity difference bigger than 2.0
 Describing Ionic compounds. XY exists as a giant ionic lattice consisting of positive cations of X and
negative anions of Y arranged alternately and held in a fixed, regular position through electrostatic
attraction. The lattice energy of the ionic bonds between the X cations and Y anions is significantly
high, thus a large amount of heat energy is required to break these ionic bonds and overcome the
forces of electrostatic attraction. Thus, the boiling/melting point is high.

3.2 – METALLIC BONDING

 Occurs between unreacted metals


 Def: Electrostatic forces of attraction between metal cations and a sea of delocalized electrons in a giant
metallic lattice
 Formation of metallic bonds
 Each metal ion delocalizes its valence electrons such that all the metal ions exist in a sea of electrons.
This forms a giant metallic lattice held together by metallic bonding.
 Factors affecting the strength of metallic bonding
 Number of delocalized valence electrons
 Charge density of cation (q/r)
 Properties of metals
 Ductile and malleable
 In metallic structure, the metal ions are held in an orderly array.
 External forces that are applied causes the layers of metal ions in the solid structure to slide past
each other, but the sea of delocalized electrons prevent repulsions between the cations.
 Moderately high melting points
 Attractions between cations and electrons need not be overcome, but only weakened during
melting
 Very high boiling points
 Boiling a metal requires each cation and its electrons to break away from others, forming gaseous
ions
 Conducts electricity
 The motion of mobile electrons when an electric field is applied constitutes an electric current
 Due to delocalized electrons that can respond to an electric field and act as mobile charge
carriers.
 Good heat conductors

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 Delocalized electrons allow for free electron diffusion which increases the rate of heat
conduction.
 Similar structure in both solid & liquid state  metals conduct heat well in both solid & liquid
state
 Luster
 Light excites the electrons into unfilled orbitals, which return to lower energy states by emitting
light of various frequencies, giving metals a shiny mirror-like surface.
 Hardness
 Depends on metallic bond strength.
 Exception – Mercury
 Mercury has had all its electron orbitals filled, therefore it can at most delocalize only 1 electron
 Heat can easily overcome the weak bonds between mercury atoms and make them separate easily
 Alloys
 Sharing of a sea of electrons by the metallic ions of different metals that are mixed evenly
 Properties
 Stronger
 Less ductile and less malleable
 Different sized atoms prevent slip movement from occurring
 Shinier appearance
 Resistant to corrosion
 Lower melting point
 Different sized ions can disrupt the packing of metal cations and reduce the strength of the
metallic bonding, causing the melting point to be lower

3.3 – COVALENT BONDS

 Covalent bonds
 Def: The electrostatic forces of attraction between the nuclei of atoms and their shared pair of
electrons
 Covalent bonds are formed by the overlap of valence atomic orbitals of two atoms that share their
valence electrons such that each attains a noble gas electronic configuration
 Bond length – Distance between the nuclei of 2 bonded atoms when their atomic orbitals overlap to
form molecular orbitals. (dependent on size of atoms)
 Bond dissociation energy
 Def: The amount of energy required to break 1 mole of that covalent molecule
 Dependent on bond length and number of covalent bonds
 Formed by sharing of overlapping electron orbitals
 Containing 1σ and (1-2)π bonds
 There can only be 1 sigma bond between two atoms
 Exceptions to octet rule
 Elements from the 3rd period onwards may have an expanded octet shell
 Available vacant d-orbitals to accept electrons in forming covalent bonds
 Electron deficient molecules (Br,Be) may cluster together and form dative bonds with each other
through the one pair of electrons. Single molecules will not have sufficient electrons to satisfy the
octet rule
 Molecules containing an unpaired lone electrons are highly reactive and are called radicals
(usually have grp VI or VII as the central atom)
 Dative bonds

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 Is a covalent bond formed by an atom sharing a pair of its own electrons with another atom
(usually for electron-deficient molecules and atoms)
 Avoid drawing dative bonds unless covalent bonds result in too many “exceptions”. Choose octet
expansion over dative bonds.
 Dative bonds usually form from less electronegative atoms to more electronegative atoms.
 Valence bond theory

 As the atoms get closer, the nucleus starts to attract the other atom’s electrons, lowering the overall
potential energy of the system.
 Nucleus-electron attraction and nucleus-nucleus and electron-electron repulsion exist simultaneously
 As the distance decreases further, the repulsive forces get more significant
 Optimum internuclear distance  Bond contains the largest amount of energy, system has minimum
potential energy.
 Types of covalent bonds
 Sigma bonds
 Formed by the over lapping of two electronic orbitals head on
 Common forms – S-P, S-S, P-P
 Stronger than pi bond
 Pi bonds
 Formed by two electronic orbital overlapping each other side-on
 Common forms – P-P (can involve d orbitals)
 Weaker than sigma bond
 Side-on overlap less efficient than head-on overlap
 they will break if the bonds rotate
 Covalent structures
 Giant covalent crystals
 Extremely high melting point (higher than that of ionic crystals)
 Covalent crystals are held together by covalent bonds
 Insoluble in water
 Covalent crystals are not made up of ions
 Extremely strong
 May or may not conduct electricity
 Dependent on availability of valence electrons (such as in graphite, where each carbon has 1
valence electron)
 Usually formed by carbon and silicon
 Every atom attains its noble gas electronic configuration
 Special note on graphite – Soft and slippery as layers of carbons are held together by weak van
derr waals forces of intermolecular attraction which can be broken easily.
 Covalent molecules
 Have a low melting point

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 Due to weak intermolecular forces


 Solubility depends on polarity of molecule
 Does not conduct electricity
 Weak

3.4 – VSPER THEORY

 Principles
1. Electron groups around a central atom locate themselves as far away as possible to minimize
electronic repulsion. Each electron group can consist of a lone pair, unpaired electron, double bond,
triple bond, or single bond
2. Extent of repulsions
 Lone Pair-Lone Pair > Lone Pair-Bond Pair > Bond Pair-Bond Pair (Electron density of lone pairs
closer to nucleus than bond pairs)
3. Repulsion between electron pairs dependent on the relative electronegativity of the central and
bonding atoms
 E.g. Bond pairs in NF3 are further away from the central nitrogen atom as compared to ammonia,
which decreases the repulsion between bond pairs, thus decreasing the bond angle. (102°)
 Only applies to shapes of covalent molecules
 N Bond pairs between the same atoms = 1 Electron pair
 Steps
1. Determine the central atom
2. Draw the lewis structure
3. Count the number of electron pairs around the central atom; differentiate the lone and bond pairs
4. Determine the general shape
5. Determine the actual shape with bond angles

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 Shapes
1. Linear (180°)
2. Trigonal Planar (120°)
 Bent (118°)
3. Tetrahedral (109.5°)
 Trigonal Pyramidal (107°)
 Bent (104.5°)
4. Trigonal Bipyramidal (120° , 90°)
 Sea-saw (89°, 103°)
 T-shape (86°)
 Linear (180°)
5. Octahedral (90°)
 Square pyramidal (85°)
 Squar planar (90°)
 Lone pairs and bond pairs always arrange themselves to minimize repulsion. E.g in the compound I 3- , the
3 lone pairs occupy the equatorial positions and the 2 bond pairs occupy the axial positions. Hence the
shape about the central iodine atom is linear.
 Always state “with respect to” which central atom

3.5 – INTERMEDIATE BONDING

 Covalent bonds with ionic character and ionic bonds with covalent characters
 Electronegativity – The relative ability of an atom in a molecule to attract the shared electrons in a
covalent bond. (higher effective nuclear charge  higher electronegativity)
 Polarizability of ions
 The larger the anion, the more easily polarized
 The higher the charge density (q/r), the higher the polarizing power of cations

 Ionic compound with covalent character

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 Cation with high polarizing power causes the distortion of the anion’s electron cloud such that there is
partial sharing of electrons from the polarized anion.
 E.g. Silver Iodide
 Polarity of covalent bonds (covalent bonds with partial ionic character)
 Bond polarity – The separation of positive and negative charges
 Polar bond – Unequal sharing of electrons due to difference in electronegativity of the bonding atoms
 Determined by difference in electronegativity and shape of molecule
 Electronegativity (0.5-2.0 for polar)
 Polar covalent bonds will be formed between two elements of different electronegativity
difference of up to 2.0 (arbitrary cutoff)
 A dipole moment is created towards the more electronegativity element
 Polarity of covalent molecules
 Determined by the presence of polar covalent bonds and the shape of the molecule
 Non-polar molecules
 Typically, if the shape does not contain any lone pairs, the molecule is not polar (due to the polar
bonds cancelling each other out) (methane)
 If dipole moments of polar bonds cancel out then the molecule is also non-polar
(tetrafluoromethane)
 Polar molecules
 Overall net dipole moment
 Molecules with lone-pairs are polar
 E.g. Dichloromethane (Cl2CH2) is polar

3.6 - INTERMOLECULAR FORCES

 Intermolecular forces are very weak compared to covalent bonds/ionic bonds and they determine the
physical properties of molecules
 Instantaneous induced dipole-dipole interactions (London dispersion forces)
 Formed by both non-polar and polar molecules
 Part of Van der Waals forces of intermolecular attraction
 Most significant intermolecular forces for non-polar molecules
 Constant movement of electrons result in an instantaneous distortion of the electron cloud from their
normal symmetrical shapes. This induces a dipole in a neighbouring molecule, resulting in
electrostatic forces of attractions between molecules.
 Also happens in polar molecules, but the significance may be reduced depending on the size of the
electron cloud
 Factors affecting the strength of dispersion forces
 Size of electron clouds
 The greater the number of electrons in the molecules or atoms, the greater the electron
cloud size and the greater the polarizability of the electron clouds, and the stronger the
dispersion forces.
 Molecular shape
 A cylindrical shape results in a larger surface area allowing for more points of contact
between molecules, resulting in stronger dispersion forces (e.g. butane)
 A spherical shape results in the exact opposite (e.g. 2,2-dimethyl propane)
 Magnitude of dispersion forces can be strong enough to allow for a whole lattice of molecules to be
held together as a solid at room temperature.
 Permanent dipole-dipole interactions
 Usually the most significance intermolecular forces for polar molecules

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 Not applicable for non-polar molecules


 Part of Van der Waals forces of intermolecular attraction
 Formed when electrons are mostly concentrated on the more electronegativity ion, hence the more
electronegative ion becomes more negative while the less electronegative ion will be more positive.
This difference in charge causes the more negatively charged site of the molecule to be attracted to
the more positively charged site of another molecule.
 May not be as significant as temporary dipole-dipole forces depending on number of electrons it
contains (E.g. HI has a higher melting point than HBr because its temporary dipole-dipole forces
outweigh its permanent dipole-dipole attraction.
 Factors affecting the strength of permanent dipole-dipole interactions
 Magnitude of dipole moment
 Hydrogen bonding
 Special case of permanent dipole-dipole attraction when the bonds are either H-F, H-N or H-O
 Strongest possible form of permanent dipole-dipole attraction with the H atom having a significant
positive charge and more electronegative ion having a significant negative charge.
 Electrostatic forces of attraction
 Not part of Van Der Waals forces of attraction
 Bonds water molecules to each other tetrahedrally in ice
 PLEASE REMEMBER TO WRITE THE DELTA +/- SIGN TO INDICATE CHARGE (δ) when drawing
 Lone pairs and hydrogen atoms contribute to hydrogen bonding.
 A hydrogen bond, as defined by IUPAC (2011) is the interaction between N-H, O-H or F-H with a
region of partial negative charge, which can be any lone pair of electrons, not just these groups.
E.g. The lone pair of electrons on oxygen in carbon dioxide can contribute to hydrogen bonding.
 Therefore to calculate the number of hydrogen bonds a molecule is capable of making, calculate
the number of lone pairs and hydrogen atoms (attached to O,F,N) per 100 molecules
 E.g. 100 hydrogen fluoride molecules have 300 lone pairs and 100 hydrogen atoms, therefore
they can form 100 hydrogen bonds.
 Types
 Intermolecular (standard)
 Intramolecular
 Formed between proximate polar functional groups in organic molecules.
 This ties up the functional groups of the molecules and prevents them from taking part in
hydrogen bonding, thus resulting in less extensive hydrogen bonding between molecules.
 E.g. 2-Nitrophenol has a lower bp than 4-Nitrophenol
 Can also exist within complex ions
 Effects
 Higher melting and boiling points
 Boiling Point of liquid depends on how many hydrogen bonds one molecule can form with
another. E.g. 2 for oxygen, 1 for ammonia (depends on number of lone pairs and hydrogen atoms
bonded)
 Molecules which can form hydrogen bonds with each other are miscible
 Lower volatility (higher boiling points)
 Allows for dimerisation

3.7 SOLUBILITY

 Depends on the intermolecular forces present


 Ionic compounds dissociate when Ion dipole interactions > lattice energy and are only soluble in
water (ion-dipole attraction does not exist when there is no overall dipole)

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 Take into account enthalpy change of solution (refer to energetic notes)


 Polar solute are miscible only in other polar solvents
 Polar solutes with hydrogen bonds are miscible with polar solvents with hydrogen bonds
 Non-polar solutes will dissolve in non-polar solvents
 E.g. HF hydrogen bonds to water rather than dissociates readily  weak acid
 Insolubility results from weak interactions between the solvent and the solute due to differing
intermolecular forces present, which is insufficient to compensate for the energy required to overcome
the stronger solvent-solvent and solute-solute interactions.

3.8 PERIODICITY

 Melting Point
 Melting point increases from group 1 to group 4, then decreases from group 5 to group 0
 From group 1 to group 3, the elements exhibit metallic bonding, hence large amounts of energy is
required to overcome the strong metallic bonding in order to melt the elements.
 Group 4 elements exist as giant covalent structures that require an even larger amount of energy
to break all the covalent bonds within the structure.
 Group 5 to Group 7 elements exist as covalent molecules, while Group 0 elements exist as atoms.
Such molecules and atoms exhibit weak van der Waals intermolecular forces and only a small
amount of energy is required for the molecules to overcome such forces and melt. Group 0 which
exists as atoms has the smallest electron cloud and thus the weakest instantaneous induced
dipole-dipole interactions and thus the lowest melting point as least energy is required to
overcome these forces.
 In period 3, phosphorus exists as P4 which has a lower melting point than sulfur which exists as S8
as S8 has a larger electron cloud, which increases the strength of its instantaneous induced
dipole-dipole interactions between S8 molecules.
 Electrical Conductivity
 Electrical conductivity decreases across the period
 Group 1 to Group 3 elements are metals that exhibit metallic bonding, hence they have
delocalized electrons within their metallic structure. As the number of electrons delocalized
increases, there are more electricity carriers which increases electrical conductivity.
 Atoms in Group 4 form giant covalent structures and their electrical conductivity is subject to the
availability of mobile valence electrons. *Silicon as a semiconductor can conduct electricity.
 Atoms in Group 5 to 7 onwards form covalent bonds with each other; hence there are no
available mobile valence electrons for the conduction of electricity.
 Atoms in Group 0 do not form any bonds and do not have any valence electrons for the
conduction of electricity

3.9 ADDITIONAL NOTES

 Describing a covalent molecule. XY exists as discrete molecules in room temperature that are held
together by weak Van Der Waals forces/hydrogen bonding. The strength of such Van Der Waals
forces/hydrogen bonds is quite low, thus only a small amount of heat energy is required to overcome
these bonds. Thus, XY has a low boiling point.
 Describing a covalent crystal. SO exists as a giant covalent crystal consisting of a S atom being
tetrahedrally covalently bonded to 4 other O atoms, which are in turn covalently bonded with N S
atoms. Due to the high bond dissociation energies of such covalent bonds, a large amount of heat
energy is required to break all the covalent bonds, thus SO has a high melting point.

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 Hydrogen bonds can exist within ions. E.g. (H2F3)- ion where two HF are hydrogen bonded to each
other and the F- ion.
 How to determine the oxidation number of an atom based on the lewis/dot-cross diagram
 Oxidation number must add up to the total charge of the compound
 Oxidation numbers of the same element may be different, like sulfur in S2O32-. In such a case,
draw out the dot-cross diagram first.
 In polar covalent bonds, the electrons will tend towards the more electronegative element, thus
assign the less electronegative the number of electrons it “loses” as its ON. In the case of sulfur,
the middle sulfur will “lose” 6 electrons, thus the ON of sulfur in the middle is +6

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4. THE GASEOUS STATE


4.1 GAS LAWS AND THE IDEAL GAS EQUATION

 Boyle’s Law (Constant amount and temperature)


1
 𝑃∝
𝑉
 When we have halve the volume of the container, the number of molecules per unit volume will be
doubled, thus the frequency of collisions of the molecules with the walls will also be doubled, causing
the pressure to double.
 When the volume of a container decreases, the distance for the molecules to travel from wall-to-wall
decreases while the frequency of collisions increase, thus increasing the average force exerted per
unit area, which increases the pressure.
 Charles’s Law (constant Pressure and Amount)
 𝑉∝𝑇
𝑇2 𝑉2
 =
𝑇1 𝑉1
 Temperature increase  Volume increase
 A rise in temperature causes the gas molecule’s KE to increase, thus it moves at higher speeds,
thus it will collide more frequently and violently with the inner walls, which will increase the
average force exerted per unit area. For the pressure to remain constant, the gas will expand
eventually if it can.
 Temperature increase  Pressure increase
 A rise in temperature of the gaseous molecules will cause the molecules to gain more kinetic
energy, causing an increase in the speed of the gaseous molecules, thus the gaseous molecules
will bombard the walls more vigorously and frequently, causing the average force per unit area to
increase. Since the volume is fixed, this will result in an increase in pressure.
 Avogadro’s Law (Constant Pressure and temperature)
 𝑉∝𝑛
 Ideal Gas Law
 Ideal Gas: A hypothetical gas whose pressure-volume-temperature behavior can be completely
accounted for by the ideal gas equation, pV = nRT
 Since 𝑃 ∝ 𝑉, 𝑉 ∝ 𝐾, 𝑉 = 24𝑛at RTP

 𝑝𝑉 = 𝑛𝑅𝑇𝑎𝑏𝑠
 Obtainable: Relative Molar Mass, Mass, Concentration, Density
 Molar gas constant, R
 For P in Pa, Volume in cm3, R = 8.31451 J K-1 mol-1
 For P in atm, V in L (dm3), R = 0.0820578
 Since n = Mass/Mr

Mass
 𝑝𝑉 = 𝑅𝑇𝑎𝑏𝑠
Mr
RMassTabs
 Mr =
PV
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 Graphical Representations
 y = mx and y = 1/x graphs
 Combined Gas Equations
𝑃1 𝑉1 𝑃2 𝑉2
 =
𝑛1 𝑇1 𝑛2 𝑇2
 Dalton’s Law of Patial Pressures
 The total pressure of a mixture of gases is the sum of the partial pressures of the constituent gases
𝑛 𝑉
 𝑝𝑎 = ∑ 𝐴 × 𝑝𝑡𝑜𝑡𝑎𝑙 = ∑ 𝐴 × 𝑝𝑡𝑜𝑡𝑎𝑙
𝑛 𝑉
 Using the syringe method to find Mr
 Insert Gas Syringe into furnace
 Furnace keeps gas syringe at a temperature 10 degrees C above the boiling point of the liquid
 Gas syringe contains air, V1 cm3 noted
 Liquid is injected using a weighed syringe, hence mass of liquid injected = (M original – MRe-weighed)
 Liquid vaporizes, causing plunger to move back. Volume of Vapour = V end – V1

4.2 KINETIC THEORY OF GASES

 Assumptions
 The Gas Particles occupy a negligible volume compared to volume of vessel
 Gaseous Particles have negligible intermolecular forces except at instance of collision
 Collisions of particles are perfectly elastic (no lost of kinetic energy, particles do not react with each
other)
 Large number of gaseous particles at all speeds and random motion
 Average kinetic energy of all the gas particles is directly proportionate to absolute temperature
 Deviation from ideal Gas Law

Condition Ideal Gas Real Gas Implications


Volume Ideal Gas Real gases have a Real gases are less compressible than ideal gases, since the
assumes volume definite volume gas particles cannot be forced into a volume of space
is negligible occupied by other gas particles. Hence, real gases deviate
from Ideal gas law at high pressure, due to there being
many gas particles per unit volume.
Larger molecule size  Greater Deviation
Inter- Ideal Gas Real gases have Inter-particle forces are greater at high pressures and low
particle assumes inter- inter-particle temperatures. The stronger the inter-particle forces of
forces of particle forces of forces of attraction, the greater the deviance.
attraction attraction is attraction
negligible Hence, real gases deviate from Ideal gas law at low
temperatures as the gas particles have low speeds and a
low average kinetic energy and are less able to overcome
intermolecular forces of attraction.

As high pressures, the gaseous molecules are close


together, thus intermolecular forces are significant.

Polar molecules have stronger intermolecular forces of


attraction such as permanent dipole-dipole interactions or
hydrogen bonding, which are not negligible

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Large molecules have a large electron cloud, thus they


experience stronger intermolecular forces.

Elasticity of Ideal gases Collisions are


Collisions assumes inelastic due to
perfectly elastic inter-particle
collision forces of
attraction

 Gases thus behave most ideally at high temperatures and low pressures
 Conversion Table

Base Unit
Volume 1 m3 1000 dm3 1 000 000 cm3 1000 L (1L = 1000 cm3)
Pressure 1 Pa (N/m2) 9.86923 x 10-6 Atm 7.50062 x 10-3Torr 7.50062 x 10-3 mmHg
1 Atm 101 325 Pa 760 Torr 760 mmHg
Temperature K -273 °C
Celsius + 273 K
Amount Moles (n)

4.3 MAXWELL-BOLTZMANN DISTRIBUTION CURVE

 Increasing the temperature of a reaction system will increase the velocity and kinetic energy of the
gaseous particles within the system.
 There are still molecules within the system that have low velocities and low kinetic energy.
 This causes the peak to shift to the right and the peak to decrease in height.

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5. ENERGETICS AND THERMODYNAMICS


5.1 ENTHALPY

 Activation Energy - The minimum energy which the reacting particles must possess in order to overcome
the energy barrier before the formation of the products
 Enthalpy – The energy content of a substance
 Endothermic reaction – A reaction in which energy is absorbed in the form of heat
 Exothermic Reaction – A reaction in which energy is released in the form of heat
 Standard Conditions
 Temperature – 298K
 Pressure – 1 atm
 Concentration of any solution – 1.0mol/dm3
 Standard state
 The physical state of a substance at standard conditions
 Have zero enthalpy
 Assumptions
 No heat loss to surroundings
 Heat capacity of any container is 0 unless otherwise specified
 Density of any solution is 1.00g/cm3 and specific heat capacity approximates that of water, 4.18 J g-1 K-1
 Hess law/ Born-Haber cycle (for ionic compounds only)
 The enthalpy change of a particular reaction is determined only by the initial and final states of the system
regardless of the pathway taken
 Electron affinity
 Ability of an atom to attract electrons

Symbol Definition Equation Sign Unit


Heat Capacity C The amount of heat required to
raise the temperature of an
ΔQ=CΔT + J K-1

object by one K/°C


Specific heat c The amount of heat required to ΔQ=mcΔT + J g-1 K-1
capacity raise the temperature of 1g of
the substance by one K/°C
Standard ∆𝐻r𝜃 The enthalpy change when ΔQ ± kJ mol-1
Enthalpy molar quantities of reactants as ∆𝐻 = ±
Change of specified by the chemical 𝑛
Reaction equation react to form
products at standard
conditions.
Standard ∆𝐻c𝜃 The heat evolved when 1 mole + kJ mol-1
enthalpy of the substance is completely
change of burnt in excess oxygen at
combustion standard conditions.
Standard ∆𝐻f𝜃 The enthalpy change when 1 ± kJ mol-1
enthalpy mole of the substance is
change of formed from its constituent
formation elements in their standard
state.
Standard 𝜃
∆𝐻neut The heat evolved when 1 mole 𝐻 + (𝑎𝑞) + 𝑂𝐻 − (𝑎𝑞) → 𝐻2 𝑂(𝑙) + kJ mol-1
enthalpy of water is formed in a
change of neutralization reaction
neutralization

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between an acid and a base at


standard conditions.

**Reactions involving weak acids/bases will be less exothermic as they do not ionize completely in dilute
aqueous solutions and energy has to be used to completely ionize the weak acid/base.

Standard ∆𝑯𝜽atom The energy required when 1 𝑨(𝒔/𝒍) → 𝑨(𝒈) + kJ mol-1


enthalpy mole of gaseous atoms are E.g.
change of formed from the element at 𝑯𝒈(𝒍) → 𝑯𝒈(𝒈)
atomization standard conditions.

The energy required to convert E.g.


1 mole of the compound into 𝐻2 𝑂(𝑙) → 2𝐻(𝑔) + 𝑂(𝑔)
gaseous atoms at standard
conditions.

**Standard enthalpy change of atomization are always positive as atomization involves bond-breaking/phase
change

***Enthalpy change of atomization of noble gases = 0 kJ mol-1

CHEMICAL BONDING DEFINITIONS – REFER TO CHEMICAL BONDING

Bond B.D.E The energy required to break 1 + kJ mol-1


Dissociation mole of a specific covalent
Energy bond in a specific compound in
the gaseous state.

**Bond dissociation energy differs from bond energy in non diatomic molecules as the environment is no
longer the same after the breaking of the first bond.

Bond Energy B.E. The average energy required to + kJ mol-1


break 1 mole of a covalent
bond in the gaseous state.
Lattice L.E. The amount of energy given off 𝑞+ × 𝑞− - kJ mol-1
Energy when 1 mole of a pure ionic 𝐿𝐸 ∝
solid is formed from its 𝑟+ + 𝑟−
+ −
constituent gaseous ions. 𝑋(𝑔) + 𝑌(𝑔) → 𝑋𝑌(𝑠)
+
Ionization I.E. The energy required to remove 𝑋(𝑔) → 𝑋(𝑔) + 𝑒 − + kJ mol-1
energy 1 mole of electrons from 1
mole of gaseous atoms to form
1 mole of unipositively charged
gaseous ions.

*KIV Atomic Structure & Physical Periodicity

Electron E.A. The enthalpy change when 1 𝑿(𝒈) + 𝒆− → 𝑿−


(𝒈) ± kJ mol-1
Affinity mole of elections is added to 1
mole of gaseous atoms to form
1 mole of uninegatively
charged gaseous anions.

**1st E.A. is usually negative as the atom has no net charge and has an affinity for the incoming electron.
Subsequent E.A. is usually positive as and energy is required to overcome the net negative charge of the atom.

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*Grp VII elements have the most negative 1st E.A as they have the highest effective nuclear charge in their
respective period.

Standard ∆𝑯𝜽hyd The heat evolved when 1 mole 𝑿+ +


(𝒈) → 𝑿(𝒂𝒒) - kJ mol-1
enthalpy of free gaseous ions is 𝒒
change of surrounded by water |∆𝑯𝜽hyd | ∝
𝒓
hydration molecules at standard
conditions.
𝜃 𝜃 𝜃 ±
Standard ∆𝐻sol The enthalpy change when 1 ∆𝐻sol = −𝐿. 𝐸. + ∆𝐻hyd kJ mol-1
enthalpy mole of solute is completely
change of dissolved in a solvent to form
solution an infinitely dilute solution at
standard conditions.

 Enthalpy Change of solution involves firstly, the breaking of the ionic lattice, followed by the hydration of
gaseous ions, where energy is evolved as ion-dipole interactions are formed.
 Enthalpy change of solution partially determines the solubility of a salt. (Use this to explain solubility of
ionic compounds in exams)

5.2 ENTROPY

 Definition: The number of ways the energy of a system can be dispersed through the motions of its particles
 More ordered state  Entropy Decreases
 Less ordered state  Entropy increases
 Second Law of Thermodynamics: The total entropy of a system always tends to increase.
 Factors affecting entropy
 Change in temperature
 An increase in temperature increases random molecular motion, thus increasing the average
kinetic energy of the molecules, which increases the number of ways for distributing this energy
among the particles, resulting in an increase in entropy.
 A decrease in temperature decreases random molecular motion, thus decreasing the average
kinetic energy of the molecules, which decreases the number of ways for distributing this energy
among the particles, resulting in a decrease in entropy.
 Change in phase
 Melting increases entropy as the order of the solid is destroyed, resulting in an increase in the ways
that energy can be distributed, thus increasing entropy.
 Vaporization increases entropy as the volume of the substance is increased, which increases the
number of ways for distributing this energy among the particles, resulting in an increase in entropy.
The gaseous state is also the most disordered state.
 Mixing of particles
 Mixing gases and liquids with similar intermolecular forms of attractions causes entropy to increase
as each gas/liquid occupies the whole container and there are more ways in which the
gaseous/liquid particles’ energies can be distributed.
 Expansion of gas
 Pressure is inversely proportionate to volume. A decrease in pressure causes the gas to
spontaneously expand, resulting in an increase in the volume of a gas at the same temperature.
This increases the number of ways in which energy can be distributed among the molecules, thus
increasing entropy.
 Change in the number of particles

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 An increase in the number of particles as a result of a chemical reaction increases the number of
ways the particles can be arranged, thus increasing the number of ways in which energy can be
distributed among the particles, increasing entropy.
 Especially true for decomposition reactions and dimerization.
 Dissolution of an ionic solid
 When an ionic solid is dissolved in water
 Entropy increases as the ions are free about to move in the solution
 Entropy decreases as water molecules that were originally free to move about become
restricted in hydration spheres
 For ions with a single charge, the overall increase in entropy is usually positive

5.3 GIBBS FREE ENERGY

 Determines if a reaction is spontaneous, dependent on both enthalpy and entropy change

 ∆𝐺 = ∆𝐻 − 𝑇∆𝑆
 ΔG – Gibbs Free Energy, expressed in kJ/mol or J/mol
 ΔH – Enthalpy change, expressed in kJ/mol or J/mol
 ΔS – Entropy change, expressed in kJ/mol/K or J/mol/K
 T – Temperature, expressed in Kelvin
 Standard Gibbs free energy change, ΔGΘ is measured at 298k and 1 atm
 Characteristics
 At G < 0 , the reaction is feasible and can take place spontaneously (the reaction is exogenic)
 At G = 0, the system is at equilibrium and there is no net change. (This happens during melting and
boiling)
 At G > 0, the reaction is not feasible and cannot take place spontaneously (the reaction is endogenic)
 Making certain assumptions
 Assume that ΔH and ΔS remain roughly constant regardless of temperature, provided that there is no
phase change
 Under such conditions, there is a large change in ΔH and ΔS

ΔH ΔS Type of reaction Examples


Positive Positive Entropy driven, Feasible Melting, boiling
at high temperatures
Negative Negative Enthalpy driven, Feasible Condensation, Freezing,
at low temperatures Precipitation
Negative Positive Exogenic at all Combustion
temperatures
Positive Negative Endogenic at all Photosynthesis
temperatures

 Kinetics consideration
 Gibbs free energy does not take into account the rate of the reaction
 Kinetic stability – Reaction occurs at a very slow rate
 E.g. While diamond may be unstable compared to graphite, it is kinetically stable and thus does not
change into graphite very fast.

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6. ELECTROCHEMISTRY
*For redox reactions refer to 1.6

6.1 ELECTROCHEMICAL CELL AND COMPONENTS

 Electrochemical Cell: A cell in which the redox reaction is spontaneous and the energy released is
converted into electrical energy
 Components
 Half-cell
 Def: A voltaic cell that contains both the oxidized and reduced species of the electrode reaction
 Oxidation/reduction takes place here
 Anode – Negative Electrode, attracts ions for oxidation
 Cathode – Positive Electrode, attracts ions for reduction
 Each half cell contains 1 half equation
 Eventually, the electrolyte in the anode becomes positively charged as electrons are
continuously removed (oxidation) while the electrolyte in the cathode becomes negatively
charged as electrons are continuously added
 Load
 Converts electrical energy into useful forms (e.g. light bulb)
 Electrons flow from the anode to the cathode
 Salt Bridge
 Releases cations into the electrolyte in the cathode and anions into the electrolyte in the anode
(The cations and anions released are unlikely to be oxidized/reduced as E is negative)
 This balances the excess positive or negative charges in the two half cells, thus maintaining
electrical neutrality
 This also completes the circuit
 The system eventually approaches equilibrium and the voltage decreases to zero

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6.1A TYPES OF HALF-CELLS

 Half-cells are always written as (Oxidized species/Reduced Species)


 Half-cell involving a metal in contact with its relevant cation in aqueous solution
 𝑀 𝑥+ (𝑎𝑞) + 𝑥𝑒 − ⇌ 𝑀(𝑠)
 E.g 𝐶𝑢2+ (𝑎𝑞) + 2𝑒 − ⇌ 𝐶𝑢(𝑠)
 The solid metal will be the electrode in the half-cell
 Half-cell containing a non-metal in contact with its ions in aqueous solution

 𝑋2 (𝑔) + 2𝑒 − ⇌ 2𝑋(𝑎𝑞)
− +
 E.g 𝐹2 (𝑔) + 2𝑒 − ⇌ 2𝐹(𝑎𝑞) ; 2𝐻(𝑎𝑞) + 2𝑒 − ⇌ 𝐻2 (𝑔)
 Half-cell containing ions of the same element in different oxidation states
3+ 2+
 E.g 𝐹𝑒(𝑎𝑞) + 𝑒 − ⇌ 𝐹𝑒(𝑎𝑞) ; 𝑀𝑛𝑂4−(𝑎𝑞) + 5𝑒 − + 5𝐻 + (𝑎𝑞) ⇌ 𝑀𝑛(𝑎𝑞)
2+
+ 4𝐻2 𝑂(𝑙)

6.1B STANDARD HYDROGEN ELECTRODE

 A half-cell with the following components


 Electrode – Platinized platinum electrode (Platinized platinum = finely divided platinum, used to
increase surface area for redox to take place)
 Electrolyte – Solution of 1 mol dm-3 H+ ions, pH = 0
 Hydrogen gas at a pressure of 1 atm and 298K
 Standard Hydrogen Electrode Potential
+
 2𝐻(𝑎𝑞) + 2𝑒 − ⇌ 𝐻2 (𝑔) , 𝐸 𝑜 (𝐻 + /𝐻2 ) = 0.00 𝑉

6.2 ELECTRODE POTENTIAL

 Electrode Potential E – The potential difference associated with a given half-reaction measured relative to
the standard hydrogen electrode
 The half-cell with the relevant elements is connected to the standard hydrogen electrode, and the
potential difference is measured.

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 Convention – If the half-reaction is written with reduction as the forward reaction, the electrode
potential is also known as the reduction potential E (oxidized species/reduced species)
 If the half-reaction is written with oxidation as the forward reaction, the electrode potential is also
known as the oxidation potential Eox (reduced species/oxidized species). Eox = - E
 Intensive property whose value does not depend on amount of electrons being transferred
 Standard Electrode Potential E0 – The potential difference associated with a given half-reaction with all
components in the standard condition measured relative to the standard hydrogen electrode
 Standard Conditions = Temperature of 298K, Pressure of 1 atm for any gas, Concentration of 1 mol
dm-3 for any aqueous ions
 All the rules for E apply for E0
 The more positive the E0 value, the more the equilibrium lies on the right (Forward Reaction >
Reverse Reaction). Hence, the oxidized species is a strong oxidizing agent (e.g. Cl2, F2)
 The more negative the E0 value, the more the equilibrium lies on the left (Reverse Reaction >
Forward Reaction). Hence, the reduced species is a strong reducing agent (e.g Na, Mg)
 Refer to electrochemical series for complete set of reactions
 Standard Cell Potential E0cell : The potential difference between two half-cells measured at standard
conditions
0
 𝐸𝑐ell = 𝐸 0 (reduction half-cell) − 𝐸 0 (oxidation half-cell)
 = 𝐸 0 (reduction half-cell) + 𝐸 0 𝑜𝑥 (oxidation half-cell)
 If E0cell is positive (i.e. > 0), the reaction is feasible
 If E0cell is negative (i.e. < 0), the reaction is unfeasible
 If E0cell is 0, the system is at equilibrium, and no reaction occurs.

Problem Solving Skill I – Determining oxidation and reduction half-


cell equations
1. Select the relevant half-cell equations. Note that one of the species must be on
the left side and the other on the right side (oxidation must be coupled with
reduction). The species present must be inside the half-cell reaction
2. Alternatively, check if the species involved can be further oxidized/reduced
3. Check if the half-cell equation is feasible in an alkaline/acidic environment (if
applicable)
4. Assign [R] to the half-cell equation with a higher E0 value (favours reduction)
5. Assign [O] to the half-cell equation with a lower E0 value (favours oxidation)
6. Combine both half equations to get the overall cell-reaction
7. Calculate E0cell using the formula
 Can be converted into Gibbs Free Energy via this equation ∆G = -neFE0cell (ne = moles of electrons
transferred, F = Faraday’s constant @ 96500 C mol-1)

6.3 LIMITATIONS OF USING STANDARD CELL POTENTIAL

**When describing E, use words such as more positive/less negative instead of decrease/increase

 E0 Does not reflect Kinetic Feasibility, thus even if it is energetically feasible, the activation energy may be
so high that the reaction proceeds at an extremely slow rate or does not proceed at all
 E0 only relates to standard conditions, changes in concentration, temperature and pressure will affect the
electrode potentials [Similar to effect of temperature, pressure & concentration on reversible reactions]

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 Effect of temperature: Since all half-cell equations are reversible, if temperature is increased or
decreased, the endothermic or exothermic reaction will be favored respectively based on Le
Chatelier’s Principle, altering the position of the equilibrium and subsequently the electrode potential
 Effect of pressure on gaseous species: If the pressure is increased or decreased, the side of the
reaction with a smaller or larger total molar gas volume will be favoured respectively
 Effect of concentration on aqueous species: If the concentration is increased or decreased, the
equilibrium will shift to offset the increase/decrease in concentration
 Effect of non-aqueous states: If a precipitate is produced, this will remove the products and by LCP,
will drive the reaction to completion even if the reaction is slightly not feasible based on E 0cell
𝑜 𝑅𝑇
 Nernst Equation: 𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − 𝑛 𝐹 𝑄𝑐
𝑒

6.3 PRACTICAL APPLICATONS OF ELECTROCHEMICAL CELLS

 Batteries
 Self-contained electrochemical cell, no additional components (other than the load) required
 Non-rechargeable batteries eventually reach equilibrium and no longer provide any energy after
equilibrium is reached.
 Rechargeable batteries rely on external power sources to reverse the half-cell equations and recharge
the cell (~electrolytic cells)
 Types
 Non-rechargeable alkaline batteries
 Non-rechargeable silver button batteries
 Rechargeable lead-acid batteries
 Rechargeable lithium-ion batteries
 Fuel Cells
 Electrochemical calls in which the reactants are supplied continuously such that the cell can operate
forever as long as the supply is maintained
 No combustion takes place as the half-cells are
separated and electrons transferred through an
external circuit
 E.g. Hydrogen Fuel Cell
 Anode Reaction – H2 +2OH − → 2H2 O+2e−
 Cathode Reaction – O2 +2H2 O + 4e− → +4OH −
 Overall Reaction – 2H2 +O2 → 2H2 O
 E.g. Molten Carbonate Fuel Cell
 Anode Reaction – H2 +CO2− 3 → H2 O+CO2 + 2e

 Cathode Reaction – 2CO2 +2O2 + 4e− → 2CO2− 3


 Overall Reaction – 2H2 +O2 → 2H2 O
 Advantages
 No pollution
 Portable
 High efficiency (up to 75%) and good energy-to-mass ratio
 Limitations
 Expensive
 High temperatures required to operate due to a high activation energy
 Alkali may absorb CO2 from the surrounding and form carbonates that clog up the porous
electrodes
 Transport of hydrogen and oxygen gas is expensive, although hydrogen can be substituted with
methanol in Direct Methanol Fuel Cells

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6.4 ELECTROLYTIC CELL & COMPONENTS

 Electrolytic Cell: A voltaic cell in which electrical energy is used to cause a non-spontaneous redox reaction
to occur; Consists of a pair of electrodes connected to an external EMF source and dipped into an
electrolyte
 Components
 Electromotive Force (EMF) Source
 Drives the non-spontaneous reaction
 Usually a battery
 Electrodes
 Anode – Positive Electrode, attracts ions for oxidation
 Cathode – Negative Electrode, attracts ions for reduction
 Electrolyte
 A liquid or an aqueous solution that contains mobile ions and can be used to conduct electricity
 Can either be liquid or aqueous

6.5 ELECTROLYSIS

 The criteria for selecting oxidation and reduced species is entirely the same except that E 0cell is <0
 In a liquid electrolyte, the ions discharged are the definitely the ones inside the liquid
 E.g. If the cell contains molten NaCl, sodium metal and chlorine gas will definitely be formed
 In an aqueous electrolyte, the ions discharged depends on their position in the electrochemical series
 In addition, water can either be oxidized or reduced

 Reduction: 2𝐻2 𝑂(𝑙) + 2𝑒 − ⇌ 𝐻2 (𝑔) + 2𝑂𝐻 − ; 𝐸 0 = −0.83𝑉


 Oxidation: 𝑂2 (𝑔) + 4𝐻 + + 4𝑒 − ⇌ 2𝐻2 𝑂(𝑙) ; 𝐸 0 = +1.23𝑉
 In acidic conditions, different equations are used
 Reduction: 2𝐻 + + 2𝑒 − ⇌ 𝐻2 (𝑔) ; 𝐸 0 = 0.00𝑉
 Oxidation: 𝑂2 (𝑔) + 4𝐻 + + 4𝑒 − ⇌ 2𝐻2 𝑂(𝑙) ; 𝐸 0 = +1.23𝑉
 In alkaline conditions, different equations are used

 Reduction: 2𝐻2 𝑂(𝑙) + 2𝑒 − ⇌ 𝐻2 (𝑔) + 2𝑂𝐻 − ; 𝐸 0 = −0.83𝑉


 Oxidation: 𝑂2 (𝑔) + 2𝐻2 𝑂(𝑙) + 4𝑒 − ⇌ 4𝑂𝐻 − ; 𝐸 0 = +0.40𝑉

Problem Solving Skill II – Determining which species to


reduce/oxidize
1. Select the relevant half-cell equations. Note that one of the species must be on
the left side and the other on the right side (oxidation must be coupled with
reduction). The species present must be inside the half-cell reaction
2. Alternatively, check if the species involved can be further oxidized/reduced
3. Check if the half-cell equation is feasible in an alkaline/acidic environment (if
applicable)
4. Assign [R] to the half-cell equation with a highest E0 value (favours reduction)
5. Assign [O] to the half-cell equation with a lowest E0 value (favours oxidation)
6. Combine both half equations to get the overall cell reaction
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6.6 FACTORS AFFECTING ELECTROLYSIS

6.6A CONCENTRATION OF SPECIES PRESENT

 Based on Le Chatelier’s Principle, if the concentration of the reduced species increases, the equilibrium
shifts to the left to offset the increased concentration of reduced species, thus reducing E
 Conversely, if the concentration of the oxidized species increases, the equilibrium shifts to the right to
offset the increased concentration of oxidized species, thus increasing E
 As a result, certain ions may be discharged preferentially as compared to other ions if concentrations of
the species are changed (e.g. Cl- being oxidized preferentially as compared to H2O)
 Note
 Concentration is not fixed. The concentration of various species can drop over time as they are
discharged, resulting in the other species being more concentrated
 pH can change. If water is not oxidized and reduce simultaneously, hydroxide or hydrogen protons
may accumulate that cause changes in pH

6.6B PH OF SOLUTION

 Affects the half-reactions available, as exemplified in the different equations used for the
reduction/oxidation of water
 E.g. Water
 E.g. Reduction of Permanaganate

 Acidic:𝑀𝑛𝑂4− + 8𝐻 + + 5𝑒 − ⇌ 𝑀𝑛2+ + 4𝐻2 𝑂; 𝐸 0 = +1.52𝑉


− + − 0
 Alkaline: 𝑀𝑛𝑂4 + 4𝐻 + 5𝑒 ⇌ 𝑀𝑛𝑂4 + 2𝐻2 𝑂; 𝐸 = +1.67𝑉

6.6C PRESENCE OF LIGANDS

*Refer to transition elements

6.6D NATURE OF ANODE

 Platinum and Graphite (carbon) electrodes are inert and do not participate in the reaction, except at
extremely high temperatures where CO2 or CO may be formed using graphite electrodes
 Anodes made of other metals such as copper electrodes must be considered in the list of half-reactions
for oxidation (e.g. if Copper anodes are used, they are likely to be oxidized to form Cu 2+ ions)
 Cathodes made of other metals are similar to those made of inert elements as the metal cannot be further
reduced.

6.6 QUANTITATIVE ELECTROLYSIS

 Relationship between Faraday’s Constant F and Avogadro’s Constant L


 Faradays Constant F, is the charge carried by 1 mole of electrons that flow through a cell
 Avogadro’s Constant, L, is the number of particles in 1 mole
 e is the charge carried by 1 electron

𝐹 = 𝐿𝑒; 𝐹 = 96500 C mol-1

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 Relationship between charge Q, F and current I


 Q is the total quantity of charge, expressed in Coulombs
 ne is the total moles of electrons, expressed in moles
 I is the current, expressed in amperes (A)
 t is time, expressed in seconds

𝑄 = 𝑛𝑒 𝐹 = 𝐼𝑡
Hence, the number of moles of a substance that undergoes oxidation/reduction is directly proportional to the
quantity of charge that passes through the cell

 Using this relationship, it is possible to find out the moles and subsequently mass/volume of substance
liberated during electrolysis by first determining n e and then using stoichiometry

6.7 PRACTICAL APPLICATIONS

6.7A ANODIZING ALUMINIUM

 Function: Used to increase the thickness of the Al 2O3 layer on the surface of Al metal by electrolysis; Al2O3
acts as a protective layer that resists corrosion and seals off the aluminum beneath it
 Components
 Electrolyte: Dilute H2SO4 (aq)
 Anode: Aluminum
 Half-reaction: 𝑂2 (𝑔) + 4𝐻 + + 4𝑒 − ⇌ 2𝐻2 𝑂(𝑙) ; 𝐸 0 = +1.23𝑉
 Cathode: Platinum
 Half-Reaction: 2𝐻 + + 2𝑒 − ⇌ 𝐻2 (𝑔) ; 𝐸 0 = 0.00𝑉
 Process: The presence of sulfuric acid in the electrolyte reacts with the thin layer of aluminum oxide and
causes pores to form. Oxygen formed by the oxidation of water then enters these pores and react with
aluminum to form more aluminum oxide. The pores are then filled by adding dye.
 Advantages
 Increases the corrosion resistance of the metal
 Provides a porous surface which can be dyed to different colours
 Used for materials for window frames, drink cans, etc.

6.7B PURIFICATION OF COPPER

 Function: Extract pure copper from impure copper via selective discharge
 Components
 Electrolyte: Dilute Copper (II) Sulfate
 Anode: Impure copper
 Cathode: Copper cathode
 Process:
 At the anode, all metals above copper in the electrochemical series get oxidized, while all metals
below copper in the electrochemical series remain as metals and get deposited as an anode sludge.
 At the cathode, copper ions are preferentially reduced into copper metal over other metal ions due to
a higher E0.

**If a cathode made of another metal is used, electroplating occurs rather than purification

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6.7C ELECTROPLATING

 Function: Coat a metallic object with a specific metal


 Components
 Anode is the metal to electroplate the object/impure metal ore
 Cathode is object to be electroplated/pure metal
 Electrolyte is a solution of the metal ion (Metal nitrate)
 Concentration of metal ions in solution remains the same
 Not 100% efficient
 The remaining metal ions may not be found at the cathode for
them to be discharged or H+ ions were discharged preferentially
as the concentration of metal ions decreases.

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7A. CHEMICAL EQUILIBRIUM


7A.1 REVERSIBLE AND IRREVERSIBLE REACTIONS

 Chemical Equilibrium can only be applied to reversible reactions (⇌)


 E.g. Reaction between Ozone and Ethene
 Concentration of reactants do not decrease to zero

7A.2 DYNAMIC EQUILIBRIUM

 Exists in a system which the forward and reverse reactions are taking place simultaneously at the same
rate, thus the concentration of each species of reactants and products remain constant.
 Only applicable for
 Reversible reactions


 Equilibrium Position
 Left  More reactants than products
 Right  More products than reactants
 Characteristics
 Forward and reverse reactions occurring at the same rate (It is not static)
 Thus, concentrations of reactants and products remain constant
 Equilibrium can be obtained from either direction (see below diagram)

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 Equilibrium can only be achieved in a closed system (no escape of products as loss of products will
cause equilibrium to shift to the right/left, completely decomposing the reactants)
 Affects the yield of the reaction

7A.3 HOMOGENOUS AND HETEROGENOUS EQUILIBRIUM

 Homogenous equilibrium  All participating substances are in the same phase


 Heterogenous equilibrium  Participating substances are in different phases

7A.4 LE CHATELIER’S PRINCIPLE

 LCP states that when a system in equilibrium is subjected to a change in conditions which disturbs the
equilibrium, the position of the equilibrium will shift in a way to offset the change.
 E.g. Addition of heat  Endothermic reaction favoured  Heat removed  Back to normal
 Factors affecting equilibrium
 Concentration/Partial Pressure
 By LCP, when concentration of reactants is increased, the reaction in equilibrium will shift to the
right, producing more products so as to ensure that the concentration of reactants decreases.
 By LCP, when concentration of products is increased, the reaction in equilibrium will shift to the
left, producing more reactants so as to ensure that the concentration of products decreases
 E.g The OH- ion of NaOH would react with H3O+ to form water. This reaction is equivalent to
removing H30+ from the equilibrium mixture. The effect would be more XXX dissociating to form
H30+ ions as the equilibrium shifts to the right.
 Total Pressure
 By LCP, when the pressure of the system is increased, the equilibrium will shift to a side with a
smaller total molar volume, causing pressure to drop.
 By LCP, when the pressure of the system is decreased (aka increase volume), the equilibrium will
shift to a side with a larger total molar volume, causing pressure to increase.
 Temperature
 Increasing the temperature will favour the endothermic reaction to take place according to Le
Chatelier’s Principle, thus the equilibrium shifts to the right/left, producing more
products/reactants.
 Decreasing the temperature will favour the exothermic reaction to take place according to Le
Chatelier’s Principle, thus the equilibrium shifts to the right/left, producing more
products/reactants.
 Catalyst
 Enables the state of equilibrium to be reached more quickly, but does not alter the position of
the equilibrium as it increases both forward and reverse reaction rates to the same extent.

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7A.5 EQUILIBRIUM LAW AND EQUILIBRIUM CONSTANTS

 The equilibrium law states that if a reversible reaction is allowed to reach equilibrium, the product of the
concentrations of each product raised to the appropriate powers divided by the product of the
concentrations of each reactant raised to the appropriate power has a constant value called the
equilibrium constant, K, at a constant temperature
 Applicable only to systems at equilibrium
 Expressed in terms of concentration, KC
 Or partial pressure, Kp
 Only affected by temperature
 Equilibrium Constant
[𝑃1 ]𝑤 …[𝑃𝑛 ]𝑦
 𝐾𝑐 = [𝑅1 ]𝑥 …[𝑅𝑛 ]𝑧
mol dm-3 (units not fixed)
𝑤 𝑦
𝑝𝑃1
… 𝑝𝑃
𝑛
 𝐾𝑝 = 𝑥 𝑧 Pa/atm (units not fixed)
𝑝𝑅 …𝑝𝑅𝑛
1
 Units must be determined based on the terms within the expression (can have no units)
 Indicates the extent of the reaction
 High K means that there is more products over reactants
 Low K (K<1) means that there is more reactants than products
 When K = 1, there are as many reactants as products
 Exceptions
 Solids or liquids in heterogenous equilibrium are not included in the K c/ Kp expression
 Solids have a constant density (concentration)
 Liquids in large excess are not included as their concentration is presumed to be constant. (only
applicable for homogenous equilibrium)
 Reaction Quotient (at a certain time)
 Qc is calculated in the same way except that instantaneous concentrations are used
 Qp is calculated in the same way except that instantaneous partial pressures are used
 At a given temperature, Q can take on any value until the reaction quotient is equivalent to the
equilibrium constant (equilibrium is reached)
 If Q < K, the forward reaction will increase
 If Q > K, the backward reaction will increase

Problem Solving Skill 1A – Using the ICE table and algebra


It is a wise choice to use the ICE table when dealing with equilibrium constants. E.g for R ⇌ 2S

R 2S
Initial Concentration/ mol dm-3 1 0
Change /mol dm-3 –x + 2x (always according to
stoichiometric coefficient)
Equilibrium Concentration/ mol 1-x 2x
dm-3
(2𝑥 )2
𝐾𝑐 = 𝑚𝑜𝑙 𝑑𝑚−3
1−𝑥

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7A.6 HABER PROCESS

 Objectives
 Increase speed at which equilibrium is attained
 Shift the equilibrium position to the right
 Conditions
 Ratio of N2 : H2 (1:3)
 Temperature: 400-450°C
 Pressure: 200 atm
 Catalyst: Iron Metal
 Equation
 N2 (g) + 3H2 (g) ⇌ 2NH3, ΔH = -92kJ mol-1
 Reasons behind choice of conditions
 Low temperature is chosen as the forward temperature is exothermic
 High pressure is chosen as the products occupy a smaller total molar volume than the reactants
 Not overwhelmingly low temperatures as rates of reactions are also taken into consideration
 Not overwhelmingly high pressures as high pressure is expensive to maintain.
 Ammonia is constantly removed as it is created (to shift equilibrium to the right)

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7B. IONIC EQUILIBRIA


7B.1 BRØNSTED-LOWRY DEFINITION OF ACID AND BASES

 Bronsted Acid – A proton donator


 A Bronsted Acid reacts with a Bronsted Base to form the Conjugate Base (negatively charged)
 The conjugate base and the Bronsted Acid forms a conjugate acid base pair
 Bronsted Base – A proton acceptor
 A Bronsted Base reacts with a Bronsted Acid to form the Conjugate Acid (positively charged)
 The conjugate acid and the Bronsted Base forms a conjugate acid base pair

Acid + Base → Conjugate Base + Conjugate Acid

 Acid Strength
 Strong Acid – An acid that dissociates completely in water to form H3O+ ions.
 Strong Acid + H2O → Conjugate Base + H3O+
 This reaction is non-reversible (reverse reaction is negligible)
 Weak Acid – An acid that dissociates partially in water to form H3O+ ions.
 Weak Acid + H2O ⇌ Conjugate Base + H3O+
 This reaction is reversible
 Alternatively, the Ka/pKa value can be used to compare the strength of acids at the same
temperatures
 Strength ≠ Concentration
 Base strength
 Strong Base – A base that dissociates completely in water to form OH- ions.
 Strong Base → Conjugate Acid + OH-
 This reaction is non-reversible (reverse reaction is negligible)
 Weak Base – A base that dissociates partially in water to form OH- ions.
 Weak Base + H2O ⇌ Conjugate Acid + OH-
 This reaction is reversible
 Alternatively, the Kb/pKb value can be used to compare the strength of bases at the same
temperatures
 Strength ≠ Concentration
 For organic acids/bases, the strength depends on how readily the conjugate acid/base is formed, which
depends on the structure of the acid/base.

7B.2 IONIC EQUILIBRIA CALCULATIONS

 pH
 𝑝𝐻 = − 𝑙𝑔[𝐻+ ] ⇔ [𝐻+ ] = 10−𝑝𝐻
 pOH
 𝑝𝑂𝐻 = − 𝑙𝑔[𝑂𝐻− ] ⇔ [𝑂𝐻 − ] = 10−𝑝𝑂𝐻
 Ionic Product of Water, Kw
 Autoionization of water  H2O + H2O ⇌ H3O+ + OH-
 Needs to be taken into account for pH/pOH calculation if the concentration of the acid/base
added is smaller than 1 x 10-7 M
 𝐾𝑤 = [𝐻+ ][𝑂𝐻− ] = 1.0 × 10−14 mol2 dm-6 at 25°C

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 𝑝𝐾𝑤 = 𝑝𝐻 + 𝑝𝑂𝐻 = 14 at 25°C


 Only Affected by temperature as it measures the degree of dissociation (which depends on the
enthalpy change of the forward & backward reaction and LCP)
 Acid Dissociation Constant, Ka
[𝐻 + ]𝑒𝑞 [𝐴− ]𝑒𝑞
 𝐾𝑎 = [𝐻𝐴]𝑒𝑞
⟺ 𝑝𝐾𝑎 = − lg 𝐾𝑎
 Depending on whether the forward reaction is exothermic or endothermic, Ka will vary with
temperature only
 For 2 acids at the same temperature, the one with a higher Ka or lower pKa is the stronger acid
 For strong acids, the Ka value is very large and pKa value very small, thus it is usually not applied to
strong acids
 Base Dissociation Constant, Kb
[𝐵𝐻 + ]𝑒𝑞 [𝑂𝐻 − ]𝑒𝑞
 𝐾𝑏 = ⟺ 𝑝𝐾𝑏 = − lg 𝐾𝑏
[𝐵]𝑒𝑞
 Depending on whether the forward reaction is exothermic or endothermic, Kb will vary with
temperature only
 For 2 bases at the same temperature, the one with a higher Kb or lower pKb is the stronger base
 For strong bases, the Kb value is very large and pKb value very small, thus it is usually not applied to
strong bases
 For any conjugate acid-base pair, 𝐾𝑎 × 𝐾𝑏 = 𝐾𝑤 ⟺ 𝑝𝐾𝑎 + 𝑝𝐾𝑏 = 𝑝𝐾𝑤
 Hence, if the acid is a strong acid, the conjugate base will be a weak base (unable to dissociate to form
a hydroxide anion)
 Conversely, if the base is a strong base, the conjugate acid will be a weak acid (unable to dissociate to
form a proton)
 Consider the reaction of Acid + Base → Conjugate Base + Conjugate Acid. If Kc is large, it shows
that the reactants are strong acids and bases, and their conjugates are weak acids and bases. The
reverse is true.

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 Degree of Dissociation, α
[𝐴− ]𝑒𝑞
 𝛼 = [𝐻𝐴] %
ini
 Affected by concentration and temperature
 For a strong acid, α ~ 1, for a weak acid, α <<1
 Note: For a weak acid, you can assume that [HA]ini =[HA]eq
[𝐻 + ]𝑒𝑞 [𝐴− ]𝑒𝑞 [𝐻 + ]2 𝑒𝑞
 Hence, 𝐾𝑎 = [𝐻𝐴]𝑒𝑞
≈ [𝐻𝐴]ini
⟺ [𝐻+ ] = √[𝐻𝐴]ini × 𝐾𝑎
 This is true because weak acids only dissociate to a very small extent
 This is applicable for weak bases as well

7B.3 SALT HYDROLYSIS

 Rule of Thumb: The conjugate base/acid of a weak acids and bases undergo hydrolysis. The conjugate
base/acid of strong acids and bases do not undergo hydrolysis.
 In all acid-base reactions to form H3O+ and OH- in water, the base/acid that the acid/base reacts with
is always a water molecule.
 Consider Acid + H2 O ⇌ Conjugate Base + H3O+
 If the acid is a strong acid, the conjugate base is a weak base. Weak bases do not hydrolyze.
 If the acid is a weak acid, the conjugate base is a strong base (inverse relationship). Strong bases are
stronger bases than water, thus it can abstract a proton from H2O to form OH-
 Strong Conjugate Base + H2 O ⇌ Weak Acid + OH −
 Consider Base + H2 O ⇌ Conjugate Acid + OH-
 If the base is a strong base, the conjugate acid is a weak acid. Weak acids do not hydrolyze.
 If the base is a weak base, the conjugate base is a strong acid (inverse relationship). Strong acids are
stronger acids than water, thus it can protonate H2O to form H3O+
 Strong Conjugate Acid + H2 O ⇌ Weak Base + H3O+
 Every salt from an acid-base reaction is made up of 1 conjugate base and 1 conjugate acid

Reaction that forms salt pH Strength of Strength of Reason


Conjugate Conjugate Acid
Base (Anion) (Cation)
Strong acid + Strong base 7 Weak Weak No hydrolysis occurs, thus solution
is neutral
Strong acid + Weak base <7 Weak Strong Conjugate acid protonates water to
form hydronium ions
Weak acid + Strong base >7 Strong Weak Conjugate base abstracts proton
from water to form hydroxide
Weak acid + Weak base ?? Strong Strong Depends on whether the conjugate
base is stronger or the conjugate
acid is stronger
Ligand formation (Al3+, <7 - - Ligand protonates water to form
Fe3+, Cr3+) hydronium ions

 Ligands (hydrated ions) are acidic as the central cation with a high charge density is able to withdraw
sufficient electrons density from the O-H bonds of the coordinated (attached) water molecules, thus
weakening the O-H bond until it breaks
 E.g [Al(H2 O)6 ]3+ +H2 O ⇌ [Al(H2 O)5 (OH)]2+ +H3 O+

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Problem Solving Skill I – Calculating pH of Salt Solution


1. Identify the weak conjugate base/acid
2. Obtain the Ka/Kb value of this weak conjugate base/acid by using the relation 𝐾𝑎 ×
𝐾𝑏 = 𝐾𝑤 (for a conjugate acid-base pair)
3. Find the [H+] or [OH-] using the relation [𝐻 + ] = √[𝐻𝐴]ini × 𝐾𝑎 or [𝑂𝐻 − ] =
√[𝐵]ini × 𝐾𝑏
4. Find pH or pOH. Convert pOH to pH using this relation 𝑝𝐻 + 𝑝𝑂𝐻 = 14

7B.4 BUFFER SOLUTIONS

 Buffer Solution – A solution which is able to resist pH changes upon the addition of a small amount of acid
or base
 Acidic Buffer: Aqueous solution of a weak acid and its conjugate base as a salt
 Alkaline Buffer: Aqueous solution of a weak base and its conjugate acid as a salt
 Principles of acidic buffer action
 The buffer contains a mixture of weak acid and its stronger conjugate base in this equilibrium
 Acid + H2 O ⇌ Conjugate Base + H3O+
 The addition of the conjugate base suppresses the dissociation of the weak acid by LCP.
 When H+ is added to the solution, the conjugate base will react with it to form weak acid and water
 Conjugate Base + H3O+ → H2 O + Weak Acid
 When OH- is added to the solution, the weak acid will react with OH- to form the conjugate base and
water
 Acid + OH − → Conjugate Base + H2O
 After the reactions, the newly added hydronium or hydroxide ions are neutralized and the weak
acid/conjugate base is formed. Due to the equilibrium of the buffer, there is a slight effect of LCP that
causes a little hydronium/hydroxide ions to be formed. Hence, pH remains almost constant.
 Principles of alkaline buffer action
 The buffer contains a mixture of weak base and its stronger conjugate acid in this equilibrium
 Base + H2 O ⇌ Conjugate Acid + OH-
 The addition of the conjugate acid suppresses the dissociation of the weak base by LCP.
 When H+ is added to the solution, the weak base will react with H + to form the conjugate acid and
water
 Weak Base + H3O+ → H2 O + Conjugate Acid
 When OH- is added to the solution, the conjugate acid will react with it to form weak base and water
 Conjugate Acid + OH − → Weak Base + H2O
 After the reactions, the newly added hydronium or hydroxide ions are neutralized and the weak
acid/conjugate base is formed. Due to the equilibrium of the buffer, there is a slight effect of LCP that
causes a little hydronium/hydroxide ions to be formed. Hence, pH remains almost constant.
 pH of acidic buffer solution
 In a buffer solution, the [HA]eq ≈ [HA]ini due to the suppression of dissociation by the conjugate base
 Similarly, [A-]eq ≈ [A-]ini since the weak acid has very low degree of dissociation
[H+ ]eq [A- ]eq [H+ ]ini [A- ]ini [Acid]
 𝐾𝑎 = ≈ ⟺ [𝐻+ ] = 𝐾𝑎
[HA]eq [HA]ini [Conjugate Base]
 In a buffer, [HA] ≠ [A ] as the conjugate base is added separately
-

 pH of alkaline buffer solution


 Similarly,

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[OH - ]eq [BH + ]eq [OH - ]ini [BH + ]ini [Base]


 𝐾𝑏 = ≈ ⟺ [𝑂𝐻− ] = 𝐾𝑏
[B]eq [B]ini [Conjugate Acid]
 Buffer Capacity
 Buffer Capacity – The quantity of H3O+ and OH- it can remove before its pH changes drastically
 The more concentrated the buffer, the greater the buffer capacity
 The more similar the concentrations of the buffer components, the greater the buffer capacity
 Maximum buffer capacity
[Acid] [Base]
 Occurs when = 1 𝑜𝑟 =1
[Conjugate Base] [Conjugate Acid]
 At maximum buffer capacity, pH = pKa, pOH = pKb
 Ideal acid/base over salt ratio is between 0.1 and 10
 Effective buffer range
 By definition, effective buffer pH range = pKa/ pKb ±1

Problem Solving Skill II – Calculating pH of Buffer after adding a strong base/acid


1. Obtain the concentration of H+/OH- by assuming that strong acids/bases dissociate completely.
2. Find the new [Weak acid/base] by assuming that all the H+/OH- have reacted with the weak
base/acid.
3. Find the new [Conjugate acid/Conjugate base] by adding the moles of weak acid/base that have
reacted to form the conjugate acid/base.
4. Find pH using the formulas provided above using the new concentrations.

Problem Solving Skill III – Finding out X mol of H+/OH- to add to obtain a pH of y
1. The concentration of the protons/hydroxide will be X/V, where V is the volume of the solution
+] [Acid] ∓ x/v
2. Use formula [𝐻 = 𝐾𝑎
[Conjugate Base] ± x/v
3. The +/- sign depends on whether a base/acid is added to the solution.
4. Solve for x/v and then multiply by v to find x.
5. This method can also be used to calculate the pH of a buffer after adding a strong acid/base

7B.5 ACID-BASE TITRATION

 Indicators (In) for acid-base titrations


 Indicators are weak acids whose acidic form
(HIn) is of a different colour than the
ionized form (In-)
 HIn ⇌ H+ + In-
 Working range of pH indicators  pK In ±1
 Choosing Indicators
 The indicator must be chosen such that
the end point coincides with the
equivalence point
 End point – The point at which the
indicator changes colour when
excess titrant is added
 Equivalence point – The point at which there is complete neutralization (formation of salt)
 Recommended table

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Reactants Suitable Indicator


Strong Acid + Strong Base Methyl Orange or Phenolphthalein
Strong Acid + Weak Base Methyl Orange
Weak Acid + Strong Base Phenolphthalein
Weak Acid + Weak Base -

 Titration Graphs – Strong Acid + Strong Base


 Characteristics
 Very Straightforward
 No buffer solution formed
 No salt solution formed
 pH at Equivalence point is always 7.00
 Important Points to note

Strong Acid + Strong Base


Point Calculating pH Calculating Volume
Half-neutralization Take the volume required for half Volume = Volume Required for
neutralization, calculate the number complete neutralization x ½
of moles of H+/OH- it neutralizes,
then calculate the pH value.
Equivalence Point 7.00 (Fixed) Complete Neutralization – Calculate
number of moles of H+/OH- required to
neutralize the original moles of
acid/base and relate back to the
volume of the Acid/Base required

 Titration Graphs – Weak Acid + Strong Base


 Characteristics
 Acidic Buffer solution formed at lower
end as acid dissociates to give a
combination of acid and the conjugate
base.
 Salt solution formed at equivalence
point
 pH at Equivalence point is always > 7.00
due to the hydrolysis of the stronger
conjugate base to form hydroxide ions
 Important Points to note

Weak Acid HA + Strong Base


Point Calculating pH Calculating Volume
Half-neutralization Half-neutralization marks the point Volume = Volume Required for
of maximum buffer capacity. At complete neutralization x ½
maximum buffer capacity, pH = pKa This stands true because of LCP
Equivalence Point Complete neutralization results in a Similar to calculating the required
pure salt solution being formed. volume of base for neutralizing a
𝐴− + 𝐻2 𝑂 ⇌ 𝐻𝐴 + 𝑂𝐻 − strong acid.

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To obtain the pH, calculate the pH of This is true because of LCP, which
the salt solution (check above) causes all the weak acid to eventually
**Remember that the volume has dissociate. (Reaction of H3O+ to form
increased after adding some titrant! water eventually pushes equilibrium to
the right to form more A-)

 Titration Graphs – Weak Acid + Strong Base


 Characteristics
 Alkaline Buffer solution formed at
higher end as the base dissociates
to give a combination of base and
the conjugate acid.
 Salt solution formed at
equivalence point
 pH at Equivalence point is always
< 7.00 due to the hydrolysis of the
stronger conjugate acid to form
hydronium ions
 Important Points to note

Strong Acid + Weak Base B


Point Calculating pH Calculating Volume
Half-neutralization Half-neutralization marks the point Volume = Volume Required for
of maximum buffer capacity. At complete neutralization x ½
maximum buffer capacity, pH = pKa This stands true because of LCP
Equivalence Point Complete neutralization results in a Similar to calculating the required
pure salt solution being formed. volume of acid for neutralizing a
𝐵𝐻 + + 𝐻2 𝑂 ⇌ 𝐵 + 𝐻3 𝑂 + strong base.
To obtain the pH, calculate the pH of This is true because of LCP, which
the salt solution (check above) causes all the weak base to eventually
**Remember that the volume has dissociate. (Reaction of OH- to form
increased after adding some titrant! water eventually pushes equilibrium to
the right to form more BH+)

*The curve is simply rotated about the centre if the weak base is the titrant. The buffer region is still at the
higher end.

 Titrating a di-acid or di-base


 Characteristics
 Principles are still the same
 Buffer regions will be formed,
obtain the pH by using pKa1 and pKa2
values
 The pH at the 1st & 2nd equivalence
points will the pH of the salt
solutions
 Volume required to reach the first
equivalence point is the same as
that of the volume required to

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neutralize the first proton formed by the first complete dissociation of the acid.
It is harder to abstract a proton from an already negatively charged molecule as compared to one that
is neutral.
 Weak acid + Weak base
 Buffer regions at both ends
 No sharp change in pH, thus no indicators can be used. Both anions and cations undergo hydrolysis.

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7C. SOLUBILITY EQUILIBRIA


 All solids are soluble to an extent
 All Sodium, Potassium and Ammonium Salts are soluble
 All Nitrate salts are soluble
 All Chloride and Iodide salts are soluble with the exception of Lead (II) and Silver
 All sulphate salts are soluble with the exception of Calcium, Barium and Lead (II) sulphates
 All oxide and hydroxide salts are insoluble with the exception of Sodium, Potassium, Barium and
Ammonium
 All carbonates are insoluble in water with the exception of Sodium, Potassium and Ammonium

7C.1 SOLUBILITY, IONIC PRODUCT & SOLUBLITY PRODUCT

 Solubility: The number of moles of salt that can be dissolved in 1 dm 3 of the solvent to form a saturated
solution at a given temperature. (g/dm3) or (mol/dm3)
 Supersaturated solution: A solution that contains a greater amount of solute tan that needed to form
a saturated solution; used for crystallization of the salt
 All ionic salts exist in this equilibrium: 𝐴𝑛 𝐵𝑚 ⇌ 𝑛𝐴𝑚+ + 𝑚𝐵𝑛−
 Ionic Product: The product of the molar concentrations of the constituent ions in the solution at any
point of time, raised to the appropriate powers (Analogous to Qc)
 Ionic Product (𝐴𝑛 𝐵𝑚 ) = [𝐴𝑚+ ]𝑛 [𝐵𝑛− ]𝑚 = 𝑄𝑐 [𝐴𝑛 𝐵𝑚 ]
 Qc cannot be used as the concentration of the ionic solid [A nBm] is always constant
 Kw = Ionic product of water at a specific temperature = [H+][OH-]
 Solubility Product: The ionic product of a salt at equilibrium (aka saturated) = The product of the molar
concentrations of the constituent ions in a saturated solution, raised to the appropriate powers
 Solubility Product 𝐾𝑠𝑝 (𝐴𝑛 𝐵𝑚 ) = [𝐴𝑚+ ]𝑛 [𝐵𝑛− ]𝑚 = 𝐾𝑐 [𝐴𝑛 𝐵𝑚 ]
 Only valid for sparingly soluble salts, as the Ksp of soluble salts will be very large and useless
 Only changes with temperature; independent of the amount of salts added to the solution

7C.2 RELATIONSHIP BETWEEN IONIC AND SOLUBILITY PRODUCT

 Relationship
 IP < Ksp : Solution is unsaturated, ionic salt will continue to dissolve (equilibrium shifts left)
 IP = Ksp : Solution is just saturated, first traces of precipitate appears
 IP > Ksp : Solution is saturated, precipitate will form upon the addition of any more ionic salt
(equilibrium shifts right)
 Thus, by comparing the IP to the Ksp, one can determine if precipitation will take place

Problem Solving Skill I – Determining minimum amount of


cation/anion to add before precipitation takes place
1. When precipitation first occurs, IP = Ksp
2. Using the Ksp value, find out the concentration of the ion that one needs to add
with reference to the concentration of the other corresponding ion already
present.
3. Find out the mass of the ionic solid containing that ion (if required)

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Problem Solving Skill II – Determining minimum amount of


cation/anion to add for selective precipitation
1. The question will involve the presence of two cations/anions in the solution,
while requiring you to add a certain amount of the oppositely charged ion to
precipitate out one salt but not the other (E.g. AgCl & BaCl2)
2. The concentrations of the two different cations/anions (Ag+ and Ba2+ in this
case) will be given. The salt that needs to be precipitated out will always be the
less soluble salt.
3. Determine the upper and lower limits of the concentration of the oppositely
charged ion using the Ksp values for the more soluble and less soluble salt
respectively & the concentrations of the respective ions in the solution.
4. The concentration of the oppositely charged ion required to precipitate the less
soluble salt is somewhere between the two limits.
5. To determine the concentration of the given cation/anion of the less soluble
salt after precipitation, use the Ksp value of that salt and the concentration of
the oppositely charged ion (e.g. Cl-).
 Ksp can be converted to solubility in both (g/dm3) as well as (mol/dm3)

Problem Solving Skill III – Calculating Ksp from solubility


1. If the solubility is in (g/dm3), convert it to (mol/dm3) first using Mr.
2. Find the concentrations of both the cation and anion in a saturated solution via
stoichiometry. (E.g. if the [CaF2]saturated = x, then [F-]saturated = 2x)
3. Multiply the various concentrations together to find Ksp

Problem Solving Skill IV – Calculating solubility from Ksp


1. If the [AnBm]saturated = x, then [Am+]saturated = nx, [Bn+] = mx, Ksp = (nx)m(mx)n
2. Since m & n are known, find x.
3. X is the molar solubility of the ionic solid, if required multiply by M r to find the
solubility in (g/dm3)

7C.3 FACTORS AFFECTING SOLUBILITY OF A SALT

 Factors
 Common ion effect
 Complex formation
 pH
 Temperature (which changes the Ksp and hence the solubility)

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7C.3A COMMON ION EFFECT

 In a solubility equilibrium, 𝐴𝑛 𝐵𝑚 ⇌ 𝑛𝐴𝑚+ + 𝑚𝐵𝑛− , if the concentrations of Am+ or Bn- are changed by
adding a soluble salt that contains either Am+ or Bn-, the solubility of the sparingly soluble salt will decrease
 Qualitative Explanation
 By Le Chatelier’s Principle, when Am+ or Bn- is added, the equilibrium position will shift to the left to
offset the increase in Am+ or Bn-, producing more ionic solid AnBm (s). This decreases the solubility of
the sparingly soluble salt.
 Quantitative Explanation
 Consider 𝐾𝑠𝑝 (𝐴𝑛 𝐵𝑚 ) = [𝐴𝑚+ ]𝑛 [𝐵𝑛− ]𝑚 & 𝐴𝑛 𝐵𝑚 ⇌ 𝑛𝐴𝑚+ + 𝑚𝐵𝑛−
 For a sparingly soluble salt, if a common ion is added (e.g. B n-), the new concentration will vastly
outweigh the initial equilibrium concentration
 Since [𝐴𝑚+ ]𝑛 [𝐵𝑛− ]𝑚 is a constant, if [Bn-] increases by a large scale, this causes [Am+] to decrease
rapidly.
 Since the solubility of AnBm is dependent on the limiting reagent, the solubility of AnBm will also drop

Problem Solving Skill V – Calculating solubility after addition of a


common ion
1. Calculate the concentration of the common ion [Bn-]
2. Considering 𝐴𝑛 𝐵𝑚 ⇌ 𝑛𝐴𝑚+ + 𝑚𝐵 𝑛− , assume the concentration of the other
ion to be x.
3. Since 𝐾𝑠𝑝 (𝐴𝑛 𝐵𝑚 ) = [𝐴𝑚+ ]𝑛 [𝐵 𝑛− ]𝑚 , Ksp = (nx)m(mx)n
4. Assuming the common ion to be Bn- , Ksp = (n[Bn-])m(mx)n
5. Find x and use stoichiometry to determine the solubility of the solid.
7C.3B COMPLEX FORMATION

 Some transition salts can form complexes that dissolve in solution due to ion-dipole interaction. This is
due to the interaction between two equilibriums (E.g)
 Salt Formation: 𝑃𝑏𝐶𝑙2 ⇌ 𝑃𝑏 2+ + 2𝐶𝑙 −
 Complex Formation: 𝑃𝑏 2+ + 4𝐶𝑙 − ⇌ [𝑃𝑏𝐶𝑙4 ]2−
 (With reference to equations above): When the chloride ion is first added into the solution, IP > K sp,
causing precipitation to take place and lead (II) chloride to be formed. However, in the presence of excess
chloride ions, the equilibrium of the 2nd equation shifts to the right, forming the lead complex. The lead (II)
ions are removed and this causes IP < Ksp, hence the lead (II) chloride dissolves.
 Complex ion formation thus increases the solubility of a sparingly soluble salt

7C.3C EFFECTS OF PH

 Only applies to basic/amphoteric salts.


 For a basic salt A(OH)2, the equilibrium is  𝐴𝐵𝑚 ⇌ 𝐴𝑚+ + 𝑚(𝑂𝐻)−
 In an acidic solution, the H3O+ ions react with the hydroxide ions. By Le Chatelier’s principle, the
equilibrium shifts to the left and the salt dissolves. Alternatively, since IP < K sp the salt dissolves.
 In a basic solution, the opposite occurs [common ion effect] and precipitation occurs at a much lower
concentration of metal ions.
 For an amphoteric salt, complexes are formed when the concentration of the hydroxide anion increases.
This increases the solubility of a salt.

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8. REACTION KINETICS
8.1 COLLISION THEORY

1. Products are only formed when


 Reactant molecules collide with a minimum amount of energy known as the activation energy
 Reactant molecules collide in the correct collision geometry
 Reactant molecules collide
2. N.a to heat-decomposition reaction (no reactant molecules)
3. Rate of reaction ∝ Frequency of effective collisions
 Only a small fraction of colliding particles have the correct orientation and the activation energy
required for an effective collision.

8.2 MAXWELL-BOLTZMANN DISTRIBUTION CURVE *EXPECTED TO DRAW

 From the curve


 Median  Most probably energy level of particles
 Few particles with very low/very high kinetic energy
 Area under graph  number of particles
 Shaded areas  Number of particles with energy greater than E A

8.3 ACTIVATION ENERGY

 The minimum energy which the reacting particles must possess in order to overcome the energy barrier
before the formation of products.
 Does not depend on ΔH
 EA ∝ Rate of Reaction
 Low EA  Larger proportion of molecules have an energy larger than the activation energy 
Increase frequency of effective collisions  Increase rate of reaction (Kinetically favourable reaction)
 High EA  Smaller proportion of molecules have an energy smaller than the activation energy 
decrease frequency of effective collisions  decrease rate of reaction (Kinetically stable reaction)

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8.4 ENERGY PROFILE DIAGRAM

 *Energy profile diagram above shows a single-step reaction


 A transition state is the arrangement of atomic nuclei and bonding electrons at the maximum potential
energy
 Transition state ≠ Intermediate Compound

8.5 RATE OF REACTIONS

Problem Solving Skill I – Determining Rates of reaction


1 𝑑[𝐴]
Rate =
𝑎 𝑑𝑡
Where A is a compound in the reaction and a is the stoichiometric coefficient of the compound. Add a
negative sign if A is a reactant.

Problem Solving Skill II – Determining Instantaneous rates of


reaction
Draw a tangent to the concentration-time graph at the instant t to determine the instantaneous rate (the
gradient). Extend this concept to calculate the initial rate of reaction (t = 0)

 The change in concentration of reactant or product per unit time (Mt -1/ mol dm-3 t-1)
 Always positive

8.6 RATE EQUATION

 An experimentally determined equation that relates the rate of reaction to the concentration of the
reactants raised to appropriate powers

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 Rate = 𝑘[𝐴]𝑚 [𝐵]𝑛


−𝐸𝐴
 k = Rate constant; 𝑘 = 𝐴𝑒 𝑅𝑇 , where A is the frequency factor, R is the molar gas constant and T is
temperature
 Determined by the slowest step in the reaction mechanism (or experimentally)
 Order of reaction
 With respect to a reactant = the exponential of the concentration of that specific reactant
 Overall = Sum of all exponentials/individual order of reactions
 Indicates the number of a specific reactant particle involved in the slowest step of the reaction
mechanism
 Half-life (t1/2)
 The time taken for the concentration of a reactant to decrease to half its initial value

Zero Order First Order Second Order


Rate Rate = k[A]0 = k Rate = k[A] Rate = k[A]2
equation Constant
Half-life Initial concentration of A ln 2 1
equation 𝑡1 = 𝑡1 = 𝑡1 =
k (Initial concentration of A)
2 2𝑘 2 𝑘 2

Constant
Units of rate mol dm-3 t-1
equation
Units of rate mol dm-3 t-1 t-1 mol-1 dm3 t-1
constant

 Pseudo-nth order reactions


 Large excess of a particular reactant  [Reactant] remains constant
 Large excess = [Reactant] 10 times that of other reactants present
 E.g. Pseudo-first order reaction for esterification as water is in large excess

Problem Solving Skill III – Proving order of reaction w.r.t a reactant


using the concentration-time graph.
For first order reaction, check that two half-lives are constant.
For zero order reaction, the graph should be a straight line graph y = mx
**Concentration-time graph can also be expressed as volume-time graphs for gases

Problem Solving Skill IV – Proving order of reaction w.r.t a reactant


given the initial rates.
Typically, a few initial rates would be given for you to compare, along with various concentrations of the
reactants involved. Either solve by introspecting the values or using a calculation

𝑅1 𝑘[𝐴1 ]𝑚 [𝐵]𝑗
=
𝑅2 𝑘[𝐴2 ]𝑚 [𝐵]𝑗

Problem Solving Skill V – Proving order of reaction w.r.t a reactant


by comparing two curves (initial rates method)
Two curves would be shown. Draw a tangent at t = 0 for both curves, calculate the initial rate. Accord for
the effects of other reactants on the rate, then use skill 8B to solve for the order of the reaction.
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 Take note
 When homogenous catalysts are used, their concentrations remain constant and can thus be
incorporated into k.
 E.g. Rate = k [H+][Sucrose] = k’ [Sucrose]
ln 2
 Hence, when calculating half-life (for overall 2nd order equation) = 𝑡1 =
2 𝑘[Catalyst]
 When heterogenous catalysts are used, the rate is usually independent of the concentration of the
substrate at very high concentrations.
 This is due to all the active sites being saturated and used up.
 Rate at high concentrations  Zero order w.r.t the substrate (Rate = k)
 Rate at low concentrations  First order w.r.t. the substrate (Rate = k [Substrate])
 You can use the linear law y = mx to check the order of the equation
 E.g. If the reaction is second order, plotting Rate against [A]2 would yield a straight line graph
 Reaction mechanisms
 A sequence of elementary steps in a chemical reaction. (Elementary steps are reactions that cannot
be broken into simpler ones)
 A reaction intermediate is a chemical species that is produces in an elementary step and consumed in
another (NOT transition state)
 Molecularity  the number of reactant particles taking part in the reaction in the elementary step
 Nomenclature  Unimolecular reaction, bimolecular … , termolecular …
 Molecularity of the slowest step determines the overall order of the reaction.
 Stoichiometric coefficients of reactants in the elementary step determine the order of reaction w.r.t.
each reactant
 Rate equations must not contain any intermediates.
 Take note: The higher the number of molecules required in an elementary step, the slower it is as
there is only a small percentage that 3 molecules with the kinetic energy being higher than the
activation energy colliding in the correct geometric orientation.

Problem Solving Skill VI – Constructing rate equations given the


reaction mechanism
1. Determine the slowest step (unless there is only one step)
2. Construct the rate equation based on the reactants and the molecularity of the reactants involved
in the slowest step
3. Replace all intermediates in the rate equation with the original reactants (this step requires
constructing rate equations for other steps)

Problem Solving Skill VII – Deducing reaction mechanisms from rate


equations
Check that

1. Elementary steps add up to the overall balanced equation


2. Elementary steps do not involve the collision of >3 particles
3. Slowest elementary step consistent with given rate equation

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8.675 INTEGRATED FORMS OF RATE EQUATIONS **NOT TESTED

 Used to relate the concentration [A] of a reactant to its initial concentration [A]0, the elapsed time t and
the rate constant k
 Previously, the differential rate equations relate the Rate (R) to the Concentration and Rate Constant
 To obtain the integrated forms of the 3 rate equations
 Consider firstly the two forms of rate (for first order reaction)
𝑑[𝐴]
1. 𝑅 = −
𝑑𝑡
2. 𝑅 = 𝑘 [𝐴]
 Next, equate the two equations
𝑑[𝐴]
 − = 𝑘 [𝐴 ]
𝑑𝑡
 Rearranging the equation, we get
1
 (𝑑[𝐴]) = −𝑘 𝑑𝑡
[𝐴 ]
 Integrating both sides of the equation, we get
1
 − ∫ [𝐴] (𝑑[𝐴]) = − ∫ 𝑘 𝑑𝑡
 ln[𝐴] = −𝑘𝑡 + ln[𝐴]0 (Since concentration at t = 0 is the initial concentration [A]0

Reaction Integrated Rate Equation y = mx + C form Gradient


Order
0 [𝐴] = [𝐴]0 − 𝑘𝑡 [𝐴] = −𝑘𝑡 + [𝐴]0 -k
−𝑘𝑡
1 [𝐴] = [𝐴]0 𝑒 ln[𝐴] = −𝑘𝑡 + ln[𝐴]0 -k

2 [𝐴]0 1 1 k
[𝐴] = = 𝑘𝑡 +
1 + 𝑘𝑡[𝐴]0 [𝐴] [𝐴]0

 Thus, by plotting the graphs of y = mx + C, one can determine if the reaction is a first order, second order
or zero order
 Obtaining half-life using these equations
 For zero order reactions
1
 [𝐴]0 = [𝐴]0 − 𝑘𝑡1
2 2
[𝐴 ]0
 𝑡1 =
2 2𝑘

 For first order reactions


1 −𝑘𝑡1
 [𝐴]0 = [𝐴]0 𝑒 2
2
1
 ln = −𝑘𝑡1
2 2
ln 2
 𝑡1 =
2 𝑘
 For 2nd order reactions
1 1
 1 = −𝑘𝑡1 +
[𝐴 ]0 2
[ 𝐴 ]0
2
1
 𝑡1 =
2 𝑘[𝐴]0

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8.7 EXPERIMENTAL TECHNIQUES FOR DETERMINING RATES OF REACTION

 Two different classes of techniques


 Continuous
 Data points for concentration are obtained at regular time intervals
 The reaction is allowed to run to completion
 All other reactants kept in large excess so that only the concentration of the reactant being
measured has an effect on the rate of reaction.
 Discontinuous
 Time taken for the reactant to reach a certain physical or chemical parameter is measured. The
reaction mixture is then quenched and discarded.
 More than one setup is used; reaction usually does not run to completion.
 Methods (discontinuous)
 Measuring the time taken for a particular colour to disappear
 E.g. Thiosulfate – Iodine reaction (measuring the rate of colour change)
 Tritrimetric method
 Every regular time interval, the sample is quenched and titration done to check the concentration
of the reactant.
 Suitable for moderately slow reactions
 Methods (continuous)
 Measuring change in gas pressure
 Applicable for reactions which involve changes in the number of moles of gases
 E.g. NO + O2  NO2
 Can also be a discontinuous technique
 Measuring changes in colour/colour intensity
 Change of colour intensity can be measured using a colourimeter or a spectrophotometer
 Measuring changes in electrical conductivity
 Applicable for reactions with a change in the number of ions

8.8 FACTORS AFFECTING RATE OF REACTIONS

 Temperature
 Increasing the temperature of a reaction system will increase the velocity of the particles within the
system, causing them to collide more frequently with each other. As a result, a greater proportion of
reactant collisions have sufficient kinetic energy to supply the activation energy required for the
formation of a product molecule. The frequency of effective collisions increases and this increases the
rate of reaction.
 Decreasing the temperature of a reaction system will decrease the velocity of the particles within the
system, causing them to collide less frequently with each other. As a result, a smaller proportion of
reactant collisions have sufficient kinetic energy to supply the activation energy required for the
formation of a product molecule. The frequency of effective collisions decreases and this decreases
the rate of reaction.

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EA


 (note: area under graph is constant)
 Concentration (Only for solution…)
 A more concentrated solution presents more particles per unit volume, allowing for more frequent
collisions of the reactant molecules which leads to a higher frequency of effective collisions between
reactant particles, increasing the rate of reaction
 A less concentrated solution presents less particles per unit volume, allowing for less frequent
collisions of the reactant molecules which leads to a lower frequency of effective collisions between
reactant particles, decreasing the rate of reaction
 Pressure (Only for gases…)
 A higher pressure presents more particles per unit volume, allowing for more frequent collisions of
the reactant molecules which leads to a higher frequency of effective collisions between reactant
particles, increasing the rate of reaction.
 A lower pressure presents less particles per unit volume, allowing for less frequent collisions of the
reactant molecules which leads to a lower frequency of effective collisions between reactant
particles, decreasing the rate of reaction
 Size of particle/Surface Area
 Increasing the surface area increases the number of particles on the surface available for collision,
thus increasing the frequency of effective collisions and increasing the rate of reaction.
 Decreasing the surface area decreases the number of particles on the surface available for collision,
thus decreasing the frequency of effective collisions and decreasing the rate of reaction.
 Effect of light
 Reactions initiated by the absorption of light are called photochemical reactions.
 Light provides energy for the breaking of chemical bonds during the reaction.
 Similar explanation to temperature.
 Nature of reaction
 Ionic reactions tend to have a low activation energy as oppositely charged ions are readily attracted
to each other.
 Reactions involving covalent compounds require high levels of activation energy to break the strong
covalent bonds in the reactants.
 Catalyst
 A catalyst is a substance that alters the rate of a chemical reaction by providing an alternative
pathway of lower activation energy without itself being chemically changed at the end of the reaction
 A catalyst provides a lower energy pathway for the reaction to occur.

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8.9 CATALYSIS

 Two types of catalyst


 Homogenous Catalyst
 Heterogenous catalyst
 Determined by the phase in which the catalyst and reactants are in (Phase = physically distinctive
form of matter)
 Homogenous catalysts
 Reactants are in the same phase as the reactant
 Allowing the reaction to proceed via a different mechanism by forming an intermediate with one of
the reactants.
 Its main function is to provide an alternative reaction pathway by forming an intermediate compound
which decomposes at a later stage to regenerate the catalyst


 E.g. Oxidation of iodide by peroxodisulfate ions
 Original Equation: 2I- (aq) + S2O82- (aq)  I2 (aq) + 2SO42- (aq)
 Iron-catalyzed reaction
 2Fe3+ (aq) + 2I- (aq)  2Fe2+ (aq) + I2 (aq)
 2Fe2+ (aq) + S2O82- (aq)  2Fe3+ (aq) + 2SO42- (aq)
 The uncatalyzed reaction is a collision between 2 negatively charged chemical species, causing
the activation energy to be high as the reactant ions repel each other.
 Fe3+ acts as an intermediate as it is positively charged and is able to easily attrasct the negatively
charged peroxodisulfate and iodide ions, thus lowering the activation energy and increasing the
rate of reaction.
 E.g. Oxidation of atmospheric SO2 to SO3 by nitrogen dioxide

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 Original Equation: SO2 + 1/2O2  SO3


 Catalyzed Reaction
 SO2 + NO2  SO3 + NO
 NO + 1/2O2  NO2
 Other examples
 Esterification (Concentrated sulphuric acid)
 Decomposition of hydrogen peroxide (ferric ion)
 Iodination of propanone (H+ ion)
 Heterogenous catalysts
 Catalyst is in a different phase as compared to the reactants (solid catalysts on liquid/gaseous
reactants)
 Catalysts with a larger surface area for adsorption to occur will allow for a faster reactions as more
catalytic sites would be available at any one time.
 Active site  A site on the surface of the heterogenous catalyst where catalysis takes place
 Mechanism
 Reactants diffuse onto catalyst surface before being adsorbed onto neighbouring sites, forming
weak partial bonds with the catalyst surface. The adsorption gives rise to a higher collision
frequency and the correct collision geometry.
 In chemisorption, a partial bond is formed between the absorbed species and the catalyst,
weakening the bonds in the reactant molecules and providing a lower activation energy for the
reaction.
 Desorption will then occur to free up catalytic sites.
 At saturation point (All active sites occupied), the order of reaction w.r.t. the reactant is zero (as all
active sites are fully occupied)
 Characteristics
 Effective in minute amounts
 Have empty d-orbitals
 Ability to exhibit various oxidation states
 Thus, transition metals or compounds of transition metals make good catalysts
 E.g. Removal of oxides of nitrogen in the exhaust gases from car gengines
 Exhaust gases passed through a honeycomb or bed of small beads made from alumina (aluminium
oxide) coated with Pt, Pd and Rh catalysts.
 E.g. Haber Process
 Conditions
 Ratio of N2 : H2 (1:3)
 Temperature: 450°C
 Pressure: 250 atm
 Catalyst: Finely divided iron catalyst  Increases rate of reaction
 Autocatalysis
 An autocatalyst is a reaction product which catalyzes the reaction itself.
 Reactions speed up at first due to autocatalysis and then slow down as reactant concentration
decreases.
 Biological Catalysts - Enzymes
 Considered homogenous catalysts
 For chemistry, no need to include specific terminology such as the four types of bonds, catalytic
sites/binding sites, etc. Do not go too much into detail for the mode of enzyme action
 No graphical questions will come up on enzyme concentration, temperature or pH (at most tested as
factors affecting enzymatic rates of reaction)
 Enzyme Kinetics

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 Initially, the order of reaction is first order w.r.t. substrate


 Once saturation is reached, the order of reaction is zero order w.r.t substrate
 Substances affecting the activity of catalysts
 Promoters (Catalysts that increase the activity of a given catalyst)
 Activators (Non-catalysts that increase the activity of certain catalysts (e.g. Zn2+ and Amlyase))
 Poisons (impurities that exert inhibitive effects on catalysts even in small amounts)
 Poisons are usually atoms or molecules possessing lone pairs of elections
 Poisons adsorb onto catalysts more strongly than reactants, thus effectively preventing their
access to the catalytic sites
 Inhibitors (substances capable of stopping or retarding a chemical reaction)
 E.g. Competitive and non-competitive inhibition

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9.1 THE PERIODIC TABLE: CHEMICAL PERIODICITY


 Group – A vertical column of elements in the periodic table that share similar chemical properties.
Elements in the same group have the same number of valence electrons.
 Period – A horizontal row of elements in the periodic table with the same highest principal quantum
number. Elements in the same period sow periodic changes in their physical and chemical quantities
 Focus is on the elements of Period III
 Na (s) – Mg (s) – Al (s) – Si (s) – P (s) – S (s) – Cl2 (g) – Ar (g)

*Where state symbols are not given, assume aqueous

9.1.3 CHEMICAL PERIODICITY OF THE ELEMENTS

Element Standard State Chemical Structure Appearance Electrical


Conductivity
Sodium Na (s) Metallic Bonding Shiny & Soft metal +
Magnesium Mg (s) Metallic Bonding Shiny Metal +
Aluminium Al (s) with thin layer of Metallic Bonding Shiny Metal +
Al2O3
Silicon Si (s) Giant Covalent Shiny Black Solid Semi-Conductor
Crystal
Phosphorus P4 (s) [White Simple Covalent Waxy Solid -
Phosphorus] Molecule Polymeric red powder
P (s) [Red Phosphorus]
Sulfur S8 (s) Simple Covalent Bright Yellow -
Molecule Crystalline Solid
Chlorine Cl2 (g) Simple Covalent Yellow-Green Toxic Gas -
Molecule
Argon Ar (g) Single Atom Colourless inert Gas -

 Trend in oxidation number of the period 3 oxides and chlorides


 Across the period, the oxidation number increases along with increasing variation in oxidation
number
 Oxidation numbers of the oxides are always positive since oxygen is the 2 nd most electronegative
element
 Metals only display one possible oxidation number, which corresponds to the loss of all their valence
electrons
 Non-metals in group 3 are able to expand their octet using vacant d-orbitals. The oxidation number
thus depends on the number of electrons used for bonding.

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9.1.2 CHEMICAL REACTIONS OF THE ELEMENTS

Chemical Reactions with Oxygen (O2)


Element Observations & Reactions Equations Appearance of oxides
Na  Tarnishes rapidly in air 2Na (s) + ½ O2 (g)  Na2O (s) White Ionic Solid
 Burns with a brilliant yellow flame
Mg  Tarnishes slowly in air Mg (s) + ½ O2 (g)  MgO (s) White Ionic Solid
 Burns with a bright white light, very
exothermic
Al  Protected from further oxidation 2Al (s) + 3/2 O2 (g)  Al2O3 (s) White Ionic Solid with
with Al2O3 some covalent
 Requires a temperature of > 800°C character
to convert much of Al to Al2O3
Si  No observable reactions Si (s) + O2 (g)  SiO2 (s) Giant Covalent
 Silicon dioxide can be formed if Crystal
silicon is heated strongly enough
P  White Phosphorous P4 catches fire 4P (s) + 3O2 (g)  P4O6 (s) White simple
spontaneously in air with a bright covalent molecules
white flame due to strained bond 4P (s) + 5O2 (g)  P4O10 (s)
angles.
 Red Phosphorous P8 burns on
heating with a soft orange flame
S  Burns on gentle heating with a pale S (s) + O2 (g)  SO2 (g) Colourless simple
blue flame covalent gas
SO2 (g)+ ½ O2 (g)  SO3 (g)
Cl  No observable reactions - -
Ar  No observable reactions - -

Chemical Reactions with Chlorine (Cl2)


Element Observations & Reactions Equations Appearance of
chlorides
Na  Burn readily, very exothermic Na (s) + ½ Cl2 (g)  NaCl (s) White Ionic Solid
Mg  Burn readily, very exothermic Mg (s) + Cl2 (g)  MgCl2 (s) White Ionic Solid
Al  Slow reaction at room Al (s) + 3/2 Cl2 (g)  AlCl3 (s) Pale yellow powder
temperature 2AlCl3 (g)  Al2Cl6 (g) Dimerizes at high
 Chlorine is usually passed over temperature
heated aluminium foil
Si  Slow reaction at room Si (s) + 2Cl2 (g)  SiCl4 (l) Colourless volatile
temperature simple covalent
 Chlorine is usually passed over molecule
heated silicon powder
P  White Phosphorous P4 burns ¼P (s) + 3/2 Cl2 (g)  PCl3 (l) Colourless simple
vigorously due to strained bond covalent molecule
angles. ¼ P (s) + 5/2 Cl2 (g)  PCl5 (s) Pale white solid
S  Chlorine is usually passed over 2S (s) + Cl2 (g)  S2Cl2 (l) Smelly orange simple
heated sulfur covalent liquid
Cl  No observable reactions - -
Ar  No observable reactions - -

Chemical Reactions with Water (H2O)


Element Observations & Reactions Equations

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Na  Rapid and violent reaction, very exothermic Na (s) + H2O (l)  NaOH + ½ H2 (g)
 Effervescence of a colourless and odourless gas
Mg  Slow reaction with cold water Mg (s) + 2 H2O (l)  Mg(OH)2 (s) + H2 (g)
 Rapid reaction with steam Mg (s) + H2O (g)  MgO (s) + H2 (g)
 Effervescence of a colourless and odourless gas
Al  No observable reactions due to Al2O3 layer -

Si  No observable reactions at room temperature Si (s) + 2 H2O (g)  SiO2 (s) + 2H2 (g)
 Reaction only occurs with steam and high
temperatures
P  No observable reactions -
S  No observable reactions -
Cl  Disproportionates in water to form an acidic Cl2 (g) + H2O (l) ⇌ HCl + HOCl
solution
Ar  No observable reactions -

9.1.3 PROPERTIES OF OXIDES

Element Standard Chemical Structure Solubility Acidity pH


State
Sodium Na2O (s) Giant Ionic Lattice Soluble Basic 13
Magnesium MgO (s) Giant Ionic Lattice Sparingly Basic 9
Aluminium Al2O3 (s) Giant Ionic Lattice Insoluble Amphoteric -
Silicon SiO2 (s) Giant Covalent Insoluble - -
Phosphorus P4O6 (s) Simple, Discrete covalent Soluble Acidic 2
P4O10 (s) molecules 2
Sulfur SO2 (g) Simple, Discrete covalent Soluble Acidic 2
SO3 (l) molecules 1

 Across the period, the bonding involved gradually changes from ionic to covalent
 This is due to the decrease in the difference in electronegativity between each element and
oxygen across the period.
 Metals have low ionization energies and tend to lose electrons to oxygen to form ionic
compounds
 Non-metals tend to have higher ionisation energies and tend to form covalent bonds
with oxygen.
 Trend in melting point
 High melting points for Na2O, MgO and Al2O3 as they are all giant ionic lattices and
require a large amount of energy to overcome the lattice energy
 The melting point of MgO is higher than that of Na2O as Mg2+ has a higher charge than
Na+, hence the lattice energy for MgO is higher than that of Na2O.
 Anomaly: Melting point of Al2O3 is lower than that of MgO due to the high charge
density of Al3+, which polarises the O2- ion and confers covalent character to Al2O3. The
lattice energy of Al2O3 is thus smaller than that of MgO.
 Silicon Dioxide has a very high melting point as it exists as a giant covalent crystal with high
bond dissociation energies of the Si-O bonds. A large amount of energy is required to overcome the
bond dissociation energy, resulting in a high melting point.
 Oxides of phosphorus and sulfur have low melting points as they exist as simple covalent molecules
held together with weak van der waals attraction.
 P4O10 sublimes at 360°C

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ACID-BASE REACTIONS OF THE OXIDES & HYDROXIDES

Oxide Reaction with H2O Reaction with H+ Reaction with OH- pH


Na2O Reacts violently with water to Dissolves in acids to - 13
form an basic solution produce a salt solution
via neutralization
Na2O (s) + H2O (l)  2NaOH
Na2O (s) + 2H+  2Na+
+ H2O (l)
NaOH - Dissolves in acids to - 13
produce a salt solution
via neutralization

NaOH + H+ Na++ H2O


(l)

MgO Slow reaction, limited Dissolves in acids to - 9


solubility. Magnesium produce a salt solution
hydroxide formed is also only via neutralization
sparingly soluble
MgO (s) + 2H+ Mg2+ +
MgO (s) + H2O (l)  Mg(OH)2 H2O (l)

Mg(OH)2 (s) ⇌ Mg2+ + 2OH-


Mg(OH)2 - Dissolves in acids to - 9
produce a salt solution
via neutralization

Mg(OH)2 + 2H+  Mg2+


+ 2H2O (l)
Al2O3 Insoluble due to high lattice Dissolves in acids to Dissolves in excess bases -
energy produce a salt solution to form a colourless
via neutralization solution

Al2O3 (s) + 6H+  2Al3+ + Al2O3 (s) + 2OH- + 3H2O (l)


3H2O (l)  2[Al(OH)4]-
Al(OH)3 Insoluble due to high lattice Dissolves in acids to Dissolves in excess bases -
energy produce a salt solution to form a colourless
via neutralization solution

Al(OH)3 (s) + 3H+  Al3+ Al(OH)3 (s) + OH- 


+ 3H2O (l) [Al(OH)4]-
SiO2 Insoluble due to high bond - Dissolves in hot, -
dissociation energy concentrated and excess
strong bases via
neutralization

SiO2 (s) + 2OH-  SiO32- +


H2O (l)
P4O6 Reacts with cold water to - Dissolves in bases to 2
form an acidic solution of produce a salt solution
disbasic phosphorous acid via neutralization

P4O6 (s) + 6H2O (l)  4H3PO3 P4O6 (s) + 8OH-  4HPO32-


+ 2H2O (l)

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H3PO3 ⇌ H2PO3- + H+
P4O10 Reacts violently with water to - Dissolves in bases to 2.15
form an acidic solution of produce a salt solution
tribasic phosphoric acid via neutralization

P4O10 (s) + 6H2O (l)  4H3PO4 P4O10 (s) + 12OH- 


4PO43- + 6H2O (l)
H3PO4 ⇌ H2PO4- + H+
SO2 Reacts with water to form an Reacts with bases to 1.8
acidic solution of disbasic produce a salt solution
sulfurous acid via neutralization

SO2 (g) + H2O (l)  H2SO3 SO2 (g) + 2OH-  SO32- +


H2O (l)
H2SO3 ⇌ HSO3-+ H+
SO3 Reacts violently with water to Reacts with bases to 1
form an acidic solution of produce a salt solution
dibasic sulfuric acid via neutralization

SO3 (g) + H2O (l)  H2SO4 SO3 (g) + 2OH-  SO42- +


H2O (l)
H2SO4 ⇌ HSO4-+ H+

9.1.4 PROPERTIES OF CHLORIDES

Element Standard Chemical Structure Solubility Acidity pH when added


State to water
Sodium NaCl (s) Giant Ionic Lattice Neutral 7
Magnesium MgCl2 (s) Giant Ionic Lattice Hydrolyses slightly 6.5
Aluminium AlCl3 (s) Giant Ionic Lattice/ Hydrolyses to a 3
Simple, Discrete covalent large extent
molecules in gaseous
Soluble
phase
Silicon SiCl4 (l) Simple, Discrete covalent Forms HCl 1
molecules
Phosphorus PCl3 (l) Simple, Discrete covalent Forms HCl 1
PCl5 (s) molecules 1

 Across the period, the bonding involved gradually changes from ionic to covalent
 This is due to the decrease in the difference in electronegativity between each element and chlorine
across the period.
 Metals have low ionization energies and tend to lose electrons to oxygen to form ionic compounds
 Non-metals tend to have higher ionisation energies and tend to form covalent bonds with oxygen.
 Trend in melting point
 High melting points for NaCl, MgCl2 and AlCl3 as they are all giant ionic lattices and require a large
amount of energy to overcome the lattice energy
 The melting point of MgCl2 is lower than that of NaCl as Mg2+ has a higher charge density than Na+,
allowing it to polarize the Cl- ion
 Anomaly: Melting point of AlCl3 is lower than that of MgCl2 due to the high charge density of Al3+, which
polarises the Cl- ion and confers covalent character to AlCl 3. The lattice energy of AlCl3 is thus smaller
than that of MgCl2.
 Since Al is electron deficient, AlCl3 sublimes at 180°C to form a dimer Al2Cl6

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 2 AlCl3 ⇌ Al2Cl6 ∆H < 0


 Silicon Dichloride and Phosphorous Trichloride exist as simple discrete covalent molecules held
together by weak dispersion forces between molecules. Since less energy is required to overcome these
forces, they have considerably lower melting points compared to the metallic chlorides.
 PCl5 exists as exist as simple discrete covalent molecules held together by weak dispersion forces
between molecules. However, it autoionizes to form PCl 4+ + PCl6- at room temperature, forming an ionic
solid (not in syllabus)

REACTION OF CHLORIDES WITH WATER

Chloride Observations Reactions pH


NaCl Solid dissolves in water NaCl (s)  Na+ + Cl- 7
to form a colourless
solution Na+ has too low a charge density to undergo hydrolysis
MgCl2 Solid dissolves in water MgCl2 (s) + 6 H2O (l)  [Mg(H2O)6]2+ + 2 Cl- 6.5
to form a colourless
solution [Mg(H2O)6]2+ + H2O (l) ⇌ [Mg(H2O)5(OH)]+ + H3O+
Magnesium has a high charge density and undergoes
slight hydrolysis to yield a weakly acidic solution
AlCl3 Addition of water In limited H2O 3
dropwise causes white AlCl3 (s) + 3 H2O (l)  Al(OH)3 (s) + 3 HCl (g)
fumes of HCl to be
produced along with In excess H2O
an insoluble white AlCl3 (s) + 6 H2O (l)  [Al(H2O)6]3+ + 3 Cl-
solid [Al(H2O)6]3+ + H2O (l) ⇌ [Al(H2O)5(OH)]2+ + H3O+

Addition of excess Aluminium has a very high charge density and


water causes the solid undergoes hydrolysis to yield an acidic solution by
to dissolve to form a polarizing and breaking the O-H bonds
colourless solution
Adding a strong base strop wise causes deprotonation
until a white ppt is formed
[Al(H2O)5(OH)]2+ + OH- (l) ⇌ [Al(H2O)4(OH)2]+ + H2O (l)
[Al(H2O)4(OH)2]+ + OH- (l) ⇌ [Al(H2O)3(OH)3](s) + H2O (l)

Adding an excess of a strong base causes the white ppt


to dissolve to form a colourless solution
[Al(H2O)3(OH)3](s) + OH- (l) ⇌ [Al(OH)4]- + 3 H2O (l)

SiCl4 Complete Hydrolysis 1


SiCl4 (l) + 4 H2O (l)  SiO2∙(H2O)2 + 4 HCl

PCl3 Complete Hydrolysis 1


PCl3 (l) + 3 H2O (l)  H3PO3 + 3 HCl
Violent Reaction
producing white fumes
of HCl gas
PCl5 Complete Hydrolysis 1
PCl5 (s) + 4 H2O (l)  H3PO4 + 3 HCl

Adding water dropwise


PCl5 (s) + H2O (l)  HOCl3 + 2 HCl (g)

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*CCl4 is inert as there is a lack of 3d orbitals to receive electrons donated by water molecules. The small carbon
atom is also shielded from attack by 4 large chloride ions. Hence CCl4 is inert unlike SiCl4

GRAPHS SUMMARY OF PERIODICITY

Melting/Boiling Point of Period 3 Elements Relative Electrical Conductivity (Al = 1)


3000 1.2

2500 1
Temperature (°C)

Electrical Conductivity
2000
0.8
1500
0.6
1000
0.4
500

0.2
0
Na Mg Al Si P S Cl Ar
0
Melting Point Boiling Point Na Mg Al Si P S Cl Ar

Melting/Boiling Point of Period 3 Chlorides Melting/Boiling Point of Period 3 Oxides


1600 3000
1400
2500
1200
Temperature (°C)

2000
Temperature (°C)

1000
800
1500
600
400 1000
200 500
0
-200 NaCl MgCl2 AlCl3 SiCl4 PCl3 PCl5 0

Melting Point Boiling Point -500

pH of Chlorides pH of Oxides
8 14

7 12
6 10
5 8
pH
pH

4 6
3 4
2 2
1 0
0
NaCl MgCl2 AlCl3 SiCl4 PCl3 PCl5

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9.2 GROUP II (ALKALINE EARTH METALS)


 Alkaline – Oxides dissolve in water to form alkaline solutions
 Earth Metals – High melting point of oxides

*Where state symbols are not given, assume aqueous

9.2.2 PHYSICAL PERIODICITY OF GROUP II ELEMENTS

 Atomic and Ionic Radii


 Down the group, the atomic and ionic radii increases due to an increase in the number of quantum
shells.
 1 and 2nd ionisation energies
st

 Down the group, the 1st and 2nd ionisation energies decrease. This is due to an increase in the shielding
effect caused by the increase in inner core shells, hence less energy is required to remove the valence
electrons down the group
 Melting and Boiling Points
 Down the group, the melting and boiling points of the group II metals decrease due to a decrease in
charge density as ionic radii increases down the group. This causes the strength of the metallic bonding
present to decrease down the group, hence less energy is required to overcome the metallic bonds
present down the group.
 Hardness & Density
 The density of the metals increases down the group as atomic mass increases to a greater extent
compared to atomic volume.
 The hardness of the metals decreases down the group due to a decrease in metallic bond strength
 Electrical & Thermal Conductivity
 Grp II metals are generally good conductors of heat and electricity due to the presence of delocalized
valence electrons which act as mobile charge carriers and facilitate thermal energy transfer.
 Solubility
 Solubility of group II sulfates decreases down the group
 Solubility of group II hydroxides increases down the group

9.2.3 CHEMICAL PROPERTIES OF GROUP II ELEMENTS

 Reducing Power & Reactivity


 The reactivity & reducing power of group II metals increased down the group due to a decrease in 1 st
and 2nd ionization energies
 This causes the E0 of the equation (M2+ + 2e- ⇌ M(s) ) to be increasingly negative
 All Alkaline Earth Metals have a fixed oxidation state of +2
 Electronic Configuration: ns2 ; the 2 valence electrons are most easily removed as the nucleus exerts a
smaller attractive force on the 2 electrons due to the shielding effect of the core electrons.
 Much higher lattice energy of M2+ ionic compounds will cause M+ compounds to disproportionate to
form M2+ and M.
 The 3rd oxidation state is not possible as the 3rd ionisation energy is much higher than either the 1st or
2nd ionization energy. The energy required cannot be compensated by the higher lattice energy of M 3+
ionic salts.
 Acidity of metallic cations
 Both magnesium and beryllium have sufficiently high charge density to undergo hydrolysis in water to
form an acidic solution

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 [Be(H2O)4]2+ + H2O (l) ⇌ [Be(H2O)3(OH)]+ + H3O+


 [Mg(H2O)6]2+ + H2O (l) ⇌ [Mg(H2O)5(OH)]+ + H3O+
 Covalency of Beryllium
 Beryllium compounds have a covalent nature due to the high charge density of beryllium
 BeCl2 exists as linear polymers in the solid state and as a simple covalent molecule in the gaseous state

Chemical Reactions with Oxygen (O2)


Element Observations & Reactions Equations Appearance of oxides
Be  Does not react with air at room Be (s) + ½ O2 (g)  BeO (s) Colourless Crystal
temperature
 Protected from further oxidation
with BeO (s)
Mg  Tarnishes slowly in air Mg (s) + ½ O2 (g)  MgO (s) White Ionic Solid
 Burns with a bright white light, very
exothermic
Ca  Tarnishes slowly in air Ca (s) + ½ O2 (g)  CaO (s) White Ionic Solid
 Burns with a brick-red light, very
exothermic
Sr  Tarnishes quickly in air Sr (s) + ½ O2 (g)  SrO (s) White Ionic Solid
 Burns with a crimson red light, very
exothermic
Ba  Tarnishes extremely quickly in air Ba (s) + ½ O2 (g)  BaO (s) White Ionic Solid
 Burns with a pale green light,
explosive

Chemical Reactions with Water (H2O)


Element Observations & Reactions Equations
Be  Does not react with water due to -
presence of BeO layer
Mg  Slow reaction with cold water to form a Mg (s) + H2O (g)  MgO + H2 (g)
white solid Mg (s) + 2 H2O (l)  Mg(OH)2 (s) + H2 (g)
 Rapid reaction with steam
 Effervescence of a colourless and
odourless gas
Ca  Slow reaction with cold water to form a Ca (s) + 2 H2O (l)  Ca(OH)2 (s) + H2 (g)
white solid
 Effervescence of a colourless and
odourless gas
Sr  Vigorous reaction with cold water Sr (s) + 2 H2O (l)  Sr(OH)2 + H2 (g)
 Effervescence of a colourless and
odourless gas
Ba  Very Vigorous reaction with cold water Ba (s) + 2 H2O (l)  Ba(OH)2 + H2 (g)
 Rapid effervescence of a colourless and
odourless gas

9.2.4 PROPERTIES OF GROUP II OXIDES

Element Standard Chemical Structure Solubility Acidity pKb


State (hydroxide)
Beryllium BeO (s) Giant Ionic Lattice with Insoluble Amphoteric -
partial covalent character
Magnesium MgO (s) Giant Ionic Lattice Sparingly Basic -

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Calcium CaO (s) Giant Ionic Lattice Sparingly Basic 2.37


Strontium SrO (s) Giant Ionic Lattice Soluble Basic -2.19
Barium BaO (s) Giant Ionic Lattice Soluble Basic -2.02

 Properties of Group II oxides


 All ionic white solids
 Extremely high melting point which decreased down the group due to a decrease in lattice energy
 All basic except for BeO
 Reactivity with water increases down the group due to a decrease in lattice energy of the compounds as
ionic radii increases.
 Beryllium Oxide is an amphoteric oxide
 BeO (s) + H+  Be2+ + H2O (l)
 BeO (s) + 2OH- + H2O (l)  [Be(OH)4]2-

REACTION OF OXIDES WITH WATER

In general, MO (s) + H2O (l)  M(OH)2

Oxide Observations Reactions


BeO No observable reactions -
MgO Sparingly soluble to form an alkaline solution MgO (s) + H2O (l)  Mg(OH)2 (s)
Mg(OH)2 (s) ⇌ Mg2+ + 2OH-
CaO Sparingly soluble to form an alkaline solution CaO (s) + H2O (l)  Ca(OH)2 (s)
Ca(OH)2 (s) ⇌ Ca2+ + 2OH-
SrO Dissolves to form an alkaline solution SrO (s) + H2O (l)  Sr(OH)2
Sr(OH)2  Sr2+ + 2OH-
BaO Dissolves to form an alkaline solution BaO (s) + H2O (l)  Ba(OH)2
Ba(OH)2  Ba2+ + 2OH-

9.2.5 THERMAL STABILITY OF GROUP II COMPOUNDS

Melting Points/Decomposition Temperature of Grp II Compounds


3500

3000

2500

2000

1500

1000

500

0
Be Mg Ca Sr Ba

Carbonates Nitrates Hydroxides Oxide

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 In general, the decomposition temperatures for carbonates, nitrates and hydroxides increases down the
group.
 The polarizing power of the cations decreases down the group due to a decrease in charge density (as
ionic radii increases). A cation with a high polarizing power such as Mg2+ is able to weaken the covalent
bonds within the large anion by polarizing the anion’s electron cloud.
 Down the group, the lower the polarizing power of the cations and the less likely covalent bonds within
the anion will be broken.
 This increases the thermal stability down the group such that a higher temperature is required to
decompose the compound
 Formulas for decomposition
 M(NO3)2 (s)  MO (s) + 2NO2 (g) + ½ O2 (g)
 M(OH)2 (s)  MO (s) + H2O (g)
 MCO3 (s)  MO (s) + CO2 (g) + H2O (g)
 Oxides do not undergo decomposition as O2- ions cannot be broken down further

9.2.6 COMPARISON WITH ALKALINE METALS (GRP I)

 Group II metals have higher melting and boiling points due to a higher charge density, which increases the
strength of the metallic bonds present.
 The carbonates & nitrates of group I metals do not undergo thermal decomposition to the same extent due
to the low charge density of group I metals
 Group I nitrates decompose to form nitrites and oxygen gas
 Group I carbonates do not undergo decomposition (except lithium, which has a higher charge density)

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9.3 GROUP VII (HALOGENS)


 Halogens – Compounds that form salts with metals

9.3.1 PHYSICAL PERIODICITY OF GROUP VII ELEMENTS

 Covalent and Ionic Radii


 Covalent Radii – Half the distance between 2 covalently bonded atoms in a diatomic molecule
 Down the group, the covalent and ionic radii increases due to an increase in the number of quantum
shells.
 Bond Energy
 Down the group, the bond energies of the X-X bond decreases due to an increase in covalent radii,
which decreases the effectiveness of orbital overlap
 Anomaly: B.E.(F-F) < B.E (Cl-Cl) since fluorine is a small atom which leads to repulsion between the lone
pairs of electrons on fluorine atoms.
 1st ionisation energies
 Down the group, the 1st ionisation energies decrease. This is due to an increase in the shielding effect
caused by the increase in inner core shells, hence less energy is required to remove the valence
electrons down the group
 1st electron affinity
 Down the group, the 1st electron affinity decrease. This is due to an increase in the shielding effect
caused by the increase in inner core shells, hence the ability of the halogen atom to accept an electron
decreases down the group, causing first electron affinity to be less exothermic.
 Anomaly: The small size of the fluorine atom causes the electron to be added to experience strong
repulsion from the electrons already present, resulting in a less exothermic first electron affinity.
 Electronegativity
 Down the group, electronegativity decreases. This is due to an increase in the shielding effect caused
by the increase in inner core shells, hence the ability of the halogen atom to accept an electron
decreases down the group.
 Melting and Boiling Points
 The halogens exist as simple discrete covalent molecules held together by weak dispersion forces.
 Down the group, the melting and boiling points of the halogens increase due to an increase in the size
of the electron cloud. This causes the strength of the dispersion forces present to increase down the
group, hence more energy is required to overcome the dispersion forces present down the group.
[Note: Iodine sublimes rather than reacts]
 Hence, the volatility of the halogens decreases down the group.
 Colour

Element Gaseous State Liquid State Solid State Aqueous Solution Non-polar Solvent
Fluorine Pale Yellow - - - Very pale yellow
Chlorine Yellow-Green - - Colourless [Dilute] Very pale green
/Pale Yellow [Conc]
Bromine Reddish-Brown Reddish- - Yellow [Dilute] / Orange-Reddish
Brown Orange [Conc] Brown
Iodine Dark Purple - Shiny Black Pale Yellow (H2O) Violet
Brown (I-)

 Solubility in water
 Solubility of the halogens vary across the group

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 Fluorine reacts with water readily while 30% of chlorine reacts


 Solubility in non-polar solvents
 Halogens are more soluble in non-polar solvents as they share similar intermolecular forces.

9.3.2 CHEMICAL PROPERTIES OF GROUP VII ELEMENTS

 Oxidation State
 For fluorine, there are only 2 oxidation states possible: 0 and -1
 Fluorine does not have any low-lying empty d-orbitals to accommodate an expanded octet shell
 Fluorine is also the most electronegative element and cannot be oxidized by any other element
 For chlorine, bromine and iodine, there are 6 oxidation states possible
 Possible oxidation states: -1, 0, +1, +3, +5, +7
 Cl, Br and I have low-lying empty d-orbitals to accommodate an expanded octet shell
 Cl, Br and I can be oxidized by other elements
 -1 is the most stable oxidation state
 Oxidizing Power
 The reactivity & oxidizing power of halogens decreases down the group due to a decrease in 1st electron
affinity
 This causes the E0 of the equation ( X2 (std) + 2e- ⇌ 2X- ) to be increasingly less positive down the group

9.3.2.1 REACTION WITH IONS AND AQUEOUS SOLUTIONS

Disproportionation Reactions with Water (H2O)


Element Observations & Reactions Equations
F  Rapid & vigorous reaction with cold 2F2 (g) + 2H2O (l)  4HF (g) + O2 (g)
water 3F2 (g) + 3H2O (l)  6HF (g) + O3 (g)
 Effervescence of a colourless and
odourless gas (Oxygen disproportionated)
 Formation of white fumes of HF
Cl  Soluble in water, forming a very pale Cl2 (g) + H2O (l) ⇌ HOCl + HCl
green solution
Br  Soluble in water, forming an orange to Br2 (l) + H2O (l) ⇌ HOBr + HBr
reddish-brown solution
I  Slightly soluble in water I2 (s) + H2O (l) ⇌ HOI + HI
 Soluble in a solution of iodide ions to I2 (s) + I- ⇌ I3-
form a brown solution

Disproportionation Reactions with hydroxide ions (OH-)


Element Conditions Equations
Cl Cold Alkali (15°C) Cl2 (g) + 2OH-  OCl- + Cl- + H2O (l)
Hot Alkali (70°C) Cl2 (g) + 2OH-  OCl- + Cl- + H2O (l)
3OCl-  2Cl- + ClO3-

Overall: 3Cl2 (g) + 6OH  ClO3- + 5Cl- + 3H2O (l)


Br Cold Alkali (15°C) Br2 (l) + 2OH-  OBr- + Br- + H2O (l)
Very cold Alkali (0°C) Br2 (l) + 2OH-  OBr- + Br- + H2O (l)
3OBr-  2Br- + BrO3-

Overall: 3Br2 (g) + 6OH  BrO3- + 5Br- + 3H2O (l)

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I Any Temperature I2 (s) + 2OH-  OI- + I- + H2O (l)


3OI-  2I- + IO3-

Overall: 3I2 (s) + 6OH-  IO3- + 5I- + 3H2O (l)

 Displacement reactions
 Halogens that are higher in the group can oxidize a halide below it. The less reactive halide is
displaced for a more reactive one.
 This causes the aqueous solution to change colour and form the less reaction halogen
 Reaction with aqueous solutions containing Fe2+ ions
 All halogens excluding iodine will oxidize Fe2+ to Fe3+ (Check Ecell value)
 Reaction with thiosulfate (S2O32-)
 All halogens will oxidize thiosulfate ions
 For fluorine, bromine and chlorine, thiosulfate (+2) is oxidized to sulphate (+6)
 4X2 + S2O32- + 5H2O (l)  8X- + 2SO42- + 10H+
 For iodine, thiosulfate (+2) is oxidized to tetrathionate (+2.5) as iodine is a weak oxidizing agent
 I2 + 2S2O32-  2I- + S4O62-

9.3.2.1 REACTION WITH METALS

 Reaction with sodium metal


 All halogens vapours react with sodium, which burn with a bright orange flame to form a white ionic
solid
 Na (s) + X2 (g)  2NaX (s)
 Reaction with iron metal
 All halogens will oxidize iron metal
 For fluorine, bromine and chlorine, iron metal (0) is oxidized to ferric ions (+3)
 3X2 (g) + Fe (s)  2FeX3 (s)
 For iodine, iron metal (0) is oxidized to ferrous ions (+2) as iodine is a weak oxidizing agent
 I2 (g) + Fe (s)  FeI2 (s)

9.3.2.1 REACTION WITH NON-METALS

 Fluorine – Reacts with almost all non-metallic elements except argon and neon
 Chlorine, Bromine and Iodine – Reacts with most non-metallic elements except noble gases
 Reaction with Phosphorus
 Conditions: Room temperature
 All Halogens: 2P (s) + 3X2 (std)  2PX3 (l)
 Further reaction: 2PX3 (l) + X2 (std) ⇌ 2PX5 (s) (PX5 must be removed immediately for high yield ; X can
only be bromine or chlorine)
 If in excess of Cl2 or Br2, 2P (s) + 5X2 (std)  2PX5 (l)

Reactions with Hydrogen (H2)


Element Observations & Reactions Equations
F  Rapid & vigorous reaction with F2 (g) + H2 (g)  2HF (g)
hydrogen gas even in the dark and at
very low temperatures
 Formation of white fumes of HF
Cl  Rapid & vigorous reaction with Cl2 (g) + H2 (g)  2HCl (g)
hydrogen gas even in the dark
temperatures

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 Slow reaction at low temperatures


<200°C
 Formation of white fumes of HCl
Br  Slow reaction, requires heat to be Br2 (g) + H2 (g)  2HBr (g)
applied at 300°C with a platinum
catalyst
 Formation of white fumes of HBr
I  Slow and reversible reaction, requires I2 (g) + H2 (g) ⇌ 2HI (g)
heat to be applied at 300°C with a
platinum catalyst
 Equilibrium mixture obtained
 Positive enthalpy change

9.3.2 CHEMICAL PROPERTIES OF HALIDES

 Physical State: All hydrogen halides exist as colourless gases at room temperature and 1 atm, forming
fumes in moist air (Discrete covalent molecules)
 Melting & Boiling Point
 HF has an abnormally high melting and boiling point due to the presence of hydrogen bonds between
HF molecules which require more energy to overcome compared to van der waals forces.
 The melting and boiling points increases from HCl to HI due to the increasing size of the electron
cloud, which increases the strength of the dispersion forces present.
 Thermal Stability
 Decomposition: 2HX (g)  H2 (g) + X2 (g)
 Down the group, thermal stability decreases due to a decrease in the strength of the H-X bond as bon
length increases. Less energy is required to overcome the H-X bond down the group, hence the
thermal stability of the hydrogen halides decreases down the group.
 Acid Strength
 HCl, HBr and HI are strong acids
 HX + H2O (l)  H3O+ + X- ; X = Cl, Br, I
 The acid strength increases down the group due to the decreasing strength of the H-X bond, which
allows for the H+ ion to be more easily released.
 HF is a weak acid as the H-F bond is too strong and H-F tends to interact via hydrogen bonds with
water molecules rather than ion-dipole interactions.

9.3.2.1 PRECIPITATION REACTIONS OF HALIDES

 Reaction with Silver ions


 Silver Fluoride is soluble
 Precipitation occurs when silver ions and halide ions (Cl, Br, I) are present in the same aqueous
solution. Complex formation takes place in the presence of aqueous ammonia.
 Ag+ + X-  AgX (s)
 Ag+ + 2NH3 ⇌ [Ag(NH3)2]+
 In the presence of aqueous ammonia, silver ions complex with aqueous ammonia to form the silver
diamine complex, which is soluble. This causes the concentration of silver ions to decrease, which
causes the ionic product of the corresponding AgX salt to drop until it is smaller than its
corresponding solubility product. As a result, the precipitate dissolves.
 For AgI, the solubility product is so low that IP (AgI) is always larger and hence AgI will not dissolve in
excess aqueous ammonia.

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Halide Ion F- Cl- Br- I-


Reaction with No ppt White ppt Cream ppt Yellow ppt
AgNO3
Solubility of AgX in - Soluble in dilute Soluble in Insoluble
aqueous ammonia aqueous ammonia concentrated
excess aqueous
ammonia

 Reaction with lead (II) ions


 Precipitation occurs when silver ions and halide ions (F, Cl, Br, I) are present in the same aqueous
solution. Complex formation takes place in the presence of excess halide ions. (Explain in a similar
way to that of AgX)
 Pb2+ + 2X-  PbX2 (s)
 Pb2+ + 4X- ⇌ [PbX4]2-
 Lead (II) Iodide is soluble, the rest of the precipitates are insoluble

9.3.2.2 ACID-BASE REACTIONS OF HALIDES

 Reaction with concentrated H2SO4


 Due to the strength of sulphuric acid, it is able to donate a proton to X - to form HX via an acid-base
reaction.
 MX (s) + H2SO4 (l)  HX (g) + MHSO4 (s)
 Concentrated sulfuric acid also acts as an oxidizing agent while iodide and bromide ions can act as
reducing agents to reduce sulfuric acid.

Acid-Base/Redox Reactions with concentrated sulfuric acid (H2SO4 (l) ) m = alkaline metal
Element Observations & Reactions Equations
F  Formation of white fumes of HF MF (s) + H2SO4 (l)  HF (g) + MHSO4 (s)

Cl  Formation of white fumes of HCl MCl (s) + H2SO4 (l)  HCl (g) + MHSO4 (s)

Br  Formation of white fumes of HBr MBr (s) + H2SO4 (l)  HBr (g) + MHSO4 (s)
 Formation of reddish-brown fumes of 2HBr (g) + H2SO4 (l)  Br2 (g) + SO2 (g) + 2H2O (l)
Br2
I  Formation of white fumes of HI MI (s) + H2SO4 (l)  Hl (g) + MHSO4 (s)
 Formation of violet fumes of I2 2HI (g) + H2SO4 (l)  I2 (g) + SO2 (g) + 2H2O (l)
 Formation of a yellow solid 6HI (g) + H2SO4 (l)  3I2 (g) + S (s) + 4H2O (l)
 Evolution of a pungent and colourless 8HI (g) + H2SO4 (l)  4I2 (g) + H2S (g) + 4H2O (l)
gas

 Reaction with concentrated sulfuric acid in the presence of MnO2 (s)


 MnO2 is a stronger oxidizing agent than concentrated sulfuric acid and can oxidize HCl (g) to Cl2 (g)
 MCl (s) + H2SO4 (l)  HCl (g) + MHSO4 (s)
 4HCl (g) + MnO2 (s)  Cl2 (g) + MnCl2 (s) + 2H2O (l)
 Reaction with concentrated phosphoric acid
 MX (s) + H3PO4 (l)  HX (g) + MH2PO4 (s)
 Phosphoric acid is a weak oxidizing agent and cannot oxidize bromide or iodide ions to bromine and
iodine

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9.4 AN INTRODUCTION TO THE


CHEMISTRY OF TRANSITION ELEMENTS
Definition: A transition element is a d-block element that forms some compounds containing its ion with an
incomplete d-subshell

Thus by definition, Zn and Sc are NOT transition elements

9.4.1 ELECTRONIC CONFIGURATION OF TRANSITION ELEMENTS

Electron in Box Diagram


Element Full Electronic Configuration 3d 4s
Ca [Ar] 4s2 ↿⇂
Sc [Ar] 3d1 4s2 ↿ ↿⇂
Ti [Ar] 3d2 4s2 ↿ ↿ ↿⇂
V [Ar] 3d3 4s2 ↿ ↿ ↿ ↿⇂
Cr [Ar] 3d5 4s1 ↿ ↿ ↿ ↿ ↿ ↿
Mn [Ar] 3d5 4s2 ↿ ↿ ↿ ↿ ↿ ↿⇂
Fe [Ar] 3d6 4s2 ↿⇂ ↿ ↿ ↿ ↿ ↿⇂
Co [Ar] 3d7 4s2 ↿⇂ ↿⇂ ↿ ↿ ↿ ↿⇂
Ni [Ar] 3d8 4s2 ↿⇂ ↿⇂ ↿⇂ ↿ ↿ ↿⇂
Cu [Ar] 3d10 4s1 ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿
Zn [Ar] 3d10 4s2 ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂ ↿⇂

 To note
 Only Chromium & Copper at its ground state has one electron in the 4s orbital
 By Hund’s rule of maximum spin multiplicity, a half-filled orbital is more stable than a fully filled orbital
due to the absence of inter-electronic repulsion, thus the reason for the electronic configurations of
Chromium and Copper.
 The 4s orbital is lower in energy than the 3d orbital, and is thus filled first before the 3d orbital
 To find the electronic configuration of the ions, remove electrons from the highest energy level orbital
depending on the charge

9.4.2 PHYSICAL PROPERTIES OF TRANSITION ELEMENTS

 Trend in Atomic Radii


 Decreases slightly (but generally invariant)
 Even though nuclear charge increases due to the increasing number of protons, the electrons are also
added to the inner 3d subshell, which increases the shielding effect. The increase in shielding effect
generally nullifies the increase in nuclear charge, resulting in an almost constant effective nuclear
charge.
 Trend in Ionic Radii
 Invariant
 Trend in 1st ionization energy
 Increases slightly (but generally invariant)
 This is due to a slight increase in nuclear charge even though the atomic radii is generally the same (as
explained above)

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 Melting and boiling points


 Melting and boiling points are generally higher than alkali and alkali earth metals as both 3d and 4s
electrons are involved in metallic bonding due to similar energy levels, causing the metallic bonds
formed to be stronger than those of s-block metals
 Electrons of shells that are stable tend not to delocalized, as well as one of the electrons that are paired,
resulting in weaker metallic bonding
 Trend in density
 Higher than s-block metals due to tighter metallic packing caused by the larger number of delocalized
electrons
 Transition metals also tend to have higher atomic masses and smaller atomic radius than s-block metals,
thus contributing to its high density
 Density increases along the period due to an increase in relative atomic mass and a small decrease in
atomic radius
 Zinc is not dense due to its inability to delocalize large number of electrons for metallic bonding as it
has a full 3d and 4s shell. The weaker metallic bonds causes the zinc to be less dense than copper
 Electrical Conductivity
 Higher electrical conductivity than s-block metals as more electrons are delocalized for metallic bonding

9.4.3 CHEMICAL PROPERTIES OF TRANSITION ELEMENTS

9.4.3A VARIABLE OXIDATION STATES

 Reason: Due to the similarity in energy levels between the 3d and 4s electrons. Once the 4s electrons are
removed, the 3d electrons can be removed without much more energy being required
Element Possible Oxidation States Common Compounds
Sc +3 Sc(OH)3
Ti +1,+2,+3,+4 TiO2
V +1,+2,+3,+4,+5 V2O5
Cr +1,+2,+3,+4,+5,+6 CrCl3, CrO42-, Cr2O72-
Mn +1,+2,+3,+4,+5,+6,+7 MnCl2 , MnO2, MnO42-, MnO4-
Fe +1,+2,+3,+4,+5,+6 FeCl2, Fe2O3
Co +1,+2,+3,+4,+5 CoO, Co(OH)3
Ni +1,+2,+3,+4 NiO
Cu +1,+2,+3 CuCl, Cu(OH)2
Zn +2 ZnO

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 Trends in oxidation states


 There is an increase in the number of oxidation states rom Sc to Mn as all the available 3d and 4s
electrons can be used in bonding
 From Mn to Zn, there is a decrease in the number of oxidation states as the paired electrons cannot be
used for bonding (suborbital fully filled)
 Lower oxidation states usually found in ionic compounds, higher oxidation states involve covalency and
oxo-anions
 The +3 oxidation state tends to be less stable than the +2 state (Except Cr)
 Redox trends
 Transition metals in a high oxidation state tend to be good oxidizing agents, while transition metals in
a low oxidation state tend to be good reducing agents (depends on E 0cell values)
 Expected to use calculate E0cell values to predict the feasibility of a redox reaction

9.4.3B CATALYTIC PROPERTIES

Definition: A catalyst is a substance that alters the rate of a chemical reaction by providing an alternative
pathway of lower activation energy without itself being chemically changed at the end of the reaction

 Important factors of transition elements that make them suitable as catalysts


 Variable Oxidation States
 Availability of partially filled 3d orbitals that can readily accept electron pairs or donate electron pairs
to the reactant molecules
 Heterogeneous catalysis (Catalyst in different state as compared to reactants)
 The catalyst in the solid state and it provides at which the reaction can take place (reactants usually
liquids or gases)
 Mode of Operation
1. The reactant molecules first diffuse and adsorb onto the surface of the transition metal catalyst
by the formation of weak bonds. This occurs due to the presence of partially filled 3d orbitals
that can readily accept electron pairs or donate electron pairs to the reactant molecules
2. This brings reactant molecules closer together and increases their surface concentration at the
catalyst surface, weakening their intra-molecular bonds and orients the molecules in the right
geometric position for the reaction to take place by lowering the activation energy.
3. The reaction occurs and the products desorb and diffuse away from the transition metal.
 All other rules of catalysis applies
 E.g.
 Haber Process – Fe Catalyst
 Contact Process – V2O5
 Polymerisation of ethene – TiCl3, Al(C2H5)6
 Removal of nitrogen oxides – Pd, Pt, Rd catalysts
 Homogenous catalysis (catalyst in same phase as reactants)
 The E0cell does not change after adding the catalyst, but the EA changes
 E.g. Oxidation of iodide by peroxodisulfate ions
 Original Equation: 2I- (aq) + S2O82- (aq)  I2 (aq) + 2SO42- (aq) E0cell = +1.47 V
 Iron-catalyzed reaction
 2Fe3+ (aq) + 2I- (aq)  2Fe2+ (aq) + I2 (aq) E0 = +0.23 V
 2Fe2+ (aq) + S2O82- (aq)  2Fe3+ (aq) + 2SO42- (aq) E0 = +1.24 V
 E0cell = +1.47 V
 Choosing the right E0 reactions
 Narrow down the equations that involve the transition metal involved (in the correct state and
oxidation number)

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 The E0 of the half equations must be between the 2 E0 values for the original uncatalysed reaction
(Otherwise one of the reactions will be unfeasible)

9.4.3C TRANSITION METAL COMPLEX

Definition: A complex is a species that contains a central metal atom/cation with dative-bonds to surrounding
anions or ligands

Definition: A ligand is an ion or molecule that has at least one lone pair of electrons that can be donated into
the vacant orbitals in the central metal atom or ion

By Convention, Transition Metal Complexes are written in square brackets (e.g. [Cu(H2O)6]2+)

 Important factors of transition elements that allows for complex formation


 High charge density and polarizing power, allowing for the formation of dative covalent bonds with
ligands
 Availability of vacant 3d orbitals that can accommodate the lone pair of electrons donated by ligands
 Types of ligands
 Monodentate – Ligand that forms one dative covalent bond to the central metal species
 Bidentate – Ligand that forms two dative covalent bonds to the central metal species
 Hexadentate – Ligand that forms six dative covalent bonds to the central metal species
 Coordination Chemistry
 Charge of Complexes
 A complex can be neutral, positively charged or negatively charged
 Total Charge = Charge of Central Metal Species + (Number of Ligands)*(Charge of a ligand) + …
(depends on number of different ligands)
 The complex is often paired with a cation or anion to balance the overall charge (e.g. KMnO 4,
[Co(NH3)6]Cl3)
 Coordination Number
 Coordination Number = Number of dative bonds formed (not the number of ligands)
 Coordination Geometry
 Determined Experimentally
 Only need to know the shapes that are in VSPER theory
 Note: A ligand that is bound to the central metal species does not dissociate when the complex is
dissolved in water
 Formation of Complexes
 Dissolution of anhydrous transitional metal salts in water (By default all transition metal ions in an
aqueous state are hexa-aqua complexes)
 E.g. CuSO4 + 6H2O  [Cu(H2O)6]2+ + SO42-
 Acidity (Hydrolysis of water ligands)
 Due to the high charge density of the transition metal species, the metal ion/atom is able to polarize
the dative bonds so such an extent that the water ligand hydrolyzes to form hydrogen atoms that
decrease the pH
 E.g. [Fe(H2O)6]3+ + H2O (l)  [Fe(H2O)5(OH)]2+ + H3O+ (aq)
 For oxidation states higher than 3, the polarizing power of the central metal species is so strong that
the release of protons and loss of water molecules result in the formation of oxo-anions
 Special Equation to note for chromate ions (not redox)

 2CrO2− + 2−
4 + 2H ⇌ Cr2 O7 + H2 O
 Hence, the chromate ion is favoured at higher pH while the dichromate favoured at lower pH

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 Ligand Exchange Reaction


 A reaction that involves the substitution of one bound ligand with a free ligand (not all the ligands need
to undergo substitution)
 E.g.
 [Fe(H2O)6]3+ + 6CN- ⇌ [Fe(CN)6]3- + 6H2O
 [Cu(H2O)6]2+ + 4NH3 ⇌ [Cu(NH3)4(H2O)2]2+ + 4H2O
 Effects
 Colour Change: Transition metals show different colours depending on the ligands attached
 Reduction Potential
 Some ligands can increase or reduce the reduction potential of the central metal species
 E.g. [Fe(H2O)6]3+ + e- ⇌ [Fe(H2O)6]2+ , E0 = + 0.77V; [Fe(CN)6]3- + e- ⇌ [Fe(CN)6]4- , E0 = + 0.36V
 Biological Function of biomolecules
 The heme group in haemoglobin consists
of an Fe2+ ion being bound to a heme
group, histidine and a gaseous molecule
 Usually, oxygen binds to the central
metal atom, forming oxyhaemoglobin.
This binding is reversible.
 Carbon monoxide (CO) can also bind
irreversibly with haemoglobin to form
carboxyhaemoglobin due to higher
affinity. A high [CO] can cause death by
disabling the haemoglobin from
transporting oxygen.

9.4.3D CRYSTAL FIELD THEORY (FOR OCTAHEDRAL LIGANDS ONLY)

 Basis
 The shapes of the 5 d
orbitals can generally
be classified into 2
groups
 Group 1: 𝑑𝑥𝑦 , 𝑑𝑥𝑧 , 𝑑𝑧𝑦
 The orbitals of this
group have lobes
that are aligned
between the x, y
or z axis
 Group 2: 𝑑𝑥 2−𝑦2 , 𝑑𝑧 2
 The orbitals of this
group have lobes
that are aligned on
the x,y or z axis

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 In a free ion, all the d-orbitals are at the same


energy level
 However in a complex, depending on the
coordination geometry of the complex, some
electrons in certain d-orbitals will face greater
repulsion compared to electrons in other d-
orbitals
 In an octahedral complex, the electrons in the
𝑑𝑥 2 −𝑦2 , 𝑑𝑧 2 orbitals face greater repulsion than
electrons in the 𝑑𝑥𝑦 , 𝑑𝑥𝑧 , 𝑑𝑧𝑦 as the lobes of
𝑑𝑥 2 −𝑦2 , 𝑑𝑧 2 collide directly with the incoming
ligands.
 This causes the d orbitals to be split into group
of different energy due to electrostatic
repulsion with the ligands.
 d → d electronic transition
 In a low-spin (ground state) state, the electrons normally reside in
the d-orbital of the lowest energy level. In an octahedral complex,
the electrons reside in the 𝑑𝑥𝑦 , 𝑑𝑥𝑧 , 𝑑𝑧𝑦 orbitals
 When light shines on the complex, the electron absorbs some of
the light energy and transits to the orbital with higher energy
levels. In an octahedral complex, the electrons will jump to the
𝑑𝑥𝑦 , 𝑑𝑥𝑧 , 𝑑𝑧𝑦 orbitals.
 The energy gap between the 2 orbital groups correspond to the
range of wavelength in the visible part of the electromagnetic
spectrum. The colour of the complex depends on which
wavelength is reflected.
 Alkali and alkaline earth metals also undergo such excitation in the presence of light, but the difference in
energy levels between the orbitals is too large and corresponds to the non-visible spectrum. Hence the
compounds are white.
 Factors affecting the colour of complexes
 Oxidation State
 Different number of electrons in the d orbitals of the transition metal ion will result in different
interactions with the electrons from the ligands. This in turn causes the energy gap between the
orbitals to be different, thus the wavelength of the light absorbed will also be different.
 In transition metal compounds that have empty or fully filled d-orbitals, the compounds will be
colourless since d → d electronic transition is not possible.
 Nature of ligands
 Different ligands will have different effects on the splitting of d-orbitals. This in turn causes the
energy gap between the orbitals to be different, thus the wavelength of the light absorbed will also
be different.
 Geometry of Complex (see annex)

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ANNEX 9.4

COLOURS OF TRANSITION METAL COMPOUNDS

Element Oxidation Formula Name Colour


State
Sc +3 [Sc(H2O)6]3+ Scandium hexaaquo Complex Colourless
Ti +4 TiO2 Titanium Dioxide White ppt
V +2 [V(H2O)6]2+ Vanadium (II) hexaaquo Complex Light Purple
+3 [V(H2O)6]3+ Vanadium (III) hexaaquo Complex Green
+4 [VO(H2O)5]2+ Vanadyl pentaaquao complex Blue
+5 [VO2(H2O)4]+ Pervanadyl tetraaquao complex Yellow
+5 V2O5 Vanadium (V) Oxide Yellow ppt
Cr +2 [Cr(H2O)6]2+ Chromium (II) hexaaquo Complex Blue
+3 [Cr(H2O)6]3+ Chromium (III) hexaaquo Complex Green
+6 CrO42- Chromate ion Yellow
+6 Cr2O72- Dichromate ion Orange
Mn +2 Mn2+ Manganese (II) Ion Faint Pink/Colourless
+4 MnO2 Manganese (IV) Dioxide Brown ppt
+5 MnO43- Hypomanganate Ion Blue
+6 MnO42- Manganate Ion Green
+7 MnO4- Permanganate Ion Purple
Fe +2 [Fe(H2O)6]2+ Ferrous hexaaquo Complex Pale Green
+2 Fe(OH)2 Ferrous Hydroxide Green ppt
+3 [Fe(H2O)6]3+ Ferric hexaaquo Complex Pale Yellow
+3 Fe(OH)3 Ferric Hydroxide Reddish brown ppt
+3 [Fe(SCN)(H2O)5]3+ Ferric pentaaquo-thiocyanate Blood Red
Complex
Ni +2 [Ni(H2O)6]2+ Nickel hexaaquo Complex Pale Green
+2 [Ni(NH3)6]2+ Nickel hexamine Complex Blue
+2 [Ni(CN)4]2- Nickel tetracyano Complex Yellow
Cu 0 Cu Copper Pink
+1 CuCl Copper (I) Chloride White ppt
+1 Cu2O Copper (I) Oxide Red
+2 [Cu(H2O)6]2+ Copper (II) hexaaquo Complex Blue
+2 [Cu(NH3)4(H2O)2]2+ Copper (II) tetraamine-diaquo Dark Blue
Complex
+2 CuCl42- Copper tetrachloride Complex Yellow
+2 Cu(OH)2 Copper (II) Hydroxide Blue
+2 CuCO3 Copper (II) Carbonate Turquoise
Zn +2 [Zn(H2O)6]3+ Zinc hexaaquo Complex Colourless
+2 [Zn(NH3)4(H2O)2]2+ Zinc tetraamine-diaquo Complex Colourless
Ag +1 [Ag(NH3)2]+ Silver diamine Complex Colourless

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CRYSTAL FIELD THEORY (EXPANDED)

 Theory
 The difference in energy between the groups of d-orbitals is denoted by ∆, which is the crystal splitting
energy. This in turn affects the colour of complexes. The higher the value of ∆, the higher the
wavelength of light absorbed.
 Factors affecting ∆
 Oxidation number on the metal ion
 As the oxidation number increases, the metal ion becomes more densely charged and causes the
negatively charged ligands to become more strongly attached to it. This decreases metal-ligand
distance and increases the electrostatic repulsion between some d-orbitals and the ligands, thus
increasing ∆
 Nature of Ligands
 Each ligand has its own physical properties such as the ionic radii. For halides, ∆ decreases down
the group as a larger ionic radius causes the charges to be more dispersed and less localized, thus
interacting less strongly with the d-orbitals.
 Ligands with localized lone pairs (NH3) tend to have higher ∆ values as the lone pair (in sp3 orbitals)
collides directly with some d-orbitals.
 Geometry
 Depending on the geometry of the complex, different d-orbitals would be grouped differently. E.g.
For a tetrahedral complex, the 𝑑𝑥𝑦 , 𝑑𝑥𝑧 , 𝑑𝑧𝑦 would experience more electrostatic repulsion than
the 𝑑𝑥 2 −𝑦2 , 𝑑𝑧 2 orbitals
 Similar effects are encountered for square planar complexes

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10.1 INTRO TO ORGANIC CHEMISTRY


10.1.1 CHEMICAL FORMULAE

10.1.1A TYPES OF CHEMICAL FORMULAE

 Empirical Formula
 Simplest formula that shows the ratio of each kind of atom in a molecule
 Molecular Formula
 Shows the actual number of each kind of atom in a molecule
 Structural formula
 Shows unambiguously how the atoms are connected to each other in a molecule
 Condensed structure formula
 Shows unambiguously how the atoms are connected to each other in a molecule without
showing the single bonds
 All double/triple bonds must be displayed
 All the atoms attached to carbon are to be together (e.g. propene CH 2=CHCH3)
 Brackets represent functional groups attached to the carbon atom preceding it
 E.g. CH2CH(CH3)CH2 is 2-Methyl-Propane
 E.g. CH2=CHCH(CH3)CH2 is 3-Methyl-But-1-ene
 E.g. CH2=CH2
 Displayed structure formula
 Shows all the bonds and relative placing of all atoms in a molecule

 Ethene:
 Skeletal formula
 Simplified representation; all C-H bonds are not shown, hydrogen atoms are not shown, C atoms
are not shown.

 Ethene:
 Stereochemical formula (a more detailed skeletal formula)
 Solid wedges represent an atom pointing out of the plane of the paper
 Dashed wedges represent an atom pointing into the plane of the paper

10.1.1B FUNCTIONAL GROUPS & HOMOLOGOUS SERIES

 Functional groups: A group of atoms with special chemical properties, usually part of a larger compound
 All compounds having the same functional group can be considered as members of the same family
with similar chemical properties
 Homologous series: A series of organic compounds in which each successive member increases by the unit
CH2; a family of organic compounds with the same functional group which follows a regular structural
pattern
 Chemicals have

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 Similar chemical properties


 Same preparatory methods
 The same general molecular formula
 A gradual change in physical properties as Mr increases
 Types
 Aliphatic Compounds (compounds with open chains, may be unbranched/branched with
double/triple bonds)
 Alicyclic compounds (compounds with closed rings, e.g. cyclohexane)
 Aromatic compounds (benzene ring)

Functional Functional Functional Formula Structure Example


group Name Group group suffix
Prefix
Acid halide - -oyl halide RCOX

ethanoyl chloride,
CH3COCl
Alcohols hydroxy -ol ROH

ethanol, C2H5OH
Aldehyde formyl -al RCHO

ethanal, CH3CHO
Alkenes - -ene R2C=CR2

ethene, C2H4

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Amide - -amide RCONH2

ethanamide, CH3CONH2
Amino group amino amine 1°: RNH2
2°: R2NH
3°: R3N

ethylamine, C2H5NH2
Carboxyl - -oic acid RCOOH
group
(carboxylic
acid)

ethanoic acid, CH3COOH


Ester - -oate RCOOR

ethyl ethanoate,
CH3COOCH3
Ethers ether ROR

ethoxyethane, CH3OCH3
Halo groups Fluoro - RX
Chloro
Bromo
Iodo

chloroethane, C2H5Cl

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Ketones oxo -one RCOR

propanone, CH3COCH3
Nitriles cyano nitrile RCN

ethanenitrile, CH3CN
Nitro nitro RNO2

nitroethane, C2H5NO2

Benzene Phenyl benzene C6H5R

Phenols - Phenol ArOH

phenol, C6H5OH

10.1.2 IUPAC NOMENCLATURE

 Constitutes
 Stem
 Suffix

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 Prefix
 Locants
 Stereochemical Descriptors (only cis and trans for H2 Chemistry)
 Steps to writing the IUPAC name
 Determine the longest carbon chain (stem)
 Determine highest priority functional group (carbon will act as carbon 1, functional group used as
suffix)
 Determine the locations and prefix names for the rest of the functional groups & side chains
 Prefixes must be placed in alphabetical order
 Add di/tri/tetra if required for prefix functional groups & side chains
 Functional Group Priority List
1. Carboxylic Acids
2. Carboxylic Acid Derivatives
a. Esters
b. Acid Halides
c. Amides
3. Nitriles
4. Aldehydes
5. Ketones
6. Alcohols
7. Amines
8. Ethers
9. Alkenes
10. Alkyne
11. Side Chains (Alkyl groups)
 Naming of alkyl groups (side chains)
1. Methyl
2. Ethyl
3. Propyl
4. Butyl
5. Pentyl
6. Hexyl
7. Heptyl
8. Octyl
9. Nonayl
 Naming of stems
1. Meth
2. Eth
3. Prop
4. But
5. Pent
6. Hex
7. Hept
8. Oct
9. Non
10. Dec

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10.1.3 PROCESSES IN ORGANIC CHEMISTRY SYNTHESIS

 Distinguishing Tests
 A chemical tests that aims to confirm the presence of a particular compound (by identifying key
functional groups via detectable chemical changes)
 Synthesis
 A process to make a chemical compound with reasonable yield and purity.
 Separating Techniques
 Heating under Reflux
 Heating a flask so that the solvent boils continuously
 Minimizes the evaporation of reactants or products
 Distillation
 Used to separate mixtures based on different boiling points

10.1.4 TYPES OF ORGANIC CHEMICAL REACTIONS

 Addition
 Reaction of two molecules to form a single molecule
 Elimination
 A single molecule becomes two molecules, with the elimination of a small molecule from the main
large molecule
 Substitution
 One of the atoms in the molecule is substituted for another
 Oxidation/Reduction
 Oxidation: Addition of oxygen to/removal of hydrogen from the molecule. Oxygen number denoted
by x[O]
 Reduction: Addition of hydrogen to/removal of oxygen from the molecule. Hydrogen number
denoted by x[H]
 Condensation
 Two molecules fuse with the removal of a water molecule
 Hydrolysis
 One molecule splits into 2 with the addition of a water molecule

10.1.5 MECHANISMS OF ORGANIC CHEMICAL REACTIONS

 Homolysis (homolytic fission)


 Involves the splitting of a single bond resulting in each product having one electron (equal share)
 Usually results in the formation of radicals
 Represented using the single-barbed arrow
 Heterolysis (heterolytic fission)
 Results in an unequal sharing of the bonding electrons to each resulting fragment
 Usually results in the formation of ions
 Represented by a full head arrow

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 Electrophiles
 Electron Deficient
 Electron seeking
 Positive charge
 Polarizable molecules that can develop an electron deficient centre (e.g. HBr)
 Nucleophiles
 Electron rich
 Nucleus seeking
 Negative Charge/Lone pair
 Reaction intermediates
 A species that is formed in one of the elementary steps and then consumed in another.
 Usually one of the following species
 Carbon Radical/ Free radical
 Carbocation (carbon with only 6 electrons, bonded to 3 other atoms, no lone pairs)
 Carboanion (carbon with 8 electrons, bonded to 3 other atoms, 1 lone pair)

10.1.5 SP HYBRIDIZATION OF CARBON

 In organic chemistry, for all single C-R bonds, the carbon has hybridized all of its 2p & 2s orbitals to form
an sp3 hybridized orbital, e.g. in methane
 As the number of bonds between the carbon and another atom increases, p orbitals are used to form π
bonds.
 Hybrid orbitals are intermediate in energy levels between the 2s and 2p orbitals
 All hybrid orbitals of the same type have the same level of energy
 Hybrid orbitals are lopsided with one large lobe and one small lobes

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Number of sigma bonds Number of pi bonds Shape w.r.t. carbon


with other molecules with another molecule atom
sp3 hybridization 4 0 Tetrahedral (109.5°)
sp2 hybridization 3 1 Trigonal Planar (120°)
sp hybridization 2 2 Linear (180°)

10.1.6 ISOMERISM

 Isomers: Molecules with the same molecular formula but different arrangement of the atoms
 Types
 Structural Isomerism: Molecules being arranged in different ways
 Stereoisomerism: Molecules in which atoms have the same connectivity but different spatial
arrangements

10.1.6A STRUCTURAL ISOMERISM

 Chain Isomerism
 Molecules with the same molecular formula and the same functional group, but different carbon
skeletons
 Similar chemical properties, different physical properties
 E.g. Hexane, 2-methylpentane; Butane, 2-methylpentane
 Positional Isomerism
 Molecules with the same molecular formula and same functional group but differ in the position of
the functional group
 Similar chemical properties, different physical properties
 E.g. Hex-1-ene, Hex-2-ene, Hex-3-ene
 Functional group isomerism
 Molecules with the same molecular formula but different functional groups
 Different chemical properties, different physical properties
 Pentan-1-ol, 1-ethoxypropane; Pentanoic acid, ethyl propionate; Pentanal, Pent-3-one
 Pairs of functional groups that qualify for functional groups isomerism
 Alcohols – Ethers
 Carboxylic Acid – Esters
 Aldehydes – Ketones

10.1.6B STEREOISOMERISM

 Geometric cis-trans isomerism


 Restricted rotation of the double bond due to the presence of π bonds, which would have to be
broken if the C=C bond undergoes free rotation.
 Geometric isomerism occurs only when
 There is at least one double bond
 The two groups on each C of the double bond must not be identical

 E.g.
 If the H atoms are on the same side, it is a cis isomer; otherwise it is a trans isomer
 Maximum number of separate geometric isomers for a molecules with n eligible double bonds = 2n

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 ****When drawing cis-trans isomer, the trigonal planar shape must be


used
 Optical Isomerism
 Optical Activity: The ability of a compound to rotate a plane of polarized light due to the interaction of
the polarized light with the unsymmetrical electric field generate by electrons in a chiral compound
 Optical isomerism only occurs when
 There is a carbon in the compound with four different groups attached to it; this causes the 2
molecules to become non-superimposable onto each other


 When drawing optical isomers, the stereochemical formula must be
used
 Enantiomers
 The two compounds above, mirror images of each other, are known as enantiomers
 The enantiomer that rotates plane polarized light in a clockwise direction is said to be
dextrorotatory, and a prefix (+) or d is added
 The enantiomer that rotates plane polarized light in an anti-clockwise direction is said to be
laevorotatory, and a prefix (-) or L is added
 A mixture containing equal proportions of both enantiomers is called a racemix misture
 Properties
 Each enantiomer rotates plane polarized light by the same angle, but in opposite directions
 Identical chemical properties
 Differs in the way they interact with other chiral compounds
 Meso compounds (achiral compounds)
 However, if a compound has 2 chiral carbons, and the chiral carbons are entirely symmetrical to
each other, the mirror image is identical to itself and it is not optically active


 For optical isomers, total number of optical isomers possible for a carbon with n eligible chiral centres
= 2n
 Total number of stereoisomers = 2n, where n is the total number of eligible
double bonds and chiral centres.

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10.2.1 HYDROCARBONS - ALKANES


 Alkanes are saturated hydrocarbons (any type of chain) with only C-C single bonds
 Alkanes are also known as saturated carbons (carbons attached to max number of hydrogen atoms)
 Alkanes only contain sp3 hybridized carbon atoms
 Shape of alkane molecules with respect to each carbon is tetrahedral

10.2.1.1 IUPAC NOMENCLATURE

 Issue: Branching
 When naming branches, always do so in alphabetical order
 E.g. Ethyl before Methyl, Methyl before Propyl
 The use of di, tri does not affect the alphabetical order (ethyl still comes before dimethyl)
 Always add the carbon position of the functional groups before the group (e.g. 2-Methyl Xane)
 Even when using di, add both numbers to the carbon position (e.g. 2,5-dimethyl Xane)
 Di means that there are two of the same alkyls present, not that they are in the same position
 Tri means three of the same alkyls present
 Naming complex substituents
 The carbon attached to the main chain is always carbon 1.
 E.g. 1-(1-methylethyl)hexane
 Issue: Alicyclic Alkanes
 Prefix the name with cyclo
 Alkanes do not have positions (no such thing as Al-1-ane) (Position numbers must add to become the
lowest as possible)

10.2.1.2 PHYSICAL PROPERTIES

 Solubility
 Alkanes are insoluble in water as both exhibit different types of intermolecular forces of attraction.
While water molecules exhibit hydrogen bonding as they are polar molecules, while alkanes exhibit
Van der waals forces of intermolecular attraction as they are non-polar molecules. As these two
forces do not interact with each other sufficiently, alkanes are insoluble in water.
 Melting and Boiling Points/Visosity
 The melting and boiling points of alkanes increase as the length of the carbon chain increases. As the
number of carbon increases, the number of electrons increases. An increase in electrons causes an
increase in the strength of the temporary dipole-dipole forces of intermolecular attraction, thus the
boiling point and melting point increases as the length of the carbon chain increases.
 Branched hydrocarbons have lower boiling points and melting points than unbranched hydrocarbons
as the surface area for van der waals forces to act is smaller.
 Density
 Less dense than water due to size of molecules and packing
 As the number of carbon atoms increase, the strength of the dispersion forces between alkane
molecules increase, resulting in a slightly smaller volume. This causes density to increase.

10.2.1.3 CHEMICAL PROPERTIES

 Reactivity

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 Alkanes are generally inert due to the non-polar nature of the C-H bonds as C and H are very similar
in electronegativity. Alkanes have no regions where electrons are permanently concentrated (such as
lone pairs, electron-rich regions, polar bonds) for electrophiles and nucleophiles to attack.
 Reactions with Halogens
 Free Radical Substitution (FRS)
 Alkane + Halogen  Halogenoalkanes + Halogen Halide
 Alkanes are saturated, thus any new bonds to be formed would have to involve the breaking of
existing C-H bonds
 Reagents and Conditions
 Any kind of light with UV (UV light/Sunlight)
 Presence of UV required for homolytic cleavage of halogens to form free radicals
 Free radicals required as only very reactive substances can react with alkanes, which are
non-polar and quite unreactive, so that bonding electrons are attracted from existing
convalent bonds to break C-H bonds.
 Presence of halogens
 Three stages
 Initiation (e.g. chlorine with methane)
 The Cl-Cl bond is cleaved homolytically using energy provided by the UV light, producing free
chlorine radicals. (Show arrows!!)
 Cl–Cl  (Presence of UV) 2Cl• (Show arrows!!)
 Propagation
 Chain reaction step as the chlorine radical is regenerated at the end of the stage
 It is thus self-sustaining and prolonged exposure to UV light is not required.
 CH4 + Cl•  CH3• + HCl , ΔH = B.E(C-H) – B.E.(H-X)
 The chlorine radical collides with a methane molecule and abstracts a hydrogen atom to
produce HCl and a methyl radical.
 CH3• +Cl2  CH3Cl + Cl• (regenerated) , ΔH = B.E(X-X) – B.E.(C-X)
 The methyl radical reacts with chlorine gas to form chloromethane and regenerate the
chlorine radical.
 Termination
 Two radicals collide and combine to form a stable product in this stage.
 Cl• +Cl•  Cl2
 Cl• + CH3•  CH3Cl
 CH3• + CH3•  CH3CH3
 Observations
 Reddish brown/Greenish colour decolourizes
 Formation of white fumes which turn damp blue litmus paper red.
 Problems
 Numerous products acquired as the extent and position of substitution is difficult to control.
 Further substation may occur in the presence of excess halogen, creating multi-substituted
products. (due to inability to control which C-H bond gets attacked)
 Probability of substitution
 In general, the probability that a carbon will be attached to a halogen depends on
 The number of hydrogen atoms the carbon has. E.g. The first carbon in butane has 3
hydrogen attached to it, thus the probability that a halogen will be attached to it increases.
 The nature of the alkyl radical formed during the propagation step
 The more stable the alkyl radical, the most likely it is to be formed and the more likely a
halogen will be attached to it.

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 The more alkyl groups present, the more stable the radical due to the inductive effect of
the alkyl groups.

 Reactivity of halogens with alkanes


 For the propagation steps, the enthalpy change depends on the bond energies of H-X and C-X
(Refer to above)
 Thus, the reactivity of halogens decrease from fluorine to iodine (least reactive)
 Combustion
 Alkanes can react with oxygen in the air during combustion to produce heat energy.
 Complete combustion (excess oxygen) produces carbon dioxide and water
 CXHY + (x+1/4y)O2  xCO2 + (1/2y)H2O
 Incomplete combustion produces carbon monoxide and water (and soot)
 However, the reaction has high activation energy, thus a mixture of methane and oxygen is stable
unless ignited by a spark.
 Cracking
 Alkane  Smaller alkane + Alkene (Or 2 alkenes + hydrogen gas)
 The process by which the C-C bonds of larger hydrocarbons are broken to produce short chain alkanes
and alkenes molecules
 Thermal Cracking
 Alkanes heated up to 500-800 degrees Celsius, causing the C-C bonds to be broken. This is then
followed by a free radical chain mechanism, thus producing a mixture of products, which can be
further separated by fractional distillation
 Reaction proceeds by free radical mechanism
 Very little rearrangement of the chains occur during thermal cracking.

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 Catalytic Cracking
 Alkanes passed over a catalyst between temperatures of 400-500 degrees Celsius
 The catalyst used is A mixture of Aluminium oxide and Silicon Dioxide. Zeolites are also used.
Catalytic cracking usually yield higher percentages of hydrocarbons between 5 and 10 carbon
atoms. Catalysts are also designed to produce high proportions of branched alkanes and aromatic
hydrocarbons.
 Involves the formation of carbocations which can undergo rearrangement
 Advantages
 Less energy required
 Ability to control proportion of desired product
 More branched chain alkanes obtained
 Catalytic Reforming
 Straight chain alkanes can be reformed into branched, cyclic or aromatic products without the loss of
any carbon atoms (but with the loss of hydrogen gas)
 Carried out by passing the vaporized alkane mixture over a platinum coated aluminium oxide catalyst
at 500°C and moderately high pressure.

10.2.1.4 AIR POLLUTION

 Carbon Monoxide
 Sources: Incomplete combustion of petrol in automobile engines due to insufficient atmospheric
oxygen available
 Equation: 2C8H18 + 17O2  18H2O + 16CO
 Effects: Interferes with oxygen-carrying capacity of the blood, reduces the amount of oxygen that can
be delivered to the tissue
 HbO2 + CO  HbCO + O2
 Solutions: Use the catalytic converter (see below)
 Nitrogen oxides
 Sources: Reaction of nitrogen and oxygen gas in the high temperatures of the internal combustion
engine
 Equations
 N2 +O2  2NO
 N2 + 2O2  2NO2
 2N2 + O2  2N2O
 2NO + O2  2NO2
 Effects: Reacts with water vapour in the atmosphere to form nitric acid; causes eye irritation,
inflammation of lung tissue, emphysema. Nitrous oxide is a greenhouse gas
 2NO2 + 2H2O + O2  4HNO3
 Solutions: Use the catalytic converter (uses Pt, Pd and Rh Catalysts which remove pollutant gases by
oxidizing or reducing them)
 2NO + 2CO  N2 + 2CO2
 2NO2 + 4CO  N2 + 4CO2
 N2O + CO  N2 + CO2
 Catalytic Converters are mandatory in cars in Singapore and they convert nitrogen dioxide and
carbon monoxide into carbon dioxide and nitrogen gas, thus reducing the amount of nitrogen dioxide
gas in the atmosphere

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10.2.2 HYDROCARBONS – ALKENES


 Alkenes are unsaturated hydrocarbons with at least one C=C.
 The alkene molecule is trigonal planar with respect to each C=C carbon. The molecule is planar

10.2.2.1 IUPAC NOMECLATURE

 Main Issue – Functional Groups


 When naming alkenes, you must always specify the location of the C=C bond (with the exception of
ethane and propene)
 E.g. But-1-ene
 If there is more than one C=C, name it like any other functional group e.g. But-1,2-diene
 Alkenes, by themselves, always take the lowest positional number
 Stereochemical descriptors are to be placed in front as a prefix, followed by a hyphen
 E.g. trans-hexa-1,3-diene.
 Naming of alkyl branches is done in the same way as that of alkanes
 Naming of cycloalkenes
 Similar to that of aliphatic alkenes
 The numbering of alkyl branches still take lower priority than the numbering of the double bond

10.2.2.2 GEOMETRIC CIS-TRANS ISOMERISM (REFER TO 10.1.6B)

 Cis isomer  Hydrogen atoms on the same side of the double bond
 Trans isomer  Hydrogen atoms on opposite sides of the double bond
 Cis-Trans Isomerism in cycloalkenes
 Cycloalkenes with up to 7 carbon atoms can only exist in this configuration
 Cycloalkenes with more than 8 carbon atoms can exist in either the cis or trans configuration.
 This is due to restricted rotation of the double bond due to the presence of π bonds, which would have to
be broken if the C=C bond undergoes free rotation.

10.2.2.3 PHYSICAL PROPERTIES OF ALKENES

 Solubility
 Alkenes are generally not soluble in water, refer to 10.2.1.2 for the explanation
 Melting and Boiling Points/Visosity
 The melting and boiling points of alkenes increase as the length of the carbon chain increases. refer to
10.2.1.2 for the explanation.
 Branched hydrocarbons have lower boiling points and melting points than unbranched hydrocarbons
as the surface area for van der waals forces to act is smaller.
 Variation in boiling points between cis and trans isomers
 Cis isomers tend to have higher boiling points than trans isomers. In the cis isomer, due to the
polarity of bond between the substituent groups and carbon, there is an overall dipole moment for
the molecule, thus permanent dipole-dipole interactions exist between cis isomers.
 However, in the trans isomer, the two dipole moments cancel each other out so that there is no
net dipole moment for the molecule, hence only weak dispersion forces exist between the trans
isomers.
 Variation in melting points between cis and trans isomers
 The trans isomer has a higher melting point

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 Due to the symmetry of the trans isomers, the trans isomers pack well as compared to the cis
isomers, which have a U shape. Thus, dispersion forces work more effectively in holding trans
isomers together as compared to cis isomers and more energy is required to overcome these
dispersion forces between trans isomers as compared to cis isomers, thus trans isomers have a
higher melting point.
 Density (similar to alkanes)
 Refer to 10.2.1.2 for the explanation

10.2.2.4 CHEMICAL PROPERTIES OF ALKENES

10.2.2.4A CARBOCATION

 Structure
 Positively charged, sp2 hybridized
 Trigonal planar shape w.r.t central carbon
 Reactivity
 Attracts nucleophiles towards it due to its positive charge
 Nucleophiles may attack from either side of the plane
 Stability depends on the number of electron donating groups attached to it, which help disperse the
positive charge on the central carbon atom
 Alkyl groups containing a carbon attached to an electronegative species generally do not act as
electron donating groups (e.g. CF3, carbonyl groups), but instead act as electron withdrawing groups.
 Electron withdrawing groups destabilize a carbocation via induction through intermediate covalent
bonds

 Markonikov’s rule
 In the addition of HX to an alkene, the H atom adds to the C atom of the double bond that has the
greater number of H atoms attached to it.

10.2.2.4B ELECTROPHILIC ADDITION OF HALOGEN HALIDES (HX)

 The π bonds, an electron rich region, attracts electrophiles (which are positively charged, polar molecules
or have a partial positive charge)

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 Polarization of the reactant in step 1 happens under the influence of the π bond in C=C
 Reagents and Conditions
 Gaseous HX
 Room Temperature
 No observable changes
 Mechanism of electrophilic addition (in ethene)

Include for all electrophilic


addition mechanisms

 Name of reaction
 Partial charges
 Real charges
 The speed of each of
the two elementary
steps
 The full arrows
 Lone Pairs

Step 1 is the rate determining step – Involves the


breaking of the π bond and the heterolytic fission of HX to form H+ and X-. H+ is then attached to one
of the carbons, producing carbocation intermediate.
 Step 2: X- acts as a nucleophile and attacks the unstable carbocation, forming a halogenoalkane
 NOTE:
 The electrophile (H+) adds in a way to generate the most stable carbocation intermediate (refer to
10.2.2.4A)
 Equal amounts of the 2 optical isomers (only applicable to carbocations attached to 3 different
groups) are produced as the planar carbocation has an equal chance of being attacked from the top
or the bottom by the nucleophile in the 2nd step

10.2.2.4C ELECTROPHILIC ADDITION OF HALOGENS (X 2 )

 Reagents and Conditions


 Pure gaseous/liquid Halogen/Halogen dissolved in tetrachloromethane (CCl4)
 Room temperature
 (Absence of light; to prevent free radical substitution, but not necessary as electrophilic addition
happens at a much faster pace than free radical substitution)
 Observations: Greenish yellow colour/Reddish brown colour decolourizes rapidly

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 Reaction with bromine results in a cyclic bromonium cation intermediate, rather than a carbocation
intermediate.

 Reaction with chlorine is similar to that of electrophilic additions of hydrogen halides


 Reactions with fluorine is highly violent and most alkenes do not react with iodine

10.2.2.4D ELECTROPHILIC ADDITION OF AQUEOUS BROMINE (BROMINE WATER)

 Reagents and Conditions


 Aqueous bromine
 Room Temperature, preferably in the absence of light
 Observations: Reddish brown colour decolourizes rapidly

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 Note: Two main products (along with HBr) are formed due to the presence of other nucleophiles, such as
the water molecule, which is in a much higher concentration as compared to bromine. Thus, the major
product will also be a monobromo-alcohol (Step 2B has a much higher chance of happening than step 2A)
 Note: It is not possible to obtain a diol using this method as the first slow step always involves the
electrophilic attack of the polarized Br2, thus the product will always have the addition of at least 1 Br
atom regardless of the types and concentration of nucleophiles present.
 Note:
 The carbocation intermediate is an electrophile

10.2.2.4E ELECTROPHILIC ADDITION OF STEAM (HYDRATION)

 Reagents and conditions (industrial)


 Steam
 300°C
 70 atm
 H3PO4 catalyst
 Reagents and conditions (laboratory)
 Concentrated H2SO4 at room temperature
 Warm with water
 Mechanism is similar to that of electrophilic addition of hydrogen halide and chlorine

10.2.2.4F ADDITION OF HYDROGEN (HYDROGENATION)

 Converts unsaturated alkenes to saturated alkanes


 Reagents and Conditions
 Hydrogen Gas
 Nickel, Palladium or Platinum catalysts
 High temperature, High pressure

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10.2.2.4G OXIDATION

 Oxidation is achieved using potassium permanganate, either in its alkaline (mild) or acidic (strong) form.
 Oxidation cannot be carried out using potassium dichromate
 Mild Oxidation
 Reagents and conditions
 Potassium Permanganate
 Aqueous Sodium Hydroxide
 Cold temperature
 Observations
 Purple KMnO4 is decolourized and a brown precipitate of MnO2 is formed

 Oxidative Cleavage (strong oxidation)


 Reagents and conditions
 KMnO4
 Concentrated H2SO4
 Heat
 Observations
 Purple KMnO4 is decolourized
 Note: In this reaction, all the C=C double bonds are cleaved to form various products. The products
form depend on the number of alkyl groups attached to the carbon on the C=C
 Note: Ethandioic Acid (AKA Oxalic Acid) (HOOCCOOH) will be further oxidized into carbon
dioxide and water due to its instability

 This is a useful test to distinguish between alkenes with terminal double bonds and those without as
the oxidation of terminal double bonds will produce carbon dioxide gas.
 Oxidative cleavage can also be used to determine the location of the C=C within the alkene.

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 For all oxidation reactions, add H2O to balance the H and [O] to balance the O
 For reduction reactions, add H2O to balance the O and [H] to balance the H

SUMMARY OF ALKENE (ETHENE) REACTIONS

Mechanism Name Reagents Conditions Products Formed Distinguishing


Test?
Halogen Gaseous HX Room Mono-Halogenoalkane No; No observable
Halides (HX) Temperature changes
Halogens (X2) Pure Room Di-Halogenoalkane Yes; Greenish
liquid/gaseous X2 Temperature yellow colour/
Electrophilic Addition of

No light (not Reddish brown


obligatory) colour
decolourizes
rapidly
Bromine Water Aqueous Room Mono-Halogenoalcohol Yes;
Bromine Temperature (Major) Reddish brown
No light (not Di-Halogenoalkane colour
obligatory) (minor) decolourizes
rapidly
Steam Steam 300°C Alcohol No; No observable
70 atm changes
H3PO4 catalyst
Addition of Hydrogen Hydrogen Gas Ni/Pt/Pd Alkane No; No observable
(Reduction/ heterogeneous changes
Hydrogenation) catalyst
High Temp
High Pressure
Mild Oxidation KMnO4; Cold Diol Yes; Purple KMnO4
NaOH (aq) Temperature Decolourizes and a
brown precipitate
of MnO2 is formed
Oxidative Cleavage KMnO4; High Carbon Dioxide and Yes; Purple KMnO4
Conc. H2SO4(aq) Temperature water Decolourizes

Carboxylic Acids Test for terminal


double bonds and
Ketones location of double
bonds

***All the above reactions use ethene as the main organic reactant

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10.2.3 HYDROCARBONS – ARENES


 Arenes – Hydrocarbons with one or more benzene rings
 Aromatic Hydrocarbons – Any compound that is stabilized by a ring of delocalized π electrons

10.2.3.1 BENZENE

 Benzene – The simplest arene, C6H6


 6 carbons, each having 3 sp2 hydrized orbitals and 1 π orbital
 Shape: Hexagonal planar, trigonal planar w.r.t each carbon
 Composition and bonding
 All carbons connected to each other via a σ bond between 2 sp2 orbitals
 All carbons connected to a hydrogen via a σ bond between an S orbital of hydrogen and an sp2
orbital of carbon
 2p orbitals overlap with neighbouring 2p orbitals, resulting in 6 electrons being delocalized in a π
electron cloud

 Stability
 Relatively stable due to the delocalization of the π electrons (+149 kJ mol-1  Resonance energy)
 Benzene only undergoes substitution reactions to preserve the aromacity of benzene. Addition
requires a significant amount of energy as it destroys the delocalized π electron system, thus it is
highly unfavoured.

10.2.3.2 PHYSICAL PROPERTIES OF BENZENES

 Low melting and boiling points


 Melting point – 6°C
 Boiling point – 80°C
 Being a non-polar molecule, only a small amount of energy is required to overcome the weak
dispersion forces between benzene molecules, thus benzene has a low melting and boiling point
 Solubility
 Benzenes are insoluble in water as both exhibit different types of intermolecular forces of attraction.
While water molecules exhibit hydrogen bonding as they are polar molecules, benzenes exhibit Van

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der waals forces of intermolecular attraction as they are non-polar molecules. As these two forces do
not interact with each other sufficiently, benzenes are insoluble in water.

1.2.3.3 IUPAC NOMENCLATURE

 Main issue: Naming of substituents


 When the benzene ring is the parent group (the suffix), it is named as “benzene” and the various
substituents are added as prefixes, similar to branched alkanes
 E.g. Nitrobenzene, MethylBenzene, 2,4,6-trinitromethylbenzene
 The positions are numbered such that the lowest total possible number is used
 The highest priority group always take carbon 1 as its location
 Main issue: Benzene as a functional group (used when benzene is attached to an alkyl group with >6
carbons, or when substituent group is too complex to be named as a prefix)
 The prefix “phenyl” is used in a way similar to the naming of other functional groups
 E.g. 2-Phenyl-3-Bromo-Hexane

10.2.3.4 CHEMICAL PROPERTIES OF BENZENE

10.2.3.4A BENZENE CARBOCATION

 All electrophilic substitution reactions with benzene will generate a carbocation, similar to the one below

H E Shape with respect to this carbon


atom – Tetrahedral, 109.5°
This carbon is sp3 hybridized

Not an aromatic compound


+ Not planar

10.2.3.4B NITRATION – ELECTROPHILIC SUBSTITUTION OF HYDROGEN WITH NITRO GROUP

 Reagents and conditions


 Concentrated HNO3
 Concentrated H2SO4
 Heat at 55°C
 Observations
 Yellowish and oily liquid formed
 Mechanism

Electrophilic Substitution (Nitration)


Step 1: Generation of Electrophile (Nitronium ion)

2H2SO4 + HNO3  H3O+ + NO2+ + 2HSO4-

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Step 2: Attack by electrophile
O2N H

NO2+ + Slow

+
Step 3: Abstraction of proton by HSO4- and the regeneration of the sulfuric acid catalyst
NO2
O2N H
..
+ HSO4- Fast + H2SO4
+

 Note
 Draw the “U” shaped carbocation correctly  The opening of the “U” must point towards the
tetrahedral carbon
 Draw the “+” charge in the carbocation intermediate
 Draw in all lone pairs
 Write the rates of the equation

10.2.3.4C HALOGENATION – ELECTROPHILIC SUBSTITUTION OF HYDROGEN WITH HALOGEN

 Reagents and conditions (bromination)


 Liquid Bromine
 Anhydrous FeBr3 as catalyst
 Warm
 Observations (bromination)
 Decolourisation of reddish-brown bromine liquid
 Formation of dense white fumes of HBr (may not appear under some circumstances)
 Reagents and conditions (chlorination)
 Gaseous Chlorine
 Anhydrous FeCl3/AlCl3 as catalyst
 Warm
 Observations (Chlorination)
 Decolourisation of greenish-yellowish bromine liquid
 Formation of dense white fumes of HCl
 Mechanism (bromination; chlorination is similar)

Electrophilic Substitution (Halogenation)


Step 1: Generation of Electrophile (X+)

X2 + FeX3  X+ + FeX4-
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Step 2: Attack by electrophile X H

X+ + Slow

+
Step 3: Abstraction of proton by FeX4- and the regeneration of the iron (III) halide catalyst; formation of HX
X
X H
.. Fast
+ FeX4- + FeX3 + HX
+

 Note:
 Reaction is highly similar to nitration, with exception of HBr being generated
 X can be either bromine or chlorine
 Iron filings can also be used in placed of FeX3 as Fe reacts with the halogen to form FeX3, thus
generating the catalyst in the reaction itself (Fe + 1.5X2  FeX3)

10.2.3.4D ELECTROPHILIC SUBSTITUTION OF HYDROGEN WITH METHYL GROUP

 Reagents and conditions


 CH3Cl
 Anhydrous AlCl3 as catalyst
 Mechanism

Electrophilic Substitution of hydrogen with methyl group

Step 1: Generation of Electrophile (CH3+)

CH3Cl + AlCl3  CH3+ + AlCl4-

Step 2: Attack by electrophile


CH3 H

Slow
CH3+ +

+
Step 3: Abstraction of proton by AlCl4- and the regeneration of the catalyst
CH3
CH3 H
.. Fast
+ AlCl4- + AlCl3
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10.2.3.4E ELECTROPHILIC SUBSTITUTION OF SUBSTITUTED BENZENES

 The presence of a substituent on the benzene ring either donates electrons or withdraws electrons from
the benzene ring.
 Donating electrons increase the electron density of the benzene ring and increases its reactivity
 Withdrawing electrons decreases the electron density of the benzene ring and decreases its reactivity
 Ways in which electrons are donated or withdrawn from the benzene ring
 Through σ bonds  Inductive effect
 Alkyl groups with no electronegative species donate electrons into the benzene ring via the sigma
bond
 Substituent groups containing an electronegative species withdraw electrons from the main
benzene ring via the sigma bond (e.g. Amine, Ether, Aldehyde, Hydroxyl, Nitro)
 Through π bonds  Resonance effect
 Substituents with extra lone pairs are able to donate electrons into the benzene ring via
resonance with the pi bond (due to overlapping of pi orbitals)
 Substituents with the atom attached to the benzene ring attached to an more electronegative
species act as electron withdrawing groups

Substituent Inductive Effect Resonance Effect* Overall effect on Effect on


Usually takes priority over reactivity of neighbouring
inductive effect benzene ring carbocation
Alkyl Group Electron Donating NA - No empty pi orbital Activates Stabilize
Hydroxyl, Electron Withdrawing: Electron Donating: Activates Stabilize
Ether, Intermediate atom is an Presence of lone pairs
Amine electronegative species
Halogens Electron Withdrawing: Electron Donating: Deactivates Stabilize
Intermediate atom is an Presence of lone pairs
electronegative species
Aldehydes, Electron Withdrawing: Electron Withdrawing: Deactivates Destabilize
Nitro, CF3, Intermediate atom is Intermediate atom is
CCl3, Esters, attached to more attached to more
Carboxylic electronegative species electronegative species
Acids

**Intermediate atom – Atom of the functional group attached to the benzene ring

 Positions of incoming electrophile


 All activating groups and halogens direct incoming nucleophiles to the 2nd and 4th position (2,4-
directing groups
 All deactivating groups (except halogens) direct incoming nucleophiles to the 3 rd position (3-directing
groups)

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10.2.3.4F RESONANCE STRUCTURES OF BENZENE CARBOCATIONS **CAN SKIP

Resonance Structures of benzene with 2,4-directing group


+
..A ..A ..A A
Attack at 2nd H H H H
position +
E E E E
+ +
..A ..A ..A ..A
Attack at **Note green
3rd position
+ +
H H H structures not
possible with
E E E methyl group
+
+
..A ..A
A

+
Attack at
4th position +
H E H E H E
Resonance Structures of benzene with 3-directing group

B B B
Attack at 2nd H H H
position +
E E E
+ +
B B B B
Attack at
3rd position
+ +
H H H
E E E
+
B B B

+
Attack at
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 2,4-directing groups
 *Assume A is a 2,4-directing group (methyl group has no lone pair to form the most stable structure
(green) )
 Notice that when the electrophile attacks at the 2 and 4th position, stable resonance structures
(green) and tertiary carbocations (orange) can be formed
 3-directing groups
 *Assume B is a 3-directing group
 Notice that when the electrophile attacks at the 2 and 4th position, highly unstable resonance
structures (red) are formed as the presence of an electron withdrawing group next to the carbocation
further intensifies the charge on it and causes the carbocation to be even more unstable
 Only an attack on the 3rd position produces no such unstable resonance structures
 The electrophile adds in a way to generate the most stable carbocation intermediate

10.2.3.4G – NITRATION (ELECTROPHILIC SUBSTITUTION ON METHYLBENZENE)

 The presence of the methyl group directs substituents to the 2nd or 4th position on the benzene ring, thus
forming 2-nitromethylbenzene and 4-nitromethylbenzene
 Reagents and conditions
 Concentrated HNO3
 Concentrated H2SO4
 30°C
Electrophilic Substitution of hydrogen on methylbenzene with nitro group (Nitration)

Step 1: Generation of Electrophile (NO2+)

HNO3 + 2H2SO4  NO2+ + H3O+ + 2HSO4-

Step 2: Attack by electrophile


CH3 CH3 CH3
H
Slow
NO2+ +
NO2
+
+ OR

H NO2
Step 3: Abstraction of proton by HSO4- and the regeneration of the catalyst

CH3
CH3 NO2
Fast
H + HSO..4-
+ H2SO4
NO2
+
2-nitromethylbenzene

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OR
CH3
CH3

+ Fast
+ HSO..4-
+ H2SO4

H NO2
NO2
4-nitromethylbenzene
 Note
 Above 30°C, disubstitution is possible and 2,4-dinitromethylbenzene is produced
 Above 110°C, trisubstitution is possible and 2,4,6-trinitromethylbenzene is produced

10.2.3.4H – HALOGENATION (ELECTROPHILIC SUBSTITUTION ON METHYLBENZENE)

 The presence of the methyl group directs substituents to the 2nd or 4th position on the benzene ring, thus
forming 2-halomethylbenzene and 4-halomethylbenzene
 Chlorination
 Reagents and conditions
 Gaseous chlorine (Cl2)
 AlCl3 Catalyst
 Room temperature
 Absence of light (to avoid FRS)
 Observations
 Decolourization of greenish-yellow Cl2 (g)
 Formation of dense white fumes of HCl
 Bromination
 Reagents and conditions
 Liquid Bromine (Br2)
 FeBr3 catalyst
 Room temperature
 Absence of light (to avoid FRS)
 Observations
 Decolourization of reddish-brown liquid bromine
 Formation of dense white fumes of HBr

Electrophilic Substitution of hydrogen on methylbenzene with chlorine (Chlorination)

Step 1: Generation of Electrophile (Cl+)

Cl2 + AlCl3  Cl+ + AlCl4-

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Step 2: Attack by electrophile Version 1.35


CH3 CH3 CH3
H
Slow
Cl +
+
Cl
+
+ OR

Step 3: Abstraction of proton by HSO4- and the regeneration of the catalyst H Cl

CH3
CH3 Cl
.. Fast
H -
+ AlCl4 + AlCl3
Cl
+
2-chlormethylbenzene

OR
CH3
CH3

+ Fast
+ AlCl..4-
+ AlCl3

H Cl
Cl
4-chloromethylbenzene

 Note: Bromination is similar except that the catalyst is changed to FeBr3 and that the reagent used is liquid
bromine

10.2.3.4I FREE RADICAL SUBSTITUTION – SIDE CHAIN REACTIONS

 Free radical substitution can occur on any alkylbenzene, including methylbenzene.


 The process is the same as that of FRS of alkanes (10.2.1.3)
 Reagents and conditions
 Cl2 (g), UV light or heat
 Greenish-yellow colour decolourizes slowly
 Similarly to FRS on alkanes, multi-substituted products can be formed (along with HCl)

10.2.3.4J SIDE CHAIN OXIDATION

 Reagents and conditions

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 Potassium Permanganate
 Dilute H2SO4
 Heat
 Observations
 Purple KMnO4 is decolourized, white precipitate of benzoic acid formed
 Mechanism
 The methyl group is readily oxidized to form a carboxylic acid group (COOH)
 Note
 Benzoic acid is always formed as long as the carbon attached to the benzoic acid has a hydrogen
attached to it
 All methyl groups attached to the methyl group on methyl benzene are oxidized to form carbon
dioxide **Distinguishing test
 All alkyl groups that have more than 1 carbon attached to the methyl group on methyl benzene are
oxidized to form their corresponding carboxylic acids
 If a basic medium (NaOH) is used, benzoate is formed instead of benzoic acid
 Purple KMnO4 is decolourized and a brown precipitate MnO2 is formed

SUMMARY OF ARENES (BENZENE) REACTIONS

Mechanism Name Reagents Conditions Products Formed Observable


Changes
Nitro (NO2) Concentrated Heat at 55°C Nitrobenzene Yellow oily liquid
HNO3 formed
Electrophilic Substitution of benzene

Concentrated
H2SO4
Halogens (X2) Pure Warm Halobenzene Decolourisation of
liquid/gaseous X2 greenish-yellow
gas/reddish-brown
Anhydrous FeX3 bromine liquid
as catalyst
Formation of
dense white fumes
of HX
Methyl (CH3) CH3Cl Warm Methybenzene No observable
Anhydrous AlCl3 (Tuolene) changes
as catalyst
Nitro (NO2) Concentrated Heat at 30°C 2/4-Nitromethylbenzene Yellow oily liquid
HNO3 30°C-100°C for formed
Electrophilic Substitution of methylbenzene

disubstitution 2,4-
Concentrated >100°C for dinitromethylbenzene
H2SO4 trisubstitution 2,4,6-
trinitromethylbenzene
Chlorination Pure gaseous Cl2 Absence of light 2/4- Decolourisation of
(Cl2) chloromethylbenzene greenish-yellow
Anhydrous AlCl3 Room gas
as catalyst Temperature
Formation of
dense white fumes
of HCl
Bromination Pure liquid Br2 Absence of light 2/4- Decolourisation of
(Br2) bromomethylbenzene reddish-brown
Anhydrous FeBr3 Room bromine liquid
as catalyst Temperature

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Formation of
dense white fumes
of HBr
Free Radical Pure gaseous Cl2 UV Light (chloromethyl)benzene Slow
Substitution Heat Decolourisation of
greenish-yellow
gas
Side Chain Oxidation Potassium Heat Benzoic acid Purple KMnO4
(with acidic medium) Permanganate decolourized,
Water White precipitate
Dilute Sulfuric ==Optional Products=== of benzoic acid
Acid Carbon Dioxide (from formed
other methyl groups*)

Carboxylic Acids**

Side Chain Oxidation Potassium Heat Benzoate Purple KMnO4


(with alkaline Permanganate MnO2 decolourized
medium) Water
Dilute Sodium ==Optional Products=== Brown precipitate
Hydroxide Carbon Dioxide (from of MnO2 formed
other methyl groups*)

Carboxylic Acids**

*Not the main methyl group attached to benzene

**From alkyl groups longer than 1 carbon (excluding main methyl group)

***Most of the above reactions use benzene/methylbenzene as the main organic reactant

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10.3 HALOGEN DERIVATIVES


 Halogen Derivatives – Aliphatic or Aromatic compounds with a halogen functional group bonded to it.
 Halogenoalkanes
 Halogenoarenes

10.3.1 IUPAC NOMENCLATURE & CLASSIFICATION

 Main Issue: Naming of halogen groups (fluoro, chloro, bromo and iodo)
 Halogen groups are always prefixed
 Similar to other substituents, the number comes before the name
 Additional prefixes such as “bi,tri” are added when necessary
 Halogenoalkanes can also be classified into primary, secondary or tertiary.
 This is similar to the system used to classify carbocations for alkenes

**Halogen groups usually represented as “X”

Primary Secondary Tertiary

H R’ R’

R C X R C X R C X

H H R’’

10.3.2 HALOGEN DERIVATIVES – PHYSICAL PROPERTIES

 Halogenoalkanes
 Boiling Points
 As compared to their corresponding alkanes, the boiling points of halogenoalkanes is higher.
 This is due to the presence of the polarized C-X bond, which causes these molecules to be polar
and be bonded to other molecules via permanent dipole-dipole interactions, which is stronger
than the London dispersion forces experienced between alkanes. More energy is required to
overcome the permanent dipole-dipole interactions as compared to the dispersion forces, thus
halogenoalkanes have a higher boiling point
 In addition, the presence of a larger electron cloud causes dispersion forces between
halogenoalkanes to be stronger than the corresponding alkane molecules. The boiling point of
halogenoalkanes is thus much higher.
 Within the hallogenoalkanes, the boiling point of iodoalkane > bromoalkane > chloroalkane. This
is due to the decreasing size of the electron cloud from iodine to chlorine, causing the dispersion
forces to be weaker.
 *Refer to section 10.2.1.2 for physical properties of alkanes
 Appearance
 Most halogenoalkanes are colourless liquids with sweetish smells
 Halogenoarenes
 Similar to that of benzene, refer to 10.2.3.2

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 Higher boiling points than corresponding benzenes due to the same explanation as that of
halogenoalkanes

10.3.3 SYNTHESIS OF HALOGEN DERIVATIVES

**Recap from previous chapters, relevant reactions will be explained in the chapter containing the reactant

Reactant Class Mechanism Name Reagents Conditions Products Formed Observations


Halogen Gaseous HX Room Mono-Halogenoalkane -
Alkenes Halides (HX) Temperature
Electrophilic Addition of

Halogens (X2) Pure Room Di-Halogenoalkane Greenish yellow


liquid/gaseous X2 Temperature colour/
No light (not Reddish brown
obligatory) colour
decolourizes
rapidly
Bromine Water Aqueous Room Mono-Halogenoalcohol Reddish brown
Bromine Temperature (Major) colour
No light (not Di-Halogenoalkane decolourizes
obligatory) (minor) rapidly
Free Radical Chlorine Gas/ UV Light Halogenoalkane; Greenish yellow
Alkanes Substitution Liquid Bromine Multiple Products colour/
Formed Reddish brown
colour
decolourizes
slowly
Chloride PCl5 (s) Room Mono-halogenoalkane Formation of
Alcohols* Temperature white fumes of HCl
Nucleophilic Substitution of OH with

SOCl2 (l) Warm Mono-halogenoalkane Formation of


white fumes of HCl
Halogen Concentrated HX Heat when Mono-halogenoalkane -
(Chlorine, Anhydrous ZnCl2 using 1° or 2°
Bromine or as catalyst when alcohol
Iodine) using 1° or 2°
alcohol
PX3 Room Mono-halogenoalkane -
Temperature
Prepare PI3 with
2P and 3I2
Electrophilic Pure Warm Halobenzene Decolourisation of
Arenes Substitution liquid/gaseous X2 greenish-yellow
Halogens (X2) gas/reddish-brown
Anhydrous FeX3 bromine liquid
as catalyst
Formation of
dense white fumes
of HX
Orange Box  Low Yield!
*Number of substituted halogens depend on the number of hydroxyl groups present (usually 1)

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10.3.4 REACTIONS OF HALOGEN DERIVATIVES

10.3.4A NUCLEOPHILIC SUBSTITUTION MECHANISM

 Nucleophile – A species that donates an electron pair in a reaction to form a new covalent bond
 Halogenoalkanes undergo nucleophilic substitution reactions due to the polar C-X bond, which causes the
carbon atom to acquire a partial positive charge (electron deficient) which causes it to be attacked by
nucleophiles
 Halogenoarenes do not undergo nucleophilic substitution as the overlap of the π-electron cloud of the
benzene ring and the p-orbital of the halogen atom causes the carbon attached to the halogen atom to be
inaccessible to nucleophiles as its partial positive charge is shielded by the negative π-electron cloud.
 Halogenoalkenes with the alkene group adjacent to the
halogen group also do not undergo nucleophilic substitution
for similar reasons (π electron overlap) Include for all nucleophilic
 Mechanism of nucleophilic substitution substitution mechanisms
 Bimolecular nucleophilic substitution SN2
 Exhibited by primary halogenoalkanes and some  Name of reaction
secondary halogenoalkanes  Partial charges
 One step mechanism  Real charges
 Involves 2 molecules in the rate determining step, Rate =  The speed of each of the
k [RX] [Nu] elementary steps
 Formation of a transition state as the bond between the  The full arrows
nucleophile and the electrophilic carbon is formed at the  Stereochemistry
same time the bond between the electrophilic carbon and  Lone Pairs
the halogen is broken. 
 The stereochemistry w.r.t the electron-deficient carbon
will be inverted after the substitution reaction.
 This occurs because the primary carbocation is unstable, hence SN1 is energetically
unfavourable for primary halogenoalkanes

Nucleophilic Substitution (SN2)

H/R H/R
H/R
+
δ δ-
Nu: C X Nu C X Nu + X-
C

R’ R’
H R’ H H

 Unimolecular nucleophilic substitution SN1


 Exhibited by tertiary halogenoalkanes and some secondary halogenoalkanes
 Two step mechanism
 Involves 1 molecules in the rate determining step, Rate = k [RX]
 There are 2 steps as the alkyl groups attached to the electrophilic carbon prevents the
simultaneous attack by the nucleophile the moment then C-X bond breaks.
 Furthermore, the alkyl groups act as electron donating groups and render the carbocation more
stable.

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 Formation of a carbocation intermediate via the heterolytic fission of the C-X bond. This is the
slow step. This carbocation is similar to the one found in alkenes
 The second (fast) step involves the attack of the carbocation by the nucleophile, forming the
bond.
 **NO need to draw stereochemistry & the transition state symbol for SN1 reactions, but need to
label slow/fast steps
 Tertiary carbocations are stable enough for SN1 to be favoured due to the alkyl electron
donating groups.

Nucleophilic Substitution (SN1)

R R

Slow


δ+ δ- +
R’ C X R’ C + X-

H/R’’ H/R’’

R R

R’ C

+
+ :Nu Fast
R’ C Nu

H/R’’ H/R’’

 Energy Profile Diagrams for both SN1 and SN2


 Since an intermediate carbocation is produced in the SN1 reaction, there are 2 peaks instead of 1.

 Left – SN2, Right – SN1


 Equal amounts of the 2 optical isomers (only applicable to carbocations attached to 3 different groups)
are produced as the planar carbocation has an equal chance of being attacked from the top or the bottom
by the nucleophile in the 2nd step
 The relative rate of nucleophilic substitution increases down the group as the length of the C-X bond
increases from fluorine to iodine, thus it is easier to break as the strength of the bond decreases.
 Fluroalkanes do not undergo nucleophilic substitution due to the strength of the C-F bond.

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10.3.4B NUCLEOPHILIC SUBSTITUTION REACTIONS

 All reactions below operate via the SN1 or SN2 route


 Alkaline Hydrolysis – Nucleophilic Substitution of Halogen group with Hydroxyl group
 R-X + OH-  R-OH + X-
 Reagents & Conditions
 Aqueous NaOH, heat
 Amine Formation – Nucleophilic Substitution of Halogen group with Amine group
 R-X + NH3  R-NH2 + X-
 Reagents & Conditions
 Ethanolic concentrated NH3, heat in sealed tube
 Note: The product R-NH2 can act as another nucleophile due to the presence of a lone pair in the
amine group. This is actually a stronger nucleophile than NH 3 thus excess ammonia must be used or
secondary, tertiary & quaternary amine compounds may be formed.
 Nitrile Formation – Nucleophilic Substitution of Halogen group with Nitrile group
 Step-Up Reaction
 R-X + CN-  R-CN + X-
 The product R-CN can undergo further oxidation or reduction to form carboxylic acids and amines
 Oxidation of C≡N
 R-CN  R-COOH
 Reagents & Conditions
 Dilute sulfuric acid, heat
 R-CN  R-COO-
 Reagents & Conditions
 Aqueous sodium hydroxide, heat
 Can be converted back to the carboxylic acid by adding hydrogen protons
 Reduction of C≡N
 R-CN  R-CH2NH2
 Reagents & Conditions
 Lithium Aluminium Hydride (LiAlH4) in dry ether

10.3.4C ELIMINATION REACTIONS

 The halo group along with a hydrogen atom from the adjacent carbon is removed together, and the
carbon that the halo group is attached to forms a double bond with the carbon the hydrogen atom is
attached to. This forms an alkene
 Reagents
 Ethanolic NaOH
 Required as in an ethanolic solution, OH- behaves as a base and is able to abstract a proton from
halogenoalkane. The C-X bond breaks at the same time and an alkene is formed.
 The ease of elimination depends on the strength of the C-X bond
 Due to the nature of alkenes, many cis and trans isomers can be formed depending on where the alkene is
formed. Refer to 10.2.2.2 for more information

10.3.4D ELECTROPHILIC SUBSTITUTION

 Halogenoarenes can undergo electrophilic substitution of hydrogen on the benzene ring with another
group. (refer to 10.2.3.4)

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 The Halo group is a weakly deactivating group (due to its electron withdrawal effect), but it is still 2,4-
directing.
 Thus, the lewis acid catalysts are still required

10.3.5 DISTINGUISHING TEST FOR HALOGENOALKANES

10.3.5A COMPARING COLOUR OF SILVER HALIDE PPT

*Note: This test cannot be used for halogenoarenes

 Principle: Halides react with silver cations in an aqueous solution to produce AgX which has various
colours
 Steps
1. Heat the halogenoalkane with aqueous NaOH (Nucleophilic Substitution)
2. Add excess dilute HNO3 to remove the excess aqueous NaOH
3. Add aqueous AgNO3 solution and observe the colour of the precipitate (AgX) formed.

Silver Halide AgCl AgBr AgI


Colour White Cream Pale Yellow
Solubility in NH3 Soluble, formation of Soluble in concentrated Not soluble
solution complex ligand NH3, formation of
[Ag(NH3)2]+ + Cl- complex ligand
[Ag(NH3)2]+ + Br-

10.3.5B COMPARING RATE OF FORMATION OF SILVER HALIDE PPT

 Due to the differing strengths of the R-X bond, AgX will be formed at different rates
 As bond strength increases, the rate of formation decreases as the bond becomes harder to break

Silver Halide AgCl AgBr AgI


Rate of Formation/min 5-8 3-5 Almost Immediate

*Note: This test cannot be used for halogenoarenes

10.3.6 HALOGENOALKANES AND THE ENVIRONMENT

 Halogenoalkanes are used as refrigerants, aerosols, etc.


 However, certain halogenoalkanes (CFCs) can drift to the ozone layer and break down in the presence of
UV light to form chlorine radicals, which react destructively with ozone to form oxygen gas.
 Similarly to the free radical substitution reaction, chlorine radicals are regenerated and act as a
catalyse to break down the ozone layer

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SUMMARY OF HALOGEN DERIVATIVES REACTION

Mechanism Name Reagents Conditions Products Formed Observable Changes


Hydroxyl (OH) Aqueous NaOH Heat Alcohol -
Nucleophilic Substitution of

Amines (NH2) Ethanolic Heat in sealed Amine + HX -


halogenoalkane

*** Concentrated tube


NH3
Nitrile (CN-) Ethanolic KCN Heat Nitrile (R-CN) -

*Further
reactions
possible, see
below
Elimination** Ethanolic NaOH Heat Alkene + HX -

Oxidation of Nitrile Dilute Sulfuric Heat Carboxylic Acid


Acid
Aqueous NaOH Heat Carboxylate Salt -
Reduction of Nitrile LiAlH4 in dry Heat Amine -
ether
Precipitation of halides Aqueous NaOH, Room AgX, [Ag(NH3)2]+ Distinguishing Test
with Ag+ Dilute Nitric Temperature Formation of a
Acid, Silver white/cream/yellow ppt
Nitrate Solution, that dissolves in excess
Aqueous dilute/concentrated NH3/
Ammonia does not dissolve in
excess NH3
Electrophilic Varies, check arenes summary
Substitution

**Cannot occur for 1-carbon compounds e.g. halomethane

***May form ionic salt (ammonium salt)

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ANNEX 10.3 – MECHANISMS FOR ELIMINATION

ELIMINATION REACTION IN ALKYL HALIDES

 Similar to nucleophilic substitution


 Mechanism (Not in syllabus)
 Proceeds via E1 and E2, very similar to SN1 and SN2
 Similar to SN1, E1 works for mostly tertiary halogenoalkanes and vice versa
 The hydroxide ions act as a bronsted base in such this scenario rather than as a nucleophile
 Factors affecting whether substitution or elimination occurs
 Type of Halogoalkane
 Primary – Mainly substitution
 Secondary – Both substitution and elimination
 Tertiary – Mainly elimination
 Solvent
 Water encourages substitution
 Ethanol encourages elimination
 Temperature
 High temperatures encourage elimination

Elimination (E2) (Not in syllabus)

R’’ H R’’ H

δ+ δ-
R’’’ C C X C C + ROH + X-

H H/R’ R’’’ H/R’


:O-R

Elimination (E1) (Not in syllabus)

R’’ R R’’ R

Slow


δ+ δ- +
R’’’ C C X R’’’ C C + X-

H H/R’ H H/R’’

R’’ R R’’ R

R’’’ C C

+ Fast
C C + ROH

H H/R’’ R’’’ H/R’’


:O-R

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10.4 HYDROXYL COMPOUNDS


 Hydroxyl compounds – Compounds with a hydroxyl (OH) group
 Alcohols
 Phenols (benzene ring with hydroxyl group)

10.4.1 IUPAC NOMENCLATURE & CLASSIFICATION

 Main Issue: Alcohols as Functional Groups


 When naming alcohols, the location of the hydroxyl group must always be specified
 E.g. But-1,2-diol
 Rest of naming similar to naming alkenes
 Note that if acid derivatives/acids are present, the hydroxyl group is named as a prefix
 Similar to other substituents, the number comes before the name
 Additional prefixes such as “bi,tri” are added when necessary
 Main Issue: Phenols as Functional Groups
 When naming phenols, the hydroxyl group and the benzene ring are named as a whole group
 Similarly to naming arenes, substituents are named as prefixes.
 If the substituents are too long, the phenol is named as a prefix “phenyl”
 Alcohols (not phenols) can also be classified into primary, secondary or tertiary.
 This is similar to the system used to classify carbocations for alkenes

Primary Secondary Tertiary

H R’ R’

R C OH R C OH R C OH

H H R’’

10.4.2 ALCOHOLS AND PHENOLS – PHYSICAL PROPERTIES

10.4.2A BASIC PHYSICAL PROPERTIES

 Alcohols
 Boiling Points
 As compared to their corresponding alkanes, the boiling points of alcohols is higher.
 This is due to the presence of the hydroxyl group which causes these molecules to exhibit
hydrogen bonding, which is stronger than the London dispersion forces experienced between
alkanes. More energy is required to overcome the hydrogen bonds as compared to the dispersion
forces, thus alcohols have a higher boiling point
 Within the alcohols the boiling point of alcohols increase as the number of carbon atoms
increase. This is due to the increasing size of the electron cloud, causing the dispersion forces to
be stronger.
 Solubility
 In general, alcohols are soluble in water as they can displace molecules of water in the hydrogen
bonding of water molecules.

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 Alcohols with longer carbon chains can form fewer hydrogen bonds than the numerous water
molecules they displace. Enthalpy considerations also make the longer chain alcohols less soluble
than those with shorter carbon chains.
 1-3 Soluble, 4-5 Sparingly, 6- insoluble
 *Refer to section 10.2.1.2 for physical properties of alkanes
 Appearance
 Most alcohols are colourless liquids
 Phenols
 Similar to that of benzene, refer to 10.2.3.2
 Higher boiling points than corresponding benzenes due to the same explanation as that of alchols

10.4.2B ACIDITY

 Alcohols
 Alcohols act as Bronsted acids by donating a proton to water molecules, which act as a Bronsted base.
This causes a hydronium ion to be formed. Alcohols are thus acidic.
+ -
 R-OH + H2 O ⇌ H3 O +R-O
 Alcohol (acid) + Water (base) ⇌ Hydronium cation (conjugate acid) + Alkoxide anion (conjugate base)
 Properties of alcohols as acids
 Alcohols do not turn blue litmus paper red
 Alcohols are weaker acids than water as the alkyl groups have a large effect on the destabilization
of the alkoxide ion as compared to the hydrogen atom as it possesses a larger electron cloud
 Since alcohols (with no other functional groups) are weaker acids than water, the above
reaction happens only to a small extent in reality.
 Stability of the alkoxide anion
 The more stable the alkoxide ion formed, the stronger the alcohol as an acid
 Electron withdrawing groups help to disperse the negative charge on the alkoxide anion and
stabilize it whereas electron donating groups intensifies the negative charge on the alkoxide anions
and destabilizes it.
 The stability of the alkoxide anion depends on the presence of electron donating or electron
withdrawing groups on the alcohol
 The effect of any individual electron donating/withdrawing group on the stability of the alkoxide
ion depends on the proximity (distance) of the group to the hydroxyl group
 Unlike arenes, the only way the electron donating/withdrawing groups can affect the alkoxide ion
is via the sigma (inductive) effect. There is no resonance effect involved. (sp3 carbons  no π bond
overlap)

Substituent Inductive Effect Effect on alkoxide anion Overall effect on acidity


of alcohols
Alkyl Group Electron Donating Destabilize Decreases
Hydroxyl, Electron Withdrawing: Stabilize Increases
Ether, Amine Intermediate atom is an
electronegative species
Halogens Electron Withdrawing: Stabilize Increases
Intermediate atom is an
electronegative species
Aldehydes, Electron Withdrawing: Stabilize Increases
Nitro, Esters, Intermediate atom is attached
Ketones, Nitrile to more electronegative
species

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*In arenes, the main ion is a carbocation, thus electron withdrawing groups have a destabilizing effect, and vice-
versa. But in alchols the main ion is an anion, thus electron withdrawing groups have a stabilizing effect. Same
goes for phenols

 Phenols
 Similarly, phenols act as bronsted acids react with water to produce hydronium ions
 Phenols are more acidic than alcohols as the phenoxide anion is more stable than an alkoxide anion.
 This is due to the resonance effect of the benzene ring, which can be used to disperse the lone pair
of electrons on oxygen over the benzene ring. This occurs due to the π bond overlap between the
oxygen atom and the sp2 hybridized carbon.
 Stability of the phenoxide anion
 Similarly to the alkoxide anion, electron withdrawing groups help to disperse the negative charge
and stabilize the phenoxide anion, while electron donating groups intensify the negative charge
and destabilizes the phenoxide anion.
 Both resonance and inductive effects are involved due to the nature of the benzene ring.
 Acidity of Phenol > Acidity of Water > Acidity of Alcohols

10.4.3 SYNTHESIS OF ALCOHOLS

**Recap from previous chapters, relevant reactions will be explained in the chapter containing the reactant

Reactant Class Mechanism Name Reagents Conditions Products Formed Observations


Electrophilic Alkene 300°C Primary/Secondary/ -
Alkenes Addition of Steam Steam 70 atm Tertiary Alcohol
H3PO4 catalyst
Mild Oxidation Alkene Cold Diol Purple KMnO4
Dilute KMnO4 Temperature Decolourizes and a
NaOH (aq) brown precipitate
of MnO2 is formed
Nucleophilic Alkyl Halide Heat Primary/Secondary/ -
Halogen Substitution of X Aqueous NaOH Tertiary Alcohol
Derivatives with OH
(Alkaline Hydrolysis)
*
Reduction of Carboxylic Acid Room Primary Alcohol -
Carboxylic carboxylic acid + 4[H] Temperature
Acid LiAlH4 in dry
ether
Ketones + 2[H] Room Secondary Alcohol -
Carbonyl LiAlH4 in dry Temperature
Compounds ether
H2 High Pressure &
Temperature
Reduction of

NaBH4 in Heat
methanol
Aldehydes H2 High Pressure & Primary Alcohol -
Temperature
NaBH4 in Heat
methanol
+ 2[H] Room
LiAlH4 in dry Temperature
ether
*Number of substituted hydroxyl groups depend on the number of halo groups present (usually 1)

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In this syllabus there is no mechanism provided for the synthesis of phenols

10.4.4 REACTIONS OF ALCOHOLS

 The polar C-O and O-H bond can both be broken in various reactions.

10.4.4A COMBUSTION

 All alcohols can be used as a fuel.


 The state of water formed is given as “liquid” as it is assumed that the system has cooled to room
temperature

10.4.4B NUCLEOPHILIC SUBSTITUTION – HALOGENATION

 Using acidic halides


 Chlorination using HCl
 Tertiary Alcohols
 Conversion of tertiary alcohols into tertiary halogenoalkanes
 Reagents and Conditions
 Concentrated HCl
 Primary and Secondary Alcohols
 Conversion of primary and secondary alcohols into primary and secondary halogenoalkanes
 Reagents and Conditions
 Concentrated HCl
 ZnCl2 as a catalyst
 Heat
 Bromination using NaBr and H2SO4 (which produces HBr)
 Primary and Secondary Alcohols
 Conversion of primary and secondary alcohols into primary and secondary halogenoalkanes
 Reagents and Conditions
 Heat solid NaBr in the presence of concentrated H2SO4
 The sulfuric acid serves as a dehydrating agent

Halogenation (using HX)

R R

Concentrated HX + H2O
R’ C OH R’ C X

R’’ R’’

R/H R/H

Concentrated HX + H2O
R’ C OH R’ C X
ZnCl2 Catalyst for
chlorination
H /H2SO4 Catalyst H
for bromination
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 Using phosphorus halide


 Distinguishing Test – Chlorination using phosphorus pentachloride (PCl5)
 Observations: Formation of dense white fumes of HCl
 Reagents and Conditions: PCl5, room temperature

R OH + PCl5 R Cl + POCl3 + HCl

 Using phosphorus trihalide


 Reagents and Conditions: PX3, room temperature
 Note: PX3 can be prepared by heating red phosphorus (P) with iodine or bromine.

2P + 3X2 2PX3 X = I, Br

R OH + PX3 3R X + H3PO3 X = Cl, I, Br


 Using Sulfur Oxide Dichloride (Thionyl Chloride)
 Distinguishing Test
 Observations: Formation of dense white fumes of HCl, formation of sulfur dioxide
 Reagents and Conditions: SOCl2, warm
 Note: The gaseous products formed can be easily isolated from the halogenoalkane

R OH + SOCl2 R Cl + SO2 + HCl

10.4.4C ELIMINATION (DEHYDRATION)

 Reagents and Conditions: Excess concentrated H2SO4, 170°C


 The hydroxyl group along with a hydrogen atom from the adjacent carbon is removed together, and the
carbon that the hydroxyl group is attached to forms a double bond with the carbon the hydrogen atom is
attached to. This forms an alkene
Elimination

R’’ R R’’ R

C C OH C C + H2O
R’’’

H R’ R’’’ R’’
*Elimination does not take when the adjacent carbon has no hydrogen atom attached

10.4.4D ACID-METAL REACTION (WITH SODIUM) (REDOX)

 Reagents and Conditions: Na(s), Room Temperature


 Observations: Slow effervescence of hydrogen gas

R OH + Na R O- Na+ + ½ H2

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10.4.4D ESTERIFCATION (CONDENSATION)

 Reaction with carboxylic acids


 Reagents & Conditions: Carboxylic Acid + Alcohol, Few drops of concentrated H 2SO4, Reflux
 Observation: Sweet Smelling liquid formed

R’ OH + HO C R ⇌ R’ O C R + H2O

O O
 Reaction with acyl chlorides
 Reagents & Conditions: Acyl chloride + Alcohol, Few drops of concentrated H 2SO4
 Observation: Sweet Smelling liquid formed
 Non-reversible
R’ OH + X C R R’ O C R + HX

O O

10.4.4E OXIDATION

 Prerequisite: Alcohol must have one hydrogen atom bonded to the carbon with the hydroxyl group
 Hence, tertiary alcohols cannot be oxidized (oxidation will result in the cleavage of C-C bonds)

R’ C OH

H
 Oxidizing Agents
 Strong: Potassium Dichromate
 Very Strong: Potassium Permanganate
 Oxidation of Primary Alcohols
 To Aldehydes
 Reagents & Conditions: K2Cr2O7, dilute H2SO4 with immediate distillation (to remove the
aldehyde before further oxidation takes place)
 Observations: Orange solution turns green
 *Potassium permanganate cannot be used
H O

R C OH + [O] R C H + H2O

 To Carboxylic Acids
 Reagents & Conditions: KMnO4, dilute H2SO4, heat under reflux
 Observations: Purple solution turns colourless

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 *Potassium dichromate can be used


H O

R C OH + 2[O] R C OH + H2O

 Oxidation of Secondary Alcohols to Ketones


 Reagents & Conditions: KMnO4, dilute H2SO4, heat under reflux
 Observations: Purple solution turns colourless
 *Potassium dichromate can be used

H O

R C OH + [O] R C R’ + H2O

R’

10.4.4F IODOFORM FORMATION

 Prerequisite: The carbon that the hydroxyl group is attached to must have a methyl (CH 3) and a hydrogen
atom attached to it
 Ethanol is the only primary alcohol that will show a positive result
 Not all secondary alcohols will show a positive result
 No tertiary alcohols will show a positive result
 Step-Down Reaction (removes 1 carbon)
 Note: Any compound with iodine attached to the methyl group listed below will also show a positive
result.
H O

R C OH + 4I2 + 6OH- R C O- + CHI3 + 5I- + 5H2O


Iodoform
Carboxylate Anion
CH3

10.4.5 REACTION OF PHENOLS

 Unlike in alcohols, the C-O bond is very strong due to the delocalization of the lone pairs of electrons of
oxygen over the benzene ring.
 There are no reactions in which the C-O bond can break, unlike alcohols
 The absence of fumes from adding PCl5 to phenols distinguishes a phenol from an alcohol

10.4.5A ACID-METAL REACTION (WITH SODIUM) (REDOX)

 Reagents and Conditions: Na(s), Room Temperature


 Observations: Slow effervescence of hydrogen gas (faster than alcohols since phenols are more acidic)

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OH + Na O- Na+ + ½ H2

10.4.5A NEUTRALIZATION

 Phenols are acidic enough to react with bases


 Reagents and Conditions: Hydroxide, Room Temperature
 Observations: Cloudy solution (insoluble phenol) turns clear
 *Phenols cannot react with carbonates

OH + NaOH O- Na+ + H2O

10.4.5B ESTERIFCATION (CONDENSATION)

 Phenols are weaker nucleophiles than alcohols and do not readily donate their lone pairs to carboxylic
acids to form esters due to the delocalization of the lone pair into the benzene ring. They do not react
with carboxylic acids.
 Phenols must first be ionized using sodium or metal hydroxides to obtain a stronger nucleophile,
the phenoxide ion
 The direct reaction of phenols with acyl halides will lead to a lower yield
 Reaction of phenoxide with acyl halides
 Reagents & Conditions: Acyl halides + Alcohol, Few drops of concentrated H 2SO4
 Observation: Sweet Smelling liquid formed
 Non-reversible

O- + X C R O C R + X-

O O

10.4.5C ELECTROPHILIC SUBSTITUTION

 No catalyst required – Due to the delocalization of the lone pair of electrons from oxygen into the
benzene ring, the electron density of the benzene ring increases, making phenol more susceptible to
electrophilic attacks.
 Hydroxyl group is 2,4-directing
 Halogenation (max substitution)
 Reagent & Conditions: Aqueous halogen, room temperature
 Observations: Reddish-Brown/Greenish-yellow Solution Decolourizes, white ppt formed
OH OH
X X
+ 3X2(aq) + 3HX

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 Halogenation (minimum substitution)


 Reagents & Conditions: Liquid Halogen dissolved in CCl4, room temperature
 Observations: Reddish-Brown/Greenish-yellow Solution Decolourizes
OH OH
OH
X
+ 2X2 (l) & + 2HX

X
 Nitration (max substitution)
 Reagent & Conditions: Concentrated Nitric Acid, room temperature
 Observations: white ppt formed
OH
OH
O2N NO2
+ 3HNO3

NO2
 Nitration (minimum substitution)
 Reagents & Conditions: Dilute nitric acid, room temperature
 Observation: None
OH OH
OH
NO2
+ 2HNO3 &

NO2
 Distinguishing Test – Ligand formation with FeCl3 (aq)
 Reagents & Conditions: Neutral FeCl3, room temperature
 Observations: Violet Complex Formed

OH
3-

FeCl3
6 O Fe

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SUMMARY OF HYDROXYL GROUP REACTIONS

Reactions of Alcohols
Mechanism Name Reagents Conditions Products Formed Observable
Changes
Combustion Alcohol + Oxygen Heat H2O + CO2 Flames
Chlorination HCl (conc) Room Alkyl halide, H2O -
3° Alcohol Temperature
HCl (conc) Heat Alkyl halide, H2O -
Nucleophilic Substitution of Alcohol with Halo Group

1°/2° Alcohol
ZnCl2 Catalyst
PCl5 (s) Room Alkyl halide, POCl3 (l), Formation of
Alcohol Temperature HCl (g) dense white fumes
of HCl**
Distinguishing
(Halogenation)

Test for OH &


COOH group
SOCl2 (l) Warm Alkyl halide, SO32 (g), HCl Formation of
Alcohol (g) dense white fumes
of HCl**
Distinguishing
Test for OH &
COOH group
Bromination NaBr Heat Alkyl halide, H2O -
H2SO4 (conc)
Alcohol
Halogenation PX3 Heat Alkyl halide, H3PO4 -
in general Alcohol
Oxidation 1° Alcohol, Heat with Aldehyde, H2O Orange solution
*Requires H atom K2Cr2O7 immediate turns green
attached to same Dilute H2SO4 distillation
carbon 1° Alcohol Heat under Carboxylic Acid, H2O Purple solution
KMnO4 reflux turns colourless
Dilute H2SO4
2° Alcohol Heat under Ketone, H2O Purple solution
KMnO4 reflux turns colourless
Dilute H2SO4
Esterification Carboxylic Acid Heat under Ester, H2O Sweet smelling
Alcohol reflux *Reversible liquid formed
H2SO4 (conc)
Acyl Halide Room Ester, H2O Sweet smelling
Alcohol Temperature *Non-Reversible liquid formed
Dehydration Excess 170°C Alkene, H2O -
(elimination) concentrated H2SO4
Alcohol
Acid-Metal (Redox) Alkaline Metal, Room Alkoxide salt, H2 (g) Slow
Alcohol Temperature effervescence of a
colourless and
odourless gas that
extinguishes a
lighted splint
Iodoform Formation I2 (aq) Warm Carboxylate anion, I-, Yellow ppt formed
*only possible for NaOH (aq) H2O, CHI3
alcohols with structure
CH(CH3-xIx)OH, x=<3

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Reactions of Phenols
Mechanism Name Reagents Conditions Products Formed Observable
Changes
Halogenation X2 in CCl4 Room 2-halophenol, 4- Decolourisation of
Phenol Temperature halophenol greenish-yellow
HX (g) gas/reddish-brown
bromine liquid
Electrophilic Substitution of phenol

Formation of
dense white fumes
of HX
X2 (aq) Room 2,4,6-trihalophenol, Decolourisation of
Phenol Temperature HX (g) greenish-yellow
gas/reddish-brown
bromine liquid

White ppt formed

Formation of
dense white fumes
of HX
Nitration Concentrated HNO3 Room 2,4,6-nitrophenol, H2O White ppt formed
Temperature
Dilute HNO3 Room 2-nitrophenol, 4- -
Temperature nitrophenol, H2O
Ligand Formation Neutral FeCl3 (aq) Room (Fe(phenol)6)3- violet Solution turns
Phenol Temperature complex violet from
yellow**
Distinguishing
Test for phenol
Esterification Acyl Halide Room Ester, H2O Sweet smelling
**No reaction with Phenoxide ion Temperature *Non-Reversible liquid formed
carboxylic acids (obtained from
phenol first via
neutralization)
Acid-Metal (Redox) Alkaline Metal, Room Phenoxide salt, H2 (g) Slow
Phenol Temperature effervescence of a
colourless and
odourless gas that
extinguishes a
lighted splint
Neutralization Phenol, Room Phenoxide salt, H2O (l) -
Hydroxide Base Temperature

**”Neutral” is very important!!

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ANNEX 10.4 – MECHANISMS FOR ELIMINATION

ELIMINATION REACTION

 Refer to annex 10.3 for more details


 Essentially the same except that an additional protonation step takes place which requires an acid, HA
that is regenerated at the end

Elimination (E2) (Not in syllabus)


R’’ H R’’ H

δ+ δ-
+
:

R’’’ C C OH H A R’’’ C C O +H A-

H H/R’ H H/R’ H

R’’ H R’’ H

δ+ δ-
R’’’ C C O+ H C C + H2O + HA

H H/R’ H R’’’ H/R’


:A-

Elimination (E1) (Not in syllabus)


R’’ H R’’ H

δ+ δ-
+
:

R’’’ C C OH H A R’’’ C C O +H A-

H H/R’ H H/R’ H

R’’ R R’’ R

Slow
δ+ δ-
⇌ R’’’ C C

+
+ H2O
R’’’ C C O+ H

H H H/R’’
H/R’ H

R’’ R R’’ R

R’’’ C C

+ Fast
C C + HA

H H/R’’ R’’’ H/R’’

:A-
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10.5 CARBONYL COMPOUNDS


10.5.1 IUPAC NOMENCLATURE & CLASSIFICATION

 Main Issue: Aldehyde as Functional Groups


 When naming aldehydes as the highest priority group, the location need not be specified as the
carbon used to form the aldehyde is listed as carbon-1. Naming of the longest chain must include this
group.
 Additional prefixes such as “bi,tri” are added when necessary. Add numbers to indicate the carbon to
which the aldehyde group is attached to. In cases of multiple aldehydes, the aldehyde’s carbon is not
considered part of the main chain.
 Aldehydes attached to a benzene ring are named as benzaldehyde
 Aldehydes attached to a cyclic ring are named as –carbaldehyde
 In the presence of a higher priority functional group, the prefix given for aldehydes is formyl
 Main Issue: Ketones as functional groups
 Ketones are named as x-one, where x is the prefix denoting the number of carbons on the main chain
 In the presence of a higher priority functional group, the prefix given for ketones is oxo
 Unless the location of the ketone is obvious, all ketones require a number that denotes the carbon
with the ketone

10.5.2 ALDEHYDES AND KETONES – PHYSICAL PROPERTIES

10.5.2A CHEMICAL STRUCTURE OF THE CARBONYL GROUP

 Bonds: One σ + one π bond


 Hybridization of carbon: sp2
 Bond angle: 120°
 C=O bond is highly polarized

10.5.2B BASIC PHYSICAL PROPERTIES

 Boiling Points
 As compared to their corresponding alkanes, the boiling points of aldehydes & ketones is higher.
 This is due to the presence of the carbonyl group which causes these molecules to exhibit permanent
dipole-dipole interactions, which is stronger than the London dispersion forces experienced between
alkanes. More energy is required to overcome the permanent dipole-dipole interactions as compared
to the dispersion forces, thus aldehydes and ketones have a higher boiling point
 Within the carbonyl compounds the boiling point increases as the number of carbon atoms increase.
This is due to the increasing size of the electron cloud, causing the dispersion forces to be stronger.
 Compared to alcohols and carboxylic acids, the boiling points are lower as hydrogen bonds are
stronger than permanent dipole-dipole interactions.
 Solubility
 In general, carbonyl compounds are soluble in water as they can displace molecules of water in the
hydrogen bonding of water molecules.
 Carbonyl compounds with longer carbon chains can form fewer hydrogen bonds than the numerous
water molecules they displace. Enthalpy considerations also make the longer chain carbonyl
compounds less soluble than those with shorter carbon chains.
 1-3 Soluble, 4-5 Sparingly, 6- insoluble

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 *Refer to section 10.2.1.2 for physical properties of alkanes

10.5.3 SYNTHESIS OF CARBONYL COMPOUNDS

Reactant Class Mechanism Name Reagents Conditions Products Formed Observations


Oxidative Cleavage KMnO4 Heat under Ketone Purple Solution
Alkenes *Alkene must have Dilute Reflux Decolourizes
no hydrogen H2SO4
atoms attached to
it
Oxidation of 1° 1° alcohol, Heat with Aldehyde Orange
Alcohols alcohols K2Cr2O7 immediate solution turns
Dilute distillation green
H2SO4
Oxidation of 2° 2° alcohol, Heat under Ketone Orange
alcohols K2Cr2O7 reflux solution turns
Dilute green
H2SO4

10.5.4 REACTIONS OF CARBONYL COMPOUNDS

10.5.4A – NUCLEOPHILIC ADDITION

 Aldehydes are more reactive than ketones due to steric hindrance caused by the additional R-group in
ketones; Aldehydes also have 1 less electron donating group compared to ketones

O δ- O--

Slow
R C+ R + :X Y R C R + Y+
δ δ- δ+

O:-- O Y
Fast
R C R Y+ R C R

X X

 Using HCN
 Reagents and Conditions: HCN with trace KCN, cold (10-20°C) [used to prevent HCN from being in the
gaseous form; KCN used as catalyst]
 Mechanism

O δ- O--

Slow
R C+ R + :CN R C R
δ

CN

O:-- OH

Fast
R C R H CN R C R + CN-
δ+ δ-
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Rate = k [Carbonyl Compound] [CN-]
 Adding KCN increases the rate of the reaction as it provides cyanide ions immediately upon
dissociation, since HCN is a weak acid  HCN + H2 O ⇌ H3 O+ +CN -
 Adding a small amount of NaOH increases the rate of reaction as it causes the equilibrium in this
reaction HCN + H2 O ⇌ H3 O+ +CN - to shift to the right (by consuming hydronium ions produced)
 Stereochemistry
 Racemix mixture formed as the cyanide ion can attack the planar carbonyl group from either
the top or the bottom plane
 Using Grignard Reagents (R-MgX)
 Commonly used to prepare complex alcohols, reagents and conditions not required to know

O δ- O--

R’ C+ R’’ + :R MgX R’ C R’’ + X-Mg+


δ δ - δ+

R

O:-- OH

R’ C R’’ H R’ C R’’ + OH-

O
R H R

10.5.4B – CONDENSATION

 In general,

O H R’

R C R’ + H N R’’’ R C N R’’’ + H2O

 Using 2,4-dinitrophenylhydrazine
 Distinguishing Test for Carbonyl Compounds
 Reagents and Conditions: 2,4-DNPH, Room Temperature
 Observations: Formation of an orange precipitate

O H H

R C R’ + H N N NO2

NO2

R’ H

C N N NO2 + H2O

NO2
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10.5.4C – REDUCTION

 Aldehydes and Ketones can be reduced to form primary and secondary alcohols respectively
 Reagents and Conditions: LiAlH4 in dry ether/NaBH4/H2 with Ni catalyst; add water after reaction is
complete to protonate the alkoxide anion to form the alcohol

O OH

R C R’ + 2[H] R C R’

H
10.5.4D – OXIDATION

 Only aldehydes can be further oxidized to form ketones


 Oxidation to Carboxylic Acids
 Reagents and Conditions: Aldehyde, KMnO4, Dilute H2SO4, Head under Reflux
 Observations: Purple solution decolourizes

O O

KMnO4
R C H + [O] R C OH
Dilute H2SO4

 Tollen’s reagent test


 Distinguishing Test for Aldehydes
 Reagents and Conditions: Aldehyde, Tollen’s Reagent ([Ag(NH 3)2]+ + NaOH), Heat
 Observations: Silver Mirror Formed
 To prepare Tollen’s Reagent, add one drop of dilute NaOH to 3cm3 of AgNO3 to form Ag2O. Add dilute
NH3 to dissolve Ag2O and form the complex anion [Ag(NH3)2]+
O O

R C H + 2[Ag(NH3)2] + 3OH- R C O- + 2Ag + 4NH3 + 2H2O


+

 Fehling’s reagent test


 Distinguishing Test for Aliphatic Aldehydes; No reaction with benzaldehyde
 Reagents and Conditions: Aldehyde, Fehling’s Solution, Heat
 Observations: Reddish-brown precipitate (Copper (I) oxide) formed
 Tartrate ions added to prevent copper ions from forming copper hydroxide

O O

R C H + 2Cu2+ + 5OH- R C O- + 2Cu2O + 3H2O

10.5.4E IODOFORM TEST (STEP-DOWN REACTION)

 Distinguishing Test for Ethanal or Methyl Ketones


 Only molecules with this structure R-C=O(CH3) will have a positive reaction
 Reagents and Conditions: Carbonyl Compound, I2 (aq) in NaOH (aq), Heat
 Observations: Formation of yellow crystals of iodoform (CHI3)
O O

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SUMMARY OF CARBONYL COMPOUNDS REACTION

Reactions of Carbonyl Compounds


Mechanism Name Reagents Conditions Products Formed Observable
Changes
Addition of Carbonyl Compound Cold Cyanohydrin -
Nucleophilic Addition

Hydrogen HCN R-C(OH)(CN)-R’


Cyanide Trace KCN as Catalyst

Addition of *Not required to know R’-C(OH)(R)-R’ -


Grignard
reagent R-MgX

Oxidation Aldehyde Heat under Carboxylic Acid, H2O Purple solution


*Requires H atom KMnO4 reflux turns colourless
attached to same Dilute H2SO4
carbon Tollen’s Reagent Heat Carboxylate Anion Silver Mirror
Aldehyde Silver Formed
Ammonia, H2O
Fehling’s Reagent Heat Carboxylate Anion Reddish-Brown
Aldehyde Copper (I) Oxide ppt formed
H2O
Condensation Carbonyl Compound Room Complicated Compound; Formation of an
2,4-DNPH Temperature Refer to notes orange precipitate
H2O Distinguishing
Test for Carbonyl
Group
Reduction Aldehyde Room 1° Alcohol -
LiAlH4 in dry Temperature
ether/NaBH4/H2 with
Ni catalyst
Ketone Room 2° Alcohol -
LiAlH4 in dry Temperature
ether/NaBH4/H2 with
Ni catalyst
Iodoform Formation I2 (aq) Warm Carboxylate anion, I-, Yellow ppt formed
*only possible for NaOH (aq) H2O, CHI3
carbonyl with
structure R-C=O(CH3-
xIx), x=<3

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ANNEX 10.5 – MECHANISM FOR HALOFORM REACTION

BASE-CATALYZED KETO-ENOL TAUTOMERIZATION

-
Oδ O:- OH
H
C H + :OH- C O C
δ+
R CH2 CH2 H CH2
R R
Enol

BASE-CATALYZED HALOGENATION OF ΑLPHA CARBONS

1. Disproportionation reaction
X2 +OH- ⇌ HOX +X-
of Iodine with Hydroxide ion
-
Oδ O-

2. Keto-Enol Tautomerization,
C H + :OH- C
forming enolate δ+
R CH2 CH2
R

3. α Substitution Reaction :O-


 Generation of X+ O
electrophile C
 Electrophilic Addition + X OH C X
CH2
R
of X onto the α carbon CH2
R
 Regeneration of
ketone group

4. Repetition of steps 2 & 3 O O


until all the hydrogen atoms on
the α-carbon have been C
C X
substituted
CH2 R CX3
R

5. Nucleophilic Addition of Oδ
-
O-
hydroxyl group on the carbonyl
carbon C C
:OH-
δ+
CX3 CX3
R R
-
6. Cleavage of C-C bond, CX3- :O OH
leaves and abstracts a proton O
from the hydroxyl group at the C
δ+
same time; carboxyl group + CHX3
CX3 C
formed R
O
R O-
H

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10.6 CARBOXYLIC ACIDS & DERIVATIVES


10.6.1 IUPAC NOMENCLATURE & CLASSIFICATION

 Main Issue: Carboxylic Acids as Functional Groups


 When naming carboxylic acids, the location need not be specified as carboxylic acids are the highest
priority functional group. The carbon used to form the carboxylic acid group is listed as carbon-1.
Naming of the longest chain must include this group.
 Additional prefixes such as “bi,tri” are added when necessary. Add numbers to indicate the carbon to
which the carboxylic acid group is attached to. In cases of multiple carboxyl groups, the carboxylic
acid’s carbon is not considered part of the main chain.
 Carboxylic acids attached to a benzene ring are named as benzoic acids. In this case the carboxylic
acid is attached to carbon 1, but no numbers are given.
 Main Issue: Carboxylic acid derivatives: Esters, Acid Halides, Amides as functional groups
 All acid derivatives take the next highest priority after carboxylic acids on naming.
 Esters as functional groups.
 Esters exist at R’COOR, where the R’ group represents the alkyl (previously alcohol) group and the
COO represents the ester group, while the R group represents the carboxylic acid group.
 When naming esters, always name the R’ group first. The location of the ester connection is
mentioned in the naming. E.g. But-2-yl denotes that the ester is attached to carbon 2. When the
ester is attached to carbon one, no location is required. No such thing as But-1-yl Propanoate.
 Name the COOR group as a whole (include that carbon in your counting) this is named as a X-ate.
E.g. Propanoate, Ethanoate
 Acid Halides as functional groups
 Name the parent carboxylic acid first, then replace “-oic acid” with “-oyl halide”. Name the halide
involved.
 Amides as functional groups
 Name the parent carboxylic acid first, then replace “-oic acid” with “amide”. Name the halide
involved.
 All groups attached to the nitrogen atom of the amide are given a position “N”. E.g. N-
methylethanamide.

10.6.2 CARBOXYLIC ACID PROPERTIES

10.6.2A PHYSICAL PROPERTIES

 Shape
 The carboxylic acid group is a planar shape due to the sp2 hybridized carbon.
 Boiling Points
 As compared to their corresponding alkanes, alcohols and halogenoalkanes the boiling points of
carboxylic acids is higher.
 This is due to the presence of the carboxylic which causes these molecules to exhibit hydrogen
bonding, which is stronger than the London dispersion forces experienced between alkanes. More
energy is required to overcome the hydrogen bonds as compared to the dispersion forces or
permanent dipole-dipole interactions, thus carboxylic acids have a higher boiling point than
halogenoalkanes or alkanes.

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 Between carboxylic acids and alcohols, the hydrogen bonding exhibited by carboxylic acids is stronger
as the carbon is even more polarized due to the C=O bond. Thus, carboxylic acids have higher boiling
points than alcohols
 Within the carboxylic acids the boiling point of alcohols increase as the number of carbon atoms
increase. This is due to the increasing size of the electron cloud, causing the dispersion forces to be
weaker.
 Carboxylic acids can also dimerize in the liquid state or in non-polar solvents. This doubles the Mr in
the resultant dimer. The strength of dispersion forces also increases, leading to an increase in boiling
point.
 Solubility
 In general, carboxylic acids are soluble in water as they can displace molecules of water in the
hydrogen bonding of water molecules.
 Carboxylic Acids with longer carbon chains can form fewer hydrogen bonds than the numerous water
molecules they displace. Enthalpy considerations also make the longer chain carboxylic acids less
soluble than those with shorter carbon chains.

10.6.2B ACIDITY

 Carboxylic Acids act as Bronsted acids by donating a proton to water molecules, which act as a Bronsted
base. This causes a hydronium ion to be formed.
+ -
 R-COOH + H2 O ⇌ H3 O +R-O
 Carboxylic Acid (acid) + Water (base) ⇌ Hydronium cation (conjugate acid) + Carboxylate anion (conjugate
base)
 Properties of alcohols as acids
 Carboxylic Acids turn blue litmus red
 Carboxylic Acids react with bases and carbonates
 Stability of the carboxylate anion
 The carboxylate anion is inherently stable due to the resonance effect. The negative charge on the
carboxylate anion can be dispersed over 2 highly charged electronegative oxygen atoms.
 The more stable the carboxylate ion formed, the stronger the alcohol as an acid
 Electron withdrawing groups help to disperse the negative charge on the carboxylate anion and
stabilize it whereas electron donating groups intensifies the negative charge on the carboxylate anions
and destabilizes it.
 The stability of the carboxylate anion depends on the presence of electron donating or electron
withdrawing groups on the carboxylic acids
 The effect of any individual electron donating/withdrawing group on the stability of the carboxylate ion
depends on the proximity (distance) of the group to the hydroxyl group
 Electron donating/withdrawing groups only affect the carboxylate ion via the sigma (inductive) effect.
There is no resonance effect involved. (sp3 carbon bonded to sp2 carbon  no π bond overlap)

 List of electron withdrawing/donating groups is the same as that of alcohols

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10.6.3 SYNTHESIS OF CARBOXYLIC ACIDS

Reactant Class Mechanism Name Reagents Conditions Products Formed Observations


Oxidative Cleavage KMnO4 Heat under Carboxylic Acids Purple Solution
Alkenes *Alkene must have 1/2 Dilute H2SO4 Reflux Decolourizes
hydrogen atoms
attached to it
Side Chain Oxidation of Alkyl Heat under Benzoic Acid Purple Solution
Arenes Alkyl Benzene Benzene, Reflux Decolourizes
KMnO4,
Dilute H2SO4
Hydrolysis of nitriles Dilute H2SO4 Heat under Carboxylic Acid + -
Halogen Reflux Ammonium
Derivatives
Dilute NaOH Heat under Carboxylic Acid +
* Dilute H2SO4 Reflux, then Ammonia
add H2SO4
Oxidation of 1° 1° alcohol, Heat under Carboxylic Acid Purple Solution
Alcohols alcohols KMnO4 Reflux Decolourizes

Nucleophilic Acyl Water, Room Carboxylic Acid + HX Rapid formation of


Carboxylic Substitution of X with Acyl Chloride Temperature dense white fumes
Acid OH in Acyl Chlorides of HX
Hydrolysis of Esters Ester, Heat under Carboxylic Acid + Alcohol -
Derivatives Dilute HsSO4 Reflux
Room
Temperature
Oxidation of aldehydes Aldehyde, Heat under Carboxylic Acid
Carbonyls KMnO4 Reflux

*Number of substituted hydroxyl groups depend on the number of halo groups present (usually 1)
**Red = Dangerous!

10.6.4 REACTIONS OF CARBOXYLIC ACIDS

 The polar O-H bond can be broken in various acid-base reactions


 The C=O bond can be reduced to CH2
 The C-O bond can be broken and OH replaced with either an alkyl group (ester) or halide (acid halide)

10.6.4A ACID-BASE REACTION

 Carboxylic acids can react with metals, bases and carbonates to form ionic carboxylate salts
 Carboxylic acids are generally weak acids

Reactant Reaction
Metals M + HA  ½ H2 + M+A-
Bases HA + MOH  H2O + M+A-
Carbonates HA + MCO3  CO2 + H2O

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10.6.4B – NUCLEOPHILIC ACYL SUBSTITUTION

 Mechanism
 Involves an addition reaction followed by eliminating the leaving group

O δ- O--

R C+ Y + :Nu H R C Y
δ

Nu+ H
:O -- O

R C Y R C + Y--

Nu+ H Nu+ H

O O

R C R C Nu + HY

Nu+ H :Y--

 Esterification (condensation, nucleophilic acyl substitution)


 Reagents & Conditions: Carboxylic Acid + Alcohol, Few drops of concentrated H 2SO4, Reflux
 Observation: Sweet Smelling liquid formed
 In this case, the nucleophile is the alcohol and the leaving group Y is hydroxide.
 Phenols do not react with carboxylic acids o produce esters

R’ OH + HO C R ⇌ R’ O C R + H2O

O O
 Formation of Acyl Chloride (Same reactions as alcohol)
 Using phosphorus halide
 Distinguishing Test – Chlorination using phosphorus pentachloride (PCl5)
 Observations: Formation of dense white fumes of HCl
 Reagents and Conditions: PCl5, room temperature

O O

R C OH + PCl5 R C Cl + POCl3 + HCl

 Using phosphorus trihalide


 Reagents and Conditions: PX3, room temperature
 Note: PX3 can be prepared by heating red phosphorus (P) with iodine or bromine.

2P + 3X2 2PX3 X = I, Br
O O

R C OH + PX3 R C Cl + H3PO3 X = Cl, I, Br


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 Using Sulfur Oxide Dichloride (Thionyl Chloride)


 Distinguishing Test
 Observations: Formation of dense white fumes of HCl, formation of sulfur dioxide
 Reagents and Conditions: SOCl2, warm
 Note: The gaseous products formed can be easily isolated from the halogenoalkane

O O

R C OH + SOCl2 R C Cl + SO2 + HCl

10.6.4C REDUCTION

 Reagents: LiAlH4 in dry ether


 Conditions: Room Temperature
 Products: Primary Alcohols
 Remarks: Water is added in the last step to destroy all the reducing agents and protonate the alkoxide
anion

LiAlH
R C OH + 4[H] R CH2OH + H2O
Dry4[H]
Ether
4
4[H]
4
10.6.4D OXIDATION

 Methanoic acid & Ethanedioic acid are unstable and can be oxidized to form CO 2 & H2O

KMnO4
H C OH + [O] CO2 + H2O
Dilute H2SO4
O

KMnO4
HOOC C OH + 2[O] 2CO2 + 2H2O
Dilute H2SO4

10.6.4E DEHYDRATION

 Methanoic acid & Ethanedioic acid can be dehydrated to form a mixture of products using concentrated
H2SO4
 Carbon Dioxide is formed from the dehydration of ethanedioic acid  Distinguish between methanoic
acid and ethanedioic acid.

Conc. H2SO4
H C OH CO + H2O

Conc. H2SO4 CO + 2H2O + CO2


HOOC C OH

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1.6.5 CARBOXYLIC ACID DERIVATIVES

 Functional Groups
 Acid Halides
 Esters
 Used as rum flavouring, apple flavouring, paints, varnishes, nitrocellulose, etc
 Amides

1.6.5A PHYSICAL PROPERTIES

 Boiling Points
 Compared to the corresponding carboxylic acid, esters and acyl chlorides have lower boiling points
due to their inability to form hydrogen bonds.
 Compared to the corresponding carboxylic acids, amides have higher boiling points due to their
ability to form hydrogen bonds (presence of N-H). From primary to tertiary amines, the boiling point
decreases as less hydrogen bonds are formed.
 Odour
 Esters have a sweet/fruity smell
 Colour
 All derivatives and carboxylic acids are colourless
 Solubility
 Acyl chlorides react explosively with water
 Esters and amides are slightly soluble in water due to hydrophobic R groups

1.6.5B CHEMICAL PROPERTIES

 All carboxylic acid derivatives undergo nucleophilic acyl substitution reactions


 A more reactive carboxylic acid derivative can be converted to a less reactive one via this mechanism
 Reactivity of Acyl Halide > Carboxylic Acids > Ester > Amides
 Alkoxy groups (O-R) groups and amino groups (N-R(R’)) donate electrons to the electron deficient
carbonyl carbon via the resonance effect, decreasing the partial positive charge on the carbon atom
such that it is less readily attacked by nucleophiles.
 Halogen substituents (Cl, Br, I) withdraw electrons from the carbonyl carbon via the inductive effect.
(Different period  No overlap). This exacerbates the positive charge and makes acyl halides more
susceptible to nucleophilic attack.

10.6.6 REACTIONS OF ACID DERIVATIVES

10.6.6A REACTIONS OF ACYL HALIDE

ESTERIFICATION (NUCLEOPHILIC ACYL SUBSTITUTION)

 Reagents & Conditions: Alcohol, acyl halide, Room Temperature


 Observations: Formation of white fumes of HCl
 Note: Non-Reversible

R’ OH + X C R R’ O C R + HX

O O

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O- + X C R O C R + X-

O O

AMIDE FORMATION (NUCLEOPHILIC ACYL SUBSTITUTION)

 Reagents & Conditions: Ammonia/Amine in excess (Required as HX produced will neutralize the amine),
Acyl Halide, Room Temperature
O

R C X + H N R’’ R C N R’’ + HX

O R’ R’

CARBOXYLIC ACID FORMATION (NUCLEOPHILIC ACYL SUBSTITUTION)

 Reagents & Conditions: Water, Acyl Halide, Room Temperature


 Silver Nitrate can be added to precipitate X- out of the solution

H2O + X C R H O C R + HX

O O

COMPARISON WITH ALKYL HALIDES AND ARYL HALIDES

Acyl Halide Alkyl Halide Aryl Halide


Hydrolysis Conditions H2O, Room Temperature Aqueous NaOH/reflux -
Related Reaction Nucleophilic Acyl Nucleophilic Substitution Electrophilic Substitution
Mechanisms Substitution (not on halo group)
Electronic Reason C-X cleaves easily as the C-X cleaves less easily as C-X has partial double
carbon atom is highly the carbon atom is only bond character due to
polarized by both Cl and polarized by Cl. the delocalization of the
O. lone pair of electrons
into the benzene ring.
Steric Factor Planar geometry around Tetrahedral geometry Bulky benzene ring
C-X carbon makes it less around C-X carbon helps hinders nucleophilic
hindered to nucleophilic to hinder nucleophilic attack and repels the
attack attack nucleophile
Reactions with AgNO3 White ppt of AgCl No ppt formed in the -
observed immediately cold
White ppt of AgCl
observed only after
addition of aqueous
NaOH and reflux

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10.6.6A REACTIONS OF ESTERS

ACID HYDROLYSIS

 Reagents and Conditions: Dilute H2SO4, reflux


 Note
 Reverse of esterification
 Reversible, a large amount of water is required to ensure that equilibrium lies to the right

R’ O C R + H2O ⇌ R’ OH + HO C R

O O

BASE HYDROLYSIS (SAPONIFICATION)

 Reagents and Conditions: Dilute NaOH, reflux


 Note
 Irreversible as carboxylate anion is very stable and does not react with alcohol
 Acid is then added to protonate the carboxylate salt at the end of the reaction

R’ O C R + NaOH R’ OH + Na+ O- C R

O O

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SUMMARY OF CARBOXYLIC ACID REACTIONS

Reactions of Carboxylic Acids


Mechanism Name Reagents Conditions Products Formed Observable
Changes
Acid Base Reactions Carboxylic Acid + Room H2, Salt Slow
Metal Temperature effervescence of a
colourless and
odourless gas that
extinguishes a
lighted splint
Carboxylic Acid + Room H2O, Salt -
Base Temperature
(Neutralization)
Carboxylic Acid + Room CO2, H2O, Salt Effervescence of a
Carbonate Temperature colourless and
odourless gas that
forms a white ppt
in Ca(OH)2
Distinguishing
Test for COOH
group
Chlorination PCl5 (s) Room Alkyl halide, POCl3 (l), Formation of
Nucleophilic Acyl Substitution of OH with

Carboxylic Acid Temperature HCl (g) dense white fumes


of HCl**
Distinguishing
Halo Group (Halogenation)

Test for OH &


COOH group
SOCl2 (l) Warm Alkyl halide, SO32 (g), HCl Formation of
Carboxylic Acid (g) dense white fumes
of HCl**
Distinguishing
Test for OH &
COOH group

Halogenation PX3 Heat Alkyl halide, H3PO4 -


in general Carboxylic Acid
Reduction LiAlH4 in dry ether, Room Water, 1° alcohol -
Add water at last Temperatue
step to protonate
alcohol

Oxidation Methanoic Heat under CO2, H2O Purple solution


Acid/Ethanedioic reflux decolourizes,
Acid, KMnO4, dilute Effervescence of a
H2SO4 colourless and
odourless gas that
forms a white ppt
in Ca(OH)2
Dehydration Methanoic Room CO, H2O for HCOOH, Effervescence
Acid/Ethanedioic Temperature CO, H2O, CO2 for
Acid, conc H2SO4 (COOH)2
Esterification Carboxylic Acid Heat under Ester, H2O Sweet smelling
Alcohol reflux *Reversible liquid formed
H2SO4 (conc)

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SUMMARY OF CARBOXYLIC ACID DERIVATIVES REACTIONS (EXCEPT AMIDES)

Reactions of Acyl Halides


Mechanism Name Reagents Conditions Products Formed Observable
Changes
Alkyl Group/ Acyl Halide, Room Ester, H2O Sweet smelling
Nucleophilic Acyl Substitution of X with

Phenoxide Phenoxide/Alcohol Temperature liquid formed


(Esterification)

Amine Ammonia/Amines Room HX, Amides -


(Amide in excess Temperature
Formation)
*Tertiary Amines
do not react
OH group H2O Room Carboxylic Acid, HX Formation of
(Carboxylic Acid Temperature dense white fumes
Formation) of HCl**
(Hydrolysis)

Reactions of Esters
Mechanism Name Reagents Conditions Products Formed Observable
Changes
Acid Hydrolysis Dilute H2SO4 Heat under Carboxylic Acid, Alcohol -
Nucleophilic Acyl Substitution of R with OH

Reflux

Base Hydrolysis/ Dilute NaOH Heat under Carboxylate Anion, -


Saponification Reflux Alcohol
Add acid
afterwards to
protonate
carboxylate anion

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10.7 NITROGEN COMPOUNDS


10.7.1 IUPAC NOMENCLATURE & CLASSIFICATION

 Main Issue: Amines as Functional Groups


 Suffix – Amine; Prefix – Amino; Add numbers to indicate the carbon to which the amino group is
attached to.
 Additional prefixes such as “bi,tri” are added when necessary.
 For all R groups attached to the amine group, the nomenclature is “N-X”, where X is the functional
group. In the presence of more than 1 functional group being attached, add multiple Ns (e.g. N,N-
diethylamine)
 Main Issue: Amides as functional groups
 Name the parent carboxylic acid first, then replace “-oic acid” with “amide”. Name the halide
involved.
 All groups attached to the nitrogen atom of the amide are given a position “N”. E.g. N-
methylethanamide.

Primary Secondary Tertiary Quaternary

H N H R’ N H R’ N R’’ R’’’

R R R R’ N R’’

*Note: Nitriles contain nitrogen but are considered under halogen derivatives

10.7.2 PROPERTIES OF NITROGEN COMPOUNDS

10.7.2A PHYSICAL PROPERTIES

 Boiling Points of Amines


 As compared to their corresponding alkanes, the boiling points of amines is higher.
 This is due to the presence of the amine group which causes these molecules to exhibit hydrogen
bonding, which is stronger than the London dispersion forces experienced between alkanes. More
energy is required to overcome the hydrogen bonds as compared to the dispersion forces, thus
amines have a higher boiling point
 Within the nitrogen compounds the boiling point increases as the number of carbon atoms increase.
This is due to the increasing size of the electron cloud, causing the dispersion forces to be stronger.
 Within the nitrogen compounds the boiling point increases from tertiary to primary amines. This is
due to the number of N-H bonds, which allows for more extensive hydrogen bonding and
subsequently a higher boiling point. Tertiary amines exhibit permanent dipole-dipole interactions,
and thus have a lower boiling point.
 Compared to alcohols and carboxylic acids, the boiling points are lower as the N-H bond is less polar
than the O-H bond. Subsequently, the hydrogen bonds between alcohol molecules is stronger than
those between amines.
 Boiling Points of Amides

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 ~To that of amines due to the presence of N-H bonds and lone pairs of electrons on oxygen.
 Solubility
 In general, nitrogen compounds are soluble in water as they can displace molecules of water in the
hydrogen bonding of water molecules.
 Nitrogen compounds with longer carbon chains can form fewer hydrogen bonds than the numerous
water molecules they displace. Enthalpy considerations also make the longer chain nitrogen
compounds less soluble than those with shorter carbon chains.
 1-3 Soluble, 4-5 Sparingly, 6- insoluble

10.7.2B BASICITY

 Amines act as Bronsted bases by accepting a proton from water molecules, which act as a Bronsted Acid.
This causes a hydroxide ion to be formed.
+ -
 R-N + H2 O ⇌ R-NH +OH
 Amine (Base) + Water (Acid) ⇌ Ammonium cation (conjugate acid) + Hydroxide Anion (conjugate base)
 Properties of alcohols as acids
 Amines turn red litmus blue
 Amines react with carboxylic acids
 Stability of the ammonium cation
 The more stable the ammonium ion formed, the stronger the amine as a base
 Electron donating groups help to disperse the positive charge on the ammonium cation and stabilize it
whereas electron withdrawing groups intensifies the positive charge on the ammonium cation and
destabilizes it.
 The effect of any individual electron donating/withdrawing group on the stability of the ammonium
cation depends on the proximity (distance) of the group to the amine group
 Unlike arenes, the only way the electron donating/withdrawing groups can affect the ammonium cation
is via the sigma (inductive) effect. There is no resonance effect involved. (sp3 carbons  no π bond
overlap)
 Alternatively, one can argue that increasing the electron density on the nitrogen atom makes the lone
pair more available for protonation and consequently increases the amine’s basicity.
 Basicity of secondary amine > primary amine > tertiary amine > ammonia
 Tertiary amines are not as basic as their conjugate acids are less soluble in water as compared to the
conjugate acids or secondary and primary amines

Substituent Inductive Effect Effect on ammonium Effect on nitrogen atom’s


cation electron density
Alkyl Group Electron Donating Stabilize Increases
Hydroxyl, Electron Withdrawing: Destabilize Decreases
Ether, Amine Intermediate atom is an
electronegative species
Halogens Electron Withdrawing: Destabilize Decreases
Intermediate atom is an
electronegative species
Aldehydes, Electron Withdrawing: Destabilize Decreases
Nitro, Esters, Intermediate atom is attached
Ketones, Nitrile to more electronegative
species

 Phenylamines
 Similarly, phenols act as bronsted bases and react with water to produce hydroxide ions

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 Phenylamine are less basic than amines as the lone pair on the nitrogen atom is delocalized over the
benzene ring due to the resonance effect of the benzene ring. This causes the lone pair to be less
available for forming a dative bond. This occurs due to the π bond overlap between the oxygen atom
and the sp2 hybridized carbon.
 Stability of the phenylammonium cation
 Similarly to the benzene carbocation, electron donating groups help to increase the electron
density of the benzene ring, causing the lone pair of electrons on the nitrogen atom to be more
readily available for donating to an acid.
 Both resonance and inductive effects are involved due to the nature of the benzene ring.
 Amides
 The lone pair of electrons on the Nitrogen atom is delocalized over the carbonyl group, causing it to
be unavailable for donation.  Amides are resonance stabilized
 Amides, similar to alcohols, give neutral solutions in water as they are less basic.
 Basicity of Amine > Basicity of Phenylamine > Basicity of Water > Basicity of Amide

10.7.3 SYNTHESIS OF NITROGEN COMPOUNDS

**Recap from previous chapters, relevant reactions will be explained in the chapter containing the reactant

Reactant Class Mechanism Reagents Conditions Products Formed Observations


Name
Nucleophilic Alkyl Halide Heat in a Primary/Secondary/ -
Halogen Substitution of X Ethanolic sealed tube Tertiary Amine
Derivatives with NH Concentrated
(Alkaline NH3 *Amines formed can
* Hydrolysis) behave as nucleophiles
and further substitute
**Using excess
ammonia increases the
chance of obtaining a
primary amine
Reduction of LiAlH4 in dry Room Primary Amine -
Nitriles ether Temperature
Reduction Nitrobenzene, Heat Phenylamine
Arenes Tin powder (Sn),
Excess *NaOH is added to
concentrated deprotonate
HCl, phenylammonium
NaOH

Nucleophilic acyl Acyl Halide Room Primary/Secondary/ Rapid


Carboxylic substitution of Ammonia/1° Temperature Tertiary Amine formation of
Acid halogen group Amine/ 2° dense white
with amine group Amine/ 3° amine Halogen Halide fumes of HX
Derivatives
*Number of substituted hydroxyl groups depend on the number of halo groups present (usually 1)

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10.7.4 REACTIONS OF NITROGEN COMPOUNDS

10.7.4A ACID-BASE REACTIONS – AMINES

 Amines can act as Bronsted bases by accepting a proton [or lewis bases by donating an electron pair]
 This forms a salt; salts are ionic and are soluble in aqueous medium. Amines can be isolated using this
method, add NaOH to deprotonate the ammonium ions.
 Amines are weak acids and their conjugate acids are relatively strong
+ -
 R-N + HA ⇌ R-NH A

10.7.4B NUCLEOPHILIC SUBSTITUTION (AMINES + PHENYLAMINES)

 Amines can act as nucleophiles (due to the lone pair) and react with alkyl halides to produce primary,
secondary and tertiary amines.
 The product formed is always one level higher than the initial product (e.g. Secondary  Tertiary);
ammonium ions cannot act as nucleophiles
 Reactions
 Primary

H N H + R’ X H N R’ + HX

R R
 Secondary
R’’ N H + R’ X R’’ N R’ + HX

R R

 Tertiary R’

R’’ N R’’’ + R’ X R’’ N+ R’’’ X-

R R

 Reagents: Ethanolic concentrated Primary, Secondary or Tertiary Amine (or ammonia)


 Conditions: Heat in sealed tube; use excess amines to prevent multiple substitutions

10.7.4C NUCLEOPHILIC ACYL SUBSTITUTION (AMINES + PHENYLAMINES)

 Amines can act as nucleophiles and react with acid halides to form amides
 Tertiary amines cannot undergo this reaction as they lack a hydrogen atom attached to the nitrogen
atom
O
 Primary

R C X + H N R’’ R C N R’’ + HX

O H H
 Secondary

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R C X + H N R’’ R C N R’’ + HX

O R’ R’

 Reagents: Ammonia/Amine + Acyl Halide


 Conditions: Room temperature, excess amines is used to neutralize the HX produced
 Observations: Dense white fumes of HX produced

10.7.4D ELECTROPHILIC SUBSTITUTION (PHENYLAMINES)

 The amine group is an activating group as it increases the electron density on the benzene ring and makes
it more prone to attack.
 Reagents: Phenylamine + Aqueous Bromine
 Conditions: Room temperature
 Observations: Yellow-orange solution decolourizes; formation of white ppt

NH2 NH2
X X
+ 3X2(aq) + 3HX

X
*It is likely that the reactions (except addition of neutral FeCl3) of phenols also apply to phenylamines

10.7.4E HYDROLYSIS (AMIDES)

 Amides can be hydrolysed in a similar manner to esters


 Ammonia is produced if primary amides undergo alkaline hydrolysis
 If secondary amines undergo alkaline

ACID HYDROLYSIS

 Reagents and Conditions: Dilute H2SO4, reflux


 Note
 Reversible, a large amount of water is required to ensure that equilibrium lies to the right

R’ N C R + H2O + H+ ⇌ R’ NH2+ + HO C R

R O R O
BASE HYDROLYSIS

 Reagents and Conditions: Dilute NaOH, reflux


 Note
 Irreversible as carboxylate anion is very stable and does not react with ammonia (both bases)

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R’ N C R + NaOH R’ NH2 + Na+ O- C R

R O R O

10.7.4F REDUCTION (AMIDES)

 Amides can be reduced to their corresponding amine. For example, a tertiary amide will be reduced to a
tertiary amine
 The oxygen atom is removed and replaced with hydrogen atoms
 Reagents: LiAlH4 in Dry Ether
 Conditions: Room Temperature

10.7.5 AMINO ACIDS

NOTE: DIFFERENCE IN EMPHASIS BETWEEN BIOLOGY AND CHEMISTRY

 Reactions
 Emphasis on the use of Ka and Kb values to determine the structure of amino acids at a certain pH
 Structure
 Less emphasis on structure but still need to know the different forms of chemical interactions in
secondary and tertiary structures
 No need to know structure vs globular protein
 No need to know the links between structure and function
 No need to know the different components of electrophoresis
 Definitions
 Less emphasis on definitions, no need to memorize definitions

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10.7.5A STRUCTURE OF AMINO ACIDS

 Naturally occurring amino acids are α-amino acids


 α carbon  Carbon adjacent to the carbon on the carboxylic acid
 Each α carbon is attached to a side chain (R group); a carboxylic acid group;
an amine group; and a hydrogen atom
 All α amino acids are chiral except glycine (H as side chain)
 Zwitter Ions
 Amino acids undergo auto-ionization to form zwitter ions, in which an electron is transferred from the
carboxylic acid group to the amine group to form an ammonium ion and a carboxylate ion.
 The amino acid is electrically neutral
 This is the form that exists at the isoelectronic pH, at other pH it either exists in the protonated or
deprotonated form

 Determining the form of the amino acid at a certain pH


1. Determine the isoelectronic pH
2. Above this pH, deprotonate the next strongest acid
3. Below this pH, protonate the next strongest base
4. Alternatively, determine the relative strength of all carboxylic acids and amines before starting on the
form at one end of the pH spectrum.

10.7.5B ELECTROPHORESIS

 Definition: The use of an electric field to separate amino acids


 Basis: Since amino acids have different isoelectronic points, they can be separated based on the charges
that they carry at a certain pH

Charge
Distance Migrated ∝
Mass

10.7.5C PROPERTIES OF AMINO ACIDS

 Physical Properties
 Amino acids form ionic lattices in their solid form due to their
ability to form zwitterions
 Amino acids are soluble in water due to ion-dipole interactions
between the zwitterions and water molecules
 Chemical Properties
 Amino acids can form peptide bonds (Amide linkages) in a
condensation reaction between 2 amino acids involving the loss
of a water molecule
 Multiple amino acids condense to form a polypeptide chain
 Can act as buffers as they are weak acids
 Features of a polypeptide chain

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 Presence of numerous side chains (R-groups)


 Made up of amino acid residues connected by peptide bonds (Amino acid residues represented by 3
letter abbreviations such as Gly for Glycine)
 N & C-termini present (N terminus  Amine group; C Terminus  Carboxylic Acid group)

10.7.6 PROTEINS

10.7.6A STRUCTURAL PROPERTIES OF PROTEINS

 Primary Structure: The sequence of amino acids in a polypeptide chain


 Linear sequence of amino acid residues from the N to the C terminus
 Secondary Structure: The regular arrangement of sections of the polypeptide chains
 Stabilized by intrachain hydrogen bonds between the lone pairs on C=O and N-H bonds
 Note: Proline does not have N-H bonds as the amide is a tertiary amide (hence it cannot form
secondary structures)
 α-helix (right handed spiral)
 Each helical turn has 3.6 amino acid residues
 N-H and C=O bonds point along the side of the axis; all N-H bonds in 1 direction and C=O bonds in
another direction (Thus hydrogen bonding occurs) [Show in drawing]
 R-groups extend outward from the core of the helix [Show in drawing]
 β-pleated sheets
 C=O and N-H bonds lie in the plane of the sheet
 Hydrogen bonding occurs between N-H and C=O groups of nearby amino acid residues
 R groups protrude above and below the plane of the sheet alternately
 Either parallel or anti-parallel
 Tertiary Structure: Overall 3D conformation of a protein formed by the folding of the polypeptide chain
 Interaction between side chains used to form the tertiary structure
 Hydrogen Bonding
 Electrostatic Attraction (Ionic linkages) between ammonium and carboxylate groups on side
chains
 London dispersion forces between hydrophobic side chains
 Disulfide bridges (oxidation of –SH side chains)
 Quaternary Structure: Structure of proteins with more than 1 polypeptide chain
 Haemoglobin
 4 polypeptide chains (two α and two β), each associated with a haem group
 Held by interactions between side-chains
 Each haem group consists of a central Fe2+ ion that has a coordination number of 6 when fully
bonded; oxygen binds to the iron ion

10.7.6B FUNCTIONS OF PROTEINS

 Enzymes acting as biological catalysts


 Antibodies that bind to and neutralize foreign antigens
 Transport
 Regulation
 Structural proteins
 Movement proteins
 Nutrient proteins serving as a source of amino acids (albumin and casein)

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10.7.6C CHEMICAL PROPERTIES OF PROTEINS

 Denaturation: A process whereby the structure of proteins is disrupted and the quaternary, tertiary and
secondary structures break down to form a randomly coiled (uncoiled) polypeptide
 Results in
 Loss of biological activity
 Decrease in solubility
 Formation of gels, susceptible to hydrolysis
 Causes
 Heat  Overcomes the hydrogen bonds and dispersion forces
 pH change  Protonate and deprotonates ionic bridges, disrupting the electrostatic attractions
which maintain the protein’s conformation
 Mechanical Agitation  Increases kinetic energy that disrupts weaker interactions such as
hydrogen bonds
 Redox reagents  Reduce disulphide bonds or forms new disulphide bonds
 Hydrophobic reagents  Improve the solubility of hydrophobic side chains, disrupting the 3D
conformation
 Heavy metals  Interfere with salt bridges formed and react with SH groups to precipitate them
out
 Hydrolysis
 Since proteins are inherently made up of amino acids joined via amide linkages (refer to reactions of
amides), they can be hydrolysed

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SUMMARY FOR NITROGEN COMPOUNDS REACTIONS

Reactions of Nitrogen Compounds


Mechanism Name Reagents Conditions Products Formed Observable
Changes
Acid Base Reactions Amine + Acid Room H2O, Salt -
(Neutralization) Temperature
Halogenation X2 in CCl4 Room 2-halophenol, 4- Decolourisation of
Phenol Temperature halophenylamine greenish-yellow
Electrophilic Substitution of phenylamine

HX (g) gas/reddish-brown
bromine liquid

Formation of
dense white fumes
of HX
X2 (aq) Room 2,4,6- Decolourisation of
Phenol Temperature trihalophenylamine, greenish-yellow
HX (g) gas/reddish-brown
bromine liquid

White ppt formed

Formation of
dense white fumes
of HX
Nucleophilic Ethanolic concentrated Heat in sealed Amine/Ammonium Ion Dense white
Substitution excess Amine/ tube fumes of HX
Phenylamine + Hydrogen Halide formed
Halogeno Alkane
Nucleophilic Acyl Excess Room Amide Dense white
Substitution Ammonia/Amine/ Temperature fumes of HX
Phenylamine + Acyl Hydrogen Halide formed
Halide
Reactions of Amides
Mechanism Name Reagents Conditions Products Formed Observable
Changes
Acid Hydrolysis Dilute H2SO4 Heat under Carboxylic Acid, -
Nucleophilic Acyl Substitution of R with OH

Reflux Ammonium ion

Base Hydrolysis/ Dilute NaOH Heat under Carboxylate Anion, -


Saponification Reflux Amine
Add acid afterwards
to protonate
carboxylate anion

Reduction Amide Room Amine -


LiAlH4 in dry ether Temperature

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REFERENCES

 Chemistry Department 2012 lecture notes for the following topics


 Atoms, molecules and stoichiometry
 Atomic structure
 Chemical Bonding
 Gaseous State
 Chemical Energetics
 Equilibria
 Reaction Kinetics
 Whole of Organic Chemistry
 Ionic Equilibria
 Inorganic Chemistry

SPECIAL THANKS TO

 Valentino Emil Chai, 12S74 for checking the C1 topic notes

DISCLAIMER

The author shall bear no responsibilities for any kind of chemistry grades achieved by simply reading these
notes; These notes shall not be photocopied or mass distributed for commercial purposes without the
permission of the author.

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