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2.3 – Shapes of Molecules and Ions

Shape of a molecule depends upon its electronic structure.

 Valence shell electrons are responsible for forming bonds

 Arrangement of these electrons determine molecular shape

Each electron region takes up a position to minimize repulsion, known as the electron pair repulsion (VSEPR) theory.

 Strength of lone pair/lone pair > lone pair/bonding pair > bonding pair/bonding pair
 This occurs because a lone pair is closer to the nucleus of the atom, and so takes up more room than a bonding pair

Bonding Lone Shape Angle Example Diagram

Pairs Pairs

2 0 Linear 180 BeCl2, CO2, BeF2

3 0 Trigonal Planar 120 BF3, AlCl3, SO3, NO3-, CO32-

4 0 Tetrahedral 109.5 CH4, SiCl4, SO42-, ClO4-, NH4+

3 1 Pyramidal 107 NH3, NCl3, PF3, ClO3

2 2 Bent 104.5 H2O, OCl2, H2S. OF2

5 0 Trigonal Bipyramidal 120 and 90 PCl5

6 0 Octahedral 90 SF6

Allotrope Structure/Properties Diagram

 Each Carbon atom is connected to four other Carbon atoms

 High melting and boiling points, strong covalent bonds
Diamond
 Hardest natural substance, useful for cutting instruments
 Electrons are taken up in bonding, thus non-conductor

 Each Carbon atom is connected to three other Carbon atoms

 Delocalized electrons, allows graphite to conduct electricity
Graphite
 Layers held by vdW forces, can slide over each other
 High melting and boiling points, strong covalent bonds

 Rolled up cylindrical structure made of grapheme layers

 High tensile strength, many strong covalent bonds
Nanotubes
 Good electrical conductor, delocalized electrons
 Potential applications: drug delivery, electronics, nanotechnology

 Buckminsterfullerene is a spherical molecule with 60 carbon atoms

Fullerenes
 Delocalised electrons can conduct electricity
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2.4 – Intermediate Bonding

Electronegativity is the strength of an atom to attract a shared pair of electrons in a covalent bond.

 Increases across a period as the number of protons increases and atomic radius decreases
 Decreases down a group as distance between nucleus and outer electrons increases and more shielding

Polar covalent (permanent dipole) bond when elements have different electronegativities.

 Unequal distribution of electrons and produces a charge separation

 Compound with small electronegativity difference will be covalent
 Compound with large electronegativity difference (>1.7) will be ionic
 Cations can distort the electron clouds of anions, leading to a degree of covalence in most ionic compounds
o Small cations with a high charge will polarise anions, therefore have a high polarising power
o Large anions do not hold on to their outer electrons well, so can be easily distorted

Symmetrical molecule will not be polar even if individual bonds within the molecules are polar.

 Individual dipoles cancel out due to symmetrical shape

 No net dipole moment, molecule is non-polar
 Molecule might have polar bonds, but if it is symmetrical it would not be a polar molecule

Experiment of charged rod on polar/non-polar liquids

 A charged rod is brought close to a jet of liquid

 Polar liquids will be attracted to the electrostatic force of the rod, stronger dipole, stronger deflection
 Non-polar liquids will not be deflected or attracted

2.5 – Intermolecular Forces

London/vdW forces occur between all molecular substances and noble gases, except in ionic substances.

 Also called instantaneous, induced dipole-dipole interactions

 Random fluctuations of moving electrons cause temporary dipoles
 Induces a dipole in neighbouring molecules
 If more electrons, more chances of temporary dipoles, stronger London forces

Permanent dipole-dipole bonding occurs between polar molecules.

 Stronger than vdW forces, compounds have higher boiling points

 Polar molecules have permanent dipoles, are asymmetrical and have a significant difference in
electronegativity

Hydrogen bonding occurs in compounds that have H attached to F, O, N.

 H strongly attracted to lone pair of electrons in F, O, N.

 Bond angle is 180o around the H atom

Solvents and Solubility

 To be soluble, the energy produced by hydrating the ions (the hydration enthalpy) must be more negative than the energy holding the ion
together (the lattice enthalpy)
 To be soluble in water, the organic substance must be able to form strong hydrogen bonds with the water molecules
 To be soluble in a non-aqueous solvent, the substance must have similar strength intermolecular forces to those in the solvent
 Propanone useful because has both polar and non-polar characteristics

Boiling Points of Alkanes Boiling Points of Hydrogen Halides

Boiling points of alkanes increases with mol. mass HF higher than expected due to hydrogen bonding

 Greater number of electrons, more chances of HCl, HBr and HI increase due to stronger vdW
temporary dipoles, stronger London force forces.
 Long straight chain alkanes have a larger
Boiling Points of Hydrides
surface area of contact between molecules so
stronger London forces Molecules with hydrogen bonding have higher
boiling points and enthalpies of vaporisation
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2.6 – Redox
Oxidation can be defined as gain of oxygen of loss of hydrogen, or is the loss of electrons. Oxidation Is Loss (OIL)

Reduction can be defined as loss of oxygen or gain of hydrogen, or is the gain of electrons. Reduction Is Gain (RIG)

Oxidation number of an atom shows the number of electrons which it has lost or gained as a result of forming a compound.

Oxidation Number Rules

1. The oxidation number of an uncombined element is 0.

2. Certain elements have fixed oxidation numbers.
 All group 1 elements are +1.
 All group 2 elements are +2.
 Hydrogen is always +1 except in hydrides.
 Fluorine is always –1.
 Oxygen is always –2 except in peroxides, superoxides and when combined with fluorine.
 Chlorine is always –1 except when combined with fluorine and oxygen.
3. The sum of oxidation numbers in a compound is always 0.
4. The sum of oxidation numbers in an ion always adds up to the charge on the ion.

Redox Reactions

e.g.: When magnesium is reacted copper sulphate, a reaction occurs which is called a displacement reaction.

Chemical equation: Mg + CuSO4 → MgSO4 + Cu

Ionic equation: Mg(s) + Cu2+(aq) →Mg2+(aq) + Cu(s)

 SO4 is unchanged so its number does not change

 Mg gains two electrons (oxidation) so it is a reducing agent
 Cu loses two electrons (reduction) so it is an oxidizing agent

These can be split into half equations by:

1. Add H2O molecules to balance any oxygen atoms

2. Add H+ ions to balance any hydrogen atoms
3. Add electrons to balance any charge in the equation.

Examples

Half equation for: Cr2O72-  2Cr3+

1. balance oxygen atoms with water Cr2O72- → 2Cr3+ + 7H2O

2. balance hydrogen atoms with hydrogen ions 14H+ + Cr2O72- → 2Cr3+ + 7H2O
3. balance the charges using electrons 6e- + 14H+ + Cr2O72- → 2Cr3+ + 7H2O

Bromine reacts with a solution of sulfur dioxide to form sulphate and bromide ions.

Half equation for the oxidation of sulfur dioxide is: SO2 + 2H2O → SO42- + 4H+ + 2e

Half equation for the reduction of bromine is: Br2 + 2e- → 2Br-

Overall equation is: SO2 + 2H2O + Br2 → SO42- + 4H+ + 2Br-

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2.7.1 – Group 2
Trends

 Atomic radius increases down the group, more electron shells

 Melting points decrease down the group, electrostatic forces between positive ions and delocalised electrons weaken
 1st ionisation energy decreases down the group, outer electron further away, more shielding, weaker attraction, easier to remove electron.

Reactions

1. Oxygen
 All group 2 metals burn in oxygen to produce the oxide, MO
o 2Mg(S) + O2 → 2MgO(s)
2. Chlorine
 On heating with chlorine all group 2 metals react to give white, ionic chlorides, MCl
o Mg + Cl2 → MgCl2
3. Water
 Magnesium slowly reacts with cold/warm water, giving a hydroxide
o Mg + 2H2O(l) → Mg(OH)2 + H2
 Magnesium burns rapidly in steam to produce an oxide and hydrogen
o Mg(s) + H2O(g) → MgO(s) + H2(g)
 Other group 2 metals all react with cold water with increasing vigour to form the metal hydroxide and hydrogen
 Calcium hydroxide is sparingly soluble in water, producing effervescence and a thick white suspension
o Ca + 2H2O → Ca(OH)2 + H2
 Hydroxides produced make the water alkaline, observations: effervescence, metal dissolving, solution heating.

Reactions of Oxides and Hydroxides

1. Water (Oxides)
 Beryllium Oxide is not attacked by water
 Other group 2 oxides are ionic and react with water to form hydroxides
o CaO + H2O → Ca(OH)2
2. Dilute Acid
 Group 2 oxides are bases so react with acids to form salt and water
o MgO + H2SO4 → MgSO4 + H2O
o CaO + 2HNO3 → Ca(NO3)2 + H2O
o BaO + 2HCl → BaCl2 + H2O
 Group 2 hydroxides are bases and react with acids to form salts and water
o Ca(OH)2 + 2HNO3 → Ca(NO3)2 + 2H2O

Solubility of Sulphates and Hydroxides

1. Sulphates become less soluble down the group

 Magnesium sulphate is very soluble, Barium sulphate is very insoluble, and is part of the test for sulphates
2. Hydroxides become more soluble down the group
 Magnesium hydroxide is insoluble in water, barium hydroxide easily dissolves in water, used for titrations

Thermal Stability of Carbonates and Nitrates

1. Carbonates become more thermally stable down the group

 Cations become larger, lower polarising effect and distort the carbonate ion less
 C-O bond is weakened less so it less easily breaks down
2. Nitrates become more thermally stable down the group
 Cations become larger, lower polarising effect and distort the carbonate ion less
 C-O bond is weakened less so it less easily breaks dow

Flame Tests Flame Colours Explanation of Flame

Method  Lithium: Red  Electrons are excited to a higher

 Sodium: Yellow energy level
1. Use a nichrome wire (unreactive metal)  Potassium: Lilac  As electrons drop back to a lower
2. Clean the wire by dipping in concentrated hydrochloric acid  Calcium: Brick Red level, they emit energy as light
then heat in Bunsen flame  Strontium: Crimson  Light is characteristic of each metal
3. Dip wire in powdered solid and put in Bunsen flame and  Barium: Apple green depending on distance between
observe flame
energy levels
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2.7.2 – Group 7
Appearances Tests

 Fluorine is a very pale yellow gas, and is highly reactive

 Chlorine is a greenish-yellow reactive gas, poisonous in high concentrations Turns blue litmus red, then bleaches it
 Bromine is a red-brown liquid that gives off dense brown-orange poisonous fumes Orange/red if dissolved in an organic solvent
 Iodine is a shiny dark grey solid that sublimes to purple gas Turns starch black

Trends

 Melting and boiling points decrease down the group

o Molecules become larger, have more electrons
o Stronger London forces between molecules

Oxidising Reactions

 Halogens are oxidising agents. Oxidising strength decreases down the group as atoms become larger, so attraction becomes weaker.

1. Reactions with Metals

 On heating, metals react with halogens to form halides
o 2Na(s) + Cl2(g) → 2NaCl(s)

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2.8 - Kinetics
Collision Theory

 Reactions can only occur when collisions between particles have sufficient energy and the correct orientation

Maxwell-Boltzmann graph shows the distribution of molecular energies

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2.9 – Equilibrium
Dynamic equilibrium occurs when forward and backward reactions are occurring at equal rates.

 Concentrations of reactants and products stays the constant

 Continuous reaction, closed system, unchanging measurable variables

Le Chatelier’s principle states that if an external condition is changed, equilibrium will shift to oppose the change.

Effect of Changing Conditions on Equilibrium

1. Temperature
 Increase
o Equilibrium moves in the endothermic direction
o To reduce temperature by absorbing heat
 Decrease
o Equilibrium moves in the exothermic direction
o To increase temperature by giving out heat
o Low temperature may give a higher yield, but results in low reaction rates
2. Pressure
 Increase
o Equilibrium moves towards the side with fewer molecules of gas
o Oppose change and reduce pressure
 Decrease
o Equilibrium moves towards the side with more molecules of gas
o Oppose change and increase pressure
 If number of gaseous moles is the same on both sides, then pressure will have no effect on position of equilibrium
 Increasing pressure may give higher yield and faster rate, but expensive to produce and contain
3. Concentration
 Increasing reactant concentration causes equilibrium to shift to the right
 Increasing product concentration causes equilibrium to shift to the left
4. Catalysts
 Have no effect on position of equilibrium
 Speed up the rate at which equilibrium is achieved

Industrial Processes

1. Haber Process
 N2 + 3H2 ⇌ 2NH3 ΔH = -ve (exo)
o Temperature: 450°C, Pressure: 200-1000 atm, Catalyst: iron
o Low temp gives good yield but slow rate: compromise temp used
o High pressure gives good yield and high rate but high energy costs to produce the pressure
2. Contact Process
 S(s) + O2(g) → SO2(g)
 SO2(g) + ½ O2(g) ⇌ SO3(g) ΔH = -ve (exo)
o Temperature: 450°C, Pressure: 10 atm, Catalyst: vanadium oxide
o Low temp gives good yield but slow rate: compromise moderate temp used
o High pressure gives slightly better yield and high rate but high energy costs to produce the pressure
3. Production of Methanol from CO
 CO(g) + 2H2(g) ⇌ CH3OH(g) ΔH = -ve (exo)
o Temperature: 400°C, Pressure: 50 atm, Catalyst: chromium oxide
o Low temp gives good yield but slow rate: compromise temp used
o High pressure gives good yield and high rate but high energy costs to produce the pressure
4. Hydration of Ethene
 CH2=CH2(g) + H2O(g) ⇌ CH3CH2OH(l) ΔH = -ve (exo)
o Temperature: 300°C, Pressure: 70 atm, Catalyst: conc. phosphoric acid
o Low temp gives good yield but slow rate: compromise temp used
o High pressure gives good yield and high rate but high energy costs to produce the pressure
o High pressure leads to unwanted polymerisation of ethene to poly(ethene)
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2.10.1 – Organic Chemistry - Alcohols
Alcohols contain the OH functional group, with the general formula CnH2n+1OH.

 Primary – zero or one carbon (R) groups attached to the Carbon bearing the OH.
 Secondary – two carbon (R) groups attached to the Carbon bearing the OH.
 Tertiary – three carbon (R) groups attached to the Carbon bearing the OH.

OH group is able to hydrogen bond, as a donor (H is δ+), or as an acceptor (two lone pairs on O atom)

1. Combustion
 All alcohols burn in air to form carbon dioxide and water.
o C2H5OH + 3O2 → 2CO2 + 3H2O
2. Sodium
 All alcohols react with sodium as they are weak acids, hydrogen in alcohol is reduced to hydrogen gas, alkoxide ions (RO-)
produced are strong bases.
 Observations: effervescence, mixture gets hot, sodium dissolves, white solid is produced.
o 2C2H5OH + 2Na → 2C2H5O-Na+ + H2
3. Phosphorus Pentachloride
 Solid PCl5 reacts with all alcohols to give a chloroalkane and HCl as white, steamy fumes
 Used as a test for the OH group, HCl turns blue litmus paper red
o C2H5OH + PCl5 → C2H5Cl + HCl + POCl3
4. Other Halogenating Agents Organic Techniques
 Chloroalkanes Distillation used as
o Heat under reflux with HCl, made in situ from NaCl and H2SO4 separation technique
 H2SO4 + NaCl → HCl + NaHSO4 to separate an
 C2H5OH + HCl → C2H5Cl + H2O organic product.
 Water in from
 Bromoalkanes
the bottom for
o Heat under reflux, alcohol with HBr, made in situ from KBr and H2SO4 efficient cooling
 KBr + H2SO4 → KHSO4 + HBr and prevent
 C2H5OH + HBr → C2H5Br + H2O back flow
o Or use sodium bromide and 50% sulfuric acid
 C2H5OH + NaBr + H2SO4 → C2H5Br + NaHSO4 + H2O
Reflux used to continuously evaporate
o Cannot use 100% sulfuric acid, will oxidise Br- into Br2 and condense organic mixtures.
 Iodoalkanes  Never seal container, build-up of
o Warm alcohol with iodine and moist red phosphorus gas could cause explosion
 3C2H5OH + PI3 → 3C2H5I + H3PO3  Anti-bumping granules added to
prevent vigorous, uneven boiling
o Cannot use conc. sulfuric acid, will oxidise I to I2
-

5. Oxidation
 Primary
o Heating with a mixture of dilute sulfuric acid with potassium
dichromate(VII) solution
o Orange dichromate ion (Cr2O72-) reduces to green Cr3+ ion
o Primary alcohols form an aldehyde through distillation Purification
 C2H5OH + [O] → CH3CHO + H2O  Place in separating funnel
o Then to carboxylic acids on further oxidation through reflux.  Wash product with Sodium
Hydrogencarbonate to neutralise
 CH3CHO + [O] → CH3COOH + H2O
any remaining reactant acid and
Sodium Chloride to help separate
organic layer from aqueous layer.
 Allow layers to separate, discard
aqueous layer
 Run organic layer to a clean, dry
 Secondary
conical flask and add drying agent
o Forms ketones through reflux, but no further oxidation takes place (anhydrous sodium sulphate)
 CH3CH(OH)CH3 + [O] → CH3COCH3 + H2O  Decant liquid into flask
 Distil

 Tertiary
o Does not react with oxidizing agents, no hydrogen atom bonded to C-OH
6. Aldehydes vs Ketones
 Aldehydes oxidised by Fehling’s solution to carboxylic acid, blue Cu2+ to red Cu2O
 Ketones will not react
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2.10.2 – Organic Chemistry – Halogenoalkanes
Halogenoalkanes are alkanes which contain the functional group R-X, with the general formula CnH2n+1X

 Primary – zero or one carbon (R) groups attached to the Carbon bearing the X.
 Secondary – two carbon (R) groups attached to the Carbon bearing the X.
 Tertiary – three carbon (R) groups attached to the Carbon bearing the X.

Reactions of Halogenoalkanes

 Nucleophilic Substitution
o Potassium Hydroxide
 Heat under reflux in aqueous solution
 C2H5Br + NaOH → C2H5OH + NaBr
o Potassium Cyanide
 Reflux in ethanolic solution
 C2H5Br + KCN → C2H5CN + KBr
o Ammonia
 Heat with conc. ethanolic ammonia in a sealed tube
 C2H5I + NH3 → C2H5NH2 + HI
o Silver Nitrate (identification)
 Heat halogenoalkane with sodium hydroxide solution
 CH3Br + NaOH → CH3OH + Na+ + Br-
 Acidify the solution with nitric acid
 Add a few drops of silver nitrate solution
 White precipitate soluble in dilute aqueous ammonia indicates chloride
 Cream precipitate soluble in conc. ammonia, indicates bromide
 Yellow precipitate insoluble in conc. ammonia, indicates iodide
 Reactivities: iodoalkanes > bromoalkanes > chloroalkanes
 Elimination
o Potassium Hydroxide
 Heat with ethanolic potassium hydroxide
 HX eliminated to give an alkene
 CH3CH2Br → CH2CH2 + HBr

Nucleophilic Substitution Mechanisms

 SN1, nucleophilic substitution mechanism for tertiary halogenoalkanes

o Br breaks away from the halogenoalkane to form a carbocation
intermediate
o Hydroxide nucleophile then attacks the positive carbon
o Primary halogenoalkanes cannot undergo SN1 since they cannot form a stable carbocation
 SN2, nucleophilic substitution mechanism for halogenoalkanes
o Hydroxide nucleophile attacks the carbon whilst C-Br bond breaks
o Undergoes a transition state
o One-step backside attack

Uses of Halogenoalkanes

 Fire retardants and refrigerants, as they are unreactive and non-combustible

o CFCs do not decompose easily so lasts long within refrigerator lifetime
o Decomposes in the atmosphere, free radicals react with ozone
o Depletes ozone layer, increase in UV radiation reaching Earth, causing skin cancers
 Non-stick frying pans and saucepans
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2.12 – Mass Spec and IR
Mass Spectrometry

If a molecule is put through a mass spectrometer it will break up and give a series of peaks caused by the fragments.

 The peak with the largest m/z, will be the molecular ion and therefore the Mr of the molecule
 Smaller versions of the molecule due to covalent bonds breaking, produces free readicals. [M]+. → X+ + Y.
 The more stable the ion, the greater the peak intensity

e.g. for Propanal

 Equation for Molecular Ion

o CH3CH2CHO → [CH3CH2CHO]+ + e- (m/z 58)
 Fragment
o [CH3CH2CHO]+ → [CHO]+ +CH2CH3 (m/z 29)
o [CH3CH2CHO]+ → [CH3CH2]+ + CHO (m/z 29)

e.g. for Propanone

 Equation for Molecular Ion

o CH3COCH3 → [CH3COCH3]+ + e- (m/z 58)
 Fragment
o [CH3COCH3]+ → [CH3CO]+ + ·CH3 (m/z 43)
o [CH3COCH3]+ → [CH3]+ + ·CH3CO (m/z 15) It is not possible for propanone to fragment a peak at 29.

Infrared Spectroscopy

Certain bonds in a molecule absorb infra-red radiation at characteristic frequencies causing the covalent bonds to vibrate.

 Each bond vibrates at a particular frequency and absorbs the light at that frequency
 Above 1500 cm-1 – Functional group identification
 Below 1500 cm-1 – Fingerprinting, unique for every compound (compare against a database)
 H2O, CO2, CH4 and NO molecules absorb IR radiation and are greenhouse gases

Bond Compound Absorption Intensity

C-H Most organic molecules 2840-3095 Medium-Strong
C=C Alkenes 1610-1680 Medium
C=O Aldehydes and Ketones 1680-1750 Strong
C-O Alcohols 1000-1300 Strong
C-X Halogenoalkanes 700-800 Strong
O-H Free 3850-3670 Strong
Alcohols 3230-3550 Strong and broad
Carboxylic Acids 2500-3300 Medium and broad
N-H Amines 3100-3500 Strong

e.g. Absorption spectrum for Propan-1-ol, then oxidised to Propanal (a change in functional group has taken place)