CHEMISTRY

EDEXCEL
MODULE 2

Valence Shell
Electron Pair
Repulsion Theory
Or VSEPR

SHAPES OF MOLECULES

Electrons repel to a
point of maximum
separation to give
minimum repulsion

Lone Pair: Lone Pair > Lone pair: Bond Pair > Bond Pair: Bond Pair

Allotrope:
different forms of
the same element
in the same state

CARBON STRUCTURES

Carbon has 3 allotropes:

Graphite, Diamond & Fullerenes

Diamond:

Each carbon atom is covalently bonded with sigma bonds to four other carbon atoms
This creates a tetrahedral shape crystal lattice structure
Properties:

High melting point (3700K)

Extremely hard
Vibrations can travel through the lattice its a good thermal conductor
Cant conduct electricity
Wont dissolve in any solvent

Graphite:

Carbon atoms arranged in sheets of flat hexagons

The 4th outer electron of each carbon atom is delocalised
Properties:

Weak bonds between layers so sheets slide over each other used as a dry lubricant
There are delocalised electrons can conduct electricity
Less dense than diamond but strong & lightweight
Strong covalent bonds high melting point
Insoluble in all solvents

Fullerenes:

Can form hollow balls or tubes

Each carbon bonds to 3 others
There are delocalised electrons

Theyre nanoparticles
Buckminsterfullerene C 60 sphere shaped
Many are soluble in organic solvents & form bright colours
Can be used to deliver drugs to specific cells of the body

Can conduct electricity

Nanotube:

Single layer of graphite rolled into a tube

They can conduct electricity

Electronegativity
measured on the
Pauling scale F = 4

E.g. CsF Large

Cation & Small
Anion

Partially
Covalent

POLAR BONDS
Al3+ - Small & High
Charge
So high charge density

Very polar due to

F being
electronegative.
E- in bond shared
unevenly

E.g. H H

Electronegativity the ability to attract the bonding electrons in a

covalent bond
e-s spend most of their time near F
F most electronegative & Cs least electronegative
Not all molecules with polar bonds are polar molecules
Trichloromethane - Polar
But, Tetrachloromethane not Polar

Stronger Bonds = Shorter Bonds

INTERMOLECULAR FORCES
VdW London Forces

Causes all atoms & molecules to be attracted to each other

When e-s are on one side of an atom they form a temporary dipole
This dipole causes another dipole in the neighbouring atom
Larger SA/molecule/chain length = Stronger

Dipole Dipole
Charges on polar molecules cause weak electrostatic attractions between
molecules

H-Bonding

Requires hydrogen covalently bonded to N, O, F

NOF are very electronegative, they attract the electrons from H
Bond is polarised & H has a high charge density
H atoms form weak bonds with lone pairs of electrons on NOF of other molecules

VdW < Dipole - Dipole < H-Bonding

Like usually dissolves like

SOLUBILITY
To dissolve:
Bonds in substance have to break
Bonds in solvent have to break
New bonds have to from between substance & solvent

Non-polar solvents will dissolve non-polar solutes

Both have VdW forces so form similar bonds with each other

Polar solvents (e.g. Water) will dissolve ionic substances

Ions are attracted to oppositely charged ends of water

Ions pulled away from lattice by H 2O, called hydration
Some ionic substance dont dissolve because the bonding is too strong
Not all molecules with polar bonds will dissolve, halogenoalkanes dont

Bond between C-X is weaker than O-H in water

Alcohols also dissolve in polar solvents

Polar O-H bond in an alcohol attracted to O-H in water
H bonds form between lone pair on oxygen atoms and the hydrogen atoms
Longer carbon chain on alcohol = less soluble

REDOX

Oxidation lose eOxidising Agents gain e- & gets reduced

Reduction gain eReducing Agents lose e- & gets oxidised

Rules:

Group 1 = +1
Group 2 = +2
Hydrogen = +1
Fluorine = -1
Oxygen = -2
Chlorine = -1

(-1 in Metal Hydrides)

(-1 in Peroxides)
( not in F & O 2)

Uncombined Element = 0

e.g. Cl2

Balancing Redox Equation:

Balance O2 by adding H2O

Balance H2 by adding H+
Balance charge add e-

GROUP 2
With water:
Produces a hydroxide e.g. Mg(OH)2
Reacts more quickly down group due to low IE

MO(s) + H2O(l) M(OH)2(aq)

Burn in oxygen:
Produces a oxide e.g. MgO

React with chlorine:

E.g. MgCl2 forms white solid

Reaction with water

M(OH)2(S) + H2O M2+(aq) + 2OH-(aq)

MO(s) + 2HCl(aq) MCl2(aq) + H2O(l)
Reaction with acid

M(OH)2(aq) + 2HCl(aq) MCl2(aq) + 2H2O(l)

Oxides & Hydroxides are bases:

Oxides react with water producing metal hydroxides

The hydroxide ions make these solutions strongly alkaline
MgO reacts slowly & its hydroxide isnt very soluble
Oxides form more strong alkaline solutions down the group due to the hydroxides being
more soluble

Hydroxide more soluble down group 2

Sulphate less soluble down group 2 (Barium Sulphate is insoluble)

FLAME TESTS
Lithium Red
Sodium Golden-Yellow
Potassium Lilac

Use Nichrome wire

Clean wire with HCl
Dip into compound
Hold it over non-luminous flame

Calcium Brick Red

Strontium Crimson Red
Electron Transition:
Barium Pale Green
Copper Blue/green
Caesium Blue
Rubidium - Red

Due to electrons
absorbing energy and moving
to a higher energy level. They
emit energy (in the form of
light) when they fall back
down

HEATING NO3S & CO3S

Group 1 Nitrates:
2KNO3 = 2KNO2 + O2

Group 2 Carbonates:
CaCO3 = CaO + CO2

Group 2 Nitrates:
2Ca(NO3)2 = 2CaO + 4NO2 + O2

Group 1 Carbonates are too

thermally stable to
decompose
Except Li2CO3
This forms Li2O & CO2

THERMAL STABILITY CO3 & NO3

More thermally stable down group 2

E- less distorted
Larger ionic radius
Smaller Cation = More Polarising

E-s are pulled

towards the
cation breaking
the O-C bond

THE HALOGENS
Electronegativity & Reactivity Decreases down the Group
Melting & Boiling Points Increase down the Group
Colour in Water

Colour in
Hexane

Chlorin
e

Virtually
Colourless

Virtually
Colourless

Bromin
e

Yellow/Orange

Orange/Red

Iodine

Brown

Pink/Violet

Disproportionation with Alkalis:

Cold:
X2 + 2NaOH NaXO + NaX + H2O
X2 + 2OH- XO- + X- + H2O
Hot:
3X2 + 6NaOH NaXO3 + 5NaX + 3H2O
3X2 + 6OH- XO3- + 5X- + 3H2O

Oxidise Metals:

F2 & Cl2 are the strongest oxidising agents so we get oxidise Fe Fe3+
Br2 is slightly weaker oxidising agent so we get Fe2+ & Fe3+
I2 is the weakest so only Fe2+ forms

Oxidise Non-Metals:

e.g. 4Cl2 + S8 4S2Cl2

THE HALIDES
Reducing power increases down the group by losing an electron
Reaction with Silver Nitrate (AgNO3):

KF/KCl with H2SO4:

Forms KHSO4(s) & HF/HCl(g)

KBr with H2SO4:

Forms KHSO4(s) & HBr(g)
HBr then reacts with H2SO4 Forms Br2(g), SO2(g), H2O(l)

KI with H2SO4:
Forms KHSO4(s) & HI(g)
HI then reacts with H2SO4 Forms I2(g), SO2(g), H2O(l)
HI then reacts with SO2 Forms H2S(g), I2(s), H2O(l)

Fluoride No Precipitate
Chloride White Precipitate - Dissolves in Dilute
NH3(aq)
Bromide Cream Precipitate Dissolves in
Concentrated NH3(aq)
Iodide Yellow Precipitate Insoluble in NH 3(aq)

Silver Halides React with Sunlight:

2AgBr 2Ag +

Purple

Hydrogen Halides are Acidic Gases:

Reacts with NH3(g) forming white fumes

Blue Litmus Red

Halide Ions are Displaced by more Reactive Halogens:

Cl2(aq) + 2Br-(aq) 2Cl-(aq) + Br2(aq)
Br2(aq) + 2I-(aq) 2Br-(aq) + I2(aq)

Br2

INDICATORS
Litmus paper:

Lead Acetate:
H2S

Red to Blue
Acid

White to Black

Alkali

K2Cr2O7:

Methyl Orange:

SO2

Yellow to Red
Alkali

Acid

Phenolphthalein:
Colourless to Pink/Red
Acid

Alkali

Starch:
Black to Colourless
I2

Orange to Green

I2 + S2O32-

Ammonia:
Hydrogen Halide

White Smoke

KINETICS
Maxwell-Boltzmann Distribution:
Total area under
curve = number
of particles

When Temp is Increased:

Particles have more energy
Greater number of particles
have the Ea
More successful collisions occur
per cm3
Faster rate of reaction

These particles have

sufficient Ea to react

Catalyst provides
alternative route
for a reaction
with a lower Ea.

10oC temp
increase = 2 x
RoR

CHEMICAL EQUILIBRIA
Reversible Reactions can Reach Dynamic Equilibrium:
H2(g) + I2(g) 2HI(g)

Concentration:

Increase reactant = more product

Increase product = more reactant

Pressure:

Increasing it shifts to side with fewer gas molecules

Decreasing it shifts to the side with more gas molecules

Temperature:

Increasing temp = shifts in the endothermic direction

Decreasing temp = shifts in the exothermic direction
Decrease Temperature

Increase Pressure
Increase Conc of Reactants

2SO2(g) + O2(g) 2SO3(g) -197 kJmol-1

Increase Conc of Products
Increase Temperature

ALCOHOLS
1o Functional group attached to a carbon which has 1 carbon attached to it Least Reactive
2o - Functional group attached to a carbon which has 2 carbons attached to it
3o - Functional group attached to a carbon which has 3 carbons attached to it Most reactive

Producing Halogenoalkanes using Phosphorus Halides:

3ROH + PX3 3RX + H3PO3 PI3 & PBr3 are made in situ using
Red Phosphorus

Properties:
Liquid at room temp due to H bonds between molecules
Low Volatility due to H bonding
Soluble in H2O due to H bonding but less soluble as chain length increases

Alcohols & Na Alkoxides:

Longer chain length = less reactive
2CH4O + 2Na 2CH3CH2O- Na+ + H2
Methanol

Sodium Methoxide

Reaction with PCl5 test for OH group:

Misty white fumes given off when NH 3(g) added
C2H5OH(aq) + PCl5(s) C2H5Cl(aq) + HCl(g) + POCl3(aq)
HCl(g) + NH3(g) NH4Cl

OXIDATION OF AN ALCOHOL
Partial oxidation limited Na2Cr2O7 & dilute H2SO4
Reflux Conc H2SO4 & excess Na2Cr2O7

Colour changes from orange to green

Reflux:

Allows reactions to happen at highest temperature without

loss of product or reactants
Water goes in at bottom to ensure constant cooling

LiAlH4 to go from Acid

to 1o or Aldehyde

Separation of Products:

Distillation

Alcohol into Halogenoalkanes:

Add PCl5
Reflux + NaBr +50% H2SO4
I2 & moist red phosphorus Iodoalkanes, react
with alcohol

PREPARATION OF ETHANAL BY
OXIDATION OF ETHANOL
50cm3 H2O in 500cm3 flask, add 17cm3 of conc H2SO4 & antibumping granules
Put flask in distillation apparatus. Still head has tap funnel &
receiving flask in ice-bath (ethanal low B point avoid evap)
Dissolve 50g of Na2Cr2O7 in 50cm3 H2O in small beaker. Add 40cm3
of ethanol. Stir thoroughly
Heat flask until boils, remove heat. Run alcohol/dichromate
solution slowly into flask, mixture becomes green, takes 20 mins.
Maintain gentle boiling
Aqueous solution of ethanal collects in receiver.

Uses:

Solvents
Refrigerants
Pesticides
Fire Extinguishers

HALOGENOALKANES

Reaction with KOH(aq):

Heat under reflux with KOH(aq) giving an alcohol

Reaction with KOH in ethanolic solution:

Eliminates hydrogen halide forming alkene

Reaction with Conc. Ammonia in Ethanol:

Heat & Pressure with Conc NH3 to produce amines Nucleophilic Addition

Preparation of 1-Bromobutane:

30cm3 of H2O, 35g NaBr, 25cm3 of Butan-1-ol

Add 25cm3 of conc H2SO4 drop by drop
occasionally cool
Reflux for 45 mins
Distil off crude 1-bromobutane (about 30cm3)
Shake distillate with water in separating funnel and run off lower layer of 1-bromobutane
Add 1-bromobutane back into funnel & add half its vol of HCl
Shake with Na2CO3 releasing pressure
Run off lower layer and add granular anhydrous CaCl2, swirl until clear
Filter into clean, dry flask and distil it. Collect fractions between 99-102 oC

NUCLEOPHILIC SUBSTITUTION
SN2 All 1o halogenoalkanes react this way

SN1 All 3o halogenoalkanes react this way

TYPES OF REACTION

Addition Joining 2+ molecules together forming a larger molecule

Polymerisation joining monomers together forming a polymer
Elimination small group of atoms breaks away from a larger molecule
Substitution one species is replaced by another
Hydrolysis splitting of a molecule by adding H + & OH- from H2O
Oxidation reaction in which an atom loses electrons
Reduction reaction in which an atom gains electrons
Redox - reaction in which electrons are transferred between 2 species

Homolytic Fission:
X-Y Xo + Yo
Forms Free-Radicals

Heterolytic Fission:
X-Y X+ + Y Forms cation & anion

Electrophiles are electron pair acceptors

They are +ve

Nucleophiles are electron pair donors

They are ve

OZONE O3
UV Radiation

Nitric Oxide breaks down Ozone too

NO

O2 + hv O + O
O + O2 O3
O2 + O O3
CCl3F CCl2F + Cl
Cl + O3 O2 + ClO
ClO + O3 2O2 + Cl
2O3 3O2

Cl

is the catalyst

INSTRUMENTAL ANALYSIS
Vapourisation Ionisation Acceleration Deflection Detection
Organic Molecule Detection:
E.g. C2H5OH can be vapourised & ionised C2H5OH+ - appears at 46m/e (parent ion
peak)

When fragmented charges allow us to be what group is present

IR Spectroscopy:
All bonds stretch and bend naturally
Polar bonds change polarity and absorb that frequency of IR as they vibrate

OH
C=O
OH
C=O
C=O
Acid

3600 wavenumber/cm-1 smooth u curve

1740 wavenumber/cm-1 steep v curve
3500 wavenumber/cm-1 smoother than O H
1690 wavenumber/cm-1 steep v curve
1710 wavenumber/cm-1

Aldehydes
Ketones
Carboxylic