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Chlorofluorocarbons

• Were used in
o Fridges
o Propellants in aerosols
o Blowing agents for expanded plastic
o Cleaning solvents
• Because
o They have low boiling points
o Low reactivity
o Low toxicity
o High stability
• When they reach the atmosphere they can undergo photodissociation
o Which turns them into chlorine radicals which can destroy ozone
 O3
• They have a lifetime in the troposphere of approximately 100 years
• Replacements for CFCs
o Hydrochlorofluorocarbons (HCFCs) & Hydrochlorocarbons (HFCs)
 Pros
• H-C bonds are broken down in the troposphere before they can reach the
stratosphere
 Cons
• Are greenhouse gases that contribute to global warming
o Alkanes
 Pros
• Don’t contain chlorine
 Cons
• Are flammable
• Are greenhouse gases

The greenhouse effect


• High energy radiation form the sun (visible light and UV radiation) reaches earth and warms it up
• Some of the energy is re-emitted, but at a lower frequency
• Some of this lower frequency energy is absorbed by atmospheric gases such as CH4 and CO2
o Which would not have absorbed the higher frequency light entering earth
o These are greenhouse gases
• The rest escapes to space
• Some of the infrared (heat) energy is re-emitted by the molecules in every possible direction
o So some is emitted to earth and some to space
• The absorption of infrared make the atmospheric gases have increased vibrational energy
o Their bond vibrate more vigorously
o Energy is transferred to other molecules by collisions
o This increases their kinetic energy and heats up the atmosphere
• This is an importance balance for maintaining the temperature of the earth
• CO2 and H2O between them absorb 2 different frequencies
o This leaves a “window” for infrared to escape without being absorbed
 70% of infrared escapes through this

Human activities
• Human activities are increasing atmospheric concentrations of
o Natural greenhouse gases
 e.g. CO2
o Not naturally present greenhouse gases
 e.g. CFCs
• Although there are only small amounts CFCs have a large global warming
potential
• This increase is causing a enhanced greenhouse effect
o This is believed to be caused by human activity
• Things to do to stop this
o Decrease CO2 concentrations, by
 Reducing consumption of fossil fuels
 Using alternative energy sources
• Wind, solar, tidal, etc
 Increasing photosynthesis
 Burying or reacting CO2

Molecules and networks


• Some elements and compounds form giant covalent structures
o These are called network or giant structures
 E.g. diamond and silicon (IV) oxide
• Diamond is made of carbon atoms
o Each carbon is tetrahedrally bonded to four other carbon atoms
 By covalent bonds
o The strong C-C bonds and highly symmetrical network structure make it the hardest naturally
occurring substance
• Silicon (IV) oxide
o Silicon atoms form 4 bonds
 Silicon bonds covalently to 4 oxygen atoms
o Quartz is a pure form of silicon (IV) oxide
 It is an extended network of SiO4 units
 Each silicon atom has a half share in 4 oxygen atoms
• Differences between CO2 and SiO2
o CO2 has a molecular structure with 3 atoms bonded in a liner arrangement
 All of the bonds are double bonds
 The intermolecular bonds are weak and so can easily be separated
• This causes it to sublime at low temperatures
o This means it goes from a solid to a gas or vice versa without ever being a
liquid
 The intramolecular bond in CO2 are polar so it dissolves in water easily
o Silicon atoms are larger than carbon atoms and have more electrons
 They are unable to make double bonds
• So separate SiO2 molecules are formed
 Silicon (IV) oxide has a giant network structure
 It requires a lot of energy to overcome the intramolecular bonds
• Bonds within the network
 So it has
• A high melting point
• A high boiling point
• Does not dissolve in water

Radiation and matter


• The atmosphere is divided into 3 sections
o The troposphere
o The stratosphere
o The ionosphere
• The troposphere is the closest to the surface of the earth
o It has a composition of
 78% nitrogen
 21% oxygen
 0.93% argon
 0.038% carbon dioxide
• Every molecule has certain energies associated with its behaviour, these include (in increasing order of
energy)
o Translational energy
 The molecule moving around as a whole
o Rotational energy
 The molecule rotating as a whole
 Can be caused by microwave radiation
o Vibrational energy
 The vibration of bonds within the molecule
 Can be caused by infrared radiation
o Electronic energy
 The electrons moving from one energy level to another
 Can be caused by visible or UV radiation
• To convert ppm (parts per million) to percentage
o Divide by 10000
• To convert percentage to ppm
o Multiply by 10000
• E=hv
o E is the energy of one photon (in joules)
o V is the frequency of the radiation
o H is the Planck constant
 6.63x10-34 JHz-1
• When a molecule absorbs visible light of UV radiation
o Electrons can be excited to a higher energy level
 They will eventually return to normal
 And release the energy that has been absorbed
o Chemical bonds can break and radicals form
 Photodissociation
o An electron can be ejected form the molecule
 Which then becomes ionised

Radiation and radicals


• For a covalently bonded pair of electrons
o In heterolytic fission both of the electrons go to one of the atoms when a bond breaks
 This forms ions
o In homolytic fission one of the two electrons in a shared pair goes to each atom
 They both now have unpaired electrons and are radicals
o If the radical formed has 2 unpaired electrons it is called a biradical
 E.g. O2
o Radicals are very reactive due to the unpaired electron
• There are three stages in radical chain reactions
o Initiation
 There are no radicals in the reactants, but radicals are formed as a product(s)
o Propagation
 There are radicals in the reactants and products of the reaction
o Termination
 The reaction is terminated when 2 or more radicals collide
 So there are radicals in the reactants but not the products
• A halogen can substitute a hydrogen in an alkane chain
o Via a radical substitution
o To produce a halogenoalkane
 Initiation
• Homolytic fission occurs because of UV
• Cl2 -> 2Cl*
 Propagation
• CH4 + Cl* -> CH3 + HCl
• CH3 + Cl2 -> CH3Cl + Cl*
 Termination
• CH3* + CH3* -> C2H6
• CH3* + Cl* -> CH3Cl
• In the stratosphere O2 molecules are hit by UV radiation
o And photodissociate into 2 O*’s
• Ozone is formed by an O* bonding with a O2
o To make O3
• Ozone is highly reactive
o If X is a radical
 X + O3 -> XO + O2
• Equation A
 XO + O* -> O2 + X
• Equation B
 O + O3 -> 2O2
o The X is involved in the reactions but is not used up
 So it is acting as a catalyst
 This is an example of a catalytic cycle
 Because of this one chlorine molecule can remove 1 million ozone molecules
• The chlorine is present due to breakdown of CFCs
• Ozone absorbs UV radiation
o Without it you could get skin cancer form the UV

Chemical equilibrium
• In an equilibrium reaction reactants form products
o But then the products then turn into the reactants again
o While the reactants are still being turned into product
o So both of these reaction happen at the same time
o When they are both going at the same rate it is dynamic equilibrium
• Chemical equilibrium can only happen in a closed system
o In an open system a series of reactions can only come to a “steady state”
 E.g. the production and destruction of ozone happens in separate reactions
 But ultimately the concentrations of reactants and products stay the same
 This is a “steady state”
• Position of equilibrium
o If more of the reactants become products before the products have become reactants
 Then the position of equilibrium is to the right
o If more of the products are changing into reactants than the reactants are becoming products
 Then the position of equilibrium is to the left
o The position of equilibrium can be changed by
 Changing the concentration of the reactants or products
 Changing the pressure gases are at
 Changing the temperature
• Le Chatelier’s principle states that if a system is in equilibrium
o And a change is made to any of the conditions
o Then the system will try to counteract the change as much as possible
• Concentration effects on position of equilibrium
o Increasing reactants
 Moves it to the right
o Increasing products
 Moves it to the left
o And the reverse is true of decreasing either
• Pressure effects on position of equilibrium
o Increasing pressure
 Shifts it to the side with fewer gas molecules
 And the reverse it true of decreasing
• Temperature effects on position of equilibrium
o Increasing temperature
 Shifting in the direction of the endothermic reaction
 And the reverse is true of decreasing

Rates of reaction
• Rates of reaction are effected by
o Concentration
o Pressure
o A catalyst
o Intensity of radiation
o Surface area
o Particle size
o Temperature
• Collision theory
o Reactions occur when particles collide with minimum kinetic energy
 It higher pressures particles are closer together and so collide more frequently
 At higher temperatures more of the particles have sufficient energy to react when they
collide
 When a reactant is in smaller particles is has more surface area
• So it has more surface for reactions to take place on
• Increasing the chance of successful collisions
 Heterogeneous catalysts provide a surface where reactants can make and break bonds
• Activation enthalpy
o The activation enthalpy is the minimum kinetic energy required for an atom to react on collision

The effect of temperature of rate


• The energy needed to overcome the energy barrier is called the activation energy barrier
• As the temperature increase so does the rate of reaction
o This is because of the distribution of energy among the reacting particles
o This distribution is called the Maxwell-Boltzmann distribution

Catalysts
• Catalysts lower the activation enthalpy of reactions
o (the reaction(s) they catalyse)
• Heterogeneous catalysts provide a surface on which a reaction can take place
o Are in a different physical state to the things they catalyse
• Homogeneous catalysts work by forming an intermediate compound with the reactants
o Are in the same physical state as the things they catalyse
o They help lower the activation enthalpy by assisting the reaction
o And then they are reformed by the reaction