Chemistry A-Level Notes D.

Clarke
Chemistry
Unit 2.1 Energetics
Enthalpy change (H) - Is the exchange of energy between a reaction mixture and
its surroundings when the reaction takes place at a constant pressure
!n exothermic reaction has a negati"e H whereas a endothermic has a positi"e
H
H
#
$%&
is the standard enthalpy change for a reaction at $%&' It refers to the
amounts shown in the e(uation at a pressure of )atm ()*)+***,m
-$
)+ with the
substances in their usual physical states under these conditions
H
#
f+ $%&
is the standard Enthalpy change of formation+ this is the enthalpy change
when one mole of a compound forms from the elements in their normal stable
states-
H
#
c+ $%&
is the standard Enthalpy change of combustion+ this is the enthalpy
change when one mole of a compound burns completely in oxygen-
H
#
neutralisation+ $%&
is the standard Enthalpy change of neutralisation+ this is the
Enthalpy change when an acid and an alkali completely neutralise each other
Hess.s /aw is used to calculate some H.s and it states the total Enthalpy change
accompanying a chemical change is independent of the route by which the
chemical change takes place-
0tandard Enthalpy changes can also be calculated using bond enthalpies 1he
amount of energy taken in by breaking the bonds and then the amount of energy
released when forming new bonds can be calculated and added together to gi"e the
o"erall enthalpy change 1his is less accurate than using Hess.s law as bond
enthalpies are a"erage "alues
Page 1
Chemistry A-Level Notes D.Clarke
Unit 2.2 Organic Chemistry I
! homologous series is a series of closely related organic compounds 1hese
compounds ha"e the same functional group and can be described by a general
formula
2.2a Isomers
Isomers are compounds with the same molecular formula but different strucural
formulae
0tructural Isomerism
1his is when the same number and type of atoms can be arranged in different
ways to form structural isomers
2eometric Isomerism
1his is caused by the presence of a 343 bond !s the 343 bond cannot be rotated
two functional groups can be on the same side or opposite sides of the 343
1he prefix cis- is gi"en if they are on the same side and the prefix trans- is gi"en
if they are on different sides
2.2b Reactions
Free radical reactions in"ol"e a free radical which is a species with an unpaired
electron
Electrophillic addition is the 5oining of two species to form a single one+ in which
the first step in"ol"es attack by an electrophile on the organic molecule
Nucleophillic substitution is the replacement of part of a ion or molecule by
another species in which the first step in"ol"es attack by a nucleophile
Elimination is the remo"al of a species from an organic molecule
Hydrolysis is a reaction with water to produce more than one new product
Reduction is gain of electrons
Oidation is loss of electrons
!olymerisation is the adding together of species to form a new molecule which
has a relati"e molecular mass which is an exact multiple of the reactant species
2.2c "l#anes
2eneral formula of 3
n
H
$n6$
1hey are saturated hydrocarbons as no 343 bond present
7ery unreacti"e as they lack any functional group
8eactions
Combustion
1hey burn in excess oxygen to produce 39
$
and H
$
9
Halogens
1hey react in the presence of :7 light with halogens due to free radical
formation
1he reaction will form a mixture of products as more of the hydrogen ca be
substituted for halogens
Page 2
Chemistry A-Level Notes D.Clarke
2.2d "l#enes
2eneral formula of 3
n
H
$n
1hey are unsaturated as they contain a 343 bond
1hey are reacti"e as 343 is a reacti"e functional group
8eactions
Hydrogen
Electrophillic addition reaction
;ass alkene and hydrogen o"er nickel catalyst to produce an alkane
8-343-8 6 H
$
44< 8-3H-3H-8
$romine and Chlorine
Electrophillic addition reaction
=issol"e alkene in hexane then mix with alkene at rtp
8-343-8 6 >
$
44< 8-3>-3>-8
Hydrogen halides
Electrophillic addition reaction
?ix gases at rtp
8-343-8 6 H> 44< 8-3H-3>-8
@hen unsymetrical alkenes are being reacted there are two possible products+
the ma5or product is found using ?arko"nikoff.s rule 1his says that the carbon
atom in the double bond with the most hydrogens attached to it will gain the
hydrogen from the hydrogen halide
Oidising agents
9xidation
8eact with '?n9
A
at rtp in a ,a9H solution
8-343-8 6 B9C 6 H
$
9 44< 8-39H -39H-8
2.2e Haloal#anes
1hey are organic compounds which contain a halogen
8eactions
NaOH
,ucleophillic substitution reaction
Doil under reflux with ,a9H
8-> 6 ,a9H 44< 8-9H 6 ,a>
%CN
,ucleophillic substitution reaction
Doil under reflux with '3, in water and ethanol
8-> 6 '3, 44< 8-3, 6 '>
NH
&
,ucleophillic substitution reaction
Heat excess conc ,H
E+
in ethanol+ with the haloalkane in a sealed tube
8-> 6 $,H
E
44< 8-,H
$
6 ,H
A
>
%OH in ethanol
Elimination
Doil under reflux with '9H dissol"ed in ethanol
8-3H
$
-3H
$
-> 6 '9H 44< 8-3H43H
$
6 '> 6 H
$
9
Page 3
Chemistry A-Level Notes D.Clarke
2.2' "lcohols
9rganic compounds with the functional group -9H
1hree types of alcohol
;rimary F 1he carbon with contains the -9H also has $ or E Hydrogen.s as well
0econdary F 1he carbon with contains the -9H also has ) Hydrogen as well
1ertiary F 1he carbon with contains the -9H doesn.t contain any Hydrogen
8eactions
Oidation (ith primary to produce aldehyde
9xidation
!dd '
$
3r
$
9
G
in dilute H
$
09
A
to hot alcohol and distil of the product
8-3H
$
-9H 6B9C 44< 8-3H49 6H
$
9
Oidation (ith primary to produce carboylic acid
9xidation
!dd '
$
3r
$
9
G
in dilute H
$
09
A
to the alcohol and boil under reflux
8-3H
$
-9H 6 $B9C 44< 8-39H49 6H
$
9
Oidation (ith secondary
9xidation
Doil the alcohol with acidified '
$
3r
$
9
G
under reflux
8
$
-3H-9H 6 B9C 44< 8
$
-349 6 H
$
9
Conc. )ulphuric acid
=ehydration
!dd excess conc 0ulphuric acid to alcohol and heat to )G*
o
3
8-3H
$
-3H
$
-9H 44< 8-3H43H
$
6 H
$
9
!Cl
*
3hlorination
9ccurs a rtp if alcohol is dry
8-9H 6 ;3l
H
44< 8-3l 6 ;93l
E
6 H3l
H$r +or HI,
Dromination
3onc H
$
09
A
is added to the alcohol and then solid 'Dr added to that to produce
HDr
8-9H 6 HDr 44< 8-Dr 6 H
$
9
Page 4
Chemistry A-Level Notes D.Clarke
Donding and reacti"ity
0ingle and double bonds
! single bond contains 1 sigma bond which is relati"ely strong
! double bond usually consists of a sigma and a pi bond ;i bonds are weaker
and more exposed and so are more easily attacked by other species making them
more reacti"e
Dond polarity
0ome bonds are polar due to the two species in the bond ha"e different
electronegati-ities+ the larger the difference in electro "alues the weaker the bond
is
1his is the case in 3-H and 3-> (>4halogen)
Iuantitati"e chemistry
Empirical 'ormula --1he empirical formula shows the simplest ratio of amounts of
elements on that compoundJ it therefore gi"es the ratio of the numbers of atoms-
.olecular 'ormula - ! formula which shows the number of atoms of each element
in a molecule-
/heoretical yield - is the mass of the product assuming the reaction goes )**K to
the chemical e(uation
"ctual yield - is the mass of the product obtained-
!ercentage yield - !ctual yield L theoretical yield M )**K
!pplied organic chemistry
Nuels
3ertain factors must be taken into accountO
Cost
3ost per 5oule released is more important but cost per 'g can be gi"en
Ease o' transport
/i(uids easier to transport
2ases must be under pressure
/i(uids ha"e high densities and so more energy per kg is usually applicable
)a'ety
;ollutants must be considered
2ases under pressure can be dangerous
Page 5
Chemistry A-Level Notes D.Clarke
;olymers
!olyethene +polythene,
0tructure
:sesO
;lastic bagsLbottles
!olypropene
0tructure
:sesO
3arpets
8opes
Nibrous materials
;lastic crates (milk crates)
!olychloroethene +poly-inylchloride !0C,
0tructure
:sesO
@indow frames
;ackaging
Electrical wiring
!olytetra'luoroethene
0tructure
:sesO
:tensils
,on-stick frying pans
?ost plastics are not biodegradable+ and so stay in the en"ironment for a long time (this
is a double edged sword) !lso polymers with a halogen attached gi"e off toxic fumes
when burnt+ or some haloalkanes can be decomposed in by :7 light producing free-
radicals
Page 6
Chemistry A-Level Notes D.Clarke
Unit 2.& %inetics I
Page 7
Chemistry A-Level Notes D.Clarke
Unit 2.1 Chemical E2uilibria
0ome chemical reactions take place in one direction only ie they go to completion and
are irre"ersible
In some reactions the products can combine and reform the reactants ie they are
re"ersible 0uch reactions will e"entually reach a state of e(uilibrium in which both
reactants and products are present
E(uilibrium reactions are dynamic Doth forward and re"erse reactions still continue (at
e(ual rates) at e(uilibrium although they appear to ha"e stopped as there is no further
change in the concentration of either reactants or products
3atalysts do not ha"e any effect of the position of e(uilibrium of a system+ they 5ust
increase the rate of reaction and therefore the rate at which the system reaches
e(uilibrium

Page 8
Chemistry A-Level Notes D.Clarke
Unit 2.* Industrial Inorganic Chemistry
$Ha 3onditions for ammonia and nitric acid manufacture
1he Haber process that turns nitrogen from the air and hydrogen (from water or
methane) into ammonia
&H
2
+g, 3 N
2
+g, 4 2NH
&
+g,
1he optimum (best) conditions for this process which gi"e the greatest yield areO
!bout 2*5 atmospheresJ high pressure increases yield
!bout 1*56C J high temperature cuts yield but increases rate
!nd the use of a catalyst+ iron (ith %OH is used+ to increase the rate
!mmonia is changed into nitric acid in the Ost(ald process 1his is another e(uilibrium
process which starts with the reaction of ammonia and oxygen
1NH
&
+g, 3 *O
2
+g, 4 1NO+g, 3 7H
2
O+g,
1he optimum (best) conditions for this process which gi"e the greatest yield areO
! pressure of 15 atmospheres
a temperature of about 855
o
C
a catalyst of platinum and rhodium
1he nitrogen monoxide is then mixed with oxygen and flows up a column down which
water flows 1he result is a solution of PHK nitric acid
1NO+g, 3 &O
2
+g, 32H
2
O+l, 999: 1HNO
&
+a2,
$Hb 3onditions for sulphuric acid manufacture
0ulphuric acid is made in the Contact process 1his takes sulphur dioxide (made by
burning sulphur) and reacts it in an e(uilibrium process with oxygen
2)O
2
+g, 3 O
2
+g, 4 2)O
&
+g,
1he optimum conditions for this process areO
a temperature of 1&5
o
C
a pressure of 192 atmospheres
a catalyst of -anadium pentoide 0
2
O
*
$Hc Explanation of choice of conditions for manufacture
1emperature
1he reaction below is exothermic+ energy gi"en out when ammonia forms+ but energy is
taken in if ammonia breaks up
N
2
+g, 3 &H
2
+g, 999: 2NH
&
+g,
Reactions resist changes (le 3hatelier.s principle)
1herefore if the temperature goes up the reaction tries to pre"ent this by taking in energy
1he reaction can take energy by breaking up ammonia and the position of e(uilibrium
mo"es to the left
@hen the temperature falls the position of the e(uilibrium mo"es to the right so more
ammonia is formed ! low temperature is best for a high yield but at a low temperature the
rate is low+ so a compromise of about AH*
o
3 is used
Page
Chemistry A-Level Notes D.Clarke
3atalyst
Has no effect on e(uilibrium+ it only increases rate
;ressure
9n the left hand side of the e(uation there are A molecules of gas+ on the right hand side
there are only $ molecules ;ressure is reduced if the position of the e(uilibrium mo"es to
the right+ so an increase in pressure causes a shift to the right so more ammonia is
formed
$Hd 1he uses of ammonia+ nitric acid and sulphuric acid
"mmonia
dyestuffs+ fibres+ detergents and soaps+ paint and pigments
Nitric acid
fertilisers+ nylon+ plastics and explosi"es
)ulphuric acid
paint and pigments+ detergents and soaps+ fibres and dyestuffs
$He 1he electrolytic extraction of aluminium
!luminium is extracted from the ore bauxite+ !l
$
9
E
$H
$
9
1he ore is purified by dissol"ing amphoteric "l
2
O
&
in hot a2ueous sodium hydroide
under pressure 1he impurities Fe
2
O
&
and )iO
2
don.t dissol"e and are remo"ed by
filtration
!luminium hydroxide is precipitated with .seed. crystals and filtered off+ it is then heated
to produce pure alumina
!luminium is manufactured by the electrolysis of alumina dissol"ed in molten cryolite
+Na
&
"lF
7
, to lower melting point 1his mixture is heated and the molten li(uid used as the
electrolyte Doth electrodes are made o' graphite +carbon,
1he carbon anode is burned a(ay by oxygen and has to be fre(uently replaced+ but
produces heat and so o"erall costs are lowered
!luminium is expensi"e despite being common because its manufacture re(uires large
amounts of electricity
$Hf :ses and properties of aluminium
9"erhead power cables
2ood electrical conductor+ low density
=rinks cans
=oes not react with water
!ircraft parts
High strength to weight ratio and low density
@indow frame
=oes not corrode due to oxide layer protection
0aucepans
2ood thermal conducti"ity
Page 1!
Chemistry A-Level Notes D.Clarke
$Hg 1he electrolysis of sodium chloride
0odium hydroxide+ chlorine and hydrogen are produced from natural deposits of sodium
chloride (rocksalt)
!t 3athodeO 2H3+a2, 3 2e9 99999: H
2
+g,
!t !node 2Cl9+a2, 99999: Cl
2
+g, 3 2e9
In the solution in the cathode compartment the e(uilibrium
H
2
O+l, ;4: H3+a2, 3 OH9+a2,
shifts to the right as H6 ion is con"erted to hydrogen gas 1here is a build up of hydroxide
ion and with the unaffected sodium ions remaining in the solution produces sodium
hydroxide
0aturated brine is pumped into the anode compartment 1he brine le"el in the anode
compartment is kept higher than the le"el in the cathode compartment so that brine seeps
through the membrane+ but hydroxide ion does not seep in the opposite direction 1he
mixing of hydroxide ions and chlorine would produce unwanted sodium chlorate(I) 1he
resulting solution lea"ing the cell+ known as cell li(uor+ contains approximately )$K
sodium hydroxide and )HK sodium chloride by mass E"aporation and crystallisation lea"e
a solution containing H*K sodium hydroxide and less than )K sodium chloride
If sodium chlorate (I) is re(uired then the sodium hydroxide solution formed abo"e is
treated with gaseous chlorine to obtain sodium chlorate (I)
Cl
2
+g, 3 2NaOH+a2, 99999: NaCl+a2, 3 NaClO+a2, 3 H
2
O+l,
$Hh :ses of chlorine and sodium chlorate (I)
3hlorineO
!s a cheap industrial oxidant
!s a bleach
!s a germicide
1o produce H3l
1o manufacture chlorinated hydrocarbon sol"ents
1o manufacture chloroethene+ a precursor for ;73
0odium chlorate(I)
!s a bleach in laundries
!s a disinfectant and in sewage treatment
2ermicide because it is a strong oxidising agent
Page 11