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Unit 4 Chemistry Notes
Unit 4 Chemistry Notes
AQA A2-LEVEL
dynamic (not static - do you know the difference!) equilibrium is achievable in a closed
system (e.g. solutions in a test tube if there are no gaseous reactants/products).
rates of the forward and reverse reactions at equilibrium are identical
concentrations are unlikely to be 50 – 50
can you unambiguously write down what LCP states (see 148 of the AS textbook)?
remember this is a predictive tool used to determine the effect on the position of equilibria
when a change in concentration, temperature or pressure is made
it is NOT an explanation of WHY it happens so avoid statements such as ‘because of LCP’,
‘LCP causes …’ and learn to state ‘LCP predicts that …..’
LCP is not suggesting that a system completely reverses a temperature change when
establishing a new equilibrium as the new equilibrium will be that for the changed
temperature
it implies that the shift in the position (in terms of reactants and products) of equilibria is in
the direction that seems to minimize the effect of that change
a new position of equilibria in which the relative rates of the forward and backward
reaction are once again in balance under the new set of conditions is eventually arrived at
the position of equilibria is changed by:
Monitoring Equilibria
remote sensing – this is non intrusive (e.g. level of absorbance of a given wavelength of light
by a coloured solution) so will not effect the position of equilibrium
titrimetric analysis – this will effect the position of equilibria (since the concentration of one
of the reactants or products will be changed) so is only applicable to a system with a slow
response to a change in conditions or where quenching (dilution or cooling) is used to slow
down the rate of reaction and thus the effect of the investigative technique
c d
[C] [D]
eqm eqm
aA + bB cC + dD Kc =
a b
[A] [B]
eqm eqm
you must be able to calculate the numerical value of Kc (possibly using data from an
experiment you will carry out yourself)
note that concentrations are used i.e. moles/volume not moles although quite often V will cancel
down or cancel out completely (when the ∑powers is the same on the top as the bottom) –
but show ALL working in exams
determination of the units of Kc – you must show workings in the exam but …..
check using (moldm-3)∑top powers - ∑bottom powers
pressure only has an effect IF gaseous particles are involved and in addition the
stoichiometric ratio of gaseous particles is unequal on either side of the equation
in all cases a pressure increase will increase the rate of reaction involving gaseous reactants
value of Kc increases as temperature increases for endothermic reactions i.e. the equilibrium
shifts to the RHS i.e. more products
value of Kc decreases as temperature increases for exothermic reactions i.e. the equilibrium
shifts to the LHS i.e. less products
Kc and Catalysts
Kinetics
Rate Equations
the rate of reaction is the rate of change of either the reactants or products in a chemical
reaction
the rate can be determined from concentration versus time graphs
the mathematical expression for the graph on page 4 of reaction A + 2B →C:
initial rate (t0) – the gradient is easiest to determine with confidence since it goes
through zero
see AS Module 2 guide for general practical techniques for monitoring progress in a given
reaction
2 clock techniques – measuring the time to an observable event from known different
initial conditions e.g. the ‘thiosulphate cross’ (the one you did at GCSE) or the ‘iodine
clock’
this must be relatively early in the reaction so that the concentration of other reagents
(other than the one being varied) can be deemed unchanged.
1
initial rate
t
each reactant may or may not affect reaction rate (so it’s not quite as clear cut as it seemed at
GCSE/AS)
ALSO it is not necessarily directly proportional when it does – we shall see why later
for a given reactant we can state
Rate [reactant]n
m and n are the order of reaction for each reagent (values are limited to 0, 1 or 2 at A-Level)
unlike with equilibria the orders of reaction and thus the overall rate equation cannot be
determined from reaction stoichiometry they can only by determined by experiments
units of k will vary depending upon the overall order of the reaction
determination of the units of k for 0, 1, 2 and 3rd order reactions overall
should be attempted as they are likely in an exam and here is
another ‘cheat’ for checking your answer:
catalysts will be involved in the rate expression (this might only be a modification of the
value of k itself for example a solid in heterogeneous catalysis)
H+
e.g. CH3COCH3(aq) + I2(aq) CH2ICOCH3(aq) + H+(aq) + I-(aq)
first order wrt [H+] and [CH3CO CH3] zero order wrt [I2] i.e. second order overall
most reactions occur in several steps (this is exemplified by organic reaction mechanisms)
each step will take place at a different rate
the slowest step will determine the overall rate of the reaction and is known as the rate
determining step
the order of the reaction regarding each reagent can provide information regarding its
involvement in the rate determining step
obviously a reactant with 0 order will not be involved in the rate determining step
study of reaction kinetics can yield important information regarding the mechanism of a
multi-step reaction
in the reaction above iodine would not be involved in the rate determining (slow) step
at this point you might ask your teacher to explain why there are variations in the mechanism
for the hydrolysis of a haloalkanes as discussed on pages 15 – 16 (or perhaps research SN1
and SN2 yourself)
rate/concentration graphs can show the order with respect to a given reagent
it is glossed over at A-Level that the other reagents will have to be present in xs so that their
concentration can be deemed to be unchanged during the course of a reaction where a series
of measurements of the concentration of a given chemical are measured.
or – in a clock technique the event measured in relatively early in the reaction so better
reflects the known initial concentration of each reagent
first order e.g. thermal decomposition of dinitrogen monoxide to nitrogen and oxygen (gold
catalyst), rate is directly proportional to concentration and will be a straight line gradient = k
(any points not on the straight line will be anomalies and require identification and
explanation (e.g. temperature variations))
second order e.g. thermal decomposition of ethanal to methane and carbon monoxide will
produce a graph that curves upwards (rate against concentration2 is a straight line)
initial reaction rates are determined by plotting the tangent to the time/concentration graph
for different initial reagent concentrations at the start of the reaction (t = 0) when reaction
concentrations are accurately known (and at a fixed temperature/catalyst)
the gradient of this line is the initial rate
orders of reaction can be determined from initial rates data by inspection
the value of k can also be determined from this data
the best way to grasp this idea is to try examples
distribution of energies amongst particles at different temperatures give rise to the Maxwell-
Boltzmann distribution curves based on the Arrhenius expression
EA
k Ae RT
the main significance of this equation (which you don’t need to know – unless you are trying
to understand the subject) is that a small rise in temperature has an exponential (i.e. big)
effect on rate
EA
Extra info for ln(k) = ln(A) –
RT
those who do
Maths – how
- E A
1
can we get ln(k) = + ln(A)
values for EA R T
and A
y = m x + c
EA
Plot ln(k) against 1/T gives gradient = - and intercept = ln(A)
R
Acid-Base Equilibria
Arrhenius definition of an acid - hydrogen ions and oxonium ions (H3O+(aq))
soluble base = alkali
alkaline solutions have relatively high [OH-(aq)]
define pH using an equation NOT in words as it is more certain to get full marks.
pH of monoprotic (release a single proton into aqueous solution) acids e.g. HCl (note: pH’s
lower than 1, including –ve values, are possible)
you should be able to calculate pH after a strong acid of known volume and concentration (or
pH) is diluted by a known volume of water
Kw
[OH-(aq)] =
[H (aq) ]
[H2O] ~ constant
given that it is a weak acid we can assume the degree of dissociation is minimal hence:
[acid]equilibrium ~ [acid]initial
-
[H (aq)][A (aq)]
Ka = Kc[H2O] =
[HA(aq)]
2
Ka = [H (aq)]
[HA(aq)]
pKa = -log10Ka
Ka = 10- pKa
relatively higher Ka / relatively lower pKa = stronger acid (given the same concentration)
value is independent of concentration and therefore more useful
you should be able to calculate the pH of a weak acid of known concentration using Ka and
calculate Ka from the pH of a weak acid of known concentration
Titration Curves
you should also be able to calculate the pH at any point in the addition of sodium
hydroxide to a monoprotic acid (and visa-versa) including weak acids
typical errors to avoid are not converting to moles and getting the stoichiometric ratio
wrong
most likely you will forget to use the total volume of the solution created and thus get
the concentration wrong and therefore the pH
another likely error with a weak acid where xs alkali has not been added is assuming
that the remaining acid is fully dissociated i.e. forgetting to use Ka to determine [H+(aq)]
equivalence point is where two solutions have reacted in stoichiometrically the correct molar
ratio – this will be the vertical point on the titration curve where the pH changes markedly
pH’s at equivalence point and appropriate curves for:
http://www.avogadro.co.uk/chemeqm/acidbase/titration/phcurves.htm
pay particular attention to the position of the initial pH for strong and weak acids and look
carefully at how it changes at the start
also carefully note the position of the equivalence point – the mid point of the vertical section
finally ensure that a sensible final pH is shown to reflect the use of a strong or a weak base.
you should be able to calculate concentrations of an unknown acid or alkali from the results
of a titration – pretty much as was the case for AS level – but there will be more likely hood
of diprotic acids cropping up (e.g. sulphuric acid)
at the half equivalence point (half neutralisation point as stated in your text book) given that:
[HA] = [A]
Ka = [H+(aq)]
pKa = pH
the half equivalence point can be determined practically by determining the pH at half the
equivalence point (half the volume) from a plotted titration curve
note that it is not half the pH value itself at the equivalence point that is used!
alternatively a titration can be repeated with half the volume of the already determined
equivalence point and the pH then measured using a pH meter
indicators can only be used for a titration curves with a vertical section of >2 pH units
suitable indicators for acid-base titration’s will have an end point and range that lie within
that vertical section i.e. will thus exhibit a sharply defined colour change
pH meters can be used on coloured solutions
indicators are weak acids
-
[H (a q ) ][In (a q ) ]
Ka (or Kin) =
[HIn (a q ) ]
pKa = pKin = pH
Buffer Solutions
the effect of pH changes e.g. lemon juice and the proteins in milk
buffers are designed to maintain pH stability
you must understand buffer solution in terms of the response of an equilibrium system to the
addition of hydrogen or hydroxide ions
Acidic Buffer
Basic Buffer
Carbonic acid-Bicarbonate Buffer in the Blood is by far the most important process for
maintaining the acid-base balance (in our bodies there are also phosphate and protein
buffers).
when [HA] = [A-] the buffer solution is equally able to deal with the addition of acid and base
by equal sized reservoirs
for this reason a weak acid with a pKa relatively close to desired pH is selected for more
effective buffering (see the calculations in the next section)
HA ⇋ H+ + A-
-
Ka = [H (aq)][A (aq)]
[HA(aq)]
but [HA] ~ [ACID]i and [A-] = [salt]
[H (aq)][SALT ]
Ka =
[ACID)]
Will the dilution
[ACID] of a buffer
[H+(aq)]= Ka solution change
[SALT]
the pH?
it is assumed that the volume of the weak acid solution is unchanged by the addition of a
small quantity of its solid salt
since all particles are present in the same total volume of solvent we can make life easier by
appreciating that the acid to salt:
the best buffer will be that obtained at half the equivalence point:
[ACID] = [SALT]
and so [H+(aq)] = Ka
pH = pKa
equimolar amounts of acid and salt produces a buffer solution with a pH of the same
numerical value as pKa
you should be able to determine the required combination of acid and salt to produce a buffer
solution of a given pH
you should also be able to demonstrate by calculation that adding acid or alkali to a buffered
solution changes the pH by less than for an un-buffered solution
How Science
Organic Nomenclature Works: H
displayed formula – every bond and every atom should be shown in examinations!!!
structural formula e.g. CH3CH2CH2OH
skeletal formula may be useful for prospective medical etc students
it is important that you understand the difference between 2-D displayed formula and the
actual 3-D molecular shape as this will prove particularly relevant later
look for the longest chain NOT the longest ‘straight’ chain of carbons
start numbering at the end of the chain that results in the lowest numbers in the name or
for the primary functional group position
alphabetical order is used where more than one type of functional group or branch is
required in the prefix
mono, di, tri and tetra indicate multiple functional groups or branches of a given type (don’t
change alphabetical order)
commas and dashes are important - so learn how to do this correctly !!!!
An “a” is added if inclusion of di, tri, etc., would put two consonants consecutively: “buta-
1,3-diene”, not “but-1,3-diene” “propanenitrile, not propannitrile or propanitrile.)
you will need to aware of nomenclature examples of the following (including cyclic
variations):
Isomerism
isomers have the same molecular formula but different chemical and/or physical
properties
remember that there are a number of ways in which isomerism exists that you have already
met:
UNIT 1
isomers
UNIT 2 UNIT 4
position chain functional geometrical optical
group
Structural Isomerism
structural isomers have the same molecular formula but different structural formula
one form of structural isomerism is called chain isomerism – unbranched chain and
branched chain – i.e. different hydrocarbon skeleton
e.g. How many versions of C4H8 can you find that represent structural isomers?
functional groups that are present at different positions are called positional isomers
(there will be different numbers in the name)
functional group isomerism exists where the molecular formula is the same but different
functional groups (and therefore chemical properties exist)
Stereoisomerism
Stereoisomers have the same molecular and structural formula but differ in the spatial
arrangement of their atoms.
How Science
Geometrical isomerism Works: A
Geometrical isomers have the same molecular formula, same structural formula but a different
spatial arrangement of the atoms due to the non rotation of the carbon-carbon double bond
the two molecules on the left above are identical even though there is a carbon-carbon double
bond as simply flipping vertically makes them super imposable
across a carbon-carbon double bond each carbon in turn must have different substituent’s
it doesn't matter whether the two groups are the same e.g. in the example on the right no
amount of flipping or rotating makes them super imposable.
For geometrical isomerism to be possible both carbon atoms on the double bond must have
different atoms/groups attached to themselves, however, the carbon atoms can still both be
identical in that respect.
where the two atoms directly bonded to the carbons of the double bond with the largest
atomic numbers (highest priority) are diagonally opposite then it is deemed an E isomer
where the two atoms directly bonded to the carbons of the double bond with the largest
atomic numbers (highest priority) on the same side then it is deemed an Z isomer
if on one of the carbons the atoms directly bonded are identical then to establish the
highest priority grouping a tie break situation arises in which you look at the next
highest priority atom attached to each of them e.g -CH2Br beats CH2Cl and so on
take care here when using older text books as some molecules deemed ‘trans’ in the old
system would actually be ‘Z’ in the new system i.e. across the double bond in one system
does not directly yield across the double bond in the other e.g. 3-bromobut-2-ene
Example: but-2-ene
Step 1: split the alkene Step 2: assign the relative Step 3: look at the relative
priorities. positions of the higher priority
The two attached atoms are groups : same side = Z,
C and H, so since the atomic hence (Z)-but-2-ene.
numbers C > H then the -CH3
group is higher priority.
The two attached atoms are C and H, so since the atomic numbers C > H then the -CH3 group
is higher priority.
Therefore the two high priority groups are on the opposite side, then this is (E)-but-2-ene.
E-Z transformations are possible given an energy source e.g. photochemistry and eyesight:
nerve impulse
to the brain
CH3 CH3 CH3
Optical Isomerism
Optical isomerism exists where there is an asymmetric (i.e. chiral) carbon with four different
groups attached.
Optical isomers are non-super imposable molecules (enantiomers) which are mirror images of
one another.
don’t just put ‘mirror images’ as they can sometimes be superimposable where a plane
of symmetry exists
if two groups are the same i.e. there is a plane of symmetry then a simple rotation yields the
same spatial arrangement so they are not enantiomers
many chemicals synthesised in the lab produce equal amounts of both enantiomers (see
lactic acid later) which is called a racemic mix
this is because the reagents are not stereo specific (rather like a left handed screwdriver)
however, living organisms tend to manufacture one enantiomer in preference to the other as
determined by the reactive sites of the optically active enzyme used to construct it
enzymes are stereo specific reagents
the way that these enantiomeric molecules interact with biological systems can be different,
for example:
a racemic mix consists of a 50:50 mix of both isomers and this will therefore NOT rotate
plane polarised light as the two enantiomers cancel one another out
How Science
Works: L
How science works Page 62 The thalidomide tragedy
Summary Questions Page 59 1-4
Exam Style Questions Page 64 2, 4, 5
Physical properties
lower Mr aldehydes and ketones are miscible with water due to polar C=O bonds ability to
hydrogen bond with water molecules
higher Mr molecules have greater VdW with one another due to increasing size of
hydrocarbon tail hence miscibility is reduced for energetic reasons
Preparation
tests are based on the fact that aldehydes can be easily oxidised to a carboxylic acid while
ketones cannot be.
Care: The above test is only applicable if it is clear that the unknown sample is not a primary
or secondary alcohol.
writing balanced redox equations under alkaline conditions is a little more involved than
acidic conditions but you will find an excellent strategy on CHEMGUIDE – see the link
below
FEHLINGS’ TEST
TOLLENS’ REAGENT
strictly speaking you will get the carboxylate anion RCOO-(aq) under alkaline conditions
rather than the carboxylic acid itself
additionally it’s worth knowing that methanoic acid (which has a hydrogen present HCOOH)
can be oxidised to carbon dioxide via carbonic acid H2CO3 which then easily breaks down
into CO2 and H2O (see if you can work out the equations)
you should be aware of changes in the IR spectra during the oxidation reactions of
compounds containing one or more oxygen atoms (and also the reduction reactions of said
molecules)
Nucleophilic Addition
polar nature of the carbonyl group - you would be wise to revise electro negativity and the
nature of nucleophiles
NA
Reaction with Hydrogen Cyanide
note: an extra carbon is introduced into the chain so this is an important synthesis step
mechanism for reaction = nucleophilic addition
a racemic mix is produced – i.e. one that is 50:50 of both isomers and this will therefore
NOT rotate plane polarised light in this case as the two enantiomers cancel one another out
symmetrical ketones do not yield enantiomers as no chiral centre is present
lactic acid synthesised this way will exist as racemates BUT that produced biologically will
not be since enzymes are stereo specific yielding only one optical isomer hence this DOES
rotate plane polarised light.
Nomenclature
be aware of different ways to write the acid functional groups RCOOH, RCO2H etc
benzenecarboxylic acid C6H5CO2H
general structural formula of esters: RCO2R` e.g. CH3CO2CH2 CH2CH3
you should be able to work out the acid/alcohol used to make an ester and visa versa
esters and carboxylic acids are functional group isomers (easily distinguished by IR or nmr
– see later - or a simple chemical test using sodium carbonate and testing for evolved CO2)
Physical properties
lower members of the carboxylic acids and esters are miscible with water due to hydrogen
bonding with water
higher members are less miscible with water as the extent of VdW with themselves becomes
prevalent (they are more soluble in sodium hydroxide solution – do you know why?)
most carboxylic acids are crystalline solids (hydrogen bonding) whilst esters are typically oils
and fats (no hydrogen bonding) compared to similar sized hydrocarbons
melting points can be used to identify and determine the purity (to some extent) of organic
solids
orange dichromate(VI) ions (Cr2O72-aq)) are reduced to green chromium(III) ions (Cr3+(aq))
A word about REAGENTS: When the examiner asks for a reagent then it is the name on the bottle
NOT the active particle introduced e.g. H+(aq) is not a reagent but H2SO4(aq) is.
the latter is a useful test for the presence of –COOH for which you will OBSERVE
effervescence and that the gas evolved turns limewater (Ca(OH)2(aq)) cloudy and thus
INFER that CO2(g) was produced suggesting a carboxylic acid.
acid catalysed esterification with an alcohol is relatively slow and gives a poor yield
ethanol + ethanoic acid ethyl ethanoate + water reflux under heat with cH2SO4
catalyst
acid + alcohol ester + water
Hydrolysis of Esters
initiated by nucleophilic attack by the water molecule on the Cδ+ of the carbonyl group
alkali (hot NaOH) catalysed (saponification) hydrolysis is quicker and goes to completion
sodium salt of the carboxylic acid is produced since the acid produced reacts with the sodium
hydroxide which will drive the equilibrium RHS as acid is removed from the system
adding xs sulphuric acid protonates the alkanoate anion carboxylic acid
Uses of Esters
solvents – e.g. ethyl ethanoate for nail varnish
they evaporate relatively easily since there is no hydrogen bonding
esters have pleasant smells (unlike carboxylic acids which typically have unpleasant smells –
rancid fats – ask to smell some butanoic acid – you’ll get the idea) so are used in perfumes
and in the food industry as flavourings:
The cost of synthesising esters is often far less expensive than extracting them from
natural sources
2-methoxyphenol is a waste product from the paper industry and can be used to make methyl
vanillin (4-hydroxy-3-methoxybenzaldehyde) an artificial vanilla – by the end of module 4
you might be able to draw its structure and suggest a possible synthesis strategy (although the
industrial process is more complex)
plasticizers – added to plastics (e.g. PVC) to make them softer and more flexible as they
weaken the IMF between polymer strands allowing them to slide over each other more
readily (loss over time makes the plastic brittle)
some phthalate based plasticizers have a possible association with birth How Science
defects although this is still a subject of some disagreement Works: I
animal fats + vegetable oils are triesters of propane-1,2,3-triol (glycerol) and fatty acids
(long chained carboxylic acids)
they are triglycerides - three alcohol groups esterified by up to three different carboxylic
acids (take care with the hydrolysis equation regarding the actual products e.g. under alkaline
conditions the anion of each acid group will be formed and each of these could be different)
oils have a higher degree of unsaturation cf fats (research E-Z isomerism and trans fats)
a greater number of double bonds reduces the relative flexibility (due to restricted rotation) of
the molecule which in turn reduces the overlap efficiency of intermolecular forces
if a triglyceride undergoes alkaline hydrolysis (NaOH(aq))(saponification) then the salt of a
fatty acid is produced e.g. sodium octadecanoate which is also known as sodium stearate and
better known as a soap
being ionic, soaps are soluble
the carboxylate anion RCOO- released is miscible
with water (due to the hydrophilic carboxylate
group) and miscible with grease (due to its
hydrophobic tail) hence can solvate grease into
water allowing its removal
soap is precipitated out of solution by adding xs
common salt (salting out) – which can be
understood from an equilibria point of view
Glycerol (glycerine)
a renewable fuel made from oils obtained from vegetable matter (e.g. rape seed) which
generally consist of a combination of any three of five common carbon chains linked by a
glycerol structure
methyl esters are produced by reacting these oils with methanol and a strong alkali at around
60oC
this is called base-catalysed transesterification
the methyl groups replace the glycerol structure on each of the fatty acids
Note: there may be three different methyl esters produced but the general formula of each is:
the ester produced does not readily mix with the propane-1,2,3-triol co product so can be
separated using a separating tank or a centrifuge
any remaining glycerol can be extracted using water (hydrogen bonding)
there may be some soap bi-product so further processing will be necessary to achieve a level
of purity acceptable for a biofuel
rape seed (the yellow stuff you see in fields) produces rape methyl ester (RME) which is very
similar to the diesel obtained from crude oil
this can be used directly or as a small % of filling station diesel
both are readily attacked by nucleophiles (book error on 79) due to very polar carbonyl group
the polarity of which is increased by the electron withdrawing effect of X
thus this group of compounds are more useful than carboxylic acids in synthesis due to their
high reactivity due to the enhanced δ+ of the carbonyl carbon and since -X is a good leaving
group cf –OH
Hydrolysis NAE
very exothermic reaction, steamy fumes of hydrogen chloride are produced even when
exposed to air (due to the reaction between HCl and water vapour), hence anhydrous
conditions essential with acyl chlorides and must be stated in exams
reaction is faster than with haloalkanes due to additional polarising effect of C=O
hydrogen chloride fumes can be tested for using:
conc. ammonia a drop at the end of a glass rod will create a white
smoke of ammonium chloride
silver nitrate solution a drop at the end of a glass rod will go cloudy as white
silver chloride is precipitated
yield of ester better than with carboxylic acid since reaction goes to completion
NOTE: acyl chlorides form esters with the phenol group unlike carboxylic acids. The
lone pair of the O in phenol is less readily available since these electrons are
delocalised into the ring system hence reducing the electron density and the thus
the effectiveness of phenol as a nucleophile (higher activation energy)
mechanism for reaction with an alcohol - ester formation is very similar to that with water
treat the alcohol as RO-H cf water as HO-H so RO- is added to the carbon rather than HO-
NOTE: H is not abstracted by Cl-
(i) the product (an acyl derivative) is a white crystalline solid with a sharp melting point
- can be recrystallised and used in the identification of the original amine
(ii) suggest reagents and mechanism for the synthesis of paracetamol N-(4-
hydroxyphenyl)ethanamide
How Science
The Synthesis of Aspirin Works: I, J
(aspirin is 2-ethanoyloxybenzoic acid – don’t panic you wont be asked for this on the exam)
the benefits of willow bark, which contains salicylic acid (2-hydroxybenzoic acid) a similar
compound to aspirin, have been known for millennia e.g. Hippocrates (~460 B.C - 377 B.C.),
African Hottentots and North American Indians
it acts as an analgesic (pain killer) and has an anti-pyretic effect (body temperature)
salicylic acid was first isolated around 1829
the next step was to find a way to synthesise it rather than rely on extraction from a natural
source as this can be problematic:
the source might be rare, or seasonal, or have a low concentration, or have harmful
contaminants
in 1860 it was synthesised from phenol (a by product of the production of town gas from
coal) using the Kolbe process (NaOH and high pressure CO2)
but the problem was that it was tough on stomachs so alternatives with a similar structure
(hence retaining the benefits) were searched for
aspirin itself had been synthetically produced in 1853 by a French chemist named Charles
Frederic Gerhardt but he didn’t realise its potential and took it no further
in 1898, a German chemist named Felix Hoffmann rediscovered Gerhardt's formula
he gave it to his father who was suffering from the pain of arthritis and with good results (he
had tried other formulations before that!!) so convinced the German pharmaceutical company
Bayer to patent it in 1900 (the patent was ignored by the allies during WW1 and thereafter
– along with the patent they held for heroin!)
its sales increased dramatically during the Spanish Flu epidemic of 1918
aspirin can be synthesised from salicylic acid using ethanoyl chloride or ethanoic anhydride
NAE
ethanoyl chloride + 2-hydroxybenzoic acid aspirin + HCl
(salicylic acid)
both are more readily attacked by nucleophiles than the corresponding acid
acid anhydrides offer certain advantages over acyl chlorides, despite being less reactive, in
that they are:
Aromatic Chemistry
involves compounds containing a benzene ring (aka arenes look out for C6H5-)
empirical formula CH, Mr =78, molecular formula C6H6
Kekule did propose a cyclic structure – but it could not account for some major aspects of the
chemistry of Benzene:
1. no electrophilic addition reactions (e.g. with Br2(aq) in the dark) unlike alkenes
2. you don’t get two isomeric (1,2) disubstituted compounds
3. X-ray diffraction studies found intermediate – between double and single – and equal C-C
bond length i.e. a symmetrical structure
4. enthalpy of hydrogenation (208 kjmol-1) is less than 3 x cyclohexene (360 kjmol-1)
Physical properties
non-polar colourless liquid and does not mix with water (no hydrogen bonding)
boiling point similar to 6 carbon aliphatic hydrocarbons but melting point is higher a planar
structure allows better packing therefore more effective VdW.
Nomenclature
some names also use ‘phenyl’ or variations of it when the benzene is regarded as a side chain
take heart – naming aromatic compounds is complex but you will only have to deal with
simple examples as it is far more important that you understand the chemistry!
Electrophilic Substitution
mechanism of formation of NO2+ the nitronium (old name = nitryl) cation (sulphuric acid
acts as a homogeneous catalyst) ES
methylbenzene 2(and 4)-nitromethylbenzene cH2SO4/cHNO3 refluxed at 50oC
the methyl group is 2, 4, and 6 directing and activates the ring towards electrophilic
substitution (hence faster rate) since it donates electron density into the ring thus making it
relatively less stable and more susceptible to attack by electrophiles.
ES
further substitution requires more vigorous conditions (higher acid conc. and temperature) as
the nitro group deactivates the ring towards electrophilic substitution by withdrawing electron
density from the ring (i.e. increasing the extent of delocalisation thus further stabilising the
ring) – TNT is an explosive
the above reaction is much simplified – (whilst this equation is acceptable do you see why the
initial product would not be phenylamine? – a possible A* question perhaps?)
phenylamine is important for the production of AZO dyes since the end of 19th century (these
replaced the old technique of mordant dying – why not read about this – it is interesting)
Friedel-Crafts Acylation
you should be able to write a full balanced equation for the above
Amines
nomenclature of primary, secondary and tertiary amines (by the way amine has ONE m in
it!!!)
note how this differs from alcohols and haloalkanes
Physical properties
boiling points are elevated by the ability to hydrogen bond but are lower than similar sized
alcohols due to the relative electronegativity of O and N compared (ASK if you don’t
understand the significance of this)
lower members are gases
liquid amines smell like rotting (fishy) flesh – adding acid removes this smell – WHY?
smaller primary amines are water soluble (hydrogen bonding) producing alkaline solutions
solubility decreases with chain length (as with alcohols) due to increased mutual VdW
phenylamine is not very soluble in water as the VdW between the rings is significant
compared to hydrogen bonding between the amine group and water
produce alkaline solutions in water when they dissolve
Basic properties
ethylamine is more basic than ammonia due to +I inductive effect of the alkyl group (its
also a better nucleophile than ammonia - see alkyl halides)
this explains the relatively more basic nature of small secondary amines but this does not
hold true for tertiary amines where reduced solubility is a factor
phenylamine is less basic than ammonia since the lone pair on the nitrogen is less available
due to delocalisation in the ring structure – diagram
(phenylmethyl)amine is as basic as primary amines as the N is NOT bonded directly to the
ring (note brackets in name – why ?)
pKa value of conjugate acid increases (i.e. is poorer) with increased basicity of the conjugate
amine
solvation of insoluble phenylamine achieved by the addition of HCl to form a soluble salt
phenylammonium chloride (reversed by adding NaOH)
Preparation
From haloalkanes
NS
bromoethane ethylamine alcoholic solution of NH3 under pressure
(lots of by-products so not a good method)
if xs bromoethane is used, since the ethylamine produced is also a nucleophile (stronger than
ammonia due to the +I inductive effect of the alkyl group) it can react with the xs
bromoethane to give diethylamine
further substitution can then occur to produce: triethylamine and tetraethylammonium
bromide (a quaternary ammonium salt cf ammonium ions)
note that acyl chlorides only yield primary amide (mechanism reminder) – lone pair
withdrawn by strong d+ on C due to the polarity of C=O caused by the electronegativity
of the O
From nitriles
(note: at AS you were also told that acid hydrolysis of nitrile yields a carboxylic acid)
LiAlH4 but not NaBH4 (not a powerful enough reducing agent) can also be used (don’t put H2 in
balanced equation in this case!!)
Aromatic Amines
Uses of Amines
Amino acids
there are 20 important naturally occurring amino acids (amine is on the C next to the acid
group –CO2H)
R can vary
R=H glycine
R = CH3 alanine
R = CO(OH)CH2
aspartic acid
etc
you should recognise that there is a CHIRAL centre hence amino acids exhibit optical
isomerism (name the exception)
some amino acids have been identified in space (those of you who are interested in science
might read the next link)
http://www.newscientist.com/article/dn7895-space-radiation-may-select-amino-acids-for-life.html
C C OOH
CH
2
Zwitterions
Zwitterions are amphoteric i.e. they exhibit both acidic and basic properties in solution
because of the two functional groups
they thus form salts with both acids and bases (note all similar groups ionised as
appropriate)
amino acids can thus act as buffers (hence regulate pH)
http://www.saburchill.com/IBbiology/chapters01/003.html
Amino acids exist as zwitterions in the solid state and thus have strongly ionic character
this explains their high solubility in polar solvents e.g. water
it also explains the high MPt (white crystalline solid when pure)
MPt too high to be accounted for by hydrogen bonding alone - supporting existence of
Zwitterions and ionic nature of amino acids in the solid state
peptide (amide) links are formed between 2 amino acids by condensation reactions (where
a small molecule such as water is eliminated) to form a dipeptide
hydrolysis of proteins is achieved by refluxing with acid, base or enzyme catalyst (cf
hydrolysis of an amide) in effect reversing the process shown in the diagram above
the liberated amino acids can then be separated by paper chromatography (developed by
treating with ninhydrin which colours amino acids violet
some enzymes are selective and only partially hydrolyse certain proteins enabling amino acid
sequences to be identified
enzymes are themselves proteins and are very specific in what they catalyse (substrate) due
to their shape
their shape is dependent on hydrogen bonding hence their activity is sensitive to elevated
temperatures where they are denatured
Polymerisation
Addition Polymerisation
ethene poly(ethene)
propene poly(propene)
heat, pressure, catalyst
chloroethane poly(chloroethene) (PVC) in all cases
Condensation Polymerisation
Polyesters
commonly just called ‘polyester’ PET, poly(ethylene terephthalate) was initially used as a
fibre (e.g. Terylene and Dacron)
it is now used extensively in plastic containers e.g. for fizzy drink bottles – it does not smash
on impact
you can find out more about plastics from renewable raw materials and biologically
degradable plastics at this site (its also a good example of (or idea for) an EPQ project!):
http://www.rsc.org/education/teachers/learnnet/green/docs/plastics.doc
Polyamides
kevlar is an example of an aromatic polyamide and is made from the monomers benzene-1,4-
dicarboxylic acid and benzene-1,4-diamine
here is a scuba diving site that has an excellent overview of natural and synthetic polymers
– have a look it is very good: http://njscuba.net/artifacts/matl_polymers.html
non biodegradability means they last a long time but you can use landfill – not ideal though
combustion yields toxic and greenhouse gases e.g CO and carbon particulates, NO2 and
HCN from polyurethane in older upholstery or HCl and dioxins released through combustion
of halogenated plastics such as PVC and of course there will always be CO2 produced
recycling is expensive as the plastics must be identified and separated from other waste
energy production is an option but as this involves combustion there will be CO2 produced
using as chemical feedstock after cracking
recycling these materials e.g. terylene will save on natural resources and energy in their initial
production (as well as reducing the need for landfill), however, as they are biodegradable
their structural integrity will diminish after repetitive usage
as with polyalkanes the cost of collection, separation and transportation (require energy and
are labour intensive) must be taken into account
Aliphatic synthesis
You should be able to write full chemical equations, and identify the type for all the reactions listed:
Mechanisms: Nucleophilic Addition NA, Nucleophilic Substitution NS, Electrophilic Addition EA,
Nucleophilic Addition-Elimination NAE, Free Radical Substitution FRS or Elimination E.
ethene + H2 ethane
Ni catalyst, ~200oC (catalytic hydrogenation)
Alcohols carbonyl (aldehyde and ketone), carboxylic acid, ester, haloalkane, alkene
ethanol ethene + H2 O
heat with excess cH2SO4 at 170oC
Esters carboxylic acids (or its salt – look for OH-(aq)) and alcohol
Aromatic Synthesis
Electrophilic Addition EA, Electrophilic Sustitution ES, Nucleophilic Addition-Elimination NAE
Modification of substituents
Polymerisation
phenylethene poly(phenylethene)
free radical peroxide initiator, high pressure
Amine
Nitrile
Haloalkane
(hydroxynitrile) Amide
(polyamide)
Ester
(polyester)
Reagents/conditions
Mechanism required
Mr Lund also 2015
03 March
55
A2 Unit 4 Kinetics, Equilibria and Organic Chemistry
To ~ 1 cm3 of the substance under test add ~ 1 cm3 of acidified (1 mol dm-3 sulphuric acid) potassium
dichromate solution then heat gently in a water bath. Acidified purple potassium
Redox reaction in which orange Cr2O72- is reduced to green Cr3+ manganate(VII) will be
Cr2O7 (aq) + 14H (aq) + 6e 2Cr (aq) + 7H2O(l)
2- + - 3+ decolourised in a similar test
Tollens’ Reagent (Silver Mirror Test) Test for aldehydes NOT ketone
To ~1 cm3 of your sample add ~ 1 cm3 of Tollen’s reagent* and warm in a hot water bath.
(*to ~2 cm3 of ~ 0.1 mol dm-3 silver nitrate solution add ~2.0 mol dm-3 sodium hydroxide solution 1
drop at a time until a brown precipitate just forms. Add ~2.0 mol dm-3 ammonia solution to it
dropwise until the precipitate just dissolves - (ammoniacal silver nitrate)).
NOTE THAT ALCOHOLS DO NOT GIVE A POSITIVE RESULT WITH THIS TEST
To a small quantity of the unknown substance in a boiling tube add ~1 cm3 of sodium carbonate
solution. Test any gas evolved using a drop of lime water at the end of a glass rod.
Acidified Silver Nitrate Solution Test for alkyl halides Don’t confuse with Tollen’s!
To test for an alkyl halide, the halogen atom must first be released as a halide ion by hydrolysis.
Dissolve ~ 1 cm3 of the alkyl halide in ~1 cm3 of ethanol, then add ~ 1 cm3 of sodium hydroxide
solution and warm in a water bath.
Add ~ 1 cm3 of silver nitrate solution that has been acidified with dilute nitric acid (this removes
excess OH-(aq) which would otherwise precipitate out Ag2O(s) thus masking the test results).
Relative rates of hydrolysis of alkyl halides are: iodo > bromo > chloro
Mass Spectrometry
this provides us with:
vaporisation
ionisation
acceleration
deflection
detection
you must be able to interpret simple mass spectra to determine the elements
present from their relative isotopic mass and also their relative abundance
the value of the relative isotopic mass can be read directly from the m/z value of a given
peak on the spectra from a mass spectrometer
relative abundance is reflected in the heights of the peaks
when a molecule is subject to ionisation a molecular ion (parent ion), which is a radical
cation, is formed (note BOTH + must be shown on the molecular ion)
M(g) M(g)+ + e-
This molecular ion can then undergo fragmentation which produces a radical (not detected)
and a positive ion (detected) which are shown with a + only
can be either way around – so both give m/z peaks – but not necessarily in equal proportions
higher peaks correspond to more stable ions and the highest is called the base peak and this
determines the 100% benchmark on the spectra
m/z Interpretation Notes
value
15 CH3+ Not much use without other data
29 CH3CH2+ Look for a 2H quartet and 3H triplet on 1H nmr
31 CH3O+ Look for a 3H singlet on 1H nmr
43 HIGH peak = CH3CO+ 43 and 29 could be butanone
CH3CH2CH2+ 43 and 15 could be propanone
43 with no 15 ethanal or acyl chloride possible
Check IR for a carbonyl group
57 CH3CH2CO+ Check IR for a carbonyl group
77 C6H5+ 77 + 29 consider ethylbenzene
77 + 43 propylbenzene or phenylethanone
105 C6H5CO+ Benzaldehyde or Benzoic acid
f
o this is particularly useful in resolving aldehydes and ketones which will both give
similar >C=O wave numbers on IR
o isomeric acids and esters should be obvious from IR (look for OH peak) data but
again will give different fragmentation patterns
o isomeric esters will give similar IR and nmr and may need fragmentation patterns to
resolve – these are harder to do
chloro-alkanes will produce two molecular ion peaks when mono substituted in a ratio
commensurate with halogen abundance.
e.g. chloromethane gives M(g)+ peaks at 50 and 52 in a 3:1 ratio
Di-substituted chloro-alkanes will yield three molecular ion peaks of relative intensity for
dichloro 9:6:1 – those who do Maths Statistics will be able to explain that:
e.g. dichloromethane gives M(g)+ peaks at 85, 87 and 89 in a 9:6:1 ratio
high resolution mass spectra can distinguish between compounds with similar Mr e.g.
~123 for C6H5NO2 and C7H7O2
when dealing with mass spec in conjunction with either/both IR and nmr it is sensible to use
mass spec initially only to establish the Mr from which a reasonable estimate of the number of
carbons can be made
this is particularly useful with IR data to indicate whether there are any oxygen atoms in the
structure thus giving a maximum for the number of carbon atoms
IR Spectroscopy
used to identify certain functional groups in particular –OH and C=O in carbonyl
compounds, acids, alcohols and esters
beam splitting occurs in the IR spectrometer through a reference and the organic sample and
comparison determines the relative % transmission creating troughs in the spectra
molecules absorb IR energy at values corresponding to a natural vibration frequency
associated with asymmetric stretching and bending of the covalent bonds present which is
dependent on the bond energy and mass involved
(the ability of CO2 to do this is why there is a relationship between atmospheric CO2 and
global warming)
the spectra produced uses a scale of % transmission vs. wave number (cm-1)
1680 – 1750 cm-1 C=O strong and sharp with slight variations in position depending on
the type of compound (see table 1 page 139)
3230 – 3550 cm-1 O-H this is broad (due to hydrogen bonding) cf the narrow C– H of
2850 – 3300 cm-1
note that the O-H for alcohols lies further to
the left than for acids revealing the narrower
C-H absorption which might be partially or
totally obscured with an acid
used with mass spec they will help establish a maximum number of carbon atoms in the
compound by indicating the presence of at least one oxygen.
significant spectral changes involving the above upon redox or esterification can be revealing
regarding the functional groups present
the fingerprint region 400 – 1500 cm-1 is unique to each organic molecule
determination of the sample uses computerised comparisons with a database
impurities will yield additional peaks in this region
electrons shield the nucleus thereby reducing the effective magnetic field and requiring an
applied radio frequency of a lower energy to cause resonance
when electrons are withdrawn from a nucleus, the nucleus is deshielded and feels a stronger
magnetic field requiring more energy (higher frequency) to cause resonance as the energy
gap is greater
NOTE: If the radio frequency is kept constant and the magnetic field varied instead to achieve
resonance then a relatively weaker magnetic field will be required for more deshielded carbon
atoms
the nmr spectra is based on the scale of chemical shifts relative to a standard reference
peak – tetramethylsilane
TMS has 4 carbon atoms in the same environment which produces a single strong peak
Si is relatively less electronegative than C so the electrons in the C-Si bonds are closer to the
carbons than in other organic compounds resulting in a peak on the spectrum at the extreme
right-hand side
Note: 3 carbons
thus, nmr provides information about a but 2 peaks carbon’s
electronic environment.
carbons attached to electron withdrawing
atoms/groups such as oxygen tend to 41 170 resonate at
higher frequencies yielding peaks 170 downfield
from TMS i.e. a higher (chemical shift)
the major differences that you will notice in 13C nmr in comparison to 1H-nmr spectra
include:
CDCl3. (i.e. hydrogen has been replaced by its isotope, deuterium) is commonly used as a
solvent (also see proton-NMR) and the line for this carbon is removed from the final
spectrum
1
H is far more abundant in organic compounds than 13C hence the spectra are much easier to
obtain
their resonance field strength will vary depending on the number of surrounding electrons
electrons shield the nucleus thereby reducing the effective magnetic field and requiring an
applied radio frequency of a lower energy to cause resonance
when electrons are withdrawn from a nucleus, the nucleus is deshielded and feels a stronger
magnetic field requiring more energy (higher frequency) to cause resonance
NOTE: If the radio frequency is kept constant and the magnetic field varied instead to achieve
resonance then a relatively weaker magnetic field will be required for more deshielded carbon
atoms
the nmr spectra is based on the scale of chemical shifts relative to a standard reference
peak – tetramethylsilane
TMS is used as
greater electron density results in relatively more shielding hence the requirement for a
higher external field to cause resonance
electronegative atoms e.g. oxygen (or unsaturated regions e.g. a benzene ring) cause
deshielding hence a lower external energy requirement
a proton free solvent is used e.g. CCl4, D2O CDCl3 (2H gives no peak)
non equivalent hydrogen’s on adjacent carbons will themselves behave as little magnets and
their effect can be seen on high resolution nmr
each creates a small magnetic field aligned with or against the external field – spin coupling
this creates small differences in the local field which modifies the radio frequency energy
required for resonance
hydrogen’s on the same atoms are identical and will not modify one another
NOTE: hydrogen’s bonded to an oxygen are not split and do not cause others to split
the more adjacent hydrogen’s there are, the more possible permutations exist
peaks are thus split into sub sets by neighbouring non equivalent H atoms
n+1 rule – if there are n H atoms in total on adjacent C atoms then the peak is split into
n+1 signals of relative intensities derived from Pascal’s triangle:
Summary Questions
Page 152 1, 2
INTEGRATED SPECTROSCOPY
you may be required to use data from more than one spectra for identification
on my CHEMISTRY - READ site I have placed a suggested flow chart
it would be useful for you to think about and develop your own strategy
IR will enable you to determine if there is/are one or two oxygen’s present
coupled with Mass Spectrometry this will allow you to establish a maximum number of
carbon atoms in the structure (which may also be derived from the M+ + 1 peak (satellite
peak) due to carbon-13) and may also indicate the number of hydrogen’s hence give clues to
the degree of saturation in the compound
fragmentation patterns in Mass Spectrometry are best left until needed or as a confirmatory
check
at this point you might want to write down the pieces of the jigsaw that are present and then
use nmr to work out what is connected to what
be alert to the possibility of carbons/hydrogen’s in identical environments e.g. in propanone
or in branched alkyl components
Sample spectra: http://home.clara.net/rod.beavon/spectra.htm
MS data
CHROMATOGRAHY
essentially the physical separation of the constituents of a mixture
a mobile phase (solution or gases called the eluent) flows through a stationary phase (a solid
or liquid supported on a solid) and in so doing the components of a mixture are separated as
they travel at different rates.
the more soluble a solid, the further (faster) it moves in a given time
the stationary phase will also determine the rate of progress of the components as a function
of its affinity for each component
hence the trick is to use a suitable combination of solvent and stationary phase to achieve the
separation of similar components
these can then be analysed separately using other techniques where required
Column Chromatography
the solid phase is a powder e.g. silica or alumina packed into a tube
a solvent (the eluent) is added at the top
the components of a mixture are separated as they travel at different rates down the column
so can be collected separately for further analysis
http://www.wfu.edu/academics/chemistry/courses/CC/index.htm
Gas-liquid Chromatography GC
this is particularly
useful in the
separation of
volatile liquids
a sample is
injected into the
device in which
there is a long
(typically 100 m)
thin (0.5 mm)
tube (coiled for
compactness)
containing the stationary phase (an inert powder coated with oil)
a carrier gas (unreactive e.g. N2 or He) is used as the eluent to provide the mobile phase
71
AS Chemistry Unit 2
72