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Chemistry
Equilibria
How Science
Works: A, B
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:
concentration (which can be easily understood using rates/collision theory)
temperature (EA will be larger for the endothermic process so it will be relatively more
favoured by a rise in temperature)
pressure (only applicable where there is an imbalance between the number of moles of
gaseous particles on either side of the equation)
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
Chemguide
[C]
aA
cC
dD
Kc =
[A]
eqm
a
eqm
[D]
[B]
d
eqm
b
eqm
Summary Questions
Exam Style Questions
bB
Page 21
Page 28
1-3
1
Summary Questions
Exam Style Questions
Page 24
Page 28
Chemguide
1
2
20 24
18 20, 22 - 27
Q 4 6, 8 - 13 on pages 18 27
Q 3 on page 33
Equilibrium equation
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
Temperature
increases
decreases
Exothermic reaction
Kc decreases
Kc increases
Endothermic reaction
Kc increases
Kc decreases
Kc and Catalysts
Page 26
Page 27
Page 28-29
Chemguide
How Science
Works: E, F
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:
Rate =
dt
d [ A]
dt
1 d[B]
2
dt
d [C ]
average rate
instantaneous rate (this is what the equations above depict) which is the gradient of
the tangent of the curve at selected values of concentration or time
initial rate is the instantaneous rate right at the start of a reaction
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
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.
initial rate
1
t
Page 5
Page 6
each reactant may or may not affect reaction rate (so its 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
moldm-3s-1
m and n are the order of reaction for each reagent (values are limited to 0, 1 or 2 at A-Level)
overall order = individual orders)
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
e.g.
2H2(g) + 2NO(g)
2H2O(g) + N2(g)
i.e.
[NO]2
The effect on
rate of the
change
here
..is raised
to this
power i.e.
its second
order wrt
to [NO]
moldm-3s-1
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:
note that if the order is 0 this term will not appear in the rate equation
e.g. A2BC0 = A2B x 1 = A2B
Maths tip:
Any number raised
to the power zero = 1
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)
moldm-3s-1
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)
Summary Questions
Page 9
Page 16
14
1
4 9, 14 - 16
46
Q1, 2, 3 on page 5-6
Order of reaction, rate expression, SN2
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
3H2(g) +
N2(g)
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
Summary Questions
Exam Style Questions
Page 13
1
Page 17 - 19 1, 3, 5
Chemguide
10 - 12
7 11
Q4 on page 8
Q1 on page 14
rate
distribution of energies amongst particles at different temperatures give rise to the MaxwellBoltzmann distribution curves based on the Arrhenius expression
k Ae
A
R
T
=
=
=
EA
RT
the main significance of this equation (which you dont 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
ln(k) =
ln(A)
EA
RT
ln(k) =
1
- E A
ln(A)
R T
x
EA
Page 17 - 18
Page 158
Chemguide
2,4
1
10 - 12
12 13
Q2-4 on page 14 - 15
Q1 on page 150
Arrhenius expression
Acid-Base Equilibria
HCl(g)
NH4Cl(s)
water is amphoteric
it behaves as an acid with NH3
and as a base HCl
variation of Kw
Summary Questions
[H+(aq)][OH-(aq)]
Page 31
Chemguide
pH Calculations
1-3
30 - 31
34 35, 36, 42 - 43
Q1 on page 35
Q6 on page 37
Brnsted, ionic product
define pH using an equation NOT in words as it is more certain to get full marks.
pH = -log10[H+(aq)]
pH of monoprotic (release a single proton into aqueous solution) acids e.g. HCl (note: pHs
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
pH of diprotic acids
[H+(aq)] = 2 x [H2SO4(aq)]
NOTE:
[H+(aq)] = 10- pH
Kw
[H
(aq)
Page 33
Page 31
Measuring pH
Questions 1 - 5
Page 50
Questions 3
Chemguide
32 35
38 40, 42 - 45
Q7 - 10 on pages 39 - 40
Q13, 14 on pages 37 38
Q 3, 4 on page 55
Q 7 on page 56
Strong acids pH
H3O+(aq)
H2O(l)
[HA(aq)][H
[H 3 O (aq)][A
2
A-(aq)
(aq)]
O (l) ]
[H2O]
constant
[A-(aq)]
[H3O+(aq)]
[H+(aq)]
given that it is a weak acid we can assume the degree of dissociation is minimal hence:
[acid]equilibrium ~
[acid]initial
[H (aq)][A
Ka
Kc[H2O]
(aq)]
[HA(aq)]
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
Summary Questions
Exam Style Questions
Page 38
Page 51
Chemguide
1-3
6
32 35
35 36, 40 42
Q11 - 12 on pages 41 - 42
Q 1 on page 55
Weak acid
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
pHs at equivalence point and appropriate curves for:
WASB
SASB
SAWB
WAWB
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)
Summary
Questions
Page 41
Chemguide
1-2
39 41
44 48
Q15 on page 45
Q 16 on page 48
Q 2, 8 on pages 55 - 56
Titration curves
at the half equivalence point (half neutralisation point as stated in your text book) given that:
[HA] =
Ka
=
pKa =
[A]
[H+(aq)]
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 titrations 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+(aq) + In-(aq)
HIn(aq)
[H
(a q )
][In (a q ) ]
Ka (or Kin)
at end point
[In-(aq)] = [HIn(aq)]
Summary Questions
Exam Style Questions
[HIn (a q ) ]
Kin
[H+(aq)]
pKa
pKin
Page 41
Page 50
Chemguide
1-2
4
39 - 41
49 51
Q17 - 18 on pages 50 51
Q 5 on page 56
Indicators
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
H+ + A-
Basic Buffer
+ H+
NH4+
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).
Added H+(aq) is removed as the
equilibrium shifts to the right
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)
Ka
[H (aq)][A
(aq)]
[HA(aq)]
but
[HA] ~ [ACID]i
Ka
[A-] = [salt]
and
[H (aq)][SALT
[ACID)]
[H+(aq)]=
[ACID]
[SALT]
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:
moles ratio
Ka
concentration ratio
the best buffer will be that obtained at half the equivalence point:
and so
[ACID]
[SALT]
[H+(aq)]
Ka
pKa
pH
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
Summary Questions
Exam Style Questions
Page 48
Page 49
Page 51
Page 160
Chemguide
1
1, 2
5
5
45 - 48
52 54
Q17 - 20 on pages 52 54
Q6, 9 on page 56
Buffer
How Science
Works: H
Organic Nomenclature
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 (dont
change alphabetical order)
commas and dashes are important - so learn how to do this correctly !!!!
An e is dropped if the next letter is a vowel: propan-2-ol, propane-1,2-diol
An a is added if inclusion of di, tri, etc., would put two consonants consecutively: buta1,3-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):
alkanesalkeneshaloalkanes
alcohols
aldehydes and ketones
carboxylic acids
esters
acyl chlorides
amines
amides
amino acids benzene and its derivatives
Summary Questions
Exam Style Questions
Page 56
Page 64
1-3
1
52 - 56
nomenclature
How Science
Works: H
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
structural isomers
position
chain
stereoisomers
UNIT 2
functional
group
UNIT 4
geometrical
optical
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)
e.g. propan-2-ol and propan-1-ol
functional group isomerism exists where the molecular formula is the same but different
functional groups (and therefore chemical properties exist)
e.g. propane-l-ol and methoxy ethane, but-2-ene and cyclobutane
Stereoisomerism
Stereoisomers have the same molecular and structural formula but differ in the spatial
arrangement of their atoms.
How Science
Works: A
Geometrical isomerism
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 substituents
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.
How Science
Works: H
How Science
Works: L
Find out about the food industry and trans fats and the
hydrogenation of vegetable oils.
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
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
light
to eye
CH3
CH3
CH3
CH3
CH3
CH3
CH3
O
Optical Isomerism
Mr Lund 03 March 2015
21
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.
dont 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:
carvone
limonene
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
Summary Questions
Exam Style Questions
Page 62
Page 59
Page 64
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
primary alcohol
aldehyde
secondary alcohol
ketone
tests are based on the fact that aldehydes can be easily oxidised to a carboxylic acid while
ketones cannot be.
Aldehyde
[O]
Carboxylic Acid
orange dichromate(VI) ions (Cr2O72-(aq)) are reduced to
green chromium(III) ions (Cr3+(aq))
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
warm with Fehlings solution
(an alkaline solution of a complexed
copper ion)
TOLLENS REAGENT
complex ion [Ag(NH3)2]+(aq) is reduced to Ag(s),
hence the silver mirror effect
strictly speaking you will get the carboxylate anion RCOO-(aq) under alkaline conditions
rather than the carboxylic acid itself
additionally its 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)
Summary Questions
Page 67
1-4
66 67, 69
65 67
Q 1 on page 66
Ionic alkaline, Tollens, Fehlings
Nucleophilic Addition
Reduction of Aldehydes and Ketones
NA
polar nature of the carbonyl group - you would be wise to revise electro negativity and the
nature of nucleophiles
aldehyde + 2[H]
primary alcohol
ketone + 2[H]
secondary alcohol
2-hydroxypropanenitrile
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
2-hydroxypropanenitrile + 2H2O + H+
2-hydroxypropanoic acid
(lactic acid)
NH4+(aq)
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.
Summary Questions
Exam Style Questions
Page 63
Page 70
Page 83
Chemguide
13
1-4
2
60 63, 68, 70
66 70, 57 62
Q 2 3 on pages 68
Q 4 -6 on page 70
Q 1, 3, 5 on page 82
Q 4 on page 149
Aldehydes, Isomerism
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)
Summary Questions
Page 73
14
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
71 - 73
71 75
Q 7 10 on pages 71 - 74
Carboxylic acids, Esters
carboxylic acid
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.
ethanoic acid
ACID
+
+
sodium hydroxide
BASE
sodium ethanoate
SALT
ethanoic acid
sodium carbonate
water
WATER
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.
Ca(OH)2(aq)
+
+
CO2(g)
CaCO3(s)
H2O(l)
acid catalysed esterification with an alcohol is relatively slow and gives a poor yield
acid
ester
alcohol
Summary Questions
Page 77
+ water
14
Hydrolysis of Esters
initiated by nucleophilic attack by the water molecule on the C+ 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
74 - 76
71 74
Q 11 on page 74
Carboxylic acids, esters hydrolysis
Uses of Esters
esters have pleasant smells (unlike carboxylic acids which typically have unpleasant smells
rancid fats ask to smell some butanoic acid youll get the idea) so are used in perfumes
and in the food industry as flavourings:
butyl butanoate
ethyl pentanoate
3-methylbutyl ethanoate
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)
How Science
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
Page 83
4
76 - 77
75
Fats and oils, soap, glycerol
nomenclature named after the parent carboxylic acid hence deemed acid derivatives (as are
esters and amides)
O
R
Acid anhydrides
X = OR
C
X
Acyl chlorides:
X = Cl
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 + of the carbonyl carbon and since -X is a good leaving
group cf OH
O
R
:Nu
Hydrolysis
NAE
ethanoyl chloride
water
ethanoic acid +
hydrogen chloride
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
Ethanoic anhydride +
water
ethanoic acid
ethanoic acid
ethanol
ethyl ethanoate
HCl
yield of ester better than with carboxylic acid since reaction goes to completion
NOTE:
NAE
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 HONOTE: H is not abstracted by Cl-
ethanoic anhydride
ethanol
ethyl ethanoate +
ethanoic acid
(i)
(ii)
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
suggest reagents and mechanism for the synthesis of paracetamol N-(4hydroxyphenyl)ethanamide
ethanoic anhydride
Summary Questions
Exam Style Questions
Page 82
Page 83
Chemguide
ammonia
ethanamide +
14
1, 3
78 - 81
76 83
Q 12 - 15 on pages 77 81
Q 1 8 pages 82 - 83
Acyl
ethanoic acid
How Science
Works: I, J
(aspirin is 2-ethanoyloxybenzoic acid dont 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 didnt 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
2-hydroxybenzoic acid
(salicylic acid)
aspirin
Ethanoic anhydride +
2-hydroxybenzoic acid
(salicylic acid)
aspirin +
ethanoic acid
ethanoyl chloride
HCl
NAE
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:
cheaper, less corrosive (no HCl liberated), less readily hydrolysed
Page 82
Page 83
Aspirin
1
82
81
Q 14 on page 81
Aspirin
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 dont 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)
Summary Questions
Exam Style Questions
Page 86
Page 93
13
6
84 - 86
84 - 87
Q 1 2 on page 87
Bonding benzene
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
methylbenzene (toluene)
chlorobenzene
nitrobenzene
ethylbenzene
benzaldehyde
(chloromethyl)benzene
some names also use phenyl or variations of it when the benzene is regarded as a side chain
phenol (instead of hydroxybenzene)
aminobenzene)
phenylamine
(aniline)
(instead
4-hydroxyphenyl ethanoate
of
2-hydroxybenzoic acid
2,4,6-trinitrotoluene
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!
Summary Questions
Page 88
14
87 - 88
Naming aromatic
mechanism of formation of NO2+ the nitronium (old name = nitryl) cation (sulphuric acid
acts as a homogeneous catalyst)
ES
methylbenzene
2(and 4)-nitromethylbenzene
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
phenylamine
cHCl/Sn or H2/Ni
C6H5NO2
6[H]
C6H5NH2
2H2O
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)
Page 90
Page 92
TNT
1, 3
89 - 90
88 - 89
Q 3, 4 on page 89
Electrophilic substitution, nitration
Friedel-Crafts Acylation
you should be able to write a full balanced equation for the above
benzene
ethanoyl chloride
Summary Questions
Exam Style Questions
phenylethanone
Page 91
Pages 92 93
Chemguide
1-4
2-5
91
91, 184
Q 7, 8 on page 91
Q 1 8 on pages 94 - 95
Acylation
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 dont
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
Summary Questions
Page 95
1-4
Basic properties
lone pair on N
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
ethylamine
hydrochloric acid
solvation of insoluble phenylamine achieved by the addition of HCl to form a soluble salt
phenylammonium chloride (reversed by adding NaOH)
phenylamine +
hydrochloric acid
Summary Questions
Exam Style Questions
Page 97
Pages 108 9
Chemguide
1-3
1
94 - 97
96 97, 99 - 100
Q 1, 2 on pages 96 97
Q 5, 6 on pages 99 - 100
Q 4 on page 104
Amine name, amine base
Preparation
From haloalkanes
NS
bromoethane
ethylamine
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
Ethanenitrile
RCN +
ethylamine
4[H]
reduction by H2/Ni
RCH2NH2
(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 (dont put H2 in
balanced equation in this case!!)
Aromatic Amines
benzene
phenylamine
Uses of Amines
Pages 100 - 1
Page 101
Pages 108
Chemguide
Sulfa drugs
1, 2
2-4
99 - 101
97 98, 101 - 105
Q 7 on page 103
Q 13, 5-8 on pages 104 - 105
Amine preparation, amine uses
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
CH
are
2
NH
CH
C
CH
C OOH
this does not necessarily mean plane polarised light is rotated the same way
if L(+) then D(-) for a given amino acid and L(-)/D(+) dont exist in our natural system
CORN law I have provided some info about this on my site it is not on the exam but it
may be helpful at your interview for medical school given the biochemical significance
Summary Questions
Page 103
Page 107
1, 2
1
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)
Adding H+
pH decreasing
you might be interested to find out how electrophoresis works by looking at this link
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
Pages 108
5, 8, 11
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
Pages 107
Page 107
Pages 109
Chemguide
Polymerisation
Addition Polymerisation
ethene
poly(ethene)
propene
poly(propene)
chloroethane
poly(chloroethene) (PVC)
phenylethene
poly(phenylethene) (polystyrene)
tetrafluoroethene
methyl 2-methylpropenoate
Summary Questions
Exam Style Questions
Page 114
Pages 122
Chemguide
perspex
1-4
4, 5
112 - 114
106 -108
Q 1-3 on page 106
Q 7, 8 on page 116
Addition polymerisation
Condensation Polymerisation
Polyesters
ethane-1,2-diol
(ethylene glycol)
benzene-1,4-dicarboxylic acid
(terephthalic acid)
PET
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
How Science
Works: I
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
1,6-diaminohexane +
hexanedioic acid
nylon-6,6
How Science
Works: I
you might be interested in the history of nylon its an ideal stocking filler for Xmas see:
http://www.cha4mot.com/p_jc_dph.html and http://inventors.about.com/od/nstartinventions/a/nylon.htm
Environmental Issues
How Science
Works: J
polyalkenes are saturated, have no polar bonds and have strong C-C and C-H bonds hence
they are relatively unreactive e.g. with acids, alkali or oxidants
this in turn makes them difficult to dispose of
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
Pages 120 - 1
Page 119
Page 121
Pages 121 - 123
Chemguide
115 - 120
108 -110
Q 4 - 8 on page 109 - 110
Q 1, 5 on pages 115 - 116
Condensation polymerisation
Aliphatic synthesis
You should be able to write full chemical equations, and identify the type for all the reactions listed:
Oxidation, Reduction, Addition, Elimination, Addition-Elimination (Condensation),
Substitution, Hydration, Dehydration, Hydrogenation, Dehydrogenation, Hydrolysis
Mechanisms: Nucleophilic Addition NA, Nucleophilic Substitution NS, Electrophilic Addition EA,
Nucleophilic Addition-Elimination NAE, Free Radical Substitution FRS or Elimination E.
Alkanes
haloalkane, alkene
methane
Cl2
chloromethane
FRS
ethene
HBr
bromoethane
EA
ethene
Br2
1,2-dibromoethane
EA
ethene
+
H2
ethane
Ni catalyst, ~200oC (catalytic hydrogenation)
+
Method 1
Method 2
Alkyl Halides
H2O
ethene
ethanol
EA
bromoethane
+
NH3
ethylamine +
HBr
heat with xs ammonia under pressure to minimise further substitution
NS
bromoethane
+
OH-(aq)
ethanol
reflux with dilute NaOH dissolved in water
NS
Br-
bromoethane
+
CN-
propanenitrile
+
boil under reflux with alcoholic NaCN or KCN (NOT HCN)
propanenitrile
+
4[H]
propylamine
reduction by H2/Ni
Br-
bromoethane
+
OH-
reflux with NaOH dissolved in ethanol
ethene
H2 O
NS
Br-
Alcohols
ethanol
+
[O]
ethanal
+
H2 O
mild conditions - K2Cr2O7(aq)/H2SO4(aq) distil off aldehyde as formed to prevent further oxidation to a
carboxylic acid
ethanol
+
2[O]
ethanoic acid
H2 O
propan-2-ol
+
[O]
propanone
H2 O
ethanol
+
ethanoic acid
ethyl ethanoate
+
reflux with glacial ethanoic acid and concentrated sulphuric acid catalyst
H2 O
ethanol
ethene
heat with excess cH2SO4 at 170oC
H2 O
ethanal
+
2[H]
ethanol
sodium tetrahydridoborate(III) (NaBH4) in aqueous ethanol
propanone
2[H]
NA
propan-2-ol
NA
ethanal
+
HCN
2-hydroxypropanenitrile
in alkaline solution to increase [CN-] as HCN is a weak acid
2-hydroxypropanenitrile + 2H2O + H+
Carboxylic Acids
NA
2-hydroxypropanoic acid
(lactic acid)
NH4+(aq)
water
WATER
a salt, ester
ethanoic acid
ACID
+
+
sodium hydroxide
BASE
sodium ethanoate
SALT
+
+
ethanoic acid
sodium carbonate
sodium ethanoate
ACID
METAL CARBONATE
SALT
+ water + carbon
dioxide
+ WATER + CO2
ethanol
ACID
+
+
ethanoic acid
ALCOHOL
ethyl ethanoate
ESTER
+
+
water
WATER
Esters
carboxylic acids (or its salt look for OH-(aq)) and alcohol
ethyl ethanoate
OH-(aq)
ethanoate ion
ethanol
ethanoate ion
+
H+(aq)
ethanoic acid
(protonation of the anion of a weak acid by a stronger acid think about the equilibria here)
Acyl Chlorides
ethonoyl chloride
+ H2O
ethanoic acid
ethanoyl chloride
+ ethanol
ethyl ethanoate
HCl
ethanoyl chloride
+ 2-hydroxybenzoic acid
(salicylic acid)
ethanoyl chloride
+ NH3
aspirin
ethanamide
NAE
HCl
NAE
HCl
NAE
N-ethylethanamide +
(secondary amide)
HCl
NAE
N-phenylethanamide +
HCl
NAE
Acid Anhydrides
ethanoic anhydride +
H2 O
2 ethanoic acid
ethonoic anhydride +
ethanol
aspirin
ethonoic anhydride +
ammonia
ethanamide
ethonoic anhydride +
4-aminophenol
(primary amine)
paracetamol +
(secondary amide)
ethanoic acid
ethanoic acid
ethanoic acid
Aromatic Synthesis
Electrophilic Addition EA, Electrophilic Sustitution ES, Nucleophilic Addition-Elimination NAE
nitrobenzene
cH2SO4/cHNO3 refluxed at 50oC (nitrating mixture)
H2 O
ES
methylbenzene
+
HNO3
cH2SO4/cHNO3 refluxed at 50oC
ES
benzene
+
ethanoyl chloride
AlCl3 catalyst anhydrous conditions
phenylethanone
HCl
ES
phenylamine
2H2O
phenylammonium chloride
H2 O
N-phenylethanamide +
HCl
NAE
HCl
NAE
Modification of substituents
nitrobenzene
cHCl/Sn or H2/Ni
6[H]
phenylamine +
HCl
phenylamine +
ethanoyl chloride
Polymerisation
phenylethene
ethanoyl chloride
ethane-1,2-diol
(ethylene glycol)
1,6-diaminohexane +
poly(phenylethene)
N-phenylethanamide +
benzene-1,4-dicarboxylic acid
(terephthalic acid)
hexanedioic acid
nylon-6,6
Terylene (a polyester)
Amine
Nitrile
(hydroxynitrile)
Haloalkane
Alkane
Alkene
Carbonyl
Amide
(polyamide)
Carboxylic
Acid
Acyl chloride
(Acid anhydride)
Alcohol
Ester
(polyester)
Reagents/conditions
Mechanism
required
also 2015
Mr Lund
03 March
55
OBSERVATION
INFERENCE
EXPLANATION
orange colourless
alkene
electrophilic addition.
product is colourless
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
manganate(VII) will be
Redox reaction in which orange Cr2O72- is reduced to green Cr3+
2+
3+
decolourised in a similar test
Cr2O7 (aq) + 14H (aq) + 6e 2Cr (aq) + 7H2O(l)
OBSERVATION
INFERENCE
orange green
1o or 2o alcohol
EXPLANATION
To ~1 cm3 of your sample add ~ 1 cm3 of Tollens 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)).
OBSERVATION
INFERENCE
aldehyde
EXPLANATION
+
Ag(NH3)2 (aq) + e- Ag(s) + 2NH3(aq)
aldehyde acid
NOTE THAT ALCOHOLS DO NOT GIVE A POSITIVE RESULT WITH THIS TEST
Fehlings Test
To ~1 cm3 of your sample add ~ 1 cm3 of Fehlings solution* (BLUE) and warm in a water bath.
(*made by mixing equal volumes of:
Fehlings A (dissolve 17g of CuSO4.5H2O in 250 cm3 of water) and;
Fehlings B (dissolve 86 g of Rochelle salt (potassium sodium 2,3-dihydroxybutanedioate (tartrate)
and 30 g of NaOH in 250 cm3 of water with gentle warming).
OBSERVATION
INFERENCE
EXPLANATION
orange-red precipitate
aldehyde
NOTE THAT ALCOHOLS DO NOT GIVE A POSITIVE RESULT WITH THIS TEST
Test for carboxylic acids
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.
OBSERVATION
INFERENCE
EXPLANATION
effervescence
gas evolved turns lime water cloudy
carboxylic acid
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).
OBSERVATION
white precipitate
soluble in ammonia
pale yellow precipitate
soluble in xs ammonia
yellow precipitate
insoluble in ammonia
INFERENCE
EXPLANATION
alkyl chloride
AgCl(s)
AgCl(s) + 2NH3(aq) Ag(NH3)2+(aq) + 2Cl-(aq)
AgCl(s)
AgBr(s) + 2NH3(aq) Ag(NH3)2+(aq) + 2Br-(aq)
AgI(s)
alkyl bromide
alkyl iodide
Relative rates of hydrolysis of alkyl halides are: iodo > bromo > chloro
Mass Spectrometry
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)
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
M(g)+
M(g)+ +
X(g)+
Y(g)
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
value
Notes
15
CH3+
29
CH3CH2+
31
CH3O+
43
57
CH3CH2CO+
77
C6H5+
105
C6H5CO+
77 + 29 consider ethylbenzene
77 + 43 propylbenzene or phenylethanone
Benzaldehyde or Benzoic acid
http://www.chem.arizona.edu/massspec/example_html/examples.html
Have a look at
these examples
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
Summary Questions
Exam Style Questions
Page 136
Page 159
Chemguide
1, 2
4
132 - 136
117 123
Q2 on page 138
Q1 6 on pages 118 - 123
Mass spectrometry
IR Spectroscopy
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)
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
Summary Questions
Page 138
Page 141
Chemguide
1, 2
1-3
137 - 141
124 127
Q7 10 on pages 124 127
Q 1 page 137
Q 5 on page 149
Infra red spectroscopy
is
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
carbonyl carbons
160-220
ppm
aromatic carbons
alcohols, esters, ethers
unsaturated aliphatic
saturated aliphatic
41
170
170
resonate at
downfield
C=O
110-160
50 - 90
90-150
5-40
C-O
C=C
C-C
ppm
ppm
ppm
ppm
the major differences that you will notice in 13C nmr in comparison to 1H-nmr spectra
include:
1.
2.
Note: 3 carbons
but 2 peaks
carbons
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
Summary Questions
Page 145
1, 2
143 - 145
Carbon 13 nmr
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
o it provides a single strong signal from 12 equivalent H atoms
o it is chemically inert
o the peak will be up field of most other peaks given the relatively low electronegativity of
silicon compared to carbon
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)
Summary Questions
How Science Works
Page 147
Pages 151-2
1
The birth of nmr
146 - 148
128 132
Q11 13 on pages 130 132
nmr spectroscopy
non equivalent hydrogens 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
hydrogens on the same atoms are identical and will not modify one another
NOTE:
hydrogens bonded to an oxygen are not split and do not cause others to split
the more adjacent hydrogens 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 Pascals triangle:
NOTE:
Your syllabus is limited to samples
yielding singlets, doublets, triplets and quartets
Chemguide
Summary Questions
Page 152
1, 2
16
2, 3, 5, 6
148 - 152
128 136
Q11 15 on pages 130 136
Q 1 4 on pages 137 -138
Q 6,11 on pages 151 - 153
Proton nmr
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 oxygens 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 hydrogens 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
MS data
m/z
value
Interpretation
Notes
15
CH3+
29
CH3CH2+
31
CH3O+
43
57
CH3CH2CO+
77
C6H5+
105
C6H5CO+
77 + 29 consider ethylbenzene
77 + 43 propylbenzene or phenylethanone
Benzaldehyde or Benzoic acid
CH
CC
C=C
C=O
CO
OH
OH
28503300
7501100
16201680
16801750
10001300
(alcohols) 3230
3550
(acids) 25003000
CHROMATOGRAHY
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
Video clip
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
data
will
also
be collected
Summary Questions
Page 154
1-3
153 - 154
Chromatography
AS Chemistry Unit 2
71
AS Chemistry Unit 2
72