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A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

AQA A2-LEVEL

Student Guide to Unit 4


Kinetics, Equilibria and Organic Chemistry

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Mr Lund 03 March 2015


1

A2 Unit 4 Kinetics, Equilibria and Organic 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

Le Chateliers Principle and Qualitative Aspects

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)

catalysts - do not affect position of equilibrium, just the time to achieve it

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

A2 Chemistry (Nelson Thornes) AQA


A2 Chemistry (Heinemann) AQA

Chemguide

20 and Chapter 9 in the AS Book


16 17
Q 1 - 3 on page 16 17
Q 1 on page 32
Chemical equilibrium

Mr Lund 03 March 2015


2

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

This equation can vary and


simply illustrates the principle
behind its construction

Equilibrium Law (i.e. equation)

[C]

aA

cC

dD

Kc =

[A]

eqm
a
eqm

[D]
[B]

d
eqm
b
eqm

only applies to systems at equilibrium so dont use initial concentrations


Kc is calculated from concentrations at equilibrium (note that the concentration of a solid is
constant and so solids do not appear in the equilibrium expression)
equilibrium constant (Kc) is related to reaction stoichiometry (a, b, c etc) and is a constant at
constant temperature
the value of Kc is an indicator of the position of equilibrium (reverse reaction = inverse value)
the value of Kc is not indicative of how fast the reaction proceeds
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

Summary Questions
Exam Style Questions

bB

Page 21
Page 28

1-3
1

determination of the concentrations of reactants/products present at equilibrium, given


appropriate data including the numerical value of Kc
this may involve the determination of an unknown value of x to solve an equation (but not a
quadratic one on this syllabus)
you may be required to realise that the equation can be simplified by taking the square root of
both the top and the bottom terms and the value of Kc(see the example on page 22 23)
you might also be asked to determine the amount of given reactant required in order to
produce a given amount of product (see the example on page 23 24)

Summary Questions
Exam Style Questions

Page 24
Page 28

A2 Chemistry (Nelson Thornes) AQA


A2 Chemistry (Heinemann) AQA

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

Mr Lund 03 March 2015


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A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Changing Conditions and Equilibria

Pressure or Concentration Change

the value of Kc does not change with variations in concentration or pressure


to improve yield wrt a more expensive reactant a cheaper reactant could be added.
removing the product as it is formed (assuming that the response of the system is fast enough)
would also improve yield whist also allowing reactants to be recycled (see Haber)

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

Kc and Temperature Change

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

value of Kc DOES NOT CHANGE when a catalyst is used


therefore catalysts do not change the position of equilibria i.e. change the yield
HOWEVER, the rate of the reaction will be faster (for both the forward and backward
reaction) hence equilibrium will be achieved sooner
adding a catalyst to a system already at equilibrium will not change its position

How science works


Summary Questions
Exam Style Questions

Page 26
Page 27
Page 28-29

A2 Chemistry (Nelson Thornes) AQA


A2 Chemistry (Heinemann) AQA

Chemguide

Development of the Haber Process


1-3
35
25 - 27
18 27
Q 4 13 on pages 18 27
Q 3, 5 on page 33
Equilibrium equation

Mr Lund 03 March 2015


4

How Science
Works: E, F

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Kinetics

review basic ideas of collision theory and activation energy from AS

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

Dont panic !! this can be explained


easily in words ask your teacher

1 d[B]
2

dt

there are different ways to express rate


(i)
(ii)
(iii)

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

Measuring Reaction Rates

see AS Module 2 guide for general practical techniques for monitoring progress in a given
reaction

generally the main methods comprise two different strategies


1

following a single reaction measuring colour change, change in conduction/pH of one


product or reactant
then plotting a concentration time graph and determining the rates at given concentrations

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

How science works


Summary Questions

1
t

Page 5
Page 6

Damn fast reactions indeed


1-5

Mr Lund 03 March 2015


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A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Rate Equations and Order of Reaction

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

for two reactants A and B the general rate expression is:


Rate [A]m[B]n

moldm-3s-1

Note that rate always has these same


units.

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)

doubling [NO] quadruples the rate i.e. double2 = 4


doubling [H2] doubles the rate
Rate [H2][NO]2

i.e.

[NO]2

The effect on
rate of the
change
here

NOT as suggested by the ratio of reactants rate [H2]2[NO]2

k is the rate constant (units depend upon overall order)


rate = k[H2][NO]2

..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:

units of k = (moldm-3)1 - overall order (s-1)

note that if the order is 0 this term will not appear in the rate equation
e.g. A2BC0 = A2B x 1 = A2B

Mr Lund 03 March 2015


6

Maths tip:
Any number raised
to the power zero = 1

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Catalysts and Rate Equations

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)


by experimentation it was found that the reaction is:
first order wrt [H+] and [CH3CO CH3]

zero order wrt [I2]

i.e. second order overall

rate [CH3COCH3]1[ H+]1[I2]0


rate = k[CH3COCH3][ H+]

moldm-3s-1

what are the units of k?

Rate Determining Step

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

A2 Chemistry (Nelson Thornes) AQA


A2 Chemistry (Heinemann) AQA
Chemguide

14
1
4 9, 14 - 16
46
Q1, 2, 3 on page 5-6
Order of reaction, rate expression, SN2

Mr Lund 03 March 2015


7

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Concentration/Time and Rate/Concentration Graphs

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

zero order e.g. decomposition of ammonia (tungsten catalyst), rate is independent of


concentration i.e. graphically it is a flat horizontal line
2NH3(g)

3H2(g) +

Do you have an idea as to why it might be zero


order?

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 Rates Method

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

A2 Chemistry (Nelson Thornes) AQA


A2 Chemistry (Heinemann) AQA

Chemguide

10 - 12
7 11
Q4 on page 8
Q1 on page 14
rate

Mr Lund 03 March 2015


8

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Variation of k with Temperature

Maxwell-Boltzmann Distribution Curve

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

Arrhenius constant (determined by collision frequency and orientation factor)


gas constant (8.31 JK-1mol-1)
absolute temperature (K)

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

Extra info for


those who do
Maths how
can we get
values for EA
and A

ln(k) =

ln(A)

EA
RT

ln(k) =

1
- E A

ln(A)

R T

Plot ln(k) against 1/T gives gradient = -

x
EA

and intercept = ln(A)

Exam Style Questions

Page 17 - 18
Page 158

A2 Chemistry (Nelson Thornes) AQA


A2 Chemistry (Heinemann) AQA

Chemguide

2,4
1

10 - 12
12 13
Q2-4 on page 14 - 15
Q1 on page 150
Arrhenius expression

Mr Lund 03 March 2015


9

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

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)]

Brnsted-Lowry Theory of Acids and Bases

Arrhenius limited to aqueous solutions but acid-base concept is broader e.g.:


NH3(g) +

HCl(g)

NH4Cl(s)

acid-base equilibria involve proton transfer


acids are proton donors, bases are proton acceptors

water is amphoteric
it behaves as an acid with NH3
and as a base HCl

conjugate acid-base pairs undergo proton exchange


competition occurs for protons between bases on either side of the equilibria
relative strength of the base determines the equilibria bias
a relatively strong base has a relatively weak conjugate acid and visa-versa
note that in the protonation of nitric acid in the nitration of benzene nitric acid acts as a base

You must make the


effort to learn the
definition of a BrnstedLowry acid and base

Ionic Product of Water (Kw)

water undergoes slight auto-ionisation (dissociation of the water molecule)


ionic product of water again the equation defines the concept and dont forget units
Kw

variation of Kw

Summary Questions

[H+(aq)][OH-(aq)]

1 x 10-14 mol2dm-6 at 298K

its value increases as temperature increases - LCP - (hence [H+(aq)]


increases and therefore the pH of a neutral solution decreases!)

Page 31

A2 Chemistry (Nelson Thornes) AQA


A2 Chemistry (Heinemann) AQA

Chemguide
pH Calculations

1-3

30 - 31
34 35, 36, 42 - 43
Q1 on page 35
Q6 on page 37
Brnsted, ionic product

Mr Lund 03 March 2015


10

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

define pH using an equation NOT in words as it is more certain to get full marks.
pH = -log10[H+(aq)]

learn to use your calculator !

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

calculating [H+(aq)] from pH values

[H+(aq)] = 2 x [H2SO4(aq)]

NOTE:

[H+(aq)] = 10- pH

learn to use your calculator !!!!!!

calculating the pH of alkalis using Kw to calculate [H+(aq)]


note for Ca(OH)2 that [OH-(aq)] = 2 x [Ca(OH)2(aq)]
but why might it give a weaker acid than sodium hydroxide?
[OH-(aq)]

Kw

[H

(aq)

How science works


Summary Questions

Page 33
Page 31

Measuring pH
Questions 1 - 5

Exam Style Questions

Page 50

Questions 3

A2 Chemistry (Nelson Thornes) AQA


A2 Chemistry (Heinemann) AQA

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

Mr Lund 03 March 2015


11

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Weak Acids and Ka

weak acids are only partially ionised


HA(aq) +
Kc =

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

A2 Chemistry (Nelson Thornes) AQA


A2 Chemistry (Heinemann) AQA

Chemguide

1-3
6
32 35
35 36, 40 42
Q11 - 12 on pages 41 - 42
Q 1 on page 55
Weak acid

Mr Lund 03 March 2015


12

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Titration Curves

as an alkali is added to an acid the pH increases and visa-versa

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

A2 Chemistry (Nelson Thornes) AQA


A2 Chemistry (Heinemann) AQA

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

Mr Lund 03 March 2015


13

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Ka of Weak Acids from 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

End Point of an Indicator

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

A2 Chemistry (Nelson Thornes) AQA


A2 Chemistry (Heinemann) AQA

Chemguide

1-2
4

39 - 41
49 51
Q17 - 18 on pages 50 51
Q 5 on page 56
Indicators

Mr Lund 03 March 2015


14

pH

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

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

Added H+(aq) is removed by A-(aq) provided by


the salt as the equilibrium shifts to the left
HA

H+ + A-

reservoir of HA provided by acid

Added OH-(aq) is removed by


reacting with H+(aq) provided
by the acid as the equilibrium
shifts to the right
NaA

An acidic buffer (for pH <7) consists of a


weak acid and its soluble salt
Na+ + A-

reservoir of A- provided by the sodium


salt of the acid

Basic Buffer

Added H+(aq) is removed by NH3 as the


equilibrium shifts to the right
NH3

+ H+

NH4+

reservoir of NH3 provided by weak base

Added OH-(aq) is removed by


reacting with NH4+(aq)
provided by the salt and the
equilibrium shifts to the left
NH4Cl

An alkaline buffer (for pH >7) consists of a


weak alkali and its soluble salt
NH4+ + Cl-

reservoir of NH4+ provided by the


ammonium salt

Mr Lund 03 March 2015


15

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Important Buffer Solutions

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

Added OH-(aq) is removed by reacting with


H+(aq) shitting the equilibrium to the left

a pH change of over 0.5 can be fatal

buffer solutions are also used in:


the food industry (acidity regulators)
fabric dyeing where AZO dyes are used
hair care products which are kept slightly acidic pH 5.5 as alkaline conditions
make hair look rough as microscopic scales on the surface of the hair are made to
stand up.
calibrating pH meters
biochemical research (enzymes are denatured by pH extremes)
and there are numerous other areas

Preparation of Buffer Solutions

a buffer solution can be made in two different ways:


1
2

adding a suitable soluble salt to an acid


partially neutralising a weak acid with a strong base up to the required pH

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)

Mr Lund 03 March 2015


16

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Calculating the pH of a Buffer Solution


HA H+ + A

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

Will the dilution


of
a
buffer
solution change
the pH?

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

A2 Chemistry (Nelson Thornes) AQA


A2 Chemistry (Heinemann) AQA

Chemguide

1
1, 2
5
5
45 - 48
52 54
Q17 - 20 on pages 52 54
Q6, 9 on page 56
Buffer

Mr Lund 03 March 2015


17

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

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

functional group one or more reactive sites on a hydrocarbon skeleton


homologous series same general formula + same functional group (hence same chemistry
as the increase in chain length has little effect on their chemical reactivity)

nomenclature is based on four criteria:


root
suffix
prefix
locant

longest unbranched hydrocarbon chain (including main functional group)


determines principal functional group (a pecking order exists)
other changes to root molecule (e.g. side chains, functional group)
position of branch or substituent (e.g. double bond) on the main chain

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

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A2 Chemistry (Nelson Thornes) AQA


Chemguide

1-3
1
52 - 56
nomenclature
How Science
Works: H

Mr Lund 03 March 2015


18

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

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

Mr Lund 03 March 2015


19

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Stereoisomerism
Stereoisomers have the same molecular and structural formula but differ in the spatial
arrangement of their atoms.
How Science
Works: A

Geometrical isomerism

this is consequential of the non-rotation of a double bond (unlike in alkanes) which is


what you will state as the fundamental requirement in the exam
this lack of free rotation is consequential of the bond present in the alkene
a single carbon-carbon bond cannot give rise to this type of isomerism as (unless a chain is
present) there is unrestricted rotation

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

whilst the minimum requirement is the presence of restricted rotation consideration


should also be given to the substituents on each carbon

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

E and Z are used to distinguish between


the two isomers (its quite EZy to do will
a little practice)
E isomers have the main grouping
diagonally across the double bond
Z isomers have the main grouping on the
same side of the double bond
cis and trans were previously used and in most cases E corresponds
to trans and Z to cis BUT NOT ALWAYS

How science works

How Science
Works: L

Find out about the food industry and trans fats and the
hydrogenation of vegetable oils.

Mr Lund 03 March 2015


20

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

the trick is to identify what the main groupings are:


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


priorities.
The two attached atoms are
C and H, so since the atomic
numbers C > H then the -CH3
group is higher priority.

Step 3: look at the relative


positions of the higher priority
groups : same side = Z,
hence (Z)-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

How many functional


groups can you see
here?
How can you test to
provide evidence for
each one?

CH3

CH3
O

Optical Isomerism
Mr Lund 03 March 2015
21

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Optical isomerism exists where there is an asymmetric (i.e. chiral) carbon with four different
groups attached.

Can you give the


systematic name for this
molecule?

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

one enantiomer tastes of spearmint the other caraway


one smells of lemons the other oranges (see if you can spot the chiral centre in
these enantiomers of limonene)

Mr Lund 03 March 2015


22

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Enantiomers rotate plane polarised light in opposite directions (clockwise and


anticlockwise).

this physical property is the means by which they can be distinguished


one enantiomer rotates the polarised light clockwise (to the right) and is the (+) enantiomer;
the other rotates the polarised light anticlockwise (to the left) and is called the () enantiomer.

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

A2 Chemistry (Nelson Thornes) AQA


Chemguide

The thalidomide tragedy


1-4
2, 4, 5
57 - 59
isomerism

Mr Lund 03 March 2015


23

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Aldehydes and Ketones


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

primary alcohol

aldehyde

heat with K2Cr2O7(aq)/H2SO4(aq), distil off


aldehyde (boiling point lower than alcohol)

secondary alcohol

ketone

reflux under heat with K2Cr2O7(aq)/H2SO4(aq)

orange dichromate(VI) ions (Cr2O72-aq)) are reduced to green chromium(III) ions


(Cr3+(aq))

Distinguishing Between Aldehydes and Ketones


ACIDIFIED POTASSIUM DICHROMATE SOLUTION

tests are based on the fact that aldehydes can be easily oxidised to a carboxylic acid while
ketones cannot be.
Aldehyde

[O]

reflux with K2Cr2O7(aq)/H2SO4(aq)

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.

Mr Lund 03 March 2015


24

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

NOTE: PRIMARY AND SECONDARY ALCOHOLS CANNOT BE OXIDISED BY


FEHLINGS OR TOLLENS HENCE DO NOT GIVE POSITIVE RESULTS WITH
THE TESTS BELOW.

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)

blue complexed Cu2+(aq) is reduced to brick


red Cu2O(s)
(this is the basis of the test for reducing sugars)

RCHO(aq) + 2Cu2+(aq) + 4OH-(aq)

RCOOH(aq) + Cu2O(s) + 2H2O(l)

TOLLENS REAGENT
complex ion [Ag(NH3)2]+(aq) is reduced to Ag(s),
hence the silver mirror effect

warm with Tollens reagent


(aqueous silver nitrate in xs ammonia)

RCHO(aq) + 2[Ag(NH3)2]+(aq) + 2OH-(l) RCOOH(aq) + 2Ag(s) + 4NH3(aq) + H2O

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

A2 Chemistry (Nelson Thornes) AQA


A2 Chemistry (Heinemann) AQA
Chemguide

1-4
66 67, 69
65 67
Q 1 on page 66
Ionic alkaline, Tollens, Fehlings

Mr Lund 03 March 2015


25

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

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

sodium tetrahydridoborate(III) (NaBH4)


in water (+ ethanol as a universal solvent
for higher (longer chain) members)

BH4- provides the hydride ion, H- which acts as a nucleophile


mechanism is required (nucleophilic attack by hydride ion)
intermediate ion then gains H+ from the water present in the aqueous solvent just show H+
in the mechanism itself
NA

Reaction with Hydrogen Cyanide


ethanal + HCN

2-hydroxypropanenitrile

HCN is made in situ using acidified sodium or potassium cyanide


HCN is a toxic gas so there are health and safety issues in its use
cyanide ions are toxic so this will not be done in the lab

note: an extra carbon is introduced into the chain so this is an important synthesis step
mechanism for reaction = nucleophilic addition

trigonal planar carbonyl group can be attacked from either side


hence products from aldehydes other than methanal exhibit optical isomerism i.e. there is
an asymmetric (i.e. chiral) carbon with four different groups attached hence two nonsuper imposable molecules (enantiomers) exist which are mirror images of one another.

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

hydroxynitriles can be converted to a carboxylic acid by undergoing acid hydrolysis


this involves refluxing with a dilute acid (below I have shown the organic as named for
clarity - although you MUST give its formula - as the other particles will always be the same
irrespective of the number of carbons in the chain)
the optical properties are preserved in the carboxylic acid

2-hydroxypropanenitrile + 2H2O + H+

2-hydroxypropanoic acid
(lactic acid)

Mr Lund 03 March 2015


26

NH4+(aq)

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

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

A2 Chemistry (Nelson Thornes) AQA


A2 Chemistry (Heinemann) AQA

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

Mr Lund 03 March 2015


27

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Carboxylic Acids and Esters


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)

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

A2 Chemistry (Nelson Thornes) AQA


A2 Chemistry (Heinemann) AQA
Chemguide

71 - 73
71 75
Q 7 10 on pages 71 - 74
Carboxylic acids, Esters

Synthesis of carboxylic acids


primary alcohol or aldehyde

carboxylic acid

reflux under heat with xs


K2Cr2O7(aq) and H2SO4(aq)

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.

Mr Lund 03 March 2015


28

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Reactions of Carboxylic Acids and Esters

carboxylic acids are weak acids understanding required in terms of equilibria


chlorine-substituted ethanoic acids are more acidic due to negative inductive (I) effect of
chlorine atoms due to their relatively high electronegativity

ethanoic acid
ACID

+
+

sodium hydroxide
BASE

sodium ethanoate
SALT

ethanoic acid

sodium carbonate

sodium ethanoate + water + carbon


dioxide

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

ethanol + ethanoic acid

ethyl ethanoate + water

acid

ester

alcohol

Summary Questions

Page 77

reflux under heat with cH2SO4


catalyst

+ water
14

Hydrolysis of Esters

ethyl ethanoate + water

ethanoic acid + ethanol

sulphuric acid catalyst

initiated by nucleophilic attack by the water molecule on the C+ of the carbonyl group

acid catalysed hydrolysis not complete due to an equilibrium being established

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

A2 Chemistry (Nelson Thornes) AQA


A2 Chemistry (Heinemann) AQA
Chemguide

74 - 76
71 74
Q 11 on page 74
Carboxylic acids, esters hydrolysis

Mr Lund 03 March 2015


29

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

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 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)

some phthalate based plasticizers have a possible association with birth


defects although this is still a subject of some disagreement

How Science
Works: I

Fats and Oils

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

Mr Lund 03 March 2015


30

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Glycerol (glycerine)

the co-product of soap making, propane-1,2,3-triol (glycerol) has numerous uses:

it is a useful solvent e.g. in medicines, food colouring


its extensive hydrogen bonding makes it good at retaining water thus preventing drying out
(e.g. facial creams)
and can be used to make nitro-glycerine (which mixed with finely divided silicon(iv) oxide =
dynamite)
How Science
Works: K
Biodiesel

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

it can also be made from animal fat and waste oil


small industrial plants tend to be batch processes but larger plants can use continuous flow
methods which are more economical

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:

CH3OOCCxHy where x and y depend on chain length and degree of unsaturation


(this can be written the other way around CxHyCOOCH3)

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

Exam Style Questions

Page 83

A2 Chemistry (Nelson Thornes) AQA


A2 Chemistry (Heinemann) AQA
Chemguide

4
76 - 77
75
Fats and oils, soap, glycerol

Mr Lund 03 March 2015


31

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Acylation using Acyl Chlorides or Acid Anhydrides

nomenclature named after the parent carboxylic acid hence deemed acid derivatives (as are
esters and amides)
O
R

-oic acid replaced with:


-oyl chloride
e.g. ethanoyl chloride = an acyl chloride

Acid anhydrides
X = OR

e.g. ethanoic anhydride

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

used to join an acyl group

O
R

:Nu

to the oxygen of water, alcohol or phenol


or the nitrogen of ammonia or an amine
(ethanoylation is specifically when R = CH3)
H+ is eliminated in each case in the final step

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

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

mechanism is nucleophilic addition-elimination (condensation)


NOTE: H is not abstracted by Cl- (think why HCl is a strong acid!)

Ethanoic anhydride +

water

ethanoic acid

Mr Lund 03 March 2015


32

ethanoic acid

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Reaction with Alcohols and Phenols


ethanoyl chloride

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

Reactions with Ammonia and Amines


NAE
ethanoyl chloride + ammonia ethanamide (a primary amide) + hydrogen chloride

violent reaction with aqueous ammonia at room temperature


ethanamide is the only product as further substitution does not occur due to strong electron
withdrawing effect of C=O which makes the lone pair of the nitrogen less readily available
than with amines (cf haloalkanes + ammonia)
NAE

ethanoyl chloride + ethylamine


(primary amine)

N-ethylethanamide + hydrogen chloride


(secondary amide)

ethanoyl chloride + phenylamine

N-phenylethanamide + hydrogen chloride

(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

A2 Chemistry (Nelson Thornes) AQA


A2 Chemistry (Heinemann) AQA

Chemguide

ammonia

ethanamide +

14
1, 3
78 - 81
76 83
Q 12 - 15 on pages 77 81
Q 1 8 pages 82 - 83
Acyl

Mr Lund 03 March 2015


33

ethanoic acid

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

How Science
Works: I, J

The Synthesis of Aspirin

(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

How science works


Exam Style Questions

Page 82
Page 83

A2 Chemistry (Nelson Thornes) AQA


A2 Chemistry (Heinemann) AQA
Chemguide

Aspirin
1
82
81
Q 14 on page 81
Aspirin

Mr Lund 03 March 2015


34

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Aromatic Chemistry

involves compounds containing a benzene ring (aka arenes look out for C6H5-)
empirical formula CH, Mr =78, molecular formula C6H6

Structure and Stability of Benzene

hydrogenation with 3 moles of H2 suggests the equivalence of 3 carbon-carbon double bonds


How Science
How science works
Page 85 Kekules dream
Works: A

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)

initially a resonance hybrid


structure was suggested

the true structure and shape of


benzene can be explained in terms of
the delocalisation of the electrons of
6 x 2p orbitals (whilst its not on the
syllabus, knowledge of orbital
How Sciencehybridisation would be helpful have
Works: F a look on Chemguide or in an older Alevel book)

delocalised electrons increase

Why is it drawn like this?

relative stability (less electron - electron repulsion)

Summary Questions
Exam Style Questions

Page 86
Page 93

A2 Chemistry (Nelson Thornes) AQA


A2 Chemistry (Heinemann) AQA
Chemguide

13
6
84 - 86
84 - 87
Q 1 2 on page 87
Bonding benzene

Mr Lund 03 March 2015


35

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

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

C6H5- phenyl group and simple monosubstituted aromatic compounds (arenes)


normally named as derivatives of benzene so benzene often forms the root of the name
mono-substituted arenes are generally of formula C6H5X e.g. benzaldehyde C6H5CHO and
yield a peak of 77 on mass spectra due to the fragment C6H5+ (see later)

methylbenzene (toluene)

chlorobenzene

benzenecarboxylic acid (benzoic acid)

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

phenylethene (instead of ethenylbenzene)

of

aromatic compounds with more than one substituent


1
2

lowest numbering possible


alphabetical order for substituents (ignore di, tri etc)

2-hydroxybenzoic acid

2,4,6-trinitrotoluene

2,4,6-trinitrophenol (picric acid)

benzene-1,4-dicarboxylic acid (Terephthalic acid)

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

A2 Chemistry (Nelson Thornes) AQA


Chemguide

14

87 - 88
Naming aromatic

Mr Lund 03 March 2015


36

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Reactions of aromatic compounds


Electrophilic Substitution

high electron density in the ring attracts electrophiles


Br2(aq) is not decolourised (in the dark) electrophile must be powerful (+ve not just +)
why benzene resists attack by poor electrophiles stability of benzene compared to alkenes
electrophilic substitution rather than addition (c.f. alkenes) since this retains the relatively
stable benzene ring structure hence is energetically more favourable

Nitration of Benzene and Methylbenzene


ES
benzene

nitrobenzene (a yellow oil)

cH2SO4/cHNO3 refluxed at 50oC


(nitrating mixture)

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

nitrobenzene (a yellow oil)

phenylamine

cHCl/Sn or H2/Ni

Dont use H2 for cHCL/Sn

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)

How Science Works


Exam Style Questions

Page 90
Page 92

A2 Chemistry (Nelson Thornes) AQA


A2 Chemistry (Heinemann) AQA
Chemguide

TNT
1, 3
89 - 90
88 - 89
Q 3, 4 on page 89
Electrophilic substitution, nitration

Mr Lund 03 March 2015


37

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Friedel-Crafts Acylation

role of the AlCl3 - halogen carrier why is it a lewis acid


anhydrous conditions - AlCl3 readily hydrolysed by water before it does its job

electrophilic substitution mechanism proceeds via an acylium ion intermediate

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

A2 Chemistry (Nelson Thornes) AQA


A2 Chemistry (Heinemann) AQA

Chemguide

warm with AlCl3 catalyst


anhydrous conditions

1-4
2-5

91
91, 184
Q 7, 8 on page 91
Q 1 8 on pages 94 - 95
Acylation

Mr Lund 03 March 2015


38

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

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

amino can sometimes be used (see amino acids later on)

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

can be a nucleophile, base or ligand depending on the context


how good it is depends on the availability of that lone pair i.e. what the N is bonded to

Brnsted-Lowry bases proton acceptors, Lewis base = lone pair donor

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 ?)

acid amides are relatively poor bases/nucleophiles/ligands as the strongly electronegative


oxygen causes the lone pair on the nitrogen to be more withdrawn

pKa value of conjugate acid increases (i.e. is poorer) with increased basicity of the conjugate
amine

Mr Lund 03 March 2015


39

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

amines react with acids to form salts in a similar manner to ammonia

ethylamine

hydrochloric acid

ethylammonium chloride + water

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

phenylammonium chloride + water

Page 97
Pages 108 9

A2 Chemistry (Nelson Thornes) AQA


A2 Chemistry (Heinemann) AQA

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

Mr Lund 03 March 2015


40

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Preparation
From haloalkanes
NS
bromoethane

ethylamine

alcoholic solution of NH3 under pressure


(lots of by-products so not a good method)

mechanism NH3 acts as nucleophile


excess ammonia is used to improve the yield of the primary amine

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

nitrobenzene (a yellow oil)

nitrobenzene (a yellow oil)

phenylamine

cH2SO4/cHNO3 refluxed at 50oC


(nitrating mixture)

reduction cHCl/Sn (or H2/Ni)

phenylammonium chloride* is initially produced, and addition of NaOH yields


phenylamine (via deprotonation) which is then obtained by steam distillation
strictly speaking its actually phenylammonium hexachlorostannate(IV)

Mr Lund 03 March 2015


41

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Uses of Amines

quaternary ammonium salts are used as cationic


surfactants (long carbon chains help) in fabric
conditioners and hair conditioning products
the positive charges present will repel and add
body to the hair/fabric whilst the tail section
associates with the fabric
if you are particularly interested in laundry see:
http://www.scienceinthebox.com/en_UK/glossary/
surfactants_en.html
http://www.chemistryquestion.com/English/Questions/ChemistryInDailyLife/27c_nonionic_s
urfactant.html
aryl amines are used in synthetic dyes
aryl amines are used to make certain drugs e.g.
paracetamol
amines are used to make polymers e.g. polyurethanes
(cavity wall insulation) and polyamides (nylons)

How Science Works


Summary Questions
Exam Style Questions

Pages 100 - 1
Page 101
Pages 108

A2 Chemistry (Nelson Thornes) AQA


A2 Chemistry (Heinemann) AQA

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

Mr Lund 03 March 2015


42

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

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

the amino acid proline is a 2o amine all the others


primary amines

CH

are
2

NH
CH

C
CH

C OOH

Extra Info for potential medical/biochemistry/pharmacy students:

amino acids in proteins are all L-isomers

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

Mr Lund 03 March 2015


43

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Zwitterions

the amino group and the carboxyl group of each


amino acid are both ionisable

the acidic carboxyl group (with a pKa of about 3


its a weak acid) is deprotonated

the basic amino group (with a pKa of around 9


its a weak base) is protonated

amino acids thus exist as zwitterions with both a


positive and negative charge present

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

Adding OHpH increasing

charge on the zwitterion ion depends on


pH, -ve at high pH and +ve at low pH
at a given pH, the isoelectric point of the
amino acid there will be no overall charge
as the + and cancel
this pH varies from amino acid to amino
acid and provides a means of separating
them
using
a
technique
called
electrophoresis.

Extra Info for potential medical/biochemistry/pharmacy students:

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

Exam Style Questions

Pages 108

5, 8, 11

Mr Lund 03 March 2015


44

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Mr Lund 03 March 2015


45

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Condensation Polymerisation and hydrolysis

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

Polypeptide (~50 amino acids) are formed


by condensation polymerisation and catalysed by
enzymes

sequence of amino acids in a protein is


called its primary protein structure

hydrogen bonding between C=O and N-H


controls shape - secondary protein structure - helix (coiled) and -pleated sheet (folded)

tertiary structure involves further


bending and twisting (a good analogy is a knotted,
multicoloured telephone coil)

the stretching of wool is dependent on


hydrogen bonding the length of which can be
reversibly increased up to a limit (very hot water
can break these ruining the fluffyness)

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

How Science Works


Summary Questions
Exam Style Questions

Pages 107
Page 107
Pages 109

A2 Chemistry (Nelson Thornes) AQA


A2 Chemistry (Heinemann) AQA

Chemguide

Robots in the lab


1, 2
6, 8 - 10
102 - 107
111 114, 57 62
Q 8 - 12 on pages 111 113
Q 2 4, 5 - 6 on pages 115 - 116
Zwitterions, peptide

Mr Lund 03 March 2015


46

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Polymerisation
Addition Polymerisation

addition across the carbon-carbon double bond of a single unsaturated monomer


occurs by a free radical mechanism (details not required) started by an initiator (e.g. a
peroxide) which is incorporated at the start/end of the polymer chain
you should be able to work out monomer from polymer and visa-versa (tip use the >C=C<
form of the monomer i.e. rewrite it)
if asked for a single repeating unit dont show brackets otherwise use [C-C]-n format

ethene

poly(ethene)

propene

poly(propene)

chloroethane

poly(chloroethene) (PVC)

phenylethene

poly(phenylethene) (polystyrene)

tetrafluoroethene

poly(tetrafluoroethene) (PTFE or Teflon)

methyl 2-methylpropenoate

Summary Questions
Exam Style Questions

Page 114
Pages 122

A2 Chemistry (Nelson Thornes) AQA


A2 Chemistry (Heinemann) AQA

Chemguide

heat, pressure, catalyst


in all cases

perspex

1-4
4, 5
112 - 114
106 -108
Q 1-3 on page 106
Q 7, 8 on page 116
Addition polymerisation

Mr Lund 03 March 2015


47

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Condensation Polymerisation
Polyesters

two different types of monomers, one a diol,


the other a dicarboxylic acid
this polymer is connected by ester linkages
you should be able to draw repeating units and
determine the monomers used to make a given
polymer colour coding diagrams helps here
condition usually involve heat + catalyst
look for CO2- in structural formula
balanced equation (dont forget 2n H2O !!!!)

ethane-1,2-diol
(ethylene glycol)

benzene-1,4-dicarboxylic acid
(terephthalic acid)

PET

the chain repeat unit of PET is:

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 read about the invention of polyester at:


http://inventors.about.com/library/inventors/blpolyester.htm
those of you doing textiles might also like to visit the polyester story at
http://schwartz.eng.auburn.edu/polyester/polyester.home.html

poly(2-hydroxypropanoic acid) used in surgery as its broken down by


enzymes/body fluids over a number of days (why is this good?)
how would you synthesise it from ethene?

How Science
Works: I

You will find it useful to look at the reaction


pathways template that I have put on line

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

Mr Lund 03 March 2015


48

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Polyamides

two different types of monomers, one a


diamine, the other a dicarboxylic acid
this polymer is connected by amide linkages
an diacyl chloride can be used instead of the
acid but what would be the pros and cons of this
nylon-6,6 is so called as both monomers have 6
carbons
nylon is a polyamide (just like proteins)

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

polyamides have extensive


hydrogen bonding between
parallel strands (cf protein
structure)
when nylon is spun into
fibres, amide groups on
adjacent
chains
form
hydrogen bonds making
nylon yarn strong.
kevlar is an example of an aromatic polyamide and is made from the monomers benzene-1,4dicarboxylic acid and benzene-1,4-diamine

Medieval chainmail similarity?

the molecule is flat because of the aromatic groups


the uses of Kevlar are related to its strength (its several times stronger
than steel)
this is related to the packing together of sheets of molecules held together
by hydrogen bonds formed between N H groups and C = O groups on
adjacent molecules
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

Mr Lund 03 March 2015


49

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

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

use biodegradable/photodegradable polymers instead is an option


polyesters and polyamides both have polar bonds hence they are potentially biodegradable
they are broken down by (catalytic) hydrolysis in acid/alkaline solution or with enzymes
although this can take a long time

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

How Science Works


Summary Questions
Exam Style Questions

Pages 120 - 1
Page 119
Page 121
Pages 121 - 123

A2 Chemistry (Nelson Thornes) AQA


A2 Chemistry (Heinemann) AQA

Chemguide

Hermann Staudinger + Q 1,2


1, 2
1-4
1, 2, 3, 6, 7

115 - 120
108 -110
Q 4 - 8 on page 109 - 110
Q 1, 5 on pages 115 - 116
Condensation polymerisation

Mr Lund 03 March 2015


50

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

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

alkanes can be used to produce alkenes by thermal cracking


Alkenes

haloalkane, alkane, alcohol, alkoxyalkane

ethene

HBr

bromoethane

EA

ethene

Br2

1,2-dibromoethane

EA

ethene
+
H2

ethane
Ni catalyst, ~200oC (catalytic hydrogenation)
+

Method 1
Method 2

cH3PO4 on a silica support with high temperature and pressure,


first react with cold cH2SO4, then warm with water

Alkyl Halides

H2O

ethene

ethanol

EA

amine, alcohol, nitrile, alkene

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

Mr Lund 03 March 2015


51

H2 O

NS

Br-

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Alcohols

carbonyl (aldehyde and ketone), carboxylic acid, ester, haloalkane, alkene

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]

reflux with K2Cr2O7(aq)/H2SO4(aq) under heat

ethanoic acid

H2 O

propan-2-ol
+
[O]

reflux with K2Cr2O7(aq)/H2SO4(aq) under heat

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

Aldehydes and Ketones

alcohol, carboxylic acid, hydroxynitrile

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

+
+

Mr Lund 03 March 2015


52

water
WATER

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

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

carboxylic acid, ester, amide

ethonoyl chloride

+ H2O

ethanoic acid

hydrogen chloride NAE

ethanoyl chloride

+ ethanol

ethyl ethanoate

HCl

ethanoyl chloride

+ 2-hydroxybenzoic acid
(salicylic acid)

ethanoyl chloride

+ NH3

aspirin

ethanamide

NAE
HCl

NAE

HCl

NAE

ethanoyl chloride + ethylamine


(primary amine)

N-ethylethanamide +
(secondary amide)

HCl

NAE

ethanoyl chloride + phenylamine

N-phenylethanamide +

HCl

NAE

Acid Anhydrides

carboxylic acid, ester, amide

ethanoic anhydride +

H2 O

2 ethanoic acid

ethonoic anhydride +

ethanol

ethyl ethanoate + ethanoic acid

ethonoic anhydride + 2-hydroxybenzoic acid


(salicylic acid)
warm with conc. sulphuric acid catalyst

aspirin

ethonoic anhydride +

ammonia

ethanamide

ethonoic anhydride +

4-aminophenol
(primary amine)

paracetamol +
(secondary amide)

Mr Lund 03 March 2015


53

ethanoic acid

ethanoic acid
ethanoic acid

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Aromatic Synthesis
Electrophilic Addition EA, Electrophilic Sustitution ES, Nucleophilic Addition-Elimination NAE

Substitution on the ring


benzene
+
HNO3

nitrobenzene
cH2SO4/cHNO3 refluxed at 50oC (nitrating mixture)

H2 O

ES

methylbenzene
+
HNO3
cH2SO4/cHNO3 refluxed at 50oC

2(and 4)-nitromethylbenzene + H2O

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

free radical peroxide initiator, high pressure


phenylamine +

ethanoyl chloride

ethane-1,2-diol
(ethylene glycol)

1,6-diaminohexane +

poly(phenylethene)

N-phenylethanamide +

benzene-1,4-dicarboxylic acid
(terephthalic acid)

hexanedioic acid

Mr Lund 03 March 2015


54

nylon-6,6

Terylene (a polyester)

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

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

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Testing for functional groups


Bromine Water (Br2(aq))

Test for alkenes (unsaturated hydrocarbons)

Add bromine water dropwise to ~1 cm3 of the unknown substance.

OBSERVATION

INFERENCE

EXPLANATION

orange colourless

alkene

electrophilic addition.
product is colourless

Acidified Potassium Dichromate Solution

Test for 10 and 20 alcohols (CARE it is also


positive with an aliphatic aldehyde)

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

1o alcohol aldehyde acid


2o alcohol ketone
aldehyde
aldehyde carboxylic acid
Methanoic acid can also be oxidized to carbon dioxide
NOT 3o alcohol or ketone

Tollens Reagent (Silver Mirror Test)

Test for aldehydes NOT ketone


Dont confuse with the test for alkyl halides

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

silver mirror formed


on test tube

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

Mr Lund 03 March 2015


56

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Fehlings Test

Test for aldehydes NOT ketone NOT benzaldehyde

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

reduction of copper(II) copper (I)


Cu2O is precipitated
aldehyde acid

NOTE THAT ALCOHOLS DO NOT GIVE A POSITIVE RESULT WITH THIS TEST
Test for carboxylic acids

Sodium Carbonate Solution

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

acid + metal carbonate


salt + water + CO2

Acidified Silver Nitrate Solution

Test for alkyl halides

Dont confuse with Tollens!

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

Mr Lund 03 March 2015


57

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Mass Spectrometry

this provides us with:


Mr, Relative abundance and fragmentation
patterns

do you know how a mass spectrometer works:


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)

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+

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+


CH3CH2CH2+

57

CH3CH2CO+

43 and 29 could be butanone


43 and 15 could be propanone
43 with no 15 ethanal or acyl chloride possible
Check IR for a carbonyl group
Check IR for a carbonyl group

77

C6H5+

105

C6H5CO+

77 + 29 consider ethylbenzene
77 + 43 propylbenzene or phenylethanone
Benzaldehyde or Benzoic acid

Mr Lund 03 March 2015


58

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

ragmentation occurs most easily at the weakest bond


Carbonyl compounds have a tendency to break adjacent to the C=O yielding the relatively
stable, hence high abundance, acylium ion RCO+ - look for m/z 43
the stability of a fragment determines its abundance on the spectra e.g. primary, secondary and
tertiary carbocations the positive inductive effect (+I) explains their relative stability

http://www.chem.arizona.edu/massspec/example_html/examples.html

Have a look at
these examples

isomers can be determined from fragmentation patterns:


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

M+ + 1 peak (satellite peak) due to carbon-13


height = 1% of M+ per carbon in the compound e.g. 5% suggests 5 carbons
7% (or higher) is likely to involve a substituted benzene derivative
note: the number carbons can be used, in conjunction with Mr to make an estimate of the
possible number of oxygens for example

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

A2 Chemistry (Nelson Thornes) AQA


A2 Chemistry (Heinemann) AQA

Chemguide

1, 2
4
132 - 136
117 123
Q2 on page 138
Q1 6 on pages 118 - 123
Mass spectrometry

Mr Lund 03 March 2015


59

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

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)

above 1500 cm-1 two important absorption values are:


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
A data sheet will be provided in the exam
similar to table 1 on page 138

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

A2 Chemistry (Nelson Thornes) AQA


A2 Chemistry (Heinemann) AQA

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

Mr Lund 03 March 2015


60

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Nuclear Magnetic Resonance Spectroscopy

nmr can be used on small samples to provide details of structure


cf wet chemical tests - limited primarily to identifying functional groups
nmr can be applied where there is an odd nucleon number e.g. 1H and 13C

these nuclei has a small magnetic field


associated with spin

an external magnetic field results in either


alignment with ( - lower energy) or against ( - higher
energy)

resonance between these two states occurs


when radio waves of appropriate energy are applied

this results in energy being absorbed which is


detected by the instrumentation

Carbon-13 (13C) nmr

organic chemicals will contain 1% carbon-13


their resonance field strength will vary
depending on the number of surrounding
electrons
the field strengths of other carbon
environments only differ slightly so the scale
measured in ppm

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

for TMS = 0 by definition

Mr Lund 03 March 2015


61

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

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

thus, nmr provides information about a


electronic environment.
carbons attached to electron withdrawing
atoms/groups such as oxygen tend to
higher frequencies yielding peaks
from TMS i.e. a higher (chemical shift)

no integration of carbon spectra


wide range (0-220 ppm) of resonances for common carbon atoms (typical range for
protons 0-12 ppm)

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

A2 Chemistry (Nelson Thornes) AQA


Chemguide

1, 2
143 - 145
Carbon 13 nmr

Mr Lund 03 March 2015


62

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Low Resolution 1H Spectra

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

for TMS = 0 by definition

hydrogens on the same atom in a molecule will experience an identical electromagnetic


environment and will thus yield a single peak at a given value on a low resolution spectra

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

number of peaks = number of non equivalent groups of H atoms


chemical shift identifies adjacent environment e.g. nearby oxygen
integrated spectra indicate the relative proportion of equivalent H atoms i.e. those in an
identical environment

Mr Lund 03 March 2015


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A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Below are common situations:

1 hydrogen strongly suggests an alcohol, acid or aldehyde


9 equivalent Hs suggests C(CH3)3
6 equivalent Hs suggests C(OH)(CH3)2 NOT CH(CH3)2 as this would be outside the
limitations for the AQA syllabus (see later)
3 equivalent Hs suggests CH3 e.g. COC H3 or -CH(OH)CH3 etc
2 equivalent Hs suggests CH2-

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

A2 Chemistry (Nelson Thornes) AQA


A2 Chemistry (Heinemann) AQA
Chemguide

1
The birth of nmr
146 - 148
128 132
Q11 13 on pages 130 132
nmr spectroscopy

Mr Lund 03 March 2015


64

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Interpretation of High Resolution Spectra

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:

these two together


are strongly
indicative of an
ethyl group

NOTE:
Your syllabus is limited to samples
yielding singlets, doublets, triplets and quartets

A2 Chemistry (Nelson Thornes) AQA


A2 Chemistry (Heinemann) AQA

Chemguide

Summary Questions
Page 152

1, 2

Exam Style Questions


Pages 155-7
Pages 158 161

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

Mr Lund 03 March 2015


65

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

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

be alert to the possibility of carbons/hydrogens in identical environments e.g. in propanone


or in branched alkyl components
Sample spectra: http://home.clara.net/rod.beavon/spectra.htm
Here are some useful tables:
Proton nmr

MS data
m/z
value

Interpretation

Notes

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+


CH3CH2CH2+

57

CH3CH2CO+

43 and 29 could be butanone


43 and 15 could be propanone
43 with no 15 ethanal or acyl chloride possible
Check IR for a carbonyl group
Check IR for a carbonyl group

77

C6H5+

105

C6H5CO+

Infra-red absorption data


Bond Wavenumber

77 + 29 consider ethylbenzene
77 + 43 propylbenzene or phenylethanone
Benzaldehyde or Benzoic acid

Mr Lund 03 March 2015


66

CH
CC
C=C
C=O
CO
OH
OH

28503300
7501100
16201680
16801750
10001300
(alcohols) 3230
3550
(acids) 25003000

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

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

the separation depends on the balance


between the solubility in the mobile phase and the
retention in the stationary phase

as in TLC (felt tip pens and paper is the


simplest form), there is an equilibrium established
between the solute adsorbed on the silica gel or
alumina and the eluting solvent flowing down through
the column.

this method is effective at separating mixtures


of amino acids

it can effectively separate fairly large amounts


of substance

different eluents can be used to extract different components

here is a practical guide to how it is done:

http://www.wfu.edu/academics/chemistry/courses/CC/index.htm

Here is a video clip of some people in white coats doing Chemistry:

Video clip

Mr Lund 03 March 2015


67

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

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

the carrier gas transports the


sample along the tube separating the
mixture in the process

separation depends on rate of


movement with the gas and retention by
the coil

the time taken for each component


to complete its journey through he coil is
called its retention time

data

will

also

be collected

regarding the relative amount of each component


the output samples can be analysed by MS, IR or nmr under computer control
this method is effective even with small sample sizes/trace amounts due to its high
sensitivity (e.g. food additives, drug usage detection)
Here is a How Science Works link that
considers the controversy surrounding the
interpretation of GC/MS data regarding
whether life has/has not been detected on
Mars there are many like this
http://www.msss.com/http/ps/life/life.htm
l
GC/MS equipment on Mars lander

Summary Questions

Page 154

A2 Chemistry (Nelson Thornes) AQA


Chemguide

1-3
153 - 154
Chromatography

Mr Lund 03 March 2015


68

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Mr Lund 03 March 2015


69

A2 Unit 4 Kinetics, Equilibria and Organic Chemistry

Mr Lund 03 March 2015


70

AS Chemistry Unit 2

71

AS Chemistry Unit 2

72