Name: ________________________

3.3.6.2 Mass spectrometry

Class: ________________________

Date: ________________________

Time: 91 min.

Marks: 87 marks

Comments:

Page 1 of 30
Q1.
Four compounds, all colourless liquids, are

• butan-2-ol
• butanal
• butanone
• 2-methylpropan-2-ol

Two of these compounds can be identified using different test-tube reactions.

Describe these two test-tube reactions by giving reagents and observations in each case.
Suggest how the results of a spectroscopic technique could be used to distinguish
between the other two compounds.

_______________________________________________________________________

_______________________________________________________________________

_______________________________________________________________________

_______________________________________________________________________

_______________________________________________________________________

_______________________________________________________________________

_______________________________________________________________________

_______________________________________________________________________

_______________________________________________________________________

_______________________________________________________________________

_______________________________________________________________________

_______________________________________________________________________
(Total 6 marks)

Q2.
Which compound forms a molecular ion with a different precise molecular mass from the
other three?

A butanone

B cyclobutanol

C dimethylpropane

D methylpropanal
(Total 1 mark)

Page 2 of 30
Q3.
The compounds in the table all have a relative molecular mass of 58.0

(a) Explain why determining the precise relative molecular mass of propanal and
prop-2-en-1-ol by mass spectrometry could not be used to distinguish between
samples of these two compounds.

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________
(2)

(b) The infrared spectrum of one of these three compounds is shown below.

Use the spectrum to identify the compound.

State the bond that you used to identify the compound and give its wavenumber
range.
You should only consider absorptions with wavenumbers greater than 1500 cm−1.

Compound _________________________________________________________

Bond used to identify compound ________________________________________

Wavenumber range of bond used to identify compound _________________ cm−1

(2)

(c) Predict the relative boiling points of these three compounds from the highest
to the lowest boiling points.

Page 3 of 30
 Justify this order in terms of intermolecular forces.

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________
(6)
(Total 10 marks)

Q4.
Butane and propanal are compounds with Mr = 58.0, calculated using data from your
Periodic Table.

(a) A mass spectrometer can be used to distinguish between samples of butane and
propanal.

The table shows some precise relative atomic mass values.

Atom Precise relative atomic mass

1
H 1.00794
12
C 12.00000

(i) Use data from the table to show that, to 3 significant figures, a more accurate
value for the Mr of butane is 58.1

______________________________________________________________

______________________________________________________________

______________________________________________________________

______________________________________________________________
(1)

Page 4 of 30
 (ii) State why the precise relative atomic mass quoted in the table for the 12C
isotope is exactly 12.00000

______________________________________________________________

______________________________________________________________
(1)

(b) Draw a displayed formula for the organic product that is formed when propanal is
oxidised by warm Tollens’ reagent.
(1)

(c) Prop−2−en−1−ol is an isomer of propanal and can be polymerised to form a

polymer represented by the following structure.

(i) Draw the structure of prop−2−en−1−ol.

(1)

(ii) Deduce the type of polymerisation that results in the formation of this polymer
from prop−2−en−1−ol.

______________________________________________________________
(1)

(iii) There are two functional groups in prop−2−en−1−ol. Each of these functional
groups contains a bond with a characteristic absorption range in the infrared
spectrum.

Use Table A on the Data Sheet to suggest a bond and its absorption range for
each of the two functional groups.

Bond 1 ___________ Absorption range _______________________

Bond 2 ___________ Absorption range _______________________

(2)

(d) Compound X is another isomer of propanal. The infrared spectrum of X shows an

absorption in the range 1680−1750 cm−1.

(i) Draw the structure of X.

Page 5 of 30
 (ii) Which of the following, A, B, C or D, represents the type of isomerism shown
by X and propanal?

Write the correct letter, A, B, C or D, in the box.

A chain isomerism
B E−Z isomerism
C functional group isomerism
D position isomerism

(1)
(Total 9 marks)

Q5.
The manufacture of food grade phosphoric acid for use in cola drinks begins with the
production of pure white phosphorus from the mineral fluoroapatite, Ca 5F(PO4)3

(a) Complete the following equation for the manufacture of phosphorus.

....Ca5F(PO4)3 + 9SiO2 + ....C 9CaSiO3 + CaF2 + ....CO + ....P

(1)

(b) As the phosphorus cools, it forms white phosphorus, P 4

Give the oxidation state of phosphorus in each of the following.

P4______________________________

H3PO4___________________________
(2)

(c) Fertiliser grade phosphoric acid is manufactured from sulfuric acid and calcium
phosphate.
Use the following precise relative atomic mass data to show how mass spectrometry
can be used to distinguish between pure sulfuric acid (H 2SO4) and pure phosphoric
acid (H3PO4) which both have Mr = 98 to two significant figures.

Atom Precise relative atomic mass

1
H 1.00794

16
O 15.99491

31
P 30.97376

32
S 32.06550

Page 6 of 30
 ___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________
(1)

(d) Concentrated phosphoric acid is used as a catalyst in the hydration of propene to

form the alcohol CH3CH(OH)CH3 as the main organic product.
The industrial name for this alcohol is isopropyl alcohol.

(i) State the meaning of the term catalyst.

______________________________________________________________

______________________________________________________________

______________________________________________________________
(1)

(ii) State the meaning of the term hydration.

______________________________________________________________

______________________________________________________________

______________________________________________________________
(1)

(iii) Write an equation for the hydration of propene to form isopropyl alcohol.
Give the IUPAC name for isopropyl alcohol.

Equation ______________________________________________________

IUPAC name ___________________________________________________

(2)
(Total 8 marks)

Q6.
Mass spectrometry is used by organic chemists to help distinguish between different
compounds.

Four isomers of C9H10O, shown below, were analysed by mass spectrometry.

Page 7 of 30
The mass spectra obtained from these four isomers were labelled in random order as I, II,
III and IV.

Each spectrum contained a molecular ion peak at m/z = 134

The data in the table below show the m/z values greater than 100 for the major peaks in
each spectrum due to fragmentation of the molecular ion. The table also shows where no
major peaks occurred.

Spectrum m/z values for major peaks No major peak at m/z

I 119 133, 105

II 133, 119 and 105

III 133, 105 119

IV 105 133, 119

(a) Two of the molecular ions fragmented to form an ion with m/z = 133 by losing a
radical.
Identify the radical that was lost.

___________________________________________________________________
(1)

(b) Two of the molecular ions fragmented to form an ion with m/z = 119 by losing a
radical.
Identify the radical that was lost.

___________________________________________________________________
(1)

(c) Three of the molecular ions fragmented to form ions with m/z = 105 by losing a
radical with Mr = 29

Identify two different radicals with Mr = 29 that could have been lost.

Radical 1 ___________________________________________________________

Radical 2 ___________________________________________________________
(2)

Page 8 of 30
 (d) Consider the structures of the four isomers and the fragmentations indicated in
parts (a) to (c).
Write the letter A, B, C or D, in the appropriate box below, to identify the compound
that produces each spectrum.

Spectrum I

Spectrum II

Spectrum III

Spectrum IV

(4)
(Total 8 marks)

Q7.
(a) Some scientists thought that the waste water from a waste disposal factory
contained two sodium halides.

They tested a sample of the waste water.

They added three reagents, one after the other, to the same test tube containing the
waste water.

The table below shows their results.

Reagent added Observations

1. Silver nitrate solution (acidified A cream precipitate formed

with dilute nitric acid)

2. Dilute ammonia solution A yellow precipitate remained

3. Concentrated ammonia solution The yellow precipitate did not

dissolve

(i) Identify the yellow precipitate that did not dissolve in concentrated ammonia
solution.
Write the simplest ionic equation for the formation of this precipitate from
silver ions and the correct halide ion.
Identify the other sodium halide that must be present in this mixture of two
sodium halides.

______________________________________________________________

______________________________________________________________

Page 9 of 30
 ______________________________________________________________

______________________________________________________________
(3)

(ii) Give one reason why the silver nitrate solution was acidified before it was
used in this test.

______________________________________________________________

______________________________________________________________

______________________________________________________________
(1)

(iii) The method that the scientists used could not detect one type of halide ion.
Identify this halide ion.
Give one reason for your answer.

______________________________________________________________

______________________________________________________________

______________________________________________________________

______________________________________________________________
(2)

(b) The scientists thought that the waste water also contained dissolved barium ions.
An aqueous solution of sodium sulfate can be used to test for the presence of
dissolved barium ions.

Write the simplest ionic equation for the reaction between barium ions and sulfate
ions to form barium sulfate.

State what is observed in this reaction.

Give a use for barium sulfate in medicine and explain why this use is possible, given
that solutions containing barium ions are poisonous.

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________
(4)

(c) The scientists also analysed the exhaust gases from an incinerator used to destroy

Page 10 of 30
 waste poly(ethene).
Mass spectrometry showed that there was a trace gas with a precise Mr = 28.03176
in the exhaust gases from the incinerator.

The table below contains some precise relative atomic mass data.

Atom Precise relative atomic mass

12
C 12.00000

1
H 1.00794
16
O 15.99491

Use the data to show that the trace gas is ethene. Show your working.

Suggest why both ethene and carbon monoxide might have been identified as the
trace gas if the scientists had used relative atomic masses to a precision of only one
decimal place.

Write an equation for the incomplete combustion of ethene to form carbon monoxide
and water only.

Ethene is used to make poly(ethene).

Draw the displayed formula for the repeating unit of poly(ethene).
Name this type of polymer.

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________
(5)
(Total 15 marks)

Q8.
A scientist used mass spectrometry to analyse a sample of the air near a fertiliser factory.
The sample of air included traces of a gas which was shown by its molecular ion to have a
precise Mr = 44.00105

(a) State the meaning of the term molecular ion.

Page 11 of 30
 ___________________________________________________________________

___________________________________________________________________
(1)

(b) (i) Use the following data to show that the trace gas was dinitrogen oxide (N 2O).

Show your working.

Atom Precise relative atomic

mass

12
C 12.00000

14
N 14.00307
16
O 15.99491

______________________________________________________________

______________________________________________________________
(1)

(ii) Propane is used as a fuel in the fertiliser factory. State why both propane and
its combustion product, carbon dioxide, might have been identified as the
trace gas if the scientist had used relative molecular masses calculated to one
decimal place.

______________________________________________________________

______________________________________________________________
(1)

(iii) State why the precise relative atomic mass for the 12C isotope is exactly
12.00000

______________________________________________________________
(1)

(c) Dinitrogen oxide is formed when ammonia is oxidised according to the following
equation.

2NH3(g) + 2O2(g) → N2O(g) + 3H2O(l)

(i) Use the standard enthalpies of formation in the table below to calculate a
value for the standard enthalpy change of this reaction.

NH3(g) O2(g) N2O(g) H2O(l)

ΔHfο/ kJ mol–1 –46 0 +82 –286

______________________________________________________________

Page 12 of 30
 ______________________________________________________________

______________________________________________________________

______________________________________________________________
(3)

(ii) State one condition necessary for enthalpies of formation to be quoted as

standard values at a specified temperature of 298 K.

______________________________________________________________
(1)
(Total 8 marks)

Q9.
Consider the following scheme of reactions.

(a) State the type of structural isomerism shown by propanal and propanone.

___________________________________________________________________
(1)

(b) A chemical test can be used to distinguish between separate samples of propanal
and propanone.

Identify a suitable reagent for the test.

State what you would observe with propanal and with propanone.

Test reagent ________________________________________________________

Observation with propanal _____________________________________________

Observation with propanone ____________________________________________

(3)

(c) State the structural feature of propanal and propanone which can be identified from
their infrared spectra by absorptions at approximately 1720 cm–1.

___________________________________________________________________
(1)

(d) The reaction of chlorine with propane is similar to the reaction of chlorine with
methane.

(i) Name the type of mechanism in the reaction of chlorine with methane.

Page 13 of 30
 ______________________________________________________________
(1)

(ii) Write an equation for each of the following steps in the mechanism for the
reaction of chlorine with propane to form l-chloropropane (CH3CH2CH2Cl).

Initiation step

______________________________________________________________

First propagation step

______________________________________________________________

Second propagation step

______________________________________________________________

A termination step to form a molecule with the empirical formula C 3H7

______________________________________________________________
(4)

(e) High resolution mass spectrometry of a sample of propane indicated that it was
contaminated with traces of carbon dioxide.

Use the data in the table to show how precise Mr values can be used to prove that
thesample contains both of these gases.

___________________________________________________________________

___________________________________________________________________

___________________________________________________________________
(2)
(Total 12 marks)

Q10.
It is necessary to use several analytical techniques to determine the structure of an
unknown compound.

An analytical chemist was asked to determine the structure of compound Q which was
found in a waste tank in a mixture of volatile liquids.

Compound Q has the molecular formula C4H7ClO. It is a volatile liquid which does not

Page 14 of 30
produce misty fumes when added to water.

(a) Suggest how the chemist could obtain a sample of Q for analysis from the mixture
of volatile liquids.

___________________________________________________________________
(1)

(b) The infra-red spectrum of Q contains a major absorption at 1724 cm –1. Identify the
bond which causes this absorption.

___________________________________________________________________
(1)

(c) The mass spectrum of Q contains two molecular ion peaks at m/z = 106 and m/z =
108.
It also has a major peak at m/z = 43.

(i) Suggest why there are two molecular ion peaks.

______________________________________________________________

(ii) A fragment ion produced from Q has m/z = 43 and contains atoms of three
different elements. Identify this fragment ion and write an equation showing its
formation from the molecular ion of Q.

Fragment ion ___________________________________________________

Equation ______________________________________________________
(3)

(d) The proton n.m.r. spectrum of Q was recorded.

(i) Suggest a suitable solvent for use in recording this spectrum of Q.

______________________________________________________________

(ii) Give the formula of the standard reference compound used in recording
proton n.m.r. spectra.

______________________________________________________________
(2)

(e) The proton n.m.r. spectrum of Q shows 3 peaks. Complete the table below to show
the number of adjacent, non-equivalent protons responsible for the splitting patterns.

Peak 1 Peak 2 Peak 3

Integration value 3 3 1

Splitting pattern doublet singlet quartet

Number of adjacent,
1
non-equivalent protons
(1)

Page 15 of 30
(f) Using the information in parts (a), (b) and (d) deduce the structure of compound Q.

(1)

(g) A structural isomer of Q reacts with cold water to produce misty fumes. Suggest a
structure for this isomer.

(1)
(Total 10 marks)

Page 16 of 30
Mark schemes

Q1.
This question is marked using levels of response. Refer to the Mark Scheme Instructions
for Examiners for guidance on how to mark this question.

How to choose the level Requirements for Stages

communication for
higher mark

Level 3 All three stages • Answer Stage 1

are covered communicates
5-6 and whole process Carries out a
marks explanation of coherently with test-tube reaction
each stage is logical to identify a
generally progression compound (or to
correct and • Chemical tests split the
virtually (appear to) start compounds into
complete – with all two groups).
leads to all compounds rather
four than selected 1a reagent
compounds compounds
• Chemical tests 1b observation
being with correct
distinguished reagents and
observations are deduction
complete and
Stage 2
correct
• Chemical tests Carries out a
leave two second test-tube
compounds to be reaction to identify
distinguished by a second
spectroscopy compound.
• Enough detail is
given about the 2a reagent
spectroscopy to
distinguish these 2b observation
two compounds with correct
• Answer is mainly deduction
Level 2 All three stages Two stages
are covered but covered and coherent
• Chemical tests Stage 3
3-4 the explanations
marks explanations of are generally reagents and Uses spectroscopy
each stage correct and observations are to distinguish two
may be virtually complete and compounds.
incomplete or complete correct
may contain • Enough detail is 3a suitable
inaccuracies given about the technique
spectroscopy to
distinguish these 3b data that will
two compounds distinguish
(if spectroscopy compounds
included)
Level 1 Two stages One stage • Chemical tests
covered but the covered and reagents and
1-2 explanations of explanation is observations are
marks each stage generally complete and
may be correct and correct (if
incomplete or virtually awarded level 1
may contain complete for one chemical
inaccuracies test stage)
• Enough detail is

Page 17 of 30
 given about the
spectroscopy to
distinguish these
two compounds
(if spectroscopy
included)
0 marks Nothing valid to warrant a mark

Possible test tube reactions Possible spectroscopic methods

for a pair
Tollens’ reagent [or Fehling’s /
Benedict’s] IR (infra-red) spectroscopy
Identifies butanal – silver mirror (or
If different functional groups: need
black ppt) [or orange/brick/red pptto identify wavenumber and bond of
with Fehling’s] key functional group signal (e.g.
(No reaction with other compounds) (alcohol) O-H 3230-3550 or C=O
1680-1750 (cm–1)).
Acidified potassium dichromate If same functional group, need idea
Reacts with butanal and butan-2-ol of using fingerprint region to look for
– goes green match to known compounds /
(No reaction with other compounds) comparing region to samples in a
database
Sodium (not on specification but
may be mentioned) Mass spectrometry
If different, can use different Mr
Reacts with butan-2-ol and
2-methylpropan-2-ol – fizzes values with values of Mr given
butanone 72(.0),
(No reaction with other compounds) 2-methylpropan-2-ol = 74(.0),
butan-2-ol = 74(.0), butanal = 72(.0)
Examples of incomplete/incorrect
reagents include “Tolling’s solution”, If compounds have same Mr, then
no acid with potassium dichromate, would have to use idea that
wrong oxidation state for Cr in fragmentation patterns would be
potassium dichromate if stated. different (not on specification but
may be mentioned)
Examples of incomplete/incorrect
observations include silver
precipitate with Tollens’, green ppt
with acidified potassium dichromate
[6]

Q2.
C
[1]

Q3.
(a) M1 have the same molecular formula
or are C3H6O
or both have the same number/amount of each type of atom or same amount
of each element
or are isomers
Not just the same atoms;
1

Page 18 of 30
 M2 identical / exactly the same / same precise (relative) molecular
mass / formula mass / Mr
Same (relative) molecular mass / formula mass / Mr is NOT
enough got score M2
Allow same accurate (relative) molecular mass / formula
mass / Mr
Ignore reference to number of decimal places
1

(b) M1 prop-2-en-1-ol
Must refer to this compound clearly by name or structure (not
to alcohol alone); ignore minor slips in name/structure
1

M2 O(-)H (alcohol) and 3230–3550 (cm−1), or

C=C and 1620–1680 (cm−1)
Marked independently from M1
Could score from bond labelled on correct signal on
spectrum
Allow any value within these ranges
If additional incorrect signals given penalise M2
Ignore signals below 1500 cm−1 and C-H signals
1

(c) (i) Determine the level by looking at the chemical content. (NB - If there is
clear breakage of covalent bonds then max level 2 (max 3 marks).

(ii) The mark within that level is then determined by looking at how coherent
and logical the answer is and by use of terminology; start at the higher
mark and penalise poor terminology/explanation; examples of
terminology that would reduce the mark to the lower one:

• reference to van der Waals ‘bonds’ or dipole-dipole ‘bonds in

relevant compounds that are being credited
• uncertainty about whether hydrogen bonds are the O-H bonds
within or are forces/bonds between molecules (if the alcohol is
being credited)
• use of ‘vdw’ or ‘dip-dip’ unless these terms ‘van der Waals’ for
‘dipole-dipole’ have been used elsewhere in answer (note that IMF
and H-bond would not be penalised)

(iii) If the answer does not achieve level 1, then 1 mark maximum could be
scored for any correct point from the list of indicative content

Level 3
• Relative order of boiling points of all three compounds
• Strongest intermolecular force of all three compounds identified
• Answer explains this coherently and logically and uses correct terminology for
all three compounds
5-6 marks

Level 2
• Relative boiling points of two compounds correctly compared
• Strongest intermolecular force for these two compounds correctly identified
• Answer explains this coherently and logically and uses correct terminology for
these two compounds

Page 19 of 30
 3-4 marks

Level 1
• One compound with the highest or lowest boiling point is correctly identified
• Strongest intermolecular force for that one compound identified
• Answer explains this coherently and logically and uses correct terminology for
this one compound
• Allow 1 mark for individual correct point from indicative content on the right if
no other mark scored
1-2 marks

Level 0
None of the indicative chemistry content given.
0 marks
Indicative chemistry content:
• Correct order (highest to lowest) = prop-2-en-1-ol >
propanal > butane
• Prop-2-en-1-ol has hydrogen bonds
• Propanal has (permanent) dipole-dipole forces
• Butane has van der Waals’ forces
• Strength of intermolecular forces:
hydrogen bonds > dipole-dipole > van der Waals
(Note - actual values for reference are prop-2-en-1-ol 97°C,
propanal 46°C and butane −1°C)
[10]

Q4.
(a) (i) C4H10

Mr = 4(12.00000) + 10(1.00794)

= 58.07940 or 58.0794 or 58.079 or 58.08

and 58.1
Working is essential, leading to the final value of 58.1 which
must be stated in addition to one of the four numbers
underlined
1

(ii) By definition
OR
The standard / reference (value / isotope)
Reference to 12C alone is not enough
1

(b)

All bonds and atoms must be drawn

Give credit for the displayed formula for the anion
1

Page 20 of 30
 (c) (i) H2C = CHCH2OH
Any correct representation including correct use of “sticks”.
Require the double bond to be shown
1

(ii) Addition (polymerisation)

ONLY this answer
1

(iii) M1 C = C (in range) 1620 to 1680 (cm−1)

M2 O ‒ H (in range) 3230 to 3550 (cm−1)

Award one mark for two correct ranges but a failure to draw
out the C = C or O‒H bonds
2

(d) (i) CH3COCH3

Any correct representation including correct use of “sticks”
1

(ii) C
1
[9]

Q5.
(a) 2Ca5F(PO4)3+ 9SiO2 +15C9CaSiO3 + CaF2 +15CO + 6P
1

(b) M1 (P4 =) 0

M2 (H3PO4 =) (+) 5
Accept Roman numeral V for M2
2

(c) H2SO4
Both numbers required

Mr = 2(1.00794) + 32.06550 + 4(15.99491)

= 98.06102 or 98.0610 or 98.061 or 98.06 or 98.1
Calculations not required

and

H3PO4

Mr = 3(1.00794) + 30.97376 + 4(15.99491)

= 97.97722 or 97.9772 or 97.977 or 97.98 or 98.0
1

(d) (i) A substance that speeds up a reaction OR alters / increases the rate of a
reaction AND is chemically unchanged at the end / not used up.
Both ideas needed
Ignore reference to activation energy or alternative route.
1

(ii) The addition of water (QoL ) to a molecule / compound

Page 21 of 30
 QoL- for the underlined words
1

(iii) M1 CH3CH=CH2 + H2O CH3CH(OH)CH3

(C3H6)
For M1 insist on correct structure for the alcohol but credit
correct equations using either C3H6 or double bond not given.

M2 propan-2-ol
2
[8]

Q6.
(a) H OR hydrogen OR H•
Ignore brackets ignore dot
penalise + or – charge
1

(b) CH3 OR methyl OR CH3• OR •CH3

Ignore brackets ignore dot
penalise + or – charge
1

(c) Either order

C2H5 OR ethyl OR CH3CH2• OR C2H5•

Ignore brackets ignore dot
penalise + or – charge
1

CHO OR HCO OR COH OR H—C=O

1

(d) I A
1

II C
1

III D
1

IV B
1
[8]

Q7.
(a) (i) M1 (yellow precipitate is) silver iodide OR AgI (which
may be awarded from the equation)

M2 Ag+ + I– → AgI (Also scores M1 unless contradicted)

M3 sodium chloride OR NaCl

Page 22 of 30
 For M2
Accept multiples
Ignore state symbols
Allow crossed out nitrate ions, but penalise if not crossed out
3

(ii) The silver nitrate is acidified to

• react with / remove ions that would interfere with the test

• prevent the formation of other silver precipitates / insoluble silver

compounds that would interfere with the test

• remove (other) ions that react with the silver nitrate

• react with / remove carbonate / hydroxide / sulfite (ions)

Ignore reference to “false positive”
1

(iii) M1 and M2 in either order

M1 Fluoride (ion) OR F–

M2 • Silver fluoride / AgF is soluble / dissolves (in water)

• no precipitate would form / no visible /observable change

Do not penalise the spelling “fluoride”,
Penalise “fluride” once only
Mark M1 and M2 independently
2

(b) M1 Ba2+ + SO42- → BaSO 4

(or the ions together)

M2 white precipitate / white solid / white suspension

M3 Barium meal or ( internal ) X-ray or to block X-rays

M4 BaSO4 / barium sulfate is insoluble (and therefore not toxic)

For M1, ignore state symbols
Allow crossed out sodium ions, but penalise if not crossed
out
For M2, ignore “milky”
If BaSO3 OR BaS used in M1 and M4, penalise once only
For M3 Ignore radio-tracing
For M4 NOT barium ions
NOT barium
NOT barium meal
NOT “It” unless clearly BaSO4
4

(c) M1 2(12.00000) + 4(1.00794) = 28.03176

Page 23 of 30
 M2 Ethene and CO or “they” have an imprecise Mr of 28.0 / 28

OR

Ethene and CO or “they” have the same Mr to one d.p.

OR

These may be shown by two clear, simple sums identifying

both compounds

M3 C2H4 + 2O2 → 2CO + 2H O 2

(H2C=CH2)

M4 Displayed formula

M5 Type of polymer = Addition (polymer)

M1 must show working using 5 d.p.for hydrogen
Penalise “similar” or “close to”, if this refers to the
imprecise value in M2, since this does not mean “the same”
For M3, accept CH2=CH2 OR CH2CH2
For M4, all bonds must be drawn out including those on
either side of the unit.
Penalise “sticks”
Ignore brackets around correct repeating unit but penalise
“n”
Penalise “additional”
5
[15]

Q8.
(a) The molecular ion is

• The molecule with one/an electron knocked off/lost

Ignore the highest or biggest m/z peak

OR

• The molecule with a (single) positive charge

OR

• the ion with/it has the largest/highest/biggest m/z (value/ratio)

Ignore “the peak to the right”

OR

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 • the ion with/it has an m/z equal to the Mr
Ignore “compound”
1

(b) (i) 2(14.00307) + 15.99491 = 44.00105

A sum is needed to show this
1

(ii) Propane/C3H8 and carbon dioxide/CO2 (and N2O) or

they or both the gases/molecules or all three gases/molecules
have an (imprecise) Mr of 44.0 (OR 44)

OR

they have the same Mr or molecular mass (to one d.p)

This could be shown in a calculation of relative masses for
propane and carbon dioxide
1

(iii) By definition

OR

The standard/reference (value/isotope)

Ignore “element”
Ignore “atom”
1

(c) (i) M1 (could be scored by a correct mathematical expression)

ΔH = ΣΔHproducts – ΣΔHreactants

OR a correct cycle of balanced equations

M1 and M2 can be scored with correct moles as follows

ΔH + 2(– 46) = +82 + 3(– 286)

ΔH – 92 = – 776

ΔH = 92 – 776 OR 92 + 82 – 858

M3
ΔH = – 684 (kJ mol–1) (This is worth 3 marks)

Award 1 mark ONLY for + 684

Full marks for correct answer.
Ignore units.
Deduct one mark for an arithmetic error.
3

(ii) The value is quoted at a pressure of 100 kPa OR 1 bar or 105 Pa

OR

All reactants and products are in their standard states/their normal

states at 100 kPa or 1 bar
Ignore 1 atmosphere/101 kPa

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 Ignore “constant pressure”
1
[8]

Q9.
(a) Functional group (isomerism)
1

(b)
M1 Tollens’ (reagent) M1 Fehling’s (solution) or
(Credit ammoniacal silver nitrate Benedict’s solution
OR a description of making (Ignore Cu2+(aq) or
Tollens’) CuSO4 on their own, but mark
(Ignore either AgNO3 or [Ag(NH3)2+] on to M2 and M3)
or “the silver mirror test” on their
own, but mark M2 and M3)
M2 Red solid/precipitate
M2 silver mirror (Credit orange or brown solid)

OR

black solid/precipitate
(NOT silver precipitate)
M3 (stays) blue
M3 (stays) colourless or no change or no reaction
or no change or no reaction

Mark on from an incomplete/incorrect attempt at the correct

reagent, penalising M1
No reagent, CE=0
Allow the following alternatives
M1 (acidified) potassium dichromate(VI) (solution)
M2 (turns) green
M3 (stays) orange/no change
OR
M1 (acidified) potassium manganate(VII) (solution)
M2 (turns) colourless
M3 (stays) purple/no change
For M3
Ignore “nothing (happens)”
Ignore “no observation”
3

(c) (Both have) C=O OR a carbonyl (group)

1

(d) (i) (Free-) radical substitution ONLY

Penalise “(free) radical mechanism”
1

(ii) Initiation
Cl2 → 2Cl•
Penalise absence of dot once only.

First propagation

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 Cl• + CH3CH2CH3 → •CH2CH2CH3 + HCl
OR C3H8
Penalise incorrect position of dot on propyl radical once only.
Penalise C3H7• once only

Second propagation
Cl2 + •CH2CH2CH3 → CH3CH2CH2Cl + Cl•

OR

C3H7Cl
Accept CH3CH2CH2• with the radical dot above/below/to the
side of the last carbon.

Termination (must make C6H14)

2 •CH2CH2CH3 → C6H14 or CH3CH2CH2CH2CH2CH3
Use of the secondary free radical might gain 3 of the four
marks
4

(e) Mr = 44.06352 (for propane)

Mr = 43.98982 (for carbon dioxide)
Mark independently

M1 a correct value for both of these Mr values.

M2 a statement or idea that two peaks appear (in the mass spectrum)

OR

two molecular ions are seen (in the mass spectrum).

2
[12]

Q10.
(a) GLC or distillation
1

(b) C=O
1

(c) (i) Cl has two isotopes

1

(ii)
1

C4H7ClO+• → + C2H4Cl•
1

(d) (i) e.g. CDCl3 or CCl4

1

(ii) Si(CH3)4
1

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(e) 0 and 3
1

(f)

(g) CH3CH2CH2COCl or (CH3)2CHCOCl

1
[10]

Page 28 of 30
Examiner reports

Q1.
Many students approached this question as if they already knew which compound was
which. They did not appreciate the need to carry out the first test with all four compounds
to start to work out which is which. Many used the test with acidified potassium
dichromate(VI) but did not realise that butanal as well as butan-2-ol would react. Few
successfully identified two compounds using two test tube reactions, leaving the other two
compounds to be distinguished by IR spectroscopy or mass spectrometry. Many did not
explain how one of these spectroscopic methods could actually be used to distinguish the
final two compounds. Overall, though, the question discriminated well.

Q2.
Students also found this question challenging (41.8% correct), with many failing to
appreciate that only one molecule did not contain any oxygen and so must have a
different value from the others.

Q3.
Organic molecules with the same Mr

Many students could know in (a) that the three molecules had the same molecular formula
or were isomers, but few stated that they had identical relative formula masses. Most
students in (b) could identify the prop-2-en-1-ol using the IR spectrum stating the use of
the O-H or C=C absorption to do so. (c) question proved challenging and discriminated
well. The best students could identify the correct order of boiling points, identify the correct
intermolecular forces and use good language to communicate this in a structured way.
Many students could identify van der Waals’ forces in butane and hydrogen bonds in
prop-2-en-1-ol, but few could identify permanent dipole-dipole forces in propanal. Indeed,
many students mistakenly thought that propanal had hydrogen bonding. In addition, many
students referred incorrectly to the breaking of covalent bonds and referred to the strength
of the covalent bonds, rather than concentrating on intermolecular forces.

Q4.
This was answered well overall. In part (a)i the answer required students to demonstrate
that they could both identify the number they were rounding and follow through with that
rounding process. Students who choose to draw displayed formulas on every occasion
that they are required to draw an organic structure are far less likely to make errors in their
structures and this proved to be the case in this question. part (c)iii was expected to be
very straightforward and 78% scored both marks; common errors included either incorrect
values for the absorption ranges taken from Table A or reference to bonds such as C−O,
C−H or C−C that are not due to functional groups. Only 69% correctly attributed functional
group isomerism in part (d)ii, with 30% choosing position isomerism.

Q5.
Balancing the equation in part (a) taxed some students but most were able to score at
least one mark in part (b). There was a need for students to use correct chemical
terminology in part (d), requiring, for example, reference to the “addition of water” in part
(d)(ii). It was surprising to see how many made simple errors in the relatively
straightforward part (d)(iii), for example, naming the alcohol as propanol rather than
propan–2–ol.

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Q6.
All parts of this question on Mass Spectrometry were answered well, especially part (c). In
part (a), an ion or radical with m/z =133 was sometimes given rather than a hydrogen
radical. In part (b), an oxygen radical or an oxide ion O– were suggested quite frequently.
Over half of the students correctly identified all four spectra in part (d).

Q7.
Inorganic chemistry is a weakness for many candidates and this question proved
challenging for some. Not surprisingly sodium bromide was a common incorrect response
in part (a)(i).

Only the better candidates knew the reason for acidifying the silver nitrate solution in part
(a)(ii) but the inability of this reagent to detect fluoride ions in part (a)(iii) was reasonably
well known. Part (b) was a good discriminator; the relatively easy equation and
observation marks eluded some. In part (c) most candidates could use the data to arrive
at the correct precise Mr value but were less effective in explaining that the Mr values are
the same when using one decimal place. The equation for complete combustion of ethene
was done well but neither the displayed formula for the repeating unit nor the type of
polymer scored highly.

Q8.
In part (a), candidates rarely knew the meaning of the term molecular ion. In part (b), most
could show why the answer for the precise Mr of N2O was 44.00105, but the fact that both
propane and carbon dioxide could be confused with N 2O using Mr values to one decimal
place, was not always explained. In part (b)(iii), the idea that the precise Mr for the 12C
isotope is defined as exactly 12.00000 was poorly understood. The calculation proved
straightforward for many candidates with 65% gaining full marks. The common mistake
was an answer of +684 kJ mol–1. Only half of the candidates knew about a standard
pressure of 100 kPa in part (c)(ii).

Q9.
Recognising functional group isomerism in part (a) proved difficult for many candidates
whereas testing for an aldehyde was generally done well in part (b). The free-radical
substitution in part (d) produced a wide range of marks and only the best candidates
scored full marks. The use of precise Mr values in part (e) was new and only 38% scored
any marks.

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