4.

3 [153 marks]
1a. [2 marks]
Compound A is in equilibrium with compound B.

Predict the electron domain and molecular geometries around the oxygen atom of
molecule A using VSEPR

Markscheme
Electron domain geometry: tetrahedral ✔
Molecular geometry: bent/V-shaped ✔
1b. [1 mark]
State the type of hybridization shown by the central carbon atom in molecule B.

Markscheme
s p2 ✔
1c. [1 mark]
State the number of sigma (σ ) and pi (π) bonds around the central carbon atom in molecule
B.

Markscheme
σ -bonds: 3
AND
π-bonds: 1 ✔
1d. [1 mark]
The IR spectrum of one of the compounds is shown:

COBLENTZ SOCIETY. Collection © 2018 copyright by the U.S. Secretary of Commerce on

behalf of the United States of America. All rights reserved.
Deduce, giving a reason, the compound producing this spectrum.
Markscheme
B AND C=O absorption/1750<¿ c m −1 >¿ 
OR
B AND absence of O H /3200− 3600<¿ c m− 1 a b s o r p t i o n>¿✔

Accept any value between 1700 −1750 c m− 1.

1e. [2 marks]
Compound A and B are isomers. Draw two other structural isomers with the formula
C 3 H 6 O.

Markscheme
Accept any two  C 3 H 6 O isomers except for propanone and propen-2-ol:
 ✔✔
 
Penalize missing hydrogens in displayed structural formulas once only.
1f. [1 mark]
The equilibrium constant, K c , for the conversion of A to B is 1.0 ×108 in water at 298 K.
Deduce, giving a reason, which compound, A or B, is present in greater concentration when
equilibrium is reached.
Markscheme
B AND K c is greater than 1/large ✔

1g. [1 mark]
Calculate the standard Gibbs free energy change, G , in k J m o l1 , for the reaction (A to B) at
❑

298 K. Use sections 1 and 2 of the data booklet.

Markscheme
¿< Δ G Θ=− R T ln K=0.00831 k J mo l − 1 K − 1 ( 298 K ) ( ln 1.0 ×108 ) =¿>¿
− 46<¿ k J m o l −1 >¿ ✔
1h. [3 marks]
Propanone can be synthesized in two steps from propene. Suggest the synthetic route
including all the necessary reactants and steps.
Markscheme

H 2 O /water «and H +¿¿ » ✔

C H 3 C H (O H ) C H 3/propan-2-ol ✔

K 2 C r 2 O7 /«potassium» dichromate(VI) AND H +¿¿

OR
K M n O4 /«acidified potassium» manganate(VII) ✔
+ ¿¿
Accept H 3 O .
 
 
1i. [2 marks]
Propanone can be synthesized in two steps from propene.
Suggest why propanal is a minor product obtained from the synthetic route in (g)(i).

Markscheme
primary carbocation «intermediate forms»
OR
minor product «of the water addition would be» propan-1-ol
OR
anti-Markovnikov addition of water ✔
primary alcohol/propan-1-ol oxidizes to an aldehyde/propanal ✔
2. [1 mark]
Which describes a resonance structure?
A.  Double bond can be drawn in alternative positions.

B.  Bonds vibrate by absorbing IR radiation.

C.  A double and a single bond in the molecule

D.  A Lewis structure

Markscheme
A
3. [1 mark]
What is the structure and bonding in SiO2 (s)?

Markscheme
A
4. [1 mark]
Which species does not have resonance structures?
A. C6H6
B. NH4+
C. CO32−
D. O3
Markscheme
B
5. [1 mark]
Which molecule contains an incomplete octet of electrons?
A. NF3
B. BF3
C. BrF
D. SF2

Markscheme
B
6a. [2 marks]
The equations show steps in the formation and decomposition of ozone in the stratosphere,
some of which absorb ultraviolet light.

Step 1    O2 → 2O•
Step 2    O• + O2 → O3
Step 3    O3 → O• + O2
Step 4    O• + O3 → 2O2
Draw the Lewis structures of oxygen, O2, and ozone, O3.

Markscheme

NOTES: Coordinate bond may be represented by an arrow.

Do not accept delocalized structure for ozone.
6b. [2 marks]
Outline why both bonds in the ozone molecule are the same length and predict the bond
length in the ozone molecule. Refer to section 10 of the data booklet.
Reason: 
Length:

Markscheme
resonance «structures»
OR
delocalization of «the double/pi bond» electrons ✔
121 «pm» < length < 148 «pm» ✔
NOTE: Accept any length between these two values.
6c. [1 mark]
Distinguish ultraviolet light from visible light in terms of wavelength and energy.

Markscheme
«UV» shorter wavelength AND higher energy «than visible» ✔
6d. [2 marks]
Discuss how the different bond strengths between the oxygen atoms in O 2 and O3 in the
ozone layer affect radiation reaching the Earth’s surface.
Markscheme
«bond» in O2 stronger than in O3 ✔

ozone absorbs lower frequency/energy «radiation than oxygen»

OR
ozone absorbs longer wavelength «radiation than oxygen» ✔
 
NOTE: Accept ozone «layer» absorbs a range of frequencies.
7a. [1 mark]
Both vinegar (a dilute aqueous solution of ethanoic acid) and bleach are used as cleaning
agents.
Outline why ethanoic acid is classified as a weak acid.

Markscheme
partial dissociation «in aqueous solution»  [✔]
7b. [3 marks]
A solution of bleach can be made by reacting chlorine gas with a sodium hydroxide
solution.
Cl2 (g) + 2NaOH (aq) ⇌ NaOCl (aq) + NaCl (aq) + H2O (l)
Suggest, with reference to Le Châ telier’s principle, why it is dangerous to mix vinegar and
bleach together as cleaners.
Markscheme
ethanoic acid/vinegar reacts with NaOH  [✔]
moves equilibrium to left/reactant side [✔]
releases Cl2 (g)/chlorine gas
OR
Cl2 (g)/chlorine gas is toxic  [✔]
 
Note: Accept “ethanoic acid produces H+ ions”.
Accept “ethanoic acid/vinegar reacts with NaOCl”.
Do not accept “2CH3COOH + NaOCl + NaCl → 2CH3COONa + Cl2 + H2O” as it does not refer to
equilibrium.

Accept suitable molecular or ionic equations for M1 and M3.

7c. [1 mark]
Bleach reacts with ammonia, also used as a cleaning agent, to produce the poisonous
compound chloramine, NH2Cl.
Draw a Lewis (electron dot) structure of chloramine.
Markscheme

 [✔]
 
Note: Accept any combination of dots/crosses or lines to represent electron pairs.
7d. [2 marks]
Deduce the molecular geometry of chloramine and estimate its H–N–H bond angle.
 
Molecular geometry:
H–N–H bond angle:

Markscheme
Molecular geometry:
«trigonal» pyramidal  [✔]
H–N–H bond angle:
107°  [✔]
 
Note: Accept angles in the range of 100–109.
8a. [1 mark]
Ethyne, C2H2, reacts with oxygen in welding torches.
Write an equation for the complete combustion of ethyne.

Markscheme
C2H2 (g) + 2.5O2 (g) → 2CO2 (g) + H2O (l)
OR
2C2H2 (g) + 5O2 (g) → 4CO2 (g) + 2H2O (l)  [✔]
8b. [1 mark]
Deduce the Lewis (electron dot) structure of ethyne.

Markscheme

  [✔]
 
Note: Accept any valid combination of lines, dots and crosses.
8c. [1 mark]
Compare, giving a reason, the length of the bond between the carbon atoms in ethyne with
that in ethane, C2H6.
Markscheme
«ethyne» shorter AND a greater number of shared/bonding electrons
OR
«ethyne» shorter AND stronger bond  [✔]
8d. [1 mark]
Identify the type of interaction that must be overcome when liquid ethyne vaporizes.

Markscheme
London/dispersion/instantaneous dipole-induced dipole forces  [✔]
 
Note: Do not accept just “intermolecular forces” or “van der Waals’ forces”.
8e. [1 mark]
Ethyne reacts with steam.
C2H2 (g) + H2O (g) → C2H4O (g)
Two possible products are:
Product A contains a carbon–carbon double bond. State the type of reactions that
compounds containing this bond are likely to undergo.

Markscheme
«electrophilic» addition/A«E»  [✔]
 
Note: Accept “polymerization”.
8f. [1 mark]
State the name of product B, applying IUPAC rules.

Markscheme
ethanal  [✔]
8g. [3 marks]
Determine the enthalpy change for the reaction, in kJ, to produce A using section 11 of the
data booklet.
Markscheme
«sum of bond enthalpies of reactants =» 2(C–H) + C≡C + 2(O–H)
OR
2 × 414 «kJ mol–1» + 839 «kJ mol–1» + 2 × 463 «kJ mol–1»
OR
2593 «kJ»  [✔]
«sum of bond enthalpies of A =» 3(C–H) + C=C + C–O + O–H
OR
3 × 414 «kJ mol–1» + 614 «kJ mol–1» + 358 «kJ mol–1» + 463 «kJ mol–1»
OR
2677 «kJ»  [✔]
«enthalpy of reaction = 2593 kJ – 2677 kJ» = –84 «kJ»  [✔]
 
Note: Award [3] for correct final answer.
8h. [1 mark]
The enthalpy change for the reaction to produce B is −213 kJ. Predict, giving a reason,
which product is the most stable.

Markscheme
B AND it has a more negative/lower enthalpy/«potential» energy
OR
B AND more exothermic «enthalpy of reaction from same starting point»  [✔]
8i. [2 marks]
The IR spectrum and low resolution 1H NMR spectrum of the actual product formed are
shown.
Deduce whether the product is A or B, using evidence from these spectra together with
sections 26 and 27 of the data booklet.
 
Identity of product:
One piece of evidence from IR:
One piece of evidence from 1H NMR:
Markscheme
Identity of product: «B»
IR spectrum:
1700–1750 «cm–1 band» AND carbonyl/CO group present
OR
no «band at» 1620–1680 «cm–1» AND absence of double bond/C=C
OR
no «broad band at» 3200–3600 «cm–1» AND absence of hydroxyl/OH group  [✔]
Note: Accept a specific value or range of wavenumbers and chemical shifts.
1
H NMR spectrum:
«only» two signals AND A would have three
OR
«signal at» 9.4–10.0 «ppm» AND «H atom/proton of» aldehyde/–CHO present
OR
«signal at» 2.2–2.7 «ppm» AND «H atom/proton of alkyl/CH next to» aldehyde/CHO
present
OR
«signal at» 2.2–2.7 «ppm» AND «H atom/proton of» RCOCH2- present
OR
no «signal at» 4.5–6.0 «ppm» AND absence of «H-atom/proton next to» double bond/C=C  
[✔]
Note: Accept “two signals with areas 1:3”.
8j. [2 marks]
Product B, CH3CHO, can also be synthesized from ethanol.
Suggest the reagents and conditions required to ensure a good yield of product B.
 
Reagents:
Conditions:

Markscheme
Reagents:
acidified/H+ AND «potassium» dichromate«(VI)»/K2Cr2O7/Cr2O72–  [✔]
Conditions:
distil «the product before further oxidation»  [✔]
 
Note: Accept “«acidified potassium» manganate(VII)/KMnO4/MnO4–/permanganate”.
Accept “H2SO4” or “H3PO4” for “H+”.
Accept “more dilute dichromate(VI)/manganate(VII)” or “excess ethanol”.
Award M1 if correct reagents given under “Conditions”.
8k. [1 mark]
Deduce the average oxidation state of carbon in product B.

Markscheme
–1  [✔]
8l. [3 marks]
Explain why product B is water soluble.
Markscheme
Any three of:
has an oxygen/O atom with a lone pair  [✔]
that can form hydrogen bonds/H-bonds «with water molecules» [✔]
hydrocarbon chain is short «so does not disrupt many H-bonds with water molecules» [ ✔]
«large permanent» dipole-dipole interactions with water [✔]
9a. [1 mark]
Both vinegar (a dilute aqueous solution of ethanoic acid) and bleach are used as cleaning
agents.
Outline why ethanoic acid is classified as a weak acid.

Markscheme
partial dissociation «in aqueous solution»    [✔]
9b. [3 marks]
A solution of bleach can be made by reacting chlorine gas with a sodium hydroxide
solution.
Cl2 (g) + 2NaOH (aq) ⇌ NaOCl (aq) + NaCl (aq) + H2O (l)
Suggest, with reference to Le Châ telier’s principle, why it is dangerous to mix vinegar and
bleach together as cleaners.
Markscheme
ethanoic acid/vinegar reacts with NaOH    [✔]
moves equilibrium to left/reactant side    [✔]
releases Cl2 (g)/chlorine gas
OR
Cl2 (g)/chlorine gas is toxic    [✔]
 
Note: Accept “ethanoic acid produces H+ ions”
Accept “ethanoic acid/vinegar reacts with NaOCl”.
Do not accept “2CH3COOH + NaOCl + NaCl → 2CH3COONa + Cl2 + H2O” as it does not refer to
equilibrium.
Accept suitable molecular or ionic equations for M1 and M3.
9c. [1 mark]
Bleach reacts with ammonia, also used as a cleaning agent, to produce the poisonous
compound chloramine, NH2Cl.
Draw a Lewis (electron dot) structure of chloramine.
Markscheme

    [✔]
 
Note: Accept any combination of dots/crosses or lines to represent electron pairs.
9d. [1 mark]
State the hybridization of the nitrogen atom in chloramine.

Markscheme
sp3    [✔]
9e. [2 marks]
Deduce the molecular geometry of chloramine and estimate its H–N–H bond angle.
Molecular geometry:
H–N–H bond angle:
Markscheme
Molecular geometry:
«trigonal» pyramidal   [✔]

H–N–H bond angle:

107°    [✔]

 
Note: Accept angles in the range of 100–109.
9f. [1 mark]
State the type of bond formed when chloramine is protonated.

Markscheme
covalent/dative/coordinate    [✔]
9g. [2 marks]
Sketch a graph of pH against volume of hydrochloric acid added to ammonia solution,
showing how you would determine the pKa of the ammonium ion.
 
Markscheme

correct shape of graph AND vertical drop at Vn    [✔]

Vn
pKa = pH at /half neutralization/half equivalence    [✔]
2
 
Note: M1: must show buffer region at pH > 7 and equivalence point at pH < 7. Graph must
start below pH = 14.
9h. [1 mark]
Suggest a suitable indicator for the titration, using section 22 of the data booklet.

Markscheme
methyl orange
OR
bromophenol blue
OR
bromocresol green
OR
methyl red    [✔]
9i. [2 marks]
Explain, using two equations, how an equimolar solution of ammonia and ammonium ions
acts as a buffer solution when small amounts of acid or base are added.

Markscheme
NH3 (aq) + H+ (aq) → NH4 + (aq)    [✔]
NH4 + (aq) + OH− (aq) → NH3 (aq) + H2O(l)    [✔]
 
Note: Accept reaction arrows or equilibrium signs in both equations.
Award [1 max], based on two correct reverse equations but not clearly showing reacting with
acid or base but rather dissociation.
10a. [1 mark]
Ethyne, C2H2, reacts with oxygen in welding torches.
Write an equation for the complete combustion of ethyne.

Markscheme
C2H2 (g) + 2.5O2 (g) → 2CO2 (g) + H2O (l)
OR
2C2H2 (g) + 5O2 (g) → 4CO2 (g) + 2H2O (l)    [✔]
10b. [1 mark]
Deduce the Lewis (electron dot) structure of ethyne.

Markscheme

    [✔]
 
Note: Accept any valid combination of lines, dots and crosses.
10c. [1 mark]
Compare, giving a reason, the length of the bond between the carbon atoms in ethyne with
that in ethane, C2H6.

Markscheme
«ethyne» shorter AND a greater number of shared/bonding electrons
OR
«ethyne» shorter AND stronger bond     [✔]
10d. [1 mark]
Identify the type of interaction that must be overcome when liquid ethyne vaporizes.

Markscheme
London/dispersion/instantaneous dipole-induced dipole forces    [✔]
10e. [1 mark]
Ethyne reacts with steam.
C2H2 (g) + H2O (g) → C2H4O (g)
Two possible products are:

State the name of product B, applying IUPAC rules.

Markscheme
ethanal    [✔]
10f. [3 marks]
Determine the enthalpy change for the reaction, in kJ, to produce A using section 11 of the
data booklet.
Markscheme
«sum of bond enthalpies of reactants =» 2(C—H)+C ≡ C + 2(O—H)
OR
2 × 414 «kJ mol-1» + 839 «kJ mol-1» + 2 × 463 «kJ mol-1»
OR
2593 «kJ»    [✔]
 
«sum of bond enthalpies of A =» 3(C—H) + C=C + C—O + O—H
OR
3 × 414 «kJ mol-1» + 614 «kJ mol-1» + 358 «kJ mol-1» + 463 «kJ mol-1»
OR
2677 «kJ»     [✔]
«enthalpy of reaction = 2593 kJ – 2677 kJ» = –84 «kJ»     [✔]
 
Note: Award [3] for correct final answer.
10g. [1 mark]
The enthalpy change for the reaction to produce B is −213 kJ.
Predict, giving a reason, which product is the most stable.

Markscheme
B AND it has a more negative/lower enthalpy/«potential» energy
OR
B AND more exothermic «enthalpy of reaction from same starting point»     [✔]
10h. [2 marks]
The IR spectrum and low resolution 1H NMR spectrum of the actual product formed are
shown.
Deduce whether the product is A or B, using evidence from these spectra together with
sections 26 and 27 of the  data booklet.
Identity of product:
One piece of evidence from IR:
One piece of evidence from 1H NMR:
 
Markscheme
Identity of product: «B»
IR spectrum:
1700–1750 «cm–1 band» AND carbonyl/CO group present
OR
no «band at» 1620–1680 «cm–1» AND absence of double bond/C=C
OR
no «broad band at» 3200–3600 «cm–1 » AND absence of hydroxyl/OH group    [✔]

1
H NMR spectrum:
«only» two signals AND A would have three
OR
«signal at» 9.4–10.0 «ppm» AND «H atom/proton of» aldehyde/–CHO present
OR
«signal at» 2.2–2.7 «ppm» AND «H atom/proton of alkyl/CH next to» aldehyde/CHO
present
OR
«signal at» 2.2–2.7 «ppm» AND «H atom/proton of» RCOCH2- present
OR
no «signal at» 4.5–6.0 «ppm» AND absence of «H atom/proton next to» double bond/C=C ✔
 
Note: Accept a specific value or range of wavenumbers and chemical shifts.
Accept “two signals with areas 1:3”.
10i. [2 marks]
Deduce the splitting pattern you would expect for the signals in a high resolution 1H NMR
spectrum.
2.3 ppm:
9.8 ppm:

Markscheme
2.3 ppm: doublet    [✔]
9.8 ppm: quartet    [✔]
10j. [2 marks]
Product B, CH3CHO, can also be synthesized from ethanol.
Suggest the reagents and conditions required to ensure a good yield of product B.
Reagents: 
Conditions:

Markscheme
Reagents:
acidified/H+ AND «potassium» dichromate«(VI)»/K2Cr2O7/Cr2O72-    [✔]
Conditions:
distil «the product before further oxidation»       [✔]
 
Note: Accept “«acidified potassium» manganate(VII)/KMnO4/MnO4-/permanganate”.
Accept “H2SO4” or “H3PO4” for “H+”.
Accept “more dilute dichromate(VI)/manganate(VII)” or “excess ethanol”.
Award M1 if correct reagents given under “Conditions”.
10k. [1 mark]
Deduce the average oxidation state of carbon in product B.
Markscheme
–1     [✔]
10l. [3 marks]
Explain why product B is water soluble.

Markscheme
Any three of:
has an oxygen/O atom with a lone pair      [✔]
that can form hydrogen bonds/H-bonds «with water molecules»     [✔]
hydrocarbon chain is short «so does not disrupt many H-bonds with water molecules»    
[✔]
«large permanent» dipole-dipole interactions with water      [✔]
11a. [1 mark]
Dinitrogen monoxide, N2O, causes depletion of ozone in the stratosphere.
Outline why ozone in the stratosphere is important.
Markscheme
absorbs UV/ultraviolet light «of longer wavelength than absorbed by O2»     [✔]
11b. [2 marks]
Dinitrogen monoxide in the stratosphere is converted to nitrogen monoxide, NO (g).
Write two equations to show how NO (g) catalyses the decomposition of ozone.

Markscheme
NO (g) + O3 (g) → NO2 (g) + O2 (g)       [✔]
NO2 (g) + O3 (g) → NO (g) + 2O2 (g)     [✔]
 
Note: Ignore radical signs.
Accept equilibrium arrows.
Award [1 max] for NO2 (g) + O (g) → NO (g) + O2 (g).
11c. [1 mark]
Different sources of N2O have different ratios of 14N : 15N.
State one analytical technique that could be used to determine the ratio of 14N : 15N.
Markscheme
mass spectrometry/MS     [✔]
11d. [2 marks]
A sample of gas was enriched to contain 2 % by mass of 15N with the remainder being 14N.
Calculate the relative molecular mass of the resulting N2O.

Markscheme
(98 ×14 )+(2 ×15)
«  =» 14.02    [✔]
100
«Mr = (14.02 × 2) + 16.00 =» 44.04    [✔]
11e. [2 marks]
Predict, giving two reasons, how the first ionization energy of 15N compares with that of
14
N.
Markscheme
Any two:
same AND have same nuclear charge /number of protons/Zeff      [✔]
same AND neutrons do not affect attraction/ionization energy/Z eff
OR
same AND neutrons have no charge       [✔]
same AND same attraction for «outer» electrons     [✔]
same AND have same electronic configuration/shielding     [✔]
 
Note: Accept “almost the same”.
“Same” only needs to be stated once.
11f. [2 marks]
Explain why the first ionization energy of nitrogen is greater than both carbon and oxygen.
Nitrogen and carbon:
Nitrogen and oxygen:
Markscheme
Nitrogen and carbon:
N has greater nuclear charge/«one» more proton «and electrons both lost from singly filled
p-orbitals»    [✔]

 
Nitrogen and oxygen:
O has a doubly filled «p-»orbital
OR
N has only singly occupied «p-»orbitals     [✔]
 
Note: Accept “greater e– - e- repulsion in O” or “lower e– - e- repulsion in N”.
Accept box annotation of electrons for M2.
11g. [1 mark]
The Lewis (electron dot) structure of the dinitrogen monoxide molecule can be
represented as:

State what the presence of alternative Lewis structures shows about the nature of the
bonding in the molecule.
Markscheme
delocalization
OR
delocalized π-electrons    [✔]
 
Note: Accept “resonance”.
11h. [1 mark]
State, giving a reason, the shape of the dinitrogen monoxide molecule.

Markscheme
linear AND 2 electron domains
OR
linear AND 2 regions of electron density    [✔]
 
Note: Accept “two bonds AND no lone pairs” for reason.
11i. [1 mark]
Deduce the hybridization of the central nitrogen atom in the molecule.
Markscheme
sp     [✔]
12. [1 mark]
How many lone pairs and bonding pairs of electrons surround the central chlorine atom in
ClF2+?
 

Markscheme
D
13. [1 mark]
Which molecule is polar?
A.   BeCl2
B.   BCl3
C.   NCl3
D.   CCl4

Markscheme
C
14. [1 mark]
Which species has the same molecular geometry as SO32−?
 
A.   BF3
B.   SO3
C.   PF3
D.   CO32−

Markscheme
C
15. [1 mark]
Which form of carbon is the poorest electrical conductor?
A.     Graphite
B.     Graphene
C.     Diamond
D.     Carbon nanotube

Markscheme
C
16. [1 mark]
What is the molecular geometry and bond angle in the molecular ion NO 3−?
Markscheme
B
17. [1 mark]
Which species has the longest carbon to oxygen bond length?
A.     CO
B.     CH3OH
C.     CH3CO2−
D.     H2CO 

Markscheme
B
18. [1 mark]
What are the predicted electron domain geometries around the carbon and both nitrogen
atoms in urea, (NH2)2CO, applying VSEPR theory?

Markscheme
B
19a. [1 mark]
Bromine can form the bromate(V) ion, BrO3−.
State the electron configuration of a bromine atom.
Markscheme
1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p5
OR
[Ar] 4s2 3d10 4p5 ✔
 
Accept 3d before 4s.
19b. [1 mark]
Sketch the orbital diagram of the valence shell of a bromine atom (ground state) on the
energy axis provided. Use boxes to represent orbitals and arrows to represent electrons.
Markscheme

Accept double-headed arrows.

19c. [1 mark]
Draw the Lewis (electron dot) structure for BrO3− that obeys the octet rule.
Markscheme

Accept dots, crosses or lines to represent electron pairs.

19d. [3 marks]
Predict, using the VSEPR theory, the geometry of the BrO3− ion and the O−Br−O bond
angles.

Markscheme
Geometry:
trigonal/pyramidal ✔
Reason:
three bonds AND one lone pair
OR
four electron domains ✔
O−Br−O angle:
107° ✔
 
Accept “charge centres” for “electron domains”.
Accept answers in the range 104–109°.
19e. [2 marks]
Bromate(V) ions act as oxidizing agents in acidic conditions to form bromide ions.
Deduce the half-equation for this reduction reaction.

Markscheme
BrO3− (aq) + 6e− + 6H+ (aq) → Br− (aq) + 3H2O (l)
correct reactants and products ✔
balanced equation ✔
 
Accept reversible arrows.
19f. [1 mark]
Bromate(V) ions oxidize iron(II) ions, Fe2+, to iron(III) ions, Fe3+.
Deduce the equation for this redox reaction.

Markscheme
BrO3− (aq) + 6Fe2+ (aq) + 6H+ (aq) → Br− (aq) + 3H2O (l) + 6Fe3+ (aq) ✔
 
20a. [2 marks]
Urea, (H2N)2CO, is excreted by mammals and can be used as a fertilizer.
Calculate the percentage by mass of nitrogen in urea to two decimal places using section 6
of the data booklet.

Markscheme
molar mass of urea «= 4 × 1.01 + 2 × 14.01 + 12.01 + 16.00» = 60.07 «g mol–1»
2× 14.01
«% nitrogen =  × 100 =» 46.65 «%»
60.07
 
 
Award [2] for correct final answer.
Award [1 max] for final answer not to two decimal places.
[2 marks]
20b. [1 mark]
Suggest how the percentage of nitrogen affects the cost of transport of fertilizers giving a
reason.

Markscheme
«cost» increases AND lower N% «means higher cost of transportation per unit of nitrogen»
OR
«cost» increases AND inefficient/too much/about half mass not nitrogen
 
Accept other reasonable explanations.
Do not accept answers referring to safety/explosions.
[1 mark]
20c. [3 marks]
The structural formula of urea is shown.

Predict the electron domain and molecular geometries at the nitrogen and carbon atoms,
applying the VSEPR theory.
Markscheme

 
Note: Urea’s structure is more complex than that predicted from VSEPR theory.
[3 marks]
20d. [2 marks]
Urea can be made by reacting potassium cyanate, KNCO, with ammonium chloride, NH4Cl.
                                      KNCO(aq) + NH4Cl(aq) → (H2N)2CO(aq) + KCl(aq)
Determine the maximum mass of urea that could be formed from 50.0 cm 3 of 0.100 mol
dm−3 potassium cyanate solution.

Markscheme
n(KNCO) «= 0.0500 dm3 × 0.100 mol dm–3» = 5.00 × 10–3 «mol»
«mass of urea = 5.00 × 10–3 mol × 60.07 g mol–1» = 0.300 «g»
 
 
Award [2] for correct final answer.
[2 marks]
20e. [1 mark]
Urea can also be made by the direct combination of ammonia and carbon dioxide gases.
                                   2NH3(g) + CO2(g) ⇌ (H2N)2CO(g) + H2O(g)     ΔH < 0
Predict, with a reason, the effect on the equilibrium constant, Kc, when the temperature is
increased.
Markscheme
«Kc» decreases AND reaction is exothermic
OR
«Kc» decreases AND ΔH is negative
OR
«Kc» decreases AND reverse/endothermic reaction is favoured
[1 mark]
20f. [1 mark]
Suggest one reason why urea is a solid and ammonia a gas at room temperature.

Markscheme
Any one of:
urea has greater molar mass
urea has greater electron density/greater London/dispersion
urea has more hydrogen bonding
urea is more polar/has greater dipole moment
 
Accept “urea has larger size/greater van der Waals forces”.
Do not accept “urea has greater intermolecular forces/IMF”.
[1 mark]
20g. [2 marks]
Sketch two different hydrogen bonding interactions between ammonia and water.
Markscheme

 
Award [1] for each correct interaction.
If lone pairs are shown on N or O, then the lone pair on N or one of the lone pairs on O MUST
be involved in the H-bond.
Penalize solid line to represent H-bonding only once.
[2 marks]
20h. [2 marks]
The combustion of urea produces water, carbon dioxide and nitrogen.
Formulate a balanced equation for the reaction.

Markscheme
2(H2N)2CO(s) + 3O2(g) → 4H2O(l) + 2CO2(g) + 2N2(g)
correct coefficients on LHS
correct coefficients on RHS
 
3
Accept (H2N)2CO(s) + O2(g) → 2H2O(l) + CO2(g) + N2(g).
2
Accept any correct ratio.
[2 marks]
20i. [2 marks]
The mass spectrum of urea is shown below.
Identify the species responsible for the peaks at m/z = 60 and 44.

Markscheme
60: CON2H4+
44: CONH2+
 
Accept “molecular ion”.
[2 marks]
20j. [2 marks]
The IR spectrum of urea is shown below.

Identify the bonds causing the absorptions at 3450 cm−1 and 1700 cm−1 using section 26 of
the data booklet.
 

Markscheme
3450 cm–1: N–H
1700 cm–1: C=O
 
Do not accept “O–H” for 3450 cm–1.
[2 marks]
20k. [1 mark]
Predict the number of signals in the 1H NMR spectrum of urea.

Markscheme
1
[1 mark]
21a. [2 marks]
Some physical properties of molecular substances result from the different types of
forces between their molecules.
Explain why the hydrides of group 16 elements (H2O, H2S, H2Se and H2Te) are polar
molecules.

Markscheme
polar bonds «between H and group 16 element»
OR
difference in electronegativities «between H and group 16 element»
 
uneven distribution of charge/electron cloud
OR
non-linear/bent/V-shaped/angular shape «due to lone pairs»
OR
polar bonds/dipoles do not cancel out
 
M2:
Do not accept “net/overall dipole moment” without further explanation.
Accept “non-symmetrical «shape/distribution of charge»”.
[2 marks]
21b. [2 marks]
The graph shows the boiling points of the hydrides of group 16 elements.

Explain the increase in the boiling point from H2S to H2Te.

Markscheme
number of electrons increases
London/dispersion/instantaneous induced dipole-induced dipole forces increase
 
M1: Accept “Mr/Ar increases” or “molecules become larger in size/mass/surface area”.
[2 marks]
21c. [2 marks]
Lewis structures show electron domains and are used to predict molecular geometry.
Deduce the electron domain geometry and the molecular geometry for the NH 2− ion.

Markscheme
Electron domain geometry:
tetrahedral
Molecular geometry:
bent/V-shaped/angular
 
Both marks can be awarded for clear diagrams. Electron domain geometry requires a 3-D
diagram showing the tetrahedral arrangement.
[2 marks]
22a. [1 mark]
State the electron configuration of a bromine atom.

Markscheme
1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p5
OR
[Ar] 4s2 3d10 4p5 ✔
 
Accept 3d before 4s.
22b. [1 mark]
Sketch the orbital diagram of the valence shell of a bromine atom (ground state) on the
energy axis provided. Use boxes to represent orbitals and arrows to represent electrons.
Markscheme

Accept double-headed arrows.

22c. [2 marks]
Draw two Lewis (electron dot) structures for BrO3−.
Markscheme
Structure I - follows octet rule:

Structure II - does not follow octet rule:

 
Accept dots, crosses or lines to represent electron pairs.
22d. [2 marks]
Determine the preferred Lewis structure based on the formal charge on the bromine atom,
giving your reasons.

Markscheme
«structure I» formal charge on Br = +2
OR
«structure II» formal charge on Br = 0/+1 ✔
 
structure II is preferred AND it produces formal charge closer to 0 ✔
 
Ignore any reference to formal charge on oxygen.
22e. [3 marks]
Predict, using the VSEPR theory, the geometry of the BrO3− ion and the O−Br−O bond
angles.

Markscheme
Geometry:
trigonal/pyramidal ✔
Reason:
three bonds AND one lone pair
OR
four electron domains ✔
O−Br−O angle:
107° ✔
 
Accept “charge centres” for “electron domains”.
Accept answers in the range 104–109°.
22f. [2 marks]
Bromate(V) ions act as oxidizing agents in acidic conditions to form bromide ions.
Deduce the half-equation for this reduction reaction.
Markscheme
BrO3− (aq) + 6e− + 6H+ (aq) → Br− (aq) + 3H2O (l)
correct reactants and products ✔
balanced equation ✔
 
Accept reversible arrows.
22g. [1 mark]
Bromate(V) ions oxidize iron(II) ions, Fe2+, to iron(III) ions, Fe3+.
Deduce the equation for this redox reaction.

Markscheme
BrO3− (aq) + 6Fe2+ (aq) + 6H+ (aq) → Br− (aq) + 3H2O (l) + 6Fe3+ (aq) ✔
 
22h. [2 marks]
Calculate the standard Gibbs free energy change, ΔGΘ, in J, of the redox reaction in (ii), using
sections 1 and 24 of the data booklet.
EΘ (BrO3− / Br−) = +1.44 V
 
Markscheme
EΘreaction = «+1.44 V – 0.77 V =» 0.67 «V» ✔
ΔGΘ = «–nFEΘreaction = – 6 × 96500 C mol–1 × 0.67 V =» –3.9 × 105 «J» ✔
 
22i. [2 marks]
State and explain the magnetic property of iron(II) and iron(III) ions.
 

Markscheme
both are paramagnetic ✔
«both» contain unpaired electrons ✔
 
Accept orbital diagrams for both ions showing unpaired electrons.
 
Printed for GREEN HILLS ACAD SEC
© International Baccalaureate Organization 2021
International Baccalaureate® - Baccalauréat International® - Bachillerato Internacional®