T13.

1N [38 marks]
1. [1 mark]
Which complex ion contains a central ion with an oxidation state of +3?

A. [PtCl6]2−
B. [Cu(H2O)4(OH)2]
C. [Ni(NH3)4(H2O)2]2+
D. [Co(NH3)4Cl2]+

Markscheme
D
2. [1 mark]
Which of these statements are correct?

I. Zinc is not a transition element.

II. Ligands are Lewis bases.
III. Manganese(II) chloride is paramagnetic.
A. I and II only

B. I and III only

C. II and III only

D. I, II and III

Markscheme
D
3. [1 mark]
Which is correct for the complex ion in [Fe(H2O)5Cl]SO4?
Markscheme
D
4a. [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.

4b. [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.

4c. [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.

4d. [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.

4e. [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°.
4f. [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.

4g. [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) ✔

4h. [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» ✔

4i. [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.

5a. [3 marks]
Trends in physical and chemical properties are useful to chemists.
Explain why the melting points of the group 1 metals (Li → Cs) decrease down the group
whereas the melting points of the group 17 elements (F → I) increase down the group.

Markscheme
Any three of:
Group 1:
atomic/ionic radius increases
smaller charge density
OR
force of attraction between metal ions and delocalised electrons decreases
Do not accept discussion of attraction between valence electrons and nucleus for M2.
Accept “weaker metallic bonds” for M2.
Group 17:
number of electrons/surface area/molar mass increase
London/dispersion/van der Waals’/vdw forces increase
Accept “atomic mass” for “molar mass”.
[Max 3 Marks]
5b. [1 mark]
Cobalt forms the transition metal complex [Co(NH3)4 (H2O)Cl]Br.
State the shape of the complex ion.

Markscheme
«distorted» octahedral
Accept “square bipyramid”.
5c. [2 marks]
Deduce the charge on the complex ion and the oxidation state of cobalt.
Markscheme
Charge on complex ion: 1+/+
Oxidation state of cobalt: +2
5d. [2 marks]
Describe, in terms of acid-base theories, the type of reaction that takes place between the
cobalt ion and water to form the complex ion.

Markscheme
Lewis «acid-base reaction»
H2O: electron/e– pair donor
OR
Co2+: electron/e– pair acceptor
6a. [6 marks]
The concentration of a solution of a weak acid, such as ethanedioic acid, can be determined
by titration with a standard solution of sodium hydroxide, NaOH (aq).
5.00 g of an impure sample of hydrated ethanedioic acid, (COOH)2•2H2O, was dissolved in
water to make 1.00 dm3 of solution. 25.0 cm3 samples of this solution were titrated against
a 0.100 mol dm-3 solution of sodium hydroxide using a suitable indicator.
(COOH)2 (aq) + 2NaOH (aq) → (COONa)2 (aq) + 2H2O (l)
The mean value of the titre was 14.0 cm3.
(i) Suggest a suitable indicator for this titration. Use section 22 of the data booklet.
(ii) Calculate the amount, in mol, of NaOH in 14.0 cm3 of 0.100 mol dm-3 solution.
(iii) Calculate the amount, in mol, of ethanedioic acid in each 25.0 cm3 sample.
(iv) Determine the percentage purity of the hydrated ethanedioic acid sample.

Markscheme
i
phenolphthalein
OR
phenol red

ii
«n(NaOH) = (1000
14.0
) dm
3 × 0.100 mol dm-3 =» 1.40 × 10-3 «mol»

iii
1
«2 × 1.40 × 10-3 =» 7.00 × 10-4 «mol»
iv
ALTERNATIVE 1:
«mass of pure hydrated ethanedioic acid in each titration = 7.00 × 10-4 mol × 126.08 g mol-1
=» 0.0883 / 8.83 × 10-2 «g»
25
mass of sample in each titration = «1000 × 5.00 g =» 0.125 «g»
0.0883g
«% purity = 0.125g
× 100 =» 70.6 «%»

ALTERNATIVE 2:
1000
«mol of pure hydrated ethanedioic acid in 1 dm3 solution = 7.00 × 10-4 × 25 =» 2.80 × 10-
2 «mol»

«mass of pure hydrated ethanedioic acid in sample = 2.80 × 10-2 mol × 126.08 g mol-1 =»
3.53 «g»
3.53g
«% purity = 5.00g × 100 =» 70.6 «%»

ALTERNATIVE 3:
5.00g
mol of hydrated ethanedioic acid (assuming sample to be pure) = = 0.03966
126.08gmol−1
«mol»
1000
actual amount of hydrated ethanedioic acid = «7.00 × 10-4 × 25
=» 2.80 × 10-2 «mol»

2.80 × 10−2
«% purity = 0.03966
× 100 =» 70.6 «%»

Award suitable part marks for alternative methods.

Award [3] for correct final answer.
Award [2 max] for 50.4 % if anhydrous ethanedioic acid assumed.
6b. [1 mark]
Draw the Lewis (electron dot) structure of the ethanedioate ion, –OOCCOO–.
Markscheme

Accept single negative charges on two O atoms singly bonded to C.

Do not accept resonance structures.
Allow any combination of dots/crosses or lines to represent electron pairs.
6c. [2 marks]
Outline why all the C–O bond lengths in the ethanedioate ion are the same length and
suggest a value for them. Use section 10 of the data booklet.
Markscheme
electrons delocalized «across the O–C–O system»
OR
resonance occurs
Accept delocalized π-bond(s).
No ECF from (d).

122 «pm» < C–O < 143 «pm»

Accept any answer in range 123 «pm» to 142 «pm».
Accept “bond intermediate between single and double bond” or “bond order 1.5”.
6d. [2 marks]
Explain how ethanedioate ions act as ligands.

Markscheme
coordinate/dative/covalent bond from O to «transition» metal «ion»
OR
acts as a Lewis base/nucleophile
can occupy two positions
OR
provide two electron pairs from different «O» atoms
OR
form two «coordinate/dative/covalent» bonds «with the metal ion»
OR
chelate «metal/ion»
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