St Dominic's Sixth Form College

Q1.This diagram represents the energy change that occurs when a d electron in a transition
metal ion is excited by visible light.

(a) Give the equation that relates the energy change ΔE to the Planck constant h and
the frequency of the visible light v.

Use this equation and the information in the diagram to calculate a value for the
frequency of the visible light, and state the units.
The Planck constant h = 6.63 × 10−34 J s.

Equation ........................................................................................................

Calculation .....................................................................................................

........................................................................................................................

........................................................................................................................

........................................................................................................................

........................................................................................................................
(2)

(b) Explain why this electron transition causes a solution containing the transition metal
ion to be coloured.

........................................................................................................................

........................................................................................................................

........................................................................................................................

........................................................................................................................

........................................................................................................................
(2)

Page 1
 St Dominic's Sixth Form College
(c) The energy change shown in the diagram represents the energy of red light and
leads to a solution that appears blue.
Blue light has a higher frequency than red light.

Suggest whether the energy change ΔE will be bigger, smaller or the same for a
transition metal ion that forms a red solution. Explain your answer.

Energy change .............................................................................................

Explanation ....................................................................................................

........................................................................................................................

........................................................................................................................

........................................................................................................................
(2)

(d) State three different features of transition metal complexes that cause a change in
the value of ΔE, the energy change between the ground state and the excited state
of the d electrons.

Feature 1 .......................................................................................................

Feature 2 .......................................................................................................

Feature 3 .......................................................................................................
(3)
(Total 9 marks)

Q2.This question is about copper chemistry.

(a) Aqueous copper(II) ions [Cu(H O) ] (aq) are blue.

2 6
2+

(i) With reference to electrons, explain why aqueous copper(II) ions are blue.

.............................................................................................................

.............................................................................................................

.............................................................................................................

.............................................................................................................

.............................................................................................................

.............................................................................................................

Page 2
 St Dominic's Sixth Form College
(Extra space) ......................................................................................

.............................................................................................................

.............................................................................................................
(3)

(ii) By reference to aqueous copper(II) ions, state the meaning of each of the
three terms in the equation ΔE = hv.

.............................................................................................................

.............................................................................................................

.............................................................................................................

.............................................................................................................

.............................................................................................................

.............................................................................................................

(Extra space) .......................................................................................

.............................................................................................................

.............................................................................................................
(3)

(iii) Write an equation for the reaction, in aqueous solution, between [Cu(H O) ] 2 6
2+

and an excess of chloride ions.

State the shape of the complex produced and explain why the shape differs
from that of the [Cu(H O) ] ion. 2 6
2+

.............................................................................................................

.............................................................................................................

.............................................................................................................

.............................................................................................................

.............................................................................................................

.............................................................................................................

(Extra space) .......................................................................................

.............................................................................................................

Page 3
 St Dominic's Sixth Form College
.............................................................................................................
(3)

(b) Draw the structure of the ethanedioate ion (C O ). 2 4

2–

Explain how this ion is able to act as a ligand.

......................................................................................................................

......................................................................................................................

......................................................................................................................

......................................................................................................................

......................................................................................................................
(2)

(c) When a dilute aqueous solution containing ethanedioate ions is added to a solution
containing aqueous copper(II) ions, a substitution reaction occurs. In this reaction
four water molecules are replaced and a new complex is formed.

(i) Write an ionic equation for the reaction. Give the co-ordination number of the
complex formed and name its shape.

.............................................................................................................

.............................................................................................................

.............................................................................................................

.............................................................................................................

.............................................................................................................

.............................................................................................................
(4)

(ii) In the complex formed, the two water molecules are opposite each other.
Draw a diagram to show how the ethanedioate ions are bonded to a copper

Page 4
 St Dominic's Sixth Form College
ion and give a value for one of the O–Cu–O bond angles. You are not required
to show the water molecules.

(2)
(Total 17 marks)

Q3. (a) State the origin of the colour of transition-metal complexes.

......................................................................................................................

......................................................................................................................
(2)

(b) Give three changes to a transition-metal complex which result in a change in colour.

Change 1 ......................................................................................................

Change 2 ......................................................................................................

Change 3 …..................................................................................................

......................................................................................................................
(3)

(c) You are provided with a 1.00 mol dm solution of iron(III) ions and a visible-light
–3

spectrophotometer (colorimeter). Outline a plan for experiments using this solution

and this apparatus which would enable you to determine the concentration of
iron(III) ions in a solution of unknown concentration.

......................................................................................................................

......................................................................................................................

Page 5
 St Dominic's Sixth Form College
......................................................................................................................

......................................................................................................................

......................................................................................................................

......................................................................................................................

......................................................................................................................

......................................................................................................................
(5)
(Total 10 marks)

Page 6
 St Dominic's Sixth Form College

M1.(a) ΔE = hv
Allow = hf
1

v = ΔE / h = 2.84 × 10−19 / 6.63 × 10−34 = 4.28 × 1014 s−1 / Hz

Allow 4.3 × 1014 s−1 / Hz
Answer must be in the range:
4.28 − 4.30 × 1014
1

(b) (One colour of) light is absorbed (to excite the electron)
If light emitted, CE = 0
1

The remaining colour / frequency / wavelength / energy is transmitted (through

the solution)
1

(c) Bigger
1

Blue light would be absorbed

OR light that has greater energy than red light would be absorbed
OR higher frequency (of light absorbed / blue light) leads to higher ΔE
Can only score M2 if M1 is correct.
1

(d) Any three from:

• (Identity of the) metal
• Charge (on the metal) / oxidation state / charge on complex
• (Identity of the) ligands
• Co-ordination number / number of ligands
• Shape

Page 7
 St Dominic's Sixth Form College
3 max
[9]

M2.(a) (i) absorbs (certain frequencies of) (white) light / photons

not absorbs white / u.v. light
1

d electrons excited / promoted

or d electrons move between levels / orbitals
d electrons can be implied elsewhere in answer
1

the colour observed is the light not absorbed / light

reflected / light transmitted
allow blue light transmitted
penalise emission of light in M3
1

(ii) ΔE is the energy gained by the (excited) electrons (of Cu2+)

allow:
• energy difference between orbitals / sub-shells
• energy of photon / light absorbed
• change in energy of the electrons energy lost by
excited electrons
• energy of photon / light emitted
1

h (Planck's) constant
1

v frequency of light (absorbed by Cu2+(aq))

do not allow wavelength
If energy lost / photon lost / light emitted in M1 do not
penalised light emitted
1

(iii) [Cu(H2O)6]2+ + 4Cl– → [CuCl4]2– + 6H2O

note that [CuCl4 ]2– is incorrect
–

penalise charges shown separately on the ligand and overall

penalise HCl
1

Page 8
 St Dominic's Sixth Form College
tetrahedral
1

Cl– / Cl / chlorine too big (to fit more than 4 round Cu)
allow
water smaller than Cl–
explanation that change in shape is due to change in
co-ordination number
1

(b)

allow:
• ion drawn with any bond angles
• ion in square brackets with overall / 2- charge shown
outside the brackets
• ion with delocalised O=C–O bonds in carboxylate
group(s)
1

lone pair(s) on O– / O
allow position of lone pair(s) shown on O in the diagram
even if the diagram is incorrect.
1

(c) (i) [Cu(H2O)6]2+ + 2C2O42– → [Cu(C2O4)2(H2O)2]2– + 4H2O

product correct
1

equation balanced
1

6
note can only score M3 and M4 if M1 awarded or if complex
in equation has 2 waters and 2 ethanedioates
1

octahedral
If this condition is satisfied the complex can have the
wrong charge(s) to allow access to M3 and M4 but not M1
1

Page 9
 St Dominic's Sixth Form College

(ii)

ignore charges
diagram must show both ethanedioates with correct bonding
ignore water
1

90°
allow 180°
mark bond angle independently but penalise if angle
incorrectly labelled / indicated on diagram
1
[17]

M3. (a) Electron transitions/electrons excitedin d shell (1) or d-d transition

Do NOT allow charge transfer

(Energy in) visible range (1)

(NOT emits in visible region)
2

(b) Change 1: (Different) oxidation states (1)

Change 2 : (Different) ligands (1)
Change 3: (Different) co-ordination number (1)
Do not allow shape as an answer
3

(c) Add an appropriate (or a given correct) ligand to intensify colour (1)
e.g. thiocyanate (CNS) or bipyridyl
—

Make up solutions of known concentration (1)

Measure absorption or transmission (1)
Plot graph of results or calibration curve (1)
Measure absorption of unknown and (1)
compare

Page 10
 St Dominic's Sixth Form College
N.B.: Allow concentration statement if included in graph
statement
Allow adsorption but circle the d
Also

5
[10]

Page 11
 St Dominic's Sixth Form College

E1.This question allowed all students to score marks but it also discriminated well. In part (a),
the equation was almost always correct but the units of frequency were less often given
correctly. In their answers to questions similar to parts (b) and (c), some students continue
to suggest incorrectly that the colour observed is due to emission of light when an electron
falls back down to a lower energy state. Students are penalised for this error. Over half of
all students scored all three marks for part (d). Weaker students appeared to misread the
question and gave general properties of transition metals, such as an incomplete d sub-
shell and catalytic activity, rather than the correct properties of complex ions, such as
shape and co-ordination number.

E2.A similar question to that in part (a)(i) has been asked on several occasions. It is, therefore,
disappointing to find that candidates continue to lose a mark for the same error. Weaker
candidates continue to insist that the blue colour of copper (II) sulfate solution is due to
emission of blue light. They should understand that the blue colour is due to transmission
of light remaining from white light after other colours have been absorbed. In part (a)(ii)
about one third of candidates scored full marks. The most common error was either to
confuse h and ν or to state that ν represents the wavelength of light. Parts (a)(iii) and (b)
were answered well. Part (c)(i) proved to be much more challenging and only 28% of
candidates scored full marks. One common error was to give a wrong charge for the
complex ion [Cu(C2O4)2(H2O)2]2–. Usually either the final 2- charge was missing or an
additional 2- charge was shown on the C2O4 ligands within the square brackets. The
other common error was to suggest a co-ordination number of four for the complex ion.
Part (c)(ii) was a testing question so it was pleasing to note that 35% of candidates scored
full marks.

E3. Whilst many candidates linked the colour of transition-metal complexes to electron
excitation in the d sub-shell in answer to part (a), rather less stated that the required
energy was absorbed from the visible light. Some candidates stated incorrectly, that
colour was due to the emission of visible light energy. Part (b) was very well answered
with most candidates scoring full marks. There were some excellent outline plans given in
part (c) but, although many were familiar with spectrophotometry, many answers were
vague and incomplete. The single most common error was failure to state that it was
necessary to add a suitable ligand to intensify the colour.

Page 12
 St Dominic's Sixth Form College

Page 13