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Meridian Junior College 2012 JC 2 Term 3 Transition Elements Revision (Suggested Answers)
Time allocation : 10 min 1(a) Aqueous, acidic solutions of cobalt (II) salts are stable in air, however acidic cobalt (II) salts in excess ammonia are unstable in air. [Co(H2O)6]3+ + e [Co(NH3)6]3+ + e O2 + 4H+ + 4e [Co(H2O)6]2+ [Co(NH3)6]2+ 2H2O E = +1.82V E = +0.10V E = +1.23V

(i) Write the formula of the cobalt (II) complex in excess ammonia. [Co(NH3)6]2+ [1] (ii) Explain the above observation by calculating appropriate Ecell values. Write the balanced equations where appropriate. [4] Reaction between [Co(H2O)6]2+ and O2 Ecell = Ered - Eoxid = 1.23 (1.82) = - 0.59V Since Ecell < 0 Reaction is not feasible [1/2]. Hence [Co(H2O)6]2+ is stable in air [1/2] as it will not be oxidized easily. Reaction between [Co(NH3)6]2+and O2 Ecell = Ered - Eoxid = 1.23 0.10 = +1.13V Reaction is feasible [1/2]. Hence [Co(NH3)6]2+ is unstable [1/2] in air. 4[Co(NH3)6]2+(aq) + O2(g)+ 4H+(aq) 4[Co(NH3)6]3+(aq) + 2H2O(l) [1]

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(b)

Antique articles made from bronze can developed black spots of copper (II) sulphide, CuS, on their surfaces during storage. The spots can be dissolved by treating the article with a solution of sodium dithiolate, Na2R2C=CS2, to form a complex ion. The diothiolate ion is a bidentate ligand, and experiments show that two moles of diathiolate ion react with one mole of CuS. S R2C=C S

(i) Explain the meaning of bidentate ligand. A ligand is defined as a molecule/ion which contains at least one lone pair of electrons [1/2] available to form dative bonds with the central metal atom/ion [1/2]. A bidentate ligand is one that is able to form 2 dative bonds per ligand [1].

(ii) Draw the shape for the complex ion and write its formula. [3] Square planar or tetrahedral (show correct drawing) [Cu(R2C=CS2)2]2-

[1]

(Group B/C) Time allocation : 20 min 2(a) What determines the colour of a particular transition metal complex or compound? [2] Nature of metal and its oxidation state [1/2] No. of d electrons [1/2] Shape of complex ion [1/2] Nature of the ligands [1/2]

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(b)

Solution F consists of [ML6]2+(aq) and solution G consists of [MJ6]2+(aq). visible absorption spectra of these two solutions, F and G, are shown below.

The

(i) What are the colours of solutions F and G. Solution F: red or orange [1/2] Solution G: violet or blue [1/2] (ii) Explain the difference in colours of solutions F and G. Solution F or [ML6] (aq) L ligand is a strong field ligand and causes large d orbital splitting [1/2], hence a large E Light of short is absorbed [1/2] Light of long is emitted [1/2] Hence, colour of complex is red Solution G or [MJ6]2+(aq) J ligand is a weak field ligand and causes small d orbital splitting [1/2], hence a small E Light of long is absorbed [1/2] Light of short is emitted [1/2] Hence colour of complex is violet
2+

[4]

(c)

Iron (III) ion forms a 1:1 complex with edta4-. Initially, equal volumes of aqueous solutions, containing 3.88 10-4 mol dm-3 of Fe3+(aq) and 4.08 10-4 mol dm-3 of edta4- were mixed. The equilibrium concentration of the complex ion formed is 1.54 10-4 mol dm-3 (i) Write down the equation for the formation of the complex ion. Fe3+ + edta4[Fe(edta)]- [1]

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(ii) Write an expression for Kc constant of the complex ion.

Kc =

[[Fe(EDTA)] ] [1] [Fe3+ ][EDTA 4 ]

(iii) Calculate the Kc constant of the complex, stating the units. [4] Initial [ ] in [ ] Eqm [ ] Fe + edta -4 1.94 10 2.04 10-4 - 1.54 10-4 -1.54 10-4 0.40 10-4 0.50 10-4 [1.54 104 ] [1] = [0.40 104 ] [0.50 10 4 ]
3+ 4-

[Fe(edta)] 0 +1.54 10-4 1.54 10-4

Kc

= 7.70 104 mol-1 dm3 [1]

(d)

Anhydrous copper(II) sulfate, CuSO4(s), is a white powder which readily dissolves in water. Describe and explain what is seen when CuSO4(s) is stirred with water, followed by the addition of NH3(aq) until in excess. [3] N03/III/4 The white powder dissolves in water to form blue solution [1/2] of CuSO4. When dilute ammonia is added gradually, [Cu(H2O)6]2+ + 2OH-.. (from ammonia) a pale blue precipitate of Cu(OH)2 [1/2] is formed, In excess ammonia, both NH3 and OH- compete to combine with [Cu(H2O)6]2+ NH3 ligands replace H2O ligands [1/2] to form a deep blue complex [Cu(NH3)4(H2O)2]2+ [1/2]. [Cu(H2O)6]2+ + 4NH3 [Cu(NH3)4(H2O)2]2+ + 4H2O [1/2] (2) Since concentration of [Cu(H2O)6]2+ is decreased, equilibrium position (1) shifts to the left. Pale-blue precipitate of Cu(OH)2 dissolves [1/2]. Cu(OH)2 + 6H2O (1)

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(Group B/C) Time allocation : 6 min

3 Aqueous Fe(II)/Fe(III) undergo the following reactions.
[Fe(H2O)6]2+ (aq) [Fe(H2O)6]3+ (aq)

CN- (aq)

CN- (aq)

Fe3+ (aq) yellow complex F prussian blue compound H

Fe2+ (aq) orange-brown complex G

(a)

Suggest the formulae of F, G and H. F: G: H: [Fe(CN)6] - [1] [Fe(CN)6]3[1] Fe3[Fe(CN)6]2 or Fe4[Fe(CN)6]3

4

[3]

[1]

(b)

The deterioration in the air of some organic substances, such as cosmetics, is accelerated by iron(II) ions Suggest why the deterioration can be slowed down by a small quantity of EDTA. [1]
CH 2COONCH2CH2 N CH 2COOCH 2COO CH 2COO -

EDTA

On adding EDTA, stable EDTA-Fe2+ complex is formed and thus it removes the catalytic effect of Fe2+ that causes deterioration. [1]
Source: ACJC 2009 Prelim P3 Q5(d)

(Group A) Time allocation : 12 min 4(a) Titanium is an important transition metal. The metal itself is a component of many high-strength low-weight alloys, and its oxide is used as an opaque agent in many paints and pigments. (i) Write out the electronic configuration of the titanium atom. Ti : 1s2 2s2 2p6 3s2 3p6 3d24s2 [1]

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(ii) Draw the energy level diagram to represent the electronic configuration of Ti2+. Electronic Configuration of Ti3+ = [Ar] 3d2
energy

3d 3p 3s

2p 2s [1 or 0] 1s (iii) Titanium forms two chlorides. Suggest possible formulae for them. Formulae of chlorides: TiCl2 [1/2] , TiCl4 [1/2] (iv) Deduce the oxidation number of Ti in the complex ion [Ti(H2O)2Cl2]2+. [4] +4 [1] (b) Predict and explain the change in colour caused by adding the following substances to separate portions of aqueous iron(III) chloride: (i) aqueous potassium thiocyanate, KSCN Initial complex present: Fe3+(aq) or [Fe(H2O)6]3+ [1/2] [Fe(H2O)5(SCN)]2+ is more stable than [Fe(H2O)6]2- [1/2] Formation of [Fe(H2O)5(SCN)]2+ is favoured SCN- ligands will replace H2O ligands in [Fe(H2O)6]2- [1/2] Colour of solution changes from yellow to deep red [1/2]. (ii) powdered zinc Zn 2+ Fe 3+ Fe 2+ Zn Fe 2+ Fe E = -0.76V E = +0.77V E = -0.44V [4] N91/III/7

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Zn (s) + 2Fe 3+ (aq)

Zn 2+ (aq) + 2Fe2+ (aq)

E cell = 0.77 (-0.76) = + 1.53 V > 0 Reaction is feasible [1/2] Zn (s) + Fe2+ (aq) Zn2+ (aq) + Fe (s)

E cell = -0.44 (-0.76) = + 0.32V > 0 Reaction is feasible [1/2] Thus, colour of solution will change from yellow (Fe3+) to pale green (Fe2+) [1/2] then to colourless and grey/black deposits of Fe [1/2] is obtained.

(Group A) Time allocation : 15 min 5(a) Explain why so many transition element complexes are coloured. [3]

In the presence of ligands, the 3d orbitals are split into 2 groups with different energies. This effect is known as d orbital splitting [1/2] __ __ __ __ __ __ __ E d-orbitals free ion __ __ __ octahedral complex

d-d transition [1] takes place whereby d electrons from the lower energy level are promoted to the higher energy level by absorbing a certain wavelength of light from the visible region of the electromagnetic spectrum [1/2]. The complex thus emits the remaining wavelength which appears as the colour of the complex observed [1].

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(b)

State and explain the general trend in the first ionisation energy across the transition metal series. (Do not discuss the anomalies in your answer). [2] Across the transition elements series 4s electrons are removed for 1st I.E. The inner 3d electrons provide effective shielding of outer 4s electrons [1/2]. increase in shielding effect offset [1/2] the increase in nuclear charge. Effective nuclear charge increases slightly [1/2] across the series. Electrostatic force of attraction between outer electrons and nucleus increases slightly Energy required to remove the outer 4s electrons increases slightly. Hence 1st I.E. increases slightly [1/2]. With the use of relevant data from the Data Booklet, state and illustrate how the relative stabilities of the Fe(II)/Fe(III) oxidation states are affected by a change in (i) ligands; [Fe(H2O)6]3+ + e [Fe(CN)6]3- + e [Fe(H2O)6]2+ E = +0.77 V [Fe(CN)6]4- E = +0.36 V [1/2]

(c)

Fe3+ is stabilized with respect to Fe2+ when complexed with CN-, hence, less positive reduction potential [1/2]. Or It is more difficult to reduce [Fe(CN)6]3(aq) as that would require the addition of an electron (i.e. negatively charged) to the negatively charged [Fe(CN)6]3(aq).) pH. [Fe(H2O)6]3+ + e Fe(OH)3 + e [Fe(H2O)6]2+ Fe(OH)2 + OHE = +0.77 V E = -0.56 V [1/2] [2]

(ii)

Fe3+ is stabilized with respect to Fe2+ by an alkaline medium hence, less positive [1/2] reduction potential. Or It is easier to reduce [Fe(H2O)6]3+ as that would require the addition of an electron to the positively charged [Fe(H2O)6]3+.

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(d)

State three characteristics that are typical of transition metals, quoting evidence from the following statements, In the presence of manganese(IV) oxide, aqueous hydrogen peroxide decomposes to oxygen and water rapidly. Manganese(IV) oxide reacts with concentrated hydrochloric acid, forming chlorine and aqueous manganese(II) chloride. Manganese(II) chloride solution contains pale pink hydrated manganese(II) ions. If manganese(IV) oxide is heated strongly with an oxidising agent and an alkali, green manganate(VI) ions are first formed. The green solution subsequently turns purple. [3] Manganese oxide is acting as a heterogenous catalyst [1] for the catalytic decomposition of H2O2. Manganese also exists in variable oxidation states [1], example, +2 in MnCl2, +4 in MnO2, +6 in MnO42-, +7 in MnO4Manganese formed coloured transition metal ions [1], example, pink Mn2+, green MnO42-, purple MnO4-

Homework Time allocation : 12 min 6(a) Using chromium and iron as examples, describe two physical and two chemical properties in which transition metals and their compounds differ from those of magnesium, aluminium and their compounds. [4] Physical properties Cr and Fe are hard and have high densities compared to Mg and Al which are softer metals and have lower densities. Cr and Fe have high melting points and boiling points compared Mg and Al which have lower melting points. [1] each, max [2] Chemical properties Cr and Fe form coloured compounds but Mg and Al form colourless compounds. Examples: Cr3+ is green and Fe2+ is pale green. Cr and Fe form compounds with variable oxidation states while Mg and Al form compounds with fixed oxidation states of only +2 and +3 respectively. Examples: Cr forms Cr 2+, Cr3+ and Fe forms Fe2+ and Fe3+. Cr and Fe and their compounds show catalytic activity (example; catalysis of S2O82-(aq) (peroxodisulfate) / I-(aq) reaction by Fe3+) but Mg and Al do not. [1] each for any 2, max [2]

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(b)

(i)

Suggest the function of haemoglobin in the body, and how it carries out this function. Haemoglobin is involved in the transport of oxygen [1] in the body for respiration. In haemoglobin, the H2O ligand bonded to Fe is replaced by an O2 ligand [1/2] to form oxy-haemoglobin in a reversible reaction [1/2]. O2 is taken up by blood and distributed to cells. haemoglobin + O2 oxy-haemoglobin

(ii)

Name one poison that can affect haemoglobin, and describe how it reacts. [4] J95/I/7 Carbon Monoxide, CO CO can form strong bonds with Fe in haemoglobin in an irreversible reaction [1], so reducing the amount of haemoglobin available for carrying O2. - O2 ligand cannot replace the stronger CO ligand [1] Hence, patient will die due to O2 starvation.

Homework Time allocation : 8 min 7 (a) Transition metal or its compounds, such as iron, can act as heterogeneous or homogeneous catalysts. Explain the difference between the terms in italics. [1]

Heterogeneous catalyst operates in a different physical phase [1/2] to the reactant. However. homogeneous catalyst operates in the same physical phase [1/2] as the reactant. (b) What feature of transition metal ions enable them to act as homogeneous catalyst? [1] Transition metals and their compounds are good heterogeneous catalyst because of their ability to exist in various oxidation states [1/2], thus facilitating the formation of reaction intermediate via alternative pathways of lower Ea [1/2].

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(c)

Explain the mechanism of homogeneous catalysis of peroxodisulfate (S2O82-) / iodide reaction by iron (II) ions. [3] Homogeneneous catalysis of S2O82-(aq) (peroxodisulfate) / I-(aq) by Fe3+(aq) Step 1: Fe3+ reacts with I2Fe3+ + 2I- 2 Fe2+ + I2 [1/2] Fe2+ intermediate reacts with S2O822Fe2+ + S2O82- 2SO42- + 2Fe3+ [1/2] S2O82- + 2I- 2SO42- + I2 [1/2]

Step 2:

Overall:

In each step, oppositely charged ions are involved and they attract each other [1/2]. Activation energy is lower [1/2] and thus reaction is faster. The Fe3+ introduced in Step 1 is regenerated [1/2] in Step 2.

Homework Time allocation : 12 min 8(a) In the presence of MnO2, aqueous hydrogen peroxide is decomposed to oxygen and water. MnO2 reacts with concentrated hydrochloric acid, forming chlorine and aqueous manganese(II) chloride. Manganese (II) chloride solution contains pale pink hydrated manganese(II) ions. If MnO2 is heated strongly with an oxidising agent and an alkali, green manganate (VI) ions are first formed, which then dissolves in water to form a purple solution. Using the account above, illustrate three characteristics typical of transition metals. [3] MnO2 acts as catalyst in the decomposition of hydrogen peroxide. Transition metals and their compounds show catalytic activity [1]. Oxidation state of Mn is +2 in MnCl2 and +6 in manganate (VI) ions Transition metals form compounds in which the transition metal shows a variety of oxidation states [1] Hydrated manganese(II) ions is pale pink and manganate (VI) ions is green Transition metals form coloured compound and ions [1]

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(b)

Using Fe as an example, and making use of relevant information from the Data Booklet, illustrate and explain how the relative stability of its oxidation state is affected by a change in pH. [2] [Fe(H2O)6]3+ + e Fe(OH)3 + e [Fe(H2O)6]2+ Fe(OH)2 + OHE = + 0.77 V E = - 0.56V (acidic) (basic)

When pH increases, E value decreases [1]. Fe(OH)3 is less likely to undergo reduction [1/2] compared to [Fe(H2O)6]3+ +3 oxidation state of iron is more stable [1/2] with respect to +2 oxidation

state of iron when pH is increased. (c) Meteorites are fragments of rock or metal that fall to the Earths surface from outer space. One such meteorite, known to consists of iron and nickel, was analysed as follows: A 0.30 g sample was dissolved in an excess of sulfuric acid, forming a solution of iron (II) sulfate and nickel (II) sulfate. On titration, this solution required 19.6 cm3 of 0.020 mol dm-3 acidified potassium manganate (VII) solution to oxidise all the iron. Calculate the percentage of iron in the meteorite. No. of mole of MnO4[3] = 19.6/1000 x 0.020 [M1/2] = 3.92 10-4 [A1/2]

MnO4- + 8H+ + 5Fe2+ Mn2+ + 4H2O + 5Fe3+ MnO4- 5Fe2+ 5Fe No. of mole of Fe = 5 3.92 10-4 [M1/2] = 1.96 10-3 Mass of Fe in sample = 1.96 10-3 55.8 = 0.109 g [A1/2] % of iron in meteorite =
0.109 100 0.30

= 36.5 % [A1/2]

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Homework Time allocation : 11 min 9 The two most common oxidation state of iron in its compounds are +2 and +3. (a) Using suitable E values from Data Booklet, predict and explain whether the iron (II) state is more powerful reducing agent under acidic or alkaline conditions. [3] Fe3+ + e- . Fe2+ +0.77 Fe(OH)2 + OH-0.56 Fe(OH)3 + eUnder alkaline conditions, the E Fe(OH)3 / Fe(OH)2 is less positive than E Fe3+/Fe2+ [1/2] Hence,Fe(OH)2 is more easily oxidised than Fe2+. [1/2]

This is because oxidation involves the removal of electrons and it is easier to remove electron from neutral Fe(OH)2 than positively charged Fe2+(aq). [1] Therefore, the iron (II) state under alkaline conditions is more easily oxidised and hence is more powerful reducing agent. [1] (b) One feature that distinguished a transition metal from an s-block element is its ability to form variable oxidation states. Suggest an explanation for this difference. [2] Transition metals possess variable oxidation states. In transition metals, the 3d and 4s orbitals are close in energies. [1/2] Hence variable number of 4s and 3d electrons can be removed to form ions of similar stability. [1/2] S-lock elements possess a fixed oxidation state of +1 (Group I) and +2 (Group II). Once the s electrons are removed, the removal of inner p electrons requires too much energy. [1] (c) Iron is a transition element which forms many complexes with ligands. One example is the complex ion [Fe(CN)6]4-. Using [Fe(CN)6]4- to explain what is meant by the terms transition element and ligand? [2] Fe is a transition element which forms Fe2+ in which the d subshell is partially filled with 6 electrons. [1]

CN- ions is a ligand that has a lone pair of electrons on C atom that can form a dative bond with the central metal ion Fe2+. [1]

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