NU1 MAYNOOTH

O l l s c o i l n a h t i r e a n n M6 N u a d

THE NATIONAL UNIVERSITY OF IRELAND MAYNOOTH

SECOND UNIVERSITY EXAMINATION IN SCIENCE - AUTUMN 2008

CHEMISTRY Module CH204 Inorganic Chemistry

Professor J. Nelson Professor J. P. Lowry Dr. G. M. McCann

11% Hour Paper

ANSWER two questions. *No material containing the Periodic Table may be used in this exam*
[SO marks per question: the

partial marks, in brackets for multi-part questions, are guides only to. the likely divisions of marks in such questions, based on the examiners' expectations.]

Carefully draw the structures of all the isomeric forms of the following complexes. All charges must be shown on the structural diagrams. (i)

Dibromoethylenediammineoxalatoferrate(II1). Use the following shorthand notations for the structures of the ethylenediammine and oxalate ( ~ ~ 0 ~ ~ 3

ethy lenediarnine (ii)

oxalate

Tetraaquochlorothiocyanatocobalt(III) chloride. The thiocyanate ligand is SCN-

(iii) p2-~eroxobis{cis-diaquotriammineruthenium(~~~)} bromide. The peroxo ligand is -0-0..

[20 marks] An aqueous solution of a complex conducts electricity but does not form a precipitate of AgCl when treated with ~ g + ions.~ ) ( ~ However, the solution of the complex does rotate plane polarised light. Which of the following complexes is consistent with these observations? Sketch the structure of your chosen complex. (en = ethylenediamine and the shorthand format of this ligand is shown in section a. part (i)).

(ii)

cis-[Fe(en)2C12]N03

(iii) Na fac-[Ru(NH3)3C13] (iv) (v) [OsCNH3)4C121Cl trans-[Co(en)2C12]NO3

C.

Consider the two complexes, high-spin [c~(&o)~]~+ and low-spin [c~(cN)~]~'. (i) (ii) Calculate the LFSE for each complex and indicate which would be expected to be inert and which would be labile. Carefully sketch the Free Energy diagrams representing ligand substitution reactions for the two complexes.
(15 marks]

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2. a.

(i) (ii)

Outline how organomercury(I1) alkyls can form from HgC12 through a biomethylation process involving the Me-BI2coenzyme. What type of functional group in biomolecules are targeted by the organomercury(I1) alkyls to produce the toxic effect?

Name and carefuIly sketch the structures of all isomers of the following complexes. Where appropriate, charges must be shown on ions. (en = ethylenediamine and the shorthand format of this ligand is shown in section a. part (i) of question 1)

(ii)

[Ni(en)s]SO4

(iii) [RhWH3)3C131 (iv) [Fe(H20)6][CoC14] {cobalt is Co(I1))

[l6 marks]

Explain what is meant by the L~+/M~'+ diagonal relationship.

[l2 marks]

In the unit cell below the metal cation M is depicted by the small spheres and the counter anion X is represented by the large spheres. Work out the chemical formula of the salt formed from M and X (show all calculations).

(I2 marks]

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3. a. (i)

Carefully sketch the Born-Haber cycle for the formation of solid potassium chloride and, from the data given below, insert the appropriate energy values into the various steps of your cycle.
Showing all of your calculations determine the net energy change for the reaction + 0.5CI~(g) KCl(s) +

(ii)

Sublimation energy for Kfs, Electron afJinity for Cl& Ionization energy for Kfd Bond dissociation energy for Clzfd K'fa + Cl-(a -+ K C I ,

+93 kJmotl -346 klmotl +450 klmot' +244 kJm01-l -660 klmol-l

Describe what occurs when a Group 1 metal is dissolved in liquid ammonia, and suggest a reason why a similar reaction will not occur when the same metal is dissolved in water. With the aid of carefilly drawn diagrams explain the following order of conductivity for Group 1 ions dissolved in HzO: CS' > ~ b > K+ > ~ a > ~ i + + +

[ l 5 marksj

(1.5 marks]

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