* Advanced Inorganic Chemistry Transition metals 10.13 Other Transition Metals e.g. silver and platinum Doc Brown's

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 Doc Brown's Chemistry  Periodic Table revision notes

Part 10. 3d block - Transition Metals -  10.13 Other Transition Metals e.g. silver and platinum

Revision notes for GCE Advanced Subsidiary Level AS Advanced Level A2 IB Revise AQA GCE Chemistry OCR GCE Chemistry Edexcel GCE Chemistry Salters Chemistry CIE Chemistry revising courses for pre-university students (equal to US grade 11 and grade 12 and Honours/honors level courses)  GCSE Periodic Table * GCSE notes Transition Metals

INORGANIC Part 10 3d block TRANSITION METALS sub-index: 10.1-10.2 Introduction 3d-block Transition Metals * 10.3 Scandium * 10.4 Titanium * 10.5 Vanadium * 10.6 Chromium * 10.7 Manganese * 10.8 Iron * 10.9  Cobalt * 10.10 Nickel * 10.11 Copper * 10.12 Zinc * 10.13 Other Transition Metals e.g. Ag and Pt * Appendix 1. Hydrated salts, acidity of hexa-aqua ions * Appendix 2. Complexes & ligands * Appendix 3. Complexes and isomerism * Appendix 4. Electron configuration & colour theory * Appendix 5. Redox equations, feasibility, Eø * Appendix 6. Catalysis * Appendix 7. Redox equations * Appendix 8. Stability Constants and entropy changes * Appendix 9. Colorimetric analysis and complex ion formula * Appendix 10 3d block - extended data * Appendix 11 Some 3d-block compounds, complexes, oxidation states & electrode potentials * Appendix 12 Hydroxide complex precipitate 'pictures', formulae and equations

Advanced Level Inorganic Chemistry Periodic Table Index * Part 1 Periodic Table history * Part 2 Electron configurations, spectroscopy, hydrogen spectrum, ionisation energies * Part 3 Period 1 survey H to He * Part 4 Period 2 survey Li to Ne * Part 5 Period 3 survey Na to Ar * Part 6 Period 4 survey K to Kr and important trends down a group * Part 7 s-block Groups 1/2 Alkali Metals/Alkaline Earth Metals * Part 8  p-block Groups 3/13 to 0/18 * Part 9 Group 7/17 The Halogens * Part 10 3d block elements & Transition Metal Series * Part 11 Group & Series data & periodicity plots * All 11 Parts have their own sub-indexes near the top of the pages

10.13. Other Transition Metals

10.13a. 4d block 2nd row elements Y to Cd

  • Yttrium, Y, Z=39, [Kr]4d15s2, is not a true transition metal and is like scandium Z=21 forming the colourless Y3+(aq) ion, e.c. = [Kr].

  • Rhodium, Rh, Z=45, [Kr]4d105s1 : Metal used as catalyst in car exhaust (see platinum below for more details).

  • Silver, Ag, Z=47, [Kr]4d105s1 

    • ?

    • linear1The silver(I) ion forms linear complexes with several ligands. The bond angle is 180o and co-ordination number 2 e.g.

    • The water molecule ligands in the aqueous silver ion [Ag(H2O)2]+(aq) can be replaced e.g. with (i) with ammonia, NH3, (neutral ligand) giving a cationic complex, (ii) with the negative cyanide ion CN- giving an anionic complex,  and (iii) the negative thiosulfate ion S2O32- forming an anionic complex:

      • [Ag(NH3)2]+(aq) solution is used as Tollen's reagent (ammoniacal silver nitrate) in organic chemistry. It is readily reduced by aldehydes (NOT ketones) to form a 'silver mirror' on the side of the test tube on warming the mixture to 60oC.

        • 2[Ag(NH3)2]+(aq), + 2R-CHO(aq) + 2OH-(aq) ==> 2Ag(s) + 2RCOOH(aq) + 4NH3(aq)

        • redox:

      • [Ag(CN)2]-(aq) solution is used in the electrolyte in silver electroplating. The object to be coated in silver is made the negative cathode electrode.

        • [Ag(H2O)2]+(aq) + 2CN-(aq) [Ag(CN)2]-(aq) + 2H2O(l)

        • The equilibrium is well over to the right but a very low concentration of silver ions gives a good even and strongly adhering surface deposit of silver metal on the conducting negative cathode electrode.

        • At the cathode (-): [Ag(H2O)2]+(aq) + e- ==> Ag(s) + 2H2O(l)

        • The silver is replenished using a silver anode

        • At the anode (+): Ag(s) + 2CN-(aq) - e- ==> [Ag(CN)2]-(aq)

      • [Ag(S2O3)2]3-(aq) is formed when sodium thiosulphate is used to remove unreacted silver bromide (AgBr) or silver iodide (AgI) crystals in developing photographic films.

        • AgBr(s) + 2S2O32-(aq) ==> [Ag(S2O3)2]3-(aq) + Br-(aq)

        • NOT a redox reaction, Ag is +1 and Br is -1 throughout the reaction. The thiosulfate ion is here acting as a ligand and not a reducing agent e.g. like with iodine.

      • -

    • The use of silver nitrate and ammonia for the halide test is described in the Chemical Tests Notes for anions

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Advanced Inorganic Chemistry Page Index and Links

10.13b. 5d block 3rd row elements La, Hf to Hg

  • Platinum, Pt, Z=78, [Xe]5d96s1 

    • Has been used as a catalyst, with rhodium, in catalytic converters of car exhausts to bring about reactions like

      • CxHy (g) + (x + y/4)O2 (g) ==> xCO2 (g) + y/2H2O (g) [to reduce unburned hydrocarbons]

      • 2CO (g) + 2NO (g) ==> N2 (g) + 2CO2 (g) [to reduce oxides of nitrogen and carbon monoxide emissions]

    • cis-diamminedichloroplatin(II), [Pt(NH3)2Cl2]0, (known as cisplatin) is one of the most effective agents against cancers of the ovaries, bladder, and head and neck and helps as co-agent in the treatment of cancers of the cervix, lung and breast. Its biggest success has been in the treatment of testicular cancer, a form of cancer previously resistant to any therapy but now considered to be curable in most cases. However, cisplatin has three drawbacks which limit its usefulness: (i) It is potentially very toxic, (ii) it only affects a few particular types of tumors and it causes the development of resistance in the tumor cell. The 'clinical point' is that you are balancing potentially harmful side effects against possible death.

      • The platinum stereochemistry is very important with the trans isomer showing no anti-cancer activity but the cis-isomer which is pharmacologically very active in its anti-carcinogenic activity (diagram below).

      • cisplatinbased on [Pt(NH3)2Cl2]

      • cis/trans-platin are neutral, square planer complexes of co-ordination number 4, exhibiting geometrical isomerism. There of two of each of the monodentate ligands, chloride ion and ammonia and the blue lines/dots show the 4 dative covalent bonds.

    • -

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Advanced Inorganic Chemistry Page Index and Links

 

Scandium * Titanium * Vanadium * Chromium * Manganese * Iron * Cobalt * Nickel * Copper * Zinc * Silver & Platinum

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