transition elements

(a) Candidates should be able to:

recall that transition elements (except Cu) possess partly filled d-orbitals and derive the electronic configuration of any first row transition metal ion using a Periodic Table; Symbo l Sc Ti V Cr Mn Fe Co #i Cu Zn

Element Scandium Titanium Vanadium Chromium Manganese Iron Co a!t #ic$e! Copper Zinc

Ground state electronic configuration

1s 2s 2p 3s 3p 3d 4s
2 2 2 2 6 6 2 2 6 6 2 3
2 2 6 2 6 1 2

1s 2s 2p 3s 3p 3d 4s 1s 2s 2p 3s 3p 3d 4s 1s 2s 2p 3s 3p 3d 4s
2 2 2 2 2 2 6 6 6 6 2 2 6 6 5 6 2 2 6 2 6 5 1

2 2

*
2 2 2

1s 2s 2p 3s 3p 3d 4s 1s 2s 2p 3s 3p 3d 4s
2 2 Z 6 7

1s 2s 2p 3s 3p 3d 4s 1s 2s 2p 3s 3p 3d 4s 1s 2s 2p 3s 3p 3d 4s
2 2 6 2 6 1% 2 2 6 2 6 1% 1 2 2 "

*
2

1s 2s 2p 3s 3p 3d 4s

The&transition&e!ements&are&shaded #ote&the&specia!&cases&o'&chromium&and&copper& - chromium&has&ha!'&'i!!ed&d(or ita!s&)ith&on!*&one&4s&e!ectron& - copper&has&comp!ete!*&'i!!ed&d(or ita!s&)ith&on!*&one&4s&e!ectron& +&ha!'('i!!ed&set&o'&d(or ita!s&and&a&comp!ete&set&o'&d(or ita!s&con'er&e,tra&sta i!it*&on& the&con'iguration-

+&transition&e!ement&ma*& e&de'ined&as&one&)hich&possesses.&or&'orms&an&ion& )hich&possesses.&an&incomp!ete&set&o'&d(or ita!s-

3"
(b) Candidates should be able to:

recall that 4s electrons are lost more readily than d electrons in ion formation; In&the&'ormation&o'&ions.&the&4s&e!ectrons&are&!ost&more&readi!*&than&the&3d&e!ectrons-& Some&ions&o'&the&'irst&transition&series&o'&e!ements-

Ion Sc &&* Ti
2/ 3/

Electronic configuration of ion 1s 2s 2p 3s 3p

2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 6 6 6 6 6 6 6 6 6 6 6 6 6 2 2 2 2 2 2 2 2 2 2 2 2 2 6 6 6 6 6 6 6 6 6 6 6 6 6 2 2 6 2 6 2 1 3 2 4 3 5 4 6 5 7 6 "

1s 2s 2p 3s 3p 3d 1s 2s 2p 3s 3p 3d 1s 2s 2p 3s 3p 3d 1s 2s 2p 3s 3p 3d 1s 2s 2p 3s 3p 3d 1s 2s 2p 3s 3p 3d 1s 2s 2p 3s 3p 3d 1s 2s 2p 3s 3p 3d 1s 2s 2p 3s 3p 3d 1s 2s 2p 3s 3p 3d 1s 2s 2p 3s 3p 3d 1s 2s 2p 3s 3p 3d
II

Ti3/ V2/ V3/

Cr
2/

Cr3/ Mn2/ Mn3/ Fe2/ Fe3/ Co2/

Co #i
3/ 2/

1s 2s 2p 3s 3p 3d 1s 2s 2p 3s 3p 3d
2 2 6 2 6 2 2 6 2 6

on!*&nic$e! &occurs&in&the&common&chemistr*&o'&nic$e!-

Cu &&* Cu
2/

1% 0

1s 2s 2p 3s 3p 3d

*&these&ions&are&not&considered&as&transition&meta!&ions&as&the*&do&not&ha1e&an&incomp!ete& set&o'&d&or ita!s

30
(c) Candidates should be able to:

explain why various oxidation states are possible in transition elements; +s&can& e&seen&'rom&the&a o1e&ta !e.&the&transition&e!ements&ha1e&more&than&one&o,idation& state-&The&reason&is&that&successi1e&ionisation&energies&'or&the&transition&e!ements&tend&to& increase&gradua!!*&)ithout&!arge&2umps&in&1a!ue-&The&energies&o'&the&d(or ita!s&are&1er*& simi!ar-&The&num er&o'&di''erent&o,idation&states&reaches&a&ma,imum&in&the&centre&o'&the& series3,idation&states&are&sho)n& e!o)&(&the&most&common&'or&each&e!ement&are&in& o!d& and&under!inedSc 3 Ti 4 3 2 V 5 4 3 2 Cr 6 3 2 Mn 7 6 4 3 2 (d) Catalytic action of transition elements Fe 6 3 2 Co 4 3 2 #i 4 2 Cu 2 1

Candidates should be able to:

recall that transition metals and their compounds are often good catalysts! give an example! and explain why this is so in terms of partially filled d-shells and variable oxidation states;

Catalyst TiC!3&or&TiC!4 V 23 5 Fe #i

Process Zieg!er(#atta&cata!*sts&in&the&po!*merisation&o'&ethene Contact&process&2S32&/&32 2S33 4a er&5rocess&&&342&/&#2 2#43 Cata!*tic&h*drogenation&o'&oi!s&6C7C8 /&42 6C4(C48 The&

cata!*tic&acti1it*&o'&the&transition&e!ements&depends&on&the&a i!it*&to&e,hi it&1aria !e& 1a!enc*&and&the&a1ai!a i!it*&o'&1acant&d(or ita!s-&The&reactants&use&1acant&d(or ita!s&to&'orm& temporar*& onds&)ith&the&cata!*st&)hich&ho!ds&the&reactants&so&that&reaction&can&ta$e&p!ace-& Most&cata!*sts&are&heterogeneous&cata!*sts-

4% 9,amp!es&o'&transition&meta!&cata!*sts (e), (f) Complex ions

Candidates should be able to:

(e) (f)

recall that many complexes are formed by co-ordinate bonding between transition metal ions and ligands; describe the bonding! colour and formulae of the approximately octahedral $( $( complex ions "Cu(#$%)&' and "Cu()# )4(#$%)$' !the approximately $! tetrahedral ion "CuCl4' and other complexes where relevant information is supplied;

+&comp!e,&ion&is&a&centra!&meta!&ion&surrounded& *&atoms&or&groups&o'&atoms&!in$ed& *&a&coordinate& ond-&The&surrounding&groups&are&ca!!ed&!igands-&I'&an&atom&or&group&o'&atoms&'orms&on!*&one& coordinate& ond&it&is&said&to& e&a&monodentate&!igand-&e-g-&ammonia&:#43#otice&that&!igands&are&a !e&to&donate&a&!one&pair&o'&e!ectrons&into&a1ai!a !e&or ita!s&o'&the&centra!&meta!& ion-&Some&mo!ecu!es&such&as&42#(C42(C42(#42&can&'orm&t)o&coordinate& onds&and&are& identate& !igands-&+n&important&species&ca!!ed&9:T+&is&a&po!*dentate&!igand&'orming&se1era!&coordinate& onds-

Transition&meta!&ions&in&a;ueous&so!ution&are&h*drated<ater&mo!ecu!es&act&as&!igandsThe&'ami!iar& !ue&co!our&o'&copper=II>&su!'ate&so!ution&is&caused& *& the&he,aa;uacopper=II>&ion.&?Cu=423>6@ &-&It&is&common&'or&si,& !igands&to&surround&the&centra!&meta!&ion&and&'orm&an&octahedra!& comp!e,&ionIn&'act.&the&he,aa;uacopper=II>&ion.&?Cu=423>6@ &is&a&s!ight!*& distorted&octahedron&)ith&t)o&)ater&mo!ecu!es& eing&'urther&a)a*& than&the&other&'our2/ 2/

There&is&o'ten&competition& et)een&!igands-&<hen&a;ueous&ammonia& is&added&in&e,cess&to&a;ueous&copper=II>&su!'ate.&a&ro*a!& !ue&so!ution& is&o tained-&The&ammonia&mo!ecu!es&rep!ace&'our&o'&the&)ater& mo!ecu!es&in&the&he,aa;uacopper=II>&ion-

?Cu=423>6@ =a;>&/&4#43=a;>&&&&&?Cu=#43>4&=423>2@ =a;>&/&4423=!> tetraamminocopper=II>&ion

2/

2/

41 I'&copper=II>&car onate&is&disso!1ed&in&concentrated&h*droch!oric& acid.&a&*e!!o)(green&or&*e!!o)( ro)n&so!ution&is&'ormed&containing& the&tetrach!orocuprate=II>&ion.&?CuC!4@ &-&This&is&a&tetrahedra!&ionC! 3nce&again&it&is&eas*&to&demonstrate&competition& *&!igandsI'&the&so!ution&o tained& *&the&action&o'&concentrated&h*droch!oric&acid&on&copper=II>&car onate&is& steadi!*&di!uted&)ith&)ater.&there&is&a&gradua!&change&in&co!our&unti!&)ith&a&!arge&e,cess&o'&)ater&the& t*pica!& !ue&co!our&o'&Cu =a;>&is&'ormed?CuC!4@
2 2/ 2

C! Cu

C!

&&&C!

&/&6423=!>&&&&&?Cu=423>6@ &&/&4C!

2/

Ai$e)ise.&i'&concentrated&h*droch!oric&acid&is&added&to&a;ueous&copper=II>&su!'ate.&the&so!ution&rapid!*& turns&green?Cu=423>6@ &&/&4C!&=a;>&&&&&?CuC!4@

2/ 2

&/&6423

(g)

Candidates should be able to: (i) (ii) explain the origins of colour in transition metal complexes and give a *ualitative account of this for octahedral &-coordinate species in terms of the splitting of the d-orbitals involved! and; show understanding of the spectroscopic conse*uences of (i) above and explain that in many cases the colours of such transition metal complexes arise from d-d transitions between the split d-orbital levels +;

The&d(or ita!s&ha1e&comp!icated&shapes&)hich&candidates do not need to rememberIn&an&iso!ated&atom&a!!&'i1e&or ita!s&ha1e&the&same&energ*&and&are&said&to& e&degenerate-

B *

42 In&octahedra!&comp!e,es.&the&e!ectrostatic&'ie!d&'rom&the&!igands&sp!it&the&or ita!s&into&t)o&!e1e!sd&or ita!s&)ith&the&same&higher&energ*

9
'i1e&d&or ita!s&)ith&the&same& energ* d&or ita!s&)ith&the&same&!o)er&energ*

Ta$e&the&ion&Cr )ith&con'iguration&&1s 2s 2p 3s 3p 3d The&three&d(e!ectrons&)i!!&occup*&the&!o)est&energ*&!e1e!s&in&the&ground&stateThis&can& e&represented& *&the&'o!!o)ing&diagram&)here&the&three&e!ectrons&occup*&the&3&!o)er&energ*& or ita!s&)ith&para!!e!&spinst)o&d&or ita!s&)ith&the&same&higher&energ*

3/

three&d&or ita!s&)ith&the&same&!o)er&energ*

9,citation&o'&the&ion&ma*&promote&one&or&more&o'&these&e!ectrons&to&the&higher&energ*& or ita!s-&Such&a&transition&is&ca!!ed&a&d(d&transition&and&in1o!1es&the&energ*&2ump&!a e!!ed&,The&1a!ue&o'&&,&)i!!&depend&upon the&identit*&o'&the&meta! its&o,idation&state the&nature&o'&the&!igands&in&the&octahedra!&comp!e, For&man*&d(d&transitions&the&1a!ue&o'&&,&corresponds&to&the&energ*&o'&a&photon&o'&1isi !e&!ight, 7 h' <here&h&is&5!anc$s&constant&and&'&is&the&'re;uenc*&o'&the&1isi !e&radiationThus&)hen&)hite&!ight&'a!!s&on&such&a&comp!e,.&some&)a1e!engths&)i!!& e&a sor ed&gi1ing&rise&to&d(d& transitions&and&producing&co!ourIt&is&one&o'&the&characteristic&properties&o'&transition&e!ements&that&man*&o'&their&compounds&are& 2/ co!oured-&Zinc&compounds&ho)e1er&are&not&co!oured& ecause&Zn &has&'u!!*&occupied&3d&or ita!s&and& 3/ scandium&compounds&are&not&co!oured& ecause&Sc &has&no&3d&e!ectrons-

43 (h) Reactions of transition metal ions ith a!ueous sodium hydroxide and a!ueous ammonia Candidates should be able to: describe the reactions of Cr
""" 3# (!

-e

$(!

-e

and Cu

$(

with excess a*ueous %# ;

=i>&Chromium &&Cr (a!) <ith&a;ueous&sodium&h*dro,ide.&the& !ue(1io!et&so!ution&containing&Cr =a;>&gi1es&a&gre*( green&ge!atinous&precipitate&o'&chromium=III>&h*dro,ideCr =a;>&/&334&=a;>

3/ 3/

Cr=34>3=s>

3n&addition&o'&e,cess&sodium&h*dro,ide&the&chromium=III>&h*dro,ide&disso!1es&and&a&green& so!ution&containing&the&chromate=III>&ion&is&'ormedCr=34>3=s>&/&334&=a;>&&&&&?Cr=34>6@ &&=a;> =ii>&"ron &and "ron &&$ %e (a!) and %e (a!) <hen&a;ueous&sodium&h*dro,ide&is&added&to&a&pa!e&green&so!ution&containing&Fe =a;>&ions.&a& dirt*&green&precipitate&o'&iron=II>&h*dro,ide&is&'ormedFe =a;>&/&234&=a;>
2/ 2/ "" """ 2# 3# 3

Fe=34>2=s>

The&precipitate&undergoes&o,idation&to&iron=III>&h*dro,ide&so&it&turns& ro)n&at&the&sur'ace3/

<hen&a;ueous&sodium&h*dro,ide&is&added&to&a&*e!!o)&so!ution&containing&Fe =a;>&ions.&a& reddish( ro)n&precipitate&o'&iron=III>&h*dro,ide&is&'ormedFe =a;>&/&334&=a;>

3/

Fe=34>3=s>

The&precipitate&is&inso!u !e&in&e,cess&sodium&h*dro,ide&so!ution=iii>&Copper &&Cu (a!) <hen&a;ueous&sodium&h*dro,ide&is&added&to&a& !ue&so!ution&containing&Cu =a;>&ions.&a& !ue&precipitate&o'&copper=II>&h*dro,ide&is&'ormed-&The&precipitate&is&not&so!u !e&in&e,cess& sodium&h*dro,ide&so!utionCu =a;>&/&234&=a;>
2/ 2/ 2/ "" 2#

Cu=34>2=s>

<hen&so!utions&containing&Cu =a;>&are&treated&)ith&a;ueous&ammonia.&copper=II>&h*dro,ide&is& precipitated.&as&a& asic&sa!t-&This&precipitate&disso!1es&in&e,cess&to&'orm&a&deep&ro*a!& !ue& so!ution&containing&the&tetraamminecopper=II>&ionCu =a;>&/&234&=a;> Cu=34>2=s>&/&4#43=a;>&&/&2423=!>

2/

Cu=34>2=s> ?Cu=#43>4&=423>2@ =a;>&/&234&=a;>

2/

44 (i) &race elements in li'ing systems Candidates should be able to: show an awareness of the economic importance of transition metals and their importance as trace elements in living systems! and give one example of economic importance and one example of trace element importance. )ote/ +The simple electrostatic model is ade*uate to account for the d-orbital splitting. Candidates should be able appropriately to allocate electrons to the split d-orbitals using the arrows in boxes techni*ue but consideration of the factors leading to high or low spin behaviour will not be re*uired.

The&d( !oc$&e!ements&are&important&in&man*& io!ogica!&s*stems&as&trace&e!ements-&The&reactions& eing ased&on&t*pica!&redo,&and&coordination&chemistr*-&The&!igands&in1o!1ed&in&transition&e!ement chemistr*&in&!i1ing&s*stems&inc!ude&)ater.&simp!e&organic&mo!ecu!es.&porph*rin&and&the&side&chains&o' amino&acidsCandidates&are&not&re;uired&to&go&into&great&detai!& ut&shou!d& e&a !e&to&reca!!&one&e,amp!e&o'&trace e!ement&importance Vanadium-&This&is&'ound&in&some&marine&creaturesManganese-&Is&'ound&in& ones.&tissues&and&some&organs-&It&is&present&in&man*&enB*me&s*stemsAi$e&man*&trace&e!ements&the&dai!*&re;uirement&is&1ague& eing&a out&3&mg&per&da*-&Ma2or&sources are&nuts&and&unre'ined&cerea!sIron-&Iron&is&present&in&the& !ood&in&haemog!o in-&The&iron&occupies&a&simi!ar&p!ace&in&the porph*rin&structure&in&haemog!o in.&to&magnesium&in&the&porph*rin&structure&in&ch!oroph*!!-&It&is present&in&a!!&tissues&and&organs&and&is&e,creted&s!o)!*& *&the& od*&so&that&iron&is&a&necessar*&part o'&a&hea!th*&diet-&Aarge&inta$es&o'&iron&are&to& e&a1oided&a!though&at&such&times&as&pregnanc*&iron supp!ements&are&usua!!*&prescri ed& *&doctors-&Common&'orms&o'&iron&supp!ements&are&in&the&'orm o'&iron=II>&su!'ate.&iron=II>&'umarate&and&iron=II>&g!uconate-&&Iron&de'icienc*&!eads&to&anaemiaCo a!t-&This&is&a&component&o'&1itamin&C12 Chromium-&This&is&a&co'actor&in&the&insu!in&hormone&s*stem&)hich&regu!ates& !ood&g!ucose&!e1e!sCopper-&This&is&important&in&the&'ormation&o'&haemog!o in&so&that&among&the&s*mptoms&o'&copper de'icienc*&is&anaemiaZinc-&This&is&'ound&in&man*&enB*me&s*stems&and&is&important&in&the&meta o!ism&o'&g!ucose-

45 &he economic importance of the transition elements

(lement Scandium

Titanium

Vanadium

Chromium

Manganese Iron Co a!t

#ic$e!

Copper

(conomic importance It&is&used&in&mercur*&1apour&!amps&to&produce&natura!&da*!ight&!ightingCan& e&a!!o*ed&)ith&a!uminium&to&'orm&meta!& ase a!!& atsTitanium&is&used&in&high&tensi!e&stee!s&and&he!icopter&rotors-&The&o,ide&is an&important&pigment-&TiC!3&and&TiC!4&are&Zieg!er&#atta&cata!*sts&in&the po!*merisation&o'&ethene-&Titanium&is&used&to&ma$e&spectac!e&'ramesIt&is&used&in&ma$ing&surgica!&p!ates&)hich&are&unreacti1e&to)ards& od* '!uidsThe& iggest&use&o'&1anadium&is&in&1anadium&stee!s&)hich&are&rust&resistant and&use'u!&in&machine&too!s-&Vanadium=V>&o,ide&is&used&in&ceramics&and as&the&cata!*st&in&the&Contact&5rocess&'or&ma$ing&su!'uric&acidChromium&is&used&in&the&manu'acture&o'&stain!ess&stee!-&4eat&resistant chromium&a!!o*s&are&used&in&high&temperature&chemica!&apparatusChromium&p!ating&gi1es& ase&meta!s&an&attracti1e&and&corrosion&resistant 'inish-&+ddition&to&g!ass&imparts&an&emera!d&green&co!ourManganese&stee!s&are&tough&and&important&in&impro1ing&ro!!ing&and 'orging&properties-&Manganese&dio,ide&is&used&in&dr*& atteriesThe&main&use&o'&iron&is&in&iron&and&stee!&manu'actureIron&is&used&as&the&cata!*st&in&the&4a er&process&'or&the&manu'acture&o' ammoniaCo a!t&is&used&as&an&a!!o*ing&e!ement&in&high&temperature&super&a!!o*s used&'or&casting&air'oi!s&and&structura!&parts&in&2et&tur ine&engines-&Co a!t impro1es&the&properties&o'&rechargea !e& atteries-&Co a!t&is&essentia!&in&the manu'acture&o'&permanent&magnets-&5ermanent&magnets&are&'ound&in&a !arge&1ariet*&o'&e!ectrica!&instruments&'rom&!oudspea$ers&to ga!1anometers#ic$e!&is&an&important&chemica!&cata!*st&in&such&processes&as&the h*drogenation&o'&1egeta !e&oi!s&and&re'orming&h*drocar ons-&#ic$e! e!ectrop!ating&protects& ase&meta!s.&o'ten&app!ied&prior&to&chromium p!ating-&#ic$e!&a!!o*s&are&used&in&the&manu'acture&o'&spectac!e&'rames#ic$e!&deposited&'rom&so!ution&)ithout&an&e!ectric&current&is&used&in computer&hard&dis$s-&It&is&a&component&o'&stain!ess&stee!Copper&is&essentia!&'or&a!!&e!ectrica!&apparatus&and&is&essentia!&in&computer manu'acture&and&operation-&It&is&essentia!&'or&printed&circuit& oards. integrated&circuits.&chip&construction.&)ire&and&po)er&supp!ies-&Copper&is 'ound&in&man*&app!ications&in&the&motor&car-