CHAPTERT TRANSITION ELEM ents becutise © f their electronic structure, In thy sock elements and their properties yy tite § ~ block which typical), Transition elements are called d-block = elem Periodic table they are between the S and P ; slements O| transitional benween the highly reactive metallic ¢ a i . vats of the P_ block which form covalen form ionic compounds and the less reactive elements compounds. se WW [Gr | Mn [Fe joo Ni | Cu Le | , 2 O1R Nis cam /016 O15 Old [013 00.14 0.13 on 043 os ye By ronegativity [1.2 13 | 145 | Is? 2 2p° '38°3p8 3d se 4s? ps et 20 sant aye Afer the 2% energy level, an overlap starts occurring between 3 and 4" Js such that 3d — sub shell is nearer to the nucleus than the 4s sub energy level ~shell but at a higher energy level- Scanned wth CmScaneeFrom the electronic contigurati iransiti s aving a partially iguration, a transition clement is i is defined as that having a partiall filled 3d ~ bshelll (has between, Vand 9) electrons in the 3d ~subshell. — Pent : We for ch ; romium and filled d ~ sub shell e.g, for copper are thermodynamically more stable i.e. extra stability is associated with either half or full d—sub shell. For Cr, the configuration is = 1s? 2s? 2p 3s? 3p* 34° 4s! AND. Not Is" 2s? 2p® 3s? 3p° 3d" 4s? For Cu the configuration is 1s? 2s? 2p 3s? 3p® 3d!” 4s! and Not Is 2s? 2p® 3s? 3p° 3d? 4s? ily oxidised to Fe™ with 3d° and why Mn? with This also explains why Fe** with 3d° is 3d is resistant to oxidation to Mn™* with 34", yn metals Jons of Tran: losing electrons first from the 4S sub — shell rather than rip Transition metals form ions first by the 3d sub-shell, Hence electronic configuration of Fe, vpf ph] |b ft Fe™* and Fe™ are Fe(eroundstate) [Ar | 3d as ppp fb pe ph _| 3d 4s pip [piri 3 48 Cr Mn | Fe Co Ni Cu syn |v cae tise [i [eit rar [ie [rie [115 17 aa ToT fom [067 [0.66 [oF [0.63 | 0.62 ene tt Me au S “;67- Scanned wth Cmcas rapidly across _ r se being ade (0 Une Her 3 Ub lectrons ate |: Atomic radius decreases les ments, the el ansition ele «the 48 electrons which In transit ing of the AS elec rough Therefore the Ad electrons produce green S¢ balances the increasing nuclear charge. areansith ails General characterising properties of Transition Metals ‘ting points. The high meig 1. Transition elements ane metals with high melting and boiling Porm tng bonding which involves the 4 and 34 and the boiling points are due fo inter atomic ny points because they have both d a, electrons i.e.transition metals have higher meltin : ronger metallic bonds . or delocalization and therefore form cy __ Ter [Mn | Fe [Co [Ni eee | sone | pubes ERIE 1900 Pe | 1540 | 1500 | 1450 | 1080 Potassium and caleium have lower melting points than transition elements in the same ]ea [Se] Ti | 4 { 140 | 1680 | group 4 because they form weaker interatomic bonding due fewer electrons used for bondi Potassium uses only one electron (valence electron) while calcium uses two electrons. Transistion metals have higher melting points than S-block elements in the same period because of stronger interatomic (metallic) bonding formed by use of electrons from both the 3d and 4s subshells Menganese and copper have abnormally low melting points because of the electronic configuration which for manganese has half filed 3d while copper has full 3d-shell shell. These configurations for Mn and Cu give a stable lattice which make the 3d electrons less available for delocalisation (bonding). The increase in melting points from Sc to Cr is due to increasing number of unpaired electrons on the 3d-subshell while the decrease in melting point from Fe to Zn is due to decrease inthe numberof unpaired electrons on the 3d-subshel Note: Melting point increases with increase inthe numb the 3d. The very low melting for Zinc is due to stabilit er Of unpaired electrons in ty assoc; . - subshell which makes the electrons less available for bo ‘i an nding. Scanned wth CmScaneeJonie Radius Their ions are s: rio Is are smaller compare i i maller compared (0 those of the alkali metals in the same period. Beew of their smaller ionie radi ir polarisi smaller ionic radius and greater charge, their polarising powers arc greater, ‘Therefore as ated anions are greatly polarised and consequently most of their compounds are less ioni pounds are less ionic than those of the $ — block metals e.g. the oxides and hydroxides, Because of gre: : les. Because of greater polarisation also, most salts of transition elements are hydrolysed and are therefore acidic e.g. FeCl . CrCl, NiSOs, CuSO, ie BeChy + 3Hy eS © FeChyy + 320g = FON + 3HClow) ‘Transition clements have variable o jon states te is defined as the charge left on the central atom when all the other atoms of the compound have been removed as ions. e.g. the oxidation state on the following metals is calculated as @ Cro” The central metal ior Overall charge on the ion = -2 Let y be the charge on each Cr Overall charge on the 7 oxygen = 7 x (-2)=-14 charge on the 2Cr + that of 7 O= -2 (overall charge) = dxyt7x() = = 2y-14 = 2 by = 12 y - 6 “charge on each Cr ion is “6 Oxidation charge on Cr ="6 (i) (Cr(H20)s €1] 2c = HHO ‘This is a complex ion with Cr the entra metal ion, ‘The salt has two free chloride ions. hparge on the complex [Cr(Hl20)s CH] is "2. Overall ¢ = Charge on Cr+ charge on 5 1,0 + charge on one Cl'= #2 Let y be the charge on CT. 10 is neutral (Charge on C1) + (Charge on 5 10) + (Charge on Cl) = +2 yesx0tix) a ‘Seamed wth CmScaneedation states because of the availability sition metals show variable ox! peing +2 and +3. ciation state rons, The commonest oxidation stat om first transition series are es shown by the The oxidation sta “ @ - Ti 2 3 ® oO - indicates the most stapj, v 23 @ 5 cr 2 ®© 6 Mn @3 ® 6 7 Fe 2 @ 6 Co @ 3 4 Ni @ 4 cu 1 @ Zn @ : The +2 and +3 oxidation states are shown by most elements from. Ti and Cu. ‘The relative stability of these two oxidation states is governed by the electrode Potential for the reaction M?"(qy +¢ ——~> Mig ea Tire -0.125 vey “00s crt icrt -0.12 Mn?*/Mn** 1s Fe™* /Fe* 40.25 Co Co” +1.75 The value for M"/M* increase from Ti to Co but M*/MP is unexpectedly high and that of Fe°*/Fe”* is unexpectedly Jovy, The more positive the value of E° ili Me, » the greater the ability for M* to convert 0 Therefore Mn" is easily converted to Mn” and Fe3* Fe* and hence Fe" is mote stable than Fe?* This is because of the electronic Configuration; 3d sub — shell is half full and stable is not easily converted t0 and Mn®* is more stable Ma". 8 of Fe™* and Mn?* in which the Seamed wth CmScaneip’ 3d® s? ap* 3s" 3p 3dSstable Mn. " 2p* 38? 3p 3d%stable —— Mn** 2p! pe 3a? Note: The Cu’ is expect is expected to be more st ates soften, we stable than Cu” because of its electronic Cut - fi a 1p" 3s? 3p" 3d! ut ip 3s? 3p" 3a” But Cu” is more sta is more stable because the heat change for Cu’gq/Cu is less exothermic ait of Cu ie than that of Cu gq) Cu mee . : : ansition metal iors and their compoun oured a - — Colourless - Green x i - Purple - Yellow : Green Nit - Green cr - Green Cli - Blue 2 : Mn’ - Pink Zn" : Colourless MnO™(Mn™) - Purple Co : Pink Scandanium and Zn are not regarded as transition metals because () Their penultimate is full for Zn”* [Ar fa? while for Sc** is empty [Ar] 34°. Zn" and Sc** and their compounds are not coloured (colourless). jements is associated with presence of Gi) Formation of coloured ions by transition el incompletely filled 3d-subshell. When visible light falls on the metal ion, the 3d-sul hen absorbs energy and jump to higher tbenergy level is split into two. The unpaired electrons in the lower energy level tl evel. The energy absorbed in this process cor th usually in the visible part of the spectra Which is not absorbed is reflected as that colour shown b; persed light from the primary colours of re compound.E.g For cop} absorbed leaving blue and green which are shown by copper compounds ‘The colour of a particular transition metal ion depends upon responds to absorption of light at energy m. The remaining visible light a wavelen| yy the transition ion or xdjblue and green is i) The nature of the ligand Jdrated copper (Il) ion amount of ammonia turns to deep blue eg. the colour of hy’ [Cu (H,0):]”*, is pale blue but on addition of sufficient Sean wth CmScaneeCu HLO)slan? + ANHyay [Cu (NEDaTan FEO [Cu QO) Pa Joop blu pale — blue jd turns the pale blue solution to Also addition of sufficient cone. Hydrochloric acl yellowish brown, > 4 41LO, laltagy F APROW ie. [CU(O)slog?” +4CK ay ST (CuClalew : pale —blue Yellow brown ii) The oxidation state of the metal ion e.g. [Cr (H20)q}”* is blue while [Cr (H20).}* is green 4. Most transition metals and their compounds have high ability of being catalyst. They are good heterogeneous catalysts. This is because of (a) Presence of 3d electrons which enables transition metal ions to form temporary bonds with reactant molecules. This increases the concentration of reactant molecules at the surface of a catalyst and weakens the bond in the reactant molecules. (b) . Their variable oxidation state which makes it possible for an alternative reaction pathway with lower activation energy. During the course of its catalytic activity, transition metal ions undergo changes in their oxidation states but is regenerated at the end of the reaction. The following reactions are catalysed by the transition metals present. V20s oe 2802) +Oxg) ~9=———> 2 S036) RCH=CH) +H2__Ni > RCH: CHs 150 (CH3CH2 — OH + % O2 Cu CH3CHO Fe 3H) +Nag) <== 2. Ns) MnO, 2KCI0x) ——————> 2K Cl + 300) Seamed wth Camscanee5. Most_transition_metal_ions_are paramagnetic, Paramagnetism is the weak attraction of substances in a magnetic field, Transition metal ions show patamagnetism because of the presence of unpaired electrons in their 3d-subshells, Paramagnetism a rises duc to the spinning of unpaired electrons on their axes which generates electric current. The magnitude of paramagnetism effect depends on the number of unpaired electrons on the 3d-subshell, The greater the number of unpaired electrons the stronger the paramagnetic effect eg. [Ar] | ‘one unpaired electron 4 4 —_ two unpaired electron cr 414 74 three unpaired electrons 7 : Fe 11 AL 114 14] five unpaired electrons Mn? Pea five unpaired electrons cut AVAL IAL 4 one unpaired electron , sc* [ no unpaired electron ant ALIAL [ALLA [11]. to unpaired electron Graphically paramagnetic moments for the ions is as follows, Paramagnetic moment oe ope CoM NB Cut Zn sot Te! Cet Mn Fe" Fe Co Ni* Cu Zn Scanned wth CamScaneeNote: amagnetic effect since they haye re @ Fe greatest number of unpaited no paramagnelle ef eatest para % and Mn?! have the grewlest P J electrons a / . fleet because they don’t have Unpaireg Gi) Se and Zn" have electrons ve!" has 5 unpaired el ee because Fe?” has 5 unp lecttons (i) Fe is more paramagnetic than Fe while Fe" has 4 unpaired electrons Is, Complex formation by Transition met / sa central metal ion bonded to other ion, atoms A complex ion is an ion which contains or molecules through dative bond. Transition metal form complexes because (i) of their small and highly charged ions (ii) of the presence of vacant d — orbitals which can accommodate lone pair of electrons donated by other groups (ligand). Complex formation is an association of two or more species each of which is capable of an independent existence, The species are called ligands and can be (a) either simple ions like CN’, CI’, [, Br’, or OH (b) Complex ions like NOs’, or C20, (©) Neutral motecules like HO, NH, HyS or NHsCH CEN, The structure of a complex metal ion is such that it consists of a central metal ion surrounded by a cluster of anions or molecule called ligands [ML,]* M = central cation eee eee ord n= umber of ligand Y= charge on complex These ligands form co-ordinate bonds with the central metal j b i ‘al metal ion by donating their unshared electrons into the vacant d orbitals of the transition m, tals i ‘ans ctals ion, The number of ligands bonded to the central metal ion jg called the co-ordi ‘o-ordination number of the central metal ion. ‘Scanned wth CamScaneeNote: The co-ordination number of a particular ion is the same whatever the ligand. For example Cu?’ ions have a co-ordination number of 4 in most of its complexes. ie. [Cu (H0),}". (Cu (NH)s), [CuCl Cu (NHp - CH) = CH -NH2)> - Cu(en)) Where en represents NH) ~ CH: ~ CH; —NH Most ions have co-ordination number of 6 [Cr(H20)<}**, [Cr(NH;)¢]*, [(Cr(H20)}s ChY Very few ion have a co-ordination number of 2 ie. [Ag(NHs)xI', fAg(CNsT Note: Because of the very high polarising power accompanied by ability to form strong bonds with oxygen atom, aqueous solution of some transition metal ions are acidie due to hydrolysis reaction.Eg [Cr HO)o) Pea+H200 [Cr (H0)s OH Pay) + HO" eg Similarly aqueous solution of FeCls, CuSO,, NiSO,, Co(NO3)p are acidic for the same reasons. [Cu(0)4]"y+HhOg—————————[Cu(H:0):0H J +450" [Co(H20)6}*"(ay#H20w === [Co(H20) OH] (ot HO") Structure of complexes Ligands with co-ordination number of 2 adopt a linear structure e.g. [Ag(NH3)2]" ——————> Ag’ <—__ §s with co-ordination number of 4 adopt tetrahedral Structures’ e.g. [Zni(NH3)1J", and some few others adopt square planar structures e.g. CuCl”, [Cu (NH3)s]"* Scanned wth CmScaneeae UT <= . Neb Nis > NHy HN ver of 6, the ligands adopt octahedral structure. In complexes with co-ordination numb Nib eg. [Cr(NH)e1” NHS HN ® Stability Constant of Complex Complex formation occurs in solution and the react _—__ Mog + 2L0q MLMq) jon is reversible and occurs in steps. . — ; ie Mth = M1 O OM OF M (M) [L] ML+L———— Mh @) & = Mil [ML] [L] Mi;+L Mis Gil), Ky = [ML.] [1] ML ¢L ML Kee IML] Mo] 11 For the overall reaction Mg + Le) ———— Mtg B = [MLn] mir 5 _iscalled stability eonstant Note; During complex formation, any ligand with ahi her stability consta splat int value disp! the other with a smaller value, ‘Scanned wth meanereg [M (ih0)]"* Bp = 108 (M NHJ" B= 108 This means that NH; ligands will displace HO ligands ie [Mh O)s]" +6 Nyy | ——____s [M(NH3)6]"" + 6420 This explains why addition of ammonia solution to an aqueous solution of copper (I!) ions, the colour changes form pale blue to deep blue, Stability constant is expressed as logio eg. For [CuCh]}* log B =5.6 [Cu(NH3),P* log B = 12.6 Addition of conc. Hydrochloric acid to aqueous solution er copper (If) ions changes colour from light blue to yellow. The yellow is due to the complex CuCl? w ie, (CuO) Pq + 4CTeg blue yellow is more stable than [Cu(H20):}°* CuCl ay ~ Isomerism Jsomerism among transition metal ion complexes arises as a result of different arrangements oftheir constituent atoms. The ions exhibit the following types of isomerism. (2) — Geometrical Isomerism: This is due to the arrangements of ligands in space giving rise to the usual cis-or trans isomers.e.g. [Cu (NHs)2 Cla] and [Co (NHs)s Cl] LE LEE Cis - dichloro diammine copper (I) ion Trans-dichloro diammine copper (II) ion Scanned wth meanHN Cis-dichloro tetra ammine cobalt (Ul) ion ion Blue - violet ) a «x vl Z£ NH. 7 HN b NH, IGN, q cl 7 d wy al rrans-diehloro tetra ammin cobalt (I) Green in colour This arises when two isomers differ in the distribution of ions between those which are directly bonded and those not directly eg. Co(NHa)s Br SOs has two isomers [Co (NH3)s Br} SO" H3N NH; Br \! Here the Br is directly bonded to be cobalt (III) ion while the SO, is free and Co so. : can be precipitated. Therefore addition \ solution of barium nitrate or barium wit Nib NH chloride would give a white precipitate. Precipitate of BaSO, Bey +801" ——————> B80) Addition of solution of silver nitrate mean while does not produce a yellow precipitate of Ag Br because the Br’ unlike the $0,2"is not free, ‘The second isomer (Co (NH3)s SO, ]* Br 7 ‘NH3 + t Sn | ‘NH3 - 78 - Seamed wth CmScanee@ In this isomer, the SO. is now directly bonded to the Co** and is not free but the Br’ is not bonded and is free and can be precipitated, Therefore, addition of a solution of silver nitrate produces a yellow precipitate of Ag Br. / Agen + Brag > AgBrs Since the SO," is not five, addition of Ba** does not produce a white precipitate. Hydrati In this isomerism, the isomers differ in the number of water molecules directly bonded to the central metal ion and those which are not. e.g. Molecular formula Cr Cl. 6 H20 has the following isomers Structural formula of |No, Of moles of ions |No. Of moles of ] Colour of isomer Isomer per mole of CI of each CrCl Cr Cl; 6H2O (deduced | 6H,O (deduced | . from conductivity) _| from precipitated) ‘A. (Cr(HaO)ej" 3Cr 4 3 Violet | B. [Cr(H20)sCl™ 2Cr [3 2 Light green ©. [Cr(H20),;Chy Cr } 2 1 Dark green qa) Q) The isomers show difference in conductivity in aqueous solution depending on the number on free ions present. The isomer A has 4 conducting ions i.e. (Cr(H20)6]* and three CI’ and therefore has, the greatest conductivity. Isomer B has 3 conducting ions and is the second most conducting while isomer C has only two conducting ions as (Cx(H;0); Ch and Cand conducts least, ‘The isomers also precipitate different amounts of silver chloride depending on the amount of free CI’. In isomer A, all the three CI’ are free and therefore all the CI ion are precipitated. TP 1M AgNO5 solution was used then 3 moles of AgC! are preeipitated, fie. [Cr(H20)1"%og + 3CT eayt 38 ——> [Cr(H2O) Jaq) + 3AgCho er B, One CI ions fixed while two are free ad therefore addition of IM 103 solution precipitates 7/3 of the CI’ or 2 moles of AgCl. ‘Seamed wth CmcaY O)sCH ay [Cx(Hs0}s CH" an + 2Clen * 2Ag'ay—— [Cr(H20)sCH eg) *2Agg 20)s C1} ayy + 2H aa CI is free therefore only '/, Of the e a sxed while one Isomer C has two CI ions fixed while ocr ie formed d or 1 mole of AgCI is forme . > (Cx(H2O)sChY fay + Agcy, aay + CK aq) + AB od) [Cr(Ha (oa) * Ag}, Naming of Comple F ‘tal atom or ion 1. The ligands are named first ,in alphabetical order,then the me! 2.All anionic ligands have their names ending in Eg .CT is called chloro, $0,” is called sulphato,NO» is called nitrito Anionic Ligands | Names - - —— a —— o~ Oxo OH . | Hydroxo CN" | Cyano G0." | Oxalato Cos” Carbonato CH3;COO™ Acetato _ For neutral ligands Neutral Ligands Names NH; Ammine HO : ‘Aqua _ Nitrosy] co HaNCH2CH,NH2 Scanned wth Cmca‘in naming co complex e.g di Name in an. nionic complex ~) Cuprate “Ferrie Plumbate Argenate Stannate jatinate Cobaltate Zincate _ - plexes.Greek p 5 are used to ndicate the numbe etra- etc while bis-.tris-,tetrakis are used instead for polydentate ligands. Examples (@ [Co(NHs):(H:0)2] Cis is called tetraamminediaquacobali(ifi) chl Note:The complex ion is inside the squared brackets(parentheses) while the three chlorides binding with the complex ion are free.Ammine ligands are named before aqua according to alphabetical order. (&) _ Ks[Fe(CN)¢] is called potassium hexacyanoferrate( ii). Note: Potassium is the cation here (©) [Cx(F:NCH:CH:NHz)3]:(S0.)s is called tis(ethylenediammine)chromium( iit) sulphate. Note:The sulphate is the counter anion .The number of the cation and anion are not included in name. (4) [Ag(CN)yJ is called dicyanoargentate(i) ion. (©) Naa[Ni(C20,)2(H20)2] is called sodium diaquabis(oxalate)nickelate(i) Note: This is a compound in which sodium is the cation while oxalate ion isa bidentate ligand. Applications of complexes 1 Some compounds which are insoluble in water are dissolved by conversion imo 2 complex .For examples Scanned wth CamScaneeInsoluble compound soluble in Complex formed © AgChAgBr NH soln, Ag(NH3),° KCN soln. Ag(CN)z° Naz$203 soln. [ Ag(S203),° @h KI soln. ly Formation of insoluble complexes. E.g Dimethylglyoxime forms a red precipitate With Ni™ used for testing for presence of Ni2* Scanned wth CamScaneeCHEMISTRY OF INDIVIDUAL MEMBERS. Titanium is attacked by oxygen when heated to give titanium (IV) oxide Tio $Ox es Tie 2 Titanium is attacked by hot concentrated hydrochloric acid to give titanium (IID) chloride 2Tig) + OFC), —————> ITIClye0) + 3) Cold cone. Sulphuric acid reacts forming Titanium (III) sulphate and sulphur dioxide. Ii + 6HsSOya) ———_5Tix(SO,)s + 6H:0y + 30x 3. With halogens (chlorine) When chlorine is passed over heated Titanium, titanium (IV) chloride is formed Tig) +2Cly —————>_TiClin Compounds of Ti im Titanium forms compounds in which it shows oxidation states of “2, “3 and “4. Tie - 1s? 2s? 2p® 3s? 3p® 3d? 4s” Tren 1s? 2s? 2p® 3s? 3p® 3d? 3+ 2 462 4p 6 23,6 aqh ealoartd TH - 1s? 2s? 2p* 3s*3p* 3d! Ti - Is? 2s? ap® 38° 3p? +2 oxidation state is unstable, In the +4 oxidation state, all the 3d and 4s electrons are lost and therefore compounds of Ti** are neither coloured nor paramagnetic. In the +3 oxidation state, the 3d sub shell has a single electron and because of this titanium({II) compounds are coloured and paramagnetic and therefore transitional. Compounds in the +2 oxidation state; ‘These compounds are very unstable. TiCl, Prepared by heating TiCl; with titanium metal TiC +7) ——— 2Tichy is a strong reducing agent and undergoes rapid aerial oxidation, Scanned wth CmScaneand is purple and uns fridhOl” © +3 oxidation state in aqueous S ene The +3 oxidation state mn aq! sidation state. and quickly being oxidised to higher ot Yo) Tey +H209 ——— 7 10 * compounds in ai 1 be prepared by re i pit duction of Ti Solutions containing [TMO! &™ vd by reduction of TiCly with zine jn sotutions with zine, For example TiCl with # prepares”? the presence of hydrochloric acid. TiCls disproportionates ie 2G TIC + TIChis * - ade are used in volumetric analysis, + Solution of titanium sulphate and titanium chloride are used in vo! ys ‘Titanium (1H) sulphate solution witch is violet is standardised by (@ Titration against acidified potassium permanganate at about 60°C. STi" q) #MNOs'gq) +819) ————_ 5TH en + Mn + 44200) (i) Titration with iron({1D) alum with ammonium thiocynate as indicator. Tq) Fe") ————> Tay +Fe™ en Compounds in the +4 Oxidation State. Titanium (IV) compounds do not show typical transition metal properties because the Ti** does not have any electron of the 3d sub-shell but tends to resemble group IV elements. TiCl. prepared by passing chlorine over heated titanium Tig +2Cly = > TiChyy TiCls is covalent and is rapidly hydrolysed in water and fumes in moist air TiCly +20) ————> Tiny + 411Cley TiCle like PbCl a group (V) compound dissolves in concentrated hydrochlor 7 chloric: formation of a complex ealled hexachloro titanium (IV) Se Ticlyy +2Cl) ———> iC ay Vanadium Electronic configuration By _ 1s? 2s? 2p* 3s’ 3p* 3d? 4s? Properties Is resistant to reaction and at room temperature it ig ae Not 3 oxidising acids and alkalis. alfectd by ain, water and not On heating in oxygen, it forms vanadium (V) oxi, ide 4V@_ +502) > 2V 2054 Seamed wth CmScaneOn heating with chlorine it forms v: Vy +2Chw, ——S s VClagy ‘anadium (LV) chloride Compounds of Vanadi Vanadium shows the following oxidation sta $ as +2, 43, +4 and +5 3a° aso 3 vee 3d +3 th 3 2 5 tu ° Hh yy 3d" a vo" yt ninoyt vi ve. 3d! pute yor Blue gee sae yw apt 32 apt of 7 id and zinc amalgam. The colour of the solutio These different oxidation states of vanadium can be demonstrated by shaking a solution. vith dilute sulphuric ammonium vanada wakes ‘a lube Zine aon cen to change from pale yellow to blue, green and finally to violet. is Oxidation state [+3 +4 133 an) Ton VO." vo" V™ or VELOVe” | V* or VERO)6™ Colour Pale yellow Blue ~~) Green | Violet } Note: Because of very high charge and small ionic radius, vanadium +5 and +4 do not exist in aqueous solution. The great polarising effect on neighbouring water molecules detaches two and one O* respectively forming VO." and vo". The changes taking place is represented by equation as + —__—_——_ a+ VO2"(aq) +2 H%eqy) +¢ VO" aq) + H20(1) Yellow i VO" (ag) + 2H ag + € > _ Ven 200 Blue green Vw e ro aa violet is sequence of colour changes is used analytically to test for the presence of vanadium. ounds +2 Oxidation State rated vanadium (II), [V(H0)6}* is violet in colour and is stable. ium (II) oxide. VO s is a black and basic solid. Itis easily oxidised to the hydrated V** in air. Scanned wth CamScanee—————— yg gas ver V20% ) +2100 3 Ovidation. State passing Compound int Vg0u gto form [yao which is green. pound in th ruse of the high pola ) Oxide, V3 Os y ammonium vanadate > 9205 * INH xe + HO ' ; si acidic solutions Tecan orange solid and is ampere. Tissoves in strongly acid (fom a, low V3" Vs09) + 6H gg) +2Cl a) ———> 2V0" en) Chap) + 320 Italso dissolves in strong alkali solution to form vanadate ion. 65) $60 a) > 2VOi%(a). + 3H20 v. Chromium Electronic configuration “Cr - 1s? 2s? 2p 3s? 3p® 3d° 4s! Reactions (@) — With oxygen chromium (Il) 11) oxide. 4Cig + 30x) ———————> 2Cn 03, (b) With water Geen - Chromium is unaffected by.cold or hot water but reacts.with steam attest heat to fom chromium (III) oxi © With acids CSOs respectively. Choy +2HChy — ey + Cte + x80 ——_ 0 * Hag These Cr salts then undergo inmcanbettattiae salts. ian a to give corresponding a ‘Seamed wth CmScaneeACH ayy FATE Gag) + O29) ——A——> ACP", + OW Mot concentiated sulphuric oxidises the chromium to Crz (SO4)s and forming sulphur dioxide, 2Ctiy + OH2SO4uq) =< > Cr($04)sray + 6H2On, + 3802) Chromium does not react with dil. HNOs but with conc. HNOs, a thin layer of Crs is formed which render @ Wi 1 Chromium reacts s dium hydroxide slowly forming sodium chromite and hydrogen gas Cry + 2 NAOH (oq) + 2 HO —-————>_ NaxCr(OH) gan) * F Sool ws cect (ce) — With halogens (chlorine) On passing a current of chlorine gas over heated chromium, chromium (II) chloride is formed. Cry + 3Clg) ————— 2CrC ls, When HC is used instead of Cr, CrClz is formed Cr) + 2HClqy) ————> CrCl) + Hoe Compounds of chromium Chromium shows three principal oxidation state of +2, +3, and +6. Gc. 1s? 2s? 2p® 3s? 3p® 3° 4s! Cet = Is? 2s? 2p® 35° 3p® 3dé cet = Ist 28? 2pé 38° ap* 30? at 1s? 2s? 2p% 38° 3p° Compound in +2 Oxidation State Ce compounds are unstable and are easily oxidised to Cr’* state, CP) ————_ on Chromium (11) hydroxide (Cr(OH) - Prepared as a yellow precipitate by addition of sodium hydroxide solut * salt. ee CO oo CJ gellew fe tion to a solution of Scanned wth CmScaneeate solution ex cous solution exig aqueow N exists ag ion , Compounds inthe SS ast a rhomiu an in é For example C is as that. Fo iple CrCl, Cras is the most stable oxidation “2 jpexia {Ci(HOy4. Hence in any solution of CFT chrome alum K»S0s, Cr(SO4)s 24120 poco of 2+ is acidic in aqueous solution beca 7 . [Cx(H,O)gf"*is acidic in aqueous eee cO¥011F "ea H0'ay (CxO) oq) +10) drolysis reaction. Chromium (111) Oxide, Cry. romium (III) hydroxide This isa green solid prepared by heating ch 2CH(OH)y) ————>_ C030) 3ELOQW poem ing Cr" g It reacts with acids forming Cr salt. The oxide, ike Al:Os, is ampoth ChOx) + 6HClaq) —————> 2. CrClyja + 3 HOW In excess alkali, it forms chromate (Il) C103) + 60H (eq) + 3H30————> 2[Cr(OM)}* aap Chromium (II) hydro: Prepared as a green gelatinous precipitate by addition of sodium hydroxide to a solution of crt. CPM ag) + 30H) —> CON); Cr(OHDs is ampotheric. It reacts with acids to form corresponding (Ill) salt Cr (OH)x9)+ 3H oq) ———> Crag) +3 Hay Cr OW)3¢) + OH) —_y CrOW)r'ag 1 oxidised by HO in the presence of an alkali to fom elromat nate, 2CH(OW)s«) + 30x) + 401, (J ———_ 2 2C104 9) + BHO Formation of yellow chromate i , ye mate is used as test for C3* ion, Chromium (Ill) hydroxide dissolves in exces [Cx(OH)g)* Cr(OH)s + 30H) =~ ———___, Green ppt excess [cr(oH),P- Dissolves in excess ammonia solution accor ling to CxO) + NH ———___ a rt 8 $0 cium hydroxide to from a green solution! &reensolution, the reaction, Hey) 30K Note: Chromium (Il) hydoxie is ts “ rec ; , ii sodium carbonate solution or sodium sulphia Pitated When to sulphide g olution, 4 solution of Cr is dae! Scanned wth CmScaneeNo chromium carbonate or sulphide is precipitated but instead chromium hydroxide is precipitated. The carbonate or sulphide initially formed because of highly charged and small Ce" (high polatizi Power) the carbonate or sulphide is readily hydrolysed to form a grey green precipit © of Cr (ON), with evolution of colourless earbondioxide gas FeO + 3CO* Gy ———_>. Cr (CO) Cr(CONyy + SHO) —> 2Cr (OW)y9) + 3COr% OR 2 Cray) +3 COS ag + 3 H20 yp >2. Cr(OH) 3 +3 COs) OR ZACH Oo} oay#3COs* ag) —> 2[CHO)s( O13 ]j#3COnig#+3H2Oy, 2Crp + 3Clay)—__—> 2CrClayy Hydrated chloride, CrCl; . 61:0, exhibits hydrate isomerism with the following as isomers. (hydrate isomerism is where the isomer differ in the number of water molecules directly bonded to the Cr’) [Cr(H20),]** 3Cl_ppts 3 moles of AgCl (i.e. all CI’ ppted) [Cr(H20); CI* 2CI ppts 2 moles of AgC! (i.e. 7/3 of CI ppted) [Cx(H20),Ch]” CI’ ppts 1 mole of AgCl (Le. V/s of CI ppt) [Cx(H:0); Clr] 3H20 does not ppt AgCl because there is no free CI ion Compounds in +6 oxidation state Because of very high polarising power it exists as’ oxoions like chromate Cr0,? or dichromate Cr:07". Chromium (V1) oxide, CrOs Prepared as a dark precipitate when cone. Solution of K3Cr20y is acidified with cone. H»SOs. CnOF%q) + 2H ey §$——> 26103) + HO ‘The oxide is triangular 0 4 \ Lo oO dissolves in water to form chromic acid C103) + H:0¢) HCO -89- ‘Seamed wth CmcaOE _ ___—_— aN a chromate, ves soluti produ Ives in alkali solution £0 P es in ana diss NaxCrOuoo CrOs is an avidie oxide. 1 LOW CrOxy) 4 INAON ayy) ———” Chromates vellow in colour. of chromic acid and are yellow in etrahedral shape. " . wes Chromates are made by adding alkali to ¢,, oOo I CHOP ay + 20H) —> 2CrOs" am) + H20p ¢\ 0 i Chromates are only stable in Alkaline solution but in acidic medium, they are converted 4 the orange dichromate ions by reaction. 2CrO4" ag) + 2H (ag > Cr207aq) + HOW Yellow Orange Note: A chromate ion Cr," can be confirmed to contain Cr°* by carrying out te following. A solution of Cr,” is first acidified to produce Crs0;7 ie. 2C10) "+2 Hq) ————> C1207" (aq) + H2Oqy To the solution of the dichromate a few drops of ethanol is added and the mixture warmed. green solution is formed. To the green solution is then added sodium hydroxide solution dropwise until in excess. Formation of a green precipitate which dissolves in excess to givea green solution confirms Cr* presence; Dichromates . Dichromates are salts of chromium in +6 state and ate orange in colour, Dichromate iot consists of two chromate ion which ‘ne tetrahedrally linked through an oxygen atom. i 9 | QI, Scanned wth CmcaDichromate is made by acidifying a solution of a chromate 2CrOF ag, +2 yellow 9) A> 6107709) + H0q) Orange Dichromates are stable only in acid solution. In basic solution they form YELLOW Chromates. Cr:07"a3 + 20H 4g > 2010, + Hy) Orange yellow Potassium dichromate ‘This is an orange salt prepared by mixing hot cone, Solution of both sodium dichromate and potassium chloride 2KChagy + It is a strong oxi Cr07° + 14H aq) +62 > 2CP "(a +7200) Its colour changes from orange to green. Since itis less powerful oxidising agent then KMnO,, its solution can be acidified using both H,SO.and HCL Some of the oxidising reactions are: (2) 6 Teg) + CraOraqy” + 14 H tog) —————> 2C¥** faq) + TH20q) + 3le(09) (b) 3803*@y + Cr20r03” + 8H ———> 380s (ep + 4420 +2CP ay (38m eq) + CHOrag” +1 ey) ——> 2CP a) + 38a ag” +720 @ — CnOP ey + INO2y + 8H'uy ———> 2CP ey + INO) + 4400 CHOP ey) $3 COP uy 114 My ———> 2a + TH2O1y + 6COr) ses on heating to produce potassium chromate and chromium © Potassium dichromate decompo: (UD oxide. 4K CO) > 4K2CrO4) +2003) Test for Cr” (a) With NaOHeq) ; green gelatinous precipitate of ‘Addition of aqueous sodium hydroxide produces dissolves in excess alkali to produce _a green +305) chromium (III) hydroxide which then solution. Cag) + 30H oy Cx(OH)3x) + 30H ew Green ppt (b) With ammonia solution 40)» > [cH 0Hol*ew Green solution ‘Seamed wth CmScane4 « elightly dissolves in excess to A ipitate is formed sich slightly diss Form a ig A grey= green pree formed. or violet solution, ow solution of a chromate ¢) ew em! of H:O2 ell (©) aa few em! of 1202.18 o> 161027 en) + BHO, ACKON) yg + UO) + HOM on - nate formed is confirmed by a yellow precipitate of ba, ‘The presence of the chron Addition of a solution of BaCl, whieh produces @ chromate, > Balu) Gi) solution of lead acetate or lead nitrate which produces a yeljo, tate of lead chromate PH" ag) + CrOW qq) ————> __ PbCrOsw (iii) Addition of a solution of silver nitrate which produces a brick red precipitate of silver chromate 2Ag" ag + CrOW aq) At Cr) (iv) Addition of a little butan-1- ol and dilute sulphuric acid produces a blue colour in the butanol (Organic) layer. (@) When a chromium (Ill) salt is heated together with an equal quantities of sodium carbonate and potassium nitrate, a yellow solid of a chromate is formed. (©) Addition of sodium carbonate solution to a solution of Cr* salt gives a green precipitate with effervescence of a colourless gas. © 2Cr 9) + 3 COs) + 3 HO ————— 39 Cr(OH) ayy +3 COs Manganese Electronic configuration "Min = As? 152 ap 322 3p6 345 4g? Reacti (a) With Oxygen Manganese burns in air to produce Mny04 3M) *20%) = — 5 pny Oxy (b) Withacids Manganese readily reacts with dilute hy drochloric ac . . form Mn®* salts, ‘Ydrochloric acid and dilute sulphuric acids © — Pasnene MnCl + Hyg Magy + HiSOx)—————_ MnSO gu) + Hy @) Nitric acid reacts with Manganese to pj 0 give varied Products -92~ ‘Seamed wth CmcaManga sulphate and sulphur dioxide gas Mn+ 2 HeSOya) (©) Wis ese Teacts with hot concentrated sulphuric acid to form manganese (II) 5 MnO.) + SOxq) +2 H20W ter Impure manganese reacts with hot water forming H2 gas Mnys) + 2120q — — > Mn(OH)¢) + Ha) Note: Manganese does not react with alkali Compounds of Manganese Manganese shows the following oxidation states +2, +3, +4, +5, +6 and +7 Ma - Is’ 2s? 2p* 33° 3p® 3a% as? Mn - Is? 2p® 3s? 3p? 35 Mn* - 1s? 2p* 3s? 3p® 3d* Mn* - 1s? 2p’ 3s? 3p® 3d? Mn* - 1s? 2s? 2p* 3s* 3p® 3d? Mn® - 1s? 2s? 2p* 3s? 3p°3d! Mn” - 1s? 2s? 2p* 3s? 3p? The +2 oxidation state is the most stable. solid by heating manganese (Il) carbonates or manganese ({1) oxalate Prepared as a green MnCOx —————> _ Mn + CO2xe) ManCz049) > MnO) + CO) + COr) Mn (OH) —————>_ Mn) + H20 Manganese (Il) oxide is strongly basic ie. MnOw +2 Hea) —————> Mn”*(aq) + HOw Manganese (I Hydroxide, Mn (OH) Prepared as a white precipitate by addition of sodium hydroxide soh 5 H) 25) Vinay) + 20H (a). ——————> Mn(OH)z2) osatto Mn0>.xHa lution to Mn** solution. white ppt. rapidly turns brown due to oxidation to (OH)5) + Ox) —————> ? MnOx9).H20. Mn(OH)2q + Ox) ————>2 M203 120 + 2 Hao . Manganese (II) salts are pink aud in solution exists as [Mn(H20)6] . (A) hydroxide is strongly basic and resembles iron (11) hydroxide. Scanned wth Cmca 2303 () Heating MnO in air, MnO + O28) 50s + Oe (i) Heating MnO, 3MnO3g-———> Mm 0x9 Ox) Mn;O, reacts with hot HNOs to precipitate MnOz OMn2 recy + 2 He ie. MnjOxy + 4H"qy) = > MnOzy + 2Ma@e) #2 F2Om Compounds in +4 Oxidation state Manganese (IV) Oxide, (black) Prepared by heating manganese (I!) nitrate, Mn (NOs)2 Mn(NO3)x) ——————>_ Mn0x) + 2NO2@) Manganese (IV) oxide is a black solid which is insoluble in water, amopheric and is not affected by dilute acids. MnO> dissolves in cold concentrated HCI due to formation of hexachloromanganese (IV) [MnCle]” MnOajs) +4H"aq) + 6Cl'e) ————> [Mn Clefagy +2209) MnO; oxidises warm cone. HCI to chlorine d + 4HCl, —_ MnO2) + 4HClrag) MnCl) + Clay +2HLOy MnO; oxidises warm conc. H2S0s to oxygen, MnOz) + 2H2S0. Ox) *2H2SOtw) ——5 MSOs) +05 + 2H:0y Note: Manganese (IV) oxide is a strong oxidising agent oxidising reactions of MnO>, The following are some of the (@) — Hot cone. HCI oxidised to Cl, MnOx) + 4HClo) = ——— 3, Mani (ii) Oxidises hot acidified solution of oxalate t0CO, MnOxy + CO + 4H y—— 5 0, (9) 2H +2COr@) Chay + Chay +2809 ‘Seamed wth CmScaneecolour, Potassium mang: nate (V1) is prepared by fusing together MnOz and KOH together in the oxygen. presence of. 2Mnx) +4KOH ag + 02g) ————> 2KQMNO4joq) + 220, K2MnOs is very powerful oxidising agent and is only STAB KaMnOy is also prepared by heating together MnO, KOH and potassium chlorate. te, 3MnOa) + OKO aq) + KCIO¥y ———> 3KaMnOyay + KCl + 3420 MnO.* is only stable in an alkaline medium. in alkaline medium. But in neutral or acidic, media undergoes disproportionation forming MnOy and MnO) In neutral medium 3K2MnO4(a)_ + 2H20¢) ———— 2KMnO.qq) + MnO2 +4KOH (0) In acidic medium 3 Mn 02 (ay +4 Haq) —————> 2. MnO (aq) MnOnyg + 2 H209) ‘Therefore dilution of MnO," or passage of CO changes the colour from dark green to purple with black solid formed. Compound of Manganese in +7 state: Potassium permanganate Prepared by fusing caustic potash in an iron crucible with potassium chlorate and MnO is added and the mixture is heated until the mass goes stiff. This mixture is cooled and boiled with water, COs is then passed through the green solution producing purple solution. Potassium permanganate is a very powerful oxidising agent and is used in volumetric analysis and its own purple colour is the end point of titration. In strongly acidic medium it behaves as MnOsq) + 8H eq) + 5€. ———* Mnaq) + 4120.9 Note: The acid used is sulphuric acid and not HCI or HNOs. This is because unlike K,CrsOr, KMn0 is powerful oxidising agent oxidising the HCI to Cla. Nitric acid is itself an oxidising agent so it will interfere with the action of MnO¢” “Some of the oxidising properties of MnO,’ are 2MnO4 aq) + 5C208"09) * 16H "ay 2M) + 10 COrie) +8H20 ey ret 2 MnOsqag + SFe*aq) + 8H" |< SFe* fay + Mn"Gaqy + 4H200) 2MnOs (ay) + 580?" aq) + VGH og ————> SSn" aq) + 2M") + SH20 0 2MinOsaq) +5H202009. + 9H aq) ————> 2Mn"(aq) + SH2Oqy + 5020p ee + 2MnO sae) +10 Tea) +16 How) IMa"9) + SHOW + Slop) . nt H : 2MnO'xq) + SNO200 + 6H" on 2Mn(aq) + 3H20q) + SNO'Haq) -95- Seamed wth Cmca2Mn""@p + 3H2On + 5 ———->- 1 +30x9 + 2200) OF yay b 6d (ii) 2MnO4a) + idic medium it behaves as die medium it b re In sligh AMNO vag) + 4H ay) In neutral or weakly alkaline medium it behaves - Hq * MnOzy) + 40H ——— ° . jon above is the reason Why it fea, MnOy +2H:0y +3e by the reaction abo The formation of brown deposits of MnOz brown deposits in the burette. Under this condition it oxidises T' to 103" by the reaction . +2 OH) 2MnOc‘ng) + HO) + Vg ——————>._ Mn In strong alkaline medium, it behaves as MnO (oq) +€ —————> MnO") i 2+. To acidified solution of MnOy’ is added g Experiment to show that MnOy contains Mn” few drops of ethanol and the mixture warmed. The colourless solution formed is then treateg + 1049) With sodjum bismuthate. Formation of a purple solution confirms Mr Test for Mn” in solution (2) With NaOH or NH,OH Addition of aqueous solution of sodium hydroxide or ammonia to a solution of Mn produces a white precipitate which rapidly turns brown on standing. Ma) + 20H gg) ————5 Mn(OH)x¢) 4 Mn(OH)2) +02) |~——-———33in, 12039) H20( +2 HO, Mn salts are oxidised to purple permanganate by heating the solid salt with cone Nitric acid and tead (IV) oxide or sodium bismuthate, 2Mn** + SNaBiO; + 14H? ——___y 2MnOs'+ SNa* + SBi* + 7H20 2 2M) + 5PbOxy) + 4H ——> 2Mn0yi4g) + SBE? (ay) + 2H20,) IRON Electronic configuration **Fe = 1s? 2s? 2p° 35 3p* 3d6 (b) Occurrence (Ores) Jron occurs naturally as @) Iron Pyrite FeS, Gi) Iron (I) oxides called Haematite, Fe,0, (ii) asan oxide called magnetite, FeO, Gv) asizon (Ill) carbonate called siderite FeCOxpathic ore) Scanned wth CmScaneen_ proces on is extracted fi s joo i cd thom its ore called hematite, Fey in inner region lined with firebricks iron ore, cok limestone used to heat air for blast The raw materials us raw materials are fed into the blast furnace from the top. ‘means of hot air supplied by te _—_—_—— gas produced is then co: Ci) + Org) carbon dioxide ide. COxg) + Cos) carbon monoxide gas produ +3C0¢) 2009 ed to remove impurit ick lime which the ne is us ” 11 combines to produce qu! as slag. _ ; CaO + CO ed in the extraction are the iron ore F ced then reduces the iron Fe +3COre ses like SiOz present. Limestone first decomposes in a blast furnace made of steel with the Hot air ‘i Slag outlet _—— Iron outlet “e203, limestone and coke. These eres the coke burs to produce carbon dioxide. reduced by the unburnt coke to produce carbon ore to iron with SiO forming calcium silicate ‘Scanned wth CmScaneeCa0p +Si0y) ————>_C#SiOwv pottom of the furnace while the slag floats on top ang they The molte en sinks t0 the olten iron then sinks (0 { iron. en iron is called pig OF rately, ‘The molt y «ig uso as the orethe Fits process isp, are then tapped off’ Note:(a) If spathie ore ,FeCOs, or iron pyrite roasting process which converts the ore (© iron III oxide,Fe20s 4FeCOx) + Ong ———32 Fex09 + 4 CO) AF eSyy) + 11 Oy ——32 Fer) +8 Or) Properties of Pig Iron ~The pig fron ig impure and contains impurities like carbon 5% phosphorous, sulphu, manganese and silicon = Ithas a low melting point = Itismainly used in making of gas stove, drainage pipes and Bunsen burner bases. Purification of Pig Iron ‘The impure pig is purified by removing most of the impurities to give steel or wrought iron by two processes called (@ The open heart process (ii) The Bessemer process. In the purification process, various impurities like carbon is oxidised to carbonmonoxide or carbon dioxide, Manganese and Silicon are converted to their oxides forming slog. Phosphorous is oxidised to PsO10, which is removed by the basic lining. Properties and uses of steel Steel is hard, tough and strong and is used as armour plate in warship and military tanks and in making cutting tools. Properties of Iron (a) Reactions with oxygen It combines with oxygen when heated to give a black oxide of triiron tetra oxide 3Feis) + 202) ——————>_ Fes), (b) Reaction with water Iron only reacts with steam at red heat in a reversible reaction forming triton tt oxide and hydrogen. ———> 3F eq) +44:0q <————. F101 + 48g Seamed wth CamScaneNote: In the presene Si i pee ¢ of air and water, iron forms a brown coating called rust. Rust is ydrated Iron (I) oxide represented as Fe,03.. x H:0 How Rusting Oce Note: Pure iron does not rust. Ordinary iron contains areas of hi fi ss is ° Contains areas of high electrode potential called the anodic areas and areas of low electrode ial ¢: ce 7 7 , le Potential called the cathodic areas. ‘Thus on exposure to an atmosphere of high oxygen concentration, the cathodic area will accept electrons from the anodic area. Electrons therefore will flow from the anodic area to the cathodic area, ‘The fetlowing reactions therefore occurs. Atanode Weg ——__ > 2Fe™fay) #40 ‘At cathode Ox) + HOw + 4¢ 0 The Fe** and OH’ formed then diffuse away and combine to form iron (If) hydroxide. a» - Fe* (aq) + 20H aq) ——-————>_ Fe(OH) The iron (II) hydroxide formed then is oxidised by air to form hydrated iron (III) oxide x HO which appears as rust (brown solid). Fe eg. 4Fe (OH) + Oxqt2 HOw ————> #FeOMs9 4 Fe (OH)x~), —————>2 Fe20. 3 H20 (Russt) Note: presence of ions from the electrolytes e.g, NaCl because the (i) Rusting is promoted by and hence assist cell presence of ions from the electrolytes increases conductivity reaction. Rusting is retarded by the presence of alkalis, This is because the presence of OH” disturbs the equilibrium reaction. Org) + 2H200 +4e —————— 40H aq) So that electron flow is disturbed. uc. backward reaction is favoured thus reducing the concentration of hydroxide ion. Rusting is prevented by app iron with zinc is called galvar vine wi (i ication of paint, tin or zine electroplating, The plating of nising, Zine prevents rusting because being more 11 be oxidised first. Galvanising is better than tin is exposed and the more reactive s oxidised electropositive than iron, plating because once tin plating 1: jron rusts while if galvanised iron is s ratched, the iron is sratched, the more reactive copositive, reacts with dilute hydrochloric and sulphuric acids to Scanned wth CmcaeClhay “Ha FeClyo Beg) + 2HCaq) ———— + Haw 7 > PeSOsoa 2 Fay. + HS) —————> Dilute nitric acid forms mixed produ vrevoviey® HEN 3140 Fe {Ona era 4 Fe yy +10 HNOxay) FeCl Cis) + 3Cly I) . Iron (11) chloride is however prepared by passing hydrogen chloride gas over heated iron Compounds of iron Iron exhibits two oxidation states of +2 and +3 Fe = 1s? 2s? 2p® 35? 3p° 3° 4s? Fe* = Is? 2s? 2p 35? 3p* 34° Fe* = Is? 2s? 2p® 35? 3p* Fe**is the most stable oxidation state since the 3d sub energy level which which is half falls regarded as stable. Compounds in +2 oxidation state Compounds in the +2 oxidation state are easily oxidised to +3 oxidation state and are green. Iron (II) oxide, FeO This is a black basic solid prepared by heating iron (11) oxalate in absence of air. FeC204) > FeOw + C0 + COxg) FeO is basic and therefore dissolves in dilute acids FeQy + 2H" ~———s"oy + 1,09 FeO is unstable and usually gets oxidized to FeO, 4FeO(s) + Ox) ———__5 2 Fe0y,, Iron (II) Hydroxide, Fe(OH), 1s prepared as green gelatinous precipitate by action Of aqueous alkali or ammonia on 8 solution of Iron (II) salt. Fe*aq) + 20H(aq) -———____ Fe(OH) It rapidly turns brown on exposure to air by oxidation to Tron (ny hydroxide Scanned wth meanerFFAOW + ZNO + Ogg, —__gFe(O1D yo Jon MD sulphate — EeSO,. 71,0 Prepared by warming Iron fillings with excess dilute sulphuric Fey + H2804, Fe 9) 5 FeSO. + Hho On heating it decomposes to form iron (IIL) oxide, Fes0s » 7:0 ———_» Kg sy THY > FeSOyay + 7H:04) 2 FeSO F + $0219) + S05) s casily oxidised on exposure to air. Ammonium iron (1) sulphate (NH,),S0,.FeSO;.61,0 Prepared by mixing hot concentated solution of equimolar iron (II) sulphate and Iron (1D) sulphate is efflorescent and ammonium sulphate. This is a green double salt which is preferred in volumetric analysis to Iron (II) sulphate because it is not efflorescent and is not easily oxidised (ie. is resistant to atmospheric oxidation). Compound in the +3 oxidation state Fe™ exists as [Fe(H20),]* in solution and is strongly acidic because of the reaction. [Fe(H:0)eP"tey*+H20y <== [Fe(Hr0),0H Pea) + HO" Because of the acidic nature of the aqueous solution of Fe™ , in the presence of @ strong base eg COs from sodium carbonate further ionization of [ Fe(Ho )sP occurs producing a brown precipitate of iron (Ill) hydroxide with bubbles of carbon dioxide gas according to the equation 2[Fe(H:0)} tes) + 3 COS) > 2[Fe(H20)3(OH) 3] +3CO2~) +3H200) OR 2 Fe* aq) +3 CO3*aq *3H2OW ~———>? Fe(OH)si) +3 COr) Iron (111) oxide Fe20s Brown solid prepared by heating iron (II) sulphate 2FeS0yy) ©< ————>_ Fads +802 + SOs Fe,0s is also prepared by heating iron pyrite 2 FeSyq) +11 Ox) ————> F209 * 4 SO By heating spathic ore, FeCOs AFeCOxg + Ox) | ————> It is ampotheric and resembles Al2O3 and Cr203 Fe:03) + 6 He —> 2Fe™ eq 3 HO Fede 20H'yy ————> 2 FEOF tw* 00 2 Fe20x3) +4 COxe) -101- Scanned wth Cmcaaqueous NAOH oF ammoniy 4 Iron (11) hy iti ‘on (IH) hydroxide on addition Prepared as brown yellowish preeipilal solution of iron (III) salt. . > Fe(OIDno Fog) + 30H) ——— Fe (OH); is a weak base 20.0 Fe (OW) + 3 HChay Iron (UD loride Prepared as a black sublimate on passing chlorine Fe FeCl 2Feq +3Clygy) ———_ Fehr - o ri hydrolysed in water forming acidic solution, sis s Fe(OH) x0) + 3HCloo Fe Chay t 3H pver heated iron wire Iron (IID) chloride like all iron (II +3H:0q) —————> Note: Fe™* can be reduced to Fe by the following reactions ium iodide. ution of potas @ — Withacidi Iodine is produced. aq) + Ma) =< ———— > Fe ay + Tee Gi) With sulphur dioxide or sulphite ion 2 FeM ag) + SOs" aq)+ HO) ———> 2 Fe“ ag +2 Hay $02") On boiling Fe** solution with Zn powder, green iron (II) is produced. 2 ii) DFM ag + Zmy — sy Fag) + Za) (iv) With TE . Fe (aq) + TE ag) —————> Fea) + Tia (v) On passing a current of hydrogen sulphide gas through a solution of Fe**. A green solution of Fe* and yellow solid of sulphur are formed. 2FeM ug) + S* (oy) —————> 2Fe™ ag) + Se Conversion of Fe” to Fe (2) With hydrogen peroxide solution 2Fe™* (ay) + 2H (oq) + HO: i o " (oq) 202409) —_, Fe ag) + ZHOwy (b) With acidified potassium manganate VII MnO4' a) + 8H" aq) + SF 2 . Bee) TSS 0) > Mn?" a+ 4HOy + SFO) (©) _ With acidified potassium dichromate solution C107 (aq) + L4H (ag) + OF ay 3 - 2 > 2g) + THRO) + OF en (@ With hot concentrated nitric acid 6Fe* (aq) + BH"(oq) + 2NO3q) ————-5. . 6Fe™ aq) + 4,0 + 2NO® Use of chlorine or bromine water, The halogen's colour is discharged lischarge © Seamed wth CmScanee| 1a) + 2CT (09) ‘on * 26 “eg cous sodium hydroxide or ammonia produces a dirty green 1 (Il) hydroxide, which readily turn brown. > FON) ution of pot sium hexacynoferrate (III) a dark blue precipitate of > _sEF7K' [Fe(Fe(CN)sF'is red solution with dimethylglyoxine solution 5 solution of sodium hydroxide or ammonia produces a reddish brown gelatinous precipitate of Iron (ill) hydroxide. > Fe(OH) or PK [Re CN)olo um thiocynate (0 solution containing Fe” produces Ko ig, + Pell (iiiy Addition of a solution of pot Cy a blood red colouration of thincynatopentaquairon (IIL) comples. WABOy)” + 80) > [Be(0)s SNP! +10 ine: red solution with dinethylglyoxin solution, tiny Fe yi Jon Obvervatio Noy OFM 09) Hi Green precipitate We" Reddish-brown precipitate Vonushun bexawyna fie”! Dirk blue precipitate of ‘Tumnbul fesrate (WN) fie!" No elange yo No ehange ovems, 4, Hotei hwanesyne fusrate N) Hie"! Durk blue precipitate prussian blue A, Hodnsshun thiowy niles VW" No ehinge occurs Vo" Antenie red coloration AOS © Sean wth meanerban ta! 4st pt ast 3p" 3d! ds Neo ation Co ie sive a mixture With Oxygen ie but on heating Peuels slowly to give FCO ey Cobalt is unatteeted by air but o CoOy Coq +140, —————> C00) 3Co) +2049) > C0304) (6) Wil Cobalt does not react with water at ordinary reacts with steam to form cobalt (II) oxide and hydrogen. Coy + H2Q) —————>_ C00) + Haye) (©) With acids Hot dilute acids such as hydrochloric or sulphuric acid slowly reacts with the meta conditions but when strongly heated forming hydrogen and then the corresponding cobalt (II) salt. Cow + 2HCly ——————> CoClyaq) + Hz) Cop) + H2SO s(aq7————> CoSO aq) + Hoye) Dilute nitric reacts with Co forming cobalt nitrate and oxides of nitrogen. Hot concentrated HySO; oxidises Cobalt to CoSO, and SO) Cos)+ 2H2804) —————_ CoSO sa) + SOrzg + 2 H20 HINO; renders Cobalt passive due to formation of C0304. @ With Carbon monoxide Cobalt reacts with carbon monoxide on heating under Pressure to form an orange powder called cobalt carbonyl, Co) +4 CO) 3.6060), The oxidation state of Co is zero in the compound, Note: Cobalt does not react with alkalis, water and halogens, Compounds of Cobalt Cobalt has two principal oxidation states of +2 4 hile that of 43 is mainly found in complexes and +3. The most Stable oxidation state is #? Co - Is? 2s? 2p® 35? 3p 3a? 432 Co* = Is? 2s? 2p* 35? 3p 3q7 Co* -, ts? 282 2p 3s? 3p 396 Scanned wth Cmcahe +2 oxidation state Compounds in. This is the most [Co(HzO).?*. Not e oxidation state of cobalt, Aqueous solution of Co?” is pink and exist as e IN and NH is oxidised even by atmospheric oxygen to Co which is yellowish — orange. ie [CoHLO)s1 + BNA) —————> [CowNTh)}"* +61b0 +e he +2 oxidation state in the presence of stronger ligands such a or {COMO} + GCN) ———-> [Co(CN)g]"" + 6IRO +e Cobalt (1D) oxide CoO Prepared as a green solid by heating CoCOs or Co(NO3)2 in the absence of air, 2Co(NO3)x), ———___5 2€00 +4NOx@) + Ox) COCO > COO + CI Cobalt (I) hydroxide. (Co(OH)» Is a blue precipitate formed by adding aqueous sodium hydroxide to Co”*, Co™ 9) + 20H) ————> Co(OHxp On left standing in air, the colour changes from blue to pink. Co(OH): dissolves in dilute acids to produce a pink colour Co (OH) x9) + 2 Hea) 5 C0") + 2H 009 Co (OH): dissolves in hot concentrated KOH solution. Its ampotheric. Cobalt (I) Sulphide: This is a black precipitate made by passing HyS through a solution of Cobalt (11) salt. Co™aq) + $*(oq) —————> CoS, The precipitate is not formed in the presence of an acid because CoS has a high Ksp value so sufficiently high conc. of S* is required. Note: When a solution of Cobalt (II) salt is treated with sufficient amount of hydrochloric acidl, the pink colour first deepens and eventually becomes deep blue owing to the formation of complex called tetrachloro cobaltate(II) ion. This is due to ligand exchange. [Co(H:0).]"aq) + 4CV eq) ——————> [CoC wa) + 64200) Pink Deep blue alt (III) like chromium (III) forms a wide range of complexes such as {Co(NH3)s)"s (CN)gf* which adopt octahedral shape. The complexes exhibit both geometrical and sm. Cobalt (III) chloride forms isomers with ammonia just like CrCl; and ical isomers 0 The empirical formula of the complex is CoCl.(NH3)s. The isomers are: Scanned wth CamScaneewhere all the 6 NILy moleeutes a i some! " fort a yellow ise ey, Therefore all the Cp : ionic “Th «CF ang jx a givenish yellow’ BONE att crave fe [CoN ICT dineetly bonded to the precipitated _ ee 12/; of the co" and 3AgClo) fee Agog $3CT oo . CO ae free. Tt has 3 j in whiel 8 3 ions Gi [Coats CH? ACh isa viele! isomer in whie conducting, “Cl free e precipi mnducting, only Ms of CI free to be precipitated, 1, GB) [CaNHACe | CT is green isomer wh has 2 ions conducting. hows geometrical jsomerism as NH; cr H3N NH3 Cis — Dichlorotetraamminecobalt(II]) chloride NH EBN, cr Co cr NH; NH3 Trans-Dichlortetraamminecobalt(III) chloride Test for Co” in solution (a) With NaOHan) Addition of aqueous NaOH to a soluti a solution of Co? i of Co™ salt produces a blue precipita!® which is insoluble in excess which cl s changes to pi i Cat) #2016) > renaming air (b) With NH,OH ‘ ay A blue precipitate soluble in excess and turns red ¢d on standing in ai ig In air. Scanned wth CamScanee© S in an alkaline solution of black precipitate of C Which like NiS does not dissolve in dilute NCloogys Coa tS" y @ — WithPo —— > CoB juin thiveynate A blue solution of tetrathioeynate cobalt (II) is formed. (©) With Potassium eynaide Adi ari : rdiedsh brown precipitate of cobalt (II) cynaide is formed soluble in excess to give & complex of potassium hexacynocobalt(I) es Saeeaeees COGN) a is) CON) x) FACN a — [CoN an ap? 33° 3p® 3u% 4s" Rea ith oxygen Reacts with 03 2INig) + Oy) —————>_ 2Ni0 () With Water Reacts with steam only forming NiO and Haq) 1 on heating to give green solid of NiO Nig) + H20@ ———> Nid + Hr (©) With Acids Reacts with dilute acids to form corresponding Ni salt faster with dil. HNO3. : . > Nit Nig +2H' ea Ni" aa + Hae Cone, HNOs renders the Ni passive. reaction with concentrated hydrochloric and sulphur and hydrogen. Reaction is No ric acid. (@ — Withhalogen ‘When heated in a current of chlorine, it forms NiCl2 7 —— fl Nig) Che Nich (©) With carbon monoxide h carbon monoxide to form nickel carbonyl. Nickel shows an oxidation Reacts with state of zero here. Nig) +4COy) ——————> Ni(CO)a) Nickel does not react with alkalis. -107- ‘Sean wth Cmcae most stable is +2 Compounds of Nickel ad #3 of whieh th jes of Ni are #2 a ap® 3d* 4s" 2p® 38° 3p® 3d* 2p 3s? 3p 3d’ Ni* compounds In aqueous solution Ni* e: Nickel (11) oxide . COs, Ni(NOs)2 of NICOMz js green in colour. s [Ni(H:O)6)"" and is green in colou This green basi ide is produced by heating Ni Ni (OH)y) > Ni0g+ FLOW > 2Ni0,) +4NOx) + One) NiCOy) = > Ni0g)_ + COr@) NiOisbasic ie NiO +2") ————> Nee i pe Prepared as a green precipitate by addition of aqueous NaOH¢aq) to a solution of Ni salt, + 20 Ni) + 20H (oq) ———_> Ni(OH)2 Nickel (H1) sulphide Prepared by a black precipitate by passing HS through an alkaline solution of Ni** Ni* ay +S" > NS Nickel carbonate: Prepared by the reaction Ni(aq) + 2HCOs"agy————>_ NiCOg)+ COxg)+ H20p The precipitate like CoS, does not dissolve in HCl also, Test for Ni** in solution (a) Using NaOH solution A green precipitate insoluble is excess. Ni*ag +20Heq) ————__5 Ni(OH)g) (b) Using Ammonia solution A green precipitate is formed which dissolves in exeess to give a blue solution due to formation of haxamminenickel(I) ion, Nig +20) = ————5 Nita g, s ren Ni(OH)z) + 6NHs(aq) —————_» INCH). ap +208 ep (© In neutral or alkaline_medium, Ni salt give a reg precipitate with dimetty! . is i “pit glyoxime solution (or Butane-2,3-dione dioxime), ipitate wit! Scanned wth CmScanee@ oN) , (0) ——————» Ni [Fe (CN) él hexaeyanoferrate (II) solution A brown precipitate formed BNI ay +2 Fe o & A yellowish green precipitate soluble in ex Nig) + ZCN oup oO ing potas CN) 6 ) ————> Nis [Fe(C otassium ey ee to form a dark yellow solution , > Ni) Ni(CN)ag) + 2CN Yo). ———>. Ni (CN) F ew @ Using 2- napthot Brown precipitate formed soluble in dilute hydrochloric acid. COPPER Electronic configuration 1s 2s? 2p° 3s? 3p% 3d! 4s! and not 132s 2p® 3s’ 3p° 3d? 4s". The former gives a full d-sub energy level which is stable. Ores ‘The chief ores of copper are Copper pyrite, CuFeS2 Copper galance, CuS Malachite, CuCOs Cu(OH)2 Copper (II) oxide in tenorite Extraction Copper is extracted from its ore called copper pyrite, copper. The first process in the extraction is the concentration process by froth floatation in which the finely ground ore is mixed with water containing a frothing agent (e.g. Xanthates of pine oil), A current of air is then blown ¢ i the earthly material which because of their high density sink to the bottom. The pyrite ore, however, floats on the surface in the froth where it is skimmed off, filtered and dried. is i the concentration of copper jn the ore. After the concentration process, the increases the © CuFeS2 which contains only about 0.6% rough the mixture producing a froth, This wets ce jon is roasted. . het of concentration 5 ide and forming Iron (il) oxide and sulphur s roasting coverts the pyrite to copper () sulpl ide gas. gq) +2FeOw + 38020 S34) +40x) ————” CurSw | Seamed wth CmScaneeCopper sulphate solution Copper dissolved away from impure anode The purification of copper Copper deposited F . ae on cathode During clectrolysis(the purification process), the Capea dissolves away from the anode and is deposited on the cathode leaving behind the impurities, Cathode Anode Cu (ay +2e —————_> Cy Cu——___, Cu ay #20 Note. Copper is also extracted under special condition like in Zambia by the TORCO process from copper (If) oxide. hydrogen in the absence of oxygen, The CuO is converted to copper (I) chloride, 2Cu0p) + 22g) + Cho > 2CuCly 4 2EL0y Scanned wth CmcaThe copper (1) chloride produc 2CuChy + Hyg ‘ed is then reduces Properti Copper meta 1 is rather inert Copper has one FON on it pmatl a 1 on its outer most ds orbital like group (1) clements but differs from group (I) clement (@) Because of having 10 electrons in the 3d sub-shell b) The poor shielding ( Door shielding by the 3d electrons makes the atoms of copper bigger in size and having a higher fitst ionisat; 'g @ higher first ionisation energy than potassium atom hence copper forms compounds less readily than potassium (©) Group (I) (¢.g. potassium) elements are more reactive than copper. Copper, however, resembles group (1) elements in the following properties. @ both are good conductors of electricity, Gi) Both have +1 oxidation state and have no transitional compounds. Reactions (@® With acids Copper being lower than hydrogen in the electrochemical series will not displace hydrogen from dilute hydrochloric acid and dilute sulphuric acid. Concentrated sulphuric acid, however reacts with copper forming sulphur dioxide Cup + 2H2SO 409) ——————-> CuSO sq) + 2420. *SO2%@) Boiling concentrated hydrochloric acid reacts with copper forming hydrogen and a complex of copper (1). Cu +H eq + 2Cl aq ————> [Cah] + Hate Nitric acid reacts with copper at all conditions. Dilute nitric acid reacts with copper forming nitric oxide. 3 Cty + 8HINO xq) ——————>_ NOW * CUNO )ne0) + 4H2O xide gas (brown Concentrated nitric acid reacts with copper forming nitrogen di gas). Cu) + 4HNOxay) > CHNOD00 + 2H20 yp +2NOr) ° i Note: (i) Copper does not react with water at any condition. Gi) With moist air a green outer layer of cop] ig a black layer of a copper (II) oxide. ii) per carbonate forms ‘At 300°C it reacts with oxygen formin: 2Cug) + Oxy ————: ACWOy ‘At 1000°C copper (I) oxide is formed instead ‘Seamed wth CamScanee2Cu00 over heated coppers | 4Cuyy + O2 ———_—_ forine gas is passed (iv) When a stream of cht Copper (It) ehloride is formed. 1 Cus) + Choo heat > CuCho Compounds of copper. Pe i ates of +L and #2 but only ple hydrated ions are found jy Copper shov solution as Cu -1 cu cu = Is From the electronic configuration, Cu’ i aw expected to be more stable than Cu” but Cu found to be more stable than Cu’ because. @ energy factors. Cu‘ te ——— Co, HOF -602 KJ mol" While Cu +22 ———> Cu) HO = -795 KJ mol Therefore since Cu®* > _Cugives more heat ther electrons so that the 4S! electron is rn it is more stable. Gi) This is also due to poor shielding of the 34"° firmly held and hence first lonisation energy is greater than the second ionization energy. (iii) Cu* shows typical transition metal properties. ¢.g. forms complexes, CuCl, Cu(NH;).%, its compounds are coloured (blue or green), has incomplete 3d? sub- energy level etc. Cut instead resembles Ag” e.g. CuCl like AgC1 is insoluble in water but dissolve in aqueous ammonia. CuCh + 2NH3(y ———————> [Cu(NF)2J"aq) + Cr AgCly +2NHs(ay > [Ag(NHb)2] "(aq + CI" Compounds of Copper in +1 state Cu" in water is very unstable and undergoes dispropotionation reaction. Disproportinatioa reaction is reaction where half of the Cu’ is oxidised to Cu* and the other half reduced to CU ——_ 2Cu'@) wy + Cy Copper (1) Oxide Isa dark red solid made by reducing copper (II) sulphate solution, Properties (i) reacts with acids to form salts which tend to dig i u roporti ivi be sopner sali proportionate giving copper Gi) Dissolves in cone. Hydrochloric acd forming Cu Cly comp plex -112- Sean wth CmscaneeCWO. + HCL Mog) ——_. CuChy + CF, > CuCl + LHOW eT) ess, Copper (l) chloride Prepared by boiling a sotution of copper (It) chloride . a in excess hydrochloric with copper auming. The belted product is then poured in boiled wat er. ‘The water must be boiled so as to ‘Wise oxidise the copper (1) salt formed ae —————— > 2uCly HCI is meant to keep the CuCl formed dri Cachyy + Cu — otf air which would othe, as a complex CuCly. Properties (i) Iseasily oxidised by air to green CuCl, Gi) Does not dissolve in water but dissolves in cone. Hydrochloric acid due to formation ofa soluble complex, CuChyy + Clq) ———————> carey Dichlorocupprate(1) ion CuCl also dissolves in ammonia because of formation of soluble complex. CuChs + 2NHa(eq) [Cu(NHs)2}(eq)" CF Diamminecopper(1) ion Compounds of the #2 state The +2 oxidation state exists in solution as [Cu(H20),] ke. (CuH0)I"ay + HO ————*_[CuH20), OH] "y+ Hs" = |)** and is acidic. The compounds are mainly blue or green Copper (M1) oxide Isa black solid prepared by (i) Heating CuCO3 CuCOs) ————> Cv + COx) Green (i) Heating Cu(OH)2 Cu(OH) a) ————> Blue (iii) Heating copper nitrate 2Cu(NOs)a5) Conner (Learns ve on aqueous ammonia or sodium hydroxide to a as a pale blue solid by addition on aqueou lution of copper (I1) ions. a ay + 20H (00) aa Cu0p, +10 ACU + ANOr® + Ore Scanned wth Camscaneea dst Fornation oF EPP K ie Properties of COND: The pale blue previpita Cyon): CuO + 1LOw - Black Blue _ on but dissoly Gi) The precipitate does not dissolve in excess NaOH solution forming a deep blue solution ¢ O Kee due to formation of a conte solution copper (Il) ion. ——— as atest for presence of Cu" called tetra amin Ca(OH). +4NH. This property of Cu(OH); is used [CuNHDsF og) + 20H" ) Copper (1) chlor This is prepared by passing chlorine gas over heated copper metal Cup + Clg —————> CuCl Properties Copper (II) chloride dissolves in water to give a blue solution le On addition of concentrated hydrochloric acid or a solution of KCI or NaCl, the blue solution tums yellowish brown. The yellowish brown solution is due to formation of a complex ion called tetrachlorocopper(t!) ion. Cua) + 4CV ag) §< > [Cu ay, When this yellowish-brown is diluted, the complex breaks up forming a pale blue solution due to formation of hydrated, copper (II) ion. fe, CuCh* ay + 4420 = ————>_[Cu(H0), a) + ACT aay yellowish brown blue Uses of copper metal 1, Because of its very good electrical conductivity, it is used in the making of cables. 2. In the making of alloy e.g. brass an alloy or zine and copper bronze and all jay of tit and copper. 3. Making of hot water pipes. Determination of the amount of copper in a given copper salt ‘There are two possible methods depending on the copper salt (@)__In this first method which is applicable to any copper salt, a solution of exces> potassium iodide is added to solution of the copper salt, A as brown mixture produced (white precipitate staj liberated. | brown). The brown colour is due to iodine Seanned wth CmScanee© Note: 2 og HAY, mm ——»¢ The fone liberate > Cibo + bya 1 ented by reactio . .. ° enslt, ae Y reaetion (1) is mow titrated with a standard solution of sodium ty ‘av + yy ——_ S06 oq) E20 (2) Combining equation (1) and (2) gives - fon ( verall equation as. Usagy + 2CU" aay T= [8:0] The concer i rCu* he oncentration of Cu" is now determined by equation (3) This method is only applicable Ctl) 1 S102 ony to copper iodate, Copper iodate is a sparingly soluble It whose solubility equation is CUOd 9 Cu ay + UOsen To the solution of the copper iodate, is added a solution of exe s potassium iodide in the presence of sulphuric acid. Iodine is liberated as a brown solution. 105 (99) + OH (agy FSV Gy) ————>_3ilayany + H20q « . (1) The iodine liberated is then titrated with a standard solution of sodium thiosulphate. Txjaq) + 2803" 3) —————> ay + S108 (2) Since 3 moles of Iodine are produced by equation (1), the equation (2) is then multiplied throughout by 3 so as to balance the number of moles of iedine. ie. 3Eb¢aq) + 68203" > Tear + 38106" (aq) 3) s are cancelled to give Equation (1) and (3) are now added noting that common specie 105 (ea) + 6H eq) + 65205" ea) ———> 3#2O * 38.06" ay + Vag From the final equation, mole of 103" reacts with 6 moles of S,0;", But in the solubility equation for Cu(1Os)2. [cu] = % [10s] [cu*] = 2010s] = "hz [805° (%(8:03") * in solution Test for Cu” ution @ i de and ammonia. ith aqueous sodium hydroxide and.am . aon droxide to a solution of Cu’, produces a Addition of aqueous solution of sodium hy Ie blue precipi dissolve in excess. pale blue p Cu ey + 20H wo ‘Addition of aqueous ammonia P nia to produce # deep blue solution. ar Cu ay + 20H eo Pale blue roduces a pale blue presipitate which dissolves in excess amm: Seamed wth CmscaneeOO > ou nthe how | 201 ny ferme IDM A s6btion gf, ver (11) hexacynolerrate, ‘1 say PANEL oa) ve SHO Ne passin estes i ra solution of. (b) Addition of a solution ¢ ae recipitate of produces a reddish ~ brow" preci 5 cusfFe(CNal “N)ct* _ 2Cu°%ay + [Be(CND a — Ive in ammonia solution. The precipitate diss Addition of potassium Lodide solution. yen of which turns white on adding ‘dit, 2. Cauley + Lan _—~_ A white ppt stained brown is: &f thiosulphate solution 2Cu?" aq) + Feo ap! 38° 3p° jal as? Ore). . ; ‘ is contaminated with lead sulphide, Anoth, rine blende, ZnS, which The main ore of Zine is ore is calamine. Extraction In the extraction of zinc, the ore is first concentrated by the method of froth floatation so as to eliminate worthless materials as much as possible, Concentration process (froth floatation) Concentration is a process of removing unwanted earthly materials (impurities from an ore so as to increase its amount). In this process, finelly ground ore is mixed with water containing frothing agents (e.g. pine oil). Air is then blown into the mixture producing a froth. This wets the earthly materials which sink because of their density. The sulphide ore, floats on the surface in the froth where they are removed, Acid is then added to break up the froth after which concentrated ore is filtered off and dried, Roasting process ‘The dried concentrated ore is now roasted in air, 2ZnS.) + 30x) ————____5 2Zn0p) + 28029) 2PbS¢ + 30%) —————____s 2Pb0,) + 280%) The ZnO and PbO produced in the roasting is then | heated with c¢ . snablast farnace (see extraction of Iron). ‘Oke and limestone in a The coke bums to give COp which is then reduced to CO by the unb inbuni Cy + Ox) ————— COxy) nt coke. COx) + Cy) —————> 20, ‘The CO produce then reduees 210 snd PLO t Zn nd Pb respeer spectively, Za +€% ———> 4 «Co, Scanned wth CamScaneePLO + CO) — > i Pay +c The limestone decomposes to quickliny 1) + COs) 7 . which combines with Si a fem calchum silicate, say, hhich combines with SiO> present as an impurity to 20x) ——————/ Ro A SiO, Cad) + COrs SaQKe 34) s) 1) Both liquid s ‘aSiO, and Tiquid lea wid lead ran to the bottom of furnace and can be separately tapped off. The zine pr S Vapour leaves the f pour leaves the fumace at the top and is then rapidly cooled in a spray of tead, Further cooling cl i hg Produces a solution of Zine in molten lead. Zine collects at the top and can be now run off, Note: a) Zinc also extracted from calamine ore, ZnCO; using the method above. Here the ; concentrated calamine ore is roasted to convert it to ZnO. ZnCOx3) ———____ Za0 y+ COr) The ZnO produced is then mixed with coke and limestone and the extraction carried out ina blast furnace similar to the extraction of iron from FeO3 Cy + Ox) —__s. COs) COxg) + Cy) ————> 2C0w) ZnO + CO ————> Zny+ COxp The limestone is used to remove impurties such as silica (©) Zinc is also extrated from the calamine ore by electrolysis process Here the calamine is first heated to form ZnO ZnCOyy ———_—> 2109 + CO ‘The ZnO is then dissolved in dilute sulphuric acid to form ZnSOs ZnO) + HO 4(ag) ————> ZnSOxeq + H200 The zinc sulphate solution is then made concentrated by addition of lime which is meant to remove Fe™* and ‘AD present as precipitates r ———>"* (s) Fe™ (eq) + 30H iy Fe (OH) ——— ) AP Gay + 30H 9) AIOH) 36) The mixture is the filtered - To the filtrate is then ‘added zine dust which removes less electropositive metals like ‘o the filtrat ' copper and cadmium present as impurtis Cur" gq + Zi") ———_ Cu) + 20 aa) cast Zn ———? Cag * 20° ‘on * 2065) The resultant solution formed which js pure zinc sul and then electrolysed- ‘At cathode Iphate solution is then acidified + —— Zing Za aay + 2€ Ms) ions of Zinc ‘Seamed wth CmScanee@ ) (@) uve to moist at. This layer of 700. expost a thin layer of ZnO 00 &XP Zine acquit , gin air to form nes farther reaction, But Zn burns in Bey pias tion azn 2Zng + Org) With water ees ing ZnO and Ho. Zine reacts with steam at red heat producing 26 Zn +HiO, __heat_, 2009 + He Wi Zn rei with hydrochloric acid (both conc: and dilute) and dilute sulphuric acid producing the corresponding salt and hydrogen. Zn) +2HChay— > Z0Chro + Hate Znyy, + Hz$O (49> 280400) * Hye) Reaction with cone, H;S0; or HNOs produces products which depend on ihe conditions of reaction. With alkali, Zine reacts with hot solution of sodium hydroxide to give sodium zincate Ziyy + 2NaOH (gq) + 2HL0) ——————>_ NanZn(OH) (aq) + Hav Compounds of Zine Zn is in the first series of transition metals. It’s however not regarded as a transition element because of the following reasons. @ x) © @ Zine atom has full 3d sub-energy level - Is? 2s? 2p®3s° 3p*3d!° 4s* unlike transition metals. Zinc has a fixed oxidation state of +2 only Zn* - 1s? 2s? 2p 3s? 3p 3a! Compounds of Zinc are colourless Zn°* and its compounds are not coloured. Zinc, however, behaves as a transitiot element because it is capable of complex formation, The co-ordination number generally is 4 with a tetrahedral structure e.g. (Zm(Hz0})", [Zm(OH)4}* Zn(CN)4]* [Zn¢N0H) Seamed wth meaner(2) His diomagneti lamagnetic because of pai cause of paired electrons on the 3deshell Zinc oxide This is a white solid but becomes yellow o Zn (OH): , ZnCOs or Zn(NO,); "1 heating. It is prepared by action of heat on 049) ~ Z is °° % TF ZN) HTHOY 2Zn(NO3)zi) ———_y a “9 > 2LNOg) + ANOg 9 + On) Zin oxide is ampotheric ie It dissolves in both acids and 7 alkalis ZnO) + Wg) 200 +208, ora 29 #10 oo * F209) ———_-_y. 7 OH) yy Zine carbonate Prepared a a white precipitate on adding sodium hydrogen carbonate solution to Zn?* aq) 2n" ea) 2HCOS ee) ———> 7nCOyg) + COngy + #20) However addition of sodium carbonate solution instead of sodium hydrogen carbonate gives a white precipitate of Zn(Oli)s. This is because NaxCOs being more alkaline and thus CO; being a stronger base leads to more ionization of Zn (H20),2" [Zn(H20)4P* + COs oq) ————> [21 (#20),(OH)» Jy +1409 +COxey Zinc hydroxide This is prepared as a white gelatinous precipitate on addition of little alkeli or ammonia solution to a solution of Zn** Zn?" aq) + 20H (aq) ———————> (OH) The precipitate, however, dissolves in excess sodium hydroxide solution due to the ‘formation of sodium zincate complex. ————> NarZn(OH) 400) Zn(OH)zg) + NaOH aa) : n excess ammonia solution due to a complex formed called The precipitate also dissolves in tetra ammine zinc (II) hydroxide. 20H, Zn{OHi)x) + 4NH3pq) —————> FIT 2089 ing H,S through a solution of ‘Zn? in the absence i ipitate metallic sulphide, But if acidic on of metallic salts, precipitate me a solution of metal ing HS into are used, the H’ of the acid sup presses the ionisation of conditions Scanned wth CmScanee“ay t Sp iy sulphides of iow x es sed hence only SUlP Rp vi, 1] be lowe 4s == : wil tration of Therefore, the precipi CaS and not ZnS. ted . Uses of Zine. ie galvanising iron on er 1 In galvanising neh is an alloy of Zine and copp' 2. Making of alloys e.g. Brass WI Test for Zn** : 24 H is a solution of Zn™ produc. 1 Addition of aqueous sodium hydroxide dropwise to , ee , \ alkali to give 2 colourless solution, white precipitate which dissolves in ©: ess Zn gy +2 OH a) ————>_ 20 (OF) - . Zn (OW) 2 Oa) ————> 2 (OH)s (aa) a 2*. 2 white precipitate is formed Addition of aqueous ammonia to a solution of Zn first which later on dissolves in exeess to produce colourless solution. Zn oq) + 2 OH (aq) > Zn (OH) 2 Zn (OW) +4 NHxoqj————>_ Zn (NH),”* 2 OH'aa) Note: ZnO produced on heating certain salts of Zn (e.g. ZnCO3 or Zn(NO3)y has a v characteristic yellow colour when it is hot and white when cold. Addition of potassium ferrocyanide solution to a solution of Zn* produces a white precipitate soluble in sodium hydroxide solution. 2 Zina + Fe (CN)oaa) ———> ms [Fe (CN) Addition of ammonium sulphide solution produces a white precipitate soluble in dl hydrochloric acid. 20a * Say) ——————> 2 8 6. Addition of potassium hexacynoferrate (I) solution to Zn* gives a yellow precipitate insoluble in ammonia solution, 3 Zn) + 2 Fe(CN)6 ay > 21 [Fe (Cny, 1 ae ; . 61266) 7 Addition of a solution of disodium } eI : Stim hydrogenphosphate to a solution of zine ions inthe presence of ammonium chloride gives a white Precipitat fe Zn qq) +2 NagHPOay) +NHsCloy) 5 zm Ha POs FNaHPO g(aqy+Na”*aqytNaClod Seamed wth CmScane