tric titrations involve the interaction of a metal cation with the ligand, the form a stable, soluble and stoichiometric complex. In the formation of a oapering agent £0 sol Soper, ametal cation acts as a Lewis acid (or electrophile) and a complexing agent acts as a Lewis “je ornucleophile. i | ‘The complexomet M* + nb —>[ML,]* fecule or an anion or some time a cation which has atleast one lone pair of rn, A ligand can donates its lone pair of electrons toa ‘<= L) between metal cation or atom and a ligand is, ‘Aligand is a neutral mol | secons and that can be donated to a metal catio el cation or atom and a coordinate bond (M"™* | med. | Acompound in which a group o! 2 ordination compound. In compl tyasimple covalent bond M—L. f ligands is linked to a metal cation or atom is called a complex or lexes the coordinate or coordinate covalent bond is represented Classification of Ligands The demisity of a ligand is the number of donor atoms attached to the metal cation oF atom. On the basis of dentisity, ligands can be classified into two categories : LL Monodentate ligands IL Polydentate ligands a caltonodentate ligands : A ligand that Cation is called a monodentate ligand. ee 'F',Cl-, OH", 0, NH, CN™, CO, NO*, NO3 ete. Ime tentate ligands : A ligand which can donate two, three, ...-« OF shx electron pair from Whuther dain six donor atoms of a ligand is called a polydentate ligand. The polydentate ligands “a ified as follows : : lentate ligands : A ligand that can donate two electron pairs from two donor atoms is called a bidentate ligand. + can donate one electron pair from one donor atom toEssen OBR, Sa aes OR DELHI 124 9 Volumetric Analysis and Inorganic Preprations CO Examples: [ (oxalato, ox), H,NCH2CH,CH,NH (,2-diaminoethane, en); coo- cata NH2CH,Coo- (glycinato, gly) etc. * Tridentate ligands : a ligand that can donate three electron pai; ’ : airs from is called a tridentate ligand, eee do Example : H2NCH,CH,NHCH,CH,NH iethylenetsamine den) OF atoms * fetradentate ligands : A ligand that can donate four electron Pairs from f ’ : our, is called a tetradentate ligand, ono omy Example : HaNCH,CH,NHCH,CH,NHCH,CH,NH, (wetylenetcmamin, ten * Rentadentate ligands : Aligand that can donate five electron Pairs from five donor is called a pentadentate ligand. om Example : HaNCH,CHNHCH,CH,NHCH,CH,NHCH,CHNH, (ceaetvienepentaming eto) * Hexadentate ligands : A ligand which can donate six electron Paits from six donor stong to a metal cation is called a hexadentate ligand, Example : The most important example of hexadentate ligand is cane NCH,GHgN rates ‘OOCCH,, ‘CH,COO- ethylenediaminetetraacetato, EDTA Since EDTA is coordinated to a metal cation through six donor atoms, it forms a highly stabe and soube complex and is used to hold metal ions in soution, EDTA* is used to rap metal ions such as Mg and Ca?* ions in hard water. EDTA * is used to treat excess ‘of metal, Specially lead poisoning. This process is called Chelate therapy. of the cheates increases with increase in number. of rings per ligand, Thus it has been observed that hexadentate ligand, EDTA‘ forms a most stable complex. Thus, EDTA* is used for estimation of Mg™,, Ca and Zn**, and for hardness of water, I Requirements for Complexometric 1. The complexation must be stoichiometric so that a basis for calculation exists. For example, EDTA forms 1 : 1 complexes with Mg, Ca*tand Zn** ions. 2. The rate of complex formation should be fast.Complexometric Titrations 125 _-he complex that is formed should be highly stable and soluble so that sharp end point is obtained. ; he complexation reaction should take place in minimum number of steps to ensure a sharp end point. ga There must be a suitable indicator for detecting the end point, * pere should be no side reaction such as precipitation or adsorption during the titration » Mperwise there will be error in the result. ‘These essential conditions for complexometric titrations are fulfilled by mainly the hexadentate aus such as EDTA‘". The complexes formed by the multidentate ligands like EDTA are called ie petaing ligands and the complexes formed by the multidentate ligands are caled the chelates. ‘esration involving the interaction of ametal cation with a polydentate ligand like EDTA *” is also Tied a chelomettic titration. gthylenediaminetetraacetate (EDTA*-) Bthylenediaminetetracetic acid H,EDTA also represented as H4Y is insoluble in water even on sing, Therefore, it can not be used as an complexing agent or a ligand. Ethylenediaminetetraacetic cid is a white crystalline solid. HOOCH.C CH,COOH DNGHCHING HOOCH,C CH,COOH Itis a tetrabasic acid with pK, = 2.0, pK2 = 2.7, pK3 = 6.2and pK, =10.3. These pK, values indicate that the two of the four hydrogen atoms are strongly acidic and the first two protons are ‘eleased much more readily than the remaining two. Thus it easily forms disodium salt rather than tetrasodium salt. "HOOCCH2 \ | CAsCOONA fi,bou ‘NCH,CH2N NadoccH,” \..cH,cooH When the disodium salt is dissolved in water; it ionizes to give Na* ions and ethylenediamine tetracetic acid which exists as a Zwitter-ion which can be represented as : HOOCCH CH,COO™ wrest -O0CCH, \cH,COOH The most. common. complexing agent (or ligand) is ethylenediaminetetraacetate (EDTA). Since all the sodium salts are water soluble, disodium salt of ethylenediaminetetraacetic acid is used forthe estimation of Mg", Ca2* or Zn ions complexometrically. ‘The complexes formed by the’polydentate ligands have ring structures and such complexes are talled chelates, and the polydentate ligands are called the chelating ligands. ome “most common complexing ligand used in, complexometric titration is ethylendiamine cetate, EDTA *-, 1¢ forms complex with 1 : 1 stoichiometry (i. ., metal : ligand is 1 : 1) and it fufisall the reqi 7 complete reaction in one step 0 Deets mA ‘A metal cation like Ca, Mg* or Zn combins with EDTA* to form an “eg (chelate). y [M (H,0)6]"* + EDTA” — IM EDTA" + 61,0 where M =Mg, Ca, Zn, Al, ete. ms ‘The structure of [M(EDTA)]” complex ion is shown in Fig. 5.1, —CH, \ CH, I 0 Fig. 5.1 Structure of [M(EDTA)* complex Stability Constants for Formation of Metal-EDTA Complexes The stability (or thermodynamic stability) of a compound is measured in terms of equilibrium constant (K) or Gibbs free energy change (AG*). The equilibrium constant is also called the stability constant or formation constant or bintag constant. M* +EDTA* == [M EDTA)> [Mm @DTA)*] (M*][epTA*] Higher the value of K, higher will be the stability of the product, i.e. [MCEDTA]™ comple AG? is releated to K as follows : = -RT InK Thus, higher the value of K or higher the negative value of AG" higher will be the stably of complex. The values of stability constants of complexes of some metal cations with EDTA‘ are aren Table 5.1.Complexometric Titrations ¢., 127 gable 5-1 Stability Constants for Complex. ‘es of Some Metal Cations with EDTA‘— 4.9x 10° 5.010! 1.3x1'6 3.21016 able 5-1 indicates that the stability of M-EDTA complex increases in the order : Ba™ < Mg* [M-EDTA]""* +EDTA*- ae (Breess), Complex (Cnrencted) Mg?" + EDTA‘ :——> [Mg - EDTA]> (Unreacted) ‘Complexine | 128.9 Volumetric Analysis a Mg” + [Hind]?> ——> [Mg -Ind]"+ Ht Pe (Blue) ‘Winered) ic Preprations For a back titration : © Kise > Kucsora otherwise Me™ displaces EDTA from M-EDTA compl i if Kygind SO that sharp colour change occurs at th \ iy eee Mg” with indicator forming thefiag ind complex Pt due @ | Sinéé Ca**-EDTA copmplex is more stable than Mg2* i determined by this titration. 2. Substitution or Replacement Titration ; Substitution titra “EDTA, therefore, gga ; ons | i i ‘ BR a tions are ys, | ions which do not react or react unsatisfactory with the indicator or for metal ig. | Ca™ which form more stable complexes with EDTA than thae formed by ot sigs such as Mg** or Zn". These metal ions displace the less ti complex with EDTA. The amount of the metal ion displaced is equivalent toth a metal ion to be titrated. "© AMoun eg The Ca* ions can be titrated by this method because in the direct titration, Ca i form stable complex with Erichrome black-T (or solochrome black) and the ghar cout isnot observed. The Ca™ ions solution is treated with the Mg™ complex with matt Ca™ fons displace Mg* ions from the Mg complex with EDTA . Ca™ +[Mg (EDTA)? —__, {Ca(EDTA)]? + mg The amount of Mg”* displaced is equivalent to the amount of Ca standard EDTA solution using Erichrome black-T as an indicator. Ca +[Mg (EDTA)]> ——_, [Ca(EDTA)]* + mg Mg” +HIn? —_, (Mg -In}-+Ht aioe (Winered) 2. Alkalimetric Titrations : When a solution of disodium ethylenediaminetetraacene Na2Hz¥ is add to a solution containing metal ions, a metal-EDTA Complex is format releasing two equivalent of hydrogen ions. M™ + H2Y* —>[Mgy]* +2H* The H* ions released can be titrated with a-standard solution of NaOH wing phenolphthalein indicator (an acid-base indicator), c ghtly bound meal onl and can be ‘trated vig, Indicators used in EDTA titrations : Metal Ion Indicators Indicators used in EDTA titrations are called metallochrome indicators or metal indicators Thee indicators are metal ion sensitive. These are the compounds that change colour when. they bind tot metal ion. These indicators must bind less tightly than EDTA does. EDTA titration are sini acid-base titrations where only the metal ions are titrated. The colour change ofthe indict ie " on the concentration of metal ions. In this regard in EDTA titrations, a pM sensi a where pM = —log [M"*]. At a certain pM range, (similar to pH range in acid-base titration), ce igher ot ion is released or attached, depending upon whether the range is approached from a higher2 | jg, 5.2)- 10 both the cases, the pM range must be located in order to make the choice of a Poirable indicator Complexometric Titrations © |e pM =-log[M"*] 1:1 complex ' 1:2 complex 1:4 complex pM EDIAS———> Fig. 5.2 fssential Requirements for Metallochrome Indicators ‘The colour reaction must be sensitive enough so that near to end-point, when almost all the metal is bound with EDTA, a sufficiently strong colour should presist in the solution. 2. The colour reaction should be specific. 3) The metal-indicator complex and the free indicator must have different colours so as to make the visual detection possible. __ 4. The metal-indicator complex must be less stable than the metal-EDTA complex, otherwise _ EDTA would not release the metal ion from the metal-indicator complex. 5. The indicator must be very sensitive to metal cations (i. c.,0 pM) so that the colour change of | indicator must occur as near the equivalence point as possible. | M-In+EDTA——>M - EDTA +In 6. The metal-indicator complex must be sufficiently stable so that the complex will not dissociate and a sharp colour change is observed at the end point. |The most common indicators which are used in EDTA titrations are = © | () Etichrome Black-T 2) Murexide @) Xylenol orange130_-p Volumetric Analysis and Inorganic Preprations (2) Eelochrome Black-T (or Solochrome black) : The stacy dng shown in Fig. 5.3. Meh ou oe i Nad, <> N= "0 l| O,N’ | Fig. 5.3 Structure Of Erichrome: black-T | Itis sodium FH epee IAS 002 shot stingy ii | is represented as Haln” regardless of pH because Na* ions of sulfonate st0up ae Strongly acidic solutions it polymerizes to a red-bro hydrogen atoms of y WN Product, The © PK, valy the phenolic groups are 6.3 and 115 respectively. Erichrome yo different colours at different pH. rome baer PH < 5.5 ~ Red due to HIn~ form, PH between 7 and 11~Blue due to HIn® form, PH > 11.5 - Yellowish orange due to In® form, Holn” Spin? 13 PHSS5 pH 711 pats us Red Blue Orange In the pH range 7-11, a metal cati Hin? +H,0 "= H30+ n> Ble Orange The end point reaction may be represented as : Pe ay: a aga Bing” + Hy SS Hin? sty where M = Mg, Ca* Zn ete, Murexide : F 0 This is the ammonium salt of purpuric acid. Here the hydrogen ions are of four amis The structural formual is shown in Fig. 5,4,Fig. 5.4 Structure of Murexide ssolution is reddish violet belwo pH 9 (H4In“), violet from pH 9 to 11 (H3In”) and blue violet pi 11. Itforms stable complexes with Co™, Ni*, Cu and Ca® ions. ij above jas Hor blue tution of murexide is unstable and must be prepared each day. | aqueous sol | xylenol Orange S ahis is a 3, S-bis IN, N-di_ (carboxymethyl)aminomethyl]-o-cresolsulphonaphthalein. Its sure is shown in Fig. 5.5. In acidic solution, the colour of the indicator is lemon-yellow and the er ofits complexes with the metal ion is intensely red. The metal ions Co**, Zn" ,Cd*, Pb™* and > can be directly titrated with EDTA*~ solution using xylenol orange as an indicator in acidic “ohition. The colour change at the end point is sharp from lemon-yellow to intensely red. OH H,C- CH,— N(CH,COOH), E CH, i ‘OH 3° 'CH,— N(CH,COOH), : HK by COOH), 5 : Fig. 5.5 Structure of Xylenol orange | Choice for a Buffer ' [buffer which is used in EDTA ttitration should be such that its species should not interfere with the metal ion, i.e, there should not be any precipitate. In EDTA titration, the most commonly used } bufferis NHy-NH.,Cl buffer (pH ~ 10.2). : Wewant to keep the metal ion as soluble salt but not as solid. The strong alkalies form unwanted Fecipitates, So addition of strong alkali is over ruled. Mg” + 20H —>Mg (OH)2 NHS buffer doés hot preefpitare Ca Mg Zn ion, a their hydroxides. Irhas two fold tion an aie i {) Itmaintains the pH! ~10.2.132 Volumetric Analysis and Inorganic Preprations (2) Ammonia molecules acts as auxiliary complexing agents for the metal ion, The metal ; this buffer are present as soluble ammine complexes, tal ons ig (3) NH present in the buffer solution abbstracts protons from HzEDTA? and indi solution resulting in the formation of EDTA‘ and In® (for Eetichrome yi, me black, fy example) and encourages the formation of M-EDTA and M-Indicator complexes, Inacidie medium, the ionization of EDTA is supressed and the equillibrium shift towards hand side. tet HY —==4Ht +" (EDTA) Object To estimate the strength of Mg ions and MgSO, -7H,0 in the given solution of magnesiur sulphate (MgSO, -7Hz0) complexometrically using EDTA solution as an intermediate solution an Erichrome black-T indicator. Prepare your own ue MgSO, -7H,0 solution. Reagents Provided @_EDTA solution (approx. M / 40) Gi) Erichrome Black-T (as indicator) Gi) NH; —NH,Cl buffer solution (pH = 10.2) (iv) Unknown MgSO, -7H,0 solution (¥) Solid MgSO, -7H,0-To prepare a standard solution of MgSO, -7H,0- 100 mL. Theory When EDTA solution is added to the solution of magnesium suflate in the bac NH3—NH,CI buffer soution, Mg? ion combines with chelating ligand EDTA™ to [Mg(EDTA)]”" chelate, Mg?*+ H,EpTa® NHo—NHsCl gg ceptay™ 2NHi The structure of {Mg(EDTA)]*- is shown in Fig. 5.1. «>. The NH; —NH,Clbuffer solution maintains the pH ~ 10and because of the co Prevents the formation unwanted precipitate of Mg(OH)2 which may be formed by a only ammonia or strong alkalies like NaOH. mmmon ion effec dition of ett132-9 Volumetric Analysis and Inorganic Preprations (2) Ammonia molecules acts as auxiliary complexing a; this buffer are present as soluble ammine complexee (or the metaig = (2) Nig present in the buffer solution abbstracts proton f he solution resulting in the formation of EDTA‘ ang fn "a Hepp 4 example) and encourages the formation of M-EDTA and ‘etna "eth Hh In acidic medium, the ionization of EDTA is supressed and the oo com hand side. © equilibrium, shige HyY —=4Ht +y- ty, aor) periment 1 To estimate the strength of Mg” ions and MgSO, -7H,0 in the given solu sulphate (MgSO, -7H,0) complexometrically using EDTA solution as an ints Erichrome black-T indicator. Prepare your own xu MgSO, -7H,0 solution, ion of edits, Reagents Provided (EDTA solution (approx. M / 40) (i) Erichrome Black-T (as indicator) NH,—NH,Cl buffer solution (pH = 10.2) (iv) Unknown MgSO, -7H,0 solution (v) Solid MgSO, -7H,0- To prepare a standard solution of MgSO, -7H,0-100mL Theory When EDTA solution is added to the solution of magnesium suflate in the preee NH3—NH,CI buffer soution, Mg* ion combines with chelating ligand EDTA‘ to fe [Mg(EDTA)]*" chelate. [Mg(EDTA)]" NH3—NH,Cl Mg” + H)EDTA® +3 NEC. 5 The structure of [Mg(EDTA)]*- is shown in Fig. 5.1. ion The NH, —NH,Clbuffer solution maintains the pH ~ 10and because of the commonest prevents the formation unwanted precipitate of Mg(OH)2 which may be formed by addition only ammonia or strong alkalies like NaOH.Complexometric Titrations 5 133 ca - Mg” + 20H” —> Mg(oH),(s) Ammonia molecules present in the buffer solution abst 2 courage the formation of [(Mg(EDTA)|* complex. abstract protons from H2EDTA™ an Ammonia molecules also abstract protons from Erichrome black-T and encourage the formation f complex of Mg” with Erichrome black-T indicator due to which the colour of soution becomes fine red. ‘The structure of Mg* —EBT complex is shown in Fig. 5.6. since the NH3—NH,Cl buffer soution maintaii Ls | ipserved in this pH range. ins the pH ~10, the sharp colour change is hs 9 ° 2 "CO Fig. 5.6 Structure of Mg-EBT complex f } When, NajH2EDTA solution is added to magnesium sulfate solution, free Mg** ions combine with EDTA‘ to form(Mg(EDTA)]* complex. Near the end point, when all the free Mg ions form [Mg(EDTA)]™ complex, the EDTA‘ replaces EBT from Mg**-EBT complex forming | [Mg(EDTA)]" complex releasing free Erichrome black-T indicator. This reaction occurs because Mg” -EBT complexis less stable than[Mg(EDTA)] complex. At the end point of the blue coour appears due to ; the presence of free Erichrome black-T. ‘ "The [Mg(EDTA)]> is more stable than Mg*-EBT complex because EDTA‘ is a hexadentate ligand and EBT is a tridentate ligand. The stability of a compex increases with increase in the dentisity of the ligand or increase in number of rings per ligand. Since EDTA*” forms five rings whereas one EBT forms two rings with metal cation. Thus [Mg(EDTA)]*” is more stable than Mg”-EBT complex. The stabilities of [Mg(EDTA)* and) Mg-EBT complexes can, also be explained { thermodynamically using entropy change during the formation of complexes.» ae | 134.0 Volumetric Analysis and Inorga i| ic Preprations (Mg(H,0)¢]** + EDTA —, [Mg(eDTA)]2- [Mg(H20)¢]?* + 2HIn*~ —> [Mg(in),)4- Blue Wind red OR 25 2 fe | (Mg(#,0)6]** + 2HEBT MEE £28 i Procedure 1. Preparation of standard MgSO, -7H.0 solution O17 40, 19 0 i Weigh out the calculated quantity of Mgso, - 7H, accurately, and transfers, flask using a funnel. Wash down MgSO, -7H,Osalt with deionized war ei a i and swril the flask to dissolve the salt. Make the Volume upto the mark, Shakey te t sa solution homogeneous. Mel, (or volumetric flask). In the titration flask, pipette oxt 10 mL of standard yoga tt soluton. To it add, 5 mL, of NHs—NH,Cl bulfer solution and 5 drops of Er het ig indicator. The colour of the solution tums cherry red, Titrate this soluion apm solution taken in the burette. The end-point is indicated when colourchangerfnme | colour to blue colour. Note this reading as final burette reading. Repeat ths, 7 a concordant readings are obtained, Im 4 8. Titration of standard EDTA solution with unknown MES0.4-711,0 soli, Hage Litration flask, pipette out 10 ml of given MgSO, -71,0 solution. To tad stg. buffer solution and 5 drops of erichrome black-T indicator "Ze colour ofthe sian soy cherry red. Titrate this solution against EDTA taken in the burette, The end point sinderst when colour changes from cherry red to blue. Note this reading and repeat thisprocestiloy | concordant readings are obtained, | Observations A. Preparation of a Standard solution of. MgSO,4.7H,0 it 10 Mass of MgSO, -7H,,0 to be taken = Molar mass Molaiy «100 Molar mass of MgSO, -7H,0 = 246.48 Mass of MgSO, -7H,0 to be taken = 246-48x 1x 100 000% 40 = 0.6162 g Mass of empty weighing bottle = ag Mass of weighing bottle + sample = b g Mass of weighing bottle after transfer = cg Mass of MgSO, -7H,0 taken, w'= (b-c)g +: Molarity of prepared MgSO4 -7H,0 = M; = re M136.0 Volume Again Mz =Molarity of EDTA V3 =Volume of EDTA M, =Molarity of given MgSO, -7H,0 solution V4 =Volume of given MgSO, -7H,0 solution MaVs =M4V, = Mave Va Strength of unknown MgSO, -7H,0 = Molarity x Molar mass Ms =Mq x 24648 8/1, Strength of Mg** ions in the given MgSO, -7H,Osolution. =Moalrity , Atomicmas of = Myx 24g, Precautions 1. Buffer solution should be stored in a stoppered bottle. 2. The colour change at the end point should be pure blue and ot violet Result The strength of given solution of magnesium sulphate is fl. The strength of Mg ions in the given MgSO, -7H0 solution =...... g/L, h: Experiment 2 Object To estimate the strength of the given solution of zinc sulphate (ZnSO, .7H,0) complexometrically using EDTA solution as an intermediate solution and Eriochrome BlaceT 3s indicator. Prepare your own He ZnSO, -7H,0 solution. Reagents Provided (EDTA solution (~ M / 40) Gi) NH3-NH,Cl buffer (pH = 10,2) (iii) Erichrome Black-T as indicatorComplexometric Titrations ©, 137 (jv) Solid ZnSO4'-7H,0- To prepare a standard solution of ZnSO, -7H,0 (M / 40) (v) Unknown ZnSO, +7H,0 solution Theory ‘When Lay solution is added to the zinc sulfate solution in the presence of NH3. —NH,Cl buffer solution, Zn™ ion combine with EDTA * to form [Zn(EDTA)]™ complex. Zn™ + HjEDTA™ —— [zneEDTA)]> —_ ‘The structure of [Zn(EDTA)]* complex is shown in Fig. 5.1. ‘The NHs—NH,Cl buffer maintains the pH ~ 10 and ammonia molecules abstract the proton from H,EDTA® and EBT indicator to encourage the formation of [Zn(EDTA)] and Zn™-EBT complexes. No precipitate of Zn (OH), is formed when the NH, —NH,Cl buffer is used. If only ammonia or @ strong base like NaOH is used, the pH may become >10 and it causes the unwanted precipitation of Zn(OH) 2. Zn™ + 20H” —> Zn(0H)2(s) Wiite po. Zn-+2NH3 + 2H,0 —» Zn(OH)2 + 2NH§ ‘Ammonia molecules present in the NH3—NH,Cl buffer also abstract the protons from Erichrome black-T indicator and help in the formation of Zn -EBT complex. ‘Since the NH NHC! buffer maintains the pH ~ 10, the sharp colour change is observed in the pH range. When EDTA solution is added to the Zn™ sulfate solution, the free Zn™ ions present in the solution combine with EDTA‘ to form [Zn(EDTA)]”" complex. Near the end point, when all the Zn ions have form [2n(EDTA)]" complex, the free EDTA™ replaces Erichrome black-T from Zn EBT complex releasing the free Erichrome black-T indicator. This reaction occurs because the[Zn(EDTA)] is more stable thanZn**-EBT complex. Because of the presence free Erichrome-black T blue colour appears at the end point. Procedure ‘1. Prepartion of standard ZnSO ,-7H,0 solution (M / 40 , 100 mL) : Weigh out the calculated amount of ZnSO, -7H,0 accurately and transfer it into a volumetric flask using a funnel, Wash down ZnSO, -7H,0 salt with deionized water. Remove the funnel and swril the flask to dissolve the salt. Make the volume upto the mark. Shake well to make the solution ~-~-homogeneous.- —— - 2. Standardisation of EDTA solution : Prepare a standard solution of ZnSO, -7H20in 100 mL standard flask. In the titration flask, pipette out 10 mL of standard ZnSO, «7H,0 solution. Toit add § ml. of buffer and 5 drops of Erichrome black-T indicator. The colour of the solution become cherry red, Titrate it against EDTA solution in the burette. At the end point the colour138 © Volumetric Analysis and Inorganic Preprations ee change is from cherry red to blue. Note this burette reading procedure till two concordant readings are obtained. 3. Titration of standard EDTA with unknown ZnSO , -7H,0 Solution ; Inthey, flask, pipette out 10 ml of given ZnSO, -7H,O solution. Toit add S mt Of utes an tn of Brchrome black-T indicator. Titrateit against EDTA solution, atthe xe Pai Soy change is from red to blue, Note this burette reading as final reading and repeat gg by till two concordant readings are obtained, a as final Teading ang he ti Observations | > 100 m1) Mass of ZnSO, -7H,0 to be taken = Molar mass» Molar «109 ~ 287.56x 1x 100 1000x 40 =0.7189 g Mass of empty weighing bottle = ag Mass of weighing bottle + salt = bg Mass of weighing bottle after transfer = cg Mass of ZnSO, -7H,Otaken, w = (b-c)g _ . wx 100 Molarity of prepared 2nSO, -7H,0 = me 1000 700! =Wxl0 28756 4 B. Titration of standard ZnSO, - 7H20 with EDTA solution Solution in the burette : EDTA solution Solution in the titration flask : (@® 10 mL Standard ZnSO, «71,0 solution = V; Wi) 5 ml NH3-NH,Cl buffer solution (iii) 5 drops of Erichrome black-T indicator Colour change at end point : Cherry red to blue —— A. Preparation of a standard solution of ZnSO, - 7H,0 ae Volume of EDTA solution used = V2 mL C. Titration of given ZnSO, - 7H,0 with Standard EDTA Solution in the burette ; EDTA solution | i i i 4 4 / ] 4140 6 Volumetric Analysis and Inorganic Preprations Precautions 1, Buffer solution should be stored in a stopper bottle, 2. The colour change at the end point should be blue, Result ‘The strength of given solution of zinc sulphate is ........ g/L. The strength of Zn™ ions in the given solution of ZnSO, -7H,0 Object Find out the total hardness of drinking water complexometrically usin 8 EDTA as an in solution and Erichrome black-T as an indicator. Prepare your own a MgSO, 74,0 ts Chemicals Required (EDTA solution (M / 40) i) NH3-NH,Cl buffer (pH = 10.2) (ii) Erichrome Black-T as indicator (iv) Solid MgSO, -7H,0 —To prepare solution of MgSO, -7H,0(M / 40) Theory Water containing soluble calcium and magnesium salts (mainly bicarbonates, chlorides end sulphates) is termed as hard water and if these salts are absent then the water is termed as oft wate. Hard water does not form lather with soaps easily. This property is due to the presence of some ss in water (mainly calcium and magnesium) which it dissolves from rocks ete. The hard nature ofwatet is due to the reason that the Mg™ andCa™ ions combine with stérate ion (main component of sop and detergent) to form the precipitate to stearate of Mg** and Ca** ions. Sterate fon Cy7H:sCO0” ion is present as sodium sterate in a soap or detergent. Cy7HgsCOO-Na* + M —— > (Cy7HysCOO)2M(s)+ 2Na* (where M = Mg orCa) Temporary hardness : Temporary hardness is generally due to the presen of calcium and magnesium and it can be removed merely by boiling. On boiling, decompose to give carbon dioxide and insoluble carbonates which can be removed ce of bicarbonates the bicarbonate’ Dy filtration Ca(HCO), HE 5CaCOs (s) + Hz0+COz (8) Mg (HCO), Hs MgCOs (5) + Hz0+ C028) aComptexome trations 0. 141 semporary hardness can also be removed by adding lime to it Ca(HCO3)2 + Ca(OH); 5 2¢aC0(s) + 24,0 Mg(HCO3)2 +Ca(OH)2 ——+CaCO(s) + MgCOs (s) + 2H,0 permanent hardness : It is due to the presence of soluble calcium and magnesium salts or tan bicarbonates). For removal of permanent hardness, following methods are employed = (rq) By precipitation : In this method, the calcium or magnesium ions (generally from solved chlorides and sulphates of these metals) are precipitated by adding calculated amount of jgluble solid carbonate (like Na,CO3). M*+COF} ——>MCO,(s); M =Mg, Ca (i) By exchange of ions : When a sample of hard water is passed through minerals such as erolites; the bivalent metals in solution (Ca™ and Mg”*) are exchanged by equivalent amounts of sodium ions in zeolite. (Ui) By sequestration of bivalent cations : Instead of removing the bivalent cations by ion xchange, they can sometimes be rendered in effective by reagents like ‘calgon’ which is the sodium sltof polymetaphosphate (NaPO3),,. CaCly + (NaPO3)q OF Nan (PO3), —>Nay2Ca(PO3)q + 2NaCl MgSO, + (NaPO3), —>Nan_2Mg(PO3), +NazSO4 ‘The total hardness of water is calculated in terms of ppm of CaCO present. | Procedure 1. Preparation of standard MgSO ,-7H,0 solution (M / 40 , 100 mL) : Weigh out the calculated quantity of MgSO, -7H,0 accurately and transfer it into a voumetric flask using a funnel, Wash down MgSO, -7H0 salt with deionized water. Remove the funnel and swril the flask to dissolve the salt. Make the volume upto the mark. Shake well to make the solution homogeneous. 2, Standardisation of EDTA solution : Ina titration flask, pipette out [Link] of standard MgSO, -7H,0 solution. To it, add 5 mL of buffer solution and 5 drops of Erichrome black-T indicator. The colour of solution turns cherry red. Titrate it against EDTA solution taken in the burette. The colour change at the end point is from cherry red to blue. Note the burette reading as final reading and repeat this procedure till two concordant readings are obtained. 3. Titration of standard EDTA solution with given water : Transfer 100 mL. of tap Water from the standard flask in the titration flask. Add S ml. of buffer and 5 drops of indicator, Colour of the solution turns cherry red. Titrate it against standard EDTA solution taken in the burette. The colour change at the end point is from cherry red to blue. Note the burette reading as final reading and repeat this procedure till two concordant readings are obtained.