(<} INORGANIC CHEMISTRY DEEYA once Cancpts of Qualitative Anas a0 7 ed from AB and added to solution containing Fe**, AP and Zn®* ions, a white precipitate of Zn(OH)y and Al(OH)s brown precipitate of Fe(OH), is formed, However in excess of NaOH precipitate of Zn(OH)y dissolves while Fe(OH); remains insoluble. Precipitate of Zn(OH)y and AI(OH)s get converted into soluble sodium zincate and sodium aluminate. The complexation reactions are: fi) Fe ions can be separ When NaOH solution %+ ions by using solution of NaOH. +2NaOH T= 7n(OH Zn(OH)2 + 2NAOH S— N. APY + 3NaAOH == A(OH)s + 3Nat AI(OH)3 + NaOH = NaAlOy + 2H0 Fett 4 3NaOH == Fe(OH)s + 3Nat Fe(OH)s + Excess NAOH —> insoluble Fe(OH)s, iii) Another application of complexation is in separation of Cu®* and Fe®*, When to the solution containing Cu2* and Fe, NHyCl (excess) and NHjOH is added, Fe(OH) gets precipitated but Cu? ions remain in the solution due to formation of stable soluble complex ion [Cu(NHy) 41” Cutt + ANHJOH — [Cu(NHy)4]2* + 41,0, Solution is deep blue coloured as a. result of highly stable soluble complex [Cu(NHs)4]2* while precipitate is reddish brown due to the formation of Fe(OH)3. Cut does not get precipitated as Cu(OH)» because formation of complex [Cu(NHs) 4]2° n umavailable for this precipi nd hence we ean separate Cu®* from 4+ 2Nat ZnOz + ZHyO QUESTIONS y Dy the term “qualitative analysiv? 2. What are the types of qualitative analysis on the basis of weight of sample? 3. How will you detect the presence of following ions in the given sample using reagent ii) COP iy S* 4. Write short note on : i) Solubility product ) Common ion effect iii) Diverse ion effect iv) Use of complex forming ability in qualitative analysis 5. i) The solubility of silver chloride is 1.5 x 10-* g dm, Calculate its solubility product [Ag = 107.9, Cl= 35.5] ii) The solubility product of lead bromide is 8 x 10-9 at 298 K. The percentage dissoci I in its saturated solution is 80, Calculate the solubility of salt in dm-, Molecular weight of PbBr is 367 g mot ~1, 2.3 x 10-5 at 25°C, Calculate its solubility i) The solubility product of silver sulphat at the same temperature in mol dm-S and gdm-3, i) Solubility product of BaSO, is 1 x 10-1” at 25°C. Calculate its solubility water or (b) 0.01 M HySO4. Comment on your answer. in (a) PureVibee YA mn = Q 66 P'S Inorganic Chemistry (FY. B.Se) (Sem, = 16 I) solution, If this extract is not acidified with HNOg then even in absence of Cl- and SOF ions, precipitation will take place according to 203 | +2NO}" J» <= BaCOg | + 2NO- Thus, if the extract is no precipitate will be formed and wrong conclusion would be arrived. ied then even in the absence of Cl, SOF ions, When HNOs is added to extract, COS are destroyed as COg according to the following reaction CO} + 2HNOs Hy Hy COs; == HO + COvt ‘ll be evolved in the form of bubbles. No preci 1- 42 5 + 2NO} on will take place if Thus COy wre absent. ¢ insoluble in neutral or little higher pH but soluble at lower pH (ic. in acidic medium). AgCl and BaSO, are however insoluble even at low pH (ie. highly «don the basis of following equilib BaSO, == Ba? + SOT AgCl === Agr + Cl . pH is lowered) cidic medium). IEHINOs is added soy + HNO; —— Ht + Noy + S07? Ht + NOY + Cr Cr + HNOs, librium, SO} ions and Cl ions do not combine with H* ions so their equ nains unaffected. Thus even at low pH ionic product exceeds concent y soluble. solubili Complexing agents tion is the phenomenon in which a metal ion combines with anions CF, Br) or neutral molecules (like NH) to form species which are more stable. This bility is useful in detection of ions in qualitative analysis. i) The best example of effect of complexation on precipitation equili confi vest for Cl- ions. When AgNOs solution is added to solution containing Clr ions precipitate of AgCl is formed. AgGI being sparingly soluble. AgChy <= Age + Cr (aq) (aq) To this precipitation equilibrium when NHjOH solution is added, stable ammonia complex of Ag? is formed Ag? + Cl + 2NH,OH [Ag(NHg)g]Cl + 2H20 soluble complex The complex is stable and this complex formation reaction is use jons in the solution. d to confirm presence of C Tov 1120 popes remainingVibec YA ial ot Pe Inorganic Chemistry (FY. B.Sc) (Sem. ~1& I) Due to increase in concentra i NH,OH = NH; + OH- is shifted to left hand side direction. This decreases the concentration of OH- ions in the solution. As concentration of free OH ions in solution is controlled the solubi Fe(OH), AI(OH)s, is exceeded and only these cations are preci preference to Ni ii) Precipitation of carbonates of group IV cations from solution containing Bat, Ca®*, Sr? and Mg?* ions. The cations Ba’ are precipitated product of ted out in Ammonium chloride ionizes as : NHyCl ——— NH} + Cl While NH OH and (NH,)2 COs ionize as: NH,OH == NHj + OH- (NHy)2 CO; = 9NHj + COS Due to the presence of strong electrolyte NHyCl the concentration of NHj ion \crease and this causes common ion effect. It will suppress the is kept low solution wi ionization of NHyOH as well as (NHy)2 CO3. The concentration of OF which prevents the precipi s Mg(OH)s. ion of (NH4)2 COs limits the concentration of COS ions in tion of Mg! n of ion Suppr the solution. This low concentration of COs” is enough for p carbonates but not for that of Mg? ions as MgCO: ation of Ba, Sr? and Ca Uncommon Ion (Diverse Ion) Effect Solubility ofa sparingly soluble salt increases in the presence of foreign ions that is ions which are not common to those of the salt. This effect is opposite to the common ion effect and is called as uncommon ion effect, diverse ion effect, salt effect or activity effect. This effect will be understood from the follo Consider an aqueous solution of AgCI at 298K, Molarity of this solution was found to De 1.0.x 10° (Kspagcy = 1-0 x 10-1). If KNOg salt is added to it (to make its concentration 0.01M) the molarity of AgCL This increase in molarity of AgCl is the result of increase in solubil is of diverse ion or uncommon ion ng discussion : increases to 1.2 x 10-5 of AgCl on addition of KNOs and explained on the effect. Solul lity product of AgCl is expressed as : ox acre jon (m) and activity coefficient (r) PAgcl y’ and is the product of molar conc . aemxr mygt Tagt_ and acre = mer x ange Tihs, Kepager = (Mage % tag!) % (mer * ter) Rearranging the terms : Kapager = (mage °— Tne eeIDEEYA Concepts of Qualitative Analysis rrr 6s ‘The quantity in the second bracket is activity coefficient which depends on the ionic strength. As ionic strength iner { decreases, Since solubility product, is constant quantity, when activity coefficient decreases molar concentration of ions must increase. KNOs is a strong electrolyte and is ghly soluble in water. Tts aqueous solution contains high concentration of Kt and NO” ions which increases ionic strength of solution and hence solubility of AgCl in water will increase. Oxidation States The effect of oxidation states of the met hydroxide is the effect of best ‘example of this factor, which affects the precipitation equilibrium. il hydroxides in which metal ions exist in different oxidation Consider following n state: Fe(OH) [Fe] Ky = 3.8 x 10-38 Fe(OH)s, [Fe®*] Kyp = 4.8 x 10-16 CO(OH)s [COM] Ky = 2.5 x 10-8 CO(OH)», [Co®*] Kyp = 1.6 x 10-16 Hence in a solution containing Fe** ions along with other ions and separation of Fe from other ions is desired then solution containing iron salt, is init led concentrated HNOs which oxidises all Fe?* to Fe and gets pr ed as Fe(OH)s with minimum concentration of [OH-] ions in solution. Buffer Action ‘The solubility of a substance depends on the pH of the solution from whieh the salt is, precipitated. The effect of pH on precipitation equilibrium can be explained on the basis of solubility product. For the formation of precipitate of a particular substance its ionic product must exceed its solubility product. Ionic product will depend on concentration of ions in solution while concentration of ion in solution will be decided by its solubility. The is function of pH ice. H* ion concentration. Hence by changing the concentration ons in solution the precipitation of desired ion can be brought about. Buller solutions are used for changing the pH of solution so that desired metal ions are ted from soluti the presence of number of other metal ions. In. qualitative analysis detection of cer ing buffer action. It will be clear from following two examples a) Consider aso takes place at pH When to the 0.01M solution of M of solution becomes 11.3 and 1g Fe ions and Mg2* ions, Precipitation of Fe(OH) a of Mg(OH)g takes place at pH 9. +, Fedt, 0.IM NH4OH solution is added the pl cy will get precipitated as hydroxides, How addition of equivalent amount of NH,CI to the same solution before addition of s pH. NH,OH, will result in the formation of buffer whose pH will be 9.25. Since 1 is not enough for precipitation of Mg? as Mg(OH): precipitation of Mg?* will start but that of Fe as Fe(OH)s will start. Thus the separation of Mg? from Fe’ can be brought about by us action, b) In the detection of Cl- and SO, from the sodium carbonate extract buffer action is made use of. Sodium carbonate extract is treated with. i) AgNOs to detect the presence of Cr and. buffer ii) Ba (NOg)2 to detect the presence of SOF ions. “Above tests are carried out by acidifying the solution with HNOs. The reason for this is explained below. Sodium carbonate extract contains excess of COs ions in o—‘VIDEEYA oF PI Inorganic Chemistry (FY. BSc) (Sem. ~ 18 M1) ration of NH} (from NH4Cl) the ionization equilibrium Due to increase in conce! NH,OH = NH} + OH-is shifted to left hand side d the concentra ions in the solution. As concentration of free OH= ions in solution is controlled the solubility product of Fe(OH)s, AKOH)s, is exceeded and only these cations are precipitated out in ‘ection. This decreases ining ‘e grouped together as members of group TV and onium carbonate in the presence of idl The cations Ba?*, Ca? are precipitated ammonitim chloride and ammonium hydra de ionizes as : NH,CL While NH,OH and (NHy)2 COs ionize NH,OH == NH} + OH- Ammonium chlo: NH; + Cl as: (NH4)2 COs = 2NHj + CO; Due to the presence of strong electrolyte NH,Cl the concentration of NHj ions in auses common ion effect. It will suppress the on of OH" is kept low increase and NH,OH as well as (NH4)2 COs. The concent Mg(OH)2. solution wi ionization which prevents the precipitation of Mg?* Suppression of ionization of (NH4)y COs limits the concentration of COS, ions in jon of COF is enough for precipitation of Ba®, 5 MgCOs. the solution, This low concet and + as carbonates but not for that of M; ‘Uncommon Ton (Diverse Ton) Effect Solubility of a sparingly soluble salt increases in the presence of foreign ions that is ions ich are not common to those of the salt, This effect is opposite to the common ion effect and is called as uncommon ion effect, diverse ion effect, salt eff y effect. This effect will be understood from the following discuss Consider an aqueous solution of AgCI at 298K. Molarity of this solution was found to be 1.0 x 10 (Kspa, 1.0 x 10-19), wl of AgCl : nolarity of AgCl is the result of increase in solubility ‘of AgCl on addition of KNOs and explained on the basis of diverse ion or uncommon ion effect. Solubility product of AgCl is expressed as : Kepagea = agt * ac ctivity and is the product of mola concentration (m) and activity coefficient (r) ie. a=mxr r= mer x ter ) e Aggt = Magt x Tag and ac Thus, Kypager (mag? * rag*) * (mer * Ter Rearranging the terms : Kypager = (mag * mer) * (ragt * Fer)r<) INORGANIC CHEMISTRY DECYA Canpts of Quaiative Anas ee “0 Problem 3 The solubility product of magnesium hydroxide is 14 « 10-!! at 208 K. Calculate its solubility in (i) mol. dm~*; (i) g dy (Mg = 24.92, 0 = 16, H= 1] Mg(OH)» dissociates as: Mg(OH)y = Mg?" + 20H- (s) (2s) Ky = [Mg?*] [OH-}* Ky = (5) (25)? Ky = 4st Since Ky = 14x 10-1! Ast Lax lorll 14x 1o-l q S = 3 FE 10-12 = 3BV35 « 1012 = 3BV35 x lot S = 1.518% 10-t mol dm Solubility in mol. dm-* = 1.518 « 10-4 lubility in g dh stu ol dm = Solubility in mol. dm mol we Solubility ing du} = Solubility in mol, dm- x mol. wt = LSIS x 10-4 x = 8.853 x 10-* gdm Common Ion Effect The common ion effect is stated ay “the decrease (suppression) in the degree of dissociation of a weak electrolyte or decrease in the solubility of a salt in the presence of a strong electrolyte, having an ion common to the electrolyte, The effet of common ion on precipitation equilibrium ean be understood from the following examples : i) Consider a sample solution which contains Fe, AP, Ni2*, Co? ions. When NHOH solution is used as precipitating agent above metal ions will precipitate as hydroxides and their separation will become diffi elfeet the separation of ult. However using common ion nd Co® from Fe® and AB is made possible, The values of solubility product for their hydroxides are given below : Fe(OH), Ky = 38x 10-98 NOH) = 8.7 x 10-8 ANH) Ky = 85x 10-2 Co(OH)2 = 1.6 10-18 Before addition of NH\OH to the solution « solution of NHACL is added. NHCI is. stro completely as: taining AM, Fe, Co? ions, ig electrolyte and hence ionizes NHACL 1g Weak electrolyte it ionizes NH\OH == NH) + OH NH,OH bee INORGANIC CHEMISTRY DEEYA 02 ee Inorganic Chemisiry (PLY. B.Sc.) (Sem. ~ Lee I) Problem The solubility product of silver chloride is 1-1 x 10-! at 298 K. Calculate its solubility in (i) Pure water and (ii) 0.01M NaCl. i) Fora saturated solution of silver chloride AgCl) = Agh + (aq) (aq) IES’ is the solubility of silver chloride then [Ag*] = [OF] = S Ry = [Ag] [er] = Sxs 110-10 Ss = Vilx1r S = 10488 10-5 M Hence the solubility of silver chloride in pure water is 1.0488 x 10° mol dm-*, ii) Solubility of AgCI in 0.01M NaCl In 0.01 MNaCl, the concentration of chloride ion from If solubility of AgC! Sis 0.01M. nd total chloride concentration is is now S! then [Ag*] = +102 Now due to common ion effect S' < 8. [ER] = 1.0488 «10-5 + 10-2 = 10-2 Now Repager = FAR?) [CF] 11x 10-1 = Age) [10-2] [Ag] = Lbetgt = 11x 10-8 mol d From above example it is seen that solubility of silver chloride decrease by 1000 times 001M NaCl This is due to common ion effect and one can use this effect in bringing about precipitation of certain metal ions in qualitative analysis. Problem 2 Given that the solubility product of silverbromide is 3.3 10-12 at 25°C, What is the concentration of NaBr required to precipitate AgBr from 0.01M AgNOs solution, AgBr dissociates as : AgBri) SS Agy + Bro (aq) (aq) Ag?) [Be] [Br] = = 33x 10-10 Hence concentration of NaBr required to precipitate AgBr from 0.01M sol be greater than 3.3 x 10-10M.@ Norcanic cHEmistRY DEEYA ——— Cnr of Quiative Analysis 90 o sample and specific reagents, Hence it is very much essential to know that whether the product will precipitate as expected or if not, what are the factors which make it remain in solution without forming precipitate. In view of this, concept of solubility and solubility product should be understood clearly so that detection of ions in the given sample becomes easy Solubility The solubility of any substance at a given temperature is defined as the amount of the substance dissolved in its saturated solution in a given solvent at that temperature, It is expressed in grams per dm* (g dm) or moles per dm (mol + dm~"). For most of the salts solubility increases wi Solubility Product When a cation precipitates itself as one of its salts it indicates that under the given conditions of pH and temperature, the salt becomes sparingly soluble in aqueous medium. AL this stage solution gets saturated with the salt. In contact with water, the salt dissolves to some extent and the dissolved salt completely dissociates into respective ions, This leads to an equilibrium between the insoluble salt and dissociated ions as shown below : temperature, McO; == Me + COR” (s) faq) Gq) equilibri This is called precipitatio ass action to sueh equilibrium we get reaction, Applying the law of n [IM*] x [CO5"] ~ TMCOsT for Ke x [MCOs] = [M¥] % (C057) Since MCOs is sparingly soluble salt, the change in concentration due to its solubility in solvent is negligible hence its concentration remains practically constant and hence we can introduce new equilibrium constant Ky, where Ky = Ke x [MCOs] ie Ry = IMM] [COS where Ky, > is called as solubility product and is defined as the product of the molar concentration [or activities) of the constituent ions raised to the appropriate power depending on the number of ions present in a saturated solution at a given temperature, ince solubility depends on temperature solubility product also. depends on temperature and increase with inerease in temperature. Any factor which is responsible for the change in the concentration of free aqueous ion, at the equilibrium will either dissolve the salt or will lead to the formation of more precipitate Thus for precipitation to occur one must remember that the product of ionic concentration of free ions exceeds the solubility product of the precipitate. The solubility product has three important applications in qualitative analysis. These are: a) To calculate the solubility of an electrolyte or the concentration of its ions in its saturated solution. b) To predict the conditions under which a precipitate of an electrolyte may be expected to form and ©) To predict the condi dissolve ns under which a solid electrolyte may be expected to.e INORGANIC CHEMISTRY Dee Subsea boots wo wo Inorganic Chemistry EY. BSe) (Sem = 1) Lead Acetate Paper Saturated solution of lead acetate in distilled water is prepared and strip of filter paper is dipped in it. This strip is used directly ay lead acetate paper. This paper is used to detect ns. When any stlphide salt is heated with HySO, it liberates HaS guts o the formation of black residue of PbS presence of which turns lead acetate paper black due s& + msoy A> West Hs —CHxCOO)PH pps Paper lack spot also be used in separation of cations into group. When from Sis to be boiled off, complete removal of HyS is confirmed the centrifugate (or filtrate) using lead acetate paper. Dimethyl Glyoxime er paper stip is soaked in warm saturated solution of dimet -ct the presence of Ni, Fe?*, Pa, V ions. In the det 2+, drop of test solution is added on the reagent paper followed by a drop of on. A red spot is developed on the reagent paper due to the formation of searlet red 1 glvoxime in ace tion of id. Itis used to de solu coloured Ni (DMG)y precipitate. Nit + 2DMG In the detection Fe?*, test solution is mixed with a sma — [Ni(DMG)»] Il exystal of tartaric acid drop of this solution is added to reagent paper followed by a drop of ammonia solution, A red colouration appears which confirms the presence of Fe2*, This test does not respond to Fe. He 1 of Fe, it is first reduced to Fe? by NHJOH * HCL and then Jops yellow coloured spot with this reagent cin the dete above. Pd2* in acidic medium de reagent paper is most usefull as it ean be used in the detection of Zn (I), Nid), AMID, Fe(II), Mgdt), Mn (I) 1% solution of $-hydroxvquinoline in ethanol is prepared. Filter paper strip is soaked in it for 20 minutes and then dried. This strip is used as oxine reagent paper. A drop of test solution containing Mg (Il) and NHjC1 is added to the reagent paper followed by a drop of ammonia. Yellow spot is developed duc to the formation of magnesium oxinate. Mg + My(CHON), * 2H - Yellow precipitate oll nu With Zn(II), Ni(II), AL(IIT), Fe(II) also yellow to green spot ix developed with oxine paper. In the case of Bi(III), the test paper is first loaded with 1% KI followed by test solution containing Bi, It develops red coloured spot. From above few examples it should be clear that in qualitative analysis using certain in anions as well as cations can be detected with y production of harmful gases or wasting so specific or selective very small amount of solution thus prev much quantity of reagents & chemicals. Precipitation Equilibria Qualitative analysis focuses on ‘what is present” for which the most important step involved is precipitation’. Precipitation is an ionic reaction which involves solutions ofe INORGANIC CHEMISTRY DEEYA Concepts of Qualitative Anakysis 292 sy Also cations are detected by separating into different groups on the basis of forn ipitates like chlorides, sulphates hydroxides ete ion of pr For understanding the precipitation phenomenon certain concepts like common ion effect, solubility product, effect of pH on solubility, ete, must be understood thoroughly well. Further discussion in this topic will help students to under in tests performed in qualitative analysis, Itis also desired to perform spot tests for deteeti certain cations and anions so that chemicals can be s: havards, nd theoretical principles n or confirmation of presence of red and also to lessen the pollution Generally in qualitative analysis semi-micro analysis is preferred as it has advantage of both macro and micro analysis. The apparatuy used in semimicro analysis are same as that nly used in the chemistry laboratory ie. test tubes, beakers flasks ct sample used is small and hence separation of precipitate needs centrifuge m: ‘Testing of Gaseous Evolutes During qualitative analysis when solid mixture is heated, some substances decompose into simple substances like carbonate to carbon dioxide gas, sulphites to sulphur dioxide as. Similarly sulphides get oxidized to sulphur dioxide gas. The gases evolved are recognized from particular odour, colour or on the basis of effects caused by these certain test papers like lium son Paper, turmeric paper, starch iodide paper or papers pregnated with potassium dichromate, lead acetate, dimethyl glyoxime or oxine reagents When evolved gases reaet with these reagent spot on test pape colour is developed duc to chemical reaction of the evolved gases with reagents. For cxample when any ammonium salt is heated stongly, it evolves NHs gas which turns moist red litmus paper blue due to basic nature of NHs, If carbonates are decomposed by hes certain characteristic if COs yas is given out, When this gas is absorbed in lime water it turns turbid due to formation of insoluble carbonates. Reactions olved CO) + Ca From following illustration detection of some ar 2. 9OH> will be ck fa ACOs | + HO r, how the use of some reagent papers make fer and easier in qualitative analy Sas well as eatio Mix 2g of soluble starch with Hmg of KE and little quantity of water to form a paste. ‘Then add one litre of boiling water to the paste. Stir it well to obtain the clear solution. Now dip the strips of the filter paper in it for about 30 minutes and then dry the strips. Dry strips of paper are used ay slareh iodide papers. Starch iodide paper can be used in the detection of CI Bry or Ly. When misture Br- or Fis heated strongly with MnOy and cone. HySOy, it will liberate if Cis present) which turns starch iodide paper blue. If Br- is present then it will liberate Bry which turns starch iodide paper yellow. Similarly iodide salts will liberate Ly which turns starch iodide paper blue, Potassium Dichromate Prepare 10% or saturated solution of Kul 0 paper in it for 20 minutes and then dry. This strip is us Alistiled water to detect SOF When sulphites are heated with dil HCL or dil HySO4, they get decomposed to evolve SOz gas, This gas when expoyed to potassium dichromate paper produces. green colouration due to the formation of chromium (IID) ions. 380, + #4 380% + 10. - Dip ast ip of filter SIFY.BSe. Inorganie Chemistry (Sem. 1 11)@ sorcanic cHemistry sy a0 Inonganic Chemistry EY. BSc) (Sem. 1 1) SEMESTER - II CHAPTER CONCEPT OF QUALITATIVE ANALYSIS One of the biggest challenge for analytical chemist is to determine the composition of sample which may be naturally occurring or prepared artificially in the laboratory. This is divided into two parts. First part deals with identifying the components present in the sample ie, qualitative analysis while second ,.KKpart deals with quantifying the identified components ie. quantitative analysis. ‘Types of Qualitative Analysis The analyte is subjected to some chemical reactions. The method to be used for analysis depends upon accuracy required and purpose of analysis. The amount of sample used for analysis is also very much important for selecting the method of estimation and therefore qual ilysis is divided into five types as follows : 1. Macro analysis, If the amount of the sample used for quali of solution its volume is about 20 — 30 em’, the type of qualitative analysis is called as ive analysis is about 0.5 —* 10g or in case 2. Semi-micro analysis If the amo 1 of sample used for analysis is about 0.05 — 0.1y or in case of solution its volume used is about lem? it is called semimicro analysis. 3. Micro anaylsis In this type of analysis the solution the volume of solution is mount of sample used is about 0.01 to 0.05g or in case of yout Lem 4. Ultra micro analysis When the amount of sample used for analysis is less than Img it is called Ultra micro analysis 5. Trace analysis When the amount of sample is v y very small, much Jess than Lmg it is called trace analysis, In semimicro qualitative analysis, identification of cations and anions is ¢ the basis of various chemical tests performed on the sample. These tests include hea test ete. Similarly action of varie gases are evolved then from the into consideratic the mixture in the dry test tube, charcoal eavity test, flame s reagents like HCI, HySO, on the mixture is studied. If colour and specific action with certain reagent is takenPaper -I__ Unit -11 1. Concept of Qualitative Analysis : (7L) a) Testing of Gaseous Evolutes, Role of Papers impregnated with Reagents in qualitative analysis (with reference to papers impregnated with starch iodide, potassium dichromate, lead acetate, dimethylglyoxime and oxine reagents). b) Precipitation equilibria, effect of common ions, uncommon ions, oxidation states, butter action, complexing agents on precipitation of ionic compounds. (Balanced chemical equations and numerical problems expected.) 2. Acid Base Theories : (8L) Arrhenius, Lowry ~ Bronsted, Lewis, Solvent ~ Solute concept of acids and bases, Hard and Soft and bases. Applications of HSAB. Applications of aci i) Understanding orgat reaction base chemistry in = reactions like Friedel Crait’s. (acylation /alkylation) ii) Volumetric analysis with special reference to calculation of titration curve involving strong, acid and strong base. Paper -II Unit=11 3. Chemical Bond and Reactivity : (7L) ‘Types of chemical bond, comparison between ionic and covalent bonds, polarizability (Fajan’s Rule), shapes of nolecules, Lewis dot structure, Sidgwick Powell Theory, basic VSEPR theory for AB, types molecules with and without lone pair of electrons, isoelectronic principles, applications and limitations of VSEPR theo 4. Oxidation Reduction Chemistry : (6L) a) Reduction potentials b) Redox potentials : half reactions; balancing redox equations, ©) Redox stability in water i) Latimer and Frost Diagrams ii) pH dependence of redox potentials. d) Applications of redox chemistry i) Extraction of elements : (example : isolation of copper by auto reduction) ji) Redox reagents in Volumetric analysis : (a) I3; (6) KMnOy iii) Titration curves : (i) single electron systems [example Ce(IV) against Fe(Il); and (ii) Multi electron systems as in KMnOy against Fe(I1)]