JSS MAHAVIDYAPEETHA JSS Academy of Technical Education JSS Campus De Viehnuvardhan Road Srinivasapure Bengaluru - 560 080 6 | 287 1 1194, Fax: 060-286112706 | 2646, in| Website: warw jopat E-mail: Ino@jnsateb. All Undergraduate Programs are Accredited by National Board of A ation (NBA) DEPARTMENT OF CHEMISTRY ENGINEERING CHEMISTRY LABORATORY MANUAL AND WORKBOOK (As per Choice Based Credit System (CBCS) Scheme) 1/Il Semester B.E. - Visvesvaraya Technological University, Belgavi name PRATIIAL...D.Chemistry Laboratory Manual CEMENT BY RAPID EDTA METHOD. (COMPLEXOMERIC TITRATION) 2 Jo estimate % Calcium oxide in the given sample of cement solution nile contains compounds of calcium, aluminum, magnesium, iron and insoluble es dissolved in acid, silica remains undissolved. On treating with ammonia, sjuminurn and iron can be precipitated as their hydroxid id separated, The provided solution Peement, therefore, contains calcium and magnesium ions. The constituents of Portland Ingredient Percentage Lime s 60-67 Silica Si 17-25 Alumina a 38 Iron oxide Fe: 05-6 Magnesia Ona d Sulphur trioxide S IS,275 Alkali 0 0.4 -1.3 Gypsum r 3-5 timate the calcium content in the-given Solution, a known volume of it is titrated EDTA solution. In the presence of magnesium, calcium can be titrated against g Patton and Reeder’s indicatorat pH values between 12 and 14. The indicator calcium ions Seago’ complex In complex (wine red) faitium ions are exhausted in the solution, further addition contiplex, consumes the calcium ions and releases free indicator, colour. 7 , the colour change is from wine red to blue. eofm ing them as hydroxide. This by adding 5 ec Tinga because magnesium salts form a complex with indicator. A sharper - obtained by adding 5 cc Glycerol to the sample solution before adding NaOH 1 of standard solution of disodium salt of EDTA. EDTA and transfer into 250 cc standard flask Dissolye_ gortenen te to |Chemistry Laboratory Manual NATION OF PERCENTAGE OF COPPER IN BRA‘ ARD SODIUM THIOSULPHATE SOLUTION (IODOMETRY) “estimate the percentage of copper in the given sample of brass. F Breas is an alloy of copper and zine. When dissolved in cone. nitric acid, both ger converted into their nitrates. It also contains small quantities of tin, lead and (Cut 4HNO3— Cu (NOs) 2 + 2H20 + 2NO> 7 (brown fumes) “| en brass solution is treated with excess of potassium iodide solution, euprie ions § ide potassium jodide to liberate equivalent quantity of iodine. © 2Cu(NOs)2 + 4 KI > Cusk + + 4 KNOs +b (white ppt.) sled jodine is titrated against sodium thiosulphate solution using starch as indicator ‘2NaiS203 + lo > Na2S4Ox (sodium tetrathionate) + 2 Nal urea destroys the oxides of nitrogen present in the brassisolution Presence of fides will be responsible for the liberation of extra iodine from Ki, as they are also ‘present in the brass solution is neutralized by.adding NH.OH solution till a i ate of Cu (OH) is obtained. Otherwise, mgean oxidizing agent, nitric acid jodine from KI and decomposes Nag The Cu (OH)2 precipitate is i preferable, as they will bring down acetic acid. Other mineral acids are.no! ‘email value, at which the liberatios’ of lz form KI by Cu** is not quantitative. eomplex. At the end point, when free ets with iodine to form a blue ed t fogs fof sodium thiosulphate dissociates the in the solution, added jlex, consumes iodine and I is di Sef blue col starch, thereby discharging the blue jlour and white ppt of Cuslz is present in ‘Thus adding starch near the end Cu** gets reduced to Cu” with Week iodine concentration is high. the liberation of Iz from KI,Engineering Chemistry Laboratory Manu: ——————— a VATION AND CALCULATION tion: Transfer the given stock solution of bra clean 250 em? volumetric flask, dilute upto the mark using ion exchange water, « Pipette out 25 cm? of this solution into a conical flask and add 1 gm of urea (approxin, spatualla), boil for two minutes & cool to room temperature, OBSE Part A: Preparation of brass solu Estimation of Copper Burette Standard sodium thiosulphate solution. Conical flask: Brass solution + NHsOH drop wise (10-15 drops) + 1/4" tt. Acetic a, 10 cc 10% KI + 1 tt, ion exchange water. Indicator 2 em’ starch solution near the end point (when the solution acquires pale y End point: Disappearance of blue colour. 1e-3 ff Burette Reading Final Reading Ifa) Reading seis sinsaassneantinnssnoais Normality of NaxS:0s (10 be given), Nia, se0s WL. of brass sample/1000 cc (to be given), Ss. Calculation (NV )waxsy0, = (NV) nine Saton aps oO yr coy enh ‘Nomality of Bi tion, Nurasssotain = ~ 25 Wt. of Copper/1000ce = Niinus soition X Eqt. Wt. of Copper = 1 X 63.54 = 6 (2) £% Copper in brass solution=————2X100_ : Weight of brass in 1000 cc Result : The percentage of Copper in Brass solution is =ite is an oxide ore of iron, existing as ferric oxi A : f iron, exis rric oxide (Fe:0s) with small amount of treating with HCl, ferric oxide dissolves in the acid as alae The insoluble filtered off and the filtrate is used for the estimation of iron. Fe20;+ 6HCI — 2FeCl; + 3H20 a ‘Since iron in FeCly is already in the highest possible stable oxidation state (Fe*"), it ‘amot be oxidized further. Therefore, it is frst reduced to ferrous stale Ferric chloride is feduced by stannous chloride in presence of hydrochloric acid. ; 2FeCls +SnCh —*> 2FeCh + SnCl, Excess of stannous chloride is added to ensure complete-reduction of FeCls to FeCl. Frees of SnCh added is destroyed by adding strong solution of mercuric chloride, since ‘gnCh can reduce potassium dichromate SnClz + 2HgCl: > SaCly + HgxCh 4 (silky white ppt.) T[Note: A silky white precipitate.of mercurous chloride should be obtained. A black precipitate of finely divided mercury. may’ be produced if too much SnCla is present or when a aurid ehloride solution is added slowly (local excess of SnCl2 is formed) or when HaCl ts rjedito the hot reaction mixture, ‘The finely divided mercury reduces K2Cr307 and also Slowly rediices ferric ions fornted, to ferrous ions. Therefore the trial must be discarded if a Black precipitate is producéd=-The trial should also be discarded if no precipitate is obtained ih the addition of méxcucja-chloride because the reduction of ferric ions to ferrous tons may not be complete. Ferrous iontuare titrated against potassium dichromate solution, which is an oxidizing agent, 6FeChy +6HCI +3[O] > 6FeCls+3H20 KC; + SHCL > 2KCI + 2CrCh +40 +10) Raho, + I4HCl + 6FeCh > 2 KCl 2erClnGkeO THEO) erat ium ferricyanide is used as an external indicator to detect the end point of the ‘Potassium ferricyanide reacts with ferrous ions 10 produce intense deep colour due e on of ferroferricyanide com lex. z PE oe sroferricyanide comp! cee 43Ret> FeslFe(CN)s + OKTlution does not develop blue colour with the indicator. pes , Ks[Fe(CN)¢] is used as an internal indicator, it reacts with Fe** ions and forms, Jored Fes{(Fe(CN)«}2 complex. This is an irreversible reaction. Hence, the ersists even at the end point and the end point cannot be marked as there is no color . The Fe’ ions which are involved in the formation of blue colored Fes[Fe(( | Procedure: Preparation of standard KzCr207 solution: ‘Weigh the given KsCrO7 crystals into a 250 cc standard flask. Dissolve the salt in little | ion exchange water. Make up the solution to the mark and shake well for uniform | - concentration. . | Estimation of Iron Pipette out 25 cc of haematite solution into a clean conical flask. Add about 5-6 drops of Cone. HCI and heat to boil. To the hot solution, add SnCl-solytion from a burette till the yellow colour is discharged completely. Add two drops in éxcess, cool the mixture. Add one {est tube of ion exchange water then add % test tube HgCl Solution at a stretch and shake, | well. A silky white precipitate should be obtained. (If black precipitate or no precipitate is | obtained, discard the mixture). Place a number of drops of freshly prepared potassium ferricyanide solution on a wax paper. With the help of a thin glass rod take-a drop of the solution in the conical flask and, bring it in contact with an indicator drop...The colour of the indicator drop turns blue. Now, add cc K2Cr20; solution at into the conical flask and after each addition of Lee KaCr0; solution, shake the yell and test the solution drops as before, Repeat this till a drop of the titrated solution'does’not develop blue colour with the indicator. This titration gives the range of the end-point. Repeat the al jure by conducting the titration drop-wise towards the endpoint | for concordant Result: Percentage of iron in the given haematite ore sample. .. _ OBSERVATION AND CALCULATION, Part A: Preparation of Standard Potassium dichromate solutionStandard K2Cr2O;solution 25 cm! ore solution + 5-6 drops of Ht Cl, heat. colourless, cool + 1 t.t ion aes perce ses Ka[Fe(CN)o] (external) Failure to develop blue colour Burette Reading Final Reading Initial Reading Volume of K2Cr207 ‘rundown in cm Expected value (to be given) Volume of K2Cr207 used for the titration Weight ofhaematite ore in 1000ce (will be given) ‘y= Calculation (NV) k,cr207 = (NV) Haematie solution Normality of Haematite ore’ Solution, Nutaemase ors a fof Iron /1 000. ~~” = Nitacmaite ore stun X Eq. Wt. of Iron X 55.85 = ZX 100 Freight of haematice in 1000 cen demand (COD) parameter has been introduced to measure the es present ee Rares This includes both, biologically oxidisable ‘inert but chemically oxidisable impurities in the water. It is “the amount en equivalent for the oxidation of biological oxidisable and biological iney Pee ears pases wiv crong chemial cxlvons, KsCroOvtn acta medium” TM _ expressed in mg/d’ or ppm of oxygen. "A known volume of the wastewater sample is refluxed with excess of K2Cr207 solution in sulphuric acid medium, in the presence of Ag»SOx and HgSOs. KCr07 oxidizes all the | ‘oxidisable impurities. Ag2SO, catalyses the oxidation of straight chain organic compounds, aromatics and pyridine. HgSO, avoids the interference of Cl ions by, forming. soluble complex with them. In the absence of HgSO,, Cl ions precipitaté silver ions as AgCl. The amount of unreacted K2Cr20; is determined by titration with standard Mohr’s salt (ferrous ammonium sulphate) solution. The amount of K2Cr20; solution corisumed corresponds to the COD of wastewater sample. To calculate the COD, a blank titration without the wastewater sample is carried out. Ferroin (1,10-phenanthraline ~ iron (II) complex) ised as the indicator in the titrati to detect the end point. The indicator is intense redsin colour. Strong oxidizing agents oxidi the indicator to iron (III) complex, which has a pale blue colour. [Fe (CiaHsN2)3]**+ eS» [Fe (Ci2HsN2) 3] ** Pale blue ae deep red As long as K2Cr20; solution is"present in the reaction mixture, the indicator is in the ‘oxidized form, imparting blue colounto the'solution. The solution becomes blue green as the titration continues due to the formation’of Cr (III) ions as a result of reduction of ‘Cr207* ions. When K2Cr20> is completely*exhausted in the solution and in presence of 1 drop of excess FAS, the oxidized form (Ee"*) Of the indicator gets reduced to Fe”” state imparting reddish’ ‘brown colour to the “Therefore, the end point is marked by the colour change from: blue-green to reddi The end point is sharp only at high acid concentration and i *pt at a very high acidity of H2SO;. n of Mohr’s salt is prepared by dissolving a known weight of the salt in a known volumé of the solution. A test tube of dil. H2SOs acid is added during dissolution’ {0 prevent the hydrolysis of the salt in the solution. The reaction between Mohr’s salt and K2CmO; can be represented as follows. K2CnO7 + 4H:S0s—> K2S0. + Cr (SO.) 3 + 4H20 + 3(0) [2FeSOs + H2S0, + (O) > Fe2 (SO4) 3 + H20] x 3 KCnO7 ¥ 6FeSOs + 7H2S0s > KaS04 + Cra (SO): + 3FexXSOgs 1 THO OEE ESO4 + TH2S Os “> KaSO4 + Cra (SO0)s + 3Fen(SOon + THRO os of standard Mohr’s salt solution: » the given Mohr’s salt and transfer into a 250em* volumetric flask. Add one lute sulphuric acid and add ion exchange water, dissolve the crystals. Dilute t r ‘water upto the mark and shake well ‘Bryn CAEChEN ‘cm? of the wastewater ‘ate solution followed by % ‘and titrate against standard Mohr’s salt: ‘brown. Repeat for the agreeing values. m out 10 cm? of standard potassium dichro i c mate | te Oh followed by 2-3 drops of feroin indicator hee a earl the colour tums blue green to reddish brown. mg/dm? : COD of given waste water is = A pcERVATION AND CALCULATION We part Az Preparation of Standard Ferrous ammonium sulphate (Mohr’s alt) solution a 4, Weight of bottle + FAS crystals w= : ¢ 5, Weight of empty bottle (Wo): = a (Wi-W2), (Ww) § Weight of FAS crystals, Normality of FAS, Nras = Back titration eer): Standard FAS solution amici fiask: 25 om’ wastewater sample + [0'em® standard KeCnO solution +% tt. LEE Sulphuric a Indicator 9.3 drops of ferrdin, iiigaist Blue green sortegtlighrOrown mL iB _ | Volume of FA‘ in cm? value given) , the volume of FAS consums od by unreacted KaCT207, ()=mg of O2 /drh* ‘of COD is, ppm of O2 = mg of O2/dm’.) ——-- m&ofQ2/dm?ng powder is a white powder consisting calcium chloride CaCl; [calcium chloride reacting calcium hydroxide or slaked lime, ching powder is ae industry as well as in domestic for d : 1 is used in sanitation to control bacteria, virus, algae and in Menile conditions are required. Bleaches generally iat ‘with aay ‘other organic” qoes; they can weaken or damage natural materials like fibers, cloth, ‘and leather. For ‘game reason, ingestion of the products, breathing of the fumes, or contact with skin or ‘ean cause health dam Chlorine, a powerful oxidizer, is the active agent in ; leaches. Since pure chlorine is a toxic corrosive gas, these products: HP gertsin hypochlorite that releases chlorine when needed. F f ae aL - chlorine is the amount of chlorine ately ‘a sample. Chlorine (Cla) is 7 bersted from bleaching powder when acetic acid i$ added to it, ic. ; Ca(OCl)+ 2CHsCOOH AERG}ECOO), + H20 + Cla IPblorine gas is a strong oxidizing agent, Poxidizes KI (taken in excess) in presence of acid. ‘and liberates an equivalent amount Piodine. CD 2KI — 2KCH* Ia FW This iodine can then be determihed by titrating against 2 standard sodium thiosulphate using: ‘| freshly prepared starch solution as an indicator. 2NaiS203 + kh + Na2SsOe + 2Nal the chlorine liberated from the bleaching powder and sodium, Ircacdiated by potassium jodide ean be obtained 2Na2S203 + Ch + 2KI—> NazSsOe + 2Nal + 2KCP Batic i cited near the end point mss not tte Ueesines iim iodide (KI) _ Leave it for few minutes. Titrate the liberated iodine against standard sodium | |} thiosulphate solution taken in the burette until the solution acquires a palé yellow color. Add. about 1 pinch of starch solution and continue titration drop wise until the blue color of the ‘starch iodine complex just disappears. Record the titre valuevand fepéat for the agreeing: OBSERVATION AND CALCULATION _ Part A: Preparation of the solution of the bleaching powder sample 1. Weight of bottle + bleaching powder (WI) = - 2. Weight of empty bottle \ (wa) Bh (ioe w= ~) Determination of mone in the above solution by iodometric titration a }s solution | Burette 2 St 2 Conical flask : te leaching powder solution + 1/4" tt acetic acid + 10cm® 10% KI few minutes) 2 (near the end point) > of blue colour000ce = B_X Equivalent wt, of Chlorine X 35.46 g(Z) ( felon in the given bleaching powder an eam ig powder is = it % of Residual chlorine in the given sample off reSTIMATION OF FAS USING STANDARD Por, DICHROMATE SOLUTION estimate the weight of Mohr’s salt dissolved in a litre of the given solution potassium dichromate solution. . potentiometric titration may be defined as a titration in which the end point is dete ; Eales Pema revAl oie ctistle cletieds (which responds tots chan concentration) during the titration. The electrode, which responds to the change in concentration the ion in the solution, is called the indicator electrode. The indicator electrode is combined with” Teferenee elecirode, (whose potential does not change during the tration) to form a cel and emf ge the so formed cell is measured during the titration. The emf of the cell changes gradually til ue equivalence point and changes rapidly at the equivalence point and again the change is gradual aes the end point. When emf Eis plotted as ordinate and the volume of titrant added. abscissa, the poi of inflection of the curve corresponds to the equivalence point ot end point Of the titration Aetier method is by plotting the first derivative curve, in which AAV is ploted aginst, ‘and the end point is obtained at the maximum of the curve. The Gitration of Mohr’s salt solution with K:Cr.O> in the fresnc® Of HsSO1 is a redox titration, 3Pe*+ Crh — 3FeC* The presence of oxidized and reduced form of thé same substance in a solution gives rise to the formation of oxidation — reduction electrode, develdpingvan electrode potential, which can be picked up by dipping a platinum wire. Thus, when the:titetion is commenced, both Fe” and Fe ions are present inthe solution, developing an electrod¢ potential, which is picked up by a platinum wire. Thue (PUFe™, Fe) is the indicator electrode, whose electrode potential is given by, 2303R7 |, [Fe] F [Fey Ttis combined with a reference Algetrode (calomel electrode) and the emf of the cell is measured. During the titration [Fe")}goes on increasing and (Fe*"] goes on decreasing as KsCuOy solution is added continuously, gradually changing the potential. Near the end point the ratio {Fe* VfFe*] increases tapidly,as [Fe*"] becomes very small, and tending to zero at the sod point. Thus. the emf increases sek close to the end point. When Fe”* is completely converted into Fe rode, ae by K2Cr0>, the (Pie, Fe™) ceases to exist. But the presence of slight excess KoChOr brings in existence Of (PUCr™ Cr") electrode, Thus after the end point, it i the electrode potential OF the (PuCr, Cr) electrode, which is going to change. Because of both the factors, ie. increase in the Feng HAFE", ad change of electrode from PUFe", Fe" to PUCY*, Cr’, there is a lange change in potential atthe end point. 2 Fala tt Of ferrous ammonium sulphate solution inio a beaker-using pipette, Add one Meanie tha cellute HsSOs. Place the electrodes in the solution and connect it te 4 potestometeh it lution. Add 0,5 em? of KCrsOy and bubble the rd the potential, continue the same procedure BY adding 0.5 em? of KCr:0, solution from bureite at a time and tabulate the readings. Determine the end point by plotting (AE/AV) versus volume as illustrated in figure Calculate the normality of the ferrous ammonium given solution. 4 Sulphate and the amount of iron present inthe JLaboratory Manual ‘(OBSERVATION AND CALCULATION: ay | strode potential E (em oe Volume of KoCr07 Caleutations: Vow, MOfFAS idm} = Nras X Equivalent weight of FAS z Neos 302 os een) a4o = 3 | Weight of FAS in 25 em? is———— © Point :2. COLORIMETRIC DETERMINATION OF COPPER given solution by colorimetie To estimate the amount of copper present in the Principle: Colorimetric analysis depends upon t colored solution. Quantitative analysis by can be expressed by the relation. og Iy/1,) = €¢ = A(Absorabance/OD) = intensity of the transmitted light, ¢ = thickness of the coloured medium, fhe measurement of quantity of light absorbed by Colorimetry is based on Beer-Lamberts law, which ‘Where, Io = intensity of the incident light, I concentration of the colored constituent in solution, € = and ¢ = molar extinction coefficient. bance or optical density of the light-absorbing The term, log (lo/I)) is called the abso: absorbatite changes linearly medium. Since ¢ is a constant and if thickness € is kept constant, with concentration at a specific concentration range. The ratio (IIo) is the transmittance, T of the solution: Therefore, absorbance, log (Io/l) = logio (1/T)==loBto T So, the same result can be obtained by plotting 1dg T against concentration also. Cuprie ions (Cu?*) react with ammonia to give a deep blue colour due to the formation of cuprammonium complex ion. Cut? + 4NHS%> TEu(NHS)«)” Deep blu A series of standard <6lutions containing cupric ions are treated with ammonia and the ‘absorbance of each these'solutions is measured at 620 nm (Amax, at which the solution shows maximum absorbance). Accalibration curve is obtained by plotting concentration against absorbance or logi/T'*Uliknown volume of the sample solution is also treated with ammonia) in the same wayeasvtlfe standards and its absorbance is measured. Its concentration is determined from the'ealibration curve. Procedure: Transfer the given copper sulphate solution (stock solution) to a burette and draw out 2, 4, 6, 8 and 10 cc of the solution into 50 cm* volumetric flasks. Add 2 cm’ of ammonia ‘solution to each of them and dilute up to the mark with ion exchange water. Stopper the flasks and mix the solution well. To the test solution given in 50 cm’ measuring flask, add 2 ‘em® of ammonia solution, then dilute up to the mark with ion exchange water and mix well. Prepare a blank solution by diluting 2 cm? of ammonia solution in a 50 em’ volumetric flask up to the mark using ion exchange water and mixing well. Measure the absorbance of the solutions against blank at 620 nm using a photoelectric colorimeter. Tabulate the reading & ‘CuSO; solution. Mark the absorbance of test solution (unknown volume) on calibration graph and find the volume of CuSOs present in the test solution. Dept. of Chemistry, SSATE, Bengaluru-60Vol. oftest soin. (0) ‘The weight of Copper in the given test solution = —_——— Volume of fest solution (X) = Se istry, JSSATE, Bengaluru-60___ Measurement of conductance can be employed to determine the end point of base titrations. When indicators are used, the end point is detected by a change in the colour. In conductometric titrations, there is a sudden change in conductance of the Solution near the end point. However, in the latter method the change of conductance jg not sharp. Hence the end point is determined graphically by plotting conductance againg, titre values. The principle underlying conductometric titration is the replacement of i Of @ particular conductance by ions of different conductance during the titration Conductometric method can be used for the analysis of a mixture of strong and weak acids upon adding a strong base to a mixture of strong acid and weak acid, the conduet falls until the strong acid is neutralized owing to the replacement of highly mobile H ign (conductivity 3509 'm~') by less mobile Na’ (conductivity 50Q*'ni-'), Then, conductivity rises as the weak acid is converted into its salt and finally rises more steeply as excess of alkali jy {introduced Which has free OH” ions (conductivity 198. Q"'m-'). A. graph of conductance against titre values is plotted. The curve has 2 equivalence points, The first equivalence point (A) corresponds to the amount of base required to neutralize the stronger acid, the difference of the tWo-equivalence points (B-A) cc corresponds to the-amOunt of base required to neutralize the ‘weak acid. Vol of NaOH — Procedure: Transfer 25 cm? of the given hydrochloric acid & 25 cm’ of given acetic acid into @ 100 cm* beaker. Fill a burette with standard NaOH solution. Place the co nductivity cell inside ‘the beaker so that the electrodes are immersed completely in the acid mixture. Connect the ell to the conductivity bridge and measure the conductance. Add 0.5 cm? of NaOH from the burette, mix the solution well. Measure the conductance of the solution (the conduetanee decreases), and continue measuring the conductance after addition of 0.5 cm’ of NaOH even time, fill there is a steep rise in conductance. Take a few more readings. Plot a graph Of conductance (ordinate) against volume of NaOH added (abscissa). Find the equivalence points.nm XV wonson a wei X Eqt. Wt. of HCI Sia X365 = yg (a) Vp-a) = Volume of NaOH consumed to | neutralize CHsCOOH, Nywon X Vow. V. | Nencoow =o | Wt. of CHyCOOH/ém* Nen,coonX Eatavtof CH;COOH. | co X 60 @e ’. Weight of CHsCOOH / 25 cm? = 4/40€ concentration is to be ever nt 5 [es fool and wir or oxypen ix uscd ax om ‘The whole analysis depends on the £ sample and dropict sve‘A2 (from \) _|_ erp in solution f Sodium in # give 7 = Weight of Potassium in 2 given solution > solution = Wt. of Sodium in g x 10°= Brx 10° = PPM Concentration of sodium in give olution = We, of Potassium in g x 10 B2x 10° = — ‘Concentration of potassium in given s ‘The concentration of sodium in the test solution is in the test solution is found to be ---PPM found to be -——--PPMWeak acid is a weak electrolyte and undergoes only partial dissociation in the solution. — For example, acetic acid when dissolved in water. Pahoa CHsCOOH «> CHsCOO" +H [CHsCOO™ } [H1*) The dissociation constant, Ka = [CH;COOH) pKa=- log Ka Higher the value of pKa, lower is the Ka value of the acid and therefore weaker is the acid. pKa value of a weak acid can be determined by the pH titration méthod. In this method a known volume of the weak acid is titrated against a strong. base, and pH of the solution is measured after each small addition of the base. During:thestitration, the pH of the solution increases gradually till very near to equivalence point and\there is a sharp increase in pH at the equivalence point. After the equivalence point the inérease in pH is again very gradually. Therefore the equivalence point is indicated by the sharp increase in pH. The equivalence point is determined by plotting volume of the base’ against ApH/AV, as indicated by the volume corresponding to the maximum of the curye. Once the titration is started, the solution contains weak acid and also its salt with strong base. Thus the mixture is a buffer mixture. The pH of such a mixture is given by Henderson's equation; : [Salt) pH =pKa + logio {acid} At half equivalen¢e point 50% of the acid is converted into salt, and therefore, [acid]= [sal]. Then pH pKa Therefore pH af half equivalence point gives the pKa value of the weak acid, Procedure Pipette out 50 cm’ of the given weak acid (acetic acid or formic acid) into a beaker. Connect the glass electrode to a pH meter, calibrate the pH meter, by dipping the glass electrode in pH 4.0 buffer solution (will be given), and set the instrument to read around 4.0 on display. Remove the electrode, rinse with ion exchange Water and immerse a glass electrode (combined glass electrode) into the weak acid. Measure the pH of the acid, Fill a burette with the base (sodium hydroxide). Add NaOH in the increment of 0.5 cc to the acid. Str solution thoroughly and measure the pH after each addition. Take few more readings fter the solution becomes alkaline. otiate y Plot a graph of pH (ordinate) against the volume of sodium hydroxide added Determine the equivalence point and hence the pH at half equivalence 7 ge of the acid, a aepKa= pH half equivalence (V2)(n) is defined as the force per unit area required to move a city difference past another parallel layer at unit distance away. he viscosity coefficient of a fluid is expressed in poises. The ‘given by poiscuille’s equation, pst shdgrtt 8V1 a a Where *V" is the volume of the liquid of viscosity edefficient “n', which flows in time |) Ae through a capillary tube of radius ‘r’ and length’/ under a pressure head of “P”- - P =hdg, h = height, d =density, g >aceeleration due to gravity | If equal volumes of two liquids are allowed to flow through the same capillary under identical "conditions. : 5 thd, gr*t svt dit, 7. Wie ahdyer't, yf, mined in Ostwald’s viscometer knowing the .d water and also knowing the viscosity coefficient of water, Viscosity siculated. Since viscosity is dependent of temperature, the experiment lias Wii be carried out‘at e6iidtant temperature, Therefore viscometer should be dipped in a jar eenlaiaii Sater in such a way'that the mark above the upper bulb is always below water, so that, the Haul E¥el fs Inside the viscometer is inside water. Small variation in atmosphere temperature will not be felt whtes The flow times for the liquid and water det “the viscometer is inside the water, dure Clean the given viscometer with water, rinse with acetone and dry it. Fix the viscometes Jastand. Transfer a known volume (say 20 em') of ion exchange water into wider limb. Suck it 1 flow freely through the capillary. When the level of Wg/cm miflipoisétm..) Doan —— millipoise nillipoise.ESTIMATION OF TOTAL HARDNESS OF WATER COMPLEXOMETRIC METHOD. it the given EDTA crystals accurately into 250 cc volumetric flask, dissolve in jon nge water and add few drops of ammonia, dilute upto the mark, mix well. Weight of EDTA X4 Mol.weight of EDTA (372.24) : Standard EDTA solution +: 25cc hard water sample + 3cc buffer solution (pH-10-11)(NHsOH-NEACI) : Eriochrome black ‘T” : Wine red to blue om the volume of EDTA consumed, calculate the total hardness of the-given water sample, Molarity of EDTA = 2. ESTIMATION OF CaO IN CEMENT BY RAPID EDTA METHOD. Weigh out the given EDTA crystals accurately into 250, ce, Voluinetric flask, dissolve in ion fe water and add few drops of ammonia, dilute upto the mark, mix well. WeightofEDTAx4 Molaveight of EDTA (372.24) standard EDTA solution. 5 ce cement solution + 5.cc glyéerol +5 cc diethylamine +10 cc 4N- NaOH atton & Reedor’s indicator Colour Change: Wine red to blue | From the volume of EDTA conSumed)icalculate the percentage of calcium oxide in the given cement sample. Molarity of EDTA 3. DETERMINATION'OF PERCENTAGE OF COPPER IN BRASS SOLUTION USING'STANDARD SODIUM THIOSULPHATE SOLUTION Transfer the gi Solution of brass into a clean 250 cm* volumetric flask, dilute upto ‘the mark sane a change water, shake well. Pipette out 25 cm? of this solution into a “conical flask and add 1 gm of urea (approximately 1 spatula), boil for two minutes & cool to. ym temperature. : Std. NagS:03 G-B7-p 9? f + Brass solution prepared above + NHOH till slight ppt. + 4 tt. CH;COOH to. dissolve the ppt. + 10 cm’ of 10% KI + | tt ion exchange water. “ : Starch — added towards the end point. 2m’), : Disappearance of blue colour. F of Na:S:01 consumed, caleulate the percentage of fol 22 ie ieee25 ec Hiacmatite ore solution + 5-6 drops of Cone. HCI, boil:+ SnCls ‘wise till colorless, add two drop excess, cool + 1 Lt ion exchange Matt. HgChe = Ks[Fe(CN)6] ~ —external §. DETERMINATION OF CHEMICAL OXYGEN DEMAND (COD) OF THE GIVEN INDUSTRIAL WASTE WATER SAMPLE. ‘volumetric flask. Add 11.1. dil. H2SQ,, and small amount of-ion exchange water, dissolve the ‘crystals, dilute upto the mark and mix well. Normality of FAS = “Burette _: Standard FAS solution ‘Conical flask: 25 ce waste water sample + 10 ce K2Cr20> (pipette out) + % tt. of 1:1 H2SOx, i :Ferroin ‘Colour change: Blue green totediish brown Perform the blank titration in the same way as above but without wastewater From the difference in the fitre values calculate the COD of waste water sample. .\CENTAGE OF AVAILBALE CHLORINE IN THE GIVEN BLEACHING POWDER (IODOMETRIC METHOD). 3 of the bleaching powder sample and transfer it into a cleaned ‘Aaid little water and rub the mixture into @ smooth paste. Add some more water and with the pestle, allow the mixture to settle and transfer the milky liqui ‘Volumetric flask. repeat the operation until complete sample has been transferred to the fl ae i + Standard Na;S20) solution [flask : 25 cm’ bleaching powder solution + 1/4" tt acetic acid + 10cm! 10%Lens SOLUTION cm’ of given FAS solution r, add one test tube full of dil the calomel (reference) and electrodes. Connect this to a ‘and measure the potential (E). ement and measure the potential after each |, Plot a graph of AE/Ay Or. Determine From the normalit against th lence point 2. COLORIMETRIC DET ut 0, 2, 4, 6, 8, 10c mate into a separate i Add 2ce of NH And also into anot iaining the test solutio gentration. Dilute well. Prepare the blan diluting 2cc of NH solution in Pflask and shake well sorbance of each of these solutions 2 ‘blank solution at 620nm. Plot a inst voloof CuSOs and ihe the conc. of CuSO% in the test upto th aph of 3. CONDUCTOMETRIC EST ‘Transfer 50 cm’ of the given mixture into & 100 cm’ beaker. Fill a burette with standard Place the conductivity cell inside t the electrodes are immersed . Add 0.5 cm! of NaOH from the the solution well and measure the ‘of the solution (the conductance ‘measuring the conductance N time, till there IMATION C NaOH SOLUTION K2CrO:, calculate the normality and the amount of FAS, in the given solution. h equivale ee ERMINATION OF COPPER ACID MIXTURE USING STANDARD NaOH, find the normality and amount of HCI & CH,COOH in the given solution.INATION OF pKa OF A WEAK AC KD USING @ Of the given weak acid into a clean b aker, Immerse the glass g mbly into it. Connect th M the burette in increments of 0.5 jet and measure the ce-and the pH afer each ition of NaOH till alkaline pH and then take fume Of NaOH and determine th W more readings, Plotay alence point. Plot another SENAOH and determine pKa value of the pH METER SCOSITY COEFFICIENT OF A GIVEN LIQU OSTWALD’s VISCOMETER Of the viscometer and suck the liquid thro 2 fixed Points, one above and one below. calculate the average x into the wider limb and det ty of the liquid and of water: MBiven liquid,fdimolving » known weight of i me of sotvent WB) Define equivalent weight of »b A defined as thc base, which An acid. Equivate 2NaOl + 1.80. IBauivaten: weight of Naot 4) What is basicity of acid? Te i defined as the by. one fin aqueous sok liydrogen atoms in onéolecule of an | migightof acid §) What is acidity of base? This defined as the power ofthe base to neutralize fan acid. It is measured by the number of ‘OH jons present in one molecule of Base of in olher wards the number of hydroxy! ‘by one molecule of the base in sits acidity. solute dissolved in Tp (1000 g) of the solvent. eX 1000, mixture of | or a weak \d. Ex.CHsCOOH H & NELCL 10) What are Indicators? i ances indicate the 1 sharp color change 11) How many types of indicators have you used? Give examples o each, Typ is, Ex: Starch, Methyl orange, Potassium ferricyanide Self indicator, Ex: potassium permanganate, Metal ton indicator, Ex: Eriochrome black- T indicator 12) Define equivatent weight of oxidizing agent. Equivalent weight of oxidizing agent isthe parts by ‘scight of oxidizing agent, which contains 6 parts bby weight of available oxygen. eene agent is titrated against an oxidizing versa. Redox titrations include N-CH-Cl-N CH:COOH Eas Re ites Serine ine Petuaawsicrsreor ‘Temporary Hardness: ‘ Dreserce of soluble Biearbonates of Ca, Mg is called temporary hardness. It is removed by boiling. Permanent Hardness: - hardness of water due to | presence of soluble chlorides, sulphates of Ca, Mg is called permanent hardness 7) What is total Kardness? The hardness of water caused due to both temporary. and permanent hardness is called total hardness, 8) Why is soft water preferred? It does not form scales on utensils, form lather with soap, $0 itis economical 9) How is total hardness expressed? Total hardness is expressed in PPM or parts per million of CaCOs, 10) Write the meaning, the total hardness of a given sample of water is 1500 ppm of CaCOs. 1500 parts of CaCO; equivalent hardness in 10° ee: of water 11) Why is total hardness expressed in terms of cacos? 1) Caleulation is easy as molecular weight of CaCOs = 100, 2) Universally accepted. 3) Most insoluble in water. 12) What is the indicator used in determination of total hardness of water sample? Eriochrome Black ~ T indicator.1 ig?” complex. Towards the EDI Ee oplees lndiea i te ecanbie complex. Hence free indicator is the end point which is blue color i ms Gs + EDTA ———. EDT A.Ca stable complex In (pHt-10) (blue) d complex (colourless) ESTIMATION OF % CALCTUM OXIDE IN CEMENT 1d cement Nomenclan Ca ALO: Fe.0: Meo SO: K.08& Nao CaSO | What Is the pH you maintain in the estimation Jn cement?-Hlow? What is the role of 14. ‘ig added to furnish OH: ions, which react esiuin fo form ppt. of Mg(OH) at pH12- 3. ESIMATION OF % COPPER IN BRASS 1) What i brass? Brass ian alloy of Cu & Zn. It also contains small smount of Pb, Sn & Fe. Cu(S0- 90 %), Za20-45 96), Sn (0.6%), Pb (0-2%), Fe (01%) ) What is an alloy? Give any two examples. neous mixture of two OF More: in, bronze. al hom nctals or non-metals Eg. Brass, du 3) What is ore? Give two examples. Naturally occurring mineral form which metal ean be extracted economically is called ore. Bx: Haematite, magnetite, bauxite. 4) How is brass solution is prepared? It is prepared by dissolving the brass sample in minimum amount of 1:1 HNOs. To tis urea is added to expel the oxides of nitrogen present in the flask and wo destroy excess HNOs 3Cu + 8HNO; —> 3 GuNovet OF NOT Reddish brown fumes '5) Why is Urea NHLOH, CHsCOOH & KI a ‘to brass solution?on adding KI due to liberation 'NasS:05. => 2Nal + NasS.O, fi) L: gets adsorbed on colloidal starch this will not react with Na:S:0s, “0 fetting adsorbed is more when Ty concentration high. - 10) What is the colour change of starch fodine complex? What is the colour change at end poin Deep blue is the colour of starch ~ iodine complex, End point is blue to colorless leaving behind white ppt. at end point 11) What is the white precipitate left at the end? Cust. Cuprotistodidé 12) What are the Oxidation states exhibited by: cu? Co), Cuprous, Cu —> Cuprie 4. ESTIMATION OF % IRON IN HAEMATITE 1) What is haematite? Write the constituents, Haematite is an ore of iron, It contains FesOs & small amount of SiO» with impurities like S, AS). 2) What is the role of SnCl:? Since Fe’* does not react with K:CrOr, (sinee, 3+ is the stable oxidation state of Fe which cannot be further oxidized) Fe’ is reduced by using ® reducing agent SiC 2FeCh + snc; —Hsl 5 2 Fech, + Snel (Fe) (Fe) 3) What happens when excess of SnCh is not removed? . It reacts with KsCr0, and excess K.CrzO> willused as Fe(CN)4] combines irreversibly with Fe® ions Mo give deep blue coloured ferroferricyanide Eomplex. Ifthis is added as an internal indicator the jon mixture turns into blue due to the ormation of ferriferrocyanide complex. As this is D reversible, end point cannot be determined (blue tolour persists even after reaching the end point), Further, Fe ions involved in the formation of {Complex will not be available for the reaction with K:Cr0; 9) What is colour change at the end point? The indicator undergoes no colour change 10) Why indicator drops fail to produce blue colour at the end point? ‘here are no Fe ions left at the-eid point as they re completely oxidized to Fe!” Indieswor does not ‘eact with Fe’” ions. 48) Why potassium févneynbide cannot be wed Bacuser, ( Frcs nga pe th Fo Fern Be Be comteed end pot cannot be feralbed 12) What is the role of 1 tt H:0 added after the formation of silky white ppt. HO js added to dilute the reaction mixture. To the end point of the titration, a glass rod is ed in the reaction mixture, ferous ion stick to rod whieh are taken Out from the conial ‘brought in contact with indicator drop. ror is introduced; to minimize this error sis diluted so that small amount of ons are removed fm the rection mist, sample doesn’t reat with the standard: performed by taking excess of another reagent hich can rect wih the sample a the sini solution. : 2) What is blank titration? Since the back titration gives the amount of reagent left in excess and not the amount of reagent used up by the sample, blank titration is performed i ‘same way as the back but without using the sample Difference between blank and the back titre values. tives the amount of reagent used 3) Define COD & BOD, Chemical Oxygen Defnand, (COD): Amount of Os required to oxidize “eompletely _ biologically oxidizable and biologieally inert substance in 1000 ce of wastewaterssample using strong oxidizing agent like acidified KxCr:O- 4 Biological OXygeh Demand (BOD) isthe amount oF dissolved oxygen consumed by the microorganisms forthe biological oxidation of the organic matter in 1 Titer of wastewater under aerobic condition at 209C for 6 period of 5 days. 4) Why is COD toad always greater than BODE BOD. isthe oxygen demand of biologically bllable substance wherever COD, fs. oxygst omand of both biologally oxidisble” and biologically inert substaee, Henee COD is greter than BOD, . 5) Why is 1 H:S0s added to (© prepare FAS solution? ‘To prevent hydrolysis of FAS. Inthe absence of feidic medium, Fe(OH» fom which Brown on odation 1 FOH)s i, Sulphuric ‘oxygen for oxidation in acidic m ii, Silver sulphate acts as the jon reaction of organica disinfectant which is ‘make potable water. 6 What happens when bleag Kept in ain : bleaching powg es Bleaching foreddish brown, | from the atmosphe jhate complex) | and chlorine. 7. Why bleaching powd treatment? powde it hypochlorous acid (HOGI) gq (OCK). HOCT kills. pata ‘ruses by breaking ales ses ferric complex to lich is reddish brown, | 8. Which is the indicator Starch What type of titration is this? Todomettic titration 1. POTENTIOMETRIC IRON 1) What is Potentiometric estimation? Potentiometric titration is an analy n Which the change in concentration of ions if Teactions is determined by a change of leet potential 2) What is the principle of potentiome titration? : ferst equation : 2.303 RT /nF lox [M"]jon begins [Fe] increases and [Fe™'] igs a result emf increases (Since E a fe"}) At the end point potential is rd? + Ecaor2. (since [Fe ] = 0) 7.V. Hence there atthe end point. ‘the end point there is gradual Wisince [C1307] increases. are the electrodes in potentiomete jlomel electrode (reference tum electrode (indicator electrode) electrode) and Why is platinum electrode also called electrode? he susceptible to the concentration of idus jin the solution. So the ch ‘ofions affect the potential devel fielectrode and it is indicated, by the -dyindicator ESTIMATION OF 1) What is co analysis? The study of in intensity of «given coloured solution with the change in concentration | of the given coloured compound in visible region is ‘alled colorimetric analysis, 2) States Beer's Law, Lambert's tay, Beer ee t's Ia, Beer ‘Transmittance it is faction of through the medium. I transmitted ight to the intensity of light = Wo Absorbance or optical density is. the logarithm of the reciprocal of transmittance, z is path Iength taken as constant in the Guim eoicentrion of the solution can Be Uetermined by comparing the optical: density of Solutions of Known concentration, only when! tie path length is constant. (Beer's law). | 5) what is the complex. formed, when NH3 shiution is added to the CuSOx solution? Cuproammonium Sulphate, [Cu(NHs)J80s. Dee blue in colour. 6) Why are different volumes of solution taken in flasks? ‘To plot the calibration taken, only one point teteSpiained the graph makes it impossible 10, ‘raph. If only one volume is ‘is obtained on the graph and sculate the Cu" concentration is unkriown Sotation which is to be calculated from the graph. Celibration curve is the graph of absorbance against ‘concentration of solution. 7 +7) Why is Ammonium is added? Why is 1¢ that The same amount of ammonium is added and the ‘at the same time? *E (volt) and resistance, R (ohm) of 8) What is specitic conductance? {is the conductance of a solution fo lectrodes of | cm? area ander ‘em ap ©) What is equivalent conductance? Itis the conductance 1-gram equivalent o two electrodes of 1 ofthe solution, which g f solute, When placed fy empir. I= ky 1006 om equivalent of so > Normality of solution 19) What is motar cond It's the conductance ofa solution which cout Boarimolecular weight ofa substance, whew esween two clectrodes of | em apart mel 11) What i mnitevice, which produces an electromotive fi and delivers an electric current as the resilf Bi chemical reaction is known as a eell, eetro chemical cell? 12) What fact Solution? Two factors dex Solution are 1) Mobility of ions (higher the mobility, the conductance and) fors determine the conductance: mining the conductance 2) Number of ions (more the number of Solution, more is the conductance)Wery Weak acids such as 11sBOs, phenol, which be titrated potentiometrically in ons, ean be titrated conductometrically an be titrated mor aqueous yecuratel; ce point obtained in the progress of the titration, chai ivity occurs. The conductivity ach addition of a small volume of ‘A graph of conductivity (on Y-axis) versus J Volume of titrant (on X-axis) is plotted when UMore straight lines are obtained. Th imersection of the two stra "equivalence point. fines gives the 16) In the titration of a mixture of acids (HCI COPE oth» strong bse (NaOH) the ance first decreases, then rises ste: finally rises steeply. Why? adding a strong base to a mixture of a strong jand a Weak acid, the conductance falls. duc,to conductance falls tillall thesH ions are till HCl is neutraliged. completely) e then riseS steadily as the weak Is sally conductance of the tance of weak acid steeply as excess of highly mobile O1F ions, emission, and for atoms excited called atomic fluorescence, for es | called fluorescence if the transition is bety states of the same spin and phosphorescence transition occurs between states of different spin. 2) What is flame photometry? Flame photometry is an atomic emission method for the routine detection of metal salts, principally Na, K, Li, Ca and Ba, Quantitative analysis of these species is performed by measuring the flame cemissi 1g the metals salts. Solutions are aspirated into the flame. of solutions containin 3) What are alkali and alkaline earth metals? The elements of the ITA group of the periodic table Be, Mg, Sr, & Ba are called alkaline earth metal 4) What are the various eyents that occur when a solution containing metal atom ion atomized through a flame? In flame ‘photometry, the following sequence of akes place 1) Aspiration of liquid sample (Containing element), into, flan 2), Formation and evaporation of liquid droplets resulting in the formation of residue, 3) Decomposition of residue into neutral atoms. 4) Excitation of atoms and emission of radiation from atoms, 5) Measurement of wavelength and intensity of emitted radiation by flame photometer. 5) What are different components of a flame photometer? An atomizer, the burner system, an optical system, photocell, amplifier, and recorder. = 7) What is the role of filter in flame Permits only the radiation element under investigation. 8) What are a© partial ly in aqueous solution, THRO © CH.COO-+ 11,0" Tis a measure of x strength of acid, 8 base jy added to a weak acid? Neutralization giving salt and 11.0, HCOOH + NaOH ——> CHCOONa + y 9 How is the end point determined? By plotting a graph of ApH/AVy base used. of the titration eainst volume of 10) What are the determination of pKa Combined electrode (I; electrode electrodes used in dhe calomel assembly) 1) How do you find pKa trom graph? BY finding the halt equ v Point and the pH corresponding to it 12) Why PH pica at hatr equiv alence Athalf equiy Valence point [Salt] point? Therefore, BUS PKa. sinc Henderson's equation redusey ned for strong acids comple the tangential fee per unit ares saany (aiMLN a unit Velocityay ee Ea es 4 | © 5) Why do you require ‘Volume of the liquid, r= radius of the be, 1 = length of the tube, P = hydrostatic essure of the liquid. — = coefficient of Unit of nis NS'm* (SI) dyne sem? (C Unit of viscosity is stoke ic. m/s, #) What are the factors that affect the viseosity D) Temperature 2) Molecular weight 3) Nature of “the liquid (Polar or non-polar), lab temperature for ‘iscosity experiment? 3s a result the viscosity decreases with 6) Why should the viscometer be dry. measurements of time flow are 8 acetone is used for rinsing the viscometer? Liquids form emulsion with water droplets the viscometer is not dry. Hence, time flow changes for emulsion and gives eros in values Acetone Bas ow boiling point (highly volatife tiquid), So itis ta for tnsig the vscoreet so tl vapors quickly leaving the apparatus dry: