CY 1204: Chemistry Laboratory Manual rete wrehhrant eer freaks TIRUPATI Department of Chemistry Indian Institute of Technology Tirupati Tirupati - 517 506 2021-2022FOREWORD In the 21* century, sustained efforts on new innovations and developments in materials science and technology have made and continue to make remarkable contributions to the needs and material comforts of our society. Understanding and learning the underlined chemistry of materials at the fundamental level primarily plays an unprecedented role in advancing modem science and technology-based innovations. In this regard, laboratory experiments provide an efficient and effective hands-on learning environment. Experience of experimentation is a delightful way of appreciating concepts and consequences of chemistry and its applicability. The experiments included in this manual have been carefully designed and developed by a dedicated team from our department with a view to providing an opportunity to the young and enthusiastic first-year undergraduate students, a taste of experimental chemistry, its range, variety, principles underlying in them and utility value. We thank profusely the entire team of colleagues who always work hard to reach out this goal. We wish all the student participants a useful and an enjoyable experience in learning chemistry through practical experimentation and demonstration. Department of Chemistry iiContents Expt. - Page No. Title No Cyele -1 T Quantitative analysis: Gravimetric estimation of nickel(I | 1 as dimethylglyoximate complex 2 Volumetric analysis: Preparation of potassium bis |5 (oxalato)cuprate(IT) dihydrate complex and volumetric estimation of oxalate content in the complex 3. Water Quality: Hardness in water by complexometry 9 7 Organic synthesis: Preparation and purification of aspirin — | 13 an analgesic drug Cycle— I 3. Selective extraction: Extraction of caffeine from tea leaves | 17 6. Cororimetric estimation: Copper content in Brass by |21 colorimeter 7. pH & Conductivity meter: Acid strength of citrus fruit [25 juices by pH meter and conductometer 8 Reaction Kineties: Ester hydrol 29Laboratory Safety: “Safety FIRST, Rest is only NEXT” Personal Safety Practices > If anything gets in your eyes or skin or clothes, immediately rinse with plenty of water and notify to your supervisor. > Dress appropriately on lab working day, tie back long hair and don’t wear dangling jewellery. In the event of Fire: 1. Leave the building immediately 2. Never use lifts, Wash hands before leaving the lab Fire safety (know the locations) Emergency shower Eye wash fountain Fire extinguisher iiiHazard Symbols (to be used in pictograms for substances of the particular class) 6 Emits Flammable Gas Organic Peroxides FLAME OVER CIRCLE—USED _|FLAME—USED FOR THESE |EXPLODING BOMB—USED FOR [FOR THESE CLASSES : |cLasses: ITHESE CLASSES: Oxides + Flammables + Explosives + Self Reactives + Self Reactives + Pyrophorics * Organic Peroxides + Selt-Heating ° ‘SKULL & CROSSBONES—USED |CORROSTON—USED FOR THESE [GAS CYLINDER—USED FOR FOR THESE CLASSES: (CLASSES: |THESE CLASSES: = Acute toxicity (severe) * Corrosives Gases Under Pressure HEALTH HAZARD—USED FOR [ENVIRONMENTAL HAZARD— [EXCLAMATION MARK—USED "THESE CLASSES: |USED FOR THESE CLASSES: [FOR THESE CLASSES: = Carcinagen + Environmental Toxicity *Trritant Respiratory Sensitizer + Dermal Sensitizer Reproductive Toxicity + Acute toxicity (harmful) + Target Organ Toxicity Narcotic Effects = Mutagenicity + Respiratory Tract Imitation Aspiration Toxicity ivKey Instructions (Strict adherence required) Y Lab dress is a must [lab coat(full sleeve), proper dress, safety goggles, shoes, hand gloves and head mask (if required)]. < Know and plan your work (If not known, ask first to know), < Know location of the safety devices [Eye wash fountain, shower area, fire blanket and fire extinguisher). Eating, drinking and smoking - strictly prohibited in the lab. No food is allowed to be stored in the lab refrigerator. No running around and cross talks in the lab. SARK Report any unsafe practice of your labmate immediately without any hesitation to prevent damage. < Never leave your work unattended in the lab. < Keep fume hood and your work area clean always and maximize your work space. Y Lab waste disposal should be proper and as per instructions [not into sink or drainage!!]. Y Never work alone in the laboratory. Y Mobile phones and music headphones are strictly prohibited in the laboratory.Experiment: 1 QUANTITATIVE ANALYSIS: Gravimetric Estimation of Nickel (II) as its Dimethylglyoximate Complex Aim: To quantitatively estimate the amount of Ni?! ions in the given sample by gravimetric method. Principle: Nickel ions form stable chelating complex with dimethylglyoxime (DMG). Amount of nickel ions can be estimated by precipitating with DMG as Ni?’-DMG complex. A~™ i Net + 2 ou dil. NHy OH DMG Glasswares/Apparatus required: Analytical balance Beaker (500 mL) with glass rod (1 no.) Pipette (20 mL, 1 no.) Watch glassMeasuring Cylinder (10 mL, | no.) Sintered crucible Dessicator with anhydrous CaCl, Chemicals required: DMG solution (1% in absolute ethanol) (10-12 mL) 1:1 Hydrochloric acid (6 mL) Ammonia solution (dilute) (25 mL/excess) 1:100 very dilute ammonia (for washing) Procedure: Nickel is precipitated by the addition of an ethanolic solution of 1% dimethylglyoxime (DMG) to a hot, faintly acidic solution of the nickel salt and then adding a slight excess of dilute ammonia solution(1:10) (free from carbonate). The pink/purple colored Ni?*-DMG complex precipitate is filtered, washed dried and weighed for constant weight. 1. Transfer exactly ~20 mL of the given unknown nickel solution into 500 mL beaker using a pipette. Cover the beaker with a watch glass. 2. Add ~S mL of 1:1 HCI and dilute it to 200 mL, 3, Heat the solution to ~70-80 °C on a hot plate, add a slight excess (~ 12-15 mL) of the dimethyl glyoxime reagent and immediately add dilute ammonia solution with constant stirring until precipitation takes place. 4, Allow this to stand on hot water bath for 15 minutes. 5. Cool to room temperature and filter through pre-weighed G-3 (pore size = 15-40 microns). 6. Sintered crucible (empty weight of the crucible to be taken first using analytical balance only).7. Keep the sintered crucible in the suction setup and wash it by draining ~20 mL of very dilute ammonia (1:100) solution through it by applying vacuum, Then transfer the precipitate quantitatively into the sintered crucible carefully without any loss. 8. Wash the precipitate with very dilute 1:100 ammonia and then with cold water (Use minimum amount of water). 9. Dryit at~110-120°C for 30-40 minutes. 10. Cool the crucible in dessicator and then weigh the crucible with precipitate, Repeat until constant weight is attained 11. Weigh the complex Ni(CsH;02N2)2, which contains 20.32% Ni**.Experiment: 2 ‘VOLUMETRIC ANALYSIS: Preparation of Potassium Bis(oxalato)cuprate(II) dihydrate Complex and Volumetric Estimation of its Oxalate Content Aim: To prepare potassium bis(oxalato)cuprate(II) dihydrate and determination of its oxalate content by volumetric analysis. Principle: Copper(II) is precipitated as its bis oxalato complex by the addition of hot aqueous solution of sodium oxalate (NaxC:0,) to a warm solution of CuSO,.5H20. In the oxalate complex, the oxalate behaves as a bidentate ligand and the complex remains in dissolved state at higher temperatures and on cooling it to < 10°C, precipitation occurs. In acid solution, permanganate, MnO [Mn(VID)] is reduced to Mn(II). The half reaction is: MnO, + 8H” + 5e" - oMn@* + 44,0 Eo=451V In basic or neutral solution, permanganate, MnO [Mn(VIN)] is reduced to Mn(IV). The half reaction is: MnO, + 4H* + 36° ——» MnO, + 240 €°=059V Sodium oxalate or oxalic acid is often used to standardize permanganate. The relevant half reaction is:6,0, ——~ 2002 + 26° £°=-0.49V Therefore the reaction with permanganate is favourable, i.e., 2Mn0, + 56,02 + 16H* ——> 2Mn2* + 10.602 + 8H,0 E°=1.02V Reaction scheme: Cuso,. 51,0 + 2 K*-o, —_——_—_> OK ° Potassium oxalate potassium bis(oxalato)euprate dinydrate Glassware required: Beaker with glass rod (100 mL, 2 no.) Sintered crucible (G-3, 1 no.) Conical flask (250 mL, 1 no.) Burette (50 mL, 1 no.) Chemicals required: (Note: use only preparative balance) Copper sulphate solid (2 g) Potassium oxalate solid (6 g) Acetone (for washing) Sulphuric acid (4N) - 10 mL Potassium permanganate solution (0.05N) — 100 mLProcedure: 1. Dissolve ~2 g of CuSO4.5H20 in 5 mL water and heat the solution to 70 (use preparative balance to weigh the starting materials). 2. Ina separate beaker, add 6 g of K; C20¢.H20 to 20 mL of water and heat the contents to dissolve completely, 3. Add slowly, warm solution of copper sulphate to oxalate solution with slow stirring and then allow the hot solution to cool. 4, Filter the precipitate through a sintered (G-3) crucible and wash with ice cold water (5 mL or minimum), followed by ice cold acetone. Dry the product at 60-70 °C (for about 20 minutes) in a hot air oven. Analysis: 1. Weigh accurately about 0.1 g (use analytical balance) of the dried copper oxalate complex and transfer into a conical flask. 2. Add 10 mL of 4N H2SO,, dilute to 50 mL and heat the contents of the flask to boiling. 3. Titrate the hot solution with 0.05N KMnO, and note the end point which is the appearance of permanent pink color. 1000 mL INKMnO, = 44.01 g of C:0,7" » 4401 in04* Vimo % oF C,0,7" in complex = T0007 7 x 100 W. = Weight of copper oxalate complex taken; Nxwnos = Normality of KMnOy; V kaos = Volume of KMnO4Experiment: 3 ORGANIC SYNTHESIS: Preparation and Purification of Aspirin — an Analgesic Drug Aim: To prepare aspirin (acetylsalicylic acid) from salicylic acid using acetyl chloride and pyridine. Principle: The synthesis of aspirin is an example of esterification reaction. Salicylic acid is a phenol as well as a carboxylic acid. It can therefore undergo two different types of esterification reactions, creating an ester either with the hydroxyl group or with the acid group. In the presence of catalytic amounts of sulphuric acid, acetyl chloride reacts with the phenolic OH of salicylic acid because of its neucleophilicity to form acetylsalicylic acid (aspirin or ASA). Reaction: on ococh, c0,H RL Pyridine CO,H yc“ ~c| Cone. HzS0, Salicylic acid Acetylchloride Acetylsalicylic acid Glassware required: Erlenmeyer Flask (100 mL) Measuring Cylinder (25 mL) Measuring Cylinder (10 mL, I no.) 9Measuring Cylinder (5 mL, 1 no.) Beaker (50 mL) Graduated Pipette (1 mL) Chemicals required: (Note: use only preparative balance) Salicylic acid (1.0 g) Acetyl chloride (2.0 mL) Pyridine (2.0 mL) Cone, Sulphuric acid (0.1 mL) Ethanol (10 mL) Procedure: 1. Take 1.0 g of salicylic acid in a 100 mL. Erlenmeyer flask. 2. Add 2.0 mL of pyridine to dissolve the salicylic acid and keep the flask in an ice-bath (just to cool, avoid precipitation) inside the fume hood, 3. Add dropwise 2.0 mL of acetyl chloride to the dissolved salicylic acid with stirring, then continue stirring for about 10 min using a glass rod (addition should be done inside the fume hood). Add 0.1 mL (2 drops) of conc. H2SOzto the solution and stir the reaction mixture for another 2 min. 4, Add 15 mL of cold distilled water to the reaction mixture and heat to 60 °C on a hot plate for complete dissolution (careful heating, don’t tum it to brown or yellow). 5. Cool to room temperature, Keep the flask in an ice-bath until crystals begin to form. Filter the mixture, wash the crystals with cold distilled water and dry between pieces of filter paper. 106. Transfer the crystals into a 50 mL beaker. Add 10 mL of ethanol and 10 mL of water. Heat the mixture until all the ethanol evaporates (volume reduced to half). 7. Cool the solution to room temperature and keep in an ice-bath so as to induce crystallization. 8. Filter the solution. Wash the crystals with cold distilled water. Dry the crystals between pieces of filter paper, weigh and calculate the % yield. Hints: motes of reactant i. Theoretical yield = moles of reactant x (“22 ot reece) x MW of Product Actual Wt. of product obtained Theoretical yleld ii, % Yield x 100 11Experiment: 4 WATER) QUALITY: Hardness in Water by Complexometry Aim: To determine the permanent and temporary hardness of the given water sample by complexometric titration using standardized ethylenediaminetetraacetic acid (EDTA) as titrant. Principle: Sodium or potassium salt of EDTA form a highly soluble 1:1 chelated complexes with most metal ions, binding through four oxygen Q and two nitrogen atoms (as shown in figure). Water hardness is nothing but a measure of the amount of calcium and magnesium salts dissolved in water. Calcium and Magnesium ions develop wine red colour with Eriochrome black-T (EBT) indicator in aqueous alkaline solution (pH 10.0 + 0.1). Thus, the water hardness can easily be determined by titrating the water sample with EDTA in alkaline condition. Hence when EDTA is added as a titrant, these divalent Calcium and Magnesium ions get complexed resulting in sharp change from wine red to blue which indicates end-point of the titration. Cat + EDTA* ——___» CaEDTA” Mg”! + EDTA* ————» MgEDTA* 13Glassware/Apparatus required: 250 mL conical flask (1 no.) 50 mL burette (1 no.) Measuring cylinder (100 mL) (1 no.) 20 mL pipette (1 no.) Funnel (1 no,) and filter paper Chemicals/Solvents required: Standard Zn$O4 solution (20 mL each time) Na2EDTA (~100 mL) Buffer solution (pH = 10) (2 mL) Eriochrome Black-T indicator (EBT) Procedure: Part I: Standardization of EDTA Take exactly 20 mL of standard ZnSO, solution provided into a clean 250 mL conical flask. Add 5 mL of buffer (pH 10) and 2-3 drops of EBT indicator which turns the solution to wine-red colour. Titrate the standard ZnSO, solution with EDTA, the colour change from wine-red to blue is noted as the end point. The titrations are repeated at least two times to get the concordant values. The molarity of EDTA solution is calculated from the formula; NiVi = N2V2 Where N and V refer to normality and volume, respectively. Part I: Total Hardness: Temporary Hardness + Permanent Hardness Pipette out 20 mL of the given water sample into a clean conical flask, add 5 mL of the buffer solution (pH 10) and 2-3 drops of EBT indicator. Titrate the wine-red solution against EDTA solution taken in a burette, till the contents of 14the conical flask turn to blue colour without any reddish tinge. Note down the volume of EDTA Repeat the titrations atleast two times to get concordant results. Let the volume of EDTA used be V; mL. The total hardness in terms of an equivalent amount of CaCOs is calculated using the following relation: 1 mL of 0.01 M EDTA = 1.00 mg of CaCO; * Boil the remaining water sample on a hot plate for 15 min, cool it to room temperature and filter it Part III: Permanent Hardness Take 20 mL of the water from boiled, cooled and filtered sample using pipette into a 250 mL conical flask. Add 5 mL of buffer solution (pH 10) and then add 2-3 drops of EBT till the solution assumes a wine-red colour. Titrate this solution against EDTA till the solution in the conical flask changes to blue colour, Repeat for concordant titre values (V2 mL). From the titre value, the molarity of the sample and hence the amount of CaCO; in mg/litre can be calculated. This gives the value of permanent hardness. 15Experiment: 5 SELECTIVE EXTRACTION: Extraction of Caffeine from Tea Leaves Aim: To extract the alkaloid natural product caffeine from tea leaves via acid-base liquid-liquid solvent extraction techniques. Principle: The technique used to separate an organic compound selectively from a mixture of compounds is called Selective extraction. Extraction process selectively dissolves one or more compounds of the mixture into a suitable solvent, The solution of these dissolved compounds is ° referred to as the Extract, Here the organic solvent / dichloromethane is used to extract caffeine from an Yq N aqueous extract of tea leaves because caffeine is more A | > soluble in dichloromethane (140 mg/ml) than it is ing N N water (22 mg/ml). However, the tannins that are | slightly soluble in dichloromethane can be eliminated by converting it to their salts (phenolic anions by adding sodium carbonate) (tannins are phenolic compounds of high molecular weight and being acidic in nature can be converted to salts by deprotonation of the -OH group) which remain in the water. Caffeine, 1,3,7 - trimethylxanthine, belongs to a wide class of compounds known as alkaloids. These are plant derived compounds with complex structure containing nitrogen, and usually have roles in physiological activity. The melting 17point of Caffeine is 238°C. Glassware/Apparatus required: Stoppered bottle (100 mL, 1 no.) Biichner funnel (1 no.) Separating funnel (100 mL, 1 no.) Beaker (100 mL, 50 mL, | no. each) Watch glass (1 or 2 no.) Glass rod (1 no.) Measuring Cylinder (10 ml, 25 mL, I no, each) Sintered crucible (1 no.) Crushed ice and Filter paper Chemicals/Solvents required: (Note: use only preparative balance) Sodium hydroxide solution (0.2 N) Tea leaves or powder (5 g) Isopropanol (1 mL) Dichloromethane (30 mL) Anhydrous sodium sulphate LR grade (5 g) n-Hexane LR grade (5 mL) Procedure: 1. Weigh about 5.0 g of tea powder and take it in a 100 mL stoppered reagent bottle. 2. Add 25 mL of dichloromethane solvent and 5 mL of 0.2 N NaOH solution followed by 5 mL of water. Stir the contents gently for 7 to 10 minutes [vigorous shaking may lead to formation of emulsion which should be 18avoided]. Keep aside the bottle undisturbed for about 10 minutes. 4, Filter the contents carefully over a Biichner funnel having filter paper by using aspirator suction. 5. Wash the contents with small amounts (<5 mL each time) of dichloromethane (2-3 times) for good extraction. Transfer the organic layer to a separating funnel (100 mL) and allow the contents undisturbed for few minutes. 6. Run down the clear organic layer into a clean and dry beaker (100 mL), add three spatula of anhyd. sodium sulphate, keep aside for about 5 minutes. 7. Filter the contents carefully over a Biichner funnel having filter paper and using aspirator suction, Transfer the organic layer to a dry beaker (50 mL) and keep the beaker covered with a watch glass on a hot plate till one gets a dry green powder (crude caffeine). [Organic solvent evaporation must be done carefully] 8. The crude product was then dissolved in a minimum amount of isopropanol using gentle heat when necessary (taken in a 25 mL conical flask). 9. Once a green coloured solution is obtained, allow it for natural cooling to RT and then add 5 mL of hexane and cool it in ice. 10.White crystalline caffeine powder is obtained which is filtered in sintered crucible and dried. 11.Both yield and melting point of the product are determined and reported. 19Experiment: 6 COLORIMETRIC ESTIMATION: Estimation of Copper in Brass Alloy by Colorimetric Method Aim: To estimate the amount of copper present in brass alloy by using colorimetric method. Principle: The Beer-Lambert law (or Beer's law), the fundamental working principle behind colorimetric estimation, suggests a linear relationship between absorbance and concentration of an absorbing species. Brass is an alloy of copper and zine. The mass percentage of copper in brass can be determined colorimetrically by utilizing the fact that the reaction of brass with concentrated nitric acid results in a solution containing pale blue copper(II) nitrate and colourless zinc(II) nitrate. Copper metal reacts readily with oxidizing agents such as concentrated nitric acid and oxidizes to the copper(II) ion. Cus) + SHNO5{2q) > Cu(NOs)o(aq) + 3NO2) + 3H20¢y As products of this reaction, a water-soluble copper(II) nitrate produces a pale blue solution, and a dense, toxic, redish brown nitrogen dioxide (NO3), gas are formed. Furthermore, the solution of copper(II) nitrate on reaction with ammonia solution forms tetramine copper(II) complex which is dark blue in colour and responsible for colometric estimation, Glassware/Apparatus required: 100 mL Conical flask (one per student) 21Spatula Distilled water bottle Measuring Cylinders 10 mL. Small funnel 50 mL Standard flask 25 mL Standard flask (seven) 5 mL pipette (one) Graduated pipette = 1,2, 3 mL. Colorimeter with 610 nm filter Chemicals/Solvents required: (Note: use only analytical balance) Brass alloy (0.12 g) 1:1 Nitric acid (10 mL) Distilled Water (10 mL) Urea (pinch) Ammonia solution (35 mL) Stock solution of Copper sulphate (5000 ppm) [15 to 20 mL of this solution per student] Procedure: Part I 1. Weigh accurately about 0.12 g of brass and transfer it into a 100 mL conical flask. 2. Add to this 10 ml (measuring cylinder) of 1:1 nitric acid and boil gently for 10 minutes over flame (or hot plate) inside the fume hood until the evolution of a reddish brown gas stops completely. 3. Then add 10 ml water and one gram (one spatula/pinch of compound) urea 22and boil for a few minutes. Cool the resultant solution to room temperature and transfer it quantitatively into a 50 ml standard flask and make up to the mark. . Pipette out § ml of this solution into a 25 ml standard flask containing 5 ml of 1:1 ammonia solution, The solution is mixed well and made up to 25 ml mark, Measure the absorbance of this solution using the instrument Colorimeter equipped with 610 nm filter. Part I: . From the stock solution of copper sulphate (5000 ppm) provided, pipette out 1, 2, 3, 4 and 5 ml of this solution into five different 25 ml standard flasks containing 5 ml of 1:1 ammonia solution in each of them and make upto the mark carefully. . Shake each of them carefully to ensure the solution in it is uniform in concentration, . Also, prepare a blank solution (all as above but without CuSO, solution) in the same way. . Measure the absorbance of each of this solution at 610 nm filter the same way. . Tabulate the readings, plota graph and determine the copper content in brass using the graph. 23Experiment: 7 pH & CONDUCTIVITY: Acid Strength of Citrus Fruit Juice by pH Meter and Conductometer Aim: To determine the strength of an acid present in a given citrus fruit juice by conductometry. Principle: Citrus fruits contain fairly a large amount of citric acid. A simple acid-base titration with a strong base can be used to determine the acid strength. However, some citrus fruits are colored and in such cases conventional volumetric titration using a suitable dye indicator is not possible and therefore, different titration techniques (such as conductometric, pH metric or spectrophotometric methods) can be employed instead. ‘The present experiment is aimed at introducing two instruments for carrying out acid-base titrations: a pH meter and a conductivity bridge. First part of the experiment involves the use of pH meter for titration of a strong acid with a strong base of unknown strength. A pH meter is a potentiometer, which uses a glass electrode sensitive to H’ ion concentration. If a strong acid is titrated against a strong base (in the burette), the pH of the solution varies as a sigmoidal curve with a very sharp increase of pH at the end point. Second part of the experiment is the conductometric titration of the citrus fruit juice, (which, in all likely hood, is supplied to you after dilution in water), with a standard sodium hydroxide solution (standardized in the first part of the experiment). A solution containing ions conduct electricity due to movement of 25ions to oppositely charged electrodes under the influence of an electric field. More the concentration of free ions in a solution, more the conductan: ‘The conductance of a weak acid is usually low, as free ions furnished in the solution is less. On titrating with a strong hydroxide solution (fully ionized), an initial decrease of conductivity is observed due to mutual suppression of ionization of the acid and the salt that is formed. However, after a few drops of titrant addition, the less ionizable acid is progressively replaced by its completely ionisable sodium salt, the conductance starts to increase linearly. Once the end point is reached and all the acid has been converted to its salt, addition of further sodium hydroxide results in a much rapid increase in the conductance as OH ion conducts more than the acid anion, The end point is thus the point where this change in slope takes place. Glassware/Apparatus required: Measuring cylinder (25 mL) 20 mL pipette (1 No’s) 50 mL burette (I No’s) 250 mL conical flask (1 No’s) pH meter Conductivity meter 100 mL beaker (2 No’s) 250 mL beaker (1 No’s) Distilled water bottle Chemicals/Solvents required: 0.1N HCI solution (20 mL) 0.1N Sodium hydroxide (100 mL) 26Procedure: Part I: Standardization of the Sodium hydroxide solution Switch on the pH meter and allow it to stabilize for 10 minutes. Standardize the pH meter with a buffer solution of pH 7. Wash the glass electrode by distilled water and immerse it into a standard acid solution provided and note the pH. Add small aliquots of sodium hydroxide solution (1 mL) of unknown strength from a burette, stir the solution well, and note the pH. Tabulate the burette reading (volume of the base) and the corresponding pH (read from the pH meter). Continue further till there is almost no change in pH. Plot ‘pH’ vs. ‘volume of base’ added. From the graph, note down the volume of base at the equivalence point and calculate the strength (normality) of the sodium hydroxide solution, Part-II: Determination for strength of the citrus fruit juice Switch on the conductivity bridge and allow it to stabilize for 10 minutes. Take the given juice solution (exactly 25 mL) in a 100 mL beaker and note its conductance read by the instrument. Titrate with standard NaOH solution with small addition (0.2 mL at a time). Note the burette readings and the corresponding conductance after each addition. At the end point you will observe a faster increase of conductance with NaOH addition. Stop the titration after 8/10 readings after the end point. Plot conductance vs. volume of base added, Itendify the equivalence point and estimate the strength of the juice solution given. 27Experiment: 8 REACTION KINETICS: Ester Hydrolysis Ai To determine the order and the rate constant for the acid catalyzed hydrolysis of an ester at room temperature. Principle: In presence of acid, an ester (e.g., methyl acetate) hydrolyzes at a measurable rate yielding alcohol (methyl alcohol) and carboxylic acid (acetic acid). CH;COOCH; + 1:0 — ci,coon + CH;0H Assuming that the rate of this reaction is proportional to the concentration of the ester and the water, the rate expression becomes: Rate = &{Ester][H:0] The reaction is performed in presence of excess water. Thus, change in its concentration is negligible and [H2O] can be considered as constant. Moreover, HCI catalyzes the reaction and hence, there is no change in its concentration. Therefore, the overall rate depends only on the ester concentration and follows a psendo first order kinetics. Rate = kpeuiolEster] where pseudo = k{[HoO] The first-order rate constant can be expressed as: 2303) [Estero t sterle k Where [Ester]y is the initial concentration of the ester and [Ester], is the 29concentration of ester at time ‘1’, A straight-line between log ele dt essentially infers that the reaction follows a first-order kinetics and the rate constant (k) can be obtained from the slope. Glasswares/Apparatus required: Stoppered bottle (250 mL, 1 no.) Pipettes (10 mL, 5 mL, 2 mL, 1 no.) Room Temperature and 80 °C Thermostats Conical flask (250 mL, 2 no.) Burette (50 mL, I no.) Measuring cylinder (100 mL, 1 no.) Stopwatch Crushed ice Chemicals/Solvents required: Cone. Hydrochloric acid Distilled Water Methylacetate (5.0 mL) Phenolphthalein indicator Sodium hydroxide (0.2 N) Procedure: Ester concentration at different times are measured by back titrating the carboxylic acid formed from the hydrolysis reaction. This is accomplised by titrating the reaction mixture at different time intervals (1) using a standardized NaOH solution. The rate constant can be expressed in terms of the volume of base consumed (V,) at time t and is given by the following equation: 302.303) [Veo Vol € Wao Vel V.-Vo corresponds to initial ester concentration and V.-V; corresponds to ester concentration at time "1", respectively. Measuement of Vo and Vi: Take ~100 mL of 0.5 N HCI into a 250 mL stoppered bottle. Keep the bottle in a trough of water at room temperature (thermostat) for about 10 minutes. Add ~5.0 mL of methyl acetate to this bottle using a pipette. Shake the bottle to ensure thorough mixing. Start the stop watch as soon as ester is added, Immediately withdraw exactly 5.0 mL of this reaction mixture using a pipette and add it to ~20 mL of ice cold distilled water already taken in a 200 mL conical flask. Add one or two drops of phenolphthalein indicator and titrate against standardized NaOH solution (0.2 N) taken in the burette. Note the end point color change. Note down the titre value (V1) at regular time intervals (f), for example; t= 0, 10, 20, 30, 40 and 50 minutes. Measurement of V: Keep the stoppered bottle in a trough of water at 80 °C for about 15 minutes. This enables entire ester to hydrolyze yielding an equivalent quantity of acetic acid [CAUTION: Hold the stopper tight while the bottle is being heated to avoid popping of stopper]. Bring it to room temperature and withdraw exactly 5 mL of the reaction mixture with a pipette, transfer it into conical flask, add phenolphthalein indicator. Titrate and note down the titre value, Vs. 31