Ak Lf LF IN HARRDIK RavaT BQOEE CAI General Chemistry Laboratory Workbook for All B.Tech Students Instructors: Dr. Rakesh Kumar Sharma, Dr. Samanwita Pal Dr. Sandip Murarka, Dr. Dibyendu Kumar Sasmal, Dr.Subrata Chakraborty Teaching Assistants Anshul Jain, Soniya Singh, Abhishek Mishra, Bhagirath Saini Vivek Sharma, Sunita, Mohit, Ghanshyam Mali, Sushanta Kumar Parida, Tushar, Vaishnavi, Prahallad Meher, Amarnath Singh Chauhan Technical Staff Ganpath Choudhary Shubham Pandey Kamal Kishore Course CYP 1010 GFR Ki 2 Uy at eam price Indian Institute of Technology Jodhpur Chemistry Department July 2021? Preparation of Nylon6,6 Objective: Synthesis of Nylon 6,6 Polymer using two reactants. peeeE Beakers (50 mL x 2), Volumetric flask (25 mL x 2), Measuring cylinder (10 mL & 25 ) welght balance, copper wire hook, dropper, watch glass, Glass rod Chemicals used: tol (5% a 5 q-) Hexamethylene di Iohexane, 0.5 MLAdipoyl chloride ylene diamine, 20% NaOH solution, 1omL Cyclohexa Theory: Polymers are macromolecules bullt from smaller molecular subunits, called monomers. Synthetic polymers can be classified into two main types according to the mechanism by which they synthetically grow from Monomer to polymer: chain-growth polymers and step-growth Polymers, This classification scheme is an update from historical nomenclature, in which polymers were classified by whether there existed a byproduct of the polymerization reaction (condensation polymerization) or not (addition polymerization). In a step-growth reaction, the Srowing polymer chains (of any molecular length) may react with each other to form longer Polymer chains, The monomer or dimer may react in just the same way as a polymer containing hundreds of monomer units. in chain-growth polymerization, however, only monomers may react with growing polymer chains. That is, two growing polymer chains cannot join together as in the case during step-growth polymerization. Nylon 66 Figure 1 Structure of Nylon-6,6 polymer The first step is the reaction between a molecule of hexamethylenediamine and a molecule of adipoyl chloride (see Scheme 1 below). The hydrogen atom of the amine group belonging to hexamethylenediamine forms a hydrochloric acid (HCI) molecule with the chloride from the acid functional group. The remaining adipoyl chloride molecule and the hexamethylenediamine molecule will join together to form a larger molecule (polymer). The molecule formed has an acid group at one end and an amine group at the other (Scheme 1) and is a nylon 6,6 unit. In acidic solution, the polymerization reaction will not occur readily. While mixing the solutions two layers are formed, pH of the mixture should be greater than 7. In the reaction of adipoyl chloride with hexamethylenediamine, HCI is a co-product which can make the solution acidic. To avoid this, add 10 drops of 20 % NaOH. It basically neutralizes HCl and keeps the solution basic. So NaOH is used as a catalyst in this reaction.Scheme 1: The Feaction Involved in the synthesis of Nylon 6,6 Step-Growth Polymerization In this reaction, monomers need not necessarily add sequentially but instead small Polymer chains may couple into larger chains. For example, nylon 6,6 is os aliphatic Polyamide that is synthesized using A-A/B-B step-growth condensation Polymerization. The two Monomers involved in this Mechanism: ‘Scheme 2: Mechanism of Nylon-6,6 synthesis 7Procedure: Prepare 25 mL of a 0.35 M_ aqueous solution of hexamethyleneciamine (16 ‘exanediamine) in 25 mL volumetric flask. For example, you would need 1.0 gram of hexanediamine in 25 mL of water to make a 0.35M solution. To do this, weigh out the solid 1,6-hexanediamine on paper using a balance, 2) acd eae we agiass stirring rod to mix the solid until It is completely dissolved in water. (Note ere yt thls solution In a graduated cylinder and set aside. * every time you pour out a solution, touch one glass container to the other to Prevent solution spills and to also ensure that all of the solution Is removed from one container to the other, if desired). 3) Prepare 20 mL of a 5X by volume solution of adipoyl chloride (e.g 1 mL of adipoy! chloride in 19 ML of solvent). Use cyclohexane as the solvent and mix gently for 30 seconds. Measure out 10 mL of this solution in a graduated cylinder and set aside. Since this solution has an organic solvent, place a cap over the graduated cylinder. 4) Add water to sodium hydroxide pellets to make 25 mL of a 20% by weight solution. You will Need to use the balance to weigh the pellets. (Caution: the sodium hydroxide will cause skin and eye irritation, Be sure wear gloves while handling and not to touch your eyes or skin after handling. Also, the reaction is exothermic and will produce heat at a temperature over 80°C). 5) Transfer the 10 mL of 1,6-hexanediamine into a 50 mL beaker and add 10 drops of the sodium hydroxide solution to it. 6) Tilt the beaker with the 1,6-hexanediamine and the sodium hydroxide solution init at 245, degree angle and SLOWLY add the 10 mL of the adipoyl chloride solution to it. Two layers will be present since these solutions are not miscible in each other and the polymer will immediately form at the liquid-liquid interface. (Note: HCL acid vapor is harmful when inhaled). 7) Asshownin Figure 4, use a copper wire with a hook at the end, slowly go around the inside wall of the beaker to free it of the polymer and in a circular motion, approach the center of the beaker. Gently pull up on the polyamide at the center of the polymers mass and a continuous rope will form out of the solution. Slowly pull the rope until a few feet of the polymer is out of the solution (if you pull it too fast the rope will break), and then cut the rope off. Lay this rope ona paper towel to dry. 8) Quickly stir the remaining solution until a bulk polymer forms inside the beaker. 9) Rinse both the bulk polymer and the polymer rope in water three times. 10) Use a paper to get dab excess water out of the fiber and then use a piece of filter paper to pull more water out of the fiber. Wrap.the polyamide in filter paper and place it aside. 11) Dispose of all organic waste in the “organic waste” container. Dispose of all water-based solution in the container marked “base waste”. Clean all glassware with water and puton the rack to dry. Throw away all paper waste. Also clean the balance. 12) Now we dip a copper wire hook into this solution and as we pull it out, we found nylon chains (these nylon chains are formed at the interface of the two liquids) now wash the nylon with water and let it dry. 43) Weigh the nylon thread, calculate the % yield and note it down. 14) Clean your work area. Replace all equipment to the correct storage location. 11Figure 4: Formation of nylon-6,6 rope by interfacial polymerization Precautions: 1) Asusual lab safety rules must be followed. 2) Hexamethylenediamine is irritating to the skin, eyes and respiratory system. 3) Adipoyl chloride may be irritating to the skin eyes and muscle membrane. 4) Always work in the hood when working with volatile liquid chemicals and when performing an exothermic reaction. 5) Do not touch the hot plate with bare hands. Results: ‘The weight of nylon threads gained finally is..220.9.... The expected weightin the ideal conditions. AdG.. The percentage yield “and Zaz! SIGNED STATEMENT: Ihave only worked with the following persons _HPRS HEENA REL 0ds for this lab experiment. I received no other help and | did not copy another person's work. Qo Signature :Example Questions: 1) What is the difference between homopolymer and co-polymer? Horne bolg mer au mod gf sams Ype vents superb rg bs Nico Co-pabgma > mocks q hog aS}. \po d¢ trendy 2) What Is polymerization and how it can be classified? Palgmoisolion \< a prous muhith amtdleales comin: b dum Jorg choi, Hh} Dh * AddiWon 7 Conclungolar 3) What are the steps of polymerization? |. Tnih'shon 8. Propageto % Terminolra, 4) What is condensation polymerization? Tre polymer formed! by Jodng small. mdeobr Sirs vwalin or nilregun from Menome js call Condymcobion Poly mor 5) What do the two numbers correspond to in the name “Nylon-6,6?” What would the chemical structure of the repeat unit be in “Nylon-2,2”? Ty rremecc umn cor bon aw signi) by © 6-6) am S927, for x Halon > 1 . [ pe", ° 136) Why is a) solution of sodium hydroxide added to the’ solution of hexamethylenediamine? “Te mie produ UCL whit domerous ond yutide by pe nauhaliged + Hen Nosits adda2 Preparation of salt of Co-ethylenediamine complex. Objective: Preparation of Tris(ethylenediamine)cobalt {llchloride Co-ordination complex [Co(en),]Cl, Apparatus: Beakers (25 mL x2), sample vial (10 mL) etc. Chemicals used: Cobalt chloride, Glass rod, measuring cylinder (10 mL), magnetic bar, spatula, Ethylenediamine, HCl, H20, and distilled water. Theory: Tris-(ethylenediamine) cobalt (II1) chloride is a {Co(en);]cl; (where "en" is the abbreviation for ethylenediamine). This complex was important in the history of coordination chemistry because of ite stability and its stereochemistry. Alfred Werner, who isolated this salt as yellow-gold needle-like crystals and first described the complex. Ethylenediamine co-ordinates with metallic ions through its both nitrogen atoms that forms 5-membered rings whi ich are very stable. It has a melting point of 275 °C and itis soluble in water. The cation [Co (en) sP* is octahedral with Co"N distances in the range 1.947-1.981 A. The N-Co-N angles are 85° within the chelate rings and 90° bw N-atoms on adjacent rings. This compound is diamagnetic in nature. coordination complex with the formula 3 an N | wwtNHy, Co _i Cc NH Hp HN > chloride anions omitted Figure 1: Isomers of Tris(ethylenediamine)cobalt(lII)chloride. The synthesis of tris(ethylenediamine)cobalt(|!!)chloride leads to the formation of two enantiomers. Enantiomers, or "optical isomers", are mirror images of one another. A mixture of two enantiomers (known as a racemic mixture) can be very difficult to separate, because enantiomers typically have the same chemical and physical properties. Indeed, there is only difference between two optical isomers is, they rotate polarized light in opposite directions. One of the enantiomers in the pair will rotate the light to the right (dextrorotatory, designated’d cs '+") and the other to the left (levorotary, designated ‘Vor '), The measurement of the rotation of polarized light is a useful analysis for identifying enantiomers and determining their purity. aobs [aa = xle 17(a) «bs specific rotation at the ggven wavelength Pom “is obruerved ronation of sample measured try “pohatimeter” © = 1s the concentration (in gn.) (= 1s the path length (in dm) ; x «isthe optical purtty where 0.5 means a racernic misture of both (+) and (-) enantiomers Is present In equal portions, and s means only one pf the enantiomer is present. Procedure: A. Synthesis of Tris( ethylenediamine }cobalt(IN{)chloride. Beaker h:(n425 ml. beaker, prepare solution of Cots, 64,0 (240 mein 5 ML). Note: clear solution should be formed. Beaker 8: In another 25 ml beaker, add 1mt of ethylenediamine followed by 1 mL of 6N HCL (for neutralization of ethylenediamine), Transfer solution of beaker h to beaker B. : 0.5 ML Of H,0, Is added to the solution and then heated at 180°C with constant stirring until it becomes 1/3°7in volume. Cool to room temperature. Add 5 mL of conc. HC (12 M) and stir it for 5 min. at room temperature, Put it inice bath for 10 min. 10 mil of ethanol is to be added if it does not precipitate. Dry and weigh the obtained crystals, ‘Molar Calculations The theoretical yield of [Cofen),]Ch is 0.001+345.69¢m = 0.3 gm or 300 mg, ay YREyay ACoCl6H20 + 2CaHs(NHz) (8) + 2HCI + H202—* 4[Co(en):]Cl. + 2Hz0 Precautions: 1. This experiment involves some very hazardous chemicals such as H;0; and conc. HCI. So avoid direct contact with them and work carefully, thoughtfully and slowly. 2. We should know the appropriate procedure about what to do and in what sequence, because any disordered steps can cause fire. 3, Waste should be dispose into the lab inorganic waste containers only. Result: 1. Thewelght of [Colen)]Clerystalsis.45....mg 2. Theyleld was found tobe. A.961 dds 3, Thecrystals are. Asi, incolor,SIGNED STATEMENT: - E022 Ihave only worked with the following persons HARSH UH CEN BQOEE 's work. for this lab experiment. I received no other help and | did not copy another person's Signature: 19Example Questions: 1. WhyCo® complexes are of interest? he f ol ol Coball complercos Co eorly prepared ound, cdoor ful, fiw nuorbe q Complox qa voridy coorlindion xpd. 2. Whatare chelates? ZAFE aM Orgone —Ceqrpourndl, Which ie formed. vhina polydundae Ugomad Kindo ba emrad meal alm, 3. Give examples of bidenatate , tridentate and hexadentate ligands? Bidinlak Cthybrv cLoomine Triduab © abelhyt Homie hexcdinlal: D1 A 4. Whatis crystallization? How does it happen? Salton tra stpnelion Kedar Prat Ts aud bo seporch froma Mod selohon Lt hoppy Chunur cool a Seveded sslohon da Ligh oid the ddr Jowe erplelr- 5. Give example of chiral complexes. o - (Co (ox) fread s[oo en, cw 2) Cla, ek 6. What are enantiomers? Draw some examples. Truyare choral trolecus Hoban roimervmeye @ cod ath. omel b& , Be ( /e ay’ cr oy Ore non suger impo s 7. What is mean by racemic mixture? Tyis a Bo0'Se ix p erombomss whith has 0 momentos Tht chiral Yrokeubs'\n eqad conte, Canals our 204 Qualitative estimation of caffeine by FTIR spectroscopy Objective: Qualitative estimation of caffeine content using FTIR with ATR technique. Equipment: Bruker ALPHA II FT-IR, ATR accessories, standard flask, dropper, Kimberly-Clark wipesitissue papers, 25 mL volumetric flask Chemicals: Sample: caffeine solutions (0.1M, 0.5M, 1M, 1.5M in 25 mL. CHCI3; used 25 mL volumetric flask). Solvents: Chloroform (for sample preparation), isopropanol for cleaning ATR crystal), Theory: Mid-Infrared (IR) spectroscopy is an extremely reliable and well recognized fingerprinting method. Simply, itis the absorption measurement of different IR frequencies by a sample positioned in the Path of an IR beam. The main goal of IR spectroscopic analysis is to determine the chemical functional groups in the sample. Different functional groups absorb characteristic frequencies of IR radiation. Using various sampling accessories, IR spectrometers can accept a wide range of sample types such as gases, liquids, and solids. Thus, IR spectroscopy is an important and popular tool for structural elucidation and compound identification. Traditionally 1R spectrometers have been used to analyze solids, liquids and gases by means of transmitting the infrared radiation directly through the sample with a sample thickness not more than a few tens of microns. This needs careful preparation of solid sample i. a) Grinding the solid sample to fine powder, and b) Evenly dispersing it in a matrix. KBr is probably the most widely used matrix material. Liquids are measured in form of a thin film. Fourier-transform infrared (FTIR) spectroscopy is based on the idea of the interference of radiation between two beams to yield an interferogram. The latter is a signal produced as a function of the change of path length between the two beams. The two domains of distance and frequency are interconvertible by the mathematical method of Fourier-transformation. The basic components of an FTIR spectrometer are shown schematically in Figure 1. The radiation emerging from the source is passed through an interferometer to the sample before reaching a detector. Upon amplification of the signal, in which high-frequency contributions have been eliminated by a filter, the data are converted to digital form by an analog-to-digital converter and transferred to the computer for Fourier-transformation. —— Source | —|imerteromerer|_{ sampie |_[Detector|_ ampuner | A004 $0%a| [compu Figure 1; Basic components of FTIR spectrometer. or a molecule to show infrared absorptions it must possess a specific feature, Le. an electric ipole moment of the molecule must change during the vibration. This is the selection rule for frared spectroscopy. Figure 2 illustrates an example of an ‘infrared-active’ molecule, a eteronuclear diatomic molecule. The dipole moment of such a molecule changes as the bond 30» molecule Is 4 inactive’ infrared-ina rolecnegthe expands and contracts. By comparison, a example of an ins zero no matter homonuclear diatomic molecule because Its dipole moment rema bond. Figure 2: Change in the dipole moment ofa heteronuclear diatomic molecule. Modes of Vibration The interactions of infrared radiation with matter may be understood in terms of changes in molecular dipoles associated with vibrations and rotations. For 2 diatomic molecule, only one vibration that corresponds to the stretching and compression of the bond is possible. This accounts for one degree of vibrational freedom. Polyatomic molecules containing many (N) atoms will have 3N degrees of freedom. Looking first at the case of molecules containing three atoms, two groups of triatomic molecules may be distinguished, i-e- linear and non-linear. A non-linear B-A-B type triatomic molecule has three modes, two of which correspond to stretching motions, with the remainder corresponding to 2 bending motion. A linear type triatomic hhas four modes, two of which have the same frequency, and are said to be degenerate. Two other concepts are also used to explain the frequency of vibrational modes. These are the stiffness of the bond and the masses of the atoms at each end of the bond. The stiffness of the bond can be characterized by a proportionality constant termedthe force constant, k (derived from Hooke’s law). The reduced mass, Hs provides a useful way of simplifying our calculations by ‘combining the individual atornic masses, ‘and may be expressed as follows: Lym) + / a/e) The equation relating the force constant, the reduced mass and the frequency of IR absorption is: Recently the technique of attenuated total reflectance (ATR) revolutionized solid and liquid sample analysis because it combats the most challenging aspects namely sample preparation and spectral reproducibility. An ttenuated total reflection accessory operates by measuring the changes that occur in a totally internally reflected infrared beam when the beam comes into contact with a sample (indicated in Figure 3). An infrared beam is directed onto an optically dense crystal with a high refractive index at a certain angle. This internal reflectance creates an evanescent wave that extends beyond the surface of the crystal into the sample held in contact wuith the crystal. It can be easier to think of this evanescent wave 28 a bubble of infrared that sit on the surface of the crystal. This evanescent wave protrudes only a few microns (0.5 B= 5 " beyond the crystal surface and into the sample. Consequently, there must be good contac between the sample and the crystal surface. In regions of the infrared spectrum where the 31sample absorbs energy, the evanescent wave will be attenuated or altered, The attenuated energy from each evanescent wave Is passed back to the IR beam, which then exits the opposite end of the crystal and Is passed to the detector In the IR spectrometer. The system then generates an infrared spectrum. There are a number of crystal materials avallable for ATR, Zinc Selenide (ZnSe) and Germanium are by far the most comma nly used for HATR sampling while diamond Is the best crystal choice due to its robustness and durability. As with all FT-IR measurements, an infrared background is collected, in this case, from the clean ATR crystal. The crystals are usually cleaned by using a solvent soaked plece of tissue. Typically water, methanol or lsopropanol are used to clean ATR crystals. The ATR crystal must be checked for contamination and carry over before sample Presentation, this is true for all liquids and solids. An attenuated total r jection (ATR) cell Sample in contact with evanescent wave armbysta yl, Figure 3: Attenuated Total Reflection Cell Methods for sample preparation IR spectroscopy is used for the characterization of solid, liquid or gas samples. Material containing sample must be transparent to the IR radiation. So, the salts like NaCl, KBr are only used, 1. Sampling of solids Various techniques used for preparing solid samples are as follows 3) _ Mull technique: In this technique, the finely crushed sample is mixed with Nujol (mulling agent) in na marble or agate mortar, with a pestle to make a thick paste. A thin film ic applied onto the salt plates. This is then mounted in a path of IR beam and the spectrum is recorded. b) Solid run in Solution - In this technique, solid sample may be dissolved in a non- aqueous solvent provided that there is no chemical interaction with the solvent and the solvent is not absorbed in the range to be studied. A drop of solutionis placed on the surface of alkali metal disc and solvent is evaporated to dryness leaving a thin film of the solute. ¢) Case film technique - If the solid is amorphous in nature then the sample is deposited on the surface of a KBr or NaCl cell by evaporation of a solution of the solid and ensured that the film is not too thick to pass the radiation. d) _ Pressed pellet technique — in this technique, a small amount of finely ground solid sample is mixed with 100 times its weight of potassium bromide and compressed into a thin transparent pellet using a hydraulic press. These pellets are transparent to IR radiation and it is used for analysis. 322. Sampling of liquids Liquid sample cells can be sandwiched using liquid sample cells of normally NaCl. Other salts such as KBr and CaF, can also are used. canbe used. used because they cannot dissolve alkali halides. Organic solvents like chloroform C20 7 The sample thickness should be selected so that the transmittance les between 15 Ee a ‘most liquids, the sample cell thickness Is 0.01-0.05 mm. Some salt plates are highlys\ water, so the sample and washing reagents must be anhydrous. ied alkali halides, rifi neha vents cannot be Aqueous sol 3+ Sampling of gases sample cell. A sample The sample cell is made up of NaCl, KBr etc. and it is similar to the liquid f how relatively weak cell with a long path length (5 - 10 cm) is needed because the gases s! absorbance. ‘el 0- HE ‘oaiG=C 0-0 Wat ec cow 308-2100 eds _ 20-2250 edu io ecrracoon Simson Figure 4: IR absorptions of common functional groups Procedure: (a) Sample preparation (caffeine) for FTIR. 1. 0.1M, 0.5M, 1M and 1.5M of caffeine samples dissolved in 25 mL of CHCl; separately (Volumetric flask, 25 ml) and shaken properly so that maximum amount of caffeine gets dissolved in CHCl. Chloroform layer might contain impurities; therefore, it is recommended to filter it again with the help of silica gel. 3. transparent clear solution of caffeine dissolved in chloroform was obtained. 4. This caffeine samples are used for.FTIR measurements. (b) Recording FTIR spectrum of caffeine in chloroform 4. smL of each of caffeine in chloroform will be used for Recording FTIR spectrum. 2. Record an open beam background spectrum through the clean diamond crystal after rinsing it with chloroform. . Prepare a layer of 0.5 mL of caffeine solution in chloroform on to the crystal. . Allow the solvent to dry. Collect the interferograms of the caffeine film formed on ATR crystal. . The transmission spectrum can be transformed into an absorption spectrum to get absorbance value. . Clean the caffeine film from the diamond crystal using chloroform before placing the next sample for measurement. 8. Repeat steps 1-6 for caffeine in chloroform extracted from coffee. 9. Identify two characteristic bands of caffeine in both samples. yaw y 33Precautions: 1. Be careful while using the equipment as itis expensive. 2. Prepare the solutions carefully. Results: Label the bonds present in the IR spectra of caffeine. The characteristic += «IR_-—=—stband-=—Ss for ~—scaffeine appeared at... 1660-2082, Measure and compare the absorbance value at 1655cm" band for both samples to qualitatively comment on the relative caffeine content for extracted sample A and sample B. Prepare a Plot of absorbance at 1655 cm” vs. increasing caffeine concentration as shown in figure 4) and explain its significance. 0.08 ise oess Caffeine concentration, ppm Figure 4. Standard curve for caffeine solution as determined by absorption at 1655 cm* SIGNED STATEMENT: I have only worked with the following persons _Hawsh "Hee: OFEO22) for this lab experiment. | received no other help and | did not copy another person's work. Signature: Qe 34Example Questions: ee ? An » jRwhich region of the electromagnetic spectrum does infrared radiation occur’ 'appens to molecule when It absorbs infrared radiation? hu Tyfromd seacbokor, occur Sugion 4 Joorm iam ‘ molecade obsorka ZR sexy ob suoonena » & P? Ce Tm spudsosespy gnaph 2) How is the wavelength controlled in an FTIR spectrometer? What is the relationship between wavelength and wavenumber? The WeLallin gth th FTIR Spudomiu is conkdlled. by tea. og a gtk. Amd Wortmmby. om Jriroae Cosel pro Coch. othw —_ 3) What are the selection rules for FTIR absorption? : 7 a selilion sul gf ee Baus hed we ibrahons os Te allowed jf rokcular clipole gnomant chanag chung Niibrakon 4) How does the IR spectrum of molecule Nz look like? Ne isa aroleudar uempouund wrth O dipole Mom 3 fume jb shows ino spec um 5) Why KBr pellets are used to prepare solid samples in FTIR? “Le become plone thm subjckd fo prasu aml Jor a skwt hid fs hromporent ty TR dugion , homes his Used. 35,6) Why diamond crystal is best choice for ATR? ‘ es defrak us ‘indie a. prrsrahion Ao Qian Can wad, foraninddana g 45°. Also 4 hoo high et conduchuily, So 141s Bed dor pape ATP 7) Draw the structure of Caffeine and try to assign peaks for all the functional groups present in the molecule. How Caffeine can affect the human health? oO Hey | N~CHO LA? ov ow N CHs Tt skmulobn eunlal nwo spktn ama Cows duin}larmrah® n- Ho wun . high Coffins. “whale com. coms Yeodochso ord Srliumal probleme 36Transmittance [%] 400.0 986 988 990 992 994 99.6 99.8 98.4 L 1485.9074 723.6920 7 8038 T T : ' 3500 2500 2000 500 4000 Wavenumber cm-1 Page 1 of 199 3 NI pom — = 3 wy 25 z i a 1 E zt 12.2307 Be 7 778.3218 4 i 3 \ oy 1480. 7045 8 val sai Ge T 7 T , 500 1000 2000 1 3000 2500 Wavenumber cmt oo 4 of 1SV \ y 1 A 2600 2000 Wavenurriber corr 1 Payo 1 of 1 776.3218Laas. 00 (ron. head VetusFR PY el —™ ; \ || Ia lw a4 py z Pt | 5 | 1485.9074 5 a4 pes i 3 J | 22.0008 ey 2500 2000 1500 1000 3500 3000 Wavenumber cn-1 . Page 1 of 1 ch cTransmittance [%] 90 98 92 88 84 1701,8250|||| 1485-9074 | | ¥660,2023 | T T T T - T r 3500 3000 2500 2000 1500 1000 Wavenumber cn+1 Page 1 of 1 N NK NOW€ Contact Angle Objective: Determination of Surface contact angle, surface tension and surface free energies of different solvents and substrates respectively. Apparatus: Contact angle meter, Surface or substrate, tissue paper. Chemicals used: n-Heptane, n-Octane, n-Undecane, n-Tetradecane, n-hexadecane, Cycloocatne, Bicyclohexyl, Acetone, Hexane, Ethanol. Theory: The interaction between a liquid and a solid involves three interfaces; the solid-liquid interface, the liquid-vapor interface and the solid-vapor interface. Each of these interfaces has an associated surface tension, y, which represents the energy required to create a unit area of that particular interface. Figure 1: Diagram of the contact angle The angle between a liquid drop and a solid surface, Young’s contact angle, is related to the surface tensions of the three interfaces according to the relationship: C05 By = (Ysotidvapor- YsotieLiquid) / Yuquié Vapor @ The magnitude of Young’s contact angle is a result of energy minimization. If the liquid-vapor surface tension is smaller than the solid-vapor surface tension (Y.v < ysv), the liquid-solid interface will increase to minimize energy. As the drop wets the surface, the contact angle approaches zero Measurement methods for contact angle 1. Half angle method (6/2): A droplet rest ona solid surface shapes a part of sphere. The cross sectional view of this droplet is captured through CCD camera. Then, both the left and right ends and the apex of the droplet are detected with image processing, and the radius o the droplet base (r) and height (h) is obtained. The contact angle @ can be obtained with the substitution of the r and h in the equatior below: tan@ = h/r 2. Tangent method: This method regards the droplet’s shape near the end points (three- end-points) as a part of circle. From the three points a virtual circle can be drawn. The centre of the circle is defined and a tangent line at the point can be drawn. The angle between the tangent line and the droplet’s base line is the contact angle of one end. Similarly the contact angle of other end can also be measured. 48the droplet Tangent method can obt: id right side of ‘ain both contact angles on the left and rig! ent method respectively. lf there is a difference between the right and the left value, tang is used. Curve fitting methods: Curve fitting method suppose that the droplet fits the part of Circle or ellipse. A curve is determined by fitting to all the observation points on the droplet profile in specified area (fit section) with the least square method. This ; calculation determines the parameter of either circle or ellipse and the contact angle is figured out by the differential coefficient at the droplet end. 3 The critical surface tension of a material, yc, is a measure of the surface’s wettability and it is Proportional to the surface free energy of the material. A liquid with a surface tension less than or equal to the critical surface tension of a particular material will “wet” that surface, i. the contact angle will be less than or equal to 900. A material’s critical surface tension can be determined from a Zisman Plot, which measures variation in Young’s contact angle as a function of the surface tension of a series of liquids. Zisman noticed empirically that a plot of cos(@) versus ytv is often linear. The value for which cos(6) extrapolates to 1 is termed the critical surface tension. . A typical Zisman Plot is shown in Figure 2. 1.0 cos, 0 Probing liquid surface tension / (mN/m) Figure 2: A typical Zisman Plot Procedure: 1. Clean the given substrate with ethanol and place it on the sample stage. 2. Clean the syringe with acetone and pre-rinse turning the syringe upside down and then fill the syringe with the test liquid and secure in the syringe holder above the sample stage. 3. Operating the instrument: 1. Contact Angle Measurement a) Click on FAMAS (software on the desktop). b) Click Setup —> Image Monitor. ©) Focus the needle manually first and then click on Needle Point Detection button. d) Click on CA measurement (sessile drop). e) Click on Measure button in the image monitor and then make a droplet. f) Wait till the droplet is deposited on the surface. After the droplet is deposited immediately contact angle is displayed on the screen. Double click the result obtained and a window will open. & 49h) Inthe Method box there will get four different methods (A Half Angle, Circle Fitting, Ellipee Fitting and Tangent method) by clicking on which we can obtain the desired contact angle 1) Glick on File —> Save Data. i) Repeat the same procedure for all other substrates " Intertacial Tension measurement a) Click Setup — > Image Monitor. b)_ Focus the needle manually first and then click on Needle Point Detection button. ©) Glick on 1.T measurement (Pendant drop). d) Click on Measure button in the image monitor and then make a droplet. e) Check that the droplet remains in the air and the interfacial tension is displayed on the screen. f) Click on File —> Save Data. g) Repeat the same procedure for all the liquid samples. lll Surface Free Energy measurement a) 4. Zisman plot Plot the mean cosine value for each liquid against its surface tension. Find the best linear fit and extrapolate this line to find the surface tension value that gives a cosine value of 1. Precautions: 1. Handle and wash the syringe carefully. 2. Be careful while using the equipment. 50Result: a | Acrylic sheet ee Stainless steel ~~ Surface "| Half Angie” “Lotus leaf Teflon plate | Contact angle of water with different surfaces Mean 0 for surface” B | Ellipse Fitting Tangent Plywood Glass slide PET sheet = Rubber Kepton tape Aluminum sheet 92,08 Copper sheet 2. Free energies of different solvents on Teflon plate as substrate Solvent Free energy value Water lol. 35 ao = Benzyl alcohol QQ Pentadecane _ Hexadecane RSS 456 eer SHS QB ‘eho 3. Plot the mean cosine value for each liquid against its surface tension. Find the best linear fit and extrapolate this line to find the surface tension value th value of 1, 51 lat gives a cosineSIGNED STATEMENT: ‘have only worked with the following persons HARSH NEENA R20¢CO22 for this lab experiment. | received no other help and I did not copy another person's work. Signature: aks 52Example Questions: 1 What i ‘at is the contact angle a measurement ‘of and where can it be found? Th ic tho oma formed by thw Ogun ad tha 3 phone howndany, iohee ov Quid geo and soi lend, The wall kmouwn younays 8", dtacubes the halonca, al the 3 phoat conlad of Solid, Had ond gor. + What do you expect to see if the Nquid surface tension Is less than or equal to the critical surface tension of a surface? Ty the sor {au lemon ts no than or equal fo the crikerd Surface lemon rt Vhe sovfou , the amaterial will tnd tv obco Or will Wet! Ia sorfoce. - C 3. Why is it difficult to measure the surface free energy of a solid? How can the Zisman plot be used to estimate this value? Rmalmrals crikcal socface krwon eam be debymined by Ziseram plot 5 tahlch Muu yartaton iy young contud amgk a a Junchion af sor face Jomion ga seiv gf Liquide Zisman nobad that the HT plot cao ve ¥ i Gre. fre volun Nolet of ces obth exhapsbtis 1s riba So¢foe tension. Sing iis ompincal amalyas. This difficuth by meanue itprecnely, 4. What is hydrophobicity and hydrophilicity? Give an example of a hydrophobic and hydrophilic surface encountered in day-to-day life. Surfoco gahich bend to absonb wate or be ¥ voelld by elm 2s calls luydvophilt Surfodo. Ard the ont eehih doer abosorls weiln ae calld hupdiophoble svrfoca. an ; Wy duo philic Paper bud, spo cloth 0 <4" [° fc a] Hydrophobic + alkamuo, gil O S40’ 53om Hexadecane | Tekadbcand | . | Gney) oltobol : Ethylene glyel | Waker sid wine odee ieee : roleiiey Asa | ae ie af rss) hs Wucdaw) J oP UP eas : , 4 abipih 4 te e Sunih #1 0 av z D {ole ali adh tod Jude qeomitetee Heitys i Lael wateloointl ng. it ‘ ns Diels anf yoe Jordi f ¥ ‘ hy oe plrtvany Se maeneirt et Wasi Fea5 -0.5 0 20 40 60 80 1007 g Cyclic Voltammetry Study of Redox Reactions u Objective: (a) To understand the theory and working principle of Cyclic Voltammet! (b) To perform CV on ferricyanide solution and understand its electroc! for example Ep, Diffusion rate, Ip ry (CV) : hemical properties odes: Pt electrode working Apparatus: CH Instrument Electrochemical Workstation, electré .ctrode, electrode (3-4 mm diameter, planar), Pt wire counter electrode and Ag/AgCl reference ele electrochemical cell (small volume), Polishing kit], Volumetric flasks (100 mL) with ground glass stoppers and pipettes. Chemical used: Potassium ferricyanide [K;Fe(CN).], Potassium nitrate [KNOs], distilled water. Theory: Cyclic Voltammetry (CV) is popular for its relative simplicity and its high information content. It is used most often as a diagnostic tool for elucidating electrode mechanisms. Cyelie Voltammetry Potential Waveform Cathodic Potential & 1 & & ' Time Figure 1: A typical waveform used and the corresponding Cyclic Voltmmogram (CV). The traces in Figure 1 are called cyclic voltammograms. The x-axis represents a parameter that is imposed on the system, here the applied potential (E), while the y-axis is the response, here the resulting current (i) passed. Each trace contains an arrow indicating the direction in which the potential was scanned to record the data. The arrow indicates the beginning and sweep direction of the first segment (or “forward scan”), and the caption indicates the conditions of the experiment. ‘A crucial parameter can be found in the caption of Figure 1: “v = 100 mV/s”. This value is called the scan rate (vu). It indicates that during the experiment the potential was varied linearly at the speed (scan rate) of 100 mV per second. The waveform of the voltage applied to a working electrode in CVis triangular shaped (ie., the forward and reverse scan). Since this voltage varies linearly with time, the scan rate is thre slope (V/s).meen on 07 os o3 Potential va Aa/Aacih Figure 2 CV for the reduction of 4.8 mM ferricyanide in 0.1 M KCl at a 4.0 mm glassy carbon electrode at a scan rate of 100 mV/s, An example of a CV for the reduction of ferricyanide to ferrocyanide Is shown in Figure 2. In this experiment, the basics of CV will be Illustrated by looking at the one electron reduction of ferricyanide to ferrocyanide. This redox couple exhibits nearly a reversible electrode Feaction without any complications of proceeding or post chemical reactions. Thus, ferricyanide/ferrocyanide couple has been a popular cholce through the years to use as a standard to demonstrate CV experiment. This equilibrium is described by the Nernst equation (eq 1). The Nernst equation relates the Potential of an electrochemical reaction. The peak shape of the reductive and reverse oxidative current versus electrode potential curve (I-E) in Figure 2 is typical of an electrode reaction in which the rate is governed by diffusion of the electroactive species to a planar electrode surface. That is, the rate of the electron transfer step is fast compared to the rate at which ferricyanide is transported (diffuses) from the bulk solution to the electrode surface due toa concentration gradient, as ferricyanide is reduced to ferrocyanide. in such a case, the Peak current, lp, is governed by the Randle-Sevcik relationship: Ip= kA DY v’ “(1) where the constant k = 2.72 x 10°; nis the number of moles of electrons transferred per mole of electroactive species (e.g., ferricyanide); A is the area of the electrode in cm? ; D is the diffusion coefficient in cm?/s; Cy is the solution concentration in mole(L; and vis the scan rate of the potential in volt/s. The Ip is linearly proportional to the bulk concentration, Ce, of the electroactive species, and the square root of the scan rate, v"*. Thus, an important diagnostic is a plot of the Ip vs. v If the plot is linear, it is reasonably safe to say that the electrode reaction is controlled by diffusion, which is the mass transport rate of the electroactive species to the surface of the electrode across a concentration gradient. The thickness, 5, of the diffusion layer can be approximated by 5 ~ [D t]", where D is the diffusion coefficient and t is time in seconds. A quiet ([.e. unstirred solution) is required. Another important diagnostic for characterizing the electrode reaction is the value of the peak potential, Ep. When the rate of electron transfer Is fast, the Ep value will be independent of the scan rate; indicating a reversible electrode reaction. Then the difference between the anodic peak potential, Epa, and the cathodic, Epc value will be equal to 57 mV/n. The electrode reaction during the scan from +600 mV to 0.0 mVis Fel(CN)6? + e- —> Fel(CN)e4 E° = 0,361V versus NHE at 25° Q) 58The electrode potential, E, Is thermodynamically determined by the Nernst relationship: E = E° + (0.0591/n) log (aox/ar) (3) where aos is the activity of the oxidized species, ferricyanide In the present case, and axis the activity of the reduced species, ferrocyanide. Experimentally, the activity Is affected by the Presence of other ions. For practicality, formal potential (E*) is defined that make use of concentration in mole/L rather than activity (which we do not know). Thus, the Nernst becomes : E=E* + (0,0591/n) log [CouCn] ~ (4) The Formal Potential, E°’, depends on the nature of electrolytes in the solution. Table 1 is the list of Formal Potentials for ferri/ferrocyanide in aqueous solutions at 25°C versus NHE: Fe(CN),* +e = Fe(CN)¢! Table t: Formal Potentials for ferri/ferrocyanide in aqueous solutions at 25°C vs. NHE S.No. Ferri/ferrocyanide Evalue different solvents) 1 01M HCl 0.56V. 2 1.0 M HCl o71V 1.0 MHCLOg o.72V The potential, E, at any point along the I-E wave should reflect the concentration of the ferricyanide and ferrocyanide at the electrode surface independent of background electrolyte. Irreversibility is when the rate of electron transfer is sufficiently slow so that the potential no longer reflects the equilibrium activity of the redox couple at the electrode surface. In such a case, the Ep values will change as a function of the scan rate. A unique feature of an electrochemical reaction is that a ‘reversible’ electrode reaction at low scan rates can become ‘irreversible’ at high scan rates. Electrode connections Holes for degassing reagent addition’ Teflon cap Glass solution reservoir Electrolyte solution ‘Working electrode Reference electrode Counter elctrode Figure 3: Schematic representation of electrochemical cell for CV experiment. 59The working electrode is Pt electrode; it carries out the electrochemical event of interest. The type of working electrode can be varied from experiment to experiment to provide different potential windows or to reduce/promote surface adsorption of the species of interest. The reference electrode is Ag/AgCl electrode, it has a well defined and stable equilibrium potential. {tis used as a reference point against which the potential of other electrodes can be measured in an electrochemical cell. The counter electrode is Pt wire. The Purpose of the counter electrode is to complete the electrical circuit. Current is recorded as electrons flow between the WE and CE. Procedure: 1 wy oy Polishing: Prepare the working glassy carbon electrode by first lightly polishing the clectrode surface with 1 um or smaller particles of alumina (wet) on a flat polishing plate. Wash the electrode carefully with pure water to remove any alumina. If a sonicator is available, fill a small beaker with de-ionized water, place the electrode (tip down) and sonicate for 1 minute. Remove, rinse with pure water and touch the edges of the tip with Clean soft lint-free tissue paper but do not touch the electrode surface. Prepare 2, 6 and 10 mM ferricyanide in 1M KNO; in 100 mL volumetric flasks. Switch on the electrochemical workstation. Make the connections for three electrode assembly by connecting appropriate crocodile clips to the respective electrode. Turn on the computer and click on the CH1660E Electrochemical Workstation(Software). Click on Setup —> Technique —> CV- Cyclic Voltammetry. window will openin that window fill the following parameters and click on Ok. a) Initial E (Vv) = b) High E(V)=0.6 ©) LowE(V) d) Finale (V)=1 e) Scan rate (V/s) = 0.01/0.05/0.1 f) Sweep Segments g) Sample Interval (V) = 0.001 h) Sensitivity (A/V) = 1.¢°°/ 1.€°°5 i) Quiet time(s) =2 Run a CV scan from an initial potential (E:) of 05.0 V to 0.6 V and then back to 0.0V at a scan rate of 50 mV/s for 4 cycles. Run duplicate CVs on each ferricyanide solution (2, 6 and 10 mM) at the scan rate of 1oomV/s. Run duplicate CVs on the 2 mM ferricyanide solution at scan rates of 20, 50 and 100 mV/s. . Label and save each CV with the “save function” if using electrochemical workstation or print out a hardcopy of what you want to save from the potentiostat. Precautions 1 Note: With computerized potentiostats you may be able to use Math function to determine Ep and Ip values. Similarly, the Ip values can often be corrected for the background charging current. Write a short summary of what you did in this experiment, noting any deviations or substitutions in the procedure. Show example cyclic voltammograms. 60Results: 1. Plot lp versus concentration of ferricyanide. Fit It linearly. Determine the conc the unknown sample of ferricyanide from this callbration plot. 2. Determine the E” value from the voltammograms. If the values vary with th plot them versus the scan rate and extrapolate to obtain the Compare this value with the tabulated formal potential of ferrifferrocyanide i 3. Tabulate the difference between Epc and Epa values ~ are they dose to the the for a reversible electrode reaction? If not, can you account for the deviation? 4. Plot Ips and Ipc vs. v"®, and from the slope, determine the value of the diffusio (must measure the electrode area). How does your value compare to the liter 0.62 x 10% cm*/s? Should there be a difference in the diffusion coefficient ferricyanide and ferrocyanide? If so, why? SIGNED STATEMENT: Ihave only worked with the following persons entration of e scan rate, £°' at zero scan rate. ino. MHCI. oretical value n coefficient rature one of for this lab experiment. | received no other help and | did not copy another person's work. Signature : Ryw- 61Example Questions: 1. What type of waveform Is used for Cyclic Voltametry experiments? Cyd Valmebry use Ilamgula venir 2. What is diffusion controlled reaction? Dfferion copholled swachons ant th tachone ‘in whidh oaac-ion vatk is equal Io Hu volt @) transport of suochor thon gh UMsciunn 3. What Is the difference between a Faradic and non-Faradlc reaction? : “Ina non fords ox" , charg. is proyeniudly shore aind comporhon ehorngs ual Ka, In Foredi. proom, negahuse chorg is consnoudy addhd te My elechode ond volo it Sucordlad , 4. How do you know if a reaction is reversible from CV measurements. ev ga porkuson Comnposh’sy vill qrue se b a dhe Est Q ihe wocken or on tet eck nod, The grep behuwn poltmbel amd, GM be pws. bo “Vf Hh ceporosi rat chav dSnbubton Ye swackon 5. How can one calculate electrochemically active surface area of the electrode from the cv measurements? diag ta eq" ec et, yh anc He graph bun Trond o% | we camge +t Slee and inenbing volun @ oder koe varriabla , surfoce awa conker frown. 6. How the current varies with scan rate? Explain. Lith Increase We Cam ZA, eww aloo ‘he Qo mon Crowd ts allouad > pam 4 Hho selobion, 7. What information can be obtained from CV measurements. Bou ofa suoclion , Lub hy , gusunb ob ebro ck con be knoun uta CV Tvonanesmenb 62current (Amp) 0.00004 0.00003 0.00002 0.00001 0.00000 -0.00001 -0.00002 -0.00003 00 O01 #02 08 04 6 Vv (vy) 0.60.00004 0.00003 0.00002 0.00001 0.00000 | -0.00001 Current ——> | -0.00002 -0.00003 iar Vive 1M D= 0.08 Vs" lomy Fe 0.02 vs" lomy H~ 0.0] vetlomyCurremt 0.00003 0.00002 0.00001 0.00000 -0.00001 -0.00002 6 conc (mM) —s— Ipc —e— Ipa 108 Color of Complexes by UV-visible Spectroscopy Objective: To Experimentally identify the Color of Com plexes with Help of UV-visible Spectrophotometry Apparatus: UV-visible spectrometer, cuvettes, standard flask, glass rods, Chemicals Fequlred: Coc..6H,0.HcI, [Cofen)scls [cucl}, [Cu(NHs)s}*, [Co(en),ch}’, distilled Theory: Most transition metal complexes are I ie pae throughs ao ip! Colored as shown in Figure 1. This imy le of the compk absorbed by the oa Plex, some of the wavelengths oft plies that as white light and the rest transmitted, so th implement complex (see Table’), ‘4, So the complementary he visible spectrum are ‘color Is imparted to the Figure 1: Colored Transition Metal Complexes Color absorbed and Color transmitted (complementary color), Table 1: Color Of Light Absorbed ete range Color Of Light Transmitted Red 700-620 Orange Green 620-580 Yellow Blue 580-560 Violet Green 560-490 Blue Red Orange 490-430 Violet 430-380 Yellow preliminary idea of color can be gained by synthesizing different complexes of the same metal ing different ligands and visually observing their celor, ectrophotometers, the ligands can be maximum absorption (Anax). Being a direct function Of Ao, the Amax ed to accurately Bs 5. ghest wavelength) absorption maximum corresponds to th and, more is its interaction with the metal ion and greater ltting; hence, smaller will be the value of Amn. Varlgtien In 4ovalues with varying ligands for = same central metal jon Bives rise to different colours (absorption spectra) of metal mplexes; based on this variation, aseries called the spectrochemical series has been develop ry Wavelengths of lowest energy can be General, the lowest energy (i.e. le Ao transition. The stronger the is the corresponding crystal field 66Paetnes S AUR reterence savent Mt cunette ant place the cute ty Cell 1 UN MAC IKK Bike —s News Spectrum Sean, Operation —S Setup —S Set alt the deainedt parameters > Ob. ick on Operation —s Bhwk (for reference measurement Sur the ampve dt the cuvette and place the cuvette in the sate cell, KCK on Operation —s Start (for sample measurement) A Te granh al De displayed on the screen Now cK on ile =o Expert to Microsoft Excel, KL Foe shutting dower the computer —selick on close button in software Swen computer —s close Hack switch of machine, mA Nwtch off the power supp trom power board langthe 34 Record the UNiMis spectra of each of the prepared compleres between wavelengt SOOM after proper mang, gn oD » Atter shuttlr S Record the Uvivisitte spectra of each of the prepared compleres between wavelengt 34O-S00 nm after peoper MAING. Precautions: Range and Wash the cuvette carefully, 3 Please shut down the main power of the equipment after use, Resutts: Btn YSIS fillin the table given below and plot your data graphically for each of t For 2 comparative study, plot the data for all the complexes of a particular metal ina sin,SIGNED STATEMENT: 2) "have only worked with the following persons HARM HeenA (RA0fEOo! 2). 's work. for this lab experiment. Ireceived no other help and! did not copy another person Rov Signature: _ 69Example Questions: 1. Explain the working principle of UV-Visible Spectroscopy. 1 a sdoh'on Wham a. benno monochromds, Ligrd is pnasd though, of adoh / Gm absorbing swbelance , tho va bsvewing iwlnshy of rodsbic rodichion, te Oe thu “thcbnam g) absorbing wabe:l fo in cidoty tedchen ad Yh cone. ¢ saboh'on, 2. Are there any limitations on Lambert beer law, domber - beep Jans compnot be adf- oped bb igh. Comenhakon qsolubone. 3. Why the CFSE values vary with the nature of ligand. fe shorgthy Pubocken gia) bgand voilhy meal in 16 dleard . Hons CRE valu obifler. 4. How CFSE values are related with the absorption of the complex. Highn sping Veluay 19, Wa hbo onngy for tedlehen of electroro. Here Yt Cevatperds b Jou wavalung ha . ene, atrorh’ns foo coll Coloves,, Ho sp ¥hing peck chosngs - 5. Can you see a charge transfer band in the UV-Visible Spectroscopy. Chovge tram}. vq reph TS Viiible jor vv OV spedrastccoy. bid hs )-volue fs Very Wig . & Explain with examples the selection rules for electronic spectroscopy. ~ Spin sdecionrak : vss allowg SS=AL forbiddey dopre veoh + 60 = 41 Wousd O Aor biddan 70ABS. 0.5 0.4 0.3 0.2 0.1 0.0 200 300 400 500 WL (nm} oe ADS: 800Ags. —— Abs. 2.5 2.0 / 15 1.0 0.5 0.0 : — 200 300 400 500 600 700 800ee ee 2.5 2.0 1.5 Abs. 1.0 0.5 200 300 400 500 600 700 800 900 WL (nm)9 Critical Micelle - Concentration of a Surfactant Srteminason of etl Mice Concentration court by conbectey mt. CA, Mexg tie Bier Wht phe to, vom tae Dp Introduction: ‘5 oon be nericric, zioric, coticric. or zits oric. Ta paance between hydrophobic at hydrophilic pas Gres Gace ropetes i oneene “ (EPID afi to ators 2 iertoces ad essecation tion farm cals Cone are Fouo is soluble in mater wat he hydrophobic group is insokible. When surfactarrs fre to mater Sey cas ae >perty can be used to determine the CMC of the surfactant using 2 conductance call. Wihe rductance cell is immersed in deionized water, the cell shows very iti backer ;ductance. When an aqueous solution of an ionic surfactants added to the cellin swall alia 1%8. 9. The contents are carefully shaken to ensure uniform concentration and the shaking must be performed carefully to avold frothing. }. Conductivity Measurements Firstly, note down the cell constant for the conductivity cell. Measure 25 mL of de-ionized water using a pipette/measuring cylinder and pour into a 100 mL beaker containing a magnetic spin bar. Place the beaker ona magnetiqstir plate and stir the water. . After thoroughly rinsing the conductivity electrode, immerse it into the beaker containing water and measure the background conductivity of the solvent water. Fill a burette up to the zero mark with the CTAB solution Sample-A. . Run 0.5 mL of the sample-A through burette to the beaker and measure the conductance. Repeat procedure (6) for 40 more aliquots (each of 0.5 mL added to the solution) and note down the conductance. The solution should be gently stirred with a magnetic stirrer throughout the experiment. Repeat the procedure (2}(8) with 0.3 mL aliquots added 40 times for other CTAB solutions, in case provided. 10. Clean working table and apparatus after finishing the experiment. Precautions: i 2 3. The solution must be prepared slowly to avoid frothing. The stirring is controlled not to be too fast during the experiment to avoid the formation of bubbles as bubbles can affect the conductivity. CTAB solution is added slowly to the water to prevent the formation of bubbles/frothing. Results and Calculations: Amount of CTAB weighed for 4mM toomL CTAB solution..s%.9... (a) Conductivity recorded for aqueous CTAB solution (sample A) S. No. Volume of stock Concentration of Conductivity solution of aqueous | CTABin solution (M) (usim) % | Goducba CTAB added (mL) 4 0 0 Q. 714 S137 2 \ OAS3 279, 20.85, 3 2) 0.9962 \9.07J0 as2s 4 g GN235 26.665 29 5 4 O.SS\7 36.344 67.18 6 Ss ObbE Y2.4 4 8643 Z 6 0-114 4Q-29 at. 18 8 1 G.81F $3.52 avy 9 g 6.969 $3.38 Jos.r 10 q Hae s.237 los-& 1 lo ft Sz. $5 lok. 2 2 i] 29 Go.0 Sh MW 3 12 1.297 61. 24h NG. 4 13 \ a 62.106 We5 1 i435 G3ies 16 ie ). 64.216 N37 7 16 1.566 ae |e 8 [5 Leia 6 s.992 | 121-8 19 iz [er 62.629 | 123-9 20 19 [4-727 67-787 28-3 24 Ze (336 (777 GX659 126-9 22 2 tale £9103 \27-4 23 22 1.949 70.005 _|lza.y i 24 “21-959 1.466 wet 3. Q4 [ 972 = Sy V3e.8 38 Qs I 720 1a 26 2.024 13.52 28.9 I ol Bron 14 Y0e I36 6 29 AL 913 WW. 387 132.5 30 24 2.142 Ty. 12. Ba) 2 ~30 2.132 76.144 BBQ 32 2 9. 214 18- 63) Bag 33 ev} [3.8245 15. 02 lMo.g 34 23 rE 76. 499 ay 35 34 I PG 16.927 $2 3 3S ; 2.233 AL. 208 92.9 38 | 39 40 a I 42 I 43 I 44 | 45 ae 46 | 47 T 48 49 50 | 51 52 | 53 | 54 55 56 | | 57. | | 58 | 59 | | 60 | 61 | | | 62 | 63 64 | { 65 I | 78Conductivity vs CTAB 30 80 +— 70 60 + 50 40 20 +— 10Example Questions 7) What electrodes are used i the conductance cell” ry A Tec plobrgAd elechdcdes Yerkd by wrt dare L 1 ? Ov uidin condactoma cell. Sa ers me tony arenes ete cnacce ee Rewskavt » Oban Cordichorna, Grew Rewshuly: a-m Gorduckuhy: tienen Ineber 3) How the conductance for song elecrolyie and for mea diecroivs varies wi Storg dadroly ke Tous teh Crdudens Grd eros, en ie in ere. Weap dabolyin nowt Jos wndechou A : i and dicrarse With int in Conankeahor 4) What does the slope of conductivity versus concentration pict for 2 srone elecraie measure?” : Copdond. 4) he he Gsoze qe gryph Gian tected ga Stare dale Ord Sings, groph xe? ional Sopa 5) When a voltage is applied across a conductance, electrolysis of the siecrraiyte s 2 pote problem. How is this overcome when measuring conductance in a conducxane cei? A.C cypuntd wad to overcome tis. borw eer eer Ser er eer el 6) Draw a cartoon structure of a surfactant molecule and a spherical micelle, What is the ty’ size of a micelle? tu sa mnbbly ( oboud lo-loo nm, feat hel a we ite aap t Hieelt 7) Inthe conductance versus concentration plot mentioned above, there isa change in the si at CMC. Why? Pliaa Celli conesnbvabon , Hae elle, «stb gornirg ovr thus Hoe }sa davase in @ndudone inthe plot. 8110 Aldol Condensation Reaction Objective: To prepare Tetraphenylcyclopentadienone using two reactants. Apparatus and chemicals required: Dibenzyl Ketone (1,3 diphenyl-2-propanone), Benzil , KOH, EtOH Beaker, flask, ice bath, condenser, weighing balance, filter paper, spatula, butter paper, Buchner funnel, water heater etc. Theory: In this experiment, we conduct an interesting aldol condensation that involves one ketone that has a- hydrogen atoms (dibenzyl ketone) and one that does not (benzil). Thus, dibenzyl ketone will serve as the nucleophile, because it will donate a Proton to a base to form an enolate. Reaction for this can be written as shown in Figure 1: > oe ~ 2 / LO. roneon ChE J ; 2H,0 ~ 2 (oo est Deno “enperrcgenateore Figure #2 Aldol reaction ‘You can work out the mechanism for the reaction by forming an enolate from dibenzyl ketone in base, allowing it to attack on carbonyl group in benzil, and eliminating water from the adduct. Repeat the Process with the remaining a-hydrogen atoms while closing the five-membered ring. The final product is a purple solid. Mechanism can be shown in Figure 2 as shown below: KOH, E10H -2H0 ee Figure 2: Mechanism of the aldol condensation reaction Procedure: 1) Mix 210 mg of benzil and 210 mg of Dibenzyl ketone and 5 ml of ethanol ina small round bottom flask. 2) Shake the mixture until It becomes uniform. 3) After shaking well, attach a reflux condenser to the flask and heat the mixture ona steam bath and shake the mixture well. At the same time take 3 mL of ethanol In another flask and mix 0.3 g KOH tot. When the first flask mixture starts boiling add the mixture of second flask (ethanol + KOH). 4