Problems and Solutions in Engineering Chemistry ei Es Dr. B. §. ChauhanPublished by : UNIVERSITY SCIENCE PRESS (An imprint of Laxmi Publications (P) Ltd.) 113, Golden House, Daryaganj, New Delhi-110002 Phone : 011-43 53 25 00 Fax: 011-43 53 25 28 www.laxmipublications.com info@laxmipublications.com © AU! rights reserved with the Publishers. 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Printed at : Ajit PrintersCONTENTS PAGES SAMPLE EXAMINATIONS 1—296 ‘Chemistry-1 1 Chemistry-2 27 Chemistry-3 a8 Chemistry-4 oo Chemistry-5 92 Chemistry-6 131 Chemistry-7 160 Chemistry-8 183 Chemistry-9 207 Chemistry-10 259 SOLUTIONS TO ENGINEERING CHEMISTRY. 297-328 Chapter 1 : 297 Chapter 2 238 Chapter 3 303 Chapter 4 304 Chapter 5 307 Chapter 7 309 Chapter 8 312 Chapter 9 313 Chapter 10 315 Chapter 1 317 Chapter 13. 318 ‘Chapter 14 322 Chapter 15 325 SOLVED NUMERICALS 329-338 Chapter 10 329 Chapter 11 33aSAMPLE EXAMINATIONS CHEMISTRY-1 Time: 3 Hours Total Points: 100 Note: Answer all 5 questions of 20 points each. Note: Answer all Questions, Q.1 (a) Define a polymer? (b) What is meant by degree of polymerization? (c) Why do alt simple organic molecules not produce polymers? (d) Why are plastics indispensable in everyday life? (¢) Why is teflon highly chemical-resistant? (f) Describe the mechanism of Diels-Alder reaction. ‘Ans. (a) Polymer: A polymer is a compound of high molecular mass formed by the combination of large number of small molecules. The small molecules which constitute the repeating units ina polymer are known as monomer units. For example, polyethylene is a polymer which is obtained by the polymerization of ethylene. The ethylene molecules are referred to as monomer units. nCH,=CH, ——+ [—CH,—CH,—], Ethylene PolyethyleneEnciveerinc CHemistry A polymer can be formed in following ways. Depending upon the mode of synthesis, the polymers are classified as: 1. Addition polymers, and 2, Condensation polynters. 1, Addition polymers. When the monomer units are repeatedly added to form long chains without the elimination of any byproduct molecules, the product formed is known as addition polymer and the process involved is known as addition polymerization. The monomer units are unsaturated compound and are usually the derivatives of alkenes. The molecular formula therefore the molecular mass of the addition polymer is an integral multiple of that of the monomer units. Some examples of addition polymerization are: @ nCH;=CH, ——> [-CH,—CH,-, Ethylene Polyethylene or Polyethene wa ncH=tH _ [CH=CH], CH, CH; Propylene ~ Polyethylene (id nCl,=CH — or, ca cl Vinyl chloride Poly vinyl chloride (PVC) (i) rH CH — [CH—-CH-}, CN CN Acrylonitrile Orlon 2. Condensation polymers. In this type of polymers, the monomers react together with the elimination of a simple molecules like H,O, ROH or NH, etc. The reaction is known as condensation and the product formed is called condensation polymer. As the process involves the elimination of byproduct molecules, the molecular mass of the polymer is not the integral multiple of the monomer units. For examples, nylon-66 is a condensation polymer of hexamethylene diamine and adipic acid.Samrce Examnanions 3. nH,N—(CH,),—NH, + nHOOC—(CH,) —COOH Hexamethylene Adipic acid diamine H H | | — [-NACH)N-EACH) EI, +2nH,O Nylon-66 Some other examples of condensation polymers are as follows: Dacron (polyester). A polymer of ethylene glycol and terepthalic acid. Bakelite. A polymer of phenol and formaldehyde. ‘Ans. (6) Degree of Polymerization. The physical properties of a polymer mainly depend upon the molecular weight of the polymer. Which in turn depends upon the number of menomer units present in the polymer molecules. The number of monomer units present in a polymer molecule is called the degree of polymerization. The degree of polymerization is denoted by [CH,],. The degree of polymerization is related to the molecular weight of the polymer [M] by the following equation. m or M=Dpnt where Dp is the degree of polymerization mis the molecular weight of the monomer unit Mis the molecular weight of the polymer Generally all the polymers or we can say that most of the polymers have molecular weight ranging between 5000-200000. Since the reaction of polymerization cannot be controlled to form a polymer having definite molecular weight, so both the molecular weight and degree of polymerization are always described as average molecular weight and average degree of polymerization. The degree of polymerization can be used to measure the physical and mechanical properties of a polymer. When the degree of polymerization is very low then the substance will not be having the properties of polymer. When a certain degree of polymerization is achieved the properties are developed of a polymer.Encineceinc: CHemistey Ans, (c) The union of two or more smaller and simple molecules of similar or different types with or without the elimination of small molecules leading to the formation of new carbon-carbon bonds is known as polymerization. All simple molecules should at least have two reactive or bonding sites in a substance which has to act as amonomer in the formation of the polymer Thereforeall simple molecules do not produce polymers, The number of bonding sites ina monomer is known as functionality, for example, in ethylene, the double bond is regarded as a site of two free valencies. As a result of rupture of double bond (—C=C—) two single bond become available for combination and therefore ethylene is bifunctional and can add to halogen atoms or two hydrogen atoms. i H-C-H oH, HCH { —- | He-C—-H Hq-H H { H-C-H g, HOCH or , H-C_H HoH a Similarly other homologous of ethylene like as propylene, butylene and vinyl CH, i] compounds like as vinyl chloride | CCI), styrene (C,H, CH=CH.) etc. have the functionality of two, because of the presence of a double bond. Acetylene can add to four halogen atoms or four hydrogen atoms and thus has functionality of four. A compound also assumes functionality because of the presence of reactive functional groups as: OH", COOH”, NCO", NH”, SH” ete, For example, CH,COOH, C,H,OH etc., are monofunctional compounds, similarly malonic acid (COOH—CH,—COOH) and ethylene CH,OH glyco! | CH,OH | are bifunctional compounds. Therefore only those organic molecules having reactive bonding sits or functionality can actas monomers in the phenomenon of polymerization.SAMPLE Exasananions 5 Ans. (d) The term plastics refers to polymers of high molecular weight, which can be molded into any desired form, when subjected to heat and pressure in the presence of a catalyst. Plastics have assumed very important position as engineering material due to some special properties like as good tensile strength, good thermal and electrical insulation; low thermal expansion coefficient: high corrosion resistance; low cost of maintenance; chemically inert to acids, oils. light; and high resistance to abrasion. Plastics have a number of uses in our daily life due to above mentioned properties. Plastics can be extruded as sheets or pipes, painted on surfaces, or molded to form countless objects. We wear these man-made materials, eat and drink from them, sit and stand on them; turn knobs pull switches, and grasp handles made of them; we live in houses and move about in vehicles that are increasingly made of them. Although plastics have many uses but it is also feared that civilization may some day be burried beneath a pile of plastic derbis-plastic cigar derbis have been found floating is Sargasso sea, but still plastics seems to be indespensable in our everyday life because with plastics we can do things neverbefore possible. By use of plastics blind people can be made to see, and cripples to walk; heart valves can be repaired and arteries be patched; damaged tracheas, larynxes, ureters, and even entite hearts can be replaced. These materials protects us against heat and cold, electric shock and fire, rust and decay. Hence is may be concluded that, though the plastics pose a great threat ta the environment protection, yet they seems to be indespensable in our everyday life. Ans. (e) Teflon (Polytetrafluoroethylene) is a highly polymerized resin obtained by the polymerization of tetrafluorvethyl gas, CF, = CF, which is prepared as HF CHCl, ——+ CHF.Cl —— CR=CR, ‘Chloroform Difluoromono: TFE chicromethane Polymerization of tetra fluoroethylene is carried out in presence of water, at elevated pressure of 68 kg/m?, temperature from 55°C to 240°C, in corrosion tank in presence of an aqueous alkali medium. Benzoyl peroxide, persulphates, H,0,, etc., are used as catalysts.Encivecrnc CHesustay Tetrafluoro Teflon ethylene Teflon is a highly crystalline and orientable polymer. It softens at 327°C and decomposes at about 400°C without charring into volatile vapors. Teflon has. great resistance to chemical attacks like of strong alkalies, acids like HCI, HNO,, aqua regia (HNO, + 3HC1) hydrofluoric acid. Only alkali metals either in molten or dissolved in liquid ammonia attack the polymer by removing fluorine from the chain. Fluorine itself can degrade the polymer under pressure and prolanged contact. Highly chemical resistant properties of teflon (CF,=CF,) are due to the presence of highly electronegative fluorine atoms and due to regular configuration of the molecule, there are very strong attractive forces between the different chains. These strong forces give teflon extreme toughness, high softening point, exceptionally high chemical resistance toward all chemicals. Ans. (f) Diels-Alder reaction involves the reaction between a diene and a dienophile to form a cycliccompound. Itconsists ir 1, 4-addition of conjugated diene to second unsaturated molecule. For example, Cot —O 1, 3-butadiene Ethene Cyclohexene (diene) (dienophite) (adduct) 2 CHCO. Co, Cc +i >So — Cx So Ss CHCO co’ Ethene Phthalic Tetrahydrophthalic anhydride anhydride Mechanism. Both diene and dienophile undergo electromeric shifts and such excited states of two molecules are created that they condense to form anadduct in 1, 4-position of the diene. It invalves following steps:Sampe Examinations 7 (i) Diene and dienophile undergoing electromeric shifts. Gow att CH CH b I « x cH, ‘CH, o oe CHCO., CHCO, I o— | Coico” HCO” (i) The excited forms of diene and dienophile get condensed in 1, 4-position of the diene to form the adduct. Q hg ct HE + CHCO, Slow HQ cHCO” HC, cHCO” oO eo 2 CH, HC CHOON 0 HC cuco” ‘CH; Tetrahydrophthalic anhydride (adduct) Fast Q2 (a) Define Corrasion. (8) Discuss the mechanism of electrochemical carrosion (©) What is meant by the term “passivity”? (d) What are the factors which affect corrosion? (e) Comment on the use of aluminium in place of zinc for cathodic protection of iron from rusting. (f) How much rust (Fe,0,3H,0) will be formed when 100 kg of iron have completely rusted away?Excmvarac CHmmerey Ans. (a) Corrosion: It is a matter of common observation that certain metals (except those which are least reactive like Au, Pd, etc.) are slowly eaten up on long exposure to atmosphere, for example, silver gets tarnished, copper develops green coating on its surface, iron rusts, and lead loses its lustre. In fact, such metals react with the gases or moisture persent in the environment to form undesirable compounds. This process in general is referred to as corrosion. Corrosion may, thus, be defined as the process of slow conversion of metals into their undesirable compounds (usually oxides) by reaction with moisture and other gases present in the atmosphere. Ans. (+) Mechanism of electrochemical corrosion: According to electrochemical theory, the impure iron surface behaves like a small electrochemical cell in presence of water containing dissolved oxygen or carbon dioxide. Such a cell is also-called corrosion cell or corrosion couple. In these miniature corrosion cells, pure iron acts as anode and impute surfaces act as cathode. Moisture having dissolved oxygen or carbon dioxide in it constitutes electrolytic solution. At anode, oxidation of Fe atoms takes place. Thus, Fe atoms pass into solution Fe** ions leaving behind electrons in the metal which are pushed into cathodic area. Fe ——> Fe"? + 27) Eo, = - 044 V ® Ateathode, the electrons are picked up by the H* ions which are produced either from HO or from HCO, (formed by dissolutien of CO, in moisture). CO, +H,O ——» Ht + HCO,” 2H*(aq) + 2e° ——> 2H The Hydrogen (H) atoms, thus, formed, reduce the dissolved oxygen as 2H4+ ; 0, —> H,0 ‘The net reduction process at the cathodic area is 1 2H? + 5 O, + 26° ——> H,0; Byg = 123 V Fe + ¢ O,+ 2+) H,O— Fe,0, .xH,0 +4RUST (Fe,0,..xH,0) Fe ANODE AREA 2H’ +20" +10, —> H,0 Fe —+ Fe" +26" The net reaction of the corrosion cell can be putas 1 o Fe +2H* + 50,——> Fe™* + H,O; Ety, = 1.67 The ferrous ions so formed more through water and come at the surface of iron object where these are further oxidized to ferric state by atmospheric oxygen. _and constitute rust which is hydrated iron (III) oxide. 1 2Fe* + 5 O, + 2H,O——> Fe,0, + 4H* Fe,0, + xH,0 —+ Fe,0,. xH,0 (Rust) ‘Ans. (c) Passivity: A process in whicha metal or analloy exhibit a much higher resistance to corrosion than expected from its positions in the electrochemical series is called passivity. It simply means the lack of activity under the conditions where metal would be expected to react readily. There are certain metals which are passive to corroding agent. For example, iron (Fe) is passive to concentrated HNO, and aluminum (Al) has no reaction with concentrated nitric acid (HNO,) in the absence of chlorides. Reason for passivity. This process is due to the formation of a highly protective thin film or the surface of the metal or an alloy, which makes the metal or alloy more noble. The film so formed is regarded as insoluble, invisible, non-poros and self-healing in nature. Metals like chromium (Cr), aluminum (Al), nickel (Ni), titanium (Ti), etc. and a variety of stainless steel alloys containing chromium are passive due to their capability of forming an oxide film on their surfaces. Passive oxide films are artificially produced on certain metals.10 ENGINEERING CHEMISTRY Ans. (d) Factors which affect Corrosion: The factors affecting the rate of corrosion are: (i) Presence of impurities. Presence of impurities helps in setting up a corrosion cell and makes the corrosion to occur rapidly. For example, pure iron does not rust. (ii) Strains in metal. Strains in metal also help in corrosion. For example, in iron articles, rusting is more pronounced on the areas having bends, dents, scratches, nicks and cuts. Reactivity of the metal. The more active metals are more prone to corrosion. (iv) Presence of electrolytes. The presence of electrolytes also makes the corrosion process faster. For example, iron rusts more rapidly in saline water in comparison to pure water, (0) Airand moisture. Airand moisture are quite helpful in corrosion. The presence of gases like CO, and SO, in air makes it still rapid. For example, no rusting is caused if iron is kept in vacuum. Ans. (e) Both aluminum and zinc can be used as sacrificial anode to protect iron from ‘the rust, since both are present higher in the electrochemical series than iron. In this process sacrificial anode gets corroded and supplies electrons to the metal. This presents the anode reaction to occur at the metal surface and therefore protects the structure. ‘Sacrificial anode Negative Protected structure. In case of aluminum and zinc to be used as sacrificial anode, the electrode potential of aluminum (AP) is - 1.66. While that of zinc (Zn?*) is - 0.763. So, aluminum is more reactive than zine, and therefore it will work more efficiently as sacrificial anode than zinc. Further, iron and aluminum are present more apart in the galvanic series as compared to iron and zinc, and therefore aluminum will suffer more corrosion as sacrificial anode than zinc and hence supply more electrons to the protected structure. Ans. (f) Rust is formed as: 2Fe + 6H,O —— Fe,0, . 3H,O + 3H RustSampte Examinations 11 According to the equation. Weight of Fe used = 2 « 56 = 112g Weight of Rust found = (2 x 56 +3 x 1643 x 18) = 112448 +54 =214 112 g of iron forms 214 g of rust + 1gofiron will forms = 24 ¢ of rust 112 214 x 100000 = 200000 g = 200 kg of rust M2 8 6 + 100000 g of iron will form = Q3° (a) Define a chemical fuel, + (b) What is meant by calorific value of a fuel? What is the difference between gross calorific value and net calorific value? (¢) Why are gaseous fuels more advantageous than solid fuels? (d) Write the constituents responsible for the permanent hardness of water, Discuss one treatment method, (e) Why does hard water consume a lot of soap. (f) Why does magnesium bicarbonate requine double amount of lime for softening? Ans, (@) Whenever a substance is burt in air or oxygen with the evolution of heat, is known as cumbustion and the substance which is burnt is called combustible substance. The heat evolved during the combustion can be used economically for industrial or other use. All the combustible substances are known as fuels. Therefore, a fuel may be defined as, any combustible substance, chemical or reactant containing carbon as the main constituent which on proper burning produces heat that can be used economically for industrial and domestic purposes and in generation of power. Fuel +O, ——> Products + Heat Depending upon the state of matter, the fuels are classified as follows: Primary fuels. These are naturally occuring fuels found freely on earth’s crust. These are further classified as, solid fuel forexample, wood, peal, lignite, coal, ete., liquid fuel such as petroleum oil and gaseous fuel for example natural gas. Secondary fuels. These fuels are either artificially manufactured or derived from primary fuels. These are further classified as solid fuels for example coke, charcoal, petroleum coke, colloidal fuel, thiokol, hydrazine, etc., liquid fuels12 Excincerina Crenister for example, gasoline, diesel oil, kerosene, coal tar and its fraction and gaseous fuel for example CNG, LPG, ete. Characteristics of a good fuel: 1. Tt should have low moisture content as moisture reduces the heating value. 2. It should not give harmful gases on its burning. 3. It should have low content of volatile matter and the ash contert should be low. 4. It should have high calorific value ie., it should produce large amount of heat on burning. 5. The fuel should have moderate ignition temperature. 6. It should be easy to handle, store and transport and burn in air with more efficiency and without smoke. Ans. (b) The amount of heat obtained by the complete combustion of a unit mass of the fuel is the calorific value of a fuel. Gross Calorific Value. Gross Calorific Value is the total heat generated when a ‘unit mass of fuel is completely burnt and the products of combustion are cooled down to 60°F or 15°C. When the fuel containing hydrogen is burnt, the hydrogen present in the fuel produce steam. If the products ofcombustion are condensed to 15°C, the latent heat of condensation of steam also gets included in the measured heat. This is called higher or gross calorific value Net Calorifie Value. Net Calorific Value is the net heat produced when one unit of fuel is completely burnt and the products are allowed to escape. Net Calorific Value = Gross Calorific Value — latent heat of condensation of the water vapor produced = Gross Calorific Value — (mass of hydrogen per unit weight of the fuel burnt « g x latent heat of vaporization of water) For the reaction H, + 0, ——> HO 2g 16g 18g 1g 8g 98 One part by weight of hydrogen gives nine parts by weight of water. The latent heat of steam is 587 cal/g of water vapor produced.Samos Examinations 13 H * Net CV = Gross CV -9 x 75 ¥ 587 (CV = Gross CV = 0.09 x H x 587 Units of Calorific Value: Calorific value of solid and liquid fuels are usually expressed in calories per gram (cals/g) or kilocalories per kilogram (kcal/kg) ot British Thermal Unit per pound (B.Th.u/Ibs). Calorific values of gaseous fuels are expressed as kilocalories per cubic meter. Ans. (c} The mainsolid fuels include wood, peat, lignite, coal, charcoal and brequetted fuels. Besides these, bagasse, spent tar, rice husk, coconut and nut shells are employed as fuels. The main gaseous fuels include natural gas, water gas, producer gas, coal gas, oil gas, biogas. Both solid fuels and gaseous fuels have their advantages and disadvantages, Gaseous fuels are considered as advantageous to solid fuels due to the following reasons: 1. Their calorific value is quite high comparison to solid fuel and these fuels can be lighted vary easily. 2. Gaseous fuels burns without any smoke and produce no ash while solid fuels give large amount of smoke and produce a lot of ash. 3. Gaseous fuels can be transported easily through a pipe line to the place of fuel while solid fuels require carrier for transport. 4. In gaseous fuels complete combustion takes place even in very little amount of air and so greater efficiency is obtained as compared to solid fuels. Ans. (id) The soap consuming capability of water is called the hardness of water. It is of two types permanent and temporary hardness. The temporary hardness of water is the presence of soluble salts of bicarbonates of calcium and magnesium and that hardness of water can be removed by boiling of water. The permanent hardness of water is due to the sulphides, chlorides and nitrate of calcium, magnesium and other metals and it cannot be removed by boiling of water. ‘Treatment of Water. There are following two methods of water treatment. 1. Lime-soda process. These are of two types: hot lime-soda and cold-lime soda process. 2. Zeolite or permutit process, Zeolite process involves softening of water by a natural or artificial zeolite. Zeolite is hydrated sodium aluminosilicate, Na,O.Al,0,35iO, yH,O. Zeolites are the substances insoluble in water and can act as base exchanger when placed in contact of water containing cations. Zeolites are also called permutits and are of two following types: (i) Natural zeolites. (ii) Synthetic zeolite prepared from sodium silicate and sodium aluminate.14 Enciveerinc CHesustey The zeolite softeners consists of a steel tank packed witha thick layer of loosly packed zeolite over a layer of course sand and gravel. The water enter from the top and passes through bed of zeolite, where following reactions occur. Na,Z + Ca(HCO,), ——= CaZ + 2NaHCO, Na,Z + Mg(HCO,), —-—+ CaZ + 2NaHCO, Na,Z + CaCl, ——> CaZ + 2NaCt Na,Z + CaSO, —— CaZ + 2Na,SO, Na,Z + MgSO, MgZ + 2Na,S0, Na,Z + MgCl, ——-—» MgZ + 2NaCI where Z = ALO,.xSiO, yH,0. Hard water Zeolite bed Soft water Zeolita softener This process removes both types of hardness temporary and permanent hardness. The utility of the processes lie in the fact that when zeolite bed gets exhausted ic,, it looses ils softening, capacity, it can be regenerated by passing 10% solution of sodium chloride solution through it. The following reaction take place, Caz + 2NaCl — Naz + CaCh (Exhausted zeolite) (Regenerated zeolite) MgZ + 2NaCl ——> Na,Z + MgCt,Samece Exawwations 15 Ans. (e) The water which does not form lather with soap and consume a lot of soap is called hard water. A soap consists of sodium salt of oleic acid, palmitic acid and stearic acid. When soap is dissolved in hard water it does not allow lather tobe formed because soap is precipitated as insoluble calcium and magnesium stearates. No lather is formed until all these ions are removed and this results in the waste of large amount of soap. 2CyHyCOONa + CaCl, —= (C,HyCOO), Cad +2NaCl 2C,sHy,COONa + Ca(HCO,), ——> (C,HyCOO), Ca L + 2NaHICO, Calcium stearate The insoluble calcium stearate is the familiar scum that forms on soapy water. The valuable stearate group, which loosens the dirt is lost completely in this way, Ans. (f) Water can be softened either by the removal of calcium and magnesium salts of by their conversion into corresponding salts of sodium. Bicarbonate present in the water causes temporary hardness which can be removed by boiling magnesium bicarbonate Mg(HCO,), can also be removed by lime-soda method which used lime and soda ash (Na,CO,). Lime is required to remove temporary hardness while soda ash is required for the removal of permanent hardness. The following reactions involved in this process. CO, + Ca(OH}, —— CaCO, ++ H,0 Ca(HCO,), + Ca(OH), ——> 2CaCO, £ + 2H,0 Mg(HCO,), + Ca(OH), ——> MgCO, + 2CaC0, £ Magnesium carbonate (MgCO,) formed further reacts in following manner: MgCO, + Ca(OH}, ——> Mg(OH), 4 + CaCO, 4 Itis clear from the above reactions that in case of temporary hardness, each unit of calcium bicarbonate requires one mole of lime whereas each unit of magnesium bicarbonate [Mg(HCO,),} requires two moles of lime. Therefore IMg(HCO,),] requires double amount of time for softening QA (a) How is ozone formed and depleted in nature? What are the consequences of depletion of ozone layer in the atmosphere. (b) Describe the characteristics of major atmospheric regions. (0) State the intermediate compound formation and adsorption theories of uatalysis and show how they explain the characteristic of a catalyzed reaction.16 Encineerinc Cresistir Ans. (a) Ozone is presentin the stratosphere. The ozone layer in the stratosphere acts as @ protective shield for life on earth, it absorbs the harmful solar radiations like as UV rays which are lethal to life causing DNA mutation and skin cancer. Also in absence of this layer the temperature of the lower atmosphere will rise to such an extent that the biosphere will turn into a blast fumace. Formation of ozone layer. The ozone layer is formed in the stratosphere by a photochemical reaction followed by a third body reaction. M2nm 0,+hv ——5 0+0 O +0, + M(N, or 0.) —— 0, +M @ Third body The third body (M) absorbs excess energy liberated by the reaction (i) and thereby stabilize the O, molecule, The thickness of the ozone layer is measured in Dobson units (DU), where, IDU =0.01 mm of the compressed gas at 0°C and 760 mm Eg pressure. Average thickness of the ozbne layer in stratosphere has been estimated to be about 230 Dobson units (DU). However, thickness varies marginally with latitudes because of different atmospheric conditions. The thickness is found comparitively low in polar region. Depletion of ozone layer. According to World Metrological Organization Geneva, ozone levels have been depleting at an average annual rate of 4.3% every decade in Northem Hemisphere and 4.1% in Southern Hemisphere, since 1997. Qzone layer is believed to be depleted by reaction with atomic oxygen, reactive hydroxyl radicals and nitric oxide, @ 0, + HO" —— 0, + HOO" HOO" + O—— HO" +0, () 0,+O—+ 0, +0, (iti) 0, +NO——> NO, +0, NO, +O——+ NO +0, Apart from the above mentioned species, chlorine also plays an important role in depleting ozone in the stratosphere in following manner: Clt +O, —+ G—O" + 0, Cl—O" + O—> Cl" + 0, oO ClO" +NO,—+ CILO—NZ Chlorine nitrateSampue Examinanions 17 As seen CI’ atoms are regenerated, so that a long chain process is involved. The depletion of ozone layer have been found to be much more acute in polar regions particularly to the formation of ozone hole, this may be because of two. reasons: (i) Cold climatic conditions and other complex atmospheric parameters including turbulences. (i) Absence of MO in these areas which destroys Cl* and checks ozone depletion. N,O at sub-zero temperature freezes into ice droplets. Consequences of ozone layer depletion. Ozone layer destruction leads tomore ultraviolet radiation reaching earth causing similar climate changes as in greenhouse effect and also these are harmful to man causing skin cancer, sun burns, leukemia, cataract of eyes, haemorrhage, edema, lung injury, lung cancer, DNA mutation and many more adverse effects. Ans. (b) Structure wise atmosphere consists of concentric layers of air and each layer has a different density. Therefore the atmosphere is not of the same thickness at all levels. It extends up to five hundred kilometers, with widely varying temperatures, even within each region. The atmosphere may be broadly divided into four regions shown as follows: Characteristics of the Major Regions of the Atmosphere “© Name of the ~,| Height above the ‘Temperature Major chemical “region earth’s surface, Km range °C species present Troposphere ou | 15 to -56 0, Ny, CO, H,0 Stratosphere 11-50 = 56 to-2 0, Mesosphere 50-85 210-92 Thermosphere 85-500 92 to 1200 The Troposphere. This atmosphere layer lies close to the earth's surface and extends up to an altitude of eleven kilometers. The upper limit may vary by a few kilometer, depending upon temperature, nature of terrestrial surface etc. The troposphere contains 70% of the mass of the atmosphere. This is the basal part of the atmosphere and composed mainly of nitrogen and oxygen. It also contains argon and carbon dioxide and traces of helium, neon and methane, etc. It is more or less homogeneous in the absence of air pollution, mainly due to the constant circulation of air masses in this region. The water content may vary due to the troposphere is also a turbulent region due to the global energy18 Encincering Ciesustrer flow arising from in balances of heating and cooling rates between the equator and the poles. The temperature in the troposphere falls of uniformly with increasing altitude from ground temperature to about - 56°C. The cold layer (- 56°C) at the top of - the troposphere is known as tropopause and marks the temperature inversion. The Stratosphere. The stratosphere lies above the tropesphere and is of quiescent nature, It ranges from eleven kilometers to fifty kilometers above the surface of the earth. In stratosphere the temperature rises from -56°C to maximum of about -2°C. Because of the very low temperatures, there are virtually no clouds, dust or water vapor. There are also no convection currents. The stratosphere exhibits many significant differences from the troposphere. It is richin ozone, which raises the temperature causing a positive lapse. It acts as a protective shield for life on earth from the injurious effects of the sun‘s ultraviolet rays and at the same time supplies the heat source for partitioning the atmosphere into a quiescent stratosphere and turbulent troposphere. In: stratosphere, the residence times of molecules or particles are quite long and if pollutants reaches in this region, they pose long term global hazards compared to their impact in toposphere. ‘The Mesosphere. Mesosphere is next to the stratosphere and is characterized by cold temperature and very low atmospheric pressure, It extends roughly between 50-80 km. In this region the temperature decreases with increasing heights and therefore shows a negative lapse rate. This is because of the low levels of ultraviolet absorbing series, specially arone. The temperature, at the top of the mesosphere reaches about— 92°C. Immediately above mesosphere is mesopause which is the region of minimum or coldest temperature in the atmosphere. “NO? and 3 are the principal chemical species in the region. The Thermosphere. The thermosphere region lies just above the mesopause and experiences a rapid increase in temperature with increasing altitudes therefore exhibiting a positive lapse rate. The maximum temperature attained in this region is 1200°C. This region is characterized by low pressures and low densities. In this region the atmospheric gases are mainly oxygen and nitric oxide, which split into atoms and also undergo ionization after absorbing radiation in far ultraviolet region. Ans. (c) Intermediate Compound Formation Theory: According to intermediate compound formation theory a catalyst enters into chemical combination with one more of the reactants forming an intermediate compound of activity greater than that of the reactants. This intermediate compound then decomposes or combine with one of the reactants to form the product and the catalyst isSammie Exaunarions 19 regenerated. Suppose a reaction involving the combination of the reactants A and B to give the product AB. A+B —— AB The reaction will be very slow in the absence of a catalyst. On the addition of small quantity of catalyst C, the reaction proceed along following stages: A+Cc —— AC (Intermediate Compound) AC+B ——+ AB+C Activated complex oo 1 2 Catalyst Catalyst © © © © a 4 Catalyst Catalyst Mechanism of contact catalysis The intermediate compound AC helps the reaction to proceed is stages with low energy of activation thereby accelerating the rate of chemical reaction. The intermediate compound formation theory can be explained with the examples given as, (#) Thermal decomposition of potassium chlorate in the presence of manganese dioxide. 2MnO, + 4KCIO, ——3 2KMn0, + 2KC1 + Cl, +40, 2KMnO,——> K,MnO, + MnO, +0, K,MnO, + Cl,——+ 2KC + MnO, + ©, Mn, Overall reaction 2KCIO, ——$2KC1 +30, (ii) Formation of water by the combination of hydrogen and oxygen in the presence of copper as catalyst.20 ENGINEERING CHEMISTRY 2Cu+ 50,— Cu,0 (Intermediate Compound) Cu,0 +H, — > 2Cu + H,0 Overall reaction 2Cu+ ; O, +H, 2Cu + H,O Drawbacks of Intermediate Compound Formation Theory ‘The intermediate compound formation theory gave adequate explanation for the homogeneous catalysis but failed to explain: () Heterogeneous catalytic reactions, when the catalyst is solid and reactants are gases. No intermediate compound formation is expected in such cases. (ii) Activation of a catalyst by a promoter or deactivation by catalytic poisons. ‘The Adsorption Theory The adsorption theory explains the mechanism of a reaction between two gases catalyzed by a solid catalyst (heterogeneous catalysis). According to the adsorption theory the catalyst has certain active sites at which there are free valencies. The reacting gases collect on the surface of the solid catalyst to form a film. This process is called adsorption. The reactants are thus adsorbed at surface of the catalyst and their high concentration increases the rate of a reaction. For example, let us suppose the following reaction: catalyst A+B—— C+D () (s) {s) co A surface reaction of this type can be broken following steps: 1, Adsorption of the reactant molecules. The reactant A and B strike the catalyst surface help up al the surface by either weak van der Waal forces or by chemical bonds. 2. Formation of activated complex. The particles of the reactants adjacent to one another join to from intermediate complex (A - B). This intermediate complex is unstable. 3. Decomposition of activated complex. The activated complex breaks to form the products C and D. The separated particles of the products hold to the catalyst surface by partial chemical bonds. 4, Desorption of products. The particles of the products are desorbed or released from surface, They are stable and can exist independantly. The adsorption theory may vary depending upon the nature of the reactants. For example, hydrogenation of ethene in presence of nickel.Sampce Exawumations 217 H. H a Noa an, MSE noc PEN TE ] H H HH The catalyst operates in following steps: (i) Hydrogen molecules get adsorbed on the nickel surface due to residual valence bonds of the nickel atoms. (ii) The H—H bond is smaller than Ni—Ni bond, thus the H—H bond of the adsorbed hydrogen molecule is stretched and weakened which finally breaks, separate into the hydrogen atoms. The separated hydrogen atoms are held to the nickel surface by chemical bonds. (iii) The chemically adsorbed hydrogen molecules then attach to ethene molecule by partial chemical bonds. The unstable complex is therefore formed. (iv) The unstable activated complex decompose to release, ethane molecules. The free catalyst surface is again available for the further action. Step H HoH 4 So cf ue aan a” HOH” MH Mechanism of the hydrogenation of ethene on nickel surface Q.5 (a) Explain the geometry and magnetic behavior of the following compounds on the basis of valence bond theory: IFeF > and K,{Fe(CN),} (b) Explain n-type and p-type semiconductors. (6) Write a short note on lubricants (d) “IR spectra is often characterized as molecular finger prints.” Comment. (¢} Calculate the pH of 0.1 N acetic acid. The K, for acetic acid is 1.85 x 107.22 ENGINEERING CHEMISTRY (f) Give IUPAC names of the fatiowing: (i) CaFeCN),J (ii) [PUNH,)] [PCL (iii) NasfCrOF ,] (iv) [Coven), Cl, OH. @) [« 1,0), Fe Son > rati0) (50), Ans. (a) Formation of (FeF,]*. The outer electronic configuration of Fe is 34° 4s, Thus Fe** has a 34° outer electronic configuration. ad 4a cermocy (CTT &) CLT [Tj Contig. otFe ion [tT] Tt] t[t]t C] (ground state) ‘Six ompty orbitals undergo sp” d* hybridization Fornuiaion For [TIT tI T17] [X] DXDXDX] KX ion I Six sp’d*hybrid bonds formed between Fe’ and 6F ions Magnetic behavior. Since the complex ion has five unpaired electrons, therefore it is paramagnetic. The spin magnetic movement is given by H,= yt +2) = (56 +2) = 35 Geometry of complex ion. Since hybridization involved is d®sp? therefore the shape is octahedral with bond angles of 90*. The complex formed is of high spin. . Formation of K, [Fe(CN),]. The outer clectronic configuration of Fe is 3d° 4s?, therefore Fe” has the electronic configuration as 32° 4s?Same Examnarions 23, 3 45 4p Electronic contig. ot Fe(z=28) [NI T[T[ Tt] T] [tl L] Contig. ot Fo" ions (oxcitod stay § [MT TI T[ TIT] [ a airing in Fe” in presence LL slid ON ered ste) At O CO ‘Six vacant orbitals for sp" hybridization Formation of [Fe(CN)l" nIRTIXIX) ><] XD 2NH, fg): SH? = — 46.11 k]/mol. Ans. (a) As we know that , pH =—log [H*] Here given [H*]=3.0 x 107 Substituting the value of H” in equation (i), we get, pH =~ log (3.0 x 1077) = (+ log 3-log 107) =7-04771 pH = 6.5229 Ans. (b) Formation of [Ni(CN),/* Complex Ion Nipg = 2,8, 16,2 = 1s%, 2s? 2p®, 3523p 348, 4s? and Nit = 158, 26? 2p, 3523p! 3d8, ds?32 Enceveeainc Creastey When 4CN" ions approach to. Ni?" ion pairing of electrons takes place such that all the 8-electrons in 3d-orbitals are paired and one empty d-orbital is available for dsp* hybridization and [Ni(CN),]* complex ion is formed as ad 4s 4p Ni atom CT ad 4s 4p Ni2* ion Nett] 3d 4s 4p Pairing of 34 electrons TTT Lj LI Orbitals available for dsp” ad 4 4p Formation af fNi(CN),F- fee) &) KX] _ 4 pairs of electrons from a : four CN Group Since there are no unpaired electrons in the complex ion so it is diamagnetic in nature. Ans. (c) Halogen acids are covalent compounds but in aqueous solution, they ionize give hydronium ions and thus, act as acids HX + H,O <== H,O* +X- The acidic strength of halogen acids in the following order: HI > HBr > HCl > HF .. HF is the weakest acid and HI is the strongest acid among these acids. HF is the weakest acid due to its high dissociation energy as: ur [ua |i 566 | 431 a Hydrogen fialide sociation energy (k]/mol). Asa result of its high dissociation energy it does not readily ionize in aqueous solution to give H* ions.Samrur Examinations 33 Ans. (4) In [Ti(H,0),]* complex ion Ti is in + 3 oxidation state. The complex ion is formed by octahedral hybridization. Its crystal field sp can be represented as: 1 ‘Ans. (¢) Formation of ammonia can be represented by the following reaction Equilibrium N,(¢) +3H,(¢) === 2NH,(g)} AH = 46.11 kJ/mol If the temperature of the system at equilibrium is increased the equilibrium will shift in the direction in which the added heat is absorbed. Therefore the equilibrium will shift in direction of the endothermic reaction ‘with increase in temperature. Alternately, the decrease in temperature will shift toward the direction in which heat is produced and, therefore will follow exothermic reaction. In this case the forward reaction is exothermic while the backward reaction is endothermic. Now the temperature will change in the direction of endothermic reaction, or temperature will lead to lesser ammonia formation. Q.3 (a) Corrosion involves ......... of iron and the chemical is ......... (Fill in the blanks) (®) Describe the process of galzanization of iron. How does it prevent the corrosion of iron? (6) Write the chemical reaction involved ist the depletion of ozone by nitric oxide? (a) How can the internal combustion engine be modified to make auto exhaust free from pollution? (e) Write the structure of graphite. Based on this suggest why this can be used as a solid lubricant. (f) What is meant by greenhouse effect? Give two examples of greenhouse gases.34 Excwereinc Crenistay Ans. (a) Corrosion involves rusting of iron and the chemical is Fe,0,.xH,0. Ans. ()) Galvanization of Iron: Galvanization of iron is employed when a metal have a coating of films of metals having low melting point zinc, tin, lead, ete. The cleaned metals to be protected are dipped in the hot solution of the metal. Therefore during hot dipping an alloy is formed where the two metals meet. The protective action of zinc is explained as follows. Galvanized iron consists a thin layer of zine which does not alley iron to have a direct contact with moisture and air, therefore, no corrosion lakes place. Zinc occupies a position above iron in electrochemical series i., it is more reactive than iron, so if even protective zinc layer is broken, iron is still protected. Therefore, in this case zinc loses electron (net iron) and then passes into. solution as zinc ions (Zn**) at the anodic area. At the cathodic area (surface of iron) hydrogen gas is discharged. In this way zinc is used in the protection of iron. The area where zinc layer is not broken, the zinc is not corroding itself because a zine oxide layer is formed on it. Ans. (c) NOand NO, are the important constituents of polluted air and are collectively designated as NO,. These constituents mainly originate from the combustion of fossil fuels and other anthropogenic activities. Bacterial decay of erganic matter yields N,O which reacts with O in stratosphere to form nitric oxide (NO), which in turn depletes ozone. The reaction takes place as: 2NO +0,——» 2NO, NO +0,-—+ NO, +0, NO +0 + M (Third body) —— NO, +M NO, formed absorbs sunlight below 398 nm undergo photodissociation and above 430 nm, forms excited molecules. NO, +hv———> NO+0 NO +0+hv——> NO, (excited moteeule) The photochemical reaction of NO, yield a series of reaction in the following manner. NO, +O,» NO, +O, NO, +O —+ NO+0, O+NO,+M—+NO,+MSampue Exaunarions 35, NO, + NO, N,.0, NO +NO,——> 2NO, O+NO+M——>NO,+M NO, finally get converted into HNO, in the following manner. 4NO, + O, + H,O—> 4HNO, N,O, + H,O ——> 2HNO, Ans. (d) The automobile exhausts generally liberate hydrocarbons, carbon monoxide (CO) and NO, in the atmosphere. Many techniques, ¢.g., tune-ups, catalytic reactors and engine modifications have been used for the control of emission. Tune-ups has a significant effect on emission of air pollutants. Far example, a high air-fuel rate reduces the concentration of CO and unburnt hydrocarbons toa great extent. The calalytic reactor oxidizes carbon monoxide (CO) to carbon dioxide (CO,) and thereby nitrogen oxidize are reduced to N,. They also oxidize the sulphur present in the fuels to sulphur trioxide (SO,) and they are also easily fouled by lead. So they are not commonly used. The modified engines havesome advantages and contain two compartments in the cylinder by which a broad flame is produced for efficient burning of fuel. Graphite Ans. (¢) Graphite and molybdenum disulfide are most common solid lubricants. Graphite has layered structure. In graphite each and every carbon atom exhibits sp? -hybridization. Therefore, it has a layer structure. in distance between two layers is 3.40A while two carbon atoms in a ring are 1.42A apart. There is a- 36 Ans. Encuveenunec. CHeMesTaey weak force of attraction between two layers therefore, one layer slides easily on the other and graphite acts as a lubricant (f) The earth is readily heated by sunlight and some part of the heat absorbed by the earth radiated back into the space. In the lower atmosphere of the earth some of the gases act as greenhouse, ie. the body which allows the short wavelength incoming solar radiation to come in but does not allow the long wavelength Infra Red (IR) radiation to escape. The net result is that the earth’s surface is heated up. Among the constituents of atmosphere, only carbon dioxide (CO,) and water vapor strongly absorb Infra Red (IR) radiations (14000-25000 im) and effectively back a large fraction of earth‘s emitted radiations. The radiations, thus absorbed by carbon dioxide (CO,) and water vapors are partly re-emitted to the earth’s surface raising the temperature of the earth and causing the phenomenon known as greenhouse effect. The greenhouse effect may, therefore, be defined as the progressive warming up of the earth’s surface due to blanketing effect of carbon dioxide (CO,) in the atmosphere. The major greenhouse gases are carbon dioxide (CO,), methane (CH), nitrous oxide (N,) and chlorofluorocarbons (CFC’s) ete. ay Among these carbon dioxide (CO,) is the most important greenhouse gas accounting 50% of the global warming, ether gases such as methane (CH,) and chlorofluorocarbons (CFC’s) contribute about 10% and 14% respectively to the global warming. (a) Write the structure of EDTA. (b) Doping silicon with a small amount of phosphorus converts it ito... semiconductor while doping with boron converts if irtto @ ...u. semiconductor. (Fill in the blanks.) (0) A sample of ground water has 150 mg/l. of Ca?* and 60 mg/L of Mg?*. Find total hardness expressed in milli-equivalents per liter and mg/L in terms of CaCO,. (d) How is the calorific bale of a solid fuel determined using bomb calorimeter experiments?Samos Exammanions = 37 (6) List the raw materials which can be utilized for biogas manufacture. How is biogas obtained from cattle dung? (f) State the zeolite process for the removal of hardness of water. Discuss its merits over soda-lime process, Ans. (a) HOOCH,C, /SH,COOH DN—CH,—CH,-NC HOOCH,C ‘CH,COOH ‘Structure of EDTA Ans. (b) Doping silicon with a smal] amount of phosphorous converts it into a n-type semiconductor while doping with boron converts it into ap-type semiconductor. Ans. (c) Calculation of CaCO, Equivalents Constituent Amoutit (nig/L)’ | Multiplication | CaCO, equivalent | factor i Magnesium ion (Mg*) 60 24 ] | | Calcium ion (Ca™*) 150 | 40 Total hardness = 250 + 375 = 625 mg/L Ans. (d) Bomb calorimeter is used for the determination of calorific value of solid or liquid. Construction: Bomb calorimeter consists of a strong cylindrical bomb of stainless steel. It is resistant to acids and of corrosion. The weight of bomb calorimeter is about 3 Kg with 250-300 mL capacity. It provided with a gas tight screw cap to which a couple of stainless steel electrodes and released valve are fitted. A small ring is also attached to this clectrode which acts as a support for the stainless steel crucible. Fuel is kept in this crucible. The bomb is placed ina copper calorimeter. It can contain 2L water. The calorimeter is surrounded by an air jacket and water-jacket in order to avoid losses due to radiation. The copper calorimeter also consists of a motor driven stirrer and Beckmann’s thermometer which can read up to 0.001°C temperature. Procedure: A known amount (in mg) of the fuel is kept on the stainless steel crucible supported over the ring. A fine magnesium wire touching the sample of the fuel is then stretched across the electrode. The bomb lid is tightly screwed38 Encuveranc CremsTay and filled with oxygen at about 25 atm pressure. Now the bomb is placed carefully in the copper calorimeter containing water. After stirring very well the temperature of water (f,°C) is noted. The electrodes are connected with battery and circuit is completed therefore, combustion of fuel takes place and heat is liberated. Now, stirring of water is continued and final temperature of ‘water (1,°C), is.noted. operated stirrer ‘Ebonite cover Sy 1H l ‘Copper i & calorimeter Bosca Stainless steel bomb fees Wator jacket ED Salas tel Air jacket Bomb calorimeter Suppose C be higher calorific value (HCV) of the fuel in cal/g and w be water equivalent of calorimeter, bomb stirrer etc. in grams. Calculation: Suppose m be mass of fuel, w be the water equivalent if the calorimeter W g is water taken in the calorimeter, t, is initial temperature of water in the calorimeter and t, is the final temperature, f, is cooling correction, Cy, Cy Cand C, are correction for Sulphuric acid (H,SO,), Nitric acid (HNO,), fused wire and cotton thread respectively. The calorific value of the fuel may be given as: (2+ Wty th + te) (C5 + Cy + Cp - Co) Gc. m and LCV. = [G.C.V. - 0.09 H = 587] cal/g (Latent heat of steam = 587 cal/g). His the percentage of hydrogen present in the sample at fuel.Saupe Examinanions 39) ‘Corrections (i) Cotton thread correction is made by weighing of dry of cotton thread used for firing. On this basis, the calorific value of celulose (C,) is 4140 cal/g. (ii) Acid correction: If the fuel consists of sulphur and nitrogen they are oxidized to H.SO, and HNO, respectively under high pressure and temperature. S + 2H +20,——> H,S0, + heat 2N + 2H +30,——> 2HNO, + heat ‘The amount formed of H,SO, and HNO, during the combustion of fuel is determined by titration. It is calculated that for each mL.of N/10 HNO, 3.6 and for each mL of N/10 H,SO,, 4.3 cal respectively must be subtracted. (iii) Fuse wire correction is made by the amount of heat given out by the ignition of the fuse wire burnt during the combustion of fuel. This amount of heat should also be subtracted. (iv) Cooling correction is made by measuring the time taken to cool the water in calorimeter from maximum temperature to room temperature. From the rate of cooling (dt° /minute) and the actual time taken for cooling (f minutes) the cooling correction (dt x £) is added to the increase in temperature. Ans. (c) Biogas is also called Gobar gas. It was known that methane gas is produced by the decay of vegetable matter, It was combustible as swamp gas. Biogas is obtained by the anaerobic fermentation of animal dung; plant wastes in the presence of water but absence of oxygen. Micro-organism like anaerobic bacteria present in the dung digest the slurry forming mainly methane and carbon dioxide. On decomposition methane, carbon dioxide, hydrogen, nitrogen etc,, are obtained, The average composition of biogas is CH, = 55%, CO, = 35%, H, = 7.5%, N, = 2.5% and H,O in traces. Its calorific value is about 5300 keal/m?. ° Advantages of Biogas: It has following advantages: 1. It is burnt in a gas stove, thus acts as a good fuel for domestic purposes. 2. Its calorific value is high. 3. It is the most common and cheapest gas. 4. It is used for street lights in villages. 5, It burns with non-smoky, flame and does not pollute environment. 6, It can be used directly thus there is no storage problem. Biogas plant: In generally following two types of biogas plants are used: 1. Floating gas holder type of biogas plant. 2. Fixed dome type biogas plant.40 Encreerrinc Cremasrey 1. Floating Gas Holder Type Biogas Plant: The diagram of this plant is presented as: Construction: Floating gas holder type biogas plant consists well shaped underground tank T made of bricks, this tank is known as digester. A gas holder H is made of steel floats in an inverted position over the dung slurry in tank T. Biogas is collected in H because the holder H floats over the dung, slurry therefore this biogas plant is called floating gas holder type plant. There is a control pipe P which control the movement of P. This gas holder is attached with gas set S fitted with gas value V. The digester tank T is divided into two compartments by a wall W. On the left side there is a mixing tank M attached with inlet pipe I made of cement. On the right side there is a outlet tank F attached with outlet pipe O also made of cement. There is a hole in outlet tank F to remove spent slurry used as a manure in fields. Floating Outlet for gas-holder biogas. ‘Slurry of cate dung & water $ iM H Gas Vaive Pv. || ‘Outtet pipe Partition wail ‘Support Underground eae digestortank T. CT Floating Gas Holder Type Blogas Plant Working of plant: The raw material for making biogas ie., cattle dung and water are mixed in equal proportion and filled in the tank through inlet pipe from mixing tank. The dung slurry and gas holder is left free for fifty to sixty days for the anaerobic fermentation. During the anaerobic fermentation, the biogas consisting mainly of methane is produced and is collected in the biogas holder. With the increasing rate of gas production, the gas holder rises. Since gas holder cannot rise beyond a certain limit, the pressure of gas over slurry increases. This takes the spent slurry into the outlet tank through pipe O. The gas collected in the gas holder is taken out through the gas control valve.Samput Exawinavions 47 Ans. (f) Zeolite process: This process involves softening of water by a natural or artificial zeolite. Zeolites are the substances insoluble in water and can act as base exchanger when in contact of water containing cations. There are two types of zeolites. 31 (1) Naturat zeolites for example, thomsonite, (Na,0, CaO) . Al,0, . 28i0, «35 H,0, natralite, Na,O .AL,O, 3SiO, . 2H,O; lamumonite, CaQ/ 1,0, .45i0, . 4H,O ete. These zeolites are derived from green sands by washing, heating and treatment with NaOH. (2) Synthetic zeolite prepared from sodium silicale and sodium aluminale. | Natural zeolites are more durable whenever synthetic zeolites have higher exchange capacity per unit weight. Zeolites are now being replaced slowly by high capacity resin having greater stability. ‘Hard water —Zeolite bed fea eet =t—Graded gravel strainer Sott water Zeollte softener The zeolite softner consists of a steel tank packed with a thick layer of loosely packed zeolite over a layer of coarse sand and gravel. The water enters at the top and passed through the bed of zeolite, where following reactions take place. Na,Z + Ca(HCO,),——> Caz + 2NaHCO, Na,Z + Mg(HCO,),——> MgZ + 2NaHCO, Na,Z + CaCl, ———+ CaZ + 2NaCi Na,Z + CaSO, ——> CaZ + 2Na,SO,42 ENGINEERING CHEMISTRY Na,Z + MgSO, ——> MgZ + 2Na,SO, Na,Z + MgCl, ——> MgZ + 2NaCl where Z = AL,Si,O, xH,0. This zeolite process removes both temporary and permanent hardness. The utility of the process lies in the fact that when zeolite bed gets exhausted i.e., itlooses its softening capacity, it can be regenerated by passing 10% solution ‘of sodium chloride of brine through it. The following reaction take place. CaZ+2NaCl ——> Na,Z+CaCl, (exhausted zeolite) (regenerated zeolite) MgZ+2NaCl ——s Na,Z+ MgCl, Advantages of zeolite process aver lime soda process: 1, The method can produce zero hardness water, 2. The method is cheap as permutit can be regenerated. 3. The equipment occupies small space and is easy to operate. 4. Tt automatically adjusts to waters of different hardness. 5. No sludge formation occurs during the process. Q.5 (a) Write the sequence of reactions invalved in the preparation of Nylon-6 from Cyelohexanone. (b) Which of the following compound would show optical isomerism — (i) H,NCH, COOH (ii) (CH,), CHCHO (iii) HJNCHO (CH), (iv) CH;—CH(OH) COOH (c) Identify the monomer (s) in the following polymers: i of {i) —C—{CH,}—C—NH—(CH,),—NH— (i) eH —CHeH - ci cl (d) Write the initiation, propagation and termination reaction involved in the polymerization of ethylene with AIBN. (©) Give examples of (i) Reimer-Tiemann Reaction (i) Diels-Alder Reaction.Sampue Examinations «43. (D Write the constituents of (i) RNA (ii) DNA (iii) Protein Ans. (a) Following are the reactions involved in the preparation of nylon-6 from cyclohexanone: 0 @ CO Oxidation: Cyclohexane Cyclohexanone Oo NOH “ O NH.OH OQ ii — Cyclohexanone Cyclohexanone Oxime NOH Beckmann's «id tec cr —_—_ss HSO/ Caprolactum H Q Nx 20 © potymeriat i (ia) Cy Iymerization, _NH-(CHY. IN Caprolactum Nylon-6 Ans. (b) Only lactic acid (iv) show optical isomerism because it has assymetric carbon atom. t i Ans. (©) (i) —C{CH,)—C—-NH—(CH,), -NH—44 Encmecrinc Corexasriy Monomers of above compound are Qo ll ll HO—C{CH,),-C —OH H,N—(CH,),—NH, Adipic acid Octamethylene diamine tio CH -CH-CH,— FH cl ch Monomer of above compound is CH,=CHCt Viny! Chloride Ans. (d) ATBN stands for azobisisobutyronitrile and is represented as: Bowl (CH,),—C—N = N—C(CH,), It is initiator compound whieh readily decompose into free radical or under the influence of light. Chain initiation: ~ s (CH),—C —N=N—C-{CH,}, ——> 2(CH,), —C" +N, Free radical This may be represented generally by x, 9 2k where X; is initiator molecule and X is free radical X +CH,=CH, ——» X—CH,—CH, Free radical Chain propagation: This step requires much less activation energy (E,) than the initiation reaction, The free radical formed may add to another molecule of ethylene in a manner similar to initiation step and regenerates a free radical which repeats the process. X—CH,—CH, + CH,==CH, ——» X—CH,—CH,—CH,—CH,Saou Examinations 45, In general, X—CH,—CH, + 1CH,=CH, —— X—(CH,), —CH,—CH, Chain termination: The growing polymer chain can be terminated in following ways: (i) Recombination: ia X—CH HC + CCH X—-——9 —X-CH, CH, —CH,—CH,—xX— 1 HH (ii) Disproportionation: re —XCH,—-c + CHA —— XCH,-—CH,—CH, + CH, = | H H Ans. (c) (i) Reimer-Tiemann’s Reaction: Examples : OH OH 3KOH, CHO + cre + 3KCl + 2H,0 rena (90%) r ™ o-Hydroxy iO benzaldehyde (10%) p-liydroxy benzaldehyde When the reaction is carried out in presence of CCI, in place of CHCL, a carboxylic group is introduced instead of aldehydic group. OH +CCl+4NaOH ——> om 4 4NaCl+2H,0 Salicylic acid46 Encineennc Creussrar Other examples include, Formation of vanillin, OH OH OCH, CHCI,/KOH OCHy Qo ~~ oH dry CHO ani = Vanilli Preparation of thiophene and pyrrole-2-aldehydes CHCl, / KOH Se 8 $7“ ~CHO Thiophene-2-aldehyde Ty) _ScheKoH Ch “N N* CHO H H Pyrrole Pyrrale-2-aldehyde (ii) Examples of Diels-Alder Reaction CH, CH, nc? CH, HC” on, | +i — | HO CH.CHO HC\,_/CH.CHO cA, CH, Butadiene Acrylaldehyde Tetrahydrobenzaldehyde CH, cI co. 2 H,c.c” CHA Near HC on CON, He “4h ° uel buco” Sy ~co “eft, CH, 2 Butadiene Maleic anhydride Adduct Ath HACC COOGH, jg, HS CO.C,H, HC ¢ . t Ce Loy iy .CO,C,H, HEC: CO.CH, SoH, 5 AdductSamput Examinations 47. Ans. (f) (i) and (ff) Constituents of RNA and DNA are: Nitrogen containing hetrocyclic base. These include: ‘The purines, adenine and guanine and pyrimidines cytosine are found in both polymers DNA and RNA. RNA contains uracil in place of thymine present in DNA. NH, o Cy my A Ww ony H H Adenine (A) Thymine (1) 9 ° NH, my x my QO wy ono ‘ H H H Guanine (G) Uracil (U) ‘Cytosine (C) Sugars. The sugar present RNA is D-Ribose and in DNA is D-2 deoxyribose. CH,OH OQ. OH CH,OH ,O. OH } on wot OH H D-2-deoxyribose Phosphate Group. It is represented as: OH48 Excmernmc Cesster (iii) Proteins are composed of a-amino acids joined through amide linkage. Amino acids R——C—— COOH NH, There are about 20 different c-amino acids, for example, NH,—CH,—COOH NH,—CH—COOH x, Glycine Alanine The amide bond linking the o-aminoacid residues in proteins is known asa peptide bond the polymers are known as polypeptides and can be represented as R R | H,N—CH—CO—{NH—CH—CO},—NH—CH—COOH CHEMISTRY—3 Time: 3 Hours ‘Total Points: 100 Note: (i) Answer all Five questions. Gi) All questions carry equal points. Q.1 Answer any two parts of the following. (a) (i) What is meant by stoichiometric and non-stoichiometric defects? (ii) Account for paramagnetic behavior of oxygen on the basis of molecular orbital theory. (b) Explain metallic bond on the basis of molecular orbital theory.Sampue Exawunanions 49° (6) How many NMR Signals ave observed in te spectrum of @) CH—CH, (i) CH,—CH,—CH, Oy (itt) CH—-O—CH, (te) CH;—CH; ii (x) CH,—-C—O—CH, Ans. (a) (i) Stoichiometric Defects: If the deviation occurs because of missing of atoms, displaced atoms, or extra atoms, in perfection in a lattice then it is called point defect or stoichiometric defect. The most common point defects are Schottky defect and Frenkel defect. Metal defect and metal deficiency defect. Schottky defect: Lattice points are unoccupied called holes or lattice vacancies. Generally Schottky defect appears in strongly ionic compounds in which the radius r*/r is not far below unity and have a high coordination number as: * NaCl, CsCl having coordination number 6 and 8. Frenkel defect arises when an ion occupies an interstitial position between the lattice points. Generally r+/r- is ions and CN is also small e.g., Ag* and Zn? . ions occupy position in between the other ions in the lattice. Non-stoichiometric Defect: These compounds do not obey strictly the law of constant proportions. The number of cation and anions present in such compounds are different fram those seen from their ideal chemical formula. Therefore the crystal structure becomes irregular and defect arise. Such defects are called non-stoichiometric defects which exist in addition to Schottky and Frenkel defects. These are of two types: i Metal excess deficiency defect when negative ions are in excess. For example, 'eO, FeS, NiO, etc. 1 Metal excess defects when positive ions are in excess. For example, KCI, ZnO, etc. (#) Electronic configuration of O, is: 26* glo"? cl. xtgiat!, atl loho*h (03,03, 0%), xin wb, %hy hy | 8-4 2 Bond order = Ne=No . 2 Since there are two unpaired electrons in the antibonding orbitals, the O, molecule is paramagnetic.50 Encweemnc Crenastier Ans. (b) According to this theory when two atomic orbitals combine they form two molecular orbitals (MOs)—one bonding and one antibonding MO. In case of three AOs, three MOs—one bonding, one non-bonding and one antibonding MOs are formed. Similarly, for four AOs, four MOs are formed—two bonding, and two antibonding. The presence of two non-bonding MOs between bonding MO and antibonding MOs reduces the energy gap between the orbitals. Forn centers, (where n is large) we may haven distinct energy levels. If is the order of 10” in a metallic crystal, the discrete level which corresponds to ms- electrons, ¢.g., is measured by overlap of many ns-orbitals into a ‘band’ of levels, which appears to be continuous and is a ‘quasi continuors’. Within the band the electrons will occupy the stage of lowest energy or greatest stability. It has been further proved that between the bands are energy gaps which are forbidden (forbidden-zones) to the electrons. M.O. [ }~ Antibonding ut Atom At TR [tt }-— Bonding MO. Antibonding Non-bending Bonding | Antibonding u-tHtHtH? ‘Atom Atom Atom Alom {tL} } Bonding Vacant MOs Many closely spaced molecular orbitals levets constituting a band Band formation in lithium metalSawpie Examinanions 51 The bandwidth increases. with the increase in overlapping of orbitals, which in tum increase with the decrease in interatomic distance. Atacertain distance between atoms, thus the two adjoining bands may be wider to such an extent that they start overlapping each other and Hence, forma single band. Ans. (c) (i) CH,—CH, One (quartet) Signal (ii) CH,—CH,—CH, Two signal (one quartet and one triplet) (iii) CH, -O—CH, ‘One signal (iv) cH.—cH-(C)-c Three signals Oo Il (v) CH; —C —O—CH, ‘Two signals Q.2_ Answer any four parts of the following (a) Which Complex has larger crystal field splitting? (ICON) I> or [Co(MH,P* (i ICo(H,O)* or {CofH,0),)* (iii) [CotNH,)P* or (Rh(NH,)P* (b} Discuss the difference between order ofa reaction and motecutarity of a reaction. Why re most of the reaction only of first oriter and second order? (c) The reaction 2NO + O, ——> 2NO, follows the rate law r = 2.0 x 10° =4 mol” L?, what is the rate of reaction when. [NO] = = 0.2 mol 1-1? KINOPIO,). If K = 1.04 mol Land {On} (d) Prove that the pH of a solution of art acid with dissociation constant K and degree of t dissociation ais given by pH = logyy = + log, = (e) Describe Bronsted and Lewis concept of acids and bases. Ans, (a) (i) (Co(CN),|* has larger crystal field spliting (CFS) than [Co(NH,),P*. Because CN-ligand is stronger than NH, ligand (while in both case Co" present) (i) [CofH,O),** has lower CFS than [Co(H,0),* because Co** is in lower oxidation state than Co* and spliting increases from lower oxidation state to higher oxidation state.52 ENGINEERING CHEMISTICY Gi) [Co(NH,),}** has lower crystal field splitting than [Rh(WH,),*. This is due to fact that Rh is of 4d and Co is of 3d series. Splitting power increases from 3d to 4d. Ans. (6) Molecilarily ‘Order of Reaction, . Ik is always whole number. . It may be whole number, zero or fractional value. . It reveals some basic facts about reaction, . It does not reveal anything about reaction mechanism. mechanism, . Ik is equal to the number of molecules of | 3. It is equal to the sum of the power of the reactants which take part ina single step molar concentration of the reactants in the of a chemical reaction rate expression. |. Ikis.a theoretical concept which depends | 4. It ts an experimentally determined on the rate determining step in the reaction} quantity which is obtained from the rate mechanism. for the overall reaction. . Itis obtained from a single balanced . It cannot be obtained from a balanced chemical equation. chemical equation Ans. (c} On substituting the given value in the rate equation. r= k[NOF [O,] We have r= [20 x 10% 5 mol L)] (0.04 mol L} [0.04 mol L*] [0.02 mol L“] = 64x 107 mol L7!s** Ans, (d) Foran acid. HA HA em H+ A (=e ae oo _ A) {HaA] tHy=K 8 @ Taking log and reversing the sign or PH = —logo# + 108,07 - a 1 PH == logy +1080 75Samet Examinations 53, Ans. (e) Bronsted-Lowry Concept According to this concept, Acid is defined as any substance (molecule or ion) that is capable of donating a proton to any other substance. For example, HCl +H,O—> H,O* + Cr Acid CH,COOH + H,0 == H,0" + CH,COO" ‘Acid Base is defined as any substance (molecule or ion) that is capable of accepting a proton given off by an acid. Forexample, H,O+NH, ==== NH*,+ OH- Base H,O+CO,) === HCO; +OH- Base ‘Thus, acid base reactions are regarded as proton transfer processes, It should be noted that a species can act as an acid only if another species capable of acting as a base is also present. For example, HC] is an acid in water HCl + H,O—— H,0" + cr because water accepts a proton donated by HCL. But HCl is not an acid in benzene or CCl, because benzene or CCI, does not accept proton from HCl. In short, Acid is proton danor and Base is proton acceptor. A species formed by adding a proton to Bronsted base is called conjugate acid and a species formed by losing a proton from Bronsted acid is called conjugate base. Bronsted base + Ht ——+ conjugate acid Bronsted acid ——> H’ + conjugate base Any acid-base reaction really involves two acids and two bases, forming conjugate pairs. Conjugate pair Acid, + Base, ==» Acid, + Base, Conjugate pair54 ENGINEERING CHEMISTRY For example, ACID, + BASE, === ACID, + BASE, NH, +H,O0 ===> H,0° +NH, a) H,S0, + H,O === H,0* + HSO; (i) HS +H,O == H,0°+ HS (iii) Lewis Concept. According to this concept, an acid is any substance (atom, molecule or ion) which is capable of accepting a pair of electrons from another substance to form a co-ordinate bond. And abase is any substance (atom, molecule or ion) which is capable of donating a pair of electrons to form a co-ordinate (dative) bond. For example, HN: + BF, ——- HN: > BF, Lewis base — Lewis acid Coordination compound Types of Lewis Acids (a) Molecules having a central atom with incomplete octet FE a x x a FxB and. Cx Al{BF,+F°[F, B— Fy} x “x E cl (b) Simple cations C Ag®*, Cu, Fe?* ete. feu +4NH, + [Cu net) ]'"t (c) Molecules having central atoms with empty d-orbitals eg. PR, SiF, and SnCl, (PF, +F [PFI] (d) Molecules containing a multiple bond between two atoms of different electronegativeties. O=C+O———> O=C-O or HCO> HO® | OH Types of Lewis bases (@) Neutral molecules (like RNH, NH, ROH, HGH) inwhich one ofthe atoms has got at least one lone pair of electrons. (b) All negative ions like F-, CI, Br-, I, OH", CN, ete.Sampur Exasananions 55 Q.3 Answer any two parts of the following: (a) Explain the mechanism of hnydvogen evottition and oxygen absorption in electrochemical corwosion. Give figures. (b) What is meant by Greenhouse effect? Describe two monitoring tecluiques for greenhouse effect. (c) Discuss the following: (i) Lapse Rate and Temperature Inversion. (ii) Earth’s Radiation Balance. Ans. (a) According to Nemst theory, all metals have tendency to pass into solution. This tendency of metals to pass into solution when immersed in a solution of its salt is measured is termed as electrode potential, when a metal having higher electrode potential comes intocontact with another metal having lower electrode potential, a galvanic cell is set up, the metal having higher electrode potential , become anode and goes into the solution i.c., corrodes to a measurable extent. Corrosion Reactions.Corrosion process involves the formation of galvanic cells. and various reactions that occur during corrosion are: 1. Anode Reactions. The anode is a metal which corrodes, and undergo oxidation, loses electrons to the environment and pass into the solution in. the form of positive ions, For example, Fe(s) ———+ Pe®* + 267 Fe?* (aq) + 20H (aq) ——> Fe(OH), This continues as long as the electrons and ions as removed from the environment. 2. Cathode Reactions. The electrons released at the anode are carried to the cathode and are responsible for following reaction: (a) Hydrogen type corrosion. In acidic solution (in absence of oxygen) the com- mon reaction is the reduction of H ions to H, gas. H* ions are present due to the ionization of water. 2H* + 2c H H,O—> 2H* +0” Such type of corrosion in which H, gas is evolved is known as hydrogen type corrosion. (b) Oxygen type corrusion. In neutral or basic solution, hydrogen ion concen- tration is very low, therefore evolution of H, gas is not favorable. In such cases reduction of oxygen to OH" ions occur. For example, +2 + 4e°-—— 40H" HO OH:56 Encncemnc Cuomistry ‘The corrosion of iron occurs by oxygen in the presence of aqueous solution. At anode iron dissolves to form ions as: . Fe Fet* 4-20" © (Atanode) At cathode, the electrons evolved by above reaction are intercepted by oxygen in the presence of water. 1 H,O + 5 O, +2e°—— 20H" (At Cathode) Overall Reaction: 1 Fe + 50, +H,O——> Fe*" + 20H" OH- ions produced reacts with the positively charged Fe** ion forming rust. Fe* + 20H" ——> Fe(OH), Rust Ans, (b) The earth is readily heated by sunlight and some of the heat absorbed by the earth radiated back into the space. In the lower atmosphere of the earth some of the gases act as greenhouse, i., the body which allows the short wavelength. incomming solar radiation to come in but does not allow the long wavelength IR radiation to escape. The net result, is that the earth's surface is heated up. Among the constituents of atmosphere, only carbon dioxide and water vapor strongly absorb IR radiation (14000-25000 mm) and effectively revert back a large fraction of earth's emmited radiation. The radiation, therefore absorbed. by carbon dioxide (CO,) and water vapors are partly re-emmited to the earth's surface raising the temperature of the earth and causing the phenomenon, is known as greenhouse effect. The greenhouse effect may, therefore, be defined as the progressive warming up of the earth’s surface due to blanketing effect of carbon dioxide (CO;) in the atmosphere. The major greenhouse gases are carbon dioxide (CO,) methane, nitrous oxide (N,O) and chloreflurocarbons (CFC’s) etc. Among these (CO,) is the most important greenhouse gas accounting 50% of the global warming, other gasés such as methane and CFC’s contribute about 10% and 14% respectively to the global warming.Samoue Exaunarions 57 way Relative contribution of active gases to temperature rise, ‘Ans. (c) () In the troposphere, the temperature of the air decreases with increasing altitude up to ‘tropopause’ where the temperature starts increasing with increasing altitude in the stratosphere. The change of temperature with height is called the Japse mie. Positive lapse rate is the decrease of temperature with increasing altitude (in the troposphere). Temperafure inversion occurs at the ‘tropopause where the transition from positive lapse rate to negative lapse rate takes place. (ii) Earth’s Radiation Balance. The earth continuously receives a very large amount of energy from the sun and at the same time bulk of this energy is given off at the same rate into the space. The earth maintains its heat balance within narrow limits through complex mechanism of energy transfer and therefore maintains optimum climatic conditions for supporting life. The earth absorbs radiation mainly in the visible region but emit radiation at the same rate in IR region. The earth's atmosphere receives 1340 watts m7? min” and if all this energy was absorbed by the earth, then it would have evaporated long ago. It absorbs about 66% of the solar flux incident on it. While scatters back about 34% (albedo) of the salar flux into space. Energy transport plays vital role in the earth’s radiation balance through following mechanism. 1. Conduction of energy through the interaction of atoms or molecules. 2. Convection of energy through massive air circulation. 3. Radiation of energy in the IR radiation (2-40 mm) from the earth. The average surface temperature of the earth is maintained around 15°C due to reabsorption of the outgoing IR radiation (2~40 mm) by water vapor (4-8 mm) CO, (12-16.3 mm) and other gases like as Methane (CH,) and re-emitting a part of this radiation to the earth’s surface. This leads to greenhouse effect which is of great significance in governing the climate on earth.58 Encierrinc CHEMISTRY Q4 Answer any four parts of the following: (a) What are chemical fuels? How are they classified? (8) Define gross calorific value of a chemical fuel. Describe with a suitable diagram, how it is determined by bomb calorimeter. (©) Cateulate the weight and volume of air required for contbustion of 3kg of carbon. (a) Why do we express hardness of water in terms of CaCO, equivalents? (e) Alkalinity of water cannot be due to the simultaneous presence of OH", COF and HCO}. Give reason. (f) 20 mi of a water sample twas treated with excess of 10% KJ solution and then titrated against N/100 hypo solution using starch as indicator 2.5 ml of hypo twas used for starch end paint. Calculate the amount of chlorine in water. Ans. (a) Chemical Fuels. Fuel is a combustible substance containing carbon as main constituent which or proper burning gives large amount of heat that can be used economically for domestic and industrial purposes. Fuel + O, ——» Products + Heat (Exothermic) Chemical Fuels On the basis of occurence and preparation Primary or Natural Secondary or Derived | ’ ‘On the basis of On the basis of state of aggregation state of aggregation Solid e.9., Liquid e.9.. Gas e.9.. Solid e.g., Liquid e.g., Gas e.9., Wood, Peat, Crude Natural Gas Coke, Charcoal, Tar, Coal gas, Lignite, Petroleum, Kerosene, Water gas, ‘Coal, Dung Coke, Goal Diesel, gasoline, iil Gas, Fuel Oi LPGSampue Examinations 59 Ans. (b) Gross calorific value (GCV) of a fuel is defined as the amount of heat liberated when a unit mass of fuel is completely burnt and the products of combustion are condensed to a temperature of 15°C or 60°F. Bomb calorimeter is used for the determination of calorific value of solid or liquid fuel. Construction: It consits of a strong cylindrical bomb of stainless steel (Cr-Ni- Mo steel). It is resistant to acids and of corrosion. Its weight is about 3kg with 250-300 ml. capacity. It is provided with a gas tight screw cap to which a couple of stainless steel electrodes and oxygen valves are fitted. A small ring is also attached to this electrode which acts as a support for the stainless steel crucible. Fuel is kept is this crucible. The bomb is placed in as copper calorimeter. It can contain 2 liter water. The calorimeter is surrounded by an air jacket and water- jacket in order to avoid loss of heat due to radiation. The copper calorimeter also contains a motor driven stirrer and Bekmann’'s thermometer which can read up to 0.001°C temperature. Procedure: A known amount (mg) of the fuel (whose calorific value is to be determined) is kept in the cruscible supported over the ring. A fine Mg-wire touching the sample of the fuel is then stretched across the electrode. The bomb lid is tightly serewed and filled with oxygen at about 25 atmospheric pressure. Now the bomb is placed carefully in the copper calorimeter containing W g water. After stirring very well the temperature af water (t,) is noted. The electrodes are connected with battery and circuit is completed. Thus, combustion of fuel takes place and heat is liberated. Now strirring of water is continued and final temperature of water t, is noted. Electrically operated stirrer Ebonite cover Copper calorimeter Stainless steel bomb Stainless steel cruscible Air jacket Bomb calorimeter60 Enciveerive CremusTRy Ans. (c) Let C be higher calorific value (HCV) of the fuel in cal/g and w be the water equivalent of calorimeter bomb stirrer etc., in grams. Calculation: Suppose m be the mass of fuel w be water equivalent of the calorimeter, W g is water taken in the calorimeter, f, is initial temperature of water in the calorimeter and #, is the final temperature .C, Cy, Cp and Cy are corrections for H,SO,. HNO,, fused wire and cotton thread respectively. The calorific value of the fuel may be given as Gow a(@*WUs=h stdnCs eeu Cy #Ce) m and L.C.V. = [G.C.¥. -0.09H x 587] cal/g {Latent heat of steam = 587 cal/g) H = Percentage of hydrogen present in the sample of fuel. Corrections (a) Cotton thread correction is made by the weighing of dry cotton thread used for firing. On this basis, the calorific value of cellulose (C,.) is 4140 cal/g. (b) Acid correction: Tf the fuel consists of sulphur and nitrogen they are oxidized to H,SO, and HNO, respectively under high pressure and temperature. $+2H +20, ——+H,S0, + heat 2N + 2H +30,——> 2HINO, + heat The amount of H,SO, and HNO, formed during the combustion of fuel is determined by titration. It is calculated that for cach ml of N/10H,SO,3.6 cal and for each mi of N/10 HNO, 1.43 cal must be subtracted. (c) Fuse wire correction is made by the amount of heat given out by the ignition of the fuse wire burnt during the combustion of fuel. This amount of heat should also be subtracted. (d) Cooling correction is made by measuring the time taken to cool the water in calorimeter from maximum temperature to room temperature. From the rate of cooling (df°/minute) and the actual time taken for cooling (dt” minutes), the cooling correction (dt x t) is added to the increase in temperature. (w +W) (ty - fy + cooling correction) — [Acid + fuse correction} Hence L= . Mass of fuel c+0,—c0, 12 gm carbon required 32 gmof O,Sami Exasinanions 61 . 32x3 3 kg carbon required az Kg of 0, 8x10" = 8 kg of ©, or mole of O, 2 In air 23% O, (By weight) or 21% ©, (By volume) is present . . 100 so ait required “3 xB kg = 34.78 kg 8x10" S57 mole of O, 8x1 o “axe x 22.4 liter of O, 32 100 8x10°x224 an RR = 26666.67 liter = 26.67 m' of air Ans, (d) Hardness of H,O is expressed in terms of CaCO, equivalents. Ithasbeen adopted as standard for expressing hardness for following reasons: @ This mode permits easy addition or subtraction of concentration of hardness causing constituents since the molecular mass is 100 and all the calculations become very easy. It is the most precipitable substance formed in hardness related experiments. Ans. (c) Alkalinity of H,O is denoted as the quantity of ions in HO that will result to neutralize H*. Most common constituents of alkalinity are HCO3, COF, o>. Alkalinity of water cannot be due to simultaneous presence of OH”, CO}, or HCO; because OH™ and HCO; ions react to give CO? ions. OH™ + HCO; ——> CO,* + H,0 N Ans. (f) 20m! of H,0 sample= 2575, hypo 20 x normality of Cl= 2.5 x iM62 ENcINEERING CHEMISTRY . 25 or nommalityof CL = 355555 25% 35.5 Strength of free Cl = Fx g/L. 25% 35.5 x 10° = 20x 100x 1000 PP = 44.375 ppm. QS Answer any too parts of the following: (a) (i) What is meant by functionality of monomers? Explain significance with suitable example. (ii) Explain oulcanization and state the improvement in properties of rubber after vulcanization is carried out. (b) What are Biopolymers? Give their uses (c) Give tite mechanism of the following reaction: (i) Riemer-Tiemann reaction, (ii) Carmizaro’s reaction. Ans. (#) (i) Functionality of Monomers: For a substance to act as a monomer. It must have at least two reactive sites or bonding sites. The number of bonding sites in a monomer is referred to as functionality. For example, in alefins the double bond can be considered as site for two free valencies. When the double bond is broken, twosimple bonds become available for combination. ii imi c=c —— CHC. If 1 HH HH ‘Therefore ethylene is considered to be bifunctional. Other groups are hydroxyl acid, amino acid, diol, poly alcohol, etc. Significance: (1) Depending upon the functionality of monomer units it is possible to obtain different type of structure for example in case of bifunctional monomer, two reactive group attach side by side to each other forming a linear or straight chain molecule linked by covalent bonds. Van der Walls force of repulsion gives the possibility of chain movement in one direction.Sampr Examnarions = 63, (2) Incase of polyfunctional groups, monomer molecules are connected to each other by covalent bonds, resulting in the fermation of 3D network. In such. polymer molecules, the movement of individual molecules is prevented by strong cross linking. (3) During the chain growth, side chain also forms resulting in branched chain molecules. Such a molecule in linear but movement is restricted than that of simple straight chain, (i) Valcanization: It consists of heating the raw rubber at 100-140°C with sulphur. ‘The sulphur combines chemically at the double bonds of different rubber springs and provides cross-linking between the chains. This cross-linking during vulcanization brings about a stiffening of the rubber by anchoring and consequently preventing intermolecular movement of rubber springs. The amount of sulphur added determines the extent of stiffness of vulcanized rubber. For example, ordinary soft vulcanized rubber (for tyres) may contain 3 ta 5% sulphur, but hard rubber (say for a battery case) may contain as much as 30% sulphur. HG LH =C cH, cH- HC cH, eect HC Sulphue ——— HCH —cH, cu, c= Sesel cH CH HC H Unvulcanized rubber springs CH, H CH, H won t—t_or—cr,-d_—_ton,— d § 4 4 -cn-b—tcn-cn-d_t ca yn cy, Vulcanized rubber Vuleanized of raw rubber with sulphur as vulcanizing agent64 Encineennc Cuemisrey Improvement in properties of vulcanized rubbers: The tensile strength of vulcanized rubber is very good, about 10 times the tensile strength of raw rubber. & Ithas excellent resilience (After the removal of deforming force, the articles made from vulcanized rubber regains their original shape). It has broader useful temperature range (= 40 to 100°C) compared to raw rubber’s useful temperature range (10 to 60°C). @ It has better resistance to moisture, oxidation and abrasion. Itis resistant to organic salvent like CCl,, benzene, gasoline, etc., but it swells in them. @ If has only slight tackiness. @ It has low elasticity. (This property depends on the extent of vulcanization. Ebonite has practically no elasticity.) Ans. (b) The polymers present in living matter, animals or plants, are termed as biopolymers. Broadly speaking there are four types of biopolymers. These four major types of biopolymers are discussed below: Biopolymers Carbohydrates Protein Nucleic acids Natural rubber (Polysaccharides) {Polyamides) (Polynucteotides) {cis-1, 4-polyisaprene) (a) Carbohydrates. They are polyhydroxy aldehydes, ketones or compounds that can be hydrolyzed to them. These are very important class of organic compounds as they provide us with the necessities of life. This is due to following: @ They are the main source of most of our food; we eat grain containing, ‘starch, or feed it to animals to be converted inte meat and fat which we then eat. @ They provide us clothing in the form of cotton, linen, rayon and cellulose. @ They also provide us shelter as we build houses from cellulose in the form of wood. @ Our present civilization depends upon cellulose, particularly as paper for communication and packaging, Starch and cellulose are polysaccharides which are produced in plants from CO, and H,O by photosynthesis. We use starch as a food: rice, potatoes, wheat, com etc, Starch (occurs chiefly in cellulose) is the chief structural material of plants, giving the plants rigidity and form. Compared tocellulose,Sammie Exammmations 65 starch is more water-soluble, more easily hydrolyzed, and hence more readily digested. (b) Proteins. Chemically, proteins are polyamides which are derived from camino carboxylic.acids. The amide bond linking the a-amino acid residues in proteins is called polypeptides bond and the polymers are called polypeptides. Proteins are the substance of life as they make up a large part of the animal body. They hold it together, and they run it. Proteins are found in all living cells. They are the principal material of skin, muscle, tendons, nerves and blood; of enzymes, antibodies and many hormones. Peptide bond ON 1 nsert R A polypeptide There are two broad classes of proteins viz. fibrous and globular. These are briofly discussed below: (@) Fibrous proteins, Its molecules are linear (long and thread like), and tend to lie side by side to form fibers. There are strong intermolecular forces (Hydrogen bonds) between them and they are insoluble in water. They serve as the chief structural materials of animal tissues. They are: @ keratin (which make up skin, hair, nails, wool, horn, ete.); 1 collagen (which make up tendons); @ myosin (which make up muscle}; and @ fibroin (which make up silk). Gi) Globular proteins. This molecules are folded into spheroidal shapes in such away that the lipophilic parts are turned inward, toward each other, and away from water and hydrophobic parts are turned outward. They have mainly intramolecular hydrogen bonding. Areas of contact between “molecules are small and there are comparatively weak intermolecular forces. Hence, they are soluble in water or aqueous solutions of acids, bases, or salts. They are very essential for the maintenance and regulation of the life process. They make up: ® hemoglobin (which transport oxygen from the lungs to the tissues); @ fibrinogen (which is converted into the insoluble fibrous protein fibrin, and thus causes the clotting of blood).66 Enceveeainc Cuemistee 8 antibodies (which are responsible for allergies and for defence against foreign organism); and ‘@ enzymes (the biocatalysts, without them we might take about 50 years to digesta single meal). Heat, strong acids or bases or various other agent cause denaturation of proteins. It appears to involve disruption of the native conformation (complex three dimensional structure) of protein leading to destruction in any biological activity. During denaturation the protein molecule uncoils from an ordered and specific conformation into.a more random conformation and precipitates from solution. (c) Nucleic Acid. The backbone of the nucleic acid molecule is a polyester chain (called a polynucleotide chain). The ester is derived fram phosphoric acid (the acid portion) and a sugar (the alcohol portion). ‘There are two broad categories of nucleicacidsviz., Ribonucleic acids (RNA) which contains D-ribose sugar and Deoxyribonucleic acids (DNA) which contains D-2-deoxyribose sugar. Ans. (c) (i) Riemer-Tiemann Reaction OH CHO cnc, 2208, o- oO J oxcisat0 (90%) o-Hydroxy con benzaldehy iehyde p-Hydroxy benzaldehyde When the reaction is carried out in presence of CCl, in place of CHCI, a carboxylic group is introduced instead of aldehydic group. COOH + CCl, +4NaOH ——> + 4NaCl +2H,O Salicylic acidSane Examuations 67 Formation of vanillin OCH, OCH, CO Ar—C—H + aH OH H |= jar ArCOO™ ArCH,CH Application: (1) Industrial application: In synthesis of pentaerythritol CH,OH HCHO + CH,CHO no HO—CH,-C—CH,OH + HCOO” CH,OH (2) Preparation if oxallic acid CHO COONa —CH,OH 2] OH] +] +H, COOH COONa ‘COOH tH o0H COOH (3) Preparation of aromatic alcohols and acids. (4) Preparational glycolic acid: qo muon, GOW GrhOH cHO COONa COOH (5) Synthesis of heterocyclic alcohol and acids: Ch _NaQH to “Ch CHO CH,OH ‘COONaSampue Exauunations 69) CHEMISTRY-4 Time: 3 Hours Total Points: 100 Note: Artstwver all questions. Q.1 Answer any four parts of the following: (a) On the basis of Molecular Orbital Theory, prove Hat the molecule of oxygen is paramagnetic in nature. (b) Discuss the Born-Haber cycle during the formation of NaCl erystal. (ch) Describe the geometry of XeO,, molecule on the basis of VSEPR theory. (d) Write the applications of UV Spectroscopy. (e) Explain the theory of metaltic bond. (f) Explain p-type and n-type senviconductor materials. Ans. (a) O, = 2, 6 = Ist, 2s2p° The Molecular orbital diagram of O, molecule may be represented as70) —— Encmecrinc Crenustey ‘These are two unpaired electrons in the antibonding x-orbitals. ©. The oxygen molecule is paramagnetic and the bond order of O, molecule _NioNa _ 10- 2 2 2 Ans. (b) Born-Haber cycle is used to determine the lattice energy of an ionicsolid, Sodium chloride (NaCl) one mole of crystalline sodium chloride (NaCl) can occur by any of the following two processes. =2 (i) Process involving direct combination of Na(s) and 1/2 CL,(g) to form NaCl(s) In this process, heat is evolved, as it is an exothermic reaction. The heat produced is equal to the heat of formation of NaCI(s), ie., ‘Na(s) + Jaw —— NaCli(s) Heat produced = Heat of formation of NaC(s) or AH=-Q (ii) Process for obtaining sodium chloride (NaCl) (a) Conversion of Na(s) to Na(g): Conversion of sodium (Na) atom form solid state to gaseous state, i.c., Na{s) ——+ Na(g) This process is known as sublimation it is an endothermic reaction. Na(s) ——> Na(g) Heat absorbed = Heat of sublimation of sodium = +S. (b) Conversion of Na(g) into Na*(g): This step involves the conversion of gas- eous sodium (Na(g)) atom into gaseous ion. It occurs by giving one elec- tron and the process is known as ionization. Itis an endothermic reaction and for this reaction energy is known as ionization eneryy, i.e., | of Na atom is absorbed. Na(g) - e° —— Na‘(g) Energy required = Heat of ionization = +1. (C) Conversion of 1/2 Cl,{g) into CXgh: In this step, chlorine molecule (Cl,) in the gaseous state is converted into chlorine atom and the process is known. as dissociation. For this reaction, the heat is known as heat of dissocia- tion (D) of chlorine molecule. It is an endothermic reaction. b 5CL— che)Sampie Exasunanions 71 Heat required = Heat of dissociation of ; C1,@) molecule = + 1 D (d) Conversion af Clg} into Cl(g): The gaseous chlorine atom Cl(g) formed in step (c) adds up one electron, given up by Na(g) in step (b) and is con- verted into CI'(g). This energy is known as the electron affinity of chlo- rine is represented as E. This change is an exothermic reaction. CL{g) +e° — Clg) Heat produced = Electron affinity of chlorine =-E (e) Combination of Na*(g) and Cl(g) ions to form NaCl(s): Na*(g) and Cl(g) ions formed in steps (b) and (d) combine together to form 1 mole of NaC! (solid). The attractive forces between Na*(g) and CI'(g) operate and the potential energy of the system is decreased and so energy is released. ‘This energy is known as the lattice energy (U) of NaCl(s). ‘ Na* () + CI4¢) > NaCl(s) Energy released = Lattice energy of NaC\(s) = - U. The formation of NaC\(s) by the above two processes is known as Born- Haber cycle. As the two processes are independent of each other, so according to Hess’ law, the heat of formation of NaCl(solid) must be the sum of both the processes. 1 * ~Q-+S5+1+ 5D-E-U Hence the lattice energy (U) can be calculated. Ans. (c) XeO, Molecule: —_Xe,, = 2, 8, 18, 18, 8 = 1s%, 2572p, 352, 3p83d!°, 4s%4pP4d!0, 5s25 pt Yee - fF) GO) COO XOivterome — [E] sp’ hybridization Forms x-bond forms o-bond om having goresvoens mo = Remains as lone pair72 EscINEERING CHEMISTRY ‘+ The hybridization invalved is sp* so the molecule is tetrahedral with one position occupied by the lone pair. + The shape of molecule is as: / Lone pair JI Ans. (d) Application of UV spectroscapy: 1. Quantitative analysis: This technique is also used for quantitative analysis of compounds. This is based on Beer’s law. In the determination of concentration of an unknown compound, wavelength of maximum absorption for compounds is selected. Then optical densities are measured for some knawn compounds. Now the optical density is plotted against concentration of salute over a range of concentration. A straight line is obtained and from this graph, the concentration of unknown is calculated. Molecular weight determination: Molecular weights if compounds can easily be determined by this technique provided suitable derivatives of these compounds could be prepared. Take a picrate, change it into aminopicrate. A known concentration of it is dissolved in one liter of solution and its optical density measured ati... = 380 nm. The concentration C is determined by the formula bad ly xt log Emax From this, C can be calculated. If the amount of dissolved solute (10) is known, the molecular weight of the solute may be calculated. eo - Qualitative analysis: Identification of compounds can be done by absorption spectrum with known compounds. A curve is plotted between wavelength (4) and degree of absorption (e). 4. The impurities present in organic compounds can easily be determined by Uv-spectroscopy.Saums Exawmanions 73 5. Chemical kinetics: This technique is helpful for studying the kinetics ‘6f a reaction. The reaction change in concentration of either a reactant or product with time is measured. As absorbance is proportional to concentration. Therefore this technique can be used to follow the course of a reaction. Ans. (¢) Molecular orbital approach of metallic bonding: According to this theory when two atomic orbital combine, they form two molecular orbitals—one bonding and one antibonding molecular orbital. In case of three antibonding orbitals AOs, three molecular orbitals MOs—one bonding, one non-bonding and one antibonding molecular orbitals are formed. Similarly for four AOs, four MOs are formed—two bonding and two antibonding orbitals. The presence of two non-bonding molecular orbitals between bonding molecular orbitals and antibonding molecular orbitals reduces the energy gap between the orbitals. Forn centers, (where 1 is large) we may haven distinct energy levels. Ifn is the order of 10 in a metallic crystal, the discrete level which corresponds to ns-electrons, ¢.g., is measured by overlap of many ns-orbitals into a ‘band’ of levels, which appears to be continuous and is a “quasi continuous’. Within the band the electrons will occupy the stage of lowest energy or greatest stability. It has been further proved that between the bands are energy gaps which are forbidden (forbidden-zones} to the electrons. MO.74 ENGINEERING CHEMISTRY | ‘Vacant MOs Lip—] Fb -----nnnn eee. " | tary gent ere ==} | molecular orbitals levels Many atoms n ~~" constituting a band Band formation In lithium metal The bandwidth increases with the increase in overlapping of orbitals, which in tum increase with the decrease in interatomic distance. At a certain distance between aloms, thus the two adjoining bands may wider to such an extent that they start overlapping each other and hence, form a single band. Ans. (f) (f) n-type semiconductors: The addition of a small amount of impurity to a semiconductor before it crystallizes is called doping. When small amount of phosphorus is added to silicon the fifth valency electron remain unshared which is surplus electron and moves through the crystal under the influence of electric field. This givesn-type semiconductor where current is carried by the flow of negative charge. Surplus electron 1 oi/l il Sie Sif Si Sie Si P'— Si Si —+Si+—+ Sie Si + Si type (extrinsic) semiconductor (ii) p-type semiconductors: When a small amount of boron is added to silicon it is surrounded by 7 valenceelectrons instead of 8. Consequently there is positive hole in the lattice. In order to fill this hole, an electron moves from the‘Sapte Exasunations 75 neighboring atom in an electric field. As such an electron deficiency is created around the atom which it leaves. This give rise to p-type semiconductor whose positive holes move through the lattice. The conductivity of semiconductors increases with increase in temperature. This is due to the formation of extra hole by the supply of heat. A large variety of semiconductors have been prepared by the combination of the different groups such as groups 13 and 14, 14 and 15, 13 and 16, and 12 and 16 with almost same size and accordingly called 13-14 compounds, 14-15 compounds, and soon. a Sie Si Si Sie Hole df Si Si Be Si a Si Sie Sie Sie ptype semiconductor The properties of semiconductors depend upon the nature of the impurities. For example, photoelectric devices are prepared by adding caesium. Combination of p- and n-types semiconductors which known as p- junction are used for converting (A.C.} to (D.C, this type of p-n junction is called rectifier. The oxides of transition metals show a wide variation in their electrical conductivity. This is due to impurities and crystal imperfection. For example, TIO, VO, Cr,O, are good conductors of electricity while TIO, V,0,,Cr,0,,MnO, Mn,0,, MnO, FeO, CoO, NiO, CuO etc. are insulators. The oxides like as TiO, ¥,0,, VO, are insulator at a certain temperature. Q.2 Answer any four of the following: (a) How many moles of sodium salt of.a weak acid should be added to prepare 1 liter buffer solution of pH 4.75, provided that the concentration of weak acid is 0.02 moles/Liter and dissociation constant for acid. K, = 1.34 x 10-5? (b) Which one of the following complex compounds has larger crystal field splitting energy? (8 [Co" (HOV, (ii) [Col (H,0),P* (iii) [Ril (H,0),P* (ie) [RA H,O9,P (¢) Show that each octahedral complex of Ni* must be outer-orbital complex. (d) Discuss the kinetics of Ist order parallel rections.76 Encierminc Cremistey (e) Describe the utility of Ziegler-Natta catalysts. (f) Mlustrate auto catalysis by giving two examples. Ans. (a) We know that Henderson equation is PH = pK, + log a @ given pH = 4.75 K, = 1.34 x 10% [Salt] =? [Acid] = 0.02 Putting these values in equation (i) [Salt] 4.75 =— log (1.34 x 10) + log ig o37 [Salt] = 0.015 moles. Ans. (b) Ofthe given four complexes [Rh (H,0,)]* will have larger crystal field splitting energy as Rh is a member of 4d-series while Co is the member of 3d-series. Ay for Rh complexes will be higher than other complexes. Among [Rh"! (H,O),?*, and Rh" (1,0), }** the charge of Rh in [Rh" (H,0),]** is higher than that [Rh"%(H,0),P*, Hence A, for [Rh"" (H,0),]* is higher. Ans. (c) The electronic configuration of Ni** ion (34°) indicates that two innerd-orbitals (3d-orbitals) can be made to allow dsp’ hybridization. However by using two 4d-orbitals sp*d? hybridization may be possible. wicy Ls ton FATE] HT AT 1) or [Ni'Lg” ion sp’ a” hybridization outer orbital octahedral complex. Ans. (d) Let the parallel reaction be,Sampte Examinations 77 Suppose ¢ mol/L be the initial concentration of A and x mol/L be the amount transformed in time ‘t’. If y and z be the amounts formed in time ‘I then the di di rates of formation of Band C are given by $4 and 5 a dy a dt dt The reaction is unimolecular and k,, is the velocity constant for the formation of B from A, then St ek(a-x) @ Similarly, the rate of formation of C is given by B nia x) where k; is the velocity constant for the formation of C. Hence, from equation (j), we have & =k, (a—x) + kfa—x) = (k, +k) @-¥) an integration, we have k, +k, =K (say) = ; log ) 7 Now in order to evaluatek, and k, separately, we must know some relationship between them, amount of B and C formed at any time will depend upon the rates of the two reactions, i.c., AmountofBatany stage _ dy/itt iy(e- 2) _ hy erga ‘Amount ofCatanystage dz/d? k,(a-x) ky The reactive amounts of B and C can be determined at the end of the reaction, the ratio of the relative amounts giving the values of K. The values of k, and canbe calculated separately from equations (i) and (ii?) forms of K and K’ which are directly measurable quantities, We have kytk=K and Sew, 1 iL K=Ki, +k = k(1+K) K RT78 ENciNerRinG CHEMISTRY KK Similarly, Ge Wegscheider’s Test for Side Reaction: According to Wegscheider’s principle, the ratio between the amount of the substances formed in two side reaction is independent of time. If distinguishes side reactions from opposing or consecutive reactions. In the reaction ad , in which both side reactions were unimolecular, it has already been shown that Rate of formation of B _ Amount of B at any stage Rate of formationof C Amount of C at any stage k@-a) ky k@-s) 7 * The constant K’ is independent of time. Examples of Side Reactions: (i) Action af KOH on ethyl bromide: CH,.CH,OH + KBr CH,CH,Br + xon—{ CH, = CH, + KBr+H,0 (ii) Reaction between dry benzene diazoninm chioride and ethyl alcohal: C,H, +N, + HCl + CH;CHO C,H = NC1 + CH,CH,OH -- C,H,0.G,H, +N, + HCl Phenetole Ans. (¢) Ziegler-Natta catalysts are solids of extremely complex structure consisting of ‘Titanium Tetrachloride or Titanium Trichloride and an alkyl aluminium compound. The most commonly used catalyst of this type is the mixture of ‘Thethyl aluminium and Titanium Tetrachloride (ALEt, - TiCl,) inan inert solvent such as heptane. The utility of these catalyst lies in the fact that: (f) Polymerization can be brought about under relatively mild conditions. (i) Linear polymer molecules are obtained and the process permits a considerable degree of stereochemical controleg., polymerization ofethyleneSamos Examnarions 79 M—CH,—CH,—CH,—CH, H,C = CH, | M—CH,—CH,—CH,—CH,—CH,—CH, Polyethylene <——— i H,C The growing chain reaction involves successive insertain of the monomer into the bond between the metal and the growing chain. Ans. (f) When one of the products formed in the reaction ilself acts as a catalyst, the substance is an auto catalyst and the phenomenon is known as auto catalysis H, Completion at reaction Reaction —» Time ——> In auto catalysis the initial rate of the reaction rises as the catalytic produet is formed, instead of decreasing. The curve plotted between reaction rate and time shows a maximum when the reaction is complete. Some examples of such phenomenon are: (#) The oxidation of oxalic acid by acidic KMnO, is catalysed by the presence of Mn®* ions formed in the reaction. In the beginning the colour of KMnO, disappears slowly, but as Mn** is formed in the solution, the color discharges rapidly. 2MnOj + §C,O0}° + 16H*——> Mn + 10CO, + 8H,O (ii) In Hydrolysis of ethyl acetate by water, the reaction is catalyzed by acetic acid formed. CH,COOC,H, + H,O-—+ CH,COOH + C,H,OH Auto catalyst Q.3 Answer any two of the following: (a) What is corrosion? Describe the mechanism of electrochemical corrosion by: (i) Hydrogen evolution (ii) Oxygen absorption80 Encimectine CHenistey (b) (@) Discuss the classification of lubricants. (ii) What is the chemistry involved in Smog formation? (c) What do you know of the following: (i) Acid rain and its harmful effects, (Hi) Greenhouse effect. Ans. (a) Corrosion is the process of gradual decreases of a metal from its surface due to the unwanted chemical or electrochemical interaction of metal with its environment. Mechanism of corrosion by electrochemical theory is as given below: Corrosion reaction: Corrosion process involves the formation of galvanic cells. The various reaction that occur during corrosion are follows: (a) Anode reactions: The anode is a metal which undergo oxidation and losses electron lo the environment and pass into solution in the form of positive ions. For example, Mis) ———» M™ + ne~ aqueows Fe(s) » Fe® + 207 aqueoiss Fe* + 20H" ———> Fe(OH), aqueous aqueous Rust This continues as long as electrons and ions ate removed from the environment. lf they are not removed the corrosion will not proceed further. ({b) Cathade reactions: The electrons released at the anode are carried to cathodes and are responsible for fallowing reactions: (i) Hydrogen electrode or hydrogen type corrosiort; In acidic solution, he com mon reaction is the reduction of H* ions to H, gas, H* ions are present due to the ionization of water. 2H? + 2e°——> H, H,O ——> 2H* +0” This type of corrosion in which hydrogen is evolved is known as Hydrogen type corrosion. At anode, the metal ions pass into the solution M—— M* + 2e" The overall reaction can be written as M + 2H*——+ H, + M?Samete Exawrnarions 81 e.g., copper corrosion in acidic solution consists of two half cell reactions Cu—— Cu" + 26° (Anode reaction) 2H +2e°—> H, (Cathode reaction) (ii) The oxygen electrede: Hydrogen ion H* concentration is very low in neu- tral orbasic solutions, therefore evolution of hydrogen gas is not favorable. In such cases reduction of oxygen to hydroxyl ion occurs. O, + 2H,0 + 4e°-—— 40H For example, the corrosion of iron occurs by oxygen in the presence of aqueous solution. At the anode, ion dissolves to form ions as Fe-—— Fe** + 2e" (Anode reaction) At cathode, the electrons evolved by above reaction will be intercepted by oxygen in presence of water. 1 2e° + 5 0, + H,O-——-+ 20H (Cathode reaction) The overall reaction will be, 1 - - Fe + 3 0, +H,O— Fe" 4201 The hydroxyl ion OH" produced reacts with the positively charge Fe* ion forming Fe(OH), or rust. Fe? + 20H-—— Fe(OH), rust ‘The corrosion proceed as long as oxygen is available. This type of corrosion is known as Oxygen type corrosion. Therefore the essential requirements of electrochemical corrosion are: @ Formation of anodic and cathodic areas. @ Electrical contact between the cathodic and anodic parts. @ An electrolyte through which + ve ions can diffuse. Ans. (b) (i) Lubricants are classified as the basis of their physical state as: (1) Solid Lubricants: These are not widely used as these contain grains of particles which may damage delicate parts of the machinery. Most common solid lubricants include graphite and molybdenum disulphide.82 Excineeninc Cnesustey (2) Sentisolid Lubricants: It is solid or semisolid combination on a petroleum product and a soap or a mixture of soaps, with or without fillers, suitable for a certain type of lubrication. These include greases and vaselene. (3) Liquid Lubricants: These are in liquid state and are further classified as: @ Vegetable oils, @ Synthetic oils @ Animal oils @ Mineral oils @ Blended oils Lubricants Animal oils Mineral Blended Synthetic oils. eg.,Whaleci, oils oils @,g., Polyalkene, Land oil, and and Glycols Tallow oil ‘Ans. (b) (if) Smog is the odd combination of smoke and fog. It consist of solid particles (carbon) dispersed in air. It is of two types: (1) Classical or london smog: This consists of caron based soot and other solid particulates and sulphur dioxide (SO,). The following reactions take place in this smog: S+0, — sO, 260, +0, — 280, 280, + H,O—— H,SO, 3HL,SO, + 0,———> 21,50, H,SO, + 2NH,——> (NH,),SO, It damages plants, posses human health hazard etc. (2) Phatochemtical smog: Photo chemical smog is initiated by photochemical dissociation of Nitrogen dioxide (NO,) and other reactions in which free radicals are formed.Samir Exammanons 83. inIC engines N, +0, —————» 2NO or furnace 2NO, ———> 2NO, UV light NO, ———> NO+[0} Hydrocarbons +O, 0,0, NO,, NO——> Peroxides, Peroxyacetyl nitrates (PAN), HCHO, Acroline etc. CH,CHO + OH CH,C6 + HO CH,CO +0, +M——> CH,(CO)00 Acetylperoxy radical CH,C(O}OO + NO, —— CH,.C(O).0ONO, (PAN) These oxidized hydrocarbons and ozone QO; in the presence of humidity cause photochemical among which dissipates at night. Ans. () (i) Acid rain: The presence of Sulphur dioxide (SO,) and Nitrogen dioxide (NO.) gases as pollutants in the atmosphere decreases the pH of rainy water (2.4), such type of rain is known as acid rain. SO +0, 50, $0, + H,O ——+ H,S0, 250, + O, + 2H, —> 2H,50, 4NO, + 0, + H,O—— 4HNO, CH, + H,O—-+H,co, Harmful Effects of Acid Rain MM It increases the rate of corrosion. It causes damage to buildings and sculptinal material made of marble, lime-stone, and slate etc. i@ It changes the rate of metabolism of animals. ‘g It damages plant leaves in the form of mist. @ It causes damage to fresh water life such as fishes ete. Ans, (c) (ii) The earth is readily heated by sunlight and some of the heat absorbed by ‘the earth radiated back into the space. In the lower atmosphere of the earth. 84 EncinegminG CHEMisTRY some of the gases act as greenhouse, ie., the body which allows the short wavelength incomming solar radiation to come in but does not allow the long, wavelength IR radiation to escape. The net result, is thal the earth’s surface is heated up. Among the constituents of atmosphere, only carbon dioxide and water vapor strongly absorb IR radiation (14000-25000 nm) and effectively revert back a large fraction of earth's emitted radiation. The radiation, therefore absorbed by carbon dioxide (CO,) and water vapors are partly re-emitted to the earth’s surface raising the temperature of the earth and causing the phenomenon, is known as greenhouse effect. The greenhouse effect may, therefore, be defined as the progressive warming up of the earth’s surface due to blanketing effect of carbon dioxide (CO,) in the atmosphere. The major greenhouse gases are carbon dioxide (CO,) methane, nitrous oxide (N,O) and chloreflureearbons (CFC’s) ete. Among these (CO,) is the most important greenhouse gas accounting 50% of the global warming, other gases such as methane and CFC’s contribute about 10% and 14% respectively to the global warming. Relative contribution of active gases to temperature rise, Consequences of Greenhouse Effect: @ Increase in global temperature effects food production. @ Ice of polar regions and glaciers will melt thereby increasing the sea level. This will threaten several island nations and our coastal cities like Kolkata, Mumbai, Chennai ete. @ It heats up the earth’s surface and evaporate the surface water. @ At higher altitudes, CO, undergoes photochemical reaction to form CO which has a toxic effect.Saurus Exawinanions 8S Q.4. Answer any two of the following : (a) (i) Compare the merits and demerits of solid and liquid fuels. (ii) Calculate the volume of air required for complete combustion of Im: of gaseous fuel having the composition: CO = 46%, CH, = 10%, H, = 4%, C,H, = 2%, N, = 1.0%, and remaining being CO, (b) (i) Explain the advantages and disadvantages of the Zeolite process for water softening. (ii) 100 mt of water sample has a hardness equivatent of 12.5 ml of 0.08 N MgSO, What is its hardness in ppm? (©) (i) Give examples of nonconventional sources of energy. (ii) Discuss proximate analysis of coal. Ans. (a) ()) Solid Fuels Liquid Fuels 1, Solid fuels have low Calorific value. 1, Liquid fuels have low Calorific value. 2. Low heating temperature. | 2. High heating temperature. 3. Higher percentage of noncombustible | 3, Lower percentage of noncombustible | © materials. materials. | 4. High value 4. Low value. | | 5. Difficult to store. | 5, Easy to store, Ans. (2) (ii) 1 m? of gaseous fuels contains: CO = 0.46 m?, CH, = 0.10 m*, H, = 0.40 m3, C,H, = 0.02 m#, N, = 0.01 m* » Combustion Reaction Volume of Oxygen Required, () CO+050, —-+C0, 046 «0.5 = 0.23 m* CH, +20, ——> CO, +2H,O 0.10 x 2.0 =0.20 m* +20, (ii) H, +050, —+H,0 0.40 x 0.5 = 0.20 m* | | (iv) CJH, +250,——+ 2CO, + H,0 0.02 x 2.5 = 0.05 m* Total = 0.68 m* 1 Volume of air required = 0.68 m* x 2 =3.2m'86 Encrvrrainc CHemisTey Ans. (8) () Zeolite (Na,O.AI,0,.x SiO, yH,O Na,Ze) have the property of exhanging their sodium ions (Na*) easily with calcium (Ca**) or magnesium ions (Mg**) when they come in contact with hard water. The process removes both types of hardness temporary as well as permanent hardness. The following reaction ‘occurs: Ca(HCO,), + Na,Ze——+ CaZe + 2NaHCO, CaSO, + Na,Ze— CaZe + Na,SO, MgSO, + Na,Ze ——> MgZe + Na,SO, Advantages of Zeolite Process: ® The equipment occupies a small space and is easy to operate. @ This process automatically adjusts itself for different types of hardness of water. @ This method can produce zero hardness. ™ This method is cheap because the regenerated zeolite can be used again. Disadvantages of Zeolite Process: @ The method leaves all acidic ions such as HCO, and CO,* in the softened water. @ When such water is boiled in water, CO, is liberated which is weakly acidic and highly corrosive. ‘@ After treatment water contains more sodium salt. High turbidity water cannot be easily treated by this method. Ans. (b) (ii) 100 ml of water sample= 12.5 ml of 0.08 N MgSO, = 12.5 ml of 0.08 ml of 1 N MgSO, = 1ml1N MgSO, = 1 ml of 1 N of CaCO, equipment = 0.001 x 50 g CaCO, equipment = 0.05 g of CaCO, equipment or 50 mg CaCO, 50 mg of CaCO, x 1000 -. 1000 ml of water sample = 700 mi = 500 mg CaCO, equipmentSampce Examinations 87° Therefore, the hardness of water sample is 500 mg CaCO, equipment per liter or ppm. Ans. (c) (i) Nonconventional sources of energy are that sources of energy which are being continuously produced in nature and are nonexhaustable. These energy sources include: wind energy, Solar energy, geothermal energy, tidal energy, ocean energy, biogas etc. Solar energy canbe directly converted into electricity by the use of photoelectric cell. Solar energy is used in making silicon solar cell used for space programming. It is also used for vaccine refrigeration and lightening of health care center in rural areas. Biogas is obtained by anaerobic fermentation of animal wastes, like animal dung in presence of water, this can sidely be used in rural areas since we have largest scale of cattle population in the world. Seventy five percent of the domestic energy needs in rural areas can be used with biogas. Ans. (c) (i) Coal is a highly carbonaceous matter thal has been produced due to the change of vegetable matter for example, plants under certain favorable conditions. It is mainly composed of carbon, Hydrogen, Nitrogen and Oxygen, besides noncombustible inorganic matter. The assessment of quality of coal is carried out by the following two type of analysis: (1) Proximate analysis (2) Ultimate analysis (1) Proximate Analysis: I! is expirical but the important analysis records moisture, volatile matter, ash and fixed carbon as percentages of the original weight of the coal sample. This analysis involves the following determinations: () Moisture: About one gram of finally powdered and dried sample of coal is taken in a silica crucible and heated in an electric oven for one hour at a temperature of 105°C to 110°C. Then the crucible is taken out, cooled in a dessicator and weighed. The amount of weight loss is reported as moisture, Loss in weight ‘Wt. of coal taken (ii) Volatile matter: The dried sample of coal left in the crucible from (i) is then covered witha lid and kept ina multiple furnace at 925+ 25° for 7 minutes. After 7 minutes, the crucible is taken out and cooled first in air and then Percentage of moisture = » 100BB Encweemc CHeesray inside the dessicator and weighted again. Loss in weight is reported as volatile matter on percentage basis. Percentage of volatile matter __ Loss in weight after the removal af volatile matter 4, Wt. of coal sample taken (iii) Ash: The residual coal in the crucible obtained from (ii) is heated without lid in a muffle furnace at a temperature of nearly 800°C for nearly 30 ‘minutes. The crucible is taken out cooled first in air then in a dessicator and weighed. Heating, cooling and weighing are repeated until a con- stant weight is obtained. . __ Weight of ash left ercentage of ash = oF coal sample taken 1? (iv) Fixed Carbon: The percentage of fixed carbon is reported as under: = 100 — % of (Moisture + Volatile matter + Ash) QS Answer any four of the following: (a) Differentiate between Addition polymers and Condensation polymers. (8) Write the chemical reactions involved during nylon—6,6 polymer synthesis. (c) Complete the following reactions: NH; JNO, oy + slycerine aso, c Benzen (ii) cC + —? SCAR Dicne —Dinophile (d) Discuss the mechanism of Cannizaro reaction. (e) Write the possible optical isomers in tartaric acid. (fF) Describe the conformational isomers of cyclohexane molecule.Sammut Exauixanions 89 Ans. (@) Addition Polymers ‘Condensation Polymers 1. Themonomers combine ina head totail | 1. The monomers units condense with the manner without the evolution of any | - release of small molecules like H,0, HCL simple molecule. etc. 2. Number of units decreases steadily throughout their formation. . Monomers disappears early in reaction. 3. These are formed by the compounds 3. These are formed by the compounds: containing double or triple bonds. containing more than one functional group. 4. High molecular mass addition 4. The molecular mass rises steadily polymers are immediately formed throughout the reaction. 5. Common examples include 5, Common examples include: Nylon, ‘CH,= CH, Polymerization terelyne, formaldehyde, resins, ? = (Ci1_-CH} polycarbonate, ete. Polyvinyl Chloride, PMMA, ete (b) Nylon-6, 6 isobtained by condensing adipic acid with hexamethylene diamine with the elimination of water molecule H,O. The chain length depends upon the temperature and time for which the process is carried out, the chemical reactions involved in the process are: oO U I HOC+CH,-C—OH + m HJN-4ACHS-NH, Adipic acid | Hexamethylenediamine n [oBacrindcn sens. Heat | Condensation 1:1 salt | polymerization ° 9 9 ° Il Il I Il n O—C-4CH;}C-| NH-{CH}- NH—C{CH,3-C-- NH-{CHy}- + NH; + (2n-= 1) HO It isa linear polymer and has very high tensile strength. It shows good resistance to abrasion. It is used in making shats, ropes, bristles for brushes and in textile.90 Enciwerninc. CHemistay NH, « Ans. (c(i) or + glycerine =e ae C Benzene @ C “Hl On SS C—-R R Diene —Dinophite Adduct Ans. (d) Cannizaro Reaction: CHO CH,OH + HCHO —CoeNSOH , 4+ HCOONa Sod. formate: OCH, OCH, p-Methoxybenzaldehyde P-Methonybenzaldehyde Mechanism: The mechanism involves a nucleophilic addition of hydroxide ion (step ()) to give the intermediate 1; and addition of an hydride ion from I (step (i9)) toa second molecule of aldehyde. The presence of the negative charge an I aids in the loss of the hydrogen ions. H H @ act 20+0H == arco? bu 1 Sy H tip met Amesp —_—> Artao + Angao? oH OH H peo Ar—COc® Ar—CH,OHSampie Examinarions 917 Applications: Production of pentaerythritol trinitrate, an intermediate for explosive manufacture. 44,50 Ho, C(CH,OH), +3HNO, ——+ HOCH, .C(CH,ONO,), ——s C(CH,ONO,), HNO, Pentaerythritol Pentaerythritol trinitrate Pentaerythritol (PETRIN) tetranitrate (PETN) Ans. (ec) Optical isomers of tartaric acid are: qoor (Go) goort HCH HOCH HCO HOE Ht —OH H-4-0H ) COOH, COOH, I 1 ut d-tartaric acid itartaric acid di-tartaric acid (ep-170°C). Occurs (mp-170°C). Does not racemic form (mp-140°C) in free state in nature occur naturally obtained Obtained by heating from resolution of racemic detartaric acid (dl) tartaric acid Ans, (f) Cyclohexane is not a planar molecule and Mohr has given two conformations of cyclohexane: Boat form Chair form All pairs of carbon-carbon bonds in the chain form are perfectly staggered and in boat form these are eclipsed. The boat form has appreciable torsional strain and steric due to crowding of C, and C, hydrogens. Therefore it should be less stable than chair form. It is seen that the chair conformation of cyclohexane has 7.0 kcal/mole less energy than boat conformation. Besides above, conformation, cyclohexane has several other conformations as: Boat form Twist boat92 Engreerninc Ciemstey CHEMISTRY-5 Time: 3 Hours Total Points: 100 Note: 1. Answerali Five questions. 2. A questions carry equal points, Q.1 Answer any two of the fatlowing: (a) (i) What type of information is obtained by studying the UV. IR, H-NMR and Mass Spectra of an organic compound? (if) Organic compound ‘A’ {Molecular weight, 58] gives a red precipitate with 2, 4- dirtitroplenyl hydrazine reagent. H-NMR spectrum of the compound shows only one signal, as singlet, corresponding to six protons. Nante the conrpound and write its structure, Or (a) (i) Discuss the importance of Biopalymers. (if) Show the configuration of atactic, isotactic and syndiotactic Polystyrene. Which stereomeric polymer of styrene is formed when polymerization renction is carried out in the presence of Ziegier-Natta catalyst? 4b) Write the chemical structures of the following polymers: (i) Nylon 6 (ii) Dacron (iif) Vulcanized rubber (iv) Buna-$ {») Polyacrylonitrile. Ans. {a) (i) Informations by studying U.V. Spectrum: (1) We can determine the conjugation in the molecule, by conjugation 2. is shifted to higher wavelength. (2) We can also identify the functional group such as C = O,-C = N, - NO,, -OHelc. (3) An unknown compound can be identified by comparing its spectrum with the spectrum of standard sample. (4) Elucidation of structure of vitamin A and K ete (5) Detection of impurities. Informations by studying 1.R. Spectrum: (1) We can distinguish the geometrical isomers, cis form has lower frequency region than trans form. (2) We-can identify the functional group such as—OH, ether, -COOH, -COOR etc,Samour Exawunations 93, (3) Two different compounds cannot have same LR. spectrum except enantiomers. In this way we can identify the compound. (4) [t can be used in studying keto-enol tautomeric equilibrium Informations by studying NMR Spectrum: (1) By counting the number of signals, we can have the idea of number of equivalent protons. (2) By counting the number of splitted signal we can say the number of surrounding protons. Informations by studying Mass Spectra: (1) We can determine the molecular weight of the compound. (2) Recognization of certain structural units in an organic compound by indicating the fragmentation sites in the molecule. (3) We can have the idea of the mechanism of the reaction. Ans. (a) (i) Compound is reacting with 2, 4 dinitrophenyl hydrazine. It means it is having, C=O group. It shows only one signal for six hydrogen, it imply all the six hydrogen atoms are equivalent. So expected structure is: i H,C—C—CH, (MLW = 58) Or Ans. (a) (i) The polymers present in living matter, animals or plants, are termed as biopolymers, Broadly speaking there are four types of biopolymers. These four major types of biopolymers are discussed below: Biopolymers, ‘Carbohydrates Protein Nucigic ackés Natural rubber (Polysaccharides) (Polyamides) (Polynuctectides) {cis-1, 4-polyisoprene) (A) Carbohydrates. They are polyhydroxy aldehydes, ketones or compounds that can be hydrolyzed to them. These are very important class of organic compounds as they provide us with the necessities of life. This is due to following:94 Encincerinc CHeaister @ They are the main source of most of our food; we eat grain containing starch, or feed it to animals to be converted into meat and fat which we then eat. @ They provide us clothing in the form of cotton, linen, rayon and cellulose. E They also provide us shelter as we build houses from cellulose in the form of wood. @ Our present civilization depends upon cellulose, particularly as paper for communication and packaging. Starch and cellulose are polysaccharides which are produced in plants from CO, and H,O by photosynthesis. We use starch as a food: rice, potatoes, wheat, com etc. Starch (occurs chiefly in cellulose) is the chief structural material of plants, giving the plants rigidity and form compared tocellulose. Starch is more water-soluble, more easily hydrolyzed, and hence more readily digested. (B) Proteins. Chemically, proteins are polyamides which are derived from G-amino carboxylic acids. The amide bond linking the a-amino acid residues in proteins is cailed polypeptides bond and the polymers are called polypeptides. Proteins are the substance of life as they make up a large part of the animal bedy. They hold it together, and they run it. Proteins are found in all living, cells. They are the principal material of: skin, muscle, tendons, nerves and blood, enzymes, antibodies and many hermones. a ertide bat ° nf—cu_lon Te R H A polypeptide There are two broad classes of proteins viz. fibrous and globular. These are briefly discussed below: (i) Fibrous proteins. Its molecules are linear (long and thread like), and tend to lie side by side to form fibers. There are strong intermolecular forces (Hydrogen bonds) between them and they are insoluble in water. They serve as the chief structural materials of animal tissues. They are:Samos Exammnarions 95, @ keratin (which make up skin, haiz, nails, wool, ham etc.); & collagen (which make up tendons); & myosin (which make up muscle); and @ fibroin (which make up silk). (i) Globtelar proteins. Its molecules are folded into spheroidal shapes in such away that the lipophilic parts are turned inward, toward each other, and away from water and hydrophobic parts are turned outward. They have mainly intramolecular hydrogen bonding. Areas of contact between molecules are small and there are comparatively weak intermolecular forces. Hence, they are soluble in water or aqueous solutions of acids, bases, ot salts. They are very essential for the maintenance and regula- tion of the life process. They make up: 1B hemoglobin (which transport oxygen from the lungs to the tissues); ® fibrinogen (which is converted into the insoluble fibrous protein fibrin, and thus causes the clotting of blood); B_ antibodies (which are responsible for allergies and for defence against foreign organism); and. @ enzymes (the biocatalysts, without them we might take about 50 years to digest a single meal). Heat, strong acids or bases or various other cause denaturation of proteins. Itappears to involve disruption of the native conformation (complex three dimensional structure) of protein leading to destruction in any biological activity. During denaturation the protein molecule uncoils from an ordered and specific conformation into a more random conformation and precipitates from solution. (C) Nucleic Acid. The backbone of the nucleic acid molecule is a polyester chain (called a polynucleotide chain). The ester is derived from phosphoric acid (the acid portion) and a sugar (the alcohol portion). There are two broad categories of nucleic acids viz., Ribonucleic acids (RNA) which contains D-ribose sugar and Deoxyribonucleic acids (DNA) which contains D-2-deoxyribose sugar.96 ENGINCERING CHEMISTRY Ans. (a) (i) Configuration of polystyrene HO L-GHs Cie | | HyH H7oNH H~ C,H, H~¢—C,H, \ \ Hoo Hos Haga cl Heng Hy H H7SSH Hei, He GH “GN, aly, HOH HTH Isotactic Syndiotactic Ans. (5) (i) Nylon 6: i CNHH(CH (ii) Dacron: ie oct —cH,-0-C-))-¢ I (iii) Buna-S: CH,—CH=CH—CH,—CH—CH, Wyn | HF CH, H~¢-H \. H77 ~CHs tecoHl CH“ A Hei Hes Gil Atactic‘Samece Exammanions 97 (iv) Vuleanized rubber: (Sulpher is crosslinked) cH, cH, —CH,—C—CH—CH,—CH,—C—CH—CH,— l t { | mcr, t dic Hy-cH, eco H, H, HH CN J, Q2 Answer any four of the following reactions: () Polyacrylonitrile: (a) Write the mechanism of the following reactions: (i) Aldol Condensation (#i) Friedal-Crafts reaction (b) (i) How would you decide whether the reaction: CH,Br+ OH === CH,OH + Br proceeds by Sy! or S,? mechanisin? (ii) Draw the energy profile diagram for the reaction: (CH) ,CBr + OH” === (CH)),COH + Br Indicate clearly the reactants, transition states, activation energies and products of the reaction. {c) (8) Allocate the symbol E or Z to each of the following compounds and explain: Ph yh Ph See 5 ae Bn” co H ‘ph [Ph—Phenyl = CH, CO.H al COW H. Nenad er — HN” Np cow a98 ENcincerinG CorenustRy (ii) Under what conditions can the terms cis and trans not be u (a) Give an example of elimination reaction and discuss its mechanism, (v) Discuss in detail, stereoisomerism is the case of an organic compound with too chiral centers. (f) Draw the potential energy diagram for the various conformations of n-butane. Ans. (a) (i) Mechanism of Aldol Condensation. The formation of aldol proceeds through a series of equilibrium steps. The hydroxide ion of base abstracts thea-hydrogen atom from aldehyde and the resulting enolate ion which acts as a nucleaphile and attacks the second molecule of acetaldehyde. The resulting ion then takes up a proton from water to produce aldol and the OH" ion is regenerated. The steps involved are: ° 1 CH,CHO+OH 2 ace +H,0 H Enolate ion 0 oO CT ts 2 CHG Ei.cho <= cH ¢—-cH,cHO H Hi y OH | | _ 3 CHF —CH.CHO +H, == CHy-G-CH.CHO +OH H H Aldol (ii) The Friedal-Crafts reaction involves the substitution of alkyl (R—) or acyl (R—C—) groups in the benzene ring in the presence of a catalyst, anhydrous aluminum chloride. Anbyvnous AICI, GH, + CH,Cl ———— C,H,—CH, + HCI Benzene Methyl Chloride Toluene Antyalrous AK, CH, + RCOCL ———— ¢,H,COR + HCI Benzene Acid Chloride KetoneSampus Exasunanions 99 Ans. (b) (i) CH,Br + OH” ===» CH,OH + Br proceeds by S,,? reaction. Ans. (b) (ii) Roaction progress Energy profile diagram of S,1 reaction. Ph Ph Ph con Ans. (0) (3) Yeocl ye Hu” co Hw OPh (2 ( FN, cl COW ,! Sec eee” cl “er HN “pr (2 (E) Ans, (c) (#i) The configuration of geometrical isomers can be represented as cis or trans. When two identical atoms or groups are on the same side of the double bond. the isomer is known as cis and if they are on the opposite side, it is known as frans. When two atoms or groups attached to double bonded carbon atoms are different cis-trans designation can not be applied. Ans. (d) Elimination reactions: The reactions mvolving the removal of two or more atoms/groups from the organic molecule under suitable conditions to form a100 Encineening Cremistay product with multiple bond are called elimination reactions. Elimination can be considered as reverse of additon. H OH Hs, C) H,C—CH, Ethane H Br | | ale KOH ti) H,C—CH, Ethyl Bromide ——> H,C=CH,+H,0 Ethane H,C=CH, + HBr Ethene Mechanism: The first step invelves the ionization of alkyl halide to give carbonium ion (slow) and the second step invelves the fast abstraction of a proton by the base adjacent to B-carbon leading to the formation of alkene CH, CH, cH, ‘Chiral Centers]: CH. Hy at Ay ¢ + cH, t-butyl Carbonium ion ClCH, ¢ + H,0 cH, 2-methyl propene Ans. (c) Compounds Containing two Dissimilar Assymetric Carbon Atoms [Two This type of compounds exist in four stereoisomeric forms according to the formula 2* (2? = 4). For example, for bromochtoro succinic acid, the four stereoisomers are all optically active. They are: goon H— coal Be—0-H COOH fa) Foou ce H—C—Br coon (b)COOH neta H— Lo coon (cy Samrue Examinanons 101 COOH cl bon Br—C—H Coot @) ‘These four stereoisomers include two pairs of enantiomers, ic., (a) and (b); (€) and (q) as (a) and (b) are the mirror images of each other. However, (a) and (c), {a) and (d}, (b) and (c}, and (b) and (4) are stereoisomers of the same compound but arenot the mirror images of each other, so are (c) and (@). These are known as distereomers. Ans. (f) Conformations of -Butane. 1-Butane is a four carbon alkane derived from ethane in which one hydrogen on each carbon is substituted by a methyl group, n-Butane has more than o1 ne staggered and eclipsed conformations and the staggering or eclipsing in these conformations may be partial or complete. CH, H CH, H. H H, H CH, H HC - H H H H cH, Hc, H Anti form Eclipsed form ‘Gauche form (e) (by cI H cH, CH, H H H. CH, H H H. H. H H CH; CH, Ach, Fully Eclipsed form Gauche form Eclipsed form @ & w Conformation of n-butane102 Encimerrinc CHenistey In the completely staggered conformation (a), called anti form. the methyl groups lie as far apart as possible. If we assume that the angle of rotation about the central C;--C, bond is zero for (a), then on rotating one of the C, or C, carbon atom through an angle of 60°, the eclipsed form (b) appears. In its back, hydrogen, rather than the methyl group is attached to the other carbon, If we rotate it by another 60°, we get staggered conformation (c), also called gauche form, in which the two methyl groups are only at 60° gives rise to eclipsed form (e), in which the two methyl groups are again at 60° apart. Further rotation by 60° gives rise to eclipsed form (/), which if rotated by another 60°, will give the anti form (a). Relative Stabilities of the Conformations of r-butane: Following figure shows the energy changes during rotation about C,—C, bond in 1-butane. The differences in energy of (a) and (¢) is 5.3 kcal mole, between (a) and (c) (ore) it is about 0.88 kcal mole“!. Therefore, (a) would be the most stable conformation of n-butane. Conformations (c) and (e) would be slightly less stable than (a); and (b) and (c) would be slightly more stable than (a). Therefore (d) is least stable. It is clear that the anti conformation (a) is only slightly more stable than gauche conformations, (c) and (b). So, the staggered conformations which possess nearly minimum energy are known as conformational isomers or conformers. These conformers differ from each other only in the spatial relationship of atoms forming them and so they are known as stereo-isomers. The two gauche forms, (c) and (¢) are non-superimposable images of each other and so they are called conformational enantiomers. The pair consisting of anti form (a) and one of the gauche forms are not mirror images of each other and so they are called conformational diastereoisomers. These conformational isomers are readily inter-convertible (unlike the conventional stereo-isomers) and so cannot be separated. As the energy difference between conformers (a) and (d) is still small (5.3 keal mole"), so they cannot be separated, n-butane at any time will be equilibrium mixture of all conformers, in which the highest proportion will be that of anti conformer, (a) and least proportion of the fully eclipsed conformer, (d)Sampis Examinarions 103 Fully Eclipsed (d) Eclipsed (b) Potential Energy ———+ 120° 240° 300° 180° Rotation ———+ Energy changes during rotation around the in n-butane, ‘central carbon-carbon bor The torsional strain can explain the greater stability of staggered conformation (a) than that of eclipsed conformation, (d). But in this case, another factor also comes into play. In n-butane, the two hydrogens, one on each of the twocentral carbons (C, and C,) have been replaced by bulkier methyl groups. In anti conformation (a) these bulky methyl groups are farthest apart, while in other gauche and eclipsed forms, they are brought closer. Due to crowding of bulky methyl groups in gauche and eclipsed forms, van der Waals forces of repulsion between the groups occur, which cause steric strain in these molecules. Duc to steric strain, the energy of such conformations increases and so the stability decreases. The anti and gauche conformations are both free of torsional strain due to staggered nature, but in gauche conformations, the bulky methyl groups are 60° apart and so they suffer steric strain. The anti conformation, (a) is, however, free of this steric strain also. Thus the gauche conformation should havehigher energy and lower stability than the anti conformation, (a). Actually, the energy of gauche form is 0.9 kcal mole” greater than anti form, (a) and so the former has lower stability: In fully eclipsed conformation (d), the steric and torsional strains occur to the maximum extent and so it has the maximum energy and minimum stability. Or Q.2 Anstver any two of the following: (a) What is corrosion of metals? Explain the basic reason of metallic corrosion. (b) How is ozone formed and depleted in nature? What are the consequences of the depletion of the O, layer in the atmosphere? (c) What are the different sunthetics used? How are they superior aver petroleum lubricants?104 — Encineeriva Cuesesrar Ans. (a) Corrosion of metals: It isa matter of common observation that certain metals (except those which are least reactive like Au, Pd, etc.) are slowly eaten up on long exposure to atmosphere. For example, silver gets tarnished, copper develops green coating on its surface, iron rusts and lead loses its lusture. In fact, such metals react with the gases or moisture present in the environment to form undesirable pounds. This process in general is reffered to as corrosion. Corrosion may thus be defined as the process of slow conversion of metals into their undesirable compounds (usually oxides) by reaction with moisture and other gases present in the atmosphere. Basic Reason of Corrosion: In nature, most of the metals (except-noble metals) exist in the combined state as their compounds, known as ores and mineralsi-c,, oxides, hydroxy carbonates, chlorides, silicates, carbonates, sulphides, etc. These compounds represent their thermedynamically stable state. The metals are extracted from these ores after expending lot of energy. Therefore unless the nature of the metal is substantially changed (for example by alloying), the metal will have a natural tendency to convert back to its natural thermodynamically stable native combined state. This is the basic reason of corrosion of metals. Ans. (b) Ozone is present in the stratosphere. The ozone layer in the stratosphere acts as a protective shield for life on earth. It absorbs the harmful solar radiations like as UV rays, which are lethal to life causing DNA mutation and skin cancer. Also in absence of this layer the temperature of the lower atmosphere will rise to such an extent that the biosphere will turn into a blast furnace. Formation of ozone layer. The ozone layer is formed in the stratosphere by a photochemical reaction followed by a third body reaction. 22nm 0, +iv ——+ 0+0 O +0, + MIN, or0,)-—— 0,+M @ The third body (M) absorbs excess energy liberated by the reaction (i) and thereby stablize the O, molecule. The thickness of the ozone layer is measured in Dobson units (DU), where, 1DU = 0.01 mm of the compressed gas at0°C and 760 mm Hg pressure. Average thickness of the ozone layer in stratosphere has been estimated to be about 230 Dobson units (DU). However, thickness varies marginally with latitudes because of different atmospheric conditions. The thickness is found comparatively low in polar region. Depletion of ozone layer. According to World Metrologicat Organization Geneva, ozone levels have been depleting at an average annual rate of 4.3% every decade in Northern Hemisphere and 4.1% in Southem Hemisphere, sinceSambue Examinations 105 1997. Ozone layer is believed to be depleted by reaction with atomic oxygen, reactive hydroxyl radicals and nitric oxide. @ 0, + HO" —> 0, + HOO" HOO* +O——> HO" +O, ti) 0,+0-——>0,+0, ii) 0, + NO——+ NO, +0, NO, +O——> NO+0, Apart from the above mentioned species, chlorine also plays an important role in depleting ozone in the stratosphere in following manner: cl +0, > Cl-0" +0, ClO" +O-—3 CI +0, As seen CI° atams are regenerated, so that a long chain process is involved. 2 No Chiorine nitrate Cl—O* + NO, —-+ Cl - O—N: The depletion of ozone layer have been found to be much more acule in polar regions particularly to the formation of ozone hole. This may be because of two reasons: (i) Cold climatic con including turbulence. (ii) Absence of N,O in these areas which destroys CO* and checks ozone depletion. N,O at sub-zero temperature freezes into ice droplets. ‘Consequences of ozone layer depletion. Ozone layer destruction leads to more ultraviolet radiation reaching earth causing similar climate changes as in greenhouse effect and also these are harmful to man causing skin cancer, sun burns, leukemia cataract of eyes haemorrhage edema, lung injury, lung cancer, DNA mutation and many more adverse effects. Ans. (c) Synthetic Lubricant Oils: These are oily liquids which are not found in nature or they donot produce directly during the normal manufacturing and refining processes of the petroleum industry. In order to meet the lubricating requirements under such peculiar operating conditions, viscous fluids have been prepared from various inorganic and organic substances, which are known as synthetic lubricants, for example, organophosphate esters, dibasic acid esters, ons and other complex atmospheric parameters106 Encineeonc CHEMISTRY poly alkylene glycals and their derivatives, silicones, fluorinated and chlorinated hydrocarbons, silicate esters, etc. Answer any two of the following: (a) Explain clearly the terms: Component, Phase and Degree of Freedom. State the Phase Rule and discuss its application to the system of water vapor, liquid water and ice, Or (a) What is meant by Auto catalysis? Illustrate your answer with some suitable examples. (0) (i) Arrange the following compounds in the increasing order of their acidic character: HOCI, HCIO,, HCIO,, HCIO, Explain with your reasoning. (ii) List the Lewis acids and Letvis bases from the following: BE, F’, AICI, NH", CH,OH, ZnCl, (c) (i) What is meant by the rate of reaction? Explain the factors which affect the rate of a reaction. (ii) Distinguish between order and molecularity of a reaction. Ans, (a) The phase rule isa generalization given by Willard Gibbs (1874), which seeks to explain the equilibria existing in heterogencous systems. It may be stated ast “provided the equilibrium between any number of phases is not influenced by gravity, or electrical, or magnetic forces, or by surface action and only by temperature, pressure and concentration, then the number of degrees of freedom (F) of the system is related to the number of components (C) and of phases (P) by the phase rule equation, Fe P+2 Sor any system at equilibriun at a definite temperature and pressure.” This rule, if properly applied, has no exception. Explanation of terms: (1) Phase: A phase is defined as “an homogeneous, physically distinct and mechanically separable portion of system, which is separated from other such parts of the system by definite boundary surfaces”. For example: (i) At freezing point, water consists of three phases: ice (s) <== Water () <==» Water vapor (g) (ii) A gaseous mixture, being thoroughly miscible in all proportions, will constitute one phase only. Thus, a mixture of N, and H,, forms one phase only. (iif) If two liquids are immiscible (#2, benzene and water), they will form two separate phases.‘Sawpue Exawnvanons 107 (id) If two liquids are miscible (f., alcohol and water), they will form one liquid phase only. (v) A solution of a substance in a solvent consists of one phase only, ¢.g., glucose solution in water. (vi) Each solid makes up a separate phase, except in the case of solid solutions, e.g. many forms of a sulphur can exist together, but these are all separate phases. (vii) A heterogeneous mixture like: CaCO(s) Hs CaOIs) + COs) consists of three phase (Ze. two solids and one gaseous). Similarly, in the equilibrium reaction, _Fe(s)+H,Olg) === FeO(s) + H,(g) there are two solid phases, Fe and FeO and one gaseous phase consisting of H,O(g) and H,(g). Thus, three phases exists in equilibrium (vit?) A homogenous solid solution of a salt constitutes a single phase. Thus, Mohr's salt [FeSO, . (NH,),SO, . 64,0] solution constitutes a single phase, although it consists of FeSO,, (NH,) SO, and H,0. (2) Component: By the term component is meant “the smallest number of independent variable constituents, taking part in the state of equilibrium, by means of which the composition of each phase can be expressed in the foran of chemical equation”. For example: (i) In the water system, Ice (s) <== Water (/) <=> Vapor (g) the chemical composition of all the three phases is H,O. Hence, it is one component system. (ii) The sulphur system consists of four phases, rhombic, monoclinic, liquid and vapor, the chemical composition of all phases is $. Hence, it is one component system, (iii) In the dissociation of NH,Cl in a closed vessel, NH,Cl(s) <== NH,Clig) === NH,(g) + HCl) the proportions of NH, and HCl are equivalent and hence, the composition of both phases (solid and gaseous) can be expressed in terms of NH,Cl alone. Hence, the number of component is one. However, if NH, or HC1is in excess, the system becomes a two component system.108 Excuinmna Cuesustry (iv) A system of saturated solution of NaCl consists of solid salt, salt solution and water vapor. The chemical compositian of all the three phases can be expressed in terms of NaCl and H.,O. Hence, it is a two component system. (v) In the thermal decomposition of CaCO, CaCO) <== Cals) +CO,() the composition of cach of the three phases can be expressed in terms of at least any two of the independently variable constituents, CaCO, CaO and CO,, Suppose CaCO, and CaO are chosen as the two components, then the composition of different phases is represented as follows Phase: CaCO, = CaCO, +0 CaO Phase: CaO =0 CaCO, + Cad Phase: CO, = CaCO, - CaO Thus, ita two component system. (vi) In the dissociation reaction, CuSO, .5H,0(6) = CuSO, .3 H,O(6) +2 H,0(@) the composition of each phase can be represented by the simplest com- ponents, CuSO, and H,O. Hence, it is two-component system. (vil) In the equilibrium, Fe(s) + H,O(g) <== FeO(s) + H,(g), the mini- mum components required to express (he composition of each phase is three. Evidently, it is a three component system. (3) Degree of freedom or variance: By the term “degree of freedom is meant by" the minimum number of independently variable factors, such as temperature, pressuere and composition of the phases, which must be arbitrarily specified in order to represent perfectly the condition ofa system”. For example: (i) In case of water system, Ice(s) qe Water(l) === Vapor(g), if all the three phases are present in equilibrium, then no condition need to be specified, as the three phases can be in equilibrium only at particular temperature and pressure. The system is, therefore, zero variant or non- variant or invariant or has no degree of freedom. If condition (e.g., tem- perature or pressure) is altered, three phases will not remain in equilib- rium and one of the phases disappears. Water System. The water system consists of three phases, viz., ice, water and water vapor. Tce (s) <== Water (/) === Water vapor (g)s Sawpur Exasinanions = 109 Since H,Q isthe only chemical compound involved, therefore, itis single or one-component system. From the phase rule, when C = 1, FeC-P+2=1-P+2=3-P ie,, the degree of freedom depends on the number of phases present at equilibrium. Three different cases are possible: (@)P=1;F=2 (bivariant system) (i) P=2;Fe1 (univariant system) (i) P=3;F=0 (invariant system) From the above, it is clear that for any one-component system, the maximum number of degrees of freedom is two. Therefore, such asystem can be represented completely by atwvo-dimensional diagram. The most convenient variables are the pressure and the temperature. The water system is shown in the following figure. The diagram consists of: Prassure (no! to scale) (1) Areas: AOB, AOC and BOC are the fields of existence of vapor, liq and ice phase respectively. Within these single-phase areas, the system is bivariant, because to locate any point in an area, temperature as well.as pressure co-ordinates need ta be known. This also follows fram phase rule equation: Fe3-P23-152. (2) Boundary lines: Separating the areas are lines OA, OB and OC, connecting the point at which twa phases cam co-exist in equilibrium. In order to locate any point ona particular line, either temperature or pressure co-ordinate should be:110 Encinesunc CHenasray known, because for fixed value of one co-ordinate, the second is automatically (fixed. In other words, any point on boundary lines has one degree of free- dom or is univariant. This also follows from phase rule equation: Fo3-P=3-2e1 (8 The curve OA, dividing the liquid from the vapor region, is called vapor pressure curve of liquid water or vaporization curve. At any given temperature, there is one and only one pressure at which water vapor is in equilibrium with liquid water. Similarly, at any given pressure, there is one temperature at which water vapor is in equilibrium with liquid water. In other words, the system is univariant,ie., hasone degree of freedom. The curve OA has a natural upper limit at + 374°C, which is the critical-point, beyond which the liquid phase merges into vapor phase and they are no longer distinguishable from each other. (if) The curve OB is the sublimation curve of ice. It gives the conditions under which water vapor is in equilibrium with solid ice. Tie point B has a natural limit at — 273°C, beyond which the two phases merge inta.cach other. The curve OC, tohich divides the solid-ice region from the liquid-water region, is called melting curve, because it indicates how the melting temperature of ice or the freezing temperature of water varies with the pressure. The slope of OC towards the pressure axis shows that the melting point of ice is decreased by incrensing pressure. (3) Triple point: The three curves OA, OB and OC meet at O, at which solid, liqitid and vapor are simultaneously at equilibrium. This point at 273.16 K (or 0.0098°C and 4.579 mm pressure), is called a triple-point, Since three phases co-exist, the system is invariant (F = 3-3 = 0). In other words, there is no degree of freedom at O, ix., neither pressure nor temperature can be al- tered, even slightly, without causing the disappearance of one of the phases. Triple point of a system is the point at which the gaseous, liquid and solid phases ofa substance co-exist in equilibrium. Por a given substance, the triple point occurs at anique set of values of the temperature, pressure and volune. For example, triple point of water is 4.58 mm Hg pressure and 0.0098°C temperature. At triple point, the system is non-variant (or zero variant). If either temperature or pressure or volume is altered, even slightly, ome of the three phase disappears and the system changes from non-variant fo univariant. Metastable curve, OB’: Metastable state is the state of supercooled water. The supercooled water remains as liquid water below 0°C, until a small crystal of ice is introduced. OB’ represents the vapor pressure curve ofSammut Examinarions 117 supercooled water. On slight disturbance, the supercooled water at once changes to solid ice. Or Ans. (a) Auto Catalysis: When one of the products formed in the reaction itself acts asa catalyst the substance is called as an auto catalystand the phenomenon is called auto catalysis, Examples: Ci (KMnO,) is catalyzed by the presence of Mn** ions formed in the solution. In the starting, the color of KMnO, disappears slowly, but as Mn** is formed in the solution, the color discharges rapidly. So, Mn?* ions acts as auto catalyst. 2MnO,; + 5C,0}° + 16H? ——> 2Mn** + 10CO, +8H,O Colorless 2. Hydrolysis of ethyl acetate by water is an auto catalytic reaction, since acetic acid liberated in this reaction acts as a catalyst. CH,COOC,H, + HO ——> CH,COOH + C,H,OH Ethyl acetate Auto catalyst Ans. (6) (i) The oxidation number of Clin HOCI, HCIO,, HCIO, and HCIO, is + 1, +3, +5 and +7 respectively. Therefore the acidic character of these acids is HOC! < HCIO, < HCIO, < HCIO,. The main reason of this is resonace. The stability of CIO] is more due to more resonating structures. Ans. (b) (if) Lewis acid: BF,, AICL,, ZnCl, NH} Lewis bases: F-, CH,OH Ans. (c) (i) Rate of Reaction: COOH 1. The oxidation of oxalic acid | | by acidic potassium permanganate (00H The rate at which the concentration of a reactant changes with time is known as rate of reaction, Factors affecting rate of reaction: (1) Effect of nature of reactants: Reactions between polar or ionic molecules eccur almost instantaneously. Those reactions in which the bonds are arranged or electrons are transferred take a comparatively longer time than the former ones,e.g.,reactions involving neutralization or double displacement are very fast, while the oxidation-reduction reactions (involving electron transfer) are slower.112 ENGiNeeRiiG CHEMISTRY (2) Effect of surface area of reactants: Surface area of reactants is of importance only for heterogeneous reactions. As particle size decreases, surface area for the same mass increases. The smaller particles thus react more rapidly than the larger particles, ¢.g., burning of coal dust in air takes place more rapidly than that of large lumps of coal. (3) Effect of concentration of reactants: The rate of a chemical reaction is influenced by the number of collisions per second between the reacting molecules. On increasing the concentration of the reactants, the number of collisions and thus the rate of reaction also increases and vice-versa. (4) Effect of temperature: With the exception of few reactions, the rate of a reaction is increased considerably with an increase in temperature. Generally, the rate of a reaction is almost double or triple by an increase of 10°C in temperature. The temperature coefficient of a reaction is, however, defined as the ratio of the specific rate constants at tivo temperature separated by 10°C, usually 25°C and 35°Cie., Tempers cocicint = f+ t (5) Effect of catalyst; A catalyst can increase or decrease the rate of chemical reaction, for example, the combination of hydrogen and oxygen to form wateris low atordinary temperatures, while it proceeds rapidly in presence of platinum. Similarly the oxidation of sodium sulphite to sodium sulphate by atmospheric oxygen becomes slow in presence of ethyl alcohol. Ans. (c) (ii) . It is always whole number. 1 . Itreveals some basic facts about reaction | 2. |. It is equal to the number of molecules | 3. It may be whole number, zero or fractional value. It does not reveal anything about mechanism. reaction mechanism. Itis equal to the sum of the power of the of reactions which take part in a single molar concentration of the reactants in step chemical reaction |. It is a theoretical concept which depends on the rate determining, step in the reaction mechanism . It is obtained from a single balanced chemical equation. the rate expression. . It is an experimentally determined quantity which is obtained form the rate for the overall reaction. It cannot be obtained from a balanced chemical equation.Sammie Eeammanions 113 QA Answer any Two of the following: (@) (i) Explain the Lime-Soda Process used for softening the hard water. ) A standard water contains 15 grams af CaCO, per liter, 20 ml of this required 25 ml of EDTA solution, while 100 ml of the sample water required 18 ml of EDTA. ‘The sample water after boiling required 12 ml EDTA solution. Calculate the temporary hardness of the given sample expressed in terms of parts per million (ppm) (b) Write short notes on: (i) Biogas (ii) Solar Energy (©) Describe how the calorific vatiee of coal or liquid fuel is determined by Bomb calorimeter. The following data is obtained in a Bomb calorimeter experiment: Weight of crucible = 3.649 ¢ Weight of crucible + Fuel = 4.678 ¢ Water equivalent of calorimeter = 570g Water taken in the calorimeter = 2200 Observed rise in temperature =23°C Cooling correction = 0.047°C Acid correction = 62.6 calories Fuse wire correetion = 3.8 calories ‘Cotton thread correction = 1.6 calories Calculate the gross calorific value of the fuel sample. If the fuel contains 6.5% H, determine the net calorific value. Ans, (a) (?) Lime-Soda Process: Generally in lime-soda process, lime milk is added to water, with calculated amount of sodium carbonate (Na,CO,) solution. This method is based on the following facts: (1) Lime removes the temporary hardness and magnesium, aluminium and iron salts remove permanent hardness. @ MgCl,+ Ca(OH), ——> Mg(OH), 4 + CaCl, (i) FeSO, + Ca(OH), —— Fe(OH), 1 + CaSO, (iii) MgSO, + Ca(OH), —— Mg(OH), 4 + CaSO, (iz) AL{SO,), + 3Ca(OH), ——> 2AK(OH), 1 + 3CaSO, (2) Mg(HCO,), + 2Ca(OH), ——+ 2CaCO,1 + Mg(OH),1 + 2H,O (wi) CO, + Ca(OH), — CaCO,} +H,0114 Encineerina CHemistRY (vif) Ca(HCO,), + Ca(OH), —> 2CaCO, + 2H, (vii) 2Fe(OH), + H,O + [O] ——> 2Fe(OH),1 (2) Lime removes free mineral acids as well as gases like H,S ete. 2HCI + Ca(OH), —— CaCl, + 2H,0 H,SO, + Ca(OH), —— CaSO, + 2H,0 (3) Soda removes all the calcium permanent hardness which is soluble in water. CaCl, + Na,CO, —> CaCO,! + 2NaCl CaSO, + Na,CO, ——> CaCO,1 + Na,SO, The LS-process may be broadly classified into two categories viz (1) Cold lime-soda process (2) Hot lime-soda process (1) Cold lime-soda process: In cold lime-soda process, calculated quantity of chemicals are mixed with water atroom temperature. The percipitate formed at room temperature is finely divided and do not settle down easily. These cannot be easily filtered. Therefore, it is essential to add a small quantity of coagulant which hydrolyzes to give flocculent and gelatinous precipitate of aluminium hydroxide and so it entraps the fine precipitate. There are two kinds of softeners used for softening water by this process. (a) Intermittent type softeners: It consists of a pair of tanks in which water and the mixture of calculated quantities of lime and soda are allowed to run simultaneously with constantstirring. ‘Sludge Intermittent type of cold lime-soda softenerSamere Exammanions 115 For fresh precipitation, a small amount of the precipitate from the previous treatment is added during stirring and filling. When the tank fills up, the reaction is completed and thus it stops. The precipitate is allowed tosettle down. The sludge is taken out from the bottom and the clear softened water is taken out through a pipe. The softened water is further supplied to the filtering station for further filteration. (b) Continuous type softener: It consists of a big steel tank with two chambers. One is inner chamber and another is outer chamber. In inner chamber raw water and chemicals are let into it at oom temperature and stirring is started. Softening of water takes place in the inner chamber and the sludge comes out from the outer chamber. The softened water goes upwards in the outer chamber where it removes all the sludge after complete filteration. Filtered soft water comes through the water outlet. The necessary sludge can be drawn from the bottom. (2) Hot lime-soda process: In Hot-soda process, only sodium carbonate is used for softening. The excess of sodium carbonate is carried out into the boiler which decomposes into sodium hydroxide (NaOH) at high pressure and temperature. Na,CO, + H,O—— 2NaOH + CO, Chemical feed inlet eee ne a aI (— Water feed inlet + coagulant Fi Stimer paddies softened ‘water outlet Continuous cold lime-soda softener116 Encmezninc Crenustey Sodium carbonate (Na,CO,) so produced goes into the softener and reacts with non-alkaline hardness of sodium and calcium carbonate. Ca(HCO,), + 2NBOH —— CaCO, + Na,CO, + 2H,0 CaCl, + Na,CO, ——> CaCO, + 2NaCl Mg(HCO,), + 4NaOH——> Mg(OH), + 2Na,CO, + 2H,O- MgCl, + 2NaOH —— Mg(OH), + 2NaCl Silica (SiO,) can also be removed from water by this process. => Softened water outlet Sludge outlet Continuous type hot lime soda softener ‘The softeners used in this process are intermittent type and continuous type. The intermittent type is same as used in cold lime-soda process and only heating coils are installed in it for heating the water. The continuous softener is used for this process. It consists of a big steel tank having an inner vertical chamber, the upper end of which is in the form of a funnel, while the lowerSame Exammnarions 117 end is open. The steam is allowed to pass through a steam inlet. When the mixture goes down, the reaction is completed and water rises up. The sludge is settled down. In this process, the residual hardness is far less as compared to lime-soda process. Advantages: Hot-lime soda process has the following ad vantages: (1) The use of lime is avoided (2) The quantity of chemicals for softening purpose is reduced. (3) The temporary hardness, free CO, and dissolved oxygen are removed by pre-heating. (4) There is saving of coal as the pre-heating of water iscompleted through hot exhaust gases of the boiler. {5) The chemical action is accelerated by high temperature. (6) The precipitate formed is granular and more dense so that it can easily settle down, Ans. (a) (ii) 1 L.(1000 mL) of sample hard water = 15g of CaCO, eq = 15000 mg of CaCO, eq * 1 ml.of sample hard water = 15000/1000 mg of CaCO, eq = 15 mg of CaCO, eq Now 25 mL of EDTA sol. = 200 mL of sample hard water = 20 x 15 mg of CaCO, eq = 300 mg of CaCO, eq 1 mL of EDTA sol. = 300/25 mg of CaCO, eq = 12 mg of CaCO, eq Calculation of total hardness of water 100 mL of hard water = 18 mL of EDTA sol. = 18 x 12 = 216 mg of CaCO, eq 1000 mL of hard water = 2160 mg of CaCO, eq Hence, total hardness = 2160 mg/L or ppm. Calculation of permanent hardness of water 100 mL of boiled water = 12 mL of EDTA sol = 12% 12 = 144 mg of CaCO,118 Enciveerine Ciessrey 1000 mL of boiled water = M40 mg of CaCO, eq Hence, permanent hardness = 1440 mg/L or ppm Calculation of temporary hardness Temporary hardness = Total hardness - permanent hardness 2160 - 1440 = 720 ppm Ans. (8) (i) Biogas: The degradation of animal and plant wastes occurs by anaerobic microorganisms in the presence of water. This process produces gases such as methane, carbon dioxide, hydrogen, hydrogen sulphide. This mixture of gases is known as biogas. The methane is the major constituent of biogas and contains 65% of it. The average gross calorific value of biogas is 1200 keal/m’. Methane is an excellent fuel, so biogas can be (a) burnt in gas stoves to give heat, (b) used for street lighting and (c) for running engines. Biogas is obtained by the anaerobic fermentation of animal wastes like animal dung in the presence of water. The fermentation is carried out by anaerobic microorganisms known as anaerobic bacteria in presence of water but in the absence of oxygen. The animal and plant wastes contain compounds like carbohydrates, proteins and fats. The degradation of these compounds occurs by an anaerobic bacteria to form methane gas. Besides methane, some other gases like CO,, H, and H,S are also formed. The cheapest.and easily obtainable biogas is gobar gas oblained from cow-dung, which is produced by the fermentation of cattle dung. Advantages of Biogas: (1) In the villages and cities the biogas is used for street lighting. (2) At many places, the engines of water pumping sets used for irrigation etc. are run on biogas instead of diesel. (3) When biogas is burnt in a gas stove, it produces lot of heat. This is a good fuel for domestic and cooking purposes because: (i) Biogas produces a large amount of heat per unit mass due to ils high calorific value. (ii) Biogas is directly supplied from the gas plant, so there is no storage prob- lem. (iii) Tt burns with non-smoky flame and does not pollute the environment.Samece Exawimarions 119° (iv) It is the most common and the cheapest gas. (v) Due to cheanliness, it is convenient to use. (4) The most important thing is that the biogas plants grip the rural energy crisis. (5) It does not contain any poisonous gas. To overcome the problems of poor families in rural areas who cannot afford the initial cost, community plants have been developed. Since India has largest scale of cattle population in the world, there is tremendous scope for community sized biogas plants. 75% of our domestic energy needs in the rural areas would be met under these community plants. Gi) Solar Energy: Sun produces an enormous amount of energy, known as solar + energy, through a series of reactions. ‘The sun offers an ideal energy source, unlimited in supply, expensive, which does not add to the earth's total heat burden and does not produce air and water. Solar energy is so abundant and readily available that it is received unequally by the earth’s surface. This is a good source of energy especially in those countries which lie between the Tropic of Cancer and Capricorn. Due to rise in the fuel prices and the end of petroleum deposits insight, the economic balance is bound to tilt in favor of solar energy. Now-a-days, solar technology is developed which is likely to cut down costs in engincering improvement and mass production. Solar-technology develops, solar heated houses. The sunlight is collected on plates on the roof and the heat is transferred to a circulating water system. The solar energy is directly converted into electricity by the use of photoelectric cell, The light is absorbed at the surface of material and generates positive and negative charges, collected at either side of the electrodes. An example of solar cell is silicon soalr cell in which n-type and p-type semiconductors are sandwiched. This cell is used for space programming. Solar energy is used for vaccine refrigeration and lighting of health care center in rural areas. Solar energy is also useful in greenhouse technology. Ans. (c) Bomb calorimeter is used for the determination of calorific value of solid or liquid fuel. Construction: It consists of a strong cylindrical bomb of stainless steel (Cr-Ni-Mo steel). It is resistant to acids and of corrosion. Its weight is about 3 kg with 250-300 ml capacity. It is provided with a gas tight serew cap to which a couple of stainless steel electrodes and released valve are fitted. A small ring120 Excineerinc Cresstey 6¥ battery Ebonite cover Copper calorimeter Stainless steel bomb Stainless steel crucible Air jacket Bomb calorimeter is also attached to this electrode which acts as a support for the stainless steel crucible. Fuel is kept in this crucible. The bomb is placed in a copper calorimeter. It can contain 2 liter water. The calorimeter is surrounded by an air jacket and water-jacket in order to avoid loss of heat due to radiation, The copper calorimeter also consists of a motor driven stirrer and Bekmann’s thermometer which can read up to 0.001°C temperature. Procedure: A known amount (mg) of the fuel (whose calorific value is to be determined) is kept on the crucible supported over the ring. A fine Mg-wire touching the sample of the fuel is then stretched across the electrode. The bomb lid is tightly screwed and filled with oxygen at about 25 atmospheric pressure. Now the bomb is placed carefully in the copper calorimeter containing W g water. After stirring very well the temperature of water (f,°C) is noted. The electrodes are connected with battery and circuit is completed. Thus, combustion of fuel takes place and heat is liberated. Now stirring of water is continued and fina] temperature of water t,°C is noted. Let C be higher calorific value (HCV) of the fuel in cal/g and w be the water equivalent of calorimeter bomb stirrer etc. in grams. ‘Calculation: Suppose m be the mass of fuel, w be water equivalent of the calorimeter, W g is water taken in the calorimeter, t, is initial temperature of water in the calorimeter and , is the final temperature.Sameue Exammavions 121 The calorific value of the fuel may be given as: c=(e2Me—m) ™ and LCV. = [G.C.V. - 0.09 H x 587] cal/g {Latent heat of steam = 587 cal/g) H = Percentage of hydrogen present in the sample of fuel. Corrections: (a) Cotton thread correction is made by the weighing of dry cotton thread used for firing. On this basis, the calorific value of cellulose (C,) is 4140 cal/g. (b) Acid correction (C,,): If the fuel consists of sulphur and nitrogen, they are oxidized to H,SO, and HNO, respectively under high pressure and temperature. $+ 2H +20, > HS0, + heat 2N + 2H +30, ——> 2HNO, + heat The amount of H,SO, and HNO, formed during the combustion of fuel is determined by titration. It is calculated that for each ml of N/10H,SO, 3.6 and for each ml of N/10 HNO, 1.43 cal must be subtracted. (c) Fuse wire correction (C,} is made by the amount of heat given out by the ignition of the fused wire burnt during the combustion of fuel. This amount of heat should also be subtracted. (a) Cooling correction (C,) is made by measuring the time taken to cool the water in calorimeter from maximum temperature toroom temperature. From the rate of cooling (df°/minute) and the actual time taken for cooling (di° minutes), the cooling correction (di x !) is added to the increase in temperature. (w+ W) (t, ~ f, + cooling correction) ~ [Acid + fuse correction + cotton thread correction] Mass of fuel We know that the gross calorific value [G.C.¥.] _ (we WME) +I -(Cy + Cp + Ce) m Hence, C= _ (2200 + 570) (2.3 + 0.047) — (62.6 + 3.8 + 1.6) ~ (4.678 - 3.649)122 Excmexnine Ciremestay ~ 1.0729 = 6251.88 calorie /gm. Net calorific value = [Gross calorific value - (0.09 H x 580)] cal/g = (6251.88 — 0.09 x 6.5 % 580) cal/g = (6251.88 — 339.3) cal/g = 5912.58 cal/g Q.5 Auster any two of the following: (a) Draw the Molecular Orbital diagram of O, and find out the bond order and its magnetic behavior. (b) Explain the crystal field splitting of d-orbital in octaledral complexes. Or What do you understand by extrinsic and intrinsic semiconductors? Explain conduction in p-type and n-type semiconductors. (c) Write short notes on: i) Chelating Complexes. (ii) High and Low Spin Complexes. (iii) Crystal Field Stabilization Energy. Or (0) What are the basic principles involved in the following equipments: {@ Nuclear Magnetic Resonance (NMRJ (ii) Atomic Absorption Spectroscopy [AAS]. Ans. (a) O,=2,6 = 1s, 26%, 2ptSampur Baminarions = 123 AO MO AO There are two unpaired electrons in the molecular orbital diagram of ©,, therefore O, is paramagnetic in character. . Ans, (b) Crystal Field Splitting of d-orbitals in Octahedral: In case of free metal ion, all the fived-orbital are degenerated, i., they have the same energy. Now assume an octahedral complex [ML,J"*, where M** is the central metal cation which is placed at the center of the octahedron and is surrounded by six ligands which are situated at the six corners of the octahedron. Position of contral motal cation, r+ and six ligands, L's in an octahedral complex, (MiL,I*124 Encieexina Coesustey — Enargy increasing —» xy yz 2x 2" x'~ yh" Suppose that both the ligands on each of the three axes X, Y and Z are allowed to approach toward the M"* from both the ends of the axes. In this process, the electrons in d-orbitals of the metal cation are repelled by negative point charge or by the negative end of the dipole of the ligands. The energy of all the five d-orbitals will increase due to this repulsion. If all the ligands approaching the central cation are situated at an equal distance from each of the d-orbitals, the energy of cach of the five d-orbitals will increase by the same amount, i-c., all the d-orbitals remain degenerate, though they will now have more energy than before. This isa hypothetical situation. Because the lobes of the two-orbitals, ie, d,, and d,;_,2 orbitals lie directly in the path of the approaching ligands, the electrons in these orbitals will experience greater force of repulsion than those in three t,, orbitals, i. d,,,d,, and d,, orbitals, whose lobes are directed in space between the path of the approaching ligands. In other words, the energy of !,, orbitals is decreased while that of c, orbitals is increased, because greater the’ rep ulsion, the greater is the increase in energy. Therefore due to the approaching ligands, the five d-orbitals which were originally degenerate in the free metallic cation are now split into two levels, viz., (1) th, level which is triply degenerate and is of lower energy. (2) ¢, level which is doubly degenerate and is of higher energy. (e) 2x-y¥ -AL......... . ¥ “No splitting state +e =* 04 2 xy yz zx 27x? By oF 1009 “2a Aa (bg) 1 et Five degenerate ‘Hypothetical degenerate Splitting of d-orbitals under the orbitals on the d-orbitals at a higher influence of six ligands in central metal cation ‘energy level ‘octahedral complex which are free from any ligand field Crystal field splitting of d-orbitals in octahedral complox In other words, the degeneracy of the five d-orbitals is removed under and effect of the ligands. Thus, the separation of fived-orbitals of the metal ion into