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Sawous Exasunanons 125 two sets having different energies is called crystal field splitting or energy level splitting. The difference in energy between t,, and ¢, levels is denoted by 4, or 10Dq, where inA,,0 shows an octahedral arrangement of the ligands around the central metal cation. This difference in energy arises due to the difference in the electrostatic field exerted by the ligands on #,, and c, sets of orbitals of the central metal cation. A, or 10Dq is thus called crystal field splitting energy (CFSE). From the geometry, it can be shown that the energy of f, orbitals is 0.44, or 4Dgq, less than that of hypothetical degenerated-orbitals. The energy of ¢, orbitals is 0.64, or 6 Dg which is above that of the hypothetical degenerate ¢- orbitals. Hence, f,, set loses an energy equal te 4Dq and ¢, set gains an energy equal to 6Dq, which are shown by negative and positive signs, respectively. Or Certain defects called impurity defects in a crystal arise from the presence of chemical impurities. One important application of these defects lies in the use of Ge and Si crystals as semiconductors in transistors. Ge and Si belonging to group 14th of the periodic table, in pure states, have very low electrical conductivity. On adding even traces of an element belonging to group 13th or 15th, the electrical conductivity is appreciably enhanced. The reason may be explained as follows: Suppose a group 15th element likes, is added to.a Ge crystal. As a Ge atom is substituted by an As atom, four of the electrons inAs form covalent bonds with the surrounding Ge atoms, but the fifth electron remains free. Therefore, an extra electron gets introduced into the crystal, which can serve to conduct electricity, ée., it behaves like a conductor-electron asin metals. So, Ge containing traces of As (called arsenic doped germanium) starts to show fairly high electrical conductivity. This type of conduction is called extrinsic conduction, which is much greater than intrinsic conduction. In this type of conduction, the current is carried by excess electrons in the normal way, itis, thus, m-type semiconduction. When asmall quantity of boron is added to pure silicon, some silicon atoms are replaced by boron atoms. Fach beron atom is linked with three Si atoms by normal two-electron covalent bonds, while it is linked with the other nearby silicon atom by one-electron bond. In one-electron bond there is an electron deficiency. This electron deficiency creates a positive hole or vacancy at the site where the electron is missing. There are as many positive hoels as there are boron atoms. The unbonded electrons on silicon atomsmove through the crystal by holding one vacancy site to another The holes move opposite to the direction of flow of electrons. Since boron has three valence-electrons and silicon atom,126 © EsciNteNG CHenasTeY has four valence-electrons, we can say that the impurity atoms have less number of valence-electrons then the parent insulator atoms. When impurity atoms, having valence-electrons less than the parent insulator atoms are introduced into them (ic., insulator atoms}, we get p-type extrinsic semiconductors (p- indicates positive holes). Free electron on phosphorus atom ldo) l t/t | carer SP So Additionof —- —Si-Si—P —Si— ea Phosphorus —Si—Si—si—P— =r a Pure silicon (Insulator) Silicon having phosphorus impurity (type extrinsic semiconductor) Representation of the formation of n-type extrinsic semiconductor. Ans. (c) (i) Chelating Complexes: The ligands having two or more sites of attachment H,C—-N—CH, DN, to the metal ion are known as polydentate ligands. The ligands having two or more sites of attachment of two or more donor sites to the same metal ion simultaneously, therefore closing one or more rings, are known as chelate ligands (chelate; a Greek word for clato). Some chelate ligands are oxalato, ethylene diamine, and ethylene diamine tetraacetato ligand (EDTA). Structures of these chelate ligands are given below: é diethyl triamine (tridentate), @ ethylene diamine tetraacetato (hexadentate), B oxalato; dimethylglyoxime (bidentate), H triethyl tetramine (tetradentate). oH “00C CH, He C00" “00C—CH, CH,—COO’Sammue Exaumanions 127 Sto Rae uf An Ns, nett on, ne “ Ne pa H noch, (fi) High Spin and Low Spin Octahedral Complexes: For octahedral complexes, containing weak ligands, the energy difference, A, betweent,, ande, sets is relatively small and so the energy of all the fived-orbital is supposed tobe the same. Consequently, the filling of ,, ande, orbitals occurs according to Hunds’ rule, i.c., electrons pair up only when each of the five d-orbitalsis atleast singly occupied. For octahedral complexes containing strong ligands, ie.,strong field complexes, all the three d-orbitals of low energy are filled up first and then the twod-orbitals of high energy ¢, sets are filled. It may be seen that the weak field octahedral complexes of d+, d5, d® and d? ions have greater number of unpaired electrons than those of strong field complexes. It is because of this, that weak field complexes of d4, d3,d°, and d? ions are known as high spin or spin free (diamagnetic) complexes. Similarly, strong field complexes are also known aslow spin orspin paired (diamagnetic) complexes, ¢.g., [Fe(CN),]* (VBT has called high spin complexes as ionic of outer orbitals complexes, while low spin complexes are known as covalent or inner orbital complexes). (ii) Crystal field stabilization energies of octahedral complexes: On the basis of the above explanation, consider ad* ion containing 4," ¢,' configuration in which pis the number of electrons in ¢,, set, q is the number of electrons in ¢, set and ¥=p+q. It can be derived that, CPSE = (-O-4p + 0.69) Ay + mp (i) = [- 4p + 6q] Dg + mp (ii) [4, = 10 Dg) (iii) Here m is the total number of paired electrons in toe and €, sets of orbitals. Equations (i) and (i) have been used to calculate the CFSE values for d° to d® ions of high spin and low spin complexes. Or Ans. (c) (i) Basic Principle of NMR: When a molecule (substance) is placed in a magnetic field, its electrons are caused tocirculate and thus, they produce secondary magnetic fields (or induced128 ENGINEERING CHEMISTRY magnetic field). Rotation of electrons about the protons itself generates a field in sucha way that at the proton, it epposes the applied field. So, the field felt by the proton is diminished and the proton is said to be shielded. Rotation of electrons (specially x-electrons) about the nearly nuclei generate a field that can either oppose or reinforce the aplied field at the proton. If the induced field opposes the applied field then proton is siad to be shielded. But if the induced field reinforces the applied field, then the proton feels a higher field strength and such proton is said to be deshielded. Shielding shifts the absorption uptield and deshielding shifts the absorption downfield to get an effective field strength necessary for absorption. Such shfits (compared with a standard reference) in the positions of NMR absorptions which arise due to the shielding or deshielding of protons by the electrons are known as chemical shifts. The chemical shift is affected by following factors: @ Inductive effect @ Van der Waals, deshielding @ Space or anisotropic effect @ Hydrogen bonding To carry out NMR studies, the compound under investigation, which is either a pure liquid or a solution in a non-protonic solvent, is mixed with a small amount of tetramethyl! silane (TMS) and the spectrum is recorded. Because the variation in field strength is very slight, so these are not measured in actual magnetic units, but with reference to the resonance conditions for an arbitrary standard tetramethyl silane Si(CH,),, ie., TMS. This compound has. been chosen as standard, because @ [tis miscible with almost all organic substances. 8 It does not take part in intermolecular association with the sample. @ It has twelve equal protons and hence has a single peak. @ It is highly volatile so it can be readily removed from the system. The spectrum shows an absorption for TMS ata magnetic flux density, B,.,.tont) and fora particular proton in the compound at say B,,,,,,,..° Thus, the chemical shifts is given by: AB 6=— x 10° 3, Al Berandard) ~ Brearwpte) By = Magnetic flux density In other words, the difference in the absorption position of the proton with respect to TMS signal is known as chemical shift (-value). The assigning value (6-value) for TMS is equal to zero.Sampe Exammarions 129 Highly shieldad-signals upfield In other wonds, the position of the peaks in an NMR spectrum relative to the reference peak is expressed in terms of the chemical shift, which is defined as, _ Ha (reference) ~ Hy (sample) 8 10° ppm Hp (reference) ‘The value of H, for the reference is usually greater than H, for the sample, so subtraction in the direction shown gives positive 6, In terms of frequency unit, 6 takes the form, x(sample) ~ 2 (reference) v (reference) 8 4108 ppm ‘The chemical shift is dimensionless and expressed in parts per mi on account of the factor 10° in the preceding equations. ion (ppm) An alternative system, which is generally used for defining the position of the resonance relative to the reference is assigned tau (1) scale. On this scale, the reference is assigned the arbitrary position of 10 and the values of other resonances are given by t=10-6 where 5 has the same significance. Ans. (c) (i) Basic Principle of Atomic Absorption Spectroscopy: The principle of atomic absorption is similar basically to that considered for absorption of UV and visible radiation by solution. Suppose that the atom isin ground state E, and excited to energy level E,, E,, ...... or higher energy levels. The transitions between two quantized energy levels, say from E, to E, correspond to the absorption of radiant energy, and the amount of energy absorbed (AE) is determined by the equation.130 Encemceninc Creaneray AE=E,-E, = ives ites where c is the velocity of light,lris Planck’s constant and v is frequency and is. the wavelength of radiation absorbed. The absorption spectrum of a given elementis usually associated with transitions from the ground state to higher energy state and is consequently simpler in character. The relationship between the ground state and excited state population is given by where, N = Number of atoms in excited state N, = Number of atoms in ground state T = Temperature in kelvin +1 Ratio of statistical weights for ground and excited states. Ho k= Boltzmann’s constant AE = Energy of excitation The atomic absorption spectra of most elements are simple in character as compared with the emission spectra. It follows that the absorption spectroscopy is less prone to inter-element interference. lt should be noted that in atomic absorption spectroscopy, as with molecular absorption, the absorbance Ais given by the logarithmic ratio of the intensity of the incident light signal I, to that of the transmitted light I, i.c., A= log ,/I,=KLN, where, N, = Concentration of atoms in the flame K = Absorption coefficient L= Path length through the flame.Saveur Examunarions = 131 CHEMISTRY-6 Time: 3 Hours Total Points: 100 Note: 1, Answersall five questions. 2. All questions carry equal points. Qu Answer any two of the following: (a) (#) Calculate the number of peaks and area tender each peak in the NMR spectrum of a sample of CH,OC,H,, (if) Give some of the important applications of electronic (UV) spectroscopy. Or Discuss the various ways by which polymers can be classified. (b) Write the differences between: (i) RNA and DNA Gi) Homopolymer and Copolymer (iii) Addition polymerization and condensation polymerization (c) What are elastomers? Discuss their structure and properties. (a3 (te Ans. (@) (i) CH,—O—CH,—CH, There are three different types of hydrogens, so the compound. will show three peaks. Ans. (a) (ii) Applications of Ultraviolet Spectroscopy (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 absarption for compounds is selected. Then optical densities are measured for some known compounds. Now the optical density is plotted against concentration of solute over a range of concentration. A straight line is ‘obtained and from this graph, the concentration of unknown is calculated, (2) Molecular Weight Determination. Molecular weights of 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 at max = 380 nm. The concentration C is determined by the formula132 Encwecenmnd Coemustiey in log i, Em From this, C is calculated. If the amount of solute dissolved (iv) is known, the molecular weight of the solute may be calculated. (3) Quatitative Analysis. Identification of compounds can be done by absorption spectrum with known compounds. A curve is plotted between wavelength (A) and degree of absorption (€). (4) The impurities present in organic compounds can easily be determined by spectroscopy. (5) Chemical Kinetics. This technique is helpful for studying the kinetics of a reaction. The change in concentration of either a reactant or product with time is measured. As absorbance is proportional toconcentration. Therefore this technique can be used to follow the course of a reaction. Or Ans. (a) Classification of Polymers: Polymers are classified in a number of ways depending upon one criterion or the other as described below: (1) Classification based upon origin or source: On the bases of source or origin the polymers are classified into two types: @ Natural polymers, ig Synthetic polymers. (2) Classification based on structures: The classification of polymers is based upon how the monomeric units are linked together. Based on their structure, the polymers are classified as: § Linear polymers, @ Branched chain polymers, and @ Cross-linked polymers. (3) Classification based upon synthesis: Depending upon the mode of synthesis the polymers are classified as: @ Addition polymers, @ Condensation polymers. (A) Classification based on interparticle forces: Polymers have been classified into the four categories on the basis of the magnitude of intermolecular forces present in them. @ Elastomers, @ Fibers, @ Thermopla: @ Thermosetting polymers.Sampus Examinations = 133, Ans. (4) (i) Difference between RNA and DNA. (#) Ribose sugar is present. (@) Deoxyribose sugar is present. (ii) A phosphoric molecule that joins one | (ti) Similar to RNA. molecule of sugar to other is present in RNA. (iff) Following Nitrogen base are present: | (iti) Following Nitrogen bases are present: (4) Purines (Adenine and Guanine}. (a) Similar to RNA. (8) Pyrimidines (Cytosin and Uracil). (®) Pyrimidines (Cytosin and Thiamine}. (iv) Four ribotides of molecules are as | (iv) Four nucleotides of molecules are as under: under: (a) Adenosine monophosphate. (a) Deoxyadenosine monophosphate, (8) Guanosine monophosphate. (®) Deoxyguanosine monophosphate. (0) Cytosine monophosphate. (0) Deoxycytosine monophosphate. (4) Uridine monophosphate. (d) Deoxythialimidine monophos- phate. (») It is found in nucleosis, nucleoplasm | (x) It is found in nucleoplasm, mitochon- and cytoplasm. dria and chloroplast. Ans, (b) (ii)Difference between Homopolymer and Copolymer. Po lomopolyinier . os Gepelymien (1) The polymers formed from one kind of | (1) The polymers formed from more than monomers are called homopolymers. one kind of monomer units are called copolymers. (2) Polyethylene is the example of (2) Buna-S rubber which is formed from homopolymer. 1, 3-butadiene (CH, = CH—CH=CH,) and styrene (C,H,CH==CH,) is an example of copolymer.134 Encineerinc CHenistay Ans. (b) (ii) Difference between Addition Polymerization and Condensation Polymerization. Addition Polymerization ‘Condensation Polymerization. (1) High molecular mass polymer is formed immediately. (2) Number of unit decreases steadily throughout the reaction. (3) Only growth reaction adds repeating units one at a time of the chain. (4) Longer reaction time do not affect molecular weight, but gives higher yields. (5) The reaction mixture contains only monomers, high polymers and nearly 10° part of growing chains. (1) Polymer molecular mass rises steadly throughout the reaction (2) Monomer disappears early in the reaction, (3) Any two molecular species present ean undergo reaction. (4) Longer reaction times increases the molecular weight. (5) The reaction mixture contains all types of molecular species at any time. Ans. (c) Elastomers. The elastomers posses the tendency to recover their original shape after they have been greatly deformed. The elastomeric molecules are long and tin and flexible which become lined up when the material is stretched. But as soon as the stretching force is removed, the molecules return to their original random conformation. This is due to the absence of highly polar groups or sites for hydrogen bonding. Moreover, the extended chains do not fit together well enough for van der Waals forces to do the job, Hence, molecules in elastomers have weak intermolecular forces. For ready extension and recovery, the long chains of an elastomer must be connected to each other by occasional cross-links. These cross-links prevent the slipping of molecules past each other but at the same time, these occasional cross-links do not deprive the chains of their flexibility. For example, Natural rubber (cis-1, 4-polyisoprene) has the structure. cH, H cH CH, CH, H weacl 7 ee ON eect —CH; CH, CH, H CH, CH,— Du to the all cis-configurations about the double bonds, the chains do not fit together well. Hence there are only weak van der Waals! forces. Cross-linking between chains is done by heating with sulphur (vulcanization). This results in the formation of sulphur bridges between molecules. To Sum up, long flexible chains, weak intermolecular forces and occasional cross~ linking are the three essential structural requirements of an clastomer.Sampce Examunations = 135, Q2 Answer any four of the following: (a) Write the mechanism of the following: (i) Hoffmann rearrangement. (Gi) Beckmann rearrangement. (b) Write short notes on the following (any two): () Carbonium ion (ii) Carbanion (iii) Free radical (c) Write short nates on the following: () Markownikoff’s Rute (ii) Kharasch’s Rule (d) Differentiate between: (i) Enantiomers and Diastereomers (ii) Racemic mixture and Meso-compounds (e) Explain with examples, R, S-system of configuration of optical isomers. (f) What is meant by the Optical Activity and Chirality? Or Q.2 Answer any two of the following: (a) Discuss various functions of tubricants. (8) Give a detailed account of various environmental segments. (c) Describe the main sources of air pollution Ans. (a) (i) Hoffmann Rearrangement. Amides of fatty acids when treated with bromine and caustic soda (10%), primary amines free from 2° and 3° amines are formed. This is known as Hoffmann rearrangement. RCONH, + Br, + 4KOH —~—» RNH, + 2KBr + K,CO, +2H,O Amide yamine Mechanism. The mechanism may be represented as: Br, + KOH ——> KOBr + HBr136 — Encwecame Coraustey ° ° oO Re + on® > Rc tha rac? NH N—Br \gi—or | -1° Amide Hypobromide H N-Bromamide ion ion N-Bromamide HO 8 2 RONE—O=0 > [RON=C=0 6 FR-N—C=O] on isocyanate Carbamie acid Acyl nitrene R—NH, +CO, 1S-arnine (i) Beckmann’s Rearrangement. When ketoximes and aldoximes are treated with acidic reagents like concentrated H,SO,, PCl., P;O, SOCL,, etc., they rearrange to form a corresponding amide. This is known as Beckmann’s rearrangement. Ry s* (9 SOCK, ether I aN, ai R'—C—NHR R ‘OH Ketoxime Amide Mechanism. The mechanism proceeds in the following manner: R . OR = os or. Scan, ets “oe ae? [r—CERR eo R—CaRR] Rr ‘OH Rv OH, Carbonium ion Ketoxime Protonated oxime HO uw ROG-NHR €—— R—CENR «= [R—C=NR o OH OH, Amide ® enol formSameue Examinations 137° Ans. (b) (i Carbonium Ions. Carbonium ions may be defined as a group of atoms that contains a carbon atom bearing positive charge and containing only six electrons in its valence shell. These ions are formed by heterolytic cleavage in which the leaving group takes along with the shared pair of electrons. i log OK a Carbonium ions are classified as primary (1°), secondary (2°) or tertiary (3°) depending upon the class of carbon bearing the positive charge. For example, if the positive charge is on primary carbon then the carbonium is primary. CH. © @ le’ CH,—CH, CH,—CH—CH, CH,—C—CH, Ethyl Carbonium ion Propyl Carbonium ion Tert buty) Carbonium ion v x * (ii) Carbanions. Carbanions may be defined as a group of atoms that contains a carbon atom bearing negative charge. Carbanions are formed by heterolytic cleavage in which shared pair remains with carbon atom. | —C-X > CF +X Carbanion. Ou OH nt Hi OH nts H,O f OH, P+ H H (ili) Free Radicals. A free radical may be defined as an atom or group of atoms which contains an unpaired electron, Free radicals are formed by homolytic cleavage of a covalent bond, e., in the presence of U.V. light chlorine gives chlorine free radicals. uy cl: Cl ——> 2c138 Encineenina Creaustar If the unpaired electron is on carbon atom then they are called alkyl free radicals. H CH,—CH, cu_cn, CH cH CH, Ethyl free radical isopropyl free radical tert butyl free radical ay @) a) Ans. (c) (i) Markownikoff’s Rule, According to this rule in addition reactions of alkenes the negative part of the addendum molecule attaches itself to the carbon atom carrying less number of H atoms. i CH,—CH=CH, + HBr ——> CH —CH-CH, Br Propene 2-Bromopropane (if) Kharasch’s Rule. In the presence of organic peroxides such as benzoyl peroxide coO—0—0—CO HBr reacts with alkyl halides to give the product against the Markownikoff's rule erode CH,—CH=CH,+HBr ———» CH,—CH,—CH,Br Propene 1 Bromo Propane This is known as Kharasch’s Rule. It may be noted that this rule applies to the addition of HBr only and not to the addition of HI or HCl.Sampue Examunations 139 Ans. (d) (i) Difference between Enantiomers and Diastereomers Enantiomers Diastereomers: The two isomers which are identical in all respects except their behavior towards plane polarized light. The two optical isomers of | a compound are always the mirror images | of each other and are, therefore called | enantiomers. For example, The two sterecisomers of the same ‘compound but are not the mirror images of each other. These stereoisomers are called diastereomers, For example, COOH COOH Hl cl—C—-H Br—C—Cl H—C—br | coon coon w@ a COOH COOH H—-C—Cl cH | HOC—tr BCH door oon | i) () (i) and (Hf, (i) and (ie), (ii) and (iii), and (i) and (iv) are diastereomers.140) Encweecema Cresistey (ff) Difference between Racemic Mixture and Meso-compounds Compounds asymmetric carbon atom exist in twostereo containing only one isomeric forms, eg. lactic acid (CH,CHOHCOOH). The two stereaisomers of lactic acid are not superimposable and thus possess dissymetry of molecule. These two forms are dextro (d) and laevo (!) and These are certain compounds which do not contain any asymmetric carbon yet they are optically active e¢., diphenyl derivatives. Further, certain forms of some compounds containing asymmetric carbon are not always optically active. These compounds are known as meso-compounds. For are mirror images of each other. When these two forms are mixed in equimolar quantities (50% 1 + 50% d) the mixture becomes example, optically inactive as the rotatory power of GOOH the two dextro and laveo are equal but _oH opposite. These type of mixtures or form which is optically inactive due to external H—C_OH compensation are known as racemic mixture. COOH Meso tartaric acid 1H, CH, “son wil ‘Coon Ans. (¢) R.S-system of configuration of optical isomers. The symbols R means right and § means left. The configuration of an optical active compound is based upon the nature of the groups attached toan assymetric carbon atom. The nature of groups is determined by the priority of the groups which depends upon some rules given as: @ The four different groups cr atoms attached to an assymetric carbon atom. are arranged in the decreasing order of priority 1, 2. 3. 4. & When four different atoms are attached to an assymetric center, priority is given to atomic number. The atom with the highest atomic number is givenSameue Examicavions = 147 ci the first priority. Hence in compound F—C—, the priority sequence of | Br four atoms is I (atomic no. 53}, Br (atomic no. 35), Cl (atomic no. 17) and F (atomic no. 9). @ If the isotope af the same element are attached to an asymmetric carbon atom, the isotope with higher mass number is given the higher priority, .¢., 17CL” is given higher priority as compared to CI. If two atoms attached to an asymmetric carbon alom the same, the priority is determined by the atomic number of next atom away from asymmetric carbon atom. For example, f CHE > CH-C— > CH-CH,— CH, CH; (Ethyl) (th butyD (sopropyl} @ An atom attached with a double (=) bond or tripple (=) bond is equivalent to two or three such atoms. For example, = Cis equivalent to 5 c = Cis equivalent to SC c ‘Ans. (f) Optical Activity. Solution of some organic compounds, when placed in the path of a plane polarized light, rotate the plane of polarized light to a certain fixed angle either left hand or right hand direction. This property of rotating the plane of polarized light is called optical activity and this phenomenon is known as optical isomerism. Chirality. An object which is non-superimposable on its mirror image is said to be chiral. These can be a pair of hands, a pair of gloves, a pair of sleepers, some letters of alphabet like E, ¥,G, conversely a chiral objects are those objects which are superimposable on their mirror image like A, V, O, M, W etc. Chiral objects are also called dissymmetric and this phenomenon is known as chirality:142 Encieeminc CHenistiey Or Q.2 (a) Various functions of Lubricant are: @ Lubricants reduce loss of energy in the form of heat by acting as a coolant. @ Lubricants reduce the expention of metal by local frictional heat. @ Lubricants prevent or minimize rough relative motion of the moving or sliding parts. @ Lubricants act as a seal in internal combustion engines § Lubricants reduce wear and lear and surface deformation, by avoiding direct contact between the rubbing surfaces. @ Lubricants minimize the liberation of frictional heat and therefore avoid seizure of moving surfaces. m Lubricants increases the efficiency of the machine by reducing the waste of energy. Ans, (b) Various Environmental Segments: The Troposphere. This atmosphere layer lies close to the earth’s surface and extends up to analtitude of 11 km. The upper limit may vary by a few kilometer, depending upon temperature, nature of terrestrial surface; ete. 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 alsocontains 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 hydrological cycle. The density of air, in the region, decreases exponentially with increasing altitude. The troposphere is also a turbulent region due to the global energy 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 troposphere and is of quiescent nature. It ranges from 1] km to 50 km 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 rich in 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 ultra violet rays and at the same time supplies the heat source for partitioning theSamme Exauinanions 143, atmosphere into a quiescent stratosphere and turbulent troposphere. In stratosphere, the residence limes of molecules or particles are quite long and if pollution reaches in this region, they pose long term global hazards compared to their impact on tropesphere. 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 ultra violet 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 ©, are the principal chemical species in the region. The Thermosphere. The thermosphere region lies just above (he mesopause and experience 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 mainly oxygen and nitric oxide, split into atoms and also undergo ionization after absorbing radiation in for ultra region. Ans. (c) Sources of Air Pollution. The sources of air pollution can be classified in following categories: (1) Combustion. It includes burning of fuel; coal and wood and, transportation. Some are described as follows: The fuel in aeroplane when burns gives CO, as pollutant. The increase in concentration of SO, creates problems for animals, human being, plant life, building ete. The combustion of coal gives off CO.SO,, oxides of Nj, hydrocarbons and aldehydes as Polutants. The combustion of gasoline, diesel oil in automobile gives off smoke containing a high percentage of CO. When it enters our system, it reacts with haemoglobin of blood and obstructs the flow of O, in our tissues. It thus produces headache. (2) Manufacturing processes. A number of chemical and industrial plants produce air pollutants as mixture of oxides of K, Al, Ca, Na and Si is a common pollution around cement factories. The dust decreases the size and number of leaves in plants. The H,SO, industry discharges SO, as air pollutant. Industries manufacturing compounds of fluorides have serious effects on animals, plants and human beings. From HNO,, plants release oxides of N, as pollutants which form toxic substances. From ‘Fe’ and steel industry SO,, metal oxides, CO and CO, are144 — Encmeenine Cemisrey given as pollutants similarly petrochemical refinery emitemission containing, CO, HCHO, NH,, gasoline, kerosene fuel, oil, NO, ete. (3) Agricultural Activity. (i) Crop-spraying. When crops are sprayed, pesticides, weedcides, etc., a number of crops organic phosphates, chlorinated hydrocarbons, Hg are released as pollutants. (ii) Sewage and domestic refuse. Cooking smells gases from domestic and sew- age, breeding and catering industries cause air pollution giving off fly- ash-CHO, hydrocarbon, CO,, CO and other obnoxious gases. (4) Solvent Usage. During the process of painting the furnitures, car, scooters, dyeing, printing decreasing a number of pollutants like hydrocarbons and organic vapors are given off to the atmosphere. (5) Nuclear Energy. Duc to radiations emitted by radioactive explosion nuclear reactions, the air is polluted due to U and Be dust radioactive falls out in the form of 8, C,"”, CH etc. A number of radio isotopes are used in research and treating diseases like cancer, thyrodism etc Q.3 Answer any two of the following: (a) Mention the criteria for choosing a catalyst for industrial processes. Or State and explain Phase Rule. Discuss the salient features of Phase Diagram of water system, (b) Explain the reason for the following: (i) HCl is stronger acid than H,S. (ii) NH, is more basic than HO. (tii) Order of acid strength is H,SO, > H,PO,> HBO, (c) How can the rate constant k, and k, be determined for the following reaction? k, P & F Ans. (a) The use of catalysts in some of the industrial processes is described below: (1) Ostwald’s process for the manufacture of HNO, 4NH, + SO, 4NO + 6H,O 2NO +0,——+ 2NO, 4NO, +2H,0 +O,» 4HNO, Catalyst used is platinized asbestos.Samere Exaumnanions 145 (2) Manufacture of methyl alcohol from water gas. CO+H,+H,——+ CH,OH water gas Catalyst used ZnO. (3) Acetic acid from acetaldehyde. 3CH,CHO + 0,» 2CH,COOH Catalyst used is V,O,. (4) Haber’s process for the manufacture of ammonia N, +3H, == > 2NH, Catalyst used is finally divided Fe. (5) Manufacture of Hydrogen by Bosch’s process. CO+H,+H,O—— C0, + H,0 Catalyst used is Fe,O,. (6) Manufacture of chlorine by Deacon’s process. 4HCl + 0, —+2H,0 +2Cl, Catalyst used is CuCl,. Or Ans, (a) The phase rule is a generalization given by Willard Gibbs (1874), which seeks to explain the equilibria existing in heterogeneous systems. It may be stated as: “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, for any system at equilibrium 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, (0 At freezing point, water consists of three phases: Ice(s) <== Water () <== Water vapor (g)146 0 Encwizeninc Cremstay (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. (iii) If two liquids are immiscible (i¢., benzene and water), they will farm two separate phases. (iv) If two liquids are miscible (.¢., alcohol and water), they will form one liquid phase only. () Asolution of a substance in a solvent consists of one phase only, e.g., glucose solution in water. (vi) Each solid makes up a separate phase, except in the case of solid solutions, eg., many forms of a sulphur can exist together, but these are all separate phases. (vii) A heterogeneous mixture like: CaCOg(s) qe CaO(s) + CO,(g) consists of three phase (iec,, two solids-and one gaseous). Similarly, in the equilibrium reaction, Fe(s)+H,0(g) === Fels) +H,(9) there are two solid phases, Fe and FeOand one gaseous phase consisting of H,O() and H,(g). Thus, three phases exists in equilibrium. (viii) A homogeneous solid solution of a salt constitutes a single phase. Thus, Mohr‘s salt [FeSO, . (NH,),5O, 6H,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 form of chemical equation”. For example, (i) In the water system. Ice (s) <== Water (I) <=> Vapor (g) the chemical composition of all the three phases of 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. (iif) In the dissociation of NH,C1 in a closed vessel, NHCl6) <—— > NHClg) <> NH,9) + HC)Sampur Examinarions 147 the proportions of NH, and HCL are equivalent and hence, the composition of both phases (salid and gaseous) can be expressed in terms of NHClalone. Hence, the number of component is one. However, if NH, or HC] is in excess, the system becomes a two component system. (iv) A system of saturated solution of NaCl consists of solid salt, salt solution and water vapor. The chemical composition of all the three phases can be expressed in terms of NaCl and H,O. Hence, it is a two component system. (0) In the thermal decomposition of CaCO, CaCOs) ——= Ca0{s) + CO,Lg) the composition of each 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 Cad Phase: CaO = 0 CaCO, + CaO Phase: CO, = CaCO, - Cad Thus, it isa two component system. (vi) In the dissociation reaction, CuSO, .5H,O(3) <== CuSO, .3H,0(s) +2 H,0%g) the composition of each phase can be represented by the simplest components, CuSO, and H,O. Hence, il is two component system. (vii) In the equilibrium, Fe(s) + H,O(g) <== FeO(s) + H,(g), the minimum components required to express the 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 ntinimunt number of independently variable factors, such as temperatire, pressure and composition of the phases, which must be arbitrarily specified in order to represent perfectly the condition of a system”. For example: (i) In case of water system, Ice(s) <== Water(!) = = 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. temperature or pressure) is altered, three phases will not remain in equilibrium and one of the phases disappears.148 — Encweernc Cuemstey Water System The water system consists of three phases, viz., ice, water and water vapor. lee(s) ——= = Water(!) —<— = Water vapor (¢) Since H,Ois the only chemical compound involved, therefore, it is single or one-component systent, From the phase rule, when C = 1, F=eC-P+2=1-P42=3-P ive,, the degree of freedom depends on the number of phases present at equilibrium, ‘Three different cases are possible: @)PslF=2 (bidariant system) ()P=2F=1 (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, sucha system can be represented completely by atwo-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: Pressure (not to scale) (1) Areas: AOB, AOC and BOC are the fields of existence of vapor, liquid and ice phase respectively. Within these single-phase areas, the system inSampue Exavinanons 149 bivariant, because to locate any point in.an area, temperature as well as pressure co-ordinate need to be known. This also follows from phase rule equation: Fs3-P=3-1=2. (2) Boundary lines: Separating the arens are lines OA, OB and OC, connecting the point at which two phases can co-exist in equilibrium. In order to locate any point on a particular line, either temperature ar pressure co-ordinate should be 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 freedom or is univariant. This also follows from phase rule equation: Fo3-Ps3-261 (i) 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. Inother words, the system isarivariant, i¢., 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. (ii) The curve OB is the sublimation curve of ice. Il gives the conditions under which water vapor is in equilibrium with solid ice. The point B has a natural limit at — 273°C, beyond which the twe phases merge into each other, (iif) The curve OC, which 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 toward the pressure axis shows that the melting point of ice is decrensed by increasing pressure. (3) Triple point: The three curves OA, OB and OC meet at O, at which solid, liquid and vapor are simultaneously at equilibrium. This point at 273.16 K (or 0.0098°C and 4.579 ment 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, i.e., neither pressure nor temperature can be altered, 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 of a substance co-exist in equilibrium. For a given substance, the triple point occurs at.a unique set of values of the temperature, pressure and volume. 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, ane of the three phase disappears and the system changes from non-variant to untoariant.150 Excaverena CHemster 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 supercooled water. On slight disturbance, the supercooled water at once changes to solid ice. Ans. (b) (i) HC1is stronger acid than H,S because HCl is approximately fully dissolved in dilute solution as compared to H,S. (ii) The strength of any base depends upon its capacity to capture protons. Therefore NH, is more basic than H,0. (iii) Order of acid strength is H,SO, > H,PO, > H,B0, Since the strength of any acid depends upon the capacity of losing protons. 4 P Ans, (0) A ky F Suppose a be the initial concentration of A and x be the amount transformed in time ‘I. If y and z be the smoun of P ue F formed in time t, then the rates of formation of P and F given ty! = * ana 4 = respectively P and F both are formed fom A dx _dy | dz S.9,8 at dt” di 0 If the reaction is unimolecular and ki is the velocity constant for the formation of P from A. dy Then he») Similarly the rate of formation of F from A is given by = ka—3) From equation (i), (a— x) + k, (ax) = tk, +h) (a—2)Sammut Exauinanions 157 On integration kyth=K=t logo ti) Now in order to evaluate k, and k, separately Amount of P atany stage _ dy/dé - ky(a—x) Amountof Fatany stage dz/dt k,(a—x) = 4. <& (uppose) (iii) ky The relative amounts of P and F can be determined at the end of the reaction, the ratio of the relative amounts giving the value of K. The values of k, and k, can be calculated separately from equations (ii) and (iii) in terms of K and K’. i k+k,=K and nok k, and 4K Q4 Answer any twa of the following: (a) (i) What is temporary hardness? How can it be removed? (ii) A sample of water on analysis was found to contain the following impurities: Impurity Quantity Molecular Weight Caf HCO,), 4 162 Mg(HCOy), 6 146 Caso, 8 136 MgSO, 10 120 Calculate the temporary, permanent, and total hardness of water in ppm, Fr and °Cl. (b) @) Write a short note on biomass as a source of energy. How does this technique differ from biogas technique? . (ii) What are fuels? Discuss their classification. (c) A sample of coal containing 89% C, 8% H, 3% ash, when tested in the laboratory for its calorific value in the bomb calorimeter, the following data were obtained: Weight of coal burnt = 0.85 gm Weight of water taken = 650 gm152 Encovermnc Crenistey Water equivalent of bomb calorimeter = 2500 gmt Rise in temperature = 2.5°C Cooling correction = = 0.03°C Fuse wire correction Acid correction Assuming that the latent heat of condensation of steam as 580 cal/gm. Calculate (i) the gross and (ii) the net calorific values of the coal int calfgm. Ans, (a) (i) Temporary Hardness: The temporary hardness is due to the presence of soluble salts of bicarbonates of calcium and magnesium. This type of hardness can easily be removed by boiling when the bicarbonate are decomposed into insoluble carbonates. ot Mg(HCO,), ——> MgCO, +H,0 +O, Soluble Insoluble Boi Ca(HCO,), ——+ CaCO, | +H,0 + CO, Soluble Insoluble (if) _J Mattiptiation Factor CaCO, Equivalent CatHCO,}, 4 100/162 4x rd =246 100 Mg(HiCo,), 6 100/146 6x Oo o4t0 146 100 caso, 8 100/136 Ba ess 100 0 100/120 tox 12 2533 MgSO, rt / > Temporary hardness = = 2.46 + 4.10 = 6.56mg/L or ppm or 6.56 x 0.07 = 0.459 °Cl or 6.56 x 0.1 = 0.656 °Fr Permanenthardness = 5.88 + 8.33 = 14.21 ppmSampce Exammanions 153 or 14.21 x 0.07 = 0.9947 °C1 or 14.21 x 0.1 = 1.421 °Fr Total hardness = 6.56 + 14.21 = 20.77 ppm or 20.77 x 0.07 = 1.45 °C1 or 20.77 « 0.1 = 2.077 °Fr Ans. (8) (i) Biomass. Biomass is the waste material of living organisms and the dead Ans, plants of living objects. It contains carbon compounds and works asa source of heat energy for domestic purpose. There are two ways of using biomass as a fuel. One is to use biomass like cattle dung or wood directly and ather method is to convert biomass into a fuel and these fuels are used for heating purposes. (i) Fuels. Whenever a substance is burnt in air or oxygen with the evolution of heat, is known as combustion 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 knownas 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 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 for example, wood, peat, lignite, coal liquid fuel for example natural gas. Secondary Fuels. These fuels are cither artificially manufactured or derived from primary fuels. These are further classified as solid fuels for example coke, charcoal, petroleum, coke, colloidal fuel, thiokol, hydrazine, ete. and liquid fuels for example gasoline, diesel oil, kerosene, coal tar and its fraction. Solid Fuels. Charcoal, coke, petroleum, coal ete. Liquid Fuels, Diesel, tar, kerosene, L.PG. fuel oil, gasoline etc. Gaseous Fuels. Oil gas, coal gas, biogas. () Weight of coal sample (x) = 0.85 gm Use of water (w) = 650 gm154 Excmvernmc CHemister Water equivalent to Bomb calorimeter (Cu) = 2500 gm Rise in temperature (f, = ,) =25°C Acid correction = 50cal Fuse wire correction =10cal Latent heat of steam = 580 cal/gm Percentage of H = 8%. Gross calorific value, (GCV) = (+ Wa =) ~ (Acid + fuse correction) x __ (650 + 2500) (2.5°) - (50 + 10) 085 3130 x 25 - 60 0.85 7875 — 60 0.85 = BE 0.85 = 9194.00 cal/g Net calorific value, (NCV) = [GCV - 0.09 x H x Latent heat of steam] = [9194 = 0.09 x 8 x 580] = 9194-4176 = 87764 Cal/g Q.5. Answer any two of the following: (a) (i) What is meant by bond order? Calculate the bond order of He** and O,* molecules. (ii) Explain in detail, Born-Habber cyete. (b) What are the crystal defects? What are Schottky and Frenkel defects in a crystal? (0) (i) Write the name of the following complexes according to IUPAC system: (A) K, JAUC,0,),] (B) [PE (NH) 1 [PICH] (CVICo (en), Cl,Sampue Exammanions «155 (D) K, [NI{CN},) (E) [Fe(NHy), Cl} (ii) Define the following terms with suitable example: (A) Ligand, (B) Coordination sphere, (C) Complex compound, Ans. (a) (i) Bond Order: The stability of the molecule can be determined from another parameter called bond order. Bond order may be defined as half the difference between number of electrons in bonding molecular orbitals and the number of electrons in anti-bonding molecular orbitals, i.e, Bond order = 3 (Number of electrons bonding MO's) = (Number of electrons in anti-bonding MO's) 1 =F INN Information Conveyed by Bond Order: The bond order conveys the following important information: (1) Dissociation energy of the molecule is directly proportional to thebond order of the molecule. In other words, greater the bond order, greater is the bond dissociation energy: (2) Knowing the bond order, the number of covalent bonds between the atoms in the molecule can be predicated. Bond order of a molecule is equal to the number of covalent bonds between the atoms in the molecule. (3) If the value of bond order is positive, it indicates a stable molecule and if the value of bond order is negative or zero, it means that the molecule is unstable and is not formed. (4) Bond length of the molecule is inversely proportional to the bond order of the molecule. In other words, greater the bond order, shorter will be the bond length. () He, Atomic number of He = 2 = 1s? He* = 1s!156 Encinerninc Cuesustay Bond order sts The bond order for He," molecule is (i) 0,2 Bond order = = a2. = gel The bond order of 0, is 1.Saume Exammanions 157 Ans. (a) (ii) Born-Haber cycle is used to determine the lattice energy of an ionic solid. Sodium chloride (NaCl) one mole of crystalline sodium chloride (NaCl) can occur by any of the following, two processes: (1) Process involving direct combination of Na(s) and 1/2 Cl,(g) to form NaCKs) In this process, heat is evalved, as it is an exthermic reaction. The heat produced is equal to the heat of formation of NaCl), i, Najs) + ; Clg} NaC (s) Heat produced = Heat of formation of NaCI(s) or AH =-Q (2) Process for obtaining sodium chloride (NaCl) (solid) Process for obtaining sodium chloride involves the following steps: (a) Conversion of Na(s) into Na(g): This process is known as sublimation, it is an endothermic reaction. Na(s) ——- Natg) Heat absorbed = Heat of sublimation of sodium = + S. (b) Conversion of Na(g) into Na*(g): This step involves the conversion of gaseous sodium [Na(g)] atom into gaseous ion. It occurs by giving one electron and the process is known as ionization. It is an endothermic reaction and for this reaction energy is known as ionization energy, f¢., 1 of Na atom is absorbed. o Na(g) + e7 ——> Nag) Energy required = Heat of ionization = + |. (c) Conversion of 1/2 CL(g) into Clfg): In this step, chlorine molecule (C1,) 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 dissociation (D) of chlorine molecule. It is an endothermic reaction. deg — Cigh Heat required = Heat of dissociation of 3 CL (g) molecule = + bp.158 — Enciwerrnc CHemstay (d) Conversion of Clig)into Cl-(g): The gaseous chlorine atom Cl(g) formed in step (c) adds up one electron, given up by Na(g) in step (6) and is converted into CF(g). This energy is known as the electron affinily of chlorine is represented as E. This change is an exothermic reaction. n Clg) + ee —> Cr) Heat produced = Electron affinity of chlorine = — E Heat produced = Electron affinity of chlorine =~ E. (¢) Combination of Na*(g) and C¥'(g) ions to form NaCl(s}: Na*(g) and Cl*(g) ions formed in steps (b) and (¢) combine together to form 1 mole of NaCl (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). Nav(g) + Cl'tg) ——> NaCl) Energy released = Lattice energy of NaCI(s) = - U. The formation of NaCl(s) by the above two processes is known as Born- Haber cycle. As the two processes are independent of each other, 50 according to Hess law, the heat of formation of NaCl (solid) must be the sum of both the processes. ” -Qe+S+1+ 2 D-£-u Hence the lattice energy (U) can be calculated. 1 Na(s) $ Chg) ———+ NaCI () [sep 1 [step 3 Na(g) Cli{g) [step 2 | seep 4 Step 5 Nag} +) CI) Born-Haber Cycle for the formation of NaCl crystal from its element. Or Ans. (b) (i) Crystal Defects: If the deviation occurs because of missing of atoms displaced atoms, or extra atoms, in perfection is called point defect or stoichiometric defect. The most common point defects are Schottky defect and Frenkel defect. Metal defect and metal deficiency defect.Samet Examnarions 159 (1) Schottky Defect: Lattice points are unoccupied called holes or lattice vacancies. Generally Schotty 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. (2) Frenkel defect arises when an ion occupies an interstitial position between the lattice points. Generally rf is ions and CN is also small e.g., Ag’ and Zn®* ions occupy position in between the other ions n the lattice. Non-Stoichiometric Defect: These compounds do not obey strictly the law .of constant proportions. The numbers cation and anions present in such compounds are difference from those seen from their ideal chemical formula. ‘Therefore the crystal structure becomes irregular and defect arise. Such defect are called non-stoichiometric defects which exist in addition it. (ii) Schottky and Frenkel defects. These are of two lypes: (a) Metal excess deficiency defect which negative ions are in excess, for example FeO, FeS, NiO etc., (b) Metal excess defects when positive ions are in excess for example KCI, ZxO- ete. Ans. ()() (A) K,[ANC,0,),] Potassium trioxalatoaluminate (II) (B) [Pt (NH,),] [PeCh,} Tetramine platinum (1!) tetrachloroplatinate (II) (C) [Cofen),ICL, Tris (ethylenediamine) cobalt (III) chloride (PD) K,INi(CN)] Potassium tetracyanonickelete (0) (E) [Fe(NH),Ch] Trichlorotriamineiron (II) (i) (A) Ligand: The molecules or ions which are attached to the central ion, are known as ligands in a complex ion, v.g., in [Fe (CN),|**. The number of ligands is six. (B) Coordination Sphere: The molecular or ionic species attached directly to the central ion constitute what is offenly known as coordination sphere. (C) Complex Compound: The compounds which contain a complex ion are known as complex compound, ¢.g., K,[Fe(CN),] is a complex compound because it has [Fe (CN),]"* complex ion.160 — Enciveennc CHemistay CHEMISTRY-7 Time: 3 Hours Total Points: 100 Note: 1. Answer all Five questions, 2. All questions carry equal points. (PART—A) ~ Q.1 (a) The compound ‘X’ on mass analysis (70 eV) gave a molecular ion peak at m/z, 44. On elemental analysis, it gave C, 54.55% and H, 9.09%. The solution of the compouttd in COCI, on a 60 MHz machine exhibited 2 down field signal (quartet), which is one- third as intense as the second signal (doublet). The compound responds to the silver mirror test. Identify the compound “X". Give your reasoning. . (b) Assign the structures (A and B) to the respective isomers on the basis of the following UV data: a-isomer shaws peak at 228 nm while the Prisomer has.a band at 296 nm. ° ° ocs OC" fA) (By Explain also. () What is the importance of ‘finger print region’ in infrared spectroscopy? Ans. (a) Compound is CH, CHO because it's molecular weight is 44 and it gives silver mirror test. Its empirical formula is C,H,O. 6 = O(TMS) Hq (applied magnotic field) “4— 6 (Chemical shitt)Samoce Exammations 161 Height ratio is 1: 3. After interaction of adjacent proton, doublat (1:1) Response —» sa = 0 (TMS) Ans. (b) [A] has conjugation so its ,,,, should be more than [B] so B-isomer is [A], and a-isomer is [B]. Ans. (c) Finger Print region: Infrared spectrum contains a large number of bonds and the possibility of same spectrum of two different compounds is exceedingly small. For this reason infrared spectrum has been called the “finger print” of a molecule. Thus if two pure samples give different infrared spectrum, the compounds must be different. If they give the superimposable spectra then they represent the same compound. The region from 4000-1500 cm (high frequency part) to the left end of infrared spectrum is useful for the identification of functional groups. The region lo the right of 1500 em! (1500-650 cm") is usually complex since both stretching and bending modes give rise to absorption here. In this region correlation of anv individual bond with a specific functional group is often difficult. However, each organic compound has its own unique absorption pattern in this region. This part of the spectrum is therefore called finger print region. (PART—B) Qu (a) Write the name and structure of the heterogeneous catalysts, in the presence of witich highly stereoregular polymers, derived fram propylene, are formed. Write the configuration of these polymers. (b) Write the chemical structures and one use (in each case) of the following macromolecules: (i) Poly-€ -caprolactum (ii) Polyethylene terephthalate (iii) cis, 1, 4-polyisoprene cross-linked through a non-metal (iv) Polynucleotide chain (@) Starch.162 Encweswnc Cwemster Ans. (a) Heterogeneous Catalysts: Solution of AIEL, of TiCl, work as a Ziegler—Natta catalyst. It produces the stereoregular polymer. The active species in Ti, and AIEt, can reduce TICI, to TICl, insita. Then one of the Cl atom is replaced by ethyl group. Double bond in ethene attaches itself to a vacant site on a Ti atom on the surface of the catalyst. A carbon shift reaction occurs, the ethene migrates and inserted between Ti and C in the Ti-Et bond. The process in repeated and the C-chain grows in length. It leads to polymerization. TiCl, + Et,Al—— TICLE + AV(ED), Hh os a Hf! LA cH, Th cH, iv i° iz I & cH dh A cl cl cl cH, n CH, (—CH,—CH,-), ———— Hu oH It is head to tail configuration. All CH, group lies on same side. Ans. (b) (i) Poly-¢ -caprolactum i -—{CH,), NH Nylon 6 It is used in fiber industry.Saurus Exavinanions 163 (i) Polyethylene terephthalate faatow Itis also known as Terylene. It is also used in cloth manufacture. (ui) cis-1, 4-polyisoprene cross-linked through a non-metal. CH, H cH feu, s 5 HC, H ne — Scr (iv) Polynucleatide chain Nucleotide is the combination of sugar (deoxyribase or Ribose), Base (Purines of Pyremidines) and phosphate.164 ENGINEERING CHemisTRY (0) Starch: It is mixture of two polysaccharides, amylose and amylopectin. Amylose is linear polymer of D-Glucose unit having o-glycosidic linkages. It is water soluble. Amylopectin is a branched chain polysaccharide insoluble in water. It also have a-Glycosidic linkage. CH,OH CH,OH H Ou H Ou H H OH H OH H “0 ° oO HOW pivjose HOH CH,OH CH,OH H OH H oO H H OH H OH oH sooo) ‘Oo HOH HOH oO CH,OH di, H QH H o, H H HH OH HI ssssooee C): oO Cone H OH HOH Amytopectin Q.2. Answer any Four of the following: (@) (i) Write the mechanism of crossed Aldal condensation involving equimalecular amounts of acetaldehyde and formaldelyde. Alsa indicate the possible side products of the reaction. (ii) In the Diels-Alder reaction, identify six groups in the dienophile, which promete the reaction. (iii) Will N-methyl acetamide undergo Hoffmann rearrangement? Explain. (b) (i) Indicate, with a suitable diagram, the potential energy changes during rotation about Cipy—Cyy, bond of n-butane, (ii) Comment on the relative stabilities of the conformers. (c) Name the elements of symmetry. Discuss with the help of an exariple an optically active compound without chirality.Sampue Exameations 165 (d) In the following molecules, arrange the functional groups in the decreasing order of preference, using the sequence rules. Give your reasoning: H, oO 4 CH —CHICH H—C—OH NH, CH,OH (¢) By using appropriate examples, discuss and illustrate the stereochemical implication of Sy1 and Sy2 reactions. (f) Draw structures for the equilibrating chair conformers of trans- and cis-1, 2-dimethyl- cyclohexanes. Show all Me/H 1, 3-diaxial interactions. Select the more stable conformation for each diastereoisomer. Ans. (a) (i) Crossed Aldol Reaction: NaOH CH,CHO + HCHO——>? Mechanism: - ¢ CH,CHO + on ——+ G4,—cHo + HOH of | HOC-H + GH,—cHO —— H,C—CH—CHO 8 - O—CH,—CH,CHO + H,O ——+ HO—CH,—CH,—CHO + OH . aldol Oo H,C—CHO + nti oH, HO—CH,—CH,— CHO Other side reactions are also possible i, CH,CHO reacts itself to form aldol and HCHO reacts itself to give cannizarro product (CH,OH and HCOO") on, & H,C—CHO+ —°#, CH,-CHO \o a H,C—CHO + CH,—CHO ——+ H,C—CH—CH,—CHO o HH H,C_CH_CH,—cHO +HOH ——> H,C—CH—CH,—CHO + OH”166 Encmernnc CHemistay (ii) Diels-Alder Reaction: In this reaction a diene reacts with dienophile to form adduct. CH, CH, qo “oN cH CH, CH ih I + 1? — | e CH, CH CH, CH, ‘CH; Diene Dienophile adduct Electron withdrawing group in dienophile enhances the rate of reaction. ie, —NO,, —CN, —COOCH,, —COOH, —COCI, —CHO CH, = CH—G, G may be any group which is mentioned above. i Cc) ne ws It will not show the Hoffmann rearrangement ‘CH, oO ° NH, + OH” + Br, ——> R-CLNE-Br + HOH Br ? oO R—C—N—Br +OH ——> Here in place of [H], CH,O=C=N—R+ Br is present which can’t be removed by OH", hence this reaction is not possible. Ans. (b) (i)1-Butane CH1— CH; —-CH:—CHs Here free rotation is taken around C,—C,, o bond.Samo Examinations 167 H CH: H. CH; H H after GO", alter 66” alter 60, CH, H H H H H (ii) Stability of conformers: Different conformers of n-butane is drawn in Ans. 20 (i). His lowest in energy because both CH, groups are anli to each other. V1 is highest in energy because both CH, group are in staggered conformation. Il has equal energy to 1V and I has equal energy to ¥, I and ] are known to partially eclipsed and gauche forms respectively. It has higher energy than [ and Hence Ul <1=V 1=V>1=IV> VI.168 — Enccenma Cremistey Ans. (c) Elements of symmetry: Different elements of symmetry are given as follows. (i) Plane of symmetry: A molecule will be said to passes a plane of symmetry if it canbe divided into two equal halves in any plane and thus the atoms or groups on one side of the plane form mirror image of those on the other COOH Plane of symmetry H COOH (ii) Center of symmetry: A center of symmetry is an imaginary point in the center of molecule from which if lines are drawn on any group on both the sides to an equal distance, it divides the molecule into two equal halves which are the mirror image of each other ¢.g., @ trusillic acid. center of symmetry Hs COOH 'H COOH GH, (iii) Proper rotation of axis: A molecule is said to posses an n-fold alternating axis of symmetry if, when it is rotated through an angle of 360°/ about this axis and then reflected across a plane perpendicular to the axis an indentical structure is obtained.e.g.,3,3-dichlore-3, 3-dimethy! hexane is found to be optically inactive due to the presence of twa fold alternating axis of symmetry. cl Gr ida i H,C—C—C,H, d Optical Active Molecules which is not having chiral carbon: Ci CH,Samete Examinanons § 169 In this molecule there is no asymmetric carbon but it is optically active because it does not have any lype of symmetry and the molecule as a whole is dissymmetric. Ans, (d) Preference is given according to the atomic number of atlached of the group t CH, For -—C_H ; the preference order of different groups will be: NH, CH, As NH,> 4 S\>-Gu oH CH, H. 0 Nf and for I ton ; the preference order will be: C HT ou —O—H > —CHO> —CH,OH > H CHO has preference to CH,OH because in —CHO, C = O group is present. Ans, (e) Unimolecular nucleophilic substitution reaction (8,1) involves heterolysis to from the carbocation as an intermediate. s Reams Row eRe Transition Carbecation Leaving tale Intermediate group Nu Nucleophite: éRacemiic mixture of products)172 Encimeeninc Cremasticr ‘Transis more stable thancis because in cis there is 1,3 Me/H diaxial interaction. Q.3 Answer any One part (A Or B): (PART—A) (a) Discuss the application of Phase Rule to water system. (b) State the significance of Triple point. (c) Im principle, is it possible fo convert solid ice into water vapor? Explain. (d) With the help of phase rule diagram, show how it is possible to havw supercooled water. Does it represent a stable phase? Ans. (a) Application of Phase Rule: It is an important tool used for the quantitative treatment of systems in equilibriume.g., it can give the data up to what condition of temperature and pressure, H,0 is solid liquid or gas. It enables us to predict the condition that must be specified for a system to exhibit equilibrium. Ans. (b) Significance of Triple point: At triple point, solid, liquid and gas phases all exist together in equilibrium. H,O —— 1,0 — + H,0 (s) w (gh C=1, P=3 F=C-P+2 =1-34+2=0 There is no independent variable, all the variables should be defined for defining the system. ie, T = 0.0075°C, P = 4.58 mm of Hg Ans. (c) H,0 == H,0 ts) @ P=2,C=1 Foi-2+2 =1 Degree of freedom is one, it means only one variable is required to define the system i.c., Temperature or pressure.174 Encmerninc Cressey POH = —log { pH + pOH = pH+130=14 = pH = 12.7 ‘Ans. (b) k,=7 x 10", T, = 280 K k= 9x 107, T, = 330K (x alk : 9x10? os °8 | F107 “sel 280 330 50 0,109 x 2.303 x 8.314 = E, oad | E, = 38.568 k}/mol QA Anstver any Teo of the following: (a) (i) Calculate the temporary hardness ard permanent hardness of a sample af water containing: Mg (HCOs), = 7.3 mg/L, Ca (HCO,), = 16.2 mg/L, MgCl, = 9.5 mg/L, CaSO, = 13.6 mg/L (Atomic weights of Mg and Ca are 24 and 40 respectively.) (ii) The hardness of 50000 liters of a semple was removed by passing it through a zeolite softener. The softener then required 200 liters af NaCl solution, containing 125 gfliter of NaC! for regeneration. Calculate the hardness of the sample of water (b) Write short notes on: (i) Characteristics of a good fuel. (ii) Relative merits of solid, liquid and gaseous fuels. (ii) Nonconventional energy sources.Same Examinations 175 (6) Calculate the weight and volume of air required for the combustion of 3 ky of carbox. Ans. (a) (i) Constituent Amount (Mg/D CaCO, equivalent ihigity — | 100 Mg(HCO,), 73 73% 755 | | 100 } Ca{HCO,), 16.2 162 « TE =10 | 1 100 MgCl, | 95 | 95x ae =10 | | & | 13.6 100 a caso, 13. i 3.6 « 1B6 1 ‘Temporary hardness = 5+ 10 = 15 Mg/L (It is due to to bicarbonate of Ca** and Mg”*) Permanent hardness = 10 + 10 = 20 Mg/L (It is due to sulphates and chlorides) (i) NaCl contained in 200 L of NaCl = 125 x 200 = 25000 g of NaCl _, 25000 x 50 585 = 2.136 x 10? mg CaCO, eq. = 21367.52 g of CaCO, eq. 50000 L of water = 2.136 x 10” mg of CaCO, eq. or 7 LL of water = 2196* 10" og of CaCO, eg. 50000 = 427.35 mg of CaCO, eq. Hence hardness of water is 427.35 ppm. Ans. (b) (i) Characteristics of Good Fuel: (1) A good fuel should have a moderate ignition temperature. It should not be too high not too low. (2) Good fuel must have a high calorific value. (3) It should be cheap. (4) The moisture content in a fuel should be low because it reduces the combustion process of a fuel.176 Encweemne CHesustey (6) A good fuel must have low content of non-combustible material as the non-combustible matter is left in the form af ash which will decrease the calorific value of fuel, (6) If the rate of combustion is low, then the required high temperature is not possible, because a part of the heat liberated may get radiated, instead of raising the temperature, On the other hand too high combustion rates are also not required. . () The combustion should not be spontaneous one, it can cause fire hazards. (8) The combustion of a fuel should be easily controllable. (9) The fuel must be easy to handle, store and transport at a low cost. (10) Storage cost of fuel in bulk should be low. (11) The size of the solid fuel should be uniform so that combustion is regular (12) The fuel, on burning should not give out objectionable and harmful gases. (13) The gaseous products of a combustion should not pollute the atmosphere. (ii) Relative merits of solid, liquid on gaseous fuels: Gas Fuel S.No. | =" YSolid Fuel, 1. | Easy storage without risk Not easy Not easy and risky 2 ‘Thrust is low Thrust is moderate ‘Thrust is high 3. Ignition temperature is | Ignition temperature is Ignition temperature is high moderate low 4. | Low cost Depends on the fuel High cost 5. Rate of combustion It ean be controlled Itean be controlled can’t be controlled 6. | Theyarenot clean to | Very less ash Very clean to operate operate (iff) Nonconventional sources of energy: Nonconventional sources of energy are those sources of energy which are being continuously produced in nature and are nonexhaustable. These energy sources include solar energy, wind energy, biogas, etc. Solar energy can be directly converted intoelectricity by the use of photeelectric cell. Solar energy is used in 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 anerobic fermentation of animal water, like animal dung in presence of water this can be used in rural area since there we have largest scale of cattle population. The domestic energy needs in rural areas.can be met with biogas.180) Encieenme Cremtstiey 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 gaseous sodium [Na(g)] atom into gaseous ion. It occurs by giving one electron and the process is known as ionization. It is an endothermic reaction and for this reaction energy is known as ionization energy. Na(g) + &*" ——+ Na*(g) Energy required = Heat of ionization = + I. (c) Conversion of 1/2 Cl,{g) into Cl(g): 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 dissociation (D) of chlorine molecule. It is an endothermic reaction. ‘ $C) — Cl) Heat required = Heat of dissociation of ; Cl{g) molecule = + 5p. (@) Conversion of Clig) 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 converted into CI'(g). This energy is known as the electron affinity of chlorine is represented as E. This change is an exothermic reaction. “ Clg) +e° > Cg) Heat produced = Electron affinity of chlorine = - E (e) Combination of Na*(g) and CI-(g) ions to form NaCl(s): Na"(g) and Cg) ions formed in step (8) (d) combine together to form 1 mole of NaCl (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*(g) + Ch'(g)>———> NaCI) Energy released = Lattice energy of NaCK(s) = - U. The formation of NaCl(s) by the abave twe 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.Samp.e Examinarions 181 -Q24S41+5D-E-U Hence the lattice energy (U) can be calculated. Na(s) Fc.) ———— > naclis) [see 1 [steps Nai) cig) |see2 [sep Step 5 Nag + CIG) Born-Haber Cycle for the formation of NaC] crystal from its element. Ans. (c) SO, It’s hybridization sp? Itis trigonal planar in nature. ° l of “o PCI, It is sp" d hybridized. It has trigonal bipyramidal structure. cl cl cl Cl cl XeO,———> It is sp" hybridized. It’s shape is tetrahedral.Samer Examinanons = 183 CHEMISTRY-8 Time: 3 Hours Total Points: 100 Note: 1. Answer all Five questions. 2. All questions carry equal points. {PART—A) Q.1 Answer any twa of the following: (a) (f) How many NMR signals do you expect from each of the following compounds. Indicate alsa the splitting pattern of the various signals: (1) CH,OCH, (2) CH,OCH,CH, (ii) Define Infrared Spectroscopy. Describe the various molecular vibrations in the technique. Or What are the characteristics of polymer? Wiy do polymers have an average molecular weight? (b) Write short notes on Nucleic acid and protein, (c) What are the limitations of raw rubber? Explain the process of Visleanization of rubber. Ans. (a) (i) (1) CH,—O—CH, There are'six hydrogen and all are equivalent so one signal is obtained. eH hog 2) ¢H, —o—CH, —CH, There are eight types of hydrogen indicated as a, b,c. 4@ is having no neighboring hydrogen so one signal is obtained, b is having three neighboring hydrogen so four signals ate obtained, c is having two neighboring hydrogen so three signals are obtained.184 Enainterine CHemstey e3H pb i2H) Ans. (a) (ii) Infrared spectroscopy is one of the most powerful analytical technique which offers the possibility of chemical identification. It involves the transitions between the vibrational energy levels of a molecule on the absorption of infrared radiations Description of the various molecular vibrations in IR spectroscopy: (1) Stretching vibrations, in it bond angle remains constant but the bond Jength changes. It is of following two types: @ Symmetric stretching vibrations. It involves alternate stretching and compression of bonds in symmetrical manner. O=C=O ns O=C=0 — For example, in case of CO, molecule, the two oxygen atoms move away from or towards the central carbon atom without change in the bond angle. @ Asymmetric stretching vibrations. In it one bond is stretched and the other is compressed and vice-versa. This is illustrated below for CO, molecule; O=C=O0 O: Cc =0 O=C =0 0=C— a (2) Bending vibrations, in it bond angle changes but bond length remains constant. Bending vibrations can either take place within the same plane ‘or out of plane. Both are of two types. @ In-piane bending vibrations: (1) Rocking, involves the movement of aloms in same direction and (I!) Scissoring, in it two atoms joined to acentral atom move toward and away from each other with the change in bond angle.Samece Examinations 185 VVIVY treplane bending vibrations: in-plane borer vibrations @ Out-of-plane bending vibrations: (I) Wagging, in it both the atoms move up and below the plane with respect to the central atom (II) Twisting, it involves the movement of one atom up and the other atom down the plane with respect to the central atom. VV ‘Twisting Outot pone pending virations Qut-of-plane bending vibrations Inout-of-plane bending vibrations, the plus sign indicates motion from the page towards the reader, and the minus sign indicates motion away from the reader. All those vibrations which are accompanied with fluctuating dipole (and thus a fluctuating electric field) give rise to a absorption band in IR-spectra. These vibrations are also known as fundamental vibrations. Sometimes, overtone bands (harmonics) also appear in the IR-spectra at integral multiple of fundamental vibrations. Moreover, beats are also observed sometimes when two frequencies (viz. A cm and B em-') interact to give combination (A + B cm~) or difference (A ~ B em”) frequencies. For a same bond, stretching absorptions appear at higher frequencies compared to bending vibrations because the former requires higher energy.186 Encwernine CHEMISTRY Or (a) (ii) The characteristics of polymer: ™ Polymeric molecules are very big molecules. There average molecular weights may approach 10° or more, That’s why, they are also known as macromolecules. They are in fact, sub-microscopic particles. ™ Polymers are semi-crystalline materials. It means they have both amorphous and crystalline regions. In fact, polymers have regions of crystallinity, called crystallites, embedded in amorphous regions. Crystallites provide strength and hardness and the amorphous regions provide flexibility to the polymeric material. w The intermolecular forces in polymers can be van der Waals’ forces, dipole-dipole attractions or hydrogen bonding. The chemical, electrical optical, mechanical and thermal properties of polymers depend on (i) size and shape of polymers, and (ii) the presence ‘or absence of characteristic intermolecular forces. These parameters not only determine the properties of the polymers, but also the performance of these materials ina given applications. Polymers show time-dependent properties. They show “creep” (their most significant mechanical characteristic). @ Polymers are combustible materials. ™ Polymers have low densities and they show excellent resistance lo corrosion. @ Generally, polymers are thermal and electrical insulators. Polymeric materials are tailor-made and are easily moldable even into complex shapes with reproducible dimensions with a minimum of fabrication and finishing cost. Average molecular weight: Generally, a polymer sample contains chains of varying length and, therefore, its molecular mass is always expressed as average. In contrast, natural polymers such as protein contain chains of identical length and hence definite molecular mass. ENM Number average molecular mass = where N; is the number of molecules of molecular mass M,. Ans. (b) There are two types of nucleic acids. @ Ribose nucleic acid (RNA) @ DNA (Deoxyribose nucleic acid)Samore Businanions 187 R.N.As RNA Consists of ——+ Ribose sugar ——+ Base (Adenine, Guanine, Cytosine, Thymine) ——+ Phosphate unit D.N.A: DNA consists of ——+ Deoxyribose sugar ——— Base (Adenine, Guanine, Cytosine, Thymine} —— Phosphate unit Proteins: 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. <\t———— Peptide bond ‘O” H Il ted noi | —co0* KVR ALR polypeptide The are two broad classes of protein 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: @ keratin (which make up skin, hair, nails, wool, horn etc.) @ collagen (which make up tendons); 1 myosin (which make up muscle) and § fibroin (which make up silk). (ii) Globular proteins. This molecules are folded into spheroidal shapes in such a way that the liophilic 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 malecules are small and there are comparatively weak intermolecular forces. Hence, they are souble 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:Same Exammarions 189 Q.2 Answer any Four of the following: (a) Write the mechanism of the following: (i) Diels-Alder reaction ii) Aldol Condensation (8) (0) Explain why benzyl carbonium: ion is more stable than ethy! carbortitem fon (ii) What are Carbonium ions? Arrange the following according to increasing stability: (1) CH,CH,CH, CH, (2) (CHC (3) CH,CH,CHCH, (c) Arrange each of the following sets of ions in decreasing order as leaving groups in nucleophilic substition: () H,0, CHK 805. Cp on =o. (i) Ho, Ch, Br, CH,CH;, HO” (d) Write the two examples of optically active compounds without chirality. (e) Write short nofes on: (i) Meso compound, (ii) Racemization (A (i) Write E and Z configuration of the following compounds: (if) Assign R or $ configuration of each of the following compounds: quo i H-C—OH and Br—-—GOOH CH,OH H Ans, (a) (i) Diels-Alder Reaction. This reaction leads to the formation of cylclic unsaturated compounds. In this, the combination takes place when a conjugated hydrocarbon Diene combines with an unsaturated compound (Dienophile). This reaction is known as Diels-Alder reaction or (Dienl’s synthesis) known after the name of the scientist. Reactant should also be in proper orientation.Samere Examinanions 1917 (ii) Homolytic Mechanism: i CH, H [COOH HG; CHCOOH 1.2.3.4 tetra hydron | + — Phthalic acid cH CHCOOH H ‘CHCOOH (Adduet) ba Maleic acid CH, 2 Dienophile Butadiene qr cH, cH, CH CH *CHCOOH HC CHCOOH 1 — Ws —+ cH HCOOH H HCOOH I. 1 CH. ch, cH, > Butadiene Diene In homolytic mechanism double bond (=) of butadiene as well as of dienophile undergo homelytic bond fission, free electrons are present on all the carbon atoms. Ans. (a) (i) Aldo! condensation. Aldol reaction is given by those carbonyl compound which possesses a-H. The hydroxide ion (OH") abstracts thea-proton from carbonyl compound. It takes place in following steps: Step I: Abstraction of Proton. 8 CH,CHO+ OH ——+ CH,—CHO+ HOH | o® cued Step Ul: Attack of carbanion onto other carbonyl molecule. ° & @ I CH;—C—H + CH;-CHO ——+ CHG —CH-CHO HSame Examonarions 193 Ans. (0) () H,ODH,C. S>on-(C))-P > Ore (i) Br-> Cl’ > CH,COO > OH" > He Any group G is the good leaving group if its conjugate acid is stronger. Ans, (d) Hy HH, H CH, Ans. (¢) (i) Meso Compounds. It is optically inactive form due to internal compensation. It has more than one asymmetric carbon. For example, (##) Racemization. The process of formation of equimolar amounts of enantiomer is called racemization For example, ° OH OH CH,~C-H + HCN ——> Hy ~c- + u—d—cn, (enantiomers) CN CN194 Encivtening Cuemuster Ans. (f) () I He ut SY OH: © oO oH It is E, but I part is neither E nor Z. Ans. (f) (if) Making even exchanges ®cHo 2 1 a, | H—-C—OH —4 1-4 3 2 SCH,0H 3 4 ey R-configuration cl 2 a. iz) Br COOH — 1 3 H ta) 4 R-configuration Q.3. Answer any ttoa of the folowing: (a) (@ Explain why KCI-NaCl-H,O should be negarded as a three-component system whereas KCI-NaBr-H,O should be regarded as @ four-componcut system. (Gi) Find the number of degree of freedom in following systems. Name the oariables that could correspond to these degree of freedom: Water (Liquid) <=> Water Vapor and Water (liquid) =me Water Vapor at 1 atmospheric pressure (b) (i) Arrange the following compounds in the increasing order of their avidic character: HOC, HCI, HCIO,, HCIO, Explain your reasoning. (ii) List the Lewis acids and their Lewis bases from the following: BF, F>, AiCl,, NH, CH,OH, ZnCl.Saurce Exammanions 195 (©) (i) What is meant by rate of reaction? Explain the factors which affect the rate of a reaction. (ii) What is activation energy? How is the rate constant of a reaction ralated to its activation energy? Ans. (a) (i) Inchemically reactive systems, where various chemical reactions take place between the species, the number of component (C) is calculated by the relation: C=S-R @ where S is the number of chemical species present in the system, and R is the number of independent chemical reactions which the various species can undergo. When ions are present in the system than the condition of electroneutrality modifies the above equation as: C=S-(R+ 1) ii) Now the KCI—NaCI-H,0 system consist of six species: KCI, NaCl, H,0, K®, Na® and Cl°. Thus, S= 6 The number of independent reactions are two, viz. NaCl ===» Na®+Cl® KCl === K?+CP° Thus, R=2 As ions are involved, there is one more condition of electroneutrality. Thus applying eq. (i), we get, C=S-(R+1)=6-2+D=3 Hence, the KC] — NaCl — H,O system should be regarded as a three component system. However, in the second system, viz. KCI—NaBr—H.O there are nine species, viz. KCL, NaBr, H,0, K®, CI°, Na® + Br®, KBr, NaCl. Thus, $ = 9 The number of independent equilibrium reactions are four, KCI ae K?+C1° NaBr =m Na® + Br? K°+ Br° => KBr Na®+Cl° === NaCl; Thus, R=4-196 Encoeeerina CHemsriey Applying eq. (ii), we get C=S-(R+1p=9-(44 1) =4 Hence, KCI—NaBr—H,0 system should be regarded as a four component system. (ii H,0@) <= H,0() Degree of freedom =? Cel P=2 F=C-P+2 Degree of freedom =1-2+2=1 Qut of PT, concentration, only one can be varied. H,0() <== H,0(g) | atm pressure Here already one variable is fixed so we are not having any choice for variation, ie., Degree of freedom = 0. Ans. (B) (i) Increasing order of acidic character is: HOCI < HCl, < HCIO, < HCIO, Because the oxidation number of central chlorine atom increases in that order. With it, the electron pulling capacity of chlorine increases which makes the release of H* ion easier. Also HCIO, is maximum acidic in nature because its conjugale base ClO[ is more stabilized by resonance. or) q i i yt ees, COPS ra i) ‘oJ %o who oS, c — nA i Ne # Incase of C1O;, CIO3, CIO” only 3, 2, | resonating structures are possible.Samere Examinations 197 Ans. (b) (ii) Lewis Acid Lewis Base BF, F AICI, NH, ZnCl, CHO-H Ans. (c) (i) Rate of reaction: It is defined as the concentration change per unit time of the reactant or product. For example, 2A + 3B —— 4C | 1d{A]__ 1 d[B}_ 1 d[C] rate of reaction zat 3 dt 4 dt It's unit is —M2__ tt changes with time. (except zero order) Factor affecting rate of reaction (1) Concentation of reactant: If the concentration is high then rate of reaction is also high so initially rate of reaction is higher and it decreases with time. (2) Nature of reactant: Rate of reaction depends on the state of reactants and it also depends on the particle size. Smaller the particle size, larger will be its surface area and hence higher will be the rate of reaction. (3) Temperature: On increasing the temperature rate of reaction will increese whether the reaction is exothermic or endothermic because on increas- ing temperature collision frequency will increase. (4) Effect of catalyst: A catalyst can increase the rate of forward reaction as well as the backward reaction because activation evergy of forward as well as backward reaction is changed by equal magnitudes so net rate of reaction can’t be effected but catalyst can help in rapid attainment of equilibrium. Ans. (c) (if) Activation energy: It is the minimum amount of energy which is required tocarryout the reaction. Relation between activation energy and rate constant is given as, kes Ag ERT where = rate constant A = Pre-exponential factor R= gas constant E, = Activation energy T= Absolute temperature198 — Encieeninc Cremstey Preceding equation is said to be Arthenius equation E, Ink=iInA- Ink= In A~ oe Q.4 Answer any two of the following: (a) (a State the zeotite process for the removal of hardness of voater. (ii) Calculate the amount of lime required for softening 50,000 liter of hard water containing: CaCO, = 25 ppm, MgCO, = 144 ppm, CaCl, = 111 ppm, MgCl, = 96 ppm, Na,SO, = 15 ppin, FeO, = 25 ppm, (b) (i) Discuss the classification of fuels. (ii) What is the chemistry involved in smog formation? (c) (@) What meant by ealorific value of a sample of coal? Distinguish betuven gross and net calorific values (ii) A sample of coal contains C = 93%, H = 6% and ash = 1%. The following data were obtained when the above coal was tested in bomb calorimeter: (a) Weight of coal burnt = 0.92 (b) Weight of water taken = 2200 ¢ (c) Water equivalent of bomb calorimeter = 550 ¢ (d) Rise in temperature = 2.42°C (e) Fuse wire correction = 10.0 cal (f) Acid correction = 50.0 cal Calculate gross and net calorific values of the coal, assuming the latent heat af condensation of steam as 580 cal/g. Ans. (a) (i) Zeolite or permutit process: Zcolite process involves softening of water by a natural or artificial zeolite. Zeolite is hydrated sodium aluminium silicate. Na,O. ALO, . $i,0, . H,O. Zeolites are the substances insuluble in water and can act as ion exchanger when placed in contact of water containing cation. Zeolites are also called permutit. The zeolite softeners consists of a steel tank placed with zeolite over a layer of sand gravel. The water enters at the top and passes through bed of zeolite, where following reactions occurs. Na,Z + Ca(HCO,), — CaZ+2NaHCO, Na,Z + Mg(HCO,), ——» CaZ + 2NaHCO, Na,Z+CaCl,———+ CaZ + 2NaCtSamne Exammanrons 199 Na,Z +CaSO, ——> CaZ + 2Na,SO, Na,Z + MgSO, ——+ MgZ + 2Na,SO, Na,Z.+ MgCl, ——> MgZ + 2NaCl where Z = ALSi,O, .xH,O 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, if it loses its softening capacity, it can be regenerated by passing 10% solution of sodium chloride solution through it. The following reactions take place. CaZ + NaCl —_ Na,Z+CaCl, (Exhausted (Regenerated Zeolite) Zeatite) MgZ + 2NaCl ——+ Na,Z + MgCl, Ans. (a) (ii) S.No.| = Amount (ppm) “| + CaCO, eq, (ppm 1 2 3 2. ua 146x100 Lana Ba 3. CaCl, m THX 100 _ 100 ML Lime Required (in CaCO, eq.) = (25 + 171.4 + 100) for MgCl, = 296.4 ppm . 296.4 Lime required = Fp 7Ams/L = 219.336 mg/L200 — Encweernc Cremester For 50,000 liter, lime required = 10.97 kg Soda Required (in CaCO, eq.)= 100 (for CaCl) 100 Soda required = jpg * 106 mg/L For 50,000 liter water, soda required = 106 x 10° mg = 10.6 kg For Mg(HCO,),, lime required is double but for MgCO,, lime required is not double as Mg(HCO,), + 2Ca(OH), ——+ Mg(OH), + 2CaCO, +2H,O MgCO, + Ca(OH), ———-+ Mg(OH), + CaCO, Na,SQ,, Fe,O, do nat impart any hardness. Ans. (b) (i) Classification of chemical fuel. Classification af chemical fuel can be done tion is done on the on the basis of their occurrence and further classifi basis of state of aggregation Chemical Fuel ‘Secondary or Derived Primary or Natural ‘On the basis of ‘On the basis. state of aggregation state of aggregation Solid Liquid Gas Solid Liquid Gas (wood, (crude cil) (Natural (Charcoal, (kerosene, (Water gas, coal, dung) gas) coal, coke} gasoline, etc, coal gas, ete.) diesel oil) Ans. (5) (ii) Smog formation: Smog which describes the “Smog fog” like conditions are best known examples of air pollution that occurs in the world. There are two types of smogs: Photochemical smog: tt occurs in warm climate and result from action of sunlight on the nitrogen oxide and hydrocarbons which are produced by automobile exhaust and result in formation of oxides of sulfur. Formation of photochemical smog: At high temperature in the engines N, and O, react to form NO. This NO jis oxidized in air to NO, which in turn absorbs energy from sunlight and breaks up into NO and nascent oxygen atom.‘Sauer Exammnarions = 207 NO,(g} “3 NO(s} + OW) QOatoms reacts with O, to form O,, Og) + O,{¢) —— Ofg) O, reacts with NO to form NO, NO +O, ——> NO, +0, O,and NO, acts as oxidizing agent and they react with hydrogen to produce: formaldehyde, acrolein, peroxyacetyl nitrate (PAN) that cause water in eyes and harmful for respiratory system. 0 i CH=CH—CHO CH,—C—O—O—NO, H——H Acrolein i Formaldehyde Peraxyacetyl Nitrate (PAN) Efforts have been made to control this problem by using catalytic converters in the automobiles which prevents the release of nitrogen oxide and hydrocarbon to atmosphere. Ans. (c) (i) 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 15°C or 60°F. When the fuel containing hydrogen is burnt, the hydrogen present in the fuel produce steam. If the products of combustion are condensed to 15°C, the latent heat of condensation of steam is also included in the measured heat. This is called higher or gross calorific value. Net calorife value: Net calorific value is the net heat produced when unit mass 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 x latent heat of vaporization of product. H, + 0, —— HO Br 6g. 18g Ig By ogSameue Examanions 203 (ec) (i) Write skort notes on the following: (0) Chelating complexes, ()) Crystal field stabilization energy (c) Coordination spheres ii) Give IUPAC names of the following: (a) [Co(NH J,CHCT,, (8) (CoSOANH,),INO, (0) KANWCN)), (a) (PUNE), ICI, (e) LILAIA, I. Ans. (a) (i) Molecular orbital diagram of Oxygen: 2 ols AG MO AO Molecular obrital configuration = o Is?, ot 1s? 0 2st, 0 2s?, 6 Op,2, np? = 2p, 2p,! = Rt Op! It is having two unpaired electron so it is paramagnetic in nature.Samrur Exammanions 205, Ans. (b) (i) NO, OH NO, OH p-Niteophenol @-Nitrophenol p-Nitrophenol is more soluble in water because it can have intermolecular H-bonding while in case of o-Nitrophenol only intramolecular H-bonding is possible. x a oO Ans, (b) (ii) Intermolecular and intramolecular H-bonding: Intermolecular H-bonding means that H-bond is formed between two molecules while in case of intramolecular H-bonding means that H-bonding is existing within a molecule. O90. Pee H a N SW fo WW ° AM iteceeeeeeee of So {Intramolecular H-bonding) {Intermolecular H-bonding) Ans. (c) (i) (a) Chelating Complexes. The multidentate ligands form complex with metal ion by surrounding them like a large claw of a crab grasping its prey. The technical term for such a complex is chelate, which comes from the Greek word meaning a pincerlike claw. The chelating complexes are more stable than other coordination complexes. The great stabilily undoubtedly results from the severalSamote Exasuanions 207 CHEMISTRY-9 Time: 3 Hours Total Points: 100 Note: 1. Answer all Questions. 2. All questions carry equal points. Q.1 (a) (i) With the help of Molecular orbital theory, explain the paramagnetic character of oxygen and diamagnetic character of nitrogen. (if) Calculate the Bond order of N3,CO, NO and OF (iii) On the basis of hybridization, discuss the geometry of water molecule. (iv) What is a metallic bond? Expiain it in terms of Electron sea theary and Resonance theory. (v) Explain why metals are malleable and ductile? Or (©) (#) Derive Bragg’s equation for diffraction of X-rays by crystals. (i) Derive an expression for the density (p) of a cubic crystal. (iii) Write short note on fullerenes, indicating the method of preparation, properties, and their applications, (iv) The density of NaC! is 2.163 gfcac. Calculate the edge of its cubic cell, assuming that four molecules of NaCl are associated per unit cell. Ans. (a) (i) Molecular Orbital Diagram of Oxygen: Molecular orbital configuration a1s*, o* Is*, a” s%, 0° 2s*, 2p?, 2p? = n2p?, Rt 2p, = nt pe! , Bond order = Bete Where N, and N, are number of bonding and antibonding electron - Wet 2 2 It is having two unpaired electron so it is paramagnetic in nature.208 — Excweemnc Cupastey 0-918", 28'2p" 18° 1s° AO MO AO Molecular Orbital Diagram of Nitrogen: Molecular orbital configuration of N,=01s?, a*1s*, 02s? ,o* 2s, 02p?, n2p? =n 2p? It means that the two nitrogen atoms are bonded with three cavalent bonds ie., a triple bond. N, molecule has no unpaired electron. So, it is diamagnetic in nature.‘Samore Exasunations 211 In case of metal there is transfer of electron from highest occupied conduction band to lower unoccupied valence band, or there may be overlap of valence and conduetion band. In this case metal works as excellent conductor e.g., In magnesium 3s band (conduction band) is fully filled but 3p band (valency band) overlaps it. So it act as a excellent conductor. 1. Classical Free Electron Theory or Electron Sea Theory: All the atoms in a metal have several unoccupied electron orbilals in their outer shells. Due to the low ionisation energies of metals they have a tendency to lose some of their valency electrons and form positive ions called metal nuclei. The nucleus of the metal atom exerts an attractive force on several adjacent charge clouds. This force of attraction between the metal atom and all the electron under ils influence is called metallic bond (figure). Mobile electrons. Positive Matal cores r Valence Bond Approach (Resonance Theory): An allernalive view of the metallic bond, on the basis of valence bond theory, was developed principally by Pauling. Considering any atom of a metallic crystal, it has go a covalent bonding with its one neighboring atom by mutually sharing an electron each. But this bond is not permanently held between these two atoms, instead it is continuously in resonance. At one moment it was in between above said twoatoms, at second moment one of the atom is already shared by other neighboring atom. At the third moment , same atom is having its bonding with any third neighboring atom. Let us take the example of lithium in which each lithium atom has eight nearest neighbors and one valency electron.212 Enciceeninc Crenstiey Li-Li Li-Li i-Li Li-Li Li-Li Li-li Li-li li-Li t il mL Ww Li-li Li-Li vi ‘Ans. (a) (0) Metallic bond results from a detocalized covalent bonding by the overlap of the vatence orbitals between nearest neighbor atoms. Thus, metallic crystal lattice consist of pasitive ions called kernels, permeated by a cloud of valency electrons called electron gases as shown in the following figure. The binding force is attraction between kernels of atoms (atom minus valency electrons) and the electron cloud. In other words, all valency electrons belong, to the crystal as a whole. These electrons are free to migrate throughout the crystal lattice, thereby giving rise to high electrical conductivity to metals. The high reflectance of metal arises, due to the ease with which the free electrons get accelerated by high frequency radiations and then, radiate immediately, virtually all the energy of the incident radiation absorbed. Thus, metais are characterized by properties such as good thermal and electrical conductivity, a bright appearance called metallic lustre, high maileability, ductility and (ensile strength, Ans. (b) (i) The horizontal lines represent parallel planes in the crystal structure, separated from one another by the distance d. Suppose a beam of X-rays, falls on the crystal at glancing angle 0, as shown. Some of these rays, will be reflected from the upper plane, at the same angle @, while some others will be absorbed and get reflected from the successive layers, as shown. Let the planes ABC and DEF be drawn perpendicular to the incident and reflected beams, respectively. The waves reflected by different layer planes will be in phase with one another (é¢., will coincide with one another in the plane DEF) only if the difference in the path lengths of the waves reflected from the successive planes is equal toan integral number of wavelengths. Drawing ‘OL and ON perpendicular to the incident and reflected beams, it will be214 Encineerine Cuenustey Then, volume of a unit cell =a" mass of the unit cell = (number of atoms in the unit cell) x (mass of each atom) =nxm but mass of an atom present in the unit cell (m) at Na Therefore, density of the unit cell of a cubic crystal (4) mass _of unit cell volume of unit cell _ xm _n(M/Nq) = oem MN) Ans. (b) (ii) Fullerenes: Fullerenesare group of polymorphic form of pure carbon compounds, whose diserete, molecule consists of a hollow spherical cluster ofa large number of carbon atoms. Each molecules is composed of a groups of carbon atoms that are bonded to one another to form both jexagon (six-carbon atoms) are pentagon (five-carbon atoms) geometrical configurations. One such molecule (see in figure} is found to consists of 20 hexagons and 12 pentagons, which arearrayed such that no two pentagons share a common side; the molecular surface thus exhibits the symmetry of a soccer ball. This material composed. of C,, molecules, is known as Buckminister fullerene after R, Buckminister Fuller, who invented the geodesic dome, in 1985, each Cy. is simply a molecular replica of such a dome. Fullerene-20 (C,,) is the smallest number of carbon atoms containing fullerene. It has been prepared synthetically. Other members isolated are Cage Cone Cope Cage Cay Cop ete Also it is thought that giant fullerene with at Teast 6000 C-atoms seems to form.Sameue Examinancons = 2175 Pemagon Structure of Buckminister’s fullerene (C,,) molecule Sree Molecular shapes other than the ball clusters have been discovered. These include nanoscale, tubular structures. Preparation of Fullerenes: () When carbon is struck under argon (0.05 to 0.1 atm pressure), a dust containing 5-15% fullerenes. On extracting this black soot like dusty material with solvents or by sublimation, fullerenes mixture can be obtained. Then, individual fullerenes can be separated by chromatographic techniques using alientina-hexane. (ii) Up to4% fullerenes containing soot can be prepared from benzene-oxygen combustion flame in a carefully diluted argon atmosphere. Properties of Fullerene-60: (2 It is mustard colored solid, which appears brown to black with increasing thickness of its film. (ii) It is moderately soluble in aromatic hydrocarbons (eg., 1 ¢/Lin tluene), giving magenta coloted solutions. (ii) On sublimation, it forms translucentmagneta face-centered cubic crystals. (iv) Asa pure solid, fullerene-60 is ctectrically insulating. However, with proper impurity additions, it can be made highly conductive and supe- reonductive. (v) By using, proper chemical reaction, additives of C,, can be obtained. For example, Cy, (anion), ¢.g-, Cjg(CHy),, (1 = upto 24); Cy, F, (it > 36):C,,0, ete. (07) On reaction with good inorganic vlectron donors {e.g., alkali metals) electrical conductivity increases several times. Stoichiometry of a superconducting216 Encmeermc: CHemesay alkali fullerides is M,Coyg. The T, (the superconducting transition temperature or critical temperature) of these alkali fullerides increases with the size of alkali metal. Thus, Ty values for K;C,y, Rb,C,y and Cs,PbCS,9 are 19 K, 28 K and 33 K respectively. T, of < 10 K has been reported for Ca,Co,g. Applications: Possible applications of fullerenes are in: (i) Preparation of superconductors (if) Electronic devices (iti) Microelectronic devices (iv) Non-linear optical devices (v) Batteries as charge (vi) Preparation of soft ferromagnet with zero remanence etc. z.M Ans. (b) (iv) a Na 2163 = 4x585 -, - 4585 6023 x10" x! 6.023 x 10"* x 2.163 or 125.6% 10% em Hence, 1=5.6 A, Q.2 (a) (i) What are the basic principles involved in infrared and }H-NMR spectroscopy? (ii) A gaseous hydrocarbon ‘A’ on passing through a quartz tube heated at 600°C, gave a liquid compound “B’ (Molecular weight: 78.armu). The jatter compound was found to undergo electrophilic substitution reactions. It gave the following physical data on analysis. The IR spectrum showed a characteristic absorption band at 3040 em™ and a UV absorption, due ton - x* transition, at 204 nm (log e' 3.84). The “H-NMR spectrum displayed a downfield singlet (6H) at 7.3 t. Identify the compound ‘A’ and ‘B’ and give your reasoning. (b) (i) Suggest a process that would cause the break up of a condensation polymer (Say, Nylon 6, 6) by essentially reversing the condensation provess. (ii) Why low density and high density polythene differ in density? (iti) Why is teflon highly chemical resistant? (iv) What is copolymerization? Gioe one example. (e) Name the type of polymerization and the method by which conducting polymers can be synthesized. Give examples of such polymers, including their applications.Samore Exasunations 217 Ans. (a) (i) Infrared spectroscopy is one of the mos! powerful analytical technique which offers the possibility of chemical identification. Il involves the transitions between the vibrational energy levels of a molecule on the absorption of infrared radiations. Description of the various molecular vibrations in IR spectrascopy: (A) Stretching vibrations, in it bond angle remains constant but the bond jength changes. It is of following two types: m1 Synumetric stretching vibrations, iL involves alternate stretching and con pression of bond in symmetrical manner. O=C=0 o==c=—0 — —> +#— For example, in case of CO, molecule, the two oxygen atoms move away from or towards the central carbon atom without change in the bond angle. § Asymmetric stretching vibrations, in it one band is stretched and the other is compressed and vice-versa. This is illustrated below far CO, molecule: O=-C=0 O=—=C=O O0=C=0 ee (B) Bending vibrations, in il bond angle changes but bond length remains constant. Bending vibrations can either take place within the same plane or out of plane. Both ate of two lypes. tt In-plane bending vibrations: (I) Rocking, involves the movement of atoms in same direction and (II) Seissoring, in it two atoms}oined te a central atom move toward and away from each other with the change in bond angle. VVIV V ‘Scissoring in-plane conden vibrations In-plane bending vibrations‘Saupe Exammarions = 219 of NMR absorptions which arise due to the shielding or deshielding of protons by the electrans are known as chemical shifts. The chemical shift is affected by following factors: ® Inductive effect Van der Waals, deshielding Space or anisotropic effect. Hydrogen bonding Tocarry out NMR studies, the compound under investigation, which i a pure liquid or a solution in a non-protonie solvent, is mixed with a small amount of tetramethyl silane (TMS) and the spectrum is recorded. Because the varis in ficld strengthis very slight, so these are not measured in actual magnetic units, but with reference to the resonance conditions for an arbitrary standard tetramethyl silane Si(CH,),, ie., TMS. This compound has been chosen as standard, because W It is miscible with almost all organic substances. '§ It does not take part in intermolecular association with the sample: her @ It has twelve equal protons and hence has a single peak. W IL is highly volatile so il can be readily removed from the The spectrum shows an absorplion for TMS at a magnetic flux density, Bctandara) And for a particular proton in the compound at say By sygjo- THUS, the chemical shifts is given by: stem, AB=B, B, Yaaryple B, = Magnetic flux density (standard) 7 In other words, the difference in the absorption position of the proton with respect to TMS signal is known as chemical shift (5-value). The assigning value (8-value) for TMS is equal to zero. ™s ‘Highly shietded-signals uptielet220 Ans. (a) (fi) The compound B shows a characteristic absorption band at 3040 cm Encinernunc CHenustaey In other words, the position of the peaks in an NMR spectrum relative to the reference peak is expressed in terms of the chemical shift, which is defined as, 5 = Horeference) - Ho (sample) 15 Hg (reference) Ppa The value of H, for the reference is usually greater than Hy for the sample, so subtraction in the direction shown gives posilived. In terms of frequency unil, 5 lakes the form, sample) - v (reference) 2 (reference) The chemical shift is dimensionless and expressed in parts per million (ppm) on account of the factor 10° in the above equations. An alternative system, which is generally used for defining the position of the resonance relative to the reference is assigned tau (t) scale. On this scale, the reference is assigned the arbitrary position of 10 and the values of other resonances are given by t=10-6 where 6 has the same significance. «10° ppm in IR spectrum indicating the presence of aromatic C—H bond and UV absorption band due to x - x* transition at 204 nm indicates conjugation in compound ‘B’. The 'H-NMR spectrum shows singlet due to 6H indicating all six hydrogen as equivalent protons. From the above data the compound may be aromatic having six equivalent hydrogen. This compound undergo electrophilic substitution reaction. On the basis of its electrophilic substitution properties the compound may be benzene which is confirmed by its molecular weighti.z., 78 amu. Hence the compound ‘B’ is benzene (C,H,). The component ‘B’ iv., benzene is formed from compound ‘A’ an hydrocarbon. It is known that acetylene (C)H,) on passing through a quartz tube at 600°C forms benzene. Hence, the component ‘A’ will be acetylene (C,H). So, the component is acetylene (C,H,) and component B is benzene (C,H,)- Ans. (5) (i Hydrolysis in the presence of base or acid as catalyst is a process that would cause the break up of a condensation polymer (say Nylon 6, 6) by essentially reversing the condensation process.Sawrte Examinations 221 H H H H | Il. | | EICH EN ACH NE CH, WENCH N= [Hout rH) i 4 i EACH FN ACH ANI 1 + HO-P{CH-f—N1Ch 1,),—-N=~ ° 3 oO o Itistobe noted that one of the acid and the amine produets will be obtained as its salt, depending upon the acidity or alkalinity of the medium, NaOH ie, —-COOH ——— —~ COO-Na* Hct . and ~-NH, ——— ~-NH,°CI Ans. (b) (ii) High density polythene has almost perfectly linear structure and therefore it can be obtained ina highly crystalline state (80 — 85% crystallinity) with high density. Incentrast, low density polythene has number of short chain and long chain branches, so it cannot be oblained in a highly crystalline state (il is just 53% crystalline). Thus, its density is less. Ans. (b) (iff) Teflon (polytetrafluorcethylene) isa highly polymerized of tetraflucrvethy? gas, CF,=CF, which is prepared as ie CHCl, ——+ CH.F,.Cl——+_ CF, =CF, (Chioroferm Difluoromone Huaroctlione: Chivromethame Polymerization of tetrafluoroethylene is carried out in presence of water, at elevated pressure of 68 kg /m?, temperature form 55°C 10 240°C in corrosion tank in presence of an aqueous alkali medium, benzoyl peroxide, persulphates, H,O,, etc. are used as catalysts. ii Li n + CC i I | FOF FOF Tetrafluorvethylene Teflon222 Emcinceninc CHemstrer Teflonis a highly crystalline polymer. If softens al 327°C and decomposes at about 400°C (without charring) into volatile vapor. Teflon has great resistance tochemical attacks of strong alkalies, acids like HCI, HNO, aquaregia (HNO, +3HCl), hydrofluoric acids. Only alkali metals either in molten or dissolved in liquid ammonia altack the Polymer. Highly chemical resistant properties of teflon (CH,=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 extreme toughness, high softening point, exceptionally high chemical resistance towards all chemicals. Ans. (b) (iv) Homopalymer and Copolymer: When polymer is formed by combination of one type of monomer then it is said to be homopolymer, iw., {A~A). eg. n CH=CH, —— (—CH,—CH,), ethylene polythene If polymers are formed by combination of more than one type, then it is called copolymer, iv., (A-B). CH=CH, CH=CH—CH=CH, + Butadiene Styrene Na — (cn scrcrcn—cnce, | BUNAS " Ans. (5) (v) Conducting Polymers: A polymer which conduct clectricity is termed as conducting polymers. Most polymeric materials are poor conductor of electricity, because of the non availability of large number of free electrons in the conduction process. Conducting pelymers are synthesized by electrochemical polymerization, AO.1 M aniline hydrochloride solution is made in 1.0 M aqueous HCL. To this, an aqueous solution of 0.1 M ammonium persulphate, (NH,);,0, is slowly added with stirring. Polymerization reaction is exothermic and hence the temperature rises. To maintain the polymerization temperature of 3 - 4°C, the reaction vessel is placed in an ice bath for one to two hours with constant stirring, During the polymerization, color changes in the following sequence:224 — Ewcmerainc Cuemstey Applications of Conducting Polymers Some important applications ef conducting polymers are as given: (i) Used in rechargeable lead-acid battery in automotive (ii) Used for making sensors for pH, O,, NO,, SO, NH, and glucose as ana- lytical sensors (iii) Used in optically display devices based on polythiophene (iv) Used in solar cells () Used in photovoltaic systems (vi) Used in electronic devices such as transistors and diodes (vii) Used in telecommunication systems (viii) Used in wiring in aircraft and aerospace components (ix) Used in antistating coatings for clothing. Q.3 Write the mechanisms of any two of the following: (a) (i) Aldol condensation, (ii) Beckmann rearrangement. (iii) Cannizzaro reaction. (iv) Diels-Alder reaction. (o) Hoffinann rearrangement. (8) (i) Discuss the terms: Carbocations, Carbanions, Free Radicals, Electrophilic reagents, and Nucleophilic reagents. (ii) Write short notes on: E, Z Nomenclature and conformation of n-butane. Ans. (a) (i) Aldol condensation: Aldol reaction is given by those carbonyl compound which possesseso-—H. The hydroxide ion (OH") abstracts thea-proton from carbonyl compound. It takes place in following steps: Step I: Abstraction of Proton. CH, CHO+OH ——> oe + HOH candSamrue Exainanions §=225 Step Il: Attack of carbanion on to other carbonyl molecule. oF Il 6 I CH,—C-H +CH,—-CHO ——> CHP CH CHO H Step IL: Transfer of proton from solvent. i e CH;—C—CH,—CHO + H,0. ——> CH —t—CH-CHO +OH H H {aldehyde + alcohol) aldol Step IV: Condensation: oO I CH,-C—CH,-CHO —— CH,—CH=CH—CHO + H,O i (a, P unsaturatedaldelyde) But-2-2r-t-al ‘Ans. (a) (i) Beckmann Rearrangement. When ketoximes and aldoximesare treated with acidic reagents like cone. H,SO,, PCl,, P,O, SOCL, etc, they rearrangements to forma corresponding amide. This is known as Beckmann rearrangement. RL, (i) SOC, ether ll c=N RC HNIIR RY Non (ii) Water Ketoxime Amide Mechanism. The mechanism process in following manner: R + OR Noe H Natt ow. e BR SN ape IR CNR oR Ce) R ‘OH R" ou, Carbonium ton Ketoxime Protonated oxime |e oe R-G-NHR <— RU-CSNR «1 [R—C=NR o OH OH, ® Amide ‘enol form226 = Encineernc CHemistay Ans. (a) (iif) Cannizzaro reaction: This reaction is given by those carbonyl compound which does not have a-H. In presence of OH, one molecule is reduced and other is oxidized oH 2HCHO » HCOO” + CH,OH coo? CH,OH HO . or OH 2 a, + Salt Alcohol Mechanism R i HC + Of + He OH eo ° nd Hogan Hatters yp don endo i Rate determining On H ll fe HOC + cHOH CES Proton ‘Ans. (a) (iv) It is the 1, 4-addition of an unsaturated compound across a conjugated diene. For example: HO=CH cH, HC—CH,—CH, 2 + 1 2 100°C 1 2 HC=CcH, CHCHO HC—CH,—CH.CHO Batael, diene Propenal Tetrahydro benzallehyde (Adduct) or in general: HC=CH, Hy HC—CH,—CH, + _— HC=CH, CHR HC—CH,—CHR ‘Conjugated diene Alkene (Adduct)Sampue Examinanions = 227 HC=CH, cH HC—CH,—CH and | ~ fi a i HC==CH, CR HC—CH,—CR Dienophile (Adduct) The dienophile should be substituted with clectron-attracting groups such as —COOR, —CN, —CF,, —NO, to enhance its reactivity. Alse the conjugated diene should have cis-configuration, For examples: HC=CH, HE COOMe CH—CH,, 14 + i — ‘NI HC=cH, HC COOMe HC a ina Yad toome COOMe cis-adeuet Mechanism: Both diene and dienophile undergo electromeric shifts simultaneously, thereby producing their respective excited state. Then, these excited states condense forming and adduct in 14-positions of the diene. For example, We, mene, — [leet en HC=2CH, shifts HC—CH, o Excited state of diene d : He ™~ Elsctromeric cHCOm HCte-~ shifts cH—co-— Excited state of dienophile Maleic Anhydride Dienophike HO=CH, Cycom, stow, | MG—CH—OH-CON To. Stow, HC=CH, CH—CO- HC—CH,—CH—CO-~ HC—CH,—CH—CO Fast iz ~~ Om, — i I or ‘Oo HC—CH,—CH—CO. - Oo Tetrahydrophtalic anhydride (Adduct)228 — Eneineening CHemister Ans. (a) (v) Hoffmann Rearrangement: Amides of fatty acids when treated with bromine and caustic soda (10%), primary amines free from 2° and 3° amines are formed. This is known as Hoffmann rearrangement. RCONH, + Br, + 4KOH——>» RNH, + 2KBr + K,CO, +2H,0 Amide T-amine Mechanism. The mechanism may be represented as: Br, + KOH ——» KOBr + HBr 0 0 . 0 ree 4 ope a rc® on, pict AIH, ‘ “gar [ne Amide Hypobromite N-Bromamide ion « Rent—c=o #2 jReN=CHOeoR-A-Cao} Sea OH Isocyanate Carbamic acid R-NH, + CO; Tamine Ans. () (i) Carbonium Lon: Carbon having positive charge is called carbonium ion. It is three types, i., 1°, 2°,3°. CH, CH, a cH.—CH,, — che” H H It is planer in shapoe with sp* hybridization. Stability order is 3° > 2° > 1°, 3° carbocation is more stable because charge dispersion in 3° is more due to attachment of three electron donating group. ‘Carbanion: Carbon having «ve charge is called carbanion. It is three types, ie. 18,27, 3Saspie Examinations 229 oe oe CH,-CH,, cH, cH? H cH, Stability order is 1° > 2° >3°. Three electron donating groups are linked in 3° carbanion and which are increasing the charge and hence it is less stable. Free Radicals: Species having non bonded electron called free radical. Nis also of three type. It is formed by Homolytic fission. CH,—CH,, CH,— cH,-¢ Stability 3° > 2° > 1°, 3° is more stable due to hyper-conjugation. Electrophilic Reagents: The reagents which show attraction towards electrons are called electrophilic reagents or electrophiles (electro = electron, philic = loving). These reagents are short of a pair of electrons as compared to the stable ones. These reagents are of two types: (a) Positive Electrophiies: These are deficient in two electrons and carry a posi- tive charge, e.g., R-CH} (carbonium ion),: Br? (bramenium ion), H" (hydrogenium), H,O* (hydronium), NO} (nitronium ion), SO,H* (sulphonium ion), NO* (nitrosonium ion) etc, (b) Neutral Electrophiles: In these the central atom has six electrons but has no charge, e.g., BF, (boron trifluoride), AICI, (aluminium chloride), SO, (sulphur dioxide), > C = O (carbonyl group), ZnCl, (zine chloride), 2 id chlori . Ro (acid chloride) ete aes € (+) . () Boron trituoride ‘Aluminium chionde230 Encoverainc Cuenstey Both types of electrophiles can attack the ion or molecule which is electron rich. Nucleophilic Reagents: The reagents which show attraction towards nucleus are called nucleophilic reagents or nucleophiles (nucleo = nucleus, phili loving). Since the nucleus is positively charged, these reagents will be negatively charged or electron rich substances. These are of lwo lypes (a) Negative nucleophiles (Anions): These have an excess of electron pair and carry a negative charge. For example, i R-C! (carbanion), OH (hydroxyl ion), X (halide ion), H CN" (cyanide ion), RO= (alkoxy ion) (6) Neutral nucleophiles: These posses lone pair of electrons but no charge. H—N: (ammonia), H—-G—H (water), R-G—H (alcohol, xmi—2-= R—G-R, (ether), Hi (amine) H Ans. (0) (ii) E and Z System of Nomenclature: li four different atoms or groups are attached to the carbon atoms af adouble bond, thencis and érms designations cannot be employed. ens I) a—n—n In such cases, Cahn, Ingold and Prelog developed E and Z system of nomenclature, which is based on a priority system. In this system, the two. atoms / groups attached to each carbon atom of the doubly bonded carbons are put in order of precedence based on sequence rules. (i) The symbol ‘E’ (from German word Entgegen = across or opposite) is assigned to the isomers in which the atoms/groups of higher precedence are on the opposite side.Samere Exanmanions 231 (ii) The symbol ‘Z' (from German word Zusammen = together) is assigned tothe isomer in which the atoms / groups of higher precedence are on the same side. Thus: 1 2 11 dad c= tod ot 201 22 Etsomer 2 isomer 1. signifies higher precedence. 2. signifies lower precedence. In large number of cases, E isomer is trans; while Z isomer is cis. However, there are many exceptions also. Sequence Rules: (i) Higher the atomic number, higher is the priority assigned to the atom. For example: Precedence order: | > Bro> c > H (di) Incase of groups, the precedence order is decided on the basis of atomic number of first atom of the group. For example: Precedence order —Cl>— SO,H>— OH>— NHCH,>— COOH t t tT T T At. no. of first 7 16 8 7 6 atom (iii) Tf the precedence order of groups cannot be settled on the basis of atomic number of first atom, then second atom or the subsequent groups are considered. For example : Precedence order —COOH = >—CH,—CH, >—CH, Conformational Isomers of n-butane: 1CH, | * n-Butane 3CH, fe232 © Encinvena ChexusTay n-Butane has free rolation about C,—C, o-bond. Different conformers of n-butane are as follows: 1 is called as Anti form, Ill and V are called as Gauche form, IV is completely eclipsed form II and IV are partially eclipsed form: energy order is: T _M* +ne~ aqueous Fe(s) —> Fe* +20 sles Fe** + 20H” ——> Fe(OH), AKHHEOMS aammean This continues as long as electrons and ions are removed from the environment. If they are not removed the corrosion will not proceed further. (b) Cathode reaction: The electrons released al the anode are carried tocath- odes and are responsible for following reactions: (i) Hydrogen electrode or hydrogen type carrosion:1n acidic solution, the 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, T 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——s MP + 20° The overall reaction can be written as M + 2H" ——+ H, + M+ Example: Copper corrosion in acidic solution consists of two half cell reactions. Cu—— Cu* + 2e" Anode reaction 2H" + 2e°-——+ H, Cathode reactionSamece Exasunarions 237 (ii) The Oxygen electrode ar Oxygen absorption: Hydrogen ion H* concentration is very low in neutral or basic solutions, therefore evolution of hydrogen gas is not favorable. In such cases reduction of ‘oxygen to hydroxyl ion occurs. O, +2H, 0+ 4e 24 OH Example: The corrosion of iron occurs by oxygen in the presence of aqueous solution. Al the anode ion dissolves to form ions as Fe Fe” +207. At cathode, the electrons evolved by above reaction will be accepted by oxygen itt presence of water 1 de +5 O,+ Hy O— 3 2011" (Cathode reactions) Overall reaction will be, Fe+ + O, + HO—— Fe** + 20H” The Hydroxy! ion OH” produced, reacts with the post Fe®* ion forming Fe(OH), (rust). Fe** + 20H —— Fe(OH), rst ely charge The corrosion proceed as long as oxygen is available. This type of corrosion is known as oxygen type corrosion. Therefore the essential requirement of electrochemical corrosion are: (1) Formation of anodic and cathodic areas. (2) Electrical contact between the cathodic and anodic parts. (3) An electrolyte through which +ve ions can diffuse. Ans. (a) (iii) When metallic surface is partially immersed in.an electrolyte and partially exposed to air. Poor oxygenated metallic part becomes anodic and undergoes oxidation Zn——> Zn** + 2e° Oxygen rich metallic part becomes cathodic, At the cathode, O, takes up electrons to form OH ions, 1 5 0, 1,04 2° — 2047 Then Zn** and OH ions interact to give Zn(OH),. Therefore, corrosion occurs at anode.238 Encineeinc CHemistey Anode Electrolyte sain. (NaCI) Ans. (a) (iv) Cathodic Protection: The principle involved in this method is to forve the metal to be protected to behave like acathode, thereby corrosion does not occur. There are two types of cathodic protection. (i) Sacrificial anodic protection method: In this protection method, the metallic structure (to be protected) is connected by a wire to a more anodic metal, so that all the corrosion is concentrated at this more active metal. The more active metal itself gets corroded slowly; while the parent structure (enthodic) is protected. The more active metal so-employed is called “sacrificial anode.” The corroded sacrificial anode block is replaced by a fresh one, when consumed completely. Metals commonly employed as sacrificial anodes are magnesium, zinc, aluminium and their alloys, Important applications of sacrificial anodic method include protection of burried pipelines, underground cables, marine structures, ship-hulls, water-tanks, piers, etc. (see figure). In cathodica protection, an anode of more strongly reducing metal sacrificed to maintain the integrity of the protected object (e.g.,) a pi (if) Impressed current cathodic protection: [nt this method, an impressed current is applied in opposite direction to nullify the corrosion current, and convert the corroding metal from anode to cathode. Usually, the impressed current is derived from a direct current source (like battery or rectifier on a.c. line) with an insoluble anode (like graphite, high silica iron, serap iron, stainlessSameue Exasunarions 239 steel or platinum). Usually, a sufficient d.c. current is applied to an insoluble anode, burried in the soil (or immersed in the corroding medium), and connected to the metallic structure to be protected (sce figure). The anode is usually, in a backfill (composed of coke breeze or gypsum) so as to increase the electrical contact with the surrounding soil. This type of cathodic protection has been applied to open water-box coolers, water-lanks, burried oil or water pipes, condensers, transmission line towers, marine piers, laid-up ships, etc. This kind of protection technique is particularly, usefully for large structures for long-term operation. In impressed-eurrent cathodic protection, electrons are supplied from and external cell so that the object itself becomes cathodic. Ans. (a) (v) These are the factors which affect corrosion: I. Nature of the Metal (i) Oxidation Potential: The extent of corrosion depends upon the position of the metal in the electrochemical series and galvanic series. When two metals are in electrical contact in presence of an electrolyte, the metal higher up in the galvanic series becomes anodic and suffers corrosion. (ii) Overvoltage: When a metal which occupies a high position in galvanic series (say zinc) is placed in IN — H,SQ,, it undergoes corrosion forming a film and evolving hydrogen gas. (iif) Relative areas of anode and cathode: When two dissimilar metals or alloys are in contact, the corrosion of the anodic part is directly Proportional to the ratio of areas of the cathodic part and the anodic part. (iv) Purity of metal (o) Physical state of the metal: The rate of corrosion is influenced by the physical state of metal. The smaller the grain size of the metal or alloy, the greater will be its solubility and hence, greater will be its corrosion. Moreover, areas under stress, even in a pure metal, tend to be anodic and corrosion takes place at these areas.Same Exammations 241 of HCI, H,SO,, ete. In presence of these gases, the acidity of the liquid adjacent to the metal surfaces increases and its electrical conductivily also increases, thereby corrosion is increased. (io) Effect of pH: The hydrogen ion concentration of the medium is another important factor in corrosion reactions as well as corrosion central. Acidic media are generally more corrosive than alkaline and neutral media, However, amphoteric metals (like Al, Zn, Pb etc.) dissolve in alkaline solution as complex ions. The corrosion rate of iron in oxygen-free water is slow, until the pH is below 5.0. The corresponding, corrosion rate in presence of oxygen is much higher. Consequently, corrosion of metals, readily attacked by acid, can be reduced by increasing the pH of the attacking environment, e.g., Zn (which is rapidly corroded, even in weakly acidic solutions such as carbonic acid) suffers minimum corrosion al pH = 11. (e) Nature of ions present: Chloride ions present in the medium destroy the passive film and corrode many metals and alloys. On the other hand, the presence of anions like silicates in the medium leads to the formation of insoluble reaction products,¢.g., silica gel, which inhibits further corrosion. {vi) Conductance of the medium: In corrosion of underground or submerged structures, the conductance of the medium is of prime importance. Conductance of dry sandy soils is lower than those of clayey and mineralized soils. Consequently, stray currents (from power leakages) will cause more severe damage to the metallic structure, burried under clayey and mineralized soils than those under dry sandy- soils, (vii) Concentration of oxygen and formation of oxygen concentration cell: The rate of corrosion increases with increasing supply of oxygen. Less oxygen concentration, ¢.g., oxide-coated part or less-exposed parts become anodic, while the more oxygenated regions or parts more exposed to oxygen become cathodic. This teads to the formation of oxygen-concentration cell in which the anodic part suffers corrosion. At cathode: 2H,0+ O, +4e-—— 40H" Moist air (Electrons are consumed) At anode: Fe——~ Fe" +2e" (Electrons are supplied) Thus, oxidation concentration cell promotes corrosion, but it occurs where the oxygen concentration is lower.242 — Encweenic Chemisty Ans. (a) (v/) Corrosion of metal depends upon the position of metal in electrochemical series metal present above in the series act as anode and corrode faster than the metal present in the lower position. Magnesium is present above than aluminium in electrochemical series. Hence, magnesium will corrode faster than aluminium. Ans. (b) (i) Orderof Reaction: [tis not necessary that the concentration of all the reactant taking part ina reaction can determine the rate of reaction. Therefore, anew term is being introduced i. the order of reaction. It can be defined as: “The arder of reaction is given by the number of atoms or molecules whose concentration alter during the chemical chauge.” Or “The order of reaction is given by total number of molecules or atoms whose concentrations determine the velocity of the reaction.” Or “The sum of the powers of concentration term in the experimentally established rate equation is known as the order of reaction.” A reaction is said to be of zero order if its rate does not depend on concentration of reactant ie., dx rs de> K A reaction is said to be of first order, if its rate, ris given by the folldwing expression dx r=, = KC, ‘The reaction is of second and third order, if its rate is given by expression d rs + =KC} or KC,.Cy- second order reaction KCA.C, or KC,.Ch when the rate of reaction is given by a dt where K is a constant, the order of the individual constituents are 1,, rz, "3 etc. and the order of the reaction as a whole, 1, is given by Mey +m, ty tow KCY.CE.CE246 0 Encineeninc Crenustey on do not produce exact shades of color. Iron and manganese salt containing water may cause colored spots on fabrics, thereby spoiling their beauty. (di) Sugar Industry: Water containing sulphates, nitrates, alkali carbonates, ete, if used in sugar refining causes difficulties in the crystallization of sugar. Moreover, the sugar so-produced may be deliquescent. (ili) Dyeing Industry: The dissolved calcium, magnesium and iron salts in hard water may react with costly dyes, forming undesirable precipi- tates, which yield impure shades and give spots on the fabrics being dyed. Ans. (a) (ii) Zeolite or permutit process: Zeolite process involves softening of water by natural or artificial zeolite. Zeolite is hydrated sodium aluminium silicate. Na,O.A1,0, Si,0,H,O. Zeolites are the substances insoluble in water and can act as ion exchange when placed in contact of water containing cation. Zeolites are also called permutit. The zeolite softeners consists of a steel tank packed with zeolite over a layer of sand gravel. The water enters at the top and passes through bed of zeolite, where follawing reactions occurs, Na,Z + Ca(HCO,), —— CaZ + 2NaHCO, Na,Z + Mg(HCO,), ——> CaZ + 2NaHCO, Na,Z + CaCl, ——> CaZ + 2NaCl Na,Z + CaSO, ——» CaZ + 2Na,SO, Na,Z + MgSO, —— MgZ + 2Na,SO, Na,Z + MgCl, ——> MgZ + 2NaCi where Z = ALSi,O,XH,O 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, i.c., it looses its softening capacity, it can be regenerated by passing 10% solution of sodium chloride solution through it. The following reaction take place. CaZ + =~ NaCl—4Na,Z + CaCl, (Exhausted Zeolite} (Regenerated Zeolite) MeZ + 2NaCl-——> Na,Z + MgCl,Continuous cold lime-sada softener Silica (SiO,) can also be removed from water by this process. ‘Studge 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. Thecontinuous250 Encinerrinc. CHemesTey 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 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. lin this process, the residual hardness is far less as compared to lime-soda process. Advantages: Hot-lime soda process has the following advantages: (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 is completed 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) (iii) 150 lit of NaCl contains = 150 lit « (150 g/lit) of NaCl = 22,500 gm NaCl = 22,500 gm x (100/117) CaCO, eq. = 1.932 x 10¢ gm CaCO, eq. = 1.932 x 107 mg CaCO, eq. Let V lit of 600 ppm (600 mg/lit) water contains hardness = 1.932 x 10’ mg: CaCO, eq. 1.932 x10" 600) No. of liters of hard water, V = = 3.219 x 10* Liters. Ans. (b) (i) Advantages of gaseous fuels 1. Their calorific value is quite high in comparison to solid fuel and these fuels can be lighted very 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, while solid fuels require carrier for transport. 4, In gaseous fuels complete combustion takes place even in very little amount of air and so high efficiency is obtained as compared to solid fuels.252 Excmermnc Cresusrey (Causes of Air Pollution: The causes of air pollution are summarized below: (i) Population explosion, (ii) industrialization, (iii) Urbanization, (io) Automobiles and (v) Natural phenomena like: Voleanic eruptions, radioactivity, forest fires etc. Air Pollutants Air Pollutants Gases Particulates CT {44-74 {] TTT 4 [ $0, H,S NO, CO CO, Hydro- Dust Smok Smog Asbestos Lead Mer- Cad- » ‘carbons cury mium There are two major groups of air pollutants (on the basis of physical state) Out of these, the most common air pollutants are: () Carbon monoxide, (if) Oxides of nitrogen, (ii) Sulphur dioxide, (iv) Hydrocarbons and (») Particulates. These are briefly discussed below: (i) Carbon Monoxide (CO): There are basically two sources of carbons monoxide in the atmosphere viz. (a) The natural processes such as volcanic activity, natural gas and marsh gas emissions, electrical discharges in the atmosphere during storms, seed germination etc. (b) The human activities such as industrial operation (¢.g., electric and blast furnaces in iron and steel industry, Petroleum refining, paper industry, gas manufacture and coal mining), Automobile exhausts and Agricultural burning. Although CO is colorless, odorless, non-corrosive, yet it is very toxic in nature. It reduces the oxygen carrying-capacity of blood, as it atlacks haemoglobin and displaces ©, to from carboxyhaemoglobin. O,Hb+CO = COHb+0, (ii) Oxides of Nitrogen (NO,)}: NO and NO, are mostly responsible for air pollution and they are jointly represented as NO,. NO, is formed by photolytic reaction in the atmosphere. Oxides of nitrogen may also be formed by natural of artificial fixation of nitrogen from the atmosphere or form nitrogen compounds present in organic matter.Saupe Exauinanions 253 NO, can also be produced by the combustion of coal, oil, natural gas and other organic matter hence, NO, is introduced into the atmosphere from incinerators, automobile exhausts, coal based power plants ete. Some of the involved reaction are: 1210-1765°C N, +O,» 2NO 2NO +0, > 2NO, is the dissociation The most important primary photochemical reacti of NO, NO, + hy (398 nm) ——> NO +O The NO so formed may be oxidized by O, (ore more slowly by O,), thus leading to cyclic chain reaction. When the NO, is completely converted into HNO, by hydration and catalytic oxidation in presence of aerosels, fog or photochemical smog, the chain may be broken. NO +0,—+ NO, +0, 2NO, +O, N,0, +0, 4NO, + 0, + 2H,O— 4HNO, N,0, + H,O—— 2HNO, HNO, and HNO, may also undergo photochemical dissociation as follows: HNO, + hv-——+ NO,H HNO, + ivw———+ NO + HO HNO, + tv ——+ NO, + HO insiratosphere NO, + OH ———> HNO, The nitric acid (HNO,) so formed is removed as acid rain because it gets precipitated as nitrates during rainfall. It is also important to note that photochemical and chemical reactions involving NO, and hydrocarbons induced by sunlight can lead to the formation of photochemical smog. The following efforts have been directed in controlling NO, emissions from various sources. (a) Use of two stage catalytic converters in automobiles (b) Use of a two-stage combustion process in power plants.Saurut Examinanions 255 smoke particles get robbed of their negalive charge, thereby the smoke particles precipitate out and settle at the bottom of the chamber itself, and only hot dust-free gases go out through the chimeny. High positive O.G. voltage Point electrodes Clean gas outlet Particulates containing <== diy gas inlet Ground — Settied particulates dust, carbon, etc. (i) For the elimination of dust, “extraction ventilation” is frequently applied. The air stream carrying suspended dust particles is first maintained al a sufficient velocity to keep the dust particles in suspension, thereafter, the rate is reduced suddenty to the extent to cause the dust particles to settle out in a “stilling chamber.” (iii) SO, Pollution can be controlled either by removing the sulphur after combustion or by, pre-combustion or desulphurization of fuel. SO, and acid fumes.can be removed by passing the stack/flue gases through a bed of alkalized alumina or activated carbon or limestone powder, when SO,, etc., are adsorbed by these. Reduction af SO, in flue gases can alternatively be done as follows: (a) By liquid ammonia: SO, containing gases (from fertilizer factory, etc.) are passed through ammonia, when ammonium sulphite is obtained as by-product. () Cairox method: Clean gases containing SO, is mixed with alkaline KMn0, solution, through sprays, when oxidation of SO, takes place. KMnO, + SO, + KOH ——> MnO, + K,SO, + H,O (©) Lime-water wash: The gases containing SO, are passed through lime-water, when SO, gas is removed from the flue gases forming calcium sulphite. Ca(OH), + SO, — CaSO, + H,O256 Encatleana Crenester (iv) Acids and chemical fumes removal can be accomplished by passing the r gases/vapors through a tower filled with coke and against if a counter-current ‘ of water is applied from the top. By this method, we can recover . «simultaneously volatile products having commercial value. . (0) The use of coal and wood as fuel should be gradually reduced and modern energy resources such as electricity, tidal power, nuclear power, geothermal power arid solar power should be used for domestic as well as industrial purposes. (vi) Zoning: The main reason of air pollution is the lack of proper planning during rapid industrialization. To avoid air pollution problems, “industrial zoning” should be done. It is desirable to have suitable “buffer-zone” between the industrial units and houses in order to facilitate dilution of air pollutants to such a degree that it is harmless even to children, by the time the pollutants, from industries reach the ground level. (vii) H,S and SO,, emitted in air at refineries, etc., can be reduced by adopting “clause process”, which yield elemental sulphur as a by-products. It isa two-stage process. The HS divided into two streams. In first stage, H,S is oxidised to SO,. 2H,S(g) + 30,(¢) —— 2H1,0%g) + 250, (9) In the second stage, HS and SO, so-formed are reacted at high temperature to get by-product sulphur. 2H,S(g) + SO,(g) ——+ 2H,0()) + 3S(1) Carbon dioxide for their food by photosyrtthesis and release oxygen in the air. Consequently, they help to reduce the excess carbon dioxide of the environment. Many plants also absorb and remove significant amounts of hydrogen sulphide and nitric acid. Moreover, the air passing through vegetation kingdom slows down considerably and helps thedeposition of suspended particulate materials (like fine silt, coal dust, etc.) on the leaves, which are cither washed down by rain or by periodic shedding of leaves. Thus, plants on the whole help in controlling the air pollution. When the trees and vegetations are removed by non-judicious cutting, there remains none tocentrol the amount of carbon dioxide, dust particles and tosome extent ozone, hydrogen sulphide and nitric acid, etc. in the air. The air then becomes more.and more rich in these harmful pollutants. ‘Ans. (¢} (fi) Acid rain: The presence of sulfurdioxide (SO,) and nitrogen dioxide (NO,) gases as pollutants in the atmosphere decreases the pH of rain water, such type of rain ks known as acid rain. It is due to formation of acids.Samece Exawinarions = 257 S+0,—— SO, SO, + HO —— 1,50, 250, + O, + 2H,O—— 2,50, 4NO, +O, + H;O——> 4HNO, CO, +H,O-——> HC, Harmful effects of rain: (1) It increase the rate of corrosion. (2) It changes the rate of metabolism of animals. (3) It damages plant leaves in the form of mist. (4) It causes damage to aquatic system. (5) It damages the monument which is made up of marble. Photochemical smog: It occurs in warm climate and result from action of sunlight on the nitrogen oxide and hydrocarbon which are produce by automobile exhaust and result in formation of oxides of sulfur. Formation of photochemical smog: A high temperature in the engines N, and O, react to form NO. This NO is oxidised in air to NO, which in tum absorbs energy from sunlight and breaks up into NO and nascent oxygen atom. NO,(g) "+ NOK) +069) Oatoms reacts with O, to forms O,. Og) + 01g) ——> O58) ‘O, reacts with NO to form NO, NO+0,——+ NO, +0, O, and NO, acts as oxidising agent and they react with hydrogen to produce formaldehyde, acrolein, peraxyacety| nitrate (PAN) that cause water in eyes and harmful for respiratory system. 9 I CH=CH—CHO CH,—C—~O—O—NO, . nen Acrolein o Formaldehyde: Peroxyacetyl Nitrate (PAN) Efforts have been made tocontrol this problem by using catalytic converters ithe automobiles which prevents the release of nitrogen oxides and hydrocarbon to atmosphere.258 — Encineeanc Cuemstey Stratospheric ozone depletion: Formation of O, layer: It is formed in stratosphere by a photochemical reaction. 0, + hv —> 20" O* +0,+M—30,+M" The third body M absorbs excess energy and stablizing O, molecule. Depletion of by NO: O, isa light bluish gas found in stratosphere absorbs U.™. radiation which is harmful to the living things. The effects of the depletion of ozone layer in the stratosphere include i increased human cataracts, skin cancer, reduction of planktons in sea water, depletion of plants and crops. The major cause of depletion is chlorofluro carbons (CFCs), Freons. They are used as solvent,aerosol, refrigrant fluid ete. U.V. radiation causes the CFCs to dissociate. CFC, + hv —> Clg) + CE, Clty) CI* +0, ClO + ©, (CI reaets with O,) ClO" generated again form Cl” ClO* + Of) —> Cl" +0, It means only one CI* destroys many O, molecules If NO, or CH, is present then it destroys the further reaction af CIO* and Clas C1O"%(g) + NO,(¢) ——> CIONO, (9) Cl"(g) + CH,(g) —— CH} (g) + HClig) It means NO, and CH, are natural sink for CIO" and Cl" But in presence of polar clouds CIONO, + H,O-———» CIOH + HNO, CIONO, + HCI—> Cl, + HNO, CIONO, reacts with H,O(g) and HCK(g) and generates CIOH and Cl, respectively CIOH and Cl, again form Cl" and in this way again ©, depletion continues.Saupe Exaumanions 259 CHEMISTRY-10 Time : 3 Hours Total Points : 100 Note: 1. Answer alf questions. 2. All questions carry equal points 3. In case of numerical problems, assume data wherever not provided. Q.1 Answer any tivo parts of the following: (10 x 2 = 20) (a) Draw molecular orbital diagrams and calculate bond arder for (i) N; (ii) CO. (8) (i) Define radius ratio and mention its application. (ii) Write short note on semiconductors. (6) (i) State Bragg’s diffraction law. (ii) What is unit cell? What are the different types of unit cell ? Ans. (a) (i) Molecular orbital energy level diagram of N, molecule Increasing energy260 Encavernnc Crewerny ©. Molecular orbital electronic configuration of N, 2 = KK o2to* 2st [a o2p3, np, x6 =3 so it is diamagnetic. 1 Bond order = > (N,—N, Ans. (0) (ii) Carbon Monoxide Molecule, CO: The electronic configurations of participating C and O.atoms as follows: C= 1s%2s?2p!2p}ap? (4 valence electrons) O= 1s°2s'2p? 2py2p! (6 valence electrons) The total number of valence electrons is 10 and the electronic configuration of CO molecule can be written as KK a(2s)? o(25)?0(28)? af2p,)? n(2p2) m(2p?). Bond order = Energy n(2p,) RE2p,) { ti } Lh] ul 2s 2s Atomic orbitals a(2s) Atomicorbitals of C atom of Oatom Molecular orbitals diagram of CO moleculeSamoce Exammanions = 2617 This shows that carbon and oxygen atom in CO are bonded to each other by a triple bond (one o bond and two m bands). There is no unpaired electron in CO molecule and hence it is diamagnetic in nature. Ans, (b) (i) Limiting Radius Ratio: In general, the size of an octahedral site is greater than the size of a tetrahedral site, which in turn is greater than the size of a trigonal site. In case of ionic crystals, the radius ofa cation which may occupy a given site created by anions can be calculated by simple geometry. It is done in terms of the ratio of the radius of cation to the anion (7/1), also known as radius ratio. 1. Radius ratio for trigonal site: A trigonal site is formed when the three anions represented by spheres lie at the vertices of an equilateral triangle and a cation shown by a small sphere occupies the Lrigonal sile (Figure). If r* and r are the radii of cation and anion, respectively, then from equilateral AEBC, BC = CE = BE = 2r- Let A be the center of the triangle and so ef the cation, the BD=randAB=rr In right angled triangle BDA, 2 ==1=0.155. *r B Itmeans that trigonal site is only about 0.155 of the size of the surrounding spheres, ie., anions.262 Ewcweemnc Cremesrer 2. Radius ratio for octahedral site: An octahedral site is shown in the following figure. It is clear that in it, four anions are at the corners of a square and the cation is at the center. One anion at the top and one anion. at the bottom of the plane formed by the four anions also touch the cation. Let each side of the square be a, and r* and r~ are the radii of the cation and anion, respectively. In a right angled triangle ABC, AC= yas? + BC?) = ya? + a®) = V2.0 ACHr+2r4+ra2r42r = sla or rere Lhe @ 2 From the figure, AB=a=2r or res (i) Dividing equation (A) by (ii), we get or 14a? rp or DeJ2 -1=1414-1=0414. 3. Radius ratio for tetrahedral site: A tetrahedral site is formed when one sphere is placed over another spheres which touch one another. In an ionic crystal, such a site can be formed by placing the anions at the alternate comers of a cube. The cation occupies the tetrahedral site. Let the length of the cube be @ and 7* and r- are the radii of the cation and anion, respectively:264 Encrmeanc CHemisrry In the figure, AB=2r=a or r=a/2 @ ‘The face diagonal, AC = fab? + BC? = faa = V2.4 The body diagonal, AD= Jac? +cb? = Za? ta aV3_a But body diagonal, ADer+2rtrsirta2rt * 2r+2rte W3a or r4rt= (ii Dividing equation (ii) by (i), we get rer Ba 2.8 a or So, the limiting radius ratio for a cubic site is 0.732. Packing in Ionic crystals (Packing on non-uniform spheres): Packing in ionic crystals depends upon the nature and the number of the constituent'ions. Ina close packed structure the cations are surrounded by anions, and the anions by cation in such a fashion that the condition of electrostatic neutrality is maintained. The number of anionic nearest neighbors is called the coordination number of cation, whereas the coordination number of the anion is the number of nearest calionic neighbors. The common coordination numbers in ionic crystals are 4, 6, 8. In ionic erystals the size of anions and cations are usually different. ‘Therefore, the lattice is viewed as a close packed arrangement of the larger ions with the oppositely charged smaller ions inserted in the holes. Since in ionic crystals the anions are generally large they occupy the main lattice sites and the cations occupy the void space. The size and type of the void space in which the smaller ions are inserted, can be determined by knowing the releative size of the anions and cations that is, by knowing the relative size of the anions and cations that is, by the knowledge of the radius ratio. This is equal to the radius of the smaller ion divided by the radius of the larger ion (usually written as. r*/r or r./c,). Conversely, from the nature of the void space we can predict the radius ratio and hence can decide as ta which type of packing a particular ionic compound should belong. From geometrical calculations it can be shown that in a270 — Encieeune CremisTay frequencies are quoted relative to the reference frequency. Therefore, chemical shift “6” may also be defined as: = HsHs b= x 106 where Hg and Hy are the strength of applied magnetic field necessary for absorption by the sample and reference compound respectively. Since Hew $= “S—XE. « 10%; where vy is oscillator frequency Or Ans. (a) ()) Functional group Absorption frequencies in em™ (a) —OH 3200 = 3600 cm“ ®) ceo 1700 = 1750 cm (—C=N ~ 2250 em (é) —CH, 2000 - 3000 cm-# Ans. (a) (ii) B-carotenes absorbs light in visible region duc to the presence of conjugation in the molecule. Ans. (b} (i) Synthetic polymers: Synthetic polymers are man-made polymers. Mest of the synthetic polymers are long-chain organic molecules containing thousand ofmonomer units. Organic polymers include compounds containing carbon, hydrogen, oxygen, nitrogen, sulphur and halogen atoms in the backbone or main chain. These include polymeric substance containing other elements. in their molecules provided the atoms of these atoms are not in the main 4+-CH,—CH;3- -CH,—CH,}- 4+CH,—CH,3, Polyethylene b & Hy ¢ Polyvinyl chloride Polystyrene —-NH-{CH,)-—€—-O{CH,),-0— oO Polyurethane272 = Enciveening Cuenustry CH, CH, “CH-tact-CHh-€H, —C=CH—CH,— ~CH—G=CH CH CH C=C CH CH, cH, Raw or unvulcanized rubber springs ‘Vulcanization (+ sulphur) cH, cH, CH} FH CHyCH,—¢ “HCH, — 8 5 ; S$ <—_ Sulphur eross-link Ld rd Cl, —¢ CCH CH © H—CH,— cH, cH, Vulcanization of raw rubber with sulphur as vulcanizing agent Ans. (c) (ii) Nylon (polyamide): These polyamide have and amide linkage. tonne Nylon 6: It is obtained from monomer caprolactam which in tur is obtained from cyclohexane (petrochemical). So chemical unit of Nylone 6: i i -NHH{CH) for Acct 5 Nylon 66: It is made by condensation polymerization of hexamethylene diamine and adipic acid so chemical unit of Nyton 66: frome gy Polystyrene: It is a type of polydienes polymers. These are obtained when a diene is polymerized with a substituted alkene, So chemical unit of polystyrene is:Samore Examinations 273. i CH=CH, ae Q.3 Answer any four parts of the following: (a) Write the mechanism of the following: (0) Cannizzaro reaction. (ii) Hoffmann rearrangement. (6) (i) Write a note on addition reaction. (if) What is carbanion? Arrange the following according to decreasing stability: (a) ucfcu, ® ncF—cH, H CH, e 2 (o Gx, (d) CH,-EH, (c) Write short notes an: (i) Enantiomers (ii) Diastereomers with example respectively. (d) Write E and Z configuration of each of the folowing compounds: OH SA nan OH (e) Provide any two examples of optically active compounds without chiral centers. (P Write the Anti and Gauche conformations of n-butane. Ans. (a) (i) Cannizzaro reaction: Aldehydes containing no a-hydrogen (such as C,H,.CHO, HCHO, (CH,),C:CHO etc.) when treated with aqueous or ethanolic alkali undergo disproportionation to a salt corresponding, acid and alcohol. This simultaneous oxidation and reduction of aldehydes is known as Cannizzaro reaction (S. Cannizzaro, 1853).274 Encineeenc CHemistey For example, formaldehyde when heated with 50% aqueous or ethanolic alkali gives methyl aleohol and a salt of formic acid. 2HCHO+NaOH ——> HCO,Na+CH,OH Ithas been observed that reaction is mainly applicable to aromatic aldehydes. 2C,H,.CHO+ NaOH ——+ C,H,CO,Na + C,H,CH,OH Sodium benzoate — Benzyl aleohol Although the Cannizzaro reaction is characteristic of aldehydes having no a-hydrogen atom, but it is not confined to them. Hausermann (1951), for example showed that certain a mono-alkylated aldehydes undergo quantitative dispreportionation when heated with aqueous sodium hydroxide at 170°C-200°C DOC 2(CH,),CH.CHO + NaQH ———> (CH,),CH.CO,Na + (CH,),CH.CH,OH As mentioned earlier, this type lakes place a simultaneous oxidation- reduction in Cannizzaro reaction. Such self oxidation-reduction (redox) reaction are called disproportionation dismutation reactions. ‘Cannizzaro reaction is not confined to the interaction of similar aldehydes. It can take place even between two different aldchydes, and this type of Cannizzaro reaction is known as ‘Crossed-Cannizzaro reaction’. For example, formaldehydeand benzaldehyde react in presence of alkali to form benzyl alcohol and salt of formic acid. Naot C,H.CHO + HCHO ——+ C,H,CH,OH + HCO,Na Itmay be pointed out that formaldehyde may undergo Cannizzaro reaction with a number of aldehydes, but the nature of the final product depends upon the structure of other aldehydes. However, ithas been observed that a Cannizzaro reaction between formaldehyde and an aldehyde lacking in a-hydrogen results in the oxidation of the former and reduction of the latter, because formaldehyde is more reactive than other aldehydes towards negatively charged groups (nucleophiles) and rapidly gives high concentration of the donor anion. The Cannizzaro reaction may be carried out in several ways; catalytically; by the use of metal catalysts, such as nickel and platinum; in 4 two phase system. i., heterogeneous system (an organic phase and strongly alkaline aqueous phase); and in homogeneous alkaline solution. This reaction is given by those carbonyl compound which does not have aH. In presence of OH, one moiecule is reduced and other is oxidizedSamet Exaninanions 277 Ans. (b} (ii) Carbanion: Carbanion are negatively charged species containing a carbon atom with three bonds and or unshared pairs of electrons. They are formed by hetrolytic fission. px — 12 The stability of carbon is influenced by resonance and inductive effect. The decreasing order of stability of given carbanions. H,C> CH,—CH? > (CH,),CH? > (CHy,-C° Ans. (c) (i) Enantiomers: Chiral molecules which are non-super impossible mirror images of each other are enantiomers. They have opposite crystals structure and configuration. The rotate plane of plane polarized light in opposite direction but to the same extent. cH, oH, 4-01 Hoe COOH COOH The physical properties of enantiomers (e.g., B.PM.P. and solubility in optically inactive solvents) are identical. In symmetrical environments, their chemical properties are also identical. This means that two optically active forms of enantiomers behave similarly towards achiral reagent, achiral solvent and achiral catalyst. The enantiomers react at different rates and form products in different amounts, in asymmetric environment. They react at different rates if, anyone of the reagent salvent or catalyst is chiral. Ans. (c) (ii) Diastereomers: Stereo isomers that are not mirror images of each other are known as diastereomers. They have different physical and chemical properties even towards achiral reagents, solvents and catalysts. This is due to the fact that they have different amount of free energy. For example: (+) tartaricacid is diastereomeric with mesotartaric acid. (a) and (b) being mirror images of each other, are enantiomers. (a) and (c) or(c) and (d) are not mirror images of each other so they are diastereomers.278 Enconeenmc Crexestey COOH H OH H OH (OOH @) (+) tartaric acid Ans. (d) Z form configuration Its E configuration is E form configuration Its Z configuration is HC A cot & CH-CH, ne HY, Hy-CH, C= TH ah COOH COOH H. ‘OH HO- H H OH HO: H COOH, COOH @ @ Meso tartaric acid CH; eo aLcn-on HA, CCH CHr- OH { “cH, CH, Ans. (¢) Optically active compound without Asymmetric Carbon Atom: (f) Allenes: Allenes have general formula: O=O=CT If the two groups attached to the terminal carbon atoms are the different then the molecule as a whole becomes disymmetric. This is because the molecule possess neither plane nor a center of symmetry and forms non- superimposable mirror image. Therefore, such allenes derivatives are optically active,Samout Examinanions 279 sp hybridized bo ke nt ATS 1 aNb sy hybridized carbon Central Carbon atom [(C—2] sp hybridized —Contain two sp -sp?.¢ bonds —has two p-orbitals which are mutually perpendicular. Terminal carbon atom [C—1] and [C—3] — sp? hybridized ‘Two p-orbitals of central carbon atom forms a bonds with p orbitals of the terminal carbon atoms. These x bonds are perpendicular to each other, The substituent at one end of the molecules are ina plane which is perpendicular to that of the substituent at the other end so that the compound exist in two forms which are non-superimposable mirror images and are optically active. CH. Hw U-GHs (a) ec C=c=c “ ous NH Mirror Non-superimposable mirror image 1, 3-Diphenyl propadiene CH. cH Hw CH, ) o =C H CH, HC Su Mirror 2, 3-Pentadiene Cs CH Cds oa: ¢ “cooch,coort cO0cH, COOH CoH Mirror (ii) Spiro compounds: When both the double bond allenes are replaced by rings the resulting compound is known as spiro compound or spiranes. The double bond may be replaced by 4,5, or 6 member ring. The two replaced rings are280) Encineeainc: CresusTay perpendicular to each other and hence suitable substitution at either end of the spiranes or Within the rings makes the molecule disymmetric. Therefore, such compounds are optically active H. ORR Ne Sous 7 2, 6-Diaminospirocycioheptane H. CH, CH, H ™~N ce” Q “a AQ a NAN ON HOOC cH; CH; COOH 1, P-dicarboxyspirocycloheptane (iii) Biphenyls: Biphenyls also exhibit optical isomerism due to restricted rotation around the single bond between the two benzene nuclei if the following conditions are satisfied. (1) Neither of the two rings have a vertical plane of symmetry (2) Presence of bulky groups at oitho position, which prevents the free rotation of two benzene rings. e.g., 05H 50,H SO,H HOS Mirror . Non-superimposable mirror image Biphenyl-2, 2'-disulphonic acid COOH NO, NO, COOH No, COOH CooH NO, Mirror 6, 6-Dinitrodiphenic acidSane Examnanions 283 dx If dx is the change in concentration then Rate of reaction = + a +ve sign refers to increases in the conc. of product. ~ve sign refers to decreases in the conc. of reactant. But the rate is always a positive quantity. Hence the rate of a chemical reaction may also be defined as--“ the decreases in concentration of product per unit time”, Unit of Rate of Reaction: The unit of concentration is moles, liter and time may be expressed in second, minute arid hour. Therefore, unils of reaction rates may be : Rate = Concentration _ mole/liter _ mole/liter _ = mol L* sec, mol L*? min“, mol L* hr! Ans. (a) (#) Molecularity of reactions: It may be defined as “The number of atoms or molecules which collide together at one and the same time for the reaction tooceur.” It is the sum of the number of molecules of various reactants that take part in a chemical reaction as represented by a balanced chemical equation. The classification of reaction according to their molecularity is: (a) Unimolecular reaction: A reaction in which only one molecule of reac- tant involved eg., (i Br, —> 2Br (ii) PCL,—§} PCI, + Cl, H—C—COOH H—C—COOH id — H—C—COOH COOH—C—H Maleic acid Fumaric acid (b) Bimolecular reaction: A reaction in which two molecules are involved eg. (@ Inversion of cane sugar: CygH.2Oy + HJO ——> C,H)20, + CH,,O, Glucose Fructose the two molecules C,,H,,0,, and H,O are taken part in this reaction, so the reaction is bimolecular.of an ester: CH,COOC,H, + H,O—-> CH,COOH + C,H,OH (iii) Decomposition of ozone: 20, —— 30, (it) Trimolecular reaction: Three molecules take part in this reaction ¢.¢.. (i) 2NO +0, > 2NO, (ii) 2FeCl, + SnCl, ——> 2FeCl, + SnCl, (iii) 2CH,COOAg + HCOONa > 2g + CO, +(CH,COOH + CH,COONa Ans. (a)(ii) Energy of activation: The additional amount of energy, that the reactant molecules having energy less than the threshold energy, must acquire in order to react to form product is known as Activation energy. The amount of energy which the reactants must absorb to pass over the threshold energy barrier is known as Activation energy. Activation energy = Threshold energy - Energy possessed by the molecules initially. Progress of reaction It is denoted by E, and is expressed in terms of kcal/mol or kJ/mol. E,=En~Ex286 — Encineemine CHenestey is completely defined if we specify temperature only. The ather two variables, i.c., composition of NaCl solution and vapor pressure have a definite value at a fixed temperature. So, the system has one degree of freedom. 3. Fora pure gas, F = 2: For a sample of pure gas, PV = RT. If the values of P and T are specified, volume (V) can have only one definite value iv. third variable is fixed automatically. Any other sample of the gas under the same pressure and temperature as specified above will be identical with the first one. So, the system containing a pure gas has two degree of freedom. Ans. (b) (iii) 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 (x) (ii) A gaseous mixture, being throughly miscible in all proportions, will con- stitute one phase only. Thus, a mixture of N, and H, forms one phase only. (iif) If two liquids are immiscible (i., benzene and water), they will form two separate phases only: (iv) If two liquids are miscible (i.¢., alcohol and water), they will form one liquid phase only. (v) A solution of a substance in a solvant consists of one phase only, e, glucose solution in water. (vi) Each solid makes up a separate phase, except in the case of solid solu- tions, e.g., many forms of a sulphur can exists together, but these are all separate phases. (wii) A heterogencous mixture like: CaCO, (s) = CaO(s) + CO,() consists of three phases (i,, two solids and one gaseous). Similarly, in the equilibrium reaction Fe(s) + H,O(g) == FeOfs) + H,(g) There are two solid phases, Fe and FeO and one gaseous phase consisting, of H,O(g) and H,(g). Thus, free phases exists in equilibrium. (viit) A homogeneous solid solution of a salt constitutes a single phase. Thus Mohr’s salt [FeSO, (NH,),SO,.6H,O] solution constitutes a single phase, although it consists of FeSO,, (NH), SO, and 1,0.288 Encivceamc Coemstey (vif) In the equilibrium, Fe(s) + H,O(g) <> FeO(s) + H2(¢) the minimum components required to express the composition of each phase is three. Evidently it is a three components system. Ans. (c) Concentration Cells: An electrode potential varies with the concentration of the ions in the solution. Hence it follows from the Nernst equation that two electrodes of the same metal but immersed in the solutions containing different concentrations of its ions , may form a cell (when connected with a wire and salt bridge). Such a cell known as a concentration cell. Concentration cell The e.m.f. of the cell will be the algebraic difference of the two potentials. Thus 0.0591 n te) -(e5 20 Bm Eey~Fea® (Ey + 19g C2) 0.0591, C = log Ge where C, > C, IfC, = 10 C,, the e.m.f. developed for monovalent ions = 0.0591 x log 10 = 0.0591 volt; while for divalent ions, the e.m-f. = og5st x log 10 = 0.0295 volt. Although these potentials seem tobe small, the concentration cells play a very important role in corrosion. In the concentration cell, the metal immersed in the dilute solution has a tendency to go into solution (i.c., itacts.as anode) while the metal immersed in the concentrated solution behaves as cathode and metal ions in the solution around the cathode get discharged and deposition on it.292 — Encineening CHewstey formed by fossilization of animal and plant remains under anaerobic conditions. In facts, the action of decay, pressure and heat convert vegetable and woody remains, deposited many years ago, into coal. The time required for coalification is of the order of 107 and 10° years. Coalification is known to take place in two stages: (@) Biochemical coalification: because biological bacterial process converts cellulosic plant materials into peat. (b) Ranking: Due to high temperature (> 300°C) pressure and long time of the order of 107-10* years chemical changes takes place. The result of these chemical changes in coals of different maturity or rank. Rank is a qualitative measure of carbon content in coal and is defined as the degree or extent of maturation. The soft coal (Peat, lignite and sub- bituminous coals) have low percent of carbon content and are known as- low rank coals. The hard coals (Bituminous and anthracite) have high percentage of carbon content and known as high rank coal. Wood Peat ——> Lignite ——* Bituminous ——* Anthracite % carbon and calorific value —® Increase ‘Ans. (B) (ii) Biomass energy: All forms of matter derived from biological activities and present on the surface and depth of earth either on land or walter is referred as “biomass.” It can be present on the surface of soil or at different depth of water bodies like lakes, rivers, sea or ocean. It may be defined as- “Living matter (Plant and animals) or its residue which are renewable in nature is called biomass”. Biomass is a source of energy. So this energy can be obtained by (a) Burning of wood (b) Waste paper (c) Cattle dung (@) Agriculture waste of a fireplace (e) Anaerobic decomposition or organic waste by certain micro-organism ‘on this basis of their sources, biomass can be described as:294 Encinerninc CHemistey 2. Bio-Conversion process: (a) Aerobic digestion (b) Anaerobic digestion (c) Enzymatic digestion (@) Degradation of cellulose and hemicellulose. Biomass used directly have the following demerits: (i) The smoke: It is harmful to human beings. It produces due to incomplete combustions of biomass. (ii) Efficiency: Its efficiency is very poor if it is used directly. However, inspite of a huge biomass material on earth, biomass energy potential is significantly under exploited due to various costraints and misconception. Ans. (c) Air pollution may be defined as the presence of one or more pollutants (or combination thereof) in the out door atmosphere in such quantities and of such duration which might be injurious to human, plant or animal life or property. ‘These pollutants may unreasonably interfere with the comfortable life or the conduct of business. Every individual person breathes approximately 20,000 times a day, intialing about 15-22 kg of air pollution is most crucial from the public health point of view. ‘Causes of Air Pollution: The causes of air pollution are summarized below: () Population explosion, (ii) Industrialization (iii) Urbanization (iv) Automobiles and (v) Natural Phenomena like: Volcanic erruptions, radioactivity, forest fires etc. Air Pollutants: There are two major groups of air pollutants (on the basis of physical state). Air Pollutants Gases Particulates: I +e Tm pao t + SO, SO, H,S NO, CO CO, Hydro Dust Smoke Smog Asbestos Lead Mercury Cadmium carbonsSame Examimarions 295 Out of these, the most common air pollutants are: (i) Carbon monoxide, (ii) Oxides of nitrogen, (iif) Sulphur dioxide, (iv) Hydrocarbons, and (v) Particulates. Control of Air Pollution: The most effective method to control air pollution is to prevent the formation of pollutants or to reduce their emission at the source itself. In the case of Industrial pollutants, the designing and development of plants may be so selected as to have minimum air pollutants. This is known as Source Correction Method. The following methods are used to cut pollutants emissions: (a) Use of Low-pollutants during combustion; (6) Preventing the formation of pollutants during combustion; (c) Removing pollutants for exhaust and the gases. The last option is generally used in controlling air pollution plants without upsetting drastically the economy of operation of the plant. When toxic substances enter lakes, streams, rivers, oceans and other water bodies, they get dissolved or lie suspended in water or get deposited on the bed. It results in deterioration of the quality of water which is called water pollution. It affects aquatic ecosystem. Classification and sources of water pollutants: The water pollutants can be broadly classified in the following five major types of water pollutants. I I Organic Inorganic Suspended Radioactive Th pollutants pollutants solids and materials poll sediments2 30. SOLUTIONS TO ENGINEERING CHEMISTRY By Dr. B.S.CHAuHAN (ISBN: 978-81-318-0293-9) CHAPTER 1 SHORT ANSWER TYPE QUESTIONS Hydrogen bonding remarkably lowers the streching frequencies of both the groups involved in it, and also the shape and intensity of the absorption bonds, Similar to the O—H group, the N—-H streching frequencies of amines are also lowered but to the lesser extent. This is because nitrogen is less electronegative than oxygenand so hydrogen bonding is weaker in amines than that for hydroxyl compounds. orm ()-€) ists Base value = 217 Ring residues = 20 Pues expected = 237 nm () The 2, for ( yec-cre{_) is caleulated as: Basic value =217 Ring residues = 20 Two exyclic bonds = 10 Ann expected = = 247 nm 297298 21. tad EncovecrinG Crtenastiey MULTIPLE CHOICE QUESTIONS C,H,CH = CH—CH = CH—C,H, HN*—C,H, (1D CHAPTER 2 SHORT ANSWER TYPE QUESTIONS In graft copolymer, a chain formed by one kind of repeating unit of monomer is grafted on to a chain of monomer units of another kind acting asa backbone of the polymer. For example, | mA AAA A AAA men i B | | In block polymers a block of repeating unit of one kind of monomer is followed by a block of another kind of monomer, then again followed by first kind and toon. For example, —ow— ~-—A-A—A-A—B-B-B- BA AAA The monomers containing vinyl group (CH,==CH—) are called vinyl monomers. For example, () CH=CH, — — Ethylene ~ (i) CH=CH — Propylene cH, (ii) CH=CH—CN — Acrylo nitrile (i) CH,=CH—C|_ — Vinyl chlorideSoiwrions 299 10. The substance which bring about the initiation of a polymerization process is known as the initiator. Free radical initiators include: 9 9 {| li (i) C,H. —C—O—0—C—C,H, — Benzoyl peroxide (if) Azo-bis-isobutyro nitrile (AIBN) cH, CH, CH. —C—N=N—C—CH, CN CN 12. (a) (i) Thenumber of repeating units (of monomer) in.a chain of a polymeris known as the degree of polymerization. It is given by: M D, where, D,~ the degree of polymerization M - Molecular weight of the polymer m= molecular weight of the monomer unit. (i) Joint polymerization of two or more monomer species is known as copolymerization. For example, butadiene and styrene copolymerize to yield Buna-S rubber. (6) Polymers contain both crystalline and amorphous regions in their structure. Crystalline region occurs when several polymer molecules an structures of polymer molecules are oriented parallel to each other. So that the weak inter- chain forces hold the molecules together conferring strength on the polymer. On the other hand when polymer molecules are nol sufficiently close to each other for these inter-chain forces to operate, amorphous region occurs. (c) The four important uses of rubber are: ® Due to excellent resistance to electricity, it is used as insulating coating on wires and cables, used for electrical power transmission. @ Due to its elasticity it is used formaking rubber bends, rubber goods, golf balls, printing rollers, tubes for automobiles aeroplanes and bicycles. @ Itisused for making toys, sports goods, head bands for helmets and goggles, elc. ® Due toits chemical resistance, it is used for making rubber lined metal tanks and vessels, used in chemical industries where carrosive metals are to be used.300 Enciversinc CHenasriey 14, a) (A) ‘Thermoplastics {i) They are formed by addition polymert- zation only. (ii) They consist of long chain linear poly- mers with negligible eross links. {iii) They soften on heating readily. (iv) By overheating to a suitable tempera- ture, they can be softened, reshaped and thus reused. (0) They are, usually soft, weak and less brittle. They are formed by condensation polymerization, They have three dimensional network structure. They donot soften on heating. They retain their shape and structure even on heating. Hence they cannot be reshaped and reused. They are usually hard, strong and more brittle. (ai) in the monomer. (if) No by product is formed. (iif) The growth of chain occurs at one active center. iv) In this process generally a thermoplastic 18 formed. poly functional monomers having functional groups with affinity for each other. Generally a byproduct is formed, The growth of chain occurs at minimum of two active centers. In this process eithers thermostat or thermoplastic can be obtained. 17. Condensation polymerization is an intermolecular combination through different functional groups present in the monomers, with the elimination of small molecules like H,O, NH,, ete. common examples of condensation polymerization are: (i) Terylene, It is formed by the condensation of ethylene glycol and terephthalic acid. n [HOCH,CH,OH] + 1 [roo -4G)-coon] Ethylene glyeat ‘Terephthalic acid ° ENS, OCH.CH —O—]| +nH,0 oO i" TeryleneSownions 301 (ii) Nyton-6, 6: [tis prepared as— fe) Il ll nh H.N-+CHa:NH, + HO—C-+4CH,3-C—OH Hexamethylene Adipic acid diamine shack z > N—(CH3-N—C{CH,},—C- Nylons, 6 (iff) Nylon-6. It is obtained by heating capro lactum with traces of water forming amino caproic acid which on polymerizes to give nylon-6. Nylen-6 ‘ N. 9 CY ey H,N-¢CH,4z COOH iy nnieny ef (iv) Novolac. [tis prepared by polymerizing o-hydroxy benzyl alcohol. HH OH OH CH,OH Polymerization CHy CH, " “HO Novolac RNA (@ Sugar mostly in DNA is deoxy- | Sugar mostly in RNA is ribose. ribose. (Hi) The common nitrogenousbases are} The common nitrogenous bases are adenine, guanine, cytosine and | adenine, guanine, cytosine and uracil. thyamine. (ii) It is normally double stranded and | It is normally single stranded and rarely rarely single stranded, double stranded. (iv) It is the usual genetic material. RNA is the genetic material of only some: viruses. alkali labile. (v) It is alkali stable. I40. = 10. i. Sounoxs 303 Important applications of conducting polymers are: @ Polythiophene is marketed under the trade name Baytron. Itcan be used tomake plastics paintable by adding the conductive agent and also in the electrodes of small, high performance tantalum capacitors found in telecommunications, compulers and automotive producis. @ Contex a fiber is coated with a conductive polymer polypyrrole can be weaven to create an antistatic fabric which can be used in carpet industry. @ These polymers are used in making button type batteries. These batteries are longer lasting and rechargeable. @ These polymers can be used in biosensors and chemical sensors. Which can convert chemical information into a measureable electrical response. @ These polymers find extensive applications in telecommunication systems, micro- electronic devices, biomedical use, etc. CHAPTER 3 SHORT ANSWER TYPE QUESTIONS Electrophile is an electron-deficient (or electron loving) chemical species. Due to the electron-deficiency, it always attacks at the center of high electron density. Common electrophiles are: (a) Positive electrophiles, ¢.¢., H*, Cl*, Br‘, NO,*, R* etc. (&) Neutral electrophiles, e.g., R*, BFy, AICI, FeCl, SnCl, ete. Nucleophile is an electron rich (or nuclets loving) chemical species. Due to the presence of a pair of free electrons it always attacks at the center of law electron density. Common nucleophiles are: (a) Negative nucleophile, ¢.g., F-, Cl", Br’, I", OH", CN* ete. (®) Neutral nucleophiles, e.g., H,O:, NH, R—OH, ete. Electrophilic reagents: H', NO,'. Nucleophilic reagents: Cr, OH”. {@) Six electrons are present in the outermost valency shell of carbon of the carbonium ion. (8) The outer most valency shell of carbon of the carbanion contains four pairs of electrons of which one pair is free. The mechanism of a reaction tells us the precise position of the atoms, as a function of time, in the reactant molecules as they are converted into products. The proposed mechanism of a reaction should be (a) energetically reasonable, (b) account for the experimental observations, and (c) be in agreement with whal is known about analogous reactions. The mechanism of a reaction can be studied by product analysis,304 ENoneeanc Cuemestey determination of the presence of an intermediate, isotopic labelling, stereochemical studies and finally kinetic evidence 19. (i) Heterolytic cleavage (ii) Homolytic cleavage (iii) Homolytic cleavage (i>) Heterolytic cleavage. 22. Reaction (a) follows S,.2 mechanism while the reaction (b) occurs by $1 mechanism. 25. Free ical (i) It is formed by the homolytic ion | [tis formed by the heterolytic fission of the of the covalent bond. covalent bond. (ii) Itis a neutral entity. It may be positively or negatively charged. (iii) Common examples are: Common examples are: RCI, Br ete. CH", CH, CH,", OH", NO," MULTIPLE CHOICE QUESTION Ans 8. (a) CHAPTER 4 on CHOH ,,@ CHO NaOH 2 +H i at, (Core) COO? cooH Glycatave ion Giyeathic acid CHO CH,OH (i) HCHO + Oo NaOH, icooNa + Sodium formate Benzyl alcohol CHO CH,OH (iia NaOH ‘CHO COOSounons 305 a (io) + | Beczns, Ss Cyclohexene 5. Applications of: (a) Cannizaro reaction (i) Synthesis of pentaerythritol. HCHO/OH? HCHO/ OH CH,CHO ———— C({CH, OH), CHO ———> C(CH, 0H), + HCOO Aldo! ° Crossed Pentacrythnited me —" Pentaerythritol is used in the production of pentaerythritol trinitrate, an intermediate for explosive manufacture. (di) Synthesis of fehydroxy aldehyde. CH,OH o RR‘CH.CHO + HCHO 24, RR CHO P-Hydroxy aldehyde (8) Hoffmann Rearrangement (i) Synthesis. of anthralinic acid ? f “ nih c oe, OOH L NaOH 7 ¢ ‘CONH, ° ° Phthalic Phthalimide fac anhydride 6 “oon IH, Anthralinic acid(ii) Synthesis of isoquinolines P.O, SS ,H.,CH=CHCH=NOH ——> Cra 2 Isoquinoline NH; CHANO, Ss % Glycerine OE, ® oO * Glycerine | Fe80,, FSO, Se Quinoline a ‘a Ec + Il Benzene O SS CHAPTER 5 SHORT ANSWER TYPE QUESTIONS 2. Examples of geometrical isomerism: OOH HY OOH ti) I and I c c a \ COOH HOOC H Maleic acid Fumaric acid (eis) (iran) HY - HY J Oe ¢ wil and I co 4 _ H cl cl H (cis) 1.2-Dichloroethene (tras) cat, Po CH oO (iti ll and tl N. N ca” B @ cu, (sym) Denzaldoxime (entiy Soumons 307308 13. 14, 15, 16. 19. EncireeeainG CHEMISTRY The ability of certain organic compounds to rotate the path of plane polarized light (PPL) is called optical activity. The compounds which rotate the PPL in clockwise direction are called dextrorotatory while those which rotate the PPL in anticlockwise direction are called daevorotatory. The common optically active compounds are lactic acid, tartaric acid, glucose, fructose, etc. The optical activity is measured in terms of specific rotation («), which is given by the equation, 1a lah = 5a where, ¢ 2. = wavelength of light t= observed angle of rotation 1 = length of liquid or solution column in decimeter d = density of liquid in g/mL of the solution. The angle of rotation of the plane polarized light («) is referred as the specific rotation. It not only depends on the kind of molecules, but it also varies considerably with the number of molecules that the light encounters. Also see Ans. 13. The two possible isomers of C,H,,O are: () Diethyl ether (C,H,OC,H,) (i) Butanol (CH,—CH,—CH,—CH,—OH) Lactic acid (CH;CHOHCOOH) has one chiral carbon atem and according lo fisher projection formula it may be represented as: lemperature v . H—C—OH HO—C—H ‘COOH COOH - of (+) lactic acid. for (-) lactic acid These two forms are non-superimposable mirror images of each other. Thus, lactic acid occurs in following three forms: () d- or (+)-lactic acid (i) l- or (-}-lactic acid (iii) dl- or + or Racemic(r) lactic acid E and Z system of nomenclature is used in naming geometrical isomers. It is based on following two steps: (9 Assign a first (1) or second (2) priority to the atoms or groups attached to each carbon atom of the double bond by comparing the atomic numbers.Sowrons 309 (ii) If the higher priority atoms or groups are on the apposite side of the double bond, the configuration is designated as E (entegen) and if the higher atomic number groups are on the similar side of the double bond, the configuration is designated as Z (Zusamen). CHAPTER 7 1. (c) The reactions which are not truly first order reactions but show first order kinetics under certain conditions are termed as pseudo-unimolecular reactions. For example, (i Acid catalyzed hydrolysis of ethyl acctate H,COOC;H, +H,0 4s CH,COOH + C,H,OH Ettyl acer Abvticacia Ethancd The apparent molecularity of the above reaction is two, but concentration of H,O is in such large excess that it does not change during the reaction, so it does not participate in the reaction. (fi) Acid catalyzed inversion of cane sugar. Cy,H2O), +H,0 “> C,H,,0, + C,H),0, Suctose Glucose Fructose: The rate of reaction is proportional to the concentration of sucrose only. 4. (©) (Temperature coefficient. The ratio of the velocity constants of a reaction at temperatures separated by 10°C is known as the temperature coefficient. The temperatures usually selected for this purpose are 25°C and 35°C. Thus, mathematically, Velocity constant at 35°C _ Kage Temperature coefficients = ONY CONSIANI NDE _ Velocity constant at25°C Koc (ii) Energy of Activation. It may be defined as the additional amount of energy to be supplied to the reactant molecules to reach the threshold energy state or activated energy state, so that their collisions may result in an actual chemical change. Threshold] _ [Energy already possessed energy (E)|~ [by the molecules 5. (a) (#) Chain Reaction. A chain reaction is a chemical or atomic process in which the products of the reaction assist in promoting the process itself. The intermediates which exist in propagating the chain reaction, are called chain Activation energy (E,) = [310 Enciveeninc Crenistey carriers. These may be radicals or ions or neutrons. Common examples of chain reactions are the reaction between the H, and C1, in presence af light, dehydrogenation of ethane to ethene, addition polymerization reactions, atomic fission, etc. . (a) Zero order Reactions. A zero order reaction is one where the reaction rate does not depend on the concentration of the reactant on the rate is proportional to the zeroth power of the concentration of reactants. For example, (@) Decomposition of N,O-on a hot platinum surface 1 H,O-———+N, +50, Rate=KIN,OF, order = 0 in of NH, at the surface of metals like Au, Pt, etc. 2NH, —"+H, + 3H, Rate=K[NH,}°, order=0 Order of Reaction Molecularity of Reaction 1, It is the sum of the power of | [tisthe numberof reacting species taking part concentration terms in the rate law. | in.a single step chemical reaction. 2. It is always determined experimen: | It isa theoretical concept. tally. 3. It may be whole number, zero or | It is always a whole number. fractional. 4. It can change with conditions such as | It is invariant for a chemical equation. pressure and temperature. 5. It gives information about the | It does not give any information about the mechanistns of reaction. mechanism of reaction.Souunons 311 1. The reactions which show first order kinetics are called first order reactions. 2. For example, 2 NH,NO,—+ N, +2H,0 Rate = K[NH,NO,] 1 N,0,{g) —+ 2NO,{9) + 5 0, Rate = K[N,O,) . The reactions whieh are not truly first order reactions but show first order kinetics under certain conditions are called pseudo first order reactions. For example, CH,COOC,H, +H,0 —HL, CH,COOH +¢,H,0H Rate = K{CH,COOC,H,] 10. Parallel reactions. The reactions in which a substances decomposes in more than one way are called parallel or side reactis ions. For example, (@ Nitration of phenol oH No, Kk —+ OH o-nitrophenol +ANO, (main reaction) ou * NO, (main reaction) Ky. caty+ H,0 (Side reaction) @) GHOH—}2 cH,CHO+H, (Side reaction) Ky, CH,.0.GH,+H,0 (Gide reaction) Reversible reactions. The reactions in which the products of chemical change react together to form the original reactant are called reversible reactions. For example,312 Exomeranc Cuemester () NH,CNO wake comnHy, k, (ii) D-glucose <=> B-D-glucose (iii) CH,COOC,H, + HO === CH,COOH + C,H,—OH CHAPTER 8 2. Water is the most common examples of the one component system, is can exist in three phases-—solid ice, liquid water and water vapors. The three phases may occur in following four possible combinations in equilibrium: (i) Liquid <——> Vapor Gi) Liquid —== Solid ii) Solid =—» Vapor iv) Solid quam Liquid = Vapor The phase diagram of water is shown below: @.0075°C 100°C s74°C Tomporature———> Phase diagram for water system (Not to scale) 3. (i) Degree of freedom. It is defined as the smallest number of independent variables such as pressure, temperature and concentration that must be specified in order to describe completely the state of the system. (ii) Transition Temperature(iii) Heterogenous System. The system in which the reactants and the products are ‘Sowmons present in two or more phases is called the heterogenous system. CHAPTER 9 rani Coo (This type of corrosion occurs through the direct action of environmental atmospheric gases such as oxygen, halogen, hydrogen suiphide, sulfur dioxide. nitrogen or anhydrous This type of corrosion occurs due to the existence of separate anodic and cathodic ateas between which current flows through the conducting solution. At anodic area oxidation occurs.and anodic part af metal is. 313. inorganic liquid with metal surfaces in | destroyed immediate proximity. (i) Common examples are: (2) Corrosion of iron at high tempera- tures, 4Fe +30, ———+ 2Fe,0, Fe + 20, — Fe,0, 2Fe + 0, —+ 2FeO (b) Tarnishing of Ag metal by HS. 2ag+H,S HO, Ag +H, Common example is: (a) Rusting of iron 1 Be + 5:0, + HJO— Fe? + OH Fe’ + 20H" ——> Fe(OH) Rust 7. Stress corrosion is the combined effect of static tensile stresses and the corrosive environment on a metal. This corrosion is seen in fabricated articles of some alloys such as zinc brasses and nickel brasses. Caustic embrittlement is a very dangerous form of stress corrosion, occuring in mild steel exposed to alkaline solutions at high temperatures and stresses. It is seen in steam boilers and heat transfer equipments. Caustic embrittlement can be controlled by addition of sodium sulphate to the boiler water and also by the used of lignin or tannin as additives. 8. The Corrosion rate is affected by: () Position in galvanic series. When two metals or alloys are in electrical contact, in the presence of an electrolyte, the more active metal suffers corrosion. The rate and severity of corrosion depends upon the difference in their positions, and greater is the difference, the faster is the corrosion of the anodic metal alloy. (ii) Effect of pH. Generally, acidic media are more corrosive than the alkaline or neutral media. The corrosion rate of iron in oxygen-free water is slow, until the pH is below 5. The corresponding corrosion rate in presence of oxygen is much higher.314 Encineemine Cremstey 12, Silver and gold metals are placed much lower than iron in the electrochemical series and thus are much less active metals. So iron suffers extensive corrosion in moist. environment but silver and gold do not suffer corrosion. 20. Anodic Inhibitors ‘Cathodic Inhibitors. @) These stifle the corrosion reaction, | In acidic solutions these slow down the occurring at anode, by farming a sparingly soluble compound with a newly produced metal ion. (ii) These include chromates, phosphates, tungstates or other ions of transition elements with high oxygen content. diffusion of hydrated H’* ions to the cathode, and or by increasing the over voltage of hydrogen. While in natural solutions these eliminate oxygen from the corroding medium. These include the use of organic inhibitors like amines, mercaptand, etc. for acidic solutions and Na,SO, or deaeration for natural solutions. Anodic Coating (i) These coatings are produced from coating metals which are anodic to the base metal ie., which is to be protected. ii) For example, coating of Zn, Al and Cd ‘on steel. (iii) If pores, breaks or discontinuties occur in such a coating, the base metal is not corroded, till all the coating metal is consumed. Cathodic Coating, These are obtained by coating a more noble metal (ie, having higher electrode potential) than the base metal. For example, coating of tin on iron. If pores breaks on discontinuties occur in such a coating, the corrosion of the base metal is speeded up. 28. Corrosion caused by direct chemical action of atmospheric gases such as oxygen, halogen, sulphur dioxide, hydrogen sulphide with metal surfaces in immediate proximity is called dry corrosion. In this type of corrosion generally a solid film of the corrosion preduct is farmed on the surface of the metal which resists further corrosion. However, if a soluble or liquid corrosion product is formed, then the metal is exposed to further attack. For example chlorine and iodine attack silver, generating a protective film of silver halide. While, during detining of tinned law carbon steel can using Cl, gas at high temperatures (over 120°C), tin is converted into volatile ‘SnCl, and hence all tin is removed. (a) Corrosion Inhibitors. These are the substances which when added to the electrolyte solution reduces the rate of corrosion. These are of two major types: 33.9. 11. Sownons 315 (i) Inorganic inhibitors such as silicates, chromates, borates, etc. suppers the rate of corrosion by acting on the anode. Alkaline NaNO, alone or in combination with other inhibitors such as phosphate have been used to control corrosion of tankers and pipelines. (ii) Organic inhibitors act by forming protective layers an the metal surface by adsorption. These include surfactants containing polar groups, organic bases such as amines, pyridines, quinoline and their derivatives, etc. (b) Passivity. It is defined as a phenomenon in which metal or an alloy exhibils a mutch higher corrosion resistance than its position in electrochemical series would indicate. This is due to the formation of a thin (0.0004 mm thick) but highly protective film of oxide on the surface of the metal or alloy. The passivated metal can be rendered active by a change in the environmental conditions. Metals which exhibit passivity include iron, chromium, nickel, titanium and alloys of these metals. CHAPTER 10 SHORT ANSWER TYPE QUESTIONS It is the intererystalline cracking of the boiler metal from the caustic attack and is caused by using highly alkaline waler in boiler. The free sodium carbonate generally left after L-S process in soften water decomposes to NaOH and CO). Na,CQ, + H,O— 2NaOH + CO, The NaOH containing water flows into the small cracks of the boiler by capillary action dissolving the iron of surrounding area inside the boiler. At there areas corrosion takes places in such a manner that intergranular cracks occur in an irregular fashion. This is called causticembittlement. It can be prevented by following methods: (i) Tannin or lignin should be added to boiler water. (ii) Sodium phosphate should be used instead of sodium carbonale during the softening process. (ii) Sodium sulphate should be added to water. . The process of formation of wet steam is known as priming, It is caused by (i) the presence of large quantities of alkali sulphate and chloride in water (ii) sudden boiling (ii) sudden increase in steam production rate (iv) improper boiler design. Foaming is the persistant formation of foam or bubbles in the boiler which do not break easily. It is due to the presence of oil which generally reduces the surface tension of water. Priming and foaming can be prevented by following methods: ()) Addition of antifoaming agents (i) Mechanical purifiers easily check priming.316 © Encinesrinc Coesustiy (iii) Addition of compounds like aluminate. (iv) Avoiding rapid change in steaming rate. 22. In lime-soda process generally lime and soda ash are used for the precipitating process of softening. The reactions involved in this process are: (i) For carbonate or temporary hardness CO, + Ca(OH), —— CaCO, 1 +H,0 Ca{HCO,), + Ca(OH), ——> 2CaCO, | +2H,O Mg(HCO,), + (CaOH), —— MgCO, + CaCO, | + 2H,0 MgCO, formed further reacts as: MgCO, + Ca(OH), ——> Mg(OH), 4 + Caco, + (i) For non-carbonale or permanent hardness CaSO, + Na,CO, ——> CaCO, | +Na,SO, MgSO, + Ca(OH), + Na,CO, > Mg(OH), J + CaCO, | + Na,SO, MgCl, + Ca(OH), + —> Mg(OH), | + CaCl, CaCl, + Na,CO, —~» CaCO, | + Na,SO, 23, The soap consuming capacity of water is known as hardness of water. Il is generally caused by calcium and magnesium ions present in water. Polyvalent ions of metals like strontium, iron, aluminium, Zine and mangneses etc., are also capable of Precipitating the soap and thus, Contribute to hardness. The water hardness may be classified as: ( Temporary hardness. This type of hardness is mainly caused by bicarbonates of calcium and magnesium ie., Ca(HCO,), and Mg(HCO,),. It can be removed by boiling Ca(HCO,), H+ Caco, | + H,0 + CO, Mg(HCO,), + 4 MgCO, + H,O + CO, (fi) Permanent hardness. This is due to the presence of sulphates and chlorides of calcium and magnesium. It can not be removed by boiling. Various units of water hardness are: = Milligram per litre (mg/L) Parts per million (ppm) m Degree clark (° Cl} Mt Degree french (° Fr)Sownons 317 CHAPTER 11 4. (a) Calorific value of a fuel is defined as the amount of heat obtained when unit mass of a fuel is completely burnt. 40 Electrically ‘operated stirrer Bomb calorimeter Working of calorimeter. A weighed amount of fuel is placed in silica cruscible supported over the ring. A fine magnesium wire touching the sample of the fuel is streched across the electrodes. Oxygen supply inforced into the bomb to a pressure of 25-30 atmosphere. The bomb is then carefully placed in the calorimetric vessel containing a known amount of water. The stirrer is driven and the initial temperature of water is noted. The electrodes are then connected toa battery and circuit is completed. The combustion of the fuel take place with the evolution of heat which is transferred to the water. Maximum temperature shown by the thermometer is recorded. The calorific value of the fuel can be calculated as: (W + w) (tp — ty) x c cal/g where, W = weight of water in calorimeter = water equivalent of calorimeter = observed rise in temperature of water = weight of the fuel.318 ENcieeunc Cremistay 5. (a) Gross Calorific value Net Calorific value Itis the total amount of heat generated when | [tis the total amount of heat generated when a unit mass of fuel is completely burnt and | a unit mass of fuel is completely burnt and the products-of combustion are cooled down | the products of combustion are allowed to to 60°F or 15°C. escape. 5. (b) Please refer to Ans 4(b). 6. (a) Proximate and ultimate analysis of coal. Proximate analysis of coal includes the determination of moisture, volatile matter, ash and fixed carbon in a given sample of coal. It gives quick and valuable information about commercial classification and suitability of a coal for a particular industrial use. Whereas, ultimate analysis gives us information about the percentage of carbon, hydrogen, sulphur, nitrogen and oxygen present in the sample of coal. & ® Analysis of flue gases. In order to have proper control on combustion process, an idea about the complete or incomplete combustion of fuel is made by the analysis of flue gas, It gives us following information: (i) If the flue gases contain considerable amount of carbon monoxide, i indicates that incomplete combustion is occuring and also indicate short supply of oxygen. (i) If the flue gases contain a considerable amount of oxygen, it indicates that the oxygen supply is in excess, though the combustion may be complete. The analysis of flue gases is made with the help of orsat’s apparatus. 8. (0) Synthetic petrol. The synthesis of motor fuels from non-petroleum sources such as oil shales lignites and bituminouscoals is known as synthetic petrol. Synthetic petrol can be obtained by following methods. (i) Polymerization of gases obtained as by products from cracking of heavy oils. (ii) Fischer-Tropsch process Wii) Hydrogenation of coal by Bergius process 31. (a) Please refer to Ans. 5{a). CHAPTER 13 11. Stoichiometric detects are of two types: (i) Schottky defects. These defect arises when a pair of one cation and one anion are missing from an ionic erystal tattice. This defect results in a decrease in the overall density of the crystalline ionic substance. There are seen in NaC! and CsClSownons 319 (ii) Frenkel defects. These defects arises when an ion leaves its lattice its lattice site and enters intersfitial site in an ionic crystal lattice. This is shown by Ag Br, CaF, ZnS ete. Non-stoichiometric defects arise as a result of the presence of small ameunt of impurities. Such impurities drastically change the properties of crystalline substances. For example, addition of a small amount of CaCl, (less than 0.1%) to NaCl can increase its conductivity 10,000 lines. 24. Acovalent bond is formed by the shairing of electrons in pairs between two atoms, both of which make equal contribution of electrons. When each atom contributes one, two, or three electrons such that two, four, or six electrons are shared in all, the union so set up is called single or double or triple covalent linkage or bond respectively. For example, H+‘H——-H:H or H-H 20: 4 :O:——5: or O=O Properties of covalent compounds: @ They are directional in nature, = Their mp. and bp. are low. B They are non-conductor of electricity in fused as well as in dissolved state. @ They are non-polar in nature. 16. p-type Semiconductors atype Semiconductors (i) Such a semiconductor is formed by doping Si or Ge with trivalent impurity (Bor A. (ii) Such a semiconductor has excess of electron holes. (iii) Conduction occur due to the movement | Such a semiconductor is formed by doping Sior Ge with pentavalent impurity (P or As). Such a semiconductor has excess of electrons. | Conduction occurs due to the movement of of electron holes. free electron. 17. Intrinsic semiconductors are extremely pure (above 99.9999%) elements like Si, Ge and Se, having four valence electrons in their atoms and their forbidden energy gap is about 1 eV. Even at ordinary temperature, there are many valence electrons, which possess sufficient energy to jump across the forbidden gap to conduction band. Extrinsic semiconductors are basically intrinsic semiconductors, whose conducting properties have been improved by adding extremely small amounts of specific substitutional impurities called doping agents or dopants. The addition of dopants further reduces the energy gap, thereby allowing more electrons to flow from valence bond to the empty conduction band, thus increasing the conductance.Sownons 321 40. (@) ‘Valence Bond Theory (VBT) Molecular Orbital Theory (MOT) (i) The atomic orbitals after combination | The atomic orbitals after combination lose retain their individual identity. their identity and new orbital called molecular orbital is formed. (ii) The bonded electron pair is localized | All electrons.are free to move along the entire between the combining atoms. molecular orbital under the influence of all nuclei. (ii) It fails to explain the paramagnetic | It explains the paramagnetic character of O, character of O, molecule. molecule. (iv) The concept of resonance is applicable to | Resonance has no role in MOT. XBT. 40, (b) Energy oes trogen Molecular. OMEN orbitals of NO Molecule Molecular arbital diagram of NO molecule322 Excincerinc Cueeusray 40. (c) Bonding Molecular Orbital Antibonding Molecular Orbitals {It is formed by the addition of overlapping atomic orbitals Vto® Va + Vo (ii) It has greater electron density in the region between the two nuclei ofbonded atoms. (ui) Electrons in BMO contribute to attraction between the two atoms. (iv) It possess lower energy than isolated atomic orbitals. It is formed by the subtraction of overlapping, atomic orbital. It has lower electron density in the region between two nuclei of the atoms. Electrons in ABMO contribute to repulsion between the two atoms. Ht possess higher energy than isolated atomic orbitals. —! CHAPTER 14 SHORT ANSWER TYPE QUESTIONS x 1, K,[Fe(CN),] — Potassium hexacyanoferrate (LI) 3. [Cr(en),]Cl, — Tris (ethylene diamine) Chromium (11) chloride 5. [COCKNH,}.ICl, — Pentaamminechlorocobalt (II) Chloride 7. [Au(CN),] — Hexacyanoaurate (IV) 9. (NH,),(2rF,] — Ammonium hexafluorozirconate (IV) 11. Na,[CO(H,O),(OH),| — Sodium diaquotetrahydroxocobalt (1) 13. [V(H,0),IC], — Hexaaquovanadium (IID chloride 15. K,[OsCl,N,] — Potassium azidopentachloroosmate (IV) NO, 17. (NH),CO—>CONHY, | — Octaammine-p-hydroxo-p-nitrodicebalt ‘OH (1) cation 19. [COfen)(NH,),C1Br]NO, — Diamminebromochloro ethylene diamine-Coballt (II) nitrate (i) Bethe and Van Bleck (i) BM (iii) Triply degenerate (iv) Crystal field splitting of octahedral complexes, crystal field splitting of tetrahedral complexes. 4.Sownons 323 6. High spin complexes are formed by the use of outer d-orbitals for hybridization. These complexes have larger number of unpaired electrons. For example, complexes such as [COF,]*, [FeF,J*, [Cu(NH,),P** etc. Low spin complexes are formed by the use of inner d-orbitals for hybridization. In these complexes, the electrons of the metal are forced to pair up and hence complex will be diamagnetic and will have lesser number of unpaired electrons. For example, {CO(NH,),J**, [Cr(NH,),F*, [Mn(CN),]* ete. Double Salt ‘Coordination Compound (i) These salts give test of all the constituents | In these compounds, individual identily of and individual component do not loose | the constituents is lost and a complex ion is their identity. formed. (ii) These donot in value coordinate | These in value coordinate bonding. bonding. 9. (a) Chelates. Chelates are those cyclic structures which arise from the union of metallic atoms with organic or inorganic molecules or ions. The rings of such compounds are called chelate rings. and phenomenon as the chelation. NH, NH, Le CH,—NH\. Ht oth M CH,—NH,~ CH,—NH —CH, where, M is the metal. Chelated compounds are normally more stable than similar non chelated compounds. The more rings that are formed, the more stable the complex. There are used in water softening, purification of metals, food preservation, separation of radioactive metals, color technology, etc. (8) Poly nuctear complexes. Complex compounds containing several central atoms are called polynuclear or bridged complexes. The common bridging groups are —OH;, —O—, —O—O—, — NH;, —NH—, —NO, etc, Common examples of such complexes are —324 Encinezunc Cremstey NH, @ Dito [oc Seon OH a ™~ ,CO— OH —CO(NH, [ws Non »| OH OH (i) Trinuclear complex (NH,),CO OH CO OH CO(NH)) OH OH Hexammine-}-hexaal-tricobalt (ILI) These complexes may be used in the catalytic reactions. (©) Ligands, Ligands are neutral molecules or ionic species which are attached with the central metal ion. Those are classified on the basis of their mode of attachment to the central metal ion. These are classified as: (i) Unidentate ligands, ¢.g., HO, NH,, CO, Br’, I", OH" ete. (i) Pridentate ligands, e.g. C,0}-, CH, — CH; ete. NH, NH, (iii) Tridentate ligands, e.g., CH, CH, — CH; hin haw NH, (CH,COO" (iv) Tetradentate ligands, e.g, NE-CH,COO” ‘CH,COO™ (0) Pentadentate ligands, ¢.g., ethylenediamine triacetic acid (vi) Hexadentate ligands, e.g., EDTA. 14. (i) K,INi(CN),1 (i) K[Mo(CN),] (iii) [Fe(CO),] (ip) [Mr(CO),C,H,]17. 21, 1. Soumons 325 The following are the major limitations of valence bond theory of coordination complexes: {9 It offers no possibility of predicting magnetic behavier excep! the number of unpaired electrons in the complex. (ii) The theory does not why a particular structure is preferred. (iii) The theory offers no convening explanation of causes of maximum pairing. (iv) In this theory too much of emphasis is given of the metal ion while the nature of the ligand is not properly stressed. (@) Please refer to Ans. (c). Alfred Werner regarded as the father of coordination chemistry, pul forward following postulates: (@) The metals possess two types of valencies, primary and secondary. The primary valency is ionizable and carves ponds to the oxidation state of the metal. The secondary valency is non-ionizable and is satisfied either by negative ions or neutral molecules. (ii) The central metal atom satisfies both primary and secondary valencies. (ii) Every metal has fixed number of secondary valancies, known as the coordination number (iv) The secondary valencies attribute to the isomerism in coordination compounds. According to Sidwick all neutral molecules or anions which are capable of being coordinated to the central metal ion have atoms with atleast one unshaired (lone) pair of electrons in their valency shells. The ligands donate the electron pair to the central metal ion and thus form a coordinate bend. According to Sidwick, the total number of electrons surrounding the coordinated metal ion is equal to the atomic number of the inert gas which follows central metal atom in the periodic table. This is called effective atomic number rule. CHAPTER 15 {a) (i) In a simple cube, atoms are located at the comers only and each atom is shaved by eight neighboring atom. So, Number of atoms per unit cell = 8 « : =1 (ii) In a body centred cube, atoms are located at the corners and one atom in the center of the cube which belong wholly to the cube. So, Number of atoms per unit cell = x 5 +1=2326 © Enciweerinc CHemistry 13. (a) Packing efficiency or atomic packing factor is the manner in which atoms or ions or molecules are arranged in the solid state in a unit cell/crystal structure. The packing arrangementof atoms depends on the relative radii of the atoms involved and on the character of bonding between atoms. The density of packing in a crystal is most convieniently determined by the atomic packing factor (APF), which is given as, Volume of the atoms per unit cell Volume of the unit cell 21. (a) Bravais in 1848 on the basis of study of crystal symmetry showed that all structures can be generated by using only 14 types of space lattice or unit cells. Thus, there are only 14 types of space lattices known as Bravais lattices. These 14 types of unit cells will give rise to 2.30 types of lattice structure by performing 32 symmetry operations as (i) translation (ii) rotation (ii) translation + rotation and (iz) reflection. All real crystals belong to any one of the 230 space groups. 25. (a) For a cubic crystal there are: APF = (é) Rectangular planes of symmetry = 3 (i) Diagonal planes of symmetry = 6 (iff) Four fold axes of symmetry = 3 (iv) Three fold axes of symmetry = 4 (v) Two fold axes of symmetry = 6 (i) Center of symmetry = 1 Total elements of symmetry = 23 in a cubic crystal. 29. (a) Ina hexagonal close packing, the third layer of spheres becomes exactly identical to the first layer. This type of packing is also referred to as ABABA ...... arrangement, It is abbreviated as HCP, HCP arrangement can be shown as: In the second way to pack the spheres in the third layer is to place them over unoccupied hallows of the first layer.Bae SUNINANHIE Haas eee: