Downloaded From BEhelp.in Gl The Online Guide For B.E. For More Downloads Visit BEhelp.inS. Brotuen’s ENGINEERING SOLVED PAPER CUM QUESTION BANK (A Unique Collection of Questions ) Strictly According to C.S.V.T.U. Syllabus (Common for all Branches) SBP S. BROTHER'S PUBLICATIONS Bajrang Chowk, Santoshi Nagar Raipur (C.G) "492001Published by: ‘S. BROTHER'S PUBLICATIONS Bajrang Chowk, Santoshl Nagar Raipur (C.G) - 492001 Phone No.: 9893201011 9827106812 9630312324 © Aillrights reserved with publisher * No part of this book may be iranslated or reproduced in any form without prior permission of the publisher. First Edition - 2009 Price : Rs. 80/- . Note: This book has been published strictly according to the syllabus. Care has been taken in all the respects during the publication of this| book . The publisher will not be responsible for any controversy. All the legal disputes in this regard will be subjected to Raipur Juris- diction only. a MM. : 80 Total Periods : 40 Total Tutorial Periods : 10 is of water alkalinity, hardness. Water for ning processes - Lime - Soda process, Zeolite and fon ex= change method, boiler feed water, boiler problems - scale, sludge, priming and foam. ing, caustic embitterment and corrosion, their causes and prevention removal of silica, removal of dissolved gases, carbonate and phosphate conditioning colloidal condi, tioning calgon treatment, Numerical problems on Lime - Soda process, Zeolite and on exchange method. INo. of Periods : 8 +2] + Fuels : Classification, combustion and chemical principles involved in it calorific ‘value : gross and net Calorific values and their determination by bomb caloriineter, ‘Solid Fuels : Proximate and ultimate analysis of coal and their importance. High ‘and low temperature carbonization, Coke. Its manufactures by Otto Hoffman oven. Liquid Fuels : Petroteum : Its chemical composition and fractional distillation, Knocking and chemical structure, octane number and cetane number and their significances, power alcohol, Analysis of flue gases by Orsat’s apparatus, Numerical ‘on calorific value, combustion, proximate and ultimate analysis of coal No. of Periods : 842] UII : Corrosion : Types of corrosion (dry, wet, atmospheric, galvanic and concen tration corrosion), theories of corrosion, protective measures against corrosion, fac tors affecting corrosion, pitting corrosion, waterline corrosion, underground corro sion, stress corrosion, micro biological corrosion, corrosion fatigue, Batteries and Battery Technology : Primary cells, secondary battcries reserve batteries, fuel cells, solar cells. (No. of Periods : 8 +2] Unit - IV : Portland Cements : Introduction, types Portland Cement, methods of mani facturing (dry and wet process), properties of cement, haracterization of constitu. tional compounds of cement, ISI specification Lubricants : Classification of lubricants and mechanisms of lubrication, Polymers : Industrial applications of thermoplastic; thermosetting, polymers, Properties and applications of the major polymers viz polyethylene, Teflon, PVC, nylon, phenol formaldehyde. Elastomers, Natural Polymers, {No. oF Pe ods : 8 +2) + -V: Introduction to Important Industrial Chemical Industrial Method of preperation (one each), properties and ,major industrial; uses of following chemicals : Ammonium Chloride, Ammonium Nitrate, Ammonium Sulphate, Bromine,Caleium Phosphate (Monocalcium Phosphate, Super Phosphate), ‘Chromic Acid (Chromium trioxide Chromic anhydride), Acrylonitrile, Benzene (Ben z0l), Butyl Acetate, Caprotactam, Carbon Tetrachloride, Cellulose Acetate, Cresol (Crysylic Acid), Chloroform (Trichloromethane), Ether (Ethyl Ether), Ethyl Alcohol (Ethanol, Industrial Alcohol), Glycerine (glycerol), and Melamine. Explosives and Propellants : Characteristics of Explosives, Oxygen Bal- ance, Classification of Explosives : Primary or Initiating Explosives or Detonators; Low Explosives or propellants; High Explosives, Preparation and Applications of Explosives, R ocket prépellants, Characteristics of a Good Propellant, Classification of Propellants. INo. of Periods : 8 +2]‘Special Features of the Q.B./ Books published by S. BROTHER’S PUBLICATIONS 1. Strictly as per C.S.U.T.U. Bhiali syllabus . 2. Answers are written in such a way that we prepare our notes. 3. Answers are given systematically point to point in a balanced way in simple and lucid language. jum marks. A sure means to obtain maxi Complete Notes for - Grand Success in Examinations CONTENTS J 4. An excellent collection of question- answers. Unit Unit name Page 1 Water 1 2 Fuels 6 3. Corrosioh m1 4. Cement, Luvricant and Polymers 151 5. Industrial chemicals, Explosives and 191 Propellents ‘ COPIERS NAGAR 16, 9584601916 KRISHNA SMRITI - 96918593; MoO, UNIT 1 WATER Syllabus : Water : Specification for water, analysis of water alkalinity, Hardness, Water for domestic use, Water, softening processes, Lime soda process, Zeolite and ion exchange ‘method, Boiler feed water, Boiler problems-scal, sludge, priming and foaming, caustic tembitterment and corrosion, their causes, and prevention removal of silica, Removal of dissolved gases, carbonate and phosphate conditioning, colloidal conditioning. calgon treat- ‘ment, Numerical problems on lime soda process, zeolite and ion exchange method. - |__Deseriptive Questions Q. 1. What is water ? Describe the different sources of water ? _ Ans. “WATER - Water is the natures most abundant and useful compound without which living organisms cannot survive. It is not only essential for the living beings but it is also essential for most of the industries. (Such’as-paper industry. ) Textile industry, chemical industry, washing, atomic energy, pro- duction of steel et. 7 Sources of water About 70% of total earth is covered by water. Out of total water, about 97% of the water is present in oceans or seas, 2.3% is trapped in polar ice caps. About 0.7% of the total water is available as fresh water which can be used for domestic, agricultural and industrial use. ‘The sources of water are broadly divided into two categories : ‘1, Surface water and 2. Underground water. 1. Surface water : This water is found.on the surface of earth. It is generally clear and colourless and acidic in nature because: of dissolved organic matter and CO,. Surface water may be of following types : (® Flowing water : e.g. (a) River water (b) Stream water Gi) Stil water : e.g. (a) Pond water (b) lake water (c) Reservoirs water. Gi) Rain water. Gy) Estuarine and sea water. (saline water) 2. Underground water : This water is found inside the earth. e.g. (@) Well water (b) Spring water.2 | SBP Q. B. Applied Chemistry Q. 2. Describe specification of water for different purposes ? Or Describe specification of water for different industrial uses. Ans. Specification of Water for Different Purposes ‘Water is an universal solvent of nature because of their polar nature. It is used as solvent in many industries. Each industry has its own specifi- cation for water. Few examples are as follows : 1. In Textile Industry (2) It should be free from turbidity : (turbidity causes uneven dyeing). (b) It should be free from colour, and salts of Fe and Mn : (these impu- Tities cause stains on the fabric). (© It should be free from hardness and organic matter : (Hard water reduces the solubility of acidic dyes and causes precipitation of ba- sic dyes . They also render the dyeing non-uniform, Organic matter may cause foul smell'of the product. . 2. In Laundries : The water should be free from colour, hardness and salts of Fe and (Hardness of water increases the consumption of soaps and detergents. Fe and Mn salts impart undesirable colour to the fabric. 3. Thermai Power Generation-Industry (@) Boiler feed Water : Free from hardness : (hard water causes scale formation on boiler metal surface, thereby reducing heat transfer efficiency and causing shut-down or even accidents.). () Cooling water : The water should be non-scale forming, non-corro- sive, and should not permit the growth of algae. Scale and algae re- duce the heat transfer efficiency and interfere with free flow of water. 4, Paper Industry ‘ (@) Free from alkalinity (alkaline water consumer more alum there by increasing the cost of production). (b) Free from hardness : (Calcium and magnesium salts increase the ash content of the paper produced. (©) Free from colour, turbidity and salts of Fe and Mn : ( colour and brightness of the paper are affected by the above impurities). (@ Free from Silica : (Silica causes creaks in the paper.) 5. Beverage Industry : The water should be pure. It should not be alkaline, because alkalinity in wathr tends to neutralize the fruit acids and distorts the taste. " 6. Dairy Industry : The water should be colourless, odourless, and tasteless. It should be free from pathogenic organisms. Water | 3 @. 3. What do you mean by atkalintty of water ? (C-S.V. LU., Sem I, Nov/Dec. 2006) Or What can be the main possible types of alkalinity in water, (CS.V.TU., Sem I, 2005) Or What is alkalinity of water ? Discuss the procedure of analysis of water alkalinity. Ans. ALKALINITY OF WATER, Alkalinity of water means the total content of those substances in water that causes an increased concentration of OH” ions upon dissociation or due to hydrolysis. The alkalinity of natural water is caused due to the presence of : 1. Salts of some weak organic acids (called humates), that bind H* ions as a result of hydrolysis and increasing OH" ior concentration. 2. The alkalinity of boiler water is also caused due to the presence of PO*, and OH ions. 3. Surface waters containing algae and treated by lime soda process, contain considerable quantities of alkalinity due to OH” and CO*»,, ‘Types of Alkalinity : Depending upon anions present in water, alka- linity may be of following typ 1, Bicarbonate Alkalinity : Water having bicarbonate alkalinity con- tains HCO"; ions. 2, Carbonate Alkalinity : Water having carbonate alkalinity contains , ions. 3.4lydroxide Alkalinity : Water with this alkalinity contain OH” ions. Estimation/ Analysis of Alkalinity ‘The Types of alkalinity present in water sample can be estimated separately by titrating an aliquot of sample with a standard acid using phe- nolphthalein and methyl orange as indicators. The reactions taking place may be represented by the following equations— L [one ]+[H"]—+4,0 4% [cor ]+[4"]—s[hico;] 3, [Hco;]+[1"]—+H,0+c0, ‘The volume of acid run down up to Phenolphthalein end point P cor-4| SBP Q. B. Applied Chemistry responds to the completion of equations : (1) and (2) while the volume of acid run down after P corresponds to the completion of equation (3) The total amount of acid used from beginning of the experiment, i.e, the methyl ‘orange end point (M), corresponds to the total alkalinity present, which represents the completion of reactions (1) to (3). Possible Combinations of Ions Causing Alkalinity : @ OH only Gi) COS only (ii) HCO; only (iv) OH” and CO}- together (v) CO} and HCO; together The possibility of OH” and HCO; ions together is rules out be causé KRISHNA COPIERS SMRITI NAGAR MO, - 9691859216, 9584601916 they combine instantaneously to form CO3- ions. OH+HCO; —>co?+H, 0. ‘Thus, OH"and HCO} ions cannot exist together in water. Similarly water. OHT and HCO; ions also can not be exist together Procedure : Take 100 ml of water sample in clean titration flask and add 2 and 3 drops of phonelphthaline indicator to it. Now titrate the sample using N/50 HSO, from burette till the pink colour is just discharged . In this solution now add 2 or 3 drops of methyi orange indicator and continue titration by adding N/SO H,SO, till pink colour reappears. Calculations : Alkalinity is generally expressed as ppm (parts per million) in term of CaCO. 1000 ml of N/S0 acid solution = 1000 mg CaCO, Hence. ity — Wolof N/S0acid solution _ine/orppm Alkalinity Vol.of sample taken for titration id Let, volume of acid used to phenolphthalein end point = V, ml; and Extra volume of acid used to methyl orange end point = V2 ml. Phenolphthalein alkalinity (in terms of CaCOs equivalents) ¥, x50% 1,000,000 ‘50% 1001000 and methyl orange alkalinity (in terms of CaCO; equivalent). ag = Lt ¥2)50%1,000,000 '50%100%1000 P= “0% ppm 10(%, + V2) ppm. Water | 5 ‘Now since phenolphthalein alkalinity indicates half carbonates (if any) plus all the hypoxide (if any), while the methyl orange alkalinity indicate total alkalinity (due to hydroxides, bicarbonates and carbonate) ; the calcu- lation of hydroxides, carbonates and bicarbonates in the various samples can be made with the help of the following table : Alkalinity OH (ppm) CO} @pm) HCO; (pm) Po ° ° M PM Porm ° ° P=12M ° P ° PcI2M o e M2P P>12M @P-M) 2(M-P) 0 . 4. Why alkalinity of water can not be due to the presence of OH" + CO™; aitd HCO"; at a time ? 7 Ans. The alkalinity of water can not be due to simultaneous presence of OH, CO and HCO; be cause OH and HCO; react to form CO? ions OH” + HCO; —+c0? +H,0 Q. 5. What is hardness of water ? Name two chemicals responsible for permanent hardness. (C.S.V-T.U. Sem. 1, Decisan. 2008-09) Or What is hardness ? What are its units ? Or * Give relationship between various units of hardness. Ans. HARDNESS Hardness is the soap consuming capacity of water. In other words the characteristics of water which prevents the leathering of soap. This is due to presence in water of certain salts of calcium. Magnesium and other heavy metalic ions (e.g. Fe"?, AI”, Mn”) dissolved in it. A sample of hard water, when treated with soap (sodium of potassium salt of higher fatty acid like oleic, palmitic or stearic) does not produce lather, but on the other hand forms a white scum or precipitate. This precipitate is formed, due to the formation of insoluble soaps of calcium and magnesium. ‘Types of Hardness : The hardness of water may be of two types : 1. Temporary or carbonate hardness. 5 2. Permanent or non-carbonate hardness.6| SBP Q. B. Applied Chemistry 1. Temporary or carbonate hardness : It is caused due to presence of dissolved bicarbonates of calcium, magnesium and other heavy metals (eg. Fe'?, AI’, Mn’) and the carbonate of iron. Temporary hardness is mostly destroyed by mere boiling of water, when bicarbonates are decom- posed, yielding insoluble carbonates or hydroxides, which are deposited as a crust at the bottom of vessel. Tius : cxgHoo,), HE , caco, | + H,0 + 00,7 Cale alia bicarbonate carbonate (Insoluble) Ma(HCO,), HE 5 Mg(OH), 4 +2C0, T Magnesium Magnesium bicarbonate hydroxide. 2, Permanent or non -carbonate hardness : It is caused due to the presence of chlorides ani sulphates of calcium ( CaSO; , CaCl;) magne- sium (MgSO,, MgCl,) iron ( FeSO,) and other heavy metals. Unlike tem- porary hardness, permanent hardness is not destroyed on boiling. Units of hardness 1. Parts per million (ppm) is the parts af calcium carbonate equivalent hardness per 10° parts of water, ie. 1 ppm=1 part of CaCOs eq hardness in 10° parts of water. 2. Milligrams per litre (mg/L) is the number of milligrams of CaCO equivalent hardness present per litre of water. Thus : 1 mg/L = 1 mg of CaCO; eq. hardness of 1 L of water But 1 L of water weighs * =I kg= 1,000g = 1,000 x 1,000 mg = 10° mg. 1 mg/L =1 mg of CaCO; eq per 10° mg of water. =I part of CaCO; eq per 10° parts of water = 1 ppm. 3. Clarke's degree (°C) is number of grains (1/7000 /b) (of CaCO; equivalent hardness per gallon (101b) of water. Orit is parts of CaCO, equivalent hardness per 70,000 parts of water. Thus : 1° Clark = 1 grain of CaCO; eq hardness per gallon of water. or 1°C1= 1 part of CaCO, eq hardness per 70,000 parts of water. 4, Degree Frenth (*Fr) is the parts of CaCO equivalent hardness per 10° parts of water . Thus ; 1° Fr=I part of CaCO; hardness eq per 10° parts of water. 5. Milliequivalent per titre (meq/L) is the number of milli equivalents of hardness present per litre. Thus : Water | 7 1 meq of CaCO; pet L of water 10 x 50 g of CaCO eq per litre ‘50 mg of CaCO eq per litre 50 mg/L of CaCO; eq = 50 ppm. Relationship between various units of hardness : 1 ppm = | mg/L = 0.1°Fr = 0.07°CI = 0.02 meq/L 1 ppm 0.1° Fr = 0.07° Cl = 0.02 meq /L 4.3 ppm = 14.3 mg / L = 0.286 meq /L 7° Cl=0.2 meqiL 50 mg/L = 50 ppm = S°Fr=0.35°C] Q. 6. Distinguish between temporary and permanent hardness. Ans. Difference Between Temporary and Permanent Hardness 1 meq ‘Temporary Hardness Permanent Hardness M1. tes caused by the presence &t | 1. Its eaused by the presinee of dissolved biearbonates of Soluble chlorides and sulphates of calcium, magnesium and other calcium, Magnesium, iron and heavy metals. other heavy metals (2. Salts which are responsible for 2. Salis which are responsible for temporary hardness are perm ancat hardeess el CaCI CaCO, +2NaCl s Or CaCl, and CaSO, CaSO, +Na;CO3~» CaCOs+NayS0,} —§ What is water softening ? Discuss lime soda process of softening of 2. | Perm. Hard. OfMgCl, | MaCh+Ca(OH)y—» Mg (OH), nn water. and MgSO, + CaCl CaCl, +NajCOs-> CaCO, Or +2NaCl Describe lime soda process of removal of dissolved salts in water. 3. | Ca(eCO,), (Temp.Ca) i Or 4. | Mg(HCo,), Ca(HCOs), + Ca(OH), + 2CaCO, a Write chemical reactions involved in water softening by lime-soda (Temp. Mg) +2H,0 Process. }S._ | HCO" (NaHCO) Mg(HCO;),+2 Ca(OH)» 2caco, | L-s ‘Ans. WATER SOFTENING . a +2H,0 (Or - Removal of Dissolved Salts) 6 | FreeacidsH+ HCland | 21CO; ci HCO; + 1p > 2CaCO, The process of removing the hardeness producing salts from water ‘Ca(OH)2 > 2CaCO, L is called softening of water. Temporary hardeness of water can be re~ 4H,0+C0F moved by prolonged heating of the water. The dissolved gases (e.g, CO, no - : | and Q;) are also removed simultaneously. woe pees 9° CaCO; + HO Las: Methods of Removing permanent Hardeness : In industry, the Pees 'a(OH), > CaCl, +2H;0 permanent hardeness of water can be removed by following three methods A sgulant FeSO, eae €aC05+2Nacl | Las : 180, + Ca(OH), > CaSO, +2H,0 | LAS 1. Lime soda process, & | Ak(SOo; CaSO, +NazCO; + CaCO, +Na,SO,] LAS 2. Zeolite process. 9. | NaAlO2 FeSO, +Ca(OH)) > Fe(OH), +CaSO,| 3. Deionization or ion exchange process. . ‘CaSO, +Na,CO3-,CaCO +Na;SO, Lime Soda Process of Water Softening 2AL(S0,)s+3Ca(OH), > 2AKOH), This is the most important of water softening The principle involved +3 CaSO, 3CaSO, +3Na,CO; > in this process is to chemically convert all the soluble, hardness causing 3CaCO; + 6Na+NaAlO, +H,0—> impurities into insoluble precipitates which may be removed by setting and AI(OH), + NaOH Now 100 parts by mass of CaCO; are equivalent to: (i) 74 parts of filtration, In this method, the soluble calcium and magnesium salts in water are chemically converted into insoluble compounds, by adding calculated amounts of lige [Ca(OH),] and soda { NazCOs]. Calcium carbonate CaCO) and magnesium hydroxide [Ma(OH)], so-precipitated, are filtered off. ‘The reactjons taking place are summarized in table 1.1 Ca(OH), and (ii) 106 parts of Na;CO3. ++ Lime requirement for softening ‘ aq | Tempe? +2 TempMg?® + Norm Mg? + Fe™ + AP* = {pp | *COz +H (Clr H,S0,)+ HCO; -Naalo, allin terms of CaCO,eq ;10 | SBP Q. B. Applied Chemistry ©. Soda requirement for softening perm.(Ca* +Mg”* + Al" +Fe”*) +H’ (HClor H,S0,)-HCOs allin terms of CaCOyeq The lime soda process may be of ‘Types of Lime Soda Processes four types : 1. Cold lime - soda process 2. Hot lime soda process. 1. Cold lime soda process In this method, calculated quantity of chemical (lime and soda) are ‘mixed with water at room temperature. At room temperature , the precipi- tates formed are finely divided, so they do not settle down easily and cannot be filtered easily. Consequently, itis essential to add small amount of coagu- lants (like alum, aluminium sulphate, sodium aluminate, etc.), which hy- drolyse to flocculent, gelatinous precipitate of aluminium hydroxide and entraps the fine precipitates. Use of sodium aluminate as coagulant also helps the removal of silica as well as oil, if present in water. Cold L-S process provides water, containing a residual hardness of 50 to 60 ppm. NaAlO; +21,0-—+ NaOH + AI(OH), Sod. aluminate Al,(SO,); +3Ca(HCO, ), —+2AKOH), | +3CaSO, +6CO; T Coagulant Cal. bicarbonate (Hardness in water) ‘There are four basic types of softeners used for softening water by bid lime process. (@) Intermittent or batch softener. Continuous or conventional softener. . iif) Catalyst or aspirator softener. ) Sludge blanket softener. (@ Intermittent or Batch Softener : The intermittent type of cold time-soda softener consists of a set of two tanks which are used in turn for softening of water. Each tank is provided which inlets for soft end water angi sludge and a mechanical stirrer (Fig 1.7) Raw water qnd calculated quantities of the chemicals are slowly sent into the tank simultaneously under agitation with the help of the stirrer. Some sludge from a previous. Thus by the time the tank is full, the reaction is more or less complete. Water | 11 Stirring is stopped and the sludge formed is allowed to settle. The clear softened water is collected through a float pipe and sent to the filtering unit. The sludge formed in the tank is removed through the sludge outlet. By employing a set of tanks planned for alternate cycles of reaction and set- ing, continuous of softened water may be ensured. aw water Chemicals cine + Soda “+ Coagulant) [| tere water ‘Studge outlet =] Fig. 1.1. Intermittent cold lime-sods softener. (ii) Continuous or conventional softener : In this process the raw water and the chemicals in calculated quantities are conti the top into an inner cham- a aes ber of vertical circular tank Motor provided with a paddle stir- rer (Fig. 1.8) The raw wa- Chemicals ter and the chemicals flow- _Seoegutann ingdownthechambercome Wood into close contact because "iter of the continuous stirring stirrer pad and the softening reactions dies Driving belt chamber take place. The sludge chember formed settles down to the stizer bottom of the outer cham- ber from where itis periodi- cally removed through the sludge outlet. The softened Sees water rising up passes (cat, through the fibre filter Me(OH), where traces of sludge are removed and filtered soft - 1.2,Continuows cold lime-Soda water passes through the outlet provided. Water treated by the cold lime - Soda process generally produces Softened water containing about 50-60 ppm residual hardness. Gil) Catalyst or aspirator softener : The Aspirator consists of a conical tank which is about two - thirds filled with finely divided granular12| SBP Q. B. Applied Chemistry Ait vent catalyst (Fig. 1.9). The tank used may be either open (for gravity op- eration) or closed (for operation) ‘or closed (for operation under pres- sure) In both the cases the raw wa- ter and the calculated quantities of chemicals enter the tank tangen- tially near the bottom of the cone and spiral upwards through the sus- pended catalyst bed. The catalyst ‘employed is a finely grainuled (0.3 to 0.06 mm diameter ) insoluble mineral substance such as graded calcite or sand or sand or green sand. The retention time is about 8 to 12 minutes. The sludge formed during the softening reactions deposits on the catalyst grains in an adherent form and hence the granules grow in size. The softened water rises to the top from where it is drawn off. ‘The catalyst or spiractor type of continuous water softener is of in- terest as it gives a granular sludge which drains and dries rapidly and can be handled easily. . . (iv) The sludge blanket soficner : The sludge blanket type of water treatment equipment is extensively used for coagulation and settling as well as water softening by cold lime soda process. These softeners differ from the conventional type in that the treated water is filtered upwardly through a suspended sludge blanket composed of previously formed precipitates. Thus in a single unit, all the three processes namely mixing, softening and clarification take place. * 2) Hot Lime Soda process : This process involves tfeating of water with softening chemicals at a temperature of 80 to 150° C. In this process only sodium carbonate is used for softening. The excess of sodium car- bonate (Na,CO;) is carried out into boiler which dicomposes into NaOH at high pressure and temperature. ‘Softend caste (enahed snd ped cate ot green sand) ‘water Wh Chemicals for enlarged catalyst Fig. 1.3. Catalyst or spiractor type cold lime-soda water Na,CO; +H,0 —HishtemP. , 2NaoH +CO, and High Pressure NaOH so produced goes into softener and react with non-alkaline hakdness of sodium and calcium carbonate. i Ca(HCO,), +2NaOH ~> CaCO, +NazCO; +2H,0 F CaCl, +Na,CO, > CaCO, +2NaCl Water | 13 Mg(HCO;), +4NaOH > Mg(OH), +2Na,CO, +2H MgCl, +2NaOH —> Mg(OH), +2NaCl. A typical hot lime-soda water softening plant consists essentially of three parts. |. a “reaction tank’ in which raw water, chemical and steam are thor- entation vessel’ in which sludge settles down , and 3. a ‘sand filter’ which ensures complete removal of sludge from the softened water. ‘The softening capacity of hot lime soda process will be several times higher than the cold process. KRISHNA COPIERS SMRITI NAGAR MO. - 9691859316,9584601916 Raw water >: Teed inlet, ‘ ep ies Super-heated 4S) " sean inet : Reaction os I Senenea Cotten seai- Conte mention sto oer Gravel set tier sage Precept -+Fitered soened [cco Mgcon emer cate Fig. 1.4. Continuous hot lime-soda softener. If water is alkaline, filtration through sand and groved beds might con- taminate the water with dissolved silica, particulates of quartz used is of ferior quality. Other filtration media used are anthracite coal, calcite and magnetite; If excess of chemicals are used over the theoretically required, more rapid and more complete removal of hardness will result. But if larger excess of chemicals are used, they will appear in the softened water. ©. 8 Describe the advantages and disadvantages oflime-soda process. Ans. Advantages of Lime Soda Process 1. Itis very economical. 2. If this process is combined sedimentation with coagulation,14| SBP Q. B. Applied Chemistry lesser amounts of coagulants shall be needed. 3. The process increases the pH value of the treated -water, thereby corrosion of the distribution pipes is reduced. 4, Besides the removal of hardness, the quantity of minerals in the water are reduced. ‘5. To certain extent, iron and manganese are also removed from ‘the water. > 6. Due to alkaline nature of treated-water, amount of pathogenic bacte- ria in water is considerably reduced. Disadvantage of L-S process 1. Foreefficient and economical softening, careful operation and skilled supervision in required. : 2. Disposal of large amounts of sludge (insoluble precipitate) poses a problem. However the sludge may be disposed off in raising low- lying areas of the city. 3. This can remove hardness only upto 15pm, which is not good for boilers. * = Q 9. Write advantages of hot lime-soda process over cold lime-soda process. Or Why does hot time-soda process better than cold soda process. ‘Ans. | Advantages of Hot Lime-soda process over cold lime-soda process Since hot lime-soda process is operated at a temperature close to the boiling point of the solution therefore itis more advantages. The advantages of hot lime-soda process are as follows— 1.The reaction proceeds faster. 2. The soft penning capacity of hot process is increased to many fold, 3. The precipitate and sludge formed settle down rapidly and hence, no coagulants are needed. 4, Much of the dissolved gases (such as CO, and air) driven out of the water. 5. Viscosity of softened water is lower, so filtration of water becomes ___ much easier. This in-tur increases the filtering capacity of filters. ‘6. Hot lime-soda process produces water of comparatively lower re- sidual hardness of 15 to 30 ppm. Q. 10. What is Zeolite ? (C.S.V.T.U. Sem-I, 2005, 2006-07) Or What do you mean by softening of water ? Explain zeolite or permutit Water | 15 process of water softening ? Ans. Softening of water : Refer Q. No. 7 ZEOLITES Zeolites are also Known as permutits. The name zeolite is derived from two Greek words (Zein + lithos) which means boiling stone. Zeolite is hydrated sodium aluminium silicate capable of exchanging reversibly its sodium ions for hardness-producing ions in water. Zeolites are also known ‘as permutits. Zeolites are of two types : 1. Natural Zeolites : Natural zeolites are non-porous. For example, natrolite, Na,O.Al,03.4SiO,.2H,0. 2. Synthetic Zeolites : Synthetic zeolites are porous and possess gel structure. They are prepared by heating together china clay, faldspar and soda ash. Such zeolites possess higher exchange capacity per unit weight than natural zeolites. Process : For softening of water by zeolite process, hard water is percolated ata specified rate through a bed of zeolite, kept in a cylinder (see Fig. 1.5). The hiardness-causing ions (Ca, Mg", etc.) are retained by the zeolite as CaZe and MgZe, while the outgoing water contains sodium sats. Reactions taking place during the softening process are : Na,Ze+Ca(HCO;), —+Caze+2NaHCO, Na; Ze + Mg(HCO,), —> MgZe + 2NaHUO, NajZe + CaCl, (orCaCO, )—+ CaZe + 2NaCl(or NaSO,) Na,Ze + MgCl, (or MgSO,) —+ MgZe + 2NaCl(or Na,SO,) os Injector = NaCl solution, storage sink Soft water outlet Fig. 15. Zeolite softener.16 | SBP Q. B. Applied Chemistry Regeneration : After some time, the zeolite is completely cunverted into calcium and magnesium zeolites and it ceases to soften water, ic. it gets exhausted. At this stage, the supply of hard water is stopped and the exhausted zeolite is reclaimed by treating the bed with a concentrated (10%) brine (NaC) solution. Citterio) + 2N —> Nee + COMO.) Exhausted zeolite Brine Reclasined Washing Zeolite ‘The washings (containing CaCl, and MgCl) are led to drain and the regenerated zeolite bed thus-obtained is used again for softening purpose. @. 11. Mention limitations, advantages and disadvantages of zeolite or permutit process ? Or Give the limitations of zeolite process for softening hard water. (CS.V.T.U., Sem. I,:Dee. /Jan. 2008-09) Ans. (a). Limitations of Zeolite or Permutit Process 1, Water having turbidity and suspended matter should not be directly fed to the zeolite softener, otherwise the turbidity will clog the pores of zeolite bed, thereby making it in active. 2. Hot water can not be used as the zeolite tends to dissolve in it, 3. If water contains large quantities of coloured ions such as Mn** and Fe", they must be removed first because these ions produce manga nese and iron zeolites, which cannot be easily regenerated. 4, Mineral acids, if present in water , destroy the zeolite bed and, there- fore, they must be neutralized with soda, before admitting the water to the zeolite softening plant. 5. Water treated by the zeolite progess contains about 25% more dis- solved solids than that of treated by lime-soda process. (b). Advantages of Zeolite or Permutit Process 1. It removes the hardness almost completely and water of about 10 ppm hardness is produced. 2. The equipment used is compact, occupying a small space. 3. No impurities are precipitated, so there is no danger of sludge forma- tion in the treated-water at a later stage. 4, The process automatically adjustitself for variation is hardness of incoming water. 5. Itis quite clean. 6. It requites less time for softening. Water | 17 7. It requires less skill for maintenance as well as operation. (©. Disadvantages of zeolite process 1. The treated -water contains more sodium salts than in lime-soda pro- cess. 2. The method only replaces Ca”* and Mg”* ions by Na+ ions, but leaves all the acidic ions (like HCO; and CO}- ) as such in the soft- ‘ened water. When such softened water (containing NaHCO, Na;CO; etc.) is used in boilers for steam generation, sodium bicarbonate decomposes producing CO. which causes corrosion, and sodium carbonate hydrolysis to sodium hydroxide, which causes caustic embrittlement. . High turbidity water cannot by treated efficiently by this method, because line impurities get eposted on the zeolite bed, thereby ating problem for Q 12. Differentiate between cold lime-soda process and hot lime soda process ? Ans. Difference Between Cold Lime -soda Process and Hot Lime -soda Process i SMRITI NAGAR MO. - 9691859316, 9584601916 KRISHNA COPIERS [= "Gad inesoda process Tot fine soda process = 1 isa rapid process [2 Thieprocessindone at room ine | 2 the pease eae at | permure 2s 30°C) semperaure(80-150°C) 3. Tthas low softening capaci. 3. Itsoftening capacity is very high 4. Congulantstue needed for his | Ths process dacs not need procees Cogan 5. Dissolved gases such as CO, are not] 5 Dissolved gases are also removed. removed to some extent 6 Softened water has residua hardnes] 6 Soften water fas todual around 60 ppm hardness around 130 pp _ perenne Q. 13. Distinguish hetwoen zeolite process (permutit process) aml lime-soda process.18 SBP Q. B. Applied Chemistry Or Compare permutit and lime-soda process at least on four points. a (C-S.V-T.U., Sem. Dec/ Jan. 2008-09) DIFFERENCE BETWEEN ZEOLITE AND LIME-SODA PROCESS. Lime-soda method Ans. Zeolite or Permutit method Water of generally, 15-50 ppm hardness is obtained. Treated -water contains lesser amount of sodium salts than in amount of sodium salts. 3. Cost of plant and material is higher. | Capital cost is lower. 14. Operation expenses are lower. Operation expenses are higher. 5. It cannot be used for treating acidic | There are no such limitations. ‘water, because the permutit material undergoes disintegration. }6. The plant ocupies less space. 7. The raw water to be softened must be free from suspended matter, otherwise the pores of permutit material are blocked and the bed = | loses its exchange capacity. }& It can operate under pressure and It cannot operate under pressure. can be made fully automatic. 19. Itinvolves no problem of settling, | It involves difficulty in settling, co- co-agulation, filtration and removal | agulation, filtration and removal of the sludges and precipitates. _| of precipitates. 10. Control test comprises only in In order to meet the changing checking the hardness of treated | hardness of incoming water, frequent control and adjustment of reagents 1. Water of 10- 15 ppm residual hardness is obtained. }2. Treated-water contains larger raw water. Plantoccupies more space. ‘There are no such limitations. water. is needed. 11, Treated-water contains more dis- | Treated -water contains lesser dis- solved solids. solved solids. Q. 14. What is softening of water ? Explain ion exchange process of softening of water. Or What is demineralizatioh of water ? (CS.V.T.U., Sem. I, May/June 2007) Water | 19 Or What is deionized mineral water ? (CS.V-TU., Sem 1, 2005, 2006-07) Ans. Softening of water : Refer Q. No. 8. Jon exchange Process of Water Softening : An ion exchange pro- cess may be defined as a reversible exchange of ions between liquid phase and a solid phase. Materials capable of exchange of cations are called cation exchangers and those which are capable of exchanging anions are called anion exchangers. Jon exchangers commonly used in water treatment includes: 1. Natural Zeolites : e., (i) Natrolite (Na,O, Al,O3, 3SiOz, 2H;0) i) Lau montite. (CaO, Al,O3. 4Si02. 4,0). 2. Synthetic Zeolites : These are prepared by heating together chinaclay, | feldspar and soda ash. "3. Carbonaceous ion exchangers : ¢.g., Zeokarb, catex 27 and catex 55. These exchangers can be operated on sodium and hydrogen cycles and are not deteriorated by waters of even very tow pH or by iron bearing waters. However these exchangers are. Vulnerable to oxida- tion by chlorine. 4. Synthetic resins : An ion exchange resin consists of an insoluble polymetric matrix that is permeable. Fixed change groups and mobile _ ‘counter ions of opposite charges ate incorporated in the matrix. These counter ions cab be exchanged for ions in the external tiquidphase. ton-exchange resins are insoluble, cross-linked, iong chain organic polymers with a micro-porous structure, and the “functional groups” at- _ tached to the chains are responsible for the ion-exchanging properties, Res- ins containing acidic functional groups (COOH, -SO,H, etc) are capable ‘of exchanging their H + ions with other cations, which comes in their cohtact; whereas those containing basic functional groups (-NH, = NH as. hydrochloride) are capable of exchanging their anions with other anions, which comes in their contact. ‘Types of ton-exchange Resins : The ion exchange resins may be of ‘wo types : @ Anion exchanges resins (RH"). Gil) Cation exchange resins (R'OH). € Anion exchange resins (R’OH") : These resins are styrene-diviny! or amine-formaldehyde copolymers, which contain amino or qua- ternary ammonium or quaternary phosphonium or tertiary sulphonium groups as an integral part of the resin matrix. After treatment with dil.20| SBP Q. B. Applied Chemistry NaOH solution these resins become capable to exchange their OH” anions with anions in water. —CH, ~CH—CH, —CH -CH, ~CH~CH, ~... ae, $F a CH,NMe$OH™ (CH, NMeSOH™ & cy cH, —- CH —— CH, «is ' ' 2és3 CH, -CH cHcH-. FFF g é * . = CH;NMejOH” CH,NMefOH™ Fig-1.6. Basie or anton exchange resin (hydroxide form) ) Cation exchange resins (RH): These are mainly styrene-di benzene copolymers. These resins, become capable to. exchange their hy- drogen ions with the Cations in the water on suiphonation and carboxyl tion. ~CH, -CH-CH, ~CH-CH, ~CH-CH, - Tr so5H* so;H" .-CH; —CH—CH, I CH-CH.-... é 6 SO;H* —-SOSH* ate Form) Figs.7. Acidic or cation exchange resin (Sulph Water | 24 Process of Softening of Water by Ion-exchange Method (Or Demineralizations or Deionization). Demineralization or deionization is the process of complete removal of soluble salts from water. With the advent of the development of com ‘mercial cation exchange and anion exchange resin, it become possible to produce demineralized or deionized water of highest purity by a two step Process Step-I : In this process, the hard water is first passed through ion- exchange column having cation exchanger (Hydrogen exchanger), which absorbs all the cations (Ca**, Mg” etc ) from it and release equivalent amount of H* ions 2RCOOH + Ca** —+(RCOO),Ca+2H* 2RSO;H +Mg"* —+(RSO,),Mg+2H* 2ROH + Mg”* —9(RO), Mg +2H" Where, R = Rest part of cation exchanger. Step-II : The cation free hard water is then passed through anion exchanger column having anion.exchanger . It removes all the anions like SO},CI” ete. present in the water and equivalent amount of OH ions are released from this column to water. ROH); +803 —+R'S0, +20H" ROH), +2Cr —>R'C1, +20H HY and OH" ions (released from cation exchange and anion exchange columns respectively) get combined to produce water molecule Ht +OH” —+H,0 Thus the water coming out from the exchanger is free from cations as well as anions. lon-free water, is known as deionized or demineralized water. Regeneration : When capacities of cation and anion exchangers to exchange H” and OH ions respectively are lost, they are then said to be exhausted. The exhausted cation exchange column is regenerated, by passing a softtion of dil. HCI or dil. H,SO,. The regeneration can be represented as : R,Ca®* + 2H" —>2RH” + Ca* (washing)22 | SBP.Q. B. Applied Chemistry Hard water, op: if Injector Injector jector Alkaline regenerator Fig, 18, Demineralization of water ‘The column is-washed with deionized water and washing (which ‘contains Ca2*, Mg2", etc. and Cl or SO}- ions) is passed to sink or drain. ‘The exhausted anion exchange column is regenerated by passing a solution of dil. NaOH. The regeneration can be represented as : R'SO}" +2NaOH — R (OH), + Na,SO, R‘Cl, + 2NaOH--—+R YOH), + 2NaCi «Exhausted (Regenerated ion exchanger) fon exchanger) . ‘The column is washed with deionised water and washing (which contains Na+ and SO}-or CI” tons) is passed to sink or drain. The regener ated jon exchange resins are then used again. Advantages : 4. The process can be used to soften highly, acidic or alkaline waters. 2. ft produces water of very low hardness (say 2 ppm). So it is very ‘good. for treating water for use in high-pressure boilers. Disadvantages : . 1. The equipment is costly and more expensive chemicals are needed. 2. If water contains turbidity, then the output of the process is reduced. ‘The turbidity must be below 10 ppm. If it is more, it has to be re- moved first by coagulation and filtration. : Water | 23 @ 15. What do you mean by boiler feed water ? Name various troubles caused due to hard water in boilers. Or What are the major boiler troubles caused by the use of unsuitable water and what ore their disadvantages ? How can they be minimized, (CSN-LU, Sem. I, NoviDee. 2007) Ans. BOILER FEED WATER In many industries, water is mainly used in boilers for generation of steam . A proper quality of water for use in boilers is very important, If impure water is made used as boiler feed water, then many problems or troubles may occurs. For boiler feed water all impurities are not necessarily eliminated ang only those impurities are eliminated or kept within prescribed range which lead to objectionable phenomenon in boilers. Requirements for boiler feed water 1. The hardness of water should be below 0.2 ppm. 2. The caustic alkalinity-should lie in the range of 015% 0.45 ppm, 3. The soda alkalinity should be from 0.45 to 1.00 ppm. 4, Excess soda ash should be 0.3 to 0.5 ppm Problems caused in Boilers due to Impure water Excess of impurities if present in boiler feed water generally cause-the following problems 1. Scale and sludge formation. 2. Priming and foaming. 3. Corrosion. 4. Caustic embrittlement. 5. Scale formation due to presence of silica. Q. 16. Write short note on scale and sludge formation. (CSV.LU. , Sem: I, Dec./Jan. 2008-09) Or How does the formation of sludge and scales affect boiler perfor. mance Or What is scale ? How it is formed ? Write the disadvantage of seale formation in boiler. Or (@) What are the disadvantages of scale formation to boilers. (C.S.V-T.U., Sem. I 2005) (6) Name any four sludge forming salts. (C.S.V:1.U., Sem I, 2005)24 | SBP Q. B. Applied Chemistry Scale and Sludge Formation water evaporates continuously and the concentration of the \crease progressively. When their concentrations reach satu- ration point, they are throwin out of water in the form of precipitates on the inner walls of the boiler. If the precipitation takes place in the form of loose and slimy precipitate, it is called sludge. On the other hard, if the precipi- tated matter forms a hard, adhering crust/ coating on the inner walls of the boiler, it is called scale. Sludge : Ita soft, loose and slimy precipitate formed within the boiler, Sludge can easily be scrapped off with a wire brush it is formed at com- paratively colder portions of the boiler and collects in areas of the system, where the flow rate is slow or at bends. Sludges are formed by substances which have greater solubilities in hot water than in cold water, e.g, MgCO3, MgCl, CaClp, MgSO,, etc. Ans. Hard adhering coating on Loose pracipitate Suspended in grater Fig. 1.9. Seale and sludge in boiters. Disadvantage of sludge formation : ; |. Sludges are poor conductor of heat, so they tend to waste a portion of heat generated, If sludges are formed along -with scales, then former gets entrapped in the latter and both get deposited as scales. 3. Excessive sludge formation disturbs the working of the boiler. It settles in the regions of poor water circulation such as pipe connec- tion, plug opening. gauge-glass connection, thereby causing even choking of the pipes. Prevention of sludge formation : 1. By using well softened water. 2. By frequently ‘blowdown operation’, ie., drawing off a portion of the concentrated water. 4 Water | 25 Scale : Scales are hard deposits, which stick very firmly to the inner surfaces of the boiler, Scales are difficult to remove, even with the help of hammer and chisel. Scales are the main source of boiler troubles. Formation of scales in the boilers : Scales formation in the boilers may be takes place due to following reasons : 1. Decomposition of Bicarbonates : When hard water is boiled in the boiler the bicarbonates of Ca and Mg get decomposed and convert into insoluble Ca and Mg carbonates. These carbonates get deposited on the inner side of the boiler. Ca(HCO;)2 —+CaCo, +CO, +H,0 Seale Mg(HCO,), —+MgCO, +CO; +H,0 Scale’ However, scale composed chiefly of calcium carbonate is soft and is the main cause of scale formation in low pressure boilers. But in high- . Pressure boiléis, CaCO; is soluble due to the formation of Ca(OH), CaCO, +H,0—+Ca(OH), +0, 4 Soluble 2, Deposition of Calcium Suiphiate : Calcium sulphate is sSluble is cold water, but almost completely insoluble in superheated water. Conse- quently, CaSO, gets precipitate as hard scale on the hotter parts of the boiler. This type of scale causes troubles mainly is high pressure boilers, This scale is quite adherent and difficult to remove, even with the help of hammer and chisel 3. Hydrolysis of Magnesium Salts : Dissolved magnesium salts get hydrolysed at high pressure inside the boiler forming magnesium hydroxide Precipitate which forms a soft type of scale. MgCl, +2H,0—>Mg(OH), 4 42HCIT Seale 4. Presence of Silica : Even if a small quantity of SiO) is present, it may deposit as calcium silicate (CaSiO) and or magnesium silicate (MgSiO;). These deposits adhere very firmly on the inner side of the boiler surface and are very difficult to remove. Disadvantages of Scale Formatibn Disadvantages of scale formation in boilers are given below : 1, Wastage of Fuel : Scales have a poor thermal conductivity, so the rate of heat transfer from boiler tosinside water is greatly reduced,26 | SBP Q. B. Applied Chemistry meee 2, Decrease in efficiency : Deposition of scales in the valves and con- - ; densers of the boiler, choke them partially. This results in decrease in 2 a What is scale ? Discus the process of prevention of scale efficiency of the boiler. formation S 3. Lowering of Boiler Safety : Over heating of boiler is to be done in LT order to maintain a steady supply due to scale formation. This causes amen Nester 2606) distortion of boiler tube and also makes the boiler unsafe to bear the Or tat What do you mean by internal treatment ? pressure of the steam. (CS.V.TU., 2005, 2006-07) 4. Danger of Explosion : When thick scales crack, due to uneven o i i ith overheated iron expansion, the water comes suddenly in contact with overheat a F : plates. This causes in formation of a large amount of steam suddenly. (cavnUstenee ee 2008-26) So sudden high pressure is developed , which may even cause explo- oF iaeaaneasees sion of the boiler. What do you mean by internal conditioning of boiler feed water. Removal of Seales (CS.V.EU,, Sem., I, Now/De-2006) ‘The scales can be removed by following methods- on om 1. With the help of scraper or piece of wood or wire brush, if they are ive brief account on calgon conditioning . loosely adhering. . (CSV-TU, Sem. I, May/Sune 2007) 2. By giving thermal shé&ks (ie., heating the boiler and then suddenly Write short note on the following : cooling with cold water), if they are brittle. 5 (@ Phosphate conditioning - 3. By dissolving them by adding them chemicals, if they are adherent (C.S.1.U., Sem, 2005, 2006-07, Dec/Jan. 2008-09) and hard, Thus, calcium carbonate scales can be dissolved by using (®) Carbonate conditioning. ~ 5-10% HC! Caicium sulphate scales can be dissolved hy adding EDTA {©} Colloida! corstitioning. (ethylene diamine tatra acetic acid), with which they form soluble ‘Ans. Scale : Refer Q. No. 16. complexes. | Prevention of Scale formation : Scale formation is boilers can be 4, By frequent blow-down operation, if the scales are loosely adhering. prevented by following two methods Q. 17, Distinguish between sludge and scale ? sect Eaeraal Treatment: Jn this method, the scale forming and cor ifferen rosive impurities are removed from water before its entry into the boiler. Ans. Difference Between Sludge and Scale The following processes are usually cmplovca ‘Sludge + Seale 1. Removal of “hardness” or scale forming salts T. Sludge is a soft, loose and slimy |1-Scales are hard adhering or coat- () Uunsacda' rocsee la (oy Zone roe precipitate, weno nee . (©) Demineralization @Distiliation. 2. It can be easily scrapped off with [2.Scal es af ick to ines since 2. Removal of silica: It can be removed by = vo @ wire brush. of boiler and are very difficult to ric sulphate process, anion-exchange process, Fluosilicate process. 3. Ibis formed by CaCl, MeChy fit is formed by substances tke eee eee It is formed by CaCl, MgCl, _]3-It is for 7 (a) Pre-treatment : sedimentati ion, sett i MgSO,, MgCO; like substances.} CaSO,, Mg(OH), etc. ia 4 ae a re " entation, coagulation, settling and filtration. 4, It is formed at colder part of the |4.1t is formed at heated part of the ftening processes. ee eee ae of tas gases : cos i 0, It is I boilers. |5.It is serous for boilers. (2) Decarbonation by aeration Pe 5. It is less dangerous for boilers. very dang: oceanic28 | SBP Q. B. Applied Chemistry 5. Removal of oil : Oil can be removed by two methods- (a) Mechanical oil-separators (6) Sodium aluminate treatment. Most of these processes have been discussed earlier and others will be discussed later, along with the methods for internal treatment. 2. Interaat Treatment : In this process an ion is prohibited to ex- hibit its original character by ‘complexing’ or converting it into other more soluble salt by adding appropriate reagent. An internal treatment is accom- plished by adding a proper chemical to the boiler water either : (a) to pre- cipitate the scale forming impurities in the form of sludges, which can be removed by blow-down operation, or (b) to convert them into compounds, which will stay in dissolved form in water and thus do not cause any harm, Some important internal treatment methods are as follows : @ Colloidal conditioning : This process prevent scale formation in low pressure boilers by adding kerosine, tannins and agar like or- ganic substances. Which get coated over'the scale forming precipi- tates, thereby yielding non-sticky and loose deposits, which can eas- ily be removed by pre-determined blow-down operations. (ii) Phosphate conditioning : This is the type of internal treatment method of water by which scale formation can be avoided in-high pressure boilers by adding sodium phosphate which reacts with hard- ness of water forming non-adherent and easily removable, soft sludge of calcium and magnesium phosphates, which can be removed by blowdown operation, eg, 3CaCl, +2Na,PO, —+Ca,(PO,), 4 +6NaCI ‘The main phosphates employed are :(a) NaH.,PO,. sodium dihydrogen phosphate (acidic); (b) NajHPO,, disodium hydrogen phosphate (weakly alkaline); (c) Na;PO,, trisodium phosphate (alkaline). (iii) Carbonate conditioning : In low-pressure boilers, scale-forma- tion can be prevented by adding sodium carbonate to boiler water, ‘when CaSO, is converted into calcium carbonage in equilibrium. CaSO, +Na,CO, CaCO, +Na,SO, Consequently, deposition of CaSO, as scale does not take place and calcium is precipitated as loose sludge of CaCO. which can be removed by blow-down operation. (iv) Calgon conditioning : It involves in adding calgon [sodium hexa ‘meta phosphage (NaPO3), to boiler water. It prevents the scale and sludge formation by forming soluble complex conjpound with CaSQ,, PIERS KRISHNA Co) Mo. Water | 29 Naz[Nay(PO5)g] <== 2Na* +[NayPsOig]? Calgon © S 2CaSO, +[Na,P,O;g]” —2[CazP,0j}°- +2Na,SO, «8 Soluble complex ion << S_(v) Treatment with sodium aluminate (NaAIO,) : Sodium aluminate g S gets hydrolysed yielding NaOH and a gelatinous precipitate of alu- Ze minium hydroxide. Thus : Es NaAlO, +2H;0—+ NaOH + AI[OH}, 4 g= Sod. meta-aluminate _ Gelatinous ppt.) @B ~The sodium hydroxide, so-formed, precipitates some of the magne- sium as Mg(OH),, i. MgCl, +2NaOH—+Mg(OH), J +2NaCt The flocculent precipitate of Mg(OH), plus Al(OH), produced inside the boiler, entraps finely suspended and colloidal impurities, including oil drops and silica. The loose precipitate can be removed by re-determined blow-down operation. 5 : Note : Sodium aluminate in thick solution form is available inplenity and at a cheap rate from bauxite refining units and this can be used as such for boiler-water treatment. (vi) Electrical conditioning : Sealed glass bulbs. containing mereury connected to a battery, are set rotating in the boiler. When water boils, mercury bulbs emit electrical discharge, which prevents scale, forming particles to adhere/stick together to form scale. (vii) Radioactive’ conditioning : Tablets containing radioactive salts are placed inside the boiler water at a few points. The energy radia- tion. emitted by these salts prevent scale formation. Q. 19. What is the difference between carbon ate conditioning and phosphate conditioning. (CS.V.L.U., Sem. I, Nov/Dec. 2007) Ans. Difference Between carbonate conditioning and Phosphate conditioning = Carbonate conditioning Phosphate conditioning 1. It is useful for low pressure boilers| 1. It is useful for high pressure boilers. 2. In this method scale formation is 2. In this method scale formation is avoided by adding NajCO, in avoided by adding NasPO, in boiler water. : boiler water. i30| SBP Q. B. Applied Chemistry Q. 20. Write short notes on priming and foaming and its prevention. (C-S.V-T.U,, 2005, 2006-07) Or Write short notes on priming and foaming. (CSV.T.U., Sem. I, Dec. / Jan. 2008-09) An (@). Priming. When a doiier is steaming (i.c., producing steam) rapidly, some par- ticles of the liquid water are carried along with the steam. This process of wet steam formation, is called priming. Priming is caused due to : 1. The presence of large amount of dissolved solid; 2. High steam velocities; 3. sudden boiling; 4. Improper boiler design, and 5. Sudden increase in steam-production rate. -Prevention of Priming : Priming can be avoided by : 7 1. Titeing mechanical steam purifiers; 2. Avoiding rapid change in steaming rate ; 3. Maintaining low water levels in boilers, and ~ 4, Bfficient softening and filtration of the boiler-feed water. ~ Foaming : Foaming is the production of persistent foam or bubbles in boilers, which do not break easily. Foaming is due to presence of sub- stances like oils (which greatly reduce the surface tension of water.) Priming and foaming, usually, occur together. They are objectionable because : 1. Dissolved salts in boiler water are carried by the wet steam to super- heater and turbine blades, where they get deposited as water evapo- rates. This deposit reduces their efficiency; 2. Dissolved salts may enter the parts of other machinery, where steam is being used, thereby decreasing the life of the machinery; 3. Actual height of the water column cannot be judged properly, thereby making the maintenance of the boiler pressure becomes difficult. " Prevention of Foaming : Foaming can be avoided by 1. Adding anti-foaming chemicals like castor oil, or 2. Removing oil from boiler water, by adding compounds like sodium aluminate. Q. 21. Why carbonate conditioning not used for high pressure boiler ? ‘Water | 31 ‘Ans. Reasons for not using carbonate conditioning for high pres- sure boiler : With an increase in pressure and temperature of the boiler water, the rate of decomposition of sodium carbonate to caustic soda in carbonate conditioning increasing rapidly. Free caustic alkalinity increase very rapidly and it is impossible to maintain the desired alkalinity needed to ensure calcium carbonate precipitation. With an increase in pressure and temperature, the CO, generating rate also increase. This CO, goes which steam and dissolves in the condensate to form carbonic acid. This lowers pH and accelerates the rate of oxygen corrosion. This is why we do not use carbonate conditioning for high pressure boilers. Q. 22 Why calgon conditioning is better than phosphate condition- ing? Ans. In calgon conditioning, when calgon added in boiler water, it forms a soluble complex compound with CaSO,, which prevent the scale and sludge, formation in boiler. In calgon conditioning the complex formed is soluble, so it does not cause any problem in the boiler. While in phosphate conditioning, sodium phosphate is added to boiler water, so that precipitate of calcium phosphate is formed, which is ion-adherent and soft. Yet it has to removed by frequent blow-down operation. Hence, calgon conditioning is definitely better than phosphate conditioning. Q. 23. What is boiler corrosion ? Describe factors responsible for it and its removal methods. (CS.VIEU. Sem. I, NovsDec. 2006) Ans. Boiler corrosion : The decay of boiler material by a chemical or electrochemical attack by its environment is called boiler corrosion. Factors Responsible for Boiler corrosi 1. Dissolved oxygen. 2. Dissolved carbon dioxide. 3. Acids from dissolved salts. 4Formation of galvanic cells. 5. presence of free acid in water. 6. Acid generated as a result of hydrolysis of some in water. 7. Acids formed by the hydrolysis of the fatty lubricant oils, 8, Presence of dissolved gases such as O2, CO2, H,S etc, in water. 9. MgCl; + Fe'+ 2H,0 —> Mg(OH), + FeCl, +H, + presence of salts like MgCl, which directly attack the boiler metal 10. Presence of salts like MinS2 which may generate H,SO, due to the oxidatiog and hydrolysis. ‘ Main factors are discussed as follows :94 | 915 YW. IS. Applied Chemistry 1. Dissolved oxygen : Water usually contains about 8 mL of dis- solved oxygen per litre at room temperature. Dissolved oxygen in water, in ath presence of prevailing high temperature, attacks boiler material : 2Fe+2H,0+0, —>2Fe(OH), + 4Fe(OH), | +0, —+2[Fe,0,.2H,0]1 (Ferrous hydroxide) (Rust) Removal of Dissolved Oxygen @. By adding calculated quantity of sodium sulphite or hydrazine or sodium sulphide. Thus ; 2Na,SO; +0, —+2Na,S0, N2H, +O, —yN, +2H,0 (Hydrazine) Na,S +20, —+Na,S0, 7 Gi). By mechanical de-aeration, ie., water spraying in a perforated plate- fitted tower, heated form sides and connected to vacuum pump (see Fig. 2) High temperature, low pressure and large exposed surface (provided by perforated plates) reduces the dissolved oxygen in wa- ter. 2. Dissolved carbon di €0; +H,0—>H, Co, _, Which has a slow corrosive effect on the boiler material. Carbon oxide is also released inside the boiler, if water used for steam generation contains bicarbonate, e.g., xide : (CC) iF carbonic aciz, Mg(HCO;), 4 > MgCo, +H,0+C0, “Tig, MONA OF Cr (1) By adding calculated quantity of ammonite, s: 2NH,OH +CO, —+(NH,),CO, +H,0 @) By mechanical-aeration process along with oxygen. ,__ @) Acids from dissolved salts : Water containing dissolved magne- sium salts liberate acids on hydrolysis, e.g., MgCl, +2H,0—+Mg(OH), 1 +2HCI __ The liberated acid reacts with tron (of the boiler) in chain-like reac- tions producing HCI again and again..Thus : ‘Water | 33 Fe+2HCI—+FeCh +H; t FeCl, +2H,0——> Fe(OH), 4 42HCI Consequently, presence of even a small amount of MgCl; will cause corrosion of iron to a large extent. OQ. 24. Write short note on caustic embrittlement and its prevention. (CS.V.T.U. Sem. 1, 2005, Dec./Jan. 2008-09) Ans. CAUSTIC EMBRITTLEMENT Caustic embrittlement is a type of boiler corrosion by using highly alkaline water in the boiler. During softening process by lime -soda pro- cess, free NazCO, is usually present in small proportion in the softened water. In high pressure boilers Na,CO3 decomposes to give sodium hy- droxide and carbon dioxide and this makes the boiler “caustic”, Na,CO; +H,0—>2NaOQH+CO, This makes the boiler water highly alkaline because of caustic forma~ tion. The NaOH containing water flows into the minute hair-cracks, always present in the inner side of boiler, by capillary action. Here water evaporates and the dissolved caustic soda concentration increases progressively. This caustic 38de attacks the surrounding are, thereby dissviving iron of boiler as sodium ferroate. This causes embrittlement of boiler parts, particularly stressed parts (like bends, joints, rivets, etc.), causing even failure of the Prevention of caustic Embrittlement : Caustic embrittlement can be prevented by the following ways : (® By using sodium phosphate as softening reagent instead of sqdium carbonate, Gi) By adding tannin or lignin to boiler water, since these blocks these blocks the hair-cracks, thereby preventing infiltration of caustic soda solution in these, (iil) By adding sodium sulphate to boiler water : NaySO, also blocks hair-cracks , thereby preventing infiltration of caustic soda solutions in these. [t has heen observed that caustic cracking can be prevented, if Na:SO, is added to boiler water so that the ratio : ‘ {Na,SO, concentration] ‘ [NaOH concentration} is kept as 1: | :2: 1 and 3: 1 in boilers working respectively at Pressures up to 10, 20 and above 20 atmospheres.34 | SBP Q. B. Applied Chemistry @. 25. What is hardness of water ? Name the methods of determi- nation of hardness of water. Ans, Hardness Water : Refer. Q. N. 5. Methods of Determination of Hardness of water : The following three methods are used for the determination of hardness of water : 1.0. Helmers method 2. Soap titration method 3. EDTA method. Q. 26. Write the chemical reactions with formula for soap titration method for determination of hardness of water. Ans. Soap Titration Method Solution soaps consists of sodium or potassium salts of higher fatty acids such as stearic acid, oleic acid and palmitic acid. When these soaps are added to hard water it does not give lather until a sufficient quantity has been added to precipitate all the hardness-producing metal ions. When all hhardness-causing ions been precipitated, further addition of soap gives lather. 2C,;HsgCOONa + Ca(HCO;)}; —W{Cy7HyCOO), Cat +2NaHCOS Sodium stearate (soap) Insoluble cal. stearate 2C;HssCOONa + MgCl, —>(C,7HjsCOO), Mg 4 +2NaC! 2C7HygCOONa + CaSO, —+(C,,H,,COO), Ca L +Na,SO, ‘The total hardness of water can be found by titrating an aliquot of the sample against a standard soap solution in alcohol. Appearance of stable lather persisting even after shaking for about 2 minutes marks the end point. In case the water sample is boiled for 30 minutes to remove the temporary hardness and then titrate with the standard soap solution as described above. The titre value corresponds to the permanent hardness of the sample. Difference between the two values corresponds to the temporary hard- ness. ‘ Q. 27. Write the chemical reactions with formula of EDTA complexometric titration for determination of hardness of water. (CS.V-T.U. Sem. I, Nov/Dec. 2006) Or Explain with reactions the application of complexometric titration by EDTA. (C-S.V.E.U, Sem. 1, May/June, 2007) ‘Ans. EDTA Method This is more afcurate and complexometirc method of determination of hardness of water. If can be performed rapidly. EDTA (Ethylene diamine tetra acetic acid) has the following structure form : Water | 35 HOOCCH: CH,.CO.OH > N-CH; -CH,-N < HO.OC.CH,’ (CH,.CO.OH It forms complexes with Ca and Mg? ions as well as with several other metal cations in aqueous solution. Hence, in a hard water sample, the total har dness can be obtained by titrating the Ca?* and Mg™* present in an aliquot of sample with NazEDTA solution using NH,CI-NH,OH buffer solu- tion of pH 10 and Eriochrome black-T as the indicator. At the end point, the colour changes from wine red to blue. Na, HY + Dizodiua EDTA in solution Mg? + HD? — MgD~ + H* 2Nat +H,Y** Blue Wine red (Mg or CayD + H,Y* -+ (MgorCa)Y? + HD? + H* Meal fndictor From Disodium Metal EDTA Free : Complex EDTA Solution Complex Indicator ‘Wine Red Colour) (Cotouress) (ioe Colour) Permanent hardness can be determined by precipitating the tempo- rary hardness by boiling water for abou: 30 minutes followed by titration with the EDTA solution as above. Difference in the value gives the tempo- rary hardness of the water samples. Q. 28. Write the method of removal of silica form turbine blades and boilers. Ans. REMOVALOF SILICA ilica may cause hard deposits on turbine blades due to carry over. Silica also forms thermally resistant boiler scales‘of magnesium or calcium silicate. Silica is removed form the boiler feed water by the following methods- 1, By the addition of magnesia (MgO ) to the water after the removal of the temporary hardens. 2. By the addition of magnesia to the water in the boiler when magnesia silica sludge is deposited. 3. By using magnesia or doloimitic lime soda process of water softening. ‘Magnesia acts as Mg (OH). In all these processes, silica is removed by magnesia by adsorption or by the formatiSn of magnesium silicate, 4. By the use of ferrous sulphate or sodium aluminate as coagulants,36 | SBP Q. B. Applied Chemistry They act as Fe (OH); or Mg (OH), and AI(OH)s, which enmesh finely suspended and colloidal impurities including oil and silica. S. By passing the demineralised water through a strongly basic special anion-exchanger which removes silica as H,SiO, or SiO"; or in some other form. The silica content is usually reduced to a fraction of a ppm. 6. By converting the silica into fluosilicate by the addition of hydrofluo- ric acid and then removing it by passing through an anion exchange resin. H,SiF, +2R3N > (R5N)) ~ HySif 7. By distillation. Q. 29. Write a short note on Break point chlorination. (C-S.V.T.U,, Sem. I, May/June, 2007, Dec/Jan 2008-09) BREAK POINT CHLORINATION (or free Residual chlorination) Itis a method of chlorination which involves in addition of sufficient amount of chlorine to oxidize z S (@) Organic matter, (b) Reducing substances and (©) Free ammonia is raw water, leaving behind mainly free chlorine hich possesses disinfecting action against disease-producing (pathogenic ) cterias. Wheit the dosage of applied chlorine to’ water rich in organic com- pound or ammonia is gradually increased, the result obtained can be de- picted graphically in Fig 12, in which appearance of four stages occurs Ans. Formation of chloro-organic ‘compounds and chloramines JOxidation £ KRISHNA COPIERS SMRITI NAGAR ‘Apblied chlorine dios —> Fig. 110. Break-point chlorination curve. 3691959216, 9584601916 m9. Water | 3 The addition of chlorine at the dip or break, is called break-poin chlorination. This indicates the point at which free residual chlorine begin to appear. Usually, all tastes, odours (chlorinous and others) disappear:a break-point resulting in appearance of water, free from bad tastes and odour: Moreover, because of the highly persistent and powerful disinfection pos sessed by available free chlorine, any type of pathogenic organisms presenti water are destroyed, thereby making disinfection highly efficient. Advantages of break-point chlorination 1. It oxidizes completely organic compounds, ammonia and other re ducing compounds. 2. It removes colour in water, due to the presence of organic matters. 3. It destroys completely (100%) all the disease-producing bacteria. 4, It removes both odour and taste from the water. 5. It prevents the growth of weeds in water. Q. 30. Explain the rote of coagulant in water treatment ? (CS.V.T.U., Sem. I, Dec/Jan. 2008-05 ‘ Or * Write short note on coagulation. Ans. COAGULATION Coagulation is a process of removing very fine suspended particle: ‘These fine particles cannot be.remaved by sedimentation . Therefore becomes necessary to apply sedimentation with coagulation for removin such particles. ‘Sedimentation with coagulation is the process of removin fine suspended and colloidal impurities by the addition of requisite amour of chemicals (called coagulants) to water before sedimentation. Coagt lant, when added to water, forms an insoluble gelatinous flocculent precip tate which descent through the water, adsorbs and entangles very fine sus pended impurities forming bigger flocs, which settle down easily. Coagulants neutralize the negative change of the colloidal clay par ticles. After losing their charge, the tiny clay particles come nearer to on another and combine to form bigger particles, which settle down, due t the force of gravity. Thus, coagulant forces even colloidal particles to setth down. The coagulants (or flocculent) are, generally, added in solution form For proper mixing of coagulants with water, mixers are employed. Prop erly mixed water is then sedimented. ‘The addition of coagulants also removes colour, odour and taste fron the water. Chemical coagulants : The following are th most commonly usec chemical coagulants: 1. Alum|[K,S0,.Al,(SO,)3.24H,0] ; It is most widely used in wate30 | SBF YW. B Appliéa Chemistry zeatment plants. Alum reacts in water in the presence of alkalinity of water. if natural alkalinity is not present, sufficient lime also added. Al;(SO,)3 +Ca(HCO, ), —>2AIOH), 4 +3CaCO, +6CO, (Coagulant) (Cal. bicarbonate Aluminium resent in water) Hydroxide Flocculant ppt.) 2, Sodium aluminate [NaAIO,]: It is obtained from bauxite refiner- jes in the form of a thick solution .This can very easily be used for treating water having no alkalinity (i. e, pH less then 7) Ph range for best results is 5.5-8.0 NaAl0, +2H,0-—-> AKOH), ¢ +NaOH Getatinous foe of aluminium hydroxide ‘The aluminium hydroxide flock causes sedimetentation. The sodium hydroxide thus produced, precipitates magnesium salts as Mg (OH) MgSO, +2NsOH —~.>Mg(OH), J +Na,SO, 3. Copperas or ferrous sulphate {[FeSO,.7H,0] : It is also com- ‘monly used for coagulation purposes. It gives good results above pH values of 8.5 (ie slightly alkaline). Copperas reacts in water in the presence the kalinity. If alkalinity is not present, sufficient lime is also added. presence. FeSO, +Mg(HCO, ), —+ Fe(OH), 4 +MgCO; +C0, +H,0 — éesgubing Mag. bicarbonate (Present ia water) PaOM,d 4 OD, + 2HO——» AFQOHy & issoves Fenic hydroxide Onyzca; (Heavy fos) Fe ¢ OfD, is in the form of heavy floc, which causes, t precipitate easily by this method. '= mater ean be easily removed hy this method. iris process also removes colour, odoure and faste from the water. [7 short Anwer and Reasoning Questions ] QJ. Distinguish between hard water and soft water. «Aus. {. Hard water is one which does not produce tether with soap solution eadily, but forms 2 white curd , while soft water gives lather Water | 39 easily on shaking it with soap solution. 2. Hard water contains dissolved calcium and magnesium salts, while soft water does not contain dissolved calcium and magnesium salts in it . Q 2. What are the salts responsible for the temporary and perma- nent hardness of water ? Ans. Temporary hardness : Ca(HCO;), and Mg(HCO;)p. Permanent hardness : CaCl, MgCl, CaSO4, MgSO,, FeSO,, AL(SO,)s, ete. @. 3. Calgon treatment prevents scale formation in boilers. Give reason. Ans. Addition of calgon [(NaPO;).] to boiler-water prevents the scale formation by forming soluble complex compound with scale forming salt CaSO,. 2CaSO, +{Na,P,O;g/” —>(Ca,P,0,g)* +2Na,SO, eS Soluble complex ion @. 4. Why can caustic embrittlement be controlled by adding so- dium suphate to boiler- feed water ? Ans. When sodium sulphate is added to boiler-feed water, it blocks hair- cracks, thereby preventing infiltration of caustic soda solution in these. in this way sodium sulphate prevents caustic embrittlement in boiler. Q. 5. Why is calgon conditioning better then phoshate conditioning ? ‘Ans. In calgon conditioning, the added calgon forms soluble complex compound with CaSO,, thereby prevents the scale and sludge formation in boiler. Since the complex formed is soluble, so dose not cause any problem in the precipitate of calcium phosphate is formed. Although this precipitate is non adherent and soft yet it has to be removed by frequent blow-down operation, Hence, calgon conditioning is definitely better that phosphate conditioning. . 6. Why is water softened before using in boiler ? Ans . Water used for steam generation should be sufficiently pure (particularly with respect to hard ness), otherwise it would cause boiler problems like scale and sludge formation, priming and foaming boiler cor- rosion etc. Hence water is properly softened (hardness removed from it) before feeding it to boiler @. 7. Why is NH;-NH,Cl buffer solution added during determina- tion of hardness of water by EDTA titration ? Ans. EDTA titration is carried out by using Eriochrome black-T indica- tor, which gives end -point (wine red.to blue) only when pH of water sample40 | SBP Q. B. Applied Chemistry is maintained around 10. Hence, basic buffer solution consisting of NH3 NH,CI mixture of proper concentration is used during EDTA titration. Q. 8. Why is demineralization process preferred over zeolite process for softening of water for use in boilers ? ‘Ans. Because demineralized water is free from all ions; whereas zeo- lite-softened water contains sodium salts (¢.g., NaCI and Na2S04), which causes caustic embrittlement in boilers. jc a & s Q. 9. The presence of CO; in boiler feed water should be avoided why? Ans. Because CO; forms carbonic acid (HjCO3), which slowly at- 9 ° tacks the boiler materials , thereby making the latter weaker and weaker progressively. : 10. Why does hard water consume lot of soap ? When hard water is used for washing and bathing, purposes, it dose-not lather fredy with soap but produces sticky precipitates of calcium and mag- nesium soaps. The formation of such insoluble precipitates consuine soap Till hardness is completely precipitated . Hence this causes wastage of a lot of soap. being ust NUMERICAL PROBLEMS: Prob. {. 100 ml of water sample has a hardness equivatent to 12. What is its hardness in ppm. ml of 0.08 N MgSO,. Sol. 100 mL of water sample 2.Smlof 0.08N MgSO, 12.5 x 0.08 ml of | N MgSO, Inn] of 1 N MgSO, ~ | ml of 1 N CaCO; eq 0.001 L of 1 N CaCOs eq = 0.001 x 50g CaCO; eq = 0.05 g CaCO, eg (or 50’ my CaCO3) 000 ml (ov/t.) of water sample _ Omg CaCOyeq «1,000 a “00m ‘ ce, the haréness of water sample is $00 mg CaCO; eq Titre or $00 Ans. OVE CaCO, eq g z Ans, Hard water contains soluble salts of calcium and magnesium. a 4 = x Water | 41 Prob. 2. 100 ml of a sample of hard water neutralizes exactly 12 ml of 0. 12 N HCl using methyl orange as indicator What kind of hardness is present ? Express the same in terms of an equivalent of CaCO; ? Sol. Hardness of water is temporary, since methyl orange indicator does not give the value for permanent hardness. Now 100 ml of sample “= 12 ml of 0.12’N HCI = 12x 0.12 ml of 1N HCL .44 ml of 1 N HCI or 1 N CaCO; eq = S Ss = 1.44% 107Lx 50g CaCO; eq L“ z3 0.072 g CaCOs eq oF 72 mg CaCO; €q gs 1,000 ml (or 1 L) of water z¢ T2mgCaCO,eqx1,000m1 es = | 3091.00 mi 720mg CaCO, eq Eg TOml B & Hence, the.temporary hardness of water is 720 ppm. Ans. Prob. 3. The hard ness of 50, 000 liters of a sample was removed by Qpassing it through a zeolite softener. The softener then required 200 litres Sof NaCt solution containing 125 g litre of NaCl for; ‘generation. Calculate the hardness of the sample of water. ~s Sol. 200L of NaC! solution =200L x 125 g/L =25,000 gNaCl = (25,000 S0y585g CaCO,eq 21, 368 g CaCO; eq. Hardness of 50,000 L water = 21, 368 g CaCO; eq. 21.368 _ 9, 4274gCaCOxeq 50,000 427.4 mg CaCO, €4, 427.4 mg/L (or ppm). Prob. 4. The hardness of 50,000 litres of a sample of water was removed passing it through zeolite softener. The softener then required 300 litres of NaCl solution containing 100 g/ litres of NaCl for regenera- tion. Calculate the hardness of the sample of water. (C-S.V.EU,, Dec/Jan. 2008-09) or hardness of | water Ans. Hence hardness of water Sol. 300 L of NaCI solution =300Lx 100 g/ = 30,000gm Nact = =25,641g CaCO3 eq. Hardness of 50,000 L water = 25,641 g CaCO; eq. (30,000 x $0)/585 g) CaCO, 2 eq. eth42 | SBP Q. B. Applied Chemistry 35641 50,000 = 512.8 mg CaCO; eq. Hence hardness of water = 512.8 mg/L (or ppm). Prob 5. A water sample has the analytical as under. or Hardness of 1 L water = 0.5128g CaCOjeq. Ans. MgCO; = = 84 mgt CaCO; 7 40 mgh CaCl, - 55.5 mgh Mg(NO)): - —-37mg/t KC = 20mg Calculate the amount the amount of lime ( 86% pure) and soda (83% pure) needed for the treatment 80,000 litres of water. Sol. CaCO; and MgCO; should be regraded as being present in the form of their bicarbonates and only their weights have been expressed in terms of CaCO, and MgCO3, KCI does not react with lime or soda and also it does not contribute to haftiness. ‘On converting the weights of each constituent in terms of their CaCO equivalent we get the following : Salt CaCO; equivatent MgCOs = 84102 = 100 mel Caco, = cach, - 100 _ Mg(NOy)p = 37100 = 25 mgt Ka - Ignored 86% pure lime required for softening 80,000 litres of the water ” 100 74 2100) 40 + 2sy x 1 ioo?*10) + i 86 Mgcos CaCO, Mg(NO,), Purity 4 factor = 18241.86. = 18.24186 kg. Water] 43 83% pure soda required for softening 80, 000 litres of the water 106, 100 80,000 “joo + 25) KC) cact, Purity grams for factor 80,000 = 7662.65 g. = “Ans. Porb. 6. 100 ml of a water sample on titration with N/SO H;SO, gave a titre value of 5.8 ml to phenolphthalein end-point and 11.6 ml to ‘methyl orange end-point. Calculate the alkalinity of the water sample in terms of CaCO; and comment on the type of alkalinity present. Sol. P= 5.8 ml; M= 11.6 ml. Since, P= Mm, it means that all the alkalinity present in the water sample is due toCO; only, while OH” and HCO} are absent, Furtiter, the volume of N/S@ HSO, equivalent toCO} present in 100 mi of the water sample =2P=2 x 5.8=11.6 ml Since Imlof INHCI = 50mg of CaCO, 11.6 ml of N/SO HCI = 50x18 a) 1.6 mg of CaCO, This is the CO;- present in 100 ml of the sample Strength of CO; in terms of CaCOs = 11.6% oe =116mg/t =116ppm Ans, Report ‘The alkalinity of the water sample is116 ppm, which is only due to CO;~ Prob. 7. 100 mi of a water sample on titration with N/50H,SO, using phenolphthalein as indicator, give the end-point when 5.0 ml of the acid were run down. Another aliquot of 100 ml of the sample alsekt} SBP Q. B. Applied Chemistry quired 5.0 ml of the acid to obtain methyl orange end-point. What is etype of alkalinity present in the sample and what is the magnitude ? Water | 4 Since P > i M, the water sample must contain only OH™ and Co; Sol. P= 5.0 ml; M= 5.0 ml. alkalinities and they cannot be any HCO; alkalinity. Since P= M, it is obvious that the water sample contains only hydrox e alkalinity and it is not a natural water sample. Further, since 1 ml of 1 NSO, = 50 mg of CaCO; ‘Sml of N/50 H,SO, = 50x25. * 150 = 5 mg of CaCO; ‘This corresponds to 100 ml of the sample only. ‘The amount of tin 1 litre r ar ‘of OH present in of the water sample of the water sumple 100 <. Alkaligity of the water sample = 50 mg // or 50 ppm. Pro. 8. Calculate the temporary and total hardness of a sample of ater containing Mg(HCO;)2= 73 mg/L; Ca(HCO)= 162 mg/L, MgCl, | 95 mg/L, CaSO, = 136 mg/L. : Calculation of CaCO, equivalents : Ans. Sel . Tonstituent CaGO3 equivalent MgHCOs),=73 me | 100/146 | 73, 100/146 = 50 mg/L « 2A(HCO5)p = 162 mg/L| 100/162 162. 100/162 =100 mg/l. | BY 4g = 95me/L | — 100/95 95x 100 95= 100 mg/L. < 280, 36 met] 100/136 | 436x 100x136 = 100meL | = ©. Temporary hardness, due to Mg(HCO3)2 and Ca(HCO3)2 = 50 + 100) mg/L =150 mg/L or 150 ppm. = ‘Total hardness, i Ans. = (50 + 100 + 100) mg/L = 350 mg/L or 350 ppm Prob. 9. 100 ml of a raw water sample on titration with N/S0 H,SO, 2quired 12.4 mi of the acid to phenolphthalein end-point and 15.2 ml of te acid to methyl orange end-point. Determine the type and extent of tkalinity present in the water sample. ‘ Sol. 12.4 ml or N/S0 HySO, 15.2 ml of N/50 H,SO, KRISHNA COPIERS the water sample ~ 9691859316, 9584601916 "10. Further, 1. The volume of N/S0 H,SO, equivalent to OH™ present in 100 ml« =[2P~M]=(2x 12.4) ml—15.2 ml 248 ml — 15.2 ml=9.6 ml 2. The volume of N/SO H;SO, equivalent to COs~ present in 10021 =2[M—P]=2[ 152-124] mt =2x 2.8 ml = 5.6 ml 3. Since the equivatént weight of CaCO, = 50 I ml of IN H,SO,=50 mg CaCO, Alkalinity due to OH- Since 1 ml of IN HjSO, = 50mg CaCO; . L = 50%9.6x 4 mgCaco, 96x55 L 109.6% mg Cac 9.6% 55mg CaCO, 9.6 mg CaCO, ‘This corresponds to 100 mi of the water sample. :, Amount of OH” present in | liter of the water sample 9.6ml of N/50H,S0, 1000 = 9.61008 - 96mi/tas Cac wae 7 96ml/tas CaCO, :. Alkalinity of the water sample due to OH"= 96 ppm Alkalinity due to CO;~ Similarly, 5.6 ml@fN/SO H,SO, = 50x5.6 mgcaco, 50 5.6 mg CaCOs This corresponds to 1000 ml of the water sample46 | SBP Q. B. Applied Chemistry <. Amount of COs” present in 1 litre of the water sample 000 _ Sémg//1asCaCOy 00 Report : The given water sample contains OH alkalinity = 96 ppm C5" alkalinity = 56 ppm Total alkalinity = 152 ppm. Ans. Prob. 10. Calculate the amount of lime (84% pure) and soda (92% seda) required for treatment of 20,000 litres of water whose analysis is as follows. (CSV.T.U., Sem. I, 2005, 2006-07) Ca(HCO;), - 40.5 ppm Mg(HCO); - —-36.5 ppm ~ MgSO, - * 30.0 ppm a CaSO, - 34.0 ppm Gaal, - 27.75 ppm nent hardness of the water sample molecular mass of above salts are 162, 146, 120, 136, H11 and 58.5 vespectivel. Sol. Salt CaCO, equivalent 100 CA(HCOs), S = 40.5555 = 25ppm or mg/1 . 100 Mg(HCO;), a = 36.5770 = 2Sppmorme/1 100 Ss = 30.0% 122 - 25pm ormg/I MgSO, Fa9 7 25PPmormg, = 34.0% 102 - 25ppmorme/t caso, - 136 7 25PPmor me: 100 cach, = 4g =27.75x740 =25ppmormg/t NaCl - Ignored as it does not contribute to hardness, Water | 47 ‘Temporary hardness = [ Ca(HCOs), ] + [Mg (HCO,),] = 25 +25 = 50 ppm. Permanent hardness MgSO,] + [ CaSO4] + [ CaCl] = 25 +25 + 25=75 ppm ime is required for Ca(HCOs),, Mg (HCO), and MgSO,. Sod: required for CaSO,, CaCl, and the CaSO, generated as a result of reaction of lime with MgSO,. Hence, 84% pure lime required for treating 20, 000 litres of water 4 100 20,000 sig (PF + @x25) + ase Fh Thee CaHCO,), Me(HCOs), MgSO, Purity grams for factor 2,000 litres = 1761.905 g = 1.7619 kg. ; Ans. Prob. 11. A water sample contains following impurities : Ca” =20ppm,Mg™ =18ppm, HCO; = 183ppm SO;? =24ppm. and Calculate the amount of lime and soda needed for softening. Soi. Conversion in to CaCO; equivalents Constituent ‘Multiplication factor] _CaCO3 equivalent Ca"* = 20pm 100/40 20x 100.40 = 50 ppm Mg?* = 18ppm 100/24 18x 100/24 = 75 ppm HCO} =183ppm 100/122 183 x 100/122 = 150 ppny Lime requirement = 74/100[Mg™* + HCO; as CaCO, eq] = 74/100{75-+150]ppm = 166.5 ppmormg/L. Soda requirement = 106/100{Ca** +Mg”* -HCO3 as CaCO, eq] = 106/100{50-+75—150}ppm = Negative ornil, Prob. 12. Calculate the quantities of lime and soda needed for softening 2,000 litres of hard water which analyzed as follows : Analysis Ca** 160ppm,Mg** = ‘72ppm; HCO; dissolved CO, = 44ppm, HCI Anciysid of treated weter : CO;? =30ppmjOH- 732ppm, 73pm. of raw water , ‘7Tppmee 48 | SBP Q. B. Applied Chemistry Water | 49 (ii) Also calculate lime -soda required for softening one litre of this Sol. Conversion in CaCO; eqiuivalents: sample of hard water. Constituents Multiplication factor] | CaCO, equivalent Sol. Conversion in to CaCO; equivalents Constituents | Multiplication factor] CaCO, equivalent 100/40 160x 100/40 =400ppm Car =30mg/L 100/40 30x 100/40 =75 mg/L 10024 Tx 100/24 300 ppm Me?" =18mg/L 10024 18 10024 ‘Sing. 100/122 732 100/122 =600ppm CO, =H mg/L. ow te =25 mg/L, aoe es ee HCO; =122mg/L 1oor122 122 100/122 = 100me/L. (i) Total hardness = (75 + 75) mg/L = 150 mg/L or 150 ppm 100160 30x 10060 =50ppm Alkalinity present 10034 17x 10034 =S50ppm oe ‘= (HCO; -CO;) = (100-25)mg/L = 75mg/Lor75ppm ane it ir ins & 2 2 - re ae amounts oF ae (in ppm of CaCO; eq) including excess Be SF — Limerequrement = 74/100[Mg** +CO, +HCO} as CaCO,eq} me = i ess =74/100{75 +25 +100}me/L = 148mg/1. Mg? 3. = 300 ppm or mg /L < ze (ii) Soda requirement =106/100{Ca”* +Mg** = HCO; asCaCO, eq] HCO; =... 600.ppm or mg/L $2 = 106/100{75 +75 ~100]mg/L =53ma/L. Ans. co, - 68.2 ppm or mg/L. O35 Prob. 14. Calculate the amount of lime and soda required for soft coz- -_ 50 ppm or mg/L ee ening 50, 000 litre of hard water containing CaCO, = 25 ppm, MgCO; oa a 50 ppm or mg/L. x a 144 ppm, CaCl, =11] ppm, MgCl, = 95 ppm, Na;S0,= 15 ppm, Fe,0, *. Lime requirement = 25 ppm. (CS.V.T.U., Sem. 1 Dec.//Jan. 2008-09) 74/100[Mg”* + HCO; +CO, + OH” as CaCO,eq.]x Vol. of water = 74/100[300 +600 + 68.2 + 50mg!/ L]x2,000L +=15,07,000mg =1.5070kg. Soda requirement = 160/100[Ca”* + Mg?* HCO; +CO;? as CaCO, eq)x Vol. of water = 106 /100[400 +300 - 600 + 50mg /L}x2, 0001. =3,18,000mg=0.318kg. Prob. 13.A sample of water on analysis gave the following results : Ca?" =30mg/L;Mg* =18mg/1;K* =19.5mg/1;CO, = Mmg/L;HCO5 =122mg/L; GI" =35.5mg/1;SO} = 48mg/L. @ Catcutate total hardness and alkalinity present in water sample. Ans. Sol. Calculation of CaCO; equivalents Constituent ‘Multiplication factor | tat 0 yequivalent CaCO; =25 ppm 100/100 25x 100/100 = 25.0 mg/L. MgCO,=144 ppm 10084 144 x 100/84 = 171.43 mg/L CaCh,=111 ppm loot 111 x 100/111 = 100.0me/L. 10095 95x 100/95=100.0mg/. Lime requirement for softening 50,000 L of hard water 4100 [C2003 +2x MCs + MgCl a8 COs ex Vo of water = 94/100 [25.0 + 2 x 171.43+100.0] mg/L x 50,000 L 74/100 [467.86 mg/L] x 50,000 L = 1,73,10,820 mg = (,73,10,820/10°) kg=17.3 11kg. 3‘50 | SBP Q. B. Applied Chemistry Soda requirement : 106 700 [MeCl, + CaCl, as CaCO equivalents Vol.of water] = {25 [100 +100}50, 000mg 106 200% 50,000 100 Prob. 15. Explain with chemical equation and calculate the amount of lime and soda needed for softening 1,00,000 litres of water containing the following : HCI = 7.3 mg/L; Al; (SO,)s = 34.2 mg/L; MgCl, = 9.5 mg/L; NaCl =29,25 mg/L. Purity of lime is 90% and that of soda is 98%, 10% of chemicals are to be used in order to complete the reaction quickly. Sol. Conversion into CaCO, equivalents : mg = 1,06,00,000 mg = 10.6 kg. Ans. Constituents Multiplication facto] CaCO, equivalent Hal 100/73 73x 10077 ALSO) loo14 34.2 100/114: MgCl, 100195 95% 10095=10mg/L | ime requirement = 74/100 [ HCI + Aly(SO,); + MgCl, as CaCO, eq] x Vol of water x (100% purity) 4/100 [ 10+ 30 + 10] mg/L-x 10° Lx (100/90) = 4.111 10° mg -111 kg. ime required (using 10% excess ) = 4.111 kgx (110/100) 522 ke, ‘ Soda requirement =106/100 [ HCl-+ Aly(SO4)3 + MgCl, as CaCO,)] x Vol of water x (100% purity) 106/100 [10 +30+10] mg/L x 10° x (100/98) 5.488 x06 mg = 5.408 kg. «Soda required (using 10% excess) = 5.408 x (110/100) = 5.949 kg. Prob. 16. Calculate the quantities of lime and soda required for cold softening of 2,00,000 litres of water using 16.4 ppm of sodium alu- ‘minate as a coagulant, The results of the analysis of raw water and soft- ened water are as follows : Ans. Water| 51 Raw water Softened water a* - 160 ppm CcOoF - 30 ppm Mg - 2ppm on 17 ppm HCO; - 732 ppm Dissolved CO, - 44 ppm. Sol. Converting each of the constituents into their respective equiva- ents of CaCO,, we have- Jon or salt Frm | CaCO; equivalent Lime required] Soda | (ppm) (ppm) | required | _| (opm [Raw Water { ce | am frerelnsoo | | 2 72x 100. Mg 2 100300 30 300 - 100 HCO; 2. -{732x1%_. 600 «on 600 . bind 100 4410 — 100 : co, “4 ise 100 i $ Naaio, | 164 | 164x512 =10 10 10 Softened Waler 100 cor 30x100 _ 59 | co} » a +50 OH, 7] 17x10 os 2 +50 | id "Foal Toa0_| 150 ‘Lime required = E1000 mg/l Lime required for 2,00,000 litres of water 5 2,00,000, ‘ =D x1040%24 = " 700 * 1040 ke = 153.93 kg Similarly, soda required = ix 190 mgt ‘Soda required for 2,00,000 litres of waterEFSBP Q. B. Applied Chemistry Water | 53 Mg7* = 100 Cac 06 2,00,000 ig ppm as Caco, Ton 190% og KS = 40.28 keg. Ans. Ca = 250 ppm as CaCOs Prob. 17. Caleulate the quantity of lime and soda required for sofi- 2 Thr seoe cate ting 50, 000 litres of water containing the following salts per titre: yy % —Limerequirement = 7 [cos +Mg® ] HCO;), = 8.1 mg; Mg(HCO,), = 7.5 mg; CaSO, = 13.6 mg; MgSO, % «8 42.0 mg; MgCl; = 2.0 mg; and NaCl = 4.7 mg. eis 4 2 = [300+ 100] = 296mg/ Sol. Calculation of CaCO; equivalents os 7991300 + 100] = 296mg/L onstituent Multiplicatio CaCO, equivatens] O22 Lime requirement for 10,000 litres of hard water factor Ze8 = 2960.01 kg =2.96 kg. Ans. €a(HCO,), = 100/162 81x 100/162 = 5.0 mg/L Bes 106 Mg(HCO;), 100/146 75x 100/146 = 5.14 mg/L} £4 3 — Soda requirement =——~[Ca* + Mg” —HCO; nae 100 €aSO, 100/136 13.6x 100/136= 5.0 me | Zo . “ MgSO, 100/120 12.0% 100/120 y = ° 106 06, che a deme TODS Samia: Tog l250-100-300]= "2 50}= s3mg/L. Lime requirement for 50, 000 L water j Soda requirement for 1,000 litre of hard water /4 /100[Ca(HCO; ), +2Mg(HCQ,) +MgSO, - = 53% 10000mg = 53>: Prob, 19. The hardness of 10,000 litres of a hard water sample was = 74 /N00{5.0+2%5.14-410.042.1 I] mg/L 50,0001 completely removed by passing it through a zeolite softener. The softener then rogue by 4 lies of Nec sotaton containg TOS ered al = 74/10427 39mg }:50.0001 = 1015,450m, for regeneration, Calesdate ie hanes of the wate saaie poe : (CSU Sem, Deed Jan, 2008-09) 1540 mgm L013 | face ae. 6. | Sol. 200 L of NaCI solution = 40L 1252/1 =:5000g NaCl ‘Soda requirement for 50, 000 L water . ' ‘| =106/1001CaS0, + MeSO, + MgC, 25 CaCO,ea] WVoLof water et ee = 106/100 [5.0 +10.0+2.11}mg/L50,000L. | = 106/100{17.11mg/LJx50,000L = “Aas. -+MgCl,as CaCO;eq]x VoL.of water or Hardness of 1 L of water = 4273. _ 9 49739 cacoy 10,000 ee ,06,830mg, =9,06,830 mgx10°mg/L = 0.9068 kg. Ans. a 427 mg CaCOs eg nce hardness of water = 4.27 mg/L (or : Prob. 18. Calculate the amount of lime soda required for softening ows e/L. (or ppm). Ans. 13900 litres of hard water having the following analysis: Prob. 20. Explain with all chemical reactions involved and Ca** ibns = 250 ppm as CaCO; * quantity of lime and soda for 1 million litres of water analysis of raw ‘Mg ions = 100 ppm as CaCO; water is as follows - HCO; alkalinity = 300 ppm as CaCO3 Mg* = 48ppm,Ca™ =100 ppm, NaCl = 234 ppm, HCO, = 18.3 ppm, H® =15ppmCO, =44ppm. (CS.V.TU., Nov./Dec. 2006) re ee oc earn ceca Sol. Chemical Reactions -Water | 55 54 | SBP Q. B. Applied Chemistry 74x1065%10° Constituent Reaction Need Ogre eee as oe ‘Ans. Ca™(permCa) Ca +Na,CO, -> CaCO, -2Na” s Soda Requirement Me™ (pemMe) e+ Ca(OH), > Mg(OH), +Ca®* = 106 «(Ca + Mg + H° -HCO;] Volume of water CaP ~>CaC0,-2Na* L-s - pepe = 196 x[(250+-2004750- 15)mg/L 10° L HCO, 2HCO,+Ca(OH), > CaCO,+2H,0#COF —L-S. (eg NaCHO,) i = ix [(1185)mg/Z]10°z €a(HCO;), —_Ca(HCO,), +Ca(OH), + 2CaCO,+2H,0 Lb (Temp.Ca) 10611855102 eee eee Mg(HCO,), — Mg(HCO,), +2Ca(OH), > he " = 12.561%10* ke = 1256 kg Ans. 2CaCO,+Mg(OH),+2H,0 a Prob. 2. Calculate the amount of lime (84% pure) and soda (92% . €0,+Ca (OH, CO, +H, 2. (O2+Ca(OH), > Ca 7 . pure) reqiired for treatment of 20,000 litres of water which when an Hi’ (Free acids, 2H*+Ca(OH), + Ca”*+2H,0 Iyzed gave following result - HCL,H,SO, ete.) Ca(CHO,), = 40.5 ppm, Mg(HCO,), = 36.5 ppm Vontmee ena MgSO, = 30.00 ppm, CaSO, = 34.00 ppm, [_Comtitucnts fAmoune CaCl, = 27.75 pin anid NaCt'= 10.00 ppm. Molecular mass of above salts are - 162,146,120,136,111 and 58.5 Ms* 48 ppm Bx respectively. CC. S.V.T.U., Sem. I, 2008) Sol. ca. 100 ppm as Constituents |" Amount | Multiplication | CaCO, Equivalent 100 | Factor Nacl 234 ppm | 100/40 100100 = 250,ppm| 46 5x10 . Cattico,), | 40.5 ppm | 100/162 + Ae 2s HCO, 18.3 ppm 100/122 So !Spem 36.5% 100 I Mg(HCO,), | 36.5 ppm | 100/146 eo =25 15100 i Ds 146 re 15ppm | 1002 = 750 ppm 30x10 100 MgSO, 30.00 ppm | 100/120 120 72° co, 44 ppm | 100/44 44190 = 100 ppm 34x100 nae caso, 34.00 ppm | 100/136 ae =2s ax[Me® +00,+H° +HCO}]> Volume of water 4 CaCl, 27.75 ppm | oon + | 22:75~100 95 = 7 x[(200+ 100+ 750+15)mg/L]10°L NaCl 10.00 ppm] 100/58. 102100 - 17.094 2 24 x[(1065) mg/L ]x10°L‘56 | SBP Q. B. Applied Chemistry 2 Lime Requirement- 2 & we “ « = joy *LCa(HCO,), +2 Me (HCO,)+ MgSO, }x Volume of water z 3 3 (100% purity). OF = S-5 m 20000 , 100 z23 4 of (25-42%25 425) x 20000, 100 Ee 00 [c +2%25-4+25) Tom a | ze? 2 gas 74, 100.20000%100 2\°s = 2, 100:20000%100 go = 1.7 Ans. 7 100" 10°xgq 8 = 1-762 ke x! Soda Requirement- 3 ~ 16 | MgSO, + CaSO, +CaCh] Volume of water (100% purity) + 106 20000 , {00 \* 106 +25) Hd) OS 25425 + 25]x 20000, 00 Ans. 75x 20000100 10% x92, = 1.728 kg ill not cause hardness) 0 Note - NaCl not take here because NaCl Prob. 22. A water sample is alkaline to both, phenolphthalein as well as methy! orange. 100 mL. of water sample on titration with N/SO HCI required 16.8 mL of the acid to phenolphthalein end point. Then few drops of methyl orange were added and the titration was continued. Yellow colour of the solution turned to pink, on addition of 26.4 mL. of total acid solution. Find out the type and amount of alkalinities present + Sem.1, May/June 2007) in the water sample. (CS.V-LU. Sol 100 mL of water upto phenolphthalein end point }6.8 mL of N 50 HCI N 6.8mL x 50 100 mL, 4 168, 1 or Normality, Ny = 405%35 Now strength of alkalinity upto phenolphthalein end point in terms of Water | $7 L To “30%50%1000ppm = 168 At 100 mL of water upto methyl orange end point =16.8+26.4 N = 43.2mLx mL xD HCI 100 mLxN,, = 423 mix 30 4 “100 0 ity upto methyl orange end point in terms of Hence, strength or alkalini or Normality, Nis CaCO, equivalent M = Ny x50x1000 ppm 43.201 M = 82,4 Nx 50x Toa“ 3p N*501000 43.204 Too” 3 *59* 1060 : M= 432 ions are present and alka- i 1 Since, P<>M. Hence, CO}- and HCOy 2P = 2168 linity due to Coe 2P = 336 ppm and alkalinity due to HCO; ‘ M-~2P = 432-336 Hence, the given water sample contains CO?- alkalinity = 96 ppm Prob. 23. Calculate the quantities of lime and soda requi Pi a im required for seening of 254000 res of hater sng 6 pp Net OS a ecn Jant. The results of analysis of raw water and softened water is as under ~ ‘Softened Water Raw Water Ca"? - 240 ppm =96 ppm CaCO, equivalent P = N, x50%1000ppm58 | SBP Q. B. Applied Chemistry Raw Water Constituents ‘Amount [Multiplication | CaCO, Equivalent Factor 240%100 ca? m 240%100 _ 690 cal 240 pp 100/40 pn 601 ; 108100 Mg 108 ppm | 100/24 ayn =4s0 100 HCO, 366 ppm | 1o0/61x2 | 29621000 88%100 CO, 88 ppm 100/44 aa 7200 286 tooe2.2 | *#S*19 5 ieteecat | Meme 82x2 Softened Water Constituents ‘Amount | Multiplication [CaCO, Equivalent| Factor 560x100 cos 60 ppm 100/60 eo 100 OH 255 ppm | 100/17x2 | 7705x285" 75] Lime Requirement ~ Te x[Mer+Hic0; +CO, -NaAlO,+ OH” ]x Vol. of hard water 74 EG x[450+300+200-15+75]+2.50.000 2. 000 jg _74%1010%2.50.000 10° = poo} ‘kg =186.85 kg Ans. Similarly, Soda Requirement « (Ca’*4Mg"* - HOO,” -NaAlO,+00*; +087 ]x Volume of water ae [600 +450 -300-15 +100 +75]2.50.000 Water | 59 ~ 106.,[910]x2.50.000C0}- 000 =i Ag = 241.15 kg Ans. Prob. 24. A sample of water on analysis gives the following results Ca** = 40 ppm, Mg" = 50 ppm, CO; = 60 ppm, HCO;= 100 ppm, K* = 10 ppm. Calculate the lime (85% pure) and soda (95% pure) required to soften 1 million litres of water. Sol. [ Constieat | Amount —] ce ‘0pom ue 50 ft ppm Cor 60 ppm 100% HCO; 100 ppm toon s0n00 81.97 10100 K 10 ppm 10029 700 225.64 .. But K* will not consume lime and soda Lime Requirement+ ZAIMe +-CO, + HCO} jx Volume of hard water Fh a08.33+13636+81 9 RS 14 100 4, xe 37146 Ta * 426.66 0° kg. ‘Ans. Soda Requirement * 106, JoplC2* +Ma®* HCO; }x Volume of hard water60 | SBP Q. B. Applied Chemistry KRISHNA CopteRs SMRITI NA Unrr - 2) MO. - 96: GAR 106, 100, 10° 91859316, 9584 Top 100*208.33-~81.97). 00 1 601916 FUELS 106 97636100 - 252.57 kg. Ans. 5 7 - 100 95 ‘calorific value: goss and net Calorific values and ther determination by bomb calorimeter Prob, 25.A sample of water on analysis has been found to contain following in ppm. Ca(HCO;), = 4.86, Mg(HCO,); = 5.84, CaSO, = 6.80, MgSO, = 8.40 Calculate the temporary and permanent hardness of the water. (Atomic weight Ca = 40, Mg = 24, O = 16, S = 32, C= 12, H=1) Sol. Conversion in to CaCO, equivalent : Constituents | A mount | Multiplication] CaCO, Equivalent Factor . = TOU Ca(HiCOs, | 4.86 100/162 4.86709 = 3pm 100 Mg(HCO;). | 5.84 100/146 5.84x7e=4ppm | CaSO, 6.80 100/136 100 Mgso, 8.40 100/120 8.40% 755 = 7PM Hence, . . ‘Temporary hardness due to Ca(HCO;), and Mg(HCO;). =G+4) = 7ppm Ans. Permanent hardness due to CaSO, and MgSO, =(S+7) ppm= 12 ppm Ans. Solid Fuels : Proximate and ultimate analysis of coal and their importance. High and low temperature carbonization, Coke. Its manufactures by Otto Hoffman oven, Liquid Fuels : Petroleum : Its chemical composition and fractional distillation, knocking and chemical structure, octane number and cetane number and their significancies, power alcohol, Analysis of flue gases by Orsat’s apparatus, Numerical on calorific value, combus- tion, proximate and ultimate analysis of coal. DESCRIPTIVE QUESTIONS ON FUELS, Q. I. What are fuels? Classify fuels along with suitable examples. < Ans. FUELS * Any combustible substance containing carbon as the main constitu: ent, which on burning liberates large amount of heat which can be used economically for domestic and industrial purposes is called fuel.. During combustion of a fuel the atom of carbon, hydrogen-etc. com- bines with oxygen and liberates large amount of heat and also forms new compounds (like CO,, H,O etc.). These new compounds have less energy. The heat released during combustion is the difference in reactants (C, H, O) and products (CO,, H,O) energy. Fuel +02 —_, Products + Heat Classification of Fuels (A). On the basis of their occurrence, fuels are of two types- 1. Natural or Primary Fuels : Fuels which are found in nature as such are called natural fuels. Eg. Wood, Coal, Peat, Petroleum etc 2, Artificial or Secondary Fuels : Fuels which are prepared form pri- mary fuel are called secondary fuels. Eg. Coke, Petrol, Biogas etc. (B) On the basis of physical state of aggregation, fuels are classi- fied in to three types - solid, liquid and gas. 1, Solid Fuels :These fuels are solid in nature, Solid fuels are of two types- i) Natural or Primdry Solid Fuels : It include naturally occurring solid fuels, Eg. Wood, coke, charcoal, peat, lignite etc. (ii) Artificial or Secondary Solid Fuels :It includes artificial solid62 |SBPQ.B. Applied Chemistry fuels, E.g. Thiokol, hydrazine, nitrocellulose etc. 2. Liquid Fuels :These fuels are liquid in nature. Liquid fuels are of two types @ Primary liquid Fuels : Eg. Crude oil or petroleum. (i) Secondary liquid Fuels : E.g. These fuels are prepared form primary fuels. Eg. Gasoline, diesel, kerosene, fuel oil, coal tar and its fractions, alcohol and synthetic spirits etc. 3. Gaseous Fuels : These fuels are gaseous in nature. Gaseous fuels are of two types @ Primary liquid Fuels : E.g. Natural gas. Gi) Secondary liquid Fuels : E.g. These fuels are prepared form primary fuels, Eg. Coal gas, coke oven gas, water gas, pro- ducer gas, carburetted water gas, oil gas, blast furnace gas, refinery oil gas, acetylene, liquid petroleum gas (LPG) etc. Q. 2. What are secondary fuels ? Give examples. (CS.V-1.U., Dec./Jan. 2007) Ans. SECONDARY FUELS Fuels which are prepared form primary fuel are called secondary fuels. Secondary fuels are of three types- 1. Secondary Solid Fueis :It inch:des: hydrazine, nitrocellulose etc. 2. Secondary liquid Fuels : E.g. These fuels are prepared form pri- mary fuels. Eg. Gasoline, diesel, kerosene, fuel oil, coal tar and its * fractions, alcohol and synthetic spirits ete. 3. Secondary liquid Fuels : E.g. These fuels are prepared form pri- mary fuels. Eg. Coal gas, coke oven gas, water gas, producer gas, carburetted water gas, oil gas, last furnace gas, refinery oil gas, acetylene, liquid petroleum gas (LPG) etc. Q. 3. Write the characteristics of good fuels. Ans. CHARACTERISTICS OF GOOD FUEL 1. High Calorific Value: A good fuel should have high calorific value, since the amount of heat liberated and temperature attained thereby depends upon the caloric value. 2. Low Moisture Content : A good fuel should have low moisture content because moisture if present in the fuel, reduces its heating value. ‘ 3. Moderate Ignition Temperature : A good fuel should have moder- ate ignition temperature. If'a fuel has low ignition temperature it can causes fire hazards during storage and transport of fuel and if fuel have high ignition temperature then it is safe for storage and transport -olid fueis. E.g. Thiokol, Fuel | 63 but their might be some difficulty during ignition. 4. Low Non-combustible Matter : A good fuel should have low non- combustible matter, because after combustion the non-combustible matter remains in the form of ash or clinker. They reduce the heating value. 5. Moderate Rate of Combustion : If the rate of combustion is low then the required high temperature may not be possible. if the rate of combustion is high then it gets out of control. So fuel must be burn with a moderate rate. 6. Harmless Combustion Products : They should not pollute the at- mosphere by emitting CO, SO, & H,S. 7. Low Cost : A good fuel should be readily available at low cost, 8. Easy to Transport : Fuel must be easily handled either solid, liquid or gas fuels can easily be transported from one place to another. 9. Uniform Size : In case of solid fuel, the size should be uniform so that combustion is regular. 10. Controllable Combustion : A good fuel should have controllable ‘combustion so that combustion can be started or stopped when re- quired, 11. A fuel should burn in air with efficiency without much smoke. 32, A good fuel should have low storage cost 0.4. Why a good fuel must have low ash contents. (CS.V.T.U., Sem. 1, Dec./Jan, 2008-09) Ans. Ash is a useless non-combustible matter present in a fuel. It re- duces the calorific value, causes hinderance in the flow of air and heat, thereby reducing the temperature attained. It often causes trouble during firing by forming cfinkers. Hence, lower the ash content, better the quality of fuel. Q. 5. Write advantages and disadvantages of solid fuels. ‘Ans, Advantages of Solid Fuels 1. Their production cost is low. 2. Their transport is easy. 3. They are convenient to store, without any risk of spontaneous explosion, 4. They posses moderate ignition temperature. Disadvantages of Solid Fuels 1. They burn with clinker formation. 2. Their ash content is hi 3. Their calorific value is lower . 4. Their combustion operations cannot be controlled easily 5. THeir cost of handling is high. ¥ 6. Their thermal efficiency is low.64 |SBPQ.B. Applied Chemistry wrt SY TAERS” SMRITI NAGAR 7. They can not be used as internal combustion engine fuels. @Q. 4. Distinguish between solid, liquid and gaseous fuels. Ans. Difference Between Solid, liquid and Gaseous fuels BR] Fest] Solid uct— | UigulaFucs | GaseousFual characterist 1. | Cost ‘Cheap. More costly than {Costly Jad feck 2 | Handiingeost | High tow Low (because it requird (abour inthe Storage, trans 3. | Thermal Least | Higher Highest | cle 4.| wrWealoriie] Least Higher tighest value 5. | Combustion | slow Quick ery rapidand rate eticient 6 | Ash Ash content high No ash problem [No ash problem] 7. | smoke Invariably | High carbon and produced | aromatic liquid fuels may produce smoke. 8. | Riskorfire | Least Greater Very high hazards (because these zi fuels are highly inflammable) 9. | Usein internal] Not possible | Possible Possible combustion . ‘capine 10.) Storage Easy ‘Should be stored |Must be stored] imelosed contai-_|inleak proof nersenly voluminous storage tanks. @ 6 Write advantages and disadvantages of liquid fuels. Or Write advantages of liquid fuels over solid fuels. (CS.V-.U., Sem. I, 2005, 2006-07) Ans, Advantages of Liquid Fuels Over Solid fuels 1. They burnt without forming dust, ash, clinker etc. 2. Their per unit mass calorific value is higher than solid fuels. MO, - 9691859316, a58qc019016 Fuel | 65 3. Their transport is easy and can be easily transported through pipes. 4, They can be stored indefinitely without any loss. They require less space for storing. 5. Their firing is easier and combustion operation can be controlled easily by stopping fuel supply. : 6. They can be used as internal combustion fuels. 7. These fuels are generally handled by pipes and one man can easily regulate a large number of furnaces simultaneously. 8. These fuels require less furnace space for combustion. 9. Their thermal efficiency is relatively high. 10. They are economic in labour. 11, They require less air for complete combustion than solid fuels. Disadvantages of Solid Fuels 1. The production cost is relatively much higher as compared to solid fuels. 2. Special storage tanks are required for storing liquid fuels. 3. Risk of fire hazard is very high in case of highly inflammable and volatile liquid fuels. 4, These fuels give dad odour. 5. Special types of burning and spraying apparatus are required for efficient burning of liquid fuels. @. 7. Write advantages and disadvantages of gaseous fuels. Why gaseous fuels are more advantageous than solid fuels ? Ans, « Advantages of Gaseous Fuels . 1 These fuels have high calorifie value. 2. Their combustion can be controlled easily. 3. They can be lighted at moment's notice. 4, They bum without any smoke and are ashless. ‘5. Handling cost is low. 6. Their thermal efficiency is highest. 7. They can be distributed and transported through pipes. 8. They can also be used as internal combustions engine fuels. § Disadvantages of Gaseous Fuels 1. Gascous fuels needs very large tanks for storage. 2. Theig cost is more as compared to solid and liquid fuels. 3. They are highly inflammable, so chances of fire hazards are high in66 | SBPQ.B. Applied Chemistry their use. . 8. What is combustion? Describe chemical principle involved in it. Ans. COMBUSTION Combustion is an exothermic chemical reaction. It is followed by the release of heat & light at a rapid rate, thus the temperature rises. During the process of combustion of fuel, the atoms of carbon, hydro- gen etc. combine with oxygen with the simultaneous liberation of heat at a rapid rate. This energy is liberated due to the formation of new compounds having less energy in them, thus the energy (heat) released during combus- tion process is the difference in energy of reactants and that of products generated. Fuel + 02 —_, Products + Heat (more heat energy) (less heat energy) For example, combustion of carbon in oxygen, liberates 97 kcal of heat. CO +9, @ —+ co, * For proper combustion, the substance must be brought to its kin- dling or ignition temperature. gt Ignition Temperature : It is the minimum temperature at which a substance ignites and burns without further addition of heat from outside. Most commoaly invoived combustiva reactions are as foliows- 1 i n, +40, — HA @ 1, +40, #0 Gi) $+0, —> so, Gi) CO +40, — co, (iv) CH, +20, ++ co, +2H,0 © —©0,+40, —s 20, +3H,0 (i) €,0, +30, —> 2C0, +2H,0 (i 02+80, —+ 200, +1,0 Q. 8. Describe the elementary principles required for the calculation of air quantities. von How would you calculate the amount of oxygen required for the complete combustion of fuel. Fuel | 67 Ans. Calculation of Air Quantities ‘The amount (volume or weight) of air (oxygen) required for the com- bustion of a unit quantity of a fuel can be calculated by applying the follow- ing chemical principles - 1. Substance always combines in definite proportion. These propor- tions are determined by their molecular masses. Eg. for the combus- tion of carbon the combustion equation is Cs) +0,@ — + co, Mass Proportion 2 + 32 44 This indicates that mass proportion of C and O, and CO, are (12:32:44). This means 12 gm of carbon requires 32 gm of oxygen and 44 gm of CO, formed. 2. 22.4 L of any gas at 0°C and 760 mm pressure has a mass equal to its 1 mol. Since the molar mass of O, is 32 gm thus 22.4 L of O, 8.TP. will have a mass of 32 gm. * 3. Air contains 21% of oxygen by volume and 23% of oxygen by mass. Hence, the amount of oxygen required by the fuel, & the amount of air, can be calculated. 23 Kg of oxygen is supplied by 100 Kg of air 1100 1 Kg of oxygen is supplied by 100 kg of air = 23 Ke, 21 mw’ of oxygen is supplied by 100 m* of air 1100 -- Lm of oxygen is supplied by 100 m? of air = “°° = 4.76 of air 4. 28.94 g mol" is taken as molar mass of air. 5. Minimum oxygen required for combustion = Theoretical oxygen required O, present in fuel. 6. Minimum O, required should be calculated on the basis of complete combustion. If the combustion products contain CO and O,, then excess O, is found by subtracting the amount of O, required to burn CO to CO,. 7. The mass of any gas can be converted to its volume by assuming that gas behaves ideally- PV =nRT ‘ Where, P= Pressure (atm), V= Volume (liters) n=No. of moles, T = Temp. (Kelvin) 8. Total amount of hydrogen is either present in the combined form (H,0) or free form. Combined form is not combustible. Rest ofKRISHNA COFIEK> SMRITI NAGAR 68 |SBPQ.B. Applied Chemistry hydrogen is called available hydrogen, takes part in combustion. 2H, + O, —_, 2H,O + Heat Mass proportion- 4 32 Now I part of hydrogen combines 8 parts by mass of oxygen, so available oxygen. [mass of hydrogen ~{Messofoosen} | 8 9. Nitrogen, ash and CO, present in fuel are non combustible matters. Hence they do not take oxygen during combustion process. 10. Total amount of oxygen consumed by the fuel will thus be given by the sum of the amount of oxygen required by the individual combus- tible constituents present in the fuel. Since air has 23% by wt. of oxygen or 21% by volume of oxygen. For complete combustion of 1 kg of fuel. 100 @ weight = Net 0, x55 em. 100 (i) Volume= Net 0, «> gm. out Conversion of volume into weight 1 im’ . (me (28258) Co a4 22.42. mol Thus, Q 9. What is Calorific Value? (CS.V.T.U., Sem. I, Nov.-Dee. 2006) Or Define ‘Net Calorific value’ and Gross calorific value’. (C.S.V.T.U., Sem. I, Dec. / Jan., 2008-09) Ans. 4 CALORIFIC VALUE The total quantity of heat liberated from the combustion of a unit ‘mass of the fuel in air or oxygen is called calorific value of a fuel. Unit of Heat : The calorific value is generally expressed in terms of Calorie, Kilo Calorie, B.Th.U./Ib and C.H.U. 1. Calorie : Calorie is the amount of heat required to increase the MO. - 9691859316, 9584601916 Fuel | 69 temperature of 1 gm of water through one degree centigrade. 2. Kilo Calorie (Or Kilogram Centigrade Units) : - It is equal to 1000 calorie, “The quantity of heat required to increase the tempera- ture of one kilogram of water through one degree centigrade”. 1 Keal = 1000 cal 3. British Thermal Unit (B.Th.U.) : “The quantity of heat required to increase the temperature of one pound of water through one degree Fahrenheit.” 1 Keal = 3.068 B.Th.U. 4, Centigrade Heat Unit (C.H.U.) : “The quantity of heat required to raise the temperature of one pound of water through one degree centigrade.” 1 Keal = 3.968 B.Th.U. = 2.2 CHU. Higher Or Gross Calorific Value (H.C. Hydrogen is present in almost all the fuels. When calorific value of such fuels is determined, hydrogen present is converted into steam. If the products are brought to room temperature the latent heat of condensation of steam also gets included in the measurement of heat, which is called Higher oF Gruss Calorific Vaiue. = So, “ the total amount of heat liberated when a unit mass or unit volume of fuel has been burnt completely and the products are cooled down to room temperature (15%C or 60°F) is called Higher or Gross Calorific Vatuc Lower or Net Calorific Value (L.C.V.) In practice in any fuel when burnt, the water vapor and moisture ete. escapes along with hot combustion gases. Since they are not condensed the lesser amount of heat is available . So “the net heat produced, when a unit mass or unit volume of the fuel is bumt completely and the combustion products are allowed to escape.” Net or lower calorific value (L.C.V.) H.C.V. ~ Latent heat of water vapor formed. H.C.V. ~ Mass of hydrogen x 9 x Latent heat of steam. because 1 part by mass of hydrogen gives 9 parts by mass of water. Latent heat of steam is 587 Keal/Kg. Ho 2gm 18gm. : tem ~9gmn. Weight of water produced from 1 gm H, H Weight of water produced from 755m H, H =9 x 79g Bm= 0.09 H gm. Latent heat of steam = 587 cal/gm. . Latent heat of water vapour formed = 0.09 H x 587 cal t or LCV = (HCV - 0.09 H x 587) cal/gm. Correction : To get more accurate results, the following corrections are applied - @ Fuse Wire Correction : The heat liberated as measured above, ludes the heat given out by ignition of fuse wire used, hence it must be subtracted from the total value. Gi) Acid Correction : Fuels having S and N are oxidized intaH,SO, and HINO. S + 2H +20, —+ H,S0,+Heat } 2N+ 2H +30, —>2HNO, + Hear Formation of acid is “exothermic reaction”. So the measured heat also MO. - 9691859316, 958! Fuel | 73 includes the heat given out during the acid formation. Hence it has to be subtracted from the total value. Gii) Cooling Correction : Time taken to cool the water in calorimeter from maximum temperature to room temperature is noted. From the rate of cooling (d T"/minute) and the actual time taken for cooling (t minutes), the cooling correction of dT tis added to the rise in temperature. Considering all the corrections, calorific value (L) can be calculated by using the formula- La (WW) (t =t, +e0oling comection) —( Acid + fuse correction) ~ ‘Mass of fuel(x) DESCRIPTIVE QUESTIONS ON SOLID FUELS Q. 11. What is coat? Describe different types of coals. Ans. COAL Coal is a highly carbonaceous solid fuel. It is regarded as a fossil fuel produced from large accumulation of vegetable debris due to partial decay and alteration by the action of heat and pressure over millions of years. Carbon, hydrogen and oxygen constitute the true coal substance and the properties of coal mostly depends upon these constituents. Small quanti of sulphur, arsenic and phosphorus also present in many coal samples. If these substances are present in appreciable amounts, the coal may be un- suitable for metallurgical applications. ‘Types of Coal : On the basis of rank or degree of alteration or coali- fication from the parent material coal can be classify in to four types ~ 1. Peat 2. Lignite 3. Bituminous and 4, Anthracite coal. 1. Peat Coal : It is brown, fibrous and jelly like mass. It may contain 80-90% water. On air drying, it buns freely. The air dried peat contains about 57% C, 6% H, 35% O and 2.5 to 6% ash contents. Its calorific value is about 5,400 kcal/kg. 2, Lignite Coal : It soft, brown coloured mass which consists of vegetable matter more than that in peat coal. It has a compact texture, con- taining 20 to 60% moisture contents ontair drying. Air dried lignite contains 60 to 70% C, 20% O and 10% H. Its calorific value is 6,500 to 7,100 kcal/kg (on air dry basis). It bums with long smoky flame. It is used as household fuel and boiler fuel. It is also used in the, production of producer gas. 3. Bituminous Coal : It is pitch-black to dark grey coal. On the basis of carbon contents, bituminous coals are classified into three categories-74 |SBPQ.B. Applied Chemistry @ Sub-bituminous coals : Their carbon content varies from 75 to 83% and oxygen contents from 10 t0 20%. Volatile contents are also high. Their calorific value is about 7,000 kcal/kg. They are non- caking coals. Gi Bituminous coals : Its carbon contents ranges from 78 to 90% and Volatile matter 20 to 45%, Their calorific value is about 8,000 to 8500 kcal/kg. This coal is used in industries for making metallurgical coke, coal gas, boilers and domestic heating. Gil) Semi-bituminous coals :It contain 90 to 95% carbon and has low Volatile matter. Their calorific value is about 8,500 to 8,600 kcal/kg. ‘These coals are used in the manufacture of coke. 4. Anthracite Coal : It is the best quality of coal. Their carbon con- tents are highest (92 to 98%) and has lowest moisture contents and volatile matter. The volatile matter is less than 8%, therefore, they ignite with difficulty, burn without smoke and give intense local heating. Their calo- rific value ranges between 8,650 to 8,700 tack/kg and ash contents is very small (about 3%). Caking pore is absent on this coal. Q. 12, Write criteria for the selection of coal for different uses. Ans. Criteria for the Selection of Coal for Different Uses ‘The selcctior¥of coal for different appiications is mainly made on the basis of the following factors- 1. Calorifie Value : The calorific value of coal should be high. 2, Moisture Contents : Moisture contents of coal should also be low because it reducing the heating value. 3. Ash contents :Ash contents of coal should be low, because it is ‘non combustion and reduces the heating value of coal, 4. Uniformity : The size of coal should be uniform from the point of view of storage, handling and efficiency in operation. 7 5. Calorific Intensity : The calorific intensity of coal should be high. 6. Sulphur and Phosphorus contents : A coal having very low sul- phur and phosphorus contents is essential for metallurgical purposes be- cause these impuirities are likely to be transferred to the metal and adversely affect its properties. 7. Coking Quality : The coking quality of coals should also be good because coking coals are selected for preparation of strong and porous coke which is suitable for metallurgical purposes. @ 13. Give definition of non-coking, caking and coking coal. (CS.V-T.U,, Sem. I, Dee. / Jan., 2008-09) Fuel | 75 Ans. 1. Non Coking coals : Coals do not produce a good coherent ‘mass during heating in the absence of air, but its rate of carbgnization is very high is called non coking coal. It has no fusing effect. They are known as ‘free burning coals’. . 2, Caking Coal : Coals that soften on heating produce a pasty or plastic mass which fuse together yielding coherent impervious to air are called caking coals. It is interesting to note that “all coking coals are caking, but all caking coals are not essentially coking coals”. 3. Coking Coals : Coals which give porous, hard and strong residue after heating in absence of air are called coking coals. The residue is usable for metallurgical purposes and is known as coke. Coking coals are suitable for metallurgical purposes because they are quite strong and not crushed under weight of ore. Q. 14, What is analysis of coal? Describe the proximate analysis of coal and discus ts significance. or Name the factors assessed in proximate analysis of coal. (CS.V-T.U., Sem. I, 2005, 2006-07) Ans. ANALYSIS OF COAL Coakis 2 highly carbonaceous fossil fuel. It is mainly composed of C, H, O, N beside non combustible organic matter. To asses the quality of coal, the following two types of analysis are carried out- 1. Proximate analysis and 2. Ultimate analysis, PROXIMATE ANALYSIS It is a type of analysis of coal by which we determine moisture, vola- tile matter, ash and fixed carbon present in coal. It also gives valuable infor- mations about the practical utility of coal. Significance of Proximate Analysis: Proximal analysis of coal pro- vides valuable informations about the quality of coal in term of moisture contents, moisture, volatile matter, ash and fixed carbon, 1. Moisture Content High % of moisture in coal is not good because - (i. It increases the cost of coal as well as transportation charges. Hence lesser the moisture content better will be the quality of coal. (ii. It quenches the fire in the furnace, but presence of moisture up to 10% produces a mort uniform fuel bed and less of fly ash. Gil). Moisture in coal evaporates during the burning. The moisture losses the calorific value of fuel. Determination of Moisture : Moisture contents of coal is deter-76 | SBPQ.B. Applied Chemistry mined by heating a small amount of coal powder in crucible at 100 - 110°C. in an electric oven. The crucible is allowed to remain in oven for | hour and then taken out, cooled in desiccator and weighing till the weight. Loss in weight is reported as moisture. . Lossin weight, Ye of moisture = ee Focataken 2, Volatile Matter (@. The volatile matters will combustible or non-combustible gases. The presence of non combustible gases is always undesirable. (i) When coal has high volatile matters then high proportion of fuel distill over as gas. So higher volatile matter in coal is undesirable. i) Coal having higher volatile matter burns with long flame, high smoke and low calorific value. (iv) When by product recovery is the main object, volatile matter has special significance. In coal gas‘plant and carbonization plants> (¥) Medium volatile matter containing coal give hard and strong coke on carbonization. Determination of Volatile Matter : To determine volatile contents of coal the dried sample of coal left in crucible after analysis of moisture is the n covered with @ Ed-and placed inside an mufflé furnace maintained ut 925°C +20°C for 7 minutes and cooled in desiccators and weighted again. {Loss in weight due removal of volatile matters, ‘weight of coal taken ‘% of volatile matter = 3. Ash ‘When all combustible substances have been burnt, only ash is left in coal. It is not needed because, . @ It causes hindrance to the flow of air and heat, It increases cost of storage. It reduces calorific value of fuel. iii) Burning of coal Becomes irregular due to formation of clinkers (fused lumps of ash). , Determination of Ash : To determine ash content of coal, the re- Sidual coal in the crucible afterheating in muffle furnace (during determina- tion of volatile matter) is burnt without lid in muffle furnace at 750°C ++ 50°C for 1/2 hour so only ash is left:The crucible is then taken out, cooled in air » then in desiccator and weighted. . weight of ash formed of ash = + eight of dyad 100 KRISHNA COPIERS SMRITI NAGAR ey MO, - 96: Ayan 91859316, 9584601916 After determination of moisture, volatile matter, and ash, the remain- ing part is known as fixed carbon. Determination of Fixed Carbon : The percentage of fixed carbon is determined by deducting the sum total of moisture, volatile matter and ash from 100%. After determination of moisture, volatile matter, and ash, the remaining part is fixed carbon. Higher the % of fixed carbon greater the calorific value. % of fixed carbon = 100 ~ % (Moisture + Volatile matter + Ash) @ 15. Name the factors assessed in ultimate analysis of coal. (CS.V.L.U., Sem. I, 2005, 2006-07) Or Write short note on ultimate analysis of coal Or What is the significance of ultimate analysis ? (CS.V-LU,, Sem. LNov.?Dec.2007) How is nitrogen of fuel estimated by Kjeldant’s method ? (CS.V-T.U,, Sem. I, May/June-2007) Ans. ULTIMATE ANALYSIS This analysis is related with the estimation of carbon, hydrogen, sulphur, oxygen nitrogen and ash. Ultimatetanalysis is wsofal for calcu the heat balances in any process for which coal is employed as a fuel. Significance of Ultimate Analysis : Ultimate analysis of coal pro- vides following informations in assessing the quality of coal- 1. Carbon and Hydrogen The quantity of carbon and hydrogen in coal determine the quality of coal. Greater the % of C and H, better is the coal and give high calorific value. Carbon % is the basis of classification of coal. Hydrogen is méstly associated with volatile matter and moisture hence it effects the calorific value of coal. Higher % is undesirable. Determination of Carbon and Hydrogen : A known quantity of coal sample (about I - 2 gm) is burnt in combustion apparatus in the presence of dry oxygen. The C and H present in coal are converted in to CO, and H,O. These gases are passed in two bulbs. One bulb contain weighted amount of anhydrous CaCl, which absorb water. CaCl, + 7H,O —; CaCl, . 74,0 c ‘Second bulb contain weighted amount of KOH which absorb co,, 2KOH +CO, —->K,CO, +0 ‘The weight of CaCl, and KOH bulbs are measured. Increase weightof78 |SBPQ.B. Applied Chemistry CaCl, bulb shows weight of H,O and increase weight of KOH bulb is weight of CO, formed. +0, —> co, 23248 Increase in wt.of KOH absorption tubex 12 = WLC = ———~wa of coal sample takenxaa 100 n% ‘wt. of coal sample taken x44 Similarly, A, + $2 — Ho 2 16 18 Increase in wt.of CaCl, absorption tubex2 99 ‘wt. of coal sample taken x18 . %ofH (ii) Nitrogen N, is inert and non combustible gas having no calorific value. Hence good qitality coal should have very little N contents. * Determination of Nitrogen (By Kjeldahal’s method) : Nitrogen estimation is carried out by Kjeldahal’s method. About 1 gm of coal is. heated with concentrated H,SO, along with K,SO, and CuSO, in a long necked Kjeldahal’s flask. When clear solution is obtained (Fe., whole nitrogen is converted into ‘ammonium sulphate ((NH,), SO,). It is treated with excess of NaOH to liberate ammonia. This ammonia thus produced is distilled over absorbed in a known volume of standard H,SO, (N/10). H,SO, and unused H,SO, is then determined from the volume of acid used by ammonia liberated, the % of N in coal is calculated as follows- N, +H,SO, —_+ (NH), SO, 8, 2NaOH ©, +2NH, +2H,0 2NH, + H,SO, —> (NH), SO, Volume of acid used x Normality x 1.4 fof N= Weight of coal sample taken Gil) Sulphur ‘The amount of sulphur determined from the washing which is ob- tained from the known mass of coal used in bomb calorimeter for the estimation of calorific value. In this process sulphure is converted into sulphate, The washings are treated with barium chloride solution, then BaSO, is precipitated is filtered, washed and heated to constant weight. The % of sulphur is the calculated by using following formula. Fuel | 79 Weight of BaSO, obtained x 32x 100 ‘Weight of coal sample taken in bomb x 233 ence? OR78EM +, The percentage of oxygen is calculated by by difer %ofS=. % of O= 100 ~ % of (C+H +S 4N + Ash) (¥) Ash : The determination of ash contents is carried out like that of proximal analysis. Q. 16. Give two disadvantages of each of moisture, volatile matter and ash in coal. (CS.V-T.U., Sem. I, Dee. / Jan., 2008-09) Ans. Disadvantage of Moisture in Coal 1, It quenches the fire in the furnace. 2. The moisture losses the calorific value of fuel. Disadvantage of Volatile Matter in Coal | When coal has high volatile matters then high proportion of fuel distill over as gas. So higher volatile matter in coal is undesirable. 2. Coal having higher volatile matter burns with long flame, high smoke and low calorific value. Disadvantage of Ash in Coal 1. It causes hindrance to the flow of air and heat, . 2. It increases cost of storage. It reduces calorific value of fuel the a,” GE 8 advantages of higher percentage of fixed carbon in (CS.V.L.U., Sem. I, Dec. / Jan., 2008-09) ‘Ans. — Advantages of higher percentage of fixed carbon +1. Higher the % of fixed carbon greater the calorific value! 2. Thé % of fixed carbon helps is i of the fire box because it burns inte soda mn Q. 18. What is carbonization ? Deseribe differe 1 ization of coke. Sees Or Write short note on carbonization. Ans. CARBONIZATION ' ‘ ‘The process of converting coal into coal is called earbonizatis : < isc nization. When a coking coal is heated in the absence of air, the porous, hard and strong residue left is called coke. :KRISHNA COPIERS SMRITI NAGAR MO. - 9691859316, 9584601916 80 |SBPQ.B. Applied Chemistry ‘Types of Carbonization : Depending on the temperature, carboniza- | tion is of two type- low temperature and high temperature carbonization. 1, Low Temperature Carbonization (L.T.C.) : In this process, the heating of coal is carried at 500 - 750°C. The yield of coke is about 75 - £0% and it contetn about § —15% volatile matter. We get smokeless and free bumning semicoke by this process. Since it is easily ignited, it is a valuable, smokeless fuel for domestic use. The by-product gas produced by this process is rich in heating value. Hence it is more useful fuel. This process is carried out both with coking and non coking coals. 2. High Temperature Carbonization (H.T.C.) : In this process, the heating of coal is carried out at 900°C — 1200°C. The yield of coke is about 65 to 75% volatile matter is 1 -3%. It is very hard, strong pure, porous so it is used in Metallurgical coke. The by product gas produced by this pro- cess is high in volume but has low calorific value. Q. 19. What is the difference between low and high temperature carbonization of coal. (CS.VLU., Sem, 1, 2005, 2006-07, Nov/Dec. 2006) Or -“Compure low temperanire carbonization and high temperature carbonization. (CS.V-T.U., Sem. 1, May/Sune 2007, Dee. / Jan., 2008-09) ‘Ans. Difference Between Low and High Temp. Carbonization High Temp. Carbonization S.N] Low Temp. Carbonization 1. | Heating temp is about 500 - 750° About 900 - 1200°C . 2. | Yield of coke will be 75-80% 65 to 75%. 3. | Volatite matter is up to 5-15% | 1-3% | i 4 | Mechanical strength low, Mechanical strength high. 5. | Calorific value is high about Low about 5400-6000 Keal/m 6500-9500 kcal/m* 6. | Quantity of by produet is about 130-150 m*/tonne. 7. | Coke produced is soft. About 300-390 m*/tonne. Coke produced is hard. 8. | Use of cbke; Domestic. Metallurgical purpose. 9. | % of aromatic hydrocarbon in gad % of aromatic hydrocarbon gasis lower. is higher. 10. | It is smokeless, It is smoky. Fuel | 81 @. 20. What is coke ? Give requisites of a metallurgical coke. Or What is coke ? Give important characteristics of good métallurgical coke. Ans. COKE When coking coal is heated strongly in the absence of air, it losses volatile matter and converted into white, porous, hard, strong and coherent ‘mass or residue known as coke, Requisites of a Metallurgical Coke or Characteristics of Good Metallurgical Coke The characteristics required for a good metallurgical coke are- 1. Cost : The coke should be cheap and easily available near the site of plant. 2 High purity : The coke should possess high carbon contents and < low moisture, sulphur, phosphorus contents as possible. 3. High porosity : The coke should be porous to provide contact between carbon and oxygen and to ensure efficient combustion of the coke in furnace. 4. Strength It should be strong enough to withstand ihe abrasion end ‘over burden of the ore, flux and fuel itself in the furnace. 5. Uniformity : The size of the coke should be moderate i.e., neither to big nor to small. 6. Combustibility : The coke should be burn easily. 7, Calorific value: The calorific value of coke should be high. Q 21. Describe in brief the manufacture of metallurgical coke by Otto Hoffman's process.. Manufacture of Metallurgical Coke; By Otto Hoffmann’s By-product Oven Method Oto Hoffmann developed modem by-product oven for manufactur- ing metallurgical coke. It is used in order to- @ Increase the thermal efficiency of carbonization process, Gil) Recovery of by products. It is heated by a portion of coal gas produced during the process itself or by producer gas or by blast furnace gas. Moredver, the heating is done on the basis of regenerative principle of heat economy. Construction of oven : The by product coke oven consists of a umber of narrow silica chambers. Each chambess is about 10-12 meter Tong, 3 - 4m. high and 0.40-0.45 m wide. These chambers are erected side Ans.82 |SBPQ.B. Applied Chemistry by side with vertical flues in between them to form a sort a battery. Each chamber has Charging Hole at the top for charging the coal and removal of Volatile matter “gas takes off). More over heating is done on the basis of “Regenerative System of heat economy’, so utilizing the waste flue gases for heating the checker work of bricks. tio Hiotfinsiiu's by-product oven with generator ‘Theory : Coking process is done in narrow ovens, which are heated from both sides because coal is poor conductor of heat. The coals adjacent to oven walls get heated first and the plastic zone formed in the case of caking coals moves away from the walls towards the central zone. The plastic zone through mobile is such a bed conductor of heat that while the inner zones are getting heated, the sime - coke at the outer zones would have been coriverted into:coke. Working :Finely crushed coal is introduced in the charging holes at the top of chamber. And cut the supply of air. The ovens are heated to 1200°C by burning gas (producer gas). Each oven is separated form an- other oven by a vertical flue in which the fuel gas bums. These ovens work on the Regenerative principle of heat economy. The flue gases produced during combustion, before escaping to chimney, pass on their heat to one or two sets of checker brick, until this brick has been raised to temperature about 1000°C. The inlet gas are passed through the heated checker brick, which get preheated, while the flue gases leave their acquired heat to one ‘generator the other generator is used for preheating the incoming air. Heat- ing is continued, until all the volatile matter has escaped. It takes about 11,- Fuel | 83 18 hrs for carbonization of a charge of coal. ‘Quenching :- After the completion of carbonization, the discharging doors are lifted by a crane and the red hot coke is pushed out into a coke car. ‘The car carries it to quenching station where the coke comes into contact, with a spray of cooling water. Then it is supplied for different purposes. In place of wet quenching, “dry quenching’ can also be done. It has many ad- vantages, because the coke produced is more strong, dense, non reactive. ‘Coke is cheaper also and contains lesser dust then ‘wet quenching’. Q. 22. Narrate the advantages of Oito Hafmann’s by-product oven process for the manufacture of coke. (C-S.V-TU., Sem. I, Dee. / Jan., 2008-09) Ans. Advantages of Otto Hafmann’s By-product Oven Process 1. The heating is done on the basis of regenerative principle of heat economy. It is heated by a portion of coal gas produced during the process itself or by producer gas or by blast furnace gas. 2. This process of manufacturing coke increase'the efficiency of car- bonization process. 3. Itrecovers valuable by-products like coal gas, ammonia, benzol, tar, naphthalene oil etc. @. 23. Give an account of recovery of by-products of Otto Hoffman’s ‘oven, (CS.V.T.U., Sem. 1, 2006-07) Ans. Recovery of By Products of Otto Hoffman’s Oven The gas coming out from the oven is known as ‘Coke Oven Gas’. It is minty consist of NH,, HS, C.H,, Tar, Naphthalene etc. 1. Recovery of Tar : The gas passed through a tower in which liquid ammonia is sprayed. Here dust and tar,get collected in a tank below, which is heated by steam coils to recover back ammonia. The am- monia is used again. 2, Recovery of Ammonia : The gas from the chamber is then passed a tower in which water is sprayed. Here ammonia goes into solution as NH,OH. NH,+H,O —+ NH,OH 2NH,OH + H,S0, —> (NH)),SO, +2H,0 3. Recovery of Naphthalene : The gas then passed a tower in which Water is sprayed at low temperature... Here naphthalene gets condensed. 4, Recovery of Benzene : The gas is then sprayed with petroleum84 | SBPQ.B. Applied Chemistry ! when benzene and its homologous can be recovered. 5. Recovery of H,S : The gas is then passed to a purifier, packed with moist Fe,O,. Here HS is retained. Fe,0, +3H,S —+ Fe,0, +3 H,0. | After some time, when all Fe,0, is converted into the purifiers exposed to atmosphere, when Fe,O, is regenerated. Fe,0, +40, —+ 2 FeO +380, t 4FeO+O, ——» 2Fe,0, Significance of Recovery of By Products Coke oven gas contains large number of valuable impurities. i 1. Tar : Tar is used for road making, it gives on fractional distillation benzene, toluene, naphthalene etc. 2. Ammonia : The removal of ammonia from the gas is necessary to avoid the blockage of gas pipes by ammonium carbonate. * 3, Naphthalene : Naphthalene and other higher aromatics present in vapors, may cause blocking of the gas pipes. 4, Benzene : Is a important solvents and raw materials for plastic. 5. H,S : Sulphur compounds may get oxidized to SO, and finally to H,SO, obtained. ~ = Q. 24. Why coke is preferred to coal in metallurgical process ? Ans. Coke is preferred to coal in metallurgical process because of the following reasons- 1. The porosity and strength of coke is greater than coal. 2. It s calorific value is high. : 1 Cokerbums with_a short flame as the mastof the volatile matter is | removed during carbonization. i DESCRIPTIVE QUESTIONS ON LIQUID FUELS @. 25. What is petrochemical ? Give its chemical composition. Ans. PETROLEUM ‘The term petroleum is derived from two Latin words petra = rock and oleum = cil. Petroleum is crude, dark, greenish brown viscous oil found deep in earth drust. It is also called mineral oil because it occurs beneath the earth, It is formed due to partial decomposition of dead animals, vegeta- tions. The catastrophic changes resulted in the formation of petroleum. Fuel | 85 Chemical composition of Petroleum : Petroleum is a complex mixture of paraffin, olefinic and aromatic hy- drocarbons with small quantities of optically active organic compounds containing O, N and sulphur and traces of metallic constituents. The com. mon constituents present in petroleum are - Composition Remarks Present about 70%. Normal, branched] cycloalkanes present. Sulphur is present in either free form ‘compounds or compound form like HS Thiols, Thiophene, Thioalkanes. (C,- C,) carboxylic acids occur in ‘compounds low boiling fractions whild naphthenic acid occur in high boiling fraction, Mainly in form of pyrrole, indole pyridine, quinoline etc. ‘These are oragano metallic compoun- ds of Cu, Fe, Ni and V. : Q. 26. Whatis fractional distillation ?Describe the process of frac-~ tional distribution. J Ans. FRACTIONAL DISTILLATION ‘The process by which the crude oil is separated into various fractions (having different boiling points) is called fraction distillation. These frac. tions are finally converted into desired specific products by removing im- purities. The process in called ‘refining of crude oil’. Fractional distillation 1s essentially a combination of distillation and rectification. Rectification Process consists of counter flow contacting’ of the vapours formed in dis- tillation with the liquid obtained by condensation of vapours. A fractional still is consists of a pipe still anda bubble tower called Fractionating Col- umn containing a number of horizontal stainless steel trays at short dis- tances... Process : The crude oil is heated to about 400°C in a pipe, where all volatile matter are evaporated. The hot vapors are then passed through a tall cylindrical tower, known as *Fractionating Column’ containing a number of horizontal stainless steel trays at short distances. These trays are pro- vided with individual Chimney which are covered with a loose cap. As the vapors go up, they become gradually coole? and fractional condensation takes place at different heights of column. Higher boiling fraction con- denses first while the lower boiling fractions turn-by-turn. ‘Various fractions obtained by fractional wistillation of crude oil are 1. Hydrocarbons 2, Sulphur containing 3. Oxygen containing 4, Nitrogen containing comipound 5. Inorganic compounds86 |SBPQ.B. Applied Chemistry given in the following table- Fig. 2.3. Fractional distillation of crude petroleum. ‘Table : Various fractions obtained by fractional distillation of crude of ‘Name uf fraction Boiling [Approximate Uses i Temp. |Composition i 7 rnd 1. Uncondensed gas | Below 30+ CoC, | UsedasLPG] , eg, ethane, propane. 2. Petroleum ether | 30 - 70°C €,toC, ,| Used as solvent } 3. Gasoline or petrol] 4010 120°C | C,toC, |} Used as fuel for] | gines solvent i 4. Naphtha 12010 180°C] C,toC,, | Solvent, in dry cleaning 5. Kerosene Oil 180° to 250°C] C,,t0C,, | Fuel, in preparing laboratory gas 6. Diesel Oil 250 to 320°C | C,toC,, | Usedas diesel engine fuel 7. Heavy Oil 320t0 400°C} C,, toC,, } For getting gasoline by cracking. Fuel | 87 This on re fra- ctionation gives @ Lubricating oil : : As lubricants (b) Vaseline - - ‘As lubricants and in cosmetics} © Grease - 5 As lubricants @ Paraffinwax 7 - Jn candles, wax paper, tarpolin cloth etc. 8. Residue may Above 400°C] C,,and above @Asphatt - : Water proofing of roofs and road making. (i) Petroleum se - ‘Asa fuel and in coke moulding are light rods @. 27. Define knocking. (CS.V.LU. Sem. I, 2005, 2006-07) or What is meant by knocking in internal combustion engine ? Ex- plain the mechanism of knocking in chemical terms, Or What is meant by knocking ? How it is related with chemical com- bustion ? _ Aus. KNOCKING:IN INTERNAL COMBUSTION (1.C.) In an intemal combustion engine, a mixture of petrol and air is com- pressed. The fuel air mixture gets heated to a temperature greater than its ignition temperature due to compression. This leads to spontaneous com- bustion even before sparking. It is also possible that the last portion of the fuel- air-mixture undergoes self - ignition after sparking and give detonat- ing shock wave (explosion). The resulting shock wave dissipates its en- ergy by hitting the cylinder walls and piston, and emitted sound is called knocking. : Knocking is depend on the nature of fuel taken, engine design, shape of head, location of plug, chemical structure of fuel, running conditions. With increase in compression ratio (C. R.) , efficiency of IC engine“which the combustior 88 |SBPQ.B. Applied Chemistry also increases but after critical C.R., tendency to knock also increases. Consequence of Knocking 1. Decreased power output. 2. Loss of efficiency of engine. 3. Mechanical damage by over heating of the cylinder parts. ‘Chemical Structure and Knocking Knocking tendency decreases with increase in the compactness of the molecules, double bonds and cyclic compound. With normal paraffins, the anti-knock properties decrease with increase in length of hydrocarbon chain. Thus octane numbers of n-butane, n- pentane, n-hexane and n-hep- tanes are 90, 60, 20 and 0 respectively. Branched chain paraffin’s have higher anti knocking properties. E.g. 2. Methyl hexane. It has an octane number of 55 while 2:2 dimethyl pen- tane has an octane number of 80. ‘Aromatic hydrocarbon such as benzene and toluene has high octane number. Olefins have higher anti-knock properties. Thus the tendency of fuel constituents to knock is in the following order- Straight chain paraffins > branched paraffins (iso paraffins) > ole- fins > cyclo-paraffins (= naphthalenes) > aromatic crudes. For straight chain hydrocarbons, ‘the knocking tendency increases with molecular weight and boiling point. E.g. n-hexane > n-pentane > n- butane. Q. 28. Define the following- (a). Ignition Temperature. _(b). Compression ratio ‘Ans. (a) Ignition Temperature: It is the minimum temperature at self start. (b). Compression Ratio (C.R.): The ratio of gaseous volume (V,) in cylinder at the end of suction- stroke to the volume at the end of compres- sion stroke of the piston (V,) is called compression ratio. The power and efficiency of internal combustion engine increases with the increase in com- pression ratio (C.R.). The C.R. is dependent on the nature of the constitu- ents present in the gasoline used. ASV,>V, —> CR= yy >a “CR indicates the extent of compression of fuel air mixture by piston’. KRISHNA COPIERS ‘SMRITI-NAGAR 9584601916 Fuel | 89 @. 29. Write short notes on the following- (@). Octane number Or What is octane number ? How is it related to the chemical Structure of fuel. Ans. (0). Anti-knocking agents, (a). OCTANE NUMBER AND OCTANE RATING’ __ The percentage by volume of iso-octane in the mixture of iso-octane which has the same anti-knock qualities as the fuels under examination is called octane number. In other Words the knocking tendency of a fuel are expressed by ‘Octane Number’. It is found that the hydrocarbon iso-oc- tane (C,H,,) having formula - ° MO. - 9691859316, ca, cH, | | cu, —c — cn, c —cH, 7 | | H cH, has very good combustion characteristics and exhibits very little tendency to detonate explosion) when mixed with air and ignited at high tempera ture, Hence its octane number is 100, (On the other hand the straight chain hydrocarbon, having formula- ~ CH,~CH, - CH, - CH, ~ CH, - CH, _ CH, knock very readily and hence its octane number is Zero (0). ‘The octane number of any fuel is numerically taken as the percent- age of iso-octane in a mixture of iso-octane and n- aptane which just matches with the knocking characteristics of the fuel under consideration. Example: If a sample of petrol gives as much of knocking as a mixture of 75 parts of iso-octane and 25 parts of n-haptane, then its octane number is taken as 75. , n- heptane (C,H,,) Graham Edgar in 1926 has given octane rating of some common hydrocarbons as follows- Fuel Octane Number ‘Character N - heptane 0 ‘Knocks severely Iso - Octane 100 High resistance to knocking | The octane ratings of ome other common hydrocarbon are as follows-90 |SBPQ.B. Applied Chemistry Hydrocarbon ‘Octane Number Benzene 100" Isopentane 90 Cyclohexane 1 2- methyl pentane n n- pentane oe n-hexane 26 Octane number of a hydrocarbon depends on its structure. The value of octane number decrease with increase in chain length. 1. Branched chain hydrocarbons have higher octane number. 2. Aromatic hydrocarbons have very high octane number. 3. Straight chain alkanes have very low octant number. 4, Unsaturated hydrocarbons have higher octane number, corresponding, to straight chain alkanes. 5. Cyclic alkanes also have, higher octane number, corresponding to straight chain alkanes. (b). ANTI- KNOCKING AGENTS T increase the octane number of any fuel, some fuels of higher anti- knock value are added. This process is called blending. This phenomenon js known as antiknocking and the agents that are used f decease the knocking of internal combustion engines are called anti knocking agents. Examples: Tetra ethyl lead (TEL) and diethy! telluride [(C,H,), Te].The adding of TEL in fuel is called ‘Doping’. About 0.5 ml of TEL per litre is added for motor spirits and about 1 ml of TEL per litre is generally added for aviation petrol. TELis a colourless liquid with sweet odour. It is highly poisonous and care should be taken to see that it does not'enter the body through cuts or bruise. TEL gives Pb and PbO, during combustion. Pb and PbO, decreases engine life, hence they must removed by adding ethylene dibromide. Pb, PbO, + C,H,Br, —+ PbBr, PbBr, is volatile and escapes in atmosphere but creates pollution prob- lem. - Q. 30. Why ethylene dibromide added to petrol, when TEL is added 40 petrol ? Or * How will you improve the antinocking value of fuel ? Ans. Refer Q.No. 29 (b) anti knocking agents Fuel | 91 @. 31. What do you mean by cetane number ? Write its signift- cance, Or Write short note on cetane number. Ans. CETANE NUMBER In a diesel engine, the fuel is exploded not by a spark, but by the application of heat and pressure. The suitability of a diesel fuel is deter- mined by its cetane value. Cetane (C, H,,) is a saturated hydrocarbon which has very short ignition compared to any other diesel fuel. ‘The cetane number of a fuel may be defined as- “the percentage of hexadetane in a mixture of hexadecane and 2-methyl naphalene, which has the same ignition characteristics as the diesel fuel in question”, In other words “the percentage of cetane and 2-methyl naphtha- lene which exactly matches in its knocking character with the oil under the same conditions is called cetane number”. ‘The cetane number of a diesel fuel can be raised by the addition of small quantity of certain cetane value improvers. These substances are called as “dopes”. Example: Ethyl nitrate, iSosmyl nitrite, acetone peroxide etc. A high speed diesel engine require a fuel of cetane number greater than 45.On the other hand, low speed diesel requires cetane number of about 25. Cet- ane number of medium speed diesel is about 35. ‘The combustion of fuel in a diesel engine is not instantanecus, the “interval between the start of fuel injection and its ignition is called the “ ignition delay”. Ignition delay may be takes place due to (a) Engine Design (b) Mixing of spray (fuel) and air (c) Chemical nature of fuel If ignition delay is Long, it will lead to fuel accumulation in the engine even before the ignition. When ignites creates explosion. This is diesel knock. Example : Saturated hydrocarbon has a short ignition lag so it’s ce- tane no. is 100 and aromatic hydrocarbon has very long ignition lag so, cetane no. is Zero (0). : Diesel fuel Cetane no. 1.Cetane C,H, 100 2. a-methy! naphthalene 0 Ignition quality order among hydrocarbon constituents of a diesel fuel is as follows- y 1 alkanes > naphthalenes > alkenes > branched-alkanes > aromatics Here, cetgne number increase from right to left. ‘ Ignition delay increases from left to right. 5 ion quality increases from right to left. Thus hydrocarbon which ‘are poor gasoline fuel are quite good diesel fuels. i Remarks Very short ignition delay Longer ignition delay92 |SBPQ.B. Applied Chemistry Q. 32. Write short note on diesel engine fuels. (C-S.V.T.U., Sem. I, 2006-07) Ans. DIESEL ENGINE FUEL Diesel engine require a crude oil fraction called diesel. It is used in diesel engines for automotive purposes in buses, lorries, diesel locomotives etc. In a diesel engine, the fuél which is expioded not by a spark, but by the application of heat and pressure is called diesel engine fuel. Diesel engine fuels have a long chain hydrocarbon, which has a very short ignition lag. This means that it is essential that the hydrocarbon mol- ecules in a diesel fuel should be ‘straight Chain’. In the diesel engine, air is first drawn into cylinder, and compressed temp. is 500°C.At the end of compression stroke, diesel is injected. The Oil @iesel) absorbs the heat from the air and it ignites spontaneously as it attains ignition temperature... The combustion of fuel in a diesel engine is not instantaneous, the “interval between:the start of fuel injection and its ignition is called the “ ignition delay”. Ignition delay is due to (a) Engine Design (b) Mixing of spray (fuel) and air (c) Chemical nature of fuel. If ignition delay is tong, it will lead to fuel accumulation in the engine even before the ignition. When ignites creates explosion. This is called die~ sel knock. The suitability of diese! engine fiiel is determined by its cetane value. It is known as cetane number. ‘The cetane number of a diesel fuel can be raised by the ad small quantity of certain cetane value improvers called “dopes”. Note : For detail refer Q. No. 32 Q. 33. Differentiate between Octane number and Cetane number. Ans. Difference Between Octane,number and Cetane number. ‘Octane No. Cetane No. L.lt's the % of iso-octane in a mixture] 1. It is the % of cetane in a mix of cetane and a-methyl naphthalene] ture of isooctane n-heptane. 2.1t is used for internal combustion 2. It is used for diesel fuel. engine 3. Octane no. can be raised by add- | 3.Cetane no. can be raised by of dopes like ethy! nitrite. addition of TEL or (C,H,) Te. 4, Hydrocarbons which are poor diesel/ 4. Hydrocarbons which are poo! fuel are good gasoline fuel. ‘gasoline are good diesel fuel. 5. Straight chain fuels are worst fuels | 5. Straight chain fuels are best ad as they give low octane number. ion of KRISHNA COPIERS SMRITI NAGAR MO, - 9691859316, 9584601916 Fuel | 93 Q. 34. Write short note on power alcohol. Ans. POWER ALCOHOL When ethyl alcohol is used as a fuel for generation of power in inter- nal combustion engine, itis called power alcohol. Ethyl alcohol is not used as a prime fuel, but it is used as an additive to motor fuel. Blends of alcohol with gasoline or with gasoline plus benzol or with ether and water used as motor fuel. Blends containing 25% of alcohol with petrol are used. Advantages 1. Ethyl alcohol has an octane value of about 90, while petrol has ‘octane value of 60-70. Thus addition of alcohol in the petrol in- creases its octane number. 2. It has a good anti knocking properties. 3. Alcohol petrol blends have lesser starting difficulties. Dis- advantages 1. Alcohol lowers the calorific value of petrol. Alcohol is difficult to atomize, particularly at low temperature, because of its consider- able surface tension. 3. Alcohol is easily oxidized to acids, hence it cause corrosion. Q, 38. Explain with the help of a diagram, how the flu gas analysis ts conducted using Orsats apparatus ? (C-S.V.TU., Sem. I, Nov.?Dec.-2007) ‘Ans. ANALYSIS OF FLUE GAS BY ORSAT’S APPARATUS The mixture of gases which is issuing out of the combustion chamber is called flue gas. E.g. CO,, CO and O, An idea about the complete or incomplete combustion of fuel is given by ‘Flue Gas Analysis’. The analysis of flue gases is carried by Orsat’s Apparatus. (i) If'the flue gases contain considerable amount of carbon monoxide, it shows incomplete combustion means short supply of oxygen. Gil If the flue gases contain considerable amount of oxygen, it shows ‘complete combustion means or excess supply of oxygen. Construction of Apparatus ‘The Orsat's Apparatus is consists of horizontal tube at the one end of this tube is three way stop cock and the other end is connected with burette, Bu- rete is surrounded with a water jacket to keep the temperature constant of gas. ‘The hurette is connected in series to a set of three absorption bulbs, each through a separate stop cock. The lower end of the jacket burette is further ‘connected to a water reservoir with the help of rubber tube. The water level in the burette can be raised or lowered by raising or lowering. The other end94 |SBPQ.B. Applied Chemistry horizontal tube is connected to aU - tube. U - tube is packed with fused CaCl, and glass wool for drying flue gas and avoiding for smoke particles. Three absorption bulbs apart from having solution for absorbing CO,, , and CO2. The first bulb has KOH solution and it absorbs only CO2. The second bulb has alkaline pyrogallic acid and it can absorbs O, and CO,. For proper analysis it is necessary that the flue gas is passed through first bulb having KOH, where CO, is absorbed. Then it is passed through second bulb having acid, where only O, will be absorbed. Finally flue gases are passed through third bulb having CuCl, where only CO will be absorbed. Procedure Step - 1: The whole apparatus is thoroughly cleaned. The absorption bulbs are filled with their respective solution and stop clock are closed. The water reservoir and jacket are filled with water. For the exclusion of air, the three way stop cock should be opened to the atmosphere. Flue gas is analyzed by lowering the water reservoir and connecting the three way stop cock to flue gas supply. ‘Stop Geek, Fig. 2.4. Orset's Apparatus. Air should be expelled by repeating the above process of sucking and expelling the flue gas by lowering and raising the water reservoir. Step - 2 : 100 ml of flue gas is carefully sucked in the burette for analysis. The three way stop cock is closed then. The flue gas is forced in the bulb 1 by opening its stop cock and raising the water reservoir. Bulb 1 have KOH which absorbs CO, for complete absorption of CO, the flue gas uel | 95 is sent 2 or 3 times, again and again in bulb 1 Step - 3: The unabsorbed gas is finally taken back in the burette and then stop cock for CO, absorption bulb is closed. The levels of water in the reservoir and burette are equalized and the value or residual gas is noted. The decrease in volume gives the volume of CO, in 100 ml of the flue gas sample. The volumes of O, and CO are similarly determined by passing the flue gas through absorption bulbs 2 and 3. Q. 36. What is the importance of analysis of flue gas. (CS.V.T.U., Sem, 1,2005, 2006-07) Ans. Importance of Analysis of Flue Gas 1. It gives idea of the complete or incomplete combustion process. Thus the presence of a high percentage of CO in the flue gas shows in- complete combustion of the fuel and also indicates the short supply of O,. On the other hand , if the flue gas contain a considerable amount of oxygen, it indicates an excess supply of O, and possibility of complete combustion. ® * 2. The analysis of flue gases generally deals with the determination of CO,, CO and O, by absorbing them in the respective solution of KOH, alkaline pyrogallic acid and alkaline cuprous chloride respectively. ‘Though in some rare gases percentage hydrogen is also determined. @. 3%. Define the foitowing- (@ Gasoline (©) Diesel Ot (c) Kerosene Oil Ans. (i) Gasoline : It is a mixture of hydrocarbon from pentane to Octane. This fraction is obtained between 40 to 120°C. This fraction is highly volatile and inflammable and used as fuel for internal combustion IC) engines. Its C. V. = 11,250 caligm. : (ii) Diesel Oil : It is mixture of hydrocarbon from C,, to C,y. This fraction is obtained between 250 to 320°C. It is used as a flel for diesel engine, Its C. V. = 11,000 cal/gm. Gi) Kerosene Oil : It is mixture of hydrocarbons from C,, 10 Cy. It does not vaporize easily. It is used as a domestic fuel, jet engine fuel. Its . V. 11,100 ca/gm. . 37. Y Calorific value of carbon is- (a) 2240 calories per gram. —_(b) 34500 calories per gram. (©) 96.96 keal. per gram. — (d) 8080 kcal. per gram. (CS.V.7.U,, Sem. I, Dec. / Jan., 2008-09)96 |SBPQ.B. Applied Chemistry (i A gasoline sample has the same knocking characteristics as the mixture containing 80% iso-octane and 20% n-heptane. The octane num- ber of gasoline must be- @o (b) 20 () 100 (d) 80 U., Sem. I, Dec. / Jan., 2008-09) (cs. a a NUMERICAL PROBLEMS Ans. (i) ¢ KRISHNA COPIER: NUMERICAL PROBLEMS BASED ON CALORIFIC VALUE Prob. 1. 0.72 g of a fuel containing 80% carbon when burnt in a bomb calorimeter, increased the temperature of water from 27.3°to 29.1°C. Ifthe calorimeter contains 250 g of water and its water equivalent is 150 ‘gms. Calculate the HCV of the fuel. Give your answer in kI/kg. (CS.V.T.U., Sem. I, 2005) O72 gm, = W=2508, w= 150g, 273°C, t,=29.1°C H= 0.72 % Latent, 387 calle. HCV of fuel = Grew pnla a) kab kg __ (250+ 150)x(29.1~273) a O72 = 1000 keallkg or = 4200 ki/kg Prob. 2. On burning 0.83 g of a solid fuel in a bomb the tempera- ture of 3,500 g of water increased from 2.5°C to 29.2°C. Water equivalent of calorimeter and latent heat of steam are 385.0 g and 587.0 cal/g. If the fuel contains 0.7% H, calculate its gross and net calorific value. Sol. Given,x = 0.83 gm, W=3500g w=385.0g, = 265C, = 29.20 H=0.7% Latent Heat = 587 cal/g. 2 HCV = Comer, calKg. _(3,500+385)(29.2-26.5) ~ 0.83 Sol. Given, kcalkg, Ans. =12,638 cal/Kg. — Sern Nee NAGAR 16, 9584601915 + 96918593 MO, Prob. 3..A sample of coal contains C= 93%, H = 6%, and as The following data were obtained when the above coal was tested in bomb calorimeter. latent heat of condensation of steam as 580 cal/g. Fuel | 97 Net calorific value = GCV -0.09H x 587 2,638 — 0.09 « .7 x 587 = 12,638 - 37 = 12,601 cag. Ans. 1%. = 0.92 g. @ wt of coal burnt (i) we. of water taken = 550g. (iii) Water eq. in bomb calorimeter = 2,200 g. (iv) Rise in temp. = 2426. () Fuse wire correction = 10.0 cal. = 50.0 cal. (vi) Acid correction Calculate gross and net calorific value of the coal, assuming the Sol. Given, (@_ wt of coal sample (x) wt. of water taken (W) i) Water eq. in bomb calorimeter (w) (iv) Rise in temp. (t, ~t,) ~() Fuse wite correction (vi) Acid correction (ii) H cov - OYE ‘Acid + fuse convection] x (550+2,200)x2.42~[50+10] ne A 168.5 calle, Ans, NCV = [GCV - 0.9H x Latent heat of steam} Ans. 7,168.5 -0.09 »6 «580. = 6,855.3 cag. Prob. 4. A sample of coal contains 89% C, 8%H, and 3% ash. When this coal was tested in the laboratory for its calorific value in the bomb calorimeter, the following data was obtained: We. of the coal burnt = 0.85 em. (i) Wt. of the water taken Water equivalent of bomb and calorimeter (i) Rise in temp. (¥) Cooling correction (vp) Fuse wire correction ; (vii) . Acid correction = 50 cal. Assuming the latent heat of =10 cal98 |SBPQ.B. Applied Chemistry codensation of steam as $80 cal/ gm, Calculate : (x) Gross and (y) net calorific values of the coal in ca/igm. (CS.V.U., Sem. I, Dec. / Jan., 2008-09) Sol. Given, @ Wt. of coal sample (x) = 0.85 gm. Gi) Wt. of the water taken (W) 650 gm, Gili) Water equivalent of calorimeter (w) = 2500 gm. Gv) Rise in temperature (t, —t,) 25°C (@) Cooling correction 0.03°C (vi) Fuse wire correction 10 cal. (ii). H 8% cv = V+ "Mt, -t,+ cooling correction) - (Fuse corre.+Acid corre.) ‘Mass of fuel — = (650 + 2500) (2.5 +'0.03) - (10 + 50) - 0.85 = 3150 x 2.53 -60 7969 - 60 = 7909.5 ca/gm Ans. =. NCV =[GCV ~ 0.09H x latent heat of steam} = [7909.5 --0.09% 8 x $80} = 7909.5 -417.6 7491.9 cag Ans. Prob. $. Calculate the gross and net calorific value of coal (Using Dulong’s Formuta) having the following composition. C = 85%, H = 8%, S= 1%, N= 2%, ash = 4% latent heat of steam = $87 ca/g. Sol. Given, C= 85%, H=8%, S=1% N=2%, ash = 4%, latent heat of steam = 587 cal/g. 1 o «dev = fefsoac+s4s0( 11-2) +2040 pst. Fg [ooxesesisan(e-2). ane tA = 7Agloes, 800+ 276000 +2240] Keal /kg. 1 7991965040] Keal/kg. = 9650 Kealkg Ans. NCV = (GCV -0.09H 587) Keal/Kg. $= (650.4 -0.09 «8 x 587) kcal / Ke. 3 y= Fuel | 99 ‘= 9227.8 Keal / Kg. Ans. Prob. 6. Calculate GCV and NCV of a coal (Using Dutong’s For- mula) having the tollowing composition C= 80%, H = 7%, O= 3%, S 3.5%, N= 2.1%, ash = 4.4%. Sol. Given, C = 80%, H=7%, O=3%, S = 3.5%, N=2.1%, ash = 4.4%, ! o « fefamtonc +s4ste(it-2)2205 eum cv « zfe[tHo~c sste(n-2) 220-5] 1 Q - «804 2) 2240%3 : shal 2000 20 24s00(7 $)+ 5]kcamwe = qqgles6400+34500%7+ 7840] Kcavks. qqpl46400 + 241,500 + 7840] Kcatkg, - Fag [895740] Keav, = 8957.4Kealkg Ans. NCV CV - 0.09H x 587 957.4 — 0.09 x 7 x 587 Keal /Kg. = 8957.4 569.81 8458 Keal/kg. Ans. NUMERICAL PROBLEMS BASED ON PROXIMATE AND ULTIMATE ANALYSIS Prob. 7. 0.5 g of a sample of coal was used in a bomb for the deter- mination of GC, Calorific value of coal has to be 8600 cal/g. The ash formed in the bomb calorimeter was extracted with acid and acid was treated with barium chloride solution and a precipitate of BaSO, was obtained. Precipitate was filtered, dried and weighted. The weight of precipitate was found to be 0.05g. Calculate the % of sulphur in the coal sample. Sol. Given, Wt. of coal sample taken 0.5 gm Weight of BaSO, precipitate 0.05 wt. of BaSO, x32 ‘whof coal taken x233 % of sulphur = 100100 |SBPQ.B. Applied Chemistry = 0.05%32%100 in ~ 05% 233 ns Prob. 8 1.0 g of a sample of coal was used for nitrogen estimation by Kjeldalil method. The evolved ammonia was collected in 25 ml N/I0 H,SO, To neutralize excess acid, 15 ml of 0.1 N NaOH was required. Determine the % of N. Sol. 15 ml of 0.1 N NaOH = excess of 0.1 NH,SO, % vol. of H,SO, used to neutralize the ammonia evolved, = 25 ml. of 0.1 N H,SO, - 15 ml of 0.1 NNaOH = 10 ml of 0.1 N. 373% = 1.373 % VoLof H,SO, used normality x14 ele wtof coal taken Ans. Prob. 9. A sample of Gondwana coal of Sharia was analyzed as follows; exactly 2.500 gm was weighted into silica crucible. After heating for I hour at 0G, the residue weighted 2.415 gm. The crucibie was ‘then covered with a vented lid and strongly heated for exactly 7 minutes at 950°C +: 20°C. The residue weighted 1.528 gm. The crucible was then heated without the cover s:2til constent weigited was objained.’ The last residue was found to weight 0.245 gm. ()) Caleulate the % of result of above analysis (i) To which type does the above description belong. Sol. Mass of coal sample = 2.5 gm. Mass of moisture in coal sample = 2.5 - 2.415 = 0.085 gm. Mass of volatile matter ~ 2.415 - 1.528 = 0.887 gm. Mass of ash = 0.245 gm. Analysis of coal .085%100 % of moisture = S500 3 gy, Ans. 0.887100 % of volatile matter = SFE=100 35.48 9% Ans. 0.245100 reormn= 258 sey ‘ 5 % of fixed carbon = 100 - (3.4 + 35.48 +9.8) = 51.32% Ans. The above description belongs to proximate analysis. COPIERS NAGAR KRISHNA ‘SMRITI Fuel | 101 NUMERICAL PROBLEMS BASED ON COMBUSTION Prob. 10. Calculate the weight and volume of air required for the combustion of one hg of carbon. . Sol. : Carbon undergoes combustion as follows - c +0, co, : 12.32 44 ‘Thus wt. of , required for combustion of 12g. of carbon = 32 gm. 12 Kg of carbon require = 32 Kg of O, = 2 2 1 Kg of carbon = x1 = 2.667 Kg of O, 3 12 8 wt of air required = 2.667 *>> = 11.59 8 S —_Now since 32 gm of oxygen occupies 22.4 | at NTP 3 24 * 3 1 gm of O, of oxygeti occupies = = . 24 o B 2.667 x 1000 gm O, will occupy == x 2.667 1000 =1866.9 1. g Hy 100 eae 5 =~ Volume ot air required = 1866.9 xy = 8890 L or 8.896 m? Ans. Prob. 11. A gas has the following composition by volume H, = 30% CR 596, CO 20%, CO, "6%, O, = 3% and N= 3496 Uf 50% excess air is used find the weight of air actually supplied per m! of this gas, molecular weight of air = 28.97. Sol, In one m! of the gas 7 Volume of O, needed “Composition (% 100) H, 0%) = 03 m@ 03 x 05=0.15m CH, (5%) = 0.05 m* 0.05 x 2 =0.1 m €O'0%) = 0.2 m 02 x 0.5=0.1 m Total = 0.35 m* .05 m? ©, (5%) = 0.05 m*, Less O, in fuel gas Net O, needed =0.35 ~ 0.05 = 0.30 m = 3001. 4 (m= 1000L) Volume of air required for 1 m? of gas using 50% excess air = 142.8 L102 |SBPQ.B. Applied Chemistry Hence, weight of air actually supplied per m? of the gas (t me (28 97. =) . mol Prob. 12. The % analysis by volume of producer gas is H, - 18.3%, CH, — 3.4%, CO — 25.4%, CO, - 5.1%, N, ~ 47.8%. Calculate the volume of air required m! az the gas. Ans. 100 + Air required per m? or volume of air = 0.2865 x5, 1.3642 n? Volume of air = 1.3642 m* Ans. Prob. 13. A gas has the following composition by volume H, -- 22%, CH, ~ 4%, CO ~ 20%, CO, ~ 6%, 0, - 3% and N, ~ 45%. If 25% excess air is used. Find the weight of air actually supplied per m of this gas. Sol. In Im? of the gas contains- H, > 22%) = 022 m', 0.20 m, CH, (4%) = 0.04 m* CO, > (6 %) = 0.60 m* Fuel | 103 = Ans. Hence, weight of air actually supplied per m? of the gas 28.97 em = 1547.61 xB" = 2001.54 gm. Or 2Kg. Ans. 224 Prob. 14. Analysis of Jharkhand coal sample is as follows - C = 80%, H = 4%, O = 5%, rest is ash. The flue gas analysis was found (By weight) CO, = 12%, CO = 2.0%, O, = 8.0%, N, = 78%. Deter- mine the (i) Minimum air required for I kg coal combustion (ii) Excess % of air used for 1 kg coal combustion (iil) Total air required for combustion of I kg coal sample. (CS.V.T.U.,Sem.1, Dec. 2006) C= 800g, O=-50g, H= 40g remaining air Minimum weight of air required for complete combustion of 1 kg of coal. = Weight of [cx(2/12) +H1x(16/2)-0}. 2 Sol. (i) 1 kg of coal contains - 32 (1s 100 =| 8002 x{ 22+ 40gx{12)—s0g | 222 [ > 40s 3) 8) 35 =(2133.34320-so 22 = 10449.13g 10.449 kg Ans. Gi) of flue gas contains - CO, = 0.120 m’, CO = 0.020 m*, O, = 0.080 m? and'N, = 0.78 m?. 0.03 m, __N, > (45%) = 0.45 m* | Conversion of Volumetric Analysis to Mass Analysis ‘Combustion reaction O, needed ] | [Gas] Volumein [Mol Mass] Vx m Massikg Flue H, +0.50, > H,0 0.22 «0.5 = 0.11 m [f= ©) | (am) ee = CH,+ 20, CO,+2H,O | 0.04 x2 = 0.08 m? co, | 0.120 “4 5.28 528 20.175 ke CO +0.50, > CO, 0.20 «0.5 = 0.10 m? a Total O,= 0.29 m* co | 002m 28 0.56 Fogg 70.0185 ke Less ©, in fuel = - 0.03 m? 2.56 Net O, is needed = 0.29 - 0.03 = 0.26 m, = 260L 9, 0.080 m* | 32 2.56 Fong ~ 0-085 ke (m= 10001) 21.84 Volume of air required for 1 m® of gas using 25% excess air N, | O78m | 28 21.84 30.24 ; a [Total = 30.24 Total104 |SBPQ.B. Applied Chemistry Mass of excess O, per kg of flue gas = Mass of O, (in flue gas — required to convert 0.0285 kg CO toCO;) 0.085 0.0185 (16/28) }ke [0.085 -0.01 I}kg = 0.074kg Mass of C present in 1 kg of flue gas = Mass of [CO, x(12/44)+COx(12/28)] i Fuel | 105 Sol. (i) 1 Kg of coal cor IS C=810gm, H=60gm, O=40gm, N = 25.2 gm. Minium waht of oxen gue fr cee Sanka = 32 16 sot [Zee lew [2x0] [22 2 810+ 8 60-40] = [2160+ 480-40] = 2600 ais 7 7 7 2 2 O'S _ Nitrogen being non-combustible will not consume oxygen. =| 0.175>{ 12.) .0.0185.{ 12 i A -[o be (2) ee (2 J] 6 OFZ Therefore, minimum weight of air required for complete combustion of =[0.048-+0.008]ke = 0.056 kg s85 Lkgcoal = Neto, «10? Mass of flue gas formed by buming 1 kg of coal gs 3 . t of C/kg of coal &kg « &? 2600 1100 on, ~ Weight of Cikg of flue gas “ 0.056 ~1429ke Excess O,/kg of coal burnt = = 11304.3 gm or 11.304 Kg. Ans. Sinaloa One mente meee en eet supp id Lateuaton of volume of dry fe gas if 30% excess air i = 0.074 « 14.29 kg = 1.057 ke. 100 1.057120, ’ a Ans. Excess air/kg of coal burnt 1.596 kg Gi) Total amount of air required for complete combustion of | kg coal = Mass of air (For combustion + Excess in flue gas) = (0.10449 + 4.596) ke = 4.7004 kg. Prob. 15. Calculate the volume of air required for complete com- bustion of 5 titers of CO. Given percentage of oxygen in air = 21. Sol. Combustion reaction CO +0.50, —> Co, Volume of O, needed = 5 literx 0.5 = 2.5 liter 100 «+ Volume of air required = 2.5% Ans. = 119 liter Ans. Prob. 16, Analysis of coal sample is as under C= 81.0%, 6.0 %, O= 4.0%, N=2.52% and ash = 6.48% . Calculate the minimum quantity of air required for complete com- bustion of 1 Kg of this coal and find out the composition of dry flue gas by volume if 30% excess air is supplied. (cs U.,Sem.1, May/Sune2007) 44 CO,= F5x810 = 2970 gm. 130,77 25.2+11304.3x 204.77. gin of air = 1131812 0010 1131812 gm Calculation of volpmetric composition of dry product of combustion. , 50 113042 5652.1 100 a We Dry products | Mol. mass] Relative vol of dry produc €0,= 2970 gm. 44 2 ~ 67.50 usie, N, . 11339.13 gm | 28 a o- seztgm | ae | 24. vy60a all ‘ [Tora = 64835 75 worco, = 75x10 = 10419 ; . ae 1% Ans. :106|SBPQ.B. Applied Chemistry 404.21 A042) 100 = WOON, = Gag 33 62.34 Ans. 176.62 % = x100 = " %oLO, = Fegy X10 = 27.24%. Ans. Prob. 17. A petroleum gas has the following composition,” Ethane - 8%, Propane 12% Butane - 36%, Butene - 6%, isobutane - 34%, Propene - 4%. Calculate the volume of air required for complete combustion of 100 Mt of the gas. (CS.V-L.U., Sem. I, May-June, 2007) Sol. 1 m? of gaseous fuel contains- Ethane - 8%, Propane 12% Butane - 36%, Butene - 6%, Isobutane - 34%, Propene - 4%. ‘The combustion reactions of the constituents of the fuel gas are- C,H,+3.50, > 2CO,+3H,0 GH, +50, + 3C0,+41,0 CH, +650, + 4CO,+5H,O CH, + 60, + 4CO,+4H,0 LCH, + 6.50, > 400, +5H,O-— ~ CH, + 4.50, > 3CO,+3H,0 Volume of oxygen required Forethane = 0.8 x3.5 = 0.28 m' For propane = 0.12 x5 = 0.60 m* For butane 36 x65 = 234m For butene 0.06 x6 = 0.36 m? For Isobutane = 0.34 x6.5 = 2.21 m? For Propene_= 0.04 «4.5 = 0.18 m? ‘Total volume of required O, = 5.97 m* 100 A Volume of air required = 5.97*77> = 28.42 m <. Volume of air required for complete combustion of 100 m? of gas = 28.4% x 100 m 842.8 m? Ans. Fuel | 107 Prob. 18. The percentage composition of a sample of bituminous coal was found to be as under- C= 75%, H=5.3 %, 0= 12.6%, N=3.2%, S= 1.3% and ash = rest. Calculate the minimum weight of air necessary fo complete com- bustion of 1 kg of coal and the percentage composition of the dry prod. ucts of the combustion by weight. (CS.V.T.U., Sem. I, Dec. / Jan., 2008-09) Sol. (i) 1 Kg of coal contains C= 754 gm, H = 53 gm, O = 126 gm, N= 32 gm., S= 13, Ash = rest. ‘Minimum weight of oxygen required for complete combustion of coal = [cc 435, 4 422, =| Exerc s2xs|- [ner Pees}o ~ [Sere esas 2a]- [Beselfesieaa}-as = [2010.66+424+13]-126 = 2321.66 em Nitrogen being non-combustible will not consume oxygen Therefore, minimum weight of air required for complete combustion of 1 kg coal = Neto, x4 Minimum amount oie =252166 +! gn, = 10094.1 gm or 10.09 Kg. Ans. Gi) Calculation of % composition of dry products of combustion Dry products ‘Amount co, Sx 754 = 2764.7 gm. 64,5. 64 Sage Ss so, Sus Sata = 26 gm N, 100941 +22 532 = 1799732 = 78D am + Total weight of dry product = Weight of (CO, + SO, +N, ) = 2764.7 + 26 em+ 7804.5 gm. = 10595.2'gm.(08 | SBPQ.B. Applied Chemistry % of CO, = 26.09% Ans. % of SO, 02.3% Ans. 7804.5 = OHS et = 73:66 %ofN, jose} 73.66% Ans. Prob. 19. The % composition by weight of sample of a cool was found to be C= 81%, H = 5%, O = 8.5%, S = 1%, N= 17%, ash = 3.5% (9 Calculate the minimurn amount of O, and air required for com- Nete combustion of 1 Kg of this coal. (i) % composition by weight of the by products of combustion. Sol. (f) Calculation of minimum amount of O, and air required for ‘omplete combustion of 1 Kg of coal 1 Kg of coal contains’ - ee ae © = 85 gm, S = 10 gm, N= 10 gm Bas] oxy. present in fuel 16 59432101 810+ 1850+ 2x10 |-85 °F 2 | “we ~ [2160+ 400+10]-85 - 2570 85 = 2485 gm Ans. 100 Minimum amount of air Net 0, * 5 100 Minimum amount of air = 2485 *422 gm, Ans. = 10804.34 gm or 10.8 Kg. Gi) % composition by weight of the by products of combustion. Dry products ‘Amount aa co, fpx810 = 2970 gm. 6 . Baio = so, ‘Ss 20 gm. . 7 10 gm in fuel +772 1080.4 = 8329.4 gm. —___________KRISHNA COPIERS. SMRITI NAGAR Fuel | 10 Total weight of dry product = Weight of (CO, + SO, +N, ) © 2 2970 -+20+8329.4 gm =11319.4 gm. 2 = 2970 = % of CO, 100 = 26.29 a s ofco,= Oe 26.2% Ans s 2 20 & % of SO, = Tz X100 = 0.177% Ans § 2” T3194 2 8329.4 3 % 33284 5100 = 73% es 8 %OfN, = Figg 73%. A 2 Prob. 20. A sample of coat contains. C= 60%; H = 4%; 0, = 6%; N,= 2%, ash = 28% Caleutate the % composition of the dry products of combustion assuming that 40% excess air is used. (C:S.V-T.U., Sem. I, Nov.-Dec., 2007) Sol. Given, C = 600 gm H=40 gm, 0,~60 gm; . N,= 20m, ash = 280.gm. Minimum weight of oxygen required for complete combustion 0: coal tx40-60] : = [1600 + 320 ~ 60] 1860 Nitrogen being non-combustible will not consume oxygen. ‘Therefore, minimum weight of air required for complete combustion ot 100 Tkgcoal = Net O, xy ‘ ‘ ini 10% Minimum amount of air= 1860 *222 gm, ; = 8086.95 gm or 8.08 Kg. Ans,110] SBPQ.B. Applied Chemistry (i) Calculation of volume of dry flue gas if 40% excess air is supplied. ©0,= #600 = 2200 gm 140° 77 = 2048086950877. gm of MD 100 100 a = 973773 am 50 5 95x50 0, = 8086.95 x 50 4043.47 gm. Calculation of volumetric composition of dry product of combustion. CorROSION ‘Syllabus : Cors ‘Types of corrosion (Dry, wet, atmospheric, galvanic and con- centration corrosion) Theories of corrosion, protective measure against corrosion, factors affecting corrosion, pitting corrosion, water line corro- sion, under ground corrosion, stress corrosion, microbiological corrosion, corrosion fatigue. Batteries and Batery Technology : Primary cells, secondary batteries, rese_rve batteries, fuel cells, solar cells [We Dry products Mol. mass] Relative vol. of dry product] ? 2200 €O,= 2200 gm. 200 0 i £0, gm. 44. aa = 50.00 N,= 8737.73 gm 28 S27 i 4043.47 gm 32 | maa Total %of CO, 10.23 % Ans. %ofN, 63.90%. Ans. 126.35 x100 = " %oO, = Gegqi 100 = 25.86%, Ans. oo ‘ Descriptive Questions on Corrosion Q 1. Define Corrosion ? (C.S.V-L.U., Sem, I, 2005, 2006-07, Dec/Jan-2008-09) Ans. CORROSION Any process of gradual deteriarastion or destruction and-consequently loss of solid metalic material through an unwanted chemical or electrochmical attack by its environment, starting at its surface is called corrosion. All metals and alloys are susceptable to corrosion. Eg. Formation of a layer of reddish scale of hydrated ferric oxide (rusting) on the surface of iron. Q. 2. What is corrosion ? Write the classification or types of cor- rosion. Ans. Corrosion : For definition refer. Q. No. I+ Classification of corrosion : The process of corrosion is classified on the basis of one of the fol- lowing factors : (a) Classification of corrosion on the basis of riature of corrodent + on the basis of nature of corrodeni, corrosion may be Bf two types : 1. Dry Corrosion and “2. Wet corrosion. Corrosion involves reaction with gases at high temperature whereas ‘Wet corrosion takes place in the presence of water or a conducting liquid () Classification of corrosion on the basis of mechanism : On the basis of mechsanism, corrosion may be of two type 1. Direct chemical attack. + 2. Indirect electrochemical attack.112| SBP Q. B. Applied Chemistry (©) Classification of corrosion on the basis of appearance of cor- roded metal : On the basis of appearance of corroded metal corrosion may be of two types : A. Uniform : Metal get corroded at some rate at is entire surface. B. Localized : Only small areas are attacked, However the following types of corrosion s are very populcar 1. Dry corrosion, 2. Wer corrosion, 3. Atmospheric corrosion, 4. Galvanic corrosion, 5. Concentration corrosion, 6. Electrochemical corrosion, 7. Pitting corrosion, 8. Intergranular corrosion, 9. Waterline corrosion, _10. Stress corrosion, 11. Possivation corrosion, 12. Mi crobiological corrosion. Q. 3. What is corrosion ? Describe the factors favouring corrosion ? Or Describe the factors that influencing corrosion. (C.S.V.T.U., Sem. I, Now/Dec. 2006) Ans. Corrosion : For definition refer Q. No. 1 ‘The rate and extent Factor Influencing or Favouring Corrosion 7 ~ ‘ef corrosion, depends on : 1. Nature of the metal and 2. Nature of the enviroment. 1, Nature of the metal : () Physical State of the metal : The rate of corrosion is influenced by the physical state of the metal. For instant the smaller the grain size of the metal or alloy, the greater will be solubility and hence, greater will be its Gi) Purity of Metal : The rte and extent of corrosion increases with the increasing exposure and extent of impurities. Thus corrosion resistance ofa metal may be improved by increasing its purity. (ii) Nature of the oxide film : In aerated atmosphere practically all metals get covered with a thin (few anagstron thick, [A= 10-!°m) surface film of metal oxide, The ratio of the volume of metal oxide to the metal is known as Specific volume ratio. Greater the volume ratio, lesser is the oxidation corrosion rate. (iv) Solubility of corrosion produets : In electrochemical corrosion, if the corrosion product in soluble is the corroding medium, then corrosion proceeds at a faster rate. On the contrary, if the corrosion product is in- soluble in the medium or it interacts with the medium to form a other in- soluble product. Then the corrosion product functions as physical barrier, thereby suppressing further corrosion. . ALSHINA COPIERS SMRITI NAGAR MO. - 9691859916, o5¢aco1916 (¥) Volatility of corrosion produets : Ifthe corrosion product is vola- tile, it volatilizes as soon as it is formed , thereby leaving the underlying metal surface exposed for further attack. This causes rapid and continuous corrosion, leading to excessive corrosion. (vi) Purity of metal : Impurities in a metal, generally, caus “heteroge- neity", and form minute / tiny electrochemical cells (at the exposed parts, and the anodic parts get corroded. The rate and extent of corrosion increase with the increasing exposure and extent of the impurities. Consequently, cor- rosion resistance of a metal may be improved by increasing. its purity. (vii) Position in galvanic series : When two metals or alloys are in electrical contact, in presence of an electrolyte, the more active metal suf- fers corrosion. The rate and severity of corosion, depends upon the differ- ence in their positions, and greater is the difference, the faster is the corro- sion of the anodic metal/alo. (viii) Overvoltage : When a metal, which occupies 2 high position in galvanié series (say zinc), is placed in IN -HSO,, it undergoes corrosion forming a film and evolving hydrogen gas, the initial rate of reaction is quite slow, because of high overvoltage (= 0.70 V ) of zinc metal, which reduces the effective electrode potential to a small value. However, if a few drops of copper sulphate (GuSO,) are added, the corrosion rate of zine is accelerated, because some copper gets deposited on the zinc metal, forming minute cathodes, where the hydrogen overvoltage is only 0.33 V. Thus, reduction in overvoltage of the corroding metal/alloy acceleratres the ocerrosion rate (Gx) Ralative areas of the anodie and cathodic parts : When two dissimi- lar metals or alloys are is contact, the corrosion of the anodic part is directly proportional to the ration of areas of the cathodic part and the anodic part. Corrosion is more rapid and severe, and lighly localized, if the anodic area is small (¢.¢., a small steel pipe fitted in a large copper tank), because the current density at a smaller anodic area is much greater, and the demand for electrons (by the large cathodic areasz) can be met by smaller anodic areas only by undergoing “corrosion more briskly”. 2. Nature of Corroding Environment : () Temperature : With increase of temperature of environment, the reaction as well as well as diffusion rate increase, thereby corrosion rate is generally enhanced. ‘ (i) Humidity : Humidity of air is the deciding factor in atmospheric corrosion. Corrosion of a metal becomes faster in humid atmosphere is that gases (CO.; O2 etc) and vapours, present in atmosphere furnish water to the electrolyte, essential for setting up an electrochemical corrosion cell. More- Corrosion |113,114 | SBP Q. B. Applied Chemistry over, the oxide film on a metal surface, although a solid body, yet possesses the property of absorbing moisture. (iil) Presence of impurities in atmosphere : Atmosphere, in the vi- cinity industrial areas, contains corrosive gases like CO2, HzS, SOz, and fumes of HCI, HzSO,, etc. In presence of these gases, the acidity of the liquid, adjacent to the metal surfaces, increases and its electrical conductiv- ity also increases. It results in an increase of corrosion current flowing, the local electrochemical cells on the exposed metal surfaces. (iv) Presence of suspended particles in atmosphere : In case of atmospheric corrosion : (a) if the suspended particles are chemically active in nature [like NaCl, (NH4), SO,), they absorb moisture and act as strong electrolytes which in turn increase corrosion; (b) if the suspended particles are chemically inactive in nature (e.g. charcoal), they absorb both sulphur ‘gases, and moisture and slowly enhance corrosion rate. (v) Influenmce of pH : Generally, acidic media (i.e., pH<7) are more corrosive than alkaline and neutral media. (vi) Nature of ions:present : Presence of anions like silicate in the medium leads to the fermation of insoluble reaction products (e.g., silica gel), which inhibit further corrosion. On the other hand, chloride ions, if present in the medium, destory the protective and passive surface film, thereby exposing the metal/ alloy surface for fresh corrosion. (vii) Conductance. of the corroding medium : In corrosion of un- derground 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 leak- ‘ages) will cause more severe damage to the metallic structures, buried un- der clayey and mineralized soils than those under dry sandy-soils. (viti) Formation of oxygen concentration cell : The corosion is promoted with the increase in suply of oxygen/air to the moist-metal sur- face. The less oxygen concentration regions becomes anodic; while the more- ‘oxygenated regions bec omes cathodic, which in tur leading to the forma- tion of oxygen concentration cell. In this call the anodic part suffers corro- sion. At the cathode surface, electrons are consumed. (Cathodic reaction) 2H,0+0, +4e" + 40H" Moist-air ‘Supply of electrons (for oxidation) take place on the anodic parts. Thus: Fe——+Fe* +2¢” (Anodic reaction) Corrosion | 115 Thus, oxidation concentration cell promotes corrosion, but it occurs where the oxygen concentration is lower. Q. 4 What do you mean by dry corrosion ? Explain its yypes and mechanism along with examples ? Ans. Dry Corrosion or Chemical Corossion : It is a type of corro- sion that takes place due to direct chemical action of almospheric gases such as Oz, COz, SO, H,S, Nz, halogen gases and anhydrous inorganic liquid with the surface of metal. ‘Types : Dry or chemical corrosion may be of three types : 1. Oxidation corrosion 2. Corrosion by other gases. 3. Liquid metal corrosion. 1, Oxidation corrosion : This type of dry corrosion is brought about by the direct action of oxygen in the absence of moisture at low or high temperatures. In general, at ordinary temperatures metals are very slightly attacked , but alkali metals (Na, K, Rb, Li etc) and alkaline earth metals (Ca,"Be,Sr etc) are rapidly oxidized at low temperature almost ali metals (except-Ag, Au and Pt) are oxidized at high temperature, sighty attacked. Alkali metals (Li, Na, K, Rb, etc.) and alkaline-earths (Be, Ca, Sr, etc.) are even rapidly oxidized at low temperatures. ‘The reaction in the oxidation corrosion are: =~, 2M—+2m" +2ne" Metal ions (Loss of electrons) Oy +2ne” —+n0> 2 Oxide ions Gain of electrons) Or 2M+30, —> 2M" +n0* Metal ions Oxide ions 3002005 Metal oxide Mechanism : Oxidation takes place first at the surface of the metal and the resulting metal oxide scale forms a barrier, that tends to restrict + oxidation. For oxidation to continue, either the metal must diffuse Outwards through the scale to the surface or the oxygen must diffuse in- wards, through the scale to the underlying metal. Both transfers occur but the outward diffusion of metal is generally, much more rapid than the in- Ward diffusion of oxygen, since the metal ion is appreciably smaller then16 | SBP Q. B. Applied Chemistry she oxygen ion and consequently of much higher mobility. ‘Nature of the oxide formed plays an important part in oxidation cor- ‘esion process. ‘Metal + Oxygen —~» Metal Oxide (corrosion product) According to Pilling-bed worth rule “an oxide is protective or non- porous, if the volume of the oxide is at-least as great as the volume of the metal from which it is formed. On the other hand, if the volume the oxide isless than the volume of metal the oxide layer is porous (or non- continuous) and hence non-protetive because t camot prvent the access of oxygen to fresh metal surface below. Thus ulkali and alkaine- earth metals (like Li, K, Na, Mg) form oxides of volme ‘ess than the volume of metals. Consequently , the Oxide layer faces stress and strains, thereby developing cracks and pores in its structure. Porous axide scale permits free access of oxygen to the underlying.metal surface “through cracks and pores) for fresh action and thus corrosion continues non-stop. Reaction a metal-metal M->M™ + ne“ (Oxidation) GZ ZZ © yard deftusion siow) of ‘oxide ions through scale ‘Atmospheric oxygen (ait) Formation of metal oxide (M0,) at the point of — smesting of M™ and OF ‘Reaction at exposed part 1/2 og oon) Direction of electrons conduction Outwards diffusion (fast) Metal Oxide scale formed by direct fofmetalionsthrough scale reaction of metal and oxygen ions Fig. 34. Oxidation of metals. 2. Corrosion By Other Gases : Gases like $02, CO, Cl;, HS, F2 stv. also cause corrosion of metals. The extent of corrosive effect depends nainly on the chemical affinity between the metal and the gas involved, The degree of attack depends on the formation of protective or non- protec- ive\films on the metal surface. ‘ @ If the film formed is protecte or- porous (¢.g. AgCI film, iesulting rom the attack of Cl, on Ag) the intensity or attack decreases, because the ‘tm: formed protects the metal from further attack. y Gi) If the film formed is non-protective or porous, the surface of the Corrosion | 117 whole metal is gradually destroyed. For example, dry gas attacks on tin (Sn) forming volatile SnCl, (which volatiliazes immediately) thereby leaving fresh metal surface for further a ttack. Similarly, in petroleum industry HS at high temperature attacks steel forming a FeS scale, which is porous and interferes with normal operations. 3. Liquid Metal Corrosion : This type of corrosion takes place due to chemical action of flowing liquid metal at high temperatures on solid metal or alloy. Such corrosion takes place in devices used for nuclear power. The corrosion reaction involes : ( dissolution of a solid metal by aliquid metal or (i) inrernal penetration of the liquid metal in to the solid metal. Both these modse of corrosion of cause weakening of the solid metal, @. 5. Give mechanism of wet corrosion (of oxygen absorption at cathode) by giving well labelled diagram and concerned redctions (ex- plaining portion should be very brief). How yellow rust is formed. 2 (CS.U.T.U., Sem. I, Dec/Jan, 2008-09) 2 Or & __ Discribe electrochemical principle of wet corcosion ? = eS Or ZB war's electrochemical corrosion ? Discribe with diagram. zg Or EB Give the electrochemicat theory of corrosion ? U., Sem. I, May/Sune-2007) : Or Give the mechanism of eectrochemical corrosion ? s (CS.V.T.U., Sem. I, April/May 2008-08) = Ans. WET CORROSION OR ELECTROCHEMICAL CORROSION Wet or electrochemical corrosion is also known to.be as immersed corrosion. It takes place in following two conditions : 1. When a conducting liquid is in direct contact with metal, “Or 2. When two different metals or alloys are partially or completely im- ‘mersed or dipped in a solution. ‘Types of wet or electrochetnical corrosion : Wet or electrochemical corrosion is of three Types 1, Chemical corrosion : It i3 a type of wet corrosion that takes place due to electrochemical or chemigal reaction between a metal and liquid surroundigngs. 2. Under water corrosion : This type of wet corrosion includes cor118 | SBP Q. B. Applied Chemistry rosion in water pipes of all types heating systems, steam boilers etc. The water is in sufficient amount, whereas the air in such type of corrosion is limited: 3. Underground or soil corrosion : This type of wet corrosion takes place in pipes and other underground structures and in ferrous metals in con- crete. It is very complicated because of various salts are presence in the soil. Principle of Wet of Electrochemical Corrosion ‘The wet or electrochemical corrosion is based on Nernst theory, ac~ cording to which all metals have a tendency to pass into solution. When immersed in a solution of its own salt, this tendency of metal is measured in terms of its electrode potential. The standard electrode potential of various metals have been determined in comparision with the standard electrode potential of hydrogen takes as zero. Wet or electrochemical corrosion takes place due to existance of sepa- rate anodic and cathodic areas or parts, between current flows through the conducting solution. * At anodic area, oxidation reaction (=liberation of free electrons) takes place, so anodic metal is destroyed by either dissolving or assuming combined state (such as oxide) so corrosion always ntakes place at anodic areas. - * At cathodic areas reduction reaction (~gain of electrons) takes place. Usually, cathode reactions do not affect the cathode, Since most metals ‘cannot be further reduced . So at cathodic part dissolved constituents in the condeting medium acepts the electrons to form some ions (like OH OH”,O~ ) The metallic ions (at an odic part) and non-metallic ions (formed at cathodic part) diffuse towards each other through conducting medium and form a cor- rosion product some where between anode and cathodic reaction . Thus we may sum up that electrochemical corrosion involves (j) the formation of an- ‘odic and cathodic areas or parts in contact with each other (ii) presence of a conductiong medium ({ii) corrosion of anodic areas only and (iv) for mation of corrosion product somewhere between anodic and cathodic areas. Mechanism of Wet or Electrochemical Corrosion Electrochemical corrosion involves flow of electron current between anodic and cathodic areas. 1. Anodic Reactions : At the anode, dissglution of metal takes plade with the release of positive corresponding metal ions and liberation of free electrons in the surrounding environment. Mgy PM "eq tm” (Oxidation) Corrosion | 119 a | (Metal) (Metal ion) 'M™ (metal ion) forms compound such as oxide ‘The extent of corrosion of metal anode depends upon the reactions at the cathode which “mop up” electons flowing from the anod: 2 le the anode and conver the metal ions formed at the anode into insoluble product. F, for core Fei) —Fe"eq) +2e" (Oxidation at anode) Fe" aq) +2H joy) —> Fe(OH), 2. Cathodic Reaction : The cathodic reaction con: lectro ion consumes el released at the anode are responsible for following cathodic reactions The electrons reléased at the anodes are conducted to the cathod and are responssible for the various cathodic resection. “ @ Electroplating : The metal ions at the cath: trons and plate out (deposit) on the cathode surface. Ey celles the elec- Cutt +2e4 —+cu ~ (ii) Liberration of hydrogen : In acid solution (i i : fn the al ‘oxygen) hydrogen ions acquire electrons and Hy gas is med neense of 2H,0* +2e"! +H, 1 42H,0 In neutral end alkalirie media afd in the absence tion taking place will be a s follows fore the rec. 2H, 0 + 2c! —+H, 1 4208 Corrosion processes in which His evolved are called hydrogen type. ; Fig. 32. Mechanism of wet corrosion by hydrogen evolution, Gil) Formation of hydroxyl is ions : (a) In presence of dissolved120| SBP Q. B. Applied Chemistry ‘oxygen and in neutral or alkaline media : 2H,0+0, +4e! —+OH™ (b) In presence of dissolved oxygen and in acidic media : 4H* +0, +4e"! —+2H,0 Corrosion processes involving O, are called oxtgen type. ‘The above mentiond reactions only represent the predominant reac- tions. In many cases, many of these reactions may take place simultaneously. ‘Thus, from the foregoing discussion it is clear that the essential re- quirements of electrochemical corrosion are (a) formation of anodic and cathodic areas, (b) electrical contact between the cathodic and anodic parts to enable the conduction of electons, and (c) an electrolyte though which the ions can diffuse or migrate. This is usually provide by moisture. Q. 6. Describe electrochemical corrosion of iron in neutral medium . (CS.V.TU., Sem. I, 2005) Or Explain wet mechamism of corrosion of iron in neutral condition with diagram only. (CS.V.T.U., Sem. I, 2005) Or What do you understand by electrochemical corrosion and explain the mechanism of rast formation in neutral medium. (CS.V.T.U., Sem. 1, Nov/Dec. 2007) Or How yellow rust is formed ? (C-S.V-T.U., Sem, I, Dec. Jan. 2008-09) Ans. Electrochemical Corrosion of Iron in Neutral Medium Or Rusting of Iron in Neutral Aqueous solution ‘The iron surface is usually coated with a thin film of iron oxide. It this film of iron oxide develops some cracks anodic areas are created on the surface, while the well-metal parts act as cathodes . It follows that the an- dic areas are small surface parts, while nearly the rest of the surface of the metal forms large cathodes. ‘ At the anodic areas of the metal (iron) dissolves as ferrous ions with liberation of electrons. Fe——>Fe* 42073 (Oxidation) KRISHNA COPIERS Corrosion | 121 i @. 7. Explain corrosion of iron in presence of acidic medium. ; (S.V. T.U., Sem. I Nov./Dec. 2006) ___ Ans. Corrosion of Iron in Presence of Acidic Medium : Corro- sion of irons is also takes place in presence of an acid. This corrosion is called rusting of iron in the atmoshere. Rusting of iron is due to the continued action of oxygen, carbon dioxide and moisture, converting the ‘metal in to a soluble ferrous bicarbonate which is furher oxidised to basic ferric carbonate and fonally to hydrated ferric oxide. Fe+0+2CO, +H,O— > Fe(HCO,), SMRITI NAGAR “MO, - 9691859316, 9584601916 2Fe(HCOs), + H;0 + O—>+ 2Fe(OH)CO, +2C0, +2H,0 2Fe(OH)CO, +2H,0 —>2Fe(OH), +20, ThiS is also called acid theroy Ported by the following facts- J, Rust analysis generally shows the presence of ferrous and ferric carbonates along with hydrated ferric oxide. 2. Retardation of it to the water in which iron is immersed. The liberated electrons flows from anodic to cathodic areas, through iron metal, where electrons are intercepeted by the dissolved oxygenas of corrosion. This theory is sup- ¢ Of wided iime or NaOH 1 - - 302 +H,0+2e" —+20H" (Reduction) The Fe%* ions (at anode) and OH ions (at cathode ) diffuse and whén they meet ferrous hydroxied is precipitated. Fe? +20” —>Fe(OH), 4 @ If enough oxygen is present, ferrous hydroxide is easily oxidise: to ferric hydroxide. Perens ely ones 4Fe(OH), +0, +2H,0—+4Fe(OH), This produt called yellow rust, actually corresponds to Fe;0;.H,O. 4 Gi) If th8 supply of oxygen is limited, the corrosion product may" even black anhydrous magnetite, FeO,. ©. 8. What is atmospheric Corrosion ? Explain factors influenc-i ing atmospheric corrosion. oman122 | SBP Q. B. Applied Chemistry ‘Ans. Atmospheric Corrosion : When a metal is exposed to the at- mosphere , an oxide film is on formed its surace due to interattion with atmospheric air. As long as this protective oxide ‘flim is maintained on the entire metal surface, further attack of corrosion does not occur. But, how- ever, if this oxide flim breaks down due to electro-chemical action on the metal surface due to the presence of moisture or any electrolyte , corrosion proceeds further. Factors influencing atmospheric corrosion : Atmospheric corro- sion is influenced by following factors— 1. Humidity. 2. Impurities present in the atmosphere. 3. Nature of corrosion products formed. 1. Humidity : Refer Q. No. 3. 2. Impurities present in the atmospheric air : Refer Q.No. 3. 3. Nature of corrosion products formed : Metals like NiCr, Al and alloys like stainless steel exhibit good resistance for atmospheric corrosion. ‘due to their tendency to form thin and firm protective oxide film. However, metals like Cu and Pb, though not capable of forming highly protective films, develop atmospheric corrosin resistance due to the formation of sec- ‘ondary layers 07 corrosion producis. These iuyers vifer corvosin resistsnee by forming physical barriers between the metal and the environment. The ‘extent of protection naturally depends upon coherence of the protective layer formed and its critical humidity. Copper forms a coherents and adher- ent layer of basic copper carbonate or basic copper sulphate which offers resistance to atmospheric corrusion. However in case of iron, the primary corrosion product, ferrous hydroxide is oxdised to basic ferric carbonate and then to hydrated feric oxide (rust), which is non-adherent and incoher- ent. One of the reasons for this behaviour is that the oxidation of Fe (OH)2 to Fe (OH) is accompanied by decrease in volume. The rate of atmospheric corrosion of iron depends upon the extent of humidity present in the atmo- sphere, the degree of pollution of the atmosheric air and the frequency of exposure to rain. Q. 9. Describe galvanic corrosion ? Explain the mechanism of gealvanic corrosion. ‘Ans. Galvanic corrosion : When two dissimilar metals such as zine and copper are electrically cohnected and exposed to an electrolyte, the ‘more electropositive metal (i.e., which is placed higher in electrochemical series) undergoes corrosion. Here metals higher in the electrocemical se- rries) ie. zinc forms the anoderis attacked and gets dissolved, while that which is lower in electrochemical seies (copper) actsas cathode. Since cor- Corrosion | 123, corro- rosion is due to the set up of a galva sion. cell, it is known as gatvar Fig. 33. Galvanic corrosion Mechanism : Galvanic corrosion (cathodic reaction) depends upon the nature of corrosive environment. In acidic solution. the corrosion oc- curs by the hydrogen evolution process, while in neutral or slightiy alkaline solution corrosion takes place by oxygen absorption method . The electron- current flows from the anodic metal zinc, which undergoes corrosion, to the ‘cathodic metal (copper). Thus corrosion occurs at the anodic metal, while the cathodic part is protected from the attack. Zn—+Zn™ 420° | (Oxidation) Fg. 1. Stee! pipe.connected to copper plumbing. 2. Steel screws in a brass in marine hardware. 3. A steel propeller shaft in bronze bearing. 4, Lead antimony solder around copper wire. Q. 10. Write short note on the following : (@) Concentration corrosion, (&) Water tine corrosion, (CS.V-LU., Sem. I, 2006-07, Dec/Jan. 2008-09) (©) Pitting corrosion, (CS.V.T.U., Sem. I, 2005, 2006-07) (@) Stress corrosion. (CS.V.T.U. Sem. I, 2005, 2006-07) Ans, (a) CONCENTRATION CORROSION. (Or Differential Aeration Corrosion) The corrosion that takes place due to electrochemical attack on metal surface, exposed to an electrolyte of varying concentration or of varying aeration, is called concentration or of varying earation, isiealled concen- tration corrosion or differential aeration corrosion. This type of corro- sion may becaused as a result of local diffeeaces in metal ioh cancentration ccqused by by local temperature di ferences or inadequaqte agitation or slow124| SBP Q. B. Applied Chemistry diffusion of metal-ions, produced by corrosion. Differential aeration corrosion (the most common type of concentra- tion cell corrosion) occurs when one part of metal is exposed to a different air concentration from the other part. This causes a difference in potential between differentty aerated areas. It has been found experimentally that poor-oxygenated parts are anédic: Therefore, a differential aeration of metal causes a flow of current, called the differential current. Differential aeration is responsible for the corrosion of metals, par- tially immersed in a solution, just below the waterline. Thus, if a metal (e.g. Zn) is partially immersed in a dilute solution of a neutral salt (e.g. NaCl) and the solution is not agitated properly, then, the parts above and closely adjacent to the waterline are more strongly aerated (because of the easy access of oxygen) show a smaller oxygen concentration and thus, become anodic. Therefore a difference of potential is created, which causes a flow of current between the two differentially -aerated areas of the same metal. Zinc will dissolve at the anodic areas and oxygen will take uelectrons at the cathodic areas to form hydroxyl ions. Zn——>2n* +26 (Oxidation) +H, +26 —>20H> (Recuction}~ Zn rod NaC solution Flow of electron Corroding anode Ens 2024267 (Less oxygenated part) Spar ttiode) 40, +1042" —208- Fig. 3.4. Mechanism of differentia! aeration attack caused by partial immersion of » metal. ‘The circuit is completed by migration of ions, through the electrolyte, and flow of electrons, through the metal, from anode to cathode. (b) WATERLINE CORROSION It is also known to bé as differential oxygen concentration corro- sion. Waterline corrosion results from differential aeration leading to the formation of oxygen concentration cells. When water is stagnant in a steel for long time, it is observedithat corrosion take place just below the water Corrosion | 125 level. The concentration of dissolved oxygen at the water surface is greater than that the under the surface. This generates an oxygen concentration cell in which the metal at the water level is cathodic with respect to the metal below the water level. Owing to the poor conductivity of water, the ions just below the water level are more readily available for the reactions and hence the metal just below the water level gets corroded. The intensity of attack may not be considerable under normal conditions but in some practical cir- cumstances, the attack may be intense. If the liquid is in motion and con- tains chlorides and anodic inhibitors such as hydroxide, carbonate, phos- phate, chromate or silicate are inadequate to stifle the corrosion reactions completely, intense attack at the water line may take place. It the water is relatively free from acidity, little corrosion take splace. Water line corrosion is a serious problem for ocean-goingships be- cause the attack is further accelerated due to the marine plants attaching to the sides of the ship. This can be combated by using special antifouling paints. & 20> 4° 4087 AHP +03 44e7 4 2420 Mighty Oxypenaies Cathodic Part (Protected) Fig. 3.5 Waterline Corrosion (© PITTING CORROSION ing corrosion is a localized accelerated attack, which results in the formation of cavities, pinholes and pits in the metal. Pitting is the result of the breakdown or cracking of the protective film on a metal at specific points. Pitting gives rise to the formation of small anodic and lange cathodic areas. ‘The breakdown of the protective film may be caused by : (® Surface roughness or non-uniform finish. Gi) Local straining of metal due to non-uniform stresses. i) Scratches or cut edges. Gv) Sliding under load. (v) Alternating stresses. + (vi) Impingements attack. (vii) Chemical attack. ‘The extraneus impurities (eg. dust, sand, scale etc). embeded on the } surface of metals, also lead to pitting.126 | SBP Q. B. Applied Chemistry When differential amount of oxygen come in contact with the metal, the small part of metal underneath the impurity becomes the anodic areas and surrounding large parts becomes cathodic areas. Therefore corossion starts just underneath the impurity. When a small pit is formed the rate of corrosion will be increased. Fe?* 4208” -+ FetotDs CCoroson product, Fig. 3.6. Pitting corrosion at the surface of iron. (@) STRESS CORROSION OR STRESS CRACKING ‘This type of corrosion or cracking due to the combined action of a static tensile stress and a corrosive environment on a metal or alloy. Stress corrosion is observed in fabricated articles of certain alloys (e.g. nickel brasses, high-zinc brasses) due to the presence of stress caused by heavy working stich 2s rolling, drawing cr insufficient cnnedling. The pure metals are relatively immune to stress corrosion. Stress corrosion involves in a localized electrochemical corrosion, takes place along narrow paths, forming anodic areas with respect to the more ‘cathodic areas at the metal surface. The presence of stress produces strains, which in turn develops localized zones of higher electrode potential. These localized zones become more chemically active and are attacked. even by a mild corrosive environment reselting in the formation of crack Thse cracks ‘grows and propagates perpendicular to the operating tensile stress until failure takes place. Cathode F] ‘Anode (strained part) ‘where corrosion take place Swressod part grain ‘boundary (anode) ‘where corosion takes place Cathode Fig. 3.7. Stress corrosion. Corrosion | 127 Examples of Stress Corrosion : 1. Season cracking or stress corrosion of brass : Pure copper is immune to stress corrosion, but presence of small quantity of alloying ele- ‘ment (such as Zn, A) increases sensitivity. Eg. Alpha brass, containing traces of amionia or amines undergoes intergranular cracking in an atmosphere. The attack takes place along the boundaries of grains, which become more anodic with respect to grain themselves. Both the alloying components of bras viz., Cu and Zn are known to form complex ions like [Cu(NH,),}°*and[Zn(NH,),}°* in ammonia solu- tions. This leads to dissolution of brass initiating in fissure and propagates. Which ultimately results in the formation of cracks in the presence of high tensile stress. 2. Caustic embrittlement : This form of corrosion occurs in mild steel exposed to alkaline solution at high temperature and stresses. Caustic ‘embrittlement is the phenomenon during which the boiler material be- comes brittle due to the accumulation of ciiustic substances. This type of boiler corrosion is caused by the use of highly alkaline water in the high pressure boiler. Q. 11. Write short notes on the following : (a) Underground corrosion, (6) Microbiological corrosion, (©) Corrosion fatigue. ‘Ans. (a)UNDERGROUND CORROSION OR SOIL CORROSION This type of corrosion is caused in underground structures like pipe- lines, (For water, gas, oil) electric cables etc. This type of corrosion is purely electrochemical in nature. ‘ Factors responsible for soil corrosion : The various factors that are responsible for soil corrosion include the following : 1. Acidity of the soil, 2. Moisture content, 3, Content of electrolytes, 4. Micro-organism present, 5. Content of organic matter, 6. Physical property of the soil. In non acid soils, the conductivity (which depends on moisture and electrolyte content is the major factor governing the corrosive character. In such coils, corrosion takes place due to the formation of differentil aeration couples and the rate of corrosion majorly depends upon the resistance be- ‘tween the anodic and cathodic areas and the rate of arrival of oxygen to the cathodic area. Thus when a cable or pipe passes under unpaved soil. Hence the protion under the paving becomes anodic and suffers corrosion. In highly acidic soils, the corrosion taking pace is of hydrogen type128 | SBP Q. B. Applied Chemistry with anodic and cathodic areas being very close to each other. The conduc tivity of the soil is not of much importance in this case. In soils which contain larger amounts of organic matter, the formatin | of soluble metal complexes and the peoptization of corrosion products may accelerate the corrosion process as compared to what is expected in the soils relatively free from organic matter. Soils rich in gravel and sand are more porous and hence are generally ‘more aerated and the corrosion of ametal pipe under such soils depends mostly on the moisture and salt content. Water logged soils may geneate anaerobic bacteria which may create conditions for microbiological corrosion. (b) MICROBIOLOGICAL CORROSION Corrosion caused by the activity of metabolic activity of various aerobioc and anaerobic micro-organisms is called microbiological corro- sion. Oxygen-consuming bacteria present in water or soils decrease the con- centration of oxygen in the anedium in contact with a metal structure. If the ‘metal structure is totally exposed to the medium in which oxygen has been depleted by bacteria, than it may reduce corrosion. But, if the structure is only partially exposed to the oxygen-depleted eowironment then the bacte- rial action may intensify the corrosion due to differential aeration. “Examples : 1. Anactébic bacteria such as Microspiza or ‘vibrié desulfurience reduce sulfates to sulfur which is used to prepare their proto- plasm. During this process, it is supposed that these bacteria convert the O, from the sulfates in to such a form which brings about a depolarization effect on the corrosion of iron. When these organisms die, sulfur is liber ated as H,S which converts a portion of the corrosion product in to FeS, which is less effective in supperessing the corrosion that the oxide or hy- Corrosion | 129 rous hydroxide. The corrosion is localized and intense. 2. The presence of iron bacteria is sometimes connected with pitting or blockage of pipes due to corrosion products. Iron and manganese bacte- ria which thrive on iron and manganese compounds in presence of oxygen deposit these metals as their insoluble hydrated oxides. These may further increase the rate of corrosion by forming differential aeration couples. 3. Desulfovibrio and clostridrum are known as corrosive bacteria Slime forming bacteria e.g, flavobacterium Aerobacter and Pseudomonos lead to corrosion in cooling tower systems. (©) Corrosion Fatigue : Corrosin fatigue is a special type of stress corrosion cracking. In this, failures are caused by repeated cyclic stresses (such as shaking, vibration, tapping, “shuttering” and flexing), in presence of a corrosive environment although the stress is well below the normal fatigure limit. Alloy steels are often more susceptible to this type of corro- sion. The stress alterations “ work-harden” small regions of metal around internal cavitiers or surface flaws, there by distorting the mefal structure and making it tess elastic. Such a work-hardened material becomes anodic with respect to the bulk metal in a moist atmosphere. Corrosion of the at ode occurs and any surface crack or internal flaw spreads through the metal. Q. 12. What-are different methods of protection from corrosion:? Or Name various methods of corrosion control. ‘Ans. Corrosion reactions are all surface reactions. Therefore, the pro- tection of the surface of the metal is to primary object to prevent corrosion is called protection against corrosion, The corrosion can be controlled by following methods : droxide. This typeof intense and localized corrosion is come across with, * | @ 1. Proper designing and material selectidn cast iron in presence of sulfates and organic matter under anaerobic condi- SP 2. Using pure metal. tions, > a 7 QI SS 3. Using metal alloys. Anodic solution of iron 7 7 F. ie 4. Cathodic and anodic protection. 8H,O ——= 8H* + 80H Fe 5. Modifying the environment. 4Fe + 8H" === 4Fe" + 8H € 6. By using inhibitors. Depolarization due to bacterial activity a RSE 7. By metallic coating. H,80,+ 8Ha== H,S + 4H,0 £ ag 8. Application of protective coating. Corrosion Progucts so Q. 13. Discuss the following protective measures against corrosion. Fe* + HS a= FeS + 2Ht ¥ (any two) (CS.V.L.U., Sem. I, Now./Dec. 2007) 3Fe* + 80H~ === 3Fe(OM), ‘Thus the principal corrosion products are black iron sulphide and fer- (a) Proper design and material selection, (©) Cathodic protection, Ly130| SBP Q. B. Applied Chemistry (c) Use of inhibnitors, (@ Modification of environment. Or . How material section and proper design can prevent corrosion. (C.S.V.T.U., Sem. I, Apri./May 2008-09) Ans. (a) Proper Designing and material selection Proper design and selection of the right type of material is the main factor for corrsion control. The choice of the metal should be made not only ‘n its cost and structrure but also on its chemical properties and its environ- ment. Principles of Designing : The important principles of designing are as follows : 1, Avoid the contact of dissimilasr metasls in the presence of a corrod- ing solution. 2. When two dissimlar metals are to be in contact the anodic material should have as large area as possible; whereas the cathodic metal should have'as much smaller area as possible. 3. If two dissimilar metals in contact have to be used, they should be as close as possible to each other in the electrochemical seri 4. Whenever the direct joining of dissimilar metals, is unavoidable, an lating fit jay be appiod in between them io avoid direct metal metal electrical contact. 5. The anodic metal should not be painted or coated. because any break in coating would lead to rapid localized corrosion. 6. A proper design should avoid in homogeneities in the metal as well as in the corrosive environment. Thus sproper design should avoid the existence of crevices between adjacent part of the structure, even in the case of same metal because crevices permit concentfation dif- ferences. However, when existence of crevices cannot be avoided in a given design, their harmful effects can be minimized by painting. 7. The design should allow adequate cleaning and flushing of the criti- cal parts of the equipment. Thus sharp corners and recesses should be avoided. 8, Whenever possible the equipment should be supported on legs to allow free circulation of air. ‘ 9. The design should be such which allows a uniform flow of the corrosing liquid because stagnant area, highly turbulant flow and high velocity can cause accelerated corrosion. Corrosion | 131 (b) CATHODIC PROTECTION ‘The principle involved in cathodic protection is to force the metal behave like a cathode. Since there wilkl not be any anodic area on the metal, corrosion does not occur. Principles of cathodic protection may be explained be considering the corrosion of a typical metal, M in an acidic environment. The electrochemi- cal reactions occurring in such a system are the dissolution of the metal and the evolution of hydrogen gas as per the following equations : M—3M"* +ne 2H* +2e——>H, (Cathodic protection can be achieved by supplying electrons to the metal structure to be protected. By examining the above two equations, itis obvious that the addition of electrons to the structure will tend to suppress metal disso- lution and increase the rate of hydrogen evolution. If current is considered to flow frem (+) to (~), as in conventional electrical theory, then a structure is projected if current enters it from the electrolyte. Conversely, accelerated cor- Tosion occurs if current passes from the metal to the elecifolyte. This current convention has been adopted in cathodic protection technology. ‘Types : There are two types of cathodic protection : 1. Galvanic or sacrificial anode protection. 2. Impressed current cathodic protection. - = i. Guivanic or Sacrificiai Anodic Frotection : it is a method of ca- thodic protection in which the metallic structure 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 itselt gets corroded slowly; while the parent structure (cathodic) 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 sacri- ficial anodes are magnesium, zinc. aluminium and their alloys. ‘ Fig. 38. In cathodic protection, an anode of a more strongly reducing metal Is sacrificed to maintain the integrity of the protected object (2g. a pipeline, bridge, ship hull or boat).132 | SBPQ. B. Applied Chemistry Applications : Sacrificial anodic method is used for the protection of buried pipelines, underground cables, marine structures, ship-hulls, water- tanks, piers, etc. 2. Impressed current cathodic protection : In this method of pro- tection, an impressed current is applied in opposite direction to mullify the corrosion current and convert the corroding metal from anode to-cathsde. Usually, the impressed current is derived from a direct current source (like battery or rectifier on ac. line) with an insoluble anode (like graphite, high silica iron, scrap iron, stainless steel or platinum). Usually, a sufficient d.c. current is applied to an insoluble anode, buried in the soil (or immersed in the corroding medium), and connected to the metallic structure to be pro- tected. The anode is, usually, in a backfill (composed of coke breeze or gypsum) so as to increase the elecical contact with the surrounding soil. This type of cathodic protection has been applied to open water-box cool- ers, watertanks, buried oil or water pipes, condensers, transmission line towers, marine piers, laid-up ships. etc. Application : This kind of protection technique is, particularly, use- ful for large structures for tong term operations, & : a os * ales - eo es e Ke & we Fig. 3.9. In impressed-current cathodic pretection, electrons are supplied from an ‘external cell so that the object itself becomes eathodic and is not oxidized. (©) PROTECTION BY USE OF INHIBITORS ‘A substance that when added in small quantities to the aqueous corro- sive environment, effectively decreases the corrosion of a metal is called corrosion inhibitor. Corrosion inhibitors are of two types : 1. Cathodic inhibitors 2. Anodic inhibitors. 1. Cathodic Inhibition ‘ ‘Tow types of cathodic inhibition takes place in two different solu- tions. The cathodic reaction Takes place in acidic solutions is the evolution of hydrogen. : ew | A gh Tus here corrosion may be reduced by two methods Corrosion | 133 2H eq) +22” Hyg Corrosion may be reduced either by slowing down the diffusion of hydrated H" ions to the cathode, and /or by increasing the overvoltage of hydrogen evolution. The diffusion of H” ions is considerable decreased by organic inhibitors (¢.g amines, hetrocyclic nitrogen compounds, heavy metal soaps), which are capable of being adsorbed at the metal surfaces. Anti- mony and aresenic oxides (or salt like sodium meta-arsenite) are used as inhibitors, because they deposit adherent film of metallic arsenic or anti- mony at the cathodic areas, thereby increasing considerably the hydrogen overvoltage. In natural solutions, the cathodic reaction resoults in the evolution of OH ions. 2Que) #40; +26" = 20H 5 se? 1, Eleminating O» from the corroding medium. 2..Retarding diffusion of O, to the cathodic areas.; 2. Anodic Inhibition : The elements with a high oxygen content that stifle the corrosion reaction, occurring at the anode, by forming a sparingly soluble compound with a newly produced metal ion. are called anodic hibitors. eg. chrometes, phosphates etc. Thy are absorbed on tive metal sur= face, forming a protective film or barrier, thereby reducing the corrosion rate. Although this type of control is effective, yet it may be dangerous, since sever local attack can occur, if certain areas are left unprotected by depletion of the inhibitor. (@) Modifications of Environment ; The corrosive nature of the en- vironment can be reduced either by removing of harmful constituents or by adding of specific substances, which neutralized the effect of corrosive con- stituents of the environment few such effects are given below 1. Deaeration : In differential oxygen concentration type of corro- sion, removal of oxygen from aqueous environment reduces metal corro- sion. Expulsion of dissolved oxygen can be done by adjustment of tempera-* ture, together with mechanical agitation. 2. Dehumidification : Dehumidification reduces the moisture con- | tent of air to such‘an extant that the amount of water condensed on metal is134| SBP Q. B. Applied Chemistry too small to cause corrosion. Alumina or silica gels, which absorbs mois- ture preferentiallyu on their surfaces, are applied only is closed areas like airconditioning shop. 3. Deactivation : Certain chemicals e.g., Na;SO3 and hydrazine are removed oxygen by combining rapidly with the oxygen present in aqueous solution. 2Na,SO, +0, —>2Na,SO, Hydrazine hydrate has advantage over sodium sulphite. because the reaction products are nitrogen N,(g) and water. NH;.NH, +0) —+N, 1 +2H,0 4, Neutralisation of Acids : Corrosive environment due to presence of acids like H,S. HCl, SO, CO; etc., can be minimised by injecting alka- line neutralizers (like NH3, NaOH, lime, napthenic soaps etc.) either in vapour of liquid form to the corroding systers The method has been widely used in controlling the corrosion of refinery equipments. Q. 14. Give brief account of galvanic series ? (CS.V.T. U., May/June, 2007) ans. GALVANIC SERIES ~ In the electochemical series (reduction electrode potential arranged down in an increasing order), a metal high in the series is more anodic and undergoes corrosion faster than the metal below it. For example, Li cor- ‘odes, faster than Mg; Zn corrodes faster than Fe; Fe corrodes faster than ‘Sn; Cu corrodes faster than Ag and so on. However, some exceptions to this Beneralization are known. For example, Ti (above Ag in the electrochemi- cal series) is less reactive than Ag.In Zn-Al couple, Zn (below Al in the electrochemical series) is corroded; while Al acts cathodic and is protected - These observations, exactly opposite to that predicted by the emf series, are due to the fact that metals like Ti and Al develop, strongly adhering oxide layers on their surfaces, thereby making their effective electrode po- tential more positive (or less negative). From the above, it is clear that electrochemical series does not ac- count for the corrosion of al’ metals and alloys. Consequently, a more prac- al series, called galvanic series (seg table 1) have been prepared by study- ing the corrosion of metals and alloys in a given environment like sea-wa- ter. Thus, galvanic series give real and useful informations for studying the corrosion of metals and alloys. Corrosion | 138 Table 1. Galvanic series. Active 1 Mg (or anodic) 2. Mgalloys 3. Zn 4 Al sd 6. Alalloys 1 Mild steel 8 Cast iron 9. High Ni cast iron 10. Pb-Sn solder M. Pb re 13. Ieonel 14, Ni-Mo-Fe alloys | 15, Brasses > 16. Monel (7 =Ni, 30 = Cu, rest = Fe) 17, Silver solder }oG 18. Ca - 19. Ni 20. Crstainless steel 21. 18-8 stainless steel 22. 18-8 Mo stainless steel 2. Ag 24, Ti + 25. Graphite ‘ Noble 26, AU (or cathodic) 27. Pt Short Answer Type Questions on Corrosion Q. 1. Why does a steel pipe in a large copper tank corrode causing rapid destruction. Ans, Iron or steel is anodic wrt to copper. When a steel pipe fitted ina lange copper tank is exposed to atmosphere, galvanic corrosionéstarts and the anodic metal (iron or steel) starts corroding. More over smallsized steel pipe (anode) in a large-sized copper tank ( cathode) causes rapid and in-136 | SBP Q. B. Applied Chemistry tense corrosion of stee! pipe. @. 2. What is meant by the term passivity ? ‘Ans. The phenomenon in which a metal or an alloy exhibits a much higher corrosion resistance than expected from the position in the galvanic series, is called passivity. Q. 3. Why does corrosion occur in steel pipe connected to copper plumbing? Ans. When iron or steel pipe connected to copper plumbing is ex- posed fo an electrolyte, then iron (the metal higher in the electrochemical series) undergoes corrosion, since iron forms the anode and is attacked and corroded; whereas copper (the metal lower in the electrochemical series) acting as cathode is protected. This type of corrosion is called galvanic corrosion. Q. 4. Bolt and nut made of the same metal is preferred in practice. Why ? ‘* Ans, Bolt and nut made of the same metal is preferred, beciiuse such combination will not permit galvanic corrosion to take place. Q. 5.A pure metal rod half-immersed vertically in water starts cor- roding at the bottom. Give reason. -Ans. This is due to differential aeration. The rod above and closely adjacent to the waterline is more strongly aerated and hence, becomes ca- thodic; while the lower part of rod immersed in water is less-oxygenated and hence, become anodic. So a difference of potential is created and electochemical corrosion takes place. This causes corrosion of the anodic art. Hence, metal rod starts corroding at the bottom. Q. 6. Impure metal corrodes faster than pure metal under identical conditions. Give reason. Ans. Impurities in a metal generally cause heterogeneity and form minute (or tiny) electrochemical cells at the exposed parts, whereby the: anodic parts get easily corroded. Q. 7. The rate of mefallic corrosion increases with increase in tem- perature. Give reason. Ans. With the increases of temperature of the environment, the rate of reaction as well as rate of diffusion increase, thereby corrosion rate in- creases. @. 8. Rusting oftiron is quicker in saline water than in ordinary water. Give reason. Ans. The presence of sodium chloride in saline water leads to creased conductivity of water layer in contact with the iron surface, therebny ‘AR . - 9691859316, 9584601916 KRISHNA COPIERS MO. Corrosion |137 corrosion current increases and rusting is speeded up. Q. 9, What is meant by rusting of iron ? Ans. The atmospheric corrosion of iron and steel, leading to the forma- tion of a layer of reddish scale and powder of oxide (Fe3O,) on the surface. Q. 10. How must rust (Fe;0;. 3H,0) will be formed, when 100 kg of iron have completely rusted away. Ans. 214 g of rust (mol. wt.) contains = 112 g of iron, 112 g of iron produces rust = 14 g or 100 kg of iron produces rust, 2a looke 91.tkg 2 Q. 11. Why in marine hardwares iron bolts are used in copper nut ? (.V..U., Sem. I Nov./Dec. 2006) ‘Ans. Iron (higher in electrochemical series) acts as anodic and is at- tacked and corroded, while copper equipment (nut) lower in electrochemical series) acts as cathode and is not attacked at all. Since anodic area is‘very small so it is completely corroded in due course of time and the action of boit is finished. Therefore in marine hardware iron bolts are used in copper nut. . 12. What is the application of sacrificial electrode ? (CS.V.T.U.,.Sem. I-May/June 2007) ‘Ans. Sacrificial electrode is used in the protection of bried pipe lines, underground cables, marine structure ship-hulls, water-tanks, piers etc, OQ. 13. Asteel screw in a brass marine hardware corrodes. Give rea- ‘Ans. This is due to galvanic corrosion. Iron (higher in series than brass) becomes anodic and is attacked and corroded; while brass (lower in series ) acts as cathodic and is not attacked at all.* Q. 14. Why does corrosion of water filled steel tanks occur below the waterline ? Ans, When water is stored in a steel tank, the area above the waterline are highly aerated and acts as cathode; whereas area just below the water- line is poorly-aerated and acts as anode. A differential aeration is set-up and anodic part Gust below the tank) gets corroded. Descriptive Questions on Battery Q 1. Define the following: (a) Batery, (CS.V-.U., Sem. I 2005, 2006-07) (6) Cell voltage, (C.S.V.T.U.,,Sem I- 2005, 2006-07) (©) Closed circuit voltage,138 | SBP Q. B. Applied Chemistry (@) Open circuit voltage. Ans. (a) Battery : The term battery is generally used to denote on or more electrically connected galvanic cells. In other words a battery is a Combination of two or more cells arranged in series or parellel that can be used as a direct electrical current and constant voltage. Battery may be considered as storehouses for electrical energy on de- mand. () Cell Voltage : The voltage that is required to bring about elec- trolysis of an electrolyte without any hinderance is called cell voltage. (©) Closed cireuit voltage : The Voltage measured across the termi- nals of the cell or battery when current is flowing into the external circuit called closed circuit voitage. (@) Open circuit voltage : This is the voltage measured across the terminals of the cell or battery when no extern al current is flowing . When measured on a songle cell, it is usually close to the thermodynamic electro- motive force (emf). = * Q. 2. What is battery ? Give Types of batteries ? ‘Ans. Battery : Refer Q. No. 1. ‘Types of Batteries : Batteries are broadly classified into the follow- ing three categories " 1. Primary battery : It is designed to be discharged only once and then discarded . . (i) Simple voltic cell (ii) Daniel cell (iii) Bichromate cell (iv) Cadmium cell (v) Carbon -Zinc Cells. (vi) Ruben-Mallory dry cells. 2. Secondary battery : It is rechargeable and can be used like the pri- mary battery, then reacharged and used again,the cycle is repeated until the capacity fades or is lost suddenly due to internal short-circut. Eg (i) Lead acid accumelators. (ii) Rechartgeable Alkaline storage batteries. (iii) Rechargeable lithium ion batteries. (vi) silver -zinc al- kaline battery. 3. Reserve battery : In this battery active materials are kept separated by a special arrangement. When it has to be actually used, an activa- tion device makes it ready. Such a battery is designed for long stor- age before use. @. 3. Discuss primary cells. (C.S.V-T.U., Sem. 1, May/June-2007) Or Describe primary or Dry cell ? ; Corrosion | 139 Ans. Primary or Dry cells ‘The cell in which the electrical energy is derived from the chemical ractrion are called primary cells. In a primary cell, a chemical reaction pro- ceeds spontaneously and its free energy is corwerted into electrical energy. ‘The production of electrical energy at the expense of the free energy of the cell is called discharging of the cell. ‘The examples of primary cells include the simple voltaic cells, Daniel cell, Lechlanche Cell, Bichromate cell, Dry cell, Weston cadmium cell, from commercial point of view, the main categories of primary cells are carbon Zine cells , (including Lechlanche cell and Zinc chloride cells), alkaline cells and lithium cells. 1. Daniell Cell: It consists of glass vessel containing satu- rated solution of copper sulphate with some H,SO, which act as de- eee polarizer. Which saturated Copper Cylinder solurated solution of copper-sul- Porous Pot phate is filled with some sulphuric aasgot ‘acid Which works as a depolar- ESO; Solution izer. To maintain the strength of cus04Cry3 the Cu SO, Solution some crys- tals are piaced atthe bottomn of the vessel. A concentric cylinder hav- ing terminal for connection is placed in this solution which acts as positive electrode. A porous pot filled with dilute sulphuric acid and containing an amal-gamated zinc rod is placed inside the cylinder. This zine rod acts as negative electrode. The following chemical reactions take place. Fig. 3.10. Daniell cet Zn—+2n"* +20 + Zn** +H,S0, —+ ZnSO, +2H" CuSO, +2H" —>H,S0, +Cu** 2e+Cu** cu The total reaction can be written as Zn + CuSO, —>Cu+ ZnSO, +2e ‘When the cell is connected in a closed circuit’Zn** ions go into solu- tion at the anode. Since the action of the c ell does not change in any way its composition, no polarisation takes place and the e.m.f. of this cell remains140| SBPQ. B. Applied Chemistry constant while in use The e.m-f. of this is about I volt. Gi) Lectanche cell : The con- . struction of a lec lanche cell is , shown in fig. 3.11. It consists of a glass vessel and has electrodes of zine and carvon in.an electrolyte of ammonium chloride solution, Mitre of Mino, The carbon electrode is fixed in a =o porous pot which is packed tightly Giese veel i ‘Ammonium with a mixture of powdered carbon Dray and an oxidzing agent manganese dioxide The effective surface area of the electrode is being increased due to po wdered carbon being porous. The porous pot is kept in a weak solution of ammonium chloride filled in the glass vessel. The purpose of ‘The porous pot is to keep the powder tightly packed round the carbon rod, ‘The e.m-f. of this cell is about 1.5 volt. The following reactions take place— Zn—+Zn"* +20 Zn** +2NH,Cl—> ZnCl, +2NH, +2H* Fig. 311 Lectanche Cet. 7 ~ 2e+2H—==>H, = ‘The overall reaction can be written as follows Zn +2NH,Cl——+ ZnCl, + NHy +H +2 By the reduction of the manganese dioxide the polarisation is pre- vented i 2MnO; +2H* —+Mn,0, +H,0 ‘Subsequently the manganese dioxide is refor med from the oxygen of the atmosphere dissolved in the solution 2Mn;0; +0; —>4Mn0,, ‘The em. due to this cell is not constant and can deliver a current of about | amp. for a minute or 5o before polarisation becomes excessive and ot quickly recovers after wards. As a result this cell is suited for use when it is not to be used const antly ie, in call bells, telephon , Wheatstone bridge etc. Q. 4. Give a brief,account of secondary batteries or cells. (C-S.V.T.U,, Sem. I, May/June-2007) Ans. SECONDARY BATTERY ‘These cells or batteries are rechargeable and can be used as primary KRISHNA COPIERS SMRITI NAGAR MO. - 9691859316, 9 4601916 Corrosion | 141 battery then recharged and used again. This cycle is repeated until the ca- pacity facles or is lost suddenly due to internal short circuit. In fact second- ary battery works as a device for temporary storage of electrical energy. ‘Such cells serve to accumulate electrical energy in the form of some chemical reaction and later on, the reaction is reversed at our will to release the electrical energy. This process is called charging the cell. secondary or rechargeable batteries may be broadly divided in to the following three cat- egories : (1) Lead Acid accumulators or Acid Batteries (2) Alkaline storage Batteries 3) Others including lithium lithium ion batteries (1) Lead Acid Accumulators : It comprises of a grid lead-antimony alloy coated with lead dioxide as positive pole (cathode) and spongy lead as negative pole (anode) The electrolyte is 2 20% Solution of H, SO, (Specific gravity 1.15 at 25°C) in which a number of the above electrode pairs , con- taining inert porous partitions in between are dipped. the electrode reac- tions which take'place during the discharge of the cell (i.e. when the current is drawn from the cell) are as under ‘Anode Pb—2e" > ppt pb? +07" > _ Pbso, 2 Pb+S0} 267 + Pbso, Cathode PLO, +4H* +26 > Pb’ 42H.O Pb" +80} > PbSsE, PLOs+4H* +SO} +26" —> PSO, +2H,0 Since the lead sulfate geat precipitated on the cathode and in the solu- tion, the cell reaction may be written as follows . Pb | Pb S04 (S) | HzS0, (aq), PbSO, (5) | PbO, (s) | Pb ‘The net cell reaction for the passage of two faradays is PhO, + Pb+2H,S0, =e > ap4S0, +2H,0 ° ‘Charging During the discharge process , the consumption of H»SO, is replaced by an equivalent quantity of water. Thus as the cell produces electric cur rent, the concentration of the sulfuric acid decreases. However, during the charging process, the reverse reaction takes place and hence sulphuric acid is generated while an equivalent water is consumed It is because of this that142 | SBP Q. B. Applied Chemistry the original strength of the acid is restored. 2, Rechargeable Alkaline Storage Batteri electrolytes which are alkaline in nature. Eg. (i) Nickel cadmium battery, (ii) Nickel hydrogen battery, (iii) Sil- ver-zine Battery, (iv) Nickel-Zinc battery, (v) Nickel-metal hyride battery. 3. Other Batteries : Eg, (i) Lithium and Lithium fon cell, Gi) Lithium - Aluminium ~FeS battery, Gii) Lithium T,-S, battery. Q 5. Write reactions of charging and discharging process by lead + These batteries cantain Storage battery ? (CS.V.TLU,, Sem-I, Nov/Dec. 2006) Or What is recharging of battery? (C.S.V-T.U. Sem. I, 2006-07) Ans. Charging and Discharging Reactions of Lead storage Batteries ‘The cell that can operate‘both as voltic cell and as an electric cell. When operating as a voltaic cell, it supplies electrical energy and as a result eventually becomes run down. It must then be recharged when being recharged, the cell operates as an electrolytic cell. Thus storage cell has the reat advantage of its ability to work both ways. to-receive electrical energy and to suppiy it. The common example of storage cell is lead -acid storage cell. Or Lead accumulator. ‘The common example of storage cell is the lead-acid storage cell One of its electrodes is made of lead. The other electrode is made of lead dioxide (PbO,) or rather a paste of PbO, is pressed into a grid, made of lead. A number of lead plates (— ve plates) are connected in paraile! and a number of lead dioxide plates (+ve) are also connected in parallel. 1. Initial charging : Two lead plates are placed in the dilute Sulpuric acid of specific gravity 1.22. When a current is passed it is followed by the evolution of hydrogen at the cathode and since it does not combine chemi- cally with lead electrode (cathode) its colour remains unchanged while the anode becomes dark brown in colour, due to the formation of lead peroxide (PbO,)on it The water in the electrolyte is ionised due to the passage of current as. H,0 > 2H* +0~ arld the hydrogen ions being positively charged move toward8 the cath- ode and oxygen ions being negatively charged move towards the anode. The oxygen liberated at anode combines with the lead and thus forms a Corrosion | 143 dark brown layer of lead dioxide (PbO,) 2. Discharging : Now if the external supply is disconnected and the anode and cathode is connected through a resistance, a current will flow in the direction opposite to the direction in which current flows during the charging process. The cell is said to be discharging and the rate of discharge will depent upon the resistance. During the dischorge process the positive ions move to- H? ions of H)SO, move towards anode and negative SO; wards the cathode as the H)SO, breaks as H,SO, —>2H* +S07- At the anode each hydrogen ion becomes a free hydrogen atom and reduces the (PbO) lead peroxide to lead which reacts with H,SO, and is ultimately converted to lead sulphate i.e., PbO, +H,SO, +2H —>PbSO, +2H,0 «« ASSOj” reaches to cathode itis converted into a free radical $0, which reacts with the metallic lead of cathode and converts into lead sulphate. Pb+SO, —+Pbso, As a result of discharging whitish lead sulphate (PbSO,) is formed on both the electrodes. 3. Recharging : Recharging is a process of charging of cells after use. During recharging H” ions will be produced at cathode and $03” ions at the anode ‘At cathode” PbSO, +2H* —+Pb+H,SO, At anode — . PbSO, +2H,0+SO, —> PbO, +H,SO, Net reaction during recharging ~ 2PbSO, +2H,0+ Energy —+ Pb + PbO, + 4H" +280; This charging results in the cowersion of the anode the dark brown PbO, form lead sulphate while lead sulphate layer on the anode plate is reduced to metallic lead. @. 6. Give brief account of reverse battery ? Ans. REVERSE BATTERIES Batteries must withstand vibration, extreme variations in tempera- tures and also must have capability of high voltage , long inactive shelf life,144 | SBP Q. B. Applied Chemistry rapid activation to the ready state as and when required and must be avail- able in different sizes and shapes. ‘These batteries can be activated by following mechanisms : 1. by mechanical means 2. by water activation using sea water or tap water 3. by electrolyte activation using only the solvent or the complete elec- trolyte 4. by gas activation , using a gas as an active cathode 5. by thermal activation, using a solid salt electrolyt that is activated by melting on application of heat. ‘Activation is usually done by adding a missing component just before use , Which should be done in a simple way such as pouring the water into an opening in the cell in case of water activated cell or in a more compli- cated manner by using valves pistons , heat pellets activated by gravita- tional or electric signals in case of thermally - activated or electroyte acti- vated cells Some.of them are described below... Applications: In recent years, there has been a requirement of cells with special characteristics for the use in proximity fuses, artillery mines, pilto balloons, guided missiles, radars, bazookas, night viewing equipment, submarine torpedo propulsion, walkle- talkies and special electronic equip- ment, ee ‘Types of Reverse Batteries : These batteries may be of following ‘types: 1. Silver chloride cell 2. Perchloric acid and Fluoboric acid cells. 3. Silver-peroxide-Zine alkaline cell. 4, Fused electrolyte cells. +5. Lithium cells. Q. 7. What is fuel cell ? (CS.V.T.U., Sem. I, 2005, 2006-07) Or Give Working of alkaline fuel cells. (C.S.V.T.U., Sem. I, May/June - 2007) Or Discuss the principle and advantages of fuel cell. (CS.V..U., Sem. I, Now/ Dec. -2007) Or Write short note on fuel cell ? ‘ * (CS.V-E.U., Sem. I, Dec/Sun. Ans. Fuel Cell A fuel cell is an electrochemical cell which can corvert the chemical energy contained in a readily available fuel oxidant system into electical en- 2008-09) Corrosion | 145 ergy by an electrochemical process-in which the fuel is oxidized at anode. In other words the cell in which electrical energy is obtained, without combustion from oxygen and a gas that can be oxidized is called is called fuel cell the fuel cell consists of an electrolyte and two electrodes. Types of fuel cells : On the basis of types of electrolyte used, fuel cells are of following types : "1, Alkaline fuel cells, 2. Hydrogen-Oxygen fuel cells, 3. Phosphoric acid fuel cells, 4. Ton-exchange membrane fuel cells et Principle of Working of Fuel Cells : ‘The conventional process of utilizing the chemical energy of a fuel may be depicted as followas: chemical energy, heat 2, mechanical energy _<, electrical energy. * ‘The losses in energy conversion in ateps (1) and (3) can be minimized but ot cannot be done in step (2) because the extent to which heat can be converetd in to mechanical work is limited by the second law of thermody- namics. Not withstanding the improvemenis-in desing ,about 50 10 95% af the chemical energy of the fuel is wasted. In contrast to heat engines, fuel cell, the chemical energy is directly converted in to electrical energy without going through an intermediate conversion in to heat. Hence the limitation imposediay the second low of the rmodynanics is not applicable to such a conversion. Therefore, this direct conversion of chemical energy in to electrical energy in a fuel cell can theoretically have an efficiency of 100% KRISHNA COPIERS SMRITI NAGAR .MO. - 9691859316, 9584601916 ‘The basic arrangement in a fuel cell can be represented as follows Fuel / Electrode / Electrolyte / Electrode / oxidant. At the anode the fuel undergoes oxidation liberating electrons and the oxidation products of the fuel. The electrons so liberated from the oxidatin process taking place the anode reduce the oxidant at the cathode. The electrons liberated at the anode can perform useful work when passing though the external circuit ‘The essential process in fuel cell is as follows : fuel + Oxygen —> Oxidation product + Electricity. Advantages of fuel cells 1. Fuel cells work at high efficiency.146 | SBP Q. B. Applied Chemistry 2. They can be built in a wide range of power requirements from a few hundred watts upto multikilo watt and enen magawat sizes. 3. The resulting emission levels are far below the permissible limits. 4. Noise level of fuel cells is very low. 5. Fuel cell resembles an engine more than does a battery. 6. In fuel cells, reactants are to supplied constantly, while products are removed constantly. 7. No emission of gases. 8. No. emission of gases. 9. Low maintenance cost. 10. Fuel cells ofter excellent method for officient use of fossiol fuels. Q. 8. Define fuel cell ? Explain the construction and wordking of Hydrogen-Oxygen fuel cell. (CS.V-T.U., Sem I, April/May 2008-09) Or Explain construction and working of hydrogen oxygen fuel cell with diagram. (CS.V-LU., sem. I, Nov/Dec. - 2007) Ans. Fuel Cell : For definition refer Q. No. 7. Construction of Hydrogen-Oxygen fuel cells It consists of two innert porous electrodes and an electrolyte solution such as 25% NaOH solution. The electrodes and electrolytes are placed in a ges chamber having passage for supply of oxygen (Oxidizer) arid hydrogen ing (fuel) and exit of water. Both the electrodes are separated by an ion-ex- ‘change membrane. Both the electrodes are placed in electrolytes. Principle of Working of Hydrogen-Oxygen Fuel Cell : ‘The working of the cell is based on following reaction— Fuel + Oxygen___, Oxidation Product + Electricity During the generation of electricity—hydrogen and oxygen gases are bubbled through the anode and cathode compartment respectively, where following reactions take place : Cathode: 0, +2H,0+4e°—+40H" This reaction occurs through the intermediate peroxy ion formation, which is followed by the merely catalytic peroxide decomposition reaction with no net flow of electons. (0; +H,0 +2" —> HO; + OH ra Ho; — 0H +50, The cathode reaction given above is the sum of the above intermedi- Corrosion |147 ate reactions occuring at the cathode. ‘At anode = 2H; +40H” —+4H,0+4e7 2H, +0, —>2H,0 Overall reaction : Fig. 3.12. Hydrogen-oxygen Fuel Cell. Hydrogen enters the pores of the anode and reaches the reaction zone + Where the gas, the liquid electrolyte (£e., aqueous potassium. hydroxide solution) and the solid conducting structure meet. The hydrogen gas dif- fuses to the electrochemically active site (e.g. a surface coatd with a pl num catalyst ) where it is absorbed and dissolved by the electrolite. If is then dissoriated and ionize to 2H". Two protons react with the hydroxye ions of the electrolyte to from water which dilutes the KOH electrolyte. ‘Two electrons are made available to the exter nal circuit. The hydroxyl ions which are thus used-up are replenished from the cathode reaction, in which148 | SBP Q. B. Applied Chemistry 02 reacts with water to produce 20H ions taking up the two electrons from the outer circuit. Ifthe reaction is related to one molecule of oxygen, the process produces a total of four electrons. These facts arere flected in the cell reactions given above. Q. 9. Give the working of alkaline fuel cell. (C-S.V.T.U., Sem. I, May/Sune-2007) Or Write short note on alkaline fuel cell. Ans. ALKALINE FUEL CELLS Itis a type of fuel cell in which 30-45% aqueous solution of KOH is used as electrolyte depending on the system. Alkaline systems generally use high purity hydrogen from electroly- sis plants as fuel and oxygen or air as oxidants. Alkline systems operate well at room temperature. They yield the highest voltage (at comparable current densities) of all fuel cell systems. The cell and electrodes can be built from low cost carbon and plastics. Because of good compatibility with many construction materials, alkaline fuel cells have long operating life. A wide choice of catalysts is available for these cells (e.g. platnum, silver, “gold, meatls oxides etc.) i: vontrast to acidis celis which are iimited to platinum group metal and tungsten carbide. Alkaline fuel cells with circu- lating electrolyte have several advantage such as removal of accumulated impurities, working as a cooling liquid and usefulness as a water removal vehicle, Example : Bacon fuel cell. Bacon Fuel cell system is a developed alkaline fuel system, which consists of porous nickel anodes and lithiated porous nickel oxide cathodes separated by a circulating 30% aqueous KOH solution. Operating temerature was 200 °C. The cell is operated under pressure (upto 5 Mpa) to prevent the electrolyte from boiling . Pure hydrogen and oxgen were used as reactants. ‘Advantages ‘The main advantages of alkaline battery over dry battery are : 1. Zine does not dissolve as readily is a basic medium. 2. The alkaline battery maintains better its yoltage as the current is drawn from 3. The life of alkaline battery is longer than dry cell since there is no corrosion of Zn. KRISHNA COPIERS AR ——————SMRITT NAGI * MO. - 9691859316, 9584601916 Corrosion | 149 Uses : Alkaline fuel cell or battery or system is used in space shuttles, camera, calculators, watches etc, @. 10. Give a brief account of solar celt.? (C.S.V.7.U., Sem. I, May/June-2007) Ans, SOLAR CELL OR BATTERY Solar cell is a device which converts solar energy into electrical en- ergy or electricity. It is also called to be as photovoltic cell. Working Principle : Semiconductors are materials possessing very low electrical conductivity, For example, silicon, galium, and germainium. ‘Thus, semiconductors are neither conductors nor insulator (which does not allow electricity to pass through it). However, it has been found that the conductivity of an semi-conductor materials increases considerably, when a certain impurities are added to them. When pentavalent impurity (say phos- phorus) is added, the semiconductors becomes excess in electron (or N- type); while it becomes excess in holes (or P type) semiconductror, when trivalent (say arsenic) impurtiy is added to it.. Moreover, cOnductivity alos increases, when light falls on a semiconductor. In a solar cell, two types (N. and P-type) of semiconductors are used. Pieces of semiconductor materials of two types (called wafers) are so ar ranged that when light falls on them, then a potential difference {of about 0.5-0.5 V) is produced between them. In an actual practice, a large number of solar cells are joined together in a definite pattern to get solar cell panel, which is capable of providing sufficient electric power to lift water from deepwell or fight a house. or operate radio and TV, etc, Structure of Solar Cell : These are comonly known as “Solar cells”, which were primarily developed for providing power supply for space sat. ellites in 1950 S. A typical solar cell consists of two very thin layers of material. The lower layer has atoms with single electrons in the outer or- bital, which are easily lost. The upper layer has atoms lacking one electron from their outer orbital and hence can readily gain electrons. The kinetic energy of light striking this “Sandwich” dislodges electrons from the lower layer, which are trapped into the upper layer, thus creating an electric po- tential between the two layers. this potential provides the electric current through the rest of the circuit, which connects the upper side through a motor or other electrical device back to the lower side. Thus without any moving parts, solar cells convert light eneregy directly to electrical power, Since there are no moving parts in them, solar cells do not wear out. How- ever, their current life sapan is abnout 20 years because they deteriorate due to exposure to weather.150 | SBP Q. B. Applied Chemistry Uses of solar cells : 1. For producing electricity on artificial satellites, space probes, etc. 2. For providing electricity for street lighting, water pump operations, and running radio, and T.V. sets in remote area. Pon junction Fig. 3.13. Use of Semiconductors as solar cells . 3. For operating electronic / quartz watches, calculators and other small instruments. 4. To provide electric power to light houses, and off-shore oil drillingrig platforms. oo Unit 4 CEMENT, LUBRICANT AND POLYMERS Introduction, types of Portland Cement, methods of ianufacturing (dry and wet process), properties of cement, characterization of constitu tional compounds of cement, IS} specification, Lubricants : Classification of lubricants and mechanisms of lubrication Polymers : Industrial applications of thermoplastic; thermosetting, poly mers, prop crties and applications of the major polymers viz polyethylene, Teflon, PVC, nylon, phenol formaldehyde. Elastomers, Natural Polymers Descriptive Questions on Portland Cement Q. 1. Whatis Pordand Cement ? . (CS.V.LU., Sem. I, Dee. / Jan., 2008-09) Ans, PORTLAND CEMENT. ‘Cement is an important binding material used in the construction of buildings. This cement was first introduced by-J. Aspdin in England. Port: Jand cement is an extremely fine cement obtained by calciting together an intimate and properly propositioned mixture of argillaceous and calcareous raw materials at about 1500°C, without the addition of anything subsequent to calcination, excepting the retarder gypsum. It has adhesive and cohesive properties so as to render it to form a good bond with other materials. It solidify when mixed with water. Portiand cement is the most important and reliable cementing mate- ial, used for constructional works. It was so named because a paste of cement with water on mixing with water on setting hardening resembled in color and hardness to Portland stone, a limestone quarried in Dorset. The ratio of these constituents in cement should be in the following order- SO, 25:4 and C20 19:24 ALO, %SIO, + % AL,O, + % Fe,0, 4 Q. 2. What is portland cement ? Describe the different yypes of portland cements in brief.182 | SBP Q. B. Applied Chemistry ‘Ans, Portland Cement : Refer Q. No. 1 ‘Types of Portland Cements : Depending upon their Portland ce- ments may be of following types- | 1. Ordinary Portland Cement, 2. Low Heat Portland Cement 3. Rapid Hardening Portland Cement, KRISHNA Cop; PIERS _SMRITI_ NAGAR TmAI78 axOrent009 4. Portland Pozzolana Cement.(v). | 5. Quick Setting Portland Cement, 6. Portland Blast Furnace Slag Cement. 7. Sulphate Resisting Portland Cement 1, Ordinary Portland Cement (O.P.C., LS. : 269) It is the most active binding medium. It ha adhesive and cohesive Properties so as to form a good bond with other material. It is used for normal concrete construction works. It solidifies when mixed with water. Ordinary Portland cement is manufactured by burning a mixture of silicious materials (containing silica), argillaceous materials (containing alu- mina) and calcareous materials (containing lime) in a definite proportion and temperature of 1400°C. The clinkers so obtained is cooled and grinded to the required fineness. The product so obtained is called cement. It is the most commonly used cement. 2. Low Heat Portland Cement (1S.: 269) When concrete is poured in ay structure, an appreciable rise in tem- perature occur and a certain amount of heat is generated during setting and hardening of cement. The heat generated in ordinary cement at the end of 3 days may be at the order of 80 calories per gram of cement, while in low heat cement it is 50 calories per gram. Low heat portland cement is used in massive constructions like retain- ing walls, abutments, damsvetc. The strength of this cement is little lower than that of ordinary cement during the first two or three months, but its strength after this period is practically the same as that of ordinary cement. The initial setting time of this cement is about one hour and final setting time is about 10 hours. 3. Rapid Hardening Portland Cement (ILS. :269) It is also known to be as high-early strength cement. It is similar to that of ordinary portland cement except that it is ground fine, posses more tricalcium silicates (up to 56%) and less dicalcium silicates than the ordi- nary portland cement. 4. Portland Pozzolana Cement (LS. :1489) This cement is specially useful in marine and under water construc- tions. Pozzolana is the narie given to volcanic ashes which is chiefly Cement, Lat int and Polymers | 153 siliceous material. Pozzolana cement is prepared by mixing and grinding clinkers and pozzolana together. Pozzolana present is cement reacts with the free lime liberated during hydration of cement and prevents disruption in concrete. The pozzolana constituent shall not be less than 10% and not more than 25% by weight of Portland pozzolana cement. Portland poz- zolana cement produces less heat of hydration and offers greater resis- tance to the atteck of water than ordinary Portland cement. Portland Pozzolana Cement has a greater resistance to chemicals. This cement produces less heat of hydration hence suitable for mass concreting and offer more resistance to attack of sulphate bearing soil than ordinary portend cement. Uses: 1.This cement is used to prepare mass concrete of lean mix and from marine structures. 2. It is also used in sewage works and for laying concrete under water. _ 5. Quick Setting Portland Cement Itisa special cement the setting action of which starts within 5 minutes and final setting is over in 30 minutes after them this cement become hard. It is therefore this cement should be mixed and placed immediately. This ce- ment is used for concrete works under water under water, or for concreting in runnjng-water Quick setting cement is prodiced by reducing gypsum content, adding small percentage of aluminium sulphate content and finely grinding the cement. It results in quick setting properties of the cement. 6. Portland Blast Furnace Slag Cement The waste product of iron manufacture (pig Iron) in blast furnace can bbe economically utilized to manufacture cement by treating the molten slag: ‘As soon as the molten slag comes out from the furnace cold water shower is sprinkled upon it. Due to this treatment slag is converted into crystalline particles known as granulated slag. This granulated slag has hydraulic prop- erty, Portland cement clinker, dry granular slag and small percentage of gyp- sum are mixed while grinding the cement clinker. The composition of slag cement is 65 percent slag and 35 percent clinker. The properties of this being slow rate of hardening and less heat of hydration. This cement'is useful for ‘mass concrete works. Since the cément is not affected by sea water it can bbe used for marine structures and all other places where OPC is preferred. 7. Sulphate Resisting Portland Cement + This cement contain strictly restricted quantity (below%) of tricalcium silicate. The chemical combination of ticalcium aluminate and tetra calcium “ alumino-ferrite renders the resistance ordinary cement to'sulphate attack. This cement is used for structures which are likely to be, damaged by se- ‘vere alkiline conditions, such as canal linings, culverts,154 | SBP Q. B. Applied Chemistry Q. 3. Discus physical requirements of portland cement? Ans. Physical Requirements of Portland Cement ‘The Indian Standards have laid the following physical requirements which are to be determined through various tests- 1. Fineness: The rate of chemical reaction depends upon the fineness of cement. Finer the grading, the greater the rate of reaction. The fineness of cement is measured in term of its specific surface. The fineness of cement should not less than 215 m*/kg. (by blain permeability method) 2, Soundness: Soundness meant he ability of a cement to maintain a constant volume. The cement having some quantity of free lime and magne- sia undergoes large changes in volume as time elapses, tending to cause cracks. 3. Heat of Hydration: When water is mixed with cement hydration, hydrolysis and gelation reaction start and some heat is liberated simultaneously. ‘Thus heat released during hydration of cement is called heat of hydration. Hydration is the chemical reaction between cement compounds and water. A lot of heat.is generated during the process of hydration of cement. (On an average, 500 ki/kg of heat is evolved during complete hydration of cement. If heat hydration is excessive the mass concrete works are likely to develop cracks. It is specified in terms of cal/g of cement after 7 days and 28 days. The order of heat of hydration of the different constitutional compounds should be as per table: 4.1 Table 4.1: The order of heat of hydration of various constituents of cement. [ Constituent ofcement | Tri-calclum Tri-ealcium juminate silicate Heat of bydration (ki/kg)| 880 > 500 => 420. ~~-250 salciure aluminoferrite cate —_ 4, Setting Time: Setting time of setting is the time taken during the ‘operation as well water is added to the cement and when the paste lose its plasticity and attained sufficient strength and hardness. Generally, for the ordinary Portland cement initial setting time should not be less than 30 minutes and final setting time should not be more than 10 hours. It is generally believed that the setting times of C,S, C,S, CA and C,AF are 28 days, 7 days, 1 day and 1 day respectively. 5. Compressive Strength: The quality of cement is judged from compressive strength of cement mortar cubes formed of one part of ée- ment with 3 parts of standard sarid, compacted by means of a vibration ‘machine. It is Specified in terms of 1 day, 3 days and 28 days of strength. (Cement, Lubricant and Polymers | 155 Q 4. What is ordinary portland cement ? Write chemical com- position of ordinary portland cement. ; Or What is ordinary portland cement ? Write role or functions of different ingredients of ordinary portland cement. Ans. ORDINARY PORTLAND CEMENT Refer Q. No. 2. Chemical Composition of Ordinary Portland Cement ‘The raw material used for the manufacture of Ordinary Portland Ce- ‘ment are lime, silica, alumina and iron oxide. The mixture of lime, silica, iron oxide and alumina was given the name portland. These oxides interact with each other and form different compounds. Proportions of these oxide compositions are responsible for influencing the various properties of ce- ment. Table 4.2 : Average compositions of Ordinary Portland cement. 'S.N.[ Component ‘Composition Percent T. | Lime CaO 60-67 2. | Silica SiO, 17-25 3. | Alumina ALO; 3.0-8.0 4, | tron Oxide FeO; 05-60 5. | Magnesia MgO 0.1 ~4.0 6. | Sulphur Trioxide so; 12.75 7. | Soda and Potash Na, KO 02-1 8._| Gypsum Caso, 3-5 Role or Functions of Various Ingredients or Raw materials of Cement ‘The various ingredients in cement have their characteristic fiunc- tions. @. Lime : It provides strength to cement. Excess of lime results in objectionable expansion. Insufficient lime reduces the strength and decreases the setting time. @)). Silica : It provides strength to cement. Excess silica may en- hance the strength but increases the setting time. ii). Alumina :It makes the cement quick setting. It brings dwn the clinking temperature acting as a flux. Excess of this ingredient lowers the strength.156 | SBP Q. B. Applied Chemistry (iv). Iron oxide : This ingredient provides colour, strength and hard- ness to the cement. It react with lime and silica during manufac- ture which reduces the calcination temperature, Its presence also imparts strength to the cement. (¥). Magnesia : When present to a small extent. This ingredient provides hardness and colour. Excess of this ingredient seriously affects the soundness of cement. (vi). Sulphur Trioxide: If it is used in excess (up to 3%), it pro- duces expansion of cement thus making it unsound and also ex- cess of SO; increases the setting” (vii). Alkalies (Soda and Potash): If present in excess, alkalies are disadvantageous as they may cause alkali aggregate reaction, efflorescence and staining of concrete and brick work. Most of alkalies which are present in the raw material are driven away * with the gases during burning, Gypsum : It helps to retard the setting action of cement. It actually enhances the initial setting time of cement. If it is not added the cement will set at the moment water is added to it, without giving any time for mixing and placement. Q. 5. What happened when the following changes are made in the composition of cement ~ 1 Uf percent of lime 3. Uf quantity of silica is more. 5. Uf quantity of alumina is more. ‘Ans. 1. If percent of lime is fess, then it will set quickly but will be weak. * 2. If percent of lime is more, then scratches appear on the surface after it is set. 3. The quantity of silica is more, then hardens slowly. 4, If cement contains iron, then itis white, but sets with difficulty. 5. If quantity of alumina is more, then cement hardens quickly. Q. 6. Explain with reason the role of gypsum in portland ceinent. - (CS.V-T.U., Sem. I, 2005) 4 2. If percent of lime is more. 4. If cement contains iron. s less. Ans. Réle of gypsum in portland cement: Refer Q. No. 4. Q. 7. What is Portland Pozzolana Cement ? Write advantages and disadvantage of Portland Pozolana Cement. ; KRIS! Cement, Lubricant and Polymers | 157 2 2 Aus Advantages of Portland Pozzolana Cement eS 3 1, It attains compressive strength with age. = 2. It can resist action of sulphates. YB 3. Wevolves less heat of hydration during setting, ZS 4. It imparts higher degree of water tightness. = 3 5. It imparts plasticity and workability to mortar and concrete pre a pared from it SE 6. tis cheap. GZ 7 t possess higher tensile strength. g Dis-advantages of Portland Pozzolana Cement $ 1. Compressive strength in early days is lesser. 2. It possesses less resistance to erosion and weathering action. @. &. Give flow chart of manufacturing of portland cement by wet method. (CS.V.T.U., Sem. I, Dec. / Jan., 2008-09) Or Discus with the help of flow chart; the wet method of manufac- ture of cement? Ans. WET PROCESS OF MANUFACTURE OF CEMENT This process involves in the following e steps- L Mixing, a ae 2. Burning and 3. Grinding, 41. Mixing: First of all the raw materials ic., limestone is crushed by rusher to smaller fragments. Then itis taken to ball or tube mill where it is mixed with clay and finely ground. Then water is added to the powder and mixed thoroughly in mill to form a liquid called slurry. The slurry is pumped to slurry tanks, where it is kept in an agitated condition by means of rotat- ing arm or by compressed air from the bottom to prevent settling or lime- stone and clay particles, mixed thoroughly in mill to form a liquid called slurry. The slurry is pumped to slurry tanks, where it is kept in an agitated condition by means of rotating arm or by compressed air from the bottom to prevent settling or limestone and clay particles. 2. Burning: The slurry is then sprayed to the upper end of a rotary kiln against heavy hanging chains. The slurry on being sprayed against a hot surface of flexible chain, losses moisture and becomes flakes. These flakes are dropped to the lower end of kiln, where, it subjected to tempera- ture of 1500-1650° C. Chemical reactions fakes place and 20 to 30% mate- rials get fused. Lime, sitica and alumina get recombined. The fused mass {ums jn to nodular form called as einker. The clinker drops ito rotary cooler where it is cooled under controlled tonditions.158 | SBP Q. B. Applied Chemistry Calcareous material : Limestone Argillaceous material : Clay i I Primary crushing by enahers ] [ Washing? by wash mill Ball mill : by wet grinding Raw slurry Clinkers linkers grinding: Adsing gypsum] Weighing and packaging Fig. 4.1. Flow chart to describe the manufacture of cement by wet process. (Reactions in Rotary Kiln ‘ ‘The rotary kiln has three different temperature zones. These three dif- ferent temperature zones and reactions tacking place in these zones are as follows- (@. Drying Zone : It is the upper part of the kiln where temperature is about 400°C. Most of the water is driven out of the slurry in this zone, because of the hot gases. Gi). Preheating Zone : It is the upper part of the kiln having a tem- perature of about 400-700°C. Decomposition of clay and magnesium car- bonatg takes place in this zone. 4 i). Calciting or Decarbonating Zone : It is the lower central part of the kiln where temperature ranges between 7000 to 1000°C. Here lime- ‘Cement, Lubricant and Polymers | 159 stone decomposed to form CaO and CO,. CaCO, —= Ca0 + CO, t Limestone Quick lime (iv). Caleiting or Decarbonating Zone : It is the lowermost hottest zone of the kiln where temperature ranges between 1350 to 1500°C. Here lime and clay react with each other forming aluminates and silicates. 2Ca0+Si0, — 2Ca0. SiO, Dicalcium silicate (C,S) 3Ca0+Si0, —, 3Ca0. SiO, Tricaleium silicate (C,$) 3Ca0+A1,0, —» — 3Ca0.Al,0, : Tricaleium aluminate (C,A) 4Ca0 +AI,0,+Fe,O,—» — 4Ca0. Al,0,, Fe, 0, ‘Tetracalcium aluminoferrte (C,AF) ‘These compounds then combine together to form small, hard, greyish pellateS called clinkers. These clinkets are very hot (100°C). 3. Cooling of Clinkers : The base of the rotary kiln is provided with another small rotary kiln. In this kiln hot clinkers fall and cooled with the help of cooled atmospheric air flowing from opposite direction. Air counter- blast. cooled the clinkers. The hot air so produced is used for drying the coal before pulverization. 4. Grinding : The cooled clinker is then ground in a ball mill with the addition of 2 to 3% of gypsum. In the ball mill particles are crushed to fine powder. The finer the cement, the greater the strength of the concrete made from it. 5. Storage and Packing : The cement coming out of the grinding mills is stored in storage silos frpm which it is fed into automatic packing machine which fills into bags. . Q. 9. Discus with the help of flow chart, the dry method of manu- facture of cement? Ans. DRY PROCESS OF CEMENT MANUFACTURE ‘This is an outdated process of cement manufacture. It is a process of manufacturing cement in which mixing and grinding of materials done in dry conditions. The raw materials (limestone and clay) are ai- dried and are crushed in gyratory crushers into pieces of nearly 25 mm size. Now these are ground to fine powder fn ball mills or tube mills. Each separate powdered ingredients are stored in separate hopper. The powdered materi- als are now mixed in required proportion to get dry raw mix, which is160 | SBP Q. B. Applied Chemistry stored in silos (storage bins). From the storage tank the raw materials are passed on to the granulator consisting a rotating drum. Water is then sprinkled to get a thick paste of which cakes are made. These are dried and burnt in a rotary kiln to obtain clinkers. The clinker drops into rotary cooler where it is cooled under controlled conditions. The cooled clinker is then ground in a ball mill with the addition of 2 to 3% of gypsum. In the ball mill articles are crushed to fine powder and filled into bags. Caleareous material: ‘Argillaccous material: Clay (Crushing by crushers _] ‘Mixing in correct proportion Storage of raw mix KRISHNA COPIERS Rotary kiln ]¢<———— Adding Coal dust [Cinkers formation Clinkers grinding |< Adding gypsum Storage in silos ‘ I ‘ Weighing and packaging Fig. 42. Flow chart for manufacture of cement by dry process. SMRITI NAGAR MO. - 9691859316, 9584001916 Cement, Lubricant and Polymers | 161 Q. 9. Write difference between dry and wet process of cement manu- facture. Ans. SN. Dry Process T._ | This process is adopted when the raw materials are quite hard] 2. | Cement produced is of inferior Difference Between Dry and Wet Process | Wet Process This process can be used for any type of raw materials. Cement produced is of superior quality. quality. 3. | This process is slow. This process is comparatively faster. 4. | Cost of cement production is | Cost of cement production is less. somewhat higher. 5. | Quality of cement is inferior. | Quality of cement is superior. Q. 10. What are the microscopic constituents of Bortland Cement? How they are formed and discuss their contribution towards the proper ties of the cement ? (C.S.V.TU., Sem. I, Nov.-Dec., 2007) Or What are the characteristics of constitutional compounds ? (CS.V-EU., Sem. 1, May-June, 2007 ) Or Name the main three constituents of Portland cement responsible for imparting strength, mentioning also their order and days required, (CS.V.LU,, Sem. 1, Dee. / Jan., 2008-09) 5 MICROSCOPIC CONSTITUENTS OF PORTLAND CEMENT ‘The constitutional compounds of cements are called microscopic con- stituents. Formation of Microscopic Constituents of Portland Cement The formation of microscopic constituents of the Portland cement takes place by the process of buming of the slurry of the raw materials in rotary kiln. The slurry is then sprayed to the upper end of a rotary kiln against heavy hanging chains. The slurry on being sprayed against a hot ‘Surface of flexible chain, losses moisture and becomes flakes. These flakes are dropped to the lower end of kiln, where, it subjected to temperature of 1500-1650° C. This zone of kiln is known as burning and clinkering zone. Here chemical reactions takes place and lime, silica and alumina get fused with each other forming afuminates and sili Al162 | SBP Q. B. Applied Chemistry 2Ca0+Si0, —, 2Ca0. SiO, Dicalcium silicate (C,S) 3C20+Si0, — 3Ca0. SiO, Tricalcium silicate (C,S) + 3Ca0+AL,0, —+ 3Ca0.Al,0, ‘Tricaleium aluminate (CA) 4Ca0. Al,O,. Fe, 0, ‘etracalcium alumino ferrite (C,AF) ‘These compounds then combine together to form small, hard, greyish pellates called clinkers. Contribution of Microscopic Constituents towards the Properties of the Cement Or Characteristics of Constitutional Compounds in Cement The properties of cement depend upci the relative proportions of thé constitutional compounds present and each of them has different charac- teristic properties. 1. Dicalcium Silicate (C,S) : Its early strength is quite low but develops ultimate strengti almost of the same order as (CS). Ht hydrate very slowly. Its rate of hydration is 37.5%. Its heat of hydration is the lowest among all the constitutional compounds of cement and is about 60 cal/gm (251 K1/kg). 2. Tricalcium Silicate (C;S) : It develop very high strength quite carly and the ultimate strength is also the highest. Its rate of hydration is ‘medium (73.5%). Its heat of hydration is about 120 cal/gm (502 KJ/kg). 3. Tetracalcium Silicate (C,S) : It does not contribute much to the strength of cement because both its early and the ditimate strength are poor and lowest among the constitutional compound. Its rate of hydration is slow (57%). Its heat of hydration is about 100 cal/gm (418.4K J/kg). 4. Tricalcium Aluminate (C,A) : Its early strength is good but ulti- mate strength is quite low. It undergoes hydration at a very fast rate. It is responsible for the initial set or flesh set. Its rate of hydration is 82.5 %. Its heat of hydration is about 210 cal/gm (879 KJ/kg) which is the highest amongst all the constitutional compounds. @. 11. Give average compound composition of portland cement along with setting time. Give characteristics of important constituents. (CS.V.T.U., Sem. I, 2005) 4Ca0 + Al,0, + Fe,0, —» (Cement, Lubricant and Polymers | 163 Ans. Average Composition of Portland Cement ‘The average compound composition of portland cement and set- ting time is as per table 4.2. Table 4.3 : Average Composition of Portland Cement and Set- Time of each compound. ting Characteristics of Important Constituents : Refer Q.No. 8. Q. 12, What are the additives of Cement ? (CS.V.T.U., Sem. 1, May-June, 2007) Ans. ADDITIVES OF CEMENT ‘Any matefial entering or added into concrete other than cement, * ‘water and aggregate is called additive or admixture. Additives or admixtures may be of following types- 1. Accelerators. 2. Retarders. 3. Water repelling agents. 4, Workability agents. 5. Gas forming materials. 6. Natural cementing materials. 7. Pozzolanic material. 1. Accelerators : The materials which are added to the concrete to increase the éarly strength development are called accelerators. E.g.. Common salt, CaCl, , some soluble carbonates, silicates, fluosilicates and some organic compounds such as triethonol amine. 4164 | SBP Q. B. Applied Chemistry 2. Retarders : These substances are used to offset the accelerating effect of temperature from hot weather concreting or hot water flows in grout- ing, to prevent the premature stiffening of some cements, or to actually delay the stiffening under difficult placing conditions. Eg. Admixtures of very small quantities of carbohydrate derivatives and calcium ligno- sulfonate. 3. Water repelling agents : These substances are used to repel wa- ter. Eg. Soaps are other fatty compounds such as calcium stearates or oleates, ammonium stearates or oleates, sodium stearates or ole- ates and petroleum oils or waxes. 4. Workability agents : These substances are employed to offset de- ficiencies in grading that tend to produce harshness or segregation and jeopardize successful placement under in accessible difficult con- ditions. Eg. Bentonite clay, diatomaceous earth, fly ash, clay, finely divided silica, hydrated lime, pulverized stone etc. 5. Gas forming materiiils : Eg. Aluminium powder . If reacts with the hydrating hydroxide in concrete to permeate the mass with minute hydrogen bubbles. 6. Natural cementing materials : These materials are used to increase ~_ workability, decrease the bleeding and segregs: of hydration and usually decrease the strength when used in larger quantity. Eg. Hydraulic lime, water-quenched blast furnace slag and lime, 7. Pozzolanic material : Pozzolana is the name given to volcanic ashes which is chiefly siliceous material. It combine with hydrated lime and water to form stable compound of cementitious value. They usually used up to 10 to 35% of the cement to lower the heat of hydration and to still greater resistance to sea water or natural acid water. Q. 13. Discuss setting and hardening of Cement. (CS.V-T.0., Sem. I, May-June, 2007 ) Ans. SETTING AND HARDENING OF CEMENT When cement is mixed with water, it forms a plastic mass called cement paste . In this process hydration reaction start, resulting in the formation of gel and crystalline products. Finally the interlocking of the crystals bind the inert particles of the aggregates into a compact rock like material. The process of solidification of cement comprises of two pro- KRISHNA COPIERS. ‘Cement, Lubricant and Polymers | 16! 1. Setting and 2. Hardening. Setting is defined as stifling of the original plastic mass due to initia gel formation. Hardiness is the development of strength due to crystalliza tion. After setting, hardiness is starts because of the gradual progress 0 crystallization in the interior of the mass. The strength developed by ce ment paste at any time, depends upon the amount of gel formed and th. extent of crystallization. It is generally believed that the setting times o GS, C,S, C,A and C,AF are 28 days, 7 days, I day and I day respectively "When cement is mixed with water, the paste becomes quite rigid withir a short time which is known as initial set or flash set. This is due hydra tion of tricalcium aluminate (C,A) and tetracalcium aluminoferrite (C,AF) a: follows- 3.CaO. AIO, + 6H,O > 3CaO. Al,O,, 6H,0 + 880 ki/kg, (A) Hydrated C,A Crystals 4Ca0 . Al, O,. Fe,0,+7H,O > 3 Ca0. Al, O,. 64,0 ‘Tricaleium aluminate (Crystalline) +CaO.Fe,O,H,0 + 420 ki/kg CF. H,0 Gel) At the same time, dicalcium silicate starts hydrolyzing to tobermonite gel. This gel have a very high surface area and hence, very high adhesive property. It also contributes to initial setting. 2[2Ca0.SiO,) + 7H,0 — 3Ca0.2Si0,.6H,0 + Ca(OH), + 250 ki/kg, ‘Tetracalcium aluminoferrite (C,AF) cs Tobermonite gel Calcium hydroxide Crystalline, Unhydrated Cement 2 = + Hydration «3 ns 33 aol is Metastable Gel ‘Crystalline Hydration Products zg J L es Stable Gel ‘Crystalline Products 25 °s Fig. 43, Setting and hardening of cement ¢166 | SBP Q. B. Applied Chemistry Final setting and hardening of cement -paste is due to the formation of tobermonite gel and crystallization of calcium hydroxide and hydrated tricalcium aluminate. 2[2Ca0.SiO,] + 6H,0 __,3Ca0.2Si0,.3H,0 + 3Ca(OH), + 500 kik cs Tobermonite gel Calcium hydroxide (Crystalline) Q. 14. Write short note on ISI specification of cement. (CS.V.T.U., Sem. I, 2005, 2006-07, Dec. / Jan., 2008-09) Ans. LS. SPECIFICATION OF CEMENT According to I. S. 269-1975, the composition of Ordinary Portland ‘cement shall satisfy the following conditions- 1. The ratio of the percentage of lime (CaO) to that of silica (SiO;), alumina (Al,0,) and iron oxide (Fe:O;) shall not be less than 0.66 and more than 1.02. A Ca0-0.7 SO, 2.8 SiO, + 1.2 Al,O, + 0.65 Fe,0, 2. The ratio of percentage of alumina to that of iron oxide shall not be less than 0.66. 3. The weight of magnesia shali-not be more than 6%. 4, Weight of insoluble residue shall not be more than 2%. 5. Total sulphur contents, calculated as sulphuric anhydride, shall not be more than 2.75%. 6. Total loss on ignition shall not exceed 4%. 7. Fineness should not exceed more than 10% after the sieving residue (*by weight) on B. S. 17 fineness test sieve. 8. The initial setting time should be 30 minutes and final setting time should be 10 hours. DESCRIPTIVE QUESTIONS ON LUBRICANTS Q. 1. What do you understand by the term lubricant and lubrication ? Why is lubricant needed ? Ans. LUBRICANTS Any substance, introduced, between two moving/ sliding surfaces to reduce the frictional resistance between them, is known as ‘lubricant’ The Process of reducing frictional resistance between moving or sliding surfaces =0.66 to 1.02 3 ‘Cement, Lubricant and Polymers | 167 by introduction of lubricants in between them is called ‘lubrication’. ‘Need of Lubricant : When two surfaces of moving, sliding or rolling parts of a machine rub against each other it may causes friction, wear and tear and generate a fot of heat Due to mutual rubbing of one part against another, a resistance is offered to their movement. This resistance is known as ‘friction’. Friction uses a lot of wear and tear of surfaces of moving parts and generate heat, there by causing loss in the efficiency of machine. The in- crease in the temperature may even leads to melting of surfaces and finally formation of welded junctions. So, to avoid friction, wear and tear , melting and seizure of the surfaces, a lubricant is introduced between them. Lubri- cant reduces frictional resistance between surfaces thereby minimizing the destruction of sliding material. Q. 2. What are lubricants ? Give their advantages. (CS.V.T.U,, Sem. I, Dec. / Jan., 2008-09) s Or s What are the functions of a lubricant? (CS.V-T.U., Sem. I, 2005) Ans. Lubricant : For definition refer Q. No. 1. Advantages or Functions of a lubricant ss, 1. Lubricant reduces friction between two surfaces. 2. It reduces surface deformation, wear and tear because the direct contact between the rubbing surface is avoided. 3. It avoids seizure (i.e. welding of two surfaces due to heat) since the use of lubricant minimizes the liberation of heat. 4. It reduces waste of energy so that efficiency of machine is en- hagced. . 5. It reduce the loss of energy equal. 6. It reduces the maintenance and running cost of the machine. 7. It acts as a coolant 8. It keeps out the dirt. 9. Sometimes it acts as a seal (to avoid the leakage of gases, etc.). 10. It also acts as rusting inhibitor as it prevents the metal surface from corrosion. 11. Heat transfer media, as it prevents metal surface from surface-to- surface contact and the heat generated is transferred to the lubricant. _@. 3. Define lubricants. How are lubricants classified ? Mention their important functions.168 | SBP Q. B. Applied Chemistry Cement, Lubricant and Polymers | 169 © Ans. Lubricant : For definition refer Q. No. 1 QB and heavy loads) Classification of Lubricants On the basis of their physical states gr $ Note : Animal and vegetable oils have very limited uses at present be- lubricants are classified into three categories- a with petroleum: vis. They are Water fi use at low temperatures (up to 15°C) only. 4, Soda based greases : These greases are prepared by mixing so- dium soaps with petroleum oils. They are suitable for use in ball bearing: where the lubricant gets heated due to friction. Q.6. What are lubricants ? Describe the mechanism of lubrication in brief. One What do you understand by the term Lubrication? Explain the mechanism of fluid film lubrication with suitable example and diagram. (C.S.V-T.U., Sem. I, Nov-Dec., 2007) Or What is Hydrodynamic lubrication? (CS.V-1U., Sem. I, May-June, 2007) ‘Ans. Lubricant : For definition refer Q. No. 1. MECHANISM OF LUBRICATION ‘The process of reducing frictional resistance between moving or slidin; surfaces by introduction of lubricants in between them is called ‘lubrication’. Tre lubrication of moving or sliding surfaces can be done by following three methods-174 | SBP Q. B. Applied Chemistry 1. Fluid film or thick film or hydrodynamic lubrication 2. Boundary or thin film lubrication. 3. Extreme pressure lubrication. FLUID FILM OR THICK FILM LUBRICATION OR HYDRODYNAMIC LUBRICATION ‘The mechanism of lubrication in which the moving/sliding surfeces are separated from each other by a thick film of lubricant (at least 1000 A thick) is called fluid film or thick film or hydrodynamic lubrication. The thick film of lubricant covers/fills the irregularities of surfaces sliding over each other so that they do not interlock together, and a thick film or layer of lubricating fluid separates these two surfaces so that sur- face-to-surface contact can be prevented. The friction occurs between the layers of lubricating fluid which is considerable low. This condition is known as fluid-film lubrication. It is also known as hydrodynamic lubrication because the hydrodynamic pres- sure keep the moving surfaces apart under such conditions. Fig. 4.5. Fluid film or thick film or hydrodynamic lubrication The internal distance between the particles of the lubricant cause small friction. Therefore the lubricant chosen should have the minimum viscosity under working conditions and at the same time it should remain in place and Separate the surfaces. In such a system, friction depends on the thickness and viscosity of the lubricant and the relative velocity and area of moving/ sliding surfaces. The coefficient of friction- ( __ Force required to cause motion (F) S 5 as low as 0.001 100 (- SEARS panei neonates Light machines like sewing machines, watches, clocks, delicate and scientific instruments are provided with fluid film lubrication. Examples of ubricants for fluid film lubrication are hydrocarbon ojjs. Hydrocarbon oils, ‘Cement, Lubricant and Polymers | 175 are blended with selected long chain polymers in order to maintain viscosity of oil constant in all seasons of the year. Bearing lining Fotating stat in floating lubricant Thick fm of lubricant Fig. 4.5. A bearing showing Hydrodynamic lubrication ‘Sometimes fractions from petroleum refining are used for such lut cation but they generally contain unsaturated hydrocarbon in small quantity which oxidized under operating conditions forming gummy products. In such cases antioxidants like aminophenol is blended with hydrocarbon oil. 2. Boundary or thin film Inbrication : Refer Q. No.7. ~ 3. Extreme pressure lubrication : Refer Q. No. 8. . Q. 7 Describe the mechanism of thin film lubrication. (CS.V.L.U., Sem. I, Dec. / Jan., 2008-09) Or Wit do you understand iy the term Zubrication? Explain ‘the mechanism of boundary or thin film lubrication with suitable example and diagram. Ans. Lubrication : The process of reducing frictional resistance be- tween moving or sliding surfaces by introduction of lubricants in between them is called ‘lubrication’ The lubrication of rpoving or stiding surfaces can be done by follow- ing three methods- 1. Fluid film or thick film or hydrodynamic lubrication 2. Boundary or thin film lubrication. 3. Extreme pressure lubrication. BOUNDARY OR THIN FILM LUBRICATION This type of lubrication is applied when a antinoise film of lubrication ‘can not be maintained and direct metal-to-metal surface contact is possible due to certain reasons. This takes place when- @ A shaft moving from rest or Gil) The speed is very'low or (ii) The load is very high and176 | SBP Q. B. Applied Chemistry Giv) Viscosity of the lubricant is too low. | In such conditions, the moving surfaces can be lubricated with proper lubricant, a thin layer of which is adsorbed by physical or chemical forces or both on the metal surfaces. The load is carried by layers of lubricant which have been adsorbed on the metal surface forming a thin film of lubricant. This kind of lubrication is known as boundary or thin film lubrication Vegetable and animal oils (glycerides of higher fatty acids) possess Property of adsorption (or surface attachment). Fatty acids have polar car- bonyl group (COOH) at one end. Such carboxyl group react with the metal surface with formation of monomolecular layer strongly adherent to the surface where as long hydrocarbon chain (R-) is oriented outwards in a Perpendicular direction. The adsorbed molecules form a continuous film on the metal surface. : * KRISHNA COPIERS SMRITI NAGAR °40. - 9691859316, 95846019} ‘Adsorbed ihm layer pero (vegetable or animal oil) Fig. 4.7. Boundary or thin film lubricgtion Under the conditions of very high loads and temperature, the solid lubricants such as Graphite and MoS, (Molybdenum disulphide) are used for boundary lubrication. For boundary lubrication, the lubricant molecules should have 1. Long hydrocarbon chain 2. Lateral attraction between the chains 3. Polar groups to promote wetting or spreading over the surface. 4. Active functional groups which can form chemical bends with the metals or other surfaces. ‘ 5. High viscosity index 6. Resistance to heat and oxidation. 7, Good oiliness. ; 8, Low pour and oxidation. ; Cement, Lubricant and Polymers | 177 Q. 8 What is extreme pressure lubrication and what are its addi- (CS.V-T.U., Sem. I, Nov.-Dec. 2006) Or Explain Extreme Pressure Lubrication (CS.V-T.U., Sem. I, May-June, 2007) Write a short note on Mechanism of extreme pressure lubrication. (CS.V-T.U., Sem. I, Dec. / Jan., 2008-09) Ans. EXTREME PRESSURE LUBRICATION When the moving surfaces are under high pressure and speed, exces- sive frictional heat is generated, and under such conditions, the liquid lubri- cant fail to stick and may decompose and even vaporize. For effective lubrication under these extreme pressure and high tem- peratures, special additives called “extreme pressure additive are added to liquid lubricants. This additives from more durable films on metal surfaces, capable of with standing very high loads and high temperatures. Important additives are organic compounds having active radicals or groups such as chlorine (as in chlorinated esters), sulphur (as m sulphurized oils) or phosphorus (as in tricresyl phosphate). These compounds react with metallic surfaces at high temperatures to form metallic chlorides, sulphides or phos- phi metallic compuunds pusiess high niéitiug pOints and serve u 200d lubricant under extreme pressure and extreme temperature condition. DESCRIPTIVE QUESTIONS ON POLYM Q.1. Define the following- (@. Polymers (b). Homopolymers - (c). Co-polymers. ‘Ans. (a). Polymers : The term polymer is derived from two Greek words poly = many and mers = unit or parts. Thus a polymer means, many units joined whether by a chemical reaction. In other words polymer is a high molecular mass or giant molecule formed by linking together of large number of small molecules. The pro- cess of the formation of polymers is called polymerization. Example: Polyethylene. Its firmed by linking together a large number ‘of small units of ethane monomer (C:H.) nCHa= CH —fermsimion_, (—CH2—CH2 ~ Jn Ethykene (monomer) Polythene (Polymer) (b). Homopolymers : Polymers which are by linking together two or more identical units of mohomer are called homopolymers. tives.178 | SBP Q. B. Applied Chemistry M-~M-M-M-M-M Example : Polythene, PVC ete. (©. Co-polymers : Polymers which are by linking to gather two or ‘more different units of monomers are called co-polymers and the process is called co-polymerization.. M,~M,—-M, — M, ~M, ~M —s-= Example : Terylene. It is a co-polymer of monomer ethylene glycol and tetra-pthalic acid. 2.2, What are polymers ? Write classification of polymers . Ans. Polymers : Refer Q. No. | Classification of Polymers Depending upon the inter molecular forces the polymer are classified into following four categories. 1. Thermoplastics polymers ~ 3. Elastomers = 1. Thermoplastics Polymers ‘The polymers which can be easily softened repeatedly when heated and hardened on cooling with little change in properties are called thermo- plastics. Their hardness is a temporary property, subject to change with rise or fall of température. Thus can be processed again and again. Since thermoplastics have low melting points and can be repeatedly moulded and remolded to the desired shapes, they have resale value. ‘Thermoplastic have either linear or branched structures. Polymeric chains are held together by weak bander walls force or dipole-dipole forces or hydrogen bonding. There are no cross-links. Examples : Polythene (PE), Poly propylene (PP), Polyvenyle chlo- ride (PVC), Polystyrene (PS), Nylon, Teflon or Polytetrafluoro ethylene (PTFE). These materials are fabricated normally by the simultaneous appli- cation of heat and pressure. 2, Thermosetting Polymers or Thermosets ‘These are the polymers which undergo permanent change on heating. When heated they get highly cross linked to form hard infusible and in- soluble products. Because of such cross-link thermosetting, plastics is per- manently rigid. Such polymers during moulding acquire three dimensional ‘cross-linked structure, with permanently strong covalent bonds. Thus these polymers once moulded cannot be reprocessed. Thermoplastics are more chemically inert. Their molecular weight is very high. Examples : Polyester (Terylene), bakelite, melamine, phenol formal- 2. Thermosetting polymers 4, Fibers * (Cement, Lubricant and Polymers | 179 | dehyde etc. 3. Elastomers or Synthetic Rubber ‘These are rubber like elastic polymers, which can be stretched at least thrice of its length and it have a tendency to recover their original shape and dimensions as soon as stretching force is released. This is due to the ab- sence of highly polar groups or site for hydrogen bonding, Moreover, ex- tended chain do not fit together well enough for vander waals forces to do the job. Hence, molecules in elastomers have weak inter molecular 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 pre- vent the slipping of molecular part, but at the same time, these occasional ‘cross-links do not deprive the chains of their flexibility. Examples : Natural rubber (cis - 1.4 poly isoprene), nylon 6 : 6, dacron, silk etc. 4, Fibres Fibfés are those polymers whose chains are held together by stfong intermolecular forces like hydrogen bonding. They are crystalline in nature. Due to strong intermolecular forces they have high tensile strength. Examples : Nylon, polyester etc. 3. Give differéices setzen ihermoseiting thermwplastic resins. (CS.V.7.U,, Sem. I, 2005, 2006-07) Or Compare between thermoplastics and thermosetting polymers. (CS.V.TU., Sem. I, Nov-Dec. 2006) Or Give differences between thermosetting and thermoplastic polymers (at least giving four points). (C.S.V.T.U., Sem. I, Dec. / Jan., 4008-09) ‘Aus. Difference Between Thermoplastics and ‘Thermosetting Polymers Thermosets ‘They are formed by condensat ion polymerization reactions. ‘Thermoplastics 1. They are formed either by condensation polymerization reactions. 2. They have either linear or br- anched structures. 3. Adjacent polymer chains are held together by either ban ‘They have three dimensfonal, cross linked network structures} Adjacent polymer chains are h. eld together by strong covalent]80 | SBP Q. B. Applied Chemistry ‘Bonds called cross-links. der waals forces, or by dip- ole forces or by H-bonds. 4, They soften on heating and stiffen on cooling 5. Low molecular weight the- rmoplastics are soluble inany solvent. 6. They can be remoulded, re- shaped and re-used. 7. They can be reclaimed from waste, ive., they can be rec- yeled. 8, During moulding of thermo- plastics, thefe is no change in their chemical composition. They do not soften on heating. ‘They are generally insoluble in “their suitable solvents. ‘They can't be re-moulded and hence cannot be recycled. ‘They cannot be re-claimed fr- om waste. They cannot be rec: yoled. ‘They undergo chemical changes such as further polymerisation and cross-linking during mouldi- ng process. ‘They are brittle materials. Exampies : PF, UR, MF, Epoxy! + XLPE ete. 9. They are tough materials. 10. Examples :PR,.PP. PVG, PMMA, PS, PTEE, Nylons, Polyestersetc. Q. 4. What are polyethylenes ? Write their properties und applica~ Ans. POLYETHYLENE OR POLYTHENE Polyethylene or polythene is d versatile thermoplastic made from eth- ‘Tene gas. It is prepared by the process at addition polymerization of ethyl- ine CH, ~ CH, During polymerization, the ethylene molecules are activated ry the breaking of the coordinate double bonds. Under suitable conditions, hese activated molecules join together to form a very long chain polymeric tydrocarbon molecule. n(CH.=CH,) ——3 n(-CH,—cH,-) —Povmenzation_y (_cH,-CH, ~), Ethane (monomer) Polythene (Polymer) ‘Types of Polyethylenes : On'the basis of their density, polythenes vTe of two types- 1. Low density polyethylene and 2. High density polyethylene. Cement, Lubricant and Polymers | 181 1. Low Density Polyethylene (LDPE) ‘These polyethylenes are prepared by polymerizing ethylene at high pressures of 1000 to 5000 atmospheres and at 250°C in the presence of free radical initiator (O,) nCH,=CH, S228", _(_CH,-CH, asec Low - density Polyethylene transfer reac- Ethene Properties : {© 1. During the propagation steps, large number of chi © tions results in the formation of branched structures. These branches a & —_aremainly short chain and occasionally long chain. These branches ZZ __donotallow the molecules to pack efficiently and hence its density ie 3 is low. Its density is about (0.91 —0.925 gm/cm?). ZS 2. Due to the same reasons, crystallinity of LDPE is also low (-55%) E&{ 3. As itis non-polar polymer so there are no strong intermolecular @ Y _ forces. Moreover, the back bone is flexible. Both these factors are 28 responsible for low softening temperature of LDPE, which is only 8 15°C, ‘4, LDPE is chemically inert and has good chemical resistance. <5. Asitis non-polar, hence i has excellent electrice! insulation proper= ties. 6. It is tough and flexible even at low temperatures. Applications. DPE is used in following applications i. The films of LDPE are used tor general packaging and carvier begs. 2. It is used to squeeze bottles particularly for detergents. 3. It is used in the manufacture of moulded toys. 4, It is used in the preparation of ink tubes for pens. 5. It is used in the manufacture of mugs. 2. High Density Polyethylene (HDPE) HDPE can be made by following two methods : 1. Using Zeigler-Natta Catalyst, ethylene is polymerized under 6-7 at- mospheric pressure at 60-70 °C temperature in the presence of [Tici, + AUCH), as catalyst] 2. Using supported metal oxide catalyst, like CrO, supported on gilica salumina, ethylene is polymerized at 35 atmospheric pressure and a ‘temperature of 60-200°C. Properties .;The HDPE molecules are linear and their packing is easy. Hence HDPE has high density (0.95 - 0.97 g / cm*) and more percentage182 | SBP Q. B. Applied Chemistry crystallinity (80 - 90%). 2. Softening temperature of HDPE (135°C) is also higher, compared to LDPE. 3. HDPE has excellent chemical resistance. 4. Ithas excellent electrical insulation properties. 5. Because of lower number of amorphous zones, HDPE has suffi- ciently low water and gas permeability. 6. Itis free from odour and toxicity. 7. It is more stiff, hard and possesses greater tensile strength com- pared to LDPEI. Applications 1. Because of crisp feel and grease proof nature, HDPE film is used as wrapping material instead of paper for food products. 2, Because of better oxidation and UV-resistance, HDPE is used for the manufacture of crates, food tubs, industrial containers and over- head tanks. * * 3. It can also be used for domestic water and gas piping. 4. Bottles for milk, household chemicals and drug packaging are also made from it. Q. 5. What is teflon ? Write their properties and applications. Ans. TEFLON OR POLYTERAFLUOROETHYLENE (PTFE) Teflon is a thermoplastic which is prepared by the polymerisation of tetrafluoro ethylene under pressure in the presence of benzoyl peroxide as catalyst. n(CF:= CF:) —Polymerization_. _(_ CP, — CF; -) ‘Tetrafluoro ethylene PTFE (Teflon) Properties : Teflon has twisted zigzag structure with fluorine atoms packing tightly in a spiral around the carbon-carbon skeleton. Due to the Presence of highly electronegative fluorine atoms, there are very strong attractive fores between different chains. These strong attractive are re- sponsible for its 1. High density (2.1 to 2.3 gm / cm*). 2. Chemical inertness over a wide temperature range ; 3. Excellent electrical insulation properties ; 4. Non-adhesive characteristics ; 5. Very low coefficient of friction and 6. Excellent toughness and heat resistance. As it is dense, chemically inert and high temperature softening so teflon behaves somewiiat like a thermosetting polymer. ‘Cement, Lubricant and Polymers | 183 Applications 1. PTFE (Teflon) is used for insulation of wire and cables. 2. Teflon is used in the manufacture of laminates for printed circuitry. 3. Teflon is used in the coatings of frying pans. Teflon is not wetted by oil or water so its coating imparts non-stick properties. 4. Teflon is used in non-tubricating bearings. 5. Teflon is used in the production of a variety of seals, gaskets, packings valve and punip parts and stopcocks for burettes. 6. Teflon is used in the insulators for motors, generators, coil trans- formers and capacitors. Q. 6. Write a short note on Poly-Vinyl Chloride. (CS.V.TLU,, Sem. 1, Sem. I, 2005, 2006-07, Dec. / Jan., 2008-09) Or Write the preparation, properties and uses of PVC. (CS.V.L.U., Sem. I, Nov.-Dec., 2007) Ans. “POLYVINYL CHLORIDE (PVC) PVCis a type of thermoplastic which is prepared from the mono- mer, veny! chloride by the process of addition polymerization (= polymer- ization reaction in which the polymer is formed by the condensation of two or morg monomers ). The venyi-chloride is 4 ons, CH=CH + HCl ~~» CH,~ CH —> (~CH,-CH-). ‘Acetylene Vinyl chloride Polyvenyle chloride (PVC) ‘Types of PVC : PVC are of two types- rigid PVC and plasticized PVC. ' 1. Rigid PVC Rigid PVC is prepared by polymerization of venyle chloride by heating its water emulsion in the presence of a small quantity of benzoyl peroxide ‘or H:O; in an autoclave under pressure. Properties : Rigid PVC has the following properties : 1. Presence of chlorine atoms on the altemate carbon atoms of PVC causes 1an increase in the interchange attraction. This increases the hardiness and stiffhess of polymer. Its softening point is also high (148°C). 2. The C-CI dipole makes PVC a polymeric polar molecule, but be- cause of the immobility of the dipole at room temperature (since Tg (PVC) = +80°C), power factor of PVC is comparatively low. 3. Itis colourless, odorless and non-inflammable.184 | SBP Q. B. Applied Chemistry 4, Ithas superior chemical resistance but is soluble in ethyl chloride and tetrahydrofuran. 5. It has excellent oil resistance and resistance to weathering. Applications of rigid PVC 1. Rigid PVC is used in acid recovery plants and in plants for handling hydrocarbons many of which adversely affect the polyolefins. This is due to its very good resistance to chemicals. 2. Rigid PVC has great potential importance to building industry since ithhas excellent resistance to weathering. When considered regard- ing initial cost, installation and maintenance cost ; it is found to be very economical. Hence, it is used for making pipes for drainage and guttering. Moreover, itis also replacing wood for making win- dow frames that neither corrode nor rot. . Rigid PVC is also used for making bottles (@ for consumable liquids (like Edible oils, fruit squashes, table wine and vinegar). Gi) for liquids of household use (like bislery mineral water, cos metics and detergents). . Plasticized PVC by adding piasticizers such as DOP dibutyl phthalate, tricresy! phosphate etc. to rigid PVC. Properties and applications of plasticized PVC 1. Plasticized PVC is very good replaced rubber insulated wire for domestic flex and is used widely industrially it is also used for sheathing in cables where PE, is employed as insulators. 2. Plasticized PVC is used for making leather cloth which is used in, Car applications in upholstery and trim, Gi) Kitchen upholstery, Bathroom curtaining and Civ) ladies handbags. 2. Its also used for making (i) Plastic rain wear, (ji) Baby-pants and Gi) All PVC-shoes for beach wear and. (iv) Garden hose. (diocty! phthalate),” Q. 7 Write the preparation, properties and uses of Nylon. : (CS.V.LU., Sem. I, Nov.Dec., 2007) ‘Ans. NYLONS : SYNTHETIC FIBER POLYAMIDES Nylon is a synthetic thermoplastic fiber. The nylon forming polya- hides are also termed as ‘polyamides’. * The important polymers of this category are - 91GLO9PeSG ‘9LEGSELE96- "ON HVS UN ENS $U3aTdOD VNHSIUW Cement, Lubricant and Polymers | 185 1, Nylon-6 Nylon-6 is prepared either by self-condensation of ¢ - amino caproic acid. ¢ wo {i tL ted -(CHy,-C amino caproic acid Nylon-6 In fact, there are four steps for the synthesis of Nylon-6 starting from cyclohexane. These steps are summarized below Step (i) : Conversion of Cyclohexane into cyclohexanone by oxidation. A ie fs eae [jew - (cH), - cofoH + HHNCH,), - COR] i Hg HG. £H, cf, Cyclohexane H, Oxidation , th oun, Step (ii) : Conversion of cyclohexanone into cyclohexanone-oxime by treatment with hydroxylamine NH,OH. rR LN So ee oe nes Be AB Ja, of, ‘a, oo Cyclohexane-oxime Step (iii) : Conversion of cyclohexanone-oxime into caprolactam by Backmann rearrangement in the presence of H,SO, you Yr E a ‘a Cs 7 de Pa Oo? “f is Cyclobexane-oxine "Copia186 | SBP Q. B. Applied Chemistry Step (iv): Ring opening polymerization of caprolactum to give Nylon-6. NH I C=O a » 1? ¥ m4 i C+ (CH),-N HCO Gy me ree Applications : Nylon 6 is mainly used for making tyre cords. 2. Nylon-6 : It is made by the condensation polymerisation of hexamethylene amine and adipic acid in 1:1 motar ratio without an external strong acid’ (unlike polyester synthesis) because the reaction rate is sufficiently high without it, Condensation ni Polymerization nH} 5 N-C+ CLC ++ 21,0 Lali yay HOlH]c Nylon- 6:6 1. Nylon-6:6 is primarily used for fibers, which find use in making socks, under-garments, carpets etc. 2. Nylon 6:6 is also used in Gears, Bearings, Bushes, Cams etc. Apart from advantageous properties listed above. * 3. Nylon 6.6 is also used for jacketing electrical ware to provide a tough, abrasion resistant outer cover to protect the primary electri- cal insulation. i Cement, Lubricant and Polymers | 187 3. Nylon 6:10 It is made by the condensation polymerization of hexamethylene amine and sebacic acid. Applications : Nylon 6:10 is suitable for monofilaments which are used for bristles, brushes etc. 4. Nylon 1 It is made by self condensation of - amino undecanoic acid. H(H) o H(H) 0 1 | u sel fensation t I u n| BN+ c+ C_ for |_Setfcondensati cte om I H H Aa ape le @ ~Amino undecanoic acid Npylon-11 Applications ;. - Nylon -11 is used for making flexible tubings for conveying petrole. Properties of Nylons : 1. The structure of nylons are linear that permits side-by-side align- ment. Moreover, the molecular chains are held together by Hydro- gen bonds. Thus, nylons have high crystallinity which imparts high strength, high melting point, elasticity, toughness, abrasion resis- tance and retention of good mechanical properties upto 125°C. 2. They are also sterilizable. 3. Since nylons are polar polymers, they have good hydrocarbon resis- tance. Larger the number of carbon atoms, greater will be ease of processing and hydrocarbon & moisture resistance. Q. 7. What are the raw materials for Nylon 6 : 6? (C.S.V.TU,, Sem. I, 2005, 2006-07) Ans. Raw materials for Nylon 6 : 6 The raw materials used for the preparation of nylon 6 : 6 are hexamethylene diamine and adipic acid in 1 : 1 molar ratio. @ 8 Show different stages of bakelite formation and its uses. (C.S.V.TU., Sem. I, Nov.-Dec. 2006) Ans. BAKELITE OR PHENOLIC RESINS OR PHENOPLASTS Bakelite belongs to phenolic resin. It is prepared by the condensation of phenol with formaldehyde in the presence of acidic / alkaline catalyst.188 | SBP Q. B. Applied Chemistry The initial reaction results in the formation of - and p - hydroximethy! phenol, which reacts to produce linear polymer, novolac. Thus At the time of moulding, hexamethylene tetramine [(CH,),N,] are added. The addi- tion of hexamethylene tetramine provides formaldehyde, which converts the soluble and fusible novolac into a hard, infusible and insoluble solid of cross-linked structure. OH OH ca chon +HCHO ——+ and 4 “CHO ao es phenol phenol “ Phenol | + | Formaldehyde - § (Excess) . aes &¢ 2 NOVOLACS EAS 29 feat an curing agent &o§ s28 £2 BAKELITE a oa Properties : 1, Phenolic resins are hard, rigid and strong materials ; 2. They have excellent heat and moisture resistance ; 3. They have good chemical resistance ; 4. They have good abrasion resistance ; 5. They have good electrical insulation characteristics ; 6. They are usually dark coloured (Pinkish brown) ; 4.7. Low molecular weight grades have excellent bondingtstrength and adhesive properties. ‘Applications : PF resins are generally used for : 3 Cement, Lubricant and Polymers | 189 1. Domestic plugs and switches, 2. Handles for cooker and saucepans, 3. Distributor heads of cars, 4. Adhesives for grinding wheels and brake linings, 5. Impregnating paper, wood and other fillers, for producing decora- tive laminates and wall coverings and industrial laminates for electrical part including printed circuits. 6. Varnishes, electrical insulation and protective coatings. 7. The production of ion-exchange resins. Q. 9. What are elastomers? What is the importance and mecha- nism of vulcanization. (CS.V-T.U., Sem. I, Noy.-Dee. 2006) Ans. Elastomers or Synthetic Rubber ‘These are rubber like elastic polymers, which can be stretched at least thrice of its length and it have a tendency.to recover their original shape and dimensions as soon as stretching force is released. This is due to the ab- sence of highly polar groups or site for hydrogen bonding, Moreover, ex- tended chain do not fit together well enough for vander waals forces to do the job. Hence, molecules in elastomers have weak inter molecular forces. For ready extensica and zecovery the jong chaifis of an elastomer must be connected to each other by occasional cross-links. These cross-links pre- vent the slipping of molecular part, but at the same time, these occasional cross-links do not deprive the chains of their flexibility, Examples : Natural rubber (cis - 1.4 poly isoprene), nylon 6 : 6, dacton, silk etc. Vulcanization 5 To improve the properties of rubber, it is compounded with some chemicals like sulphur, hydrogen sulphide, benzoyl chloride ete. at 100 to 140°C. This process is called vulcanization. Sulphur is the best ingredient for this process. Mechanism of Vuleanization : During the process of vulcanization raw rubber is heated ay 100-140°C with sulphur. The added sulphur com- ines chemically at the double bonds of different rubber springs and pro- vides cross-linking between the chains. ‘The cross-linking during Vulcanization brings about a stiffening of rubber by anchoring and consequently preventing inter molecular move- ment of rubber springs. The extent of stiffness of vulcanized rubber is determined by the amount of S added to it. Example : Ordinary soft vulca-190 | SBP Q. B. Applied Chemistry nized rubber (for tyres) may contains 3 to 5 % sulphur, but hard rubber ( say for battery case) may contain as much as 30% sulphur. cH, CH, _cu, -¢=cH-cH, cu,-€=cH-cH, + Sulphur ...- CH, -C = CH-CH, - CH, -C = CH-CH, du, cH, ‘Raw unvuleanized rubber springs cH, cH, -cH,-€ CH CH, CHC -GH- CH. ss SS <—supmur ‘eross link lod I ~ CH, -€ -CH-CH,- CH, dai -cu,- cH, cH, ~ Vulcanized rubber springs Fig. 46 Vulcanization of raw rubber with sulphur Importance of Vuleanization : 1. Vulcanization brings about stiffening of the rubber . 2. It tremendously increases elasticity, tensile strength of rubber. 3. It also increases resistance to swelling in rubber 4. It develops higher resistance to oxidation and to abrasion. INDUSTRIAL CHEMICALS, EXPLOSIVES AND PROPELLENTS ‘Syllabus + Introduction to Important Industrial Chemicals : Industrial Method of reparation (one each, properties and major industrial; uses of following chemi- als : Ammonium Chloride, Ammonium Nitrate, Ammonium Sulphate, Bromine,Calcium Phosphate (Monocalelum Phosphate, Super Phosphate), Chro: ‘mie Acid (Chromium troxide Chromic anhydride), Acrylonitrile, Benzene (Ben- 20)), Butyl Acetate, Caprolactam, Carbon Tetrachloride, Cellulose Acetate, Cresol (Ceysylie Acid), Chloroform (Trichloromethan), Ether (Ethyl Ether) Ethyl Alco- hol (Ethanol, Industrial Alcohol), Glycerine (glycerol), and Melamine. Explosives and Propellants : Characteristics of Explosives, Oxygen Balance, Classification of Explosives: Primary or Initiating Explosives or Detonators; Low Explosives or propellants; High Explosives, Preparation and Applications of Ex- plosives, Rocket propellants, Characteristics of « Good Propellant, Clasifistion of Propellant. DESCRIPTIVE QUESTIONS ON INDUSTRIAL CHEMICALS. @. 1. Explain industrial method of preparation and synthetic use of ammonium cklorlée. {CSN.EU., Sem. I, Nov.-Dec. 2006) Or Write short notes on Ammonium chloride (CS.V.L.U., Sem. I, Nov.-Dec., 2007) Ans. AMMONIUM CHLORIDE (NH,Cl) Industrial Preparation’: On industrial level ammonium chloride is prepared by followjng methods- 1. First Method : Ammonium chloride is generally manufactured by the boiling of ammonium sulphate and sodium chloride solutions. (NH, ), SO, +2NaCl—> Na,SO, +2NH,CI Ammonium sulphate and sodium chloride (in 5% excess) are added to a residual ammonium chloride solution. The mixture is heated to 100°C while it is violently agitated. The resulting mixture (containing only suffi- cient water to hold the ammonium chloride in solution)is almost pastes like because of the comparatively low solubility of sodium sulphate. This pasty mixture is vacuum-fil-tered, and the precipitated sulphate is washed free of ammonium chloride: the wash water is returned to process. The filtrate is192 | SBP Q. B. Applied Chemistry sent to acid-resistant concentrating pans, where it is concentrated and cooled. Ammonium chloride crystallises and is recovered by filtration or centrifugation, washing and drying. The mother liquor is returned to the next batch as indicated. The by-product sodium sulphate, may be discarded Ammonium Mother liquor Sulphate ‘Wash water Sodium | chloride — > Reactor} +] Fitter |_—+| Crystallization} Plant vain | | Ammonium chloride 1. Flow diagram for manufacturing of ammonium chloride from ammonium sulphate alia sodium ehloride. 2. Second Method : In this method ammonium sulphate is boiled with calcium hydroxide. In this reaction ammonia gas is evolved. This ammonia reacts with hydrochloric acid form ammonium chloride Sodium sulphate washins Fig. “ (NH, );SO, +Ca(OH,) > Ca,SO, +2NH, #25,0 NH, + HCI NH,CI Properties 1. Ammonium chloride is a white erystalline solid. 2. It is Fairly soluble in water (29.4 g/100 g at O*C ; 77.3 g/100 g at 100°C) and in ammonia. 3. On heating it dissociates into ammonia and HCI and these two re- on cooling. NHC] == NH, + HCI Uses. 1. Ammonium chloride is used in soldering. 2.Itis employed in Leclanche cells, dry cells, in dyeing callico printing and in med cine. 3. Itis a useful laboratory reagent. 4. It is also used in galvanising flux; leatller; Food etc. @. 2. Write short notes on Ammonium nitrate. (CS.VT.U., Sem. 1, 2006-07, May-June, 2007, Dec. / Jan., 2008-09) (a 5 PWOUA TIES gvaldod VNHSTE® ab opeuse ‘st ease tase - OW Industrial chemicals, explosives and Propellents | 193 Explain industrial method of preparation and synthetic use of am- monium chloride. Ans. AMMONIUM NITRATE (NH,NO,) Industrial Preparations : Ammonium nitrate is prepared at indus- trial level by neutralization of ammonia by nitric acid under controlled con- ditions. The whole process is carried out in an enclosed vessel maintained under a pressure of several atmospheres to prevent loss of reactant. ‘The hot NH,NO, (about 95 %) formed during the reaction charged through a valve at the top. The hot concentrated solution of NH, NO, is then sprayed over the wall of a chamber in the form of spherical drops along with a spray of cold water. It causes the droplets to solidify. ‘This process is called prilling. The prilled material is dried in a scries of driers. HNO, + NH, ~ NH,NO, Ammoniom Nitrate Properties 1. Ammonium nitrate is a white hygroscopic crystalline substance. 2. It is relatively unstable, forming explosive mixtures with combus- tible materials or when contaminated with certain organic compounds. 3. ft is very soluble in water (55% at 0°C, 90% at 100°C), 4, It decomposes gentle heating to give nitrous oxide NH,NO, + N,0+2H,0 5. On rapid heating, it detonates. 2NH,NO, -> 2N, +0, +4H,0 Uses : 1 Ammoniurh nitrate is used in the manufacture of nittrogenous fertilizers." 2. It is used in fire works and explosives. Q. 3. Write a method of prepartion, properties and uses of am- monium sulphate. (CS.V-TU., Sem. I, 2005, 2006-07) Or Write a note on Ammonium sulphate. (CS.V.LU., Sem. I, Dec. / Jan., 2008-09) Ans: | AMMONIUM SULPHATE (NH,),SO, A Industrial Preparations : Ammonium sulphate is an important fer- tilizer. At industrial level it is prepared by following methods- 1. From coal gas : Ammonium sulphate is produced as a by-prod- , uct during the production of coke from coal. During dry distillation of coal *194 | SBP Q. B. Applied Chemistry a liquor obtained as by-product contain 1-3% NH, in the form of its salts. ‘The liquor is heated in stills with steam and milk of lime to decompose ammonium salts. The NH, gas evolved is passed through 60% H,SO, taken in lead lined tank. Here ammonium sulphate crystallizes out. 2NH,CI + Ca(OH), ——+ CaCl, + 2H,O + 2NH, 2NH,+H,SO, > (NH,),SO, ‘The ammonium sulphate product is recovered by crystallisation, which is controlled carefully to yield large uniformly sized particles. The yield is practically 100%. 2. From Gypsum : Ammonium sulphate may also be produced using gypsum instead of sulphuric acid, 2NH, + H,O + CO, + CaSO, —» (NH,),SO,+ CaCO, Finely ground gypsum (CaSO,.2H,0) or anhydrite (CaSO, ) is sus- pended by agitation in about twice its weight of water. Ammonia and carbon dioxide are passed into the mixture, forming ammonium carbon- ate, which then reacts with the calcium sulphate (gypsum), forming cal- cium carbonate and ammonium sulphate, the latter dissolving in the wa- ier. 2 aa At the end of the reaction, the 25% ammonium sulphate sulution is filtered to remove the insoluble calcium carbonate. The clear solution is, concentrated in evaporators to crystallise out the ammonium sulphate. The crystals are centrifuged and may be further dried in a rotary dryer. Properties: 1. Ammonium sulphate is a.white to brownish gray crystals. 2. It is soluble in water (70.6 g/100 ml at 0°C, 103.8 2/100 ml at 100°C), very slightly soluble in athanol. Insoluble in acetone. 3. On heating it looses NH, (NH,,SO, —+ 3 NH,HSO, + 3NH, Further heating, 3 NH,HSO,, NH, +N, + 2SO, + 6H,O. Uses : 1. Itextensively used as nitrogenous fertilliser 2. Itis used for the preparation of other ammonium salts. 3. It is also used in water tregtment, fermentation, fireproofing and Industrial chemicals, explosives and Propellents | 195 tanning. Q. 4. Write the industrial method of preparation, properties and major industrial uses of bromine. Or Give brief account of bromine. (CS.V.T.U., Sem. I, May-June, 2007) Ans. BROMINE (Br,) Bromine is very reactive substance, therefore it does not occur free in nature. Industrial Preparations : 1. From Ocean Water : Ocean water contains potassium bromide (KBr) and magnesium bromide (MgBr,). To extract bromine from ocean water, the ocean water is acidified and chlorine is passed through it. During this process bromone vapour is released. This bromine vapour is made to get absorbed in sodium carbonate to obtain a mixture of sodium bromide and sodium bromate. Bromine is obtained from this solution by the addition of sulphuric acid. 3Br, +3Na,CO, ——> SNaBr + NaBrO, +3CO, SNaBr + NaBrO,+3H.SO, —> 3Na,S0,.+3H,0+3Br, ‘The crude bromine goes to a distillation column, where it is separated from high-boiling impurities, mostly halogenated hydrocarbons. The bro- mine vapours are condensed and fed to a stripping column, where the re- maining traces of chlorine are distilled off for return to the tower; refined bromine is removed from the bottom ot the column, dried and packaged. 2. By Reaction of Chlorine : Camalite (KCI.MgCl,,6H,O) contains ‘MgBr, «as impurity in small amounts. At industrial level, bromine is ex- tracted from this MgBr,. In metallurgy of magnesium, the mother liquor is left behind after the crystallization of chlorides from carnalite (KCI.MgCl,.6H,0).It contains one per cent of bromide salts (KBr. MgCl,.6H,0). This hot mother liquor is sent into a tower containing earthern ware balls. Chlorine enters the tower from the base and liberates bromine from percolating mother liquor. The vapours of bromine evolved are condensed into loquid. Steam is also passed to remove last traces of bromine vapours. The uncondensed vapours are passed into a chamber of iron filling as Fe,Br, ‘ MgBr, +Cl, > MgCl, + Br, 3Fe + 4Br, > Fe,Br,196 | SBP Q. B. Applied Chemistry Properties: - It has following properties - Physical Properties : 1. Bormine is a dark brown heavy liquid. 2. Itis soluble in water, the solution is called bromine water. 3. It is soluble in organic solvent like ether, chloroform, alcohol, ac- ‘etone, carbon tetra chioride, carbon di-sulphide and benzene to form & brown coloured solution. 4, It produces wounds on skin which take long time to heal. Chemical Properties 1, Reaction with water : Bromine dissolves in water to give reddish solution of hydrogen bromide. 2Br, +2H,O + 4HBr +0, 2. Bromine is neither combustible nor supports combustion. 3. Combination with metals and non-metals: It react wth metals ‘ind non-metals to form their bromides. 7 (® Reaction with Metals : It is less reactive mtals. It reacts with copper, iron, Zn, Na, K, As, Sb, to form their bromides. E.g.- Cu+Br, > CuBr, 3Fe+4Br, > Fe,By :E6S81696 - ‘OW gteLogre: 2n+Br, > ZnBr, (ii) Reaction with Non-metals: 2P + 3Br, > 2PBr, (Phosphorous tri-bromide) 2S +Br, — P,Br, ( Sulphur monobromide) 4. Oxidising Properties : Bromine is an oxidising agent. It oxidizes nitrites to nitrates. Sulphites to sulphate, H,S to colloidal sulphur, SO, to sulphuric acid and thiosulphate to sulphates. KNO, + Br, + H,0 > KNO, +2HBr 5. Reaction with Organic and Inorganic Compounds : It react with organic and inorganic compounds to produce their bromide. (i) Reaction with ethylene. + CH, +Br, > C,H,Br, Ethylene Ethylene bromide Reaction with benzene. C,H, +3Br, —!"+C,H,Br, (Benzene hexabromide ) } Industri chemicals, explosives and Propellents | 197 Uses of Bromine : 1. Bromine is used'in preparation of bromates, bromides, hypobromite and hydrobromic acid. 2. Bromides are used in photography and in preparation of medicines. 3. It is used as insecticide. 4. It is used in fire extinguishers and flame retardants. 5. Itis used in the manufacture of dyes and explosives. 6. It is used as an oxidising agent in laboratory. Q. 5. Write short notes on preparation, properties and of normal superphosphate. (CS.V.T.U., Sem. I, 2005, 2006-07) Or Write short notes on calcium phosphate. (CS.V.T.U., Sem. I, Dee. / Jan., 2008-09) CALCIUM PHOSPHATE (CaH(PO,), (Monocalcium Phosphate, Superphosphate) Industrial Method of preparation : or normal superphosphate, pri- marily the monocalcium salt of phosphoric acid, is made by the reaction of dilute H,SO, with phosphate rock, which is fluoroapatite or calcium fluophosphate (Ca,(PO,),CaF,). ‘The rock phosphate. Ca,(PO,), is insoluble in water and hence is not assimilated by plants. It is therefore. COnverted into soluble super phos- phate, Ca(PO,),.The product formed in above reaction is a mixture of pri- mary calcium phosphate and gypsum and is commercially known as “su- per phosphate of lime”, Properties : |. Pure monocalcium phosphate is white crystalline powder. 2. It is moderately soluble in water (1.8 g/100 g at 18°C). Uses : Super phosphate is an important fértilizer. Being readily soluble in water it is assimilated by plants. It helps the plant in growth and resisting diseases. Q.6. Write short notes on chromic acid (CS.V-T.U., Sem. I, Nov.-Dec., 2007) ‘CHROMIC ACID (H,Cr0,) (Chromium trioxide or Chromoum anhydride) Preparation : Chromium trioxide or chromic anhydride (CrO,) is com- mercially, though erroneously, called chromictacid. It is produced by the action of concentrated sulphuric acid on a solution of chromate or potas- sium dichromate (K,Cr,0,). K,Cr,0, + 2H,S0, —= 2KHSO, + H,O + 2Cr0, S¥3TdOD VNHSTUW Ans. Ans.198 | SBP Q. B. Applied Chemistry Potassium dichromate and water are charged into an acidulator in a weight ratio of 3 : 2 to 1 : 1, at room temperature. Altemnativly, a saturated solution of potassium dichromate from the evaporator or crystallizer in the potassium dichromate plant may be used. Concentrated sulphuric acid is slowly added to the potassium dichromate solution with cooling and good agitation. The potassium dichromate is converted to deep red crystals of chromium trioxide (CrO,), with the formation of potassium bisulphate.The chromium trioxide (CrO,)are separated by filtration through asbestos and then dried by passing hot air. When heated, chromium trioxide (CrO,)melts at 196°C and on further heating to 420°C, it gives chromic oxide with the evolution of oxygen. 4CrO, == 2Cr,0, + 30, Chromic oxide Chromic oxide dissolves in wate. The solution is strongly acidic and contains mostly dichromic acid (H,Cr,0,), with smaall amount of chromic acid (H,CrO,). The chromic acid crystallises out during the acidification. The reaction product is filtered to remove precipitated chromi¢ acid. Properties = 1. The erystals of chromic acid are deep red to reddish-brown. 2. It volatilises at about 100°C. 3. Jt is sclubte iz water, sulphuric acid,and ethancl. 4. Slow decomposition starts at 197°C; the rate of decomposition increases with temperature. Uses: 1. Itis used in laboratory in cleaning glass apparatus. 2. It is used in the manufacture of glass and pottery. + Q. 7. Write short notes on preparation and properties of Acry- lonitrite. (CS.V.T.U., Sem. I, 2005, 2006-07) Or Give the chemical formula of acrylonitrile. (CS.V-T.U., Sem. I, Dec. / Jan., 2008-09) Or Write short notes on Arcylonitrile (CS.V.L.U., Sem. I, Dec. / Jan., 2008-09) Ans. ACRYLONITRILE (CH, = CHCN) * Preperation : Acrylonitrile is prepared by following methods- 1. From Propylene and ammonia : Acrylonitrile is produced by re~ acting a mixture of propylene, ammonia, and air in the presence of a cata- Industrial chemi ls, explosives and Propellents | 199 lyst Bio, or MoO,. 2CH,CH= CH, + 2NH, +30, —52CH, = CN=CH,+H,0 Acrylonitrile 2, From acetylene and hydrocyanic acid : Acrylonitrile can also be prepared by the reaction of acetylene over hydrocyanic acid. The reaction is carried out under pressure at 80°C in liquid medium, containing cuprous chloride, which acts as a catalyst. CH=CH+HCN —O2Cb_, cH. =cH ! cN Acrylonitrile Properties : 1. Acrylonitrile is a colourless, flammable, mobile liquid with a mold odour. 2, It is soluble in ethanol, ether, carbon disulphide, and most, organic solvents but slightly soluble in water (6 /100 ml). Uses 1. Acrylonitrile is use in making acrylic and modacrylic fibres which are used in making sweater, coats, carpets, blankets and filter clothes. 2, It isalso used in mcking ABS and SAN pi Exports ete. @ 8 Write short note on Benzene. (CS.V-T.U., Sem. I, Dec. / Jan., 2008-09) Ans. BENZENE (BENZOL) Preparation : Benzine is prepared by following methods- 1. From Petroleum by Catalytic Reforming : Benzene may be pro- duced by dehydrogenation of selected pertoleum stocks rich in naphthene hydrocarbons. The process is carried out in the presence of hydrogen-rich recycle gas (to suppress coke formation) and is therefore, often generally known as hydroforming. The charge stock is usually a specially treated virgin naphtha; several different catalysts are used. 2, From Toluene by Hydrodealkylation : Benzene may be produced by the dealkylation of toluene or toluene-containing stocks such as heavy catalytic reformates, catalytic cycle oils, and the like Fig. 20.23. Several processes, both catalytic and thermaf, are available. The dealkyation is carrid out in the presence of hydrogen, quite often catalytic reformer hydrogen.200 | SBP Q. B. Applied Chemistry Properties: 1. Benzine is a clear, colourless, flammable liquid with a pleasant char- acteristics odour. 2. Liquid is highly refractive, and the vapours burn with a smoky flame. 3. Itis insoluble in water but soluble in all organic solvents. Ii itself is a very good solvent for organic compounds. Uses : 1. It is used as a solvent for fats, oils, resins etc. 2. Itis used for drycleaning woolen clothes. 3. It is used for the manufacture of styrene, phenol, cyclohexane, ni trobenzene, gammexine etc. Q. 9. Write short notes on butyl acetate. (C-S.V-T.U., Sem. I, Nov.-Dec., 2007) Ans. BUTYL ACETATE. Preparation : From Butyl Alcohol and Acetic Acid by Esterifica- tion. Acetic acid and n-butyl alcohol (10% excess) are charged into a batch still. About 0.1% sulphuric acid (66Be, 96%) is added as catalyst. The acetic acid should be free from other acids, but its water content is not cai ; 80% to glacialacetic acid is most commonly used. The amount of water present determines the length of distillation and limits the capacity of the equipment. z 2 2 & Supe aie z : 4 er 3 * 2 raseae Acotcacia $ waste Torecovery = Fig. 52. Preparation of butyl alcohol from butyl alcohol and aceti ‘acid by esterification., ‘The still is heated under total reflux by jacketed steam until the head temperature of the distilling column becomes constant (about 89°C). After this equilibrium has been reached, the distillate is withdrawn from the col- * SVOWN Hy WaTdOO VNHSTUy Industrial chemicals, explosives and Propellents | 201 umn as rapidly as possible without raising the heat temperature. The vapour mixture (approximating the ternary azeotrope; 35.3% n-butyl acetate, 27.4% ‘n-butyl alcohol, and 37.3% water, bp 89.4°C) is condensed and sent to an automatic separator. Here two layers are formed. The top layer, constitut- ing about 75% of the distillate, contains approximately 81% ester, 13% alcohol, and 6% water. This oil layer is continuously returned to the distill ing column. The lower layer(about 25% of the distillate) contains approxi- mately 1% ester, 3% alcohol, and 96% water. Either this aqueous layer is run to waste, or the alcohol and ester are recovered by distillation, depend- ing on the economics involved. ‘The distillation is continued, and the binary azeotrope (53% ester and 47% alcohol, bp 117.2°C) is next obtained. After the alcohol has been ex- hausted, pure n-butyl acetate (bp 126.5°C) conies over and is collected. The alcohol and ester fraction may be blended or added to the next batch. Technical (90 to 92%) butyl acetate is obtained at the beginning of the last fraction. Pure (99%) butyl acetate may be obtained in the middle to the last fraction. The overall yield of n-butyl acetate based on thé acetic acid charged averages about 95%. Properties: 1. n-butyl acetate colourless liquid with a fruity odour. is soluble in’sthanol and ether ir al! proportions at room temperi+ Q. 10. Write short notes on caprolactum (CS.V.LU., Sem. I, Dec. / Jan., 2008-09) Ans. CAPROLACTAM Preparation From Cyclohexanone : Caprolactum is prepared from cyclohex- ane in following steps- 1. First of all cyclohexane is oxidized into cyclohexanone as follows. Cyclohexane —2—» Cyclohexanol —°—> Cyclohexanone 2. Cyclohexanon is then treated with hydroxylamine to form eyclo- hexanone oxime. Cyclohexanone + NH,OH + Cyclohexanone oxime + H,O in third step ¢yclohexanone oxime undergoes Backmann arrange- ‘ment in the presence of H,SO, to produce caprolactum. Cyclohexandne oxime —Osidaion_, Caprolactum + H,OProperties 1, Caprolactum isfound in the form of tranculent , whitish flakes. 2. It is soluble water, chlorinated solvents petroleum distillates and cyclohexane. 3, It undergoes self polymerization. Uses : Caprolactum is used for making nylon- 6 fibres ; Nylon 6 plastics and film ; Nylon 6 resins, ropes, cords etc. Q. 11. Write a note on carbon tetrachloride. .U., Sem. I, 2005, 2006-07) Write industrial method of preparation, properties and uses of car- bon tetrachloride or tetrachloro methane. Ans. CARBON TETRACHLORIDE Methods of Preparation : 1. By the action of chlorine.on carbon disulphide : Carbon tetra- chloride is prepared at commercial or industrial level by the action of chlo- tine on carbon disulphide. In this method a solution of carbon disulphide (CS,) in carbon tetrachloride (approxiately 40% carbon disulphide, 50% carbon tetrachloride and 10% sulphur monochloride) is charged into a lead- linet! or steel chlorinater fitted with colting coils. Chlorine is bubbled through the solution, which contains iron brings or powder as catalyst The iron remains in the chlorinator form batch to batch and is replenished when warranted. The temperature is maintained at about 30°C by cooling water. An excess of chlorine is used to insure complete conversion of carbon disulphide (about 0.5% remains unchanged). ‘The reaction products, consisting of carbon tetrachloride (60%) and sulphur monochloride (40%), are passed to a-distilling column, where they are separated. CS, +3C1, #2, CCI,+5,C1, CS, +28,Cl —+CCI, +65 ‘The carbon tetrachloride, distillate, containing less then 1% sulphur monochloride, is sent to a neutraliser and dryer, where acidic materials are neutralised by agitation with alcoholic sodium hydroxide solution or by pas- sage over alkaline desiccants. The moisture content is also decreased. Des- iccants that may be used include anhydrous c&lcium chloride, sodium car- bonate, and silica gel. The dried material may be redistilled if warranted to Industrial chemicals, explosives and Propeltents | 203 ive carbon tetrachloride of 99.8 to 99.9% purity. ron catalyst Chior ool Carbon disulty ise Neutralizer and dryer ‘Carbon disulphide Carbdh tetrachloride Air ‘monochloride Air stil Sulphur (to recovery) Fig. 5.3. Manufacture of carbon tetrachloride from carbon disulphide and chiorine. 2. From Methane by chlorination : Carbon tetrachloride may also be produced by the chlorination of metharié and higher aliphatic hydrocarbons in the presence of sunlight. It gives chlorine derivatives from which carbon tetrachloride is separated by fractional distillation. 4CH, +10BCI, —"#*»CH,Cl+CH,Cl, +CHCI, +CCI, +10HCL : Carbon ‘etrachloride) In this method impure carbon tetrachloride is obtained. Properties : 1. It is colourless, heavy liquid with sickly smell. 2. Itis insoluble in water but soluble in organic compound. 3. Its vapours are non-inflammable in hance, it is used in fire extin- guisher. Uses: 1. Carbon tetrachloride is used as a solvent for oils, fats etc. 2. It is used in fire extinguishers by the name pyrine. 3. It is used as an insecticide. 4. It is also used in dry cleaning. @. 12. Write short notes on cellulose aceate. ‘ (CS.V.T.U., Sem. I, 2006-07)* or Give preparation, properties and uses of cellulose acetate. And also204 | SBP Q. B. Applied Chemistry give their flow sheet diagram. Ans. CELLULOSE ACETATE Method of Preparation From Cellulose by Acetylation. Cellulose acetate is prepared by the reaction of natural cellulose with acetic anhydride or glacial aeetic acid in presence of a catalest like sulphuric acid. ‘The action of acetic anhydride on chemical cellulose produces cellu- lose triacetate. Various commercial grades of cellulose acetate, ranging from about 51 to 625 combined acetic acid content are obtained by sub- sequent hydrolysis. [€.H,0, (OH), ], +3CH,COOH 28> [c.H,0, (OCOCH,), ]. +3H,0 (Cellulose triacetate). (Cetiuloss) [c.H,0, (OCOCH, ), ], + nH,O #284» (Cellulose triacetate) [¢,H,0, {0H)(OCOCH, ), ], +ACH,COOH (Cellulose diacetate) Reaviator [+ Avatonzer Glacial i" eens 8 ae Pr itati 3 reciptatng | $ Tank hol Dryer }+—[Puriving tank Fig. 54. flow chart for maniifacture of cellulose acetate 2.It is soluble in acetone, methyl ethyl ketone, glacial acetic acid, “OW 9161090856 ‘gi e6ce1696 iS S¥3Id09 VNHSTay Industrial chemicals, explosives and Propellents | 205 chloroform, and various mixtures of organic solvents, depending on the degree of acetylation. Insoluble in water and ethanol, Resistant to weak acids, oils, greases, and fats. 3. They have high tensile strength. 4, They possess high dielectric strength. 5. They have some resistance to the mineral acid. 6. They can be spun into fibres or used in the form of plastic. Uses 1. Cellulose acetate is used in the manufacture of radio appliances, goggles, combs, and medical instruments etc. 2. It is used in the manufacture of textile yarn, cigarette filter, plastics, ete. @. 13. Write short notes on Cresol. (CS.V.L.U., Sem. I, Nov.-Dee., 2007) Ans. resol (Cresylic Acid) Cresol (cresylic acid) in an isomeric mixture (o-, m-, and p- cresol). Preparation : Cresol is manufactured by following methods- 1. From Petroleum (Cracked Naphtha), Cresol is manufactured when cracked naphtha 1s passed through a vertical, parked contact col- ‘umn countercurrent to a solution of sodium hydroxide (caustic soda). oft gases to Socio hydroxide urtor Cresyle aca & Water Recycle ‘Sulphuric 3 + t E z 2 cractea| % 3 8 Settling tant Chiorne Jo} Naphina T T Sotlum Waste Phosphate ‘ ’ Fig. 5.5. Manufacture of eresol from petroieum (cracked naphtha) ‘Synthetic Routes to Cresols. Two routes have been used to produce P-cresol. Both, of them are classic phenol processes. The first is the206 | SBP Q. B. Applied Chemistry sulphonation to toluene to make predominantly p-toluenesulphonic acid. Fusion of the alkali salt with caustic soda yields the salt of p-cresol from which the latter can be recovered by acidification. Pure p-cresol can be isolated by distillation. The second route to p-cresol is via p-cymene. The cymene is treated with oxygen to give the hydroperoxide. Treatment of the hydroperoxide with strong acids cleaves it tc give p-cresol and acetone. 2. From Coal Tar. It is also obtained by refining the so-called tar acids. These acids comprise the phenolic constituents present in coal tar. The by-products coking of coal yields an everage of 42 litres of coal ter/ metric ton of coal. The tar is distilled, and a fraction known as middle oil, cresote oil, or tar-acid oil is collected. This fraction, constituting 10 to 20% of the tar (average about 17%), is first processed to remove most of the naphthalene. The phenols and cresols, present in the tar to the extent of 0.3 to 1.1%, are then removed (Fig. 28.33). Properties : . . 1It is yellowish liquid with a phenol like odour. 2. It is soluble in athanol, ether, chloroform, and dilute sodium hy- droxide. Slightly soluble in water. @, 14, Write methods of preparation, properties and uses of chloro~ form. or Write short notes on chloroform. (C-S.V.T.U. Sem. I, May-June, 2007, Dec. / Jan., 2008-09 ) Ans. CHLOROFORM OR TRICHLOROMETHANE (CHCI,) Industrial Methods of Preparation : Chloroform is prepared by following methods - 1. By partial reduction of carbon tetrachloride : In this method, chloroform is prepared by partial reduction of carbon tetrachloride by iron ‘alings and water. CCl, + 2[H]—2 > CHCI, + HCI 2. By Chlorination of Methane : In presence of partially reduced cupric chloride (as catalyst), the chlorination of methane by means of chlorine diluted with nitrogen, gives a mixture of trichloromethanes and Carbon tetrachloridis. Industrial chemicals, explosives and Propellents | 207 CH, —" 5.CH,CI— +.CH,Cl, > CHCI, = >-CCl, Chloroform Carbon tetrachloride Chloroform and other components of this mixture are separated by fractional distillation. Properties A. Physical Properties: 1. .Jtis a colourless and pleasant smelling liquid. 2. It’s boiling points is 334 K, density 1.485. 3. Itis sparingly soluble in water but completely soluble in ether and alcohol 4: It causes unconsciousness when inhaled for a long time. 5. Itis non-inflammable and on ignition it bums with a green edged flame. B. Chemical Properties : 1. Oxidation : In presence of air and Sunlight, chloroform slowly ‘oxidises to carbonyl chloride or phosgene (a poisonous gas). 2CHCI, +O, —AetSiste" 5 2COCI, +2HCI Air Carbonyl chleride 4CHCI, +30, —S##" + 4COCI, +2CI, +2H,O. Excess air Phosgene 2. Reduction : (i) On heating with Zn and HCI, it reduces to form methylene dichlo- ride. CHCI, +2[H] #5 CH,CI, + HCL Chloroform “Methylene chloride (ii) Methane is formed, on heating with zinc dust and water. CHCI, + 6[H] 24H, +3H1CI Chloroform Methane Gil) Hydrolysis : On boiling chloroform with aqueous solution of KOH form potassium format due to hydrolysis - ‘ CHCl, +4KOH — HCOOK +3KCI+2H,0 Chloroform Potassium format208 | SBP Q. B. Applied Chemistry (iv) Carbylamine Reaction or Isocyanide Test : On heating chloro- form with any primary amine (suchas aniline) and alcoholic potash a very pungent smelling substance isocyanide is produced. This substance is also called carbylamine. C\H.NH, +CHCl, +3KOH—*>C,H,N =C+3KC1+3H,0 Aniline Phenyl isocyanide (Pungent smell) Both chloroform and primary amine can be detected by this test this, reaction is also called isocyanide test. (¥) Riemer-Tiemann Reaction : When a mixture of chloroform and phenol is heated with strong alkali at 330-340 K then a mixture of ortho and para hydroxy benzaldehyde is obtained. ‘o1e6se1696-‘ow VN LIAS avD! SU31d09 YNHSTUN ‘916 109P8s6 C,H,OH+CHCI, +3NaOH—*>C,H, +NaCl+2H,0 (Phenol) (Chloroform) (Orthe and Para hydroxyben.....-) ~ Uses Ss 1. Chloroform is used as an anaesthatic in surgery. 2. It is used as a solvent of fat rubber, iodine and wax etc. 3. It is used as preservative in preservation of anatomical specimens Q. 15. Why ethanol is added to chloroform? (CS.V-L.U., Sem. I, 2005, 2006-07) Ans. In the presence of air and sunlight, chloroform slowly oxidises to carbonyl chloride or phosgene (a poisonous gas). Therefeor a little quan- tity of ethanol is generally added to the chloroform to check the formation of phosgene. Ethanol react with phosgene and convert it into a non poison- ous and non-volatile neutral ethyl carbonate. —Hesndsunle 5 2COCI, + 2HCI Carbonyl chloride 2CHCI, +0, Air CoC, + 2C,H,OH ——> OC (C,H), + 2HCI Carbonyl chloride Ethanol Ethyl carbonate @. 16. Give industrial methods of preparation, physical properties, chemical properties and uses of ethyl alcohol (or ethanol). Or Write flow chart for method of preparation of ethyl alcohol . (CS.V-T.U., Sem. I, Nov-Dec. 2006) Or Industrial chemicals, explosives and Propellents | 209 Describe a method in brief for industrial production of ethyl alcohol. (CSV.LU., Sem. I, Dec. / Jan., 2008-09) Or Give brief account of Ethyl Alcohol (CS.V.T.U., Sem. I, May-June, 2007) Or Write short notes on Ethyl Alcohol (C.S.V.TLU., Sem. I, Dec. / Jan., 2008-09) Ans. ETHYL ALCOHOL OR ETHANOL (C,H,OH) Industrial Method of Preparation : Ethyl alcohol is prepared in in- dustrial level by the following methods - 1, From Ethylene by Esterification and Hydrolysis In this method ethyl alcohol issynthesized from ethylene obtained by the cracking of petroleum and natural gas. The method consists of two steps - * @_ Absorption of ethylene’in concentrated sulphuric aciil (989%) at 73-80,C and atmosphere pressure, when ethyl hydrogen sulphate, is pro-, duced C,H, +H,S0, > C,H,HSO, Eifene ~ "Bthys njdregen Salphate Gd Hydrolysis of ethy! hydrogen sulphate by dilution with water fol- lowed by boiling. cc: Ethyl hydrogen syiphate 2. By Fermentation In this method alcohol is synthesized by fermerttation of following substances - (@) Substance containing sugar. e.g. molasses. (b) Substance containing starch. e.g. potatoes, maize. barley, rice and wheat etc. Alcohol Production from Molasses ‘Molasses is a dark brown coloured viscous liquid which remains be- hind after the crystallization of sugar from sugarcane juice in sugar indus- tries. It is a waste product in sugar industries from whjch no more sugar sHSO, +H,0 > C.H,OH +H,S0, Ethyl alcohol * can be extraced. Fermentation of molasses in presence of yeast results in the produc- tion of alcohol. It involves in the following steps-210| SBP Q. B. Applied Chemistry @ Formation of Wash : Concentrated solution of molases is not suitable for fermentation hence, it is diluted by water to get 8 to 10% solu-: tion of sugar. A small amount of dilute H,SO, is added. It checks the growth of bacteria. If the growth of bacteria is not checked then lactic acid and acetic acid are also formed. To this solution, a small quantity of ammonium sulphate and phosphate is added which acts as nutrition for yeast (fermen- tation). This liquid is now taken in a fermentation tank and some yeast is added to it and temperature of the liquid is maintained at 398 to 403 K (25 to 30°C). The enzymes invertase and zymase present in yeast bring about the . conversion of sugar solution into alcohol. * cH,,0,, +H,O + C,H,,0, +C,H,,0, (invert Sugar) (Ethanol) C,H,,0, > 2C,H,OH +2CO, (Glucose and Fructose) (Ethanol) ‘The process is completed in 2-3 days when the evolution of CO, ceases. Yeast is filtered and separated. The filtrate is called wash or wort. About 6-10% ethanol, 3-5% glycerol, high alcoho, acetaldehyde and potas- ‘sium hydrogen: tartarate are present in wash. Gi) Distillation of Wash : Fractional distillation of wash is done which results in 90% alcohol. This distillation is done in special type os fractionat- ing columns known as analyser and rectifier. Both these columns are of similar shape. They are provided with many perforated horizontal plates of copper having values opening upwards. Coffey still works on the principle of counter current, as steam and alcohol travel in opposite direction. Molasses Water pea aeor 1. Sat Wan . Mixing tank i E (NiiguS04+ HaSO« < 8 “|g : eg BT conor 75% bE Ej steam ‘ cH ‘ Fig. 5.6. » Flow chart of manufacture of ethyl alcohol from molasses Industral chemicals, explosives and Propellents | 211 Gi) Rectification : On fractional distillation of 90% alcohol obtained above, the following fractions are obtained - 1, First Fraction : It contains substances having low boiling point, eg. acetaldehyde. " 2. Second Fraction : It contains 93-95 % ethyl alcohol. It is called rectified spirit. 3. Last Fraction : It contains water and fusel oil. Fusel oil is a mix- ture of n-propyl, n-butyl, n-amyl, jso-amyl and optically active amyl alcohols. Properties A. Physical Properties : 1. Ethanol is a calourless, sweet smelling inflammable liquid. 2u It is sedative 3. Its boiling point is 351.2°C. B. Chemical Properties 1. Reaction with Ammonia : Itreacts with ammonia form ethylamine C,H,OH + NH, —™->C,H,NH, 630k — Ethylamine 2. Reaction with PCI, - It reacts with PCI, form ethyl chloride, C,H,OH+PCl, > C,H,Cl #POCI, + HCI Ethyl Chloride 3. Reaction with Acetyl Chloride : It reacts with acetyl chloride form ethyl acetate. C,H,OH+CH,COCI > C,H,COOCH, (Ethyl Acetate) _, 4: Reaction with Chlorine ; It reacts with chlorine form chloral or trichloro acetaldepyde. C,H,OH+Cl, —+CH,CHO—%->CHCI,CHO—%-+CC1,CHO+HCI Trichloro Aldehyde or chloral 5. Reaction of Ethanol in Excess of H,SO,: Ethnol reacts with excess of H,SO, at 440° K form ethylene. C,H,OH —_H2SOx inexeess_ CH, = CH, +H,O 440K Ethylene Uses : 1. It is used in the preparation of compounds, such as acetal- dehyde, chloroform, chloral and ether etd. 2. In the formation of wines and different type. 3.Itis used as solvents of paints, varnishes, gums and dyes and thinners.212 | SBPQ. B. Applied Chemistry 4, It is also used as a power alcohol. Q. 17. Give industrial methods of preparation, properties, chemical and uses of ether or diethyt etrher. Ans. ETHER OR DIETHYL ETRHER (C,H,OC,H) Method of Preoaration 7 From Ethyl Alcohol by Dehydration. Diethyl ether is prepared in lidustrial level bt the Williamson continuous etherification method. In this metho concentrated sulphuric acid and 95% ethanol are charged into a lead-lined steel reaction kettle. Generally, about 3 parts of acid are charged per 1 part of alcohol. The mixture is heated to 125 to 140°C by raeans of a steam jacket or internal steam coils. In this temperature range, the reaction is initiated. Vapourised alcohol is allowed to flow into the reac- tor at a rate determined by the reaction temperature; that is, the rate of alcohol and steam is adjusted so that the temperature is maintained at ap- proximately 127°C. * & C,H,OH + H,SO, _373K_, C,H,HSO, + H,O Ethanol Ethyl hydrogen sulphate CSO, + HOCH; 43K, co'CH, + H,S0, Ethyl hydrogen Diethyl ether sulphate Sodium hydroxide soutien [> thy ether : g 3 Sulphur ais [ & Reactor z E 28 ‘Spent acid T waste Ethyl alcoho! Fig!5.7, Manufacture of ether from ethyl alcohol by dehydration? UVOVN ILIuHS S¥ITdOD VNHSTUM 9161090856 ‘916581696 -"OW Industrial chemicals, explosives and Propellents | 213 A mixture of ether, alcohol, and water distils from the reactor and passes to a scrubber. The vapours pass counterurrently to a slow-moving stream of dilute sodium hydroxide solution which removes mechanically entrained sulphuric acid as well as any acidic reaction products. The alkali solution containing small amounts of ether and alcohol passes from the bottom of the scrubber to the lower section of a fractionating column. Here the alcohol and ether are removed, and the water is discharged to waste. This process in practically continuous and may be run for months before recharging with sulphuric acid. Side reactions, which form tarry products, as well as reduction of some of the sulphuric acid with evolution of sulphur dioxide, necessitate periodic recharging. The yield of technical ethyl ether is 94 to 95% based on the weight of ethanol processed. Properties - Colourless, very volatile, highly flammable liquid with a pleasant, aro- matic, ethereal odour and a sweetish burning taste. . Sollible in ethanol, chloroform, bénzene, and petroleum eher. Slightly soluble in water Uses. Chemical manufacture; Solvent and government purchases; Medicinals and pharmaceuticals. Q. 17. rite short notes on glyceroi (CS.V.T.U., Sem. I, Dec. / Jan., 2008-09) Or Give two properties and two industrial uses of glycerol. (C.S.V.T.U., Sem. I, Dec. / Jan., 2008-09) GLYCEROL (Propane 1,2,3-triol, CHjOH.CHOH.CH,OH) Glycerine is a trhydric alcohol. ‘Method of preparation : Glycerol is prepared as a biproduct during, the production of soap from oils and fats. The soap is prepared by the hydrolysis of fat of oil-During soap formation, the sodium or potassium salts of higher fatty acids (Soap) and glycerol Ans, ‘CH,OOCR HOH 1 1 . CHOOCR + 3NaOH —» FHOH + 3RCOONa CH,OOCR CHOH Soap is filtered and separated and the filtrate is called spent iye which contains approximately 5-6% glycerol. {t is heated by steam after the addi-214 | SBP Q. B. Applied Chemistry tion of alum or aluminium sulphate. Free alkali precipitates out as Al(OH), and the soluble soap converts into insoluble soap. Solution is filtered and concentrated by vaporizatio. NaCl present in precipitates out. It is filtered and separated. It is then distilled by steam at low oressure. A concentrated solution of glycefol is obtained. Properties. 1, Glycerol is a clear, colourless, sirupy, odourless, hygroscopic liquid with a sweet, warm taste. 2. It is soluble in in water and ethanol, insoluble in benzene, chloro- form, ether, and petroleum ether. 3. Itabsorbs moisture from the air, also sulphur dioxide and hydrogen sulphide, if present. Uses: 1. Glycerol is used in the preparation of transparent soaps and cosmetics. 2. It is used in the manufacture of drugs. 3. It is used in the preparation of alkyd resins and ester gums. 4. It is used in the preparation of cellophane. 5. It is also used in the preparation of nitroglycerine which is used in making explosives such as dynamite, cordite etc.. Q. 18. Write flow chart for method of preparation of malamine. (CS.V-T.U., Sem. 1, Nov.-Dec. 2006) Or Write short notes on Melamine. (CS.V.T.U,, Sem. 1, Nov.-Dec., 2007) Ans: MELAMINE Method of Preparation From Urea. Melamine is derived from urea. The, process is best Carried out in conjunction with urea manufacture in order to permit off- grases to be recycled. Fertiliser-grade urea is melted into a catalyst bed, an aluminosilicate, fluidised with ammonia gas, and heated by a molten salt system. The reac- tion is carried out at 330 at 450°C and under about 8 atm (800 kPa) absolute Pressure. The reaction products, melamine vapour, carbon dioxide, and ammo- nia gas, are directed from the reactor to a quench tower, where they are led to below the sublimation temperature of melamine. Crystalline prod- uct, after washing to remove gas, is collected at the base of the tower. The crystalline suspension is then thickened in a liquid cyclone to a 45 wt % Industrial chemicals, explosives and Propellents | 215 concentrate and expanded by steam in a stripper to remove the bulk of the dissolved gases. Thakenng on petvated ro ‘arto tue met 5 . 1 sles z ~ 32 BL rossonn elie ET ta Ammonia. Sa an at Lr reopete Fiter [+ Srstatizer]_ sf Separator Cc ~ Fig. 5.7 Flow Chart for prejuration of melamine polymer fréin urea. The crude melamine crystals are dissolved in returned mother liquor to remove the solid condensation impurities, melan, melem, and melon. By- products ammelide, ammeline, and coloured contaminants are removed using activated carbon. After filtration to remove these solids, puro meiamine is recovered in + % yield by vacuum-crystallisation, thickening and centrifuging. Ammonia is returned to the reactor as carrier gas, Other off-gases, after conversion to ammonium carbonate, are returned to the urea plant. This one-step process has the advantage of lower heat re- quired ments and capital consts. Properties: 1. It is a white, monoclinic crystalline Nonflammable.substance. 2. Itis sparingly soluble in water, glycol, glycol, glycerol, pyridine; very slightly soluble in ethanol; insoluble in ether, benzene, and carbon tetrachloride. ‘Uses: It is used in laminates, moulding compounds, coatings; Textile treatment resins; Paper-treating resins; Adhesives, DESCRIPTIVE QUESTIONS ON EXPLOSIVES AND PROPALLANTS: Q. 1. What are explosives ? Write the characteristics and uses of explosives. ox Ans sift 006 2th.216 | SBP Q. B. Applied Chemistry Or What do you understand by explosive material ?Describe its characteris- tics and uses. (CS.V.T.U., Sem. I, Dec. / Jan., 2008-09) What are the characteristics of an explosive? (CS.V.TLU., Sem. I, 2005, 2006-07) : Or Give uses of explosives (CS.V-E.U., Sem. I, 2005, 2006-07) Or ‘What are explosives ? (C.S.V.T-U., Sem. I, Dec. / Jan., 2008-09) Or ‘ies of an explosive (Ans. in 50-60 words). (C.S.VL.U., Sem. I, Dee. / Jan., 2008-09) Ans. EXPLOSIVES A sulestance or a mixture which under the influerce of mechanical or Give four required qual thermal shock decomposes sportaneously and rapidly into product of great increased volume with the evolution of a great amount of heat is known as explosive. In other words explosive is “a substance or a mixture, which when subjected to thermal or mechanical shock, gets very rapidly oxidised exothermically into products of greatly increased volume, with a sudden release of patential energy.” The amount of power available from a given weight (ot volume) of explosive, is called power C,H,O, (NO,), +3H,0 Dry gun-cotton explodes very rapidly, when set on fire, but when wet, itis set off by a small amount of another explosive. Gv) Cordite : It is made by dissolving gun-cotton (65 parts). nitroglyc- erin (30 parts). and petroleum jelly or “vaseline” (5 parts) in ac- tore. (W). Gelignite = It consists of 65% blasting gelatin and 35% of absorbing powder. It is a powerful explosive, which can be used under water.Industrial chemicals, explosives and Propellents | 221 220 SBP-Q. B. Applied Chemistry 2-(x+¥)tex100 E-(-3)}! Q. 4. Detonators are used in conjunction with high explosives, why? (CS.V.T.U., Sem. I, 2005, 2006-07) Oxygen-balance = Mol. wt. of C,H, 0, Ans. High explosivs are quite stable and nearly insensitive to fire and mechanical shock. Therefore, in order to fire it, a small amount of a deto- nator (or primary explosive) is placed in contact with it. on receiving a slight shock or fire, detonator explodes, thereby initiating the explosion of = For suecessful combustions, materials with negative oxygen balance must be admixed with some other material with positive oxygen-balance, For example, TNB and TNT, with a negative oxygen-balance, are mixed high explosive. 0 : 7 3 With ammonium nitrate Q. 5. What is meant by oxygen balance of an explosive? aa Oxygen balance of some important explosives is as follows- (C-S.V..U. Sem. I, Dee. / Jan., 2008-09) £3 1, Oxygen-balance of C,H,(NO,), (TNB) : Oxygen-balance of TNB Oe} BX whose molecular weight 213, ‘can be calculated as follows - Write short note on oxygen balance. 32 , 5 (C. S.V-T.U., Sem. I, May/June., 2007) 5 a a(x +h )e6-6-Fa-15 Or a>8 Comment on oxygen balance and calculate the value of oxygen 22 Oxygen-batance = —/5%16%100 _ 1 5 nee balance of TNB. * (CS.V-EU., Sem. I; Nov-Dec. 2006) 3] Ft ce 213 * or Z 2 2. Oxygen-balance of C,H,O, (TNT) : Oxygen-balance of TNT Cateutate the oxygen balance of NHNO, 2 whose molecular weight 227, can be calculated as follows - (C.S.V-LU., Sem. 1, Dec. / Jan., 2008-09) ae : owe [et5 = Calculate the oxygen balance of Ammonium Nitrate. (CS.V-LU., Sem. I, Nov.-Dec., 2007) Oxygen-balance = "SoA = 24.7 Ans. Ans. ‘OXYGEN BALANCE 3. Onygen-balance of Ammonium Nitrate (NH,NO,) : Qryzen-oal The oxygen balance is a measure of the oxygen contained in the mol- ance of NH,NO, whose molecular weight 80, can be caléulated as follows ~ ecule which is used to oxidise the C to CO, and H to H,O respectively. eae Generally, oxygen-balance is expressed as a percentage surplus or defi- . oe . ciency of oxygen by weight. 7 ioneeios Usually oxygen-balance is expressed as a percentage surplus or defi- Oxygen-balance = ~tEX*0° — 20 Ans. ciency of oxygen by weight ; 3. Oxygen-balance of RDX (C,H,N,O,) : Oxygen-balance of RDX Eg. The oxidation of a molecule. (C, H, O,) whose molecular weight 222, can be calculated as follows - 6 C.H,0, + xco, +2H,042-(x+¥ 2-(x+2}-6-(3+$)-0 Ho. -9300, +2i104[2-(x+¥ Jo, s2)no (8 ‘Oxygen-balance = 0 Ans. 2.6 What are characteristics of good propellant? Write the Blassifi- (CS.V.T.U,, Sem. I, Nov-Dec. 2006) cation of propeltent, Or z atoms of oxygen are required to oxidize x atoms of C and y/2 atoms What are propellants ? How are they classified ? What are the of oxygen are required to oxidize y atoms @f hydrogen. ‘Thus surplus oxygen222 | SBP Q. B. Applied Chemistry requirements for the selection of a propellant ? (CS.V.T.U., Sem. I, Dec. / Jan., 2008-09) Or What is a monopropellant? Give an example. (C.S.V.T.U.; Sem. 1, 2005, 2006-07) Or Write a short note on low explosives or propellant. Ans. LOW EXPLOSIVES (OR PROPELLANT) ‘These explosives simply bum and do not explode suddenly. The rate, ‘of combustion or chemical reactions taking place in such explosives is comparatively slow (20 cm per second). The gases evolved after explo- sion, disperse readily, without building high pressure, and consequently, they can be controlled easily. These explosives are used as propellants (to propel missiles) and in the wars. Characters of Good Propellents or Requirements for the selec- tion of a propellant : Refer Q. No. 7 Classification of Propellant : The chemical propellants are two types- solid and liquid propellants. 1. Solid Propetiants They are mixture of solid fuel and a solid oxidizer. They may be ho- mogenous or heterogenous. (@) Homogenous or Compound Solid Propellants : The solid propel- lants in which mixture of propellant is thoroughly mixed in a colloidal state are called homogenous solid propellents. These propellents are of two types- (®. Single base propellant : When a single propelant is used it is called a single base propellant. E.g. Nitro-cellulose (or gun -cotton or smokeless powder). ). Double base propellant : A solid propellant which has two m: terials, is called is called double base peopellant. E.g. Ballistite and cordite. Ballistite contains, mixture of nitro-cellulose and n troglycerine, Ballistite is a powerfull solid propellent. Cordite is a mixture of 65% nitri-cellulose, 30% nitro-glycerine and 5% of petrolieum jelly. Here petrolieum jelly functions as a plasticizer. (b) Heterogenous or composite solid propellant : When an oxidising agent is dispersed ina fuel mass, the solid propellant is said to be heteiogerous or composite. Eg - Gun powder. It is 3:1 mixture of KCIO, and asphalt oil 4:1 mixture of NH,OCIO, and resin bindes etc. Generally that oxidizing agent is setected which is non-hygroscopic, Industrial chemicals, explosives and Propellents | 223 stable in contact with fuel and does not form any corrosive products. Advantages of solid propellants : (® They can be easily and safely stored, handeled and transported. (i) They are stored in the combustion chamber belt. (ii) They are more economical in use. 2. Liquid Propellents These propellents are found in the form of liquid. They possess many advantages over the solid propellant. Thus, liquid propellants are more versatile and the engine using them can be checked and calibrated more easily. However, unlike solid propellants, the engine using liquid propellants quite delicate and cannot with stand any rough handling. Liquid propeliants may be of two types-monopropellants and bipro- pellants. (a) Monopropellant : A monopropellant has fuel as well as oxidizer in the same molecule or in a solution containing both these. For example : Hydrogen peroxide, nitromethane, ethylene oxide, hy- drazine propyl nitrate and a mixture of 21.4% methanol and 78.6% hydro- gen peroxide are some of the common monopropellants. A monopropellant must be safe to store and at the same time, It should burn smoothly. Hydro- gen peroxide is not easy to store and handle, due to its respectively. (®) Bipropeliants : Bipropetiants are more widely used. In these liq- uid fuel plus oxidizer, kept separately, are injected in the combustion cham- ber separately. Commonly used fuels are liquid hydrogen. hydrazine, cths! alcohol, aniline and kerosene oil. Ethyul alcohol admixed with 25% water is a good fuel. Addition of water, although reduces flame temperature, yet it reduces the molar-mass of combustion gases, which compensate for re- duction in the performance. The common oxidizers employed are liquid oxygen, ozone, hydrogen peroxide, fuming nitric atid and liquid fluorine. Liquid oxygen is non-toxic, safe and good oxidizing agent, but it has to be stored under pressure in insulated containers. Ozone is very powerful oxi- dizing agent, but it is quite toxi and can explode at high concentrations. Liquid fluorine is vloatile, toxic, corrosive, very reactive, but very good oxidizing agent. Also it is difficult to store and handle. Q. 7. Give important characteristics of a good propellant. (C.S.V.T.U., Sem. I, 2005, 2006-07) Or + Give brief account of Characteristics of good propellant. (CS.V.T.U., Sem. I, May-June, 2007)224 | SBP Q. B. Applied Chemistry ‘Ans. CHARACTERISTICS OF AGOOD PROPELLANT (Requirements for the Selection of a Propellant) A good propellent should mainly have the following characteristics- 1. Itshould have high specific impulse (specific impulse) is the thrust delivered by the rate of propellant burnt. . 2. It should produce high temperature on combustion. 3. Itshould produce low molecular weight products (like H,,CO,CO, and N,) during combustion, 4. It bum at a slow and steady rate. 5. Itshould possess low ignition delay (ignition delay is the time taken by the propellant to catch fire in the presence of an oxidizing agent. it is expressed in milli second) 6. It should possess high density. 7. It should be stable over a wider range of temperatures. 8, It should be safe to handle and store under ordinary condition. 9. It should be readily ignitable burning rate. 10. It should be non-corrosion and non-hydroscopic. 11. It should not produce toxic products. 12. should produce high temperature on combustion . & What is smokeless powder and gun powder? (C.S.V.T.U., Sem. I, Nov.-Dec. 2006) Ans. (a) Smokeless Powder (or Nitro-cellutose) It is prepared by treating cellulose with nitric (HNO*) and sulphuric (H,SO,) acids. The nitrocellulose so-formed is dissolved in a mixture of ether and alcohol and then, solvent is evaporated, when a jelly-like solid is Teft behind. Since the product is likely to react with traces of acid, liberated during storage, so “stabilizer” like diphenylamine is added, to it and the product then pressed into cylindrical rods. It is called smokeless powder, because it produces CO,, CO, N,, water vapour and almost no smoke. (b) Black Powder (or Ggun powder) Itis a mixture of 75% potassium nitrate, 15% charcoal and 10% sul- phur. It contains sufficient oxygen to combine with the other elements presint, when it is ignited. The decomposition reaction is - 10KNO, +3S+8H -$ 3K,SO, +2K,CO, +6CO, T+5N, T The excess of carbon and sulphur take part in the slower reduction processes, leading to the evolution of more gases. ‘916L09p856 “aL c6sB1696-‘OW YVOVN ILIMWS: ~~ S¥3Id09 VNHSINy Industrial chemicals, explosives and Propeltents | 225 178+ > K,SO, +3K,S, +400, 7 4K,CO, AK SO, +7C+ > 2K,CO, +2K,8, +5C Large volume of gaseous products account for its explosive effect. It is an excellent and cheap explosive for blasting down of coal as its low velocity (about 400 metres/sec) gives it a slow having action that does not shatter the coal unduly. its other important uses are time in delay-fuses. for blasting and in shelis, igniters and primer assemblies for propellants, prac- tice bombs, and saluting charges. Q. 9. What is rocket propellant? (CST. or Write short notes on Rocket propellant. (CS.V.T.U., Sem. 1, Nov.-Dec., 2007) ~ Or * What is rocket propellant? (Answer in 30-40 lines) (CS.V-.U., Sem. 1, Dee. / Jan., 2008-09) Ans. Rocket Propellont Rocket propellont is either a high oxygen containing fuel as a mixture of fuel pius cxidet, it» combustion takes place in # detivite and conivotied ‘manner with the evolution of hudge volume of gas, In rocket engine. the propellont is burnt in the combustion chamber Sem. 1, 2005, 2006-07) vi 300 kyimn-) escape theough the nozzle at very hugh velucity (called su: personic velocity). This act of pushing the gases downwards produces an equal and opposite reaction (Newton's third law of motion) which moves the rocket upward. ‘The main force responsible for the push i.e. propulsion ar thrisst (w) is proportional to- (i) the rate of which the fuel is burnt (v) and (ii) the velocity of exhaust gases (v,). Hence the performance of the rocket depends upon the exhaust ve- locity, The main parametes for the functioning of a rocket is the specific thrust or specific impulse (Isp). * Isp is the thrust delivered per unit mass of fuel consumed per sec. Isp depend on /7/)226 | SBP Q. B. Applied Chemistry where, T= temperature at which fuels barns M = Mean molecular weight of the gaseous products of combustion. More effective peopellents require higher T and loanes M. Uses : Rockets are used for phrotechnic effect signalling, carrying a life, hurning explosives at an enemy, putting space capsule into orbit, etc Q. 10. What is RDX (chemically) ? (C.S.V-T.U., Sem. I, 2008, 2006-07) Ans. RDX or Cyclonite is a powerful high explosive. It is chemically cyclotrimethylene trinitroamine. Itcan be prepased by treating hexamethylene tetra amine with concentrated HNO, (CH,),N, + 4HNO, —> (CH,NNO,) +NH,NO,+3HCHO RDX Farmaldehyde examethylene tetra amine RDX in shite ceys talline, grates -insolable compound. It isa pouseful. high explosive. It is more Sensitive but less toxic then TNT. Q. 1. What is dynamite ? (Ans, in one line) (CS.V.TLU., Sem. I, Dec. / Jan., 2008-09) Or Wrie short note on dynamite. Ans. DYNAMITE yeerge trinitrate (nia glye Nitroglycerine is an aily - liguid, which detonates by peessues, shock as spontane usly above 50°C. 4C,H,(NO,), —>10H,0 T+6N, 7 +12C0, +0. 7 10,000 Volumes at explosion temperature. ‘The explosion is so sudden that nitroglycerine would shatter the breech of rifle, before the bullet had time to move. It also pulverizes rock, instead of breaking it into fragments of usable size. For these reason as well as on account of the danger in handling and the impossiblity of safley transport- ing the substance, it is usnally mixed with an inert absorbent such as wood pulp, starch meals, saw dust etc. The amount of absorbent that is added to dynamite varies with its relative strenght. ‘ ° S. Brotner’s ENGINEERING TEXT BOOK OF ENVIRONMENT AND ECOLOGY For B.F First Year (SEM. II) Author Dr. N.B. SINGH MSc., Phi. Assistant Professor Department of Botany, Biotechnology and Microbiology Govt. Nagarjun P. G. College of Science Raipur(C.G.) A Unique Text Book Strictly as Rer C.S.V.T.U. Syllabus