40% ERING CHEmistay (GGsiru) INTRON a DUCTION 7 Years man’s dependence on energy has increased pramnge biped — chiefly fran, in the standard of living and rapid technological advances. eee Y from the fossil fuels such as Petroleum, coal and natural gas. Since these sources of enery “ever hence their proper utilization is the main concer these days. In un hap wing the basic understanding of the various fuels available to the mankind. T 8 IS necessary also for their proper ublization and conservation for future use wit Will never tast fo, We will be ha: understandin, @ ‘DEFINITION AND CLASSIFICATION OF FUELS __{GGSEPU, Ist Term 1999 : End Term Dec. 2557) vee ‘A fuel can be defined as any combustible substance which during combustion gives large amount of industrially and/or domestically useful heat. 'emical Fuel can be defined as any combustibie substance containing carbon as the im constituent wich during combustion gives large amount of industrially and/or domestically useful heat. Heat evolved by burnin; c 18 of fuels is used mainly for heating purposes, it can also perform other very important functions like coal, in locomotive engines ; and petrol, in intemal combustion ee Pl engines, are used for doing mechanical work. Coal is also used asa reducing agent in blast furnace. P Ew Classification {S6SIPU, Ist Term 1999 ; End Term 2002, 07]. Fuels can be classified « T Yh On the basis of their occurrence E Rd © Natural or primary fuels. Fuels which are found in nature as such are called natural fuels R £8» wood, coal, peat, petroleum and natural gas. ® Artificial or secondory oil, petrol, coal gas etc. ) On the Basis of physical state of aggregation. On this basis, there are three types of fuels viz. solid, liquid and gaseous. ‘The important examples of above categories (A) and (B) of fuels are tabulated below Table 1 Classifications of Chemical Fuels T Type of Fuel Natural or Primary | Artificial or Secondary Solid Wood, peat. lignite, Dung, bitu- | Charcoal. coke etc minous coal and anthracite coal | oo Lipa ds Crude oil | Petrol diesel and various other frachons of : petroleum pa tural gas | Coal 23s, oil gas. Bio gas. wa The primary or main sources of Fuels like coals and Petroleum oils are dwindling day-by-day. These are also called ‘Fossil Fuels’FUELS 5 3 _scuaficrenisries OF A GOOD FUEL (THE CRITERIA FOR SELECTING A GOOD FUEL) [GGSIPU, End Term, 2000. 21 iF High Colorific value! G6SIPU, End Term 2011]. Calorific value of a fuel is the total quantity of heat liberated, from combustion of a unit mass (or volume) of the fuel in air or oxygen. A good fuel should possess high calorific value, since the amount of heat liberated and temperature attained thereby depends upon this property of fuel -® Moderate ignition temperature!S6SIPU. Und Term, 2005, 06, 10, End Term 2011] The lowest temperature to which the fuel must be pre-heated so that it starts burning smoothly is called ignition temperature. Low ignition temperature (can cause fire hazards) during storage and transport of fuel, on the other hand, fuel with high ignition temperature is safe for storage, handling and transport but their might be some difficulty during ignition of fuel. Hence, an ideal fuel should have moderate ignition temperature. ‘tow Moisture content, The moisture if present in the fuel reduces its heating value. This ultimately leads to loss of money, because moisture is paid for at the same rate as the fuel. Hence, fuel should have low moisture content. _-Actow non-combustible matier content or low ash content (SGSIPU. Lind Term. Nov. 2005], The non-combustible matter remains in the form of ash or clinker, after combustion. It also reduces the heating value. There is additional cost of storage, handling and disposal of the waste involved with il. Hence, a fuel should have low content of non-combustible matter _S-Moderate rate of combustion. If the rate of combustion is low, then a part of the heat libefated may get radiated, instead of raising the temperature hence the required high temperature may not be attained. On the other hand, too high combustion rates are also not required because then it gets out of control. For a continuous supply of heat, fuel must burn with a moderate rate «Harmless combustion products. They should not pollute the atmosphere by emitting CO,SO,, H,S and other poisonous gases. 7 High suitability. A good fuel is one which is most suitable for the desired use. For example, coke made from bituminous coal is most suitable for blast furnace and also as a foundry fuel High calorific intensity(GSIPU. Nov. 2005]. Catorific intensity of a fuel is the maximum temperature attained when fuel is burnt. The calorific intensity of fuel should be high enough to melt the metal. }Greater flexibility and control. “Flexibility” means the rate of response in heat liberation withthe variation in operating conditions such as fuel or air supply, A fuel which can be easily ignited, which can be burnt at varied rates so that the heat generation is rapid or slow as desired. which can be easily handled, or to sum up, which has a greater flexibility, proves itself to be more preferable and worthy than a fuel which has high calorific value but lower flexibility. “Availability at low cost. A good fuel is one which is readily and economically available in desiréd quantity.apamaverrte 6 ENGINEERING CHEMISTRY (GOSIPU) Jr bay fo hansport. The transportation of a jood (uel is conventent and easy Low storage cost. A good quality fuel In waxy to store safely at a low cont 19¢ Controllable combustion so that combustion ean be started of stopped when required, 14,Oniform size, In case of solid fuel, the size should be uniform so that combustion iy regular’ 19¢Etlicioncy. A fuel should burn in air with efficiency without much smoke. Rel tive merits of solid, liquid and gaseous fuels are tabulated below in Table 2 yble 2 Relative Merits of Solid, Liquid and Gaseous Fuels "Solid Fuels Liquid Fuels Gaseous Fuels | : ee es — 5 Cheap More costly than solid | Costly fuel Easy Should be stored in Must be stored in leak | closed containers only | proof voluminous storage tanks Risk of fire Least Greater Very high (because azanis these fuels are highly fe tet inflammable) (2) Combustion | Slow process Quick Very rapid and rate efficient. (b) Combustion | Not easy control Can be controlled or | Possible by con-trolling ______| stopped when needed _| air supply. | 5. Handling cost High (Because labour is | Low (Because Liquid required in their storage, | and gaseous fuels can transport etc.) be easily transported = | through pipes) Low | 6. Ash Ash is always produced | No ash robles fo a m and its disposal is a : a | : = problenn | 7. Smoke Invariably produced ing i ‘but | Smoke u | Burning is clean but high carbon and aromatic liquid fuels = | may produce smoke 8 Use in Internal | Not possible fou ane combustion sible engine Smoke is not produced 9. Calorifie value Th mal efficiencytt 7 aaa FUELS 7 @ CALORIFIC VALUE (G6SIP, Dee. 2012} \_Splofific vatue of a fuel is “The total quantity of heat liberated from the combustion of a unit mass (or unit volume) of the fuel in air or oxygen”. Units of Heat <7Calorie’ is the amount of heat required to increase the temperature of 1 gm of water through one degree centigrade. “Kilocalorie’ (or “kilogram centigrade units”) is equal to 1,000 calories, This is the unit of heat in metric system and may be defined as “the quantity of heat required to increase the temperature of one kilogram of water through one degree centigrade. Thus 1 keal = 14000 cal 8° British Thermal Unit’. (B.Th.U,) is defined as “the quantity of heat required to increase the temperature of one pound of water-through one degree Fahrenheit. This is the English system unit. 1.B.Th. U.=252 cal=0.252 kcal or kee 968 B. Th. U. \— Centigrade heat unit’ (C.H.U.) is “the quantity of heat required to raise the-tem perature of 1 pound of water through one degree ces i Thus : Tkeal =3.968 B. Th. U.=2.2 C.H.U. a or gross calorific value (HCV) (GGSIPU, 2001, 06. 12), Hydrogen is found to be present in-afmost all fuels and when the calorific value of hydrogen-containing fuel is determined experimentally, the hydrogen is converted into steam. If the products of combustion are cundensed to the room temperature, the latent heat of condensation of steam also gets included in the measured heat, which is then called “higher or gross calorific value.” Highter or gross calorific value (HCV) is “the total amount of heat liberated, when unit ‘mass or unit volume of the fuel has been burnt completely and the products of combustion. are cooled to room temperature.” Lowpror net calorific value (LCV) [GGSIPU, 2001, 06, 12]. tp actual use of any fuel, the water vapousdnd moisture, ete. escape as such alongwith hot combustion gases. Since they are not C01 sed. Hence, a lesser amount of heat is available. So, Lower or net calorific value (LCV) is “the net heat produced, when unit mass or unit volume of the fuel is burnt completely and the combustion products are allowed to escape.” Alternatively, net or lower calorific value (LCV) 10) att =HCV -Latent heat of water vapour formed (page Since 1 part by mass of hydrogen produces 9 parts by mass of water. Hence LCV= HCV ~mass of hydrogen x 9 Latent heat of steam. The latent heat of steam is 587 kcal /kg or 1,060 B.Th.U,/Ib of water vapour formed at room temperature (i.e, 15° Q.8 ENGINEERING, ‘CHEMISTRY (GosiPu) wis salon value — °F solid or liquid fuel ; u For Gaseous fuels : Relation between various units 1 kcal / kg= calorie/gram or kilocalorie/kg + British Thermal unit (B.Th.U.) Kilocalorie/cubic metre ; B.Th.U,/Cubic feet. 3 18x B.Th.U//ib ; 1 kcal /m? =0.1077 x B.Thu.U/ft? ;1B.Th.U/ft? =9.3 keal/ m3, 1 Differences between NCV and GCV (G6SIPU, Lind Term 2002, 03, 11 ; End Term 2000, 01, 02, 11) [SH orcas cubic (ny) Gross or Higher Calorific Value (GOV) | ( | NCV is net calorific value, GCV is gross calorific value. (ii) It is defined as “the net heut produced, when unit mass or unit volume of the fuel is burnt completely and the combustion products are allowed to escape.” NCV Nev. GCV is also known as higher calorific value. Dulong’s formula : GCV = 1 es + 2240%S cals / gm 400 J where %C, %H, %O and %S are percentages of carbon, Hydrogen, oxygen and sulphur respectively. | [som 2c atsoo( th letermination of Calorific Value by Bomb Calorimeter [GGSIPU, Lind Term 2000, 01, 02, 09, 10, 12 ; End Term 2006, 09, 10] Principle. A known mass of the fuel i it juantity of heat luced is absorbed in water and mura Dene lyfe scaly oege tome tatscoans Bomb calorimeter is an apparatus used to find the calorific value Otsott iqusid-fuels, Construction, Bomb calorimeter -onsists ofa strong cylindrical stainless steel bomb, Bomb : ithstanding high pressures, and it is corrosion resistant also) in which the combustion of etna: ace. The bomb is provided with a lid, which can be screwed to the body of fuel is made to fake PPT gas tight seal. The lid is provided with two stainless steel electrodes bomb so as to make aie To one of the electrodes, a small ring is attached. In this ring, a nickel or and an oe eshaaaes be supported. The bomb is placed in a copper calorimeter, having a known stainless steal crucit?FUELS 9 weight of water. The copper calorimeter is surrounded by an air-jacket and water-jacket to prevent Joss of heat due to radiation. The calorimeter is provided with an electrical stirrer (lor suring water) and Beckmann’s thermometer (which can read accurately temperature di degree). erence upto 1/100" of a Beckmann’s — thermometer _- Electrical Electrodes to whicha ning, is attached Copper calorimeter Stainless ste bomb ‘of given fuel — Stainless steet sample crucible Bomb Calorimeter. Working. A weighed amount (about 0.5 to 1.0 gm) of the given fuel is taken in clean crucible. The crucible is then supported over the ring. A fine Mg wire, touching the fuel sample, is then stretched across the electrodes. The bomb lid is tightly screwed and bomb filled with oxygen to 25-30 atmospheric pressures. The bomb is then lov vred into copper calorimeter, containing a known mass of water. The initial temperature of the water is noted after thorough stirring. The electrodes are then connected to 6 volt battery and circuit is then completed. The ignition is initiated by passing a large voltage across a bare fuse wire which has been suitably fixed into the fuel sample. This fixing is normally performed by tying one end of a known mass and length of cotton thread around the fuse and the other and around the sample. The voltage shorts out the fuse which triggers the combustion reaction. The sample burns and heat is liberated which is transferred to water. Uniform stirring of water is continued and the maximum temperature attained is recorded. The calorific value of the fuel can now be calculated as below : Calculations : Let x =mass of fuel sample taken in crucible (in gms) ; W = mass of water in the calorimeter (in gms) w = water equivalent of calorimeter, stirrer, thermometer, bomb, etc. in gms [=mass x specific heat of apparatus =W' x S] nitial temperature of water in calorimeter ; = final temperature of water in calorimeter ; L= higher (eg., gross) calorific value of fuel (in cal/gm) = specific heat10 ENGINEERING CHEMISTRY (GGSIPU) Heat liberated by burning of fuel = x Leal au : And heat absorbed by water sve $ethoT fa echuaiad awa and Heat absorbed by apparatus = (W's S4(T,—T,) | ye, m is weight o(T, Ty) i 5 is specific heat ! ae is Temp. difference SINCE specific heat of water cal and 1 eal «4186 for 42 J Hence, total heat absorbed by water, apparatus etc : ‘at absorbed by water, appara ME (Wo Lely Ty) swe Le Cy TMV + WMT Td But heat berated by the fuel = Heat absorbed by water, apparatus etc LW 4 w(t 1) Or HCV of fuet (1) = eE ~7 Y cali gm or keal / kg x Fuels used for Determination of Water Equivalent of Calorimeter {GGSIPU End Term, March 2001 The water equivalent of the calorimeter (w) is determined by burning a fuel of known calorific value and using the above equation. The fuels used for this purpose are benzoic acid (HCV = 6,325 keal/kg) and naphthalene (HCV - 9,688 kcal/kg) Let H=% of hydrogen in fuel Then gms of hydrogen pre: pmavr zo H sent fuel=1x sentin gm fuel= 1 FF gm Asall fuels contain some hydrogen and when the calorific value is determined experimentally, hydrogen is converted into steam accor H, +40, —+ H,0 of hydrogen containing fuel rding to 2gm 1Bgm tgm 9 gm fe, weight of water produced from 1 gm H, =9 gm weight of water produced from a 8m H, (or | gm fuel) =9 x a 8m =009 Hgm Moreover, Latent heat of steam = 587 cal/ gm Heat taken by water in forming steam (or Latent heat of water vapour formed) =0.09 Hx 587 cal LCV = HCV — Latent heat of water vapour formed or LCV =(HCV -0.09 Hx 587) cal/ gm Rifas nd Term, 2006, 2010) 7 Bet more accurate results, cory ns must be considered while the following calculating the calorific value of a fuel Ali) Fuse wire correction. The heat liberated, as measured above, includes the heat ignition of the fuse wire used. Hence it must be subtracted from the tot: Biven out by al value. 7Fuss 17 (8) Agd correction, Fuels containing S and N are oxidized, under high pressure and temperature of ignition, to H,SO, and HNO, respectively S+H, +20, -» H,SO, + Heat 2N+H, +30, ——»2 HNO, + Heat Formation of these acids are exothermic reactions, So, the measured heat also includes the heat given out during the acid formation. The amount of these acids is analysed from washing of bomb by titration ; while H, SO, alone is determined by precipitation as BaSO, The correction for 1 mg of $ is 2.25 cal ; while for mL of N/10 HNO, formed is 1.43 cal “rity Cooling correction time taken to cool the water in calorimeter from maximum femperarire to room temperature is noted. From the rate of cooling (d T’/minute) and the actual time taken tor cooling (t minutes), the cooling correction of dT x t is added to the rise in temperature. \GierCotton thread correction. As cotton thread is used for igniting the fuel, so its burning aise generates haat Gross calorific value (GCV) = { Weight of , reek .| Rise in| Cooling )_{ Acid | Tuse wite Cott calorimy "Weight of fuel 52 Calculations of Gross Calorific Value (GCV) and Net Calorific Value (NCV) by Dulong’s formula using Ultimate Analysis Data for Coal Formulas used 1 : %0 GeV = 8080 Yi C-+38500 | % ) +2240 %S| cal / gm (1) NCV = [GCV -0.09 %H x 587] cal/gm 2) NOTES (a) GeV = HCY and NCV = Lev 2H, + 0, —> 240 (b) %C = Percentage of carbon in coal sample, 6 2 36 1 8 9 ‘4H = Percentage of hydrogen in coal sample, : Thus, 8 parts of oxygen combine with 1 part %0 = Percentage of oxygen in coal sample, of hydrogen to form H,0. ‘%S = Percentage of sulphur in coal sample. Fixed Hydrogen ~ Mass of oxygen inthe fuet (Q) % (C+ H+N+S + Ash] = 100 8 ~@) Amount of hydrogen available for combustion (d) The oxygen, if present in the fuel, is = Total hydrogen ~ Fixed hydrogen assumed to be present in the combined form ° with hydrogen as fixed hydrogen. -( 7 5)al SO ty 12 ENGINEERING CHemistRY (ccsiPuy , 2001, 2011) , 1 [GGSIPU. End Term. extermination of Clore Ve by toys Gs Clone ining the calorific values of mit Boy's gas calorimeter is a standard apparatus used for deter Saseous fuels and those liquid fuels which are easily vaporized. charles Vernon Boys F.RS. The Boys Gas Calorimeter was designed by the late Sir oeasorific values of a wide (1855-1944), to provide a simple but accurate method of ascertaining the a Tange of gaseous fuel currently in use Rubber ~ tubing Water inlet {_— Insulated container 4 toner Cucoil A— outer Caco Trough to collect F condensed water Condensed L-=@Q—= — Gaseous steam liquid tuel Figure 2 Boy's gas calorimeter, Principle ‘The gaseous fuel is bummed in a vessel at a constant rate in such a manner that the entire heat is absorbed by water which is circulated in a chimney around the burner From the volume of the Baseous fuel bumt, the volume of water collected and the rise of temperature of water, the calorific value of the fuel is determined, Construction The apparatus consists of a suitable gas bumer in which a kn burt ata known pressure and at uniform rate of3 —4litres per minute Around the a combustion chamber or chimney which has a copper tubing coiled incite as Water at a constant rate is passed through the coil Water enters from the t moves to the bottom of the chimney and then goes up through the ner coil thermometers give the temperatures of the incoming (T,) and outgoing water (T,) respectively During the process of down and up movement through the coil, the flowing water takes away practically whole of the heat of burner and the steam formed during combustion gets, condensed and can be collected as water. The lower portion of chimney is provided wumy a frough where water condensed from the products of combustion is collected and can be remover through the side tube for measurement of its volume. The whole assembly is enclosed in an insulated chamber. : ‘Op of the outer coil, to the exit at top. Therues 13 Working Circulation of water and burning of gaseous f : for initial warming up the calorimeter. WI “rates for about 15 minut atmospheric pressure. Heal_produced by burning of gaseous fuel is transte eed to water in the copper coil and the steam formed is condensed back into water which is collected when the steady conditions are established. Then readings are taken simultaneously of Wcthe volume of gaseous fuel burnt at given temperature and pressure in a certesr time period ; <_2Fhe quantity of water passing through the coil in the same time ; \2c“The steady rise in temperature, i., (7, ~T,). and ~Ac“weight of water condensed during this time. Observations Volume of gas burnt at STP in time = Vm? Weight of water passed through the coil in time t -W kg, Temperature of incoming water =, °C Note : Temperature of outgoing water = T, °C ade abacoen ee Fie Weight of condensed water (steam) =W" kg i ‘ight Let Higher (gross) calorific value of fuel = C kcal /m? sae mie ree s is specific heat Specific heat of water = 1 kcal/kg °C Os Temp. difference Calculations al heat absorbed by circulating water =W (I, -T,)+1 kg °C * Re 8 Heat produced by the combustion of fuel = Vx Cm ‘Assuming no heat loss, we get Heat produced = Heat absorbed = vxC=W(T, -T) W(t, - v ‘As Latent heat of steam is heat liberated in condensing, water vapour and cooling the condensate and is equal to 587 cal/gm or keal/kg, > c 1) geal m? Weight of water condensed from 1m? of gas = * karim? wk Vm v So, Latent heat of steam per mv’ ot gas. = 587 keal/ kg» value of the fuel = Higher calorific value Latent heat of steam per m? of gas W" x 587 = Lcv v14 Pn CHEMISTRY (GGsipu) Numericals Based on sing Boy's Gas Example 1 Calorific Value Determinations Calorimeter Data : The following data were obtained in a Boy's gas calorimeter experiment. Volume of gas used =0.1 mi? at tp © V Weight of water heated =26 kg = W Temperature of inlet water =26°C ef, 1 ‘y S Temperature of outlet water = 36°C 2 T> F ies Weight of steam condensed =0.030 kg W'® ach sabia, Caleulate the higher and lower cal "WS water vapor and cooling the con: Solution. (i) Given : ‘ XS sHV— Ww XS) [e v Weight of water heated = W =26 kg vrific value per m? at STP. Take the heat liberated in Condens: idensate as 58 kcal ‘Temperature of outlet water =T, =36°C ‘Temperature of inlet water =T, =26°C Volume of gas used = V =0.1 m? Let Higher calorific value = HCV ‘ ia 4 In a Boy's gas calorimeter experiment : on HEV = y a > Hcy = 2606-26) | cat)? 0o1 a HCV = 2600 k cal/m? ~@) (ii) Given, =W’ =0.030 kg ight of steam condensed =W’ f = liberated in condensing water vapor and Cooling the condensate = 580 k callkg eat liber Let Lower calorific value = LCV In a Boy's gas calorimeter experiment : (3) Lev= Lcv -[ > : a LCV = 2426 k cal/m i:runs 15 [Example 2 Calculate grows and net calorific value of a gaseous fuel from the following stata Volume of kaseous fuel burnitat STP 60.09 mi, werght of water ued for cooling 25049 Temperature of let wouter = 25°C temperature of outlet water = 30°C, weight of water produced by steane comeseation 01.02 kg, latent heat of steam © 587 k cal/kg Solution, (1) Given, We2Sky, 7, 9d0'CG 19 28°C, Ved0¥m! In a Boy's gas calorimeter experiment wih, 1 Gey Oy atym! “ 25 (0-2 = cy 500-25), catim? 0.09 2 GOV © 1388.9 k cal/m * @ (ti) Given W’ = 0.02 kg, Latent heat of steam = 587 k cal/ky, Ina Boy's gas calorimeter experiment nev -lcev W387) i cat fm? B) ved > NCV [ra paren 0.09 = NCV = 1258.5 k cal/m? (a) Example 3. Calculate gross and net calorific value of a gaseous fuel from the following data obtained from calorimeter experiment. Volume of gascous fuel burnt at STP =0.1 n°, weight of water used for cooling 35.0 kg, temperature of inlet water =26.0°C, temperature of oullet water is 42.0°C, weight of water produced by steam condensation = 0.03 kg, latent heat of steam = 587 k callkg. Solution. () Given Wa35kg 7, =42°G 1, = 26°C, V=0.1m! Ina Boy's gas calorimeter experiment : Mz Ty) ccv keal/m* a) 35(42- 26) = Gcv = Kcal/m? > GCV = 5600 k cal/m? Q)_L97Using Bomb’s Calorimeter Data: Fxample 4 The follozing data were obtained in a bomb calorimeter experiment : | weight of coal burnt =0.996 g = i ’ weight of water in calorimeter =2490 > ‘ tvight of tomb elorineter et, = 39008 aS aa | 4 rise in temperature of water =2.592 C272" J we = 1 ‘mean specific heat of apparatus = 0.0992 $ H If the fuel contains 6% hydrogen, calculate its lower calorific value assuming 587 cal/gm as latent hieat of steam. He & — (G6SIPU, Beech Hind Term, Nov. 2006, 2001, Oct 2013) Solution. Let | 16 ENGINEERING CHEMISTRY (GGSIPU) | | ; | ; i x= mass of fuel sample taken in crucible (in gms) ; W = mass of water in the calorimeter (in gms) w= water equivalent of calorimeter, stirer, thermometer, bomb, etc. in gms ‘Pitas x specific heat) of apparatus =W' x $ =3900>0.099] T, = initial temperature of water in calorimeter ; T, = final temperature of water in calorimeter ; L= higher (e.g., gross) calorific value of fuel (in cal/gm) S= specific heat : HCV of fuel (1) = * 2B -h) x cal/ gm or kcal/kg (1) LCV =(HCV -0.09 Hx 587) cal/ gm (2) Hcy (2490+ 3900 0.099)1(2.592) 0.996 = 7484.8 calsigm LCV =7484.8 -0.09x 6x 587 = 7167.82 cals/gm Example 5 A sample of coal was tested for its crlo rific value using Bomb's calorimeter. Following data was obtained : weight of coal burn! 1.920 gm tweight of water taken =550 gm toater equivalent of Lomb and calorimeter ~2200 gm rise in temperature =2.42 °C fuse wire correction = 10 cal Acid correction = 50 cal Assuming con! to contain C=98%, H=6% and ash =1% r calculate s tau of coal. The latent heat of condensation of steam is 580 catl@n, Sd Met eMloifcrues 17 Solution. Gross calorific value (GCV) {weight ot WaT | (Rein | Cooling | {water aameten | (temperature "correction / Acid Fuse wire Cotton thread (correction ‘correction correction » Weight of fuel ‘ (550 +2200)(2.42)-(50-+ 10) > Ve — = 7168: aon 168.5 cals/gm => NCV =[GCV ~0.09 % Hx 580} cals/ gm (2) = 7168.5 0.09 x 6x 580 = 6855.3 cals/gm xample 6 In abomb calorimeter experiment, the following data was obtained : Weight of coal = 0.834 Weight of water taken in the calorimeter =1365 g ; Water equivalent of the calorimeter = 135g Observed rise in temperature =3.74° C; Calculate gross and net calorific values of cou, if it contains 8% of hydrog IGGSIPU, Oct. 2011 ; End Term Dec. 2010 °C; x=0.834 gm Solution. (a) Given, W = 1365 gm ; w=135 gm ; (T) -T,)=3- Substituting the above values in Eqn. (1), we get cy = 1365+ 13518-74)] 0.834 = cv = 1500x374 0.834 = GCV = 6726.46 cal/ gm (0) Given %H =6 Substituting this %H and value of GCV in Eqn. (2), we get NCV = (67266 ~ 0,09 x 8x 587) cal/ gm = NCV = 6303.98 cal/gm Example 7 A sample of coal contains 92% C, 54% Hand 3% ash When this coal was tested for its calorific value in the bomb calorimeter, the following results were obtained : Weight of coal =0.95 x Weight of water taken in the calorimeter =700g ; Water equivalent of bomb calorimeter = 2000. in temperature «248°C ; Acid correction =60.0 cal ; Cooling correction =0.02 °C ; Fuse wvire correction =10.0 cal. Calculate gross and net calorific values of coal. Given latent heat of condensation of steam = 587 calle. Solution. (a) Given, W=700 gm; = 2000 gm; (Ty -Ty)=248°C; CC=0.02°C AC=60 cal; FWC=10 cal ; CTC =0 cal, x=0.95 gm Increas‘V8 ENGINEERING CHEMISTRY (GGSIPU) Substituting the above values in Eqn. (1), we get 4 cy = L1700+2000)2.48 + 00291-01109 gry Sere 095 | ae cy = 2700%2.50} - £70} cal/gm | 0.95 ' > GCV = 7031.58 cal/gm (b) Given %H =5 bay Substituting this %H and value of GCV in Eqn. (2), we get NCV =(7031.58 ~ 0.09 5587) cal/ gm ‘ > NCV = 6767.43 cal/gm. | ein Dutong’s formula Ple§ Calculate GCV and NCV for a coal having flowing composition by weight : clols|wlaslw» Gosipu Col aoe bx | 25s | vas fase rest (B.Tech, Und Term, Nov. 2002 | i), 75% 12% | rest j 32% | 45% | sam (B.Tech., November 2001) (iii) 70% | 161% | (iv) aaa 3% | 05% | 05% | 25% rest | (B.Tech, End Term, Masch 2000) | ©) me | a1 27/2 85% rest | 32% | 4.5% | 6.2% (B.Tech, October 2000) 5.2% | (B.Tech, TInd Term ; End Term, Dec. 2000) ni ax | an | os | sy | (Tech, tind Term ; End Term, Dec, 2006) Solution, Dulong’s Formulas ev 5 [som ee +20 xs] cal/gm _) NCV=[GCV 0.09 %H x 587) cal/gm 2) NOTES (@) OCV=HCV and Nev = Ley (0) %C = Percentage of carbon in coal sample, ‘GH = Percentage of hydvogen in coal sample, WO = Percentage of oxygen in coal sample, ‘%S = Percentage of sulphur in coal sample, N = Percentage of nitrogen in coal sample. (0) % [C+ H4+N+S+Ash +0} = 100 (3)@ oH = 100 -[% C4 %O+%S + %N + % Ash) 100 [8045 52.5 +1.4+2.1]=100-91=9 ccv- 1 100) NCV 8762.5 ~ 0.09 « 9 x 587 = 8287.03 kcal/kg (ii) S=100-[75+5.2412.143.2+45]=0 1 100 NCV = 7332.18 — 0.09 5.2 x 587 = 7057.47 keallkg, GCV= [s080x75.+34500| 5.2- 21) 22400 t \ (ii) $= 100-[70+16.143.2 + 45+6.2]=0 ccv- [soso 7013400 62 100 16.1 8 ) NCV = 7100.69 — 0.09 x 6.2 x 587 = 6773.14 kcal/kg, (iv) %H=100-[9043+05+0.5+25]=35 GCV= AS 100 NCV = 8361.33 -0.09x3.5x 587 = 8176.43 kcal/kg 1 128 8080 80 + 34500{ 9 3 22402 5| = 8762.5 kcal/kg 7332.18 kcal/kg, }+2240%0] = 7100.69 keal/kg [roo x90 +34500{ 3.5 — 3 } +2240 0s] = 8361.33 kcal/kg, (vy) GCV=— [sov0.75--4500 52-8 )} 22012] 7328.88 kcal/kg, 100 NCV = 7328.88 - 0.09% 5.2 x 587 = 7054.16 kcal/kg, (vi) GCV= |8080x85 +34500/ 8 100. : 0) NCV = 9650.4 ~ 0.09x8x 587 = 9227.76 kcal/kg, +2240 | = 9650.4 keal/kg [Example 9A cual sample contains C=80% H=7% $=3.5% N=2.1% O=3% and ash =44% Calculate GCV and NCV of fucl. The latent heat of steam =587 cal/g Solution. Given, %C =80 ; %H=7 ; %O =3 ; %5 =3.5 (a) Substituting these values in Eqn. (1), we get IGGSIPU, IInd Term, Nov. 2010] ccv- | {soso a0 +34500(7- 3) + 240135] cal/ gm 100 | 8 = GCV = 8828.03 cal /gm20 ENGINEERING CHEMISTRY (GGSIPU) (6) Substituting %H =10.5 in Eqn. (2), we get NCV = (8828.03 -0.097 587) cal/gm = NCV = 8458.2 cal/gm Example 10. The ultimate analysis ofcoal have the following results: C=B4% ; H =5.5% jO=84% and 5=1.5% Calculate the gross and net calorific value of coal using Dulong’s formula. {GGSIPU, IInd Term, Nov. 2009] Solution. Given, C=84%; H=5.5%; O=84% and $=15% (a) Substituting these values in Eqn. (1), we get ceve [toso= st a4s00[5s a] ra0x15| cal/gm > GCV = 8356.05 cal/gm (b) Substituting %H =5.5 in Eqn. (2), we get NCV = (8356.05 -0.09 5.5 587) cal/gm > NCV = 8065.485 cal/gm | Example 11. A coal has the following composition by weight :C =90%, 0=3.0% $ Net calorific value of the coal was and higher calorific value of coal. Solution. Given, C=90% 0=3.0% $=0.5% and Ash=2.5% . %H=[100 = (%C + %O + %S + %Ash)] = %H=100 ~ (90 +3 +05 +25) = %H=100 - 96=4 S%and ash =2.5%. {found t0 be 8490.5 keallkg, Calculate the percentage of hydrogen IGGSIPU, End Term, Jan. 2011] (a) Substituting these values in Eqn. (1), we get 7 [ronox90--se00(« = 2) + 2210-05] kcal/kg, > GCV = 8533.825 keal/ kg (0) Alternative solution Given NCV =84905 kcal/kg ; %H=4 Rearranging Eqn. (2), we get “GCV =NCV+0.09 %Hx587 = CCV =81905 +0,09 «44587 GCV = 8701.82 keal/kg. (2a) woe)rues 21 6 PETROLEUM \._Petraletim or crude oil is a source of many liquid fuels that are in current use. The word petroleum is derived from latin (Petra = rock ; oleum = oil), Petroleum is also called mineral oil because it occurs beneath the earth. _ The composition (average) of petroleum {GGSIPU, Hind Term, Mov. 2005] See (C=80t0 87%); (H=111t0 15%); =011035%) i (O=0.1 to 0.9%) and (N=04100.9%) Petroleum is a complex mixture of paraffinic, olefinic and aromatic hydrocarbons with small quantities of organic ai nitrogen_and sulphur. The common constituents present ble 3 below Table 3 Constituents of Petroleum Constituent | aa Hydrocarbons | These are present to the extent of Apart from normal, branched and | cycloalkanes. lower boiling fractions also contain afky! benzenes. Higher boiling | fractions contain polynuclear aromatics like naphthalenes. Terpenes are also present to smail extent Sulphur conts Sulphur is also present either in elemental form or in the form of inorganic | | compounds |_ofganic sulphur compounds, oz. H | | Oxygen containing | (C, ~ Ca) carboxylic acids occur in low boiling fractions while naphthenic acids | | compounds | occur in high-boiling fractions. Trace amounts of phenals and cresols also present. Nitrogen containing | These are present in traces and are mainly pytrote, indole, pyridine, quinoline compounds ete ae Inorganic _compounds | These are organometallic compounds of Cu. Fe. Ni and ¥ to very little extent. 6:4 Refining of Crude Oil The crude oil is separated into various fractions (having different boiling ranges) by fractional distillation. These fractions are finally converted into desired specific products by removing objectionable impurities. The process is called “refining of crude oil” and the plants set up for this purpose are called oil refineries. The of refining involve the following stages : ser Sort twtr (Cottrel’s process) The crude oil is separated from water by allowing the crude to flow between two highly charged electrodes. The colloidal water-droplets coalesce to form large drops, which separate out from the oil. _{b) Removal of harmful sulphur compounds Sulphur compounds are removed by treating the crude oil with copper oxide. Treatment results in the formation of copper sulphide in solid form which can be removed by filtration.RE 22 NGINEERING CHEMISTRY (GGSIPU) Why is it ? Necessary to re ds from oil and natural gas ? move sulphur compoun idee te ate ty of untreated petroleum distillates, such as LPG, Retosere aasoline ete, npounds such as thioalcohols or thiols or more commonly known as Present. ai the pe TeaPtaRs are undesirable in finished petroleum products because they odveteely oles © Product's odour, quality, stability, apart from being corrosive to the refining an han ing equipment. Specially an aryl mercaptan (or thiophenol) is undesirable in finished gasoline Pecause it produces an unstable gasoline by promoting hydroperoxidation of olefins to gum. Removal of Sulphur compoun a ahd trol ducts by Doctor's treatment pounds from gasoline or other petroleum prot oF Sweetening of Petrot . [GGSIPU, Nov. 2005] In a wide variet organic sulphur com Mercaptans are Removal of mercaptan can be done with Doctor solution. The Doctor treatment consists of contacting the oil with a little sulphur and alkaline sodium plumbite solution : +Nay 2RsH — 2, (Rs), Pb + 2NaOH +S A (RS),P>_ ——+_ R,S, + PbS Phumbite can be regenerated from lead sulfide () Meatng in ar (150-175 F) Me Pes Na, Pb O, (amon (c) Fractional distillation {GGSIPU, IInd Term, 2003, 2005] = The crude oil is heated to about 400°C in a pipe still whereby all volatile constituents are * evaporated. The hot_vapours_are then rough a tall cylindrical tower, known as ‘fractionating column, containing a number of horizontal stainless steel trays at short distances. These =] eet re nai Residue Furnace 400°C oil pipe from upper plate gare 3 Fractional estilaton of cude ol (etleum) idr oie <> f FUELS 23 ye are provided with individual chimneys which are covered with a loose cap. As the vapours goup. fractional condensation takes place at different heights of column. Higher boiling tractions condenses first? while the lower boiling fr. ons condenses later as shown in Fig. 3. AP Condensed liquid runs down from tray to tray through overflow pipes. ® Vapour rises from tray me to tray by bubbling through the condensed liquid by raising the . ee : Various principal fractionation products are given in Table 4. ‘Table 4 Major Fractions Obtained by Distillation of Crude Oil {{GESIPU, Und Term, 2003, 2005) Ss. i ‘Approx. composition in ‘ee | Fraction’s Nome | , Siting | Terms of hydrocarbon Applications . temperature containing C atoms 1. | Uncondensed gas. | <30°C GtoG Used as domestic (Refinery gas) (such as ethane, propane, | industrial fuel under the — isobutane) Lower name LPG. (Liquefied pe a : ___| rea mere | petroleum yas). = Petroleum ether. | 30° to 70°C_ | C.-C Used as a solvent Gasoline or petrol or | 40 to 120°C (calorific value | Used ay fuel for IC engines, motor spirit. | 11.250) keatskg._| solvent and in dey cleaning. _ Naphtha or solvent | 120 to 180°C | C, ~ Go As solvent for paints, spirit. ' and vamishes and in _| dry cleaning, Kerosene oil 180 to 250°C | Go ~ Gg (calorific value | As an illuminant jet engine fuel 1.000 keal/kp)_|_and for preparing laboratory gas. «(calorific value | used as diesel engine fuel. soil, ______4 211,000 keal/kg)_| —————— Heavy oil. 320 to 400°C | Gz = Cy For getting gasoline by | cracking, on refractionation gives : (0 Lubricating oil. Diesel oil or fuel oil OF gas oil. 250 to 320°C As lubricants {ii) Petroleum jelly. (Vaseline) (iii) Grease. In cosmetics and medicines. As lubricant. (iv) Paraffin wax. In candles, boot polishes, wax ses — — _______| paper, tarapaulin cloth, ete. 8. | Residue may be > 400°C Cyy and above Used for Waterproofing of cither : roofs and road making. ( Asphalt. (id or Petroleum coke. ‘Asa fuel and in moulding are light rods. i compounds are not found in gases or gasoline fractions because of their higher boiling temperatures. : {GGSIPU, Und Term, Nov. 2005}c 4 A P T E R 24 EN SINEERING CHEmistay (GcsiPu) 6, brief description of three most important Liquid fuels viz. Gasoline, rosene and Diesel Oi a) Gasoline or intane to octane. This Petrol fraction. It ‘ture of hydrocarbons from pentane to eons obtained between aoa on "This fractions highly volatile and int ble and used el for s engines. Its calorific value i about 11,250 cal/gm. 's a mixture of higher hydrocarbons (C,5 to Cy} This fraction is obtained 520°C It is used as a fuel for diesel engine anid ifs calorific value is about eL Oil. Ut is saa Reese i ily. It iapetiae agama oil. 1Lis a mixture of hydrocarbons (Cp to C,,)-It does not vaporise easily. It is io Mestic fuel in stoves, as jet engine fuel and for maKing oil gas. It calorific value is about 100 cal/gi Hee E \ FSSC Of Gasoline Fuel with Diesel Fuel S.No. Characteristics Gasoline Fuel 1 [cae i iii Consumption per unit of power produced 3. | Thermai efficiency | | Polluting and formed in higher | Polluting and formed in lesser | am | amounts | 4. | Nature of exhaust gases 5. | Combustion process internal Requires compressed air and combustion engine since ‘complex, more expensive fuel compressed air is not needed for | injection device combustion of gasoline 7 rues Fon TERNAL COMBUSTION (IC) EN : “in an IC engine, a mixture of fuel and air is ignited in a cylinder, either pom ret electric spark (spark-ignition engine ¢g, petrol engine) or by compressing the air (compression- ignition engine e.g., diesel engine) and the gases evolved under hij down, thus providing the power stroke In a 4stroke IC engine (Fig 4), following four strokes complete their working cycle: (i) Intake stroke. A mix suction stroke of the cycle. igh pressure force the piston ‘ture of fuel vapour and air is drawn into the cylinder during the NOTE _ Gasoline in petrol is a liquid at ordinary temperatures but eva sporates readily === (ooiling point range 30° ~ 200°C) in air to form an easily inflammable mixture. (ii) Compression Stroke. The piston compresses the mixture in the compression part of the cycle.YS oh. ues 25 Exhaust b) &} (intake cic (i) Compression (ii Power (ie) Exhaust Figure 4 The operation of a four-stroke engine can be divided into four cycles + intake, compression, power and exhaust stages. Gii) Power Stroke. Spark ignites compressed air-gasoline mixture in the immediate vicinity of the spark plug. The hot gaseous products of combustion expand and a flame front travelsat regular and orderly rate through the remainder of the fuel mixture. The hot products 0 combustion increases the pressure and pushes the piston out, providing an output of power. (iv) Exhaust Stroke. In the last part (Exhaust stroke) of the cycle the piston ascends and expels the exhaust gases from the cylinder. A second cycle starts again with the piston descending, down. For optimum efficiency, the following, points are worth consideration : ‘The fuel must completely evaporate in the carburetter and if it does not, there is incomplete combustion and this leads to ‘starting-trouble’, experienced especially during winter. In summer, the engine will be hot and even if some oil-drops instead of vapour are drawn into the: cylinder, they are instantaneously vaporized and starting is easy. However, if the fuel evaporates before setting into the carburetter, the vapour lock formed in the fuel supply line stops the engine. The vapour pressure should not exceed 0.63 kg/cm” (about 9 psi) for gasolines used in summer and 0.77 kg/cm? (about 11 psi) for those in winter months. Aviation gasoline should not have vapour pressure exceeding 0.49 kg/ cm? (about 7 psi). ‘Another problem arising out of any less volatile, unbumt fuel remaining in the cylinder is the dilution of lubricating oil,,This promotes friction and wear. ‘A brief comparison of Petrol and Diesel engines is given in Table 6. le 6 Comparison of Petrol and Diesel Engines 5.No. Description Petrol Engine Diesel Engine () | Fuel (Petrol + air) mixture | (Diesel + air) mixture (i) | Ignition By spark plug, By compression of air (iii) | Cause of knocking Pre-ignition Delayed-ignition (iv) | Knocking characteristics expressed in Octane rating Cetane rating (0) _| Examples of additives to reduce knocking | TEL, Diethyl telluride _| Alkyl nitrites = a26 ENGINE ( ( S_AXNockine teasrpU, ind Term 700? ; End Term, 2000, 2006] \e \—Temninology : ERING CHEMISTRY (GGSIPU) combustion is ae (2) Ignition temperature. It is the minimum erature_at which the SSeupporting. This is also referred to as spontaneo! fions Femi (b) Compression ratio (GGSIPU. Ind Term. Nov. 2005], The power output and efficiency af anIC engine depends on a factor called compression ratio (CR). It is define! as the ratio 2 sescous volume (V,) in the cylinder at the end of the suctionrstroke to the volume (Va).at the end of compression-stroke of the piston, The CR obviously indicates the extent of compression of fuel-air mixture by the piston. Knocking and Compression Ratio The fuel-air miature gets heated to a temperature greater than its ignition temperature as a result of compression. This leads to spontaneous combustion evencbefore sparking? : It is also possible that the last portion of the fuel-air mixture undergoes self-ignition after sparking. It is due to the heating and compression of the unburned fuel, by the spreading flame- front sweeping across the cylinde! The resulting shock wave dissipates its energy by hitting the cylinder walls and the piston. In view of the characteristic rattling sound emitted, this is called knocking. The CR at which fuel tends to knock is vailed critical compression ratio. io limit, the ignition nperature of the fuel gets reduced and the ignition takes place before the piston head reaches the end of the compression stroke. As a result, combustion of fuel takes place much rapidly. The remaming fuel in the cylinder burns in an explosive manner and disorderly fashion ahead of the flame front and so produces the characteristic ratling sound called “knocking”. 278 When gnitzon of fuel/air minture takes place at the ight time, the fuel power generated is utilized in driving the internal combustion engines of scooters, cars etc. ~A When ignition occurs much earlier, that is before the end of compression stroke, the combustion energy is lost in producing metallic sound, called as knocking. en ee ae = Knocking is a sharp metallic sound similar to rattling of hammer which is produced in the internal combustion engine due to immature ignition of the air/fuel mixture. To Summarize : With increase i CR, tendency to knock also increases. * —Consequences of knocking # Decreased power output, —® Mechanical damage by over heating of the cylinder parts. Probable Mechanism of chemical reactions that lead to knocking CR. efficiency of IC engine also increases but after critical Free_radical_chain reaction leading to Cracking and Oxidation of the hydrocarbons is probably the mechanism of chemical reactions that Tead to knocking. esFactors on which knocking depend: Ma Engine desig aes pi ‘Gi Running conditions and Meat) ructure of the fuel hydrocarbons, For instance : ® knocking tende = eney decreases in the ord. ralkanes > mono-substituted alkane es > mono-subs tuted alkanes > cyclo alkanes > alkenes: > poly substituted alkenes. > aroma And, for straight ah; i : rs chain hydrocatbons, weight and boiling poin ae or s the tendency to knock increases with molecular ing properties than paraffins and olefins. 02, 05 ; End Term 2000, 02, 06, 12] e resistance offered by gasoline to knocking cannot be defined in_absolute terms. It is fecal expressed on an arbitrary scale, known as Octane rating (proposed by Graham Fdgar Fuel Octane number Characteristics heptane 0 Knocks severely iso-octane 100 High resistance to knocking ‘ The % of iso-octane in the heptane — iso-octane blend which has the same knocking characteristics as the gasoline sample, under the same set of conditions is known as octane number. 9.1 Influence of Structure of the Fuel on the Octane Rating [GGSIPU, Ind Term 2002 ; End Term 2000, 2006} (i) As straight chain (or normal) hydrocarbons knock severely in petrol engines so they have lowest octane numbers. (ii) As the knocking tendency of rralkanes increases with the increase in the length of carbon chain so anti-knocking properties (and thus octane numbers) also decrease with increase in the length of the carbon chain. x For example : 5 cae n-paraffin Octane number Methane 12 Ethane 101 Propane 96 n-butane 89 pentane 60 hexane 2 mheptane 0 snonane. 245 - arya —— 28 En GINEERING CHEMISTRY (GGSIPU) knock so they have higher anti: | chain paraffins. of branches and theit posit ii , frotens ?) Branched chain paraffins have lower tendency to Ses (and thus octane numbers) in comparison to normal Fi ; i Furthermore, resistance to knock increases with thenumbe For example : = 2, 2edimethy! pentane, 80 Hydrocarbon irheptane 2methy! hexane | Octane number {| a 3, Recently, the hydrocarbon 2,2,3~trimethylpentane called tiptane has been assigned an octane number, 125. () Knocking tendency decreases.with the increase in the number of carbot bonds in the hydrocarbon fuel. Thus, olefins have higher anticknack properties (and thus octane number) than the paraffins ber) increases as the position of same carbon-chain Tength ncy (and thus octane nym! y= of chain. cenbel ascgbe b the compactness of the molecules. As a higher than sralkanes, branched- arbon double Furthermore, the anti-knacking, of the double bond approaches the (®) The knocking tendency decreases with incr result, octane number of cyclo-paraifins (Napth c fi alkanes and alkenes A (v2) Aromatic-hydrocarbons such as benzene and toluene have less knocking tendency than P naphthenes so th Fe ie | hexane Cyclohexane Benzene f [octane aumber | 26 77 100+ To sum up Straight-chain paraffins 4 Branched-chain paraffins Knocking tendency decreases as we move it downwards Otefins © Antiknocking property of fuel increases as ’ we move downwards sas in shthe © Octane number of fuel increases as we Cycloparaffi : (Naphthenes) Pee down Aromatics To remember in reverse, use acronym : ACO BS (ci) In cracked and reformed gasoline, it is the presence of olefins, iso-paraffins and aromatic hydrocarbons that increase its anti-knocking properties and thus the octane number. NoTE _ Gasoline used in automobiles should have an octane number 80 or higher, while === gasoline used in aeroplanes has an octane numbers 100 or even higher.[ . rues 29 Engine oh | 1pm Getane | j teed di i | Fuel | Getane | Application | Taw speed diesel engine | 150 - 500 | nib jetot || ¥ sium speed diese Low speed diesel fuel 25. | Ships | | Medium speed diesel engine igh speed diese engine | 500-1500] Medium speed diesel fuel | > 35. | Tractors or hesundion | speed diesel engine | ee engine | 15002000] High speed dies fuel |_>45_ | Tracks and buses _| attire oe eee {[GestPu, End Term, 2000] Tetra ethyl lead (TEL) ; additives TOMS, P ) and diethyl telluride {(C3H,), Te) are the most commonly used ! ~ 7 TEL gives rise ni 5 inhibitors eh neciore and PbO during combustion. These particles act as free- radical chain - ey 1e propagation of the explosive chain reactions responsible for knocking, ficiency of e preferred. cy of TEL decreases in. presence of sulphur hence Desulphurized Gasoline is Pb and PbO, decrease engine life henc i Pb and PbO, decreas eth + be removed along with & es b addingeethylene dibromide. ey must be removed along with exhaust gases PY (Pb, PbO, + C,H,Br) —> PbBr,) Because PbBr, formed is volatile it escapes into atmosphere. But poltution problem still exists. Another cause of pollution is incomplete combustion leading. to the formation of CO, NO, NO, 50, $0; etc. Hence catalytic convertors based on Pt are employed which will catalyze combustion reaction to completion. eg, co —> CO, But Pt is poisoned by Pb, so Unleaded Petrol should be used. Benzene is added for decreasing knocking. Since benzene 'S carcinogenic, very low concentration of benzene should be used (/4.0_PNCEADED PETROL __ a 7 i The petrol whose octane number is Nous without the addition of lead compounds is referred to a: ‘unleaded pet \ The Octane number of a fuel can be increased by : (i Reforming. This process increases the contents of molecules having branched and aromatic ring structures. ‘Thus, by molecular reforming, the contents of isopentane, isooctane, ethyl penzene and isopropyl benzene increases in the given fuel. oe opropy’ oes (ii) Methyl tertiary butyl ether (MTBE), can also be added to improve the octane rallh of the fuel. MTBE has oxygen in the form of ether group and supplies oxygen for the combustion of the petrol in internal combustion engine thus reducing the formation of Peroxy compounds.30 f NGINEERING CHEMISTRY (Gesipuy A \dvantages of Using Unleaded Petrol Because of the abse () untéade nice of lead “ petrol is free from lead-pollution. (0) it allows the use of a catalytic converter to be automobiles, . Note =— attached to the exhaust in the like 7 sh converts toxic gases Catalytic converter contains athodium catalyst which converts Be St CO. NO etc. into harmless gases lke CO,, N; etc. It ing th hydrocarbons into (0, and H,0. Lead poisons the Rh catalyst by destroying the active sites, 1} Oleset (OR COMPRESSION IGNITION) ENGINE AND CETANE NUMBER Tg QU, Lind Term 2000, 02. 05 ; End Term 2000, 02, 06, 12) In the diesel engine, air is first drawn into the cylinder and compressed to a pressure of about 500 psi (352 ‘accompanied by a rise in temperature to about 500°C. x10” kg/m?). This compression Towards the end of the compression stroke, diesel is injected in the form of finely-divided Spray into air in the cylinder heated to about 500°C by compression. The oil absorbs the heat from the air and it ignites spontaneously as it attains ignition temperature. This raises the temperature and pressure. The piston is pushed by expanding gases in the power stroke. The combustion of tuel in a diesel engine is not instantaneous, the interval between the start injection and its ignition is called ‘the ignition delay’ Ignition delay is due fo the time taken for the vaporization of the individual droplets and raising of the vapour to its ignition temperature. It depends on the ay Bfigine design ; (b) Efficiency of mixing of the spray and air ; (©) The injector design and (@) Mostly on the chemical nature of the fuel. For example, ignition delay is shorter for paraffinic fuel, than for olefinic, naphthalenic and aromatic fuels. of fuel amavEexrod If the ignition delay is Jong, it will lead to fuel accumulation in the engine even before the ignition. When ignited, an explosion results as the combined effect of increased temperature and pressure. This is responsible for diesel kntock. The diesel fuel should have a spontancous ignition temperature less than the temperature produced by compression. As the temperature to which air can be heated by compression is limited by various constraints, it is desirable to have fuels with short ignition delay but the ignition delay must be long enough for the-compression stroke to be completed In order to grade the diesel fuels, cetane rating is employed.a furs 31 cacane Number Itis a measure of the ease with which loess Tenia?! iti the same Diesel fuel Cotane CH. 1 -hexadecane CH3(CH. a tuel will ignite under compression the % of hexad adecane ina eno anced mixture of hexadeeane and I-methyl naphthal s iis dle fal Is ae yyl naphthalene which has —— iesel fuel in question | Lorn ‘emethyl naphthalene CO cH, nd composition of its hydrocarbons: call For instance, consider the following series : Tealkanes > naphthenes (ie., cycloalkanes) > alkenes > branched alkanes 7 @ ignition delay increases from left to right @ ignition quality increases from right to left @ cetane no. increases from right to left As, straight chain alkanes like n-cetane have low ignite readily on compression-while aromatics donot ignt ‘gh cetane-no. fuels eliminate “The cetane no. of diesel fuel may be r thyl nitrite, amylnitrite diesel knock, aised by the addition of pre-ignition dopes such a8 etc. alky! nitrites such 2,4, 4,6, 8, S-hepta methyl nonane (MN) cH, CH, TCHS | | | \ cH, = C-CHy ~C-CHly = CCH CEs l I | \ [oh os : ered as the low quality diesel in view of its easy availability with a cetane rating of 15 is new consid and purity. On the revised scale Jus 1 of the % HMN. HIMN plus 555 of the (MN reference) the cetane number (CN) represenis the % cetanein the blend with HMN has a cetane rating of ‘Thus, a blend of 50% cetane and 50% 5 so « 150-375 M. K. JHA (9971212340) Otte ‘Specimen Copy For Principal arid Teachers NOT FOR SALEamawerpin NN 32 NGINEERING. CHEMISTRY (GGSIPU) marized beloxe : ‘The difter fences betroven the Octane number and Cetane number are sue 05, 10; End Term 2001, 11] {G6SIPU, lInd Term 2003 7 Cetane No. 1 T fr is the % of heradecane in a mixture of ssooctane (2 2. 4-trmethy! pentane) and hecadecane and I-methyl naphthalene which mheptane. which matches the fuel under test | has the same ignition ‘characteristics as the mm knocking charactenstics. eg. an 60-octane | diesel fuel in question: fuel is one wich has the same combustion | charactenstics as a 60. 40 minture of 150 | CH; and heptane | ' CH, - (CH, -CH, { > Hanan 1 Kooks very-badty (Octane mo : es . {methyl naphthalen’ | cH, cH, | (Cetane no. = 0 CH, ~C -CH, -<¢ -CH - “1 7 \ CH, -(CHphs “CH cH, cH. ' poHeradecane eowtane of 124 Trumethy! Pentane: (Cetane no = 100) Grows very bthe knocking { i } etane ne = 100 | +} 1 Zz sed for finding suitability of gasoline or | It is used for finding suitability of a diesel " | ans other intemal combustion engine fuel. | fuel — + 3 The Octane number of LC tuels can be raised | The cetane number of diesel fuel can be raised bythe addcnon of tetraethy! lead (CoH), Pb | by the addition of small quantity of certain or TEL and Drethy! teltunde (C)Hs); Te | “Pre-ignition dopes’ like ethyl nitrite, isoamyl - fo J _| nitrite, acetone pero Lad a Hydrocarbons whach are poor diesel fuels are | Ignition quality order among hydrocarbon | quite good gasobne fuels | constituent of a diesel fuel is as follows = | n-alkanes > naphthalenes > alkenes | > branched alkanes > aromatics. j | ‘Thus, hydrocarbons which are poor gasoline 7 | fuels are quite good diesel fuels. {57 | Straight chain hydrocarbon molecules are } Straight chain hydrocarbon molecules are | best, as they have high cetane numbers. worst fucis As they have low-Oxtane numbers (GGSIPU, Lind Term, Dec. 2001, Nov. 2007] \ Bs (12 errceane eee \ 4 Gracking is defined as the decomposition of high molecular weight hydrocarbons of high piling points into simpler Jower molecular weight hydrocarbons of low boiling points. CH: SS CH + Cstho Decane pentane pentene TC BP. = 30°C BP.Fueis 33 Importance. Of all the fractions obtained by fractionation of petroleum, gasoline has the highest demand as a motor fuel, but the yield of this fraction is only 20% of the crude. Also the quality of so-called ‘straight-run’ gasoline is not so good Hence, it is used only after suitable blending. Moreover, there is a surplus of heavier petroleum fractions. To overcome these difficulties, the middle and heavy fractions are cracked to get more valuable low boiling fractions. a For instance, the petrol made by cracking has_far_better engine is concerned) than ‘straight-run’ petrol. \g straight-run’ pet (as far as the IC Types of Cracking | ‘Thermal Catalyne Liquid phase Vapoue phase Fed bed | thermal erckang thermal cracking catalytic cracking shh MT (et hecit) ( Teoh) {[ecs1PU, 2005) 7 When the heavy oils are subjected to high temperature and pressure in the absence of catalyst, it is called thermal cracking, In a thermal cracking process, the heavy oil residue (from primary distillation of crude oil) : (a) is heated to a temperature greater than its boiling pownt to promote rupture of the carbon-carbon bonds and (t) subjected to high pressures to prevent the vaporization of the cracked residues. In thermal cracking, the bigger hydrocarbon molecules break down to give smaller molecules of the paraffin, olefins plus some hydrogen. It is of two types viz. liquid and vapour phase thermal cracking. The operating conditions depend on the desired product. Low pressures and high temperature (that is conditions for vapour phase thermal cracking) tend to produce more low-molecular weight and volatile hydroc arbors than those produced under high pressure and low temperature conditions (that is under liquid phase thermal cracking). A comparative account of these two is given in Table 7. v1 AY dy ousue “Table 7 Comparison of Liquid and Vapour phase Thermal Cracking [GGSIPU, IInd Term 2003}. Characteristic Liquid-phase-Thermal Vapour Phase—Thermal— . __ Crackin 0 mi Crackin, Cracking temperature 475 ~ 530°C “ 600 - 650°C ST Pressure 100 kg, m sec? === pranched-chains paraffins > olefins > naphthalenes > aromatics. \a%Kio external fuel is necessary for cracking, The heat required for cracking is derived from the coal, embedded in the catalyst.38 ENGINEERING CHEWUSIRY essiru) ow tendency to form mos on ts tormedd it will she Se ee than four carbon atoms. if will f. converted t 3° carbonium ion. (eo) Whenever a secondary @ were qiabke fertiary G9 carbonium son, U2" carbonium soe has moe Sranched-chain compounds by skeletal rearrangement 35 115-6 R CH, * Branched o C-H + chain Re compounds oo CH, R . Hu YF carbonium 100 [ f | (Ato! ste) * ROH rots LS Rec c-CH Least ro _— CH, H Wearbenium ton (Least stable) () Aromatic compounds might also form from alkenes and carbonium ion though a sequence of steps involving cyclization, and aromatization. NOTE. Reforming. The antiknock characteristics of gasoline (prepared by the fractional SESS distillation of crade oil or by cracking) can be improved by ‘reforming’ which in effect brings about structural modifications in the components of feed-stock either thermalty or catalytically. > and their Formation [6GSIPY, Ind Term, Nov. 2005} ‘ga! is formed from the fossilised remains of animals and plants, hence it is known as frssi! _fuel. Coal and other fossil tuels are used up much more rapidly than it is replenished by nature. Thus it might ulfimately result in a fuel shortage. But it has been estimated that last for several hundred years. The factors which are in farwur of usage of coals.in huge tonnage quantities are : Ay cost, least risk of fire hazards and easy storage — eS Salley, baw coal reserves may In fact, the action of decay, pressure and heat convert Vegetable and woody renva: deposited many years ago, into coal. The time required for wwlyication is of the order oe 10” and 10° years. Coalificatton is known to take place in two stages : During the fneraaes “GaTATUsic plant materials are converted into peat by y streptococcus micro organisms. (TRIS stage is also Known as Fockemtcal cauiiin processes predominate in this stage). In the second stage, the agenere changes are high fempérature (>> 300° © pressure and long ti muctoccus and vanous other since_biclogical bacterial responsible tor the chenucal Of the order of 10 10" vears. As} i Abe rues 39 the effect of these agencies is of varying degrees, the result is coals of different maturity or rank Rank is a qualitative measure of carbon.content in coal and is defined as the degree or extent of _maturation. The soft coals (Peat, lignite and sub-bituminows coals) have low %of casbon contents and are known as Tow-rank coals In contrasthard coals (hike bituminaus and anthra¢ ite) have high % of carbon content and are thus classed as high rank. — The progressive transformation pr wood to anthracite can be written as : Wood -»|Peat > Lignite—> Bituminous ~> Anthracite _ Saec |B 4 Ligniter Bituminous 7 Anas C It results in increase in carbon content, hardness and calorific value 4nd decrease in volatile matter, moisture and H, O, N and § contents. ‘The carbon contents, calorific values and main applications of these solid fuels are summarized below in Table 8. Differences between Bituminus coal and Anthracite [G6SIPU, End Term, March 2001] Fabl} 8 Calorific values and main applications of solid fuels. Le saat Percentage | Calorific value ose i carbon | (kcal/kg) Moin applications a | s ~ 50 | 4000 to 4500 | Domestic fuel 9 “57 __|_ 4125 to 5400_| Used when there is deficiency of high rank coals 3. Lignite 67 6500 to 7100 | Used for steam generation in thermal power plants E and for the production of producer gas. 4. Bituminous | 83 2000 to 8500 | Used for steam generation in thermal plants and for — domestic heating, It is also used for making coal gas and metallurgical coke. 5. Anthracite 3 2650 to $700 | Used in metallurgical purposes where no smoke and _ high local heat is desired. Its also used in household | purposes and steam raising 13.1 Pulverized Coal “pulverized coal is a fine powdered form of coal.” ‘As the coal is crushed, ground and pulverized, its surface area is increased and it comes in contact with air more easily ensuring better and efficient combustion. The necessary degree of fineness of pulverization of coal depends on the density of coal, the percentage of volatiles and the volume of combustion chamber_available. The smaller the eeunbustion chamber and lower the volatiles, the finer and more uniform should be the grinding. India’s coal deposits have high ash contents. Coal up to 40% ash can be burnt by pulverising, with a loss of only 5% combustible, that is, with 95% efficiency Generally a limit is imposed on fineness of coal particles. This is because power is consumed for grinding and pulverising and it is sometimes uneconomical to reduce particle size beyond a certain limit.40 ENGINEERING CHEMISTRY (GGSIPU) Advantages of Pilverized Coal Pulverised coal has the following advantages (0 Pulverized coal has a large surface area per unit mass of coal, thus the rate of combustion is high. (1) Because of greater surtace area of pulverized coal, less excess air is required for complete combustion. . (4) Pulverization of any coal from peat to anthracite can be done for better, and efficient combustion. cessful (iv) Control of combustion of pulverized coal is easy and possible. Better combustion control enables the system to respond quickly to extensive load variation. (©) Pulverized coal is suitable for super thermal power stations where the rate of steam. | Reneration is as high as 2000 tonnes per hour. This is because of release of large amount of heat on the combustion of pulverized coal. Thermal efficiency is higher and higher temperatures are obtained. (vi) Less fumace volume is required for the combustion of pulverized coal. (vii) No clinker formation takes place. Thus, clinkering problems are low. 1 (viii) Ash handling problem is also low. Ve mn Disadvantages of Pulverized Coal ha Pulverised coal has the following disadvantages : ye is (i) Large quantities of pulverized coal are suspended in air during transfer from the iT powdered coal mill to the thermal power plant. Explosions have occurred when the ; flow of fuel drops and flames in the burning chamber pass back along the ductwork jE iad PS B Pai Mie delivering fuel. p To sum up, pulverized coal is a significant dust explosion hazard, (ii) An extra cost is involved for pulverization. By burning pulverized coal, ash in finely divided state is generated. About 75% of it goes along with the flue gases and is discharged on the surrounding area, causing \ nuisance. To avoid this problem, cottrell's precipitators must be used for the removal i of ash from the waste combustion gases. 14 11s oF COAL Generally coal is not analysed by measuring well-defined physicochemical properties since s composition varies according to the source and age. Mostly consumer-oriented, empirical tests are performed for the sack of exmparison and for getting some meaningful insights. In order to ascertain the quality of coal, itis subjected to two types of analysis, viz. proximate awd Yitimate analysis. nces between Promixate and Ultimate Analysis (GGSIPU, 2001, 05) Proximate analysis isso called because the data collected vary with the procedure adopted. It fos valuable information about the practical utility of coal. in other words, we can assess the Guality of coal by proximate analysis. It includes the determination of Moisture, Volatile matter, y Ash and Fixed carbon. termination of Moist ema ~ — _____[ges1rv, 2005, 06,10)rues 41 The ultimate analysis is useful f 's useful for combustion calculations. It includes determination of urinate constituents pret indy ae ce tuo oogen cat Hyg, trogen, Sulphur, Ash and [GGSIPU, 2001, 02. 06, 07, 09, 10} ‘roximate Analysis involves in the following, determinations Ap potsare Content High percentage of moisture is undesirable because : 1. It increases the cost of coal as well as its transportation charges. Hence, lesser the ‘moisture content, better the quality of coal as a fuel. 2. It quenches the fire in the furnace. However, presence of moisture upto 10%, produces a more uniform fuel-bed and less of “fly-ash” 3. Moisture in coal evaporates during the burning of coal and it takes some of the liberated heat in the form of latent heat of evaporation. Therefore, moisture lows the effective calorific value of coal. Determination of moisture : It is the loss of weight of coal when heated at about 105°C in 2 crucible. A known amount of the finely powdered coal sample, taken in a silica crucible, is heated in an electric hot air oven. Heating is done at a temperature of 105° - 110° Cfor about one hour. After which crucible is taken out with the help of tongs, cooled in'a desiccator and weighed. The process of heating, cooling and weighing is repeated till the weight of the crucible containing anhydrous coal becomes constant. Loss in weight is reported as moisture (on percentage basis). Loss in weight due to removal of moisture % of moisture = ————?_-—__—___—. weight of coal sample taken (Ons Matter 1. The volatile matter present in the coal may be combustible gases (such as, hydrogen, CO, methane and other Lower hydrocarbons) or non-combustible gases (Tike CO, and N,). 100 The presence of non-combustible gases is always undesirable, since they do not add to the heat value. Moreover, the volume of the furnace required is also large. When a coal has high volatile matter content then a large proportion of fuel distill over as gas or vapour, a large proportion of which escapes unbumt. So, higher volatile content in coal is undesirable. A high volatile matter containing coal bums with (i) a long flame, (ii) high smoke and (ii) low calorific value. Hence, lesser the volatile matter, better the rank of the coal. The volatile matter affects the furnace volume and arrangement of heating space ‘A furnace with small combustion volume is not suitable for burning high volatile coals at high rates of combustion. This is because a large proportion of volatile matter will escape unburt in such circumstances.