The bomb calorimeter The energy content or heating value of a solid or liquid substance may be determined by burning @ measured quantity of the substance in an enclosed vessel (bor mb) in the presence in a can which contains a mesnired Guantiy of oan, The bom Mater temperature before and after FnnBs The Meerated ad by measuring the Wale very accurate thermomect ited Wi AN Seas) so that water temperature can be measured to three decimal pl ie the Heat loa In some designe of calorimeter, insulation is used to minimise 1 Mest Ot and in gy, cases, iis necessary to plot @ temperature-time (TTT Ge bomb eaarimee t temperature rae to take into account the heat oss. In the adiaberts ONY cHloimeter 4.6), such eorreetion is not necessary because the heat loss is VINNY Tt In this adiaba calorimeter, instead of insulation, the jacket contains water and the temperature of the Watey of oxygen. The bomb is immersed is thermometer eyepiece — Ww tia cml 0 “Le adiabatic if jacket | jacket thermistor fing wire and cotton Fig. 4.6 Aciabatic bomb calorimeterjg controlled by thermistors connected to an external heating system. Hence the jacket water temperature is, at all times, Kept the same as the temperature of the water in the can Gontaining the bomb, Since there is no temperature difference, no heat loss occurs. "The bomb calorimeter is an isolated system; hence all the energy of combustion is transferred into the internal energy of the water in the can and of the metal in the bomb and the can, It is customary to account for the heat absorbed by the metal parts by fist using the bomb with a substance of known and constant energy content (e.g. benzoic acid), and from the observed temperature rise of the water, the heat capacity of the metal parts can be determined. Once this has been established, it will not change and may be used for all future determinations. If the energy content of the substance is required with great accuracy, several other corrections are necessary, namely that for the heat content of the firing wire and cotton, and for the heat of formation of acids and nitrous compounds formed under the high-pressure and pure-oxygen conditions in the bomb. These corrections arc small and will not be considered in the examples which follow. Note that it is not necessary to correct for the energy added by the stirrer, as this is also negligible, Example 4.6 Ina bomb calorimeter, the can is filled with 2-1 kg of water, 1-2 g of benzoic acid are bumt and the observed temperature rise is 2-94°C. If the energy content of the benzoic acid is 26-442 MJ/kg, determine the heat capacity of the metal parts of the calorimeter. The specific hheat capacity of water over the temperature range is 4187 kI/kg K. Solution Heat to water = mc AT 21 x 4187 x 2-94 = 258515 Heat of combustion = I-2 x 10? x 26-442 x 10” (KJ) ETB KS < Heat absorbed by metal parts = 31-73 ~ 25°85 588 kT Example 4.7 The calorimeter given in Example 4:6 was used with a fuel of unknown energy content. The mass of fuel burnt was 0-975 g; the mass of water in the can was 2-23 kg; the temperature after firing was 23-506°C and before firing was 20-484°C. Determine the energy content of the fuel. Solution Temperature rise = 23°506 - 20-484 022°C Heat to water = 2-23 x 4-187 x 3022 = 28-216 KSHeat to metal = 2-0 < 3-022 = 6-044 kt <. Heat from fuel = 28-216 + 6-044 = 34:26 kIT :. Energy content of fuel = 34-26 __ 0-975 x 10 = 35-1 M3/kg srermine the energy concent Of a gas, rit the Simmunee calorimeter wines rer (Fig. 4.16) is used to de which all operate in the same basie way, itr Gas calorimeter ne gas calorimet A eal eo each ‘x the Boy’ calorimeter See a construction and appearance bu a waa wha in cone pron # constant-pressre regulator und then though 3 aecuge snes 88 Bass Neg cnt air and burnt a constant presse. THE hot combed ragucrs pase ever a number of coils through which water circu lates. ‘The water enters products pass over 2ara constant level (head) so that the set Now ratc remains cong leaves the calorie determined by diverting the water that is leaving the calorimeter gs easuring evlinder, and measuring the amount collected in a given time. water Ty = gas temperature in Tz = exhaust gas temperature constant-| T; = water temperature in heed T, = water temperature out {° rain water measuring gas-pressure manometer Te exhaust gas out gas in Fig. 4.16 A gas - ‘G08 calorinete, waterThe gas calorimeter is therefore the flow counterpart of the bomb calorimeter (non-flow): in the bomb calorimeter, combustion takes place in a elosed system under constant-volumme conditions, whereas in the gas calorimeter, combustion takes ph ustion takes place in an open system under constant-pressure conditions. Ako, in the gas ealorimeter itis not NECESSAry {0 compensate for the metal parts hecause readings are not taken until steady-state conditions are reached. ‘The heat loss from the calorimeter walls and in the exhaust gas is usually negligible ifthe flow rate of water is set so that the sas temperature out of the calorimeter is only a litle above ambient temperature. Under these conditions, the gas calorimeter is essentially a heat exchanger where the heat of combustion is transferred to an enthalpy increase of the water. Example 4.14 A five-minute test with a pas calorimeter yielded the following data: Gas-meter reading: start = 2:85 1; finish = 6°52 L Water temperature: in = 20:5%C; out = 353°C Volume of water collected = 1:95 1. Determine the energy content of a gas sample at inlet conditions. Solution Heat transfer to the water, Q@ = me(T; - Ti) 195 x iBT x (355 ~ 205) = 120-83 ks Gas but = 6-52 - 2-85 = 3-67L 12083 367 329 K/L = 32-9 MJ/m! Energy content of the gas Notes (a) The energy content obtained in this way is for a cubic metre of gas 2t inlet conditions. Since the volume of a gas will vary with both pressure and temperature, itis necessary to convert the value to reference conditions.* These conditions are often taken as 20°C. and 101.3 kPa. (b) The energy content so obtained is also known as the ‘higher’ value because it isthe total energy available. Often in practice, it is undesirable to cool the exhaust gas to a temperature below which water condenses (about 100°C) as this means that any acids formed by combustion will condense and corrode the metal surfaces they contact. So 2 ‘lower’ value of the energy content is sometimes used and it can be obtained from the higher value by measuring the water condensed and deducting the enthalpy content of this water.