In this research, we explored the calorific or heat value of alcohol fuels as well as blends with kerosene by using both glass and bomb calorimeters. The heat values of each blend is greater as the percent of alcohol increases, but as the percent alcohol exceeds the percent ketone, the heat value starts to decrease.
In this research, we explored the calorific or heat value of alcohol fuels as well as blends with kerosene by using both glass and bomb calorimeters. The heat values of each blend is greater as the percent of alcohol increases, but as the percent alcohol exceeds the percent ketone, the heat value starts to decrease.
In this research, we explored the calorific or heat value of alcohol fuels as well as blends with kerosene by using both glass and bomb calorimeters. The heat values of each blend is greater as the percent of alcohol increases, but as the percent alcohol exceeds the percent ketone, the heat value starts to decrease.
International Journal of Research in Chemistry and Environment Vol. 2 I ssue 2 April 2012(102-105) ISSN 2248-9649 Research Paper
Calorimetric Determination of Energy Content of Alcohol fuels and Blends with Kerosene
*Linus N. Okoro 1 , David Okwuanalu 1 , Clifford Nwaeburu 2
1 Department of Petroleum Chemistry, School of Arts and Sciences, American University of Nigeria, Lamido Zubairu Way, Yola By-Passs. P.M.B. 2250 Yola, Adamawa State, NIGERIA 2 Ruprecht-Karls-University of Heidelberg, Heidelberg, GERMANY
(Received 25 th January 2012, Accepted 18 th February 2012)
Abstract- In this research we explored the calorific or heat value of alcohol fuels as well as blends with kerosene by using both glass and bomb calorimeters comparatively. The calorific values obtained from the combustion of alcohol fuels from glass calorimeter were very much lower than those obtained from bomb calorimeter, as a result of heat loss in glass calorimer. The heat values, obtained by glass calorimeter, of methanol, ethanol, propanol, butanol, and pentanol gave 6.3MJ/Kg, 10.64MJ/Kg, 15.27MJ/Kg, 20.84MJ/Kg, and 22.56MJ/Kg respectively, while the heat values of methanol, ethanol, propanol, butanol, and pentanol, using the bomb calorimeter gave 16.36MJ/kg, 21.6MJ/Kg, 30.75MJ/Kg, 32.13MJ/Kg, and 36.1MJ/Kg respectively. It is observed that the heat value of each blend is greater as the percent of alcohol increases, but as the percent alcohol exceeds the percent kerosene, the heat value starts to decrease. Generally, the heating values of alcohol fuels increase as the carbon atoms increases and the heating values of these alcohol fuels increase as the percent oxygen decreases.
Introduction Alcohol fuels are obtained from alcohols and have been used a lot in the past. Methanol, ethanol and other alcohols are very good fuels with very high octane ratings [1] . Alcohol fuels are often called bio alcohols because of their sources. The most common bio-alcohols are methanol and ethanol. Fossil fuels and biomass are the main sources of methanol and ethanol. Mathewson had earlier stated that methanol and ethanol are two types of alcohol fuels used in cars [2] .
Whereas ethanol is produced from a variety of renewable resources, most commonly corn and sugarcane, methanol is produced from renewable resources as well, but mainly from natural gas. Mathewson further confirmed that although ethanol indeed reduces the toxicity of car exhaust, it can as well be very corrosive, and can absorb water and dirt easily, which can result to damage as well as corrode the inside of block engine, if the ethanol contaminants are not properly filtered.
Blume, in one of his recent papers affirmed alcohol as an excellent alternative motor fuel for gasoline engines, and that the major advantage of alcohol is that it can be burned in existing vehicles with little or no modification, with little emissions released, thereby reducing air pollution [1,3] .
Alcohol Fuels: Runnion reported that ethanol is produced from fermentation of the sugars found in grains, such as corn and wheat, potato wastes, cheese whey, corn fiber, rice straw, sawdust, urban wastes, and yard clippings [4] . Ethanol, due to its possible environmental and long-term economical advantages over fossil fuel when used as a fuel for the internal combustion of car engines, often in combination with other fuels, is attracting so much attention [5] . On the other hand, methanol is known as a light, volatile, colorless, and flammable, and is used for producing biodiesel via the transesterification reaction [6] .
Other useful alcohol fuels include propanol, which is formed naturally in little quantity during most fermentation processes [7] ; Butanol, has been found naturally as a minor product in the fermentation of sugars and other carbohydrates is a product of petrochemical feedstock, propylene; as well, 1-pentanol which according to Lide et al, can be used as a replacement for gasoline [8] .
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Table 2 List of Materials and Their Manufacturers
Materials Source Methanol 99.8% pure, Fluka, Sigma-Aldrich Labochemikalien Ethanol 96% v/v. Fisher Scientific, UK Propanol 99%. Fisher Scientific, UK Butanol 99% extra pure. Acros Organics, New Jersey, USA Pentanol 99% +. Acros Organics, New Jersey, USA Analytical Balance Adam PW 254 Bomb Calorimeter ECO CAL 2K Thermometer Kerosene NNPC Mega Station Yola, Adamawa State
The glass calorimetric method and the bomb calorimetric method were employed in this research to determine the heating values [12] .
Keenan reported that the latent heat of vaporization, defined as the amount of extra heat required to change the liquid to a gas when boiled, should be considered alongside volatility [9] . He found that gasoline has a latent heat of about 140 Btu/lb; methanol, 474 Btu/lb; and ethanol, 361 Btu/lb. In his research, Brinkman observed that, gasoline fuel vaporization of the gasoline fuel in air leads to a drop in temperature of about 40 o F [10] .
Hence, that following the trend therefore, the temperature drop for ethanol will be more than twice that of gasoline, and that of methanol will be over three times as much [10] . The effect of these drops in temperature is that the mass density of the fuels becomes greater when the fuel is entering the engine. Therefore, this shows that alcohol fuels have greater mass density than gasoline. It can therefore be said that the greater the latent heat, the greater the heat required and this is the clear reason why alcohols require more heat than gasoline. It has been observed that shortening the distance travelled by the fuel to the cylinder could reduce the chances of condensation and fuel distribution problems. Practically, for engines that have been converted to alcohol, enough heat should be supplied once they are warmed up, and according to Cavagnaro, the problem with high performance racing engines is starting the engine when it is cold [11] .
Further, when burning a particular fuel, energy is released and the amount of energy released is a very important property of such fuel, and is referred to as the energy content of that fuel. Turner et al, in one of his comparative study of the heat value of both the gasoline and ethanol observed that the oxygen of the alcohol has no effect on the fuel value because the hydroxyl group combines with a hydrogen atom to produce water [6] . Methanol volatility, defined as the ability of a substance to be vaporized, has been found to contain less than half the heating value of gasoline whereas ethanol contains about 60% of the heat value of gasoline [10] . In this research we explored the calorific or energy content of alcohol fuels as well as blends with kerosene calorimetrically.
Material and Methods Determination of Heat Content of Alcohol Fuels Using a Glass Calorimeter: A 100ml round bottom flask was weighed empty in grams, and was filled with 100 ml iced water of about 4 o C and reweighed in grams. 20ml of the alcohol fuel is measured with a pipette and poured into a reagent bottle and this was weighed in grams (g). The reagent bottle is placed under the round bottom flask and the alcohol fuel is lit and allowed to heat up the water in the round bottom flask to about 40 o C. The reagent bottle is now reweighed in order to get the weight of the reagent bottle after combustion. This weight is now subtracted from the previous weight of the reagent bottle and with this; the mass of fuel burned was obtained. In order to calculate the heat of combustion of the alcohol, the heat, q, is calculated using the formula: q = mCT .. (1)
The m above is the mass of water that is heated; C p is the specific heat capacity of water and has a value of 4.18J/ o C and T is the change in temperature of the water as it is heated. Dividing equation 1 above by mass of fuel burnt, gives the heat of combustion. q = mC p T/Kg ... (2) Okoro et al. Int. J. Res. Chem. Environ. Vol.2 Issue 2 April 2012(102-105)
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Table 3 Heat Content of Alcohol Fuels Obtained Using Glass Calorimeter
Methanol Ethanol Propanol Butanol Pentanol Trial 1 Trial 2 Trial 1 Trial 2 Trial 1 Trial 2 Trial 1 Trial 2 Trial 1 Trial 2 Mass of fuel burnt 2.81 2.94 1.82 1.89 1.28 1.28 1.0 0.9 0.89 0.87 Temp. change ( o C) 32 33 36 37 36 36 37 36 37 37 Heat of water (MJ) 17.36 17.89 19.45 20.07 19.54 19.56 20.04 19.47 20.04 20.10 Average heat of combustion (MJ/Kg) 6.30 10.64 15.27 20.84 22.56
Determination of Heat Content of Alcohol Fuels Using Bomb Calorimeter: The bomb calorimeter was used in this research to determine the heat of combustion of alcohol fuels.
Results and Discussion Glass Calorimeter: Using the glass calorimeter, the heat content of the methanol, ethanol, propanol, butanol and pentanol were obtained. From Table 3 and Figure 1, it is observed that as the carbon atoms increases, the heat of combustion increases. Meanwhile, as the carbon atom increases, the percentage oxygen also decreases in each alcohol thereby making the heat of combustion to increase.
Figure 1: Heat of Combustion of Alcohol Fuels
Figure 2: Heat Values of Alcohol Fuels Bomb Calorimeter: Accurate and standard heat values for each alcohol fuel were obtained using the bomb calorimeter to determine the heat of combustion. The heat of combustion obtained for methanol was 16.36MJ/Kg; for ethanol was 21.9MJ/Kg; for propanol was 30.75MJ/Kg; for butanol was 32.13MJ/Kg; and for pentanol was 36.1MJ/Kg. From figure 2, it is observed that the heat value increases as the level of alcohol increases. This is because of the increase in the number of carbon atoms in the alcohols.
Comparison of Heat Values Obtained From Bomb Calorimeter and Glass Calorimeter: Comparison of the heat values gotten from glass calorimeter and the bomb calorimeter is very important. The heat values, determined by glass calorimeter, of methanol, ethanol, propanol, butanol, and pentanol gave 6.3MJ/Kg, 10.64MJ/Kg, 15.27MJ/Kg, 20.84MJ/Kg, and 22.56MJ/Kg respectively while the heat values of methanol, ethanol, propanol, butanol, and pentanol, using the bomb calorimeter gave 16.36MJ/kg, 21.6MJ/Kg, 30.75MJ/Kg, 32.13MJ/Kg, and 36.1MJ/Kg respectively. This follows that for both calorimetric determinations, all the heat values follow an ascending trend, which is clearly seen in figures 1 and 2, due to the increase in carbon atoms and reduction in percent oxygen. There is therefore a clear difference in the heat values obtained from both calorimeters. This is practically because, during the use of the glass calorimeter, the heat lost to the fuel is equal to the heat gained by water and the heat lost to the surrounding. Therefore, due to the heat lost to the surrounding by the fuel, the heat gained by the water is reduced; hence, the heat value of the alcohol fuel is drastically reduced.
Nevertheless, using the bomb calorimeter which is adiabatic, there is no heat lost to the surrounding so all the heat lost by the fuel is equally gained. This is the reason why the bomb calorimeter calorific values obtained gave a more accurate heat value for substances better than the glass calorimeter.
Blend of Kerosene and Alcohols: Blending alcohol with kerosene is observed to give very high heat values. 0.332g of a blend of 95% kerosene and 5% methanol (M5) gave a Okoro et al. Int. J. Res. Chem. Environ. Vol.2 Issue 2 April 2012(102-105)
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heating value of 38.76MJ/Kg. 0.328g M10 blend gave a heat value of 39.33MJ/Kg, and 0.328g M15 gave a heat value of 39.54MJ/Kg. Furthermore, 0.321g of a blend of 95% kerosene and 5% ethanol (E5) gave a heat value of 48.75MJ/Kg. 0.33g of E10 gave a heat value of 49.22MJ/Kg. 0.323g of E15 had a heat value of 49.51MJ/Kg and 0.323g E80 heat value was determined to be 45.95MJ/Kg. The blending of alcohol fuels and kerosene follows a pathway, which is clearly seen in figure 3 below. The heat value of each blend is greater as the percent of alcohol increases, but as the percent alcohol exceeds the percent kerosene, the heat value starts to decrease.
Figure 3: Heat of Combustion for Blends of Kerosene with Alcohols
Comparison of Kerosene Blends with Pure Alcohols: Pure methanol and ethanol have heating values of 16.3- 6MJ/Kg and 21.6MJ/Kg respectively. Kerosene blends with these alcohols M5, M10, M15, E5, E10, E15, and E80 have heating values of 38.76MJ/Kg, 39.33MJ/Kg, 39.54MJ/Kg, 48.75MJ/Kg, 49.22MJ/Kg, 49.51MJ/Kg, and 45.95MJ/Kg respectively. From the data, the heat values of blends are greater than the heat values of pure methanol and ethanol respectively. This is due to excess carbon atoms in kero- sene.
Comparison of Kerosene Blends with Pure Kerosene: Pure kerosene has a heating value of 46.2MJ/Kg. The ble- nds of ethanol with kerosene had heat values greater than kerosene although E80 was lower but close to the heat value of kerosene. The blending of kerosene with these alcohols is what reduces the carbon emission to the atmos- phere when the blended kerosene is used as cooking fuels at home.
Comparison of Pure Alcohols with Pure Kerosene and Pure Gasoline: Pure alcohols such as methanol, ethanol, propanol, butanol, and pentanol have heating values of 16.36MJ/kg, 21.6MJ/Kg, 30.75MJ/Kg, 32.13MJ/Kg, and 36.1MJ/Kg respectively. The heating value of pure kerosene is 46.2MJ/Kg and the heating value of pure gasoline is 46MJ/Kg. Therefore, it is seen that the heating values of the alcohol fuels will approach the heating values of kerosene and gasoline if the carbon atom of the alcohol fuels increases. However, blending both fuels with kerosene and gasoline produces better fuels that have higher octane ratings and fuels that emit little or no carbon to the surroundings when it is combusted.
Conclusion Accurate heating values of alcohol fuels can be obta- ined by using a bomb calorimeter. The heating values of alcohol fuels increase as the carbon atoms increases and the heating values of these alcohol fuels increase as the percent oxygen decreases. It was observed that blending is a better way of making gasoline and kerosene emit lesser amounts of carbon when combusted. In this case, blending kerosene, which is mainly used as a cooking fuel in homes, reduces the soot carbon emissions that stick on cooking pots.
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