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Enthalpy of Formation and Enthalpy of Combustion

ME372 Instructor: Jesse Adams May 1, 2001 By: Chun Lee

Introduction Have you ever wonder how people on National Geographic can walk across a bed of red-hot coals, like figure 1? The answer to this question is not magic and its not because the walkers have supernatural powers. The answer is in simple

concept in thermodynamics called enthalpy. Enthalpy is equal to the quantity of U + PV, where U is equal to internal energy of a system, P is the pressure of the system, and V is the volume of the system. Human tissue is mainly composed of water, which has a relatively high specific heat capacity, which means that a relatively large amount of energy must be transferred from the hot coals to significantly change the temperature of the feet. But, during the brief contact between the walkers feet and the coals, there is relatively little time for energy to flow, so the feet do not reach a high enough temperature to cause damage. Secondly, although the surface of the coals has a very high temperature, the redhot layer is very thin, resulting in a very small volume in the system. Therefore, the quantity of energy available to heat the feet is smaller than might be expected. These two factors result in a very small enthalpy change between the coals the firewalkers feet. This factor points out the difference between temperature and heat. Temperature reflects the intensity of the random kinetic energy in a given sample of matter. The amount of energy available for heat flow, on the other hand, depends on the quantity of matter at a given temperature. For example, the tiny spark from a sparkler does not hurt when it hits your hands. The spark has a very high temperature but has so little mass that no
Figure 1: Picture of a person walking on hot coals8

significant energy transfer occurs to your hand. This same argument applies to the very thin layer on the coals. First Law of Thermodynamics The first law of thermodynamics states that in any closed system, energy is conserved. Which means that energy cannot be created nor destroyed, but it can only change forms. Meaning: Esys = 0 and Eproducts = -Ereactants The molecules of a closed system possess energy in various forms such as sensible and latent energy, chemical energy, and nuclear energy1. All of these forms must balance out in the reactants and products to give the system a net energy of zero. This paper will mainly focus on the chemical energy within the molecules of a closed system that involve a chemical reaction. During a chemical reaction, some

chemical bonds that bind the atoms into molecules are broken and new ones are formed. The chemical energy associated with this process is usually different for the reactants and products1. Since energy cannot be created, according to the first law of thermodynamics, the difference between the reactants to the products in a closed system can be accounted for in change of volume, pressure, internal energy, or heat. Enthalpy Enthalpy is the system we use to measure that change in energy of a closed system due to chemical bonds being broken. As stated above, enthalpy is a property of a system equal to U + PV, where U is equal to internal energy of a system, P is the pressure of the system, and V is the volume of the system. At constant pressure, where only PV work is allowed, the change in enthalpy equals the energy flow as heat2. Most chemical

reactions involve a change of heat. The enthalpy change that occurs in a chemical reaction is called the reaction enthalpy and is given the symbol H. The reaction enthalpy is the heat change that will be, or would be, observed when, or if, the reaction occurs. Reaction enthalpies are real physical quantities for which numeric values can be calculated or measured. In order to put the calculation into algebraic form, chemists use the defined equation3: H = Hf(products) - Hf(reactants) The reaction enthalpy, which is the enthalpy change that occurs in the reaction, is always calculated as the sum of the enthalpies of the products minus the sum of the enthalpies of the reactants, because when this is done the sign of H has a real physical meaning. If the sign of H is negative, then heat will be observed to flow out of the reaction into its surroundings. The reaction is then called exothermic. If the sign of H is positive, then heat will be observed to flow into the reaction from its surroundings. The reaction is then called endothermic. Standard Reference State Since composition of a system at the end of a process is no longer the same as that at the beginning of the process, theres a need to use a standard condition in which to make the measurements from. This standard condition is called the standard reference point, which are2: For a gas the standard state is a pressure of exactly 1atm

For a substance present in a solution, the standard state is a concentration of exactly 1 mole at an applied pressure of 1 atm

For a pure substance in a condensed state (liquid or solid), the standard state is the pure liquid or solid

For an element the standard state is the form in which the element exists (is most stable) under conditions of 1 atm and temperature of interest (usually 25C or 77F)

Enthalpy is a state function whose value depends only upon conditions and not upon history. In a reaction enthalpy a state function depends only upon the initial and final conditions of the reactants and products and not upon the course of the reaction or the conditions under which the reaction actually occurs (if it occurs at all). Hydrogen and oxygen burn with a very hot flame, but the enthalpy difference between hydrogen and oxygen as gases at 25oC and their combustion product water at 25oC is independent of the flame temperature, or even its existence3. The superscript is used to indicate property values at the standard state. The defined equation above, under standard conditions, becomes: H = Hf(products) - Hf(reactants) Enthalpy of Combustion The enthalpy of reaction in a combustion process is called the enthalpy of combustion (symbolized by hc). The calculation for an enthalpy of combustion is done for 1 kmol (1 kg) of fuel is burned completely at a specified temperature and pressure and can be expressed1: hc = Hprod Hreact

The following example shows calculation of an enthalpy of combustion for a reaction1: Example 14-5 Evaluation of the Enthalpy of Combustion Determine the enthalpy of combustion of gaseous octane (C8H18) at 25C and 1 atm, using enthalpy of-formation data from Table A26. Assume the water in the products is in the liquid form. Solution The stoichiometric equation for this reaction is C8H18 + ath(O2 +3.76N2) 8CO2 +9H2O(l) + 3.76 ath N2 Both the reactants and the products are at the standard reference state of 25C and 1 atm. Also N2 and O2 are stable elements, and thus their enthalpy of formation is zero. Then the enthalpy of combustion of C8H18 becomes: hc = Hprod Hreact = Nphfp - Nrhfr = (Nhf)CO2 + (Nhf)H20 - (Nhf)octane Using hf values from Table A-26, we get: hc = (8 kmol)(-393,520 kJ/kmol) + (9 kmol)(-285,830 kJ/kmol) (1 kmol)(-208,450 kJ/kmol) = -5,512,180 kJ/kmol C8H18 which is practically identical to the listed value of 5512,200 kJ thats listed in Table A-27. Since the water in the products are assumed to be in the liquid phase, this hc value corresponds to the HHV of C8H18.

The problem with using the enthalpy of combustion as a property for analyzing a combustion process of fuels is that there is an abundant amount of fuel out there to list in one table and the process requires the combustion to be complete. Enthalpy of Formation The enthalpy of formation is defined as the enthalpy of a substance at a specified state due to its chemical composition1. This property makes analyzing easier because it represents chemical energy of an element or a compound at the standard reference state. The property values are obtained by first assigning all of the elements in its chemically stable form at the standard reference state a value of zero (such N2, O2, N2, C). Then we use Hesss Law to find the enthalpy of a compound. Hesss Law states that in going from a particular set of reactants to a particular set of products, the change in enthalpy is the

same whether the reaction takes place in one step or in a series of steps. This is because enthalpy is a state function, which means that the change in enthalpy in going from some initial state to some final state is independent of the pathway to get there. So we can use this concept to find the enthalpy of formation of individual compounds by adding up the enthalpy for each reaction it takes to react some of the chemically stable elements to get the compound. Calorimeter The changes in temperature caused by a reaction, combined with the values of the specific heat and the mass of the reacting system makes it possible to determine the heat of a reaction. Heat energy can be measured by observing how the temperature of a known mass of water (or other substance) changes when heat is added or removed. This is basically how most heats of reaction are determined. The reaction is carried out in some insulated container, where the heat absorbed or evolved by the reaction causes the temperature of the contents to change. This temperature change is measured and the amount of heat that caused the change is calculated by multiplying the temperature change by the heat capacity of the system. The apparatus used to measure the temperature change for a reacting system is called a calorimeter. The science of using such a device and the data obtained with it is called calorimetry. The design of a calorimeter is not standard and different calorimeters are used for the amount of precision required. One very
Figure 2:Picture of a simple calorimeter4

simple design used in many general chemistry labs is the styrofoam "coffee cup" calorimeter, which usually consists of two nested styrofoam cups, as seen in figure 1. The inner cup holds the solution in which the reaction occurs. The second cup provides insulation to the reaction, which allows the analyzation to be considered in a close system, so that accurate measurements can be taken and used. When a reaction occurs at constant pressure inside a Styrofoam coffee-cup calorimeter, the enthalpy change involves heat, and little heat is lost to the lab (or gained from it). If heat is evolved in the reaction, very nearly all of it stays inside the

calorimeter; the amount of heat absorbed or evolved by the reaction is calculated. Bomb Calorimeter A type of calorimeter used in very precise measurements of heats of

reaction is called the bomb calorimeter. It is used to measure energy changes for reactions that will not happen until they are deliberately initiated, for example, combustions which must be ignited. The reactants are put into the "bomb",
Figure 3: Diagram of a Basic Bomb Calorimeter5

which is then sealed and immersed in a large, well-insulated vat of water. When the reaction is set off, the bomb, the water, and any piece of the equipment sticking into the water absorb any heat that is
Figure 4:Picture of an actual bomb calorimeter6

liberated, and the temperature of the entire contents of the vat rises. The stirrer ensures that any heat released becomes uniformly

distributed before the final temperature is read. From the temperature change and the heat capacity of the calorimeter (water plus everything in the water), the heat liberated is calculated5. Conclusion The enthalpy of formation and combustion are both very important properties of thermodynamics that explain the energy changes within a normal or combustion reaction at a standard reference state. Using Hesss law, we can calculate the enthalpy of a system by using elements in their standard elemental forms and concisely form the actual reaction we are analyzing.

1. Enthalpy of Formation and Enthalpy of Combustion. pg. 772-776 Cengel, Yunus and Michael Boles.Thermodynamics: An Engineering Approach Hightstown: McGraw Hill, 1998. 2. Hesss Law. & Standard Enthalpies of Formation pg. 361-371 Zumdahl, Steven S. Chemical Principles, Third Edition Boston: Houghton Mifflin Company, 1998 3. Chemical Sciences http://www.chem.ualberta.ca/~plambeck/che/p101/p01076.htm 4. Using a Calorimeter http://www.dartmouth.edu/~chemlab/techniques/calorimeter.html 5. Measuring Heats of Reaction: Calorimetry http://www.ucdsb.on.ca/tiss/stretton/chem2/enthal06.htm 6. Calorimeters http://www.ampletc.com/products/productlist_parr.html 7. Firewalking Gallery http://www.sundoor.com/firewalkingphotos/gallery1.htm