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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. during the brief contact between the walker’s feet and the coals. the redhot layer is very thin. For example. Therefore. the quantity of energy available to heat the feet is smaller than might be expected. on the other hand. But. The spark has a very high temperature but has so little mass that no Figure 1: Picture of a person walking on hot coals8 2 . The amount of energy available for heat flow. although the surface of the coals has a very high temperature. P is the pressure of the system. resulting in a very small volume in the system. and V is the volume of the system. The answer is in simple concept in thermodynamics called enthalpy. Temperature reflects the intensity of the random kinetic energy in a given sample of matter. These two factors result in a very small enthalpy change between the coals the firewalker’s feet. Secondly. there is relatively little time for energy to flow. This factor points out the difference between temperature and heat. so the feet do not reach a high enough temperature to cause damage. depends on the quantity of matter at a given temperature. the tiny spark from a sparkler does not hurt when it hits your hands. Enthalpy is equal to the quantity of U + PV. Human tissue is mainly composed of water. where U is equal to internal energy of a system. 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. like figure 1? The answer to this question is not magic and it’s not because the walkers have supernatural powers.

This paper will mainly focus on the chemical energy within the molecules of a closed system that involve a chemical reaction. enthalpy is a property of a system equal to U + PV. or heat.significant energy transfer occurs to your hand. This same argument applies to the very thin layer on the coals. Since energy cannot be created. and V is the volume of the system. and nuclear energy1. Enthalpy Enthalpy is the system we use to measure that change in energy of a closed system due to chemical bonds being broken. During a chemical reaction. Which means that energy cannot be created nor destroyed. At constant pressure. As stated above. pressure. The chemical energy associated with this process is usually different for the reactants and products1. chemical energy. P is the pressure of the system. energy is conserved. some chemical bonds that bind the atoms into molecules are broken and new ones are formed. where only PV work is allowed. the change in enthalpy equals the energy flow as heat2. Meaning: ∆Esys = 0 and ∆Eproducts = -∆Ereactants The molecules of a closed system possess energy in various forms such as sensible and latent energy. but it can only change forms. All of these forms must balance out in the reactants and products to give the system a net energy of zero. according to the first law of thermodynamics. internal energy. First Law of Thermodynamics The first law of thermodynamics states that in any closed system. Most chemical 3 . where U is equal to internal energy of a system. the difference between the reactants to the products in a closed system can be accounted for in change of volume.

or if. the reaction occurs. chemists use the defined equation3: ∆H = Σ∆Hf(products) . The reaction enthalpy is the heat change that will be. 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. 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. If the sign of ∆H is positive. Reaction enthalpies are real physical quantities for which numeric values can be calculated or measured. which are2: For a gas the standard state is a pressure of exactly 1atm 4 .reactions involve a change of heat. The reaction is then called exothermic. This standard condition is called the standard reference point. is always calculated as the sum of the enthalpies of the products minus the sum of the enthalpies of the reactants. or would be. there’s a need to use a standard condition in which to make the measurements from. The enthalpy change that occurs in a chemical reaction is called the reaction enthalpy and is given the symbol ∆H. In order to put the calculation into algebraic form. then heat will be observed to flow into the reaction from its surroundings. The reaction is then called endothermic.Σ∆Hf(reactants) The reaction enthalpy. observed when. which is the enthalpy change that occurs in the reaction.

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). under standard conditions. Hydrogen and oxygen burn with a very hot flame. 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 25°C or 77°F) Enthalpy is a state function whose value depends only upon conditions and not upon history. 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 5 .- For a substance present in a solution. The superscript “°” is used to indicate property values at the standard state. 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 defined equation above. or even its existence3. 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. becomes: ∆H° = Σ∆H°f(products) .Σ∆H°f(reactants) Enthalpy of Combustion The enthalpy of reaction in a combustion process is called the enthalpy of combustion (symbolized by hc).

ΣNrhf°r = (Nhf°)CO2 + (Nhf°)H20 .830 kJ/kmol) (1 kmol)(-208. Since the water in the products are assumed to be in the liquid phase. Then the enthalpy of combustion of C8H18 becomes: hc = Hprod – Hreact = ΣNphf°p . Also N2 and O2 are stable elements. Then we use Hess’s Law to find the enthalpy of a compound.450 kJ/kmol) = -5. 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 N2.180 kJ/kmol C8H18 which is practically identical to the listed value of –5512. - 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. O2.76 ath N2 Both the reactants and the products are at the standard reference state of 25°C and 1 atm. this hc value corresponds to the HHV of C8H18. the change in enthalpy is the 6 . and thus their enthalpy of formation is zero.512.200 kJ that’s listed in Table A-27. N2.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 25°C and 1 atm. Enthalpy of Formation The enthalpy of formation is defined as the enthalpy of a substance at a specified state due to its chemical composition1. Hess’s Law states that in going from a particular set of reactants to a particular set of products. Solution The stoichiometric equation for this reaction is C8H18 + ath(O2 +3.(Nhf°)octane Using hf° values from Table A-26.520 kJ/kmol) + (9 kmol)(-285.76N2) Æ 8CO2 +9H2O(l) + 3. C). This property makes analyzing easier because it represents chemical energy of an element or a compound at the standard reference state. we get: hc = (8 kmol)(-393. using enthalpy –of-formation data from Table A26. Assume the water in the products is in the liquid form.

The reaction is carried out in some insulated container. The apparatus used to measure the temperature change for a reacting system is called a calorimeter. 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. 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. The design of a calorimeter is not standard and different calorimeters are used for the amount of precision required.same whether the reaction takes place in one step or in a series of steps. 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. One very Figure 2:Picture of a simple calorimeter4 7 . This is because enthalpy is a state function. Calorimeter The changes in temperature caused by a reaction. This is basically how most heats of reaction are determined. 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. 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. where the heat absorbed or evolved by the reaction causes the temperature of the contents to change. The science of using such a device and the data obtained with it is called calorimetry.

The stirrer ensures that any heat released becomes uniformly 8 . and little heat is lost to the lab (or gained from it). combustions which must be ignited. The reactants are put into the "bomb". well-insulated vat of water.simple design used in many general chemistry labs is the styrofoam "coffee cup" calorimeter. the bomb. the enthalpy change involves heat. The inner cup holds the solution in which the reaction occurs. and any piece of the equipment sticking into the water absorb any heat that is Figure 4:Picture of an actual bomb calorimeter6 liberated. Figure 3: Diagram of a Basic Bomb Calorimeter5 which is then sealed and immersed in a large. and the temperature of the entire contents of the vat rises. as seen in figure 1. When a reaction occurs at constant pressure inside a Styrofoam coffee-cup calorimeter. the water. for example. When the reaction is set off. which usually consists of two nested styrofoam cups. It is used to measure energy changes for reactions that will not happen until they are deliberately initiated. 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. so that accurate measurements can be taken and used. very nearly all of it stays inside the calorimeter. which allows the analyzation to be considered in a close system. The second cup provides insulation to the reaction. If heat is evolved in the reaction.

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. From the temperature change and the heat capacity of the calorimeter (water plus everything in the water). Using Hess’s law. the heat liberated is calculated5. 9 . 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.distributed before the final temperature is read. “Measuring Heats of Reaction: Calorimetry” http://www. “Enthalpy of Formation and Enthalpy of Combustion. “Using a Calorimeter” http://www. Third Edition – Boston: Houghton Mifflin Company.” pg.Sources 1. “Firewalking Gallery” http://www. “Chemical Sciences” http://www. “Hess’s Law.htm 10 Steven S.” & “Standard Enthalpies of Formation” pg. 1998. Yunus and Michael Boles.on. 2.htm 4. 361-371 1998 3.dartmouth.chem. 772-776 Cengel.Thermodynamics: An Engineering Approach – Hightstown: McGraw Hill. Chemical Principles. “Calorimeters” http://www.html 7.ampletc.html 5.htm 6.