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Principles of Energy Conversion

Jeffrey S. Allen

Part 9. Chemical Energy & Fuels
November 2, 2015
Copyright © 2015 by J. S. Allen

1 Introduction to Fuels 3

2 Hydrocarbon Chemistry 4
2.1 Aliphatic Hydrocarbons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.2 Alicyclic Hydrocarbons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.3 Aromatic Hydrocarbons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

3 Conversion of Chemical Energy 7
3.1 Chemical Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.1.1 Moles and Mass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.1.2 Conservation of Mass . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.2 Complete Combustion in Oxygen . . . . . . . . . . . . . . . . . . . . . . . . 9
3.3 Complete Combustion in Air . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.4 Complete (stoichiometric) Combustion of Hydrocarbon . . . . . . . . . . . 10
3.5 Theoretical and Excess Air . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

4 Enthalpy Change in Chemically Reacting Flows 11
4.1 Sensible Heat . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
4.2 Latent Heat . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
4.3 Enthalpy of Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
4.3.1 Example – Enthalpy of Formation: Methane . . . . . . . . . . . . . 14
4.4 Enthalpy of Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
4.4.1 Example – Enthalpy of Reaction: Octane . . . . . . . . . . . . . . . 15
4.5 Enthalpy of Combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
4.5.1 Example – Enthalpy of Combustion: Carbon . . . . . . . . . . . . . 18
4.6 Heating Values . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
4.7 Adiabatic Flame Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . 20

5 Equivalent Hydrocarbon 20
5.1 Equivalent Hydrocarbon for Natural Gas Turbines . . . . . . . . . . . . . . . 21

6 Solid Fuels 22
6.1 Coal & Coal Classifications . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
6.2 Proximate and Ultimate Analysis . . . . . . . . . . . . . . . . . . . . . . . . 25
6.3 Coal Reserves . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
6.3.1 US Demonstrated Reserve Base (DRB) . . . . . . . . . . . . . . . . 25
6.4 Biomass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28

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6.5 Manufactured . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
6.6 Refuse . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28

7 Liquid Fuels 29
7.1 Petroleum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
7.1.1 Fuels for Power Production . . . . . . . . . . . . . . . . . . . . . . . 29
7.2 Petroleum Refining . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
7.3 Liquid Fuel Ratings for Internal Combustion . . . . . . . . . . . . . . . . . . 35
7.3.1 Octane # . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
7.3.2 Cetane # . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
7.4 Petroleum-Like Liquid Fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
7.5 Liquid Bio-Fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
7.6 Manufactured Liquid Fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
7.7 Refuse . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36

8 Gaseous Fuels 37
8.1 Natural Gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
8.2 Manufactured Gaseous Fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
8.3 Manufactured from Solid Fuels . . . . . . . . . . . . . . . . . . . . . . . . . 37
8.4 Refuse . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37

References 38

2

Introduction to Fuels
The term fuel almost always indicates a source of chemical energy to be combusted
for conversion to thermal energy. Fuels may also be used to produce light (elec-
tromagnetic energy) and electrical energy through electrochemical devices such as
batteries and fuel cells. Sources of chemical energy for direct conversion to elec-
trical energy are commonly referred to as reactants. The most commonly used
combustible fuels are fossil fuels; coal, petroleum and natural gas. The most com-
mon combustible elements in these fuels are carbon (C), hydrogen (H), and sulfur
(S). Hydrocarbon fuels are comprised of carbon atoms bonded in a chain with side
bonds of hydrogen.

Combustion is the conversion of a fuel into combustion products and energy release.
The energy released is nearly always in the form of heat (transient thermal energy).
Combustion requires a chemical reaction between a fuel and an oxidizer. Oxygen is
the most common oxidizer and most often the source of oxygen is air. The amount
of energy released can be measured using a calorimeter.

fuel + oxidizer Ô⇒ combustion species +energy
´¹¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¸¹¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¶ ´¹¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¸¹¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¶
reactants products

Fuels are commonly divided into solid, liquid and gaseous forms. Solid fuels, such
as coal, are generally specified in terms of the mass fraction of chemical elements.
Carbon (C), hydrogen (H2 ), and sulfur (S) are three common combustible elements
found in fuels. Carbon oxidation is slower and more difficult than hydrogen or sul-
fur. It is a common assumption that both H2 and S will burn completely in a fuel
before any carbon burns. Liquid fuels, such as gasoline, are specified in terms of the
mass fraction of hydrocarbon compounds (butane, octane, 2,2,4-trimethylpentane).
Gaseous fuels, such as natural gas, are generally specified in terms of mole fractions
of chemical compounds (methane, propane, isobutane). All three forms of fuel,
solid, liquid and gaseous, are found naturally and can by synthesized or manufac-
tured.

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Crude oil (petroleum) may have millions of different hydrocarbon compounds. are saturated hydrocarbons with the number of carbon and hydrogen atoms corresponding to Cn H2n+2 . Extremely long hydrocar- bon chains form solids. which are composed of carbon and hy- drogen. that is share a single electron. Alicyclic and aromatic hy- drocarbon compounds form carbon-atom “rings”. C4 H10 Nonane. Alkanes with carbon-atom branches. also known as paraffins.Hydrocarbon Chemistry Many fuels are classified as hydrocarbons. CH4 . C8 H18 ⋅ Butane. Common examples include: Methane. The n. C7 H16 ⋅ Propane. Fuels are generally a mixture of hydrocarbons. C9 H20 Hexadecane. the difference between the two has to do with the structure of the ring. Alkanes. CH4 Hexane. between each carbon atom of the chain or ring. alicyclic. The chemical and physical properties may be extremely different for hydrocarbon compounds having the same number of carbon and hydrogen atoms but with different structures. are prefixed with “iso-”. Saturated hydrocar- bons have a single bond. Aliphatic Hydrocarbons Aliphatic hydrocarbons are naturally found in all fossil fuels and are in the form of carbon “chains”. C10 H22 ⋅ Normal alkanes. The simplest hydrocarbon is methane. two in the K shell and four in the L shell.and iso. and aromatic. typically in the form of a methyl group (CH−3 ). the fraction of hydrogen to carbon decreases and the hydrocarbon compound becomes less volatile. alkenes. There are three subgroups of the aliphatic hydrocarbons: alkanes. C6 H14 ⋅ Ethane. C2 H6 Heptane. Hydrogen has a single electron (in the K shell) and needs to share an additional electron. A hydrocarbon compound may be saturated or unsatruated. C3 H8 Octane.forms 4 . This is why hydrogen gas is always found as H2 . Aromatic hydrocarbons form benzene rings. leaving the L shell 4 electrons short of being full. C16 H34 Pentane. that is sharing two or three electrons. As the number of atoms increases. are saturated hydrocarbons in which the carbon atoms are connected in a single chain. in which 4 hydrogen atoms all share a single electron with a carbon atom. Unsaturated hydrocarbons have at least two carbon atoms with multiple bonds. C5 H12 Decane. Hydrocarbon compounds are divided into three major groups referred to as aliphatic. Carbon atoms have 6 electrons. prefixed with “n-”. & alkynes. Aliphatic hydrocarbon compounds form carbon-atom “chains” and are the primary makeup of fossil fuels. As such carbon can share four electrons with other elements. The chain may be a single line of carbon atoms or there may be branches of carbon chains.

4-trimethylpentane. C6 H12 Alkynes. Cn H2(n−1) acetylene. also known as acetylenes. C2 H2 H ethylacetylene. 2nd. are unsaturated hydrocarbons with one triple bond between two carbon atoms. butanol: C4 H9 OH Alkenes. For example: methyl alcohol. H If one hydrogen atom in an alkane is replaced by OH− . methanol: CH3 OH ethyl alcohol. C2 H4 H H H propylene.2. C3 H6 ←→ C C C H butene. C5 H10 hexene. H H H H C C C C C H There are 3 methyl groups (CH3 ) at- tached to a pentane backbone at the H H H H 2nd. ethanol: C2 H5 OH propyl alcohol. are unsaturated hydrocarbons with one double bond between two carbon atoms. C4 H8 H H pentene.of octane (C8 H18 ) are: n-octane: C8 H18 H H H H H H H H H C C C C C C C C H H H H H H H H H iso-octane: C8 H18 H H This particular arrangement of iso- octane is technically known as H C H H C H 2. also known as olefins. and 4th carbon atom posi- H C H tions. C4 H6 ←→ H C C C CH3 H 5 . Cn H2n ethylene. proponal: C3 H7 OH butyl alcohol. the hydrocarbon becomes an alcohol.

Alicyclic Hydrocarbons Alicyclic hydrocarbons are saturated carbon atom “rings” with two hydrogen atoms for every carbon atom. and cyclopentane (C5 H10 ). C5 H10 Aromatic Hydrocarbons Aromatic hydrocarbons are composed of benzene “rings”. The alicyclic name is the same as the alkene group preceded by “cyclo”. C10 H8 6 . cyclobutane (C4 H8 ). toluene (C7 H8 ). Double-ring molecules have a C-H ratio of Cn H2n−12 . Common examples include benzene (C6 H6 ). which is the same as the alkene subgroup of aliphatic hydrocarbons but without any double carbon bonds and now in a ring structure. H H H H C C C C H C C C H H C C H H C C C H C C C C H H H H benzene. C6 H6 naphthalene. Single-ring molecules have a C- H ratio of Cn H2n−6 . xylene (C8 H10 ). New hydrocarbon compounds can be created by adding methyl groups (CH−3 ) to the ring(s) in place of a hydrogen atom. and naphthalene (C10 H8 ). Com- mon examples include cyclopropane (C3 H6 ). H H H H C H H H C C H H C C H H C C H H C C H H H H H cyclobutane. which are formed from six carbon atoms with a double bond every other atom. Cn H2n . C4 H8 cyclopentane.

The number atoms of each element must be balanced in and out of the device. One mole is the number of a parts in a substance that is equal to the number of atoms per 12 grams of carbon-12. kmol. the molecular mass of carbon-121 is 12. gmol ≡ 12 g of carbon-12 1 The 12 indicates the isotope of carbon which is identified by the number of nuclear particles (6 neutrons and 6 protons) in the nucleus. For methane reacting with oxygen. This is to indicate the mass relationship. One mole of carbon dioxide (CO2 ) is formed from one mole of carbon and one mole of oxygen gas (O2 ). 7 . Similarly. A gmol of H2 is equivalent to 2. kgmol ≡ 12 kg of carbon-12 lbmol ≡ 12 lbm of carbon-12 slugmol ≡ 12 slug of carbon-12 mol. The integer coefficients that balance the reactant and product elements are the molar proportions for which the species react. For combustion of a fuel such as methane with exactly the correct amount of oxygen. 8 neutrons) and is radioactive. mass = mols × molecular mass m = nM Note the use of gmol instead of the common abbreviation mol. which shows 1 mole of methane (CH4 ) being reacted with 2 moles of oxygen (O2 ) to form 1 mole of carbon monoxide (CO) and 2 moles of water (H2 O). Thus. also known as the molecular weight. Moles and Mass A mole is directly related to the mass of a substance through the molecular mass. There is 1 mole of carbon in both the reactants and in the products.00000 g/gmol. the mass of a substance is equal to the number of moles times the molecular mass.Conversion of Chemical Energy Chemical Reactions Complete combustion of carbon and hydrogen requires a mole balance of each element. the coefficients are known as stoichiometric coefficients. For example. there are 4 moles of hydrogen in the reactants and the products. 2 Molecules are chemically being split and recombined in different forms so both mass and species must be conserved. C + O2 Ð→ CO2 One mole of water is formed from one mole of hydrogen gas (H2 ) and one-half mole of oxygen gas (O2 ). the chemical balance is: CH4 + 2O2 Ð→ CO2 + 2H2 O .016 g. Carbon-14 is another carbon isotope that has 14 nucleons (6 protons. Similarly. 1 H2 + O2 Ð→ H2 O . or 2 moles of atomic hydrogen (H) and 1 mole of atomic oxygen (O).

NA = 6.59237 gmol. the specific volume of oxygen is v02 = 11.S.819 ) = 378. the molal volume of hydrogen at 60 ○ F and 1 atm is: lbm ft3 ft3 v̄H2 = (2. Another useful measure is molal volume. complete combustion of methane is CH4(g ) + 2O2(g ) Ð→ CO2(g ) + 2H2 O(l) Using the molecular masses of the reactants and the number of moles per species. And these are not equivalent. etc. On a molar basis. 1 mol refers to 1 gmol. Conservation of Mass While the total number of moles may not be conserved.02214129 × 1023 particles/lbmol The particles may be anything – atoms. 1 lbmol = 453.21 lbmol lbm lbmol The bar over the volume symbol indicates volume on a per mole basis. the total mass of the reactants and products is conserved though not by species or elements.016 ) (197. Always be certain of the unit system within which you are working! The number of particles in 1 gmol is fixed and defined as Avagadros number. at 60 ○ F and 1 atm. A good approximation of volume of any gas at 60 ○ C and 1 atm is 379 ft3 /lbm. which is the volume occupied by a gas. molecule. the total mass of reactants (CH4 + 2O2 ) is: 12 kg 1 kg 16 kg ( C) (1 kmol C) + ( H) (4 kmol H) + ( O) (4 kmol O) = 80 kg kmol kmol kmol The total mass of the products (CO2 + 2H2 O) is: 12 kg 16 kg 1 kg ( C) (1 kmol C) + ( O) (2 kmol O) + 2 ( H) (2 kmol H) kmol kmol kmol 16 kg + 2( O) (1 kmol O) = 80 kg kmol 8 . NA . For example. electrons.819 ft3 /lbm. In a similar fashion. power industry 1 mol often refers to 1 lbmol. neutrons. As an example.45 lbmol lbm lbmol Notice the similarity in molal volumes. in the U.02214129 × 1023 particles/gmol – or – NA = 6.723 ) = 378. However. the specific molar volume (molal volume) is: lbm ft3 ft3 v̄O2 = (32 ) (11.Typically.

76 lbmol O2 0.Complete Combustion in Oxygen When there is just enough oxygen to react with all of the fuel.76 lbmol O2 0. There is insufficient oxygen for complete combustion of carbon. 2. (l) indicate the species is in a solid. Stoichiometric conditions for carbon combustion are: C(s) + O2(g ) Ð→ CO2(g ) .15 N2 78. gaseous.2315 lbm O2 9 .03 76. nitrogen and air are: lbmol air 1 ft3 air = = 4.32 lbm O2 0. The product is carbon monoxide which is still combustible. The subscripts (s).99 23. There is no excess oxygen or combustible species remaining in the products. Table 1 gives the percent composition of dry air. (v ). Table 1. argon. respectively.7685 lbm N2 = = 3.85 inert 0. Complete Combustion in Air The most common source of oxygen for combustions is air.2099 ft3 O2 lbm air 1 lbm air = = 4. the reaction occurs under stoichiometric conditions. For example.2099 ft3 O2 lbmol N2 0.2315 lbm O2 lbm N2 0.7901 ft3 N2 = = 3. (g ). vapor or liquid form. The amount of oxygen required for complete combustion of carbon is: (32 kg O2 /kmol O2 ) (1 kmol O2 ) 2.66 kg of oxygen is required for complete oxidation.66 lbm O2 1 kmol O2 = = ≡ (16 kg C/kmol C) (1 kmol C) kg C lbm C kmol C Thus for each kg of carbon in a fuel. the inert components (CO2 . For the purposes of combustion. a non-stoichiometric reaction is: 2C(s) + O2(g ) Ð→ 2CO(g ) .66 kg O2 2.98 – The respective mass and mole fractions with oxygen.32 lbm O2 0. Composition of dry air % by volume % by mass O2 20. neon) are combined with and treated as nitrogen.

air-fuel ratio.76N2 ) ←Ð CO2 + 2H2 O + 7.76N2 ) Ð→ xCO2 + H2 O + 3. Quantification of the amount of air used varies among energy fields. is defined as the mass of air to the mass of fuel.Thus. theoretical and excess air are: A/F % theoretical air = 100 { ○} A/F 10 . stoichiometric combustion of carbon monoxide (CO) in air is: 2CO + (O2 + 3.21 Theoretical and Excess Air Most combustion processes incorporate more air than necessary for stoichiometric combustion. Theoretical Air is the amount of air required for complete combustion. The percent excess air is: air supplied − theoretical required % excess air = ( ) × 100 theoretical required and % theoretical air = % excess air + 100 The air-fuel ratio. and equivalence ratio. A/F. and M is the molecular mass.76 (x + ) N2 (2) 4 2 4 The amount of dry air required for the stoichiometric reaction is: mols of dry air (x + y /4) (1 + 3. excess air. in other words stoichiometric conditions. Using the air-fuel ratio.76) x + y /4 = = (3) mols of Cx Hy 1 0. stoichiometric combustion of a hydrocarbon becomes: y y y Cx Hy + (x + ) (O2 + 3.54N2 Complete (stoichiometric) Combustion of Hydrocarbon Complete combustion of a hydrocarbon in oxygen follows a general reaction of the form: y y Cx Hy + (x + ) O2 Ð→ xCO2 + H2 O (1) 4 2 In air.76N2 and complete (stoichiometric) combustion of methane (CH4 ) is: CH4 + 2 (O2 + 3. For a stoichiometric reaction the air-fuel ration becomes: ○ mair 4. The most common measures of the amount of air are theoretical air. or 100% theoretical.76N2 ) ←Ð 2CO2 + 2H2 O + 3.76 (x + y /4) Mair A/F = ( ) = ⋅ mfuel stoich 1 Mfuel where the ○-superscript indicates stoichiometric.

Conser- vation of mass is applied to each species separately. there is insufficient air for complete combustion and some fuel components will appear in the products of the chemical reaction. vapor or liquid. Q̇ − Ẇ = Ė ∣out − Ė ∣in . such as liquid or gas flowing through a heat exchanger. (5) out in assuming negligible changes in any other fluid energies besides enthalpies. If the equivalence ratio is greater than one (Φ > 1). that is the same gas. which is the actual fuel-to-air ratio divided by the theoretical fuel-to-air ratio. Ḣout − Ḣin . For example. then the fuel-air mixture is considered rich. (4) In the absence of significant changes in kinetic energy (inertial potential) or grav- itation potential the change in fluid energy becomes the change in fluid enthalpy. ∆Ḣs . When there is multiple species flowing through the energy converter. 100 % theoretical air = Φ 1−Φ % excess air = ( ) × 100 Φ When the equivalence ratio is equal to one (Φ = 1). 11 . then conservation of energy becomes: Q̇ − Ẇ = ∑ ( ṁh∣air + ṁh∣water ) − ∑ ( ṁh∣air + ṁh∣water ) . that is. Enthalpy Change in Chemically Reacting Flows When a single species is flowing through a device. Sensible Heat The fluid flowing out is chemically identical to the fluid flowing in. if air and water are co-flowing through a device. then conservation of energy reduces to the First Law of Thermodynamics. Φ. A/F . If the equivalence ratio is less than one (Φ < 1). then the combustion reaction occurs under stoichiometric conditions. F/A A/F○ Φ≡ = F/A○ A/F Theoretical and excess air can be expressed in terms of the equivalence ratio. then the fuel-air mixture is considered lean.A/F○ % excess air = 100 { } A/F○ The last measure of air to be discussed is the equivalence ratio. then the change in enthalpy is known as a sensible heat. then the change in enthalpy for each species must be considered.

77 ○ F) and 1 atm. or latent heat. is hfg = 2257 kJ/kg. The enthalpy change for this process.On a per mass basis. 2 Q̇3 = Ḣ3 − Ḣ2 = ṁ (hs. because the fluid remains the same species.3 = h3 − h(298K ) = 3666 kJ/kg − 104. The reference temperature enthalpies will not cancel for reacting flows in which the species change. The resulting change in enthalpy. Water vapor at 582 ○ C. The most common reference state is 298 K (25 ○ C. For non-reacting species such as water vapor.1 kJ/kg − 104.2 = h2 − h(298K ) = 2676 kJ/kg − 104.8 kJ/kg. conden- sation will occur without a change in fluid temperature until all of the vapor has become liquid. is known as latent heat. etc) are relative to a reference state. 1 atm is cooled to 100 ○ C. This cancella- tion will not be true for reacting mixtures. 1 atm and remains in the vapor state. Hvapor − Hliquid .8 kJ/kg and hs. The resulting change in specific enthalpy is 989. where hs. enthalpy. Latent Heat If the heat is further extracted from the water vapor as shown in Figure 2. Again.8 kJ/kg .3 − hs. 5 8 2 oC 1 0 0 oC 1 a tm 1 a tm H 2O (v ) H 2O (v ) (2 ) (3 ) Q Figure 1.8 kJ/kg and h4 = hf (373K ) − h(298K ) = 419. Cooling of water vapor. H2 O.8 kJ/kg . 3 Q̇4 = ṁ (h3 − h4 ) where h3 = hg (373K ) − h(298K ) = 2676 kJ/kg − 104. 12 . the reference temperature enthalpies cancel out. sensible heat is the difference in the enthalpy relative to the enthalpy of a reference state. the reference temperature enthalpies cancel out. hs = h(T ) − h(Tref ) (6) All measures of energy (internal energy.2 ) . Consider the case of steam (water vapor) being cooled as shown in Figure 1.

. R 13 . .2 The ○-superscript indicates the value at the standard state. 298 K and 1 atm. The standard state is not always the same for different tabulations! 2 5 oC 1 a tm 5 8 2 oC 1 0 0 oC 1 0 0 oC 2 5 oC 2 H 1 a tm s e n s ib le 1 a tm la t e n t 1 a tm 1 a tm 2 (g ) s e n s ib le c o m b u s t io n H 2O H 2O h e a t H 2O ( l) O (v ) h e a t (v ) h e a t 2 (g ) (2 ) (3 ) (4 ) (5 ) (1 ) Q Q Q Q n e t Figure 3. Consider the formation of water vapor by the combustion of hydrogen with oxygen. Exercise caution when looking up values for the enthalpy of formations. ∆hf○ . Combustion of hydrogen and cooling the combustion product (water) back to the reference state. For hydrogen and oxygen at the reference state. the change in fluid energies must include a chemical and a thermal component. 1 0 0 oC 1 0 0 oC 1 a tm 1 a tm H 2O (v ) H 2O ( l) (3 ) (4 ) Q Figure 2.T . which is typically 298 K and 1 atm. Enthalpies of formation are determined by chemically reacting species and then adding or subtracting thermal energy until the products are returned to the stan- dard state. There are many different symbolic representations for the enthalpy of formation. .T . Figure 3 shows the sequence of processes for the com- bustion of hydrogen to form water vapor and then cooling and condensing the water 2 This is also referred to as the constant pressure heat of formation and heat of formation. Enthalpy of formation is also referred to as constant pressure heat of formation. the enthalpy entering the process must include the chemical energy of each species plus the sensible heat plus the latent heat. R hf○. Condensation of water vapor. Enthalpy of Formation During a chemical reaction the species change during conversion of energy. ∆hf○. htotal = hf○ + hs + hfg where hf○ is the enthalpy of formation. As an example. 2H2 + O2 Ð→ H2 O For this type of process.

Table 4 lists enthalpies of formation on a per mass basis for various gases at 1 atm and various temperatures. h(T ) − h(Tref ). and nitrogen (N2 ) also have an enthalpy of formation of zero. For water vapor. Gases in their base state such as hydrogen (H2 ). Example – Enthalpy of Formation: Methane As illustrated in Figure 4.g.298K )] −ṁH2 [hf○. The enthalpy of formation for elements such as carbon (C) and sulfur (S) are zero.O2 − hO2 .298K. Table 2 lists the enthalpy of formations on a per mass basis for a number of compounds with a standard state of 298 K and 1 atm.H2 O(l) The measured value of the enthalpy of formation for liquid water is 15 575. or 2 moles of H2 . the difference between the liquid water and water vapor enthalpy of formations is the latent heat of vaporization. multiply by the molecular mass of the compound.C + [HC (T ) − HC (298K )] + Hf0.5 kJ/kg. Therefore the difference in sensible heat change is zero for each of the species. For convenience. the inlet and exit conditions are at the reference state. h5 − hH2 O. oxygen (O2 ). methane is a hydrocarbon compound formed from 1 mole of carbon and 4 moles of elemental hydrogen.H2 0(l) + (h5 − hH2 0. Table 3 lists from another source enthalpies of formation on a per mole basis.CH4 + [HCH4 (T ) − HCH4 (298K )]} − {Hf0.298K.H2 O(v ) = 13 430. The net heat extracted is: Q̇net = Ḣout − Ḣin = ṁH2 0 [hf○. resulting in: Q̇net = Ḣout − Ḣin = ṁH2 O hf○.298K = 0.H2 + [HH2 (T ) − HH2 (298K )]} 14 . Q = {Hf0.vapor back to the reference temperature.H2(g ) + (h1.H2 − hH2 .O2(g ) + (h1. C + 2H2 Ð→ CH4 A change in temperature is associated with the chemical conversion. Returning to the energy balance described by Figure 3. hf○. The temper- ature may increase.298K )] Table 2 lists values of enthalpy of formation on a per mass basis for various com- pounds at a standard state of 25○ C (298 K) and 1 atm.298K.298K )] −ṁO2 [hf○. To convert from a mass to a molar basis. The enthalpy of formation at temperatures other than the reference temperature are found by including the change in sensible heat. or decrease in an endothermic process.8 kJ/kg. which is an exothermic process. e.

Enthalpy of Reaction The enthalpy of reaction. Example – Enthalpy of Reaction: Octane For example. conservation of energy for this scenario reduces to: Q = Hproducts − Hreactants 15 . Heat is added until the temperature of the products (methane) is returned to the standard state. equal zero for all reactants and products because the temperature begins and ends at the reference state. Btu/lbm CH4 ). the heat transfer is the resulting enthalpy of formation.CH4 The enthalpy of formation is tabulated on a per mass or per mol basis. C8 H18(l) + 12 12 O2 Ð→ 7CO2 + CO + 9H2 O(v ) + 21 O2 With all species at 298 K and 1 atm.298K. Carbon monoxide (CO) is also combustible so this combustion process is considered incomplete. resulting in: Q = Hf0. respectively. Btu/lbmol CH4 ) and h is on a per mass basis (kJ/kg CH4 .CH4 where h̄ is on a per mol basis (kJ/kmol CH4 .298K. The enthalpy of reaction is the difference in total enthalpy of the products and reactants. Complete combustion would leave only carbon dioxide (CO2 ) and water (H2 O). Q m e { C C r e a c ta n ts c a r b o n m e th a n e 2 9 8 K m H 2 e H 2 h y d r o g e n m C H 4 e C H 4 Figure 4. H2 O. Q = nCH4 h̄f0.298K .CH4 = mCH4 hf0. is the heat transferred for 1 mole of a specific compound reaction with the reactants and products at the standard state. h e a t. If the reactants (C and H2 ) are initially at the standard state (25○ C) and the methane formed is brought back to the standard state. H(T) .H(298K).298K. The sensible heats. CO. incomplete combustion of octane could result in the production of C02 . The initial temperature of the carbon and hydrogen is at a standard state of 298 K. Hf○. Also the enthalpies of formation for the carbon and hydrogen are zero.298K . h̄r○. n and m are the number of moles and mass. Formation of methane.

[2] 16 .Table 2. Enthalpy of Formation per mole at 25 ○ C (77 ○ F) and 1 atm. Enthalpies of Formation per mass at 25 ○ C (77 ○ F) and 1 atm. [1] Table 3.

5 mol O2 ○ − {( ) h̄C8 H18 + ( ) h̄O2 } mol C8 H18 mol C8 H18 For these product species. [1] On a per mole basis: 7 mol CO2 ○ 1 mol CO ○ 9 mol H2 O ○ 1 mol O2 q̄ = {( ) h̄CO2 + ( ) h̄CO +( ) h̄H2 O(v ) + ( ) h̄○ } mol C8 H18 mol C8 H18 mol C8 H18 2 mol C8 H18 O2 1 mol C8 H18 ○ 12. the enthalpy of reaction for combustion of octane is: J J J J q̄ = {7 (−393 520 ) + 1 (−110 525 ) + 9 (−241 818 ) + 0. Table 4.5 (0 ) +} mol mol mol mol J J − {1 (−249 957 ) + 12. Enthalpies of formation [Btu/lbm] at various temperatures and 1 atm.5 (0 )} mol mol = = 4 791 570 J/mol C8 H18 17 .

is the heat transferred when 1 mole of a compound is completely combusted and the products cooled back to the standard state. Applying conservation of energy on a per mole basis. where m is the mass. 2CO + O2 Ð→ 2CO2 + QCO2 In each reaction. hc. a portion of chemical potential energy of the reactants is converted into thermal energy.298K. The total heat released during the reaction is dependent upon the mass being reacted. or the number of moles reacted. On a per mole basis.CO = mCO hf○.O2 + (h̄(298K ) − h̄(Tref ))] The overbar (h̄) indicates enthalpies on a per mole basis (kJ/kmol. Oxidation of two moles of carbon produces two moles of carbon monoxide.C + (h̄((298K ) − h̄(Tref ))] − [h̄f○. 2C + O2 Ð→ 2CO + QCO then to carbon dioxide (CO2 ) provided sufficient oxygen is present. The heat released during combustion of CO to CO2 can be similarly examined. Hf○.CO .O2 + (T (298K ) − Tref )] 18 .298K. Btu/lbmol).CO + (T (298K ) − Tref )] − [hf○. the heat released is q̄ = h̄f○. and M = m/n is the molecular mass of the compound. QCO2 = 2 [hf○. Example – Enthalpy of Combustion: Carbon Carbon burns as a solid. QCO = 2 [h̄f○.298K. The complete combustion is what distinguishes the enthalpy of combustion from enthalpy of reaction.298K.298K.CO = −110 530 kJ/kmol CO . the carbon is assumed to first completely oxidize to carbon monoxide (CO).298K .Enthalpy of Combustion ○ The Enthalpy of Combustion.CO = nCO h̄f○.CO2 + (T (298K ) − Tref )] −2 [hf○.298K. Measuring the heat extracted from the reactor (combustion vessel) to return the products to the standard state temperature provides the change in chemical potential energy.298K. In analyzing carbon oxidation. n is the number of moles.298K.CO + (h̄(298K ) − h̄(Tref ))] −2 [h̄f○.298K. And since the final temperature is equal to the reference temperature there is no change in sensible heat (∆h). The heat of formation for Carbon (C) and Oxygen (O2 ) are zero.298K.

Lower heating value is the total enthalpy change when the product water remains in the vapor state.298K. the heat of formation of CO2 is equal to the heating value (HV). mwater HHV = LHV + ( ) hfg mfuel 19 . Higher heating value is the enthalpy released due to the reaction in which the water vapor is condensed. Heating values are the enthalpy difference between the products and the reactants with all compounds brought back to the standard state.With the reactants and products at the standard state on a per mole basis.CO2 − h̄f○. For complete (stoichiometric) combustion of carbon. The latent heat released during condensation is included in the total heat of reaction. the heat released is known as a heating value (HV) for the fuel.CO = −282 990 kJ/kmol CO .298K. the heat released from oxidation of CO is q̄ = h̄f○. ⎡ ⎤ ⎢ ⎥ HV = ⎢⎢ ∑ (nh̄f ) − ∑ (nh̄f )⎥⎥ ⎢products ⎥ ⎣ reactants ⎦standard state The heating value is often qualified as the higher heating value (HHV) or the lower heating value (LHV). The complete chemical balance combustion of carbon is C + O2 Ð→ CO2 with a subsequent heat of formation equal to the sum of the heats released during oxidation of carbon and then of carbon monoxide. Carbon dioxide is the final oxidization state of carbon. (−110 530 kJ/kmol) + (−282 990 kJ/kmol) = −393 520 kJ/kmol CO2 ´¹¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹¸ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¶ ´¹¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹¸ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¶ [C-to-CO] [CO-to-CO2 ] Heating Values Under stoichiometric conditions and when the reactants products are at a standard state.

008) kg H = = 0.474 1. Q = 0 Ô⇒ ∑ (nh̄f ) = ∑ (nh̄f ) products reactants The temperature at which the total enthalpy of the products equals the total en- thalpy of the reactants is the adiabatic flame temperature.008 kg 22.281 mC 1.484(12.264 total 1. compound % volume mol fraction carbon hydrogen methane. C2 H6(g ) 16.674 2. For example. Table 5 shows the range of molar composition for selected U. The molar mass of this fuel can be determined using the equivalent hydrocarbon. the total enthalpy of reaction can be de- termined. Consider the following gaseous fuel comprised of methane.674 0. The nitrogen present in the air has a thermal capacitance that results in a lower temperature of the reactants.8 0.01) kg C 20 .484 kgmol C 12.008 propane.Adiabatic Flame Temperature The adiabatic flame temperature is determined by isolating the chemical reaction from any heat or work exchange with the environment.01 kg 4.83 kg ( )( )+( )( )= kgmol fuel kgmol C kgmol fuel kgmol H kg fuel The mass fraction of hydrogen to carbon is: mH 4.968 . This is referred to as a dilution effect. a lean combustion mixture (> 100% theoretical air) will have a lower temperature than a stoichiometric or rich combustion mixture due to dilution effects.968 kgmol H 1.4 0.484 H4. CH4(g ) 67.000 1.336 1. C3 H8(g ) 15. This temperature will change depending on the stoichiometric conditions.8 0.968(1. 1. A convenient method for these calculations is to derive an equivalent hydrocarbon for the multi-compound fuel.484 4. natural gases.696 ethane.968 the equivalent hydrocarbon is C1.158 0. From the molar fractions.S. This is particularly true for natural gases and biofuels. Equivalent Hydrocarbon Many fuels are composed of multiple combustible compounds the fraction of which varies depending upon the source of the fuel. Similarly.168 0. ethane and propane. the adiabatic flame temperature will be higher for a compound completely combusted in oxygen as compared to air.

H] Equivalent Hydrocarbon for Natural Gas Turbines A commonly used approximation for natural gases combusted in a power generating Brayton cycle is CH2.53625 2. fuel gases. [3. 5526N2 21 .76 (1 + ) N2 2 4 ´¹¹ ¹ ¹ ¹ ¹ ¹ ¹¸ ¹ ¹ ¹ ¹ ¹ ¹ ¹¶ ´¹¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¸¹¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¶ 1.53625O2 +11.76N2 ) Ð→ 4 ´¹¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¸¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹ ¹¶ 1.145(g ) +2 (1.145 CH2. App.145 [? ].0725H2 O(g ) +1. Table 5.145(g ) + (1 + ) (O2 + 3.53625) (O2 + 3. Molar composition of selected U.145 2.145 CO2(g ) + ( ) H2 O(g ) + 3.0725 1.76N2 ) Ð→ CO2(g ) +1. the reaction equation for this equivalent fuel is: 2. the reaction equation becomes CH2. For stoichiometric combustion.S.0725 At 200% theoretical air.

It is bituminous. Medium- volatile bituminous. sub-bituminous: This type of coal is soft and sometimes referred to a black lignite. Coal & Coal Classifications Using the American Society for Testing Materials standard ASTM D 388 [3]. respectively. lignite: This coal is brown with a woody structure and generally has a high moisture content. volatiles are not considered when determining the heating value of a coal since these compounds have usually been driven off with heating prior to combustion. 22 . Heating values are relatively low relative to the preceding coal ranks and it pulverizes easily. Within this rank are three distinct groups of coal. smoke-free that is low in volatile matter and high in carbon. lower in fixed carbon and higher in volatiles. brown coal: peat: cannel coal: This type of coal does not fall under any particular system of classi- fication. bituminous and lignite. solid fuels are predominantly coal. but with an extra high hydrogen content. anthracite: This type of coal is hard. wood and biowaste from farming. It is characterized by high volatile content and low fixed carbon. Volatiles are light hydrocarbons that are released from the coal with slight heating. Coal ranks vary in hardness and carbon content. Sub- bituminous A. Within this type are Low-volatile bituminous. Metaanthracite is the hardest and has the highest carbon content with greater than 98% fixed carbon. Figure 5 illustrates the ranking of coals based on fixed carbon content and heating value. Sub-bituminous B. respectively. The hardest coal is known as anthracite. Anthracite has the next highest fixed carbon equal or greater than 92% and Semianthracite has a fixed carbon content equal or greater than 86%. The primary differences are in the fixed carbon content and volatile content. semi-bituminous. coal is ranked by carbon and volatile (light hydrocarbons) composition. Fixed carbon indicates carbon not contained in volatiles. followed by semi-anthracite. and Sub-bituminous C are groups within this type with decreasing heating values.Solid Fuels In the United States. Generally. bituminous: This type of coal is less hard than anthracite. and High-volatile C bituminous. High-volatile B bituminous. Lignite A and Lignite B are the two major groups with heating values between 6300 .8300 Btu/lbm and less than 6300 Btu/lbm. In many parts of the world manure or peat are the most common solid fuels. High-volatile A bituminous. Often is is used in the manufacture of gas.

7) (24. in percent Medium S = sulfur.1) (19.08A + 0.300 6.000 13. Mm .55S)) 86 Dry.6) (30.000 14.free VM =100 . in percent volatile Mm = mineral matter bituminous Mj/Kg = megajoules per kilogram lb = pound 69 60 High volatile A bituminous High volatile B bituminous High volatile C bituminous Subbituminous A Subbituminous B Subbituminous C 50 Lignite A Lignite B 40 16.55S)) Low volatile bituminous DEFINITIONS Btu = gross calorific value.(M + 1.15S) / (100 .(1. British thermal units per pound FC = fixed carbon. from East [4] 23 .Percent 100 Meta-anthracite 98 Anthracite 92 Semianthracite FORMULA Dry. Mm . in percent A = ash.free Btu = 100(Btu .free FC = 100(FC . Mm .500 10.free) 78 M = moisture.500 8.free FC Moist. in percent Fixed Carbon (dry. Mm .000 11.4) (22. mineral matter .08A + 0.500 9.3) (14.3) (32.Dry.0. in percent VM = volatile matter.2) (26. mineral matter-free) Figure 5.50S) / (100 .7) (Mj/Kg) Calorific Value (moist.300 Btu/lb (37. General coal ranks.

ASTM D 388. [5] 24 . Classification of coals by rank.Figure 6.

5% of DRB. Monatana. mostly found in Texas. 1. 37% of DRB. 9% of DRB. all located west of the Mississippi River lignite.Proximate and Ultimate Analysis [update] Coal Reserves US Demonstrated Reserve Base (DRB) anthracite. subbituminous. 53% of DRB. and North Dakota [from US Energy Information Agency] 25 . concentrated in northeastern Pennsylvania bituminous.

Kraushaar and Ristinen [6] Ristinen and Kraushaar [7] 26 .

U. coal field map from USGS Open-File Report OF 96-92. (need to update) East [4] 27 .Figure 7.S.

often classified with coal • garbage • manure Manufactured Refuse 28 . As we exhaust them. George Washington Carver [1864 . which is God’s true storehouse and can never be exhausted. we must be prepared to fall back on our farms. We can learn to synthesize material for every human need from things that grow.1943] • wood • peat.Biomass I believe that the great Creator has put ores and oils on this earth to give us a breathing spell.

nitrogen. 4 is low in sulfur. The later may have 83-87% carbon (11-14% H2 ). 5 (heavy). water.No.Liquid Fuels Petroleum Crude oil contains an infinite number and variety of hydrocarbons. 6 . separation of similar weight hydrocarbons 2. H2 O & high viscosity Crude most suitable for direct firing is called sweet. O2 . 4 . No. low sulfur content. cleaning of undesirable impurities such as sulfur 4. 5 (light).No. 1. conversion of hydrocarbons – from heavy-to-light and light-to-heavy 3. 5 heavy is high in sulfur. H2 O. CO2 . No. 2. Petroleum (crude oil) is separated into groups of similar hydrocarbons to create products for specific applications. No. blending of hydrocarbons for creation of specific products 29 . There is also sulfur. and mineral impurities. Cn Hm . Fuels for Power Production Distillates: No. The range of hydrocarbon molecular weights ranges from very light gaseous hydrocarbons (low- n-to-m ratio) to heavy tar-like liquids and waxes (high-n-to-m ratio). Petroleum Refining Refining of crude petroleum consists of four basic processes: 1. No. dirt & low viscosity Residual Oils: No.

30 .Figure 8. Hydrocarbon molecular weights for various petroleum products [6].

1973] Figure 9. [Obert. Petroleum products [8]. 31 .

Figure 10. Cracking large hydrocarbon molecules into small molecules [9]. 32 . Distillation (separation) of light hydrocarbons from crude [9]. Figure 11.

[9].Figure 12. 33 .

34 .

on one of 4 C-atoms closest to common C-atoms for both rings The cetane # is the %∀ of n-hexadecane which has the same combustion charac- teristics in a CFR engine. C11 H10 1 H atom in α-position. C8 H18 (isooctane) “hard to break” & resists detonation 0-octane fuel Ð→ n-heptane. alcohols or other additives. C7 H16 The octane # of an unknown fuel is determined using a Cooperative Research Engine (CFR engine).4-trimethylpentane.single-cylinder with adjustable compression ratio from rv ≈ 4:1 to ≈ 14:1 .2.typical gasolines: 85 to 90 octane Some gasolines are rated at octane numbers greater than 100 due to the addition of lighter hydrocarbons. .2. C16 H34 (n-cetane) 0-cetane fuel Ð→ alpha-methyl naphthalene.burn unknown fuel in engine and increase rv slowly until “knock” (detonation) is detected .%∀ of 2. .Liquid Fuel Ratings for Internal Combustion After refining.blends of standard fuels are burned at same rv until same “knock” is obtained .4-trimethylpentane is octane # of fuel . Cetane # 100-cetane fuel Ð→ n-hexadecane.typical diesels: 30 to 60 cetane 35 . liquid fuels are rated for combustion. Octane # 100-octane fuel Ð→ 2. The two most common ratings are the Octane Number used for spark-ignition engines and the Cetane Number used for compression-ignition engines.

Petroleum-Like Liquid Fuels shale oil: Shale oil is actually a substance known as kerogen trapped in marlstone. Kerogen is a wax-like solid hydrocarbon in which the hydrocarbon molecules are heavily cross linked. tar sands: Liquid Bio-Fuels • ethanol • methanol • bio-diesel • vegetable oil • palm oil • algae oil • whale oil Manufactured Liquid Fuels • coal-to-liquid (CTL) Refuse • black liquor 36 . Typically there is a significant sulfer and nitrogen content.

Gaseous Fuels Natural Gas Manufactured Gaseous Fuels • propane via distillation • butane via distillation • hydrogen Manufactured from Solid Fuels • syngas • town gas Refuse • anerobic & aerobic digesters – methane 37 .

Wakil. [5] Archie Culp. McGraw-Hill. [8] Edward F. [9] Jack Ott. Energy and Problems of a Technical Society. Ristinen and Jack J.References [1] M. 1979. one sheet. Ristinen. 2006. Inc.usgs. Coal fields of the conterminous United States national coal resource assessment updated version:... [6] Jack J. Kraushaar. [2] William W. The McGraw-Hill Companies. Principles of Energy Conversion. Inc. 2nd ed. The Sohioan. 1973. McGraw-Hill. How a refinery works. 1971. Technical Report Open-File Report 20121205.gov/of/2012/1205/. M. Publishers. [7] Robert A.. Inc. Harper & Row. Bathie. Geological Survey.. 1984. Kraushaar and A. 38 . Inc. [3] Archie Culp. Internal Combustion Engines and Air Pollution.S. East. ISBN 0-471-86285-1TJ778. 1984. scale 1:5. [4] Joseph A. Jr. 1991. Powerplant Technology. John Wiley & Sons. Principles of Energy Conversion. Jr. 2013. 2nd edition. John Wiley & Sons. U. John Wiley & Sons. Energy and the Environment. 2nd edition. Inc.B34.000. 1993. Fundamentals of Gas Turbines. Robert.000 available at http://pubs. Obert.