The heating value (or energy value or calorific value) of a substance, usually a

fuel A fuel is any material that can be made to react with other substances so that it releases energy as thermal energy or to be used for work. The concept was originally applied solely to those materials capable of releasing chemical energy b ...

food Food is any substance consumed by an organism for nutritional support. Food is usually of plant, animal, or fungal origin, and contains essential nutrients, such as carbohydrates, fats, proteins, vitamins, or minerals. The substance is in ...

(see food energy), is the amount of

heat In thermodynamics, heat is defined as the form of energy crossing the boundary of a thermodynamic system by virtue of a temperature difference across the boundary. A thermodynamic system does not ''contain'' heat. Nevertheless, the term is ...

released during the combustion of a specified amount of it. The ''calorific value'' is the total

energy In physics, energy (from Ancient Greek: ἐνέργεια, ''enérgeia'', “activity”) is the quantitative property that is transferred to a body or to a physical system, recognizable in the performance of work and in the form of ...

released as heat when a substance undergoes complete

combustion Combustion, or burning, is a high-temperature exothermic redox chemical reaction between a fuel (the reductant) and an oxidant, usually atmospheric oxygen, that produces oxidized, often gaseous products, in a mixture termed as smoke. Combus ...

with

oxygen Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements ...

under standard conditions. The chemical reaction is typically a

hydrocarbon In organic chemistry, a hydrocarbon is an organic compound consisting entirely of hydrogen and carbon. Hydrocarbons are examples of group 14 hydrides. Hydrocarbons are generally colourless and hydrophobic, and their odors are usually weak or ...

or other organic molecule reacting with oxygen to form

carbon dioxide Carbon dioxide ( chemical formula ) is a chemical compound made up of molecules that each have one carbon atom covalently double bonded to two oxygen atoms. It is found in the gas state at room temperature. In the air, carbon dioxide is t ...

and

water Water (chemical formula ) is an inorganic, transparent, tasteless, odorless, and nearly colorless chemical substance, which is the main constituent of Earth's hydrosphere and the fluids of all known living organisms (in which it acts as ...

and release heat. It may be expressed with the quantities: * energy/ mole of fuel * energy/mass of fuel * energy/volume of the fuel There are two kinds of enthalpy of combustion, called high(er) and low(er) heat(ing) value, depending on how much the products are allowed to cool and whether compounds like are allowed to condense. The high heat values are conventionally measured with a

bomb calorimeter A bomb is an explosive weapon that uses the exothermic reaction of an explosive material to provide an extremely sudden and violent release of energy. Detonations inflict damage principally through ground- and atmosphere-transmitted mechanica ...

. Low heat values are calculated from high heat value test data. They may also be calculated as the difference between the

heat of formation In chemistry and thermodynamics, the standard enthalpy of formation or standard heat of formation of a compound is the change of enthalpy during the formation of 1 mole of the substance from its constituent elements in their reference state, w ...

Δ''H'' of the products and reactants (though this approach is somewhat artificial since most heats of formation are typically calculated from measured heats of combustion). By convention, the (higher) heat of combustion is defined to be the heat released for the complete combustion of a compound in its standard state to form stable products in their standard states: hydrogen is converted to water (in its liquid state), carbon is converted to carbon dioxide gas, and nitrogen is converted to nitrogen gas. That is, the heat of combustion, Δ''H''°_comb, is the heat of reaction of the following process: : (std.) + (''c'' + - ) (g) → ''c'' (g) + (''l'') + (g) Chlorine and sulfur are not quite standardized; they are usually assumed to convert to hydrogen chloride gas and or gas, respectively, or to dilute aqueous hydrochloric and sulfuric acids, respectively, when the combustion is conducted in a bomb calorimeter containing some quantity of water.

Ways of determination

Gross and net

Zwolinski and Wilhoit defined, in 1972, "gross" and "net" values for heats of combustion. In the gross definition the products are the most stable compounds, e.g. (l), (l), (s) and (l). In the net definition the products are the gases produced when the compound is burned in an open flame, e.g. (g), (g), (g) and (g). In both definitions the products for C, F, Cl and N are (g), (g), (g) and (g), respectively. Dulong's Formula The heating value of a fuel can be calculated with the results of ultimate analysis of fuel. From analysis, percentages of the combustibles in the fuel (

carbon Carbon () is a chemical element with the symbol C and atomic number 6. It is nonmetallic and tetravalent—its atom making four electrons available to form covalent chemical bonds. It belongs to group 14 of the periodic table. Carbon ma ...

hydrogen Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula . It is colorless, odorless, tasteless, non-to ...

sulfur Sulfur (or sulphur in British English) is a chemical element with the symbol S and atomic number 16. It is abundant, multivalent and nonmetallic. Under normal conditions, sulfur atoms form cyclic octatomic molecules with a chemical formul ...

) are known. Since the heat of combustion of these elements is known, the heating value can be calculated using Dulong's Formula: LHV J/g 33.87m_C + 122.3(m_H - m_O ÷ 8) + 9.4m_S where m_C, m_H, m_O, m_N, and m_S are the contents of carbon, hydrogen, oxygen, nitrogen, and sulfur on any (wet, dry or ash free) basis, respectively.

Higher heating value

The higher heating value (HHV; ''gross energy'', ''upper heating value'', ''gross calorific value'' ''GCV'', or ''higher calorific value''; ''HCV'') indicates the upper limit of the available thermal energy produced by a complete combustion of fuel. It is measured as a unit of energy per unit mass or volume of substance. The HHV is determined by bringing all the products of combustion back to the original pre-combustion temperature, and in particular condensing any vapor produced. Such measurements often use a standard temperature of . This is the same as the thermodynamic heat of combustion since the

enthalpy Enthalpy , a property of a thermodynamic system, is the sum of the system's internal energy and the product of its pressure and volume. It is a state function used in many measurements in chemical, biological, and physical systems at a constant ...

change for the reaction assumes a common temperature of the compounds before and after combustion, in which case the water produced by combustion is condensed to a liquid. The higher heating value takes into account the latent heat of vaporization of

in the combustion products, and is useful in calculating heating values for fuels where

condensation Condensation is the change of the state of matter from the gas phase into the liquid phase, and is the reverse of vaporization. The word most often refers to the water cycle. It can also be defined as the change in the state of water vapo ...

of the reaction products is practical (e.g., in a gas-fired

boiler A boiler is a closed vessel in which fluid (generally water) is heated. The fluid does not necessarily boil. The heated or vaporized fluid exits the boiler for use in various processes or heating applications, including water heating, central ...

used for space heat). In other words, HHV assumes all the water component is in liquid state at the end of combustion (in product of combustion) and that heat delivered at temperatures below can be put to use.

Lower heating value

The lower heating value (LHV; ''net calorific value''; ''NCV'', or ''lower calorific value''; ''LCV'') is another measure of available thermal energy produced by a combustion of fuel, measured as a unit of energy per unit mass or volume of substance. In contrast to the HHV, the LHV considers energy losses such as the energy used to vaporize water - although its exact definition is not uniformly agreed upon. One definition is simply to subtract the

heat of vaporization The enthalpy of vaporization (symbol ), also known as the (latent) heat of vaporization or heat of evaporation, is the amount of energy (enthalpy) that must be added to a liquid substance to transform a quantity of that substance into a gas. T ...

of the water from the higher heating value. This treats any H₂O formed as a vapor. The energy required to vaporize the water therefore is not released as heat. LHV calculations assume that the water component of a combustion process is in vapor state at the end of combustion, as opposed to the higher heating value (HHV) (a.k.a. ''gross calorific value'' or ''gross CV'') which assumes that all of the water in a combustion process is in a liquid state after a combustion process. Another definition of the LHV is the amount of heat released when the products are cooled to . This means that the latent heat of vaporization of

and other reaction products is not recovered. It is useful in comparing fuels where condensation of the combustion products is impractical, or heat at a temperature below cannot be put to use. One definition of lower heating value, adopted by the

American Petroleum Institute The American Petroleum Institute (API) is the largest U.S. trade association for the oil and natural gas industry. It claims to represent nearly 600 corporations involved in production, refinement, distribution, and many other aspects of the ...

(API), uses a reference temperature of . Another definition, used by Gas Processors Suppliers Association (GPSA) and originally used by API (data collected for API research project 44), is the

of all combustion products minus the enthalpy of the fuel at the reference temperature (API research project 44 used 25 °C. GPSA currently uses 60 °F), minus the enthalpy of the stoichiometric oxygen (O₂) at the reference temperature, minus the heat of vaporization of the vapor content of the combustion products. The definition in which the combustion products are all returned to the reference temperature is more easily calculated from the higher heating value than when using other definitions and will in fact give a slightly different answer.

Gross heating value

Gross heating value accounts for water in the exhaust leaving as vapor, as does LHV, but gross heating value also includes liquid water in the fuel prior to combustion. This value is important for fuels like

wood Wood is a porous and fibrous structural tissue found in the stems and roots of trees and other woody plants. It is an organic materiala natural composite of cellulose fibers that are strong in tension and embedded in a matrix of lignin ...

coal Coal is a combustible black or brownish-black sedimentary rock, formed as rock strata called coal seams. Coal is mostly carbon with variable amounts of other elements, chiefly hydrogen, sulfur, oxygen, and nitrogen. Coal is formed when ...

, which will usually contain some amount of water prior to burning.

Measuring heating values

The higher heating value is experimentally determined in a

. The combustion of a stoichiometric mixture of fuel and oxidizer (e.g. two moles of hydrogen and one mole of oxygen) in a steel container at is initiated by an ignition device and the reactions allowed to complete. When hydrogen and oxygen react during combustion, water vapor is produced. The vessel and its contents are then cooled to the original 25 °C and the higher heating value is determined as the heat released between identical initial and final temperatures. When the lower heating value (LHV) is determined, cooling is stopped at 150 °C and the reaction heat is only partially recovered. The limit of 150 °C is based on

acid gas Acid gas is a particular typology of natural gas or any other gas mixture containing significant quantities of hydrogen sulfide (H2S), carbon dioxide (CO2), or similar acidic gases. A gas is determined to be acidic or not after it is mixed with w ...

dew-point. Note: Higher heating value (HHV) is calculated with the product of water being in liquid form while lower heating value (LHV) is calculated with the product of water being in vapor form.

Relation between heating values

The difference between the two heating values depends on the chemical composition of the fuel. In the case of pure carbon or carbon monoxide, the two heating values are almost identical, the difference being the sensible heat content of carbon dioxide between 150 °C and 25 °C (

sensible heat Sensible heat is heat exchanged by a body or thermodynamic system in which the exchange of heat changes the temperature of the body or system, and some macroscopic variables of the body or system, but leaves unchanged certain other macroscopic vari ...

exchange causes a change of temperature, while latent heat is added or subtracted for

phase transition In chemistry, thermodynamics, and other related fields, a phase transition (or phase change) is the physical process of transition between one state of a medium and another. Commonly the term is used to refer to changes among the basic states ...

s at constant temperature. Examples: heat of vaporization or

heat of fusion In thermodynamics, the enthalpy of fusion of a substance, also known as (latent) heat of fusion, is the change in its enthalpy resulting from providing energy, typically heat, to a specific quantity of the substance to change its state from a s ...

). For hydrogen, the difference is much more significant as it includes the sensible heat of water vapor between 150 °C and 100 °C, the latent heat of condensation at 100 °C, and the sensible heat of the condensed water between 100 °C and 25 °C. All in all, the higher heating value of hydrogen is 18.2% above its lower heating value (142MJ/kg vs. 120MJ/kg). For hydrocarbons, the difference depends on the hydrogen content of the fuel. For

gasoline Gasoline (; ) or petrol (; ) (see ) is a transparent, petroleum-derived flammable liquid that is used primarily as a fuel in most spark-ignited internal combustion engines (also known as petrol engines). It consists mostly of organic c ...

and

diesel Diesel may refer to: * Diesel engine, an internal combustion engine where ignition is caused by compression * Diesel fuel, a liquid fuel used in diesel engines * Diesel locomotive, a railway locomotive in which the prime mover is a diesel engi ...

the higher heating value exceeds the lower heating value by about 10% and 7%, respectively, and for natural gas about 11%. A common method of relating HHV to LHV is: :

\mathrm = \mathrm + H_\mathrm\left(\frac\right)

where ''H''_v is the heat of vaporization of water, ''n''_,out is the number of moles of water vaporized and ''n''_fuel,in is the number of moles of fuel combusted. * Most applications that burn fuel produce water vapor, which is unused and thus wastes its heat content. In such applications, the lower heating value must be used to give a 'benchmark' for the process. * However, for true energy calculations in some specific cases, the higher heating value is correct. This is particularly relevant for

natural gas Natural gas (also called fossil gas or simply gas) is a naturally occurring mixture of gaseous hydrocarbons consisting primarily of methane in addition to various smaller amounts of other higher alkanes. Low levels of trace gases like carbon d ...

, whose high hydrogen content produces much water, when it is burned in

condensing boiler Condensing boilers are water heaters typically used for heating systems that are fueled by gas or oil. When operated in the correct circumstances, a heating system can achieve high efficiency (greater than 90% on the higher heating value) by cond ...

s and power plants with flue-gas condensation that condense the water vapor produced by combustion, recovering heat which would otherwise be wasted.

Usage of terms

Engine manufacturers typically rate their engines fuel consumption by the lower heating values since the exhaust is never condensed in the engine, and doing this allows them to publish more attractive numbers than are used in conventional power plant terms. The conventional power industry had used HHV (high heat value) exclusively for decades, even though virtually all of these plants did not condense exhaust either. American consumers should be aware that the corresponding fuel-consumption figure based on the higher heating value will be somewhat higher. The difference between HHV and LHV definitions causes endless confusion when quoters do not bother to state the convention being used. since there is typically a 10% difference between the two methods for a power plant burning natural gas. For simply benchmarking part of a reaction the LHV may be appropriate, but HHV should be used for overall energy efficiency calculations if only to avoid confusion, and in any case, the value or convention should be clearly stated.

Accounting for moisture

Both HHV and LHV can be expressed in terms of AR (all moisture counted), MF and MAF (only water from combustion of hydrogen). AR, MF, and MAF are commonly used for indicating the heating values of coal: * AR (as received) indicates that the fuel heating value has been measured with all moisture- and ash-forming minerals present. * MF (moisture-free) or dry indicates that the fuel heating value has been measured after the fuel has been dried of all inherent moisture but still retaining its ash-forming minerals. * MAF (moisture- and ash-free) or DAF (dry and ash-free) indicates that the fuel heating value has been measured in the absence of inherent moisture- and ash-forming minerals.

Heat of combustion tables

; Note * There is no difference between the lower and higher heating values for the combustion of carbon, carbon monoxide and sulfur since no water is formed during the combustion of those substances. * BTU/lb values are calculated from MJ/kg (1 MJ/kg = 430 BTU/lb).

Higher heating values of natural gases from various sources

The

International Energy Agency The International Energy Agency (IEA) is a Paris-based autonomous intergovernmental organisation, established in 1974, that provides policy recommendations, analysis and data on the entire global energy sector, with a recent focus on curbing car ...

reports the following typical higher heating values per Standard cubic metre of gas: *

Algeria ) , image_map = Algeria (centered orthographic projection).svg , map_caption = , image_map2 = , capital = Algiers , coordinates = , largest_city = capital , relig ...

: 39.57MJ/Sm³ *

Bangladesh Bangladesh (}, ), officially the People's Republic of Bangladesh, is a country in South Asia. It is the eighth-most populous country in the world, with a population exceeding 165 million people in an area of . Bangladesh is among the mo ...

: 36.00MJ/Sm³ *

Canada Canada is a country in North America. Its ten provinces and three territories extend from the Atlantic Ocean to the Pacific Ocean and northward into the Arctic Ocean, covering over , making it the world's second-largest country by to ...

: 39.00MJ/Sm³ *

China China, officially the People's Republic of China (PRC), is a country in East Asia. It is the world's List of countries and dependencies by population, most populous country, with a Population of China, population exceeding 1.4 billion, slig ...

: 38.93MJ/Sm³ *

Indonesia Indonesia, officially the Republic of Indonesia, is a country in Southeast Asia and Oceania between the Indian and Pacific oceans. It consists of over 17,000 islands, including Sumatra, Java, Sulawesi, and parts of Borneo and New Gui ...

: 40.60MJ/Sm³ *

Iran Iran, officially the Islamic Republic of Iran, and also called Persia, is a country located in Western Asia. It is bordered by Iraq and Turkey to the west, by Azerbaijan and Armenia to the northwest, by the Caspian Sea and Turkmeni ...

: 39.36MJ/Sm³ *

Netherlands ) , anthem = ( en, "William of Nassau") , image_map = , map_caption = , subdivision_type = Sovereign state , subdivision_name = Kingdom of the Netherlands , established_title = Before independence , established_date = Spanish Netherl ...

: 33.32MJ/Sm³ *

Norway Norway, officially the Kingdom of Norway, is a Nordic countries, Nordic country in Northern Europe, the mainland territory of which comprises the western and northernmost portion of the Scandinavian Peninsula. The remote Arctic island of ...

: 39.24MJ/Sm³ *

Pakistan Pakistan ( ur, ), officially the Islamic Republic of Pakistan ( ur, , label=none), is a country in South Asia. It is the world's List of countries and dependencies by population, fifth-most populous country, with a population of almost 24 ...

: 34.90MJ/Sm³ *

Qatar Qatar (, ; ar, قطر, Qaṭar ; local vernacular pronunciation: ), officially the State of Qatar,) is a country in Western Asia. It occupies the Qatar Peninsula on the northeastern coast of the Arabian Peninsula in the Middle East; it sh ...

: 41.40MJ/Sm³ *

Russia Russia (, , ), or the Russian Federation, is a transcontinental country spanning Eastern Europe and Northern Asia. It is the largest country in the world, with its internationally recognised territory covering , and encompassing one-ei ...

: 38.23MJ/Sm³ *

Saudi Arabia Saudi Arabia, officially the Kingdom of Saudi Arabia (KSA), is a country in Western Asia. It covers the bulk of the Arabian Peninsula, and has a land area of about , making it the fifth-largest country in Asia, the second-largest in the Ara ...

: 38.00MJ/Sm³ *

Turkmenistan Turkmenistan ( or ; tk, Türkmenistan / Түркменистан, ) is a country located in Central Asia, bordered by Kazakhstan to the northwest, Uzbekistan to the north, east and northeast, Afghanistan to the southeast, Iran to the s ...

: 37.89MJ/Sm³ *

United Kingdom The United Kingdom of Great Britain and Northern Ireland, commonly known as the United Kingdom (UK) or Britain, is a country in Europe, off the north-western coast of the continental mainland. It comprises England, Scotland, Wales and ...

: 39.71MJ/Sm³ *

United States The United States of America (U.S.A. or USA), commonly known as the United States (U.S. or US) or America, is a country Continental United States, primarily located in North America. It consists of 50 U.S. state, states, a Washington, D.C., ...

: 38.42MJ/Sm³ *

Uzbekistan Uzbekistan (, ; uz, Ozbekiston, italic=yes / , ; russian: Узбекистан), officially the Republic of Uzbekistan ( uz, Ozbekiston Respublikasi, italic=yes / ; russian: Республика Узбекистан), is a doubly landlocked co ...

: 37.89MJ/Sm³ The lower heating value of natural gas is normally about 90% of its higher heating value. This table is in Standard cubic metres (1 atm, 15°C), to convert to values per Normal cubic metre (1atm, 0°C), multiply above table by 1.0549.

References

External links

NIST Chemistry WebBook
* {{DEFAULTSORT:Heat Of Combustion Engineering thermodynamics Combustion Fuels Thermodynamic properties Nuclear physics Thermochemistry