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Standard enthalpy 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, with all substances in their standard states. The standard pressure value p = 105 Pa (= 100 kPa = 1 bar) is recommended by IUPAC, although prior to 1982 the value 1.00 atm (101.325 kPa) was used.[1] There is no standard temperature. Its symbol is ΔfH. The superscript Plimsoll on this symbol indicates that the process has occurred under standard conditions at the specified temperature (usually 25 °C or 298.15 K).

Standard states are defined for various types of substances. For a gas, it is the hypothetical state the gas would assume if it obeyed the ideal gas equation at a pressure of 1 bar. For a gaseous or solid solute present in a diluted ideal solution, the standard state is the hypothetical state of concentration of the solute of exactly one mole per liter (1 M) at a pressure of 1 bar extrapolated from infinite dilution. For a pure substance or a solvent in a condensed state (a liquid or a solid) the standard state is the pure liquid or solid under a pressure of 1 bar.

For elements that have multiple allotropes, the reference state usually is chosen to be the form in which the element is most stable under 1 bar of pressure. One exception is phosphorus, for which the most stable form at 1 bar is black phosphorus, but white phosphorus is chosen as the standard reference state for zero enthalpy of formation.[2]

For example, the standard enthalpy of formation of carbon dioxide is the enthalpy of the following reaction under the above conditions:

All elements are written in their standard states, and one mole of product is formed. This is true for all enthalpies of formation.

The standard enthalpy of formation is measured in units of energy per amount of substance, usually stated in kilojoule per mole (kJ mol−1), but also in kilocalorie per mole, joule per mole or kilocalorie per gram (any combination of these units conforming to the energy per mass or amount guideline).

All elements in their reference states (oxygen gas, solid carbon in the form of graphite, etc.) have a standard enthalpy of formation of zero, as there is no change involved in their formation.

The formation reaction is a constant pressure and constant temperature process. Since the pressure of the standard formation reaction is fixed at 1 bar, the standard formation enthalpy or reaction heat is a function of temperature. For tabulation purposes, standard formation enthalpies are all given at a single temperature: 298 K, represented by the symbol ΔfH
298 K
.

Hess's law edit

For many substances, the formation reaction may be considered as the sum of a number of simpler reactions, either real or fictitious. The enthalpy of reaction can then be analyzed by applying Hess's Law, which states that the sum of the enthalpy changes for a number of individual reaction steps equals the enthalpy change of the overall reaction. This is true because enthalpy is a state function, whose value for an overall process depends only on the initial and final states and not on any intermediate states. Examples are given in the following sections.

Ionic compounds: Born–Haber cycle edit

 
Standard enthalpy change of formation in Born–Haber diagram for lithium fluoride. ΔlattH corresponds to UL in the text. The downward arrow "electron affinity" shows the negative quantity –EAF, since EAF is usually defined as positive.

For ionic compounds, the standard enthalpy of formation is equivalent to the sum of several terms included in the Born–Haber cycle. For example, the formation of lithium fluoride,

 

may be considered as the sum of several steps, each with its own enthalpy (or energy, approximately):

  1. Hsub, the standard enthalpy of atomization (or sublimation) of solid lithium.
  2. IELi, the first ionization energy of gaseous lithium.
  3. B(F–F), the standard enthalpy of atomization (or bond energy) of fluorine gas.
  4. EAF, the electron affinity of a fluorine atom.
  5. UL, the lattice energy of lithium fluoride.

The sum of these enthalpies give the standard enthalpy of formation (ΔfH) of lithium fluoride:

 

In practice, the enthalpy of formation of lithium fluoride can be determined experimentally, but the lattice energy cannot be measured directly. The equation is therefore rearranged to evaluate the lattice energy:[3]

 

Organic compounds edit

The formation reactions for most organic compounds are hypothetical. For instance, carbon and hydrogen will not directly react to form methane (CH4), so that the standard enthalpy of formation cannot be measured directly. However the standard enthalpy of combustion is readily measurable using bomb calorimetry. The standard enthalpy of formation is then determined using Hess's law. The combustion of methane:

 

is equivalent to the sum of the hypothetical decomposition into elements followed by the combustion of the elements to form carbon dioxide (CO2) and water (H2O):

 
 
 

Applying Hess's law,

 

Solving for the standard of enthalpy of formation,

 

The value of   is determined to be −74.8 kJ/mol. The negative sign shows that the reaction, if it were to proceed, would be exothermic; that is, methane is enthalpically more stable than hydrogen gas and carbon.

It is possible to predict heats of formation for simple unstrained organic compounds with the heat of formation group additivity method.

Use in calculation for other reactions edit

The standard enthalpy change of any reaction can be calculated from the standard enthalpies of formation of reactants and products using Hess's law. A given reaction is considered as the decomposition of all reactants into elements in their standard states, followed by the formation of all products. The heat of reaction is then minus the sum of the standard enthalpies of formation of the reactants (each being multiplied by its respective stoichiometric coefficient, ν) plus the sum of the standard enthalpies of formation of the products (each also multiplied by its respective stoichiometric coefficient), as shown in the equation below:[4]

 

If the standard enthalpy of the products is less than the standard enthalpy of the reactants, the standard enthalpy of reaction is negative. This implies that the reaction is exothermic. The converse is also true; the standard enthalpy of reaction is positive for an endothermic reaction. This calculation has a tacit assumption of ideal solution between reactants and products where the enthalpy of mixing is zero.

For example, for the combustion of methane,  :

 

However   is an element in its standard state, so that  , and the heat of reaction is simplified to

 

which is the equation in the previous section for the enthalpy of combustion  .

Key concepts for enthalpy calculations edit

  • When a reaction is reversed, the magnitude of ΔH stays the same, but the sign changes.
  • When the balanced equation for a reaction is multiplied by an integer, the corresponding value of ΔH must be multiplied by that integer as well.
  • The change in enthalpy for a reaction can be calculated from the enthalpies of formation of the reactants and the products
  • Elements in their standard states make no contribution to the enthalpy calculations for the reaction, since the enthalpy of an element in its standard state is zero. Allotropes of an element other than the standard state generally have non-zero standard enthalpies of formation.

Examples: standard enthalpies of formation at 25 °C edit

Thermochemical properties of selected substances at 298.15 K and 1 atm

Inorganic substances edit

Species Phase Chemical formula ΔfH /(kJ/mol)
Aluminium Solid Al 0
Aluminium chloride Solid AlCl3 −705.63
Aluminium oxide Solid Al2O3 −1675.5
Aluminium hydroxide Solid Al(OH)3 −1277
Aluminium sulphate Solid Al2(SO4)3 −3440
Barium chloride Solid BaCl2 −858.6
Barium carbonate Solid BaCO3 −1216
Barium hydroxide Solid Ba(OH)2 −944.7
Barium oxide Solid BaO −548.1
Barium sulfate Solid BaSO4 −1473.3
Beryllium Solid Be 0
Beryllium hydroxide Solid Be(OH)2 −903
Beryllium oxide Solid BeO −609.4
Boron trichloride Solid BCl3 −402.96
Bromine Liquid Br2 0
Bromide ion Aqueous Br −121
Bromine Gas Br 111.884
Bromine Gas Br2 30.91
Bromine trifluoride Gas BrF3 −255.60
Hydrogen bromide Gas HBr −36.29
Cadmium Solid Cd 0
Cadmium oxide Solid CdO −258
Cadmium hydroxide Solid Cd(OH)2 −561
Cadmium sulfide Solid CdS −162
Cadmium sulfate Solid CdSO4 −935
Caesium Solid Cs 0
Caesium Gas Cs 76.50
Caesium Liquid Cs 2.09
Caesium(I) ion Gas Cs+ 457.964
Caesium chloride Solid CsCl −443.04
Calcium Solid Ca 0
Calcium Gas Ca 178.2
Calcium(II) ion Gas Ca2+ 1925.90
Calcium(II) ion Aqueous Ca2+ −542.7
Calcium carbide Solid CaC2 −59.8
Calcium carbonate (Calcite) Solid CaCO3 −1206.9
Calcium chloride Solid CaCl2 −795.8
Calcium chloride Aqueous CaCl2 −877.3
Calcium phosphate Solid Ca3(PO4)2 −4132
Calcium fluoride Solid CaF2 −1219.6
Calcium hydride Solid CaH2 −186.2
Calcium hydroxide Solid Ca(OH)2 −986.09
Calcium hydroxide Aqueous Ca(OH)2 −1002.82
Calcium oxide Solid CaO −635.09
Calcium sulfate Solid CaSO4 −1434.52
Calcium sulfide Solid CaS −482.4
Wollastonite Solid CaSiO3 −1630
Carbon (Graphite) Solid C 0
Carbon (Diamond) Solid C 1.9
Carbon Gas C 716.67
Carbon dioxide Gas CO2 −393.509
Carbon disulfide Liquid CS2 89.41
Carbon disulfide Gas CS2 116.7
Carbon monoxide Gas CO −110.525
Carbonyl chloride (Phosgene) Gas COCl2 −218.8
Carbon dioxide (un–ionized) Aqueous CO2(aq) −419.26
Bicarbonate ion Aqueous HCO3 −689.93
Carbonate ion Aqueous CO32– −675.23
Monatomic chlorine Gas Cl 121.7
Chloride ion Aqueous Cl −167.2
Chlorine Gas Cl2 0
Chromium Solid Cr 0
Copper Solid Cu 0
Copper(II) bromide Solid CuBr2 −138.490
Copper(II) chloride Solid CuCl2 −217.986
Copper(II) oxide Solid CuO −155.2
Copper(II) sulfate Aqueous CuSO4 −769.98
Fluorine Gas F2 0
Monatomic hydrogen Gas H 218
Hydrogen Gas H2 0
Water Gas H2O −241.818
Water Liquid H2O −285.8
Hydrogen ion Aqueous H+ 0
Hydroxide ion Aqueous OH −230
Hydrogen peroxide Liquid H2O2 −187.8
Phosphoric acid Liquid H3PO4 −1288
Hydrogen cyanide Gas HCN 130.5
Hydrogen bromide Liquid HBr −36.3
Hydrogen chloride Gas HCl −92.30
Hydrogen chloride Aqueous HCl −167.2
Hydrogen fluoride Gas HF −273.3
Hydrogen iodide Gas HI 26.5
Iodine Solid I2 0
Iodine Gas I2 62.438
Iodine Aqueous I2 23
Iodide ion Aqueous I −55
Iron Solid Fe 0
Iron carbide (Cementite) Solid Fe3C 5.4
Iron(II) carbonate (Siderite) Solid FeCO3 −750.6
Iron(III) chloride Solid FeCl3 −399.4
Iron(II) oxide (Wüstite) Solid FeO −272
Iron(II,III) oxide (Magnetite) Solid Fe3O4 −1118.4
Iron(III) oxide (Hematite) Solid Fe2O3 −824.2
Iron(II) sulfate Solid FeSO4 −929
Iron(III) sulfate Solid Fe2(SO4)3 −2583
Iron(II) sulfide Solid FeS −102
Pyrite Solid FeS2 −178
Lead Solid Pb 0
Lead dioxide Solid PbO2 −277
Lead sulfide Solid PbS −100
Lead sulfate Solid PbSO4 −920
Lead(II) nitrate Solid Pb(NO3)2 −452
Lead(II) sulfate Solid PbSO4 −920
Lithium fluoride Solid LiF −616.93
Magnesium Solid Mg 0
Magnesium ion Aqueous Mg2+ −466.85
Magnesium carbonate Solid MgCO3 −1095.797
Magnesium chloride Solid MgCl2 −641.8
Magnesium hydroxide Solid Mg(OH)2 −924.54
Magnesium hydroxide Aqueous Mg(OH)2 −926.8
Magnesium oxide Solid MgO −601.6
Magnesium sulfate Solid MgSO4 −1278.2
Manganese Solid Mn 0
Manganese(II) oxide Solid MnO −384.9
Manganese(IV) oxide Solid MnO2 −519.7
Manganese(III) oxide Solid Mn2O3 −971
Manganese(II,III) oxide Solid Mn3O4 −1387
Permanganate Aqueous MnO
4
−543
Mercury(II) oxide (red) Solid HgO −90.83
Mercury sulfide (red, cinnabar) Solid HgS −58.2
Nitrogen Gas N2 0
Ammonia (ammonium hydroxide) Aqueous NH3 (NH4OH) −80.8
Ammonia Gas NH3 −46.1
Ammonium nitrate Solid NH4NO3 −365.6
Ammonium chloride Solid NH4Cl −314.55
Nitrogen dioxide Gas NO2 33.2
Hydrazine Gas N2H4 95.4
Hydrazine Liquid N2H4 50.6
Nitrous oxide Gas N2O 82.05
Nitric oxide Gas NO 90.29
Dinitrogen tetroxide Gas N2O4 9.16
Dinitrogen pentoxide Solid N2O5 −43.1
Dinitrogen pentoxide Gas N2O5 11.3
Nitric acid Aqueous HNO3 −207
Monatomic oxygen Gas O 249
Oxygen Gas O2 0
Ozone Gas O3 143
White phosphorus Solid P4 0
Red phosphorus Solid P −17.4[5]
Black phosphorus Solid P −39.3[5]
Phosphorus trichloride Liquid PCl3 −319.7
Phosphorus trichloride Gas PCl3 −278
Phosphorus pentachloride Solid PCl5 −440
Phosphorus pentachloride Gas PCl5 −321
Phosphorus pentoxide Solid P2O5 −1505.5[6]
Potassium bromide Solid KBr −392.2
Potassium carbonate Solid K2CO3 −1150
Potassium chlorate Solid KClO3 −391.4
Potassium chloride Solid KCl −436.68
Potassium fluoride Solid KF −562.6
Potassium oxide Solid K2O −363
Potassium nitrate Solid KNO3 −494.5
Potassium perchlorate Solid KClO4 −430.12
Silicon Gas Si 368.2
Silicon carbide Solid SiC −74.4,[7] −71.5[8]
Silicon tetrachloride Liquid SiCl4 −640.1
Silica (Quartz) Solid SiO2 −910.86
Silver bromide Solid AgBr −99.5
Silver chloride Solid AgCl −127.01
Silver iodide Solid AgI −62.4
Silver oxide Solid Ag2O −31.1
Silver sulfide Solid Ag2S −31.8
Sodium Solid Na 0
Sodium Gas Na 107.5
Sodium bicarbonate Solid NaHCO3 −950.8
Sodium carbonate Solid Na2CO3 −1130.77
Sodium chloride Aqueous NaCl −407.27
Sodium chloride Solid NaCl −411.12
Sodium chloride Liquid NaCl −385.92
Sodium chloride Gas NaCl −181.42
Sodium chlorate Solid NaClO3 −365.4
Sodium fluoride Solid NaF −569.0
Sodium hydroxide Aqueous NaOH −469.15
Sodium hydroxide Solid NaOH −425.93
Sodium hypochlorite Solid NaOCl −347.1
Sodium nitrate Aqueous NaNO3 −446.2
Sodium nitrate Solid NaNO3 −424.8
Sodium oxide Solid Na2O −414.2
Sulfur (monoclinic) Solid S8 0.3
Sulfur (rhombic) Solid S8 0
Hydrogen sulfide Gas H2S −20.63
Sulfur dioxide Gas SO2 −296.84
Sulfur trioxide Gas SO3 −395.7
Sulfuric acid Liquid H2SO4 −814
Titanium Gas Ti 468
Titanium tetrachloride Gas TiCl4 −763.2
Titanium tetrachloride Liquid TiCl4 −804.2
Titanium dioxide Solid TiO2 −944.7
Zinc Gas Zn 130.7
Zinc chloride Solid ZnCl2 −415.1
Zinc oxide Solid ZnO −348.0
Zinc sulfate Solid ZnSO4 −980.14

Aliphatic hydrocarbons edit

Formula Name ΔfH /(kcal/mol) ΔfH /(kJ/mol)
Straight-chain
CH4 Methane −17.9 −74.9
C2H6 Ethane −20.0 −83.7
C2H4 Ethylene 12.5 52.5
C2H2 Acetylene 54.2 226.8
C3H8 Propane −25.0 −104.6
C4H10 n-Butane −30.0 −125.5
C5H12 n-Pentane −35.1 −146.9
C6H14 n-Hexane −40.0 −167.4
C7H16 n-Heptane −44.9 −187.9
C8H18 n-Octane −49.8 −208.4
C9H20 n-Nonane −54.8 −229.3
C10H22 n-Decane −59.6 −249.4
C4 Alkane branched isomers
C4H10 Isobutane (methylpropane) −32.1 −134.3
C5 Alkane branched isomers
C5H12 Neopentane (dimethylpropane) −40.1 −167.8
C5H12 Isopentane (methylbutane) −36.9 −154.4
C6 Alkane branched isomers
C6H14 2,2-Dimethylbutane −44.5 −186.2
C6H14 2,3-Dimethylbutane −42.5 −177.8
C6H14 2-Methylpentane (isohexane) −41.8 −174.9
C6H14 3-Methylpentane −41.1 −172.0
C7 Alkane branched isomers
C7H16 2,2-Dimethylpentane −49.2 −205.9
C7H16 2,2,3-Trimethylbutane −49.0 −205.0
C7H16 3,3-Dimethylpentane −48.1 −201.3
C7H16 2,3-Dimethylpentane −47.3 −197.9
C7H16 2,4-Dimethylpentane −48.2 −201.7
C7H16 2-Methylhexane −46.5 −194.6
C7H16 3-Methylhexane −45.7 −191.2
C7H16 3-Ethylpentane −45.3 −189.5
C8 Alkane branched isomers
C8H18 2,3-Dimethylhexane −55.1 −230.5
C8H18 2,2,3,3-Tetramethylbutane −53.9 −225.5
C8H18 2,2-Dimethylhexane −53.7 −224.7
C8H18 2,2,4-Trimethylpentane (isooctane) −53.5 −223.8
C8H18 2,5-Dimethylhexane −53.2 −222.6
C8H18 2,2,3-Trimethylpentane −52.6 −220.1
C8H18 3,3-Dimethylhexane −52.6 −220.1
C8H18 2,4-Dimethylhexane −52.4 −219.2
C8H18 2,3,4-Trimethylpentane −51.9 −217.1
C8H18 2,3,3-Trimethylpentane −51.7 −216.3
C8H18 2-Methylheptane −51.5 −215.5
C8H18 3-Ethyl-3-Methylpentane −51.4 −215.1
C8H18 3,4-Dimethylhexane −50.9 −213.0
C8H18 3-Ethyl-2-Methylpentane −50.4 −210.9
C8H18 3-Methylheptane −60.3 −252.5
C8H18 4-Methylheptane ? ?
C8H18 3-Ethylhexane ? ?
C9 Alkane branched isomers (selected)
C9H20 2,2,4,4-Tetramethylpentane −57.8 −241.8
C9H20 2,2,3,3-Tetramethylpentane −56.7 −237.2
C9H20 2,2,3,4-Tetramethylpentane −56.6 −236.8
C9H20 2,3,3,4-Tetramethylpentane −56.4 −236.0
C9H20 3,3-Diethylpentane −55.7 −233.0

Other organic compounds edit

Species Phase Chemical formula ΔfH /(kJ/mol)
Acetone Liquid C3H6O −248.4
Benzene Liquid C6H6 48.95
Benzoic acid Solid C7H6O2 −385.2
Carbon tetrachloride Liquid CCl4 −135.4
Carbon tetrachloride Gas CCl4 −95.98
Ethanol Liquid C2H5OH −277.0
Ethanol Gas C2H5OH −235.3
Glucose Solid C6H12O6 −1271
Isopropanol Gas C3H7OH −318.1
Methanol (methyl alcohol) Liquid CH3OH −238.4
Methanol (methyl alcohol) Gas CH3OH −201.0
Methyl linoleate (Biodiesel) Gas C19H34O2 −356.3
Sucrose Solid C12H22O11 −2226.1
Trichloromethane (Chloroform) Liquid CHCl3 −134.47
Trichloromethane (Chloroform) Gas CHCl3 −103.18
Vinyl chloride Solid C2H3Cl −94.12

See also edit

References edit

  1. ^ IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006–) "standard pressure". doi:10.1351/goldbook.S05921
  2. ^ Oxtoby, David W; Pat Gillis, H; Campion, Alan (2011). Principles of Modern Chemistry. Cengage Learning. p. 547. ISBN 978-0-8400-4931-5.
  3. ^ Moore, Stanitski, and Jurs. Chemistry: The Molecular Science. 3rd edition. 2008. ISBN 0-495-10521-X. pages 320–321.
  4. ^ "Enthalpies of Reaction". www.science.uwaterloo.ca. from the original on 25 October 2017. Retrieved 2 May 2018.
  5. ^ a b Housecroft, C. E.; Sharpe, A. G. (2004). Inorganic Chemistry (2nd ed.). Prentice Hall. p. 392. ISBN 978-0-13-039913-7.
  6. ^ Green, D.W., ed. (2007). Perry's Chemical Engineers' Handbook (8th ed.). Mcgraw-Hill. pp. 2–191. ISBN 9780071422949.
  7. ^ Kleykamp, H. (1998). "Gibbs Energy of Formation of SiC: A contribution to the Thermodynamic Stability of the Modifications". Berichte der Bunsengesellschaft für physikalische Chemie. 102 (9): 1231–1234. doi:10.1002/bbpc.19981020928.
  8. ^ "Silicon Carbide, Alpha (SiC)". March 1967. Retrieved 5 February 2019.
  • Zumdahl, Steven (2009). Chemical Principles (6th ed.). Boston. New York: Houghton Mifflin. pp. 384–387. ISBN 978-0-547-19626-8.

External links edit

  • NIST Chemistry WebBook

standard, enthalpy, formation, chemistry, thermodynamics, standard, enthalpy, formation, standard, heat, formation, compound, change, enthalpy, during, formation, mole, substance, from, constituent, elements, their, reference, state, with, substances, their, s. 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 with all substances in their standard states The standard pressure value p 105 Pa 100 kPa 1 bar is recommended by IUPAC although prior to 1982 the value 1 00 atm 101 325 kPa was used 1 There is no standard temperature Its symbol is DfH The superscript Plimsoll on this symbol indicates that the process has occurred under standard conditions at the specified temperature usually 25 C or 298 15 K Standard states are defined for various types of substances For a gas it is the hypothetical state the gas would assume if it obeyed the ideal gas equation at a pressure of 1 bar For a gaseous or solid solute present in a diluted ideal solution the standard state is the hypothetical state of concentration of the solute of exactly one mole per liter 1 M at a pressure of 1 bar extrapolated from infinite dilution For a pure substance or a solvent in a condensed state a liquid or a solid the standard state is the pure liquid or solid under a pressure of 1 bar For elements that have multiple allotropes the reference state usually is chosen to be the form in which the element is most stable under 1 bar of pressure One exception is phosphorus for which the most stable form at 1 bar is black phosphorus but white phosphorus is chosen as the standard reference state for zero enthalpy of formation 2 For example the standard enthalpy of formation of carbon dioxide is the enthalpy of the following reaction under the above conditions C s graphite O 2 g CO 2 g displaystyle ce C s graphite O2 g gt CO2 g All elements are written in their standard states and one mole of product is formed This is true for all enthalpies of formation The standard enthalpy of formation is measured in units of energy per amount of substance usually stated in kilojoule per mole kJ mol 1 but also in kilocalorie per mole joule per mole or kilocalorie per gram any combination of these units conforming to the energy per mass or amount guideline All elements in their reference states oxygen gas solid carbon in the form of graphite etc have a standard enthalpy of formation of zero as there is no change involved in their formation The formation reaction is a constant pressure and constant temperature process Since the pressure of the standard formation reaction is fixed at 1 bar the standard formation enthalpy or reaction heat is a function of temperature For tabulation purposes standard formation enthalpies are all given at a single temperature 298 K represented by the symbol DfH 298 K Contents 1 Hess s law 2 Ionic compounds Born Haber cycle 3 Organic compounds 4 Use in calculation for other reactions 5 Key concepts for enthalpy calculations 6 Examples standard enthalpies of formation at 25 C 6 1 Inorganic substances 6 2 Aliphatic hydrocarbons 6 3 Other organic compounds 7 See also 8 References 9 External linksHess s law editFor many substances the formation reaction may be considered as the sum of a number of simpler reactions either real or fictitious The enthalpy of reaction can then be analyzed by applying Hess s Law which states that the sum of the enthalpy changes for a number of individual reaction steps equals the enthalpy change of the overall reaction This is true because enthalpy is a state function whose value for an overall process depends only on the initial and final states and not on any intermediate states Examples are given in the following sections Ionic compounds Born Haber cycle edit nbsp Standard enthalpy change of formation in Born Haber diagram for lithium fluoride DlattH corresponds to UL in the text The downward arrow electron affinity shows the negative quantity EAF since EAF is usually defined as positive For ionic compounds the standard enthalpy of formation is equivalent to the sum of several terms included in the Born Haber cycle For example the formation of lithium fluoride Li s 1 2 F 2 g LiF s displaystyle ce Li s 1 2 F2 g gt LiF s nbsp may be considered as the sum of several steps each with its own enthalpy or energy approximately Hsub the standard enthalpy of atomization or sublimation of solid lithium IELi the first ionization energy of gaseous lithium B F F the standard enthalpy of atomization or bond energy of fluorine gas EAF the electron affinity of a fluorine atom UL the lattice energy of lithium fluoride The sum of these enthalpies give the standard enthalpy of formation DfH of lithium fluoride D H f D H sub IE Li 1 2 B F F EA F U L displaystyle Delta H text f Delta H text sub text IE text Li frac 1 2 text B F F text EA text F text U text L nbsp In practice the enthalpy of formation of lithium fluoride can be determined experimentally but the lattice energy cannot be measured directly The equation is therefore rearranged to evaluate the lattice energy 3 U L D H sub IE Li 1 2 B F F EA F D H f displaystyle U text L Delta H text sub text IE text Li frac 1 2 text B F F text EA text F Delta H text f nbsp Organic compounds editThe formation reactions for most organic compounds are hypothetical For instance carbon and hydrogen will not directly react to form methane CH4 so that the standard enthalpy of formation cannot be measured directly However the standard enthalpy of combustion is readily measurable using bomb calorimetry The standard enthalpy of formation is then determined using Hess s law The combustion of methane CH 4 2 O 2 CO 2 2 H 2 O displaystyle ce CH4 2 O2 gt CO2 2 H2O nbsp is equivalent to the sum of the hypothetical decomposition into elements followed by the combustion of the elements to form carbon dioxide CO2 and water H2O CH 4 C 2 H 2 displaystyle ce CH4 gt C 2H2 nbsp C O 2 CO 2 displaystyle ce C O2 gt CO2 nbsp 2 H 2 O 2 2 H 2 O displaystyle ce 2H2 O2 gt 2H2O nbsp Applying Hess s law D comb H CH 4 D f H CO 2 2 D f H H 2 O D f H CH 4 displaystyle Delta text comb H ominus text CH 4 Delta text f H ominus text CO 2 2 Delta text f H ominus text H 2 text O Delta text f H ominus text CH 4 nbsp Solving for the standard of enthalpy of formation D f H CH 4 D f H CO 2 2 D f H H 2 O D comb H CH 4 displaystyle Delta text f H ominus text CH 4 Delta text f H ominus text CO 2 2 Delta text f H ominus text H 2 text O Delta text comb H ominus text CH 4 nbsp The value of D f H CH 4 displaystyle Delta text f H ominus text CH 4 nbsp is determined to be 74 8 kJ mol The negative sign shows that the reaction if it were to proceed would be exothermic that is methane is enthalpically more stable than hydrogen gas and carbon It is possible to predict heats of formation for simple unstrained organic compounds with the heat of formation group additivity method Use in calculation for other reactions editThe standard enthalpy change of any reaction can be calculated from the standard enthalpies of formation of reactants and products using Hess s law A given reaction is considered as the decomposition of all reactants into elements in their standard states followed by the formation of all products The heat of reaction is then minus the sum of the standard enthalpies of formation of the reactants each being multiplied by its respective stoichiometric coefficient n plus the sum of the standard enthalpies of formation of the products each also multiplied by its respective stoichiometric coefficient as shown in the equation below 4 D r H n D f H products n D f H reactants displaystyle Delta text r H ominus sum nu Delta text f H ominus text products sum nu Delta text f H ominus text reactants nbsp If the standard enthalpy of the products is less than the standard enthalpy of the reactants the standard enthalpy of reaction is negative This implies that the reaction is exothermic The converse is also true the standard enthalpy of reaction is positive for an endothermic reaction This calculation has a tacit assumption of ideal solution between reactants and products where the enthalpy of mixing is zero For example for the combustion of methane CH 4 2 O 2 CO 2 2 H 2 O displaystyle ce CH4 2O2 gt CO2 2H2O nbsp D r H D f H CO 2 2 D f H H 2 O D f H CH 4 2 D f H O 2 displaystyle Delta text r H ominus Delta text f H ominus text CO 2 2 Delta text f H ominus text H 2 text O Delta text f H ominus text CH 4 2 Delta text f H ominus text O 2 nbsp However O 2 displaystyle ce O2 nbsp is an element in its standard state so that D f H O 2 0 displaystyle Delta text f H ominus text O 2 0 nbsp and the heat of reaction is simplified to D r H D f H CO 2 2 D f H H 2 O D f H CH 4 displaystyle Delta text r H ominus Delta text f H ominus text CO 2 2 Delta text f H ominus text H 2 text O Delta text f H ominus text CH 4 nbsp which is the equation in the previous section for the enthalpy of combustion D comb H displaystyle Delta text comb H ominus nbsp Key concepts for enthalpy calculations editWhen a reaction is reversed the magnitude of DH stays the same but the sign changes When the balanced equation for a reaction is multiplied by an integer the corresponding value of DH must be multiplied by that integer as well The change in enthalpy for a reaction can be calculated from the enthalpies of formation of the reactants and the products Elements in their standard states make no contribution to the enthalpy calculations for the reaction since the enthalpy of an element in its standard state is zero Allotropes of an element other than the standard state generally have non zero standard enthalpies of formation Examples standard enthalpies of formation at 25 C editThermochemical properties of selected substances at 298 15 K and 1 atm Inorganic substances edit Species Phase Chemical formula DfH kJ mol Aluminium Solid Al 0 Aluminium chloride Solid AlCl3 705 63 Aluminium oxide Solid Al2O3 1675 5 Aluminium hydroxide Solid Al OH 3 1277 Aluminium sulphate Solid Al2 SO4 3 3440 Barium chloride Solid BaCl2 858 6 Barium carbonate Solid BaCO3 1216 Barium hydroxide Solid Ba OH 2 944 7 Barium oxide Solid BaO 548 1 Barium sulfate Solid BaSO4 1473 3 Beryllium Solid Be 0 Beryllium hydroxide Solid Be OH 2 903 Beryllium oxide Solid BeO 609 4 Boron trichloride Solid BCl3 402 96 Bromine Liquid Br2 0 Bromide ion Aqueous Br 121 Bromine Gas Br 111 884 Bromine Gas Br2 30 91 Bromine trifluoride Gas BrF3 255 60 Hydrogen bromide Gas HBr 36 29 Cadmium Solid Cd 0 Cadmium oxide Solid CdO 258 Cadmium hydroxide Solid Cd OH 2 561 Cadmium sulfide Solid CdS 162 Cadmium sulfate Solid CdSO4 935 Caesium Solid Cs 0 Caesium Gas Cs 76 50 Caesium Liquid Cs 2 09 Caesium I ion Gas Cs 457 964 Caesium chloride Solid CsCl 443 04 Calcium Solid Ca 0 Calcium Gas Ca 178 2 Calcium II ion Gas Ca2 1925 90 Calcium II ion Aqueous Ca2 542 7 Calcium carbide Solid CaC2 59 8 Calcium carbonate Calcite Solid CaCO3 1206 9 Calcium chloride Solid CaCl2 795 8 Calcium chloride Aqueous CaCl2 877 3 Calcium phosphate Solid Ca3 PO4 2 4132 Calcium fluoride Solid CaF2 1219 6 Calcium hydride Solid CaH2 186 2 Calcium hydroxide Solid Ca OH 2 986 09 Calcium hydroxide Aqueous Ca OH 2 1002 82 Calcium oxide Solid CaO 635 09 Calcium sulfate Solid CaSO4 1434 52 Calcium sulfide Solid CaS 482 4 Wollastonite Solid CaSiO3 1630 Carbon Graphite Solid C 0 Carbon Diamond Solid C 1 9 Carbon Gas C 716 67 Carbon dioxide Gas CO2 393 509 Carbon disulfide Liquid CS2 89 41 Carbon disulfide Gas CS2 116 7 Carbon monoxide Gas CO 110 525 Carbonyl chloride Phosgene Gas COCl2 218 8 Carbon dioxide un ionized Aqueous CO2 aq 419 26 Bicarbonate ion Aqueous HCO3 689 93 Carbonate ion Aqueous CO32 675 23 Monatomic chlorine Gas Cl 121 7 Chloride ion Aqueous Cl 167 2 Chlorine Gas Cl2 0 Chromium Solid Cr 0 Copper Solid Cu 0 Copper II bromide Solid CuBr2 138 490 Copper II chloride Solid CuCl2 217 986 Copper II oxide Solid CuO 155 2 Copper II sulfate Aqueous CuSO4 769 98 Fluorine Gas F2 0 Monatomic hydrogen Gas H 218 Hydrogen Gas H2 0 Water Gas H2O 241 818 Water Liquid H2O 285 8 Hydrogen ion Aqueous H 0 Hydroxide ion Aqueous OH 230 Hydrogen peroxide Liquid H2O2 187 8 Phosphoric acid Liquid H3PO4 1288 Hydrogen cyanide Gas HCN 130 5 Hydrogen bromide Liquid HBr 36 3 Hydrogen chloride Gas HCl 92 30 Hydrogen chloride Aqueous HCl 167 2 Hydrogen fluoride Gas HF 273 3 Hydrogen iodide Gas HI 26 5 Iodine Solid I2 0 Iodine Gas I2 62 438 Iodine Aqueous I2 23 Iodide ion Aqueous I 55 Iron Solid Fe 0 Iron carbide Cementite Solid Fe3C 5 4 Iron II carbonate Siderite Solid FeCO3 750 6 Iron III chloride Solid FeCl3 399 4 Iron II oxide Wustite Solid FeO 272 Iron II III oxide Magnetite Solid Fe3O4 1118 4 Iron III oxide Hematite Solid Fe2O3 824 2 Iron II sulfate Solid FeSO4 929 Iron III sulfate Solid Fe2 SO4 3 2583 Iron II sulfide Solid FeS 102 Pyrite Solid FeS2 178 Lead Solid Pb 0 Lead dioxide Solid PbO2 277 Lead sulfide Solid PbS 100 Lead sulfate Solid PbSO4 920 Lead II nitrate Solid Pb NO3 2 452 Lead II sulfate Solid PbSO4 920 Lithium fluoride Solid LiF 616 93 Magnesium Solid Mg 0 Magnesium ion Aqueous Mg2 466 85 Magnesium carbonate Solid MgCO3 1095 797 Magnesium chloride Solid MgCl2 641 8 Magnesium hydroxide Solid Mg OH 2 924 54 Magnesium hydroxide Aqueous Mg OH 2 926 8 Magnesium oxide Solid MgO 601 6 Magnesium sulfate Solid MgSO4 1278 2 Manganese Solid Mn 0 Manganese II oxide Solid MnO 384 9 Manganese IV oxide Solid MnO2 519 7 Manganese III oxide Solid Mn2O3 971 Manganese II III oxide Solid Mn3O4 1387 Permanganate Aqueous MnO 4 543 Mercury II oxide red Solid HgO 90 83 Mercury sulfide red cinnabar Solid HgS 58 2 Nitrogen Gas N2 0 Ammonia ammonium hydroxide Aqueous NH3 NH4OH 80 8 Ammonia Gas NH3 46 1 Ammonium nitrate Solid NH4NO3 365 6 Ammonium chloride Solid NH4Cl 314 55 Nitrogen dioxide Gas NO2 33 2 Hydrazine Gas N2H4 95 4 Hydrazine Liquid N2H4 50 6 Nitrous oxide Gas N2O 82 05 Nitric oxide Gas NO 90 29 Dinitrogen tetroxide Gas N2O4 9 16 Dinitrogen pentoxide Solid N2O5 43 1 Dinitrogen pentoxide Gas N2O5 11 3 Nitric acid Aqueous HNO3 207 Monatomic oxygen Gas O 249 Oxygen Gas O2 0 Ozone Gas O3 143 White phosphorus Solid P4 0 Red phosphorus Solid P 17 4 5 Black phosphorus Solid P 39 3 5 Phosphorus trichloride Liquid PCl3 319 7 Phosphorus trichloride Gas PCl3 278 Phosphorus pentachloride Solid PCl5 440 Phosphorus pentachloride Gas PCl5 321 Phosphorus pentoxide Solid P2O5 1505 5 6 Potassium bromide Solid KBr 392 2 Potassium carbonate Solid K2CO3 1150 Potassium chlorate Solid KClO3 391 4 Potassium chloride Solid KCl 436 68 Potassium fluoride Solid KF 562 6 Potassium oxide Solid K2O 363 Potassium nitrate Solid KNO3 494 5 Potassium perchlorate Solid KClO4 430 12 Silicon Gas Si 368 2 Silicon carbide Solid SiC 74 4 7 71 5 8 Silicon tetrachloride Liquid SiCl4 640 1 Silica Quartz Solid SiO2 910 86 Silver bromide Solid AgBr 99 5 Silver chloride Solid AgCl 127 01 Silver iodide Solid AgI 62 4 Silver oxide Solid Ag2O 31 1 Silver sulfide Solid Ag2S 31 8 Sodium Solid Na 0 Sodium Gas Na 107 5 Sodium bicarbonate Solid NaHCO3 950 8 Sodium carbonate Solid Na2CO3 1130 77 Sodium chloride Aqueous NaCl 407 27 Sodium chloride Solid NaCl 411 12 Sodium chloride Liquid NaCl 385 92 Sodium chloride Gas NaCl 181 42 Sodium chlorate Solid NaClO3 365 4 Sodium fluoride Solid NaF 569 0 Sodium hydroxide Aqueous NaOH 469 15 Sodium hydroxide Solid NaOH 425 93 Sodium hypochlorite Solid NaOCl 347 1 Sodium nitrate Aqueous NaNO3 446 2 Sodium nitrate Solid NaNO3 424 8 Sodium oxide Solid Na2O 414 2 Sulfur monoclinic Solid S8 0 3 Sulfur rhombic Solid S8 0 Hydrogen sulfide Gas H2S 20 63 Sulfur dioxide Gas SO2 296 84 Sulfur trioxide Gas SO3 395 7 Sulfuric acid Liquid H2SO4 814 Titanium Gas Ti 468 Titanium tetrachloride Gas TiCl4 763 2 Titanium tetrachloride Liquid TiCl4 804 2 Titanium dioxide Solid TiO2 944 7 Zinc Gas Zn 130 7 Zinc chloride Solid ZnCl2 415 1 Zinc oxide Solid ZnO 348 0 Zinc sulfate Solid ZnSO4 980 14 Aliphatic hydrocarbons edit Formula Name DfH kcal mol DfH kJ mol Straight chain CH4 Methane 17 9 74 9 C2H6 Ethane 20 0 83 7 C2H4 Ethylene 12 5 52 5 C2H2 Acetylene 54 2 226 8 C3H8 Propane 25 0 104 6 C4H10 n Butane 30 0 125 5 C5H12 n Pentane 35 1 146 9 C6H14 n Hexane 40 0 167 4 C7H16 n Heptane 44 9 187 9 C8H18 n Octane 49 8 208 4 C9H20 n Nonane 54 8 229 3 C10H22 n Decane 59 6 249 4 C4 Alkane branched isomers C4H10 Isobutane methylpropane 32 1 134 3 C5 Alkane branched isomers C5H12 Neopentane dimethylpropane 40 1 167 8 C5H12 Isopentane methylbutane 36 9 154 4 C6 Alkane branched isomers C6H14 2 2 Dimethylbutane 44 5 186 2 C6H14 2 3 Dimethylbutane 42 5 177 8 C6H14 2 Methylpentane isohexane 41 8 174 9 C6H14 3 Methylpentane 41 1 172 0 C7 Alkane branched isomers C7H16 2 2 Dimethylpentane 49 2 205 9 C7H16 2 2 3 Trimethylbutane 49 0 205 0 C7H16 3 3 Dimethylpentane 48 1 201 3 C7H16 2 3 Dimethylpentane 47 3 197 9 C7H16 2 4 Dimethylpentane 48 2 201 7 C7H16 2 Methylhexane 46 5 194 6 C7H16 3 Methylhexane 45 7 191 2 C7H16 3 Ethylpentane 45 3 189 5 C8 Alkane branched isomers C8H18 2 3 Dimethylhexane 55 1 230 5 C8H18 2 2 3 3 Tetramethylbutane 53 9 225 5 C8H18 2 2 Dimethylhexane 53 7 224 7 C8H18 2 2 4 Trimethylpentane isooctane 53 5 223 8 C8H18 2 5 Dimethylhexane 53 2 222 6 C8H18 2 2 3 Trimethylpentane 52 6 220 1 C8H18 3 3 Dimethylhexane 52 6 220 1 C8H18 2 4 Dimethylhexane 52 4 219 2 C8H18 2 3 4 Trimethylpentane 51 9 217 1 C8H18 2 3 3 Trimethylpentane 51 7 216 3 C8H18 2 Methylheptane 51 5 215 5 C8H18 3 Ethyl 3 Methylpentane 51 4 215 1 C8H18 3 4 Dimethylhexane 50 9 213 0 C8H18 3 Ethyl 2 Methylpentane 50 4 210 9 C8H18 3 Methylheptane 60 3 252 5 C8H18 4 Methylheptane C8H18 3 Ethylhexane C9 Alkane branched isomers selected C9H20 2 2 4 4 Tetramethylpentane 57 8 241 8 C9H20 2 2 3 3 Tetramethylpentane 56 7 237 2 C9H20 2 2 3 4 Tetramethylpentane 56 6 236 8 C9H20 2 3 3 4 Tetramethylpentane 56 4 236 0 C9H20 3 3 Diethylpentane 55 7 233 0 Other organic compounds edit Species Phase Chemical formula DfH kJ mol Acetone Liquid C3H6O 248 4 Benzene Liquid C6H6 48 95 Benzoic acid Solid C7H6O2 385 2 Carbon tetrachloride Liquid CCl4 135 4 Carbon tetrachloride Gas CCl4 95 98 Ethanol Liquid C2H5OH 277 0 Ethanol Gas C2H5OH 235 3 Glucose Solid C6H12O6 1271 Isopropanol Gas C3H7OH 318 1 Methanol methyl alcohol Liquid CH3OH 238 4 Methanol methyl alcohol Gas CH3OH 201 0 Methyl linoleate Biodiesel Gas C19H34O2 356 3 Sucrose Solid C12H22O11 2226 1 Trichloromethane Chloroform Liquid CHCl3 134 47 Trichloromethane Chloroform Gas CHCl3 103 18 Vinyl chloride Solid C2H3Cl 94 12See also editCalorimetry ThermochemistryReferences edit IUPAC Compendium of Chemical Terminology 2nd ed the Gold Book 1997 Online corrected version 2006 standard pressure doi 10 1351 goldbook S05921 Oxtoby David W Pat Gillis H Campion Alan 2011 Principles of Modern Chemistry Cengage Learning p 547 ISBN 978 0 8400 4931 5 Moore Stanitski and Jurs Chemistry The Molecular Science 3rd edition 2008 ISBN 0 495 10521 X pages 320 321 Enthalpies of Reaction www science uwaterloo ca Archived from the original on 25 October 2017 Retrieved 2 May 2018 a b Housecroft C E Sharpe A G 2004 Inorganic Chemistry 2nd ed Prentice Hall p 392 ISBN 978 0 13 039913 7 Green D W ed 2007 Perry s Chemical Engineers Handbook 8th ed Mcgraw Hill pp 2 191 ISBN 9780071422949 Kleykamp H 1998 Gibbs Energy of Formation of SiC A contribution to the Thermodynamic Stability of the Modifications Berichte der Bunsengesellschaft fur physikalische Chemie 102 9 1231 1234 doi 10 1002 bbpc 19981020928 Silicon Carbide Alpha SiC March 1967 Retrieved 5 February 2019 Zumdahl Steven 2009 Chemical Principles 6th ed Boston New York Houghton Mifflin pp 384 387 ISBN 978 0 547 19626 8 External links editNIST Chemistry WebBook Retrieved from https en wikipedia org w index php title Standard enthalpy of formation amp oldid 1219871035, wikipedia, wiki, book, books, library,

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