Higher alkane

Higher alkanes refer to alkanes with a high number of carbon atoms. There does not exist a formal definition for when an alkane is classified as a 'higher alkane', but one definition distinguishes the higher alkanes as the n-alkanes that are solid under room temperature.^{[according to whom?]}

Synthesis

Higher alkanes are naturally present in crude oil and can be obtained via fractional distillation. Saturated fatty acids decarboxylate to higher alkanes. Long olefins can be hydrogenated to yield higher alkanes. n-alkanes can be isolated via the formation of urea clathrates.They can also be synthesized through Kolbe electrolysis or other coupling reactions like the Wurtz reaction.

Uses

Alkanes from nonane to hexadecane (those alkanes with nine to sixteen carbon atoms) are liquids of higher viscosity, which are less suitable for use in gasoline. They form instead the major part of diesel, kerosene, and aviation fuel. Diesel fuels are characterised by their cetane number, cetane being an older name for hexadecane. However the higher melting points of these alkanes can cause problems at low temperatures and in polar regions, where the fuel becomes too thick to flow correctly. Mixtures of the normal alkanes are used as boiling point standards for simulated distillation by gas chromatography.^[1]

Alkanes from hexadecane upwards form the most important components of fuel oil and lubricating oil. In latter function they work at the same time as anti-corrosive agents, as their hydrophobic nature means that water cannot reach the metal surface. Many solid alkanes find use as paraffin wax, used for lubrication, electrical insulation, and candles. Paraffin wax should not be confused with beeswax, which consists primarily of esters.

Alkanes with a chain length of approximately 35 or more carbon atoms are found in bitumen (asphalt), used (for example) in road surfacing. However, the higher alkanes have little value and are usually split into lower alkanes by cracking.

Names

Some alkanes have non-IUPAC trivial names:

cetane, for hexadecane
cerane, for hexacosane^[2]

Properties

Nonane is the lightest alkane to have a flash point above 25 °C, and is classified as flammable under the US National Library of Medicine. ^[3]

The properties listed here refer to the straight-chain alkanes (or: n-alkanes).

Nonane to hexadecane

This group of n-alkanes is generally liquid under standard conditions.^[4]

	Nonane	Decane	Undecane	Dodecane	Tridecane	Tetradecane	Pentadecane	Hexadecane
Formula	C₉H₂₀	C₁₀H₂₂	C₁₁H₂₄	C₁₂H₂₆	C₁₃H₂₈	C₁₄H₃₀	C₁₅H₃₂	C₁₆H₃₄
CAS number	[111-84-2]	[124-18-5]	[1120-21-4]	[112-40-3]	[629-50-5]	[629-59-4]	[629-62-9]	[544-76-3]
Molar mass (g/mol)	128.26	142.29	156.31	170.34	184.37	198.39	212.42	226.45
Melting point (°C)	−53.5	−29.7	−25.6	−9.6	−5.4	5.9	9.9	18.2
Boiling point (°C)	150.8	174.1	195.9	216.3	235.4	253.5	270.6	286.8
Density (g/ml at 20 °C)	0.71763	0.73005	0.74024	0.74869	0.75622	0.76275	0.76830	0.77344
Viscosity (cP at 20 °C)	0.7139	0.9256	1.185	1.503	1.880	2.335	2.863	3.474
Flash point (°C)	31	46	60	71	79	99	132	135
Autoignition temperature (°C)	205	210		205		235		201
Explosive limits	0.9–2.9%	0.8–2.6%					0.45–6.5%

Heptadecane to tetracosane

From this group on, the n-alkanes are generally solid at standard conditions.

	Heptadecane	Octadecane	Nonadecane	Icosane	Heneicosane	Docosane	Tricosane	Tetracosane
Formula	C₁₇H₃₆	C₁₈H₃₈	C₁₉H₄₀	C₂₀H₄₂	C₂₁H₄₄	C₂₂H₄₆	C₂₃H₄₈	C₂₄H₅₀
CAS number	[629-78-7]	[593-45-3]	[629-92-5]	[112-95-8]	[629-94-7]	[629-97-0]	[638-67-5]	[646-31-1]
Molar mass (g/mol)	240.47	254.50	268.53	282.55	296.58	310.61	324.63	338.66
Melting point (°C)	21	28–30	32–34	36.7	40.5	42	48–50	52
Boiling point (°C)	302	317	330	342.7	356.5	224 at 2 kPa	380	391.3
Density (g/ml)	0.777	0.777	0.786	0.7886	0.792	0.778	0.797	0.797
Flash point (°C)	148	166	168	176

Pentacosane to triacontane

	Pentacosane	Hexacosane	Heptacosane	Octacosane	Nonacosane	Triacontane
Formula	C₂₅H₅₂	C₂₆H₅₄	C₂₇H₅₆	C₂₈H₅₈	C₂₉H₆₀	C₃₀H₆₂
CAS number	[629-99-2]	[630-01-3]	[593-49-7]	[630-02-4]	[630-03-5]	[638-68-6]
Molar mass (g/mol)	352.69	366.71	380.74	394.77	408.80	422.82
Melting point (°C)	54	56.4	59.5	64.5	63.7	65.8
Boiling point (°C)	401	412.2	422	431.6	440.8	449.7
Density (g/ml)	0.801	0.778	0.780	0.807	0.808	0.810

Hentriacontane to hexatriacontane

	Hentriacontane	Dotriacontane	Tritriacontane	Tetratriacontane	Pentatriacontane	Hexatriacontane
Formula	C₃₁H₆₄	C₃₂H₆₆	C₃₃H₆₈	C₃₄H₇₀	C₃₅H₇₂	C₃₆H₇₄
CAS number	[630-04-6]	[544-85-4]	[630-05-7]	[14167-59-0]	[630-07-9]	[630-06-8]
Molar mass (g/mol)	436.85	450.88	464.90	478.93	492.96	506.98
Melting point (°C)	67.9	69	70–72	72.6	75	74–76
Boiling point (°C)	458	467	474	285.4 at 0.4 kPa	490	265 at 130 Pa
Density (g/ml)	0.781 at 68 °C^[5]	0.812	0.811	0.812	0.813	0.814

Heptatriacontane to dotetracontane

	Heptatriacontane	Octatriacontane	Nonatriacontane	Tetracontane	Hentetracontane	Dotetracontane
Formula	C₃₇H₇₆	C₃₈H₇₈	C₃₉H₈₀	C₄₀H₈₂	C₄₁H₈₄	C₄₂H₈₆
CAS number	[7194-84-5]	[7194-85-6]	[7194-86-7]	[4181-95-7]	[7194-87-8]	[7098-20-6]
Molar mass (g/mol)	520.99	535.03	549.05	563.08	577.11	591.13
Melting point (°C)	77	79	78	84	83	86
Boiling point (°C)	504.14	510.93	517.51	523.88	530.75	536.07
Density (g/ml)	0.815	0.816	0.817	0.817	0.818	0.819

Tritetracontane to octatetracontane

	Triatetracontane	Tetratetracontane	Pentatetracontane	Hexatetracontane	Heptatetracontane	Octatetracontane
Formula	C₄₃H₈₈	C₄₄H₉₀	C₄₅H₉₂	C₄₆H₉₄	C₄₇H₉₆	C₄₈H₉₈
CAS Number	[7098-21-7]	[7098-22-8]	[7098-23-9]	[7098-24-0]	[7098-25-1]	[7098-26-2]
Molar mass (g/mol)	605.15	619.18	633.21	647.23	661.26	675.29
Boiling point (°C)	541.91	547.57	553.1	558.42	563.6	568.68
Density (g/ml)	0.82	0.82	0.821	0.822	0.822	0.823

Nonatetracontane to tetrapentacontane

	Nonatetracontane	Pentacontane	Henpentacontane	Dopentacontane	Tripentacontane	Tetrapentacontane
Formula	C₄₉H₁₀₀	C₅₀H₁₀₂	C₅₁H₁₀₄	C₅₂H₁₀₆	C₅₃H₁₀₈	C₅₄H₁₁₀
CAS number	[7098-27-3]	[6596-40-3]	[7667-76-7]	[7719-79-1]	[7719-80-4]	[5856-66-6]
Molar mass (g/mol)	689.32	703.34	717.37	731.39	745.42	759.45
Boiling point (°C)	573.6	578.4	583	587.6	592	596.38
Density (g/ml)	0.823	0.824	0.824	0.825	0.825	0.826

Pentapentacontane to hexacontane

	Pentapentacontane	Hexapentacontane	Heptapentacontane	Octapentacontane	Nonapentacontane	Hexacontane
Formula	C₅₅H₁₁₂	C₅₆H₁₁₄	C₅₇H₁₁₆	C₅₈H₁₁₈	C₅₉H₁₂₀	C₆₀H₁₂₂
CAS number	[5846-40-2]	[7719-82-6]	[5856-67-7]	[7667-78-9]	[7667-79-0]	[7667-80-3]
Molar mass (g/mol)	773.48	787.50	801.53	815.58	829.59	843.6
Boiling point (°C)	600.6	604.7	?	612.6	?	620.2
Density (g/ml)	0.826	0.826	?	0.827	?	0.827

References

^ ASTM D5399-09, Standard Test Method for Boiling Point Distribution of Hydrocarbon Solvents by Gas Chromatography
^ Donald Mackay, Handbook of Physical-Chemical Properties and Environmental Fate for Organic Chemicals, ISBN 1420044397, p. 206
^ "Nonane". PubChem. 26 October 2024.
^ Karl Griesbaum, Arno Behr, Dieter Biedenkapp, Heinz-Werner Voges, Dorothea Garbe, Christian Paetz, Gerd Collin, Dieter Mayer Hartmut Höke "Hydrocarbons" in Ullmann's Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH, Weinheim. doi:10.1002/14356007.a13_227
^ Weast, Robert C., ed. (1982). CRC Handbook of Chemistry and Physics (63rd ed.). Boca Raton, Fl: CRC Press. p. C-561.

External links

International Chemical Safety Card 1245 (nonane)
NIOSH Pocket Guide to Chemical Hazards (nonane)
International Chemical Safety Card 0428 (decane)

[1] ASTM D5399-09, Standard Test Method for Boiling Point Distribution of Hydrocarbon Solvents by Gas Chromatography

[2] Donald Mackay, Handbook of Physical-Chemical Properties and Environmental Fate for Organic Chemicals, ISBN 1420044397, p. 206

[3] "Nonane". PubChem. 26 October 2024.

[4] Karl Griesbaum, Arno Behr, Dieter Biedenkapp, Heinz-Werner Voges, Dorothea Garbe, Christian Paetz, Gerd Collin, Dieter Mayer Hartmut Höke "Hydrocarbons" in Ullmann's Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH, Weinheim. doi:10.1002/14356007.a13_227

[5] Weast, Robert C., ed. (1982). CRC Handbook of Chemistry and Physics (63rd ed.). Boca Raton, Fl: CRC Press. p. C-561.

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