Alkane

, the simplest alkane]]

Alkanes (also known as paraffins or saturated hydrocarbons) are chemical compounds that consist only of the elements carbon (C) and hydrogen (H) (i.e., hydrocarbons), wherein these atoms are linked together exclusively by single bonds (i.e., they are saturated compounds). Alkanes belong to a homologous series of organic compounds in which the members differ by a constant relative molecular mass of 14.

Each carbon atom must have 4 bonds (either C-H or C-C bonds), and each hydrogen atom must be joined to a carbon atom (H-C bonds). A series of linked carbon atoms is known as the carbon skeleton or carbon backbone. In general, the number of carbon atoms is often used to define the size of the alkane (e.g., C₂-alkane).

An Alkyl group, generally abbreviated with the symbol R, is a functional group or side-chain that, like an alkane, consists solely of single-bonded carbon and hydrogen atoms, for example a methyl or ethyl group.

The simplest possible alkane (the parent molecule) is methane, CH₄. There is no limit to the number of carbon atoms that can be linked together, the only limitation being that the molecule is acyclic, is saturated, and is a hydrocarbon. Saturated oils and waxes are examples of larger alkanes where the number of carbons in the carbon backbone tends to be greater than 10.

Alkanes are not very reactive and have little biological activity. Alkanes can be viewed as a molecular tree upon which can be hung the interesting biologically active/reactive portions (functional groups) of the molecule.sommetimes more often.

Structure classification

Saturated hydrocarbons can be: linear (general formula ) wherein the carbon atoms are joined in a snake-like structure branched (general formula , n > 3) wherein the carbon backbone splits off in one or more directions cyclic (general formula , n > 2) wherein the carbon backbone is linked so as to form a loop.

According to the definition by IUPAC, the former two are alkanes, whereas the third group is called cycloalkanes. Saturated hydrocarbons can also combine any of the linear, cyclic (e.g., polycyclic) and branching structures, and they are still alkanes (no general formula) as long as they are acyclic (i.e., having no loops).

Isomerism

and isobutane are the two C₄H₁₀ isomers; cyclobutane and methylcyclopropane are the two C₄H₈ isomers. Bicyclo[1.1.0]butane is the only C₄H₆ compound and has no isomer; tetrahedrane (not shown) is the only C₄H₄ compound and has also no isomer.]]

Alkanes with more than three carbon atoms can be arranged in numerous different ways, forming different structural isomers. An isomer is like a chemical anagram, in which the atoms of a chemical compound are arranged or joined together in a different order. The simplest isomer of an alkane is the one in which the carbon atoms are arranged in a single chain with no branches. This isomer is sometimes called the n-isomer (n for "normal", although it is not necessarily the most common). However the chain of carbon atoms may also be branched at one or more points. The number of possible isomers increases rapidly with the number of carbon atoms . For example:

C₁: no isomers: methane

C₂: no isomers: ethane

C₃: no isomers: propane

C₄: 2 isomers: n-butane, isobutane

C₅: 3 isomers: pentane, isopentane, neopentane

C₆: 5 isomers: hexane

C₁₂: 355 isomers

C₃₂: 27,711,253,769 isomers

C₆₀: 22,158,734,535,770,411,074,184 isomers, many of which are not stable.

Branched alkanes can be chiral: 3-methylhexane and its higher homologues are chiral due to their stereogenic center at carbon atom number 3. Chiral alkanes are of certain importance in biochemistry, as they occur as sidechains in chlorophyll and tocopherol (vitamin E). Chiral alkanes can be resolved into their enantiomers by enantioselective chromatography.

In addition to these isomers, the chain of carbon atoms may form one or more loops. Such compounds are called cycloalkanes.

Nomenclature

The IUPAC nomenclature (systematic way of naming compounds) for alkanes is based on identifying hydrocarbon chains. Unbranched, saturated hydrocarbon chains are named systematically with a Greek numerical prefix denoting the number of carbons and the suffix "-ane".

August Wilhelm von Hofmann suggested systematizing nomenclature by using the whole sequence of vowels a, e, i, o and u to create suffixes -ane, -ene, -ine (or -yne), -one, -une, for the hydrocarbons. The first three name hydrocarbons with single, double and triple bonds; "-one" represents a ketone; "-ol" represents an alcohol or OH group; "-oxy-" means an ether and refers to oxygen between two carbons, so that methoxy-methane is the IUPAC name for dimethyl ether.

It is difficult or impossible to find compounds with more than one IUPAC name. This is because shorter chains attached to longer chains are prefixes and the convention includes brackets. Numbers in the name, referring to which carbon a group is attached to, should be as low as possible, so that 1- is implied and usually omitted from names of organic compounds with only one side-group; "1-" is implied in nitro-octane. Symmetric compounds will have two ways of arriving at the same name.

Linear alkanes

Straight-chain alkanes are sometimes indicated by the prefix n- (for normal) where a non-linear isomer exists. Although this is not strictly necessary, the usage is still common in cases where there is an important difference in properties between the straight-chain and branched-chain isomers, e.g., n-hexane or 2- or 3-methylpentane.

The members of the series (in terms of number of carbon atoms) are named as follows: :methane, CH₄ - one carbon and four hydrogen :ethane, C₂H₆ - two carbon and six hydrogen :propane, C₃H₈ - three carbon and 8 hydrogen :butane, C₄H₁₀ - four carbon and 10 hydrogen :pentane, C₅H₁₂ - five carbon and 12 hydrogen :hexane, C₆H₁₄ - six carbon and 14 hydrogen

These names were derived from methanol, ether, propionic acid and butyric acid, respectively. Alkanes with five or more carbon atoms are named by adding the suffix -ane to the appropriate numerical multiplier prefix with elision of any terminal vowel (-a or -o) from the basic numerical term. Hence, pentane, C₅H₁₂; hexane, C₆H₁₄; heptane, C₇H₁₆; octane, C₈H₁₈; etc. The prefix is generally Greek, with the exceptions of nonane which has a Latin prefix, and undecane and tridecane which have mixed-language prefixes. For a more complete list, see List of alkanes.

Branched alkanes

of isopentane (common name) or 2-methylbutane (IUPAC systematic name)]] Simple branched alkanes often have a common name using a prefix to distinguish them from linear alkanes, for example n-pentane, isopentane, and neopentane.

IUPAC naming conventions can be used to produce a systematic name.

The key steps in the naming of more complicated branched alkanes are as follows:

Identify the longest continuous chain of carbon atoms

Name this longest root chain using standard naming rules

Name each side chain by changing the suffix of the name of the alkane from "-ane" to "-yl"

Number the root chain so that sum of the numbers assigned to each side group will be as low as possible

Number and name the side chains before the name of the root chain

If there are multiple side chains of the same type, use prefixes such as "di-" and "tri-" to indicate it as such, and number each one.

Add side chain names in alphabetical (disregarding "di-" etc. prefixes) order in front of the name of the root chain

Cyclic alkanes

So-called cyclic alkanes are, in the technical sense, not alkanes, but cycloalkanes. They are hydrocarbons just like alkanes, but contain one or more rings.

Simple cycloalkanes have a prefix "cyclo-" to distinguish them from alkanes. Cycloalkanes are named as per their acyclic counterparts with respect to the number of carbon atoms, e.g., cyclopentane (C₅H₁₀) is a cycloalkane with 5 carbon atoms just like pentane (C₅H₁₂), but they are joined up in a five-membered ring. In a similar manner, propane and cyclopropane, butane and cyclobutane, etc.

Substituted cycloalkanes are named similar to substituted alkanes — the cycloalkane ring is stated, and the substituents are according to their position on the ring, with the numbering decided by Cahn-Ingold-Prelog rules.

There are two determinants for the strength of the van der Waals forces:

the number of electrons surrounding the molecule, which increases with the alkane's molecular weight

the surface area of the molecule

Under standard conditions, from CH₄ to C₄H₁₀ alkanes are gaseous; from C₅H₁₂ to C₁₇H₃₆ they are liquids; and after C₁₈H₃₈ they are solids. As the boiling point of alkanes is primarily determined by weight, it should not be a surprise that the boiling point has almost a linear relationship with the size (molecular weight) of the molecule. As a rule of thumb, the boiling point rises 20 - 30 °C for each carbon added to the chain; this rule applies to other homologous series.

The melting points of branched-chain alkanes can be either higher or lower than those of the corresponding straight-chain alkanes, again depending on the ability of the alkane in question to packing well in the solid phase: This is particularly true for isoalkanes (2-methyl isomers), which often have melting points higher than those of the linear analogues.

Conductivity and Solubility

Alkanes do not conduct electricity, nor are they substantially polarized by an electric field. For this reason they do not form hydrogen bonds and are insoluble in polar solvents such as water. Since the hydrogen bonds between individual water molecules are aligned away from an alkane molecule, the coexistence of an alkane and water leads to an increase in molecular order (a reduction in entropy). As there is no significant bonding between water molecules and alkane molecules, the second law of thermodynamics suggests that this reduction in entropy should be minimized by minimizing the contact between alkane and water: Alkanes are said to be hydrophobic in that they repel water.

Their solubility in nonpolar solvents is relatively good, a property that is called lipophilicity. Different alkanes are, for example, miscible in all proportions among themselves.

The density of the alkanes usually increases with increasing number of carbon atoms, but remains less than that of water. Hence, alkanes form the upper layer in an alkane-water mixture.

===Molecular geometry=== .]] The molecular structure of the alkanes directly affects their physical and chemical characteristics. It is derived from the electron configuration of carbon, which has four valence electrons. The carbon atoms in alkanes are always sp³ hybridized, that is to say that the valence electrons are said to be in four equivalent orbitals derived from the combination of the 2s orbital and the three 2p orbitals. These orbitals, which have identical energies, are arranged spatially in the form of a tetrahedron, the angle of cos⁻¹(−⅓) ≈ 109.47° between them.

Bond lengths and bond angles

An alkane molecule has only C – H and C – C single bonds. The former result from the overlap of a sp³-orbital of carbon with the 1s-orbital of a hydrogen; the latter by the overlap of two sp³-orbitals on different carbon atoms. The bond lengths amount to 1.09×10⁻¹⁰ m for a C – H bond and 1.54×10⁻¹⁰ m for a C – C bond.

The spatial arrangement of the bonds is similar to that of the four sp³-orbitals—they are tetrahedrally arranged, with an angle of 109.47° between them. Structural formulae that represent the bonds as being at right angles to one another, while both common and useful, do not correspond with the reality.

Conformation

The structural formula and the bond angles are not usually sufficient to completely describe the geometry of a molecule. There is a further degree of freedom for each carbon – carbon bond: the torsion angle between the atoms or groups bound to the atoms at each end of the bond. The spatial arrangement described by the torsion angles of the molecule is known as its conformation. s of the two rotamers of ethane]]

Ethane forms the simplest case for studying the conformation of alkanes, as there is only one C – C bond. If one looks down the axis of the C – C bond, one will see the so-called Newman projection. The hydrogen atoms on both the front and rear carbon atoms have an angle of 120° between them, resulting from the projection of the base of the tetrahedron onto a flat plane. However, the torsion angle between a given hydrogen atom attached to the front carbon and a given hydrogen atom attached to the rear carbon can vary freely between 0° and 360°. This is a consequence of the free rotation about a carbon – carbon single bond. Despite this apparent freedom, only two limiting conformations are important: eclipsed conformation and staggered conformation.

The two conformations, also known as rotamers, differ in energy: The staggered conformation is 12.6 kJ/mol lower in energy (more stable) than the eclipsed conformation (the least stable).

This difference in energy between the two conformations, known as the torsion energy, is low compared to the thermal energy of an ethane molecule at ambient temperature. There is constant rotation about the C-C bond. The time taken for an ethane molecule to pass from one staggered conformation to the next, equivalent to the rotation of one CH₃-group by 120° relative to the other, is of the order of 10⁻¹¹ seconds.

The case of higher alkanes is more complex but based on similar principles, with the antiperiplanar conformation always being the most favored around each carbon-carbon bond. For this reason, alkanes are usually shown in a zigzag arrangement in diagrams or in models. The actual structure will always differ somewhat from these idealized forms, as the differences in energy between the conformations are small compared to the thermal energy of the molecules: Alkane molecules have no fixed structural form, whatever the models may suggest.

Spectroscopic properties

Virtually all organic compounds contain carbon – carbon and carbon – hydrogen bonds, and so show some of the features of alkanes in their spectra. Alkanes are notable for having no other groups, and therefore for the absence of other characteristic spectroscopic features.

Infrared spectroscopy

The carbon–hydrogen stretching mode gives a strong absorption between 2850 and 2960 cm⁻¹, while the carbon–carbon stretching mode absorbs between 800 and 1300 cm⁻¹. The carbon–hydrogen bending modes depend on the nature of the group: methyl groups show bands at 1450 cm⁻¹ and 1375 cm⁻¹, while methylene groups show bands at 1465 cm⁻¹ and 1450 cm⁻¹. Carbon chains with more than four carbon atoms show a weak absorption at around 725 cm⁻¹.

NMR spectroscopy

The proton resonances of alkanes are usually found at δ_H = 0.5 – 1.5. The carbon-13 resonances depend on the number of hydrogen atoms attached to the carbon: δ_C = 8 – 30 (primary, methyl, -CH₃), 15 – 55 (secondary, methylene, -CH₂-), 20 – 60 (tertiary, methyne, C-H) and quaternary. The carbon-13 resonance of quaternary carbon atoms is characteristically weak, due to the lack of Nuclear Overhauser effect and the long relaxation time, and can be missed in weak samples, or sample that have not been run for a sufficiently long time.

Mass spectrometry

Alkanes have a high ionization energy, and the molecular ion is usually weak. The fragmentation pattern can be difficult to interpret, but, in the case of branched chain alkanes, the carbon chain is preferentially cleaved at tertiary or quaternary carbons due to the relative stability of the resulting free radicals. The fragment resulting from the loss of a single methyl group (M−15) is often absent, and other fragment are often spaced by intervals of fourteen mass units, corresponding to sequential loss of CH₂-groups.

Chemical properties

In general, alkanes show a relatively low reactivity, because their C bonds are relatively stable and cannot be easily broken. Unlike most other organic compounds, they possess no functional groups.

They react only very poorly with ionic or other polar substances. The acid dissociation constant (pK_a) values of all alkanes are above 60, hence they are practically inert to acids and bases (see: carbon acids). This inertness is the source of the term paraffins (with the meaning here of "lacking affinity"). In crude oil the alkane molecules have remained chemically unchanged for millions of years.

However redox reactions of alkanes, in particular with oxygen and the halogens, are possible as the carbon atoms are in a strongly reduced condition; in the case of methane, the lowest possible oxidation state for carbon (−4) is reached. Reaction with oxygen (if an amount of the least is enough to meet the reaction stoichometry) leads to combustion without any smoke; with halogens, substitution. In addition, alkanes have been shown to interact with, and bind to, certain transition metal complexes in (See: carbon-hydrogen bond activation).

Free radicals, molecules with unpaired electrons, play a large role in most reactions of alkanes, such as cracking and reformation where long-chain alkanes are converted into shorter-chain alkanes and straight-chain alkanes into branched-chain isomers.

In highly branched alkanes, the bond angle may differ significantly from the optimal value (109.5°) in order to allow the different groups sufficient space. This causes a tension in the molecule, known as steric hindrance, and can substantially increase the reactivity.

Reactions with oxygen (combustion reaction)

All alkanes react with oxygen in a combustion reaction, although they become increasingly difficult to ignite as the number of carbon atoms increases. The general equation for complete combustion is: :C_nH_2n+2 + (1.5n+0.5)O₂ → (n+1)H₂O + nCO₂ In the absence of sufficient oxygen, carbon monoxide or even soot can be formed, as shown below:

:C_nH_(2n+2) + nO₂ → (n+1)H₂O + nCO

For example methane: :2CH₄ + 3O₂ → 2CO + 4H₂O :CH₄ + 1.5O₂ → CO + 2H₂O

See the alkane heat of formation table for detailed data. The standard enthalpy change of combustion, Δ_cH^o, for alkanes increases by about 650 kJ/mol per CH₂ group. Branched-chain alkanes have lower values of Δ_cH^o than straight-chain alkanes of the same number of carbon atoms, and so can be seen to be somewhat more stable.

Reactions with halogens

Alkanes react with halogens in a so-called free radical halogenation reaction. The hydrogen atoms of the alkane are progressively replaced by halogen atoms. Free-radicals are the reactive species that participate in the reaction, which usually leads to a mixture of products. The reaction is highly exothermic, and can lead to an explosion.

These reactions are an important industrial route to halogenated hydrocarbons. There are three steps:

Initiation the halogen radicals form by homolysis. Usually, energy in the form of heat or light is required.

Chain reaction or Propagation then takes place—the halogen radical abstracts a hydrogen from the alkane to give an alkyl radical. This reacts further.

Chain termination where step the radicals recombine.

Experiments have shown that all halogenation produces a mixture of all possible isomers, indicating that all hydrogen atoms are susceptible to reaction. The mixture produced, however, is not a statistical mixture: Secondary and tertiary hydrogen atoms are preferentially replaced due to the greater stability of secondary and tertiary free-radicals. An example can be seen in the monobromination of propane: Also on Titan, a methane-spewing volcano was spotted and this volcanism is believed to be a significant source of the methane in the atmosphere. There also appear to be Methane/Ethane lakes near the north polar regions of Titan, as discovered by Cassini's radar imaging. Methane and ethane have also been detected in the tail of the comet Hyakutake. Chemical analysis showed that the abundances of ethane and methane were roughly equal, which is thought to imply that its ices formed in interstellar space, away from the Sun, which would have evaporated these volatile molecules. Alkanes have also been detected in meteorites such as carbonaceous chondrites.

Occurrence of alkanes on Earth

Traces of methane gas (about 0.0001% or 1 ppm) occur in the Earth's atmosphere, produced primarily by organisms such as Archaea, found for example in the gut of cows.

The most important commercial sources for alkanes are natural gas and oil. They protect the plant against water loss, prevent the leaching of important minerals by the rain, and protect against bacteria, fungi, and harmful insects. The carbon chains in plant alkanes are usually odd-numbered, between twenty-seven and thirty-three carbon atoms in length

Ecological relations

)]] One example, in which both plant and animal alkanes play a role, is the ecological relationship between the sand bee (Andrena nigroaenea) and the early spider orchid (Ophrys sphegodes); the latter is dependent for pollination on the former. Sand bees use pheromones in order to identify a mate; in the case of A. nigroaenea, the females emit a mixture of tricosane (C₂₃H₄₈), pentacosane (C₂₅H₅₂) and heptacosane (C₂₇H₅₆) in the ratio 3:3:1, and males are attracted by specifically this odor. The orchid takes advantage of this mating arrangement to get the male bee to collect and disseminate its pollen; parts of its flower not only resemble the appearance of sand bees, but also produce large quantities of the three alkanes in the same ratio as female sand bees. As a result numerous males are lured to the blooms and attempt to copulate with their imaginary partner: although this endeavor is not crowned with success for the bee, it allows the orchid to transfer its pollen, which will be dispersed after the departure of the frustrated male to different blooms.

Production

Petroleum refining

at Martinez, California.]] As stated earlier, the most important source of alkanes is natural gas and crude oil. removes hydroxyl groups from alcohols e.g. : scheme]]

and the Clemmensen reduction removes carbonyl groups from aldehydes and ketones to form alkanes or alkyl-substituted compounds e.g.: :

Applications

The applications of a certain alkane can be determined quite well according to the number of carbon atoms. The first four alkanes are used mainly for heating and cooking purposes, and in some countries for electricity generation. Methane and ethane are the main components of natural gas; they are normally stored as gases under pressure. It is, however, easier to transport them as liquids: This requires both compression and cooling of the gas.

Propane and butane can be liquefied at fairly low pressures, and are well known as liquified petroleum gas (LPG). Propane, for example, is used in the propane gas burner, butane in disposable cigarette lighters. The two alkanes are used as propellants in aerosol sprays.

From pentane to octane the alkanes are reasonably volatile liquids. They are used as fuels in internal combustion engines, as they vaporise easily on entry into the combustion chamber without forming droplets, which would impair the uniformity of the combustion. Branched-chain alkanes are preferred as they are much less prone to premature ignition, which causes knocking, than their straight-chain homologues. This propensity to premature ignition is measured by the octane rating of the fuel, where 2,2,4-trimethylpentane (isooctane) has an arbitrary value of 100, and heptane has a value of zero. Apart from their use as fuels, the middle alkanes are also good solvents for nonpolar substances.

Alkanes from nonane to, for instance, hexadecane (an alkane with sixteen carbon atoms) are liquids of higher viscosity, less and less suitable for use in gasoline. They form instead the major part of diesel and aviation fuel. Diesel fuels are characterized by their cetane number, cetane being an old 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.

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, for example, in candles. This should not be confused however with true wax, which consists primarily of esters.

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

Some synthetic polymers such as polyethylene and polypropylene are alkanes with chains containing hundreds of thousands of carbon atoms. These materials are used in innumerable applications, and billions of kilograms of these materials are made and used each year.

Environmental transformations

When released in the environment, alkanes don't undergo rapid biodegradation, because they have no functional groups (like hydroxyl or carbonyl) that are needed by most organisms in order to metabolize the compound.

However, some bacteria can metabolize some alkanes (especially those linear and short), by oxidizing the terminal carbon atom. The product is an alcohol, that could be next oxidized to an aldehyde, and finally to a carboxylic acid. The resulting fatty acid could be metabolized through the fatty acid degradation pathway.

Hazards

Methane is explosive when mixed with air (1 – 8% CH₄). Other lower alkanes can also form explosive mixtures with air. The lighter liquid alkanes are highly flammable, although this risk decreases with the length of the carbon chain. Pentane, hexane, heptane, and octane are classed as dangerous for the environment and harmful. The straight-chain isomer of hexane is a neurotoxin. Halogen-rich alkanes, like chloroform, can be carcinogenic as well.

See also

Alkene

Alkyne

Cycloalkane

Basketane

References

Further reading

Virtual Textbook of Organic Chemistry

Category:Hydrocarbons Category:Organic compounds Category:Functional groups