The physical properties of alkenes and alkynes are generally similar to those of alkanes or cycloalkanes with equal numbers of carbon atoms. Alkynes have higher boiling points than alkanes or alkenes, because the electric field of an alkyne, with its increased number of weakly held π electrons, is more easily distorted, producing stronger attractive forces between molecules.

Chemical properties

Alkenes react with a much richer variety of compounds than alkanes. The characteristic reaction of alkanes is substitution; that of alkenes and alkynes is addition to the double or triple bond. Hydrogenation is the addition of molecular hydrogen (H₂) to a multiple bond, which converts alkenes to alkanes. The reaction occurs at a convenient rate only in the presence of certain finely divided metal catalysts, such as nickel (Ni), platinum (Pt), palladium (Pd), or rhodium (Rh).

Hydrogenation is used to prepare alkanes and cycloalkanes and also to change the physical properties of highly unsaturated vegetable oils to increase their shelf life. In such processes the liquid oils are converted to fats of a more solid consistency. Butter substitutes such as margarine are prepared by partial hydrogenation of soybean oil.

Significant progress has been made in developing catalysts for enantioselective hydrogenation. An enantioselective hydrogenation is a hydrogenation in which one enantiomer of a chiral molecule (a molecule that can exist in two structural forms, or enantiomers) is formed in greater amounts than the other. This normally involves converting one of the carbons of the double bond to a stereogenic centre.

Typical catalysts for enantioselective hydrogenation are based on enantiomerically homogeneous ligands bonded to rhodium. Enantioselectivities exceeding 90 percent of a single enantiomer are commonplace in enantioselective hydrogenations, a major application of which is in the synthesis of enantiomerically pure drugs.

The halogens bromine and chlorine add to alkenes to yield dihaloalkanes. Addition is rapid even at room temperature and requires no catalyst. The most important application of this reaction is the addition of chlorine to ethylene to give 1,2-dichloroethane, from which vinyl chloride is prepared.

Compounds of the type HX, where X is a halogen or other electronegative group, also add to alkenes; the hydrogen atom of HX becomes bonded to one of the carbon atoms of the C=C unit, and the X atom becomes bonded to the other.

If HX is a strong acid, such as hydrochloric (HCl) or hydrobromic (HBr) acid, the reaction occurs rapidly; otherwise, an acid catalyst is required. One source of industrial ethanol, for example, is the reaction of ethylene with water in the presence of phosphoric acid.

When the two carbon atoms of a double bond are not equivalent, the H of the HX compound adds to the carbon that has the greater number of directly attached hydrogen atoms, and X adds to the one with the fewer. (This generalization is called the Markovnikov rule, named after Russian chemist Vladimir Markovnikov, who proposed the rule in 1869.) Thus, when sulfuric acid (H₂SO₄) adds to propylene, the product is isopropyl hydrogen sulfate, not n-propyl hydrogen sulfate (CH₃CH₂CH₂OSO₃H). This is the first step in the industrial preparation of isopropyl alcohol, which is formed when isopropyl hydrogen sulfate is heated with water.

The term regioselective describes the preference for a reaction that occurs in one direction rather than another, as in the addition of sulfuric acid to propylene. A regiospecific reaction is one that is 100 percent regioselective. The Markovnikov rule expresses the regioselectivity to be expected in the addition of unsymmetrical reagents (such as HX) to unsymmetrical alkenes (such as H₂C=CHR).

Boron hydrides, compounds of the type R₂BH, add to alkenes to give organoboranes (hydroboration), which can be oxidized to alcohols with hydrogen peroxide (H₂O₂) (oxidation). The net result is the same as if H and ―OH add to the double bond with a regioselectivity opposite to the Markovnikov rule. The hydroboration-oxidation sequence is one of a large number of boron-based synthetic methods developed by American chemist Herbert C. Brown.

Vicinal diols, compounds with ―OH groups on adjacent carbons, are formed when alkenes react with certain oxidizing agents, especially potassium permanganate (KMnO₄) or osmium tetroxide (OsO₄). The most widely used methods employ catalytic amounts of OsO₄ in the presence of oxidizing agents such as tert-butyl hydroperoxide [(CH₃)₃COOH].

Alkenes are the customary starting materials from which epoxides, compounds containing a three-membered ring consisting of one oxygen atom and two carbon atoms, are made. The simplest epoxide, ethylene oxide (oxirane), is obtained by passing a mixture of ethylene and air (or oxygen) over a heated silver catalyst. Epoxides are useful intermediates for a number of transformations. Ethylene oxide, for example, is converted to ethylene glycol, which is used in the synthesis of polyester fibres and films and as the main component of automobile antifreeze. On a laboratory scale, epoxides are normally prepared by the reaction of an alkene and a peroxy acid.

Conjugated dienes undergo a novel and useful reaction known as the Diels-Alder cycloaddition. In this reaction, a conjugated diene reacts with an alkene to form a compound that contains a cyclohexene ring. The unusual feature of the Diels-Alder cycloaddition is that two carbon-carbon bonds are formed in a single operation by a reaction that does not require catalysts of any kind. The German chemists Otto Diels and Kurt Alder received the Nobel Prize for Chemistry in 1950 for discovering and demonstrating the synthetic value of this reaction.

Alkynes undergo addition with many of the same substances that react with alkenes. Hydrogenation of alkynes can be controlled so as to yield either an alkene or an alkane. Two molecules of H₂ add to the triple bond to give an alkane under the usual conditions of catalytic hydrogenation.

Special, less active (poisoned) catalysts have been developed that permit the reaction to be halted at the alkene stage, and the procedure is used as a method for the synthesis of alkenes. When stereoisomeric alkenes are possible reaction products, the cis isomer is formed almost exclusively.

Alkynes react with Br₂ or Cl₂ by first adding one molecule of the halogen to give a dihaloalkene and then a second to yield a tetrahaloalkane.

Compounds of the type HX, where X is an electronegative atom or group, also add to alkynes. When acetylene (HC≡CH) reacts with HCl, the product is vinyl chloride (CH₂=CHCl), and, when HCN adds to acetylene, the product is acrylonitrile (CH₂=CHCN). Both vinyl chloride and acrylonitrile are valuable starting materials for the production of useful polymers (see below Polymerization), but neither is prepared in significant quantities from acetylene, because each is available at lower cost from an alkene (vinyl chloride from ethylene and acrylonitrile from propylene).

Hydration of alkynes is unusual in that the initial product, called an enol and characterized by an H―O―C=C― group, is unstable under the conditions of its formation and is converted to an isomer that contains a carbonyl group.

Although they are very weak acids, acetylene and terminal alkynes are much more acidic than alkenes and alkanes. A hydrogen attached to a triply bonded carbon can be removed by a very strong base such as sodium amide (NaNH₂) in liquid ammonia as the solvent.

The sodium salt of the alkyne formed in this reaction is not normally isolated but is treated directly with an alkyl halide. The ensuing reaction proceeds with carbon-carbon bond formation and is used to prepare higher alkynes.