A carbon-carbon triple bond may be located at any unbranched site within a carbon chain or at the end of a chain, in which case it is called terminal. Because of its linear configuration ( the bond angle of a sp-hybridized carbon is 180º ), a ten-membered carbon ring is the smallest that can accomodate this function without excessive strain.

Since the most common chemical transformation of a carbon-carbon double bond is an addition reaction, we might expect the same to be true for carbon-carbon triple bonds. Indeed, most of the alkene addition reactions discussed earlier also take place with alkynes, and with similar regio- and stereoselectivity.

1. Catalytic Hydrogenation

The catalytic addition of hydrogen to 2-butyne not only serves as an example of such an addition reaction, but also provides heat of reaction data that reflect the relative thermodynamic stabilities of these hydrocarbons, as shown in the diagram to the right.

From the heats of hydrogenation, shown in blue in units of kcal/mole, it would appear that alkynes are thermodynamically less stable than alkenes to a greater degree than alkenes are less stable than alkanes.

The standard bond energies for carbon-carbon bonds confirm this conclusion. Thus, a double bond is stronger than a single bond, but not twice as strong. The difference ( 63 kcal/mole ) may be regarded as the strength of the π-bond component.

Similarly, a triple bond is stronger than a double bond, but not 50% stronger. Here the difference ( 54 kcal/mole ) may be taken as the strength of the second π-bond. The 9 kcal/mole weakening of this second π-bond is reflected in the heat of hydrogenation numbers ( 36.7 - 28.3 = 8.4 ).

Since alkynes are thermodynamically less stable than alkenes, we might expect addition reactions of the former to be more exothermic and relatively faster than equivalent reactions of the latter.

In the case of catalytic hydrogenation, the usual Pt and Pd hydrogenation catalysts are so effective in promoting addition of hydrogen to both double and triple carbon-carbon bonds that the alkene intermediate formed by hydrogen addition to an alkyne cannot be isolated.

A less efficient catalyst, Lindlar's catalyst, prepared by deactivating (or poisoning) a conventional palladium catalyst by treating it with lead acetate and quinoline, permits alkynes to be converted to alkenes without further reduction to an alkane.

The addition of hydrogen is stereoselectively syn (e.g. 2-butyne gives cis-2-butene). A complementary stereoselective reduction in the anti mode may be accomplished by a solution of sodium in liquid ammonia.