Reactivity Of Hydrogen - Encyclopedia Britannica

Hydrogen bond

Some covalently bonded hydrides have a hydrogen atom bound simultaneously to two separate electronegative atoms, which are then said to be hydrogen bonded. The strongest hydrogen bonds involve the small, highly electronegative atoms of fluorine (F), oxygen, and nitrogen. In the bifluoride ion, HF2−, the hydrogen atom links two fluorine atoms. In the crystal structure of ice, each oxygen atom is surrounded by four other oxygen atoms, with hydrogen atoms between them. Some of the hydrogen bonds are broken when ice melts, and the structure collapses with an increase in density. Hydrogen bonding is important in biology because of its major role in determining the configurations of molecules. The helical (spiral) configurations of certain enormous molecular chains, as in proteins, are held together by hydrogen bonds. Extensive hydrogen bonding in the liquid state explains why hydrogen fluoride (HF), water (H2O), and ammonia (NH3) have boiling points much higher than those of their heavier analogues, hydrogen chloride (HCl), hydrogen sulfide (H2S), and phosphine (PH3). Thermal energy required to break up the hydrogen bonds and to permit vaporization is available only at the higher boiling temperatures.

The hydrogen in a strong acid, such as hydrochloric (HCl) or nitric (HNO3), behaves quite differently. When these acids dissolve in water, hydrogen in the form of a proton, H+, separates completely from the negatively charged ion, the anion (Cl− or NO3−), and interacts with the water molecules. The proton is strongly attached to one water molecule (hydrated) to form the oxonium ion (H3O+, sometimes called hydronium ion), which in turn is hydrogen-bonded to other water molecules, forming species with formulas such as H(H2O)n+ (the subscript n indicates the number of H2O molecules involved). The reduction of H+ (reduction is the chemical change in which an atom or ion gains one or more electrons) can be represented as the half reaction: H+ + e− → 1/2H2. The energy needed to bring about this reaction can be expressed as a reduction potential. The reduction potential for hydrogen is taken by convention to be zero, and all metals with negative reduction potentials—i.e., metals that are less easily reduced (more easily oxidized; e.g., zinc: Zn2+ + 2e− → Zn, − 0.763 volt)—can, in principle, displace hydrogen from a strong acid solution: Zn + 2H+ → Zn2+ + H2. Metals with positive reduction potentials (e.g., silver: Ag+ + e−→ Ag, + 0.7995 volt) are inert toward the aqueous hydrogen ion.