Hydron (chemistry)

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Hydron
Hydron.svg
Names
Systematic IUPAC name
Hydron [1] (substitutive)
Hydrogen(1+) [1] (additive)
Other names
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
KEGG
PubChem CID
UNII
  • InChI=1S/p+1 Yes check.svgY
    Key: GPRLSGONYQIRFK-UHFFFAOYSA-N Yes check.svgY
  • [H+]
Properties
H+
Molar mass 1.007 g·mol−1
Thermochemistry
Std molar
entropy
(S298)
108.95 J K−1 mol−1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

In chemistry, the hydron, informally called proton, [2] is the cationic form of atomic hydrogen, represented with the symbol H+
. The general term "hydron", endorsed by the IUPAC, encompasses cations of hydrogen regardless of their isotopic composition: thus it refers collectively to protons (1H+) for the protium isotope, deuterons (2H+ or D+) for the deuterium isotope, and tritons (3H+ or T+) for the tritium isotope.

Contents

Unlike most other ions, the hydron consists only of a bare atomic nucleus. The negatively charged counterpart of the hydron is the hydride anion, H
.

Properties

Solute properties

Other things being equal, compounds that readily donate hydrons (Brønsted acids, see below) are generally polar, hydrophilic solutes and are often soluble in solvents with high relative static permittivity (dielectric constants). Examples include organic acids like acetic acid (CH3COOH) or methanesulfonic acid (CH3SO3H). However, large nonpolar portions of the molecule may attenuate these properties. Thus, as a result of its alkyl chain, octanoic acid (C7H15COOH) is considerably less hydrophilic compared to acetic acid.

The unsolvated hydron (a completely free or "naked" hydrogen atomic nucleus) does not exist in the condensed (liquid or solid) phase. Although superacids are sometimes said to owe their extraordinary hydron-donating power to the presence of "free hydrons", such a statement is highly misleading: even for a source of "free hydrons" like H
2
F+
, one of the superacidic cations present in the superacid fluoroantimonic acid (HF:SbF5), detachment of a free H+
still comes at an enormous energetic penalty on the order of several hundred kcal/mol. This effectively rules out the possibility of the free hydron being present in solution, even as a fleeting intermediate. For this reason, in liquid strong acids, hydrons are believed to diffuse by sequential transfer from one molecule to the next along a network of hydrogen bonds through what is known as the Grotthuss mechanism. [3]

Acidity

The hydron ion can incorporate an electron pair from a Lewis base into the molecule by adduction:

[H]+
+ :L → [HL]+

Because of this capture of the Lewis base (L), the hydron ion has Lewis acidic character. In terms of Hard/Soft Acid Base (HSAB) theory, the bare hydron is an infinitely hard Lewis acid.

The hydron plays a central role in Brønsted–Lowry acid–base theory: a species that behaves as a hydron donor in a reaction is known as the Brønsted acid, while the species accepting the hydron is known as the Brønsted base. In the generic acid–base reaction shown below, HA is the acid, while B (shown with a lone pair) is the base:

HA + :B → [HB]+
+ :A

The hydrated form of the hydrogen cation, the hydronium (hydroxonium) ion H
3
O+
(aq), is a key object of Arrhenius' definition of acid. Other hydrated forms, the Zundel cation H
5
O+
2
, which is formed from a proton and two water molecules, and the Eigen cation H
9
O+
4
, which is formed from a hydronium ion and three water molecules, are theorized to play an important role in the diffusion of protons though an aqueous solution according to the Grotthuss mechanism. Although the ion H
3
O+
(aq) is often shown in introductory textbooks to emphasize that the hydron is never present as an unsolvated species in aqueous solution, it is somewhat misleading, as it oversimplifies infamously complex speciation of the solvated proton in water; the notation H+
(aq) is often preferred, since it conveys aqueous solvation while remaining noncommittal with respect to the number of water molecules involved.

Isotopes of hydron

  1. Proton, having the symbol p or 1H+, is the +1 ion of protium, 1H.
  2. Deuteron, having the symbol 2H+ or D+, is the +1 ion of deuterium, 2H or D.
  3. Triton, having the symbol 3H+ or T+, is the +1 ion of tritium, 3H or T.

Other isotopes of hydrogen are too unstable to be relevant in chemistry.

History of the term

The term "hydron" is recommended by IUPAC to be used instead of "proton" if no distinction is made between the isotopes proton, deuteron and triton, all found in naturally occurring undifferentiated isotope mixtures. The name "proton" refers to isotopically pure 1H+. [4] On the other hand, referring to the hydron as simply hydrogen ion is not recommended because hydrogen anions also exist. [5]

The term "hydron" was defined by IUPAC in 1988. [6] [7] Traditionally, the term "proton" was [2] and is[ citation needed ] used in place of "hydron". The latter term is generally only used in the context where comparisons between the various isotopes of hydrogen is important (as in the kinetic isotope effect or hydrogen isotopic labeling). Otherwise, referring to hydrons as protons is still considered acceptable, for example in such terms as protonation, deprotonation, proton pump, or proton channel. The transfer of H+
in an acid-base reaction is usually referred to as proton transfer. Acid and bases are referred to as proton donors and acceptors correspondingly.

99.9844% of natural hydrons (hydrogen nuclei) are protons, and the remainder (about 156 per million in sea water) are deuterons (see deuterium), except for some very rare natural tritons (see tritium).

See also

Related Research Articles

<span class="mw-page-title-main">Acid</span> Chemical compound giving a proton or accepting an electron pair

An acid is a molecule or ion capable of either donating a proton (i.e. hydrogen ion, H+), known as a Brønsted–Lowry acid, or forming a covalent bond with an electron pair, known as a Lewis acid.

<span class="mw-page-title-main">Acid–base reaction</span> Chemical reaction between an acid and a base

In chemistry, an acid–base reaction is a chemical reaction that occurs between an acid and a base. It can be used to determine pH via titration. Several theoretical frameworks provide alternative conceptions of the reaction mechanisms and their application in solving related problems; these are called the acid–base theories, for example, Brønsted–Lowry acid–base theory.

<span class="mw-page-title-main">Deuterium</span> Isotope of hydrogen with one neutron

Deuterium (hydrogen-2, symbol 2H or D, also known as heavy hydrogen) is one of two stable isotopes of hydrogen (the other is protium, or hydrogen-1). The deuterium nucleus, called a deuteron, contains one proton and one neutron, whereas the far more common protium has no neutrons in the nucleus. Deuterium has a natural abundance in Earth's oceans of about one atom of deuterium among every 6,420 atoms of hydrogen (see heavy water). Thus deuterium accounts for about 0.0156% by number (0.0312% by mass) of all hydrogen in the oceans: 4.85×1013 tonnes of deuterium – mainly in form of HOD (or 1HO2H or 1H2HO) and only rarely in form of D2O (or 2H2O) – in 1.4×1018 tonnes of water. The abundance of deuterium changes slightly from one kind of natural water to another (see Vienna Standard Mean Ocean Water).

<span class="mw-page-title-main">Heavy water</span> Form of water

Heavy water is a form of water whose hydrogen atoms are all deuterium rather than the common hydrogen-1 isotope that makes up most of the hydrogen in normal water. The presence of the heavier isotope gives the water different nuclear properties, and the increase in mass gives it slightly different physical and chemical properties when compared to normal water.

A conjugate acid, within the Brønsted–Lowry acid–base theory, is a chemical compound formed when an acid gives a proton to a base—in other words, it is a base with a hydrogen ion added to it, as it loses a hydrogen ion in the reverse reaction. On the other hand, a conjugate base is what remains after an acid has donated a proton during a chemical reaction. Hence, a conjugate base is a substance formed by the removal of a proton from an acid, as it can gain a hydrogen ion in the reverse reaction. Because some acids can give multiple protons, the conjugate base of an acid may itself be acidic.

In chemistry, hydronium (hydroxonium in traditional British English) is the common name for the cation [H3O]+, also written as H3O+, the type of oxonium ion produced by protonation of water. It is often viewed as the positive ion present when an Arrhenius acid is dissolved in water, as Arrhenius acid molecules in solution give up a proton (a positive hydrogen ion, H+) to the surrounding water molecules (H2O). In fact, acids must be surrounded by more than a single water molecule in order to ionize, yielding aqueous H+ and conjugate base. Three main structures for the aqueous proton have garnered experimental support: the Eigen cation, which is a tetrahydrate, H3O+(H2O)3, the Zundel cation, which is a symmetric dihydrate, H+(H2O)2, and the Stoyanov cation, an expanded Zundel cation, which is a hexahydrate: H+(H2O)2(H2O)4. Spectroscopic evidence from well-defined IR spectra overwhelmingly supports the Stoyanov cation as the predominant form. For this reason, it has been suggested that wherever possible, the symbol H+(aq) should be used instead of the hydronium ion.

<span class="mw-page-title-main">Base (chemistry)</span> Type of chemical substance

In chemistry, there are three definitions in common use of the word "base": Arrhenius bases, Brønsted bases, and Lewis bases. All definitions agree that bases are substances that react with acids, as originally proposed by G.-F. Rouelle in the mid-18th century.

<span class="mw-page-title-main">Hydride</span> Molecule with a hydrogen bound to a more electropositive element or group

In chemistry, a hydride is formally the anion of hydrogen (H), a hydrogen atom with two electrons. The term is applied loosely. At one extreme, all compounds containing covalently bound H atoms are also called hydrides: water (H2O) is a hydride of oxygen, ammonia is a hydride of nitrogen, etc. For inorganic chemists, hydrides refer to compounds and ions in which hydrogen is covalently attached to a less electronegative element. In such cases, the H centre has nucleophilic character, which contrasts with the protic character of acids. The hydride anion is very rarely observed.

In chemistry, an amphoteric compound is a molecule or ion that can react both as an acid and as a base. What exactly this can mean depends on which definitions of acids and bases are being used.

Muon-catalyzed fusion is a process allowing nuclear fusion to take place at temperatures significantly lower than the temperatures required for thermonuclear fusion, even at room temperature or lower. It is one of the few known ways of catalyzing nuclear fusion reactions.

The self-ionization of water (also autoionization of water, and autodissociation of water, or simply dissociation of water) is an ionization reaction in pure water or in an aqueous solution, in which a water molecule, H2O, deprotonates (loses the nucleus of one of its hydrogen atoms) to become a hydroxide ion, OH. The hydrogen nucleus, H+, immediately protonates another water molecule to form a hydronium cation, H3O+. It is an example of autoprotolysis, and exemplifies the amphoteric nature of water.

In chemistry, protonation (or hydronation) is the adding of a proton (or hydron, or hydrogen cation), usually denoted by H+, to an atom, molecule, or ion, forming a conjugate acid. (The complementary process, when a proton is removed from a Brønsted–Lowry acid, is deprotonation.) Some examples include

A hydrogen ion is created when a hydrogen atom loses an electron. A positively charged hydrogen ion (or proton) can readily combine with other particles and therefore is only seen isolated when it is in a gaseous state or a nearly particle-free space. Due to its extremely high charge density of approximately 2×1010 times that of a sodium ion, the bare hydrogen ion cannot exist freely in solution as it readily hydrates, i.e., bonds quickly. The hydrogen ion is recommended by IUPAC as a general term for all ions of hydrogen and its isotopes. Depending on the charge of the ion, two different classes can be distinguished: positively charged ions and negatively charged ions.

In electrochemistry, the standard hydrogen electrode, is a redox electrode which forms the basis of the thermodynamic scale of oxidation-reduction potentials. Its absolute electrode potential is estimated to be 4.44 ± 0.02 V at 25 °C, but to form a basis for comparison with all other electrochemical reactions, hydrogen's standard electrode potential is declared to be zero volts at any temperature. Potentials of all other electrodes are compared with that of the standard hydrogen electrode at the same temperature.

The Brønsted–Lowry theory (also called proton theory of acids and bases) is an acid–base reaction theory which was first developed by Johannes Nicolaus Brønsted and Thomas Martin Lowry independently in 1923. The basic concept of this theory is that when an acid and a base react with each other, the acid forms its conjugate base, and the base forms its conjugate acid by exchange of a proton (the hydrogen cation, or H+). This theory generalises the Arrhenius theory.

In chemistry, a superacid (according to the original definition) is an acid with an acidity greater than that of 100% pure sulfuric acid (H2SO4), which has a Hammett acidity function (H0) of −12. According to the modern definition, a superacid is a medium in which the chemical potential of the proton is higher than in pure sulfuric acid. Commercially available superacids include trifluoromethanesulfonic acid (CF3SO3H), also known as triflic acid, and fluorosulfuric acid (HSO3F), both of which are about a thousand times stronger (i.e. have more negative H0 values) than sulfuric acid. Most strong superacids are prepared by the combination of a strong Lewis acid and a strong Brønsted acid. A strong superacid of this kind is fluoroantimonic acid. Another group of superacids, the carborane acid group, contains some of the strongest known acids. Finally, when treated with anhydrous acid, zeolites (microporous aluminosilicate minerals) will contain superacidic sites within their pores. These materials are used on massive scale by the petrochemical industry in the upgrading of hydrocarbons to make fuels.

<span class="mw-page-title-main">Isotopes of hydrogen</span> Hydrogen with different numbers of neutrons

Hydrogen (1H) has three naturally occurring isotopes, sometimes denoted 1
H
, 2
H
, and 3
H
. 1
H
and 2
H
are stable, while 3
H
has a half-life of 12.32(2) years. Heavier isotopes also exist, all of which are synthetic and have a half-life of less than one zeptosecond (10−21 s). Of these, 5
H
is the least stable, while 7
H
is the most.

<span class="mw-page-title-main">Acid catalysis</span> Chemical reaction

In acid catalysis and base catalysis, a chemical reaction is catalyzed by an acid or a base. By Brønsted–Lowry acid–base theory, the acid is the proton (hydrogen ion, H+) donor and the base is the proton acceptor. Typical reactions catalyzed by proton transfer are esterifications and aldol reactions. In these reactions, the conjugate acid of the carbonyl group is a better electrophile than the neutral carbonyl group itself. Depending on the chemical species that act as the acid or base, catalytic mechanisms can be classified as either specific catalysis and general catalysis. Many enzymes operate by general catalysis.

<span class="mw-page-title-main">Trihydrogen cation</span> Polyatomic ion (H₃, charge +1)

The trihydrogen cation or protonated molecular hydrogen is a cation with formula H+
3
, consisting of three hydrogen nuclei (protons) sharing two electrons.

Hydrogen–deuterium exchange is a chemical reaction in which a covalently bonded hydrogen atom is replaced by a deuterium atom, or vice versa. It can be applied most easily to exchangeable protons and deuterons, where such a transformation occurs in the presence of a suitable deuterium source, without any catalyst. The use of acid, base or metal catalysts, coupled with conditions of increased temperature and pressure, can facilitate the exchange of non-exchangeable hydrogen atoms, so long as the substrate is robust to the conditions and reagents employed. This often results in perdeuteration: hydrogen-deuterium exchange of all non-exchangeable hydrogen atoms in a molecule.

References

  1. 1 2 "hydron (CHEBI:15378)". Chemical Entities of Biological Interest (ChEBI). UK: European Bioinformatics Institute.
  2. 1 2 Bunnet, J.F.; Jones, R.A.Y. (1968). "Names for hydrogen atoms, ions, and groups, and for reactions involving them (Recommendations 1988)" (PDF). Pure Appl. Chem. 60 (7): 1115–6. doi:10.1351/pac198860071115. [T]he word proton is used not only for the 1H+ ion but commonly, and incorrectly, for H+ in natural abundance. In many contexts this creates no ambiguity and it is likely that this usage will continue.
  3. Archived 2011-09-27 at the Wayback Machine Computer modeling of proton-hopping in superacids.
  4. Nomenclature of Inorganic Chemistry-IUPAC Recommendations 2005 IR-3.3.2, p.48
  5. Compendium of Chemical Terminology, 2nd edition McNaught, A.D. and Wilkinson, A. Blackwell Science, 1997 ISBN   0-86542-684-8, also online Archived 2005-12-12 at the Wayback Machine
  6. IUPAC , Compendium of Chemical Terminology , 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006) " hydron ". doi : 10.1351/goldbook.H02904
  7. Bunnet, J.F.; Jones, R.A.Y. (1968). "Names for hydrogen atoms, ions, and groups, and for reactions involving them (Recommendations 1988)" (PDF). Pure Appl. Chem. 60 (7): 1115–6. doi:10.1351/pac198860071115.