Chemical bond

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https://en.wikipedia.org/wiki/Chemical_bond

Covalent bonding of two hydrogen atoms to form a hydrogen molecule, H
₂. In (a) the two nuclei are surrounded by a cloud of two electrons in the bonding orbital that holds the molecule together. (b) shows hydrogen's antibonding orbital, which is higher in energy and is normally not occupied by any electrons.

A chemical bond is a lasting attraction between atoms or ions that enables the formation of molecules, crystals, and other structures. The bond may result from the electrostatic force between oppositely charged ions as in ionic bonds, or through the sharing of electrons as in covalent bonds. The strength of chemical bonds varies considerably; there are "strong bonds" or "primary bonds" such as covalent, ionic and metallic bonds, and "weak bonds" or "secondary bonds" such as dipole–dipole interactions, the London dispersion force, and hydrogen bonding.

Since opposite electric charges attract, the negatively charged electrons surrounding the nucleus and the positively charged protons within a nucleus attract each other. Electrons shared between two nuclei will be attracted to both of them. "Constructive quantum mechanical wavefunction interference" stabilizes the paired nuclei (see Theories of chemical bonding). Bonded nuclei maintain an optimal distance (the bond distance) balancing attractive and repulsive effects explained quantitatively by quantum theory.

The atoms in molecules, crystals, metals and other forms of matter are held together by chemical bonds, which determine the structure and properties of matter.

All bonds can be described by quantum theory, but, in practice, simplified rules and other theories allow chemists to predict the strength, directionality, and polarity of bonds. The octet rule and VSEPR theory are examples. More sophisticated theories are valence bond theory, which includes orbital hybridization and resonance, and molecular orbital theory which includes the linear combination of atomic orbitals and ligand field theory. Electrostatics are used to describe bond polarities and the effects they have on chemical substances.

Overview of main types of chemical bonds

A chemical bond is an attraction between atoms. This attraction may be seen as the result of different behaviors of the outermost or valence electrons of atoms. These behaviors merge into each other seamlessly in various circumstances, so that there is no clear line to be drawn between them. However it remains useful and customary to differentiate between different types of bond, which result in different properties of condensed matter.

In the simplest view of a covalent bond, one or more electrons (often a pair of electrons) are drawn into the space between the two atomic nuclei. Energy is released by bond formation. This is not as a result of reduction in potential energy, because the attraction of the two electrons to the two protons is offset by the electron-electron and proton-proton repulsions. Instead, the release of energy (and hence stability of the bond) arises from the reduction in kinetic energy due to the electrons being in a more spatially distributed (i.e. longer de Broglie wavelength) orbital compared with each electron being confined closer to its respective nucleus. These bonds exist between two particular identifiable atoms and have a direction in space, allowing them to be shown as single connecting lines between atoms in drawings, or modeled as sticks between spheres in models.

In a polar covalent bond, one or more electrons are unequally shared between two nuclei. Covalent bonds often result in the formation of small collections of better-connected atoms called molecules, which in solids and liquids are bound to other molecules by forces that are often much weaker than the covalent bonds that hold the molecules internally together. Such weak intermolecular bonds give organic molecular substances, such as waxes and oils, their soft bulk character, and their low melting points (in liquids, molecules must cease most structured or oriented contact with each other). When covalent bonds link long chains of atoms in large molecules, however (as in polymers such as nylon), or when covalent bonds extend in networks through solids that are not composed of discrete molecules (such as diamond or quartz or the silicate minerals in many types of rock) then the structures that result may be both strong and tough, at least in the direction oriented correctly with networks of covalent bonds. Also, the melting points of such covalent polymers and networks increase greatly.

In a simplified view of an ionic bond, the bonding electron is not shared at all, but transferred. In this type of bond, the outer atomic orbital of one atom has a vacancy which allows the addition of one or more electrons. These newly added electrons potentially occupy a lower energy-state (effectively closer to more nuclear charge) than they experience in a different atom. Thus, one nucleus offers a more tightly bound position to an electron than does another nucleus, with the result that one atom may transfer an electron to the other. This transfer causes one atom to assume a net positive charge, and the other to assume a net negative charge. The bond then results from electrostatic attraction between the positive and negatively charged ions. Ionic bonds may be seen as extreme examples of polarization in covalent bonds. Often, such bonds have no particular orientation in space, since they result from equal electrostatic attraction of each ion to all ions around them. Ionic bonds are strong (and thus ionic substances require high temperatures to melt) but also brittle, since the forces between ions are short-range and do not easily bridge cracks and fractures. This type of bond gives rise to the physical characteristics of crystals of classic mineral salts, such as table salt.

A less often mentioned type of bonding is metallic bonding. In this type of bonding, each atom in a metal donates one or more electrons to a "sea" of electrons that reside between many metal atoms. In this sea, each electron is free (by virtue of its wave nature) to be associated with a great many atoms at once. The bond results because the metal atoms become somewhat positively charged due to loss of their electrons while the electrons remain attracted to many atoms, without being part of any given atom. Metallic bonding may be seen as an extreme example of delocalization of electrons over a large system of covalent bonds, in which every atom participates. This type of bonding is often very strong (resulting in the tensile strength of metals). However, metallic bonding is more collective in nature than other types, and so they allow metal crystals to more easily deform, because they are composed of atoms attracted to each other, but not in any particularly-oriented ways. This results in the malleability of metals. The cloud of electrons in metallic bonding causes the characteristically good electrical and thermal conductivity of metals, and also their shiny lustre that reflects most frequencies of white light.

History

Main articles: History of chemistry and History of molecular theory

Examples of Lewis dot diagrams used to represent electrons in the chemical bonds between atoms, here showing carbon (C), hydrogen (H), and oxygen (O). Lewis diagrams were developed in 1916 by Gilbert N. Lewis to describe chemical bonding and are still widely used today. Each line segment or pair of dots represents a pair of electrons. Pairs located between atoms represent bonds.

Early speculations about the nature of the chemical bond, from as early as the 12th century, supposed that certain types of chemical species were joined by a type of chemical affinity. In 1704, Sir Isaac Newton famously outlined his atomic bonding theory, in "Query 31" of his Opticks, whereby atoms attach to each other by some "force". Specifically, after acknowledging the various popular theories in vogue at the time, of how atoms were reasoned to attach to each other, i.e. "hooked atoms", "glued together by rest", or "stuck together by conspiring motions", Newton states that he would rather infer from their cohesion, that "particles attract one another by some force, which in immediate contact is exceedingly strong, at small distances performs the chemical operations, and reaches not far from the particles with any sensible effect."

In 1819, on the heels of the invention of the voltaic pile, Jöns Jakob Berzelius developed a theory of chemical combination stressing the electronegative and electropositive characters of the combining atoms. By the mid 19th century, Edward Frankland, F.A. Kekulé, A.S. Couper, Alexander Butlerov, and Hermann Kolbe, building on the theory of radicals, developed the theory of valency, originally called "combining power", in which compounds were joined owing to an attraction of positive and negative poles. In 1904, Richard Abegg proposed his rule that the difference between the maximum and minimum valencies of an element is often eight. At this point, valency was still an empirical number based only on chemical properties.

However the nature of the atom became clearer with Ernest Rutherford's 1911 discovery that of an atomic nucleus surrounded by electrons in which he quoted Nagaoka rejected Thomson's model on the grounds that opposite charges are impenetrable. In 1904, Nagaoka proposed an alternative planetary model of the atom in which a positively charged center is surrounded by a number of revolving electrons, in the manner of Saturn and its rings.

Nagaoka's model made two predictions:

• a very massive atomic center (in analogy to a very massive planet)
• electrons revolving around the nucleus, bound by electrostatic forces (in analogy to the rings revolving around Saturn, bound by gravitational forces.)

Rutherford mentions Nagaoka's model in his 1911 paper in which the atomic nucleus is proposed.

At the 1911 Solvay Conference, in the discussion of what could regulate energy differences between atoms, Max Planck stated: "The intermediaries could be the electrons." These nuclear models suggested that electrons determine chemical behavior.

Next came Niels Bohr's 1913 model of a nuclear atom with electron orbits. In 1916, chemist Gilbert N. Lewis developed the concept of electron-pair bonds, in which two atoms may share one to six electrons, thus forming the single electron bond, a single bond, a double bond, or a triple bond; in Lewis's own words, "An electron may form a part of the shell of two different atoms and cannot be said to belong to either one exclusively."

Also in 1916, Walther Kossel put forward a theory similar to Lewis' only his model assumed complete transfers of electrons between atoms, and was thus a model of ionic bonding. Both Lewis and Kossel structured their bonding models on that of Abegg's rule (1904).

Niels Bohr also proposed a model of the chemical bond in 1913. According to his model for a diatomic molecule, the electrons of the atoms of the molecule form a rotating ring whose plane is perpendicular to the axis of the molecule and equidistant from the atomic nuclei. The dynamic equilibrium of the molecular system is achieved through the balance of forces between the forces of attraction of nuclei to the plane of the ring of electrons and the forces of mutual repulsion of the nuclei. The Bohr model of the chemical bond took into account the Coulomb repulsion – the electrons in the ring are at the maximum distance from each other.

In 1927, the first mathematically complete quantum description of a simple chemical bond, i.e. that produced by one electron in the hydrogen molecular ion, H₂⁺, was derived by the Danish physicist Øyvind Burrau. This work showed that the quantum approach to chemical bonds could be fundamentally and quantitatively correct, but the mathematical methods used could not be extended to molecules containing more than one electron. A more practical, albeit less quantitative, approach was put forward in the same year by Walter Heitler and Fritz London. The Heitler–London method forms the basis of what is now called valence bond theory. In 1929, the linear combination of atomic orbitals molecular orbital method (LCAO) approximation was introduced by Sir John Lennard-Jones, who also suggested methods to derive electronic structures of molecules of F₂ (fluorine) and O₂ (oxygen) molecules, from basic quantum principles. This molecular orbital theory represented a covalent bond as an orbital formed by combining the quantum mechanical Schrödinger atomic orbitals which had been hypothesized for electrons in single atoms. The equations for bonding electrons in multi-electron atoms could not be solved to mathematical perfection (i.e., analytically), but approximations for them still gave many good qualitative predictions and results. Most quantitative calculations in modern quantum chemistry use either valence bond or molecular orbital theory as a starting point, although a third approach, density functional theory, has become increasingly popular in recent years.

In 1933, H. H. James and A. S. Coolidge carried out a calculation on the dihydrogen molecule that, unlike all previous calculation which used functions only of the distance of the electron from the atomic nucleus, used functions which also explicitly added the distance between the two electrons. With up to 13 adjustable parameters they obtained a result very close to the experimental result for the dissociation energy. Later extensions have used up to 54 parameters and gave excellent agreement with experiments. This calculation convinced the scientific community that quantum theory could give agreement with experiment. However this approach has none of the physical pictures of the valence bond and molecular orbital theories and is difficult to extend to larger molecules.

Bonds in chemical formulas

Because atoms and molecules are three-dimensional, it is difficult to use a single method to indicate orbitals and bonds. In molecular formulas the chemical bonds (binding orbitals) between atoms are indicated in different ways depending on the type of discussion. Sometimes, some details are neglected. For example, in organic chemistry one is sometimes concerned only with the functional group of the molecule. Thus, the molecular formula of ethanol may be written in conformational form, three-dimensional form, full two-dimensional form (indicating every bond with no three-dimensional directions), compressed two-dimensional form (CH₃–CH₂–OH), by separating the functional group from another part of the molecule (C₂H₅OH), or by its atomic constituents (C₂H₆O), according to what is discussed. Sometimes, even the non-bonding valence shell electrons (with the two-dimensional approximate directions) are marked, e.g. for elemental carbon _.^'C^'. Some chemists may also mark the respective orbitals, e.g. the hypothetical ethene⁻⁴ anion (_\^/C=C_/^{\ −4}) indicating the possibility of bond formation.

Strong chemical bonds

Typical bond lengths in pm and bond energies in kJ/mol. Bond lengths can be converted to Å by division by 100 (1 Å = 100 pm).
Bond	Length (pm)	Energy (kJ/mol)
H — Hydrogen
H–H	74	436
H–O	96	467
H–F	92	568
H–Cl	127	432
C — Carbon
C–H	109	413
C–C	154	347
C–C=	151
=C–C≡	147
=C–C=	148
C=C	134	614
C≡C	120	839
C–N	147	308
C–O	143	358
C=O		745
C≡O		1,072
C–F	134	488
C–Cl	177	330
N — Nitrogen
N–H	101	391
N–N	145	170
N≡N	110	945
O — Oxygen
O–O	148	146
O=O	121	495
F, Cl, Br, I — Halogens
F–F	142	158
Cl–Cl	199	243
Br–H	141	366
Br–Br	228	193
I–H	161	298
I–I	267	151

Strong chemical bonds are the intramolecular forces that hold atoms together in molecules. A strong chemical bond is formed from the transfer or sharing of electrons between atomic centers and relies on the electrostatic attraction between the protons in nuclei and the electrons in the orbitals.

The types of strong bond differ due to the difference in electronegativity of the constituent elements. Electronegativity is the tendency for an atom of a given chemical element to attract shared electrons when forming a chemical bond, where the higher the associated electronegativity then the more it attracts electrons. Electronegativity serves as a simple way to quantitatively estimate the bond energy, which characterizes a bond along the continuous scale from covalent to ionic bonding. A large difference in electronegativity leads to more polar (ionic) character in the bond.

Ionic bond

Main article: Ionic bonding

Crystal structure of sodium chloride (NaCl) with sodium cations (Na⁺) in purple and chloride anions (Cl⁻) in green. The yellow stipples represent the electrostatic force between the ions of opposite charge.

Ionic bonding is a type of electrostatic interaction between atoms that have a large electronegativity difference. There is no precise value that distinguishes ionic from covalent bonding, but an electronegativity difference of over 1.7 is likely to be ionic while a difference of less than 1.7 is likely to be covalent. Ionic bonding leads to separate positive and negative ions. Ionic charges are commonly between −3e to +3e. Ionic bonding commonly occurs in metal salts such as sodium chloride (table salt). A typical feature of ionic bonds is that the species form into ionic crystals, in which no ion is specifically paired with any single other ion in a specific directional bond. Rather, each species of ion is surrounded by ions of the opposite charge, and the spacing between it and each of the oppositely charged ions near it is the same for all surrounding atoms of the same type. It is thus no longer possible to associate an ion with any specific other single ionized atom near it. This is a situation unlike that in covalent crystals, where covalent bonds between specific atoms are still discernible from the shorter distances between them, as measured via such techniques as X-ray diffraction.

Ionic crystals may contain a mixture of covalent and ionic species, as for example salts of complex acids such as sodium cyanide, NaCN. X-ray diffraction shows that in NaCN, for example, the bonds between sodium cations (Na⁺) and the cyanide anions (CN⁻) are ionic, with no sodium ion associated with any particular cyanide. However, the bonds between the carbon (C) and nitrogen (N) atoms in cyanide are of the covalent type, so that each carbon is strongly bound to just one nitrogen, to which it is physically much closer than it is to other carbons or nitrogens in a sodium cyanide crystal.

When such crystals are melted into liquids, the ionic bonds are broken first because they are non-directional and allow the charged species to move freely. Similarly, when such salts dissolve into water, the ionic bonds are typically broken by the interaction with water but the covalent bonds continue to hold. For example, in solution, the cyanide ions, still bound together as single CN⁻ ions, move independently through the solution, as do sodium ions, as Na⁺. In water, charged ions move apart because each of them are more strongly attracted to a number of water molecules than to each other. The attraction between ions and water molecules in such solutions is due to a type of weak dipole-dipole type chemical bond. In melted ionic compounds, the ions continue to be attracted to each other, but not in any ordered or crystalline way.

Covalent bond

Main article: Covalent bond

Non-polar covalent bonds in methane (CH₄). The Lewis structure shows electrons shared between C and H atoms.

Covalent bonding is a common type of bonding in which two or more atoms share valence electrons more or less equally. The simplest and most common type is a single bond in which two atoms share two electrons. Other types include the double bond, the triple bond, one- and three-electron bonds, the three-center two-electron bond and three-center four-electron bond.

In non-polar covalent bonds, the electronegativity difference between the bonded atoms is small, typically 0 to 0.3. Bonds within most organic compounds are described as covalent. The figure shows methane (CH₄), in which each hydrogen forms a covalent bond with the carbon. See sigma bonds and pi bonds for LCAO descriptions of such bonding.

Molecules that are formed primarily from non-polar covalent bonds are often immiscible in water or other polar solvents, but much more soluble in non-polar solvents such as hexane.

A polar covalent bond is a covalent bond with a significant ionic character. This means that the two shared electrons are closer to one of the atoms than the other, creating an imbalance of charge. Such bonds occur between two atoms with moderately different electronegativities and give rise to dipole–dipole interactions. The electronegativity difference between the two atoms in these bonds is 0.3 to 1.7.

Single and multiple bonds

A single bond between two atoms corresponds to the sharing of one pair of electrons. The Hydrogen (H) atom has one valence electron. Two Hydrogen atoms can then form a molecule, held together by the shared pair of electrons. Each H atom now has the noble gas electron configuration of helium (He). The pair of shared electrons forms a single covalent bond. The electron density of these two bonding electrons in the region between the two atoms increases from the density of two non-interacting H atoms.

Two p-orbitals forming a pi-bond.

A double bond has two shared pairs of electrons, one in a sigma bond and one in a pi bond with electron density concentrated on two opposite sides of the internuclear axis. A triple bond consists of three shared electron pairs, forming one sigma and two pi bonds. An example is nitrogen. Quadruple and higher bonds are very rare and occur only between certain transition metal atoms.

Coordinate covalent bond (dipolar bond)

Adduct of ammonia and boron trifluoride

A coordinate covalent bond is a covalent bond in which the two shared bonding electrons are from the same one of the atoms involved in the bond. For example, boron trifluoride (BF₃) and ammonia (NH₃) form an adduct or coordination complex F₃B←NH₃ with a B–N bond in which a lone pair of electrons on N is shared with an empty atomic orbital on B. BF₃ with an empty orbital is described as an electron pair acceptor or Lewis acid, while NH₃ with a lone pair that can be shared is described as an electron-pair donor or Lewis base. The electrons are shared roughly equally between the atoms in contrast to ionic bonding. Such bonding is shown by an arrow pointing to the Lewis acid. (In the Figure, solid lines are bonds in the plane of the diagram, wedged bonds point towards the observer, and dashed bonds point away from the observer.)

Transition metal complexes are generally bound by coordinate covalent bonds. For example, the ion Ag⁺ reacts as a Lewis acid with two molecules of the Lewis base NH₃ to form the complex ion Ag(NH₃)₂⁺, which has two Ag←N coordinate covalent bonds.

Metallic bonding

Main article: Metallic bonding

In metallic bonding, bonding electrons are delocalized over a lattice of atoms. By contrast, in ionic compounds, the locations of the binding electrons and their charges are static. The free movement or delocalization of bonding electrons leads to classical metallic properties such as luster (surface light reflectivity), electrical and thermal conductivity, ductility, and high tensile strength.

Intermolecular bonding

Main article: Intermolecular force

There are several types of weak bonds that can be formed between two or more molecules which are not covalently bound. Intermolecular forces cause molecules to attract or repel each other. Often, these forces influence physical characteristics (such as the melting point) of a substance.

Van der Waals forces are interactions between closed-shell molecules. They include both Coulombic interactions between partial charges in polar molecules, and Pauli repulsions between closed electrons shells.

Keesom forces are the forces between the permanent dipoles of two polar molecules. London dispersion forces are the forces between induced dipoles of different molecules. There can also be an interaction between a permanent dipole in one molecule and an induced dipole in another molecule.

Hydrogen bonds of the form A--H•••B occur when A and B are two highly electronegative atoms (usually N, O or F) such that A forms a highly polar covalent bond with H so that H has a partial positive charge, and B has a lone pair of electrons which is attracted to this partial positive charge and forms a hydrogen bond. Hydrogen bonds are responsible for the high boiling points of water and ammonia with respect to their heavier analogues. In some cases a similar halogen bond can be formed by a halogen atom located between two electronegative atoms on different molecules.

At short distances, repulsive forces between atoms also become important.

Theories of chemical bonding

In the (unrealistic) limit of "pure" ionic bonding, electrons are perfectly localized on one of the two atoms in the bond. Such bonds can be understood by classical physics. The forces between the atoms are characterized by isotropic continuum electrostatic potentials. Their magnitude is in simple proportion to the charge difference.

Covalent bonds are better understood by valence bond (VB) theory or molecular orbital (MO) theory. The properties of the atoms involved can be understood using concepts such as oxidation number, formal charge, and electronegativity. The electron density within a bond is not assigned to individual atoms, but is instead delocalized between atoms. In valence bond theory, bonding is conceptualized as being built up from electron pairs that are localized and shared by two atoms via the overlap of atomic orbitals. The concepts of orbital hybridization and resonance augment this basic notion of the electron pair bond. In molecular orbital theory, bonding is viewed as being delocalized and apportioned in orbitals that extend throughout the molecule and are adapted to its symmetry properties, typically by considering linear combinations of atomic orbitals (LCAO). Valence bond theory is more chemically intuitive by being spatially localized, allowing attention to be focused on the parts of the molecule undergoing chemical change. In contrast, molecular orbitals are more "natural" from a quantum mechanical point of view, with orbital energies being physically significant and directly linked to experimental ionization energies from photoelectron spectroscopy. Consequently, valence bond theory and molecular orbital theory are often viewed as competing but complementary frameworks that offer different insights into chemical systems. As approaches for electronic structure theory, both MO and VB methods can give approximations to any desired level of accuracy, at least in principle. However, at lower levels, the approximations differ, and one approach may be better suited for computations involving a particular system or property than the other.

Unlike the spherically symmetrical Coulombic forces in pure ionic bonds, covalent bonds are generally directed and anisotropic. These are often classified based on their symmetry with respect to a molecular plane as sigma bonds and pi bonds. In the general case, atoms form bonds that are intermediate between ionic and covalent, depending on the relative electronegativity of the atoms involved. Bonds of this type are known as polar covalent bonds.

Pnictogen

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https://en.wikipedia.org/wiki/Pnictogen

↓ Period
2	Nitrogen (N) 7 Other nonmetal
3	Phosphorus (P) 15 Other nonmetal
4	Arsenic (As) 33 Metalloid
5	Antimony (Sb) 51 Metalloid
6	Bismuth (Bi) 83 Other metal
7	Moscovium (Mc) 115 other metal

A pnictogen (/ˈpnɪktədʒən/ or /ˈnɪktədʒən/; from Ancient Greek: πνῑ́γω "to choke" and -gen, "generator") is any of the chemical elements in group 15 of the periodic table. Group (V) is also known as the nitrogen group or nitrogen family. Group (V) consists of the elements nitrogen (N), phosphorus (P), arsenic (As), antimony (Sb), bismuth (Bi), and moscovium (Mc).

Since 1988, IUPAC calls it Group (V). Before that, in America it was called Group VA, owing to a text by H. C. Deming and the Sargent-Welch Scientific Company, while in Europe it was called Group VB and IUPAC recommended that in 1970. (Pronounced "group five A" and "group five B"; "V" is the Roman numeral 5). In semiconductor physics, it is still usually called Group V. The "five" ("V") in the historical names comes from the "pentavalency" of nitrogen, reflected by the stoichiometry of compounds such as N₂O₅. They have also been called the pentels.

Characteristics

Chemical

Like other groups, the members of this family show similar patterns in electron configuration, especially in the outermost shells, resulting in trends in chemical behavior.

Z	Element	Electrons per shell
7	nitrogen	2, 5
15	phosphorus	2, 8, 5
33	arsenic	2, 8, 18, 5
51	antimony	2, 8, 18, 18, 5
83	bismuth	2, 8, 18, 32, 18, 5
115	moscovium	2, 8, 18, 32, 32, 18, 5 (predicted)

This group has the defining characteristic that all the component elements have 5 electrons in their outermost shell, that is 2 electrons in the s subshell and 3 unpaired electrons in the p subshell. They are therefore 3 electrons short of filling their outermost electron shell in their non-ionized state. The Russell–Saunders term symbol of the ground state in all elements in the group is ⁴S_3⁄2.

The most important elements of this group to life on Earth are nitrogen (N), which in its diatomic form is the principal component of air, and phosphorus (P), which, like nitrogen, is essential to all known forms of life.

Compounds

Binary compounds of the group can be referred to collectively as pnictides. Pnictide compounds tend to have exotic properties such as being diamagnetic and paramagnetic at room temperature, being transparent, or generating electricity when heated. Other pnictides include the ternary rare-earth (RE) main-group variety of pnictides. These are in the form of RE_aM_bPn_c, where M is a carbon group or boron group element and Pn is any pnictogen except nitrogen. These compounds are between ionic and covalent compounds and thus have unusual bonding properties.

These elements are also noted for their stability in compounds due to their tendency to form covalent double bonds and triple bonds. This property of these elements leads to their potential toxicity, most evident in phosphorus, arsenic, and antimony. When these substances react with various chemicals of the body, they create strong free radicals that are not easily processed by the liver, where they accumulate. Paradoxically, this same strong bonding causes nitrogen's and bismuth's reduced toxicity (when in molecules), because these strong bonds with other atoms are difficult to split, creating very unreactive molecules. For example, N₂, the diatomic form of nitrogen, is used as an inert gas in situations where using argon or another noble gas would be too expensive.

Formation of multiple bonds is facilitated by their five valence electrons whereas the octet rule permits a pnictogen for accepting three electrons on covalent bonding. Because 5 > 3, it leaves unused two electrons in a lone pair unless there is a positive charge around (like in NH+4). When a pnictogen forms only three single bonds, effects of the lone pair typically result in trigonal pyramidal molecular geometry.

Oxidation states

The light pnictogens (nitrogen, phosphorus, and arsenic) tend to form −3 charges when reduced, completing their octet. When oxidized or ionized, pnictogens typically take an oxidation state of +3 (by losing all three p-shell electrons in the valence shell) or +5 (by losing all three p-shell and both s-shell electrons in the valence shell). However heavier pnictogens are more likely to form the +3 oxidation state than lighter ones due to the s-shell electrons becoming more stabilized.

−3 oxidation state

See also: nitride, phosphide, arsenide, antimonide, and bismuthide

Pnictogens can react with hydrogen to form pnictogen hydrides such as ammonia. Going down the group, to phosphane (phosphine), arsane (arsine), stibane (stibine), and finally bismuthane (bismuthine), each pnictogen hydride becomes progressively less stable (more unstable), more toxic, and has a smaller hydrogen-hydrogen angle (from 107.8° in ammonia to 90.48° in bismuthane). (Also, technically, only ammonia and phosphane have the pnictogen in the −3 oxidation state because, for the rest, the pnictogen is less electronegative than hydrogen.)

Crystal solids featuring pnictogens fully reduced include yttrium nitride, calcium phosphide, sodium arsenide, indium antimonide, and even double salts like aluminum gallium indium phosphide. These include III-V semiconductors, including gallium arsenide, the second-most widely-used semiconductor after silicon.

+3 oxidation state

See also: nitrite, phosphite, arsenite, antimonite, and bismuthite

Nitrogen forms a limited number of stable III compounds. Nitrogen(III) oxide can only be isolated at low temperatures, and nitrous acid is unstable. Nitrogen trifluoride is the only stable nitrogen trihalide, with nitrogen trichloride, nitrogen tribromide, and nitrogen triiodide being explosive—nitrogen triiodide being so shock-sensitive that the touch of a feather detonates it (the last three actually feature nitrogen in the -3 oxidation state). Phosphorus forms a +III oxide which is stable at room temperature, phosphorous acid, and several trihalides, although the triiodide is unstable. Arsenic forms +III compounds with oxygen as arsenites, arsenous acid, and arsenic(III) oxide, and it forms all four trihalides. Antimony forms antimony(III) oxide and antimonite but not oxyacids. Its trihalides, antimony trifluoride, antimony trichloride, antimony tribromide, and antimony triiodide, like all pnictogen trihalides, each have trigonal pyramidal molecular geometry.

The +3 oxidation state is bismuth's most common oxidation state because its ability to form the +5 oxidation state is hindered by relativistic properties on heavier elements, effects that are even more pronounced concerning moscovium. Bismuth(III) forms an oxide, an oxychloride, an oxynitrate, and a sulfide. Moscovium(III) is predicted to behave similarly to bismuth(III). Moscovium is predicted to form all four trihalides, of which all but the trifluoride are predicted to be soluble in water. It is also predicted to form an oxychloride and oxybromide in the +III oxidation state.

+5 oxidation state

See also: nitrate, phosphate, arsenate, antimonate, and bismuthate

For nitrogen, the +5 state is typically serves as only a formal explanation of molecules like N₂O₅, as the high electronegativity of nitrogen causes the electrons to be shared almost evenly. Pnictogen compounds with coordination number 5 are hypervalent. Nitrogen(V) fluoride is only theoretical and has not been synthesized. The "true" +5 state is more common for the essentially non-relativistic typical pnictogens phosphorus, arsenic, and antimony, as shown in their oxides, phosphorus(V) oxide, arsenic(V) oxide, and antimony(V) oxide, and their fluorides, phosphorus(V) fluoride, arsenic(V) fluoride, antimony(V) fluoride. At least two also form related fluoride-anions, hexafluorophosphate and hexafluoroantimonate, that function as non-coordinating anions. Phosphorus even forms mixed oxide-halides, known as oxyhalides, like phosphorus oxychloride, and mixed pentahalides, like phosphorus trifluorodichloride. Pentamethylpnictogen(V) compounds exist for arsenic, antimony, and bismuth. However, for bismuth, the +5 oxidation state becomes rare due to the relativistic stabilization of the 6s orbitals known as the inert-pair effect, so that the 6s electrons are reluctant to bond chemically. This causes bismuth(V) oxide to be unstable and bismuth(V) fluoride to be more reactive than the other pnictogen pentafluorides, making it an extremely powerful fluorinating agent. This effect is even more pronounced for moscovium, prohibiting it from attaining a +5 oxidation state.

Other oxidation states

• Nitrogen forms a variety of compounds with oxygen in which the nitrogen can take on a variety of oxidation states, including +II, +IV, and even some mixed-valence compounds and very unstable +VI oxidation state.
• In hydrazine, diphosphane, and organic derivatives of the two, the nitrogen or phosphorus atoms have the −2 oxidation state. Likewise, diimide, which has two nitrogen atoms double-bonded to each other, and its organic derivatives have nitrogen in the oxidation state of −1.
  • Similarly, realgar has arsenic–arsenic bonds, so the arsenic's oxidation state is +II.
  • A corresponding compound for antimony is Sb₂(C₆H₅)₄, where the antimony's oxidation state is +II.
• Phosphorus has the +1 oxidation state in hypophosphorous acid and the +4 oxidation state in hypophosphoric acid.
• Antimony tetroxide is a mixed-valence compound, where half of the antimony atoms are in the +3 oxidation state, and the other half are in the +5 oxidation state.
• It is expected that moscovium will have an inert-pair effect for both the 7s and the 7p_1/2 electrons, as the binding energy of the lone 7p_3/2 electron is noticeably lower than that of the 7p_1/2 electrons. This is predicted to cause +I to be a common oxidation state for moscovium, although it also occurs to a lesser extent for bismuth and nitrogen.

Physical

The pnictogens consist of two non-metals (one gas, one solid), two metalloids, one metal, and one element with unknown chemical properties. All the elements in the group are solids at room temperature, except for nitrogen which is gaseous at room temperature. Nitrogen and bismuth, despite both being pnictogens, are very different in their physical properties. For instance, at STP nitrogen is a transparent non-metallic gas, while bismuth is a silvery-white metal.

The densities of the pnictogens increase towards the heavier pnictogens. Nitrogen's density is 0.001251 g/cm³ at STP. Phosphorus's density is 1.82 g/cm³ at STP, arsenic's is 5.72 g/cm³, antimony's is 6.68 g/cm³, and bismuth's is 9.79 g/cm³.

Nitrogen's melting point is −210 °C and its boiling point is −196 °C. Phosphorus has a melting point of 44 °C and a boiling point of 280 °C. Arsenic is one of only two elements to sublimate at standard pressure; it does this at 603 °C. Antimony's melting point is 631 °C and its boiling point is 1587 °C. Bismuth's melting point is 271 °C and its boiling point is 1564 °C.

Nitrogen's crystal structure is hexagonal. Phosphorus's crystal structure is cubic. Arsenic, antimony, and bismuth all have rhombohedral crystal structures.

History

The nitrogen compound sal ammoniac (ammonium chloride) has been known since the time of the Ancient Egyptians. In the 1760s two scientists, Henry Cavendish and Joseph Priestley, isolated nitrogen from air, but neither realized the presence of an undiscovered element. It was not until several years later, in 1772, that Daniel Rutherford realized that the gas was indeed nitrogen.

The alchemist Hennig Brandt first discovered phosphorus in Hamburg in 1669. Brandt produced the element by heating evaporated urine and condensing the resulting phosphorus vapor in water. Brandt initially thought that he had discovered the Philosopher's Stone, but eventually realized that this was not the case.

Arsenic compounds have been known for at least 5000 years, and the ancient Greek Theophrastus recognized the arsenic minerals called realgar and orpiment. Elemental arsenic was discovered in the 13th century by Albertus Magnus.

Antimony was well known to the ancients. A 5000-year-old vase made of nearly pure antimony exists in the Louvre. Antimony compounds were used in dyes in the Babylonian times. The antimony mineral stibnite may have been a component of Greek fire.

Bismuth was first discovered by an alchemist in 1400. Within 80 years of bismuth's discovery, it had applications in printing and decorated caskets. The Incas were also using bismuth in knives by 1500. Bismuth was originally thought to be the same as lead, but in 1753, Claude François Geoffroy proved that bismuth was different from lead.

Moscovium was successfully produced in 2003 by bombarding americium-243 atoms with calcium-48 atoms.

Names and etymology

The term "pnictogen" (or "pnigogen") is derived from the ancient Greek word πνίγειν (pnígein) meaning "to choke", referring to the choking or stifling property of nitrogen gas. It can also be used as a mnemonic for the two most common members, P and N. The term "pnictogen" was suggested by the Dutch chemist Anton Eduard van Arkel in the early 1950s. It is also spelled "pnicogen" or "pnigogen". The term "pnicogen" is rarer than the term "pnictogen", and the ratio of academic research papers using "pnictogen" to those using "pnicogen" is 2.5 to 1. It comes from the Greek root πνιγ- (choke, strangle), and thus the word "pnictogen" is also a reference to the Dutch and German names for nitrogen (stikstof and Stickstoff, respectively, "suffocating substance": i.e., substance in air, unsupportive of breathing). Hence, "pnictogen" could be translated as "suffocation maker". The word "pnictide" also comes from the same root.

The name pentels (from Greek πέντε, pénte, five) also at one time stood for this group.

Occurrence

A collection of pnictogen samples

Nitrogen makes up 25 parts per million of the Earth's crust, 5 parts per million of soil on average, 100 to 500 parts per trillion of seawater, and 78% of dry air. The majority of nitrogen on earth is in the form of nitrogen gas, but some nitrate minerals do exist. Nitrogen makes up 2.5% of a typical human by weight.

Phosphorus makes up 0.1% of the earth's crust, making it the 11th most abundant element there. Phosphorus makes up 0.65 parts per million of soil, and 15 to 60 parts per billion of seawater. There are 200 Mt of accessible phosphates on earth. Phosphorus makes up 1.1% of a typical human by weight. Phosphorus occurs in minerals of the apatite family which are the main components of the phosphate rocks.

Arsenic makes up 1.5 parts per million of the earth's crust, making it the 53rd most abundant element there. The soils contain 1 to 10 parts per million of arsenic, and seawater contains 1.6 parts per billion of arsenic. Arsenic makes up 100 parts per billion of a typical human by weight. Some arsenic exists in elemental form, but most arsenic is found in the arsenic minerals orpiment, realgar, arsenopyrite, and enargite.

Antimony makes up 0.2 parts per million of the earth's crust, making it the 63rd most abundant element there. The soils contain 1 part per million of antimony on average, and seawater contains 300 parts per trillion of antimony on average. A typical human contains 28 parts per billion of antimony by weight. Some elemental antimony occurs in silver deposits.

Bismuth makes up 48 parts per billion of the earth's crust, making it the 70th most abundant element there. The soils contain approximately 0.25 parts per million of bismuth, and seawater contains 400 parts per trillion of bismuth. Bismuth most commonly occurs as the mineral bismuthinite, but bismuth also occurs in elemental form or in sulfide ores.

Moscovium is produced several atoms at a time in particle accelerators.

Production

Nitrogen

Nitrogen can be produced by fractional distillation of air.

Phosphorus

The principal method for producing phosphorus is to reduce phosphates with carbon in an electric arc furnace.

Arsenic

Most arsenic is prepared by heating the mineral arsenopyrite in the presence of air. This forms As₄O₆, from which arsenic can be extracted via carbon reduction. However, it is also possible to make metallic arsenic by heating arsenopyrite at 650 to 700 °C without oxygen.

Antimony

With sulfide ores, the method by which antimony is produced depends on the amount of antimony in the raw ore. If the ore contains 25% to 45% antimony by weight, then crude antimony is produced by smelting the ore in a blast furnace. If the ore contains 45% to 60% antimony by weight, antimony is obtained by heating the ore, also known as liquidation. Ores with more than 60% antimony by weight are chemically displaced with iron shavings from the molten ore, resulting in impure metal.

If an oxide ore of antimony contains less than 30% antimony by weight, the ore is reduced in a blast furnace. If the ore contains closer to 50% antimony by weight, the ore is instead reduced in a reverberatory furnace.

Antimony ores with mixed sulfides and oxides are smelted in a blast furnace.

Bismuth

Bismuth minerals do occur, in particular in the form of sulfides and oxides, but it is more economic to produce bismuth as a by-product of the smelting of lead ores or, as in China, of tungsten and zinc ores.

Moscovium

Moscovium is produced a few atoms at a time in particle accelerators by firing a beam of Calcium-48 ions at Americium until the nuclei fuse.

Applications

• Liquid nitrogen is a commonly used cryogenic liquid.
• Nitrogen in the form of ammonia is a nutrient critical to most plants' survival. Synthesis of ammonia accounts for about 1–2% of the world's energy consumption and the majority of reduced nitrogen in food.
• Phosphorus is used in matches and incendiary bombs.
• Phosphate fertilizer helps feed much of the world.
• Arsenic was historically used as a Paris green pigment, but is not used this way anymore due to its extreme toxicity.
• Arsenic in the form of organoarsenic compounds is sometimes used in chicken feed.
• Antimony is alloyed with lead to produce some bullets.
• Antimony currency was briefly used in the 1930s in parts of China, but this use was discontinued as antimony is both soft and toxic.
• Bismuth subsalicylate is the active ingredient in Pepto-Bismol.
• Bismuth chalcogenides are being studied in cancerous mice as a candidate for use in improving radiation therapy in human cancer patients.
• Moscovium doesn't have a use due to it not being able to be seen in macroscopic quantities, and because of its high radioactivity.

Biological role

Nitrogen is a component of molecules critical to life on earth, such as DNA and amino acids. Nitrates occur in some plants, due to bacteria present in the nodes of the plant. This is seen in leguminous plants such as peas or spinach and lettuce. A typical 70 kg human contains 1.8 kg of nitrogen.

Phosphorus in the form of phosphates occur in compounds important to life, such as DNA and ATP. Humans consume approximately 1 g of phosphorus per day. Phosphorus is found in foods such as fish, liver, turkey, chicken, and eggs. Phosphate deficiency is a problem known as hypophosphatemia. A typical 70 kg human contains 480 g of phosphorus.

Arsenic promotes growth in chickens and rats, and may be essential for humans in small quantities. Arsenic has been shown to be helpful in metabolizing the amino acid arginine. There are 7 mg of arsenic in a typical 70 kg human.

Antimony is not known to have a biological role. Plants take up only trace amounts of antimony. There are approximately 2 mg of antimony in a typical 70 kg human.

Bismuth is not known to have a biological role. Humans ingest on average less than 20 μg of bismuth per day. There is less than 500 μg of bismuth in a typical 70 kg human.

Toxicity

Nitrogen gas is completely non-toxic, but breathing in pure nitrogen gas is deadly, because it causes nitrogen asphyxiation. The build-up of nitrogen bubbles in the blood, such as those that may occur during scuba diving, can cause a condition known as the "bends" (decompression sickness). Many nitrogen compounds such as hydrogen cyanide and nitrogen-based explosives are also highly dangerous.

White phosphorus, an allotrope of phosphorus, is toxic, with 1 mg per kg bodyweight being a lethal dose. White phosphorus usually kills humans within a week of ingestion by attacking the liver. Breathing in phosphorus in its gaseous form can cause an industrial disease called "phossy jaw", which eats away the jawbone. White phosphorus is also highly flammable. Some organophosphorus compounds can fatally block certain enzymes in the human body.

Elemental arsenic is toxic, as are many of its inorganic compounds; however some of its organic compounds can promote growth in chickens. The lethal dose of arsenic for a typical adult is 200 mg and can cause diarrhea, vomiting, colic, dehydration, and coma. Death from arsenic poisoning typically occurs within a day.

Antimony is mildly toxic. Additionally, wine steeped in antimony containers can induce vomiting. When taken in large doses, antimony causes vomiting in a victim, who then appears to recover before dying several days later. Antimony attaches itself to certain enzymes and is difficult to dislodge. Stibine, or SbH₃, is far more toxic than pure antimony.

Bismuth itself is largely non-toxic, although consuming too much of it can damage the liver. Only one person has ever been reported to have died from bismuth poisoning. However, consumption of soluble bismuth salts can turn a person's gums black.

Moscovium is too unstable to conduct any toxicity chemistry.

Phase (matter)

From Wikipedia, the free encyclopedia
https://en.wikipedia.org/wiki/Phase_(matter)

In the physical sciences, a phase is a region of material that is chemically uniform, physically distinct, and (often) mechanically separable. In a system consisting of ice and water in a glass jar, the ice cubes are one phase, the water is a second phase, and the humid air is a third phase over the ice and water. The glass of the jar is another separate phase. (See state of matter § Glass.)

More precisely, a phase is a region of space (a thermodynamic system), throughout which all physical properties of a material are essentially uniform. Examples of physical properties include density, index of refraction, magnetization and chemical composition.

The term phase is sometimes used as a synonym for state of matter, but there can be several immiscible phases of the same state of matter (as where oil and water separate into distinct phases, both in the liquid state). It is also sometimes used to refer to the equilibrium states shown on a phase diagram, described in terms of state variables such as pressure and temperature and demarcated by phase boundaries. (Phase boundaries relate to changes in the organization of matter, including for example a subtle change within the solid state from one crystal structure to another, as well as state-changes such as between solid and liquid.) These two usages are not commensurate with the formal definition given above and the intended meaning must be determined in part from the context in which the term is used.

A small piece of rapidly melting argon ice shows the transition from solid to liquid.

Types of phases

Iron-carbon phase diagram, showing the conditions necessary to form different phases

Distinct phases may be described as different states of matter such as gas, liquid, solid, plasma or Bose–Einstein condensate. Useful mesophases between solid and liquid form other states of matter.

Distinct phases may also exist within a given state of matter. As shown in the diagram for iron alloys, several phases exist for both the solid and liquid states. Phases may also be differentiated based on solubility as in polar (hydrophilic) or non-polar (hydrophobic). A mixture of water (a polar liquid) and oil (a non-polar liquid) will spontaneously separate into two phases. Water has a very low solubility (is insoluble) in oil, and oil has a low solubility in water. Solubility is the maximum amount of a solute that can dissolve in a solvent before the solute ceases to dissolve and remains in a separate phase. A mixture can separate into more than two liquid phases and the concept of phase separation extends to solids, i.e., solids can form solid solutions or crystallize into distinct crystal phases. Metal pairs that are mutually soluble can form alloys, whereas metal pairs that are mutually insoluble cannot.

As many as eight immiscible liquid phases have been observed. Mutually immiscible liquid phases are formed from water (aqueous phase), hydrophobic organic solvents, perfluorocarbons (fluorous phase), silicones, several different metals, and also from molten phosphorus. Not all organic solvents are completely miscible, e.g. a mixture of ethylene glycol and toluene may separate into two distinct organic phases.

Phases do not need to macroscopically separate spontaneously. Emulsions and colloids are examples of immiscible phase pair combinations that do not physically separate.

Phase equilibrium

Left to equilibration, many compositions will form a uniform single phase, but depending on the temperature and pressure even a single substance may separate into two or more distinct phases. Within each phase, the properties are uniform but between the two phases properties differ.

Water in a closed jar with an air space over it forms a two-phase system. Most of the water is in the liquid phase, where it is held by the mutual attraction of water molecules. Even at equilibrium molecules are constantly in motion and, once in a while, a molecule in the liquid phase gains enough kinetic energy to break away from the liquid phase and enter the gas phase. Likewise, every once in a while a vapor molecule collides with the liquid surface and condenses into the liquid. At equilibrium, evaporation and condensation processes exactly balance and there is no net change in the volume of either phase.

At room temperature and pressure, the water jar reaches equilibrium when the air over the water has a humidity of about 3%. This percentage increases as the temperature goes up. At 100 °C and atmospheric pressure, equilibrium is not reached until the air is 100% water. If the liquid is heated a little over 100 °C, the transition from liquid to gas will occur not only at the surface but throughout the liquid volume: the water boils.

Number of phases

See also: Multiphasic liquid

A typical phase diagram for a single-component material, exhibiting solid, liquid and gaseous phases. The solid green line shows the usual shape of the liquid–solid phase line. The dotted green line shows the anomalous behavior of water when the pressure increases. The triple point and the critical point are shown as red dots.

For a given composition, only certain phases are possible at a given temperature and pressure. The number and type of phases that will form is hard to predict and is usually determined by experiment. The results of such experiments can be plotted in phase diagrams.

The phase diagram shown here is for a single component system. In this simple system, phases that are possible, depend only on pressure and temperature. The markings show points where two or more phases can co-exist in equilibrium. At temperatures and pressures away from the markings, there will be only one phase at equilibrium.

In the diagram, the blue line marking the boundary between liquid and gas does not continue indefinitely, but terminates at a point called the critical point. As the temperature and pressure approach the critical point, the properties of the liquid and gas become progressively more similar. At the critical point, the liquid and gas become indistinguishable. Above the critical point, there are no longer separate liquid and gas phases: there is only a generic fluid phase referred to as a supercritical fluid. In water, the critical point occurs at around 647 K (374 °C or 705 °F) and 22.064 MPa.

An unusual feature of the water phase diagram is that the solid–liquid phase line (illustrated by the dotted green line) has a negative slope. For most substances, the slope is positive as exemplified by the dark green line. This unusual feature of water is related to ice having a lower density than liquid water. Increasing the pressure drives the water into the higher density phase, which causes melting.

Another interesting though not unusual feature of the phase diagram is the point where the solid–liquid phase line meets the liquid–gas phase line. The intersection is referred to as the triple point. At the triple point, all three phases can coexist.

Experimentally, phase lines are relatively easy to map due to the interdependence of temperature and pressure that develops when multiple phases form. Gibbs' phase rule suggests that different phase are completely determined by these variables. Consider a test apparatus consisting of a closed and well insulated cylinder equipped with a piston. By controlling the temperature and the pressure, the system can be brought to any point on the phase diagram. From a point in the solid stability region (left side of diagram), increasing the temperature of the system would bring it into the region where a liquid or a gas is the equilibrium phase (depending on the pressure). If the piston is slowly lowered, the system will trace a curve of increasing temperature and pressure within the gas region of the phase diagram. At the point where gas begins to condense to liquid, the direction of the temperature and pressure curve will abruptly change to trace along the phase line until all of the water has condensed.

Interfacial phenomena

Further information: Surface science

Between two phases in equilibrium there is a narrow region where the properties are not that of either phase. Although this region may be very thin, it can have significant and easily observable effects, such as causing a liquid to exhibit surface tension. In mixtures, some components may preferentially move toward the interface. In terms of modeling, describing, or understanding the behavior of a particular system, it may be efficacious to treat the interfacial region as a separate phase.

Crystal phases

A single material may have several distinct solid states capable of forming separate phases. Water is a well-known example of such a material. For example, water ice is ordinarily found in the hexagonal form ice I_h, but can also exist as the cubic ice I_c, the rhombohedral ice II, and many other forms. Polymorphism is the ability of a solid to exist in more than one crystal form. For pure chemical elements, polymorphism is known as allotropy. For example, diamond, graphite, and fullerenes are different allotropes of carbon.

Phase transitions

Main article: Phase transition

When a substance undergoes a phase transition (changes from one state of matter to another) it usually either takes up or releases energy. For example, when water evaporates, the increase in kinetic energy as the evaporating molecules escape the attractive forces of the liquid is reflected in a decrease in temperature. The energy required to induce the phase transition is taken from the internal thermal energy of the water, which cools the liquid to a lower temperature; hence evaporation is useful for cooling. See Enthalpy of vaporization. The reverse process, condensation, releases heat. The heat energy, or enthalpy, associated with a solid to liquid transition is the enthalpy of fusion and that associated with a solid to gas transition is the enthalpy of sublimation.

Phases out of equilibrium

While phases of matter are traditionally defined for systems in thermal equilibrium, work on quantum many-body localized (MBL) systems has provided a framework for defining phases out of equilibrium. MBL phases never reach thermal equilibrium, and can allow for new forms of order disallowed in equilibrium via a phenomenon known as localization protected quantum order. The transitions between different MBL phases and between MBL and thermalizing phases are novel dynamical phase transitions whose properties are active areas of research.