Bonding in solids

Last updated

Solids can be classified according to the nature of the bonding between their atomic or molecular components. The traditional classification distinguishes four kinds of bonding: [1]

Contents

Typical members of these classes have distinctive electron distributions, [2] thermodynamic, electronic, and mechanical properties. In particular, the binding energies of these interactions vary widely. Bonding in solids can be of mixed or intermediate kinds, however, hence not all solids have the typical properties of a particular class, and some can be described as intermediate forms. Paper

Basic classes of solids

Network covalent solids

A network covalent solid consists of atoms held together by a network of covalent bonds (pairs of electrons shared between atoms of similar electronegativity), and hence can be regarded as a single, large molecule. The classic example is diamond; other examples include silicon, [3] quartz and graphite.

Properties

Their strength, stiffness, and high melting points are consequences of the strength and stiffness of the covalent bonds that hold them together. They are also characteristically brittle because the directional nature of covalent bonds strongly resists the shearing motions associated with plastic flow, and are, in effect, broken when shear occurs. This property results in brittleness for reasons studied in the field of fracture mechanics. Network covalent solids vary from insulating to semiconducting in their behavior, depending on the band gap of the material.

Ionic solids

A standard ionic solid consists of atoms held together by ionic bonds, that is by the electrostatic attraction of opposite charges (the result of transferring electrons from atoms with lower electronegativity to atoms with higher electronegativity). Among the ionic solids are compounds formed by alkali and alkaline earth metals in combination with halogens; a classic example is table salt, sodium chloride.

Ionic solids are typically of intermediate strength and extremely brittle. Melting points are typically moderately high, but some combinations of molecular cations and anions yield an ionic liquid with a freezing point below room temperature. Vapour pressures in all instances are extraordinarily low; this is a consequence of the large energy required to move a bare charge (or charge pair) from an ionic medium into free space.

Metallic solids

Metallic solids are held together by a high density of shared, delocalized electrons, resulting in metallic bonding. Classic examples are metals such as copper and aluminum, but some materials are metals in an electronic sense but have negligible metallic bonding in a mechanical or thermodynamic sense (see intermediate forms). Metallic solids have, by definition, no band gap at the Fermi level and hence are conducting.

Solids with purely metallic bonding are characteristically ductile and, in their pure forms, have low strength; melting points can[ inconsistent ] be very low (e.g., Mercury melts at 234 K (−39 °C). These properties are consequences of the non-directional and non-polar nature of metallic bonding, which allows atoms (and planes of atoms in a crystal lattice) to move past one another without disrupting their bonding interactions. Metals can be strengthened by introducing crystal defects (for example, by alloying) that interfere with the motion of dislocations that mediate plastic deformation. Further, some transition metals exhibit directional bonding in addition to metallic bonding; this increases shear strength and reduces ductility, imparting some of the characteristics of a covalent solid (an intermediate case below).

Solids of intermediate kinds

The four classes of solids permit six pairwise intermediate forms:

Ionic to network covalent

Covalent and ionic bonding form a continuum, with ionic character increasing with increasing difference in the electronegativity of the participating atoms. Covalent bonding corresponds to sharing of a pair of electrons between two atoms of essentially equal electronegativity (for example, C–C and C–H bonds in aliphatic hydrocarbons). As bonds become more polar, they become increasingly ionic in character. Metal oxides vary along the iono-covalent spectrum. [4] The Si–O bonds in quartz, for example, are polar yet largely covalent, and are considered to be of mixed character. [5]

Metallic to network covalent

What is in most respects a purely covalent structure can support metallic delocalization of electrons; metallic carbon nanotubes are one example. Transition metals and intermetallic compounds based on transition metals can exhibit mixed metallic and covalent bonding, [6] resulting in high shear strength, low ductility, and elevated melting points; a classic example is tungsten.

Molecular to network covalent

Materials can be intermediate between molecular and network covalent solids either because of the intermediate organization of their covalent bonds, or because the bonds themselves are of an intermediate kind.

Intermediate organization of covalent bonds:

Regarding the organization of covalent bonds, recall that classic molecular solids, as stated above, consist of small, non-polar covalent molecules. The example given, paraffin wax, is a member of a family of hydrocarbon molecules of differing chain lengths, with high-density polyethylene at the long-chain end of the series. High-density polyethylene can be a strong material: when the hydrocarbon chains are well aligned, the resulting fibers rival the strength of steel. The covalent bonds in this material form extended structures, but do not form a continuous network. With cross-linking, however, polymer networks can become continuous, and a series of materials spans the range from Cross-linked polyethylene, to rigid thermosetting resins, to hydrogen-rich amorphous solids, to vitreous carbon, diamond-like carbons, and ultimately to diamond itself. As this example shows, there can be no sharp boundary between molecular and network covalent solids.

Intermediate kinds of bonding:

A solid with extensive hydrogen bonding will be considered a molecular solid, yet strong hydrogen bonds can have a significant degree of covalent character. As noted above, covalent and ionic bonds form a continuum between shared and transferred electrons; covalent and weak bonds form a continuum between shared and unshared electrons. In addition, molecules can be polar, or have polar groups, and the resulting regions of positive and negative charge can interact to produce electrostatic bonding resembling that in ionic solids.

Molecular to ionic

A large molecule with an ionized group is technically an ion, but its behavior may be largely the result of non-ionic interactions. For example, sodium stearate (the main constituent of traditional soaps) consists entirely of ions, yet it is a soft material quite unlike a typical ionic solid. There is a continuum between ionic solids and molecular solids with little ionic character in their bonding.

Metallic to molecular

Metallic solids are bound by a high density of shared, delocalized electrons. Although weakly bound molecular components are incompatible with strong metallic bonding, low densities of shared, delocalized electrons can impart varying degrees of metallic bonding and conductivity overlaid on discrete, covalently bonded molecular units, especially in reduced-dimensional systems. Examples include charge transfer complexes.

Metallic to ionic

The charged components that make up ionic solids cannot exist in the high-density sea of delocalized electrons characteristic of strong metallic bonding. Some molecular salts, however, feature both ionic bonding among molecules and substantial one-dimensional conductivity, indicating a degree of metallic bonding among structural components along the axis of conductivity. Examples include tetrathiafulvalene salts.

See also

Related Research Articles

<span class="mw-page-title-main">Chemical bond</span> Lasting attraction between atoms that enables the formation of chemical compounds

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.

<span class="mw-page-title-main">Covalent bond</span> Chemical bond that involves the sharing of electron pairs between atoms

A covalent bond is a chemical bond that involves the sharing of electrons to form electron pairs between atoms. These electron pairs are known as shared pairs or bonding pairs. The stable balance of attractive and repulsive forces between atoms, when they share electrons, is known as covalent bonding. For many molecules, the sharing of electrons allows each atom to attain the equivalent of a full valence shell, corresponding to a stable electronic configuration. In organic chemistry, covalent bonding is much more common than ionic bonding.

Electronegativity, symbolized as χ, is the tendency for an atom of a given chemical element to attract shared electrons when forming a chemical bond. An atom's electronegativity is affected by both its atomic number and the distance at which its valence electrons reside from the charged nucleus. The higher the associated electronegativity, the more an atom or a substituent group attracts electrons. Electronegativity serves as a simple way to quantitatively estimate the bond energy, and the sign and magnitude of a bond's chemical polarity, which characterizes a bond along the continuous scale from covalent to ionic bonding. The loosely defined term electropositivity is the opposite of electronegativity: it characterizes an element's tendency to donate valence electrons.

<span class="mw-page-title-main">Hydrogen bond</span> Intermolecular attraction between a hydrogen-donor pair and an acceptor

In chemistry, a hydrogen bond is primarily an electrostatic force of attraction between a hydrogen (H) atom which is covalently bonded to a more electronegative "donor" atom or group (Dn), and another electronegative atom bearing a lone pair of electrons—the hydrogen bond acceptor (Ac). Such an interacting system is generally denoted Dn−H···Ac, where the solid line denotes a polar covalent bond, and the dotted or dashed line indicates the hydrogen bond. The most frequent donor and acceptor atoms are the period 2 elements nitrogen (N), oxygen (O), and fluorine (F).

<span class="mw-page-title-main">Ionic bonding</span> Chemical bonding involving attraction between ions

Ionic bonding is a type of chemical bonding that involves the electrostatic attraction between oppositely charged ions, or between two atoms with sharply different electronegativities, and is the primary interaction occurring in ionic compounds. It is one of the main types of bonding, along with covalent bonding and metallic bonding. Ions are atoms with an electrostatic charge. Atoms that gain electrons make negatively charged ions. Atoms that lose electrons make positively charged ions. This transfer of electrons is known as electrovalence in contrast to covalence. In the simplest case, the cation is a metal atom and the anion is a nonmetal atom, but these ions can be more complex, e.g. molecular ions like NH+
4
or SO2−
4
. In simpler words, an ionic bond results from the transfer of electrons from a metal to a non-metal to obtain a full valence shell for both atoms.

An intermolecular force (IMF) is the force that mediates interaction between molecules, including the electromagnetic forces of attraction or repulsion which act between atoms and other types of neighbouring particles, e.g. atoms or ions. Intermolecular forces are weak relative to intramolecular forces – the forces which hold a molecule together. For example, the covalent bond, involving sharing electron pairs between atoms, is much stronger than the forces present between neighboring molecules. Both sets of forces are essential parts of force fields frequently used in molecular mechanics.

<span class="mw-page-title-main">Metallic bonding</span> Type of chemical bond in metals

Metallic bonding is a type of chemical bonding that arises from the electrostatic attractive force between conduction electrons and positively charged metal ions. It may be described as the sharing of free electrons among a structure of positively charged ions (cations). Metallic bonding accounts for many physical properties of metals, such as strength, ductility, thermal and electrical resistivity and conductivity, opacity, and lustre.

<span class="mw-page-title-main">Chemical polarity</span> Separation of electric charge in a molecule

In chemistry, polarity is a separation of electric charge leading to a molecule or its chemical groups having an electric dipole moment, with a negatively charged end and a positively charged end.

<span class="mw-page-title-main">Delocalized electron</span> Electrons that are not associated with a single atom or covalent bond

In chemistry, delocalized electrons are electrons in a molecule, ion or solid metal that are not associated with a single atom or a covalent bond.

<span class="mw-page-title-main">Van Arkel–Ketelaar triangle</span> A triangle showing varying degrees of ionic, metallic and covalent bonding

Bond triangles or Van Arkel–Ketelaar triangles are triangles used for showing different compounds in varying degrees of ionic, metallic and covalent bonding.

In chemistry, a non-covalent interaction differs from a covalent bond in that it does not involve the sharing of electrons, but rather involves more dispersed variations of electromagnetic interactions between molecules or within a molecule. The chemical energy released in the formation of non-covalent interactions is typically on the order of 1–5 kcal/mol. Non-covalent interactions can be classified into different categories, such as electrostatic, π-effects, van der Waals forces, and hydrophobic effects.

An intramolecular force is any force that binds together the atoms making up a molecule or compound, not to be confused with intermolecular forces, which are the forces present between molecules. The subtle difference in the name comes from the Latin roots of English with inter meaning between or among and intra meaning inside. Chemical bonds are considered to be intramolecular forces which are often stronger than intermolecular forces present between non-bonding atoms or molecules.

The covalent radius of fluorine is a measure of the size of a fluorine atom; it is approximated at about 60 picometres.

<span class="mw-page-title-main">Molecular solid</span> Solid consisting of discrete molecules

A molecular solid is a solid consisting of discrete molecules. The cohesive forces that bind the molecules together are van der Waals forces, dipole-dipole interactions, quadrupole interactions, π-π interactions, hydrogen bonding, halogen bonding, London dispersion forces, and in some molecular solids, coulombic interactions. Van der Waals, dipole interactions, quadrupole interactions, π-π interactions, hydrogen bonding, and halogen bonding are typically much weaker than the forces holding together other solids: metallic, ionic, and network solids. Intermolecular interactions, typically do not involve delocalized electrons, unlike metallic and certain covalent bonds. Exceptions are charge-transfer complexes such as the tetrathiafulvane-tetracyanoquinodimethane (TTF-TCNQ), a radical ion salt. These differences in the strength of force and electronic characteristics from other types of solids give rise to the unique mechanical, electronic, and thermal properties of molecular solids.

In chemistry, a Zintl phase is a product of a reaction between a group 1 or group 2 and main group metal or metalloid. It is characterized by intermediate metallic/ionic bonding. Zintl phases are a subgroup of brittle, high-melting intermetallic compounds that are diamagnetic or exhibit temperature-independent paramagnetism and are poor conductors or semiconductors.

This glossary of chemistry terms is a list of terms and definitions relevant to chemistry, including chemical laws, diagrams and formulae, laboratory tools, glassware, and equipment. Chemistry is a physical science concerned with the composition, structure, and properties of matter, as well as the changes it undergoes during chemical reactions; it features an extensive vocabulary and a significant amount of jargon.

<span class="mw-page-title-main">Chemical compound</span> Substance composed of multiple elements that are chemically bonded

A chemical compound is a chemical substance composed of many identical molecules containing atoms from more than one chemical element held together by chemical bonds. A molecule consisting of atoms of only one element is therefore not a compound. A compound can be transformed into a different substance by a chemical reaction, which may involve interactions with other substances. In this process, bonds between atoms may be broken and/or new bonds formed.

A network solid or covalent network solid is a chemical compound in which the atoms are bonded by covalent bonds in a continuous network extending throughout the material. In a network solid there are no individual molecules, and the entire crystal or amorphous solid may be considered a macromolecule. Formulas for network solids, like those for ionic compounds, are simple ratios of the component atoms represented by a formula unit.

In theoretical chemistry, the charge-shift bond is a proposed new class of chemical bonds that sits alongside the three familiar families of covalent, ionic, and metallic bonds where electrons are shared or transferred respectively. The charge shift bond derives its stability from the resonance of ionic forms rather than the covalent sharing of electrons which are often depicted as having electron density between the bonded atoms. A feature of the charge shift bond is that the predicted electron density between the bonded atoms is low. It has long been known from experiment that the accumulation of electric charge between the bonded atoms is not necessarily a feature of covalent bonds.

<span class="mw-page-title-main">Properties of nonmetals (and metalloids) by group</span>

Nonmetals show more variability in their properties than do metals. Metalloids are included here since they behave predominately as chemically weak nonmetals.

References

  1. Maksic, Zvonimir (1990). "The Concept of the Chemical Bond in Solids". Theoretical Models of Chemical Bonding. New York: Springer-Verlag. pp. 417–452. ISBN   0-387-51553-4.
  2. Mori-Sánchez, Paula; A. Martín Pendás; Víctor Luaña (2002). "A Classification of Covalent, Ionic, and Metallic Solids Based on the Electron Density". Journal of the American Chemical Society . American Chemical Society. 124 (49): 14721–14723. doi:10.1021/ja027708t. PMID   12465984.
  3. Properties of Period 3 Elements. youtube
  4. Lenglet, M. (2004). "Iono-Covalent Character of the Metal–Oxygen Bonds in Oxides: A Comparison of Experimental and Theoretical Data". Active and Passive Electronic Components. 27: 1–60. doi: 10.1080/0882751031000116142 .
  5. Belashchenko, D.K; Ostrovski, O.I (2001). "Molecular dynamics simulation of oxides with ionic–covalent bonds". Thermochimica Acta. 372 (1–2): 143–152. doi:10.1016/S0040-6031(01)00452-X.
  6. Nguyenmanh, D; Vitek, V; Horsfield, A (2007). "Environmental dependence of bonding: A challenge for modelling of intermetallics and fusion materials". Progress in Materials Science. 52 (2–3): 255. doi:10.1016/j.pmatsci.2006.10.010.