Ionic bonding

https://en.wikipedia.org/wiki/Ionic_bonding
From Wikipedia, the free encyclopedia
Jump to navigation Jump to search

Sodium and fluorine atoms undergoing a redox reaction to form sodium fluoride. Sodium loses
its outer electron to give it a stable electron configuration, and this electron enters the fluorine
atom exothermically. The oppositely charged ions – typically a great many of them – are then
attracted to each other to form a solid.

Ionic bonding is a type of chemical bonding that involves the electrostatic attraction between
oppositely charged ions, and is the primary interaction occurring in ionic compounds. It is one of Commented [M1]: definisi
the main bonds along with Covalent bond and Metallic bonding. Ions are atoms that have gained
one or more electrons (known as anions, which are negatively charged) and atoms that have lost
one or more electrons (known as cations, which are positively charged). 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 of a more complex nature,
e.g. molecular ions like NH+
2−
4 or SO

4. In simpler words, an ionic bond is the transfer of electrons from a metal to a non-metal in order

to obtain a full valence shell for both atoms.

It is important to recognize that clean ionic bonding – in which one atom or molecule completely
transfers an electron to another cannot exist: all ionic compounds have some degree of covalent
bonding, or electron sharing. Thus, the term "ionic bonding" is given when the ionic character is
greater than the covalent character – that is, a bond in which a large electronegativity difference
exists between the two atoms, causing the bonding to be more polar (ionic) than in covalent
bonding where electrons are shared more equally. Bonds with partially ionic and partially
covalent character are called polar covalent bonds.

Ionic compounds conduct electricity when molten or in solution, typically as a solid. Ionic
compounds generally have a high melting point, depending on the charge of the ions they consist
of. The higher the charges the stronger the cohesive forces and the higher the melting point. They
also tend to be soluble in water; the stronger the cohesive forces, the lower the solubility.
Overview
Atoms that have an almost full or almost empty valence shell tend to be very reactive. Atoms
that are strongly electronegative (as is the case with halogens) often have only one or two empty
orbitals in their valence shell, and frequently bond with other molecules or gain electrons to form
anions. Atoms that are weakly electronegative (such as alkali metals) have relatively few valence
electrons, which can easily be shared with atoms that are strongly electronegative. As a result,
weakly electronegative atoms tend to distort their electron cloud and form cations.

Formation
Ionic bonding can result from a redox reaction when atoms of an element (usually metal), whose
ionization energy is low, give some of their electrons to achieve a stable electron configuration.
In doing so, cations are formed. An atom of another element (usually nonmetal) with greater
electron affinity accepts the electron(s) to attain a stable electron configuration, and after
accepting electron(s) an atom becomes an anion. Typically, the stable electron configuration is
one of the noble gases for elements in the s-block and the p-block, and particular stable electron
configurations for d-block and f-block elements. The electrostatic attraction between the anions
and cations leads to the formation of a solid with a crystallographic lattice in which the ions are
stacked in an alternating fashion. In such a lattice, it is usually not possible to distinguish discrete
molecular units, so that the compounds formed are not molecular in nature. However, the ions
themselves can be complex and form molecular ions like the acetate anion or the ammonium
cation.

For example, common table salt is sodium chloride. When sodium (Na) and chlorine (Cl) are
combined, the sodium atoms each lose an electron, forming cations (Na+), and the chlorine atoms
each gain an electron to form anions (Cl−). These ions are then attracted to each other in a 1:1
ratio to form sodium chloride (NaCl).

Na + Cl → Na+ + Cl− → NaCl

However, to maintain charge neutrality, strict ratios between anions and cations are observed so
that ionic compounds, in general, obey the rules of stoichiometry despite not being molecular
compounds. For compounds that are transitional to the alloys and possess mixed ionic and
metallic bonding, this may not be the case anymore. Many sulfides, e.g., do form non-
stoichiometric compounds.

Many ionic compounds are referred to as salts as they can also be formed by the neutralization
reaction of an Arrhenius base like NaOH with an Arrhenius acid like HCl

NaOH + HCl → NaCl + H2O

The salt NaCl is then said to consist of the acid rest Cl− and the base rest Na+.
Representation of ionic bonding between lithium and fluorine to form lithium fluoride. Lithium
has a low ionization energy and readily gives up its lone valence electron to a fluorine atom,
which has a positive electron affinity and accepts the electron that was donated by the lithium
atom. The end-result is that lithium is isoelectronic with helium and fluorine is isoelectronic with
neon. Electrostatic interaction occurs between the two resulting ions, but typically aggregation is
not limited to two of them. Instead, aggregation into a whole lattice held together by ionic
bonding is the result.

The removal of electrons from the cation is endothermic, raising the system's overall energy.
There may also be energy changes associated with breaking of existing bonds or the addition of
more than one electron to form anions. However, the action of the anion's accepting the cation's
valence electrons and the subsequent attraction of the ions to each other releases (lattice) energy
and, thus, lowers the overall energy of the system.

Ionic bonding will occur only if the overall energy change for the reaction is favorable. In
general, the reaction is exothermic, but, e.g., the formation of mercuric oxide (HgO) is
endothermic. The charge of the resulting ions is a major factor in the strength of ionic bonding,
e.g. a salt C+A− is held together by electrostatic forces roughly four times weaker than C2+A2−
according to Coulombs law, where C and A represent a generic cation and anion respectively.
The sizes of the ions and the particular packing of the lattice are ignored in this rather simplistic
argument.

Commented [M2]: struktur

Structures
Main article: Ionic compound

Ionic compounds in the solid state form lattice structures. The two principal factors in
determining the form of the lattice are the relative charges of the ions and their relative sizes.
Some structures are adopted by a number of compounds; for example, the structure of the rock
salt sodium chloride is also adopted by many alkali halides, and binary oxides such as
magnesium oxide. Pauling's rules provide guidelines for predicting and rationalizing the crystal
structures of ionic crystals

Strength of the bonding

Main article: Lattice energy

For a solid crystalline ionic compound the enthalpy change in forming the solid from gaseous
ions is termed the lattice energy. The experimental value for the lattice energy can be determined
using the Born–Haber cycle. It can also be calculated (predicted) using the Born–Landé equation
as the sum of the electrostatic potential energy, calculated by summing interactions between
cations and anions, and a short-range repulsive potential energy term. The electrostatic potential
can be expressed in terms of the interionic separation and a constant (Madelung constant) that
takes account of the geometry of the crystal. The further away from the nucleus the weaker the
shield. The Born-Landé equation gives a reasonable fit to the lattice energy of, e.g., sodium
chloride, where the calculated (predicted) value is −756 kJ/mol, which compares to −787 kJ/mol
using the Born–Haber cycle.[1][2]

Polarization effects
Ions in crystal lattices of purely ionic compounds are spherical; however, if the positive ion is
small and/or highly charged, it will distort the electron cloud of the negative ion, an effect
summarised in Fajans' rules. This polarization of the negative ion leads to a build-up of extra
charge density between the two nuclei, that is, to partial covalency. Larger negative ions are
more easily polarized, but the effect is usually important only when positive ions with charges of
3+ (e.g., Al3+) are involved. However, 2+ ions (Be2+) or even 1+ (Li+) show some polarizing
power because their sizes are so small (e.g., LiI is ionic but has some covalent bonding present).
Note that this is not the ionic polarization effect that refers to displacement of ions in the lattice
due to the application of an electric field.

Comparison with covalent bonding

In ionic bonding, the atoms are bound by attraction of oppositely charged ions, whereas, in
covalent bonding, atoms are bound by sharing electrons to attain stable electron configurations.
In covalent bonding, the molecular geometry around each atom is determined by valence shell
electron pair repulsion VSEPR rules, whereas, in ionic materials, the geometry follows
maximum packing rules. One could say that covalent bonding is more directional in the sense
that the energy penalty for not adhering to the optimum bond angles is large, whereas ionic
bonding has no such penalty. There are no shared electron pairs to repel each other, the ions
should simply be packed as efficiently as possible. This often leads to much higher coordination
numbers. In NaCl, each ion has 6 bonds and all bond angles are 90°. In CsCl the coordination
number is 8. By comparison carbon typically has a maximum of four bonds.

Purely ionic bonding cannot exist, as the proximity of the entities involved in the bonding allows
some degree of sharing electron density between them. Therefore, all ionic bonding has some
covalent character. Thus, bonding is considered ionic where the ionic character is greater than
the covalent character. The larger the difference in electronegativity between the two types of
atoms involved in the bonding, the more ionic (polar) it is. Bonds with partially ionic and
partially covalent character are called polar covalent bonds. For example, Na–Cl and Mg–O
interactions have a few percent covalency, while Si–O bonds are usually ~50% ionic and ~50%
covalent. Pauling estimated that an electronegativity difference of 1.7 (on the Pauling scale)
corresponds to 50% ionic character, so that a difference greater than 1.7 corresponds to a bond
which is predominantly ionic.[3] Ionic character in covalent bonds can be directly measured for
atoms having quadrupolar nuclei (2H, 14N, 81,79Br, 35,37Cl or 127I). These nuclei are generally
objects of NQR nuclear quadrupole resonance and NMR nuclear magnetic resonance studies.
Interactions between the nuclear quadrupole moments Q and the electric field gradients (EFG)
are characterized via the nuclear quadrupole coupling constants

QCC = e2qzzQ/h

where the eqzz term corresponds to the principal component of the EFG tensor and e is the
elementary charge. In turn, the electric field gradient opens the way to description of bonding
modes in molecules when the QCC values are accurately determined by NMR or NQR methods.

In general, when ionic bonding occurs in the solid (or liquid) state, it is not possible to talk about
a single "ionic bond" between two individual atoms, because the cohesive forces that keep the
lattice together are of a more collective nature. This is quite different in the case of covalent
bonding, where we can often speak of a distinct bond localized between two particular atoms.
However, even if ionic bonding is combined with some covalency, the result is not necessarily
discrete bonds of a localized character. In such cases, the resulting bonding often requires
description in terms of a band structure consisting of gigantic molecular orbitals spanning the
entire crystal. Thus, the bonding in the solid often retains its collective rather than localized
nature. When the difference in electronegativity is decreased, the bonding may then lead to a
semiconductor, a semimetal or eventually a metallic conductor with metallic bonding.