TheInfoList

Electronegativity, symbolized as '' χ'', is the tendency for an
atom An atom is the smallest unit of ordinary matter In classical physics and general chemistry, matter is any substance that has mass and takes up space by having volume. All everyday objects that can be touched are ultimately composed of ato ...

of a given
chemical element Image:Simple Periodic Table Chart-blocks.svg, 400px, Periodic table, The periodic table of the chemical elements In chemistry, an element is a pure substance consisting only of atoms that all have the same numbers of protons in their atomic nu ...
to attract shared
electron The electron is a subatomic particle, symbol or , whose electric charge Electric charge is the physical property of matter that causes it to experience a force when placed in an electromagnetic field. There are two types of electric charge: ...
s (or
electron density In quantum chemistry, electron density or electronic density is the measure of the probability of an electron The electron is a subatomic particle, symbol or , whose electric charge Electric charge is the physical property of matter tha ...
) when forming a
chemical bond A chemical bond is a lasting attraction between atoms, ions or molecules that enables the formation of chemical compounds. The bond may result from the Coulomb's law, electrostatic force of attraction between oppositely charged ions as in ionic ...
. An atom's electronegativity is affected by both its
atomic number 300px, The Rutherford–Bohr model of the hydrogen atom () or a hydrogen-like ion (). In this model it is an essential feature that the photon energy (or frequency) of the electromagnetic radiation emitted (shown) when an electron jumps from one ...
and the distance at which its
valence electrons In chemistry Chemistry is the scientific discipline involved with Chemical element, elements and chemical compound, compounds composed of atoms, molecules and ions: their composition, structure, properties, behavior and the changes they under ...
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 In chemistry Chemistry is the scientific discipline involved with Chemical element, elements and chemical compound, compounds composed of atoms, molecules and ions: their composition, structure, properties, behavior and the changes they under ...
, and the sign and magnitude of a bond's chemical polarity, which characterizes a bond along the continuous scale from
covalent A covalent bond is a chemical bond A chemical bond is a lasting attraction between atoms, ions or molecules that enables the formation of chemical compounds. The bond may result from the Coulomb's law, electrostatic force of attraction bet ...
to
ionic bonding Ionic bonding is a type of chemical bond A chemical bond is a lasting attraction between atoms, ions or molecules that enables the formation of chemical compounds. The bond may result from the Coulomb's law, electrostatic force of attraction be ...

. The loosely defined term electropositivity is the opposite of electronegativity: it characterizes an element's tendency to donate valence electrons. On the most basic level, electronegativity is determined by factors like the
nuclear charge The effective nuclear charge (often symbolized as Z_ or Z^\ast) is the net positive charge experienced by an electron The electron is a subatomic particle, symbol or , whose electric charge Electric charge is the physical property of mat ...

(the more
protons A proton is a subatomic particle, symbol or , with a positive electric charge Electric charge is the physical property of matter that causes it to experience a force when placed in an electromagnetic field. There are two types of electric cha ...
an atom has, the more "pull" it will have on electrons) and the number and location of other electrons in the atomic shells (the more electrons an atom has, the farther from the
nucleus ''Nucleus'' (plural nuclei) is a Latin word for the seed inside a fruit. It most often refers to: *Atomic nucleus, the very dense central region of an atom *Cell nucleus, a central organelle of a eukaryotic cell, containing most of the cell's DNA ...
the valence electrons will be, and as a result, the less positive charge they will experience—both because of their increased distance from the nucleus and because the other electrons in the lower energy core orbitals will act to
shield A shield is a piece of personal armour held in the hand, which may or may not be strapped to the wrist or forearm. Shields are used to intercept specific attacks, whether from melee weapon, close-ranged weaponry or projectiles such as arrows, by ...
the valence electrons from the positively charged nucleus). The term "electronegativity" was introduced by
Jöns Jacob Berzelius Baron Jöns Jacob Berzelius (; by himself and his contemporaries named only Jacob Berzelius, 20 August 1779 – 7 August 1848) was a Swedish chemist. Berzelius is considered, along with Robert Boyle Robert Boyle (; 25 January 1627 – ...

in 1811, though the concept was known before that and was studied by many chemists including . In spite of its long history, an accurate scale of electronegativity was not developed until 1932, when
Linus Pauling Linus Carl Pauling (; February 28, 1901 – August 19, 1994) was an American chemist, biochemist, chemical engineer, peace activist, author, and educator. He published more than 1,200 papers and books, of which about 850 dealt with scientific top ...

proposed an electronegativity scale which depends on bond energies, as a development of
valence bond theory In chemistry Chemistry is the scientific discipline involved with Chemical element, elements and chemical compound, compounds composed of atoms, molecules and ions: their composition, structure, properties, behavior and the changes they unde ...
. It has been shown to correlate with a number of other chemical properties. Electronegativity cannot be directly measured and must be calculated from other atomic or molecular properties. Several methods of calculation have been proposed, and although there may be small differences in the numerical values of the electronegativity, all methods show the same
periodic trends Image:Periodic trends.svg, The periodic trends in properties of elements Periodic trends are specific patterns in the properties of chemical elements that are revealed in the periodic table of elements. Major periodic trends include electronegativ ...

between elements. The most commonly used method of calculation is that originally proposed by Linus Pauling. This gives a
dimensionless quantity In dimensional analysis, a dimensionless quantity is a quantity to which no physical dimension is assigned, also known as a bare, pure, or scalar quantity or a quantity of dimension one, with a corresponding unit of measurement in the International ...
, commonly referred to as the Pauling scale (''χ''r), on a relative scale running from 0.79 to 3.98 (
hydrogen Hydrogen is the chemical element Image:Simple Periodic Table Chart-blocks.svg, 400px, Periodic table, The periodic table of the chemical elements In chemistry, an element is a pure substance consisting only of atoms that all have the same ...

= 2.20). When other methods of calculation are used, it is conventional (although not obligatory) to quote the results on a scale that covers the same range of numerical values: this is known as an electronegativity in ''Pauling units''. As it is usually calculated, electronegativity is not a property of an atom alone, but rather a property of an atom in a
molecule File:Pentacene on Ni(111) STM.jpg, A scanning tunneling microscopy image of pentacene molecules, which consist of linear chains of five carbon rings. A molecule is an electrically neutral group of two or more atoms held together by chemical bo ...

. Even so, the electronegativity of an atom is strongly correlated with the first ionization energy, and negatively correlated with the
electron affinityThe electron affinity (''E''ea) of an atom An atom is the smallest unit of ordinary matter In classical physics and general chemistry, matter is any substance that has mass and takes up space by having volume. All everyday objects that can ...
. It is to be expected that the electronegativity of an element will vary with its chemical environment, but it is usually considered to be a transferable property, that is to say that similar values will be valid in a variety of situations.
Caesium Caesium (IUPAC spelling) (American and British English spelling differences, also spelled cesium in American English) is a chemical element with the Symbol (chemistry), symbol Cs and atomic number 55. It is a soft, silvery-golden alkali ...
is the least electronegative element (0.79);
fluorine Fluorine is a chemical element with the Chemical symbol, symbol F and atomic number 9. It is the lightest halogen and exists at Standard conditions for temperature and pressure, standard conditions as a highly toxic, pale yellow Diatomic molecule, ...

is the most (3.98).

# Methods of calculation

## Pauling electronegativity

PaulingPauling is a surname In some cultures, a surname, family name, or last name is the portion of one's personal name that indicates their family, tribe or community. Practices vary by culture. The family name may be placed at either the start of ...

first proposed the concept of electronegativity in 1932 to explain why the
covalent bond A covalent bond is a chemical bond that involves the sharing of electron pairs between atoms. These electron pairs are known as shared pairs or bonding pairs, and the stable balance of attractive and repulsive forces between atoms, when they sh ...
between two different atoms (A–B) is stronger than the average of the A–A and the B–B bonds. According to
valence bond theory In chemistry Chemistry is the scientific discipline involved with Chemical element, elements and chemical compound, compounds composed of atoms, molecules and ions: their composition, structure, properties, behavior and the changes they unde ...
, of which Pauling was a notable proponent, this "additional stabilization" of the
heteronuclear A heteronuclear molecule is a molecule File:Pentacene on Ni(111) STM.jpg, A scanning tunneling microscopy image of pentacene molecules, which consist of linear chains of five carbon rings. A molecule is an electrically neutral group of two or ...
bond is due to the contribution of
ionic Ionic or Ionian may refer to: Arts and entertainment * Ionic meter, a poetic metre in ancient Greek and Latin poetry * Ionian mode, a musical mode or a diatonic scale Places and peoples * Ionian, of or from Ionia, an ancient region in western An ...
canonical form In mathematics Mathematics (from Ancient Greek, Greek: ) includes the study of such topics as quantity (number theory), mathematical structure, structure (algebra), space (geometry), and calculus, change (mathematical analysis, analysis). I ...
s to the bonding. The difference in electronegativity between atoms A and B is given by: $, \chi_ - \chi_, = ()^ \sqrt$ where the dissociation energies, ''E''d, of the A–B, A–A and B–B bonds are expressed in
electronvolt In physics Physics is the natural science that studies matter, its Elementary particle, fundamental constituents, its Motion (physics), motion and behavior through Spacetime, space and time, and the related entities of energy and force. "P ...
s, the factor (eV) being included to ensure a dimensionless result. Hence, the difference in Pauling electronegativity between hydrogen and
bromine Bromine is a chemical element with the symbol Br and atomic number 35. It is the third-lightest halogen, and is a volatile red-brown liquid at room temperature that evaporates readily to form a similarly coloured vapour. Its properties are interm ...
is 0.73 (dissociation energies: H–Br, 3.79 eV; H–H, 4.52 eV; Br–Br 2.00 eV) As only differences in electronegativity are defined, it is necessary to choose an arbitrary reference point in order to construct a scale. Hydrogen was chosen as the reference, as it forms covalent bonds with a large variety of elements: its electronegativity was fixed first at 2.1, later revised to 2.20. It is also necessary to decide which of the two elements is the more electronegative (equivalent to choosing one of the two possible signs for the square root). This is usually done using "chemical intuition": in the above example,
hydrogen bromide Hydrogen bromide is the inorganic compound In chemistry Chemistry is the scientific discipline involved with Chemical element, elements and chemical compound, compounds composed of atoms, molecules and ions: their composition, structure, pr ...
dissolves in water to form H+ and Br ions, so it may be assumed that bromine is more electronegative than hydrogen. However, in principle, since the same electronegativities should be obtained for any two bonding compounds, the data are in fact overdetermined, and the signs are unique once a reference point is fixed (usually, for H or F). To calculate Pauling electronegativity for an element, it is necessary to have data on the dissociation energies of at least two types of covalent bonds formed by that element. A. L. Allred updated Pauling's original values in 1961 to take account of the greater availability of thermodynamic data, and it is these "revised Pauling" values of the electronegativity that are most often used. The essential point of Pauling electronegativity is that there is an underlying, quite accurate, semi-empirical formula for dissociation energies, namely: $E_() = \frac 2 + (\chi_ - \chi_)^2$ or sometimes, a more accurate fit $E_() =\sqrt+1.3(\chi_ - \chi_)^2$ This is an approximate equation but holds with good accuracy. Pauling obtained it by noting that a bond can be approximately represented as a quantum mechanical superposition of a covalent bond and two ionic bond-states. The covalent energy of a bond is approximate, by quantum mechanical calculations, the
geometric mean In mathematics, the geometric mean is a mean or average, which indicates the central tendency or typical value of a set of numbers by using the product of their values (as opposed to the arithmetic mean In mathematics and statistics, the arit ...

of the two energies of covalent bonds of the same molecules, and there is additional energy that comes from ionic factors, i.e. polar character of the bond. The geometric mean is approximately equal to the
arithmetic mean In mathematics and statistics, the arithmetic mean (, stress on first and third syllables of "arithmetic"), or simply the mean or the average (when the context is clear), is the sum of a collection of numbers divided by the count of numbers in the ...
—which is applied in the first formula above—when the energies are of a similar value, e.g., except for the highly electropositive elements, where there is a larger difference of two dissociation energies; the geometric mean is more accurate and almost always gives positive excess energy, due to ionic bonding. The square root of this excess energy, Pauling notes, is approximately additive, and hence one can introduce the electronegativity. Thus, it is this semi-empirical formula for bond energy that underlies the concept of Pauling electronegativity. The formulas are approximate, but this rough approximation is in fact relatively good and gives the right intuition, with the notion of the polarity of the bond and some theoretical grounding in quantum mechanics. The electronegativities are then determined to best fit the data. In more complex compounds, there is an additional error since electronegativity depends on the molecular environment of an atom. Also, the energy estimate can be only used for single, not for multiple bonds. The energy of the formation of a molecule containing only single bonds can subsequently be approximated from an electronegativity table and depends on the constituents and sum of squares of differences of electronegativities of all pairs of bonded atoms. Such a formula for estimating energy typically has a relative error of an order of 10% but can be used to get a rough qualitative idea and understanding of a molecule.

## Mulliken electronegativity

Robert S. Mulliken proposed that the
arithmetic mean In mathematics and statistics, the arithmetic mean (, stress on first and third syllables of "arithmetic"), or simply the mean or the average (when the context is clear), is the sum of a collection of numbers divided by the count of numbers in the ...
of the first
ionization energy In physics and chemistry Chemistry is the scientific discipline involved with Chemical element, elements and chemical compound, compounds composed of atoms, molecules and ions: their composition, structure, properties, behavior and the c ...
(Ei) and the
electron affinityThe electron affinity (''E''ea) of an atom An atom is the smallest unit of ordinary matter In classical physics and general chemistry, matter is any substance that has mass and takes up space by having volume. All everyday objects that can ...
(Eea) should be a measure of the tendency of an atom to attract electrons. As this definition is not dependent on an arbitrary relative scale, it has also been termed absolute electronegativity, with the units of kilojoules per mole or
electronvolt In physics Physics is the natural science that studies matter, its Elementary particle, fundamental constituents, its Motion (physics), motion and behavior through Spacetime, space and time, and the related entities of energy and force. "P ...
s. $\chi = \frac 2$ However, it is more usual to use a linear transformation to transform these absolute values into values that resemble the more familiar Pauling values. For ionization energies and electron affinities in electronvolts, $\chi = 0.187(E_ + E_) + 0.17 \,$ and for energies in kilojoules per mole, $\chi = (1.97\times 10^)(E_ + E_) + 0.19.$ The Mulliken electronegativity can only be calculated for an element for which the electron affinity is known, fifty-seven elements as of 2006. The Mulliken electronegativity of an atom is sometimes said to be the negative of the
chemical potential In thermodynamics Thermodynamics is a branch of physics that deals with heat, Work (thermodynamics), work, and temperature, and their relation to energy, radiation, and physical properties of matter. The behavior of these quantities is governed ...
. By inserting the energetic definitions of the ionization potential and electron affinity into the Mulliken electronegativity, it is possible to show that the Mulliken chemical potential is a finite difference approximation of the electronic energy with respect to the number of electrons., i.e., $\mu(\rm Mulliken) = -\chi(\rm Mulliken) = -\frac 2$

## Allred–Rochow electronegativity

A. Louis Allred and Eugene G. Rochow considered that electronegativity should be related to the charge experienced by an electron on the "surface" of an atom: The higher the charge per unit area of atomic surface the greater the tendency of that atom to attract electrons. The
effective nuclear charge The effective nuclear charge (often symbolized as Z_ or Z^\ast) is the net positive charge experienced by an electron The electron is a subatomic particle, symbol or , whose electric charge Electric charge is the physical property of mat ...

, ''Z''eff, experienced by
valence electron In chemistry Chemistry is the scientific discipline involved with Chemical element, elements and chemical compound, compounds composed of atoms, molecules and ions: their composition, structure, properties, behavior and the changes they under ...
s can be estimated using
Slater's rules In quantum chemistry, Slater's rules provide numerical values for the effective nuclear charge in a many-electron atom. Each electron is said to experience less than the actual atomic nucleus, nuclear charge, because of Shielding effect, shielding ...
, while the surface area of an atom in a molecule can be taken to be proportional to the square of the
covalent radius The covalent radius, ''r''cov, is a measure of the size of an atom An atom is the smallest unit of ordinary matter In classical physics and general chemistry, matter is any substance that has mass and takes up space by having volume. All ...
, ''r''cov. When ''r''cov is expressed in
picometre The picometre (international spelling as used by the International Bureau of Weights and Measures; SI symbol: pm) or picometer ( American spelling) is a unit of length in the metric system, equal to , or one trillionth of a metre The m ...
s, $\chi = 3590 + 0.744$

## Sanderson electronegativity equalization

R.T. Sanderson has also noted the relationship between Mulliken electronegativity and atomic size, and has proposed a method of calculation based on the reciprocal of the atomic volume. With a knowledge of bond lengths, Sanderson's model allows the estimation of bond energies in a wide range of compounds. Sanderson's model has also been used to calculate molecular geometry, ''s''-electrons energy,
NMR Nuclear magnetic resonance (NMR) is a physical phenomenon in which nuclei in a strong constant magnetic field A magnetic field is a vector field that describes the magnetic influence on moving electric charges, electric currents, and ma ...

spin-spin constants and other parameters for organic compounds. This work underlies the concept of electronegativity equalization, which suggests that electrons distribute themselves around a molecule to minimize or to equalize the Mulliken electronegativity. This behavior is analogous to the equalization of chemical potential in macroscopic thermodynamics.

## Allen electronegativity

Perhaps the simplest definition of electronegativity is that of Leland C. Allen, who has proposed that it is related to the average energy of the
valence electron In chemistry Chemistry is the scientific discipline involved with Chemical element, elements and chemical compound, compounds composed of atoms, molecules and ions: their composition, structure, properties, behavior and the changes they under ...
s in a free atom, $\chi =$ where ''ε''s,p are the one-electron energies of s- and p-electrons in the free atom and ''n''s,p are the number of s- and p-electrons in the valence shell. It is usual to apply a scaling factor, 1.75×10−3 for energies expressed in kilojoules per mole or 0.169 for energies measured in electronvolts, to give values that are numerically similar to Pauling electronegativities. The one-electron energies can be determined directly from , and so electronegativities calculated by this method are sometimes referred to as spectroscopic electronegativities. The necessary data are available for almost all elements, and this method allows the estimation of electronegativities for elements that cannot be treated by the other methods, e.g.
francium Francium is a chemical element with the Symbol (chemistry), symbol Fr and atomic number 87. Prior to its discovery, it was referred to as Mendeleev's predicted elements, eka-caesium. It is extremely radioactive; its most stable isotop ...

, which has an Allen electronegativity of 0.67.The widely quoted Pauling electronegativity of 0.7 for francium is an extrapolated value of uncertain provenance. The Allen electronegativity of caesium is 0.66. However, it is not clear what should be considered to be valence electrons for the d- and f-block elements, which leads to an ambiguity for their electronegativities calculated by the Allen method. In this scale
neon Neon is a chemical element with the symbol A symbol is a mark, sign, or word that indicates, signifies, or is understood as representing an idea, Object (philosophy), object, or wikt:relationship, relationship. Symbols allow people to go b ...

has the highest electronegativity of all elements, followed by
fluorine Fluorine is a chemical element with the Chemical symbol, symbol F and atomic number 9. It is the lightest halogen and exists at Standard conditions for temperature and pressure, standard conditions as a highly toxic, pale yellow Diatomic molecule, ...

,
helium Helium (from el, ἥλιος, Helios, lit=Sun) is a chemical element Image:Simple Periodic Table Chart-blocks.svg, 400px, Periodic table, The periodic table of the chemical elements In chemistry, an element is a pure substance consisting ...

, and
oxygen Oxygen is the chemical element with the chemical symbol, symbol O and atomic number 8. It is a member of the chalcogen Group (periodic table), group in the periodic table, a highly Chemical reaction, reactive nonmetal, and an oxidizing a ...

.

# Correlation of electronegativity with other properties

, against the sum of the Pauling electronegativities of the halide substituents (''x''-axis). The wide variety of methods of calculation of electronegativities, which all give results that correlate well with one another, is one indication of the number of chemical properties that might be affected by electronegativity. The most obvious application of electronegativities is in the discussion of bond polarity, for which the concept was introduced by Pauling. In general, the greater the difference in electronegativity between two atoms the more polar the bond that will be formed between them, with the atom having the higher electronegativity being at the negative end of the dipole. Pauling proposed an equation to relate the "ionic character" of a bond to the difference in electronegativity of the two atoms, although this has fallen somewhat into disuse. Several correlations have been shown between of certain bonds and the electronegativities of the atoms involved: however, this is not surprising as such stretching frequencies depend in part on bond strength, which enters into the calculation of Pauling electronegativities. More convincing are the correlations between electronegativity and chemical shifts in
NMR spectroscopy Nuclear magnetic resonance spectroscopy, most commonly known as NMR spectroscopy or magnetic resonance spectroscopy (MRS), is a spectroscopic Spectroscopy is the study of the interaction between matter In classical physics and general che ...
or isomer shifts in
Mössbauer spectroscopy Mössbauer spectroscopy is a spectroscopic technique based on the Mössbauer effect. This effect, discovered by Rudolf Mössbauer (sometimes written "Moessbauer", German: "Mößbauer") in 1958, consists of the nearly recoil Recoil (often cal ...
(see figure). Both these measurements depend on the s-electron density at the nucleus, and so are a good indication that the different measures of electronegativity really are describing "the ability of an atom in a molecule to attract electrons to itself".

# Trends in electronegativity

## Periodic trends

upright=1.35, The variation of Pauling electronegativity (''y''-axis) as one descends the main groups of the periodic table from the second period to the sixth period In general, electronegativity increases on passing from left to right along a period and decreases on descending a group. Hence,
fluorine Fluorine is a chemical element with the Chemical symbol, symbol F and atomic number 9. It is the lightest halogen and exists at Standard conditions for temperature and pressure, standard conditions as a highly toxic, pale yellow Diatomic molecule, ...

is the most electronegative of the elements (not counting
noble gas The noble gases (historically also the inert gases; sometimes referred to as aerogens) make up a class of chemical elements with similar properties; under Standard conditions for temperature and pressure, standard conditions, they are all odorle ...
es), whereas
caesium Caesium (IUPAC spelling) (American and British English spelling differences, also spelled cesium in American English) is a chemical element with the Symbol (chemistry), symbol Cs and atomic number 55. It is a soft, silvery-golden alkali ...
is the least electronegative, at least of those elements for which substantial data is available. This would lead one to believe that
caesium fluoride Caesium fluoride or cesium fluoride is an inorganic compound In chemistry Chemistry is the scientific discipline involved with Chemical element, elements and chemical compound, compounds composed of atoms, molecules and ions: their compositi ...

is the
compound Compound may refer to: Architecture and built environments * Compound (enclosure), a cluster of buildings having a shared purpose, usually inside a fence or wall ** Compound (fortification), a version of the above fortified with defensive structu ...
whose bonding features the most ionic character. There are some exceptions to this general rule.
Gallium Gallium is a chemical element with the Symbol (chemistry), symbol Ga and atomic number 31. Discovered by France, French chemist Paul-Émile Lecoq de Boisbaudran in 1875, Gallium is in boron group, group 13 of the periodic table and is s ...

and
germanium Germanium is a chemical element Image:Simple Periodic Table Chart-blocks.svg, 400px, Periodic table, The periodic table of the chemical elements In chemistry, an element is a pure substance consisting only of atoms that all have the same nu ...

have higher electronegativities than
aluminium Aluminium (aluminum in American American(s) may refer to: * American, something of, from, or related to the United States of America, commonly known as the United States The United States of America (USA), commonly known as the Unit ...
and
silicon Silicon is a chemical element with the Symbol (chemistry), symbol Si and atomic number 14. It is a hard, brittle crystalline solid with a blue-grey metallic lustre, and is a Tetravalence, tetravalent metalloid and semiconductor. It is a member ...

, respectively, because of the
d-block contraction The d-block contraction (sometimes called scandide contraction) is a term used in chemistry to describe the effect of having full d orbitals on the period 4 elements. The elements in question are gallium Gallium is a chemical element Ima ...

. Elements of the fourth period immediately after the first row of the transition metals have unusually small atomic radii because the 3d-electrons are not effective at shielding the increased nuclear charge, and smaller atomic size correlates with higher electronegativity (see Allred-Rochow electronegativity, Sanderson electronegativity above). The anomalously high electronegativity of
lead Lead is a chemical element with the Symbol (chemistry), symbol Pb (from the Latin ) and atomic number 82. It is a heavy metals, heavy metal that is density, denser than most common materials. Lead is Mohs scale of mineral hardness#Intermediate h ...

, in particular when compared to
thallium Thallium is a chemical element Image:Simple Periodic Table Chart-blocks.svg, 400px, Periodic table, The periodic table of the chemical elements In chemistry, an element is a pure substance consisting only of atoms that all have the same nu ...

and
bismuth Bismuth is a chemical element Image:Simple Periodic Table Chart-blocks.svg, 400px, Periodic table, The periodic table of the chemical elements In chemistry, an element is a pure substance consisting only of atoms that all have the same numbe ...
, is an artifact of electronegativity varying with oxidation state: its electronegativity conforms better to trends if it is quoted for the +2 state with a Pauling value of 1.87 instead of the +4 state.

## Variation of electronegativity with oxidation number

In inorganic chemistry, it is common to consider a single value of electronegativity to be valid for most "normal" situations. While this approach has the advantage of simplicity, it is clear that the electronegativity of an element is ''not'' an invariable atomic property and, in particular, increases with the
oxidation state The oxidation state, or oxidation number, is the hypothetical charge Charge or charged may refer to: Arts, entertainment, and media Films * ''Charge, Zero Emissions/Maximum Speed'', a 2011 documentary Music * Charge (David Ford album), ''Charge' ...
of the element. Allred used the Pauling method to calculate separate electronegativities for different oxidation states of the handful of elements (including tin and lead) for which sufficient data were available. However, for most elements, there are not enough different covalent compounds for which bond dissociation energies are known to make this approach feasible. This is particularly true of the transition elements, where quoted electronegativity values are usually, of necessity, averages over several different oxidation states and where trends in electronegativity are harder to see as a result. The chemical effects of this increase in electronegativity can be seen both in the structures of oxides and halides and in the acidity of oxides and oxoacids. Hence CrO3 and Mn2O7 are
acidic oxide Acidic oxides, or acid anhydride, are oxides that react with water to form an acid, or with a base to form a salt. They are oxides of either nonmetals or of metal A metal (from Ancient Greek, Greek μέταλλον ''métallon'', "mine, q ...
s with low
melting point The melting point (or, rarely, liquefaction point) of a substance is the temperature at which it changes state of matter, state from solid to liquid. At the melting point the solid and liquid phase exist in Thermodynamic equilibrium, equilibrium. ...

s, while Cr2O3 is
amphoteric In chemistry, an amphoteric compound is a molecule or ion that can react both as an acid and as a base (chemistry), base. What exactly this can mean depends on acid–base reaction, which definitions of acids and bases are being used. The prefix of ...
and is a completely
basic oxide Basic oxides are oxide of rutile. Ti(IV) centers are grey; oxygen centers are red. Notice that oxygen forms three bonds to titanium and titanium forms six bonds to oxygen. An oxide () is a chemical compound that contains at least one oxygen ...
. The effect can also be clearly seen in the dissociation constants of the
oxoacid An oxyacid, oxoacid, or ternary acid is an acid An acid is a molecule or ion capable of donating a proton (hydrogen ion H+) (a Brønsted–Lowry acid–base theory, Brønsted–Lowry acid), or, alternatively, capable of forming a covalent bo ...
s of
chlorine Chlorine is a chemical element with the Symbol (chemistry), symbol Cl and atomic number 17. The second-lightest of the halogens, it appears between fluorine and bromine in the periodic table and its properties are mostly intermediate betwe ...
. The effect is much larger than could be explained by the negative charge being shared among a larger number of oxygen atoms, which would lead to a difference in p''K''a of log10() = –0.6 between
hypochlorous acid Hypochlorous acid (HOCl or HClO) is a weak acid An acid is a molecule or ion capable of donating a proton (hydrogen ion H+) (a Brønsted–Lowry acid–base theory, Brønsted–Lowry acid), or, alternatively, capable of forming a covalent bo ...
and
perchloric acid Perchloric acid is a mineral acid with the formula Hydrogen, HChlorine, ClOxygen, O4. Usually found as an aqueous solution, this colorless compound is a stronger acid than sulfuric acid, nitric acid and hydrochloric acid. It is a powerful oxidizer w ...
. As the oxidation state of the central chlorine atom increases, more electron density is drawn from the oxygen atoms onto the chlorine, diminishing the partial negative charge of individual oxygen atoms. At the same time, the positive partial charge on the hydrogen increases with a higher oxidation state. This explains the observed increased acidity with an increasing oxidation state in the oxoacids of chlorine.

## Electronegativity and hybridization scheme

The electronegativity of an atom changes depending on the hybridization of the orbital employed in bonding. Electrons in s orbitals are held more tightly than electrons in p orbitals. Hence, a bond to an atom that employs an sp''x'' hybrid orbital for bonding will be more heavily polarized to that atom when the hybrid orbital has more s character. That is, when electronegativities are compared for different hybridization schemes of a given element, the order holds (the trend should apply to non-integer hybridization indices as well). While this holds true in principle for any main-group element, values for the hybridization-specific electronegativity are most frequently cited for carbon. In organic chemistry, these electronegativities are frequently invoked to predict or rationalize bond polarities in organic compounds containing double and triple bonds to carbon.

# Group electronegativity

In organic chemistry, electronegativity is associated more with different functional groups than with individual atoms. The terms group electronegativity and substituent electronegativity are used synonymously. However, it is common to distinguish between the
inductive effect In chemistry Chemistry is the scientific discipline involved with Chemical element, elements and chemical compound, compounds composed of atoms, molecules and ions: their composition, structure, properties, behavior and the changes they underg ...
and the
resonance effect In chemistry, resonance, also called mesomerism, is a way of describing bonding in certain molecules or ions by the combination of several contributing structures (or ''forms'', also variously known as ''resonance structures'' or ''canonical stru ...
, which might be described as σ- and π-electronegativities, respectively. There are a number of linear free-energy relationships that have been used to quantify these effects, of which the
Hammett equation The Hammett equation in organic chemistry describes a linear free-energy relationship relating reaction rates and equilibrium constants for many reactions involving benzoic acid derivatives with meta- and para- substituents to each other with ...
is the best known. Kabachnik parameters are group electronegativities for use in
organophosphorus chemistry Organophosphorus compounds are organic compounds containing phosphorus. They are used primarily in pest control as an alternative to chlorinated hydrocarbons that persist in the environment. Some organophosphorus compounds are highly effective inse ...
.

# Electropositivity

Electropositivity is a measure of an element's ability to donate
electrons The electron is a subatomic particle In physical sciences, subatomic particles are smaller than atom An atom is the smallest unit of ordinary matter In classical physics and general chemistry, matter is any substance that has ma ...
, and therefore form
positive Positive is a property of Positivity (disambiguation), positivity and may refer to: Mathematics and science * Converging lens or positive lens, in optics * Plus sign, the sign "+" used to indicate a positive number * Positive (electricity), a po ...
ions An ion () is an atom or molecule with a net electric charge, electrical charge. The charge of an electron is considered negative by convention and this charge is equal and opposite to charge of a proton, which is considered positive by convent ...

; thus, it is antipode to electronegativity. Mainly, this is an attribute of
metals A metal (from Greek Greek may refer to: Greece Anything of, from, or related to Greece Greece ( el, Ελλάδα, , ), officially the Hellenic Republic, is a country located in Southeast Europe. Its population is approximately 10.7 mi ...
, meaning that, in general, the greater the metallic character of an
element Element may refer to: Science * Chemical element Image:Simple Periodic Table Chart-blocks.svg, 400px, Periodic table, The periodic table of the chemical elements In chemistry, an element is a pure substance consisting only of atoms that all ...
the greater the electropositivity. Therefore, the
alkali metals The alkali metals consist of the chemical elements lithium (Li), sodium (Na), potassium (K),The symbols Na and K for sodium and potassium are derived from their Latin names, ''natrium'' and ''kalium''; these are still the origins of the names fo ...
are the most electropositive of all. This is because they have a single electron in their outer shell and, as this is relatively far from the nucleus of the atom, it is easily lost; in other words, these metals have low ionization energies.Electropositivity
"
Microsoft Encarta ''Microsoft Encarta'' was a digital multimedia Multimedia is a form of communication that combines different content forms such as text, audio, images, animations, or video into a single presentation, in contrast to traditional mass media, ...
Online Encyclopedia 2009. (Archived 2009-10-31).
While electronegativity increases along periods in the
periodic table The periodic table, also known as the periodic table of elements, is a tabular display of the chemical element Image:Simple Periodic Table Chart-blocks.svg, 400px, Periodic table, The periodic table of the chemical elements In chemistry ...

, and decreases down
groups A group is a number of people or things that are located, gathered, or classed together. Groups of people * Cultural group, a group whose members share the same cultural identity * Ethnic group, a group whose members share the same ethnic identi ...
, electropositivity ''decreases'' along periods (from left to right) and ''increases'' down groups. This means that elements in the upper right of the periodic table of elements (oxygen, sulfur, chlorine, etc.) will have the greatest electronegativity, and those in the lower-left (rubidium, caesium, and francium) the greatest electropositivity.

*
Chemical polarity In chemistry Chemistry is the science, scientific study of the properties and behavior of matter. It is a natural science that covers the Chemical element, elements that make up matter to the chemical compound, compounds composed of atoms, ...
*
Electron affinityThe electron affinity (''E''ea) of an atom An atom is the smallest unit of ordinary matter In classical physics and general chemistry, matter is any substance that has mass and takes up space by having volume. All everyday objects that can ...
* Electronegativities of the elements (data page) *
Ionization energy In physics and chemistry Chemistry is the scientific discipline involved with Chemical element, elements and chemical compound, compounds composed of atoms, molecules and ions: their composition, structure, properties, behavior and the c ...
*
Metallic bonding Metallic bonding is a type of chemical bond A chemical bond is a lasting attraction between atoms, ions or molecules that enables the formation of chemical compounds. The bond may result from the Coulomb's law, electrostatic force of att ...

*
Miedema's modelMiedema is a surname. Notable people with the surname include: *Hessel Miedema (1929–2019), Dutch art historian *Lars Miedema (born 2000), Dutch footballer, brother of Vivianne *Vivianne Miedema (born 1996), Dutch footballer See also

*Medema ...
*
Orbital hybridization In chemistry Chemistry is the scientific discipline involved with Chemical element, elements and chemical compound, compounds composed of atoms, molecules and ions: their composition, structure, properties, behavior and the changes they unde ...
*
Oxidation state The oxidation state, or oxidation number, is the hypothetical charge Charge or charged may refer to: Arts, entertainment, and media Films * ''Charge, Zero Emissions/Maximum Speed'', a 2011 documentary Music * Charge (David Ford album), ''Charge' ...
*
Periodic table The periodic table, also known as the periodic table of elements, is a tabular display of the chemical element Image:Simple Periodic Table Chart-blocks.svg, 400px, Periodic table, The periodic table of the chemical elements In chemistry ...

* *