Electronegativity is a chemical residential property that defines the tendency of one atom or a functional team to attract electrons towards itself.

You are watching: List the following bonds in decreasing electronegativity difference.

From: Principles and Applications the Quantum Chemistry, 2016

Related terms:

Robert J. Ouellette, J. David Rawn, in principles of necessary Chemistry, 2015


Electronegativity is a measure up of the attraction of an atom because that bonding electrons in molecules compared to that of other atoms. The electronegativity worths devised by Linus Pauling, an American chemist, space dimensionless amounts that range from slightly less than one for the alkali steels to a preferably of four for fluorine. Huge electronegativity values show a more powerful attraction for electrons than tiny electronegativity values.

Electronegativities boost from left come right across the periodic table (Figure 1.3). Elements on the left the the regular table have actually low electronegativities and also are often called electropositive elements. The stimulate of electronegativities F > O > N > C is vital property that us will usage to define the chemical properties of necessary compounds. Electronegativities diminish from optimal to bottom in ~ a team of elements. The order of decreasing electronegativities F > Cl > Br > I is another sequence that we will use to translate the chemical and also physical nature of organic compounds.

Figure 1.3. Electronegativity

View chapterPurchase book
Read complete chapter
URL: https://www.historicsweetsballroom.com/science/article/pii/B978012802444700001X

Characterization of chemical Reactions

V.P. Gupta, in Principles and also Applications that Quantum Chemistry, 2016

12.14 Electronegativity and Group Electronegativity

12.14.1 Electronegativity

Electronegativity is a chemical residential or commercial property that defines the propensity of an atom or a functional group to tempt electrons toward itself. The electronegativity of an atom is influenced by both its atomic number and also the distance that the valence electron reside native the fee nuclei. The ide of electronegativity was first proposed by Pauli in 1932 as an explanation that the truth that the covalent bond between two various atoms (AB) is stronger than would be supposed by taking the average of the staminas of the AA and BB bonds. This additional stabilization the the heteronuclear bond has actually been described by the valence bond theory due to the contribution of the ionic canonical forms to the bonding. Electronegativity is a relative term and only the distinctions in the electronegativity are defined. Thus, Pauli proposed


where χA and also χB are electronegativities of atom A and B and D(AB), D(AA), and also D(BB) space the dissociation energies of bonds AB, AA, and also BB, respectively, expressed in devices of electron volts (eV). The consist of of (eV)−1/2 expresses χA–χB as a dimensionless quantity. In order to build an electronegativity scale, Pauli chose hydrogen as reference as it develops covalent bonds with a large variety that elements and also fixed the electronegativity at 2.1, i beg your pardon was later revised come 2.20. The atomic electronegativity range so built is well-known as Pauli's electronegativity scale. Electronegativity was originally characterized as one invariant property of atoms. Recently several employees have argued that electronegativity of one atom relies upon its atmosphere in the molecule. Thus, it depends on hybridization and oxidation state of the element.

Mulliken <38> presented the concept of pure electronegativity and also proposed the the arithmetic typical of the an initial ionization energy (I) and also the electron affinity (A) of an facet should it is in the measure of the propensity of one atom to tempt electrons.


This expression based upon the meanings of I and A, follows from straightforward considerations. Thus, if X and also Y room two solution of interest, climate the problem that they have actually equal electronegativity is the the energy transforms for the reactions




are equal.


By definition, E(X+) − E(X) = I(X) is the ionization power of X and E(X) − E(X−) = A(X) is that electron affinity.

Hence indigenous equation (12.14.3), I(X) – A(Y) = I(Y) – A(X)

(12.14.4)or,for systemX=for systemY

It, therefore, provides sense to specify electronegativity as (I + A). The factor 1/2 in Eq. (12.14.2) was presented by Mulliken together he considered that χ as an arithmetic median of I and A is an easily grasped concept.

12.14.2 group Electronegativity

Most of the do the efforts to build electronegativity scale taken into consideration electronegativity as an atomic property although native Pauli's initial definition, electronegativity is the strength or propensity of a group of atom in a molecule to entice electrons come themselves. In necessary chemistry, electronegativity is associated much more with various functional groups rather than through individual atoms. The electronegativity associated with functional groups is because of this called team electronegativity or substituent electronegativity. Despite computational advancements and ease of access of large number of experimental data <39,40>, not plenty of theoretical studies have actually been report for group electronegativity. Relatively couple of methods have been proposed for the evaluation of group electronegativity and most that them have actually been supplied to advice only little subsets of the chemically interesting groups of atoms. The is typical to distinguish in between the inductive effect and the resonance result which are explained as σ- and π-electronegativities, respectively. The quantization the the induction and also resonance impacts is most often done by using Hammett's equations. Gupta et al. <12> learned isodesmic substituent stabilization energies in disubstituted ketenes loved one to alkenes and also correlated lock with team electronegativities. They also analyzed the duty of induction effect (F) and resonance result (R) parameters the the substituent groups on charge distribution. A similar study has actually been reported by McAllister and also Tidwell <41>. Boyd and Boyd <42,43> presented the bond an important point design for the decision of team electronegativities and also reported worths for end 100 groups from ab initio calculations.

The electronegativity of a group A to be calculated from the properties connected with the AH bond vital point in AH. For example, the electronegativity χ of the methoxy group CH3O– was acquired by determining the place of the oh bond crucial point in CH3OH and also substituting the ideal values in the adhering to equations:


where FA is the electronegativity aspect of the atom A, rH is the distance from the bond an important point come hydrogen nucleus, NA is the variety of valence electrons of atom A (atom O in situation of CH3OH), ρ(rc) is the thickness at the bond critical point, and also rAH is the internuclear distance. The bond crucial point and the electron thickness at this point are established by utilizing the quantum theory of atoms-in-molecules. The group electronegativities of some of the essential functional groups determined by Boyd and also Boyd <43> making use of Eq. (12.14.5b) at the HF/6-31G∗//HF/6-31G∗ level space given in Table 12.4. In this table, the worths in the parenthesis be separated by a comma were derived using HF/6-31G∗//experimental geometries and also extended communication set//experimental geometry.

Table 12.4. Group electronegativities of some essential functional groups

CH32.55(2.55,2.56)CCl2F2.71(2.67, –)
CH2CH32.55(2.55,2.56)CCl32.70(2.66, –)
CH2CH2CH32.55(2.55, –)NH23.12(3.10,3.10)
CH2CH(CH3)22.54(2.53, –)NHCH33.13(3.11, –)
CH2CN2.58(2.56, –)NHCOH3.18(3.17, –)
CH2COH2.58(2.56, –)N(CH3)23.13(3.08, –)
CH2COO−2.52(–, –)NCO3.18(3.20,3.22)
CH2COOH2.58(–, –)NC3.26(3.26,3.30)
CH2COF2.59(2.58, –)NHNH23.13(3.12, –)
CH2CSH2.58(2.57, –)NNN3.15(3.23, –)
CH2COCl2.59(2.57, –)NO3.12(3.05,3.06)
CH(CH3)22.55(2.54, –)NHF3.19(–, –)
CH(CH2)22.57(2.56, –)NF23.25(–, –)
CHCH22.58(2.57,2.61)O-3.36(–, –)
CHCCH22.58(2.57, –)OH3.55(3.52,3.64)
CHCCO2.61(–, –)OH2+3.57(–, –)
CHCO2.58(2.57, –)OCH33.53(3.51,3.70)
C(CH3)32.55(2.53, –)OCN3.57(–, 3.73)
C6H52.58(2.58, –)OCOH3.56(3.50,3.65)
CCH2.66(2.65,2.66)OCOCH33.57(–, –)
CCF2.66(2.66, –)ONH23.58(3.54, –)
CCCl2.66(2.66, –)ONO3.55(3.49, –)
CH2NH22.55(2.54, –)OO.3.58(3.51, –)
CH2NHCH32.57(2.57, –)Of3.60(3.56, –)
CH2NO22.62(2.61, –)OPH2O3.54(–, –)
CHNH2.59(2.56, –)MgH1.30(1.31,1.33)
CHNN2.60(2.60, –)AlH21.60(1.61,1.62)
CN2.69(2.68,2.69)SiH1.87(1.87, –)
CNO2.69(2.73, –)SiH31.90(1.89,1.91)
CH2OH2.59(2.58,2.59)SiF1.88(–, –)
CH2OOCH32.61(2.60, –)SiF2H1.93(–, –)
COH2.60(2.58,2.60)SiCl1.89(1.85, –)
COCH32.59(2.59, –)SiClH21.91(1.90, –)
CONH22.61(2.60, –)SiCl2H1.93(1.92, –)
−CO2−2.49(–, –)SiCl31.95(1.94, –)
COOCH32.64(2.62, –)PH2O2.21(–, –)
CO2.57(2.54,2.57)PH(OH)O2.22(–, –)
COF2.67(2.65, –)P(OH)2O2.25(–, –)
COCl2.66(2.64, –)S-2.52(–, –)
CF2H2.65(2.64, –)SCH32.65(2.65, –)
CF32.71(2.68, –)SCN2.70(–, –)
CClH22.61(2.60, –)SSH2.68(2.67, –)
CClFH2.66(2.63, –)

1988, American chemical Society.

Electronegativity is an table of contents of the tendency of an atom to entice electrons. The is proportional to the difference between an atom’s ionization potential and also its electron affinity. Linus Pauling put electronegativity worths on a range of slightly much less than 1.0 for alkali metals to a best of 4.0 because that fluorine (Figure 1.3). The alkali metals and also alkaline earth metals often tend to lose an electron to acquire an inert gas configuration. Thus, teams I and also II contain the least electronegative atoms. In reality they space electropositive. On the other end of the scale, halogens, in group VII, have tendency to obtain an electron to offer an inert gas configuration. Thus, we discover that electronegativity increases from left come right throughout the periodic table. Electronegativity values increase in period 2 in the bespeak C

Robert R. Crichton, in organic Inorganic Chemistry (Second Edition), 2012

Ionic Bonding

Electronegativity is the propensity of one atom to entice electrons in a molecule. Large differences in electronegativity in between atoms in a offered molecule often reason the complete transfer of one electron from the unfilled outer shell of one atom come the unfilled covering of another. The resulting charged types (ions) are held together by electrostatic forces. Such bonds are highly polarised and are referred to as ionic bonds. Ionic bonding is the simplest type of chemistry bonding encountered. NaCl, deserve to be created as , the sodium atom providing up one electron come resemble the secure neon atom, while the chlorine atom acquires an extra electron to resemble the stable argon atom. MgCl2 and CoBr3 space other examples of ionic compounds.

Therald Moeller, ... Clyde Metz, in Chemistry: With inorganic Qualitative Analysis, 1980

10.8 Electronegativity and also oxidation state

Electronegativity worths are helpful in determining oxidation numbers in instances where it can otherwise be challenging to decide which atom has the positive and also which the negative oxidation number. In binary covalent compounds and polyatomic ions such as PO43- or ClO4−, the much more electronegative atom is arbitrarily assigned the negative oxidation number corresponding to the charge it would have actually if it were existing as one ion. This pipeline assignment the a confident oxidation number come the much less electronegative element. Together a result, oxidation numbers stand for the family member electronegativities of atoms and also the direction the the polarity of a bond. For example, in iodine trichloride, ICl3, chlorine is assigned the -1 oxidation number since it is the an ext electronegative that the two atoms. To accomplish the important neutrality, iodine is assigned one oxidation number of + 3 in this compound.

where a, b, c room the number of atom the a given element (A, B, C, etc.).

As an applications of the electronegativity equalization principle (EEP), Parr and Pearson <18> obtained Eqs. (26) and (27) to measure up the lot of charge move ΔN and the energy readjust ΔE associated with the development of A:B complex from acid A and also base:B.

These expression are really useful in expertise the acid-base reaction mechanism. The is vital to keep in mind that the electronegativity difference drives the electron move whereas the hardness sum offers a resistance to it. Because of this both χ and also η are to be taken into consideration in assessing these processes.

The molecular Electronegativity distance Vector (MEDV) is a vectorial descriptor, which contains 91 terms that contain information around the loved one electronegativities.252 The electronegativities are represented by the modification E-state indices and topological distances in between each possible pair that 13 atom types. In the first step that the MEDV descriptor calculation, one needs to assign each atom in the molecule to one of the previously mentioned atom types. The atom types are based upon the many frequently occurring atoms in organic molecules and also the variety of bonded nonhydrogen atom (vertex degree).230 The solitary molecular descriptor have the right to be calculated with this equation:


where u and v are the atom types, S* to represent the amendment E-state index, dij is the topological distance between vi and also vj vertices.

There is likewise an expansion of MEDV-13, referred to as Molecular Holographic street Vector (MHDV).253 it is developed to describe an ext specific molecular structures prefer peptide sequences, which contain heteroatoms and multiple bonds.

View chapterPurchase book

E. Negishi, in an extensive Organometallic Chemistry, 1982 Electronegativity and Size

The electronegativity that boron has actually been estimated at 2.0,15 i m sorry is reasonably close come the matching value the 2.5 because that carbon15 and also is greater than those the the alkali and alkaline planet metals, e.g. lithium, and also those of basically all shift metals. Utilizing an empirical equation correlating shortcut ionicity and also difference in electronegativity propose by Pauling,15a the boron–carbon bond may be approximated to be around 90% covalent and also only 10% ionic.

The boron–carbon bond length in trimethylborane16 is 1.56 Å, which should be compared with the carbon–carbon bond size of 1.54 Å because that ethane17 and also the aluminum–carbon link lengths of 1.97 Å (terminal) and also 2.14 Å (bridging) for dimeric trimethylalane.18

The low ionicity and the relatively short bond length integrate to add to the reality that the bonding electron of the boron–carbon link of organoboranes have tendency to be highly inaccessible to exterior electrophilic reagents. In various other words, organoboranes, unequal organolithium and also Grignard reagents, space of low nucleophilicity.

L.H. Hall, ... L.M. Hall, in considerable Medicinal Chemistry II, 2007 Valence State Electronegativity

Valence state electronegativity (VSE) is characterized as the capability of one atom, in the valence state, to tempt electron thickness to itself from surrounding atoms v the sigma bonding network of the molecule. An speculative measure of VSE has been developed by Hans Jaffeé and co-workers,18 based upon the Mulliken definition of electronegativity.19 In the Mulliken definition, electronegativity is based upon the average of the ionization potential (Ip) and electron affinity (EA) because that an atom. Hinze and Jaffeé extended the Mulliken an interpretation to valence says by using Ip and EA data bring away from digital spectroscopic data because that atomic orbitals; they occurred numerical worths for valence states. This strategy permits the testimonial of XMJ worths for assorted hybrid valence states.

The Mulliken–Jaffeé valence state electronegativity values (XMJ) characterize one atom in its several valence says unlike the much less sensitive Pauling worths which are the exact same for every valence states. For example, the Pauling worth for carbon is the same for carbons atom in ethane, ethylene, and also acetylene.20 However, the XMJ values are various for these three hydrocarbons, equivalent to the raising acidity of the hydrogen atoms in these three molecules. The bigger valence state electronegativity for the acetylenic carbon correlates through the higher acidity that the hydrogen atom in acetylene and the better polarity the the C–H bond. Comparable information is residents in the XMJ worths for all atoms in your valence state (see Table 3).

Table 3. Delta values and also experimental valence state electronegativity values

GroupNδδvδv– δXMJ (eV)a

ar2=0.965, s=0.55, n=19. See message for discussion.

In the advancement of the E-state formalism, we included valence state electronic information because it characterizes the necessary molecule effectively. For this reason, we adopted the Mulliken–Jaffeé valence state electronegativity values as a reference for atom properties that are vital to electron density. The an initial step in this advancement is the recognize of a relationship between XMJ and molecular framework information. The linkage can be construed from the point of see of the source of electronegativity in a molecule. This impact arises native the reliable nuclear charge on the atom, that is, the attraction the electrons arising from unshielded protons in the cell nucleus of the atom.5,17

As a reference point, us can think about that a carbon atom in one sp3 valence state has 4 valence electrons in 4 sigma orbitals. Each valence electron in its sigma orbital, as part of the sigma bond, efficiently shields one nuclear proton. The efficient nuclear charge for this sp3 carbon is required to be zero and also the equivalent VSE is also taken to be zero.

For an sp2 carbon atom, one valence electron is in a pi orbital and also three space in sigma orbitals. In this case, the pi electron, who electron thickness is primarily outside of the sigma bonding orbital, does not effectively screen the core charge. The efficient nuclear charge might be taken as one. The resulting electronegativity the the sp2 carbon is higher than for the sp3 carbon. Following the same line of argument, the reliable nuclear charge for an acetylenic carbon (sp) is much higher than the of the sp2 carbon, based upon two unshielded protons. More generally, for carbon valence state electronegativity, the complying with ranking is observed in properties and described through valence state electronegativity:


This method to valence state electronegativity can be generalized. The ineffective shielding arises from the truth that pi and also lone pair electron density has low or zero probability follow me the heat of the shortcut axis. Together a result, pi and also lone pair electrons carry out not screen nuclear proton as successfully as electron in sigma orbitals that room directed follow me the bond axis.5,17

The counting of the pi and lone pair electron on a bonded atom have the right to be justified as a version of the electronegativity of its bound atom top top both experimental and also theoretical grounds. The work of Slater has presented that the pi and lone pair electrons, being further from the core than the sigma electrons, an outcome in much less shielding hence a higher influence that the core on the sigma bonding electrons.23 This is the essence of electronegativity.

See more: Reflection Across X=-3 - Reflecting Shapes (Article)

The count of pi and lone pair electrons might be conveniently related come the efficient nuclear fee and, as a result, come the valence state electronegativity:

This expression, because that second-row elements, contains the counting of the extrajacent electron on a sigma-bonded atom, that is, the counting of pi (π) and lone pair (n) electrons. For aspects beyond fluorine, the additional screening the the extr core electrons must be taken into account. To incorporate valence states for facets beyond fluorine, the primary quantum variety of the valence electron (N) is included, as follows:

This expression was offered in a design of VSE for 19 valence states, causing a high correlation with XMJ v a traditional error that regression that philosophies the known experimental errors, mostly in the decision of electron affinity values.5,17 Table 3 mirrors values because that VSE for 19 atom valence claims with the corresponding values for the delta values.