Chemical polarity

From Wikipedia, the free encyclopedia

 

A water molecule, a commonly used example of polarity. The two charges are present with a negative charge in the middle (red shade), and a positive charge at the ends (blue shade).

In chemistry, polarity refers to a separation of electric charge leading to a molecule or its chemical groups having an electric dipole or multipole moment. Polar molecules interact through dipole–dipole intermolecular forces and hydrogen bonds. Molecular polarity is dependent on the difference in electronegativity between atoms in a compound and the asymmetry of the compound's structure. Polarity underlies a number of physical properties including surface tension, solubility, and melting and boiling-points.

Polarity of bonds

In a molecule of hydrogen fluoride (HF), the more electronegative atom (fluoride) is shown in yellow. Because the electrons spend more time by the fluorine atom in the H-F bond, the red represents partially negatively charged regions, while blue represents partially positively charged regions.

Not all atoms attract electrons with the same force. The amount of "pull" an atom exerts on its electrons is called its electronegativity. Atoms with high electronegativities — such as fluorine, oxygen, and nitrogen — exert a greater pull on electrons than atoms with lower electronegativities. In a bond, this leads to unequal sharing of electrons between the atoms, as electrons will be drawn closer to the atom with the higher electronegativity.

Because electrons have a negative charge, the unequal sharing of electrons within a bond leads to the formation of an electric dipole: a separation of positive and negative electric charge. Because the amount of charge separated in such dipoles is usually smaller than a fundamental charge, they are called partial charges, denoted as δ+ (delta plus) and δ− (delta minus). These symbols were introduced by Christopher Ingold and his wife Hilda Usherwood in 1926.^[1] The bond dipole moment is calculated by multiplying the amount of charge separated and the distance between the charges.

These dipoles within molecules can interact with dipoles in other molecules, creating dipole-dipole intermolecular forces.

Classification

Chemists classify the polarity of chemical bonds into three groups:

• Non-polar bonds occur when the difference in electronegativity between the two atoms is less than 0.4
• Polar bonds occur when the difference in electronegativity between the two atoms is between 0.4 and 2.0
• Ionic bonds occur when the difference in electronegativity between the two atoms is greater than 2.0^{[citation needed]}

Bonds can fall between one of two extremes — being completely nonpolar or completely polar. A completely nonpolar bond occurs when the electronegativities are identical and therefore possess a difference of zero. A completely polar bond is more correctly called an ionic bond, and occurs when the difference between electronegativities is large enough that one atom actually takes an electron from the other. The terms "polar" and "nonpolar" are usually applied to covalent bonds, that is, bonds where the polarity is not complete. To determine the polarity of a covalent bond using numerical means, the difference between the electronegativity of the atoms is taken. On the Pauling scale, if the result is less than 0.4, the bond is generally nonpolar covalent. If the result is between 0.4 and 1.7, the bond is generally polar covalent. If the result is greater than 1.7 the bond is generally considered ionic.

Pauling considered that the partial ionic character of a bond is an approximate function of the difference in electronegativity between the two bonded atoms. He estimated that a difference of 1.7 corresponds to 50% ionic character, so that a greater difference corresponds to a bond which is predominantly ionic.^[2]

Polarity of molecules

While the molecules can be described as "polar covalent", "nonpolar covalent", or "ionic", this is often a relative term, with one molecule simply being more polar or more nonpolar than another. However, the following properties are typical of such molecules.

A molecule is composed of one or more chemical bonds between molecular orbitals of different atoms. A molecule may be polar either as a result of polar bonds due to differences in electronegativity as described above, or as a result of an asymmetric arrangement of nonpolar covalent bonds and non-bonding pairs of electrons known as a full molecular orbital.

Polar molecules

The water molecule is made up of Oxygen and Hydrogen, with respective electronegativities of 3.44 and 2.20. The dipoles from each of the two bonds (red arrows) add together to make the overall molecule polar.

A polar molecule has a net dipole as a result of the opposing charges (i.e. having partial positive and partial negative charges) from polar bonds arranged asymmetrically. Water (H₂O) is an example of a polar molecule since it has a slight positive charge on one side and a slight negative charge on the other. The dipoles do not cancel out resulting in a net dipole. Due to the polar nature of the water molecule itself, polar molecules are generally able to dissolve in water. Another example includes sugars (like sucrose), which have many polar oxygen–hydrogen (-OH) groups and are overall highly polar.

If the bond dipole moments of the molecule do not cancel, the molecule is polar. For example, the water molecule (H₂O) contains two polar O-H bonds in a bent (nonlinear) geometry. The bond dipole moments do not cancel, so that the molecule forms a molecular dipole with its negative pole at the oxygen and its positive pole midway between the two hydrogen atoms. In the figure each bond joins the central O atom with a negative charge (red) to an H atom with a positive charge (blue).

The ammonia molecule, polar as a result of its molecular geometry. The red represents partially negatively charged regions.

The hydrogen fluoride, HF, molecule is polar by virtue of polar covalent bonds — in the covalent bond electrons are displaced towards the more electronegative fluorine atom. Ammonia, NH₃, molecule the three N–H bonds have only a slight polarity (toward the more electronegative nitrogen atom). However, the molecule has two lone electrons in an orbital, that points towards the fourth apex of the approximate tetrahedron, (VSEPR). This orbital is not participating in covalent bonding; it is electron-rich, which results in a powerful dipole across the whole ammonia molecule.

In the ozone - O₃ - molecule the two O–O bonds are nonpolar (there is no electronegativity difference between atoms of the same element). However, the distribution of other electrons is uneven — since the central atom has to share electrons with two other atoms, but each of the outer atoms has to share electrons with only one other atom, the central atom is more deprived of electrons than the others (the central atom has a formal charge of +1, while the outer atoms each have a formal charge of −1/2). Since the molecule has a bent geometry, the result is a dipole across the whole ozone molecule.

Nonpolar molecules

A molecule may be nonpolar either when there is an equal sharing of electrons between the two atoms of a diatomic molecule or because of the symmetrical arrangement of polar bonds in a more complex molecule. For example, boron trifluoride (BF₃) has a trigonal planar arrangement of three polar bonds at 120°. This results in no overall dipole in the molecule.

In a molecule of boron trifluoride, the trigonal planar arrangement of three polar bonds results in no overall dipole.

Carbon dioxide has two polar C-O bonds in a linear geometry.

Not every molecule with polar bonds is a polar molecule. Carbon dioxide (CO₂) has two polar C-O bonds, but the geometry of CO₂ is linear so that the two bond dipole moments cancel and there is no net molecular dipole moment; the molecule is non-polar.

In methane, the bonds are arranged symmetrically (in a tetrahedral arrangement) so there is no overall dipole.

Examples of household nonpolar compounds include fats, oil, and petrol/gasoline. Therefore (per the "oil and water" rule of thumb),^{[clarification needed]} most nonpolar molecules are water-insoluble (hydrophobic) at room temperature. However, many nonpolar organic solvents, such as turpentine, are able to dissolve polar substances. When comparing a polar and nonpolar molecule with similar molar masses, the polar molecule in general has a higher boiling point, because the dipole–dipole interaction between polar molecules causes greater attachment. The most common form of such an interaction is the hydrogen bond, which is also known as the H-bond.

In the methane molecule (CH₄) the four C–H bonds are arranged tetrahedrally around the carbon atom. Each bond has polarity (though not very strong). However, the bonds are arranged symmetrically so there is no overall dipole in the molecule. The diatomic oxygen molecule (O₂) does not have polarity in the covalent bond because of equal electronegativity, hence there is no polarity in the molecule.

Hybrids

Large molecules that have one end with polar groups attached and another end with nonpolar groups are good surfactants. They can aid in the formation of stable emulsions, or blends, of water and fats. Surfactants reduce the interfacial tension between oil and water by adsorbing at the liquid–liquid interface.

• This complex molecule has several polar groups (hydrophilic, water-loving) on the right side and a long nonpolar chain (lipophilic, fat-loving) at the left side. This gives it surfactant properties
• 

  A micelle — the lipophilic ends of the surfactant molecules dissolve in the oil, while the hydrophilic charged ends remain outside in the water phase, shielding the rest of the hydrophobic micelle. In this way, the small oil droplet becomes water-soluble.
• 

  Phospholipids are effective natural surfactants that have important biological functions
• 

  Cross section view of the structures that can be formed by phospholipids. They can form a micelle and are a vital in forming cell membranes

Predicting molecule polarity

• This classification table gives a good general understanding of predicting molecular dipole of some general molecular structures. However, one should not interpret it literally:

	Formula	Description	Example
Polar	AB	Linear Molecules	CO
	HAx	Molecules with a single H	HF
	AxOH	Molecules with an OH at one end	C2H5OH
	OxAy	Molecules with an O at one end	H2O
	NxAy	Molecules with an N at one end	NH3
Nonpolar	A2	Diatomic molecules of the same element	O2
	CxAy	Most carbon compounds	CO2

• Determining the point group is a useful way to predict polarity of a molecule. In general, a molecule will not possess dipole moment, if the individual bond dipole moments of the molecule cancel each other out. This is because dipole moments are euclidean vector quantities with magnitude and direction, and a two equal vectors who oppose each other will cancel out.

Any molecule with an centre of inversion ( "i" ) or a horizontal mirror plane ( "σ_h ") will not possess dipole moments. Likewise, a molecule with more than one C_n axis will not possess dipole moment because dipole moments cannot lie in more than one dimension. As a consequence of that constraint, all molecules with D symmetry (Schönflies notation) will, therefore, not have dipole moment because, by definition, D point groups have two or multiple C_n axis.

Since C₁, C_s,C_∞h C_n and C_nv point groups do not have a centre of inversion, horizontal mirror planes or multiple C_n axis, molecules in one of those point groups will have dipole moment.

Electronegativity

From Wikipedia, the free encyclopedia

This electrostatic potential map shows how the oxygen atom has a more negative charge (red) than the positive (blue) hydrogen atoms of a water molecule .

Electronegativity, symbol χ, is a chemical property that describes the tendency of an atom or a functional group to attract electrons (or electron density) towards itself.^[1] 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 number, the more an element or compound attracts electrons towards it. First proposed by Linus Pauling in 1932 as a development of valence bond theory,^[2] 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 between elements.

The most commonly used method of calculation is that originally proposed by Linus Pauling. This gives a dimensionless quantity, commonly referred to as the Pauling scale, on a relative scale running from around 0.7 to 3.98 (hydrogen = 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.

Electronegativity, as it is usually calculated, is not strictly a property of an atom, but rather a property of an atom in a molecule.^[3] Properties of a free atom include ionization energy and electron affinity. It is to be expected that the electronegativity of an element will vary with its chemical environment,^[4] 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.

On the most basic level, electronegativity is determined by factors like the nuclear charge (the more protons an atom has, the more "pull" it will have on electrons) and the number/location of other electrons present in the atomic shells (the more electrons an atom has, the farther from the nucleus 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 the valence electrons from the positively charged nucleus).

The opposite of electronegativity is electropositivity: a measure of an element's ability to donate electrons.
Francium is the least electronegative element in the periodic table (=0.7), while fluorine is the greatest one (=3.98).

Electronegativities of the elements

Periodic table of electronegativity by Pauling scale
→ Atomic radius decreases → Ionization energy increases → Electronegativity increases →
	1	2	3	4	5	6	7	8	9	10	11	12	13	14	15	16	17	18
Group →
↓ Period
1	H 2.20																	He
2	Li 0.98	Be 1.57											B 2.04	C 2.55	N 3.04	O 3.44	F 3.98	Ne
3	Na 0.93	Mg 1.31											Al 1.61	Si 1.90	P 2.19	S 2.58	Cl 3.16	Ar
4	K 0.82	Ca 1.00	Sc 1.36	Ti 1.54	V 1.63	Cr 1.66	Mn 1.55	Fe 1.83	Co 1.88	Ni 1.91	Cu 1.90	Zn 1.65	Ga 1.81	Ge 2.01	As 2.18	Se 2.55	Br 2.96	Kr 3.00
5	Rb 0.82	Sr 0.95	Y 1.22	Zr 1.33	Nb 1.6	Mo 2.16	Tc 1.9	Ru 2.2	Rh 2.28	Pd 2.20	Ag 1.93	Cd 1.69	In 1.78	Sn 1.96	Sb 2.05	Te 2.1	I 2.66	Xe 2.60
6	Cs 0.79	Ba 0.89		Hf 1.3	Ta 1.5	W 2.36	Re 1.9	Os 2.2	Ir 2.20	Pt 2.28	Au 2.54	Hg 2.00	Tl 1.62	Pb 1.87	Bi 2.02	Po 2.0	At 2.2	Rn 2.2
7	Fr 0.7	Ra 0.9		Rf	Db	Sg	Bh	Hs	Mt	Ds	Rg	Cn	Uut	Fl	Uup	Lv	Uus	Uuo
			La 1.1	Ce 1.12	Pr 1.13	Nd 1.14	Pm 1.13	Sm 1.17	Eu 1.2	Gd 1.2	Tb 1.1	Dy 1.22	Ho 1.23	Er 1.24	Tm 1.25	Yb 1.1	Lu 1.27
			Ac 1.1	Th 1.3	Pa 1.5	U 1.38	Np 1.36	Pu 1.28	Am 1.13	Cm 1.28	Bk 1.3	Cf 1.3	Es 1.3	Fm 1.3	Md 1.3	No 1.3	Lr 1.3
Values are given for the elements in their most common and stable oxidation states.

Methods of calculation

Pauling electronegativity

Pauling first proposed^[2] the concept of electronegativity in 1932 as an explanation of the fact that the covalent bond between two different atoms (A–B) is stronger than would be expected by taking the average of the strengths of the A–A and B–B bonds. According to valence bond theory, of which Pauling was a notable proponent, this "additional stabilization" of the heteronuclear bond is due to the contribution of ionic canonical forms to the bonding.

The difference in electronegativity between atoms A and B is given by:

where the dissociation energies, E_d, of the A–B, A–A and B–B bonds are expressed in electronvolts, the factor (eV)^−½ being included to ensure a dimensionless result. Hence, the difference in Pauling electronegativity between hydrogen and bromine 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^[2] at 2.1, later revised^[5] 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 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 is 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 bond formed by that element. A. L. Allred updated Pauling's original values in 1961 to take account of the greater availability of thermodynamic data,^[5] 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:

or sometimes, a more accurate fit

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 approximately, by quantum mechanical calculations, the geometric mean of the two energies of covalent bonds of the same molecules, and there is an additional energy that comes from ionic factors, i.e. polar character of the bond.

The geometric mean is approximately equal to the arithmetic mean - which is applied in the first formula above - when the energies are of the 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 a 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 Pauling electronegativity concept.

The formulas are approximate, but this rough approximation is in fact relatively good and gives the right intuition, with the notion of 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 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 formation of a molecule containing only single bonds then can 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 relative error of order of 10%, but can be used to get a rough qualitative idea and understanding of a molecule.

Mulliken electronegativity

The correlation between Mulliken electronegativities (x-axis, in kJ/mol) and Pauling electronegativities (y-axis).

Robert S. Mulliken proposed that the arithmetic mean of the first ionization energy (E_i) and the electron affinity (E_ea) should be a measure of the tendency of an atom to attract electrons.^[6][7] As this definition is not dependent on an arbitrary relative scale, it has also been termed absolute electronegativity,^[8] with the units of kilojoules per mole or electronvolts.

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,^[9]

and for energies in kilojoules per mole,^[10]

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. 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.,

Allred–Rochow electronegativity

The correlation between Allred–Rochow electronegativities (x-axis, in Å⁻²) and Pauling electronegativities (y-axis).

A. Louis Allred and Eugene G. Rochow considered^[11] 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, Z_eff, experienced by valence electrons can be estimated using Slater's rules, while the surface area of an atom in a molecule can be taken to be proportional to the square of the covalent radius, r_cov. When r_cov is expressed in picometres,^[12]

Sanderson electronegativity equalization

The correlation between Sanderson electronegativities (x-axis, arbitrary units) and Pauling electronegativities (y-axis).

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.^[13] With a knowledge of bond lengths, Sanderson's model allows the estimation of bond energies in a wide range of compounds.^[14] Sanderson's model has also been used to calculate molecular geometry, s-electrons energy, NMR spin-spin constants and other parameters for organic compounds.^[15][16] 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.^[17] This behavior is analogous to the equalization of chemical potential in macroscopic thermodynamics.^[18]

Allen electronegativity

The correlation between Allen electronegativities (x-axis, in kJ/mol) and Pauling electronegativities (y-axis).

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 electrons in a free atom,^[19]

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 spectroscopic data, 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, which has an Allen electronegativity of 0.67.^[20] 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 has the highest electronegativity of all elements, followed by fluorine, helium, and oxygen.

Electronegativity using the Allen scale
Group →	1	2	3	4	5	6	7	8	9	10	11	12	13	14	15	16	17	18
↓ Period
1	H 2.300																	He 4.160
2	Li 0.912	Be 1.576											B 2.051	C 2.544	N 3.066	O 3.610	F 4.193	Ne 4.789
3	Na 0.869	Mg 1.293											Al 1.613	Si 1.916	P 2.253	S 2.589	Cl 2.869	Ar 3.242
4	K 0.734	Ca 1.034	Sc 1.19	Ti 1.38	V 1.53	Cr 1.65	Mn 1.75	Fe 1.80	Co 1.84	Ni 1.88	Cu 1.85	Zn 1.59	Ga 1.756	Ge 1.994	As 2.211	Se 2.434	Br 2.685	Kr 2.966
5	Rb 0.706	Sr 0.963	Y 1.12	Zr 1.32	Nb 1.41	Mo 1.47	Tc 1.51	Ru 1.54	Rh 1.56	Pd 1.59	Ag 1.87	Cd 1.52	In 1.656	Sn 1.824	Sb 1.984	Te 2.158	I 2.359	Xe 2.582
6	Cs 0.659	Ba 0.881	Lu 1.09	Hf 1.16	Ta 1.34	W 1.47	Re 1.60	Os 1.65	Ir 1.68	Pt 1.72	Au 1.92	Hg 1.76	Tl 1.789	Pb 1.854	Bi 2.01	Po 2.19	At 2.39	Rn 2.60
7	Fr 0.67	Ra 0.89

Correlation of electronegativity with other properties

The variation of the isomer shift (y-axis, in mm/s) of [SnX₆]²⁻ anions, as measured by ¹¹⁹Sn Mössbauer spectroscopy, 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 which 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 "ionic character" of a bond to the difference in electronegativity of the two atoms,^[3] although this has fallen somewhat into disuse.

Several correlations have been shown between infrared stretching frequencies of certain bonds and the electronegativities of the atoms involved:^[21] 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^[22] or isomer shifts in Mössbauer spectroscopy^[23] (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".^[1][3]

Trends in electronegativity

Periodic trends

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 is the most electronegative of the elements (not counting noble gases), whereas caesium is the least electronegative, at least of those elements for which substantial data is available.^[20]

There are some exceptions to this general rule. Gallium and germanium have higher electronegativities than aluminium and silicon, respectively, because of the d-block contraction. 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, in particular when compared to thallium and bismuth, appears to be an artifact of data selection (and data availability)—methods of calculation other than the Pauling method show the normal periodic trends for these elements.

Variation of electronegativity with oxidation number

In inorganic chemistry it is common to consider a single value of the 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 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 was available.^[5] 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.

Acid	Formula	Chlorine oxidation state	pKa
Hypochlorous acid	HClO	+1	+7.5
Chlorous acid	HClO2	+3	+2.0
Chloric acid	HClO3	+5	–1.0
Perchloric acid	HClO4	+7	–10

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 oxides with low melting points, while Cr₂O₃ is amphoteric and Mn₂O₃ is a completely basic oxide.

The effect can also be clearly seen in the dissociation constants of the oxoacids of chlorine. 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 pK_a of log₁₀(¼) = –0.6 between hypochlorous acid and perchloric acid. As the oxidation state of the central chlorine atom increases, more electron density is drawn from the oxygen atoms onto the chlorine, reducing the partial negative charge on the oxygen atoms and increasing the acidity.

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 and the resonance effect, 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 is the best known. Kabachnik parameters are group electronegativities for use in organophosphorus chemistry.

Electropositivity

Electropositivity is a measure of an element's ability to donate electrons, and therefore form positive ions; thus, it is opposed to electronegativity. Mainly, this is an attribute of metals, meaning that, in general, the greater the metallic character of an element the greater the electropositivity. Therefore the alkali metals are 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.^[24]

While electronegativity increases along periods in the periodic table, and decreases down groups, electropositivity decreases along periods (from left to right) and increases down groups.

Electropositive shark repellent utilizes electropositive metals as shark repellents, since they generate measurable voltages in a seawater electrolyte relative to a shark.