Electronegativity

From Wikipedia, the free encyclopedia

Electrostatic potential map of a water molecule, where the oxygen atom has a more negative charge (red) than the positive (blue) hydrogen atoms

Electronegativity, symbol χ, is a chemical property that describes the tendency of an atom 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.

The term "electronegativity" was introduced by Jöns Jacob Berzelius in 1811,^[2] though the concept was known even before that and was studied by many chemists including Avogadro.^[2] In spite of its long history, an accurate scale of electronegativity had to wait until 1932, when Linus Pauling proposed an electronegativity scale, which depends on bond energies, as a development of valence bond theory.^[3] 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 (χ_r), 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.

As it is usually calculated, electronegativity is not a property of an atom alone, but rather a property of an atom in a molecule.^[4] 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,^[5] 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.

Caesium is the least electronegative element in the periodic table (=0.79), while fluorine is most electronegative (=3.98). Francium and caesium were originally both assigned 0.7; caesium's value was later refined to 0.79, but no experimental data allows a similar refinement for francium. However, francium's ionization energy is known to be slightly higher than caesium's, in accordance with the relativistic stabilization of the 7s orbital, and this in turn implies that francium is in fact more electronegative than caesium.^[6]

Electronegativities of the elements

v t e 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	La 1.1		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[en 1]	Ra 0.9	Ac 1.1		Rf	Db	Sg	Bh	Hs	Mt	Ds	Rg	Cn	Nh	Fl	Mc	Lv	Ts	Og
					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
					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[en 2]
Values are given for the elements in their most common and stable oxidation states. See also: Electronegativities of the elements (data page)

Electronegativity of francium was chosen by Pauling as 0.7, close to that of caesium (also assessed 0.7 at that point). The base value of hydrogen was later increased by 0.10 and caesium's electronegativity was later refined to 0.79; however, no refinements have been made for francium as no experiment has been conducted and the old value was kept. However, francium is expected and, to a small extent, observed to be more electronegative than caesium. See francium for details.

See Brown, Geoffrey (2012). The Inaccessible Earth: An integrated view to its structure and composition. Springer Science & Business Media. p. 88. ISBN 9789401115162.

Methods of calculation

Pauling electronegativity

Pauling first proposed^[3] 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:

${\displaystyle |\chi _{\rm {A}}-\chi _{\rm {B}}|=({\rm {eV}})^{-1/2}{\sqrt {E_{\rm {d}}({\rm {AB}})-[E_{\rm {d}}({\rm {AA}})+E_{\rm {d}}({\rm {BB}})]/2}}}$

where the dissociation energies, E_d, of the A–B, A–A and B–B bonds are expressed in electronvolts, the factor (eV)^{− 1⁄₂} 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^[3] at 2.1, later revised^[7] 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 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 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,^[7] 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:

${\displaystyle E_{\rm {d}}({\rm {AB}})=[E_{\rm {d}}({\rm {AA}})+E_{\rm {d}}({\rm {BB}})]/2+(\chi _{\rm {A}}-\chi _{\rm {B}})^{2}eV}$

or sometimes, a more accurate fit

${\displaystyle E_{\rm {d}}({\rm {AB}})={\sqrt {E_{\rm {d}}({\rm {AA}})E_{\rm {d}}({\rm {BB}})}}+1.3(\chi _{\rm {A}}-\chi _{\rm {B}})^{2}eV}$

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.^[8][9] As this definition is not dependent on an arbitrary relative scale, it has also been termed absolute electronegativity,^[10] with the units of kilojoules per mole or electronvolts.

${\displaystyle \chi =(E_{\rm {i}}+E_{\rm {ea}})/2\,}$

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,^[11]

${\displaystyle \chi =0.187(E_{\rm {i}}+E_{\rm {ea}})+0.17\,}$

and for energies in kilojoules per mole,^[12]

${\displaystyle \chi =(1.97\times 10^{-3})(E_{\rm {i}}+E_{\rm {ea}})+0.19.}$

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. 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.,

${\displaystyle \mu ({\rm {Mulliken)=-\chi ({\rm {Mulliken)=-(E_{\rm {i}}+E_{\rm {ea}})/2\,}}}}}$

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^[13] 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,^[14]

${\displaystyle \chi =3590{{Z_{\rm {eff}}} \over {r_{\rm {cov}}^{2}}}+0.744}$

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.^[15] With a knowledge of bond lengths, Sanderson's model allows the estimation of bond energies in a wide range of compounds.^[16] Sanderson's model has also been used to calculate molecular geometry, s-electrons energy, NMR spin-spin constants and other parameters for organic compounds.^[17][18] 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.^[19] This behavior is analogous to the equalization of chemical potential in macroscopic thermodynamics.^[20]

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,^[21] ,^[22] ,^[23]

${\displaystyle \chi ={n_{\rm {s}}\varepsilon _{\rm {s}}+n_{\rm {p}}\varepsilon _{\rm {p}} \over n_{\rm {s}}+n_{\rm {p}}}}$

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.^[24] 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.

v t e 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 4.787
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 2.424	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 1.58	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,^[4] 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:^[25] 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^[26] or isomer shifts in Mössbauer spectroscopy^[27] (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][4]

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.^[24] This would lead one to believe that caesium fluoride is the compound whose bonding features the most ionic character.

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.^[7] 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( ¹⁄₄) = –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.^[28]

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.

Chemical polarity

From Wikipedia, the free encyclopedia

A water molecule, a commonly used example of polarity. 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 is a separation of electric charge leading to a molecule or its chemical groups having an electric dipole or multipole moment.

Polar molecules must contain polar bonds due to a difference in electronegativity between the bonded atoms. A polar molecule with two or more polar bonds must have an asymmetric geometry so that the bond dipoles do not cancel each other.

Polar molecules interact through dipole–dipole intermolecular forces and hydrogen bonds. 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 Kelk Ingold and Edith Hilda Ingold in 1926.^[1][2] 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

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 used.

Bond polarity is typically divided into three groups that are loosely based on the difference in electronegativity between the two bonded atoms. According to the Pauling scale:

• Nonpolar bonds generally occur when the difference in electronegativity between the two atoms is less than 0.5
• Polar bonds generally occur when the difference in electronegativity between the two atoms is roughly between 0.5 and 2.0
• Ionic bonds generally occur when the difference in electronegativity between the two atoms is greater than 2.0

Pauling based this classification scheme on the partial ionic character of a bond, which 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.^[3]

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. Other examples include 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, NH₃, 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 toward the more electronegative fluorine atom. Ammonia, NH₃, molecule the three N−H bonds have only a slight polarity (toward the more electronegative nitrogen atom). 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 ozone (O₃) molecules, 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.
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 results in stronger intermolecular attractions. One common form of polar interaction is the hydrogen bond, which is also known as the H-bond. For example, water forms H-bonds and has a molar mass M = 18 and a boiling point of +100 °C, compared to nonpolar methane with M = 16 and a boiling point of –161 °C.

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 nonpolar.

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, most nonpolar molecules are water-insoluble (hydrophobic) at room temperature. Many nonpolar organic solvents, such as turpentine, are able to dissolve polar substances.

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.

Amphiphilic molecules

Large molecules that have one end with polar groups attached and another end with nonpolar groups are described as amphiphiles or amphiphilic molecules. They are good surfactants and 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 amphiphilic 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

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

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 a 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.

Hydrogen bond

From Wikipedia, the free encyclopedia

 

AFM image of napthalenetetracarboxylic diimide molecules on silver-terminated silicon, interacting via hydrogen bonding, taken at 77  K.^[1] ("Hydrogen bonds" in the top image are exaggerated by artifacts of the imaging technique.^[2][3])

Model of hydrogen bonds (1) between molecules of water

A hydrogen bond is the electrostatic attraction between two polar groups that occurs when a hydrogen (H) atom covalently bound to a highly electronegative atom such as nitrogen (N), oxygen (O), or fluorine (F) experiences the electrostatic field of another highly electronegative atom nearby.
Hydrogen bonds can occur between molecules (intermolecular) or within different parts of a single molecule (intramolecular).^[4] Depending on geometry and environment, the hydrogen bond free energy content is between 1 and 5 kcal/mol. This makes it stronger than a van der Waals interaction, but weaker than covalent or ionic bonds. This type of bond can occur in inorganic molecules such as water and in organic molecules like DNA and proteins.

Intermolecular hydrogen bonding is responsible for the high boiling point of water (100 °C) compared to the other group 16 hydrides that have much weaker hydrogen bonds.^[5] Intramolecular hydrogen bonding is partly responsible for the secondary and tertiary structures of proteins and nucleic acids. It also plays an important role in the structure of polymers, both synthetic and natural.
In 2011, an IUPAC Task Group recommended a modern evidence-based definition of hydrogen bonding, which was published in the IUPAC journal Pure and Applied Chemistry. This definition specifies:

The hydrogen bond is an attractive interaction between a hydrogen atom from a molecule or a molecular fragment X–H in which X is more electronegative than H, and an atom or a group of atoms in the same or a different molecule, in which there is evidence of bond formation.^[6]

An accompanying detailed technical report provides the rationale behind the new definition.^[7]

Bonding

An example of intermolecular hydrogen bonding in a self-assembled dimer complex reported by Meijer and coworkers.^[8] The hydrogen bonds are represented by dotted lines.

Intramolecular hydrogen bonding in acetylacetone helps stabilize the enol tautomer.

A hydrogen atom attached to a relatively electronegative atom will play the role of the hydrogen bond donor.^[9] This electronegative atom is usually fluorine, oxygen, or nitrogen. A hydrogen attached to carbon can also participate in hydrogen bonding when the carbon atom is bound to electronegative atoms, as is the case in chloroform, CHCl₃.^[10][11][12] An example of a hydrogen bond donor is the hydrogen from the hydroxyl group of ethanol, which is bonded to an oxygen.

In a hydrogen bond, the electronegative atom not covalently attached to the hydrogen is named proton acceptor, whereas the one covalently bound to the hydrogen is named the proton donor.

Examples of hydrogen bond donating (donors) and hydrogen bond accepting groups (acceptors)

Cyclic dimer of acetic acid; dashed green lines represent hydrogen bonds

In the donor molecule, the electronegative atom attracts the electron cloud from around the hydrogen nucleus of the donor, and, by decentralizing the cloud, leaves the atom with a positive partial charge. Because of the small size of hydrogen relative to other atoms and molecules, the resulting charge, though only partial, represents a large charge density. A hydrogen bond results when this strong positive charge density attracts a lone pair of electrons on another heteroatom, which then becomes the hydrogen-bond acceptor.

The hydrogen bond is often described as an electrostatic dipole-dipole interaction. However, it also has some features of covalent bonding: it is directional and strong, produces interatomic distances shorter than the sum of the van der Waals radii, and usually involves a limited number of interaction partners, which can be interpreted as a type of valence. These covalent features are more substantial when acceptors bind hydrogens from more electronegative donors.

The partially covalent nature of a hydrogen bond raises the following questions: "To which molecule or atom does the hydrogen nucleus belong?" and "Which should be labeled 'donor' and which 'acceptor'?" Usually, this is simple to determine on the basis of interatomic distances in the X−H···Y system, where the dots represent the hydrogen bond: the X−H distance is typically ≈110 pm, whereas the H···Y distance is ≈160 to 200 pm. Liquids that display hydrogen bonding (such as water) are called associated liquids.

Hydrogen bonds can vary in strength from very weak (1–2 kJ mol⁻¹) to extremely strong (161.5 kJ mol⁻¹ in the ion HF−
2).^[13][14] Typical enthalpies in vapor include:

• F−H···:F (161.5 kJ/mol or 38.6 kcal/mol)
• O−H···:N (29 kJ/mol or 6.9 kcal/mol)
• O−H···:O (21 kJ/mol or 5.0 kcal/mol)
• N−H···:N (13 kJ/mol or 3.1 kcal/mol)
• N−H···:O (8 kJ/mol or 1.9 kcal/mol)
• HO−H···:OH+
  3 (18 kJ/mol^[15] or 4.3 kcal/mol; data obtained using molecular dynamics as detailed in the reference and should be compared to 7.9 kJ/mol for bulk water, obtained using the same molecular dynamics.)

Quantum chemical calculations of the relevant interresidue potential constants (compliance constants) revealed^[how?] large differences between individual H bonds of the same type. For example, the central interresidue N−H···N hydrogen bond between guanine and cytosine is much stronger in comparison to the N−H···N bond between the adenine-thymine pair.^[16]

The length of hydrogen bonds depends on bond strength, temperature, and pressure. The bond strength itself is dependent on temperature, pressure, bond angle, and environment (usually characterized by local dielectric constant). The typical length of a hydrogen bond in water is 197 pm. The ideal bond angle depends on the nature of the hydrogen bond donor. The following hydrogen bond angles between a hydrofluoric acid donor and various acceptors have been determined experimentally:^[17]

Acceptor···donor	VSEPR geometry	Angle (°)
HCN···HF	linear	180
H2CO···HF	trigonal planar	120
H2O···HF	pyramidal	46
H2S···HF	pyramidal	89
SO2···HF	trigonal	142

History

In the book The Nature of the Chemical Bond, Linus Pauling credits T. S. Moore and T. F. Winmill with the first mention of the hydrogen bond, in 1912.^[18][19] Moore and Winmill used the hydrogen bond to account for the fact that trimethylammonium hydroxide is a weaker base than tetramethylammonium hydroxide. The description of hydrogen bonding in its better-known setting, water, came some years later, in 1920, from Latimer and Rodebush.^[20] In that paper, Latimer and Rodebush cite work by a fellow scientist at their laboratory, Maurice Loyal Huggins, saying, "Mr. Huggins of this laboratory in some work as yet unpublished, has used the idea of a hydrogen kernel held between two atoms as a theory in regard to certain organic compounds."

Hydrogen bonds in water

Crystal structure of hexagonal ice. Gray dashed lines indicate hydrogen bonds

The most ubiquitous and perhaps simplest example of a hydrogen bond is found between water molecules. In a discrete water molecule, there are two hydrogen atoms and one oxygen atom. Two molecules of water can form a hydrogen bond between them; the simplest case, when only two molecules are present, is called the water dimer and is often used as a model system. When more molecules are present, as is the case with liquid water, more bonds are possible because the oxygen of one water molecule has two lone pairs of electrons, each of which can form a hydrogen bond with a hydrogen on another water molecule. This can repeat such that every water molecule is H-bonded with up to four other molecules, as shown in the figure (two through its two lone pairs, and two through its two hydrogen atoms). Hydrogen bonding strongly affects the crystal structure of ice, helping to create an open hexagonal lattice. The density of ice is less than the density of water at the same temperature; thus, the solid phase of water floats on the liquid, unlike most other substances.

Liquid water's high boiling point is due to the high number of hydrogen bonds each molecule can form, relative to its low molecular mass. Owing to the difficulty of breaking these bonds, water has a very high boiling point, melting point, and viscosity compared to otherwise similar liquids not conjoined by hydrogen bonds. Water is unique because its oxygen atom has two lone pairs and two hydrogen atoms, meaning that the total number of bonds of a water molecule is up to four. For example, hydrogen fluoride—which has three lone pairs on the F atom but only one H atom—can form only two bonds; (ammonia has the opposite problem: three hydrogen atoms but only one lone pair).

H−F···H−F···H−F

The exact number of hydrogen bonds formed by a molecule of liquid water fluctuates with time and depends on the temperature.^[21] From TIP4P liquid water simulations at 25 °C, it was estimated that each water molecule participates in an average of 3.59 hydrogen bonds. At 100 °C, this number decreases to 3.24 due to the increased molecular motion and decreased density, while at 0 °C, the average number of hydrogen bonds increases to 3.69.^[21] A more recent study found a much smaller number of hydrogen bonds: 2.357 at 25 °C.^[22] The differences may be due to the use of a different method for defining and counting the hydrogen bonds.

Where the bond strengths are more equivalent, one might instead find the atoms of two interacting water molecules partitioned into two polyatomic ions of opposite charge, specifically hydroxide (OH⁻) and hydronium (H₃O⁺). (Hydronium ions are also known as "hydroxonium" ions.)

H−O⁻ H₃O⁺

Indeed, in pure water under conditions of standard temperature and pressure, this latter formulation is applicable only rarely; on average about one in every 5.5 × 10⁸ molecules gives up a proton to another water molecule, in accordance with the value of the dissociation constant for water under such conditions. It is a crucial part of the uniqueness of water.

Because water may form hydrogen bonds with solute proton donors and acceptors, it may competitively inhibit the formation of solute intermolecular or intramolecular hydrogen bonds. Consequently, hydrogen bonds between or within solute molecules dissolved in water are almost always unfavorable relative to hydrogen bonds between water and the donors and acceptors for hydrogen bonds on those solutes.^[23] Hydrogen bonds between water molecules have an average lifetime of 10⁻¹¹ seconds, or 10 picoseconds.^[24]

Bifurcated and over-coordinated hydrogen bonds in water

A single hydrogen atom can participate in two hydrogen bonds, rather than one. This type of bonding is called "bifurcated" (split in two or "two-forked"). It can exist, for instance, in complex natural or synthetic organic molecules.^[25] It has been suggested that a bifurcated hydrogen atom is an essential step in water reorientation.^[26]

Acceptor-type hydrogen bonds (terminating on an oxygen's lone pairs) are more likely to form bifurcation (it is called overcoordinated oxygen, OCO) than are donor-type hydrogen bonds, beginning on the same oxygen's hydrogens.^[27]

Hydrogen bonds in DNA and proteins

The structure of part of a DNA double helix

Hydrogen bonding between guanine and cytosine, one of two types of base pairs in DNA.

Hydrogen bonding also plays an important role in determining the three-dimensional structures adopted by proteins and nucleic bases. In these macromolecules, bonding between parts of the same macromolecule cause it to fold into a specific shape, which helps determine the molecule's physiological or biochemical role. For example, the double helical structure of DNA is due largely to hydrogen bonding between its base pairs (as well as pi stacking interactions), which link one complementary strand to the other and enable replication.

In the secondary structure of proteins, hydrogen bonds form between the backbone oxygens and amide hydrogens. When the spacing of the amino acid residues participating in a hydrogen bond occurs regularly between positions i and i + 4, an alpha helix is formed. When the spacing is less, between positions i and i + 3, then a 3₁₀ helix is formed. When two strands are joined by hydrogen bonds involving alternating residues on each participating strand, a beta sheet is formed. Hydrogen bonds also play a part in forming the tertiary structure of protein through interaction of R-groups. (See also protein folding).

The role of hydrogen bonds in protein folding has also been linked to osmolyte-induced protein stabilization. Protective osmolytes, such as trehalose and sorbitol, shift the protein folding equilibrium toward the folded state, in a concentration dependent manner. While the prevalent explanation for osmolyte action relies on excluded volume effects, that are entropic in nature, recent Circular dichroism (CD) experiments have shown osmolyte to act through an enthalpic effect.^[28] The molecular mechanism for their role in protein stabilization is still not well established, though several mechanism have been proposed. Recently, computer molecular dynamics simulations suggested that osmolytes stabilize proteins by modifying the hydrogen bonds in the protein hydration layer.^[29]

Several studies have shown that hydrogen bonds play an important role for the stability between subunits in multimeric proteins. For example, a study of sorbitol dehydrogenase displayed an important hydrogen bonding network which stabilizes the tetrameric quaternary structure within the mammalian sorbitol dehydrogenase protein family.^[30]

A protein backbone hydrogen bond incompletely shielded from water attack is a dehydron. Dehydrons promote the removal of water through proteins or ligand binding. The exogenous dehydration enhances the electrostatic interaction between the amide and carbonyl groups by de-shielding their partial charges. Furthermore, the dehydration stabilizes the hydrogen bond by destabilizing the nonbonded state consisting of dehydrated isolated charges.^[31]

Hydrogen bonds in polymers

Para-aramid structure

A strand of cellulose (conformation I_α), showing the hydrogen bonds (dashed) within and between cellulose molecules.

Many polymers are strengthened by hydrogen bonds in their main chains. Among the synthetic polymers, the best known example is nylon, where hydrogen bonds occur in the repeat unit and play a major role in crystallization of the material. The bonds occur between carbonyl and amine groups in the amide repeat unit. They effectively link adjacent chains to create crystals, which help reinforce the material. The effect is greatest in aramid fibre, where hydrogen bonds stabilize the linear chains laterally. The chain axes are aligned along the fibre axis, making the fibres extremely stiff and strong. Hydrogen bonds are also important in the structure of cellulose and derived polymers in its many different forms in nature, such as wood and natural fibres such as cotton and flax.

The hydrogen bond networks make both natural and synthetic polymers sensitive to humidity levels in the atmosphere because water molecules can diffuse into the surface and disrupt the network. Some polymers are more sensitive than others. Thus nylons are more sensitive than aramids, and nylon 6 more sensitive than nylon-11.

Symmetric hydrogen bond

A symmetric hydrogen bond is a special type of hydrogen bond in which the proton is spaced exactly halfway between two identical atoms. The strength of the bond to each of those atoms is equal. It is an example of a three-center four-electron bond. This type of bond is much stronger than a "normal" hydrogen bond. The effective bond order is 0.5, so its strength is comparable to a covalent bond. It is seen in ice at high pressure, and also in the solid phase of many anhydrous acids such as hydrofluoric acid and formic acid at high pressure. It is also seen in the bifluoride ion [F−H−F]⁻.

Symmetric hydrogen bonds have been observed recently spectroscopically in formic acid at high pressure (>GPa). Each hydrogen atom forms a partial covalent bond with two atoms rather than one. Symmetric hydrogen bonds have been postulated in ice at high pressure (Ice X). Low-barrier hydrogen bonds form when the distance between two heteroatoms is very small.

Dihydrogen bond

The hydrogen bond can be compared with the closely related dihydrogen bond, which is also an intermolecular bonding interaction involving hydrogen atoms. These structures have been known for some time, and well characterized by crystallography;^[32] however, an understanding of their relationship to the conventional hydrogen bond, ionic bond, and covalent bond remains unclear. Generally, the hydrogen bond is characterized by a proton acceptor that is a lone pair of electrons in nonmetallic atoms (most notably in the nitrogen, and chalcogen groups). In some cases, these proton acceptors may be pi-bonds or metal complexes. In the dihydrogen bond, however, a metal hydride serves as a proton acceptor, thus forming a hydrogen-hydrogen interaction. Neutron diffraction has shown that the molecular geometry of these complexes is similar to hydrogen bonds, in that the bond length is very adaptable to the metal complex/hydrogen donor system.^[32]

Advanced theory of the hydrogen bond

In 1999, Isaacs et al.^[33] showed from interpretations of the anisotropies in the Compton profile of ordinary ice that the hydrogen bond is partly covalent. However, this interpretation was challenged by Ghanty et al.,^[34] who concluded that considering electrostatic forces alone could explain the experimental results. Some NMR data on hydrogen bonds in proteins also indicate covalent bonding.
Most generally, the hydrogen bond can be viewed as a metric-dependent electrostatic scalar field between two or more intermolecular bonds. This is slightly different from the intramolecular bound states of, for example, covalent or ionic bonds; however, hydrogen bonding is generally still a bound state phenomenon, since the interaction energy has a net negative sum. The initial theory of hydrogen bonding proposed by Linus Pauling suggested that the hydrogen bonds had a partial covalent nature. This remained a controversial conclusion until the late 1990s when NMR techniques were employed by F. Cordier et al. to transfer information between hydrogen-bonded nuclei, a feat that would only be possible if the hydrogen bond contained some covalent character.^[35] While much experimental data has been recovered for hydrogen bonds in water, for example, that provide good resolution on the scale of intermolecular distances and molecular thermodynamics, the kinetic and dynamical properties of the hydrogen bond in dynamic systems remain unchanged.

Dynamics probed by spectroscopic means

The dynamics of hydrogen bond structures in water can be probed by the IR spectrum of OH stretching vibration.^[36] In the hydrogen bonding network in protic organic ionic plastic crystals (POIPCs), which are a type of phase change material exhibiting solid-solid phase transitions prior to melting, variable-temperature infrared spectroscopy can reveal the temperature dependence of hydrogen bonds and the dynamics of both the anions and the cations.^[37] The sudden weakening of hydrogen bonds during the solid-solid phase transition seems to be coupled with the onset of orientational or rotational disorder of the ions.^[37]

Hydrogen bonding phenomena

• Dramatically higher boiling points of NH₃, H₂O, and HF compared to the heavier analogues PH₃, H₂S, and HCl.
• Increase in the melting point, boiling point, solubility, and viscosity of many compounds can be explained by the concept of hydrogen bonding.
• Occurrence of proton tunneling during DNA replication is believed to be responsible for cell mutations.^[38]
• Viscosity of anhydrous phosphoric acid and of glycerol
• Dimer formation in carboxylic acids and hexamer formation in hydrogen fluoride, which occur even in the gas phase, resulting in gross deviations from the ideal gas law.
• Pentamer formation of water and alcohols in apolar solvents.
• High water solubility of many compounds such as ammonia is explained by hydrogen bonding with water molecules.
• Negative azeotropy of mixtures of HF and water
• Deliquescence of NaOH is caused in part by reaction of OH⁻ with moisture to form hydrogen-bonded H
  3O−
  2 species. An analogous process happens between NaNH₂ and NH₃, and between NaF and HF.
• The fact that ice is less dense than liquid water is due to a crystal structure stabilized by hydrogen bonds.
• The presence of hydrogen bonds can cause an anomaly in the normal succession of states of matter for certain mixtures of chemical compounds as temperature increases or decreases. These compounds can be liquid until a certain temperature, then solid even as the temperature increases, and finally liquid again as the temperature rises over the "anomaly interval"^[39]
• Smart rubber utilizes hydrogen bonding as its sole means of bonding, so that it can "heal" when torn, because hydrogen bonding can occur on the fly between two surfaces of the same polymer.
• Strength of nylon and cellulose fibres.
• Wool, being a protein fibre, is held together by hydrogen bonds, causing wool to recoil when stretched. However, washing at high temperatures can permanently break the hydrogen bonds and a garment may permanently lose its shape.