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   Ionic and covalent bondinganimation 1 min 57 sec - 15 Apr 2008 www.youtube.com

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IONIC (ELECTROVALENT) BONDING This page explains what ionic (electrovalent) bonding is. It starts with a simple picture of the formation of ions, and then modifies it slightly for A'level purposes. A simple view of ionic bonding The importance of noble gas structures At a simple level (like GCSE) a lot of importance is attached to the electronic structures of noble gases like neon or argon which have eight electrons in their outer energy levels (or two in the case of helium). These noble gas structures are thought of as being in some way a "desirable" thing for an atom to have. You may well have been left with the strong impression that when other atoms react, they try to organise things such that their outer levels are either completely full or completely empty.
	Note: The central role given to noble gas structures is very much an over-simplification. We shall have to spend some time later on demolishing the concept!
Ionic bonding in sodium chloride Sodium (2,8,1) has 1 electron more than a stable noble gas structure (2,8). If it gave away that electron it would become more stable. Chlorine (2,8,7) has 1 electron short of a stable noble gas structure (2,8,8). If it could gain an electron from somewhere it too would become more stable. The answer is obvious. If a sodium atom gives an electron to a chlorine atom, both become more stable. The sodium has lost an electron, so it no longer has equal numbers of electrons and protons. Because it has one more proton than electron, it has a charge of 1+. If electrons are lost from an atom, positive ions are formed. Positive ions are sometimes called cations. The chlorine has gained an electron, so it now has one more electron than proton. It therefore has a charge of 1-. If electrons are gained by an atom, negative ions are formed. A negative ion is sometimes called an anion. The nature of the bond The sodium ions and chloride ions are held together by the strong electrostatic attractions between the positive and negative charges. The formula of sodium chloride You need one sodium atom to provide the extra electron for one chlorine atom, so they combine together 1:1. The formula is therefore NaCl. Some other examples of ionic bonding magnesium oxide Again, noble gas structures are formed, and the magnesium oxide is held together by very strong attractions between the ions. The ionic bonding is stronger than in sodium chloride because this time you have 2+ ions attracting 2- ions. The greater the charge, the greater the attraction. The formula of magnesium oxide is MgO. calcium chloride This time you need two chlorines to use up the two outer electrons in the calcium. The formula of calcium chloride is therefore CaCl2. potassium oxide Again, noble gas structures are formed. It takes two potassiums to supply the electrons the oxygen needs. The formula of potassium oxide is K2O. THE A'LEVEL VIEW OF IONIC BONDING Electrons are transferred from one atom to another resulting in the formation of positive and negative ions. The electrostatic attractions between the positive and negative ions hold the compound together. So what's new? At heart - nothing. What needs modifying is the view that there is something magic about noble gas structures. There are far more ions which don't have noble gas structures than there are which do. Some common ions which don't have noble gas structures You may have come across some of the following ions in a basic course like GCSE. They are all perfectly stable , but not one of them has a noble gas structure. Fe3+ [Ar]3d5 Cu2+ [Ar]3d9 Zn2+ [Ar]3d10 Ag+ [Kr]4d10 Pb2+ [Xe]4f145d106s2 Noble gases (apart from helium) have an outer electronic structure ns2np6.
	Note: If you aren't happy about writing electronic structuresusing of s, p and d notation, follow this link before you go on. Return to this page via the menus or by using the BACK button on your browser.
Apart from some elements at the beginning of a transition series (scandium forming Sc3+ with an argon structure, for example), all transition elements and any metals following a transition series (like tin and lead in Group 4, for example) will have structures like those above. That means that the only elements to form positive ions with noble gas structures (apart from odd ones like scandium) are those in groups 1 and 2 of the Periodic Table and aluminium in group 3 (boron in group 3 doesn't form ions). Negative ions are tidier! Those elements in Groups 5, 6 and 7 which form simple negative ions all have noble gas structures. If elements aren't aiming for noble gas structures when they form ions, what decides how many electrons are transferred? The answer lies in the energetics of the process by which the compound is made.
	Warning! From here to the bottom of this page goes beyond anything you are likely to need for A'level purposes. It is included for interest only.
What determines what the charge is on an ion? Elements combine to make the compound which is as stable as possible - the one in which the greatest amount of energy is evolved in its making. The more charges a positive ion has, the greater the attraction towards its accompanying negative ion. The greater the attraction, the more energy is released when the ions come together. That means that elements forming positive ions will tend to give away as many electrons as possible. But there's a down-side to this. Energy is needed to remove electrons from atoms. This is calledionisation energy. The more electrons you remove, the greater the total ionisation energy becomes. Eventually the total ionisation energy needed becomes so great that the energy released when the attractions are set up between positive and negative ions isn't large enough to cover it. The element forms the ion which makes the compound most stable - the one in which most energy is released over-all. For example, why is calcium chloride CaCl2 rather than CaCl or CaCl3? If one mole of CaCl (containing Ca+ ions) is made from its elements, it is possible to estimate that about 171 kJ of heat is evolved. However, making CaCl2 (containing Ca2+ ions) releases more heat. You get 795 kJ. That extra amount of heat evolved makes the compound more stable, which is why you get CaCl2 rather than CaCl. What about CaCl3 (containing Ca3+ ions)? To make one mole of this, you can estimate that you would have to put in 1341 kJ. This makes this compound completely non-viable. Why is so much heat needed to make CaCl3? It is because the third ionisation energy (the energy needed to remove the third electron) is extremely high (4940 kJ mol-1) because the electron is being removed from the 3-level rather than the 4-level. Because it is much closer to the nucleus than the first two electrons removed, it is going to be held much more strongly.

Chemical bond

From Wikipedia, the free encyclopedia

A chemical bond is an interaction between atoms or molecules and allows the formation of polyatomic chemical compounds. A chemical bond is the attraction caused by the electromagnetic force between opposing charges, either between electrons and nuclei, or as the result of adipole attraction. The strength of bonds varies considerably; there are "strong bonds" such as covalent or ionic bonds and "weak bonds" such as dipole-dipole interactions, the London dispersion force and hydrogen bonding.

Since opposite charges attract via a basic electromagnetic force, the negatively-charged electrons orbiting the nucleus and the positively-charged protons in the nucleus attract each other. Also, an electron positioned between two nuclei will be attracted to both of them. Thus, the most stable configuration of nuclei and electrons is one in which the electrons spend more time between nuclei, than anywhere else in space. These electrons cause the nuclei to be attracted to each other, and this attraction results in the bond. However, this assembly cannot collapse to a size dictated by the volumes of these individual particles. Due to the matter wave nature of electrons and their smaller mass, they occupy a very much larger amount of volume compared with the nuclei, and this volume occupied by the electrons keeps the atomic nuclei relatively far apart, as compared with the size of the nuclei themselves.

In general, strong chemical bonding is associated with the sharing or transfer of electrons between the participating atoms. Molecules, crystals, and diatomic gases— indeed most of the physical environment around us— are held together by chemical bonds, which dictate the structure of matter.

Examples of Lewis dot-style chemical bonds betweencarbon C, hydrogen H, and oxygen O. Lewis dot depictures represent an early attempt to describe chemical bonding and are still widely used today.

Contents [hide] 1 Overview of main types of chemical bonds 2 History 3 Valence bond theory 4 Comparison of valence bond and molecular orbital theory 5 Bonds in chemical formula 6 Strong chemical bonds 6.1 Covalent bond 6.2 Ionic bond 6.3 One- and three-electron bonds 6.4 Bent bonds 6.5 3c-2e and 3c-4e bonds 6.6 Aromatic bond 6.7 Metallic bond 7 Intermolecular bonding 8 Electrons in chemical bonds 9 References 10 External links

[edit]Overview of main types of chemical bonds

In the simplest view of a so-called covalent bond, one or more electrons (often a pair of electrons) are drawn into the space between the two atomic nuclei. Here the negatively charged electrons are attracted to the positive charges of both nuclei, instead of just their own. This overcomes the repulsion between the two positively charged nuclei of the two atoms, and so this overwhelming attraction holds the two nuclei in a fixed configuration of equilibrium, even though they will still vibrate at equilibrium position. In summary, covalent bonding involves sharing of electrons in which the positively charged nuclei of two or more atoms simultaneously attract the negatively charged electrons that are being shared. In a polar covalent bond, one or more electrons are unequally shared between two nuclei.

In a simplified view of an ionic bond, the bonding electron is not shared at all, but transferred. In this type of bond, the outer atomic orbital of one atom has a vacancy which allows addition of one or more electrons. These newly added electrons potentially occupy a lower energy-state (effectively closer to more nuclear charge) than they experience in a different atom. Thus, one nucleus offers a more tightly-bound position to an electron than does another nucleus, with the result that one atom may transfer an electron to the other. This transfer causes one atom to assume a net positive charge, and the other to assume a net negative charge. The bond then results from electrostatic attraction between atoms, and the atoms become positive or negatively charged ions.

All bonds can be explained by quantum theory, but, in practice, simplification rules allow chemists to predict the strength, directionality, and polarity of bonds. The octet rule and VSEPR theory are two examples. More sophisticated theories are valence bond theory which includesorbital hybridization and resonance, and the linear combination of atomic orbitals molecular orbital method which includes ligand field theory.Electrostatics are used to describe bond polarities and the effects they have on chemical substances.

[edit]History

Main articles: History of chemistry and History of the molecule

Early speculations into the nature of the chemical bond, from as early as the 12th century, supposed that certain types of chemical specieswere joined by a type of chemical affinity. In 1704, Isaac Newton famously outlined his atomic bonding theory, in "Query 31" of his Opticks, whereby atoms attach to each other by some "force". Specifically, after acknowledging the various popular theories in vogue at the time, of how atoms were reasoned to attach to each other, i.e. “hooked atoms”, “glued together by rest”, or “stuck together by conspiring motions”, Newton states that he would rather infer from their cohesion, that "particles attract one another by some force, which in immediate contact is exceedingly strong, at small distances performs the chemical operations, and reaches not far from the particles with any sensible effect."

In 1819, on the heels of the invention of the voltaic pile, Jöns Jakob Berzelius developed a theory of chemical combination stressing the electronegative and electropositive character of the combining atoms. By the mid 19th century, Edward Frankland, F.A. Kekule, A.S. Couper, A.M. Butlerov, and Hermann Kolbe, building on the theory of radicals, developed the theory of valency, originally called “combining power”, in which compounds were joined owing to an attraction of positive and negative poles. In 1916, chemist Gilbert N. Lewis developed the concept of the electron-pair bond, in which two atoms may share one to six electrons, thus forming the single electron bond, a single bond, a double bond, or a triple bond; in Lewis's own words, "An electron may form a part of the shell of two different atoms and cannot be said to belong to either one exclusively."^[1]

That same year, Walther Kossel put forward a theory similar to Lewis' only his model assumed complete transfers of electrons between atoms, and was thus a model of ionic bonds. Both Lewis and Kossel structured their bonding models on that of Abegg's rule (1904).

In 1927, the first mathematically complete quantum description of a simple chemical bond, i.e. that produced by one electron in the hydrogen molecular ion, H₂⁺, was derived by the Danish physicist Oyvind Burrau.^[2] This work showed that the quantum approach to chemical bonds could be fundamentally and quantitatively correct, but the mathematical methods used could not be extended to molecules containing more than one electron. A more practical, albeit less quantitative, approach was put forward in the same year by Walter Heitler and Fritz London. The Heitler-London method forms the basis of what is now called valence bond theory. In 1929, the linear combination of atomic orbitals molecular orbital method (LCAO) approximation was introduced by Sir John Lennard-Jones, who also suggested methods to derive electronic structures of molecules of F₂ (fluorine) and O₂ (oxygen) molecules, from basic quantum principles. This molecular orbital theory represented a covalent bond as a orbitals formed by combining the quantum mechanical Schrödinger atomic orbitals which had been hypothesized for electrons in single atoms. The equations for bonding electrons in multi-electron atoms could not be solved to mathematical perfection (i.e., analytically), but approximations for them still gave many good qualitative predictions and results. Most quantitative calculations in modern quantum chemistryuse either valence bond or molecular orbital theory as a starting point, although a third approach, Density Functional Theory, has become increasingly popular in recent years.

In 1935, H. H. James and A. S. Coolidge carried out a calculation on the dihydrogen molecule that, unlike all previous calculation which used functions only of the distance of the electron from the atomic nucleus, used functions which also explicitly added the distance between the two electrons.^[3] With up to 13 adjustable parameters they obtained a result very close to the experimental result for the dissociation energy. Later extensions have used up to 54 parameters and give excellent agreement with experiment. This calculation convinced the scientific community that quantum theory could give agreement with experiment. However this approach has none of the physical pictures of the valence bond and molecular orbital theories and is difficult to extend to larger molecules.

[edit]Valence bond theory

Main article: Valence bond theory

In the year 1927, valence bond theory was formulated which argued essentially that a chemical bond forms when two valence electrons, in their respective atomic orbitals, work or function to hold two nuclei together, by virtue of system energy lowering effects. In 1931, building on this theory, chemist Linus Pauling published what some consider one of the most important papers in the history of chemistry: “On the Nature of the Chemical Bond”. In this paper, building on the works of Lewis, and the valence bond theory (VB) of Heitler and London, and his own earlier work, he presented six rules for the shared electron bond, the first three of which were already generally known:

1. The electron-pair bond forms through the interaction of an unpaired electron on each of two atoms.

2. The spins of the electrons have to be opposed.

3. Once paired, the two electrons cannot take part in additional bonds.

His last three rules were new:

4. The electron-exchange terms for the bond involves only one wave function from each atom.

5. The available electrons in the lowest energy level form the strongest bonds.

6. Of two orbitals in an atom, the one that can overlap the most with an orbital from another atom will form the strongest bond, and this bond will tend to lie in the direction of the concentrated orbital.

Building on this article, Pauling’s 1939 textbook: On the Nature of the Chemical Bond would become what some have called the “bible” of modern chemistry. This book helped experimental chemists to understand the impact of quantum theory on chemistry. However, the later edition in 1959 failed to address adequately the problems that appeared to be better understood by molecular orbital theory. The impact of valence theory declined during the 1960s and 1970s as molecular orbital theory grew in popularity and was implemented in many large computer programs. Since the 1980s, the more difficult problems of implementing valence bond theory into computer programs have been largely solved and valence bond theory has seen a resurgence.

[edit]Comparison of valence bond and molecular orbital theory

In some respects valence bond theory is superior to molecular orbital theory. When applied to the simplest two-electron molecule, H₂, valence bond theory, even at the simplest Heitler-London approach, gives a much closer approximation to the bond energy, and it provides a much more accurate representation of the behavior of the electrons as chemical bonds are formed and broken. In contrast simple molecular orbital theory predicts that the hydrogen molecule dissociates into a linear superposition of hydrogen atoms and positive and negative hydrogen ions, a completely unphysical result. This explains in part why the curve of total energy against interatomic distance for the valence bond method lies above the curve for the molecular orbital method at all distances and most particularly so for large distances. This situation arises for all homonuclear diatomic molecules and is particularly a problem for F₂, where the minimum energy of the curve with molecular orbital theory is still higher in energy than the energy of two F atoms.

The concepts of hybridization are so versatile, and the variability in bonding in most organic compounds is so modest, that valence bond theory remains an integral part of the vocabulary of organic chemistry. However, the work of Friedrich Hund, Robert Mulliken, and Gerhard Herzbergshowed that molecular orbital theory provided a more appropriate description of the spectroscopic, ionization and magnetic properties of molecules. The deficiencies of valence bond theory became apparent when hypervalent molecules (e.g. PF₅) were explained without the use of d orbitals that were crucial to the bonding hybridisation scheme proposed for such molecules by Pauling. Metal complexes and electron deficient compounds (e.g. diborane) also appeared to be well described by molecular orbital theory, although valence bond descriptions have been made.

In the 1930s the two methods strongly competed until it was realised that they are both approximations to a better theory. If we take the simple valence bond structure and mix in all possible covalent and ionic structures arising from a particular set of atomic orbitals, we reach what is called the full configuration interaction wave function. If we take the simple molecular orbital description of the ground state and combine that function with the functions describing all possible excited states using unoccupied orbitals arising from the same set of atomic orbitals, we also reach the full configuration interaction wavefunction. It can be then seen that the simple molecular orbital approach gives too much weight to the ionic structures, while the simple valence bond approach gives too little. This can also be described as saying that the molecular orbital approach is too delocalised, while the valence bond approach is too localised.

The two approaches are now regarded as complementary, each providing its own insights into the problem of chemical bonding. Modern calculations in quantum chemistry usually start from (but ultimately go far beyond) a molecular orbital rather than a valence bond approach, not because of any intrinsic superiority in the former but rather because the MO approach is more readily adapted to numerical computations. However better valence bond programs are now available.

[edit]Bonds in chemical formula

The 3-dimensionality of atoms and molecules makes it difficult to use a single technique for indicating orbitals and bonds. In molecular formulae the chemical bonds (binding orbitals) between atoms are indicated by various different methods according to the type of discussion. Sometimes, they are completely neglected. For example, in organic chemistry chemists are sometimes concerned only with the functional groups of the molecule. Thus, the molecular formula of ethanol (a compound in alcoholic beverages) may be written in a paper inconformational, 3-dimensional, full 2-dimensional (indicating every bond with no 3-dimensional directions), compressed 2-dimensional (CH₃–CH₂–OH), separating the functional group from another part of the molecule (C₂H₅OH), or by its atomic constituents (C₂H₆O), according to what is discussed. Sometimes, even the non-bonding valence shell electrons (with the 2-dimensional approximate directions) are marked, i.e. for elemental carbon _.^'C^'. Some chemists may also mark the respective orbitals, i.e. the hypothetical ethene⁻⁴ anion (_\^/C=C_/^{\ −4}) indicating the possibility of bond formation.

[edit]Strong chemical bonds

Typical bond lengths in pm and bond energies in kJ/mol. Bond lengths can be converted to Å by division by 100 (1 Å = 100 pm). Data taken from [1].
Bond	Length (pm)	Energy (kJ/mol)
H — Hydrogen
H–H	74	436
H–O	96	366
H–F	92	568
H–Cl	127	432
C — Carbon
C–H	109	413
C–C	154	348
C=C	134	614
C≡C	120	839
C–N	147	308
C–O	143	360
C–F	134	488
C–Cl	177	330
N — Nitrogen
N–H	101	391
N–N	145	170
N≡N	110	945
O — Oxygen
O–O	148	145
O=O	121	498
F, Cl, Br, I — Halogens
F–F	142	158
Cl–Cl	199	243
Br–H	141	366
Br–Br	228	193
I–H	161	298
I–I	267	151

Strong chemical bonds are the intramolecular forces which hold atoms together in molecules. A strong chemical bond is formed from the transfer or sharing of electrons between atomic centers and relies on theelectrostatic attraction between the protons in nuclei and the electrons in the orbitals. Although these bonds typically involve the transfer of integer numbers of electrons (this is the bond order), some systems can have intermediate numbers. An example of this is the organic molecule benzene, where the bond order is 1.5 for each carbon atom.

The types of strong bond differ due to the difference in electronegativity of the constituent elements. A large difference in electronegativity leads to more polar (ionic) character in the bond.

[edit]Covalent bond

Main article: Covalent bond

Covalent bonding is a common type of bonding, in which the electronegativity difference between the bonded atoms is small or nonexistent. Bonds within most organic compounds are described as covalent. See sigma bonds and pi bonds for LCAO-description of such bonding.

A polar covalent bond is a covalent bond with a significant ionic character. This means that the electrons are closer to one of the atoms than the other, creating an imbalance of charge. They occur as a bond between two atoms with moderately different electronegativities, and give rise to dipole-dipole interactions.

A coordinate covalent bond is one where both bonding electrons are from one of the atoms involved in the bond. These bonds give rise to Lewis acids and bases. The electrons are shared roughly equally between the atoms in contrast to ionic bonding. Such bonding occurs in molecules such as the ammonium ion(NH₄⁺) and are shown by an arrow pointing to the Lewis acid.

Molecules which are formed primarily from non-polar covalent bonds are often immiscible in water or otherpolar solvents, but much more soluble in non-polar solvents such as hexane.

[edit]Ionic bond

Main article: Ionic bond

Ionic bonding is a type of electrostatic interaction between atoms which have a large electronegativity difference. There is no precise value that distinguishes ionic from covalent bonding but a difference of electronegativity of over 1.7 is likely to be ionic and a difference of less than 1.7 is likely to be covalent.^[4]Ionic bonding leads to separate positive and negative ions. Ionic charges are commonly between −3e to +3e. Ionic bonding commonly occurs in metal salts such as sodium chloride (table salt).