CHAPTER 5 Stoichiometry is a branch of chemistry that deals with the relative quantities of reactants and products in chemical reactions.

In a balanced chemical reaction, the relations among quantities of reactants and products typically form a ratio of whole numbers. For example, in a reaction that forms ammonia (NH3), exactly one molecule of nitrogen (N2) reacts with three molecules of hydrogen (H2) to produce two molecules of NH3: N2 + 3H2 2NH3 Stoichiometry can be used to calculate quantities such as the amount of products (in mass, moles, volume, etc.) that can be produced with given reactants and percent yield (the percentage of the given reactant that is made into the product). Stoichiometry calculations can predict how elements and components diluted in a standard solution react in experimental conditions. Stoichiometry is founded on the law of conservation of mass: the mass of the reactants equals the mass of the products. Reaction stoichiometry describes the quantitative relationships among substances as they participate in chemical reactions. In the example above, reaction stoichiometry describes the 1:3:2 ratio of molecules of nitrogen, hydrogen, and ammonia. Composition stoichiometry describes the quantitative (mass) relationships among elements in compounds. For example, composition stoichiometry describes the nitrogen to hydrogen (mass) relationship in the compound ammonia: i.e., one mole of nitrogren and three moles of hydrogen are in every mole of ammonia. A stoichiometric amount or stoichiometric ratio of a reagent is the amount or ratio where, assuming that the reaction proceeds to completion: 1. 2. 3. all reagent is consumed, there is no shortfall of reagent, and no residues remain.

A nonstoichiometric mixture, where reactions have gone to completion, will have only the limiting reagent consumed completely. While almost all reactions have integer-ratio stoichiometry in amount of matter units (moles, number of particles), some nonstoichiometric compounds are known that cannot be represented by a ratio of welldefined natural numbers. These materials therefore violate the law of definite proportions that forms the basis of stoichiometry along with the law of multiple proportions. Gas stoichiometry deals with reactions involving gases, where the gases are at a known temperature, pressure, and volume, and can be assumed to be ideal gases. For gases, the volume ratio is ideally the same by the ideal gas law, but the mass ratio of a single reaction has to be calculated from the molecular masses of

the reactants and products. In practice, due to the existence of isotopes, molar masses are used instead when calculating the mass ratio.

Stoichiometry rests upon the law of conservation of mass, the law of definite proportions (i.e., the law of constant composition) and the law of multiple proportions. In general, chemical reactions combine in definite ratios of chemicals. Since chemical reactions can neither create nor destroy matter, nor transmute one element into another, the amount of each element must be the same throughout the overall reaction. For example, the amount of element X on the reactant side must equal the amount of element X on the product side. Stoichiometry is often used to balance chemical equations (reaction stoichiometry). For example, the two diatomic gases, hydrogen and oxygen, can combine to form a liquid, water, in an exothermic reaction, as described by the following equation:

Reaction stoichiometry describes the 2:1:2 ratio of hydrogen, oxygen, and water molecules in the above equation. The term stoichiometry is also often used for the molar proportions of elements in stoichiometric compounds (composition stoichiometry). For example, the stoichiometry of hydrogen and oxygen in H2O is 2:1. In stoichiometric compounds, the molar proportions are whole numbers. Stoichiometry is not only used to balance chemical equations but also used in conversions, i.e., converting from grams to moles, or from grams to millilitres. For example, to find the number of moles in 2.00 g of NaCl, one would do the following:

In the above example, when written out in fraction form, the units of grams form a multiplicative identity, which is equivalent to one (g/g=1), with the resulting amount of moles (the unit that was needed), is shown in the following equation,

Stoichiometry is also used to find the right amount of reactants to use in a chemical reaction (stoichiometric amounts). An example is shown below using the thermite reaction,

This equation shows that 1 mole of aluminium oxide and 2 moles of iron will be produced with 1 mole of iron(III) oxide and 2 moles of aluminium. So, to completely react with 85.0 g of iron(III) oxide (0.532 mol), 28.7 g (1.06 mol) of aluminium are needed.

Often, more than one reaction is possible given the same starting materials. The reactions may differ in their stoichiometry. For example, the methylation of benzene (C6H6), through a Friedel-Crafts reaction using AlCl3 as catalyst, may produce singly methylated (C6H5CH3), doubly methylated (C6H4(CH3)2), or still more highly methylated products, as shown in the following example,

In this example, which reaction takes place is controlled in part by the relative concentrations of the reactants.

The Mole Given the equation above, we can tell the number of moles of reactants and products. A mole simply represents 23 Avogadro's number (6.022 x 10 ) of molecules. A mole is similar to a term like a dozen. If you have a dozen 23 carrots, you have twelve of them. Similarly, if you have a mole of carrots, you have 6.022 x 10 carrots. In the equation above there are no numbers in front of the terms, so each coefficient is assumed to be one (1). Thus, you have the same number of moles of AgNO3, NaCl, AgCl, NaNO3. Converting between moles and grams of a substance is often important. This conversion can be easily done when the atomic and/or molecular mass of the substance(s) are known. Given the atomic or molecular mass of a substance, that mass in grams makes a mole of the substance. For example, calcium has an atomic mass of 40 atomic mass units. So, 40 grams of calcium makes one mole, 80 grams makes two moles, etc. Balancing Chemical Equations Sometimes, however, we have to do some work before using the coefficients of the terms to represent the relative number of molecules of each compound. This is the case when the equations are not properly balanced. We will consider the following equation: Al + Fe3O4---> Al2O3 + Fe Since no coefficients are in front of any of the terms, it is easy to assume that one (1) mole of Al and one (1) mole of Fe3O4 react to form one (1) mole of Al2O3. If this were the case, the reaction would be quite spectacular: an aluminum atom would appear out of nowhere, and two (2) iron atoms and one (1) oxygen atom would magically disappear. We know from the Law of Conservation of Mass (which states that matter can neither be created nor

destroyed) that this simply cannot occur. We have to make sure that the number of atoms of each particular element in the reactants equals the number of atoms of that same element in the products. To do this we have to figure out the relative number of molecules of each term expressed by the term's coefficient. Balancing a simple chemical equation is essentially done by trial and error. There are many different ways and systems of doing this, but for all methods, it is important to know how to count the number of atoms in an equation. For example we will look at the following term. 2Fe3O4 This term expresses two (2) molecules of Fe3O4. In each molecule of this substance there are three (3) Fe atoms. Therefore in two (2) molecules of the substance there must be six (6) Fe atoms. Similarly there are four (4) oxygen atoms in one (1) molecule of the substance so there must be eight (8) oxygen atoms in two (2) molecules. Now let's try balancing the equation mentioned earlier: Al + Fe3O4---> Al2O3+ Fe Developing a strategy can be difficult, but here is one way of approaching a problem like this. 1. 2. Count the number of each atom on the reactant and on the product side. Determine a term to balance first. When looking at this problem, it appears that the oxygen will be the most difficult to balance so we'll try to balance the oxygen first. The simplest way to balance the oxygen terms is: Al + 3 Fe3O4---> 4 Al2O3+ Fe Be sure to notice that the subscript times the coefficient will give the number of atoms of that element. On the reactant side, we have a coefficient of three (3) multiplied by a subscript of four (4), giving 12 oxygen atoms. On the product side, we have a coefficient of four (4) multiplied by a subscript of three (3), giving 12 oxygen atoms. Now, the oxygens are balanced. 3. Choose another term to balance. We'll choose iron, Fe. Since there are nine (9) iron atoms in the term in which the oxygen is balanced we add a nine (9) coefficient in front of the Fe. We now have: Al +3 Fe3O4---> 4Al2O3+ 9Fe 4. Balance the last term. In this case, since we had eight (8) aluminum atoms on the product side we need to have eight (8) on the reactant side so we add an eight (8) in front of the Al term on the reactant side. Now, we're done, and the balanced equation is: 8Al + 3Fe3O4 ---> 4Al2O3 + 9 Fe Limiting Reagents Sometimes when reactions occur between two or more substances, one reactant runs out before the other. That is called the "limiting reagent". Often, it is necessary to identify the limiting reagent in a problem. Example: A chemist only has 6.0 grams of C2H2 and an unlimited supply of oxygen and he desires to produce as much CO2 as possible. If she uses the equation below, how much oxygen should she add to the reaction? 2C2H2(g) + 5O2(g) ---> 4CO2(g) + 2 H2O(l)

To solve this problem, it is necessary to determine how much oxygen should be added if all of the reactants were used up (this is the way to produce the maximum amount of CO2). First, we calculate the number of moles of C2H2 in 6.0 g of C2H2. To be able to calculate the moles we need to look at a periodic table and see that 1 mole of C weighs 12.0 g and H weighs 1.0 g. Therefore we know that 1 mole of C2H2 weighs 26 g (2 12 grams + 2 1 gram). 1 mol C2H2 6.0 g C2H2 x (24.0 + 2.0)g C2H2 Then, because there are five (5) molecules of oxygen to every two (2) molecules of C 2H2, we need to multiply the result by 5/2 to get the total molecules of oxygen. Then we convert to grams to find the amount of oxygen that needs to be added: 5 mol O2 0.25 mol C2H2 x 2 mol C2H2 Percent Composition It is possible to calculate the mole ratios (also called mole fractions) between terms in a chemical equation when given the percent by mass of products or reactants. percentage by mass = mass of part/ mass of whole There are two types of percent composition problems-- problems in which you are given the formula (or the weight of each part) and asked to calculate the percentage of each element and problems in which you are given the percentages and asked to calculate the formula. In percent composition problems, there are many possible solutions. It is always possible to double the answer. For example, CH and C2H2 have the same proportions, but they are different compounds. It is standard to give compounds in their simplest form, where the ratio between the elements is as reduced as it can be-- called the empirical formula. When calculating the empirical formula from percent composition, one can convert the percentages to grams. For example, it is usually the easiest to assume you have 100 g so 54.3% would become 54.3 g. Then we can convert the masses to moles; this gives us mole ratios. It is necessary to reduce to whole numbers. A good technique is to divide all the terms by the smallest number of moles. Then the ratio of the moles can be transferred to write the empirical formula. Example: If a compound is 47.3% C (carbon), 10.6% H (hydrogen) and 42.0% S (sulfur), what is its empirical formula? To do this problem we need to transfer all of our percents to masses. We assume that we have 100 g of this substance. Then we convert to moles: 47.3 grams Carbon: 1 10.6 grams Hyrdrogen: Sulfur: 1 42.0 grams x x 1.008 grams 1 mole x 12.01 grams 1 mole = 10.52 moles = 1.310 moles 1 mole = 3.94 moles x 1 mol O2 32.0 g O2 = 20 g O2 = 0.25 mol C2H2

32.07 grams

Now we try to get an even ratio between the elements so we divide by the number of moles of sulfur, because it is the smallest number: 3.94 Carbon: 1.310 10.52 Hydrogen: 1.310 1.310 Sulfur: 1.310 So we have: C3H8 S Example: Figure out the percentage by mass of hydrogen sulfate, H 2SO4. In this problem we need to first calculate the total mass of the compound by looking at the periodic table. This gives us: 2(1.008) + 32.07 + 4(16.00) g/mol = 98.09 g/mol Now, we need to take the weight fraction of each element over the total mass (which we just found) and multiply by 100 to get a percentage. 2(1.008) hydrogen: 98.09 32.07 sulfur: 98.09 4(16.00) oxygen: 98.09 = 98.09 = 98.09 = 0.327 100 = 32.7% 64.00 = 0.652 100 = 65.2% 2.016 = 0.0206 100 = 2.06% =1 =8 =3

Now, we can check that the percentages add up to 100% 65.2 + 2.06 + 32.7 = 99.96 This is essentially 100 so we know that everything has worked, and we probably have not made any careless errors. So the answer is that H2SO4 is made up of 2.06% H, 32.7% S, and 65.2% O by mass. Empirical Formula and Molecular Formula While the empirical formula is the simplest form of a compound, the molecular formula is the form of the term as it would appear in a chemical equation. The empirical formula and the molecular formula can be the same, or the molecular formula can be any positive integer multiple of the empirical formula. Examples of empirical formulas: AgBr, Na2S, C6H10O5. Examples of molecular formulas: P2, C2O4, C6H14S2, H2, C3H9.

One can calculate the empirical formula from the masses or percentage composition of any compound. We have already discussed percent composition in the section above. If we only have mass, all we are doing is essentially eliminating the step of converting from percentage to mass. Example: Calculate the empirical formula for a compound that has 43.7 g P (phosphorus) and 56.3 grams of oxygen. First we convert to moles: 43.7 grams P x 1 56.3 grams O x 1 Next we divide the moles to try to get an even ratio. 1.41 Phosphorus: 1.41 3.52 Oxygen: 1.41 When we divide, we did not get whole numbers so we must multiply by two (2). The answer = P 2O5 Calculating the molecular formula once we have the empirical formula is easy. If we know the empirical formula of a compound, all we need to do is divide the molecular mass of the compound by the mass of the empirical formula. It is also possible to do this with one of the elements in the formula; simply divide the mass of that element in one mole of compound by the mass of that element in the empirical formula. The result should always be a natural number. Example: if we know that the empirical formula of a compound is HCN and we are told that a 2.016 grams of hydrogen are necessary to make the compound, what is the molecular formula? In the empirical formula hydrogen weighs 1.008 grams. Dividing 2.016 by 1.008 we see that the amount of hydrogen needed is twice as much. Therefore the empirical formula needs to be increased by a factor of two (2). The answer is: H2C2N2. Density Density refers to the mass per unit volume of a substance. It is a very common term in chemistry. Concentrations of Solutions The concentration of a solution is the "strength" of a solution. A solution typically refers to the dissolving of some solid substance in a liquid, such as dissolving salt in water. It is also often necessary to figure out how much water to add to a solution to change it to a specific concentration. The concentration of a solution is typically given in molarity. Molarity is defined as the number of moles of solute (what is actually dissolved in the solution) divided by the volume in liters of solution (the total volume of what is dissolved and what it has been dissolved in). = 2.50 = 1.00 16.00 grams 30.97 grams 1 mol 1 mol = 1.41 moles = 3.52 moles

moles of solute Molarity = liters of solution Molarity is probably the most commonly used term because measuring a volume of liquid is a fairly easy thing to do. Example: If 5.00 g of NaOH are dissolved in 5000 mL of water, what is the molarity of the solution? One of our first steps is to convert the amount of NaOH given in grams into moles: 5.00g NaOH x 1 (22.9 + 16.00 + 1.008)g 1 mole = 0.125 moles

Now we simply use the definition of molarity: moles/liters to get the answer 0.125 moles Molarity = 5.00 L of soln So the molarity (M) of the solution is 0.025 mol/L. Molality is another common measurement of concentration. Molality is defined as moles of solute divided by kilograms of solvent (the substance in which it is dissolved, like water). moles of solute Molality = kg of solvent Molality is sometimes used in place of molarity at extreme temperatures because the volume can contract or expand. Example: If the molality of a solution of C2H5OH dissolved in water is 1.5 and the mass of the water is 11.7 kg, figure out how much C2H5OH must have been added in grams to the solution. Our first step is to substitute what we know into the equation. Then we try to solve for what we don't know: moles of solute. Once we know the moles of solute we can look at the periodic table and figure out the conversion from moles to grams. moles solute Molality = kg solvent Now we simply use the definition of molarity: moles/liters to get the answer moles solute Molality = kg solvent 1.5 mols = moles solute = 0.025 mol/L

kg moles 1.5 kg 17.55 moles

11.7 kg x 11.7 kg = 17.55 moles (2 12.01) + (6 1.008) + 16 x = 808.5 g C2H5OH 1 moles

It is possible to convert between molarity and molality. The only information needed is density. Example: If the molarity of a solution is 0.30 M, calculate the molality of the solution knowing that the density is 3.25 g/mL. To do this problem we can assume one (1) liter of solution to make the numbers easier. We need to get from the molarity units of mol/L to the molality units of mol/kg. We work the problem as follows, remembering that there are 1000 mL in a Liter and 1000 grams in a kg. This conversion will only be accurate at small molarities and molalities. 0.3 mol x 1L 3.25 g 1 mL x 1000 mL 1L x 1 kg 1000 g = 0.09 mols / kg

It is also possible to calculate colligative properties, such as boiling point depression, using molality. The equation for temperature depression or expansion is T= Kf m Where: T is temperature depression (for freezing point) or temperature expansion (for boiling point) (C) Kf is the freezing point constant (kg C/mol) m is molality in mol/kg Example: If the freezing point of the salt water put on roads is -5.2 C, what is the molality of the solution? (The Kf for water is 1.86 C/m.) This is a simple problem where we just plug in numbers into the equation. One piece of information we do have to know is that water usually freezes at 0 C. T = Kf * m T/Kf = m m = 5.2/1.86 m = 2.8 mols/kg

CHAPTER 6
A chemical bond is an attraction between atoms that allows the formation of chemical substances that contain two or more atoms. The bond is caused by the electromagnetic force attraction between opposite charges, either betweenelectrons and nuclei, or as the result of a dipole attraction. The strength of chemical 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 simple 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 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. The atoms in molecules, crystals, metals and diatomic gases indeed most of the physical environment around us are held together by chemical bonds, which dictate the structure of matter.

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 bothnuclei, 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. The last and rarely mentioned type of bonding is metallic bond. 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 includes orbital 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.

Early speculations into the nature of the chemical bond, from as early as the 12th century, supposed that certain types of chemical species were 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, Jns 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." 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. 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. Thismolecular orbital theory represented a covalent bond as an orbital formed by
+

combining the quantum mechanical Schrdinger 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 chemistry use 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. 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.

In 1927, valence bond theory was formulated and it argues 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 effects of lowering system energies. Building on this theory, the chemist Linus Pauling published in 1931 what some consider one of the most important papers in the history of chemistry: "On the Nature of the Chemical Bond". In this paper, elaborating on the works of Lewis, and the valence bond theory (VB) of Heitler and London, and his own earlier works, Pauling 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 adequately address 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 usefulness as

it was implemented in large digital computer programs. Since the 1980s, the more difficult problems of implementing valence bond theory into computer programs have been solved largely, and valence bond theory has seen a resurgence.

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 Herzberg showed 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 deficientcompounds (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.

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 the electrostatic 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, which respresents one transferred electron or two shared electrons), some systems can have intermediate numbers of bonds. An example of this is the organic molecule benzene, where the bond order is 1.5 for each carbon atom, meaning that it has 1.5 bonds (shares three electrons) with each one of its two neighbors. 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. The electronegativity of these bonds is 0.3 to 1.7 . 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. Also known as non-polar covalent bond, the electronegativity of these bonds range from 0 to 0.3. Molecules which are formed primarily from non-polar covalent bonds are often immiscible in water or other polar 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). A typical feature of ionic bonds is that the species form into ionic crystals, in which no ion is specifically paired with any single other ion, in a specific directional bond. Rather, each species of ion is surrounded by ions of the opposite charge, and the spacing between it and each of the oppositely charged ions near it, is the same for all surrounding atoms of the same type. It is thus no longer possible to associate an ion with any specific other single ionized atom near it. This is a situation unlike that in covalent crystals, where covalent bonds between specific atoms are still discernable from the shorter distances between them, as measured by with such techniques as Xray diffraction.

Ionic crystals may contain a mixture of covalent and ionic species, as for example salts of complex acids, such as sodium cyanide, NaCN. Many minerals are of this type. X-ray diffration shows that in NaCN, for example, the bonds between sodium cations (Na+) and the cyanide anions (CN-) are ionic, with no sodium ion associated with any particular cyanide. However, the bonds between C and N atoms in cyanide are of the covalent type, making each of the carbon and nitrogen associated with just one of its opposite type, to which it is physically much closer than it is to other carbons or nitrogens in a sodium cyanide crystal. When such salts dissolve into water, the ionic bonds are typically broken by the interaction with water, but the covalent bonds continue to hold. In solution, the cyanide ions, still bound together as single CN- ions, move independently through the solution, as do sodium ions, as Na+. These charged ions move apart because each of them are more strongly attracted to a number of water molecules, than to each other. The attraction between ions and water molecules in such solutions is due to a type of weak dipoledipole type chemical bond.

One- and three-electron bonds

Bonds with one or three electrons can be found in radical species, which have an odd number of electrons. The simplest example of a 1-electron bond is found in the hydrogen molecular cation, H2+. One-electron bonds often have about half the bond energy of a 2electron bond, and are therefore called "half bonds". However, there are exceptions: in the case of dilithium, the bond is actually stronger for the 1-electron Li2+ than for the 2-electron Li2. This exception can be explained in terms of hybridization and inner-shell effects. The simplest example of three-electron bonding can be found in the helium dimer cation, He2+, and can also be considered a "half bond" because, in molecular orbital terms, the third electron is in an anti-bonding orbital which cancels out half of the bond formed by the other two electrons. Another example of a molecule containing a 3-electron bond, in addition to two 2-electron bonds, is nitric oxide, NO. The oxygen molecule, O2 can also be regarded as having two 3-electron bonds and one 2-electron bond, which accounts for its paramagnetism and its formal bond order of 2. Molecules with odd-electron bonds are usually highly reactive. These types of bond are only stable between atoms with similar electronegativities.

Bent bonds
Bent bonds, also known as banana bonds, are bonds in strained or otherwise sterically hindered molecules whose binding orbitals are forced into a banana-like form. Bent bonds are often more susceptible to reactions than ordinary bonds.

3c-2e and 3c-4e bonds

In three-center two-electron bonds ("3c2e") three atoms share two electrons in bonding. This type of bonding occurs in electron deficient compounds like diborane. Each such bond (2 per molecule in diborane) contains a pair of electrons which connect the boron atoms to each other in a banana shape, with a proton (nucleus of a hydrogen atom) in the middle of the bond, sharing electrons with both boron atoms.

Three-center four-electron bonds ("3c4e") also exist which explain the bonding in hypervalent molecules. In certain cluster compounds, so-called four-center two-electron bonds also have been postulated. In certain conjugated (pi) systems, such as benzene and other aromatic compounds (see below), and in conjugated network solids such as graphite, the electrons in the conjugated system of -bonds are spread over as many nuclear centers as exist in the molecule, or the network.

Aromatic bond
In organic chemistry, certain configurations of electrons and orbitals infer extra stability to a molecule. This occurs when orbitals overlap and combine with others on different atomic centres, forming a long range bond. For a molecule to bearomatic, it must obey Hckel's rule, where the number of electrons fit the formula 4n + 2, where n is an integer. The bonds involved in the aromaticity are all planar. In benzene, the prototypical aromatic compound, 18 (n = 4) bonding electrons bind 6 carbon atoms together to form a planar ring structure. The bond "order" (average number of bonds) between the different carbon atoms may be said to be (18/6)/2=1.5, but in this case the bonds are all identical from the chemical point of view. They may sometimes be written as single bonds alternating with double bonds, but the view of all ring bonds as being equivalently about 1.5 bonds in strength, is much closer to truth. In the case of heterocyclic aromatics and substituted benzenes, the electronegativity differences between different parts of the ring may dominate the chemical behaviour of aromatic ring bonds, which otherwise are equivalent.

Metallic bond
In a metallic bond, bonding electrons are delocalized over a lattice of atoms. By contrast, in ionic compounds, the locations of the binding electrons and their charges are static. The freely-moving or delocalization of bonding electrons leads to classical metallic properties such as shininess (surface light reflectivity), electrical and thermal conductivity, ductility, and high tensile strength.

An outline is a list of the main features of a given topic, often used as a rough draft or summary of the content of a document. A hierarchical outline is a list arranged to show hierarchical relationships, and is a type of tree structure. Writers of fiction and creative nonfiction, such as Jon Franklin, may use outlines to establish plot sequence, character development and dramatic flow of a story, sometimes in conjunction with freewriting. Merriam-Webster's manual for writers and editors (1998, p. 290) recommends that the section headings of an article should, when read in isolation, combine to form an outline of the article content. Garson (2002) distinguishes a 'standard outline', presented as a regular table of contents from a refined tree-like 'hierarchical outline', stating that "such an outline might be appropriate, for instance, when the purpose is taxonomic (placing observed phenomena into an exhaustive set of categories). ... hierarchical outlines are rare in quantitative writing, and the researcher is well advised to stick to the standard outline unless there are compelling reasons not to."

Alphanumeric Outline The alphanumeric outline is the standard format most people learned in high school English. Each main heading, or topic, is noted by a Roman numeral and can be separated into two or more distinct classifications. These subheadings would be indented and then noted by a capital letter. The third level of subheadings can be separated into two or more distinct classifications and noted by Arabic numbers. The fourth level of subheadings can be separated into two or more distinct classifications and noted by lower-case letters. Not all headings or subheadings will be separated into further classifications. Full Sentence Outline The full sentence outline is similar to the alphanumeric outline in that it follows the same format. The primary difference is that each topic, or thought, is written out as a full sentence. This can be helpful, as it ensures the complete thought is recorded on the outline and will not be forgotten when it comes time to write the paper. It is also helpful because these sentences can be transferred directly to the paper later. Decimal Outline The decimal outline is similar to the alphanumeric outline. The primary difference between is that the decimal outline is written using decimals to note each heading and subheading. The main heading would be noted by a whole number. Each subheading would be noted by a decimal building from the main heading. For example, the main heading would be noted as 1. The first subheading under that section would be noted as 1.1. If there were another level of subheadings, that line would be noted as 1.1.1. The main benefit of using a decimal outline is that each section can be clearly identified back to the main heading. The decimal outline can be written as individual thoughts or in complete sentences.