Chemical bonding

Atomic Bonding
As we have suggested in earlier lessons, there are more substances in the universe than 109 elements. Most matter we run into on a day-to-day basis is composed of compounds - substances in which 2 or more elements have bonded together to form a material with unique chemical properties. One such compound is water. A water molecule consists of 2 atoms of hydrogen bonded to one atom of oxygen. Another common compound is table salt. Table salt is the compound sodium chloride. Each molecule of salt is composed of one atom of sodium bonded to one atom of chlorine. This bond gives the molecule completely different chemical properties than its parent elements. Salt, for example, is a solid material that is relatively nontoxic (as demonstrated by the large amounts we eat every day). We can mix it with food or water with little consequence. Yet sodium is a metal that is violently reactive with water. If sodium comes into contact with water, the hydrogen gas that is released will actually burst into flames. And chlorine is a highly toxic, greenish-colored gas. Chlorine is so toxic that it was used during World War II as a poison gas. So what is chemical bonding and why does it happen?

If we ignore the transition metals in the Periodic Table, it becomes apparent that every electron shell beyond the 1st has a total capacity for 8 valence (outer shell) electrons (the 1st shell has a capacity for 2 valence electrons). We can represent the actual number of electrons in an atom's valence shell by drawing each valence electron as a dot surrounding the element symbol. This is called the Lewis dot structure and some examples follow:

...etc.

As it turns out, atoms bond together for a very simple reason: atoms like to have full valence shells.

 So, if one atom has a much greater affinity for electrons than another, the two may form an ionic bond. If two atoms have equal electron affinities they form covalent bonds. What if two atoms are slightly unequal? In a molecule of water for example, oxygen has a greater affinity for electrons than hydrogen, but not enough to pull the electrons away completely and form ionic bonds. This is possible because there are 2 types of covalent bonds. Non-polar covalent bonds are formed when atoms share electrons equally, such as in the examples above. But when one atom has a greater affinity for electrons in a molecule, the shared electrons will spend more time around that atom and the bond formed will be a polar covalent bond. This is the case with the water molecule. Each water molecule consists of 2 atoms of hydrogen bonded to 1 atom of oxygen and thus has the chemical formula H2O. In H2O, the electrons tend to spend more time around the oxygen atom than the hydrogen atoms. The unequally shared electrons will cause a partial electrical charge (called a dipole) to form across the molecule as illustrated in the animation available below:

Skills to develop
Explain material structures in terms of chemical bonds. Describe various concepts developed for chemical bonds. Expand the concept of chemical bond (to be innovative, and creative). Describe the octet rule and apply it to write Lewis dot structures for ions and molecules.

A Brief Past on Chemical Bond Concepts

Various concepts or theories have been proposed to explain the formation of compounds. In particular, chemical bonds were proposed to explain why and how one element reacted with another element. In 1852, E. Frankland proposed the concept of valence. He suggested that each element formed compounds with definite amounts of other elements due to a valence connection. Each element has a definite number of valance. Five years later, F.A. Kekule and others proposed a valence of 4 for carbon. Lines were used to represent valance, and this helped the development of organic chemistry. The structure of benzene was often quoted as an achievement in this development. More than 10 years later, J.H. van't Hoff and le Bel proposed the tetrahedral arrangement for the four valences around the carbon. These theory helped chemists to describe many organic compounds. In the mean time, chemical bonds were thaught to be electric nature. Since electrons have not been discovered as the negative charge carriers, they were thought to be involved in chemical bonds. Following the discoveries of electrons by J.J. Thomson and R. A. Millikan, G.N. Lewis proposed to use dots to represent valence electrons. His dots made the valence electrons visible to chemists, and he has been credited as the originator of modern bonding theory.

Lewis Dot Structures

For the elements in the 2nd and 3rd periods, the number of valence electrons range from 1 to 8. Lewis dot structure for them are as indicated:

Using dots, Lewis made the valence electron visible. The stability of noble gases is now associated with the 8 valence electrons around it. The stability of 8 valence electrons led him to conclude that all elements strive to acquire 8 electrons in the valence shell, and the chemical reaction takes place due to elements trying to get 8 electrons. This is the octet rule. For the hydrogen and helium atoms, 2 electrons instead of 8 are required.

For example, the octet rule applies to the following molecules:

 To draw a Lewis dot structure, all the valence electrons are represented. A good way is to draw a type of dot for the valence electrons of one atom different from types in another. To do this on the computer screen using only type fonts is difficult, but you should draw a few by hand on paper. When a dash is used to represent a bond, it represents a pair of electrons. Thus, in the following representations, a dash represents two electrons, bonding or lone pairs.

Exceptions to the Octet Rule

Elements in the 3rd and higher periods may have more than 8 valence electrons. A possible explanation for this is to say that these atoms have d-type atomic orbitals to accommodate more than 8 electrons. In the following molecules, the number of valence electrons in the central atoms are as indicated:

Molecule No. of valence electrons for central atom

SF6 PCl5 12 10

ICl3 XeF4 10 12

 Draw the Lewis dot structures for the above molecules, and count the number of valence electrons for the central atoms. For H2SO4, the S atom has 12 electrons in the structure shown on your right. Each dash represent a chemical bond, which has two electrons. There is a total of 6 bonds around the S atom,

 When B, Be, and some metals are the central atoms, they have less than 8 valence electrons. The following compounds do form, but the octet rule is not satisfied. These are electron defficient molecules.

Isoelectronic Molecules and Ions

Counting the number of valence electrons often help us understand the formation of many molecules and ions. For example, all the following molecules have the 11 valence electrons:

NO CO- O2+ N2 The charged molecule do exist under special circumstance.

 The molecules of O2 are paramagnetic, and thus, they have unpaired electrons. The first dot structure does not agree with this observed fact, but the second one does. However, the second one does not obey the octet rule. Later, you will learn that the molecular orbital (MO) theory provides a good explanation for the electronic configuration for O2.

Why are chemical bonds formed ?

Chemical bonds form to lower the energy of the system, the components of the system become more stable through the formation of bonds. Everything wants to be more stable - its easy to lie down than stand up, bonding is Nature's way of allowing the elements to lie down. There are several types of chemical bond. Initially we will concern ourselves with three basic types, ionic bonding, which involves the transfer of electron(s), covalent bonding, which involves sharing of electrons and metallic bonding, which in some ways can be considered as a combination of both.

 If we examine the periodic table, we find that the elements in Group VIII (or 18), helium, neon, argon and so on, are particularly stable, so much so that they were once labeled the "inert gases". We now know that these elements are not inert, indeed xenon forms a range of compounds, but, nevertheless, they are very stable (although now we refer to these elements as the noble gases). This stability is the result of their electronic configuration, they have a full valence shell of electrons (ns2, np6) and this imparts stability. G. N. Lewis (1916) suggested that bonds (covalent) formed to enable elements to attain this "noble gas configuration". We can extend this idea to ionic compounds, in a compound such as sodium chloride, one element loses electron(s) to gain this stable electronic configuration whilst the other gains electron(s) to achieve the same result.

Properties of compounds.

We can make some general statements about the properties of compounds based on the bonding present. These are general statements and so you will find exceptions to these descriptions but they should prove useful for a basic understanding of the chemistry involved.

Ionic Compounds
Ionic compounds are generally solids at room temperature and have high melting and boiling points. They are hard but brittle solids and are poor conductors of electricity in the solid state (good conductors when molten or in solution). To explain these properties we must examine the nature of the bonding in these compound. Ionic bonds are "strong" and omnidirectional (i.e. the ions are attracted to ions of opposite charge in all directions). The ions are (to an extent) fixed in their position within the crystal lattice and have difficulty moving from these positions, being held in position by their attraction to the surrounding ions. If the ions are moved (say through physical force) this attraction is broken and alignment of like charges can occur resulting in repulsion - hence the solid is brittle. The observation that electrical conduction (however low) does occur is caused by defects in the crystal structure and this subject forms part of another series of my lectures (catch them if you can !). In solution (or when molten) the ions are able to move more easily and hence conduction (through the movement of these ions) is possible. As a side note, there are compounds which are essentially ionic which do conduct electricity rather well. These are called solid electrolytes, this is a rather speciallised area and I don't want to confuse you by spending time on this subject - if you are interested look up "silver iodide" or "-alumina" in a solid state chemistry text book.

Covalent Compounds
In general, covalent compounds have the property of being boring at least in terms of their physical properties. They represent most of that branch of chemistry known as organic chemistry, which perhaps explains a lot. Im joking, organic chemistry is very interesting, especially if you are an organic chemist (I am not!). Covalent compounds are not boring. Maybe a little dull, but definitely not boring. What can we say about covalent compounds ? In general they are gases or liquids at room temperature.

That about says it. Okay, one or two are solids because of extended 3 dimensional networks (diamond for example) but most are not solids (and in any case, most of these interesting ones belong in inorganic chemistry!). I suppose theres some interest in polar covalent compounds (polar means a little ionic) but really thats about it as far as properties go. There is some interesting chemistry of covalent compounds (I suppose) and we will look at that later but for now if you want to find out more about the properties then look elsewhere (ask an organic chemist - they are instantly recognisable).

 A single water molecule is made up of two atoms of hydrogen and one atom of oxygen. The atoms are joined by chemical bonds which are forces of attraction that hold atoms together. It is the bonds between atoms that give molecules different properties than the atoms they are composed of.

Ionic Bonding
Let's look at an example. Chlorine (Cl) has 17 total electrons: 2 in its 1st shell, 8 in the 2nd, and 7 in the 3rd. We know that the capacity of the 3rd shell is 8, so chlorine will try to pick up another electron to fill its outermost shell. Where does it get this electron? For some atoms it is easier to lose electrons than to pick up new ones. Sodium (Na), for example, has 11 total electrons: 2 in the 1st shell, 8 in the 2nd and 1 in the 3rd. For sodium to have a full valence shell it can do one of 2 things: pick up 7 new electrons (which is a very difficult thing to do) or give up one. If sodium gave up the 1 electron in its 3rd shell, this shell would now be empty and the 2nd shell (which is filled with 8 electrons) would become its valence shell. Thus chlorine and sodium are a perfect match for each other. One needs an electron and the other wants to lose an electron. When this transfer takes place, sodium loses an electron and becomes positively charged (the number of protons in an element never changes, so after losing an electron sodium will have one more positively charged proton than it does negatively charged electrons). And since chlorine gains an electron it becomes negatively charged. In this way both atoms now become ions. The opposite charges on the Na+ and Cl- ions will cause them to attract each other and form an ionic bond. Thus Na and Cl react to form the compound NaCl (the chemical formula of a compound is written using the atomic symbols joined together). To view a simulation of this reaction, click below:

 Ions are produced when atoms can obtain a stable number of electrons by giving up or gaining electrons. For example Na (sodium) can donate an electron to Cl (chlorine) generating Na+ and Cl-. The ion pair is held together by strong electrostatic attractions.

 In ionic bonding, electrons are completely transferred from one atom to another. In the process of either losing or gaining negatively charged electrons, the reacting atoms form ions. The oppositely charged ions are attracted to each other by electrostatic forces which are the basis of the ionic bond. For example, during the reaction of sodium with chlorine:

 sodium (on the left) loses its one valence electron to chlorine (on the right), resulting in

a positively charged sodium ion (left) and a negatively charged chlorine ion (right).

Covalent Bonding
What about reactions between 2 nonmetals? Many nonmetals do bond together. Hydrogen atoms, for example, often react with other hydrogen atoms. Which will become positively charged and which negative? Actually neither. Neither atom has any stronger pull (or affinity) for electrons than the other, so these reactions do not form ions. In fact, the 2 atoms share each others' electrons in what is called a covalent bond. 2 hydrogen atoms equally share electrons to form a covalent bond. Every pair of shared electrons forms one covalent bond. In the hydrogen example above, one bond is formed between the two atoms. Each covalent bond is represented by a line in the Lewis dot structure, so the molecule shown above would be represented as H-H and the chemical formula would be H2 (the subscript indicates the number of atoms of a single type in a compound). Atoms can form multiple covalent bonds if they need more than one electron to complete their valence shells. Oxygen, for example, bonds with itself to form 2 bonds between the atoms (since each atom needs to share 2 electrons). The Lewis dot structure would be, showing that each oxygen atom has 4 shared electrons (2 per bond) and 4 unshared electrons, giving each a total of 8 and filling the valence shells.

 Methane has four covalent bonds between carbon (C) and hydrogen (H). The figure below shows the methane molecule in four different views. Notice how these different views represent the atoms and their bonds differently. Electronegativity refers to the tendency for atoms to bind electrons. Oxygen (0) with an electronegativity of 3.5 has a strong affinity. Hydrogen (H)(2.1) and carbon (C)(2.5) each have lower affinities. A bond between C and H will have nearly equal sharing of electrons. Oxygen and hydrogen form a highly polar bond because of the much stronger affinity for electrons by O.

Insulin is a complicated molecule called a protein. We will later consider simpler ways to consider the complicated molecules of life.

Hydrogen Bonds
Hydrogen bonds are formed when a hydrogen atom is shared between two molecules. Hydrogen bonds have polarity. The hydrogen atom above (+) in water is covalently attached to a very electronegative oxygen atom (to right). It also shares its partial positive charge with a second electronegative oxygen atom (left).

Metallic Bonding
Bonding bewteen atoms with low electronegativity.ie 1,2 or 3 valence electrons, therefore there are many vacancies in valence shell. When electron clouds overlap, electrons can move into electron cloud of adjoining atoms. Each atom becomes surrounded by a number of others in a 3-D lattice, where valence electrons move freely from 1 valence shell to another. Delocalised valence electrons moving between nuclei generate a binding force to hold the atoms together.

Bond Energy
Bond Energy is the amount of energy released when a bond forms. It is a direct measure of the amount of stability gained when two atoms establish a chemical bond. Inversely, bond energy corresponds to the amount of energy that is required to break a bond. The amount that is required to break a bond is exactly equal to the amount released when the bond formed. The magnitude of the bond energy corresponds to the vertical drop that appears in a potential energy well at the lowest point, or most stable position, in the curve. An equation that represents a bond formation process would appear as A + B = AB + Energy. The energy term corresponds to the energy released, or bond energy.

Bond Length
Bond Length is the average distance between the centers of two bonded atoms. Because bonded atoms experience some vibration, moving towards and away from each other, the distance between bonded atoms will vary slightly over a period of time. The term Bond Length specifically refers to the average positions of the two atoms during the harmonic vibrations that they undergo. On the Potential Energy Well, the Bond Length is the position on the horizontal coordinate that corresponds to the bottom of the well, or the position of lowest energy for the system.

Bond Mechanism
The Bond Mechanism is the actual force that holds bonded atoms together. The mechanism differs from the bond motivation. The motivation explains WHY atoms would like to bond. Mechanism refers to the force that keeps them together after they have bonded. In all cases, regardless of bond type, the mechanism is an electrostatic force of attraction (Coulombic Force). The primary difference between the various types of bonds is the location of the charged areas that are responsible for establishing the electrostatic forces. For instance, in ionic systems the electrostatic force is established between the cation and the anion. In covalent types of systems, the electrostatic force is established between the positive nuclei and the negative electron cloud that exists between the nuclei.

Bond Motivation
Bond Motivation refers to the reasons behind why bonds are established. At a very fundamental level all bonds form in order to release energy. This loss of energy, or a negative change in Enthalpy, corresponds to fulfilling one of the two driving forces. All bond formation processes are exothermic. At another level, the motivation is interpreted as the desire of an atom to achieve some specific type of electronic configuration that is more stable that the configuration of the unbonded atom. For instance, if an atom can duplicate a Noble Gas configuration by bonding to another atom, then that could serve as a motivation. Removal of all valence level electrons or removal of all valence level p-orbital electrons will also provide levels of increases stability. In these cases, such electronic configurations would also be a motivation for bonds being established. Ultimately, though, in all these cases, those "special" electronic configurations are more stable because of their lower energy content. In other words, motivation still returns to the idea that all atoms want to loss energy by bonding.

Bond Order
Bond Order is the term used to distinguish between the number of bonds that exist between two atoms. The three primary bond orders are one, two and three. They would correspond to a single bond, double bond and triple bond. Under some conditions, atoms may find themselves with an average bond that appears to be half-way between a single and a double. In that case, the bond order would by 1.5. Other more exotic systems may have bond orders such as 1.33. These may be a result of bonded electrons switching between positions through a process known as resonance. As a result, the average appearance of the bond over a period of time will be the bond order.

 While there are only 118 or so elements listed on the periodic table, there are obviously more substances in nature than 118 pure elements. This is because atoms can react with one another to form new substances called compounds. Formed when two or more atoms chemically bond together, the resulting compound is unique both chemically and physically from its parent atoms. Let's look at an example. The element sodium is a silver-colored metal that reacts so violently with water that flames are produced when sodium gets wet. The element chlorine is a greenish-colored gas that is so poisonous that it was used as a weapon in World War I. When chemically bonded together, these two dangerous substances form the compound sodium chloride, a compound so safe that we eat it every day common table salt!

 In 1916, the American chemist Gilbert Newton Lewis proposed that chemical bonds are formed between atoms because electrons from the atoms interact with each other. Lewis had observed that many elements are most stable when they contained eight electrons in their valence shell. He suggested that atoms with fewer than eight valence electrons bond together to share electrons and complete their valence shells. While some of Lewis' predictions have since been proven incorrect (he suggested that electrons occupy cube-shaped orbitals), his work established the basis of what is known today about chemical bonding. We now know that there are two main types of chemical bonding, ionic bonding and covalent bonding.